JPS6347112B2 - - Google Patents
Info
- Publication number
- JPS6347112B2 JPS6347112B2 JP56073137A JP7313781A JPS6347112B2 JP S6347112 B2 JPS6347112 B2 JP S6347112B2 JP 56073137 A JP56073137 A JP 56073137A JP 7313781 A JP7313781 A JP 7313781A JP S6347112 B2 JPS6347112 B2 JP S6347112B2
- Authority
- JP
- Japan
- Prior art keywords
- nickel
- molybdenum
- lithium ions
- added
- electrode
- 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
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 58
- 229910052759 nickel Inorganic materials 0.000 claims description 29
- 239000003792 electrolyte Substances 0.000 claims description 15
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 14
- 229910001416 lithium ion Inorganic materials 0.000 claims description 14
- 239000011149 active material Substances 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- GDXTWKJNMJAERW-UHFFFAOYSA-J molybdenum(4+);tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Mo+4] GDXTWKJNMJAERW-UHFFFAOYSA-J 0.000 claims description 5
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- 239000011733 molybdenum Substances 0.000 claims description 4
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims description 3
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims description 3
- 229910052793 cadmium Inorganic materials 0.000 claims description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims 1
- 239000007788 liquid Substances 0.000 claims 1
- 229910052725 zinc Inorganic materials 0.000 claims 1
- 239000011701 zinc Substances 0.000 claims 1
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 18
- -1 molybdenum trioxide compound Chemical class 0.000 description 9
- 239000000654 additive Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 5
- 239000013078 crystal Substances 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000007774 positive electrode material Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 2
- 150000002642 lithium compounds Chemical class 0.000 description 2
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 239000005078 molybdenum compound Substances 0.000 description 1
- 150000002752 molybdenum compounds Chemical class 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- QELJHCBNGDEXLD-UHFFFAOYSA-N nickel zinc Chemical compound [Ni].[Zn] QELJHCBNGDEXLD-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium 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
- H01M4/36—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
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
-
- 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)
Description
本発明はニツケル―カドミウム電池、ニツケル
―亜鉛電池などのように正極活物質としてニツケ
ルを用いるアルカリ蓄電池に関するものである。
正極活物質としてのニツケルは耐アルカリ性に
富み、且サイクル特性に優れるという利点を有す
るものの利用率が悪いという欠点がある。そのた
め従来ではニツケル極の利用率の向上のためにリ
チウムやコバルトを添加している。
本発明者はニツケル極或いは電解液中への種々
の添加剤について実験検討した結果、ニツケル極
に金属モリブデン、酸化モリブデン、水酸化モリ
ブデンのうちから選ばれた少なくとも１種のもの
を添加し、且リチウムイオンを含むアルカリ電解
液を併用することにより、ニツケル極の利用率を
さらに改善しうることを見出した。
本発明は上記事実に基づいてなされたものであ
り、以下本発明の実施例を詳述する。
活物質としての試薬水酸化ニツケル粉末80重量
％、導電剤としてのニツケル金属粉末５重量％、
カーボン粉末５重量％、結着剤としてのポリエス
テル５重量％及び添加剤としての三酸化モリブデ
ン５重量％をよく混合し、この混合粉末を予備成
型圧100〜500Kg／cm2で成型し成型ペレツトを50〜
200メツシユの金属金網にて被覆したのち300Kg／
cm2で最終成型して正極とする。
一方、電解液としては25％のカ性カリ（KOH）
溶液に10ｇ／の水酸化リチウム（LiOH）を添
加したものを用い、且周知のカドミウム極と組合
せて本発明電池Ａを作成した。
尚、比較のため下表に示す如き構成の比較電池
Ｂ，Ｃ，Ｄを作成し、これらを10mAで放電した
ときの放電特性を第１図に示す。
The present invention relates to alkaline storage batteries that use nickel as a positive electrode active material, such as nickel-cadmium batteries and nickel-zinc batteries. Nickel as a positive electrode active material has the advantage of being highly resistant to alkali and having excellent cycle characteristics, but has the disadvantage of poor utilization rate. Therefore, conventionally, lithium and cobalt have been added to improve the utilization rate of nickel electrodes. As a result of experimental studies on various additives to the nickel electrode or electrolyte, the present inventor added at least one selected from metal molybdenum, molybdenum oxide, and molybdenum hydroxide to the nickel electrode, and We have discovered that the utilization rate of nickel electrodes can be further improved by using an alkaline electrolyte containing lithium ions. The present invention has been made based on the above facts, and examples of the present invention will be described in detail below. 80% by weight of reagent nickel hydroxide powder as active material, 5% by weight of nickel metal powder as conductive agent,
5% by weight of carbon powder, 5% by weight of polyester as a binder, and 5% by weight of molybdenum trioxide as an additive are thoroughly mixed, and this mixed powder is molded at a preforming pressure of 100 to 500 kg/cm 2 to form molded pellets. 50～
300Kg/ after covering with 200 mesh metal wire mesh
Final molding in cm 2 is used as a positive electrode. On the other hand, the electrolyte is 25% caustic potassium (KOH).
A battery A of the present invention was prepared by using a solution containing 10 g of lithium hydroxide (LiOH) and combining it with a well-known cadmium electrode. For comparison, comparative batteries B, C, and D were prepared as shown in the table below, and FIG. 1 shows the discharge characteristics when these batteries were discharged at 10 mA.
【表】
第１図を参照すると、比較電池Ｃ或いはＤのよ
うにニツケル極に三酸化モリブデン化合物を添加
するのみ或いは電解液にリチウムイオンを含有せ
しめたのみの電池では何も添加しない比較電池Ｂ
に比して特性の向上が顕著でないが、ニツケル極
に三酸化モリブデン化合物を添加し、且リチウム
イオンを含有せるアルカリ電解液を併用した本発
明電池Ａに依れば電池容量が明らかに増大してい
ることがわかる。
このような本発明の効果について考察すると、
リチウムイオンがニツケル極の利用率の向上に効
果があることは前述したが、その理由はリチウム
イオンが充電時に水酸化ニツケルの結晶中に侵入
してニツケルの酸化を促進させることにより充電
効率を高めその結果としてニツケル極の利用率を
改善するものであると考えられている。この現象
は第１図の比較電池ＢとＤを対比させると明らか
である。
又、比較電池Ｃのようにニツケル極に三酸化モ
リブデン化合物を添加し、リチウムイオンを含ま
ないアルカリ電解液を用いた場合には、ニツケル
極の利用率は向上するどころかむしろ劣化してい
る。この結果から三酸化モリブデン化合物はニツ
ケル極の利用率に何ら影響を及ぼさずニツケル極
内におけるニツケル活物質量の充填量が三酸化モ
リブデン化合物の添加分だけ減少した結果として
容量が減少したと思われる。
ところが、三酸化モリブデン化合物とリチウム
イオンとを共存させた場合には、三酸化モリブデ
ンが、アルカリ電解液と反応して水酸化モリブデ
ンを生成し、充電時、リチウムイオンがこの水酸
化モリブデン結晶中に侵入して、リチウム―水酸
化モリブデンを形成する。このリチウム―水酸化
モリブデンはニツケル活物質の結晶格子間隔を広
げ、ニツケル結晶中のプロトン（H+）移動を促
進させる。この結果、ニツケル極の充放電効率に
好影響を与え、ニツケル極の利用率を向上させる
ものであると考えられる。
第２図はリチウムイオンを含むアルカリ電解液
の存在下における三酸化モリブデンの添加量とニ
ツケル極の利用率との関係を示し、三酸化モリブ
デンの添加量が５重量％の時のニツケル極の利用
率を100％として表わしたものであり、添加量と
しては2.5〜15重量％の範囲が好ましい。
尚、本発明においてリチウムイオンを含むアル
カリ電解液とは実施例で示したように電解液中に
リチウム化合物を添加するものに限定されず、予
じめニツケル極の作成時にリチウム化合物を組込
んでおき電池組立時点において極板から溶出した
リチウムイオンを含むアルカリ電解液であつても
良い。
又、本発明において実施例では添加剤として酸
化モリブデンの一例である三酸化モリブデンを用
いたが、酸化物の形態であれば、これに限定され
るものではない。また他の添加剤としては金属モ
リブデン、水酸化モリブデンを用いても同様の効
果が得られる。
上述した如く、本発明は正極活物質としてニツ
ケルを用いるアルカリ蓄電池に関するものであ
り、ニツケル極にモリブデン又は／及びモリブデ
ン化合物を添加し、且リチウムイオンを含むアル
カリ電解液を併用することによりニツケル極の利
用率を改善して電池特性を改良しうるものであ
り、その工業的価値は極めて大である。[Table] Referring to Figure 1, compared to comparative batteries C and D in which only a molybdenum trioxide compound is added to the nickel electrode or only lithium ions are added to the electrolyte, comparative battery B does not contain any additives.
Although the improvement in characteristics is not remarkable compared to the battery of the present invention, the battery capacity is clearly increased by using the battery A of the present invention in which a molybdenum trioxide compound is added to the nickel electrode and an alkaline electrolyte containing lithium ions is used. It can be seen that Considering such effects of the present invention,
As mentioned above, lithium ions are effective in improving the utilization rate of nickel electrodes, and the reason for this is that lithium ions penetrate into the nickel hydroxide crystals during charging and promote oxidation of the nickel, thereby increasing charging efficiency. As a result, it is believed that the utilization rate of nickel poles will be improved. This phenomenon becomes clear when comparing comparative batteries B and D in FIG. Furthermore, when a molybdenum trioxide compound is added to the nickel electrode and an alkaline electrolyte containing no lithium ions is used, as in Comparative Battery C, the utilization rate of the nickel electrode does not improve but rather deteriorates. From this result, it appears that the molybdenum trioxide compound has no effect on the utilization rate of the nickel electrode, and the capacity decreases as a result of the amount of nickel active material filled in the nickel electrode being reduced by the amount of the molybdenum trioxide compound added. . However, when a molybdenum trioxide compound and lithium ions coexist, molybdenum trioxide reacts with an alkaline electrolyte to generate molybdenum hydroxide, and during charging, lithium ions are mixed into the molybdenum hydroxide crystals. enters to form lithium-molybdenum hydroxide. This lithium-molybdenum hydroxide widens the crystal lattice spacing of the nickel active material and promotes the movement of protons (H + ) in the nickel crystal. As a result, it is thought that this has a positive effect on the charging and discharging efficiency of the nickel electrode and improves the utilization rate of the nickel electrode. Figure 2 shows the relationship between the amount of molybdenum trioxide added and the utilization rate of the nickel electrode in the presence of an alkaline electrolyte containing lithium ions, and the utilization of the nickel electrode when the amount of molybdenum trioxide added is 5% by weight. The ratio is expressed as 100%, and the amount added is preferably in the range of 2.5 to 15% by weight. In the present invention, the alkaline electrolyte containing lithium ions is not limited to one in which a lithium compound is added to the electrolyte as shown in the example, but it may be one in which a lithium compound is incorporated in advance at the time of making the nickel electrode. The electrolyte may be an alkaline electrolyte containing lithium ions eluted from the electrode plates at the time of assembling the battery. Further, in the examples of the present invention, molybdenum trioxide, which is an example of molybdenum oxide, was used as an additive, but the additive is not limited to this as long as it is in the form of an oxide. Similar effects can also be obtained by using metal molybdenum or molybdenum hydroxide as other additives. As mentioned above, the present invention relates to an alkaline storage battery using nickel as a positive electrode active material, and by adding molybdenum or/and a molybdenum compound to the nickel electrode and using an alkaline electrolyte containing lithium ions in combination, the nickel electrode can be heated. It is possible to improve battery characteristics by improving the utilization rate, and its industrial value is extremely large.
第１図は本発明電池と比較電池との放電特性比
較図、第２図はリチウムイオンを含むアルカリ電
解液の存在下における三酸化モリブデンの添加量
とニツケル極の利用率との関係を示す図である。
Ａ…本発明電池、Ｂ，Ｃ，Ｄ…比較電池。
Figure 1 is a comparison diagram of the discharge characteristics of the battery of the present invention and a comparison battery, and Figure 2 is a diagram showing the relationship between the amount of molybdenum trioxide added and the utilization rate of the nickel electrode in the presence of an alkaline electrolyte containing lithium ions. It is. A: Batteries of the present invention, B, C, D: Comparative batteries.
Claims (1)
リブデン、水酸化モリブデンのうちから選ばれた
少なくとも１種のものを添加した正極と、カドミ
ウム、亜鉛などを活物質とする負極と、リチウム
イオンを含むアルカリ電解液とを備えたアルカリ
蓄電池。1 A positive electrode made of a nickel active material added with at least one selected from metal molybdenum, molybdenum oxide, and molybdenum hydroxide, a negative electrode made of cadmium, zinc, etc. as an active material, and an alkaline electrolyte containing lithium ions. Alkaline storage battery with liquid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56073137A JPS57187868A (en) | 1981-05-14 | 1981-05-14 | Alkaline storage battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56073137A JPS57187868A (en) | 1981-05-14 | 1981-05-14 | Alkaline storage battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS57187868A JPS57187868A (en) | 1982-11-18 |
| JPS6347112B2 true JPS6347112B2 (en) | 1988-09-20 |
Family
ID=13509510
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP56073137A Granted JPS57187868A (en) | 1981-05-14 | 1981-05-14 | Alkaline storage battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS57187868A (en) |
-
1981
- 1981-05-14 JP JP56073137A patent/JPS57187868A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS57187868A (en) | 1982-11-18 |
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