JP6733402B2 - Lead acid battery - Google Patents
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- JP6733402B2 JP6733402B2 JP2016149382A JP2016149382A JP6733402B2 JP 6733402 B2 JP6733402 B2 JP 6733402B2 JP 2016149382 A JP2016149382 A JP 2016149382A JP 2016149382 A JP2016149382 A JP 2016149382A JP 6733402 B2 JP6733402 B2 JP 6733402B2
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- 239000007773 negative electrode material Substances 0.000 claims description 132
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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
本発明は、鉛蓄電池に関するものである。 The present invention relates to a lead storage battery.
鉛蓄電池の負極電極材料に、有機防縮剤（エキスパンダ）を添加する技術が開示されている（特許文献１参照）。そして、有機防縮剤を添加することにより、良好な低温高率放電性能が得られることが示されている。 A technique of adding an organic shrinkage preventer (expander) to a negative electrode material of a lead storage battery is disclosed (see Patent Document 1). It has been shown that good low-temperature high-rate discharge performance can be obtained by adding an organic shrink-proofing agent.
ところで、サイクル使用による高率放電容量の減少を緩和するには、活物質量を増やして、負極電極材料の密度を増大させる方法が考えられていた。
しかしながら、負極電極材料の密度を増大させると、負極板内の電解液量が減少し、却って高率放電容量を制限してしまうおそれがあった。また、負極電極材料の密度を増大させると原価面で不利であった。
本発明は、上記従来の実情に鑑みてなされたものであって、負極電極材料の密度を下げても、サイクル使用した場合の高率放電容量を高い水準で維持できる鉛蓄電池を提供することを目的とする。
By the way, in order to mitigate the decrease in the high rate discharge capacity due to the cycle use, a method of increasing the amount of the active material and increasing the density of the negative electrode material has been considered.
However, if the density of the negative electrode material is increased, the amount of the electrolytic solution in the negative electrode plate is decreased, which may rather limit the high rate discharge capacity. Further, increasing the density of the negative electrode material is disadvantageous in terms of cost.
The present invention has been made in view of the above-mentioned conventional circumstances, and provides a lead storage battery capable of maintaining a high rate discharge capacity when used in a cycle at a high level even when the density of a negative electrode material is reduced. To aim.
本発明者らは、上記従来技術を鑑み、鋭意研究を重ねた結果、新規な鉛蓄電池を開発した。
そして、この新規な鉛蓄電池は、負極電極材料の密度を下げても、サイクル使用した場合の高率放電容量を高い水準で維持できるという事実を見いだした。本発明は、この知見に基づいてなされたものである。
The inventors of the present invention have developed a new lead storage battery as a result of intensive studies in view of the above-mentioned conventional techniques.
Then, they found that this new lead-acid battery can maintain a high rate discharge capacity at a high level when it is cycled, even if the density of the negative electrode material is lowered. The present invention has been made based on this finding.
すなわち、本発明の一側面に係る鉛蓄電池は、
正極板と、
負極板と、
電解液と、を備えた鉛蓄電池であって、
前記負極板は、負極電極材料を備え、
単セル内の電解液の理論容量の、単セル内の負極理論容量に対する比〔単セル内の電解液の理論容量／単セル内の負極理論容量〕が百分率にて４５％以上であり、
前記負極電極材料は、有機防縮剤を含有し、
前記負極電極材料は、硫酸バリウムを含有し、
前記有機防縮剤中の硫黄元素（Ｓ元素）の含有量は、３０００μｍｏｌ／ｇより大きく、
化成後の満充電状態の前記負極電極材料の密度が、３．１ｇ／ｃｍ ３ 以上４．２ｇ／ｃｍ ３ 以下である。
That is, the lead storage battery according to one aspect of the present invention,
A positive electrode plate,
Negative electrode plate,
A lead acid battery including an electrolytic solution,
The negative electrode plate includes a negative electrode material,
The ratio of the theoretical capacity of the electrolytic solution in the single cell to the theoretical capacity of the negative electrode in the single cell [theoretical capacity of the electrolytic solution in the single cell/the theoretical capacity of the negative electrode in the single cell] is 45% or more in percentage,
The negative electrode material contains an organic shrink proofing agent,
The negative electrode material contains barium sulfate,
The content of sulfur element (S element) in the organic expander agent is much larger than 3000μmol / g,
The density of the fully charged negative electrode material after chemical conversion is 3.1 g/cm 3 or more and 4.2 g/cm 3 or less .
本発明の一側面によれば、負極電極材料の密度を下げても、サイクル使用した場合の高率放電容量を高い水準で維持できる鉛蓄電池を提供できる。 According to one aspect of the present invention, it is possible to provide a lead storage battery which can maintain a high rate discharge capacity at a high level when used in a cycle even if the density of the negative electrode material is reduced.
本発明における好ましい実施の形態を説明する。 A preferred embodiment of the present invention will be described.
１．鉛蓄電池
本発明の一態様の鉛蓄電池は、正極板と負極板と電解液とを備える。負極板は、負極電極材料を備える。単セル内の電解液の理論容量の、単セル内の負極理論容量に対する比〔単セル内の電解液の理論容量／単セル内の負極理論容量〕が百分率で４５％以上である。負極電極材料は、有機防縮剤を含有する。負極電極材料は、硫酸バリウムも含有する。有機防縮剤中の硫黄元素（Ｓ元素）の含有量は、３０００ｍｏｌ／ｇより大きい。
なお、電極材料は、反応物質だけでなく、それ以外の添加剤も全て含めたものである。そして、負極板は、負極電極材料と集電体および場合により電極表面被覆材とからなる。よって、負極電極材料は、負極板から集電体および電極表面被覆材を除いた残り全てを意味する。
1. Lead-Acid Battery A lead-acid battery according to one aspect of the present invention includes a positive electrode plate, a negative electrode plate, and an electrolytic solution. The negative electrode plate includes a negative electrode material. The ratio of the theoretical capacity of the electrolytic solution in the single cell to the theoretical capacity of the negative electrode in the single cell [theoretical capacity of the electrolytic solution in the single cell/the theoretical capacity of the negative electrode in the single cell] is 45% or more in percentage. The negative electrode material contains an organic shrink proofing agent. The negative electrode material also contains barium sulfate. The content of elemental sulfur (S element) in the organic anti-shrink agent is larger than 3000 mol/g.
The electrode material includes not only the reaction substance but also all other additives. The negative electrode plate is composed of a negative electrode material, a current collector, and optionally an electrode surface coating material. Therefore, the negative electrode material means the rest of the negative electrode plate excluding the current collector and the electrode surface coating material.
２．正極板
正極板の種類は特に限定されない。正極板として、例えば、クラッド式極板、ペースト式極板を用いることができる。クラッド式極板としては、例えば、ガラス繊維をチューブ状に編み上げ、その中に正極活物質である鉛粉を含む正極電極材料を充填した極板が用いられる。ペースト式極板は、例えば、エキスパンド、鋳造、パンチング等の集電体（格子体）に、正極活物質を含む正極電極材料のペーストを充填後、熟成乾燥して得られる。正極電極材料のペーストは、鉛粉等を水と希硫酸で練合して得ることができる。正極電極材料のペーストには、正極活物質の他に種々の添加物を添加してもよい。
2. Positive Electrode Plate The type of positive electrode plate is not particularly limited. As the positive electrode plate, for example, a clad type electrode plate or a paste type electrode plate can be used. As the clad-type electrode plate, for example, an electrode plate in which glass fibers are woven into a tube shape and filled with a positive electrode material containing lead powder as a positive electrode active material is used. The paste-type electrode plate is obtained, for example, by filling a current collector (lattice body) for expanding, casting, punching or the like with a paste of a positive electrode material containing a positive electrode active material, and aging and drying. The positive electrode material paste can be obtained by kneading lead powder or the like with water and dilute sulfuric acid. Various additives may be added to the paste of the positive electrode material in addition to the positive electrode active material.
３．負極板
３．１ 極板の種類
負極板の種類は特に限定されない。負極板として、例えば、ペースト式極板を用いることができる。ペースト式極板としては、例えば、純鉛や鉛合金を鋳造して作製した鋳造、純鉛や鉛合金シートを加工して作製するエキスパンドやパンチング等の集電体（格子体）にペースト状にした負極電極材料を塗り込んだ極板が用いられる。
ペースト式極板は、例えば、集電体に負極電極材料のペーストを充填後、熟成乾燥して得られる。負極電極材料のペーストは、活物質の原料たる鉛粉等を水と希硫酸で練合して得ることができる。負極電極材料のペーストには、負極活物質の他に種々の添加物を添加してもよい。
3. Negative Electrode Plate 3.1 Type of Electrode Plate The type of negative electrode plate is not particularly limited. As the negative electrode plate, for example, a paste type electrode plate can be used. As a paste type electrode plate, for example, a casting made by casting pure lead or a lead alloy, and a paste form on a collector (lattice) for expanding or punching made by processing a pure lead or lead alloy sheet An electrode plate coated with the negative electrode material is used.
The paste-type electrode plate is obtained, for example, by filling a current collector with a paste of a negative electrode material and then aging and drying. The negative electrode material paste can be obtained by kneading lead powder, which is a raw material of the active material, with water and dilute sulfuric acid. Various additives may be added to the paste of the negative electrode material in addition to the negative electrode active material.
３．２ 負極電極材料の密度
本発明の一態様の鉛蓄電池では、負極電極材料の密度は特に限定されない。負極電極材料の密度は、好ましくは３．１ｇ／ｃｍ３以上４．２ｇ／ｃｍ３以下である。
本発明の一態様の鉛蓄電池では、密度を下げ、充放電を繰り返しても（例えば６００サイクル目でも）、高率放電容量を確保することができる。
なお、負極電極材料の密度は化成後の満充電状態の負極電極材料のかさ密度の値を意味し、以下のようにして測定する。化成後の電池を満充電してから解体し、入手した負極板を、水洗と乾燥とを施すことにより負極板中の電解液を除く。次いで負極板から負極電極材料を分離して、未粉砕の測定試料を入手する。測定容器に試料を投入し、真空排気した後、0.5〜0.55psiaの圧力で水銀を満たして、負極電極材料のかさ容積を測定し、測定試料の質量をかさ容積で除すことにより、負極電極材料のかさ密度を求める。尚、測定容器の容積から、水銀の注入容積を差し引いた容積をかさ容積とする。
3.2 Density of Negative Electrode Material In the lead storage battery of one embodiment of the present invention, the density of the negative electrode material is not particularly limited. The density of the negative electrode material is preferably 3.1 g/cm 3 or more and 4.2 g/cm 3 or less.
In the lead storage battery of one embodiment of the present invention, a high rate discharge capacity can be secured even if the density is lowered and charging/discharging is repeated (for example, even at the 600th cycle).
The density of the negative electrode material means the value of the bulk density of the fully charged negative electrode material after chemical formation, and is measured as follows. The battery after chemical formation is fully charged and then disassembled, and the obtained negative electrode plate is washed with water and dried to remove the electrolytic solution in the negative electrode plate. Then, the negative electrode material is separated from the negative plate to obtain an uncrushed measurement sample. Put the sample in the measuring container, evacuate it, and then fill it with mercury at a pressure of 0.5 to 0.55 psia, measure the bulk volume of the negative electrode material, and divide the mass of the measurement sample by the bulk volume to obtain the negative electrode. Find the bulk density of the material. The volume obtained by subtracting the injection volume of mercury from the volume of the measurement container is defined as the bulk volume.
３．３ 有機防縮剤
３．３．１ 有機防縮剤の含有量
本実施形態の鉛蓄電池では、負極電極材料には、有機防縮剤が含有される。有機防縮剤の含有量は特に限定されない。有機防縮剤の含有量は、既化成で、満充電状態の負極電極材料１００ｍａｓｓ％に対して、好ましくは０．０５ｍａｓｓ％以上０．３５ｍａｓｓ％以下であり、より好ましくは０．１ｍａｓｓ％以上０．２５ｍａｓｓ％以下である。有機防縮剤がこの範囲であると、高率放電容量が増加する傾向にある。
3.3 Organic Strain Reducing Agent 3.3.1 Content of Organic Strain Reducing Agent In the lead storage battery of the present embodiment, the negative electrode material contains an organic shrink proofing agent. The content of the organic anti-shrink agent is not particularly limited. The content of the organic anti-shrink agent is preferably 0.05 mass% or more and 0.35 mass% or less, more preferably 0.1 mass% or more and 0.1 mass% or less with respect to 100 mass% of the negative electrode material in the already-formed and fully charged state. It is 25 mass% or less. When the organic anti-shrink agent is in this range, the high rate discharge capacity tends to increase.
３．３．２ 有機防縮剤の詳細
本実施形態における有機防縮剤の種類は、特に限定されない。有機防縮剤は、１種類を単独で用いてもよく、また、２種以上併用してもよい。
有機防縮剤は、天然物由来の防縮剤と、合成防縮剤に分類される。
天然物由来の防縮剤としては、例えば、スルホン化リグニン等が挙げられる。
なお、リグニンのアルキル側鎖にスルホン酸基を導入する場合、このアルキル側鎖にスルホン酸基1個以上を導入することは難しい。このため、リグニンのアルキル側鎖に、スルホン酸基、スルホニル基を導入せずに、間接的に導入したリグニンを用いることもできる。すなわち、リグニンのフェニル基にスルホン酸基及び／又はスルホニル基を導入することができる。このようにリグニンにスルホン酸基及び／又はスルホニル基を導入すると、硫黄元素（Ｓ元素）の含有量を高めることができる。
3.3.2 Details of Organic Anti-shrink Agent The type of organic anti-shrink agent in the present embodiment is not particularly limited. The organic anti-shrink agents may be used alone or in combination of two or more.
Organic shrink proofing agents are classified into natural product-derived shrink proofing agents and synthetic shrink proofing agents.
Examples of the natural product-derived anti-shrink agent include sulfonated lignin and the like.
When introducing a sulfonic acid group into the alkyl side chain of lignin, it is difficult to introduce at least one sulfonic acid group into this alkyl side chain. Therefore, it is also possible to use lignin that is indirectly introduced without introducing a sulfonic acid group or a sulfonyl group into the alkyl side chain of lignin. That is, a sulfonic acid group and/or a sulfonyl group can be introduced into the phenyl group of lignin. Introducing a sulfonic acid group and/or a sulfonyl group into lignin in this way can increase the content of sulfur element (S element).
また、有機防縮剤として、フェノール性水酸基を複数有する化合物とアルデヒド類との反応生成物、ナフタレン系化合物とアルデヒド類との反応生成物等が挙げられる。その他、ポリアクリル酸、アクリルアミド・ターシャリーブチル・スルホン酸Ｎａの重合物（ＡＴＢＳポリマー：ＡＴＢＳは登録商標）、Ｎ，Ｎ´−（スルホニルジ−４，１−フェニレン）ビス（１，２，３，４−テトラヒドロ−６メチル−２，４−ジオキソピリミジン−５−スルホンアミド）を用いた縮合物も用いることができる。
ポリアクリルアミド・ターシャリーブチル・スルホン酸Ｎａの重合物では、基本骨格とスルホン酸基量との比は、特に限定されないが、基本骨格とスルホン酸基量との比が１：１以上であることが好ましい。
Examples of the organic anti-shrink agent include a reaction product of a compound having a plurality of phenolic hydroxyl groups and an aldehyde, a reaction product of a naphthalene compound and an aldehyde, and the like. In addition, polyacrylic acid, a polymer of acrylamide/tert-butyl/sulfonic acid Na (ATBS polymer: ATBS is a registered trademark), N,N′-(sulfonyldi-4,1-phenylene)bis(1,2,3 , 4-tetrahydro-6methyl-2,4-dioxopyrimidine-5-sulfonamide) can also be used.
In the polyacrylamide/tertiary butyl/Na sulfonate polymer, the ratio of the basic skeleton to the amount of the sulfonic acid group is not particularly limited, but the ratio of the basic skeleton to the amount of the sulfonic acid group is 1:1 or more. Is preferred.
フェノール性水酸基を複数有する化合物としては、フェノール性水酸基を有していれば特に限定されず、フェノール性水酸基を複数有していてもよい。これらの化合物は、単独で用いてもよく、また、２種以上併用してもよい。
フェノール性水酸基を複数有する化合物として、ビスフェノール類が好適に用いられる。ビスフェノール類とは、２個のヒドロキシフェニル基を有する化合物である。ビスフェノール類としては、例えばビスフェノールＡ、ビスフェノールＳ、ビスフェノールＦ、ビスフェノールＡＰ、ビスフェノールＡＦ、ビスフェノールＢ、ビスフェノールＢＰ、ビスフェノールＣ、ビスフェノールＥ、ビスフェノールＧ、ビスフェノールＭ、ビスフェノールＰ、ビスフェノールＰＨ、ビスフェノールＴＭＣ、ビスフェノールＺ等が例示される。これらは、単独で用いてもよく、また、２種以上併用してもよい。
The compound having a plurality of phenolic hydroxyl groups is not particularly limited as long as it has a phenolic hydroxyl group, and may have a plurality of phenolic hydroxyl groups. These compounds may be used alone or in combination of two or more.
Bisphenols are preferably used as the compound having a plurality of phenolic hydroxyl groups. Bisphenols are compounds having two hydroxyphenyl groups. Examples of the bisphenols include bisphenol A, bisphenol S, bisphenol F, bisphenol AP, bisphenol AF, bisphenol B, bisphenol BP, bisphenol C, bisphenol E, bisphenol G, bisphenol M, bisphenol P, bisphenol PH, bisphenol TMC, bisphenol Z. Etc. are illustrated. These may be used alone or in combination of two or more.
アルデヒド類としては、特に限定されない。アルデヒド類としては、例えば、ホルムアルデヒド、パラホルムアルデヒド、トリオキサン、テトラオキシメチレン等が挙げられる。これらは、単独で用いてもよく、また、２種以上併用してもよい。フェノール性水酸基を複数有する化合物との反応性が高いことから、ホルムアルデヒドが好適に用いられる。 The aldehydes are not particularly limited. Examples of aldehydes include formaldehyde, paraformaldehyde, trioxane, tetraoxymethylene and the like. These may be used alone or in combination of two or more. Formaldehyde is preferably used because it has high reactivity with a compound having a plurality of phenolic hydroxyl groups.
また、フェノール性水酸基を複数有する化合物と、アルデヒド類との反応生成物にさらにスルホン酸基（スルホ基）を導入してもよい。スルホン酸基を導入することで、合成防縮剤中の硫黄元素（Ｓ元素）の量を高めることができる。
なお、スルホン酸基はフェノール性水酸基を複数有する化合物の芳香環（例えば、ビスフェノール類のフェニル基）に直接結合している必要はない。例えば芳香環にアルキル鎖が結合し、このアルキル鎖にスルホン酸基が結合してもよい。
また、Ｓ元素はスルホン酸基として含まれていても、あるいはスルホニル基として含まれていても、合成防縮剤としての性能はほぼ同じである。
Further, a sulfonic acid group (sulfo group) may be further introduced into the reaction product of the compound having a plurality of phenolic hydroxyl groups and the aldehyde. By introducing a sulfonic acid group, the amount of elemental sulfur (S element) in the synthetic shrinkproofing agent can be increased.
The sulfonic acid group need not be directly bonded to the aromatic ring of the compound having a plurality of phenolic hydroxyl groups (for example, the phenyl group of bisphenols). For example, an alkyl chain may be bonded to the aromatic ring and a sulfonic acid group may be bonded to this alkyl chain.
Whether the S element is contained as a sulfonic acid group or a sulfonyl group, the performance as a synthetic shrinkproofing agent is almost the same.
本実施形態の一態様の鉛蓄電池では、有機防縮剤中の硫黄元素（Ｓ元素）の含有量は、３０００μｍｏｌ／ｇより大きく、好ましくは４０００μｍｏｌ／ｇ以上であり、より好ましくは６０００μｍｏｌ／ｇ以上であり、さらに好ましくは８０００μｍｏｌ／ｇ以上である。
硫黄元素（Ｓ元素）をこの範囲とすると、特に良好な高率放電性能が得られる傾向にある。
なお、有機防縮剤中の硫黄元素（Ｓ元素）の含有量の上限値は、特に限定されないが、９０００μｍｏｌ／ｇを超えて硫黄含有量が増加しても、高率放電容慮の増加は見られない上、有機防縮剤の製造原価が上昇するため、９０００μｍｏｌ／ｇを上限の目安としている。
In the lead storage battery according to one aspect of the present embodiment, the content of the sulfur element (S element) in the organic anti-shrink agent is larger than 3000 μmol/g, preferably 4000 μmol/g or more, and more preferably 6000 μmol/g or more. Yes, and more preferably 8000 μmol/g or more.
When the sulfur element (S element) is within this range, particularly good high rate discharge performance tends to be obtained.
The upper limit of the content of elemental sulfur (S element) in the organic anti-shrink agent is not particularly limited. However, even if the sulfur content exceeds 9000 μmol/g and the sulfur content increases, an increase in high rate discharge consideration is not found. In addition, since the manufacturing cost of the organic anti-shrink agent increases, the upper limit is set to 9000 μmol/g.
有機防縮剤の分子量は、特に限定されない。有機防縮剤の重量平均分子量（Ｍｗ）は、好ましくは１０００以上１００００００以下であり、より好ましくは１０００以上１０００００以下であり、さらに好ましくは１０００以上２００００以下である。この範囲内が有機物の合成の観点から好ましい。
なお、分子量の測定は、ゲルパーミエイションクロマトグラフィー（ＧＰＣ）によって求められる。分子量を求める際に使用する標準物質は、ポリスチレンスルホン酸ナトリウムとする。
分子量の測定は以下の装置、条件を用いて測定できる。
GPC装置：ビルドアップGPCシステム
SD-8022/DP−8020/AS-8020/CO-8020/UV-8020 (東ソー製)
カラム ：TSKgel G4000SWXL, G2000SWXL (7.8 mmI.D.×30cm) (東ソー製)
検出器 ：UV検出器 λ=210nm
溶離液 ：1mol/L NaCl ： アセトニトリル（7：3）
流速 ：1ml/min.
濃度 ：10mg/mL
注入量 ：10μL
標準物質 ：ポリスチレンスルホン酸Na
（Mw＝275,000、35,000、12,500、7,500、5,200、1,680）
The molecular weight of the organic anti-shrink agent is not particularly limited. The weight average molecular weight (Mw) of the organic anti-shrink agent is preferably 1,000 or more and 1,000,000 or less, more preferably 1,000 or more and 100,000 or less, and further preferably 1,000 or more and 20,000 or less. This range is preferable from the viewpoint of synthesizing organic substances.
The molecular weight is measured by gel permeation chromatography (GPC). The standard substance used to determine the molecular weight is sodium polystyrene sulfonate.
The molecular weight can be measured using the following devices and conditions.
GPC device: Build-up GPC system
SD-8022/DP-8020/AS-8020/CO-8020/UV-8020 (manufactured by Tosoh Corporation)
Column: TSKgel G4000SWXL, G2000SWXL (7.8 mm I.D.×30 cm) (manufactured by Tosoh Corporation)
Detector: UV detector λ=210nm
Eluent: 1mol/L NaCl: Acetonitrile (7:3)
Flow rate: 1 ml/min.
Concentration: 10mg/mL
Injection volume: 10 μL
Standard substance: Na polystyrene sulfonate
(Mw=275,000, 35,000, 12,500, 7,500, 5,200, 1,680)
有機防縮剤としては、具体的には、スルホン酸基を導入したビスフェノールＡのホルムアルデヒドによる縮合物、スルホン酸基を導入したビスフェノールＳのホルムアルデヒドによる縮合物、β−ナフタレンスルホン酸のホルムアルデヒドによる縮合物を好適に用いることができる。なお、ビスフェノールＳを用いた場合には、有機防縮剤内には、スルホン酸基、及びビスフェノールＳ内のスルホニル基（−ＳＯ２−）構造に由来するＳ元素が存在することになる。 Specific examples of the organic anti-shrink agent include a condensate of sulfonic acid group-introduced bisphenol A with formaldehyde, a condensate of sulfonic acid group-introduced bisphenol S with formaldehyde, and a condensate of β-naphthalenesulfonic acid with formaldehyde. It can be preferably used. In addition, when bisphenol S is used, the S element derived from the sulfonic acid group and the sulfonyl group (—SO 2 —) structure in bisphenol S is present in the organic anti-shrink agent.
ビスフェノール類の縮合物は、常温より高い温度環境を経験しても、低温での性能が損なわれないので、常温より高い温度環境におかれる鉛蓄電池に適している。
ナフタレンスルホン酸の縮合物は、ビスフェノール類の縮合物に比べ、分極が小さくなりにくいので、減液特性が重要な鉛蓄電池に適している。
A condensate of bisphenols is suitable for a lead storage battery that is exposed to a temperature environment higher than room temperature because the performance at a low temperature is not impaired even if it experiences a temperature environment higher than room temperature.
Compared to condensates of bisphenols, the condensate of naphthalene sulfonic acid is less likely to have smaller polarization, and is therefore suitable for lead-acid batteries where liquid reduction characteristics are important.
ここで、ビスフェノール類の縮合物の好適な合成方法の一例を示す。ビスフェノール類（ビスフェノールＡ、Ｓ、Ｆ等）、ホルムアルデヒド、亜硫酸塩を混合して、ビスフェノール類のホルムアルデヒド縮合物を得る。この際に、防縮剤のＳ量は、ビスフェノールＳの量および亜硫酸塩の量を必要量に応じて、増減させて調整する。
ただし、亜硫酸塩とホルムアルデヒドは、略等モル含有して反応させることが好ましい。なお、アルカリ条件化では重合が進むため、ｐＨ調整剤として、ＮａＯＨ等を使用し、ｐＨ＝１２程度（ｐＨ＝１０〜１３）にすることが好ましい。
Here, an example of a suitable synthesis method of a condensate of bisphenols will be shown. Bisphenols (bisphenol A, S, F, etc.), formaldehyde and sulfite are mixed to obtain a formaldehyde condensate of bisphenols. At this time, the amount of S of the shrink-proofing agent is adjusted by increasing or decreasing the amount of bisphenol S and the amount of sulfite according to the required amount.
However, it is preferable that the sulfite and the formaldehyde are contained in approximately equimolar amounts and reacted. In addition, since polymerization proceeds under alkaline conditions, it is preferable to use NaOH or the like as a pH adjuster and set the pH to about 12 (pH=10 to 13).
反応温度は、特に限定されず、好ましくは、１４０℃以上２００℃以下である。反応の際には、攪拌しても攪拌しなくてもよい。 The reaction temperature is not particularly limited and is preferably 140° C. or higher and 200° C. or lower. The reaction may or may not be stirred.
なお、予め温度・反応時間に対する重量平均分子量を求め、所望の重量平均分子量の縮合物となるように、温度・時間条件を調整することができる。特に好ましくは、重量平均分子量（Ｍｗ）が９０００程度（６０００〜１３０００）になるよう、温度・時間条件を調整して反応させることが好ましい。 The temperature/time conditions can be adjusted so that the weight average molecular weight with respect to the temperature/reaction time is obtained in advance and a condensate having a desired weight average molecular weight is obtained. Particularly preferably, the temperature and time conditions are adjusted so that the weight average molecular weight (Mw) is about 9000 (6000 to 13000) and the reaction is preferably performed.
有機防縮剤中のＳ元素の安定形態はスルホニル基あるいはスルホン酸基として含まれていることが多い。有機防縮剤のＳ元素含有量は、スルホン酸基及び／又はスルホニル基に含まれるＳ元素の量が主となる。
なお、上述のように、有機防縮剤中のＳ元素はスルホニル基あるいはスルホン酸基として含有されている事が多い。これらの基は極性が強い親水性基であり、これらの基同士の静電反発等のため、電解液中では、これらの基は、有機防縮剤が形成するコロイド粒子の表面に表れる傾向にある。これにより、有機防縮剤の会合が制限され、有機防縮剤が形成するコロイド粒子のサイズ、言い換えると有機防縮剤のコロイド粒子径が小さくなる。
The stable form of the S element in the organic anti-shrink agent is often contained as a sulfonyl group or a sulfonic acid group. The S element content of the organic anti-shrink agent is mainly the amount of the S element contained in the sulfonic acid group and/or the sulfonyl group.
In addition, as described above, the S element in the organic anti-shrink agent is often contained as a sulfonyl group or a sulfonic acid group. These groups are hydrophilic groups with strong polarity, and due to electrostatic repulsion between these groups, in the electrolyte, these groups tend to appear on the surface of the colloidal particles formed by the organic shrink proofing agent. .. As a result, the association of the organic anti-shrink agent is limited, and the size of the colloid particles formed by the organic anti-shrink agent, in other words, the colloid particle diameter of the organic anti-shrink agent is reduced.
有機防縮剤について、硫酸中での平均コロイド粒子径を小さくするには、例えば、フェノール性水酸基を複数有する有機防縮剤1gあたりの親水性官能基（スルホニル基、スルホン酸基、水酸基等）の量を多くすることが有効である。
有機防縮剤について、硫酸中での平均コロイド粒子径を小さくするには、例えば、フェノール性水酸基を複数有する化合物１分子当たりの親水性官能基（スルホニル基、スルホン酸基、水酸基等）の量を多くすることが有効である。
有機防縮剤の平均コロイド粒子径を測定するには、濃度が１〜１０ｍｇ／ｍＬの有機防縮剤の水溶液を、比重が１．２６の硫酸により、容積比で２０倍に希釈し、比重１．２５の硫酸の溶液とする。硫酸で２０倍希釈した試料を、例えば堀場製作所製のレーザー回折／散乱式粒子径分布測定装置ＬＡ−９５０Ｖ２を用い、２５℃で、バッチ式のセルを用い、マグネチックスターラーで撹拌しながら測定し、体積基準の平均コロイド粒子径を求める。なお鉛イオン、アルミニウムイオン、ナトリウムイオン等の共存イオンは、平均コロイド粒子径の測定値にほとんど影響しない。
なお、有機防縮剤の水溶液は、例えば鉛蓄電池の負極板から電極材料を取り出し、水洗して硫酸を除いた後に、１．０ＭのＮａＯＨ水溶液等のアルカリに溶解して、有機防縮剤を抽出することにより得られる。
To reduce the average colloidal particle size in sulfuric acid, for example, the amount of hydrophilic functional groups (sulfonyl group, sulfonic acid group, hydroxyl group, etc.) per 1g of organic anti-shrink agent having multiple phenolic hydroxyl groups It is effective to increase.
Regarding the organic anti-shrink agent, in order to reduce the average colloidal particle size in sulfuric acid, for example, the amount of hydrophilic functional groups (sulfonyl group, sulfonic acid group, hydroxyl group, etc.) per molecule of a compound having a plurality of phenolic hydroxyl groups can be adjusted. It is effective to do more.
In order to measure the average colloidal particle size of the organic anti-shrink agent, an aqueous solution of the organic anti-shrink agent having a concentration of 1 to 10 mg/mL was diluted 20 times by volume with sulfuric acid having a specific gravity of 1.26 to give a specific gravity of 1. 25 solution of sulfuric acid. A sample diluted 20-fold with sulfuric acid is measured, for example, using a laser diffraction/scattering particle size distribution measuring device LA-950V2 manufactured by Horiba Ltd. at 25° C. with a batch stirrer while stirring with a magnetic stirrer. , Find the volume-based average colloidal particle size. Coexisting ions such as lead ions, aluminum ions, and sodium ions have almost no effect on the measured value of the average colloidal particle size.
The aqueous solution of the organic shrink proofing agent is extracted, for example, by taking out the electrode material from the negative electrode plate of the lead storage battery, washing it with water to remove sulfuric acid, and then dissolving it in an alkali such as 1.0 M NaOH aqueous solution to extract the organic shrink proofing agent. It is obtained by
有機防縮剤のＳ元素含有量は、ビスフェノールＳ、ナフタレンスルホン酸等の化合物の使用割合、スルホン化の条件等によって調整することができる。 The S element content of the organic anti-shrink agent can be adjusted by the use ratio of compounds such as bisphenol S and naphthalene sulfonic acid, and the sulfonation conditions.
３．３．３ 有機防縮剤の種類の特定
負極電極材料中の有機防縮剤種の特定は、以下の様にして行う。満充電された鉛蓄電池を分解し、負極板を取り出し水洗により硫酸分を除去し、乾燥する。負極板から活物質を含んだ負極電極材料を分離し、１ｍｏｌ／ＬのＮａＯＨ水溶液に負極電極材料を浸漬して有機防縮剤を抽出する。抽出液から、不溶成分を濾過で取り除いた溶液を脱塩した後、濃縮・乾燥して粉末試料を得る。脱塩には、脱塩カラムやイオン交換膜が用いられる。
このようにして得た有機防縮剤の粉末試料を用いて測定した赤外分光スペクトルや、粉末試料を蒸留水で希釈し紫外可視吸光度計で測定した紫外可視吸収スペクトル、重水等の所定の溶媒で希釈し、得られた溶液のＮＭＲスペクトルなどから得た情報を組み合わせて用いて、有機防縮剤種を特定する。
なお、満充電状態にする補充電条件は以下の通りある。
（１）液式電池の場合、２５℃、水槽中、０．２ＣＡで２．５Ｖ／セルに達するまで定電流充電をおこなった後、さらに０．２ＣＡで２時間、定電流充電をおこなう。
（２）ＶＲＬＡ電池（制御弁式鉛蓄電池）の場合、２５℃、気槽中、０．２ＣＡ、２．２３Ｖ／セルの定電流定電圧充電をおこない、定電圧充電時の充電電流が１ｍＣＡ以下になった時点で充電を終了する。
3.3.3 Identification of Organic Strain Retardant Type Identification of the organic shrink proof agent in the negative electrode material is performed as follows. The fully charged lead acid battery is disassembled, the negative electrode plate is taken out, washed with water to remove the sulfuric acid content, and dried. The negative electrode material containing the active material is separated from the negative electrode plate, and the negative electrode material is immersed in a 1 mol/L NaOH aqueous solution to extract the organic shrink proofing agent. A solution obtained by removing insoluble components by filtration from the extract is desalted, and then concentrated and dried to obtain a powder sample. A desalting column or an ion exchange membrane is used for desalting.
Infrared spectroscopic spectrum measured using a powder sample of the organic anti-shrink agent thus obtained, UV-visible absorption spectrum measured with an ultraviolet-visible spectrophotometer by diluting the powder sample with distilled water, with a predetermined solvent such as heavy water Diluted and combined with information obtained from the NMR spectra of the resulting solutions and used to identify the organic shrinkage agent species.
The supplementary charging conditions for making the battery fully charged are as follows.
(1) In the case of a liquid battery, constant current charging is performed at 25° C. in a water tank at 0.2 CA until reaching 2.5 V/cell, and then at 0.2 CA for 2 hours.
(2) In the case of VRLA battery (control valve type lead storage battery), constant current constant voltage charging of 0.2 CA, 2.23 V/cell is performed at 25° C. in a gas tank, and the charging current during constant voltage charging is 1 mCA or less. The charging will be terminated when it becomes.
３．３．４ 有機防縮剤の含有量の測定
負極電極材料中の有機防縮剤の含有量は以下の様にして測定する。
満充電された鉛蓄電池を分解し、負極板を取り出し水洗により硫酸分を除去し、乾燥する。負極板から負極電極材料を分離し、１ｍｏｌ／ＬのＮａＯＨ水溶液３００ｍＬに負極電極材料１００ｇを浸漬して有機防縮剤を抽出する。抽出液から、不溶成分を濾過で取り除いた後、紫外可視吸収スペクトルを測定し、予め作成した検量線を用いて負極電極材料中の有機防縮剤の含有量を測定する。
他社製の電池を入手して有機防縮剤の含有量を測定する際に、有機防縮剤の構造式の厳密な特定ができないために検量線に同一の合成防縮剤が使用できない場合には、当該電池の負極から抽出した有機防縮剤と、紫外可視吸収スペクトル、赤外分光スペクトル、およびＮＭＲスペクトルなどが類似の形状を示す、別途入手可能な有機防縮剤を使用して検量線を作成することで、紫外可視吸収スペクトルを用いて有機防縮剤の含有量を測定する。
3.3.4 Measurement of Content of Organic Strain Retardant The content of the organic shrink proof agent in the negative electrode material is measured as follows.
The fully charged lead acid battery is disassembled, the negative electrode plate is taken out, washed with water to remove the sulfuric acid content, and dried. The negative electrode material is separated from the negative electrode plate, and 100 g of the negative electrode material is immersed in 300 mL of a 1 mol/L NaOH aqueous solution to extract the organic shrink proofing agent. After removing the insoluble component from the extract by filtration, the UV-visible absorption spectrum is measured, and the content of the organic shrinking agent in the negative electrode material is measured using a calibration curve prepared in advance.
When obtaining the battery of another company and measuring the content of the organic strain suppressor, if the same synthetic strain suppressor cannot be used for the calibration curve because the structural formula of the organic strain suppressor cannot be rigorously specified, By creating a calibration curve using an organic shrinkage agent extracted from the negative electrode of the battery and an organic shrinkage agent that is separately available and shows a similar shape to the UV-visible absorption spectrum, infrared spectrum, and NMR spectrum. The content of the organic shrink proofing agent is measured using the UV-visible absorption spectrum.
３．３．５ 有機防縮剤中のＳ元素含有量の測定
負極活物質中の有機防縮剤のＳ元素含有量（以下単に「Ｓ元素含有量」ともいう）は以下のようにして測定する。
満充電された鉛蓄電池を分解し、負極板を取り出し水洗により硫酸分を除去し、乾燥する。負極板から負極電極材料を分離し、１ｍｏｌ／ＬのＮａＯＨ水溶液に負極電極材料を浸漬して有機防縮剤を抽出する。抽出液から、不溶成分を濾過で取り除いた溶液を脱塩した後、濃縮・乾燥して粉末試料を得る。脱塩には、脱塩カラムやイオン交換膜が用いられる。
酸素燃焼フラスコ法によって、０．１ｇの有機防縮剤中の硫黄元素を硫酸に変換する。このとき、吸着液を入れたフラスコ内で粉末試料を燃焼させることで、硫酸イオンが吸着液に溶け込んだ溶出液が得られる。そして、トリンを指示薬として溶出液を過塩素酸バリウムで滴定して、粉末試料０．１ｇ中のＳ元素含有量を求める。このＳ元素含有量を１ｇ当たりの数量に変換して、有機防縮剤中のＳ元素含有量とする。
3.3.5 Measurement of S Element Content in Organic Strain Retardant The S element content (hereinafter also simply referred to as “S element content”) of the organic shrink agent in the negative electrode active material is measured as follows.
The fully charged lead acid battery is disassembled, the negative electrode plate is taken out, washed with water to remove the sulfuric acid content, and dried. The negative electrode material is separated from the negative electrode plate, and the negative electrode material is immersed in a 1 mol/L NaOH aqueous solution to extract the organic shrink proofing agent. A solution obtained by removing insoluble components by filtration from the extract is desalted, and then concentrated and dried to obtain a powder sample. A desalting column or an ion exchange membrane is used for desalting.
The elemental sulfur in 0.1 g of organic shrinkage inhibitor is converted to sulfuric acid by the oxygen combustion flask method. At this time, by burning the powder sample in the flask containing the adsorbent, an eluate in which sulfate ions are dissolved in the adsorbent can be obtained. Then, the eluate is titrated with barium perchlorate using trin as an indicator to determine the S element content in 0.1 g of the powder sample. The S element content is converted into a quantity per 1 g to obtain the S element content in the organic shrink proofing agent.
３．４ 硫酸バリウム
負極電極材料は、硫酸バリウムを含有する。硫酸バリウムを有機防縮剤とともに含有することで、負極電極材料の密度を下げても、サイクル使用した場合の高率放電容量を高い水準で維持できる。
負極電極材料中の硫酸バリウムの含有量は特に限定されない。負極電極材料は、既化成の満充電された負極電極材料１００ｍａｓｓ％に対し、硫酸バリウムを１．５ｍａｓｓ％以上２．５ｍａｓｓ％以下含有していることが好ましい。
また、負極電極材料の密度との関係では、含有量は次の範囲であることが好ましい。
3.4 Barium Sulfate The negative electrode material contains barium sulfate. By containing barium sulfate together with the organic shrinkage-preventing agent, even if the density of the negative electrode material is lowered, the high rate discharge capacity in the case of cyclic use can be maintained at a high level.
The content of barium sulfate in the negative electrode material is not particularly limited. The negative electrode material preferably contains 1.5 mass% or more and 2.5 mass% or less of barium sulfate based on 100 mass% of the already-formed fully charged negative electrode material.
Further, in relation to the density of the negative electrode material, the content is preferably in the following range.
化成後の満充電状態での負極電極材料の密度が３．１ｇ／ｃｍ３以上３．５ｇ／ｃｍ３以下である場合に、負極電極材料は、既化成の満充電された負極電極材料１００ｍａｓｓ％に対し、硫酸バリウムを１．５ｍａｓｓ％以上２．１ｍａｓｓ％以下含有していることが好ましい。
また、化成後の満充電状態での負極電極材料の密度が３．５ｇ／ｃｍ３以上４．２ｇ／ｃｍ３以下である場合に、負極電極材料は、既化成の満充電された負極電極材料１００ｍａｓｓ％に対し、硫酸バリウムを１．５ｍａｓｓ％以上２．５ｍａｓｓ％以下含有していることが好ましい。
When the density of the negative electrode material in a fully charged state after chemical formation is 3.1 g/cm 3 or more and 3.5 g/cm 3 or less, the negative electrode material is 100% by mass of the already-formed fully charged negative electrode material. On the other hand, it is preferable that barium sulfate is contained in an amount of 1.5 mass% or more and 2.1 mass% or less.
Moreover, when the density of the negative electrode electrode material in a fully charged state after formation is 3.5 g/cm 3 or more and 4.2 g/cm 3 or less, the negative electrode material is the already formed fully charged negative electrode electrode material. It is preferable that barium sulfate is contained in an amount of 1.5 mass% or more and 2.5 mass% or less with respect to 100 mass%.
３．５ その他の成分
負極電極材料には、上述の成分以外の他の成分を含有させても良い。例えばカーボンブラックやグラファイトや合成樹脂繊維等を含有させても良い。
3.5 Other Components The negative electrode material may contain components other than the above components. For example, carbon black, graphite, synthetic resin fiber or the like may be contained.
４．電解液
電解液は希硫酸であることが好ましい。電解液の比重は特に限定されない。比重は、下記の添加剤が含まれない状態で１．１５（硫酸濃度２１.４重量％に相当）以上で１．３５以下（同４５.３％に相当）である。なお、電解液の比重は、２０℃における値である。
電解液には、アルカリ金属イオン、アルミニウムイオン等のその他の成分が含有されていてもよい。
4. Electrolytic Solution The electrolytic solution is preferably dilute sulfuric acid. The specific gravity of the electrolytic solution is not particularly limited. The specific gravity is 1.15 (corresponding to a sulfuric acid concentration of 21.4% by weight) or more and 1.35 or less (corresponding to 45.3% of the same) when the following additives are not included. The specific gravity of the electrolytic solution is the value at 20°C.
The electrolyte solution may contain other components such as alkali metal ions and aluminum ions.
５．単セル内の電解液の理論容量／単セル内の負極理論容量の比
本発明の一態様の鉛蓄電池では、単セル内の電解液の理論容量の、単セル内の負極理論容量に対する比〔単セル内の電解液の理論容量／単セル内の負極理論容量〕は、百分率で４５％以上である。単セル内の電解液の理論容量の、単セル内の負極理論容量に対する比の上限値は、特に限定されないが、通常、百分率で５６％である。
なお、単セル内の電解液の理論容量（Ａｈ）とは、単セル内の総硫酸量（ｇ）を３．６５６（ｇ／Ａｈ）で除した値である。
また、負極理論容量は以下の方法で算出する。
〔１〕満充電後の電池内の負極電極材料の総重量Ｓ（ｇ）を測定する。
〔２〕この中から該負極電極材料を約５ｇとり、その重量ａを秤量する。これを重量濃度１０％の硝酸水溶液３０ｃｍ３中に投入し、加熱溶解する。冷却後、脱イオン水で１００ｃｍ３にして３０分静置し上澄液を別ビーカーに移す。残りの沈殿物に酢酸アンモン２０ｇと水３０ｃｍ３を加え、加熱溶解する。これを先のビーカー中に合し、更に５分間沸騰加熱する。その後１時間放置する。この溶液を重量既知のメンブレンフィルターでろ過し、充分に洗浄する。このメンブレンフィルターを１１０℃で２時間乾燥した後に、その重量を測定する。この際の質量増分を不溶残分重量ｂとする。その後、重量既知の磁製ルツボに入れ、灼熱灰化する。該ルツボをデシケーター中で室温まで冷却し、灼熱残分の重量ｃを求める。ここで、硫酸バリウムおよび有機防縮剤の双方を除く添加剤（カーボンや有機繊維など）の含有量Ａ（重量%）を以下の式により算出する。
Ａ＝１００×（ｂ−ｃ）／ａ
〔３〕上記〔２〕のろ液をメスフラスコにとり、脱イオン水を加えて２５０ｃｍ３とし、この液より原子吸光法で、Ａｉｒ−Ｃ２Ｈ２炎で５５３.６ｎｍのスペクトル線を選び、原子吸光度を測定する。標準濃度のＢａ塩溶液により作成した検量線を基に上記吸光度から、可溶性硫酸バリウムの含有量Ｂ（重量％）を以下の式で算出する。
Ｂ＝ １００×１.６９９×（検量線より求めたバリウム元素重量（ｍｇ）／ａ）
〔４〕上記〔２〕の灼熱残分量ｃより、不溶性硫酸バリウム含有量Ｃ（重量％）を以下の式で算出する。
Ｃ＝ １００×ｃ／ａ
〔５〕該負極電極材料の有機防縮剤の含有量Ｄ（重量%）を、段落〔００３２〕の方法で測定する。
〔６〕負極電極材料中の金属鉛の含有量Ｅ（重量%）を以下の式で算出する。
Ｅ＝ １００−Ａ−Ｂ−Ｃ―Ｄ
〔７〕電池内の負極電極材料中の金属鉛（負極活物質）の理論容量Ｑ−（Ａｈ）を、以下の式で算出する。この理論容量Ｑ−（Ａｈ）が負極理論容量である。
Ｑ− ＝ （Ｓ×Ｅ／１００）／３.８６６
なお、満充電状態での負極電極材料中の硫酸バリウム含有量（重量％）は、上記〔３〕，〔４〕でそれぞれ算出したＢとＣとの合計である。
5. Ratio of theoretical capacity of electrolytic solution in single cell/theoretical capacity of negative electrode in single cell In the lead storage battery according to one embodiment of the present invention, the ratio of the theoretical capacity of the electrolytic solution in the single cell to the theoretical capacity of the negative electrode in the single cell [ The theoretical capacity of the electrolytic solution in the single cell/the theoretical capacity of the negative electrode in the single cell] is 45% or more in percentage. The upper limit of the ratio of the theoretical capacity of the electrolytic solution in the single cell to the theoretical capacity of the negative electrode in the single cell is not particularly limited, but is usually 56% in percentage.
The theoretical capacity (Ah) of the electrolytic solution in the single cell is a value obtained by dividing the total amount of sulfuric acid (g) in the single cell by 3.656 (g/Ah).
The negative electrode theoretical capacity is calculated by the following method.
[1] The total weight S(g) of the negative electrode material in the battery after fully charged is measured.
[2] About 5 g of the negative electrode material is taken from this, and the weight a is weighed. This is put into 30 cm 3 of a nitric acid aqueous solution having a weight concentration of 10%, and heated and dissolved. After cooling, the mixture is made to be 100 cm 3 with deionized water and allowed to stand for 30 minutes, and the supernatant is transferred to another beaker. To the remaining precipitate, 20 g of ammonium acetate and 30 cm 3 of water are added and dissolved by heating. Combine this in the beaker and heat to boiling for a further 5 minutes. Then leave for 1 hour. The solution is filtered through a membrane filter of known weight and washed thoroughly. After drying this membrane filter at 110° C. for 2 hours, its weight is measured. The mass increment at this time is defined as the insoluble residue weight b. After that, it is put into a porcelain crucible of known weight and burnt into ash. The crucible is cooled to room temperature in a desiccator, and the weight c of the burning residue is determined. Here, the content A (% by weight) of the additive (carbon, organic fiber, etc.) excluding both barium sulfate and the organic shrink-proofing agent is calculated by the following formula.
A=100×(bc)/a
[3] Take the filtrate of the above [2] in a volumetric flask, add deionized water to 250 cm 3, and select the 553.6 nm spectrum line from this solution by an atomic absorption method with an Air-C 2 H 2 flame. Measure atomic absorption. The soluble barium sulfate content B (% by weight) is calculated from the above absorbance based on a calibration curve prepared using a Ba salt solution having a standard concentration by the following formula.
B=100×1.699× (barium element weight (mg)/a determined from the calibration curve)
[4] The insoluble barium sulfate content C (% by weight) is calculated by the following formula from the burning residual amount c of the above [2].
C=100×c/a
[5] The content D (% by weight) of the organic shrinkproofing agent in the negative electrode material is measured by the method of paragraph [0032].
[6] The content E (% by weight) of metallic lead in the negative electrode material is calculated by the following formula.
E=100-A-B-C-D
[7] The theoretical capacity Q − (Ah) of metallic lead (negative electrode active material) in the negative electrode material in the battery is calculated by the following formula. This theoretical capacity Q − (Ah) is the negative electrode theoretical capacity.
Q − = (S×E/100)/3.866
The barium sulfate content (% by weight) in the negative electrode material in the fully charged state is the sum of B and C calculated in [3] and [4] above.
化成は、鉛蓄電池の電槽内の硫酸を含む電解液中に、未化成の負極板を含む極板群を浸漬させた状態で、極板群を充電することにより行うことができる。ただし、化成処理は、鉛蓄電池または極板群の組み立て前に行ってもよい。化成により、海綿状鉛が生成する。
なお、この明細書における満充電状態にする補充電条件は以下の通りある。
（１）液式電池の場合、２５℃、水槽中、０．２ＣＡで２．５Ｖ／セルに達するまで定電流充電をおこなった後、さらに０．２ＣＡで２時間、定電流充電をおこなう。
（２）ＶＲＬＡ電池（制御弁式鉛蓄電池）の場合、２５℃、気槽中、０．２ＣＡ、２．２３Ｖ／セルの定電流定電圧充電をおこない、定電圧充電時の充電電流が１ｍＣＡ以下になった時点で充電を終了する。
この明細書における１ＣＡは電池の公称容量を１時間で放電する電流値であり、例えば公称容量が３０Ａｈの電池であれば１ＣＡは３０Ａであり、１ｍＣＡは３０ｍＡである。
The formation can be performed by charging the electrode plate group while the electrode plate group including the unformed negative electrode plate is immersed in the electrolytic solution containing sulfuric acid in the battery case of the lead storage battery. However, the chemical conversion treatment may be performed before assembling the lead storage battery or the electrode plate group. By formation, spongy lead is produced.
In addition, the auxiliary charging conditions for making the battery fully charged in this specification are as follows.
(1) In the case of a liquid battery, constant current charging is performed at 25° C. in a water tank at 0.2 CA until reaching 2.5 V/cell, and then at 0.2 CA for 2 hours.
(2) In the case of VRLA battery (control valve type lead storage battery), constant current constant voltage charging of 0.2 CA, 2.23 V/cell is performed at 25° C. in a gas tank, and the charging current during constant voltage charging is 1 mCA or less. The charging will be terminated when it becomes.
1CA in this specification is a current value for discharging the nominal capacity of the battery in 1 hour. For example, in the case of a battery having a nominal capacity of 30Ah, 1CA is 30A and 1mCA is 30mA.
本発明の一態様は、負極活物質を削減する技術である。電解液の理論容量を、負極理論容量（負極活物質の理論容量）の４５％以上にする設計により、所定の放電条件下で負極活物質の実質的な利用率は４０％以上に到達する。本発明の一態様は、この放電時の高い負極利用率の下で、サイクル使用に耐える鉛蓄電池を提供するものである。 One embodiment of the present invention is a technique for reducing the negative electrode active material. By designing the theoretical capacity of the electrolytic solution to be 45% or more of the negative electrode theoretical capacity (theoretical capacity of the negative electrode active material), the substantial utilization rate of the negative electrode active material reaches 40% or more under a predetermined discharge condition. One aspect of the present invention is to provide a lead-acid battery that withstands cycle use under this high negative electrode utilization rate during discharge.
以下、実施例により本発明を更に具体的に説明する。 Hereinafter, the present invention will be described in more detail with reference to examples.
１．鉛蓄電池の作製
正極板にクラッド式正極板を用いた。正極板にクラッド式正極板を用いた。具体的には、正極板には幅１４５ｍｍのクラッド式正極板を３枚用意した。この時、この正極板は、外径１０ミリ、活物質充填部の高さ３５０ｍｍ、のチューブを用いて作製した。負極板にペースト式極板で、充填部の高さ３６０ｍｍ、幅１４５ｍｍ、厚み４.３ｍｍの負極板〔１〕を２枚と、負極板〔１〕と高さ，幅が同じで厚みが３.０ｍｍの負極板〔２〕を２枚準備した。これらの正極板、負極板をタンク化成の後にセパレータを介して積層し、サンプル電池を作製した。
その際、原則として、負極板〔１〕を極群の内部に、負極板〔２〕を極群の外側に配置した。ただし、サンプル電池Ｇ２には内側の負極板２枚に、平面の寸法は負極板〔１〕と同じで厚みが３.９ｍｍである負極板〔３〕を使用した。正極板の合計の活物質量は二酸化鉛に換算して３６００ｇであり、その理論容量は８０７Ａｈである。各サンプル電池の電解液は濃度３７.４重量％の希硫酸である。なお、各サンプル電池の電解液／負極理論容量比を３０〜５６％まで変化させる方法は、電解液濃度は変えず、電槽内寸を変えて極板群の外側に保持される電解液の量を増減させて行った。各サンプル電池の電解液量は表１ないし４に、２０℃にて測定した体積値で表示した。
これらの電池の公称容量は、表１〜４の各サンプル電池系列の中の、電解液／負極理論容量比が４５％の物で、いずれも２１０Ａｈ（５時間率）である。（また、他のサンプル電池は前記サンプル電池とは電解液量が異なるが、極板の内容と枚数が同じなので、これらの５時間率定格容量も２１０Ａｈとする。）
また有機防縮剤は満充電された負極電極材料１００ｍａｓｓ％に対して０.１ｍａｓｓ％、カーボンは同じく０.２ｍａｓｓ％含有するように調整した。これらのサンプル電池を、同種類の電池を３個ずつ作製した。
なお、負極電極材料の密度は、島津製作所製、自動ポロシメータ、オートポアＩＶ９５０５を用い、化成後の電池を満充電してから解体して、前述の方法を用いて測定した。（自動ポロシメータの、接触角、表面張力の入力値はかさ容積とは関係がなく、測定値に影響を与えない。 装置の都合で接触角、表面張力の入力が必要な場合には、任意の値を入力して操作を実施する。）満充電条件は、前述の通りである。
負極電極材料に占める有機防縮剤の量の比率においては、製作した電池から取り出した負極から前述の方法で分離して定量して求めた値は、電極作製時に混合した比率からいくぶん異なった値となる。本発明の実施例において、有機防縮剤中の硫黄元素（Ｓ元素）の含有量（μｍｏｌ／ｇ）が、６００、３０００、４０００、６０００、８０００の電池のそれぞれ各一つにおいて、次の比率Ｒを求めた。
Ｇ＝製作した電池から取り出した負極から前述の方法で分離して定量した合成防縮剤の負極電極材料に対する重量比（ｍａｓｓ％）
Ｈ＝電池作製時に混合した合成防縮剤の負極電極材料に対する重量比（ｍａｓｓ％）
Ｒ＝Ｇ／Ｈ
表１〜５に記載の負極電極材料中の合成防縮剤の含有量（ｍａｓｓ％）は、各電池における電池作製時の負極電極材料に対する、混合した合成防縮剤の重量比（ｍａｓｓ％）に、合成防縮剤中の硫黄元素（Ｓ元素）の含有量が同じ電池について求めた上記のＲをかけたものである。
有機防縮剤中のＳ元素量（μｍｏｌ／ｇ）については、
負極電極材料として混合する前と、電池から解体して抽出し測定した値には差がないことを確認した。（そのため、表１〜５に記載の合成防縮剤中のＳ元素量（μｍｏｌ／ｇ）については、負極電極材料として混合する前の有機防縮剤のそれぞれにおいて測定して求められた値が記載されている。）
なお、硫酸バリウムは、満充電状態の負極電極材料１００ｍａｓｓ％に対し、後述の表１〜５に示す組成になるように調整した。なお、満充電状態での負極電極材料中の硫酸バリウム含有量（重量％）は、前述の方法〔３〕，〔４〕でそれぞれ算出したＢとＣとの合計である。
満充電状態の負極電極材料に占める硫酸バリウムの比率は、製作時に混合した比率と製作した電池から取り出した負極から前述の方法で分離して定量して求めた値とは、若干差がある。化成後の満充電状態の負極電極材料に占める硫酸バリウムの比率に０．９５をかけた比率で製作時に混合することで、表１〜５の組成になるよう調整した。例えば、化成後の満充電状態の負極電極材料に１ｍａｓｓ％含有させる場合には作製時に負極電極材料に対して０．９５ｍａｓｓ％含有させる。
1. Production of Lead Acid Battery A clad positive electrode plate was used as the positive electrode plate. A clad positive electrode plate was used as the positive electrode plate. Specifically, as the positive electrode plate, three clad type positive electrode plates having a width of 145 mm were prepared. At this time, this positive electrode plate was produced using a tube having an outer diameter of 10 mm and a height of the active material filled portion of 350 mm. The negative electrode plate is a paste type electrode plate, and two negative electrode plates [1] having a filling portion height of 360 mm, a width of 145 mm and a thickness of 4.3 mm, and a negative electrode plate [1] having the same height and width and a thickness of 3 mm. Two 0.0 mm negative electrode plates [2] were prepared. The positive electrode plate and the negative electrode plate were laminated with a separator formed after the formation of a tank to prepare a sample battery.
At that time, in principle, the negative electrode plate [1] was arranged inside the pole group, and the negative electrode plate [2] was arranged outside the pole group. However, for the sample battery G2, two inner negative plates were used, and a negative plate [3] having the same planar dimensions as the negative plate [1] and a thickness of 3.9 mm was used. The total amount of active material of the positive electrode plate is 3600 g in terms of lead dioxide, and its theoretical capacity is 807 Ah. The electrolyte of each sample battery is dilute sulfuric acid having a concentration of 37.4% by weight. In addition, the method of changing the electrolytic solution/negative electrode theoretical capacity ratio of each sample battery to 30 to 56% is the same as the electrolytic solution held outside the electrode plate group by changing the inner size of the battery case without changing the electrolytic solution concentration. The amount was increased or decreased. The amount of the electrolytic solution of each sample battery is shown in Tables 1 to 4 as the volume value measured at 20°C.
The nominal capacity of these batteries is 210 Ah (5 hour rate) in each of the sample battery series of Tables 1 to 4 with an electrolyte/negative electrode theoretical capacity ratio of 45%. (Although other sample batteries have different amounts of electrolytic solution from the above sample batteries, since the content and the number of plates are the same, their 5-hour rated capacities are also 210 Ah.)
Further, the organic anti-shrink agent was adjusted to contain 0.1 mass% and carbon of 0.2 mass% based on 100 mass% of the fully charged negative electrode material. Three of these sample batteries of the same type were produced.
The density of the negative electrode material was measured by the above-described method using an automatic porosimeter, Autopore IV9505 manufactured by Shimadzu Corp., after the battery after chemical formation was fully charged and then disassembled. (The input values of the contact angle and surface tension of the automatic porosimeter are not related to the bulk volume and do not affect the measurement values. Enter the value to perform the operation.) Full charge conditions are as described above.
Regarding the ratio of the amount of the organic shrink proofing agent to the negative electrode material, the value obtained by quantitatively separating from the negative electrode taken out from the manufactured battery by the above-mentioned method was slightly different from the value mixed at the time of manufacturing the electrode. Become. In the examples of the present invention, in each of the batteries in which the content (μmol/g) of elemental sulfur (S element) in the organic anti-shrink agent is 600, 3000, 4000, 6000, 8000, the following ratio R I asked.
G = Weight ratio (mass%) of the synthetic shrinkproofing agent to the negative electrode material, which was separated and quantified from the negative electrode taken out from the manufactured battery by the above method
H=weight ratio (mass%) of the synthetic shrinkproof agent mixed at the time of battery preparation to the negative electrode material
R=G/H
The content (mass%) of the synthetic shrink-proofing agent in the negative electrode material shown in Tables 1 to 5 is the weight ratio (mass%) of the mixed synthetic shrink-proofing agent to the negative electrode material at the time of battery production in each battery, It is a value obtained by multiplying the above-mentioned R obtained for batteries having the same sulfur element (S element) content in the synthetic shrink-proofing agent.
Regarding the amount of S element (μmol/g) in the organic anti-shrink agent,
It was confirmed that there was no difference between the value before mixing as the negative electrode material and the value measured by disassembling and extracting from the battery. (Therefore, as for the amount of S element (μmol/g) in the synthetic shrink-proofing agents shown in Tables 1 to 5, the value obtained by measuring in each of the organic shrink-proofing agents before being mixed as the negative electrode material is described. ing.)
In addition, barium sulfate was adjusted so as to have a composition shown in Tables 1 to 5 below with respect to 100 mass% of the negative electrode material in a fully charged state. The barium sulfate content (% by weight) in the negative electrode material in the fully charged state is the sum of B and C calculated by the above methods [3] and [4].
The ratio of barium sulfate occupying the fully charged negative electrode material is slightly different from the ratio mixed at the time of manufacturing and the value obtained by quantitatively separating the negative electrode taken out from the manufactured battery by the above method. The composition of Tables 1 to 5 was adjusted by mixing the ratio of barium sulfate occupying in the fully charged negative electrode material after formation by 0.95 at the time of production. For example, when 1 mass% is included in the fully charged negative electrode material after chemical formation, 0.95 mass% is included in the negative electrode material during manufacturing.
２．性能評価試験（試験パターン１）
２．１ ６００サイクル目高率放電容量試験
電解液／負極理論容量比を３０〜５６％まで変化させたサンプル電池を３個ずつ準備し、３０℃、電流４０Ａで端子間電圧が１.７０Ｖに達するまで放電し、放電量の１２５％を電流３０Ａで充電する充放電サイクルを６００回繰り返した。その後、満充電状態から各サンプル電池を３０℃、２１０Ａで放電し、その際の同一種類のサンプル電池３個の放電容量の平均値を高率放電容量として、表１〜４に記した。
2. Performance evaluation test (test pattern 1)
2.1 600th cycle high-rate discharge capacity test Prepare three sample batteries each with the electrolyte/negative electrode theoretical capacity ratio varied from 30 to 56%, and set the terminal voltage to 1.70V at 30°C and current 40A. The battery was discharged until it reached, and a charging/discharging cycle of charging 125% of the discharged amount with a current of 30 A was repeated 600 times. After that, each sample battery was discharged at 30° C. and 210 A from the fully charged state, and the average value of the discharge capacities of three sample batteries of the same type at that time was set as the high rate discharge capacity and shown in Tables 1 to 4.
３．結果
３．１ 有機防縮剤中の硫黄元素（Ｓ元素）の含有量、及び負極電極材料の密度の検討
各サンプル電池の構成、及び性能評価の結果を表１〜４に示し、表１〜４から導き出されたグラフを図１〜４に示す。なお、図１は表１に対応し、図２は表２に対応し、図３は表３に対応し、図４は表４に対応している。
3. Results 3.1 Examination of Sulfur Element (S Element) Content in Organic Strain Retardant and Density of Negative Electrode Material Tables 1 to 4 show the configurations and performance evaluation results of each sample battery, and Tables 1 to 4 Graphs derived from the above are shown in FIGS. 1 corresponds to Table 1, FIG. 2 corresponds to Table 2, FIG. 3 corresponds to Table 3, and FIG. 4 corresponds to Table 4.
図１〜４は、有機防縮剤中の硫黄元素（Ｓ元素）の含有量、及び負極電極材料の密度を変化させたサンプル電池において、電解液の理論容量／負極理論容量の比（％）と、６００サイクル目の高率放電容量との関係を示すグラフである。
硫黄元素（Ｓ元素）の量が３０００μｍｏｌ／ｇより大きい各サンプル電池（図２のＢ２系列、Ｃ２系列、Ｄ２系列、Ｇ２系列、図３のＢ３系列、Ｃ３系列、Ｄ３系列、Ｇ３系列、図４のＢ４系列、Ｃ４系列、Ｄ４系列、Ｇ４系列）は、電解液の理論容量／負極理論容量が４５％以上の場合に、硫黄元素（Ｓ元素）の量が６００μｍｏｌ／ｇのサンプル電池（Ｇ０系列）と比較して、６００サイクル目の高率放電容量を高い水準で維持できた。他方、これらの硫黄元素（Ｓ元素）の量が３０００μｍｏｌ／ｇより大きいサンプル電池に比べて、硫黄元素（Ｓ元素）の量が３０００μｍｏｌ／ｇの各サンプル電池（図１のＢ１系列、Ｃ１系列、Ｄ１系列、Ｇ１系列）は、電解液の理論容量／負極理論容量が４５％以上の場合に、６００サイクル目の高率放電容量の水準が低くなった。
以上の結果から、負極電極材料が有機防縮剤及び硫酸バリウムを含有し、有機防縮剤中の硫黄元素（Ｓ元素）が３０００μｍｏｌ／ｇより大きい場合には、６００サイクル目の高率放電容量を高い水準で維持できることが確認された。
FIGS. 1 to 4 show the ratio (%) of the theoretical capacity of the electrolytic solution/the theoretical capacity of the negative electrode in the sample batteries in which the content of the sulfur element (S element) in the organic anti-shrink agent and the density of the negative electrode material were changed. , Is a graph showing the relationship with the high rate discharge capacity at the 600th cycle.
Each sample battery in which the amount of elemental sulfur (S element) is larger than 3000 μmol/g (B2 series, C2 series, D2 series, G2 series of FIG. 2, B3 series, C3 series, D3 series, G3 series of FIG. 3, FIG. B4 series, C4 series, D4 series, G4 series) are sample batteries (G0 series) in which the amount of sulfur element (S element) is 600 μmol/g when the theoretical capacity of the electrolyte solution/theoretical capacity of the negative electrode is 45% or more. ), the high rate discharge capacity at the 600th cycle could be maintained at a high level. On the other hand, compared with the sample batteries in which the amount of the sulfur element (S element) is larger than 3000 μmol/g, the sample batteries in which the amount of the sulfur element (S element) is 3000 μmol/g (B1 series, C1 series in FIG. 1, In the D1 series and G1 series), the level of the high rate discharge capacity at the 600th cycle was low when the theoretical capacity of the electrolytic solution/the negative electrode theoretical capacity was 45% or more.
From the above results, when the negative electrode material contains an organic shrinkage agent and barium sulfate and the sulfur element (S element) in the organic shrinkage agent is larger than 3000 μmol/g, the high rate discharge capacity at the 600th cycle is high. It was confirmed that the level could be maintained.
特に、硫黄元素（Ｓ元素）の量が３０００μｍｏｌ／ｇより大きい各サンプル電池の中でも、負極電極材料の密度が、３．１ｇ／ｃｍ３以上４．２ｇ／ｃｍ３以下の各サンプル電池（図２のＣ２系列、Ｄ２系列、Ｇ２系列、図３のＣ３系列、Ｄ３系列、Ｇ３系列、図４のＣ４系列、Ｄ４系列、Ｇ４系列）は、６００サイクル目の高率放電容量を非常に高い水準で維持できることが確認された。
これらの電池の６００サイクル目の高率容量は、電解液の理論容量／負極板理論容量の比（％）を４５％以上にした場合に、電極材料の密度を下げても、硫黄元素（Ｓ元素）の量が６００μｍｏｌ／ｇの鉛蓄電池（Ｇ０系列）の電解液の理論容量／負極板理論容量の比（％）を４５％にした場合に比べると、同等か、かなり大きい値になっている。
In particular, among the sample batteries in which the amount of elemental sulfur (S element) is more than 3000 μmol/g, the density of the negative electrode material is 3.1 g/cm 3 or more and 4.2 g/cm 3 or less in each sample battery (see FIG. 2). C2 series, D2 series, G2 series, C3 series, D3 series, G3 series of FIG. 3, C4 series, D4 series, G4 series of FIG. 4) have a high rate discharge capacity at the 600th cycle at a very high level. It was confirmed that it could be maintained.
The high-rate capacity at the 600th cycle of these batteries is such that when the ratio (%) of the theoretical capacity of the electrolyte solution/the theoretical capacity of the negative electrode plate is set to 45% or more, even if the density of the electrode material is lowered, the sulfur element (S The amount of element is 600 μmol/g, and the ratio (%) of the theoretical capacity/negative electrode plate theoretical capacity of the electrolytic solution of the lead storage battery (G0 series) is 45%, which is the same as or considerably larger than that. There is.
３．２ 硫酸バリウムの含有量及び負極電極材料の密度の検討
表５は、サンプル電池の構成、及び性能評価の結果を示している。なお、図５〜８は表５から導いたものである。なお、この実験に供したサンプル電池は、各サンプル電池系列の中でも電解液／負極理論容量比を４５％とした物を選び、それぞれ３個ずつ製作した。これらのサンプル電池の公称容量は、２１０Ａｈ（５時間率）である。
3.2 Examination of Barium Sulfate Content and Density of Negative Electrode Material Table 5 shows the configuration of the sample battery and the result of performance evaluation. 5 to 8 are derived from Table 5. The sample batteries used in this experiment were manufactured by selecting three of the sample battery series having an electrolyte/negative electrode theoretical capacity ratio of 45%, and manufacturing three of each. The nominal capacity of these sample batteries is 210 Ah (5 hour rate).
次にこれらのサンプル電池を、次に示す性能評価試験（試験パターン２）にて評価した。この試験の目的は、負極利用率を同一にして、硫酸バリウム含有量の影響を調べることである。
表５に示すサンプル電池を、３０℃で、表５に示す各負極理論容量の４１％を５時間で放電する際の電流値で、５時間または端子間電圧が１.７０Ｖに達するまでの時間の短い方の時間にて放電し、充電は各サイクルの放電量の１２５％を７時間かけて行う充放電サイクルを６００回繰り返した。その最後のサイクルの各サンプル電池３個の放電容量の平均値をそれぞれ図６、図８に、５時間率容量として示す。
次にこれらの電池を満充電後、さらに３０℃にて２１０Ａで放電した。その際に該サンプル３個の、端子間電圧が１.７Ｖに低下するまでの放電容量の平均値をそれぞれ図５、図７に、高率放電容量として示す。
Next, these sample batteries were evaluated in the following performance evaluation test (test pattern 2). The purpose of this test is to investigate the effect of barium sulphate content at the same negative electrode utilization.
The sample battery shown in Table 5 is a current value when 41% of the theoretical capacity of each negative electrode shown in Table 5 is discharged in 5 hours at 30° C., for 5 hours or until the terminal voltage reaches 1.70V. Was discharged in the shorter time, and charging was performed by repeating a charging/discharging cycle in which 125% of the discharged amount in each cycle was carried out for 7 hours, 600 times. The average values of the discharge capacities of the three sample batteries in the last cycle are shown in FIGS. 6 and 8 as a 5-hour rate capacity.
Next, these batteries were fully charged and then further discharged at 210 A at 30°C. At that time, the average values of the discharge capacities of the three samples until the terminal voltage dropped to 1.7 V are shown as high rate discharge capacities in FIGS. 5 and 7, respectively.
図５は、負極電極材料の密度を変化させたサンプル電池において、硫酸バリウムの含有量と、６００サイクル目の高率放電容量との関係を示すグラフである。
図６は、負極電極材料の密度を変化させたサンプル電池において、硫酸バリウムの含有量と、６００サイクル目の５時間率容量との関係を示すグラフである。
FIG. 5 is a graph showing the relationship between the content of barium sulfate and the high rate discharge capacity at the 600th cycle in the sample batteries in which the density of the negative electrode material was changed.
FIG. 6 is a graph showing the relationship between the barium sulfate content and the 5-hour rate capacity at the 600th cycle in sample batteries in which the density of the negative electrode material was changed.
図５及び図６の結果から、負極電極材料の密度が３．１ｇ／ｃｍ３以上であり、かつ、負極板が、既化成の満充電された負極電極材料１００ｍａｓｓ％に対し、硫酸バリウムを１．５ｍａｓｓ％以上２．１ｍａｓｓ％以下含有していると、６００サイクル目の高率放電容量及び６００サイクル目の５時間率容量が良好であることが確認された。 From the results of FIG. 5 and FIG. 6, the density of the negative electrode material was 3.1 g/cm 3 or more, and the negative electrode plate contained 1% barium sulfate per 100 mass% of the already-formed fully charged negative electrode material. It was confirmed that the high rate discharge capacity at the 600th cycle and the 5 hour rate capacity at the 600th cycle were good when the content was 0.5 mass% or more and 2.1 mass% or less.
図７は、負極電極材料の密度を変化させたサンプル電池において、硫酸バリウムの含有量と、６００サイクル目の高率放電容量との関係を示すグラフである。
図８は、負極電極材料の密度を変化させたサンプル電池において、硫酸バリウムの含有量と、６００サイクル目の５時間率容量との関係を示すグラフである。
FIG. 7 is a graph showing the relationship between the barium sulfate content and the high rate discharge capacity at the 600th cycle in the sample batteries in which the density of the negative electrode material was changed.
FIG. 8 is a graph showing the relationship between the barium sulfate content and the 5-hour rate capacity at the 600th cycle in the sample batteries in which the density of the negative electrode material was changed.
図７及び図８の結果から、負極電極材料の密度が３．５ｇ／ｃｍ３以上４．２ｇ／ｃｍ３以下であり、かつ、負極板が、既化成の満充電された負極電極材料１００ｍａｓｓ％に対し、硫酸バリウムを１．５ｍａｓｓ％以上２．５ｍａｓｓ％以下含有していると、６００サイクル目の高率放電容量及び６００サイクル目の５時間率容量が良好であることが確認された。 From the results of FIG. 7 and FIG. 8, the density of the negative electrode material is 3.5 g/cm 3 or more and 4.2 g/cm 3 or less, and the negative electrode plate is 100 mass% of the already-formed fully charged negative electrode material. On the other hand, when barium sulfate was contained in an amount of 1.5 mass% or more and 2.5 mass% or less, it was confirmed that the high rate discharge capacity at the 600th cycle and the 5 hour rate capacity at the 600th cycle were good.
４．考察
鉛蓄電池の容量とサイクル寿命性能を維持しつつ、負極活物質を削減する技術が求められている。発明者は、防縮剤を工夫することでこの技術を達成しようとするものである。防縮剤の工夫による、その期待する効果は、第１に、負極活物質の比表面積を大きくし、負極板の放電容量、特に高率放電容量を向上させることである。
4. Discussion There is a demand for a technology that reduces the amount of negative electrode active material while maintaining the capacity and cycle life performance of lead acid batteries. The inventor intends to achieve this technique by devising a shrinkproofing agent. The expected effect of devising the shrink-proofing agent is, firstly, to increase the specific surface area of the negative electrode active material and improve the discharge capacity of the negative electrode plate, particularly the high rate discharge capacity.
第２に、充放電を繰り返すサイクル使用において、負極板の充電受入性能を向上させ、その寿命を維持、向上させることである。 Secondly, it is to improve the charge acceptance performance of the negative electrode plate and to maintain and improve the life of the negative electrode plate in a cycle use in which charging and discharging are repeated.
第３に、フォークリフトや電気自動車など動力用電源では、サイクル使用の中で特に劣化が著しい高率放電容量を維持することが期待される。 Thirdly, it is expected that a power source for power such as a forklift or an electric vehicle will maintain a high rate discharge capacity that is significantly deteriorated during cycle use.
上記第１の効果について説明する。負極の放電容量、特に、高率放電容量は負極板内の電解液量に影響されるとともに、負極活物質の表面積に概ね比例して増減する。負極活物質の表面積を増加させるためには、活物質量を増やすか、または活物質の比表面積を増大させればよい。しかしながら、前者は原価面で不利になる。さらに、負極活物質量を増やすためには負極板を厚くするか、負極活物質を主成分とする負極電極材料の密度を増大させる必要がある。しかしながら、限られた単セルの寸法の中で負極板の厚みを増やすことには限界があり、また負極電極材料の密度を増大させると負極板内の電解液量が減少し、高率放電容量を制限する側面が現れるので、いずれも電池設計上の限界がある。そこで、防縮剤の第１の効果は、負極活物質量を削減しても、その比表面積を増大させることで放電容量を維持、向上させることである。 The first effect will be described. The discharge capacity of the negative electrode, in particular, the high rate discharge capacity is affected by the amount of the electrolytic solution in the negative electrode plate and increases/decreases substantially in proportion to the surface area of the negative electrode active material. In order to increase the surface area of the negative electrode active material, the amount of active material may be increased or the specific surface area of the active material may be increased. However, the former is disadvantageous in terms of cost. Further, in order to increase the amount of the negative electrode active material, it is necessary to thicken the negative electrode plate or increase the density of the negative electrode material containing the negative electrode active material as a main component. However, there is a limit to increasing the thickness of the negative electrode plate within the limited size of a single cell, and increasing the density of the negative electrode material reduces the amount of electrolyte solution in the negative electrode plate, resulting in a high rate discharge capacity. Since there is an aspect that limits the battery, there is a limit in battery design. Therefore, the first effect of the shrink-proofing agent is to maintain and improve the discharge capacity by increasing the specific surface area even if the amount of the negative electrode active material is reduced.
次に、上記第２の効果について説明する。負極板を放電すると負極活物質たる金属鉛の微粒子が硫酸鉛に変化する。この硫酸鉛の結晶が充電する際に金属鉛に還元されず硫酸鉛結晶のまま残ることがあり、この硫酸鉛結晶が負極板に蓄積するとその放電容量が低下し、負極板および電池の寿命を迎える。また、硫酸鉛の結晶は時間とともに体積増加し、その分比表面積が小さく充電されにくい結晶に変化する。さらに、負極活物質の削減により、負極活物質の理論容量に対する放電量の比率（「負極活物質の利用率」と定義する）を大きくすると、言い換えれば利用率を高くすると、放電終了時に負極板に生じている硫酸鉛の体積割合が大きくなり、これが負極活物質の充電経路を断ち切り、充電を妨げるよう作用する。防縮剤の第２の効果は、この現象に関わるものである。第２の効果は、硫酸鉛の結晶を微細化し充電されやすい硫酸鉛の結晶形状を維持すること、および充電時の導電経路を確保することによる以下の効果である。すなわち、負極活物質を削減してその利用率を高めても、負極活物質の充電受入性能を維持、向上させることである。なお、硫酸鉛の結晶を微細化することは、還元後の金属鉛の比表面積を増大させる上でも有効である。 Next, the second effect will be described. When the negative electrode plate is discharged, fine particles of metallic lead, which is the negative electrode active material, are changed to lead sulfate. When this lead sulfate crystal is charged, it may not be reduced to metallic lead and may remain as a lead sulfate crystal, and if this lead sulfate crystal accumulates on the negative electrode plate, its discharge capacity decreases and the life of the negative electrode plate and the battery is shortened. Welcome. In addition, the lead sulfate crystal increases in volume with time, and changes into a crystal that has a small specific surface area and is difficult to be charged. Furthermore, by reducing the negative electrode active material, increasing the ratio of the discharge amount to the theoretical capacity of the negative electrode active material (defined as “utilization ratio of the negative electrode active material”), in other words, increasing the utilization ratio, causes the negative electrode plate at the end of discharge. The volume ratio of lead sulfate generated in the anode increases, which cuts off the charging path of the negative electrode active material and acts to prevent charging. The second effect of the shrinkproofing agent is related to this phenomenon. The second effect is the following effect obtained by refining the crystal of lead sulfate and maintaining the crystal shape of lead sulfate which is easily charged, and ensuring a conductive path during charging. That is, even if the negative electrode active material is reduced and the utilization rate is increased, the charge acceptance performance of the negative electrode active material is maintained and improved. Note that refining the crystal of lead sulfate is also effective in increasing the specific surface area of metallic lead after reduction.
リグニンスルフォン酸やビスフェノール類などの有機物（有機防縮剤）は、負極板に添加されて、第１の効果を発揮するものと推測される。また、硫酸バリウムにも硫酸鉛の結晶を微細化することで、第１の効果を発揮するものと推測される。第２の効果のためには、硫酸バリウムとカーボンとの混合物等が添加される方が好ましい。この混合物のうち、硫酸バリウムの作用は硫酸鉛の結晶を微細化し維持することであると推測される。 It is presumed that an organic substance (organic shrinkage inhibitor) such as lignin sulfonic acid or bisphenols is added to the negative electrode plate to exert the first effect. Further, it is presumed that the first effect can be exerted by refining lead sulfate crystals in barium sulfate. For the second effect, it is preferable to add a mixture of barium sulfate and carbon. Of this mixture, it is speculated that the action of barium sulfate is to refine and maintain lead sulfate crystals.
第３の効果について説明する。サイクル使用中に負極活物質の比表面積は縮小することがある。たとえば有機防縮剤としてリグニンを採用した場合、程度の差はあるが、サイクル中にリグニンが活物質から溶出、分解し、効果が低減する場合がある。硫酸バリウムは溶出、分解の恐れがないので、リグニンを補う防縮剤として採用できる。 The third effect will be described. The specific surface area of the negative electrode active material may be reduced during cycling. For example, when lignin is used as the organic anti-shrink agent, the lignin may be eluted and decomposed from the active material during the cycle, and the effect may be reduced, although there are differences in degree. Since barium sulfate has no risk of elution or decomposition, it can be used as a shrinkproofing agent that supplements lignin.
〔１〕放電容量を増加させること、〔２〕負極板の寿命を向上させること、及び〔３〕活物質の利用率向上により活物質を削減すること、すなわち原価を低減すること、は相反する性質を有する。従って、負極板の設計上の自由度を上げるため、従来、より有効な負極防縮剤が求められてきた。特に、サイクル使用による高率放電容量の減少を緩和するには、鉛活物質量を増やすことが従来の主な対策であった。しかし、この対策では、原価面の問題に加え、その効果には限度があり、より有効な負極防縮剤が求められてきた。本実施例の一態様の鉛蓄電池はこの要請に応えるものである。 [1] Increasing the discharge capacity, [2] improving the life of the negative electrode plate, and [3] reducing the active material by improving the utilization rate of the active material, that is, reducing the cost are contradictory. It has the property. Therefore, in order to increase the degree of freedom in designing the negative electrode plate, a more effective negative electrode shrink proof agent has been conventionally required. In particular, increasing the amount of the lead active material has been the conventional main measure to alleviate the decrease in the high rate discharge capacity due to the cycle use. However, in this measure, in addition to the problem of cost, its effect is limited, and a more effective negative electrode shrink proof agent has been demanded. The lead-acid battery of one embodiment of this embodiment meets this demand.
すなわち、本実施例の一態様の鉛蓄電池は、サイクル寿命、及び高率放電容量を維持しつつ、負極活物質の利用率を、従来に比べて高めて、負極活物質の量を削減することを可能としているのである。 That is, the lead storage battery according to one aspect of the present embodiment is capable of increasing the utilization rate of the negative electrode active material and reducing the amount of the negative electrode active material while maintaining the cycle life and the high rate discharge capacity. Is possible.
有機防縮剤に期待される作用として、次の作用が挙げられる。すなわち、期待される作用は、〔１〕負極活物質の表面積を維持、増大させること、〔２〕利用率４０％を繰り返す深い放電においても、負極活物質の充電受入、すなわち硫酸鉛還元の電気化学的過程を円滑に進めることである。前者のために既述の有機防縮剤が有効であり、後者のためには硫酸バリウムが有効であると推測される。さらに、カーボンの適切な配合も有効である。 The actions expected of the organic anti-shrink agent include the following actions. That is, the expected effects are [1] maintaining and increasing the surface area of the negative electrode active material, and [2] accepting the charge of the negative electrode active material, that is, reducing the electric power of lead sulfate reduction, even in deep discharge in which the utilization rate is 40%. It is to facilitate the chemical process. It is presumed that the organic shrinkage inhibitor described above is effective for the former and barium sulfate is effective for the latter. Furthermore, proper blending of carbon is also effective.
しかしながら、例えば、硫酸バリウムは負極活物質の比表面積増大と充電受入性能の向上に寄与する一方で、過剰に含有させると充電時の導電経路を遮断し還元（充電）過程を妨げるおそれがある。導電経路を形成するカーボンも、これを過剰に含有させると負極電極材料ペーストの充填を妨げ製造工程に支障をもたらす場合がある。従って、負極電極材料の密度と、添加剤の含有量を適切に選択することも重要な場合がある。 However, for example, barium sulfate contributes to an increase in the specific surface area of the negative electrode active material and an improvement in the charge acceptance performance, but when it is contained in excess, it may interrupt the conductive path during charging and hinder the reduction (charging) process. The carbon forming the conductive path may interfere with the filling of the negative electrode material paste and hinder the manufacturing process if it is excessively contained. Therefore, it may be important to properly select the density of the negative electrode material and the content of the additive.
なお、有機防縮剤としては、β−ナフタレンスルホン酸のホルムアルデヒドによる縮合物等のナフタレン系防縮剤を用いた場合であっても、（１）単セル内の電解液の理論容量の、単セル内の負極理論容量に対する比〔単セル内の電解液の理論容量／単セル内の負極理論容量〕が百分率にて４５％以上であり（２）負極電極材料は、有機防縮剤を含有し、（３）負極電極材料は、硫酸バリウムを含有し、（４）有機防縮剤中の硫黄元素（Ｓ元素）の含有量は、４０００μｍｏｌ／ｇ以上であると、ビスフェノール系防縮剤を用いた場合と同様の効果が得られる。 Even when a naphthalene-based shrink-proofing agent such as a condensation product of β-naphthalenesulfonic acid with formaldehyde is used as the organic shrink-proofing agent, (1) the theoretical capacity of the electrolytic solution in the single-cell The ratio [theoretical capacity of the electrolytic solution in the single cell/the theoretical capacity of the negative electrode in the single cell] to the theoretical capacity of the negative electrode of 45% or more (2) The negative electrode material contains an organic shrinkage inhibitor, 3) The negative electrode material contains barium sulfate, and (4) the content of the elemental sulfur (S element) in the organic shrink proofing agent is 4000 μmol/g or more, as in the case of using the bisphenol-based shrink proofing agent. The effect of is obtained.
本発明は上記記述及び図面によって説明した実施例に限定されるものではない。 The invention is not limited to the embodiments described by the above description and drawings.
本発明は、負極電極材料の密度を下げても、サイクル使用した場合の高率放電容量を高い水準で維持できる鉛蓄電池に広く適用することができる。 INDUSTRIAL APPLICABILITY The present invention can be widely applied to lead-acid batteries that can maintain a high rate discharge capacity at a high level when used in cycles even if the density of the negative electrode material is reduced.
Claims (2)
負極板と、
電解液と、を備えた鉛蓄電池であって、
前記負極板は、負極電極材料を備え、
単セル内の電解液の理論容量の、単セル内の負極理論容量に対する比〔単セル内の電解液の理論容量／単セル内の負極理論容量〕が百分率にて４５％以上であり、
前記負極電極材料は、有機防縮剤を含有し、
前記負極電極材料は、硫酸バリウムを含有し、
前記有機防縮剤中の硫黄元素（Ｓ元素）の含有量は、３０００μｍｏｌ／ｇより大きく、
化成後の満充電状態の前記負極電極材料の密度が、３．１ｇ／ｃｍ ３ 以上４．２ｇ／ｃｍ ３ 以下である、鉛蓄電池。 A positive electrode plate,
Negative electrode plate,
A lead acid battery including an electrolytic solution,
The negative electrode plate includes a negative electrode material,
The ratio of the theoretical capacity of the electrolytic solution in the single cell to the theoretical capacity of the negative electrode in the single cell [theoretical capacity of the electrolytic solution in the single cell/the theoretical capacity of the negative electrode in the single cell] is 45% or more in percentage,
The negative electrode material contains an organic shrink proofing agent,
The negative electrode material contains barium sulfate,
The content of sulfur element (S element) in the organic expander agent is much larger than 3000μmol / g,
A lead storage battery in which the density of the negative electrode material in a fully charged state after chemical formation is 3.1 g/cm 3 or more and 4.2 g/cm 3 or less .
（要件Ａ）
化成後の満充電状態の前記負極電極材料の密度が３．１ｇ／ｃｍ３以上３．５ｇ／ｃｍ３以下であり、かつ、
化成後の満充電状態の前記負極板は、既化成負極電極材料１００ｍａｓｓ％に対し、硫酸バリウムを１．５ｍａｓｓ％以上２．１ｍａｓｓ％以下含有している。
（要件Ｂ）
化成後の満充電状態の前記負極電極材料の密度が３．５ｇ／ｃｍ３以上４．２ｇ／ｃｍ３以下であり、かつ、
前記負極板は、化成後の満充電状態の負極電極材料１００ｍａｓｓ％に対し、硫酸バリウムを１．５ｍａｓｓ％ 以上２．５ｍａｓｓ％以下含有している。 The lead acid battery according to claim 1 , which satisfies the following requirement A or requirement B.
(Requirement A)
The density of the fully charged negative electrode material after chemical formation is 3.1 g/cm 3 or more and 3.5 g/cm 3 or less, and
The fully charged negative electrode plate after chemical formation contains barium sulfate in an amount of 1.5 mass% or more and 2.1 mass% or less with respect to 100 mass% of the already-formed negative electrode material.
(Requirement B)
The density of the negative electrode material in a fully charged state after chemical formation is 3.5 g/cm 3 or more and 4.2 g/cm 3 or less, and
The negative electrode plate contains 1.5 mass% or more and 2.5 mass% or less of barium sulfate based on 100 mass% of the fully charged negative electrode material after chemical formation.
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| JP7424037B2 (en) * | 2019-12-20 | 2024-01-30 | 株式会社Ｇｓユアサ | lead acid battery |
| CN121693815A (en) | 2023-09-08 | 2026-03-17 | 株式会社杰士汤浅国际 | Liquid lead accumulator |
| CN121394409B (en) * | 2025-12-24 | 2026-04-14 | 武汉长光电源有限公司 | Negative electrode composite additive for improving performance of lead-acid storage battery and preparation method thereof |
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| JPH0665065B2 (en) * | 1986-03-12 | 1994-08-22 | 日本電池株式会社 | Sealed lead acid battery |
| JP3185508B2 (en) * | 1993-12-29 | 2001-07-11 | 日本電池株式会社 | Sealed lead-acid battery |
| WO1997037393A1 (en) * | 1996-03-29 | 1997-10-09 | Aisin Seiki Kabushiki Kaisha | Lead storage battery |
| JP5598532B2 (en) * | 2010-03-02 | 2014-10-01 | 新神戸電機株式会社 | Lead acid battery |
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| WO2016114315A1 (en) * | 2015-01-14 | 2016-07-21 | 日立化成株式会社 | Lead-acid battery, micro-hybrid vehicle, and vehicle having idling stop system |
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