JP2006294330A - Positive plate for lead-acid battery and its manufacturing method - Google Patents
Positive plate for lead-acid battery and its manufacturing method Download PDFInfo
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 10
- 239000002253 acid Substances 0.000 title abstract description 19
- 239000000835 fiber Substances 0.000 claims abstract description 72
- 239000002002 slurry Substances 0.000 claims abstract description 65
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 46
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000002003 electrode paste Substances 0.000 claims abstract description 22
- 238000004898 kneading Methods 0.000 claims abstract description 21
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 238000003860 storage Methods 0.000 claims description 31
- YADSGOSSYOOKMP-UHFFFAOYSA-N dioxolead Chemical compound O=[Pb]=O YADSGOSSYOOKMP-UHFFFAOYSA-N 0.000 claims description 20
- -1 polyethylene terephthalate Polymers 0.000 claims description 12
- 229920002972 Acrylic fiber Polymers 0.000 claims description 11
- 230000032683 aging Effects 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 6
- 239000004952 Polyamide Substances 0.000 claims description 5
- 239000004743 Polypropylene Substances 0.000 claims description 5
- 229920002647 polyamide Polymers 0.000 claims description 5
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 5
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 5
- 229920001155 polypropylene Polymers 0.000 claims description 5
- 239000011149 active material Substances 0.000 abstract description 31
- XMFOQHDPRMAJNU-UHFFFAOYSA-N lead(ii,iv) oxide Chemical compound O1[Pb]O[Pb]11O[Pb]O1 XMFOQHDPRMAJNU-UHFFFAOYSA-N 0.000 abstract 2
- 230000002708 enhancing effect Effects 0.000 abstract 1
- 239000007774 positive electrode material Substances 0.000 description 22
- 230000000052 comparative effect Effects 0.000 description 20
- 230000005484 gravity Effects 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- PIJPYDMVFNTHIP-UHFFFAOYSA-L lead sulfate Chemical compound [PbH4+2].[O-]S([O-])(=O)=O PIJPYDMVFNTHIP-UHFFFAOYSA-L 0.000 description 8
- 238000000034 method Methods 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000002142 lead-calcium alloy Substances 0.000 description 5
- 239000007773 negative electrode material Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000010030 laminating Methods 0.000 description 3
- 229920000098 polyolefin Polymers 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 229910000464 lead oxide Inorganic materials 0.000 description 2
- OCWMFVJKFWXKNZ-UHFFFAOYSA-L lead(2+);oxygen(2-);sulfate Chemical compound [O-2].[O-2].[O-2].[Pb+2].[Pb+2].[Pb+2].[Pb+2].[O-]S([O-])(=O)=O OCWMFVJKFWXKNZ-UHFFFAOYSA-L 0.000 description 2
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229910000882 Ca alloy Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000002431 foraging effect Effects 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000009828 non-uniform distribution Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
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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
Abstract
Description
本発明は鉛蓄電池用正極板及びその製造方法に関するものである。 The present invention relates to a positive electrode plate for a lead storage battery and a method for manufacturing the same.
特許文献１や特許文献２に示されているように、二酸化鉛を含む鉛丹スラリーと鉛粉とを混練してなる正極ペースト（活物質）を格子体に充填した構造の鉛蓄電池用正極板が用いられている。この種の正極板を製造する際には、鉛丹と希硫酸とをミキサーに供給して、両者を混合することにより二酸化鉛を含む鉛丹スラリーを製造した後、この鉛丹スラリーを鉛粉と共にペースト練合機に供給して混練することにより鉛蓄電池用正極ペーストを製造し、この正極ペーストを集電体である格子体に充填して、熟成、乾燥することにより正極板を完成させている。
As shown in Patent Document 1 and
また鉛丹を用いて製造される鉛蓄電池用正極板においては、その性能を向上させるために、鉛丹スラリー中に種々の添加物を加えることが提案されている。例えば、特許文献３には、正極ペースト中にチューブ状繊維または微細な孔を有するポリエチレン繊維を添加して、繊維の細孔内に電解液を保有させることにより、鉛蓄電池の寿命を延ばし、エネルギ密度を高める提案がなされている。
鉛蓄電池用正極板を製造する過程で、鉛丹スラリーと鉛粉とを練合機に入れて混練する際に鉛丹スラリーと鉛粉とが接触すると、鉛丹スラリー中にある硫酸鉛と鉛粉とが反応して三塩基性硫酸鉛の被膜が鉛丹スラリーの周囲に形成され、このことにより、直径約１［mm］以上の鉛丹スラリーの凝集粒子が正極ペースト中に存在する状態になる。このように凝集粒子が存在する正極ペーストを用いて未化成正極板を製作すると、未化活物質中に凝集した鉛丹スラリーが局部的に存在するため、鉛丹スラリーの分布が不均一な未化成正極板が出来上がる。特許文献３には、正極ペースト中に微細な孔を有するポリエチレン繊維を添加することが提案されているが、このような繊維を正極ペースト中に添加しても、正極ペースト中に鉛丹スラリーの凝縮粒子が形成されるのを防ぐことはできない。このように、鉛丹スラリーと鉛粉とを混練して正極活物質を形成する従来の正極板の製造方法では、鉛丹スラリーの凝集粒子の形成を抑制して、化成効率及び電池性能を損なうことなく正極板を製造することが難しかった。
In the process of producing a positive electrode plate for a lead storage battery, when the red lead slurry and the lead powder come into contact with each other when the red lead slurry and the lead powder are mixed in a kneading machine, lead sulfate and lead in the red lead slurry The powder reacts to form a tribasic lead sulfate film around the red lead slurry, which causes aggregated particles of the red lead slurry with a diameter of about 1 [mm] or more to exist in the positive electrode paste. Become. When an unformed positive electrode plate is produced using a positive electrode paste in which aggregated particles are present in this way, aggregated red lead slurry is locally present in the unactivated active material, and thus the distribution of the red lead slurry is not uniform. A conversion positive electrode plate is completed.
また、鉛丹スラリーと鉛粉とを混練して形成した正極ペーストを格子体に充填した正極板では、活物質を熟成する際に水分の減少により活物質が収縮するため、活物質と格子体との密着性が低下するという問題があった。またこの種の正極板では、充放電サイクルを繰り返した際に正極活物質が崩壊して格子体から脱落することがあるため、サイクル寿命が短くなるという問題があった。 In addition, in a positive electrode plate in which a positive electrode paste formed by kneading red lead slurry and lead powder is filled in a grid, the active material shrinks due to a decrease in moisture when the active material is aged. There was a problem that the adhesiveness with was lowered. In addition, this type of positive electrode plate has a problem in that the cycle life is shortened because the positive electrode active material may collapse and fall off from the lattice when the charge / discharge cycle is repeated.
本発明の目的は、正極活物質の化成効率及び電池性能を向上させ、かつサイクル寿命特性を向上させることができる鉛蓄電池用正極板及びその製造方法を提供することにある。 The objective of this invention is providing the positive electrode plate for lead acid batteries which can improve the chemical conversion efficiency and battery performance of a positive electrode active material, and can improve a cycle life characteristic, and its manufacturing method.
本発明に係わる鉛蓄電池用正極板は、二酸化鉛を含む鉛丹スラリーと鉛粉とを混練して形成した正極ペーストを格子体に充填した構造を有するもので、本発明においては、正極ペースト中に親水性繊維が均一に分散させられていることを特徴とする。 The positive electrode plate for a lead storage battery according to the present invention has a structure in which a positive electrode paste formed by kneading a lead oxide slurry containing lead dioxide and lead powder is filled in a grid, and in the present invention, in the positive electrode paste It is characterized in that hydrophilic fibers are uniformly dispersed.
上記親水性繊維としては、アクリル繊維、ポリアミド繊維、ポリエチレンテレフタレート繊維及びポリプロピレン繊維から成る繊維群から選択された少なくとも１つの繊維を用いるのが好ましい。 As the hydrophilic fiber, it is preferable to use at least one fiber selected from a fiber group consisting of acrylic fiber, polyamide fiber, polyethylene terephthalate fiber and polypropylene fiber.
上記の正極板は、鉛丹、親水性繊維及び希硫酸を混合して二酸化鉛を含む鉛丹スラリーを製造する工程と、鉛丹スラリーを鉛粉と共に混練することにより鉛蓄電池用正極ペーストを製造する工程と、前記正極ペーストを格子体に充填し、熟成、乾燥する工程とを行なうことにより製造される。 The above positive electrode plate produces a lead paste slurry for a lead-acid battery by mixing lead lead, hydrophilic fiber and dilute sulfuric acid to produce a lead red slurry containing lead dioxide, and kneading the lead red slurry with lead powder. And a step of filling the positive electrode paste into a lattice, aging and drying.
上記の正極板はまた、鉛丹及び希硫酸を混合して二酸化鉛を含む鉛丹スラリーを製造する工程と、この鉛丹スラリーに親水性繊維と鉛粉とを加えて混練することにより鉛蓄電池用正極ペーストを製造する工程と、正極ペーストを格子体に充填し、熟成、乾燥する工程とを行なうことによっても製造することができる。 The above positive electrode plate is also a lead acid battery by mixing a red lead and dilute sulfuric acid to produce a red lead slurry containing lead dioxide, and adding and kneading hydrophilic fiber and lead powder to the red lead slurry. It can also be produced by performing a step of producing a positive electrode paste for use and a step of filling the positive electrode paste into a lattice, aging and drying.
前述のように、ペースト練合機中において鉛丹スラリーと鉛粉とが接触すると、鉛丹スラリー中にある硫酸鉛と鉛粉が反応して三塩基性硫酸鉛の被膜が鉛丹スラリーの周囲に形成される。このことにより、直径約１［mm］以上の鉛丹スラリーの凝集粒子が正極ペースト中に存在する状態になって、鉛丹スラリーの分布が不均一な未化成正極板が得られる。親水性繊維は鉛丹スラリーと良くなじむため、本発明のように、鉛丹スラリーに親水性の繊維を添加すると、該親水性繊維はスラリー中に均一に分散することになる。親水性繊維が均一に分散した鉛丹スラリーに鉛粉を加えて混練すると、分散した親水性繊維が鉛丹スラリーの凝集を抑える働きをするため、鉛丹スラリーの凝集粒子が形成されるのを抑制して、正極未化成活物質中に鉛丹スラリーを均一に分散させることができる。鉛丹スラリーが均一に分散した正極板は充電が均一に行なわれるため、正極活物質を化成する際に効率よく充電を行なって化成効率を高めることができる。 As mentioned above, when the red lead slurry and lead powder come into contact with each other in the paste kneading machine, the lead sulfate and lead powder in the red lead slurry react to form a tribasic lead sulfate coating around the red lead slurry. Formed. As a result, aggregated particles of red lead slurry having a diameter of about 1 [mm] or more are present in the positive electrode paste, and an unformed positive electrode plate with non-uniform distribution of red lead slurry is obtained. Since the hydrophilic fiber is well compatible with the red lead slurry, when the hydrophilic fiber is added to the red lead slurry as in the present invention, the hydrophilic fiber is uniformly dispersed in the slurry. When lead powder is added to and kneaded with a red lead slurry in which hydrophilic fibers are uniformly dispersed, the dispersed hydrophilic fiber functions to suppress the red lead slurry from agglomerating. It is possible to suppress and uniformly disperse the red lead slurry in the positive electrode unformed active material. Since the positive electrode plate in which the red lead slurry is uniformly dispersed is charged uniformly, it can be efficiently charged when forming the positive electrode active material to increase the conversion efficiency.
また鉛丹スラリー中に鉛丹及び親水性繊維を均一に分散させておくと、親水性繊維が活物質の構造を強固に維持する働きするため、活物質を熟成する際に水分の減少により生じる活物質の収縮を抑制して、活物質と格子体との密着性が低下するのを防ぐことができる。 In addition, when the red lead and the hydrophilic fiber are uniformly dispersed in the red lead slurry, the hydrophilic fiber works to maintain the structure of the active material firmly. The shrinkage of the active material can be suppressed and the adhesion between the active material and the lattice can be prevented from being lowered.
また鉛丹スラリーと鉛粉とを混練して形成した正極活物質を使用した鉛蓄電池では、充放電サイクルを繰り返した際に活物質が崩壊して集電体から脱落するという問題が生じていたが、鉛丹スラリー中に親水性活物質を分散させておくと、正極活物質中に親水性繊維が均一に分散した状態で存在することになり、該親水性繊維が活物質の構造を強固に維持する働きするため、充放電サイクル中の活物質の脱落を最小限に抑えることができる。 In addition, in a lead-acid battery using a positive electrode active material formed by kneading a red lead slurry and lead powder, there was a problem that the active material collapsed and dropped from the current collector when the charge / discharge cycle was repeated. However, if the hydrophilic active material is dispersed in the red lead slurry, the hydrophilic fibers are present in a uniformly dispersed state in the positive electrode active material, and the hydrophilic fibers strengthen the structure of the active material. Therefore, it is possible to minimize the loss of the active material during the charge / discharge cycle.
従って、本発明によれば、活物質と格子体との密着性の低下を抑制できることと、充放電サイクル中の活物質の脱落を抑えることができることとが相俟って、寿命サイクルに強い正極板を得ることができる。 Therefore, according to the present invention, it is possible to suppress a decrease in the adhesion between the active material and the lattice, and to suppress the falling off of the active material during the charge / discharge cycle, and thus a positive electrode that is resistant to a life cycle. A board can be obtained.
本発明に係わる正極板の製造方法を実施するに当たり、親水性繊維は、鉛丹及び希硫酸をミキサーにより混合して鉛丹スラリーを製造する際に鉛丹及び希硫酸とともにミキサーに供給することにより、鉛丹スラリーに添加するようにしてもよく、鉛丹及び希硫酸をミキサーにより混合して二酸化鉛を含む鉛丹スラリーを製造した後に、該鉛丹スラリーに親水性繊維を添加して、親水性繊維と鉛丹スラリーとを混合するようにしてもよい。 In carrying out the method for producing a positive electrode plate according to the present invention, the hydrophilic fiber is mixed with red lead and dilute sulfuric acid by a mixer to produce a red lead slurry and supplied to the mixer together with red lead and dilute sulfuric acid. In addition, a red lead slurry containing lead dioxide can be prepared by mixing red lead and dilute sulfuric acid with a mixer, and then hydrophilic fiber is added to the red lead slurry, You may make it mix a property fiber and a red lead slurry.
また鉛丹及び希硫酸を混合して得た鉛丹スラリーに鉛粉を加えて混練する際に、親水性繊維を鉛丹スラリー及び鉛粉とともに混練機に供給して、混練機内で親水性繊維を鉛丹スラリー中に分散させるようにしてもよい。 In addition, when adding lead powder to the red lead slurry obtained by mixing red lead and dilute sulfuric acid and kneading them, the hydrophilic fibers are supplied to the kneader together with the red lead slurry and lead powder, and the hydrophilic fibers are mixed in the kneader. May be dispersed in the red lead slurry.
以上のように、本発明によれば、鉛丹スラリーに親水性繊維を添加することにより、鉛丹スラリーと鉛粉とを混練する際に鉛丹スラリーの凝縮粒子が形成されるのを抑制することができるので、正極活物質中に鉛丹スラリーを均一に分布させて化成効率を高め、電池性能を高めることができる。 As described above, according to the present invention, by adding hydrophilic fibers to the red lead slurry, it is possible to suppress the formation of condensed particles of the red lead slurry when the red lead slurry and the lead powder are kneaded. Therefore, it is possible to uniformly distribute the red lead slurry in the positive electrode active material to increase the chemical conversion efficiency and improve the battery performance.
更に本発明によれば、正極活物質中に親水性繊維を均一に分散させて、該親水性繊維に、活物質の構造を強固に維持する働きをさせることができるため、熟成時に生じる正極活物質の収縮により正極活物質と格子体との密着性が低下するのを防ぐことができるだけでなく、充放電サイクルを繰り返した際に活物質が崩壊して格子体から脱落するのを抑制することができ、これらにより、鉛蓄電池のサイクル寿命特性を改善することができる。 Furthermore, according to the present invention, the hydrophilic fibers can be uniformly dispersed in the positive electrode active material, and the hydrophilic fibers can function to maintain the structure of the active material firmly. Not only can the adhesion between the positive electrode active material and the grid body be reduced due to the shrinkage of the material, but also the active material can be prevented from collapsing and falling off the grid body when the charge / discharge cycle is repeated. Thus, the cycle life characteristics of the lead storage battery can be improved.
以下、本発明の好ましい実施形態を、実施例及び比較例と共に詳細に説明する。
本発明の好ましい実施形態では、鉛丹と、親水性繊維と、希硫酸とをミキサーに供給して、これらを混合することにより二酸化鉛を含む鉛丹スラリーを製造した。次いで、このようにして得られた鉛丹スラリーを鉛粉とともにペースト練合機に供給して両者を混練することにより鉛蓄電池用正極ペーストを作成し、この正極ペーストを格子体に充填して、熟成、乾燥することにより鉛蓄電池用正極板を製造した。
Hereinafter, preferred embodiments of the present invention will be described in detail together with examples and comparative examples.
In a preferred embodiment of the present invention, a red lead slurry containing lead dioxide was produced by supplying red lead, hydrophilic fibers, and dilute sulfuric acid to a mixer and mixing them. Next, a lead paste slurry obtained in this manner is supplied to a paste kneader together with lead powder to prepare a positive electrode paste for a lead storage battery by kneading both, and this positive electrode paste is filled into a lattice body, A positive electrode plate for a lead storage battery was produced by aging and drying.
本発明者は、本発明に係わる方法により製造された正極板を用いて組み立てた鉛蓄電池を実施例１とし、従来の方法により製造された正極板を用いて組み立てた鉛蓄電池を比較例１及び２として、正極活物質中の残存硫酸鉛量と充電時間との関係を調べる試験と、放電容量と充放電サイクル数との関係を調べる充負荷寿命試験とを行なったので、これらの試験について以下に説明する。 This inventor made the lead acid battery assembled using the positive electrode plate manufactured by the method concerning this invention into Example 1, and compared the lead acid battery assembled using the positive electrode plate manufactured by the conventional method with Comparative Example 1 and 2, a test for examining the relationship between the amount of lead sulfate remaining in the positive electrode active material and the charging time and a charge load life test for examining the relationship between the discharge capacity and the number of charge / discharge cycles were conducted. Explained.
［実施例１］
実施例１では、次のようにして鉛蓄電池を製造した。
この実施例では、以下のようにして正極板を製作した。先ず鉛丹１５［ｋｇ］、親水性の繊維であるアクリル繊維１．５［ｋｇ］と、希硫酸（比重１．２６：２０［℃］）１１０［ｌ］とを、混練ミキサー中に投入して鉛丹スラリーを作った。次いでこの鉛丹スラリーと鉛粉８５０［ｋｇ］とをペースト練合機に投入し、これを２００［ｌ］の水とを混練して正極活物質ペーストを作成した。次に、この正極活物質ペースト１００［ｇ］を鉛−カルシウム合金からなる格子体に充填してから、温度５０［℃］、湿度９５％中に１８時間放置して熟成した後、温度１１０［℃］中に２時間放置することにより乾燥して未化成正極板を作った。
また以下のようにして負極板を作った。先ず、鉛粉と、この鉛粉に対して１５質量％の希硫酸（比重１．２６：２０［℃］）と、該鉛粉に対して１２質量％の水とを混練して負極活物質ペーストを作った。次に、負極活物質ペースト８０［ｇ］をカルシウム合金の格子体からなる集電体に充填してから、温度５０［℃］、湿度９５％中に１８時間放置して熟成した後に温度１１０［℃］中に２時間放置して乾燥して未化成負極板を作った。
次に、未化成負極板８枚と未化成正極板７枚とをセパレータを介して交互に積層することにより鉛蓄電池の各セルの極板群を構成し、２５［℃］の雰囲気で２２．５Ａ、９時間の定電流で充電を行うことにより化成を行なった。充電に用いた硫酸の比重はs.g.１．２５０とし、この硫酸を各セルに７００［ｍｌ］注入した。
以上の手順により、定格電圧が１２Ｖ、定格容量（５時間率容量）が５５Ａｈである、実施例１の自動車用鉛蓄電池８０Ｄ２６（ＪＩＳＤ５３０１記載）を完成した。
[Example 1]
In Example 1, a lead storage battery was manufactured as follows.
In this example, a positive electrode plate was manufactured as follows. First, 15 kg of red lead, 1.5 [kg] of acrylic fiber, which is a hydrophilic fiber, and 110 [l] of dilute sulfuric acid (specific gravity 1.26: 20 [° C.]) are put into a kneading mixer. Made a red lead slurry. Next, this red lead slurry and lead powder 850 [kg] were put into a paste kneader and kneaded with 200 [l] of water to prepare a positive electrode active material paste. Next, after filling this positive electrode active material paste 100 [g] into a lattice body made of a lead-calcium alloy, the positive electrode active material paste 100 [g] was left to mature in a temperature of 50 [° C.] and a humidity of 95% for 18 hours. [° C.] for 2 hours to dry and produce an unformed positive electrode plate.
Moreover, the negative electrode plate was made as follows. First, a negative electrode active material obtained by kneading lead powder, 15% by mass of diluted sulfuric acid (specific gravity 1.26: 20 [° C.]) with respect to the lead powder, and 12% by mass of water with respect to the lead powder. I made a paste. Next, 80 [g] of the negative electrode active material paste was filled in a current collector made of a calcium alloy lattice, and then left to mature in a temperature of 50 [° C.] and a humidity of 95% for 18 hours. [Deg.] C.] for 2 hours and dried to prepare an unformed negative electrode plate.
Next, an electrode plate group of each cell of the lead storage battery is configured by alternately laminating eight unformed negative electrode plates and seven unformed positive electrode plates with separators interposed therebetween, in a 25 [° C.] atmosphere. Chemical conversion was performed by charging at a constant current of 5 A for 9 hours. The specific gravity of sulfuric acid used for charging was sg 1.250, and 700 [ml] of sulfuric acid was injected into each cell.
By the above procedure, the automotive lead storage battery 80D26 (described in JIS D5301) of Example 1 having a rated voltage of 12 V and a rated capacity (5-hour rate capacity) of 55 Ah was completed.
［比較例１］
上記実施例と比較するため、比較例１の鉛蓄電池を次のようにして作製した。
比較例１では以下のようにして正極板を作った。先ず、鉛丹１５［ｋｇ］と、希硫酸（比重１．２６：２０［℃］）１１０［ｌ］とを混練ミキサー中に投入して鉛丹スラリーを作った。次いでこの鉛丹スラリーと、鉛粉８５０［ｋｇ］と、ポリオレフィン繊維１．５［ｋｇ］とをペースト練合機に投入し、更に１００［ｌ］の水を加えてこれらを混練することにより正極活物質ペーストを作った。次に、この正極活物質ペースト１００［ｇ］を鉛−カルシウム合金からなる格子体に充填してから、温度５０［℃］、湿度９５％中に１８時間放置して熟成した後、温度１１０［℃］中に２時間放置することにより乾燥して未化成正極板を作った。
また以下のようにして負極板を作った。先ず、鉛粉と、該鉛粉に対して１５質量％の希硫酸（比重１．２６：２０［℃］）と、該鉛粉に対して１２質量％の水とを混練して負極活物質ペーストを作った。次に、この負極活物質ペースト８０［ｇ］を鉛−カルシウム合金の格子体からなる集電体に充填してから、温度５０［℃］、湿度９５％中に１８時間放置して熟成した後、温度１１０［℃］中に２時間放置することにより乾燥して未化成負極板を作った。
次に、未化成負極板８枚と未化成正極板７枚とをセパレータを介して交互に積層することにより鉛蓄電池の各セルの極板群を構成し、２５［℃］の雰囲気で２２．５Ａ、１２時間の定電流で充電を行うことにより化成を行なった。充電に用いた硫酸の比重はs.g.１．２４０とし、この硫酸を各セルに７００［ｍｌ］注入した。
以上の手順により、定格電圧が１２Ｖ、定格容量（５時間率容量）が５５Ａｈである、比較例１の自動車用鉛蓄電池８０Ｄ２６（ＪＩＳＤ５３０１記載）を完成した。
[Comparative Example 1]
In order to compare with the said Example, the lead acid battery of the comparative example 1 was produced as follows.
In Comparative Example 1, a positive electrode plate was made as follows. First, 15 [kg] of red lead and 110 [l] of dilute sulfuric acid (specific gravity 1.26: 20 [° C.]) were put into a kneading mixer to make a red lead slurry. Next, this lead paste slurry, lead powder 850 [kg] and polyolefin fiber 1.5 [kg] are put into a paste kneader, and further 100 [l] of water is added to knead them to obtain a positive electrode. An active material paste was made. Next, after filling this positive electrode active material paste 100 [g] into a lattice body made of a lead-calcium alloy, the positive electrode active material paste 100 [g] was left to mature in a temperature of 50 [° C.] and a humidity of 95% for 18 hours. [° C.] for 2 hours to dry and produce an unformed positive electrode plate.
Moreover, the negative electrode plate was made as follows. First, a negative electrode active material obtained by kneading lead powder, 15% by mass of diluted sulfuric acid (specific gravity 1.26: 20 [° C.]) with respect to the lead powder, and 12% by mass of water with respect to the lead powder. I made a paste. Next, after filling this negative electrode active material paste 80 [g] into a current collector made of a lead-calcium alloy lattice, it was left to mature in a temperature of 50 [° C.] and a humidity of 95% for 18 hours. Then, it was left to stand at a temperature of 110 [° C.] for 2 hours to produce an unformed negative electrode plate.
Next, an electrode plate group of each cell of the lead storage battery is configured by alternately laminating eight unformed negative electrode plates and seven unformed positive electrode plates with separators interposed therebetween, in a 25 [° C.] atmosphere. Chemical conversion was performed by charging at a constant current of 5 A for 12 hours. The specific gravity of sulfuric acid used for charging was sg 1.240, and 700 [ml] of sulfuric acid was injected into each cell.
By the above procedure, a lead acid battery for automobile 80D26 (described in JIS D5301) of Comparative Example 1 having a rated voltage of 12 V and a rated capacity (5-hour rate capacity) of 55 Ah was completed.
［比較例２］
比較例２においては、次のようにして正極板を作った。先ず、鉛丹１５［ｋｇ］と、ポリオレフィン繊維１．５［ｋｇ］と、希硫酸（比重１．２６：２０［℃］）１１０［ｌ］とを混練ミキサー中に投入して混合することにより鉛丹スラリーを作った。次いでこの鉛丹スラリーと鉛粉８５０［ｋｇ］とをペースト練合機に投入し、更に２００［ｌ］の水を投入してこれらを混練することにより正極活物質ペーストを作った。次に、この正極活物質ペースト１００［ｇ］を鉛−カルシウム合金からなる格子体に充填してから、温度５０［℃］、湿度９５％中に１８時間放置して熟成した後、温度１１０［℃］中に２時間放置することにより乾燥して未化成正極板を作った。
次に以下のようにして負極板を作った。先ず、鉛粉と、該鉛粉に対して１５質量％の希硫酸（比重１．２６：２０［℃］）と、該鉛粉に対して１２質量％の水とを混練することにより負極活物質ペーストを作った。次に、この負極活物質ペースト８０［ｇ］を鉛−カルシウム合金の格子体からなる集電体に充填し、これを温度５０［℃］、湿度９５％中に１８時間放置して熟成した後、温度１１０［℃］中に２時間放置することにより乾燥して未化成負極板を作った。
次に、上記のようにして得られた未化成負極板８枚と未化成正極板７枚とをセパレータを介して交互に積層することにより鉛蓄電池の各セルの極板群を構成し、２５［℃］の雰囲気で２２．５Ａ、１２時間の定電流で充電を行うことにより化成を行なった。充電に用いた硫酸の比重はs.g.１．２５０とし、この硫酸を各セルに７００［ｍｌ］注入した。
以上の手順により、定格電圧が１２Ｖ、定格容量（５時間率容量）が５５Ａｈである、比較例２の自動車用鉛蓄電池８０Ｄ２６（ＪＩＳＤ５３０１記載）を完成した。
[Comparative Example 2]
In Comparative Example 2, a positive electrode plate was produced as follows. First, lead 15 kg [kg], polyolefin fiber 1.5 [kg] and dilute sulfuric acid (specific gravity 1.26: 20 [° C.]) 110 [l] are charged into a kneading mixer and mixed. A red lead slurry was made. Subsequently, this lead paste slurry and lead powder 850 [kg] were put into a paste kneader, and further 200 [l] of water was added and kneaded to prepare a positive electrode active material paste. Next, after filling this positive electrode active material paste 100 [g] into a lattice body made of a lead-calcium alloy, the positive electrode active material paste 100 [g] was left to mature in a temperature of 50 [° C.] and a humidity of 95% for 18 hours. [° C.] for 2 hours to dry and produce an unformed positive electrode plate.
Next, a negative electrode plate was made as follows. First, a negative electrode active is obtained by kneading lead powder, 15% by mass of dilute sulfuric acid (specific gravity 1.26: 20 [° C.]) with respect to the lead powder, and 12% by mass of water with respect to the lead powder. Made a substance paste. Next, the negative electrode active material paste 80 [g] was filled in a current collector made of a lead-calcium alloy lattice, and this was left to stand for 18 hours in a temperature of 50 [° C.] and a humidity of 95% for aging. Then, it was left to stand at a temperature of 110 [° C.] for 2 hours to produce an unformed negative electrode plate.
Next, the electrode plate group of each cell of the lead storage battery is configured by alternately laminating eight unformed negative electrode plates and seven unformed positive electrode plates obtained as described above via separators, Chemical conversion was performed by charging in an atmosphere of [° C.] at a constant current of 22.5 A for 12 hours. The specific gravity of sulfuric acid used for charging was sg 1.250, and 700 [ml] of sulfuric acid was injected into each cell.
By the above procedure, a lead acid battery for automobile 80D26 (described in JIS D5301) of Comparative Example 2 having a rated voltage of 12 V and a rated capacity (5-hour rate capacity) of 55 Ah was completed.
図１の曲線ａ，ｂ及びｃはそれぞれ実施例１，比較例１及び比較例２の鉛蓄電池について、充電時間を変えたときの正極活物質中の残存硫酸鉛量（正極活物質中に残存している硫酸鉛の量）の変化を示したものである。 Curves a, b, and c in FIG. 1 indicate the amount of residual lead sulfate in the positive electrode active material (remaining in the positive electrode active material) when the charging time was changed for the lead storage batteries of Example 1, Comparative Example 1, and Comparative Example 2, respectively. This shows the change in the amount of lead sulfate.
比較例１及び２の鉛蓄電池では、図１の曲線ｂ及びｃから分かるように、約１２時間で正極活物質中の残存硫酸鉛量の変化が無くなり、充電が完了したと言える。このことから比較例１及び２では、前述のように充電時間を１２時間とした。これに対し、実施例１の鉛蓄電池では、図１の曲線ａから分かるように、約９時間以上の充電で残存硫酸鉛量の変化が無くなり、充電が完了したと言える。このことから実施例１の鉛蓄電池では、前述のように充電時間を９時間とした。 In the lead acid batteries of Comparative Examples 1 and 2, as can be seen from the curves b and c in FIG. 1, it can be said that the change in the amount of residual lead sulfate in the positive electrode active material disappeared in about 12 hours, and the charging was completed. Therefore, in Comparative Examples 1 and 2, the charging time was 12 hours as described above. On the other hand, in the lead storage battery of Example 1, as can be seen from the curve a in FIG. 1, it can be said that the remaining lead sulfate amount did not change after charging for about 9 hours or more and the charging was completed. Therefore, in the lead storage battery of Example 1, the charging time was set to 9 hours as described above.
図１から分かるように、本発明を適用した正極板を用いた実施例１の鉛蓄電池は、活物質中に鉛丹が均一に分散していることから、比較例１にくらべて充電性が良く、充電時間を短くすることができた。また実施例１の鉛蓄電池では、鉛丹スラリーに添加する繊維として、親水性に富むアクリル繊維を用いて、鉛丹スラリーの分散性を良好にしているため、充電性を良好することができたが、比較例１及び２の鉛蓄電池では、疎水性の繊維であるポリオレフィン繊維を用いているため、鉛丹スラリーの分散性が悪く実施例１の鉛蓄電池に比べ充電性が悪くなっている。 As can be seen from FIG. 1, the lead storage battery of Example 1 using the positive electrode plate to which the present invention is applied has chargeability as compared with Comparative Example 1 because lead oxide is uniformly dispersed in the active material. Well, the charging time could be shortened. Moreover, in the lead acid battery of Example 1, since the dispersibility of the red lead slurry was made favorable using the acrylic fiber rich in hydrophilicity as a fiber added to the red lead slurry, the chargeability could be improved. However, in the lead acid batteries of Comparative Examples 1 and 2, since polyolefin fibers that are hydrophobic fibers are used, the dispersibility of the red lead slurry is poor and the chargeability is worse than that of the lead acid battery of Example 1.
図２は重負荷寿命試験のサイクル容量変化を示したものである。試験条件は４０［℃］の周囲温度で２０Ａ、１時間放電した後に、５Ａで５時間充電する充放電を１サイクルとして充放電を繰り返し、２５サイクル毎に２０Ａで端子電圧が１０．２Ｖになるまで連続放電を行い、放電持続時間を測定した。寿命サイクル数は、容量が５時間率容量の半分、即ち２２．５Ａｈとなる回数とした。図２において曲線ａは実施例１の鉛蓄電池のサイクル容量変化を示し、曲線ｂ及びｃはそれぞれ比較例１及び２の鉛蓄電池のサイクル容量変化を示している。また破線ｄは、寿命判定容量を示している。 FIG. 2 shows the cycle capacity change of the heavy load life test. The test conditions were 20A at an ambient temperature of 40 [° C.] for 1 hour, and then charging / discharging was repeated with 5A charging for 5 hours as one cycle, and the terminal voltage was 10.2V at 20A every 25 cycles. Continuous discharge was performed until the discharge duration was measured. The number of life cycles was the number of times that the capacity was half of the 5-hour rate capacity, that is, 22.5 Ah. In FIG. 2, a curve a shows a change in cycle capacity of the lead storage battery of Example 1, and curves b and c show a change in cycle capacity of the lead storage batteries of Comparative Examples 1 and 2, respectively. A broken line d indicates the life determination capacity.
図２に示した試験結果から、実施例１の鉛蓄電池では、サイクル容量変化が図２の曲線ｂ及びｃでそれぞれ示される比較例１及び２の鉛蓄電池にくらべて、充放電サイクル後半の容量低下が少なく、比較例１及び２の鉛蓄電池に比べて放電用量が寿命判定容量を下回るまでのサイクル数が多くなり、サイクル寿命特性が改善されることが明らかになった。実施例１の鉛蓄電池のように、親水性のアクリル繊維が活物質中に均一に分散していると、活物質の形態が長期に渡り維持され、活物質崩壊による容量低下が抑制される。またアクリル繊維のような親水性の繊維は活物質とのなじみが良いため、親水性繊維を活物質中に分散させておくと、熟成時に起こる水分の減少に伴う活物質の収縮を抑制することができ、活物質の収縮により活物質と集電体（格子体）との密着性が低下するのを防止することができる。 From the test results shown in FIG. 2, in the lead storage battery of Example 1, the capacity of the latter half of the charge / discharge cycle compared to the lead storage batteries of Comparative Examples 1 and 2 in which the cycle capacity change is shown by curves b and c in FIG. It has been found that the number of cycles until the discharge dose falls below the life determination capacity is increased and the cycle life characteristics are improved as compared with the lead storage batteries of Comparative Examples 1 and 2 with little decrease. When the hydrophilic acrylic fiber is uniformly dispersed in the active material as in the lead storage battery of Example 1, the form of the active material is maintained over a long period of time, and the capacity reduction due to the collapse of the active material is suppressed. In addition, hydrophilic fibers such as acrylic fibers have a good affinity with the active material. Dispersing hydrophilic fibers in the active material suppresses the shrinkage of the active material that accompanies a decrease in moisture that occurs during aging. It is possible to prevent the adhesiveness between the active material and the current collector (lattice body) from being lowered due to the shrinkage of the active material.
このように、本発明によれば、充放電サイクルを繰り返した際に、活物質の崩壊による容量の低下が抑制されることと、熟成時に生じる活物資の収縮が抑制されて活物質と集電体との密着性が低下するのが防止されることとが相俟って、鉛蓄電池のサイクル寿命特性が改善される。 Thus, according to the present invention, when the charge / discharge cycle is repeated, the decrease in capacity due to the collapse of the active material is suppressed, and the contraction of the active material that occurs during aging is suppressed, and the active material and the current collector are suppressed. Combined with the prevention of a decrease in adhesion to the body, the cycle life characteristics of the lead-acid battery are improved.
上記の実施例では、親水性繊維としてアクリル繊維を用いたが、本発明で用いる親水性繊維はアクリル繊維に限定されない。鉛丹スラリーに添加するのに適した親水性繊維としては、アクリル繊維の外に、ポリアミド繊維、ポリエチレンテレフタレート繊維、ポリプロピレン繊維等がある。また鉛丹スラリーに添加する親水性繊維は、必ずしも１種類の繊維である必要はなく、２種類以上の親水性繊維からなっていてもよい。 In the above embodiment, acrylic fibers are used as the hydrophilic fibers, but the hydrophilic fibers used in the present invention are not limited to acrylic fibers. Examples of hydrophilic fibers suitable for addition to the red lead slurry include polyamide fibers, polyethylene terephthalate fibers, and polypropylene fibers in addition to acrylic fibers. Moreover, the hydrophilic fiber added to a red lead slurry does not necessarily need to be one type of fiber, and may consist of two or more types of hydrophilic fibers.
本発明において、鉛丹スラリーに添加し、最終的に正極活物質中に均一に分散させる親水性繊維は、アクリル繊維、ポリアミド繊維、ポリエチレンテレフタレート繊維及びポリプロピレン繊維から成る繊維群から選択された少なくとも１つの繊維とすることが好ましいが、これらに限定されるものではない。 In the present invention, the hydrophilic fiber added to the red lead slurry and finally uniformly dispersed in the positive electrode active material is at least one selected from a fiber group consisting of acrylic fiber, polyamide fiber, polyethylene terephthalate fiber and polypropylene fiber. Although it is preferable to set it as one fiber, it is not limited to these.
Claims (5)
前記正極ペースト中に親水性繊維が均一に分散させられていることを特徴とする鉛蓄電池用正極板。 In a positive electrode plate for a lead storage battery formed by filling a grid with a positive electrode paste formed by kneading a lead powder slurry containing lead dioxide and lead powder,
A positive electrode plate for a lead storage battery, wherein hydrophilic fibers are uniformly dispersed in the positive electrode paste.
The positive electrode plate for a lead storage battery according to claim 3 or 4, wherein the hydrophilic fiber comprises at least one fiber selected from a fiber group consisting of acrylic fiber, polyamide fiber, polyethylene terephthalate fiber and polypropylene fiber. Manufacturing method.
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| JP2021061127A (en) * | 2019-10-04 | 2021-04-15 | 昭和電工マテリアルズ株式会社 | Lead acid battery positive electrode and lead acid battery |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2021061127A (en) * | 2019-10-04 | 2021-04-15 | 昭和電工マテリアルズ株式会社 | Lead acid battery positive electrode and lead acid battery |
| JP7410683B2 (en) | 2019-10-04 | 2024-01-10 | エナジーウィズ株式会社 | Positive electrode for lead-acid batteries and lead-acid batteries |
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