JP3679658B2 - Method for producing alkaline storage battery - Google Patents
Method for producing alkaline storage battery Download PDFInfo
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- JP3679658B2 JP3679658B2 JP30881699A JP30881699A JP3679658B2 JP 3679658 B2 JP3679658 B2 JP 3679658B2 JP 30881699 A JP30881699 A JP 30881699A JP 30881699 A JP30881699 A JP 30881699A JP 3679658 B2 JP3679658 B2 JP 3679658B2
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- 238000003860 storage Methods 0.000 title claims description 10
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 136
- 229910052759 nickel Inorganic materials 0.000 claims description 67
- 238000001035 drying Methods 0.000 claims description 57
- 239000000758 substrate Substances 0.000 claims description 46
- 239000011149 active material Substances 0.000 claims description 34
- 238000002441 X-ray diffraction Methods 0.000 claims description 19
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 15
- 229910002651 NO3 Inorganic materials 0.000 claims description 14
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 14
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 14
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 14
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 claims description 10
- RJNPRNCPYHCHHV-UHFFFAOYSA-N cobalt(2+) dinitrate tetrahydrate Chemical compound O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O RJNPRNCPYHCHHV-UHFFFAOYSA-N 0.000 claims description 10
- UKDHSAZUXNLNLV-UHFFFAOYSA-N nickel(2+) dinitrate tetrahydrate Chemical compound O.O.O.O.[Ni++].[O-][N+]([O-])=O.[O-][N+]([O-])=O UKDHSAZUXNLNLV-UHFFFAOYSA-N 0.000 claims description 10
- 239000003513 alkali Substances 0.000 claims description 9
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 239000012670 alkaline solution Substances 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 238000007598 dipping method Methods 0.000 claims 2
- 238000000034 method Methods 0.000 description 24
- 150000004687 hexahydrates Chemical class 0.000 description 13
- 239000000126 substance Substances 0.000 description 11
- 238000011282 treatment Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 9
- 239000000243 solution Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000005520 cutting process Methods 0.000 description 7
- 150000004685 tetrahydrates Chemical class 0.000 description 7
- 238000004804 winding Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000005470 impregnation Methods 0.000 description 5
- 230000002378 acidificating effect Effects 0.000 description 4
- 150000002815 nickel Chemical class 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 2
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 2
- 239000002562 thickening agent Substances 0.000 description 2
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 150000001869 cobalt compounds Chemical class 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- -1 hexahydrate salt Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Images
Classifications
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- 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
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- Battery Electrode And Active Subsutance (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明はニッケル・カドミウム蓄電池、ニッケル・水素蓄電池などのアルカリ蓄電池の製造方法に係り、特に、多孔性ニッケル焼結基板に高密度に活物質が充填された焼結式ニッケル極板を備えたアルカリ蓄電池の製造方法に関する。
【０００２】
【従来の技術】
従来、アルカリ蓄電池の正極に使用されるニッケル極板としては、活物質の利用率が高く、極板の導電性がよくて放電性能やサイクル特性に優れるなどの特徴を有する焼結式ニッケル極板が広く使用されている。このような焼結式ニッケル極板は多孔性ニッケル焼結基板に、所謂、化学含浸法により活物質を充填して製造される。具体的には、まず、ニッケル粉末とカルボキシメチルセルロースなどの増粘剤を水で混練したスラリーを導電性芯体に塗着した後、還元性雰囲気で焼結して多孔性ニッケル焼結基板を作製する。
【０００３】
この後、得られた多孔性ニッケル焼結基板を酸性ニッケル塩（例えば、硝酸ニッケル、硫酸ニッケルなど）を主体とする溶液に浸漬して、酸性ニッケル塩を多孔性ニッケル焼結基板の細孔中に含浸する。ついで、乾燥した後、アルカリ溶液中に浸漬して、多孔性ニッケル焼結基板の細孔中に含浸した酸性ニッケル塩を水酸化物に活物質化し、水洗、乾燥する。このような化学含浸法にあっては、酸性ニッケル塩の含浸→中間乾燥→活物質化するアルカリ処理→水洗、乾燥の一連の処理が１サイクルとなるが、１サイクルだけでは必要な活物質量を多孔性ニッケル焼結基板中に充填することができず、通常、必要な充填量が得られるまで充填サイクルを繰り返して行うようにしている。
【０００４】
ところで、この種の焼結式ニッケル極板において、多孔性ニッケル焼結基板が腐食されるのを防止するとともに、活物質利用率を向上させるために、多孔性ニッケル焼結基板表面にニッケルとコバルトの化合物層を設けることが、特開昭６３−４０２５５号公報にて提案されるようになった。この特開昭６３−４０２５５号公報にて提案された方法においては、多孔性ニッケル焼結基板を硝酸コバルト水溶液に浸漬後、空気中で２１０℃で熱処理することによって多孔性ニッケル焼結基板の表面および空孔内表面に第１のコバルト酸化物層を形成させる。ついで、この基板を硝酸ニッケル水溶液に含浸させてアルカリ処理して活物質を充填した後、硝酸コバルト水溶液に再浸漬して乾燥させた後、アルカリ処理するようにしている。
【０００５】
また、多孔性ニッケル焼結基板表面にニッケルとコバルトの化合物層を設ける方法が特開平４−７５２５７号公報にて提案されるようになった。この特開平４−７５２５７号公報にて提案された方法においては、ニッケルとコバルトの混合硝酸塩溶液に多孔性ニッケル焼結基板を浸漬し、９０℃〜１００℃の温度で中間乾燥を行った後、アルカリ処理を行って、ニッケルとコバルトの共晶水酸化物層を設けるようにしている。
【０００６】
【発明が解決しようとする課題】
しかしながら、上述した特開昭６３−４０２５５号公報にて提案された方法にあっては、中間乾燥の乾燥温度が８０℃と高温であり、また、上述した特開平４−７５２５７号公報にて提案された方法にあっては、中間乾燥の乾燥温度が９０℃〜１００℃と高温であるため、過剰乾燥状態となって、後の化成工程や切断工程あるいは巻取工程において活物質の脱落量が多いという問題があった。
【０００７】
そこで、本発明者等は種々の実験を行って、これらの問題が生じた原因を究明した。その結果、中間乾燥が９０℃〜１００℃の高温で過剰乾燥状態になると、多孔性ニッケル焼結基板に含浸された硝酸ニッケルおよび硝酸コバルトが４水塩となったり、あるいは４水塩と６水塩とが混在して、アルカリ処理後の活物質が多孔性ニッケル焼結基板の内部に保持されず、多孔性ニッケル焼結基板の表面付近に活物質が偏在するために、活物質の脱落量が増えることが分かった。
【０００８】
ここで、中間乾燥において過剰乾燥状態とならないような乾燥状態（加熱状態）にすれば、硝酸ニッケルおよび硝酸コバルトは６水塩が主体となって、アルカリ処理後の活物質が多孔性ニッケル焼結基板の内部に保持されるようになり、後の化成工程や切断工程あるいは巻取工程において活物質の脱落量が減少するであろうという知見を得て本発明がなされたものであって、活物質の充填サイクルでの中間乾燥において、多孔性ニッケル焼結基板に含浸された硝酸塩が６水塩主体となるような乾燥方法を提供することを目的とするものである。
【０００９】
【課題を解決するための手段およびその作用・効果】
上記課題を解決するために、本発明のアルカリ蓄電池の製造方法は、充填サイクルの中間乾燥工程において、該中間乾燥工程の終了時に多孔性ニッケル焼結基板に含浸された硝酸塩が６水塩主体となるような乾燥条件に調整して製造するようにしている。このように、中間乾燥工程の終了時に多孔性ニッケル焼結基板に含浸された硝酸塩が６水塩主体となるように乾燥条件を調整すると、アルカリ処理後の活物質が多孔性ニッケル焼結基板の内部に保持されるようになり、後の化成工程や切断工程あるいは巻取工程において活物質の脱落量が減少する。
【００１０】
ここで、中間乾燥の乾燥条件を調整するためには、乾燥温度および乾燥時間を調整する必要がある。そして、６水塩が主体となる硝酸塩は硝酸ニッケル６水塩のＸ線回折ピーク（２θ＝１６．２°：ＣｕＫα）に対する硝酸ニッケル４水塩のＸ線回折ピーク（２θ＝１３．１°：ＣｕＫα）の積分強度比が０．５以下であると、多孔性ニッケル焼結基板の内部に活物質が保持され、後の化成工程や切断工程、巻取り工程での活物質の脱落量を低減させることが可能となる。
【００１１】
また、６水塩が主体となる硝酸塩は硝酸コバルト６水塩のＸ線回折ピーク（２θ＝４１．０°：ＣｕＫα）に対する硝酸コバルト４水塩のＸ線回折ピーク（２θ＝３４．６°：ＣｕＫα）の積分強度比が０．５以下であると、多孔性ニッケル焼結基板の内部に活物質が保持され、後の化成工程や切断工程、巻取り工程での活物質の脱落量を低減させることが可能となる。
【００１２】
【発明の実施の形態】
ついで、本発明のアルカリ蓄電池の製造方法の好適な実施の形態を以下に説明する。なお、本発明は以下の実施の形態に何ら限定されるものではなく、その要旨を変更しない範囲において適宜変更して実施することが可能なものである。
【００１３】
１．ニッケル焼結基板の作製
ニッケル粉末にカルボキシメチルセルロース等の増粘剤および水を混練してスラリーを調整し、このスラリーをニッケル多孔体からなる導電性芯体に塗着する。この後、スラリーを塗着した導電性芯体を還元性雰囲気下で焼結して、多孔度が８０％で、厚みが０．５５ｍｍの多孔性ニッケル焼結基板を作製した。
【００１４】
２．ニッケル電極の作製
（１）実施例１
上述のようにして作製した多孔性ニッケル焼結基板を以下の▲１▼〜▲４▼の処理工程を所定回数（例えば、１０回）繰り返して、実施例１の焼結式ニッケル極板ａを作製した。即ち、
▲１▼常温で析出する高濃度の硝酸塩を含有する含浸液（例えば、硝酸ニッケル：硝酸コバルトのモル比が８０：２０である比重が１．７０の水溶液）を７０℃の温度となるように加熱した後、この含浸液中に上述のようにして作製した多孔性ニッケル焼結基板を６０分間浸漬して、多孔性ニッケル焼結基板の空孔表面に硝酸塩を含浸させる。
【００１５】
▲２▼ついで、多孔性ニッケル焼結基板を含浸液から引き上げた後、５５℃の温風中で３０分間だけ加熱して中間乾燥を行う。
▲３▼中間乾燥後、濃度が２５％で温度が８０℃の水酸化ナトリウム水溶液中に６０分間浸漬して、空孔表面に析出させた硝酸塩を水酸化ニッケルおよび水酸化コバルトに置換する活物質化処理を行う。
▲４▼活物質化処理を行った後、イオン交換水中で６０分間水洗した後、９０℃の温風中で６０分間加熱して乾燥する。
【００１６】
その後、再び上記▲１▼の工程に戻り、上記と同様な▲１▼〜▲４▼の処理工程を所定回数（例えば、１０回）繰り返して行うことにより、所定の活物質充填量を確保して実施例１の焼結式ニッケル極板ａを作製した。なお、▲２▼の中間乾燥における乾燥温度および乾燥時間は、１回目が５５℃で３０分間であり、２回目以降は８０℃で３０分間とした。
【００１７】
（２）実施例２
上述のようにして作製した多孔性ニッケル焼結基板を上述した▲２▼の中間乾燥以外は上述した▲１▼〜▲４▼の処理工程を所定回数（例えば、１０回）繰り返して、実施例２の焼結式ニッケル極板ｂを作製した。なお、本実施例２の▲２▼の中間乾燥における乾燥温度および乾燥時間は、１回目が６５℃で５分間であり、２回目以降は６５℃で３０分間とした。
【００１８】
（３）比較例１
上述のようにして作製した多孔性ニッケル焼結基板を上述した▲２▼の中間乾燥以外は上述した▲１▼〜▲４▼の処理工程を所定回数（例えば、１０回）繰り返して、比較例１の焼結式ニッケル極板ｘを作製した。なお、本比較例１の▲２▼の中間乾燥における乾燥温度および乾燥時間は、全回数において、８０℃で３０分間とした。
【００１９】
（４）比較例２
上述のようにして作製した多孔性ニッケル焼結基板を上述した▲２▼の中間乾燥以外は上述した▲１▼〜▲４▼の処理工程を所定回数（例えば、１０回）繰り返して、比較例２の焼結式ニッケル極板ｙを作製した。なお、本比較例２の▲２▼の中間乾燥における乾燥温度および乾燥時間は、全回数において、６５℃で３０分間とした。
【００２０】
３．Ｘ線回折の積分強度比の測定
ついで、上述したようにして各焼結式ニッケル極板ａ，ｂおよびｘ，ｙを作製するに際して、中間乾燥後の各焼結式ニッケル極板ａ，ｂおよびｘ，ｙのＸ線回折分析を行い、硝酸コバルト６水塩の回折ピーク（２θ＝４１．０°：ＣｕＫα）に対する硝酸コバルト４水塩の回折ピーク（２θ＝３４．６°：ＣｕＫα）の積分強度比、および硝酸ニッケル６水塩の回折ピーク（２θ＝１６．２°：ＣｕＫα）に対する硝酸ニッケル４水塩の回折ピーク（２θ＝１３．１°：ＣｕＫα）の積分強度比をそれぞれ測定した。これを表に示すと下記の表１に示すような結果となった。
【００２１】
【表１】
なお、上記表１において、硝酸コバルトは、硝酸コバルト６水塩の回折ピーク（２θ＝４１．０°：ＣｕＫα）に対する硝酸コバルト４水塩の回折ピーク（２θ＝３４．６°：ＣｕＫα）の積分強度比を表し、硝酸ニッケルは、硝酸ニッケル６水塩の回折ピーク（２θ＝１６．２°：ＣｕＫα）に対する硝酸ニッケル４水塩の回折ピーク（２θ＝１３．１°：ＣｕＫα）の積分強度比を表している。
【００２３】
一方、上述したようにして作製した実施例１，２および比較例１，２の各焼結式ニッケル極板ａ，ｂおよびｘ，ｙをそれぞれ用いて、これらの各焼結式ニッケル極板ａ，ｂおよびｘ，ｙをそれぞれ化成して、化成時の活物質の脱落量をそれぞれ測定した。これを表に示すと下記の表２に示すような結果となった。
【００２４】
【表２】
ついで、硝酸コバルト６水塩の回折ピーク（２θ＝４１．０°：ＣｕＫα）に対する硝酸コバルト４水塩の回折ピーク（２θ＝３４．６°：ＣｕＫα）の積分強度比、および硝酸ニッケル６水塩の回折ピーク（２θ＝１６．２°：ＣｕＫα）に対する硝酸ニッケル４水塩の回折ピーク（２θ＝１３．１°：ＣｕＫα）の積分強度比をそれぞれ横軸とし、活物質脱落量を縦軸としてグラフに表すと、図１に示すような結果となった。
【００２６】
図１より明らかなように、中間乾燥後の極板において、Ｘ線回折ピークの硝酸コバルト６水塩に対する硝酸コバルト４水塩の積分強度比が０．５以下、あるいはＸ線回折ピークの硝酸ニッケル６水塩に対する硝酸ニッケル４水塩の積分強度比が０．５以下であれば活物質の脱落量が低減し、少ない含浸量で効率的に含浸を行うことができることが分かる。
【００２７】
これは、多孔性ニッケル焼結基板を硝酸ニッケルと硝酸コバルトの混合溶液に浸漬させた後、中間乾燥すると、硝酸ニッケルあるいは硝酸コバルトが４水塩となったり、４水塩と６水塩とが混在したりする場合は、即ち、Ｘ線回折ピークにおいて、硝酸コバルト６水塩に対する硝酸コバルト４水塩の積分強度比が０．５より大きかったり、あるいは硝酸ニッケル６水塩に対する硝酸ニッケル４水塩の積分強度比が０．５より大きかった場合は、多孔性ニッケル焼結基板の内部に活物質が保持されないために、活物質の脱落量が増大したと考えられる。
【００２８】
一方、多孔性ニッケル焼結基板を硝酸ニッケルと硝酸コバルトの混合溶液に浸漬させた後、中間乾燥して、硝酸ニッケルあるいは硝酸コバルトが６水塩となったり、４水塩と６水塩とが混在しても、Ｘ線回折ピークにおいて、硝酸コバルト６水塩に対する硝酸コバルト４水塩の積分強度比が０．５以下であったり、あるいは硝酸ニッケル６水塩に対する硝酸ニッケル４水塩の積分強度比が０．５以下である場合には、多孔性ニッケル焼結基板の内部に活物質が保持され、活物質の脱落量が低減したと考えられる。
【００２９】
このことから、中間乾燥後の極板において、Ｘ線回折ピークの硝酸コバルト６水塩に対する硝酸コバルト４水塩の積分強度比が０．５以下、あるいはＸ線回折ピークの硝酸ニッケル６水塩に対する硝酸ニッケル４水塩の積分強度比が０．５以下であれば、後の化成工程や切断工程、巻取り工程での活物質の脱落量が低減させることが可能となる。また、中間乾燥後の極板の硝酸塩が６水塩主体となるように乾燥条件を設定して活物質脱落量低減効果を発揮させるためには、上述した充填サイクルの何回目でもよいが、特に、充填サイクルの１回目の中間乾燥時に乾燥温度および乾燥時間を調整するようにすると、活物質脱落量低減効果が大きくなる。
【００３０】
なお、多孔性ニッケル焼結基板を硝酸ニッケルと硝酸コバルトの混合溶液に浸漬させた後、１回目の中間乾燥の条件としては、実施例１の極板ａにおいては５５℃で３０分間とし、実施例２の極板ｂにおいては６５℃で５分間としたが、中間乾燥後のＸ線回折ピークにおいて、硝酸コバルトあるいは硝酸ニッケルの６水塩に対する４水塩の積分強度比が０．５以下であれば、乾燥温度と乾燥時間はどのようであってもよく、要は、Ｘ線回折ピークにおいて、硝酸コバルトあるいは硝酸ニッケルの６水塩に対する４水塩の積分強度比が０．５以下となるような乾燥条件に調整すればよい。
【００３１】
上述したように、本発明においは、中間乾燥工程の終了時に多孔性ニッケル焼結基板に含浸された硝酸塩が６水塩主体となるように乾燥条件を調整しているので、アルカリ処理後の活物質が多孔性ニッケル焼結基板の内部に保持されるようになり、後の化成工程や切断工程あるいは巻取工程において活物質の脱落量が減少する。
【００３２】
なお、上述した実施の形態においては、多孔性ニッケル焼結基板に水酸化ニッケルを充填する充填サイクルを１０回繰り返す例について説明したが、この充填サイクルは１０回に限らず、用いる焼結基板の多孔度、硝酸塩の濃度などにより適宜選択すればよい。
【図面の簡単な説明】
【図１】 Ｘ線回折ピークにおける硝酸コバルト６水塩に対する硝酸コバルト４水塩の積分強度比、および硝酸ニッケル６水塩に対する硝酸ニッケル４水塩の積分強度比と、活物質の脱落量の関係を示す図である。
【符号の説明】
ａ…実施例１、ｂ…実施例２、ｘ…比較例１、ｙ…比較例２[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for producing an alkaline storage battery such as a nickel / cadmium storage battery or a nickel / hydrogen storage battery, and more particularly, an alkali having a sintered nickel electrode plate in which a porous nickel sintered substrate is filled with an active material at a high density. The present invention relates to a method for manufacturing a storage battery.
[0002]
[Prior art]
Conventionally, as a nickel electrode plate used for a positive electrode of an alkaline storage battery, a sintered nickel electrode plate having features such as a high utilization rate of an active material, good conductivity of the electrode plate, and excellent discharge performance and cycle characteristics. Is widely used. Such a sintered nickel electrode plate is manufactured by filling a porous nickel sintered substrate with an active material by a so-called chemical impregnation method. Specifically, first, a slurry obtained by kneading nickel powder and a thickener such as carboxymethyl cellulose with water is applied to the conductive core, and then sintered in a reducing atmosphere to produce a porous nickel sintered substrate. To do.
[0003]
Thereafter, the obtained porous nickel sintered substrate is immersed in a solution mainly composed of acidic nickel salt (for example, nickel nitrate, nickel sulfate, etc.), and the acidic nickel salt is immersed in the pores of the porous nickel sintered substrate. Impregnate into. Next, after drying, it is immersed in an alkaline solution to convert the acidic nickel salt impregnated into the pores of the porous nickel sintered substrate into a hydroxide, which is washed with water and dried. In such a chemical impregnation method, a series of treatments of impregnation of acidic nickel salt → intermediate drying → alkali treatment to make active material → water washing and drying is one cycle, but the amount of active material required in only one cycle Can not be filled in the porous nickel sintered substrate, and the filling cycle is usually repeated until the required filling amount is obtained.
[0004]
By the way, in this kind of sintered nickel electrode plate, in order to prevent the porous nickel sintered substrate from being corroded and to improve the active material utilization rate, nickel and cobalt are formed on the surface of the porous nickel sintered substrate. It has been proposed to provide a compound layer of JP-A 63-40255. In the method proposed in Japanese Patent Laid-Open No. 63-40255, the surface of the porous nickel sintered substrate is obtained by immersing the porous nickel sintered substrate in an aqueous cobalt nitrate solution and heat-treating it in air at 210 ° C. And a 1st cobalt oxide layer is formed in a void | hole inner surface. Next, the substrate is impregnated with an aqueous nickel nitrate solution and filled with an active material by alkali treatment, then dipped in an aqueous cobalt nitrate solution and dried, followed by alkali treatment.
[0005]
A method for providing a nickel and cobalt compound layer on the surface of a porous nickel sintered substrate has been proposed in Japanese Patent Laid-Open No. 4-75257. In the method proposed in Japanese Patent Laid-Open No. 4-75257, after a porous nickel sintered substrate is immersed in a mixed nitrate solution of nickel and cobalt and subjected to intermediate drying at a temperature of 90 ° C. to 100 ° C., Alkali treatment is performed to provide a eutectic hydroxide layer of nickel and cobalt.
[0006]
[Problems to be solved by the invention]
However, in the method proposed in Japanese Patent Laid-Open No. 63-40255 described above, the drying temperature of intermediate drying is as high as 80 ° C., and also proposed in Japanese Patent Laid-Open No. 4-75257 described above. In the method, since the drying temperature of the intermediate drying is as high as 90 ° C. to 100 ° C., it becomes an excessively dried state, and the amount of the active material dropped off in the subsequent chemical conversion process, cutting process or winding process There were many problems.
[0007]
Therefore, the present inventors conducted various experiments to find out the cause of these problems. As a result, when intermediate drying becomes an excessively dried state at a high temperature of 90 ° C. to 100 ° C., nickel nitrate and cobalt nitrate impregnated on the porous nickel sintered substrate become tetrahydrate, or tetrahydrate and 6 water. The active material after alkali treatment is not held inside the porous nickel sintered substrate due to the presence of salt, and the active material is unevenly distributed near the surface of the porous nickel sintered substrate. It turns out that increases.
[0008]
Here, if the dried state (heated state) does not become an excessively dried state during intermediate drying, nickel nitrate and cobalt nitrate are mainly composed of hexahydrate, and the active material after alkali treatment is sintered with porous nickel. The present invention has been made with the knowledge that the amount of falling off of the active material will be reduced in the subsequent chemical conversion process, cutting process or winding process. It is an object of the present invention to provide a drying method in which nitrates impregnated in a porous nickel sintered substrate are mainly hexahydrates in intermediate drying in a substance filling cycle.
[0009]
[Means for solving the problems and their functions and effects]
In order to solve the above-mentioned problems, the alkaline storage battery manufacturing method of the present invention is characterized in that, in the intermediate drying step of the filling cycle, the nitrate impregnated into the porous nickel sintered substrate at the end of the intermediate drying step is a hexahydrate salt The production conditions are adjusted to such dry conditions. As described above, when the drying conditions are adjusted such that the nitrate impregnated in the porous nickel sintered substrate at the end of the intermediate drying step is mainly hexahydrate, the active material after the alkali treatment is converted into the porous nickel sintered substrate. As a result, the amount of the active material is reduced in the subsequent chemical conversion process, cutting process or winding process.
[0010]
Here, in order to adjust the drying conditions of the intermediate drying, it is necessary to adjust the drying temperature and the drying time. The nitrate mainly composed of hexahydrate is an X-ray diffraction peak (2θ = 13.1 °) of nickel nitrate tetrahydrate with respect to an X-ray diffraction peak (2θ = 16.2 °: CuKα) of nickel nitrate hexahydrate. When the integrated intensity ratio of CuKα) is 0.5 or less, the active material is held inside the porous nickel sintered substrate, and the amount of active material falling off in the subsequent chemical conversion process, cutting process, and winding process is reduced. It becomes possible to make it.
[0011]
The nitrate mainly composed of hexahydrate is an X-ray diffraction peak (2θ = 34.6 °) of cobalt nitrate tetrahydrate with respect to an X-ray diffraction peak (2θ = 41.0 °: CuKα) of cobalt nitrate hexahydrate. When the integrated intensity ratio of CuKα) is 0.5 or less, the active material is held inside the porous nickel sintered substrate, and the amount of active material falling off in the subsequent chemical conversion process, cutting process, and winding process is reduced. It becomes possible to make it.
[0012]
DETAILED DESCRIPTION OF THE INVENTION
Next, a preferred embodiment of the method for producing an alkaline storage battery of the present invention will be described below. In addition, this invention is not limited to the following embodiment at all, It can change and implement suitably in the range which does not change the summary.
[0013]
1. Preparation of Nickel Sintered Substrate A thickener such as carboxymethyl cellulose and water are kneaded with nickel powder to prepare a slurry, and this slurry is applied to a conductive core made of a nickel porous body. Thereafter, the conductive core coated with the slurry was sintered in a reducing atmosphere to prepare a porous nickel sintered substrate having a porosity of 80% and a thickness of 0.55 mm.
[0014]
2. Production of nickel electrode (1) Example 1
The sintered nickel electrode plate a of Example 1 is obtained by repeating the following steps (1) to (4) for the porous nickel sintered substrate produced as described above a predetermined number of times (for example, 10 times). Produced. That is,
(1) An impregnating solution containing a high concentration of nitrate precipitated at room temperature (for example, an aqueous solution having a nickel nitrate: cobalt nitrate molar ratio of 80:20 and a specific gravity of 1.70) is adjusted to a temperature of 70 ° C. After heating, the porous nickel sintered substrate produced as described above is immersed in this impregnating solution for 60 minutes, and the pore surface of the porous nickel sintered substrate is impregnated with nitrate.
[0015]
(2) Next, after the porous nickel sintered substrate is pulled up from the impregnating solution, it is heated in a warm air of 55 ° C. for 30 minutes for intermediate drying.
(3) After intermediate drying, an active material that substitutes nickel hydroxide and cobalt hydroxide for nitrate deposited on the pore surface by immersing in an aqueous solution of sodium hydroxide having a concentration of 25% and a temperature of 80 ° C. for 60 minutes. Process.
{Circle around (4)} After performing the active material treatment, the material is washed in ion-exchanged water for 60 minutes, and then heated and dried in 90 ° C. warm air for 60 minutes.
[0016]
Thereafter, the process returns to the above step (1) again, and the same processing steps (1) to (4) as described above are repeated a predetermined number of times (for example, 10 times) to ensure a predetermined active material filling amount. Thus, a sintered nickel electrode plate a of Example 1 was produced. In addition, the drying temperature and drying time in the intermediate drying of (2) were set to 55 ° C. for 30 minutes for the first time and 30 minutes at 80 ° C. for the second time and thereafter.
[0017]
(2) Example 2
The porous nickel sintered substrate produced as described above was repeated a predetermined number of times (for example, 10 times) except for the intermediate drying of the above-mentioned (2), and the examples were repeated. 2 sintered nickel electrode plates b were prepared. In addition, the drying temperature and drying time in the intermediate drying of (2) in Example 2 were set to 65 ° C. for 5 minutes for the first time and 30 minutes for 65 minutes at the second time and thereafter.
[0018]
(3) Comparative Example 1
The porous nickel sintered substrate produced as described above was subjected to the above-mentioned treatment steps (1) to (4) a predetermined number of times (for example, 10 times) except for the intermediate drying of the above (2), and a comparative example 1 sintered nickel electrode plate x was produced. In addition, the drying temperature and drying time in the intermediate drying of (2) of Comparative Example 1 were set to 80 ° C. for 30 minutes in all times.
[0019]
(4) Comparative Example 2
The porous nickel sintered substrate produced as described above was subjected to the above-mentioned treatment steps (1) to (4) a predetermined number of times (for example, 10 times) except for the intermediate drying of the above (2), and a comparative example 2 sintered nickel electrode plates y were prepared. The drying temperature and drying time in the intermediate drying of (2) of Comparative Example 2 were set to 65 ° C. for 30 minutes in all the times.
[0020]
3. Measurement of integrated intensity ratio of X-ray diffraction Next, when producing each sintered nickel electrode plate a, b and x, y as described above, each sintered nickel electrode plate a, b after intermediate drying and X-ray diffraction analysis of x and y was performed, and the diffraction peak of cobalt nitrate tetrahydrate (2θ = 34.6 °: CuKα) with respect to the diffraction peak of cobalt nitrate hexahydrate (2θ = 41.0 °: CuKα) was integrated. The intensity ratio and the integrated intensity ratio of the nickel nitrate tetrahydrate diffraction peak (2θ = 13.1 °: CuKα) to the nickel nitrate hexahydrate diffraction peak (2θ = 16.2 °: CuKα) were measured. When this is shown in the table, the results shown in Table 1 below were obtained.
[0021]
[Table 1]
In Table 1, cobalt nitrate is the integral of the diffraction peak of cobalt nitrate tetrahydrate (2θ = 34.6 °: CuKα) with respect to the diffraction peak of cobalt nitrate hexahydrate (2θ = 41.0 °: CuKα). Intensity ratio, nickel nitrate is the integrated intensity ratio of the nickel nitrate tetrahydrate diffraction peak (2θ = 13.1 °: CuKα) to the nickel nitrate hexahydrate diffraction peak (2θ = 16.2 °: CuKα). Represents.
[0023]
On the other hand, each of the sintered nickel electrode plates a, b and x, y of Examples 1 and 2 and Comparative Examples 1 and 2 manufactured as described above was used. , B and x, y were respectively formed, and the amount of the active material dropped during the formation was measured. When this is shown in the table, the results shown in Table 2 below were obtained.
[0024]
[Table 2]
Next, the integrated intensity ratio of the diffraction peak of cobalt nitrate tetrahydrate (2θ = 34.6 °: CuKα) to the diffraction peak of cobalt nitrate hexahydrate (2θ = 41.0 °: CuKα), and nickel nitrate hexahydrate The integrated intensity ratio of the nickel nitrate tetrahydrate diffraction peak (2θ = 13.1 °: CuKα) to the diffraction peak of (2θ = 16.2 °: CuKα) is taken as the horizontal axis, and the amount of active material loss is taken as the vertical axis. When represented on a graph, the results shown in FIG. 1 were obtained.
[0026]
As is apparent from FIG. 1, in the electrode plate after intermediate drying, the integrated intensity ratio of cobalt nitrate tetrahydrate to cobalt nitrate hexahydrate in the X-ray diffraction peak is 0.5 or less, or nickel nitrate in the X-ray diffraction peak. It can be seen that when the integral strength ratio of nickel nitrate tetrahydrate to hexahydrate is 0.5 or less, the amount of the active material falling off is reduced and the impregnation can be efficiently performed with a small amount of impregnation.
[0027]
This is because when a porous nickel sintered substrate is immersed in a mixed solution of nickel nitrate and cobalt nitrate and then intermediate dried, nickel nitrate or cobalt nitrate becomes tetrahydrate, or tetrahydrate and hexahydrate are formed. In other words, the integrated intensity ratio of cobalt nitrate tetrahydrate to cobalt nitrate hexahydrate is greater than 0.5 at the X-ray diffraction peak, or nickel nitrate tetrahydrate to nickel nitrate hexahydrate. When the integrated intensity ratio of is larger than 0.5, the active material is not held inside the porous nickel sintered substrate, and thus it is considered that the amount of the active material falling off increased.
[0028]
On the other hand, after the porous nickel sintered substrate is immersed in a mixed solution of nickel nitrate and cobalt nitrate, intermediate drying is performed, and nickel nitrate or cobalt nitrate becomes hexahydrate or tetrahydrate and hexahydrate. Even if they are mixed, the integrated intensity ratio of cobalt nitrate tetrahydrate to cobalt nitrate hexahydrate is 0.5 or less at the X-ray diffraction peak, or the integrated intensity of nickel nitrate tetrahydrate to nickel nitrate hexahydrate. When the ratio is 0.5 or less, it is considered that the active material is retained inside the porous nickel sintered substrate, and the amount of the active material falling off is reduced.
[0029]
Therefore, in the electrode plate after intermediate drying, the integrated intensity ratio of cobalt nitrate tetrahydrate to cobalt nitrate hexahydrate at the X-ray diffraction peak is 0.5 or less, or relative to nickel nitrate hexahydrate at the X-ray diffraction peak. If the integrated intensity ratio of nickel nitrate tetrahydrate is 0.5 or less, it is possible to reduce the amount of active material falling off in the subsequent chemical conversion process, cutting process, and winding process. Further, in order to set the drying conditions so that the nitrate on the electrode plate after the intermediate drying is mainly hexahydrate, and exhibit the effect of reducing the amount of falling out of the active material, it may be any number of times in the above filling cycle, If the drying temperature and drying time are adjusted during the first intermediate drying of the filling cycle, the effect of reducing the amount of active material dropout is increased.
[0030]
In addition, after the porous nickel sintered substrate was immersed in a mixed solution of nickel nitrate and cobalt nitrate, the first intermediate drying was performed at 55 ° C. for 30 minutes in the electrode plate a of Example 1. The electrode plate b of Example 2 was set at 65 ° C. for 5 minutes. However, in the X-ray diffraction peak after intermediate drying, the integrated intensity ratio of tetrahydrate to hexahydrate of cobalt nitrate or nickel nitrate was 0.5 or less. If so, the drying temperature and drying time may be whatever. In short, the integral intensity ratio of tetrahydrate to hexahydrate of cobalt nitrate or nickel nitrate is 0.5 or less at the X-ray diffraction peak. What is necessary is just to adjust to such drying conditions.
[0031]
As described above, in the present invention, the drying conditions are adjusted so that the nitrate impregnated in the porous nickel sintered substrate is mainly hexahydrate at the end of the intermediate drying step. The substance is held inside the porous nickel sintered substrate, and the amount of the active material falling off is reduced in the subsequent chemical conversion process, cutting process or winding process.
[0032]
In the above-described embodiment, the example in which the filling cycle for filling the porous nickel sintered substrate with nickel hydroxide is repeated 10 times has been described. However, this filling cycle is not limited to 10 times. What is necessary is just to select suitably by porosity, the density | concentration of nitrate, etc.
[Brief description of the drawings]
FIG. 1 shows the relationship between the integrated intensity ratio of cobalt nitrate tetrahydrate to cobalt nitrate hexahydrate and the integrated intensity ratio of nickel nitrate tetrahydrate to nickel nitrate hexahydrate at the X-ray diffraction peak, and the amount of active material falling off. FIG.
[Explanation of symbols]
a ... Example 1, b ... Example 2, x ... Comparative Example 1, y ... Comparative Example 2
Claims (1)
前記充填サイクルの中間乾燥工程において、該中間乾燥工程の終了時に前記多孔性ニッケル焼結基板に含浸された前記硝酸塩が硝酸ニッケル６水塩のＸ線回折ピーク（２θ＝１６．２°：ＣｕＫα）に対する硝酸ニッケル４水塩のＸ線回折ピーク（２θ＝１３．１°：ＣｕＫα）の積分強度比が０．５以下で、硝酸コバルト６水塩のＸ線回折ピーク（２θ＝４１．０°：ＣｕＫα）に対する硝酸コバルト４水塩のＸ線回折ピーク（２θ＝３４．６°：ＣｕＫα）の積分強度比が０．５以下となるように乾燥させたことを特徴とするアルカリ蓄電池の製造方法。A dipping step in which a porous nickel sintered substrate is immersed in an aqueous solution mainly composed of nitrate composed of nickel nitrate and cobalt nitrate, and the nitrate is impregnated in the porous nickel sintered substrate, and porous nickel immersed in the aqueous solution A filling cycle comprising an intermediate drying step of heating and drying the sintered substrate and an alkali dipping step of immersing the intermediate dried porous nickel sintered substrate in an alkaline solution, and the filling cycle is repeated a predetermined number of times Repetitively, a method for producing an alkaline storage battery in which a predetermined amount of an active material is filled in the porous nickel sintered substrate,
In the intermediate drying step of the filling cycle, the nitrate impregnated in the porous nickel sintered substrate at the end of the intermediate drying step is an X-ray diffraction peak of nickel nitrate hexahydrate (2θ = 16.2 °: CuKα). The integral intensity ratio of the X-ray diffraction peak (2θ = 13.1 °: CuKα) of nickel nitrate tetrahydrate with respect to the X-ray diffraction peak of cobalt nitrate hexahydrate (2θ = 41.0 °: A method for producing an alkaline storage battery, wherein the integral intensity ratio of an X-ray diffraction peak (2θ = 34.6 °: CuKα) of cobalt nitrate tetrahydrate with respect to (CuKα) is 0.5 or less .
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