JPS6347113B2 - - Google Patents
Info
- Publication number
- JPS6347113B2 JPS6347113B2 JP56073139A JP7313981A JPS6347113B2 JP S6347113 B2 JPS6347113 B2 JP S6347113B2 JP 56073139 A JP56073139 A JP 56073139A JP 7313981 A JP7313981 A JP 7313981A JP S6347113 B2 JPS6347113 B2 JP S6347113B2
- Authority
- JP
- Japan
- Prior art keywords
- nickel
- titanium
- added
- utilization rate
- lithium ions
- 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
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 20
- 239000003792 electrolyte Substances 0.000 claims description 15
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 12
- 229910001416 lithium ion Inorganic materials 0.000 claims description 12
- 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
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 claims description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- 239000010936 titanium Substances 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-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
- 239000004408 titanium dioxide Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 7
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 5
- -1 titanium dioxide compound Chemical class 0.000 description 5
- 239000000654 additive Substances 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 239000007774 positive electrode material Substances 0.000 description 3
- FZDGTNXIMISDHS-UHFFFAOYSA-I [Ti+4].[OH-].[Li+].[OH-].[OH-].[OH-].[OH-] Chemical compound [Ti+4].[OH-].[Li+].[OH-].[OH-].[OH-].[OH-] FZDGTNXIMISDHS-UHFFFAOYSA-I 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 150000002642 lithium compounds Chemical class 0.000 description 2
- 238000000465 moulding Methods 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
- 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
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 239000000203 mixture Substances 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
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 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
- 150000003609 titanium compounds Chemical class 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
金属チタン、酸化チタン、水酸化チタンのうちか
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二酸化チタン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 in nickel electrodes or electrolytes, the present invention has been developed by adding at least one selected from metal titanium, titanium oxide, and titanium hydroxide to nickel electrodes, and adding lithium to nickel electrodes. We have discovered that the utilization rate of nickel electrodes can be further improved by using an alkaline electrolyte containing 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 titanium dioxide as an additive.
Mix the weight% well and apply this mixed powder to pre-molding pressure.
Molded with 100~500Kg/ cm2 and made 50~200 molded pellets.
300Kg/cm 2 after covering with mesh metal wire mesh
The final molding is performed to form the 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
うにニツケル極に二酸化チタ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、ニツケル極に二
酸化チタン化合物を添加し、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案すると、
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二酸化チ
タン化合物を添加し、リチウムを含まないアルカ
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
果から二酸化チタ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二酸化チタン化合物の添
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、二酸化チタン化合物とリチウムイオ
ンとを共存させた場合には、二酸化チタンが、ア
ルカリ電解液と反応して水酸化チタンを生成し、
充電時、リチウムイオンがこの水酸化チタン結晶
中に侵入して、リチウム―水酸化チタンを形成す
る。このリチウム―水酸化チタンはニツケル活物
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
の存在下における二酸化チタンの添加量とニツケ
ル極の利用率との関係を示し、二酸化チタンの添
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
化チタンの一例である二酸化チタンを用いたが、
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チタン、水
酸化チタ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、ニツケル極にチタン又は／及びチタン化合物
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 titanium dioxide compound is added to the nickel electrode or only lithium ions are added to the electrolyte, compared to comparative battery B in which nothing is added. Although the improvement in characteristics is not as remarkable as compared to the battery A of the present invention in which a titanium dioxide compound is added to the nickel electrode and an alkaline electrolyte containing lithium ions is also used.
It can be seen that the battery capacity has clearly increased. When 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 titanium dioxide compound is added to the nickel electrode and an alkaline electrolyte containing no lithium 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 titanium dioxide compound had no effect on the utilization rate of the nickel electrode, and the capacity decreased as a result of the amount of nickel active material filled in the nickel electrode being reduced by the amount of the titanium dioxide compound added. However, when titanium dioxide compounds and lithium ions coexist, titanium dioxide reacts with the alkaline electrolyte to produce titanium hydroxide.
During charging, lithium ions penetrate into the titanium hydroxide crystals to form lithium-titanium hydroxide. This lithium-titanium 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 titanium dioxide added and the utilization rate of the nickel electrode in the presence of an alkaline electrolyte containing lithium ions, and the utilization rate of the nickel electrode when the amount of titanium dioxide added is 5% by weight. 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. Furthermore, in the examples of the present invention, titanium dioxide, which is an example of titanium oxide, was used as an additive.
It is not limited to this as long as it is in the form of an oxide. Similar effects can also be obtained by using titanium metal or titanium 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 titanium or/and a titanium compound to the nickel electrode and also using an alkaline electrolyte containing lithium ions, 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二酸化チタンの添加量とニ
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 comparative battery, and Figure 2 is a diagram showing the relationship between the amount of titanium dioxide added and the utilization rate of the nickel electrode in the presence of an alkaline electrolyte containing lithium ions. be. A: Batteries of the present invention, B, C, D: Comparative batteries.
Claims (1)
ン、水酸化チタ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 titanium, titanium oxide, and titanium 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 |
|---|---|---|---|
| JP56073139A JPS57187869A (en) | 1981-05-14 | 1981-05-14 | Alkaline storage battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56073139A JPS57187869A (en) | 1981-05-14 | 1981-05-14 | Alkaline storage battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS57187869A JPS57187869A (en) | 1982-11-18 |
| JPS6347113B2 true JPS6347113B2 (en) | 1988-09-20 |
Family
ID=13509567
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP56073139A Granted JPS57187869A (en) | 1981-05-14 | 1981-05-14 | Alkaline storage battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS57187869A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4578038B2 (en) * | 2001-04-17 | 2010-11-10 | 三洋電機株式会社 | Nickel electrode for alkaline storage battery and alkaline storage battery |
-
1981
- 1981-05-14 JP JP56073139A patent/JPS57187869A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS57187869A (en) | 1982-11-18 |
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