JPH0355030B2 - - Google Patents
Info
- Publication number
- JPH0355030B2 JPH0355030B2 JP60189139A JP18913985A JPH0355030B2 JP H0355030 B2 JPH0355030 B2 JP H0355030B2 JP 60189139 A JP60189139 A JP 60189139A JP 18913985 A JP18913985 A JP 18913985A JP H0355030 B2 JPH0355030 B2 JP H0355030B2
- Authority
- JP
- Japan
- Prior art keywords
- cadmium
- electrode plate
- negative electrode
- paste
- intramolecular
- 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 - Lifetime
Links
- 239000011149 active material Substances 0.000 claims description 21
- CXKCTMHTOKXKQT-UHFFFAOYSA-N cadmium oxide Inorganic materials [Cd]=O CXKCTMHTOKXKQT-UHFFFAOYSA-N 0.000 claims description 19
- CFEAAQFZALKQPA-UHFFFAOYSA-N cadmium(2+);oxygen(2-) Chemical compound [O-2].[Cd+2] CFEAAQFZALKQPA-UHFFFAOYSA-N 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 11
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 10
- 229910052793 cadmium Inorganic materials 0.000 claims description 10
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 10
- 150000003839 salts Chemical class 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 238000003860 storage Methods 0.000 claims description 6
- 235000010323 ascorbic acid Nutrition 0.000 claims description 5
- 239000011668 ascorbic acid Substances 0.000 claims description 5
- 229960005070 ascorbic acid Drugs 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- 239000011230 binding agent Substances 0.000 claims description 2
- PGRHXDWITVMQBC-UHFFFAOYSA-N dehydroacetic acid Natural products CC(=O)C1C(=O)OC(C)=CC1=O PGRHXDWITVMQBC-UHFFFAOYSA-N 0.000 claims description 2
- PEQJBOMPGWYIRO-UHFFFAOYSA-N n-ethyl-3,4-dimethoxyaniline Chemical compound CCNC1=CC=C(OC)C(OC)=C1 PEQJBOMPGWYIRO-UHFFFAOYSA-N 0.000 claims description 2
- PLLZRTNVEXYBNA-UHFFFAOYSA-L cadmium hydroxide Chemical compound [OH-].[OH-].[Cd+2] PLLZRTNVEXYBNA-UHFFFAOYSA-L 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- 239000002994 raw material Substances 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 235000010378 sodium ascorbate Nutrition 0.000 description 1
- 229960005055 sodium ascorbate Drugs 0.000 description 1
- PPASLZSBLFJQEF-RKJRWTFHSA-M sodium ascorbate Substances [Na+].OC[C@@H](O)[C@H]1OC(=O)C(O)=C1[O-] PPASLZSBLFJQEF-RKJRWTFHSA-M 0.000 description 1
- PPASLZSBLFJQEF-RXSVEWSESA-M sodium-L-ascorbate Chemical compound [Na+].OC[C@H](O)[C@H]1OC(=O)C(O)=C1[O-] PPASLZSBLFJQEF-RXSVEWSESA-M 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
- H01M4/62—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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/24—Electrodes for alkaline accumulators
- H01M4/26—Processes of manufacture
-
- 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)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Description
【発明の詳細な説明】
産業上の利用分野
本発明はアルカリ蓄電池用ペースト式カドミウ
ム負極板の製造法に関するものである。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a method for manufacturing a paste-type cadmium negative electrode plate for alkaline storage batteries.
従来の技術とその問題点
ペースト式カドミウム負極板を製造するに際
し、原料の活物質粉末としては、金属カドミウ
ム、水酸化カドミウム、酸化カドミウムが考えら
れるが、金属カドミウム粉末は他に比べて価格が
高いことや粒子径が大きく活性が低いなどの理由
で、活物質の主原料として用いるのは適切でな
い。水酸化カドミウムの場合は、酸化カドミウム
に比べて密度が小さく、電導性および活物質利用
率が劣るなどの不利な点がある。以上のことか
ら、活物質原料としては酸化カドミウムを用いる
のが望ましい。一方、ペースト調製に用いる溶媒
としては有機溶剤と水が考えられるが、それぞれ
に長所と短所がある。例えば、エチレングリコー
ルなどの有機溶剤を溶媒として用いた場合は、粘
度の安定した活物質ペーストが得られ、作業性も
良い反面、原料コストが水に比して高いだけでな
く、その使用においては火災や公害の面から激し
い規制があり、製造工程が複雑になる。これに対
し、水を溶媒として用いた場合の問題点は、酸化
カドミウムが水と反応して水酸化カドミウムに変
化して極板のエネルギー密度が低下すると共に、
活物質ペーストが短時間のうちに硬化し、塗布の
作業性が著しく損なわれることにある。Conventional technology and its problems When manufacturing a paste-type cadmium negative electrode plate, metal cadmium, cadmium hydroxide, and cadmium oxide are considered as the raw material active material powder, but metal cadmium powder is expensive compared to other powders. It is not appropriate to use it as the main raw material for active materials because of its large particle size and low activity. Cadmium hydroxide has disadvantages such as lower density, lower conductivity and lower active material utilization than cadmium oxide. From the above, it is desirable to use cadmium oxide as the active material raw material. On the other hand, organic solvents and water are conceivable as solvents used for paste preparation, but each has advantages and disadvantages. For example, when an organic solvent such as ethylene glycol is used as a solvent, an active material paste with stable viscosity can be obtained and workability is good. There are strict regulations from the standpoint of fire and pollution, and the manufacturing process becomes complicated. On the other hand, the problem with using water as a solvent is that cadmium oxide reacts with water and changes to cadmium hydroxide, reducing the energy density of the electrode plate.
The active material paste hardens within a short period of time, significantly impairing the workability of coating.
これらのことから、ペースト式カドミウム負極
板の製造法としては、活物質ペーストの安定性お
よび塗布の作業性が良好で、製造コストの安い方
法が望まれていた。 For these reasons, as a method for manufacturing a paste-type cadmium negative electrode plate, a method that has good stability of the active material paste, good workability of coating, and low manufacturing cost has been desired.
本発明は以上のような従来技術の問題点を解決
することを目的とするものである。 The present invention aims to solve the problems of the prior art as described above.
問題点を解決するための手段
本発明はアルカリ蓄電池用ペースト式カドミウ
ム負極板の製造法において、酸化カドミウムを含
む活物質粉末を接着剤および水を主体とする溶媒
と共に混練してペースト状とするに際し、ヒドロ
キシカルボン酸の分子内エステル化物およびその
塩のうち少なくとも１つを添加することを特徴と
するものである。Means for Solving the Problems The present invention is a method for producing a paste-type cadmium negative electrode plate for alkaline storage batteries, in which an active material powder containing cadmium oxide is kneaded with an adhesive and a solvent mainly composed of water to form a paste. , an intramolecular ester of hydroxycarboxylic acid, and a salt thereof.
作 用
酸化カドミウムと水が反応して水酸化カドミウ
ムに変化することについて検討したところ、酸化
カドミウムと水を混合するに際し、ヒドロキシカ
ルボン酸の分子内エステル化物およびその塩のう
ち少なくとも１つを添加すれば、酸化カドミウム
が水酸化カドミウムに変化するのを抑制すること
がわかつた。このことは活物質ペースト調製に用
いる溶媒として原料および製造コストの安い水を
使用しているにもかかわらず、活物質ペースト塗
布の作業性や極板のエネルギー密度および活物質
利用率が改善され、溶媒に有機溶剤を用いたのと
同様の効果が得られる。Effects We investigated the reaction of cadmium oxide and water to change to cadmium hydroxide, and found that when mixing cadmium oxide and water, at least one of an intramolecular esterified product of hydroxycarboxylic acid and its salt should be added. For example, it was found that it suppresses the conversion of cadmium oxide to cadmium hydroxide. This means that although water is used as a solvent for preparing the active material paste, which is a low raw material and low in production cost, the workability of applying the active material paste, the energy density of the electrode plate, and the active material utilization rate are improved. The same effect as using an organic solvent as the solvent can be obtained.
なお、これらの物質は有機物であるため、電池
内では酸化を受け、炭酸根の原因となるため、そ
の使用量は少なくすべきであるが、最適な添加量
は活物質ペーストを調製するのに使用する混合機
の撹拌速度によつて異なつてくる。非常にゆるや
かな撹拌においては、酸化カドミウムに対し0.05
重量％以上の酸化カドミウムの水和反応抑制添加
剤を加えることによつて、活物質ペーストの粘度
を数時間程度安定に保つことが可能であるが、ホ
モミキサー等の高速撹拌機を用いて活物質ペース
トを調製する場合は、酸化カドミウムに対し約５
重量％の添加剤を加えないと、活物質ペーストの
粘度を安定に保つことができない。なお、添加剤
の量が0.05重量％未満では非常にゆるやかな撹拌
でも酸化カドミウムと水が徐々に反応して粘度が
不安定になるため、最適な添加量は酸化カドミウ
ムに対し0.05〜５重量の範囲である。 Furthermore, since these substances are organic substances, they undergo oxidation in the battery and cause carbonic acid radicals, so the amount used should be small, but the optimal amount of addition is determined by the amount used to prepare the active material paste. It depends on the stirring speed of the mixer used. 0.05 for cadmium oxide with very gentle agitation.
It is possible to keep the viscosity of the active material paste stable for several hours by adding an additive that inhibits the hydration reaction of cadmium oxide in an amount of % or more by weight, but it is possible to keep the viscosity of the active material paste stable for several hours. When preparing a material paste, approximately 5% of the cadmium oxide
Without adding a weight percent additive, the viscosity of the active material paste cannot be kept stable. If the amount of additive is less than 0.05% by weight, cadmium oxide and water will gradually react with water even with very gentle stirring, making the viscosity unstable. range.
ヒドロキシカルボン酸の分子内エステル化物お
よびその塩が前記の効果を持つ理由は明らかでな
いが、酸化カドミウム粒子の表面で不溶性の化合
物を形成していると思われる。 The reason why the intramolecular esterified product of hydroxycarboxylic acid and its salt has the above-mentioned effect is not clear, but it is thought that an insoluble compound is formed on the surface of the cadmium oxide particles.
実施例 以下、本発明を実施例に基づいて説明する。Example Hereinafter, the present invention will be explained based on examples.
実施例 １
酸化カドミウム100部、ニツケル粉末10部、メ
チルセルロース２部とアスコルビン酸0.6部およ
び水80部を混練してペースト状とし、このペース
トを鉄にニツケルメツキした金属多孔板に所定の
厚さ塗布した後、90℃にて乾燥し、最終的にプレ
スによつて厚み調節した負極板を作製し、これを
試料Ａとした。Example 1 100 parts of cadmium oxide, 10 parts of nickel powder, 2 parts of methylcellulose, 0.6 parts of ascorbic acid, and 80 parts of water were kneaded to form a paste, and this paste was applied to a predetermined thickness on a perforated metal plate made of nickel plated iron. Thereafter, it was dried at 90°C, and finally a negative electrode plate whose thickness was adjusted by pressing was produced, and this was designated as Sample A.
実施例 ２
前記実施例１におけるアスコルビン酸の代わり
にアスコルビン酸ナトリウムを用い、実施例１と
同様の方法で負極板を作製し、これを試料Ｂとし
た。Example 2 A negative electrode plate was prepared in the same manner as in Example 1, using sodium ascorbate instead of ascorbic acid in Example 1, and this was designated as Sample B.
実施例 ３
前記実施例１におけるアスコルビン酸の代りに
テトロン酸を用い、実施例１と同様の方法で負極
板を作製し、これを試料Ｃとした。Example 3 A negative electrode plate was prepared in the same manner as in Example 1 except that tetronic acid was used instead of ascorbic acid in Example 1, and this was designated as Sample C.
また比較のために前記実施例１からアスコルビ
ン酸のみを除いた配合で、実施例１と同様の方法
で負極板を作製し、これを試料Ｄとした。 For comparison, a negative electrode plate was prepared in the same manner as in Example 1 except that only ascorbic acid was removed from Example 1, and this was designated as Sample D.
以上のようにして得た試料Ａ〜Ｄを40×40mmの
寸法に切断した後、比重1.250（20℃）のKOH水
溶液中で試料と同寸法の焼結式ニツケル正極板２
枚を対極として用い、試料の理論容量に対し0.2C
(A)の通電電流で充放電した場合の放電時活物質利
用率を第１図に、放電電気量を第２図に示す。 After cutting the samples A to D obtained as above into a size of 40 x 40 mm, sintered nickel positive electrode plate 2 of the same size as the sample was placed in a KOH aqueous solution with a specific gravity of 1.250 (20℃).
0.2C with respect to the theoretical capacity of the sample using a plate as a counter electrode.
FIG. 1 shows the active material utilization rate during discharge when charging and discharging with the applied current of (A), and FIG. 2 shows the amount of discharged electricity.
これらの図から明らかなように、ヒドロキシカ
ルボン酸の分子内エステル化物あるいはその塩を
添加し、酸化カドミウムが水酸化カドミウムに変
化するのを抑制した試料Ａ〜Ｃはそうでない試料
Ｄに比べ、極板性能がかなり改善されている。ま
た活物質ペーストが硬化するまでの可使時間は試
料Ａ〜Ｃは約30〜50時間であるのに対し、試料Ｄ
では約20分ほどであつた。これらのことから、ヒ
ドロキシカルボン酸の分子内エステル化物および
その塩の添加効果は明らかである。 As is clear from these figures, samples A to C in which an intramolecular esterified product of hydroxycarboxylic acid or its salt was added to suppress the conversion of cadmium oxide to cadmium hydroxide were significantly more effective than sample D in which this was not done. Board performance has been significantly improved. In addition, the pot life until the active material paste hardens is approximately 30 to 50 hours for samples A to C, while sample D
It took about 20 minutes. From these facts, the effect of adding intramolecular esterified products of hydroxycarboxylic acids and salts thereof is clear.
発明の効果
以上のように本発明では酸化カドミウムを含む
活物質粉末を結着剤および水を主体とする溶媒と
共に混練してペーストとするのに際し、ヒドロキ
シカルボン酸の分子内エステル化物およびその塩
のうち少なくとも１つを添加することによつて、
酸化カドミウムが水と反応して水酸化カドミウム
に変化するのを抑制して、作業性の低下を防ぐと
共に、エネルギー密度および活物質利用率の高い
ペースト式カドミウム負極板を得ることができ
る。Effects of the Invention As described above, in the present invention, when an active material powder containing cadmium oxide is kneaded with a binder and a solvent mainly composed of water to form a paste, intramolecular esterification products of hydroxycarboxylic acids and salts thereof are used. By adding at least one of them,
By suppressing cadmium oxide from reacting with water and changing into cadmium hydroxide, a paste-type cadmium negative electrode plate can be obtained that prevents deterioration in workability and has high energy density and active material utilization.
第１図は充放電サイクルにおける放電時活物質
利用率を比較した図、第２図はその放電電気量を
比較した図である。
FIG. 1 is a diagram comparing the active material utilization rate during discharge during charge/discharge cycles, and FIG. 2 is a diagram comparing the amount of discharged electricity.
Claims (1)
よび水を主体とする溶媒と共に混練してペースト
状となし、該ペーストを集電体に塗布・乾燥する
ものにおいて、前記ペースト中にヒドロキシカル
ボン酸の分子内エステル化物およびその塩のうち
少なくとも１つを添加することを特徴とするアル
カリ蓄電池用カドミウム負極板の製造法。 ２ 前記ヒドロキシカルボン酸の分子内エステル
化物およびその塩の全添加量が重量比で酸化カド
ミウム100部に対して0.05〜５部である特許請求
の範囲第１項記載のアルカリ蓄電池用カドミウム
負極板の製造法。 ３ 前記ヒドロキシカルボン酸の分子内エステル
化物がアスコルビン酸である特許請求の範囲第１
項記載のアルカリ蓄電池用カドミウム負極板の製
造法。 ４ 前記ヒドロキシカルボン酸の分子内エステル
化物がテトロン酸である特許請求の範囲第１項記
載のアルカリ蓄電池用カドミウム負極板の製造
法。[Scope of Claims] 1. An active material powder containing cadmium oxide is kneaded with a binder and a solvent mainly composed of water to form a paste, and the paste is applied to a current collector and dried. A method for producing a cadmium negative electrode plate for an alkaline storage battery, which comprises adding at least one of an intramolecular esterified product of hydroxycarboxylic acid and a salt thereof. 2. The cadmium negative electrode plate for an alkaline storage battery according to claim 1, wherein the total amount of the intramolecular esterified product of hydroxycarboxylic acid and its salt added is 0.05 to 5 parts by weight based on 100 parts of cadmium oxide. Manufacturing method. 3. Claim 1, wherein the intramolecular esterified product of hydroxycarboxylic acid is ascorbic acid.
A method for producing a cadmium negative electrode plate for an alkaline storage battery as described in . 4. The method for producing a cadmium negative electrode plate for an alkaline storage battery according to claim 1, wherein the intramolecular esterified product of hydroxycarboxylic acid is tetronic acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60189139A JPS6247960A (en) | 1985-08-27 | 1985-08-27 | Manufacture of cadmium negative plate for alkaline storage battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60189139A JPS6247960A (en) | 1985-08-27 | 1985-08-27 | Manufacture of cadmium negative plate for alkaline storage battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6247960A JPS6247960A (en) | 1987-03-02 |
| JPH0355030B2 true JPH0355030B2 (en) | 1991-08-22 |
Family
ID=16236062
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60189139A Granted JPS6247960A (en) | 1985-08-27 | 1985-08-27 | Manufacture of cadmium negative plate for alkaline storage battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6247960A (en) |
-
1985
- 1985-08-27 JP JP60189139A patent/JPS6247960A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6247960A (en) | 1987-03-02 |
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| Date | Code | Title | Description |
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| LAPS | Cancellation because of no payment of annual fees |