DE112018002253T5 - LEAD ACID BATTERY - Google Patents

Abstract

A lead battery includes a negative electrode plate, a positive electrode plate, and an electrolytic solution. The negative electrode plate includes a negative electrode material containing a carbon material and an organic expander, and the carbon material includes a first carbon material with a particle size of 32 µm or more and a second carbon material with a particle size of less than 32 pm. A ratio R2 / R1 of the powder resistance R2 of the second carbon material to the powder resistance R1 of the first carbon material is 15 or more and 155 or less. The organic expander includes a first organic expander with an aromatic ring and a second organic expander with an aromatic ring. An elemental sulfur content in the first organic expander is 4000 µmol / g or more, and the elemental sulfur content in the second organic expander is 2000 µmol / g or less.

Description

TECHNICAL AREA

The present invention relates to a lead-acid battery.

STATE OF THE ART

Lead-acid batteries are used in various applications, in addition to automotive and industrial applications. The lead-acid battery includes a negative electrode plate, a positive electrode plate, and an electrolytic solution. The negative electrode plate contains a current collector and a negative electrode material. An organic expander is added to the negative electrode material. For example, Patent Document 1 suggests adding sodium lignin sulfonate to a negative electrode plate. Patent Document 2 suggests adding a bisphenol sulfonic acid polymer and sodium lignin sulfonate to a negative electrode plate.

DOCUMENTS ON THE PRIOR ART

PATENT DOCUMENTS

• Patent document 1: WO 2015/087749 A
• Patent document 2: WO 2012/017702 A

SUMMARY OF THE INVENTION

PROBLEMS TO BE SOLVED BY THE INVENTION

Lead-acid batteries are sometimes used in a poorly charged state called a partial state of charge (PSOC). For example, lead-acid batteries are used in the PSOC for charging control and for idling stop / start (ISS; idling stop / start). Therefore, the lead-acid batteries in a cycle test under PSOC conditions must have an excellent service life (hereinafter referred to as PSOC service life). To improve this life, it is effective to increase an amount of carbon black added to a negative electrode material. However, since lignin (including lignin sulfonic acid or its salt) of an organic expander is adsorbed on carbon black, the addition of a large amount of carbon black causes the negative electrode material to shrink, resulting in a decrease in the low-temperature, high-speed discharge performance after high-temperature cycles.

MEANS TO SOLVE THE PROBLEMS

One aspect of the present invention relates to a lead battery, the lead battery includes a negative electrode plate, a positive electrode plate, and an electrolytic solution. The negative electrode plate includes a negative electrode material containing a carbon material and an organic expander. The carbon material includes a first carbon material with a particle size of 32 µm or more and a second carbon material with a particle size of less than 32 µm, a ratio R2 / R1 of the powder resistance R2 of the second carbon material to the powder resistance R1 of the first carbon material is 15 or more and 155 Or less. The organic expander includes a first organic expander with an aromatic ring and a second organic expander with an aromatic ring, an elemental sulfur content in the first organic expander is 4000 µmol / g or more and the elemental sulfur content in the second organic expander is 2000 µmol / g or fewer.

ADVANTAGES OF THE INVENTION

In lead-acid batteries, the low-temperature, high-speed discharge is improved after high-temperature cycles and, at the same time, a long PSOC life is guaranteed.

list of figures

• 1 12 is an exploded perspective view, partially cut away, showing an external appearance and an internal structure of a lead battery according to an embodiment of the present invention.

MODE FOR CARRYING OUT THE INVENTION

One aspect of the present invention is a lead battery, and the lead battery includes a negative electrode plate, a positive electrode plate, and an electrolytic solution. The negative electrode plate includes a negative electrode material containing a carbon material and an organic expander. The carbon material includes a carbon material (first carbon material) with a particle size of 32 µm or more and a carbon material (second carbon material) with a particle size of less than 32 µm. A ratio R2 / R1 of the powder resistance R2 of the second carbon material to the powder resistance R1 of the first carbon material is 15 or more and 155 or less. The organic expander includes a first organic expander with an aromatic ring and a second organic expander with an aromatic ring. The elemental sulfur content in the first organic expander is 4000 µmol / g or more and the elemental sulfur content in the second organic expander is 2000 µmol / g or less.

In the present description, the elemental sulfur content in the organic expander X µmol / g means that the elemental sulfur content in 1 g of the organic expander is X µmol.

Generally, carbon black is added to the negative electrode material from the viewpoint of improving the conductivity. However, it is known that carbon black tends to accumulate in the negative electrode material and it is difficult to form a conductive network, so it is difficult to achieve a sufficient PSOC life. Therefore, it has generally been believed that it is beneficial to increase a quantity of carbon black added from the viewpoint of improving PSOC life performance. On the other hand, lignin is conventionally often used as an organic expander in the negative electrode material. However, since soot adsorbs lignin, the negative electrode material shrinks significantly with increasing soot addition with the adsorption of lignin, so that the low-temperature high-speed discharge decreases significantly after high-temperature cycles. A synthetic organic expander can be used in a conventional negative electrode material. However, it is known that when carbon black is added to a negative electrode material with a synthetic expander, a synthetic organic expander leaks at high temperature cycles and a pore structure of the negative electrode material cannot be maintained, so that the PSOC life decreases.

In contrast to the above aspect of the present invention, when the second organic expander is used alone, it is difficult to improve the low-temperature high-speed discharge performance after high-temperature cycles even when a large amount of the second organic expander is added to the negative electrode material. This is because the second organic expander tends to leak out of the negative electrode material at high temperatures. When the first organic expander is used, the amount of electrolyte loss after the cycle increases, so that it is generally difficult to increase the amount of the first organic expander used to keep the amount of electrolyte loss low. Thus, even if the first organic expander is used alone in such an amount that the amount of electrolyte loss is not significant, it is difficult to sufficiently improve the PSOC life. Even when two types of organic expanders are used in combination, in the case of using an organic expander with an elemental sulfur content of 2000 µmol / g or less and an organic expander with an elemental sulfur content of more than 2000 µmol / g and less than 4000 µmol / g the effect of improving the low-temperature high-speed discharge performance after high-temperature cycles is insufficient. The details are not clear, but in this case this is probably due to the organic expander exiting the negative electrode material during high temperature cycles and it is difficult to maintain the pore structure of the negative electrode material.

Carbon materials with various types of powder resistance are known. It is known that the powder resistance of a powder material depends on e.g. the particle shape, the particle size, the particle internal structure and / or the particle crystallinity varies. In the conventional technical understanding, the powder resistance of the carbon material is not directly related to the resistance of the negative electrode plate and is not regarded as an influence on the PSOC life and the low-temperature high-speed discharge after high-temperature cycles.

On the other hand, according to the above aspect of the present invention, the first organic expander with an elemental sulfur content of 4000 µmol / g or more and the second organic expander with an elemental sulfur content of 2000 µmol / g or less are combined and the first carbon material and the second carbon material are used , The first carbon material and the second Carbon materials have different particle sizes, and a powder resistance ratio R2 / R1 of the first and second carbon materials is in a range of 15 or more and 155 or less. Thus, in the above aspect, the first organic expander and the second organic expander are combined, and the first carbon material and the second carbon material are combined, whereby the low-temperature high-speed discharge performance can be improved after the battery is repeatedly charged and discharged at high temperature (after high-temperature cycles) has been. This is believed to be due to the fact that the level of adsorption of the second organic expander to the second carbon material is suppressed. In addition, it is believed that the low-temperature, high-speed discharge performance is improved by suppressing the drainage of the organic expander from the negative electrode material during the high-temperature cycles and maintaining the pore structure of the negative electrode material. This is presumably because colloidal particles of the first organic expander with a suitable particle size can be easily formed by combining the first organic expander with an elemental sulfur content of 4000 µmol / g or more with the second organic expander and the drain of the organic one Expanders can be completely suppressed.

In the above aspect of the present invention, a high PSOC life can be achieved by regulating the powder resistance ratio R2 / R1 of the first carbon material and the second carbon material contained in the negative electrode plate in the range of 15 or more and 155 or less , This is probably for the following reasons. First, if the powder resistance ratio R2 / R1 is regulated in the above range, a conductive network can be easily built in the negative electrode material. In addition, since the outflow of the organic expander from the negative electrode material is suppressed during high-temperature cycles, the effect of the organic expander is sufficiently shown and the pore structure of the negative electrode material is retained. The conductive network formed is therefore easy to maintain even when performing a PSOC cycle. That is, the effects of the first organic expander and the second organic expander can be said to be enhanced by combining the first carbon material and the second carbon material having the powder resistance ratio as described above with the first organic expander and the second organic expander ,

The content of the first organic expander in the negative electrode material is preferably 0.02 mass% or more and 0.12 mass% or less. On the other hand, the content of the second organic expander in the negative electrode material is preferably 0.05 mass% or more and 0.7 mass% or less. If the content of each organic expander is within such a range, the effect of improving the PSOC life and the low-temperature high-speed discharge performance after high-temperature cycles can be further improved. This is because the pore structure of the negative electrode material can be obtained by effectively suppressing the shrinkage of the negative electrode material.

The content of the organic expander contained in the negative electrode material is a content of negative electrode material which is taken from a molded lead-acid battery in a fully charged state by the method mentioned below.

A ratio s2 / s1 of a specific surface s2 of the second carbon material to a specific surface s1 of the first carbon material is preferably 20 or more and 240 or less. If the specific surface area ratio s2 / s1 is 20 or more, the reduction reaction of lead sulfate proceeds easily; it is therefore possible to suppress a decrease in the regenerative charge acceptance and at the same time to ensure a long service life of the PSOC. If the specific surface area ratio s2 / s1 is 240 or less, in this case, the specific surface area of each carbon material is in an appropriate range, the adsorption of the organic expander is further suppressed. This makes it possible to ensure higher performance at low temperatures and high discharge rates. In addition, despite unclear details, it is possible to reduce an increase in electrolyte loss after the cycle.

An average aspect ratio of the first carbon material is preferably 1.5 or more and 35 or less. In this case, an excellent PSOC life is easy to achieve, and the discharge characteristics at low temperatures with a high discharge rate after high temperature cycles can easily be further improved. This is presumably because when the average aspect ratio is in such a range, the conductive network is easily formed in the negative electrode material, and at the same time, the formed conductive network can be easily maintained.

Although the lead-acid battery according to the embodiment of the present invention is set forth for each main component element below, this invention is not limited to the following embodiment.

(Negative electrode plate)

The negative electrode plate can usually consist of a negative electrode current collector (negative electrode grid) and a negative electrode material. The negative electrode material is obtained by removing the negative electrode current collector from the negative electrode plate.

Elements such as a mat and adhesive paper can be applied to the negative electrode plate. If the negative electrode plate includes such an element (application element), the negative electrode material is obtained by removing the negative electrode current collector and the application element. However, the thickness of an electrode plate is the thickness including the mat. When the mat is applied to a separator, the thickness of the mat is included in the thickness of the separator.

The negative electrode material includes a negative electrode active material (lead or lead sulfate) that has capacity through an oxidation reduction reaction. Although the active material of the negative electrode is a spongy metallic lead when charged, the unshaped negative electrode plate is usually made with lead powder. The negative electrode material contains a carbon material and an organic expander. The negative electrode material may further contain barium sulfate or the like and may contain other additives if necessary.

The content of barium sulfate in the negative electrode material is, for example, preferably 0.1% by mass or more, preferably 0.2% by mass or more, can be 0.5% by mass or more, 1.0% by mass or more or 1, 3 mass% or more. On the other hand, the content of barium sulfate in the negative electrode material is preferably 3.0 mass% or less, more preferably 2.5 mass% or less, and further preferably 2 mass% or less. Each of these minimum and maximum values can be combined.

A determination method for barium sulfate in the negative electrode material is described below. Before the quantitative analysis, the formed lead-acid battery is fully charged and then disassembled to obtain a negative electrode plate for analysis. The obtained negative electrode plate is washed with water and dried to remove an electrolytic solution in the negative electrode plate. The negative electrode material is then separated from the negative electrode plate and an unground initial sample is obtained.

The unground first sample is ground and 50 ml (1 + 2) nitric acid are added to 10 g of the ground first sample and heated for about 20 minutes to dissolve a lead component as lead nitrate. A solution containing lead nitrate is then filtered in order to separate solids such as carbon-containing material and barium sulfate.

The resulting solid is dispersed in water to obtain a dispersion, and then components other than a carbonaceous material and barium sulfate (e.g. reinforcing material) are removed from the dispersion with a sieve. The dispersion is then subjected to suction filtration using a membrane filter, the mass of which has been measured beforehand, and the membrane filter, together with the filtered sample, is dried in a dryer at 110 ° C. The sample separated by filtration is a mixed sample of carbonaceous material and barium sulfate. A mass (A) of the composite sample is measured by subtracting the mass of the membrane filter from the total mass of the dried composite sample and the membrane filter. The dried mixed sample is then placed in a crucible together with the membrane filter and ashed at 700 ° C or higher. The remaining residue is barium oxide. The mass (B) of barium sulfate is obtained by converting the mass of barium oxide into the mass of barium sulfate.

(Organic expander)

In the present embodiment, an organic expander includes a first organic expander with an aromatic ring and a second organic expander with an aromatic ring. The elemental sulfur content in the first organic expander is 4000 µmol / g or more and the elemental sulfur content in the second organic expander is 2000 µmol / g or less. Every organic expander is an organic polymer that contains elemental sulfur. Any organic expander can contain an aromatic ring in the molecule, but preferably contains a variety of aromatic rings.

The organic expander preferably contains elemental sulfur as a sulfur-containing group. Among the sulfur-containing groups, a sulfonic acid group or a sulfonyl group, which is a stable form, is preferable. The sulfonic acid group can be in acid form or in salt form such as a Na salt.

In contrast to lignin, the first organic expander is preferably a synthetic organic expander that is obtained by synthesis. The first organic expander can be used alone or in combination with two or more of them. The first organic expander is preferably a condensation product of an aldehyde compound from an aromatic ring compound. A condensation product using a polyacrylamide tertiary butyl sulfonic acid Na salt polymerization product (ATBS (registered trademark) polymer) and N, N '- (sulfonyldi-4,1-phenylene) bis (1,2,3,4-tetrahydro-6- methyl-2,4-dioxopyrimidine-5-sulfonamide) can also be used as the first organic expander.

The compound with an aromatic ring can have a variety of aromatic rings. Examples of the aromatic ring are a benzene ring and a naphthalene ring. When the compound having an aromatic ring has a plurality of aromatic rings, the plurality of aromatic rings may be connected through a direct bond, a connecting group (such as an alkylene group or a sulfone group), or the like. Examples of such a structure are biphenyl, bisphenylalkane and bisphenylsulfone. Examples of the compound having an aromatic ring are a compound having the aromatic ring described above and, for example, a hydroxyl group, an amino group and / or a sulfonic acid group. The hydroxy group, amino group or sulfonic acid group can be bonded directly to the aromatic ring or as an alkyl chain with a hydroxyl group, an amino group or a sulfonic acid group. As a compound having an aromatic ring, a bisphenol compound, a hydroxybiphenyl compound, a hydroxynaphthalene compound, a phenol compound, benzenesulfonic acid, naphthalenesulfonic acid and the like are preferred. The compound having an aromatic ring may further have a substituent. The organic expander can contain one or more types of residues of these compounds.

Among the aromatic ring compounds, bisphenol compounds and naphthalenesulfonic acid are particularly preferable. Examples of bisphenol compounds are “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 ”and“ Bisphenol Z ”. Among these bisphenol compounds, "bisphenol S" has a sulfonyl group (-SO2-), making it easy to increase the elemental sulfur content. In a bisphenol compound condensation product, the bisphenol compound condensation product is suitable for a lead-acid battery that is used in a temperature environment that is above the normal temperature, because the starting performance at low temperatures is not even in an environment that is above the normal temperature is affected. Since the polarization hardly becomes smaller when using the condensation product of naphthalenesulfonic acid compared to the condensation product of bisphenols, the condensation product of naphthalenesulfonic acid is suitable for a lead-acid battery in which the properties of the electrolyte solution decrease are important.

The aldehyde compound to be condensed with the aromatic ring compound is not particularly limited. Examples of the aldehyde compound are formaldehyde, paraformaldehyde and aldehyde condensation products such as trioxane and tetraoxymethylene. The aldehyde compound can be used alone or in combination with two or more thereof. Formaldehyde is preferred from the viewpoint of high reactivity with the compound having an aromatic ring.

The sulfur-containing group can be bonded directly to the aromatic ring contained in the compound and, for example, can be bonded to the aromatic ring as an alkyl chain with a sulfur-containing group. For example, a monocyclic aromatic compound such as aminobenzenesulfonic acid or alkylaminobenzenesulfonic acid can be condensed with an aldehyde compound together with the compound having the aromatic ring. A sulfonic acid group (sulfo group) can further be introduced into a condensation product of the compound having an aromatic ring and the aldehyde compound. The elemental sulfur content in the first organic expander can be increased by introducing the sulfonic acid group. The sulfur element can be contained as a sulfonic acid group or sulfonyl group.

As the first organic expander, a condensation product of “bisphenol A” with the introduced sulfonic acid group and formaldehyde, a condensation product of “bisphenol S” with the introduced sulfonic acid group and formaldehyde and a condensation product of B-naphthalenesulfonic acid and formaldehyde (trade name “DEMOL” from Kao Corporation ) be used. When using “Bisphenol S”, a sulfonic acid group and an elemental sulfur from a sulfonyl group (-SO2-) structure are present in “Bisphenol S” in a synthetic expander.

The elemental sulfur content in the first organic expander can be 4000 µmol / g or more, and is preferably 6000 µmol / g or more from the viewpoint of achieving a longer PSOC life. From the point of view of reducing the electrolyte loss after the cycle, the elemental sulfur content in the first organic expander is, for example, preferably 9000 µmol / g or less and particularly preferably 8000 µmol / g or less. Each of these minimum and maximum values can be combined. The elemental sulfur content in the first organic expander can be, for example, 4000 µmol / g or more and 9000 µmol / g or less, 4000 µmol / g or more and 8000 µmol / g or less, 6000 µmol / g or more and 9000 µmol / g or less , or 6000 µmol / g or more and 8000 µmol / g or less.

A weight average molecular weight (Mw) of the first organic expander is, for example, 4000 or more, preferably 7000 or more. The weight average molecular weight of the first organic expander is, for example, 100,000 or less and can be 20,000 or less.

In the present description, the weight average molecular weight is determined by gel permeation chromatography (GPC). A standard substance used in the determination of the weight average molecular weight is sodium polystyrene sulfonate.

• GPC-Gerät: Built-up GPC-System SD-8022/DP-8020/AS-8020/CO-8020/CO-8020/UV-8020 (hergestellt von Tosoh Corporation)
• Säule: TSKgel G4000SWXL, G2000SWXL (7,8 mm I.D. × 30 cm) (hergestellt von Tosoh Corporation)
• Detektor: UV-Detektor, λ = 210 nm
• Elutionsmittel: 1 mol/l NaCl: Acetonitril (Volumenverhältnis = 7 : 3)
• Durchfluss: 1 ml/min.
• Konzentration: 10 mg/ml
• Injektionsvolumen: 10 pl
• Standardsubstanz: Poly(Natriumstyrolsulfonat) (Mw = 275.000, 35.000, 12.500, 7.500, 5.200, 1.680)

The weight average molecular weight is measured under the following conditions with the following device.

• GPC device: Built-up GPC system SD-8022 / DP-8020 / AS-8020 / CO-8020 / CO-8020 / UV-8020 (manufactured by Tosoh Corporation)
• Column: TSKgel G4000SWXL, G2000SWXL (7.8mm ID × 30cm) (manufactured by Tosoh Corporation)
• Detector: UV detector, λ = 210 nm
• Eluent: 1 mol / l NaCl: acetonitrile (volume ratio = 7: 3)
• Flow: 1 ml / min.
• Concentration: 10 mg / ml
• Injection volume: 10 pl
• Standard substance: poly (sodium styrene sulfonate) (Mw = 275,000, 35,000, 12,500, 7,500, 5,200, 1,680)

An organic expander synthesized by known methods can be used for the first organic expander, or a commercially available product can be used. The condensation product of a bisphenol compound can be obtained, for example, by reacting a bisphenol compound with an aldehyde compound. For example, an organic expander containing elemental sulfur can be obtained by this reaction in the presence of sulfite or using a bisphenol compound containing elemental sulfur (such as “bisphenol S”). The content of elemental sulfur in the first organic expander can be adjusted by adjusting the amount of sulfite and / or the amount of the elemental sulfur-containing bisphenol compound. The organic expander can also be obtained using this method if other raw materials are used.

The second organic expander can be a synthetic organic expander obtained by synthesis or lignin. The synthetic organic expander can be selected from those described for the first organic expander, except that the elemental sulfur content is different. Examples of lignins are lignin and lignin derivatives such as lignin sulfonic acid or its salts (such as alkali metal salts such as sodium salts).

The elemental sulfur content in the second organic expander can be 2000 µmol / g or less, and is preferably 1000 µmol / g or less, and more preferably 800 µmol / g or less from the viewpoint of enhancing the effect of suppressing electrolyte loss after the cycle. The lower limit of the elemental sulfur content in the second organic expander is not particularly limited, but is preferably 400 µmol / g or more from the viewpoint of improving the effect of improving the PSOC lifetime performance.

The weight average molecular weight (Mw) of the second organic expander is, for example, 3000 or more and 20,000 or less, and preferably 4000 or more and 10,000 or less, and may be 4,000 or more and less than 7,000.

The content of the first organic expander in the negative electrode material is preferably 0.02 mass percent or more from the viewpoint of a longer PSOC life. In order to further improve the low-temperature high-speed discharge performance after high-temperature cycles, the content of the first organic expander in the negative electrode material is preferably 0.05 mass% or more, and preferably 0.08 mass% or more. The content of the first organic expander in the negative electrode material is, for example, 0.12% by mass or less, and preferably 0.10% by mass or less, in order to enhance the effect of reducing the electrolyte loss after the cycle. Each of these minimum and maximum values can be combined. The content of the first organic expander in the negative electrode material may be, for example, 0.02 mass% or more and 0.12 mass% or less, 0.05 mass% or more and 0.12 mass% or less or 0.08 Mass% or more and 0.12 mass% or less. The upper limit can be set to 0.10 mass percent or less to reduce post cycle cycle electrolyte loss in these areas.

The content of the second organic expander in the negative electrode material may be 0.02% by mass or more, and is preferably 0.05% by mass or more to further enhance the effect of improving the PSOC lifetime performance. The content of the second organic expander in the negative electrode material is, for example, 0.7% by weight or less, and preferably 0.5% by weight or less, and preferably 0.3% by weight or less from the viewpoint of an easily attainable excellent regenerative charge acceptance. Each of these minimum and maximum values can be combined. The content of the second organic expander in the negative electrode material may be, for example, 0.02 mass% or more and 0.7 mass% or less, 0.02 mass% or more and 0.5 mass% or less, 0.02 Mass% or more and 0.3 mass% or less, 0.05 mass% or more and 0.7 mass% or less, 0.05 mass% or more and 0.5 mass% or less be.

The content of the first organic expander and the content of the second organic expander in the negative electrode material are adjusted as described above, so that the effect of improving the PSOC life and the low-temperature high-speed discharge performance after high-temperature cycles can be further enhanced.

In the organic expander contained in the negative electrode material, the total amount of the first organic expander and the second organic expander is preferably 90 mass% or more, and preferably 95 mass% or more.

A method for analyzing the organic expander and a method for determining the physical properties are described below.

Analysis of the organic expander

Identification of the type of organic expander

The type of an organic expander in the negative electrode material is identified as follows.

A fully charged lead-acid battery is disassembled, a negative electrode plate is removed, washed with water to remove a sulfuric acid component, and vacuum dried (dried under a pressure below atmospheric pressure). A negative electrode material containing an active material is separated from the negative electrode plate and immersed in a 1 mol / l NaOH water solution to extract an organic expander. A first organic expander and a second organic expander are then separated from the extract. For each separated material containing each organic expander, the solution, which has been insolubilized by filtration, is desalted, then concentrated and freeze-dried to obtain a powder sample. A desalination column or an ion exchange membrane is used for desalination. The type of an organic expander is identified on the basis of information, for example from the infrared spectrum and the NMR spectrum measured with the powder sample of the organic expander thus obtained and a UV / VIS absorption spectrum measured with a UV / VIS absorption spectrometer after the powder sample was diluted with distilled water.

The first organic expander and the second organic expander are separated from the extract as follows. First, the extract is measured by infrared spectroscopy, NMR and / or GC-MS to determine whether a variety of types of organic expanders are contained or not. Then, a molecular weight distribution is measured by GPC analysis of the extract, and if a variety of kinds of organic expanders can be separated by molecular weight, the organic expander is separated by column chromatography based on a difference in molecular weight. If the separation is difficult due to the different molecular weights, one of the organic expanders is separated by a precipitation separation method using a different solubility which varies depending on the kind and / or amount of the functional groups of the organic expander. In particular, an aqueous sulfuric acid solution is added dropwise to a mixture obtained by dissolving the extract in an aqueous NaOH solution to adjust the pH of the mixture and thereby to aggregate and separate one of the organic expanders. As described above, insoluble matters are removed by filtration from a solution obtained by redissolving the separated material in an aqueous NaOH solution. Furthermore, the remaining solution is concentrated after the separation of one of the organic expanders. The resulting concentrate contains the other organic expander, and insolubles are removed from this concentrate by filtration as described above.

In the present description, the full charge state of the lead-acid battery is a state in which, in the case of a flooded battery, after the battery has been charged in a water bath at 25 ° C. with a constant current of 0.2 CA, to 2.5 V / cell is reached, the battery is charged for a further two hours with a constant current of 0.2 CA. In the case of a valve-regulated battery, the full state of charge is a state in which a constant current constant voltage charging is carried out at 0.2 CA and 2.23 V / cell in a thermostatic bath of 25 ° C, and the charging is terminated as soon as a charging current occurs during the constant current constant voltage charging 1 mCA or less reached.

In the present description, 1 CA is a current value (A) with the same value as a nominal capacity (Ah) of the battery. For example, if the battery has a nominal capacity of 30 Ah, 1 CA is 30 A and 1 mCA 30 mA.

Measurement of the organic expander content

The content of the organic expander in the negative electrode material is measured as follows.

Following the same procedure as above (A-1), after removing insoluble matter by filtration, a solution is obtained for each separated material containing each organic expander. The UV / VIS absorption spectrometer is measured for each solution obtained. Then, on the basis of the UV / VIS absorption spectrometer, the contents of the first organic expander and the second organic expander in the negative electrode material are measured using a calibration curve previously created.

If the content of a synthetic expander is measured with a battery manufactured by another company when the same organic expander cannot be used for a calibration curve because a structural formula of the organic expander cannot be specified exactly, the content of each organic expander is marked with a UV / VIS absorption spectrometer measured by creating a calibration curve with an organic expander extracted from the negative electrode of this battery and a separately available organic expander in which the UV / VIS absorption spectrometer, the infrared spectrum, the NMR spectrum and the like have similar shapes.

Measurement of the elemental sulfur content in organic expanders

0.1 g of the powder sample of the first organic expander and 0.1 g of the powder sample of the second organic expander, which are separated similarly to (A-1), are taken out to obtain an eluate in which an S element in the Powder sample is converted to sulfuric acid by an oxygen combustion piston process. The eluate is then titrated with barium perchlorate using thorin as an indicator to determine the elemental sulfur content in 0.1 g of the powder sample. This elementary Sulfur content is converted to an amount per 1 g to maintain the elemental sulfur content in each organic expander.

(Carbon material)

The carbon material includes a first carbon material with a particle size of 32 µm or more and a second carbon material with a particle size of less than 32 µm. The first carbon material and the second carbon material are separated and distinguished by a method described later.

Examples of each carbon material are carbon black, graphite, hard coal and soft coal. Examples of carbon black are acetylene black, ketjen black, furnace black and lamp black. As the graphite, any carbon material comprising a graphite type crystal structure can be used, and any artificial graphite and natural graphite can be used.

Regarding the first carbon material, a carbon material having an intensity ratio _{ID / IG of} a peak (D band) appearing in a range of 1300 cm-1 or more and 1350 cm-1 or less of the Raman spectrum, and of a peak (G band) appearing in a range of 1550 cm-1 or more and 1600 cm-1 or less, 0 or more and 0.9 or less, referred to as graphite.

In the first carbon material and the second carbon material, the type, the specific surface area and / or the aspect ratio of the carbon material used for producing the negative electrode material can be selected or adjusted so that the ratio R2 / R1 of the powder resistance R2 of the second carbon material to Powder resistance R1 of the first carbon material is 15 or more and 155 or less. In addition to these factors, the particle size of the carbon material to be used can be adjusted. The powder resistance of each of the first carbon material and the second carbon material can be adjusted by selecting or adjusting the above factors, so that the powder resistance ratio R2 / R1 can be adjusted.

For example, at least one from the group of graphite, hard coal and soft coal is preferred as the first carbon material. In particular, the first carbon material preferably contains at least graphite. The second carbon black material preferably contains at least carbon black. When using these carbon materials, it is easy to set the powder resistance ratio R2 / R1.

The ratio of the powder resistance R2 of the second carbon material to the powder resistance R1 of the first carbon material (powder resistance ratio R2 / R1) may be 15 or more and 155 or less. In order to further improve the low-temperature high-speed discharge performance after high-temperature cycles, the powder resistance ratio R2 / R1 is preferably 30 or more and may be 50 or more. From the same point of view, it is also preferable that the powder resistance ratio R2 / R1 is 130 or less. Each of these minimum and maximum values can be combined. The powder resistance ratio R2 / R1 may be 30 or more and 155 or less, 30 or more and 130 or less, 50 or more and 155 or less, 50 or more and 130 or less or 15 or more and 130 or less. If the powder resistance ratio R2 / R1 is in such a range, an excellent PSOC life is also guaranteed.

The ratio s2 / s1 of the specific surface s2 of the second carbon material to the specific surface s1 of the first carbon material is 10 or more and 500 or less, for example. From the viewpoint of suppressing a reduction in regenerative charge acceptance and a significant increase in the amount of electrolyte loss after the cycle while ensuring the low-temperature high-speed discharge performance after high-temperature cycles and a long PSOC life, the specific surface area ratio s2 / sl is 20 or more, and preferably 240 Or less. In view of a higher regenerative charge acceptance, the specific surface ratio s2 / s1 is preferably 30 or more and can be 40 or more. From the viewpoint of further improving the low-temperature high-speed discharge performance after high-temperature cycles and reducing the amount of electrolyte loss after the cycle, the specific surface area ratio s2 / sl is preferably 240 or less, and more preferably 120 or less. Each of these minimum and maximum values can be combined. The specific surface area ratio s2 / s1 can be, for example, 30 or more and 500 or less, 30 or more and 400 or less, 30 or more and 240 or less, 30 or more and 120 or less, 40 or more and 500 or less, 40 or more and 40 or more and 400 or less, 40 or more and 240 or less, 40 or more and 120 or less, 10 or more and 240 or less, 20 or more and 240 or less, 10 or more and 120 or less.

The average aspect ratio of the first carbon material is, for example, 1 or more and 200 or less. From the viewpoint of ensuring a long PSOC life, the average aspect ratio of the first carbon material is preferably 1.5 or more and 100 or less. From the viewpoint of easily ensuring higher low-temperature high-speed discharge performance, the average aspect ratio of the first carbon material is preferably 1.5 or more and 35 or less, and may be 5 or more and 35 or less or 5 or more and 30 or less. If the average aspect ratio of the first carbon material is 1.5 or more, a conductive network easily forms in the negative electrode material, and the effect of improving the PSOC lifetime performance can be further increased. When the average aspect ratio of the first carbon material is 30 or less, it is easy to ensure the adhesion between the particles of the active material so that cracking in a plate is suppressed and a long PSOC life is easily ensured.

The content of the first carbon material in the negative electrode material is, for example, 0.05 mass% or more and 3.0 mass% or less, preferably 0.1 mass% or more and 2.0 mass% or less and preferably 0, 1 mass% or more and 1.5 mass% or less. If the content of the first carbon material is 0.05% by weight or more, the effect of improving the PSOC life can be further improved. If the content of the first carbon material is 3.0% by weight or less, it is easy to ensure the adhesion between active material particles so that the formation of cracks in the negative electrode plate is suppressed and a long PSOC life is more easily ensured.

The content of the second carbon material in the negative electrode material is, for example, 0.03 mass% or more and 1.0 mass% or less, preferably 0.05 mass% or more and 0.5 mass% or less, and preferably 0 , 05 mass% or more and 0.3 mass% or less. If the content of the second carbon material is 0.03% by weight or more, the effect of improving the PSOC lifetime performance can be further improved. If the content of the second carbon material is 1.0% by weight or less, the adsorption of the organic expander is further suppressed, so that the high throughput performance at low temperatures can be further improved.

A method for determining or analyzing the physical properties of the carbon material is described below.

Analysis of carbon material

Separation of carbon material

The resultant fully charged lead-acid battery is disassembled, a negative electrode plate is taken out, washed with water to remove sulfuric acid, and vacuum dried (dried under a pressure below atmospheric pressure). The negative electrode material is then collected from the dried negative electrode plate and ground. 30 ml of an aqueous nitric acid solution with a concentration of 60% by mass are added to 5 g of the ground sample and heated to 70 ° C. To this mixture, 10 g of disodium ethylenediaminetetraacetate, 30 ml of aqueous ammonia at a concentration of 28% by weight and 100 ml of water are further added, and heating is continued to dissolve soluble components. The sample pretreated in this way is obtained by filtration. The collected sample is passed through a sieve with an opening of 500 µm to remove large-sized components such as a reinforcing material and thus collect components that have passed through the sieve as carbon material.

When the collected carbon material is sieved by a wet sieving method with a sieve with an opening of 32 µm, the carbon material remaining on the sieve without passing through the sieve is used as the first carbon material, and the carbon material passing through the sieve is used as the second carbon material , This means that the particle size of each carbon material depends on the size of the sieve opening. For wet screening, reference is made to JIS Z8815: 1994.

In particular, the carbon material is placed on a sieve with an opening of 32 µm, and the sieving is carried out by gently shaking the sieve for 5 minutes while using ion-exchange water is sprayed. The first carbon material remaining on the screen is collected from the screen by pouring ion exchange water and separated from the ion exchange water by filtration. The second carbon material that has passed through the sieve is collected from nitrocellulose by filtration with a membrane filter (mesh size: 0.1 μm). The collected first carbon material and the second carbon material are each dried at a temperature of 110 ° C for 2 hours. A sieve with a sieve mesh with a nominal opening of 32 µm according to JIS Z 8801-1: 2006 is used as the sieve with an opening of 32 µm.

The content of each carbon material in the negative electrode material is determined by measuring the mass of each carbon material separated by the above method and calculating a ratio (mass%) of this mass in a 5 g soil sample.

Powder resistance of the carbon material

For each of the first carbon material and the second carbon material separated in the process of (B-1), the powder resistance R1 of the first carbon material and the powder resistance R2 of the second carbon material are values measured by a four-point probe method by 0.5 g a sample into a powder resistance measuring system (model MCP-PD51 manufactured by Mitsubishi Chemical Analytech Co., Ltd.) and using a low-resistance measuring device (Loresta-GX MCP-T700 manufactured by Mitsubishi Chemical Analytech Co., Ltd.) according to JIS K 7194 : 1994 under a pressure of 3.18 MPa.

Specific surface of the carbon material

• Messgerät: TriStar3000 hergestellt von Micromeritics Instrument Corporation
• Adsorptionsgas: Stickstoffgas mit einer Reinheit von 99,99% oder mehr
• Adsorptionstemperatur: Siedepunkttemperatur von Flüssigstickstoff (77K)
• Verfahren zum Berechnen der spezifischen BET-Oberfläche: Entspricht 7.2 von JIS Z 8830: 2013

The specific surface s1 of the first carbon material and the specific surface s2 of the second carbon material are each BET-specific surface areas of the first carbon material and the second carbon material. The specific BET surface area is determined using a BET equation by a gas adsorption method, each of the first carbon materials and the second carbon material being separated by the method (B-1). Each carbon material is pretreated by heating in a stream of nitrogen at a temperature of 150 ° C for 1 hour. Using the pretreated carbon material, the BET specific surface area of each carbon material is determined under the following conditions with the following device.

• Meter: TriStar3000 manufactured by Micromeritics Instrument Corporation
• Adsorption gas: nitrogen gas with a purity of 99.99% or more
• Adsorption temperature: boiling point temperature of liquid nitrogen (77K)
• Method for calculating the specific BET surface area: Corresponds to 7.2 of JIS Z 8830: 2013

Average aspect ratio of the first carbon material

The first carbon material separated by the method (B-1) is observed with an optical microscope or an electron microscope, any ten or more particles are selected, and an enlarged photo thereof is taken. Then a photo of each particle is processed to produce a maximum diameter d1 of the particle and a maximum diameter D2 in a direction orthogonal to the maximum diameter d1, and d1 divided by d2 to determine the aspect ratio of each particle. The average aspect ratio is calculated by averaging the aspect ratios obtained.

(Other)

The negative electrode current collector can be formed by casting lead (Pb) or a lead alloy or by working a sheet obtained by rolling lead or a lead alloy plate. Examples of the processing method are expanding and punching.

The lead alloy used for the negative electrode current collector can be any one of a Pb-Sb alloy, a Pb-Ca alloy and a Pb-Ca-Sn alloy. The lead or the lead alloys can also contain at least one from the group consisting of Ba, Ag, Al, Bi, As, Se, Cu and the like as an additional element.

The negative electrode plate can be formed by filling, aging and drying a negative electrode current collector with a negative electrode paste to produce an unshaped negative electrode plate, and then forming the unshaped negative electrode plate. The negative electrode paste is produced by adding water and sulfuric acid to a lead powder, an organic expander, a carbon material and, if appropriate, various additives, and the mixture is kneaded. As aging progresses, it is preferable to age the unshaped negative electrode plate at a temperature above room temperature and high humidity.

The formation of the negative electrode plate can be carried out by charging the element in a state in which the element including the unshaped negative electrode plate is immersed in an electrolytic solution containing sulfuric acid in the container of the lead battery. However, the formation can be carried out before assembling the lead battery or the element. Spongy metallic lead is created by the formation.

(Positive electrode plate)

There is a paste type and a plated type of the lead-acid battery positive electrode plate.

A pasty positive electrode plate is equipped with a positive electrode current collector and a positive electrode material. The positive electrode material is held by the positive electrode current collector. The positive electrode current collector can be constructed similarly to the negative electrode current collector and can be formed by casting lead or a lead alloy or by machining a lead or lead alloy sheet.

A plated positive electrode plate is made up of a plurality of porous tubes, a core metal inserted in each tube, a power take-off section that connects the metal cores, a positive electrode material filled in the tube in which the metal core is inserted, and a connection that the plurality of Connects tubes, equipped. The metal core and the current collector section that connects the metal cores are collectively referred to as a positive electrode current collector.

The lead alloy used for the positive electrode current collector is preferably a Pb-Ca alloy, a Pb-Sb alloy or a Pb-Ca-Sn alloy in terms of corrosion resistance and mechanical strength. The positive electrode current collector can have lead alloy layers of different compositions, and a variety of alloy layers can be provided.

The positive electrode material includes a positive electrode active material (lead dioxide or lead sulfate) that has capacity through an oxidation reduction reaction. The positive electrode material can contain further additives if necessary.

An unshaped, pasty, positive electrode plate is obtained by filling, storing and drying a positive electrode current collector with a positive electrode paste, as with the negative electrode plate. The positive electrode paste is produced by kneading lead powder, additives, water and sulfuric acid.

The plated positive electrode plate is formed by filling a tube in which a core metal is inserted with a lead powder or mud-shaped lead powder and connecting a plurality of tubes with a joint.

The unshaped positive electrode plate to be formed is molded. The formation produces lead dioxide. The positive electrode plate can be formed before the lead battery or element is assembled.

(Separator)

As a rule, a separator is arranged between a negative electrode plate and a positive electrode plate. A nonwoven fabric, a microporous film or the like is used for a separator. The thickness and number of the separators arranged between the negative electrode plate and the positive electrode plate can be selected according to an electrode distance.

A nonwoven is a mat that traps fibers without being woven and mainly contains fibers. For example, 60 mass% or more of the separator is formed from fibers. As the fiber, glass fiber, polymer fiber (such as polyolefin fiber, acrylic fiber or polyester fiber such as polyethylene terephthalate fiber), cellulose fiber or the like can be used. Among these fibers, glass fiber is preferred. The nonwoven fabric may contain components other than fibers, such as acid-resistant inorganic powder, a polymer such as a binder, and the like.

On the other hand, a microporous film is a porous film mainly composed of components other than a fiber component, and after, for example, a composition containing a pore-forming agent (such as polymer powder and / or oil) is extruded into a film, the pore-forming agent becomes removed to form pores, thereby obtaining the microporous film. The microporous film preferably consists of a material with acid resistance and preferably mainly of a polymer component. Polyolefins such as polyethylene and polypropylene are preferred as the polymer component.

For example, a separator can only consist of a nonwoven or only a microporous film. The separator may be a laminate of a nonwoven fabric and a microporous film, if necessary, a product obtained by applying different types or the same types of materials, or a product obtained by crosslinking irregularities in different types or the same types of materials.

(Electrolyte solution)

The electrolyte solution is an aqueous solution with sulfuric acid and can be gelled if necessary. A specific weight of the electrolyte solution in the lead battery formed in the fully charged state at 20 ° C. is, for example, 1.10 g / cm3 or more and 1.35 g / cm3 or less, preferably 1.20 g / cm3 or more and 1.35 g / cm3 or less.

10 shows the appearance of an example of the lead-acid battery according to the embodiment of the present invention.

A lead-acid battery 1 includes a container 12 with one element 11 and an electrolytic solution (not shown). The container 12 is through the partitions 13 in a variety of cell chambers 14 divided. Each of the cell chambers 14 saves an item 11 , An opening of the container 12 is through a lid 15 with a negative electrode connection 16 and a positive electrode connection 17 tightly closed. In the lid 15 is a vent plug for each cell chamber 18 intended. When adding water, remove the vent plug 18 Refill water supplied. The vent plug 18 can have a function to drain from in the cell chamber 14 generated gas from the battery.

The element 11 is by stacking a plurality of negative electrode plates 2 and a variety of positive electrode plates 3 with a separator in between 4 configured. Inside is the bag-shaped separator 4 to accommodate the negative electrode plate 2 shown, but the shape of the separator is not particularly limited. In the cell chamber 14 located at one end of the container 12 is a negative electrode band 6 , the ear sections 2a the variety of negative electrode plates 2 connects in parallel with one implementation 8th connected, and a positive electrode tape 5 , the ear sections 3a the variety of positive electrode plates 3 connects in parallel is with a positive electrode pole 7 connected. The positive electrode pole 7 is with the positive electrode connection 17 outside the lid 15 connected. In the cell chamber 14 at the other end of the container 12 is the negative electrode pole 9 with the negative electrode band 6 and the implementation 8th with the positive electrode band 5 connected. The negative electrode pole 9 is with the negative electrode connection 16 outside the lid 15 connected. Each of the bushings 8th passes through one in the partition 13 provided through hole and connects the elements 11 the neighboring cell chamber 14 in row.

• (1) Ein Aspekt der vorliegenden Erfindung ist eine Bleibatterie, die Bleibatterie beinhaltet eine negative Elektrodenplatte, eine positive Elektrodenplatte und eine Elektrolytlösung, die negative Elektrodenplatte beinhaltet ein negatives Elektrodenmaterial, das ein Kohlenstoffmaterial und einen organischen Expander enthält, das Kohlenstoffmaterial beinhaltet ein erstes Kohlenstoffmaterial mit einer Partikelgröße von 32 µm oder mehr und ein zweites Kohlenstoffmaterial mit einer Partikelgröße von weniger als 32 µm, ein Verhältnis R2/R1 der Pulverbeständigkeit R2 des zweiten Kohlenstoffmaterials zur Pulverbeständigkeit R1 des ersten Kohlenstoffmaterials 15 oder mehr und 155 oder weniger beträgt, wobei der organische Expander einen ersten organischen Expander mit einem aromatischen Ring und einem elementaren Schwefelgehalt von 4000 µmol/g oder mehr und einen zweiten organischen Expander mit einem aromatischen Ring und einem elementaren Schwefelgehalt von 2000 µmol/g oder weniger beinhaltet.
• (2) In dem vorstehenden (1) ist der Gehalt des ersten organischen Expanders im negativen Elektrodenmaterial vorzugsweise 0,02 Massen-% oder mehr und 0,12 Massen-% oder weniger, und der Gehalt des zweiten organischen Expanders ist vorzugsweise 0,05 Massen-% oder mehr und 0,7 Massen-% oder weniger.
• (3) In den vorstehenden (1) oder (2) ist ein Verhältnis s2/sl einer spezifischen Oberfläche s2 des zweiten Kohlenstoffmaterials zu einer spezifischen Oberfläche s1 des ersten Kohlenstoffmaterials vorzugsweise 20 oder mehr und 240 oder weniger.
• (4) In einem der vorstehenden (1) bis (3) beträgt das durchschnittliche Seitenverhältnis des ersten Kohlenstoffmaterials vorzugsweise 1,5 bis 35.
• (5) In einem der vorstehenden (1) bis (4) beträgt der elementare Schwefelgehalt im ersten organischen Expander vorzugsweise 9000 pmol/g oder weniger.
• (6) In einem der vorstehenden (1) bis (5) beträgt der elementare Schwefelgehalt im ersten organischen Expander vorzugsweise 6000 µmol/g oder mehr.
• (7) In einem der vorstehenden (1) bis (6) beträgt der elementare Schwefelgehalt im zweiten organischen Expander vorzugsweise 1000 µmol/g oder weniger.
• (8) In einem der vorstehenden (1) bis (7) beträgt der elementare Schwefelgehalt im zweiten organischen Expander vorzugsweise 400 µmol/g oder mehr.
• (9) In einem der vorstehenden (1) bis (8) beträgt der Gehalt des ersten organischen Expanders im negativen Elektrodenmaterial vorzugsweise 0,05 Masse-% oder mehr.
• (10) In einem der vorstehenden (1) bis (9) beträgt der Gehalt des ersten organischen Expanders im negativen Elektrodenmaterial vorzugsweise 0,10 Masse-% oder weniger.
• (11) In einem der vorstehenden (1) bis (10) beträgt der Gehalt des zweiten organischen Expanders im negativen Elektrodenmaterial vorzugsweise 0,5 Masse-% oder weniger.
• (12) In einem der vorstehenden (1) bis (11) beträgt der Gehalt des ersten Kohlenstoffmaterials im negativen Elektrodenmaterial vorzugsweise 0,05 Masse-% oder mehr.
• (13) In einem der vorstehenden (1) bis (12) beträgt der Gehalt des ersten Kohlenstoffmaterials im negativen Elektrodenmaterial vorzugsweise 0,3 Massen-% oder weniger.
• (14) In einem der vorstehenden (1) bis (13) beträgt der Gehalt des zweiten Kohlenstoffmaterials im negativen Elektrodenmaterial vorzugsweise 0,03 Massen-% oder mehr.
• (15) In einem der vorstehenden (1) bis (14) beträgt der Gehalt des zweiten Kohlenstoffmaterials im negativen Elektrodenmaterial vorzugsweise 1,0 Massen-% oder weniger.
• (16) In einem der vorstehenden (1) bis (15) ist das Verhältnis R2/R1 vorzugsweise 30 oder mehr.
• (17) In einem der vorstehenden (1) bis (16) ist das Verhältnis R2/R1 vorzugsweise 130 oder weniger.
• (18) In einem der vorstehenden (1) bis (17) ist das Verhältnis s2/s1 vorzugsweise 30 oder mehr.
• (19) In einem der vorstehenden (1) bis (18) ist das Verhältnis s2/s1 vorzugsweise 120 oder weniger.
• (20) In einem der vorstehenden (1) bis (19) ist das durchschnittliche Seitenverhältnis des ersten Kohlenstoffmaterials vorzugsweise 5 oder mehr.
• (21) In einem der vorstehenden (1) bis (20) ist das durchschnittliche Seitenverhältnis des ersten Kohlenstoffmaterials vorzugsweise 30 oder weniger.
• (22) In einem der vorstehenden (1) bis (21) beinhaltet das erste Kohlenstoffmaterial vorzugsweise mindestens Graphit und das zweite Kohlenstoffmaterial vorzugsweise mindestens Ruß.

The lead-acid battery according to one aspect of the present invention is described in summary below.

• (1) One aspect of the present invention is a lead battery, the lead battery includes a negative electrode plate, a positive electrode plate and an electrolytic solution, the negative electrode plate includes a negative electrode material containing a carbon material and an organic expander, the carbon material includes a first carbon material a particle size of 32 µm or more and a second carbon material with a particle size of less than 32 µm, a ratio R2 / R1 of the powder resistance R2 of the second carbon material to the powder resistance R1 of the first carbon material is 15 or more and 155 or less, the organic expander having a first organic expander with an aromatic ring and an elemental sulfur content of 4000 µmol / g or more and a second organic expander with an aromatic ring and an elemental sulfur content of Contains 2000 µmol / g or less.
• (2) In the above (1), the content of the first organic expander in the negative electrode material is preferably 0.02 mass% or more and 0.12 mass% or less, and the content of the second organic expander is preferably 0.05 Mass% or more and 0.7 mass% or less.
• (3) In the above (1) or (2), a ratio s2 / sl of a specific surface s2 of the second carbon material to a specific surface s1 of the first carbon material is preferably 20 or more and 240 or less.
• (4) In one of the above (1) to (3), the average aspect ratio of the first carbon material is preferably 1.5 to 35.
• (5) In one of the above (1) to (4), the elemental sulfur content in the first organic expander is preferably 9000 pmol / g or less.
• (6) In one of the above (1) to (5), the elemental sulfur content in the first organic expander is preferably 6000 µmol / g or more.
• (7) In one of the above (1) to (6), the elemental sulfur content in the second organic expander is preferably 1000 µmol / g or less.
• (8) In one of the above (1) to (7), the elemental sulfur content in the second organic expander is preferably 400 µmol / g or more.
• (9) In any one of (1) to (8) above, the content of the first organic expander in the negative electrode material is preferably 0.05 mass% or more.
• (10) In one of the above (1) to (9), the content of the first organic expander in the negative electrode material is preferably 0.10 mass% or less.
• (11) In any of the above (1) to (10), the content of the second organic expander in the negative electrode material is preferably 0.5 mass% or less.
• (12) In any one of the above (1) to (11), the content of the first carbon material in the negative electrode material is preferably 0.05 mass% or more.
• (13) In one of the above (1) to (12), the content of the first carbon material in the negative electrode material is preferably 0.3 mass% or less.
• (14) In any one of the above (1) to (13), the content of the second carbon material in the negative electrode material is preferably 0.03 mass% or more.
• (15) In any one of (1) to (14) above, the content of the second carbon material in the negative electrode material is preferably 1.0 mass% or less.
• (16) In any of the above (1) to (15), the ratio R2 / R1 is preferably 30 or more.
• (17) In any of the above (1) to (16), the ratio R2 / R1 is preferably 130 or less.
• (18) In any of the above (1) to (17), the ratio s2 / s1 is preferably 30 or more.
• (19) In any of the above (1) to (18), the ratio s2 / s1 is preferably 120 or less.
• (20) In one of the above (1) to (19), the average aspect ratio of the first carbon material is preferably 5 or more.
• (21) In any one of (1) to (20) above, the average aspect ratio of the first carbon material is preferably 30 or less.
• (22) In one of the above (1) to (21), the first carbon material preferably includes at least graphite and the second carbon material preferably contains at least carbon black.

The present invention is described in detail below with reference to examples and comparative examples. However, it should be noted that the present invention is not limited to these examples.

<< Lead acid battery A1 >>>>

Production of a negative electrode plate

A condensation product consisting of a lead powder, water, dilute sulfuric acid, barium sulfate, a carbon material and a bisphenol compound containing sulfonic acid groups with formaldehyde (first organic expander with an elemental sulfur content of 6000 µmol / g, Mw = 7500) and lignin (second organic expander with an elemental sulfur content of 600 µmol / g, Mw = 5500) are mixed to obtain a negative electrode paste. The negative electrode paste is filled in a network portion of an expanded Pb-Ca-Sn alloy mesh, then aged and dried to obtain an unshaped negative electrode plate. Carbon black (average particle size D50: 40 nm) and graphite (average particle size D50: 110 µm) are used as carbon material.

With regard to the elemental sulfur content (µmol / g) in each organic expander, there is essentially no difference between a pre-negative electrode material value and a value measured by disassembling the lead battery and extracting each organic expander. Thus, like the elemental sulfur content in each organic expander described for each battery, a value for each organic expander before the production of the negative electrode material is described below.

The amount of each organic expander added is adjusted so that the content of the first organic expander contained in 100 mass% of the negative electrode material formed after full charge is 0.05 mass% and the amount of the second organic expander is 0. Is 1% by mass and the organic expanders are added to a negative electrode paste.

Production of a positive electrode plate

A lead powder, water and sulfuric acid are kneaded to make a positive electrode paste. The positive electrode paste is filled in a network portion of an expanded Pb-Ca-Sn alloy mesh, then aged and dried to obtain an unshaped positive electrode plate.

Manufacture of lead-acid batteries

An unshaped negative electrode plate is housed in a bag-shaped separator made of a microporous polyethylene film, and an element is composed of five unshaped negative electrode plates and four unshaped positive electrode plates per cell.

The element is inserted into a polypropylene container, an electrolytic solution is injected, the formation takes place in the container and a flooded lead acid battery A1 with a nominal voltage of 12 V and a nominal output of 30 Ah (5-hour rate) is installed.

For one of the lead batteries manufactured, the content (c1 (% by mass)) of each organic expander contained in the negative electrode material (% by mass) taken out from the negative electrode plate is determined by the method described above. The content of each organic expander quantified in this way is a slightly different value than the content (c2 (mass%)) of each organic expander in the negative electrode material (mass%) that is produced in the manufacture of a lead acid battery. Thus, a ratio R (= c1 / c2) of these contents c1 and c2 is determined in advance, and the content c2 of each organic expander is adjusted using the ratio R so that the content c1 of each organic expander becomes a predetermined value. For each battery, the ratio R is determined for each elemental sulfur content of the organic expander used, and for the negative electrode material using the organic expander with the same elemental sulfur content, the content c2 of the organic expander is set based on the ratio R obtained.

In this lead-acid battery, the content of the first carbon material is 1.0% by mass and the content of the second carbon material is 0.5% by mass. The powder resistance ratio R2 / R1 is 15. The average aspect ratio of the first carbon material is 1.5. However, these values are values obtained as the content of each carbon material contained in the negative electrode material (100% by mass) when the negative electrode plate is removed from the lead-acid battery produced and the carbon material contained in the negative electrode material according to that described above Process is separated into the first carbon material and the second carbon material. The powder resistance R1 and R2 of each carbon material, the powder resistance ratio R2 / R1 and the average aspect ratio of the first carbon material are also obtained from the lead battery manufactured by the method described above.

<< Lead acid batteries A2 to A9 >>>>

The powder resistance ratio R2 / R1 is changed as shown in Table 2 by adjusting the average particle size D50 and the specific surface area of each carbon material used, as well as the average aspect ratio of the first carbon material. Apart from this, the lead-acid batteries A2 to A9 are constructed similarly to the lead-acid battery A1, except that a negative electrode plate is made similar to the lead-acid battery A1 and the obtained negative electrode plate is used.

<< Lead acid batteries B1 to B9 >>>>

The amount of the first organic expander added is adjusted so that the content of the first organic expander contained in 100 mass% of the negative electrode material formed after fully charged is 0.1 mass%, and the organic expander becomes one negative electrode paste added. Otherwise, a negative electrode plate is formed similarly to the lead batteries A1 to A9. The lead-acid batteries B1 to B9 are constructed similarly to the lead-acid battery A1, except that the negative electrode plate obtained is used.

<< Lead acid batteries C1 to C9 >>>>

The amount of a sulfonic acid group which is introduced into a condensation product of a bisphenol compound with formaldehyde is adjusted so that the elemental sulfur content of the first organic expander is 4000 μmol / g. A negative electrode plate is similar to the lead-acid batteries B1 to B9, except that an organic expander (Mw = 9500) with an elemental sulfur content of 4000 µmol / g is used. A lead-acid battery is constructed similarly to the lead-acid battery A1, except that the negative electrode plate obtained is used.

<< Lead acid batteries D1 to D9 >>>>

The amount of a sulfonic acid group which is introduced into a condensation product of a bisphenol compound with formaldehyde is adjusted so that the elemental sulfur content of the first organic expander is 8000 μmol / g. A negative electrode plate is similar to the lead acid batteries B1 to B9, except that an organic expander (Mw = 9500) with an elemental sulfur content of 8000 µmol / g is used. The lead-acid batteries D1 to D9 are constructed similarly to the lead-acid battery A1, except that the negative electrode plate obtained is used.

<< Lead acid batteries E1 to E9 >>>>

The amount of the second organic expander added is adjusted so that the content of the second organic expander contained in 100 mass% of the negative electrode material formed after being fully charged is 0.5 mass%, and the organic expander becomes negative Electrode paste added. Otherwise, a negative electrode plate is formed similar to the lead acid batteries B1 to B9. The lead-acid batteries E1 to E9 are constructed similarly to the lead-acid battery A1, except that the negative electrode plate obtained is used.

<< Lead acid battery Z1 >>>>

Only carbon black (average particle size D50: 40 nm) and only lignin (second organic expander with an elemental sulfur content of 600 µmol / g, Mw = 5500) are used as the carbon expander. In this lead-acid battery, the content of the second carbon material is 0.3 percent by mass. Apart from that, a negative electrode plate is formed similarly to the lead-acid battery A1. A lead battery Z1 is constructed similarly to the lead battery A1, except that the negative electrode plate obtained is used.

<< Lead acid battery Z2 >>>>

A negative electrode plate is formed similarly to the lead-acid battery Z1, except that the content of the second carbon material is 1.5 mass%. A lead-acid battery Z2 is constructed similarly to the lead-acid battery A1, except that the negative electrode plate obtained is used.

«Lead acid batteries Z3 and Z4» »

The amount of the second organic expander added is adjusted so that the content of the second organic expander contained in 100 mass% of the negative electrode material formed after full charge is 0.5 mass% (lead acid battery Z3) or 0.8 mass % (Lead acid battery Z4), and the organic expander is added to a negative electrode paste. Otherwise, a negative electrode plate is formed similar to the lead-acid battery Z2. The lead batteries Z3 and Z4 are constructed similarly to the lead battery A1, except that the negative electrode plate obtained is used.

<< Lead acid batteries Z5 to Z7 >>>>

Only carbon black (average particle size D50: 40 nm) is used as the carbon material, and only an condensation product of a bisphenol compound containing sulfonic acid groups with formaldehyde (first organic expander with an elemental sulfur content of 6000 μmol / g, Mw = 9500) is used as the organic expander. In this lead-acid battery, the content of the second carbon material is 1.5% by weight. The amount of the first organic expander added is adjusted so that the content of the first organic expander contained in 100 mass% of the negative electrode material formed after fully charged is 0.05 mass% (lead battery Z5), 0.1 mass -% (lead battery Z6) or 0.12 mass% (lead battery Z7), and the organic expander is added to a negative electrode paste. Apart from that, a negative electrode plate is formed similarly to the lead-acid battery A1. The lead-acid batteries Z5 to Z7 are constructed similarly to the lead-acid battery A1, except that the negative electrode plate obtained is used.

<< Z8 lead-acid battery >>>>

Only carbon black (average particle size D50: 40 nm) is used as the carbon material. In the present embodiment, the content of the second carbon material is 1.5 mass percent. Apart from that, a negative electrode plate is formed similarly to the lead-acid battery B1. A lead-acid battery Z8 is constructed similarly to the lead-acid battery A1, except that the negative electrode plate obtained is used.

Rating 1: PSOC life and electrolyte loss after the cycle].

The loading / unloading is carried out according to the pattern shown in Table 1. The number of cycles until a terminal voltage reaches 1.2 V per unit cell is used as an index for the PSOC service life. The number of cycles is expressed as a ratio when the result of the Z1 lead-acid battery is 100.

[Table 1] step detail test condition Temperature (° C) Note Current, voltage or the number of repetitions termination condition 1 CC-discharge 1ca 59 seconds 40 2 CC-discharge 300A 1 second 3 CV-charge 2.4V / cell, maximum 50A 10 seconds 4 CC-discharge 1ca 5 seconds 5 Repeat steps 3 and 4. 5 times - The previous steps are carried out for 135 seconds (1 cycle). 6 Repeat steps 1 through 5. 50 times - 7 CV charge 2.4V / cell, maximum 50A 900 seconds The previous steps are carried out for approx. 2 hours (50 cycles). 8th Repeat steps 1 through 7. 72 times - 9 Break 15 hours - The previous steps are carried out for 1 week (3600 cycles). 10 Back to step 1 - - * CC discharge: constant current discharge CV charge: constant voltage charge

The mass of the lead battery after the evaluation of the PSOC lifetime is measured and subtracted from the mass before the evaluation, so that the amount of electrolyte loss after the cycle is determined. The amount of electrolyte loss after the cycle is expressed as a ratio when the amount of electrolyte loss in the lead battery Z1 is 100.

[Rating 2: Low-temperature high-speed discharge performance after high-temperature cycles]

480 charge / discharge cycles are performed under the conditions of a flat cycle endurance test according to JIS D5301: 2006. In particular, in the flat cycle endurance test, a constant current discharge at 25 A for 240 seconds in a water bath at 40 ° C. and a constant voltage charge for 600 seconds at 2.47 V per unit cell with a maximum current of 25 A are carried out. Then discharge at -15 ° C with a discharge current (150 A) according to JIS D5301: 2006 until the terminal voltage reaches 1 V per unit cell and the discharge time is reached at this point. The discharge time is used as an index for the low temperature high speed discharge power after high temperature cycles. The number of cycles is expressed as a ratio when the result of the Z1 lead-acid battery is 100.

[Evaluation 3: Regenerative Charge Acceptance]

A fully charged lead-acid battery is discharged at 25 ° C and 0.2 CA by 10% of the nominal capacity and then left at room temperature for 12 hours. Then the constant voltage charge is performed at 2.42 V per unit cell, and the amount of electricity for the first 10 seconds at this time is obtained and used as an index for evaluating the regenerative charge acceptance. The number of cycles is expressed as a ratio when the result of the Z1 lead-acid battery is 100.

Table 2 shows the results of the lead batteries A1 to A9, B1 to B9, C1 to C9, D1 to D9, E1 to E9 and Z1 to Z8.

[Table 2] First carbon material (mass%) Second carbon material (mass%) Pulverwid first ratio R2 / R1 First organic expander Second organic expander (mass%) PSOC lifetime performance Low-temperature high-speed discharge performance after high-temperature cycles Regenerative charge acceptance Electrolyte losses (Dimensions %) S-element content (µmol / g) Z1 0.0 0.3 0 0.1 100 100 100 100 Z2 1.5 0.1 115 49 100 99 Z3 0.5 121 65 99 100 Z4 0.8 110 62 90 99 Z5 00:05 6000 0 113 88 100 102 Z6 0.1 119 92 100 104 Z7 00:12 122 95 99 110 Z8 0.1 0.1 123 93 98 103 A8 1.0 0.5 11 00:05 6000 0.1 105 102 99 101 A1 15 116 109 99 101 A2 32 117 114 99 101 A3 57 118 120 100 100 A4 83 122 119 100 100 A5 103 122 118 100 100 A6 127 120 116 99 99 A7 152 118 111 100 100 A9 169 109 105 99 100 B8 1.0 0.5 11 0.1 6000 0.1 106 103 99 102 B1 15 116 112 100 102 B2 32 118 118 100 102 B3 57 120 122 100 101 B4 83 124 120 100 101 B5 103 123 119 100 101 B6 127 122 117 100 101 B7 152 119 112 99 100 B9 169 110 107 99 100 C8 1.0 0.5 11 0.1 4000 0.1 109 105 99 101 C1 15 115 110 99 102 C2 32 116 115 99 101 C3 57 118 114 100 102 C4 83 119 113 100 101 C5 103 117 112 100 101 C6 127 152 118 112 100 101 C7 117 111 99 100 C9 169 105 106 99 101 D8 1.0 0.5 11 0.1 8000 0.1 104 102 101 104 D1 15 119 115 101 102 D2 32 120 116 101 102 D3 57 122 120 101 102 D4 83 125 122 101 101 D5 103 128 123 100 101 D6 127 127 122 100 101 D7 152 126 119 100 101 D9 169 115 107 100 101 E8 1.0 0.5 11 0.1 6000 0.5 102 105 99 102 E1 15 115 115 99 102 E2 32 120 118 99 101 E3 57 119 119 99 101 E4 83 119 121 98 100 E5 103 118 123 98 100 E6 127 117 122 98 101 E7 152 114 115 98 101 E9 169 107 106 98 101

As shown in Table 2, in a lead-acid battery made of only the second carbon material, the effect of improving the low-temperature high-speed discharge performance after high-temperature cycles is small even when the first organic expander and the second organic expander are used in combination (Z1). This is because the adsorption of the second organic expander to the second carbon material becomes remarkable. On the other hand, when the first organic expander and the second organic expander are used in combination, and the first carbon material and the second carbon material are combined, the adsorption of the second organic expander to the second carbon material is suppressed, thereby improving the low-temperature, high-speed discharge performance after high-temperature cycles (A1 to A9, B1 to B9, C1 to C9, D1 to D9, E2 to E9). In addition, in a lead-acid battery in which the ratio R2 / R1 is in the range of 15 to 155, the conductive network is easily formed in the negative electrode material, and the action of the organic expander is sufficient to maintain the conductive network; therefore a long PSOC lifespan is guaranteed (A1 to A7, B1 to B7, C1 to C7, D1 to D7, E2 to E7).

<< Lead acid batteries F1 to F5 >>>>

The amount of a sulfonic acid group which is introduced into a condensation product of a bisphenol compound with formaldehyde is adjusted so that the elemental sulfur content of the first organic expander is the value given in Table 3. A negative electrode plate is formed similarly to the lead-acid battery A1, except that the first organic expander to be obtained is used. The lead-acid batteries F1 to F5 are constructed similarly to the lead-acid battery A1, except that the negative electrode plate obtained is used. A lead-acid battery F2 using the first organic expander with an elemental sulfur content of 6000 µmol / g is identical to the lead-acid battery A1. Mw of the first organic expander is 9500 in all cases.

<< Lead acid batteries G1 to G5 >>>>

The amount of the first organic expander added is adjusted so that the content of the first organic expander contained in 100 mass% of the negative electrode material formed after fully charged is 0.1 mass%, and the organic expander becomes one negative electrode paste added. Otherwise, a negative electrode plate is formed similar to the lead batteries F1 to F5. The lead batteries G1 to G5 are constructed similarly to the lead battery A1, except that the negative electrode plate obtained is used. A lead-acid battery G2 using the first organic expander with an elemental sulfur content of 6000 µmol / g is identical to the lead-acid battery B1.

<< Lead acid batteries H1 to H5 >>>>

The amount of a sulfonic acid group which is introduced into a condensation product of a bisphenol compound with formaldehyde is adjusted so that the elemental sulfur content of the first organic expander is the value given in Table 3. A negative electrode plate is formed similarly to the lead-acid battery A7, except that the first organic expander to be obtained is used. The lead-acid batteries H1 to H5 are constructed similarly to the lead-acid battery A1, except that the negative electrode plate obtained is used. A lead-acid battery H2 using the first organic expander with an elemental sulfur content of 6000 µmol / g is identical to the lead-acid battery A7.

<< Lead acid batteries J1 to J5 >>>>

The amount of the first organic expander added is adjusted so that the content of the first organic expander contained in 100 mass% of the negative electrode material formed after fully charged is 0.1 mass%, and the organic expander becomes one negative electrode paste added. Otherwise, a negative electrode plate is formed similar to the lead batteries H1 to H5. The lead-acid batteries J1 to J5 are constructed similarly to the lead-acid battery A1, except that the negative electrode plate obtained is used. A lead-acid battery J2 using the first organic expander with an elemental sulfur content of 6000 µmol / g is identical to the lead-acid battery B7.

For lead-acid batteries F1 to F5, G1 to G5, H1 to H5 and J1 to J5, evaluations 1 to 3 are carried out analogously to lead-acid battery A1. The evaluation results are shown in Table 3.

[Table 3] First carbon material (mass%) Second carbon material (mass%) Powder wide ratio R2 / R1 First organic expander Second organic expander (mass%) PSOC · Lifetime performance Low-temperature high-speed charging power Regenerative charge acceptance Electrolyte losses (Dimensions%) S-element content (µmol / g) F5 1.0 0.5 15 00:05 3000 0.1 111 105 97 100 F1 4000 114 109 99 100 F2 6000 116 109 99 101 F3 8000 117 112 99 100 F4 9000 117 111 99 101 G5 1.0 0.5 15 0.1 3000 0.1 110 106 98 101 G1 4000 115 110 99 102 G2 6000 116 112 100 102 G3 8000 119 115 101 102 G4 9000 118 114 101 103 H5 1.0 0.5 152 00:05 3000 0.1 108 106 98 99 H1 4000 117 110 100 100 H2 6000 118 111 100 100 H3 8000 123 115 100 100 H4 9000 123 116 101 101 J5 1.0 0.5 152 0.1 3000 0.1 107 106 98 99 J1 4000 117 111 99 100 J2 6000 119 112 99 100 J3 8000 126 119 100 101 J4 9000 127 118 100 102

As shown in Table 3, when using an organic expander with an elemental sulfur content of 3000 µmol / g in combination with the second organic expander, the effect of improving the low-temperature high-speed discharge performance after high-temperature cycles is reduced (F5, G5, H5, J5). This is probably due to the fact that the organic expander with an elemental sulfur content of 3000 µmol / g tends to run out at high temperature cycles, making it difficult to maintain the pore structure of the negative electrode material. On the other hand, when the first organic expander with an elemental sulfur content of 4000 µmol / g or more is used in combination with the second organic expander, high low-temperature high-speed discharge performance after high-temperature cycles is ensured while ensuring a long PSOC life (F1 to F4, G1 to G4, H1 to H4, J1 to J4) reached. It is assumed that a high, low-temperature, high-speed discharge is achieved, since the outflow of the organic expander during the high-temperature cycles is suppressed by the use of the first organic expander and the pore structure of the negative electrode material is ensured.

«Lead acid batteries K1 to K6 >>>>

The amount of the first organic expander added is adjusted so that the content of the first organic expander contained in 100 mass% of the negative electrode material formed after fully charged corresponds to the value shown in Table 4, and the organic expander becomes one negative electrode paste added. Otherwise, a negative electrode plate is formed similar to that of the lead-acid battery A1. The lead-acid batteries K1 to K6 are constructed similarly to the lead-acid battery A1, except that the negative electrode plate obtained is used. The lead-acid battery K2, in which the content of the first organic expander is 0.05% by mass, is identical to the lead-acid battery A1.

<< Lead-acid batteries L1 to L6 >>>>

The amount of the first organic expander added is adjusted so that the content of the first organic expander contained in 100 mass% of the negative electrode material formed after fully charged corresponds to the value shown in Table 4, and the organic expander becomes one negative electrode paste added. Otherwise, a negative electrode plate is formed similar to that of the lead-acid battery A7. The lead-acid batteries L1 to L6 are assembled similarly to the lead-acid battery A1, except that the negative electrode plate obtained is used. The lead-acid battery L2, in which the content of the first organic expander is 0.05% by mass, is identical to the lead-acid battery A7.

<< Lead acid batteries M1 to M7 >>>>

The amount of the second organic expander added is adjusted so that the content of the second organic expander contained in 100 mass% of the negative electrode material formed after fully charged corresponds to the value shown in Table 4, and the organic expander becomes one negative electrode paste added. Otherwise, a negative electrode plate is formed similar to that of the lead-acid battery A7. The lead-acid batteries M1 to M7 are constructed similarly to the lead-acid battery A1, except that the negative electrode plate obtained is used. The lead-acid battery M3, in which the content of the second organic expander is 0.1% by mass, is identical to the lead-acid battery A7.

<< Lead acid batteries N1 to N7 >>>>

The amount of the second organic expander added is adjusted so that the content of the second organic expander contained in 100 mass% of the negative electrode material formed after fully charged corresponds to the value shown in Table 4, and the organic expander becomes one negative electrode paste added. Otherwise, a negative electrode plate is formed similarly to the lead-acid battery B7. The lead-acid batteries N1 to N7 are constructed similarly to the lead-acid battery A1, except that the negative electrode plate obtained is used. The lead-acid battery N3, in which the content of the second organic expander is 0.1% by mass, is identical to the lead-acid battery B7.

For lead batteries K1 to K6, L1 to L6, M1 to M7 and N1 to N7, evaluations 1 to 3 are carried out analogously to lead battery A1. The evaluation results are shown in Table 4.

[Table 4] First carbon material (mass%) Second carbon material (mass%) Powder resistance ratio R2 / R1 First organic expander Second organic expander (mass%) PSOC lifetime performance Low temperature high speed discharge power Regenerative charge acceptance Amount of electrolyte lost (Dimensions%) Item contains (pmo l / g) K6 1.0 0.5 15 0 6000 0.1 97 90 98 100 K1 00:02 114 109 99 100 K2 00:05 116 110 99 101 K3 00:08 116 111 99 101 K4 0.1 116 112 100 102 K5 00:12 110 110 99 111 L6 1.0 0.5 152 0 6000 0.1 101 88 99 99 L1 00:02 115 110 100 99 L2 00:05 118 111 100 100 L3 00:08 120 113 99 100 L4 0.1 119 112 99 100 L5 00:12 115 111 99 116 M7 1.0 0.5 152 00:05 6000 0 103 102 100 100 M1 00:02 110 109 100 100 M2 00:05 115 110 100 100 M3 0.1 118 111 100 100 M4 0.3 119 112 99 100 M5 0.5 116 113 98 99 M6 0.7 110 112 93 99 N7 1.0 0.5 152 0.1 6000 0 105 103 100 101 N1 00:02 111 110 100 101 N2 00:05 118 111 99 101 N3 0.1 119 112 99 100 N4 0.3 116 115 99 100 N5 0.5 114 115 98 101 N6 0.7 112 114 94 101

As shown in Table 4, when the first organic expander is 0.02 mass% or more, a long PSOC life can be achieved (K1 to K5, L1 to L5). Further, when the content of the second organic expander is 0.02 mass% or more, a long PSOC life can be achieved (M1 to M6, N1 to N6). This is presumably because in these cases, the effect of suppressing the shrinkage of the negative electrode material is enhanced, so that the pore structure of the negative electrode material is preserved.

When the content of the first organic expander is 0.05% by mass or more or 0.08% by mass or more, the low-temperature high-speed discharge performance becomes low High temperature cycles further improved (K2 to K5, L2 to L5). If the content of the second organic expander is 0.05 mass% or more, the PSOC life and the low-temperature high-speed discharge performance after high-temperature cycles can be further ensured (M2 to M6, N2 to N6). In these cases, a finer pore structure of the negative electrode material is still sufficiently obtained. If the content of the first organic expander is 0.10 mass% or less, the effect of reducing the electrolyte loss after the cycle is high (K1 to K4, K6, L1 to L4, L6). If the content of the second organic expander is 0.5 mass% or less or 0.3 mass% or less, excellent regenerative charge acceptance (M1 to M5, M7, N1 to N5, N7) is obtained.

«Lead-acid batteries O1 to O7 >>>>

By adjusting the specific surface area of each carbon material used, the specific surface area ratio s2 / sl obtained by the above-described method is set to the value shown in Table 5. Apart from that, the lead-acid batteries O1 to O7 are constructed similarly to the lead-acid battery A1, except that a negative electrode plate is made similar to the lead-acid battery A7 and the obtained negative electrode plate is used.

«Lead-acid batteries P1 to P7» »

By adjusting the specific surface area of each carbon material used, the specific surface area ratio s2 / s1 obtained by the above-described method is set to the value shown in Table 5. Apart from this, the lead-acid batteries P1 to P7 are constructed similarly to the lead-acid battery A1, except that a negative electrode plate is made similar to the lead-acid battery B7 and the obtained negative electrode plate is used. The lead-acid battery P3 with a specific surface area ratio s2 / s1 of 33 is identical to the lead-acid battery B7.

<< Lead acid batteries Q1 to Q7 >>>>

By adjusting the specific surface area of each carbon material used, the specific surface area ratio s2 / s1 obtained by the above-described method is set to the value shown in Table 5. Apart from this, the lead acid batteries Q1 to Q7 are constructed similarly to the lead acid battery A1, except that a negative electrode plate is made similar to the lead acid battery C7 and the obtained negative electrode plate is used. The lead-acid battery Q3 with a specific surface area ratio s2 / s1 of 33 is identical to the lead-acid battery C7.

<< Lead acid batteries S1 to S7 >>>>

By adjusting the specific surface area of each carbon material used, the specific surface area ratio s2 / s1 obtained by the above-described method is set to the value shown in Table 5. Apart from this, a lead-acid battery is constructed similarly to the lead-acid battery A1, except that a negative electrode plate is made similar to the lead-acid battery D7 and the obtained negative electrode plate is used. The lead-acid battery S3 with a specific surface ratio s2 / s1 of 33 is identical to the lead-acid battery D7.

«Lead acid batteries T1 to T7 >>>>

By adjusting the specific surface area of each carbon material used, the specific surface area ratio s2 / s1 obtained by the above-described method is set to the value shown in Table 5. Apart from this, the lead-acid batteries T1 to T7 are constructed similarly to the lead-acid battery A1, except that a negative electrode plate is made similar to the lead-acid battery B1 and the obtained negative electrode plate is used. The lead-acid battery T3 with a specific surface ratio s2 / s1 of 28 is identical to the lead-acid battery B1.

For lead batteries O1 to O7, P1 to P7, Q1 to Q7, S1 to S7 and T1 to T7, evaluations 1 to 3 are carried out similarly to lead battery A1. The evaluation results are shown in Table 5.

[Table 5] Powder resistance ratio R2 / R1 Ratio of the specific surface s2 / s1 First organic expander Second organic expand er (mass%) PSOC lifetime performance Low temperature high speed discharge performance Regenerative charge acceptance Amount of electrolyte lost (Dimensions%) s element contains content (µmol / g) O1 152 16 00:05 6000 0.1 115 112 97 100 O2 24 118 112 99 100 O3 33 119 111 100 100 O4 40 120 110 100 101 O5 112 122 110 101 102 O6 237 121 110 102 103 O7 376 116 109 104 106 P1 152 16 0.1 6000 0.1 116 109 98 100 P2 24 118 111 99 100 P3 33 119 112 99 100 P4 40 121 112 99 100 P5 112 123 113 100 101 P6 237 120 112 100 102 P7 376 118 110 102 107 Q1 152 16 0.1 4000 0.1 114 109 97 100 Q2 24 116 110 99 100 Q3 33 117 111 99 100 Q4 40 118 112 100 100 Q5 112 120 112 100 101 Q6 237 116 111 101 102 Q7 376 112 109 103 105 S1 152 16 0.1 8000 0.1 120 117 98 100 S2 24 125 119 99 100 S3 33 126 119 100 101 S4 40 125 118 100 101 S6 112 122 116 100 101 S6 237 119 115 101 103 S7 376 116 113 104 108 T1 15 6 0.1 6000 0.1 112 110 96 101 T2 20 115 111 99 101 T3 28 116 112 100 102 T4 36 117 113 100 102 T5 109 118 112 101 102 T6 223 116 111 101 103 T7 362 115 109 103 106

As shown in Table 5, at a specific surface area ratio s2 / sl of 20 or more, the low-temperature high-speed discharge performance after high-temperature cycles is further improved while maintaining a long PSOC life, and a high regenerative charge acceptance can be partially guaranteed (O2 to O7, P2 to P7, Q2 to Q7, S2 to S7, T2 to T7). The reason why a high low temperature high speed discharge can be achieved is presumably because the adsorption of the organic expander is suppressed because the specific surface area of each carbon material is in an appropriate range. PSOC lifetime performance is significantly improved when the specific surface area ratio s2 / sl is 20 or more, compared to the specific surface area ratio s2 / sl of less than 20. This is because the reduction reaction of lead sulfate proceeds easily when the specific surface area ratio s2 / sl is 20 or more. If the specific surface area ratio s2 / sl is 240 or less, the details are not clear, but the increase in electrolyte loss after the cycle is suppressed (O1 to O6, P1 to P6, Q1 to Q6, S1 to S6, T1 to T6).

<< Lead-acid batteries U1 to U8 >>>>

By adjusting the average aspect ratio of the carbon material used, the average aspect ratio obtained by the above-described method is adjusted to the value shown in Table 6. Apart from this, the lead-acid batteries U1 to U8 are constructed similarly to the lead-acid battery A1, except that a negative electrode plate is made similar to the lead-acid battery A7 and the obtained negative electrode plate is used.

<< Lead acid batteries V1 to V8 >>>>

By adjusting the average aspect ratio of the carbon material used, the average aspect ratio obtained by the above-described method is adjusted to the value shown in Table 6. Apart from that, the lead-acid batteries V1 to V8 are constructed similarly to the lead-acid battery A1, except that a negative electrode plate is made similar to the lead-acid battery B7 and the obtained negative electrode plate is used.

<< Lead acid batteries W1 to W8 >>>>

By adjusting the average aspect ratio of the carbon material used, the average aspect ratio obtained by the above-described method is adjusted to the value shown in Table 6. Apart from this, the lead-acid batteries W1 to W8 are constructed similarly to the lead-acid battery A1, except that a negative electrode plate is made similar to the lead-acid battery C7 and the obtained negative electrode plate is used.

<< Lead acid batteries X1 to X8 >>>>

By adjusting the average aspect ratio of the carbon material used, the average aspect ratio obtained by the above-described method is adjusted to the value shown in Table 6. Apart from this, the lead-acid batteries X1 to X8 are constructed similarly to the lead-acid battery A1, except that a negative electrode plate is made similar to the lead-acid battery D7 and the obtained negative electrode plate is used.

<< Lead acid batteries Y1 to Y8 >>>>

By adjusting the average aspect ratio of the carbon material used, the average aspect ratio obtained by the above-described method is adjusted to the value shown in Table 6. Apart from this, the lead-acid batteries Y1 to Y8 are constructed similarly to the lead-acid battery A1, except that a negative electrode plate is made similar to the lead-acid battery B2 and the obtained negative electrode plate is used.

For lead-acid batteries U1 to U8, V1 to V8, W1 to W8, X1 to X8 and Y1 to Y8, similar to lead-acid battery A1, the PSOC lifespan is evaluated by evaluation 1 and evaluation 2. The evaluation results are shown in Table 6. When the average aspect ratio of the first carbon material is set, the powder resistance ratio R2 / R1 and the specific surface ratio s2 / sl also change. Table 6 shows these values together.

[Table 6] PulverwiderstandsverhältnisR2 / R1 Specific surface ratios2 / s1 First average aspect ratio of the carbon material First organic expander Second organic expander (mass%) PSOC lifetime) performance Low-temperature high-rate discharge performance (Dimensions%) s element content (µmol / g) U1 105 23 1 00:05 6000 0.1 114 109 U2 110 23 1.5 116 110 U3 125 23 5 118 110 U4 138 24 11 119 111 U5 143 24 16 120 111 U6 148 24 30 119 112 U7 152 24 35 118 112 U8 154 26 45 111 110 V1 105 23 1 0.1 6000 0.1 114 110 V2 110 23 1.5 117 111 V3 125 23 5 119 112 V4 138 24 11 119 112 V5 143 24 16 121 113 V6 148 24 30 120 112 V7 152 24 35 118 111 V8 154 26 45 112 109 W1 105 23 1 0.1 4000 0.1 113 109 W2 110 23 1.5 115 110 W3 125 23 5 116 111 W4 138 24 11 117 111 W5 143 24 16 117 112 W6 148 24 30 116 111 W7 152 24 35 116 110 W8 154 26 45 111 109 X1 105 23 1 0.1 8000 0.1 120 115 X2 110 23 1.5 123 116 X3 125 23 5 125 117 X4 138 24 11 126 119 X5 143 24 16 128 119 X6 148 24 30 126 119 X7 152 24 35 125 119 X8 154 26 45 112 110 Y1 15 109 1 0.1 6000 0.1 114 109 Y2 17 109 1.5 117 110 Y3 20 109 5 117 111 Y4 24 110 11 118 112 Y5 27 110 16 117 111 Y6 30 110 30 116 110 Y7 32 111 35 115 110 Y8 35 112 45 110 109

As shown in Table 6, when the average aspect ratio of the first carbon material is 1.5 or more, the PSOC life is further improved (U2 to U8, V2 to V8, W2 to W8, X2 to X8, Y2 to Y8). This is presumably because at an average aspect ratio of 1.5 or more, a conductive network is easily formed in the negative electrode material and the formed conductive network can be easily maintained because the drainage of the organic expander is suppressed during high temperature cycles. On the other hand, the PSOC lifetime and the low-temperature high-speed discharge performance tend to decrease with increasing average aspect ratio of the first carbon material (U8, V8, W8, W8, X8, Y8). This is probably because it becomes difficult to form a conductive network because cracks may appear on the surface of the negative electrode plate when the negative electrode plate is manufactured. From the viewpoint of further enhancing the effect of improving the PSOC lifetime performance and low temperature high speed discharge performance after high temperature cycles, the average aspect ratio of the first carbon material is preferably 1.5 or more and 35 or less (U2 to U7, V2 to V7, W2 to W7, X2 to X7, Y2 to Y7).

INDUSTRIAL APPLICABILITY

The lead-acid battery according to an aspect of the present invention is applicable to a valve-regulated lead-acid battery and a flooded lead-acid battery, and can be used as a power source for starting a car, a motorcycle, or the like, and as a power source for an industrial electrical storage device for storing natural energy, in electric vehicles (such as forklifts) and the like.

LIST OF REFERENCE NUMBERS

1:

Lead-acid battery

2:

Negative electrode plate

2a:

Ear portion of the negative electrode plate

3:

Positive electrode plate

4:

seperator

5:

Positive electrode band

6:

Negative electrode band

7:

Positive electrode pole

8th:

execution

9:

Negative electrode pole

11:

element

12:

container

13:

partitions

14:

cell chamber

15:

cover

16:

Connection for negative electrodes

17:

Connection for positive electrode

18:

vent plug

QUOTES INCLUDE IN THE DESCRIPTION

This list of documents listed by the applicant has been generated automatically and is only included for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

Patent literature cited

• WO 2015/087749 A [0002]
• WO 2012/017702 A [0002]

Claims (22)

Lead-acid battery, comprising: a negative electrode plate; a positive electrode plate; and an electrolytic solution, wherein the negative electrode plate includes a negative electrode material containing a carbon material and an organic expander, the carbon material includes a first carbon material with a particle size of 32 pm or more and a second carbon material with a particle size of less than 32 μm, a ratio R2 / R1 of the powder resistance R2 of the second carbon material to the powder resistance R1 of the first carbon material is 15 or more and 155 or less, the organic expander includes a first organic expander with an aromatic ring and a second organic expander with an aromatic ring, an elemental sulfur content in the first organic expander is 4000 µmol / g or more, and the elemental sulfur content in the second organic expander is 2000 µmol / g or less. Lead-acid battery after Claim 1 wherein the content of the first organic expander in the negative electrode material is 0.02 mass% or more and 0.12 mass% or less and the content of the second organic expander is 0.05 mass% or more and 0.7 mass% % or less. Lead battery after Claim 1 or 2 , wherein a ratio s2 / s1 of a specific surface s2 of the second carbon material to a specific surface s1 of the first carbon material is 20 or more and 240 or less. Lead-acid battery according to one of the Claims 1 to 3 , wherein an average aspect ratio of the first carbon material is 1.5 or more and 35 or less. Lead acid battery according to one of the Claims 1 to 4 , wherein the elemental sulfur content in the first organic expander is 9000 µmol / g or less. Lead acid battery according to one of the Claims 1 to 5 , wherein the elemental sulfur content in the first organic expander is 6000 µmol / g or more. Lead acid battery according to one of the Claims 1 to 6 , wherein the elemental sulfur content in the second organic expander is 1000 µmol / g or less. Lead acid battery according to one of the Claims 1 to 7 , wherein the elemental sulfur content in the second organic expander is 400 µmol / g or more. Lead-acid battery according to one of the Claims 1 to 8th wherein a content of the first organic expander in the negative electrode material is 0.05 mass% or more. Lead-acid battery according to one of the Claims 1 to 9 wherein a content of the first organic expander in the negative electrode material is 0.10 mass% or less. Lead-acid battery according to one of the Claims 1 to 10 wherein a content of the second organic expander in the negative electrode material is 0.5 mass% or less. Lead-acid battery according to one of the Claims 1 to 11 wherein a content of the first carbon material in the negative electrode material is 0.05 mass% or more. Lead-acid battery according to one of the Claims 1 to 12 wherein a content of the first carbon material in the negative electrode material is 3.0 mass% or less. Lead-acid battery according to one of the Claims 1 to 13 wherein a content of the second carbon material in the negative electrode material is 0.03 mass% or more. Lead-acid battery according to one of the Claims 1 to 14 wherein a content of the second carbon material in the negative electrode material is 1.0 mass% or less. Lead-acid battery according to one of the Claims 1 to 15 wherein the ratio R2 / R1 is 30 or more. Lead-acid battery according to one of the Claims 1 to 16 wherein the ratio R2 / R1 is 130 or less. Lead-acid battery according to one of the Claims 1 to 17 , the ratio s2 / sl being 30 or more. Lead-acid battery according to one of the Claims 1 to 18 , wherein the ratio s2 / sl is 120 or less. Lead-acid battery according to one of the Claims 1 to 19 , wherein an average aspect ratio of the first carbon material is 5 or more. Lead-acid battery according to one of the Claims 1 to 20 , wherein an average aspect ratio of the first carbon material is 30 or less. Lead-acid battery according to one of the Claims 1 to 21 wherein the first carbon material includes at least graphite and the second carbon material includes at least carbon black.

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