JPS6012665A - Reversible copper electrode - Google Patents
Reversible copper electrodeInfo
- Publication number
- JPS6012665A JPS6012665A JP58119731A JP11973183A JPS6012665A JP S6012665 A JPS6012665 A JP S6012665A JP 58119731 A JP58119731 A JP 58119731A JP 11973183 A JP11973183 A JP 11973183A JP S6012665 A JPS6012665 A JP S6012665A
- Authority
- JP
- Japan
- Prior art keywords
- copper
- electrode
- symbol
- prepared
- constitution
- 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
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 24
- 239000010949 copper Substances 0.000 title claims abstract description 24
- 230000002441 reversible effect Effects 0.000 title claims description 4
- 150000001875 compounds Chemical class 0.000 claims abstract description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 6
- 239000007784 solid electrolyte Substances 0.000 abstract description 6
- 239000003990 capacitor Substances 0.000 abstract description 5
- 229910002804 graphite Inorganic materials 0.000 abstract description 4
- 239000010439 graphite Substances 0.000 abstract description 4
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052799 carbon Inorganic materials 0.000 abstract description 2
- 229910000510 noble metal Inorganic materials 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 229910003092 TiS2 Inorganic materials 0.000 abstract 1
- 230000001747 exhibiting effect Effects 0.000 abstract 1
- 229910052961 molybdenite Inorganic materials 0.000 abstract 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 abstract 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 abstract 1
- 239000003792 electrolyte Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 5
- 238000007599 discharging Methods 0.000 description 4
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 3
- 229910001431 copper ion Inorganic materials 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000002427 irreversible effect Effects 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- VMQMZMRVKUZKQL-UHFFFAOYSA-N Cu+ Chemical compound [Cu+] VMQMZMRVKUZKQL-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 241000269838 Thunnus thynnus Species 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/54—Electrolytes
- H01G11/56—Solid electrolytes, e.g. gels; Additives therein
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
- H01M10/0562—Solid materials
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/48—Conductive polymers
-
- 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
-
- 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
- Y02E60/13—Energy storage using capacitors
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Electrochemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- General Chemical & Material Sciences (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
本発明は・銅イオン（Ｃｕ＋）伝導性の固体電解質を用
いる二次電池や電気二重層キャパシタなどに利用される
可逆性銅電極に関する。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a reversible copper electrode used in secondary batteries, electric double layer capacitors, etc. that use copper ion (Cu+) conductive solid electrolytes.
従来例の構成とその問題点
最近、高い銅イオン伝導性の固体電解質がつぎつぎと見
出されている。これらは従来の銅イオン伝導性の固体電
解質とほぼ同程度のイオン伝導率と分解電圧を持つとこ
ろから・同程度の電流が流せ、エネルギー蓄積ができる
安価な電池やキャパシタが得られる可能性かある。しか
し、その実現を阻む一つの問題点として、可逆性の銅電
極が無いことが挙げられる。Structure of conventional examples and their problems Recently, solid electrolytes with high copper ion conductivity have been discovered one after another. Since these have almost the same ionic conductivity and decomposition voltage as conventional copper ion-conducting solid electrolytes, there is a possibility that inexpensive batteries and capacitors that can flow the same current and store energy can be obtained. . However, one problem that prevents this from happening is the lack of a reversible copper electrode.
銅を電極とすると、その端子電圧は電解質の分解電圧に
近くできる可能性全もつが、酸化反応が非可逆的で、早
期に短絡を起こす欠点がある。酸化反応が非可逆的にな
るのは、酸化生成物が表面を覆−て反応を阻害するため
と思われる。If copper is used as an electrode, there is a possibility that the terminal voltage can be close to the decomposition voltage of the electrolyte, but the oxidation reaction is irreversible and short circuits may occur at an early stage. The reason why the oxidation reaction becomes irreversible is thought to be because oxidation products cover the surface and inhibit the reaction.
そこで、Ｃｕ２５ｉ添加したり、ＧｕｙＴｉＳ２（ｏ、
ｅｃｓ（ｙ＜０．９１で表される化合物を用いることが
提案されたーこれらの電極の可逆性を示す範囲は余り広
（な（、ＣｕｚＳの添加におりては・ＣｕｚＳが３ｏ〜
４０重量％、ＣｕｙＴｉＳ２でｙ値にしてＯ１Ｓ〜０．
９程度の所が最適中で、その範囲をはずれると銅の電位
より貴の方にはずれたり・可逆性が悪（な−たりする欠
点をもっている。Therefore, we added Cu25i, GuyTiS2(o,
It was proposed to use a compound represented by ecs (y < 0.91).The range of reversibility of these electrodes is too wide.
40% by weight, CuyTiS2 with a y value of O1S~0.
A value of about 9 is optimal, and if it is outside this range, it has the disadvantage that the potential deviates to a higher level than that of copper and the reversibility is poor.
発明の目的
本発明は、自然電位が銅の電位に近（、広い電流中にわ
たって可逆性金示す銅電極全提供すること上目的とする
。OBJECTS OF THE INVENTION It is an object of the present invention to provide a copper electrode with a natural potential close to that of copper, which exhibits reversibility over a wide range of currents.
発明の構成
本発明の銅電極は、式ＧｕｓＭｏａＳｓ士Ｘ（ただしＯ
≦Ｘ≦０．５）で表わされる化合物により構成したもの
である。Structure of the Invention The copper electrode of the present invention has the formula GusMoaSs
≦X≦0.5).
実施例の説明 第１図は本発明の銅電極を用いた電気化学装置を示す。Description of examples FIG. 1 shows an electrochemical device using the copper electrode of the present invention.
１：ｉ正極？、二次電池ノ場合’ｕ 、 Ｔｉ５ｚ 、
７Ｓ２ 。1:i positive electrode? , for secondary batteries 'u, Ti5z,
7S2.
ＭＯ８２のような周期律表Ｎ、Ｖ、■族元素の二酸化物
または二硫化物を用い電気二重層キャパシタの場合、カ
ーボンのような分極性電極を用いる。In the case of an electric double layer capacitor using a dioxide or disulfide of an element of Group N, V, or ■ of the periodic table, such as MO82, a polarizable electrode such as carbon is used.
２は銅イオン伝導性の固体電解質層で、式ＲｂＣｕ４１
１．７−ｙ Ｇ ｌ） ３．３＋ ｙ（０≦ｙ ≦０．
２ ） テＨｈすｈる化合物や前記式中Ｒｈの２５％’
ｉｉＫで置換したものなどを用いる。３は負極である、
４１′ｉ正極の集電体で、グラファイト・貴金属のよう
に電気化学的に不活性な物質を用いる。５は負極の集電
体で銅を用いる。2 is a copper ion conductive solid electrolyte layer with the formula RbCu41
1.7-y G l) 3.3+ y (0≦y≦0.
2) Compounds containing 25% of Rh in the above formula
Use one substituted with iiK. 3 is the negative electrode,
41'i The current collector of the positive electrode uses an electrochemically inert substance such as graphite or noble metal. 5 is a negative electrode current collector made of copper.
以上が単セルの構成で、最大電圧は０．５Ｖであり、必
要な電圧を得るためには、複数の単セル全グラファイト
ペーストで直列に接続する。The above is the configuration of a single cell, and the maximum voltage is 0.5V, and in order to obtain the necessary voltage, a plurality of single cells are connected in series using all graphite paste.
本発明の銅電極に用いる化合物は銅、モリブデン、イオ
ウの粉末を原子比でｔｓ ： ｅ ： ｓ、５の割合で
混合し、プレス成形した後、密封容器に入れ、一度真空
に引き、その状態で４００℃の温度で１２時間、次いで
１ＱＯｏ℃で２４時間加熱することによって製造するこ
とができる。The compound used for the copper electrode of the present invention is made by mixing powders of copper, molybdenum, and sulfur in an atomic ratio of ts:e:s, 5, press-molding the mixture, placing it in a sealed container, evacuating it once, and keeping it in that state. It can be produced by heating at a temperature of 400° C. for 12 hours and then at 1QOo° C. for 24 hours.
次に、本発明の銅電極を二次電池に適用した実施例を説
明する。Next, an example in which the copper electrode of the present invention is applied to a secondary battery will be described.
正極−として・活物質のＴｉＳｚ２０ｏｍｇと電解質の
Ｒｂ Ｃｕ４Ｉｔ、ｓ Ｃ１３，ｓ ６００ ｍｇの混
合物、電解質層には前記電解質５００ｍｇ、負極には、
Ｃｕ５ Ｍ２Ｓ Ｓｓ、３５０ ｍｇと同様の電解質２
０ｍｇの混合物をそれぞれ用い、成形して第１図のよう
な構成で直径１０ｍ＋ｎの電−池を作った。なお、電解
質層には、第１図に示すように、基準極として銅線６を
打ち込んで負極の電位変化全測定した。As a positive electrode - A mixture of 20 omg of TiSz as an active material and 600 mg of RbCu4It, s C13,s as an electrolyte, 500 mg of the electrolyte in the electrolyte layer, and 500 mg of the electrolyte in the negative electrode.
Cu5 M2S Ss, 350 mg and similar electrolyte 2
Using 0 mg of each of the mixtures, a battery having a diameter of 10 m+n was made with the configuration shown in FIG. 1 by molding. Incidentally, as shown in FIG. 1, a copper wire 6 was inserted into the electrolyte layer as a reference electrode, and all potential changes of the negative electrode were measured.
上記の電池をＡとし、比較例として、負極活物質に銅を
用いた電池をＢ ＋ Ｃｕｏ、９ＴｉＳ２ｆ用いた電池
をＣ１銅粉とＣｕｚＳ との重量３：２の混合物を用い
た電池をＤとする。The above battery is designated as A, and as a comparative example, a battery using copper as the negative electrode active material is designated as B + Cuo, a battery using 9TiS2f is designated as C1, a battery using a 3:2 mixture of copper powder and CuzS by weight is designated as D. do.
第２図は、これらの電池の放電電流密度と平坦電圧との
関係を示す。第３図はｉｏｏμＡ／ｃｒｌ で・ 放電
したときの電位変化を示す。また、第４図は１００μＡ
／ｃｄで３時間充電い同電流密度で３時間放電する充放
電を繰り返したときの５０サイクル毎の負極の容量変イ
は示す。なお、終止電圧はｏ、ａｙとした。FIG. 2 shows the relationship between discharge current density and flat voltage for these batteries. Figure 3 shows the potential change when discharging at iooμA/crl. In addition, Fig. 4 shows 100μA
The change in capacity of the negative electrode every 50 cycles when charging and discharging for 3 hours at /cd and discharging for 3 hours at the same current density is shown. Note that the final voltages were o and ay.
本発明の負極は、放電分極が少なく、２０００サイクル
程度の充放電に十分耐えることが明ら力１である。It is clear that the negative electrode of the present invention has little discharge polarization and can sufficiently withstand about 2000 cycles of charging and discharging.
なお、本発明の負極活物質化合物は、上記一般式にかけ
るＸの値の範嬰全用いることができる。In addition, the negative electrode active material compound of the present invention can be used in all the ranges of the values of X in the above general formula.
発明の効果
以上のように、本発明銅電極の自然電位は、銅や銅とＣ
ｕｚＳの混合物を用いる電極に較べてやや貴であるが、
放電分極が小さく、長寿命であり、銅イオン導電性の固
体電解質を使った二次電池や電気二重層容量素子を可能
にするものである。Effects of the Invention As described above, the natural potential of the copper electrode of the present invention is
Although slightly more noble than electrodes using mixtures of uzS,
It has low discharge polarization and long life, making it possible to create secondary batteries and electric double layer capacitors using copper ion conductive solid electrolytes.
第１図は本発明の銅電極を用いた電気化学装置の基本的
構成を示す縦断面図、第２図は各種銅電極の電流−電位
特性を示す図、第３図は放電時の電位変化を示す図・第
４図は負極のサイクル寿命を示す図である。
１・・・・・・正極、２・・・・・・電解質層、３・・
・・・・銅電極。
代理人の氏名 弁理士 中 尾 敏 男 ほか１名。
第１図
４
２図
紋質Ａ屯’ｌ”−ｓ窮攬 （）’４／ｃｍす第３図
２ピζ１也゛日４ ハｆｌ（Ａ＊）
第４図
サイクル較Figure 1 is a longitudinal cross-sectional view showing the basic configuration of an electrochemical device using the copper electrode of the present invention, Figure 2 is a diagram showing the current-potential characteristics of various copper electrodes, and Figure 3 is a diagram showing potential changes during discharge. Figure 4 shows the cycle life of the negative electrode. 1... Positive electrode, 2... Electrolyte layer, 3...
...Copper electrode. Name of agent: Patent attorney Toshio Nakao and one other person. Fig. 1 4 2 Fig. Atun 'l'' - s poverty ()'4/cm Fig. 3 2 pi ζ 1 ゛ day 4 Hafl (A*) Fig. 4 Cycle comparison
Claims (1)
．５）で表わされる化合物よりなる可逆性銅電極。Formula Cus Mo aF3s±X (however, 0≦X≦0
．． 5) A reversible copper electrode made of a compound represented by.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58119731A JPS6012665A (en) | 1983-06-30 | 1983-06-30 | Reversible copper electrode |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58119731A JPS6012665A (en) | 1983-06-30 | 1983-06-30 | Reversible copper electrode |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6012665A true JPS6012665A (en) | 1985-01-23 |
| JPH0467302B2 JPH0467302B2 (en) | 1992-10-27 |
Family
ID=14768725
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP58119731A Granted JPS6012665A (en) | 1983-06-30 | 1983-06-30 | Reversible copper electrode |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6012665A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5944007A (en) * | 1996-02-08 | 1999-08-31 | Tokyo Rope Mfg. Co., Ltd. | Wire type slicing machine and method |
| CN103367756A (en) * | 2013-07-22 | 2013-10-23 | 山东大学 | Preparation method of porous copper based lithium ion battery anode material |
| CN105016391A (en) * | 2015-07-23 | 2015-11-04 | 江苏新光环保工程有限公司 | Preparation method of three- dimensional MoS2 |
| US20180251990A1 (en) * | 2015-10-29 | 2018-09-06 | Sakaegumi Corporation | Device for repairing crack in wall |
-
1983
- 1983-06-30 JP JP58119731A patent/JPS6012665A/en active Granted
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5944007A (en) * | 1996-02-08 | 1999-08-31 | Tokyo Rope Mfg. Co., Ltd. | Wire type slicing machine and method |
| CN103367756A (en) * | 2013-07-22 | 2013-10-23 | 山东大学 | Preparation method of porous copper based lithium ion battery anode material |
| CN105016391A (en) * | 2015-07-23 | 2015-11-04 | 江苏新光环保工程有限公司 | Preparation method of three- dimensional MoS2 |
| US20180251990A1 (en) * | 2015-10-29 | 2018-09-06 | Sakaegumi Corporation | Device for repairing crack in wall |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0467302B2 (en) | 1992-10-27 |
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