JP2002367613A - Lead storage battery - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a lead storage battery with higher efficiency of charging property than before, and to obtain a carbon material with excellent charge acceptability used for the lead storage battery. SOLUTION: The efficiency of charging property of the lead storage battery is heightened and charge acceptability is improved by using carbon materials like activated carbon or carbon black to which, a simple substance or a compound, having desulfurization catalysis function or SOx oxidation catalysis function, is added or made to hold, as additives to the negative electrode activator. By applying the lead storage battery, having the negative electrode containing the carbon material to which, such an additives is added or made to hold, to an electric automobile with high input and output properties, various kinds of hybrid automobiles, electric power storage systems, elevators, electric power tools, power source systems like uninterrupted power source or scattered power sources, a stable control is made possible.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a lead-acid battery,
Particularly, the present invention relates to a carbon material for a lead storage battery having excellent high-rate charging performance.

[0002]

2. Description of the Related Art Lead-acid batteries are relatively inexpensive and have stable performance as secondary batteries, and thus have become widespread for use as power sources for automobiles as well as for power supplies for portable equipment and for backup of computers. Further, recently, new functions have been reviewed not only as a main power source for electric vehicles but also as a starting power source for hybrid electric vehicles and simple hybrid vehicles and for recovering regenerative current. In these applications, it is particularly important to achieve both high output performance and high input performance.

However, various studies have been made on the high output performance, but the high input performance has not yet reached a level superior to other battery systems.

[0004] High input performance, that is, high rate charging characteristics is largely determined by the characteristics of lead sulfate present in the negative electrode. In a negative electrode active material in a lead-acid battery, in a discharge reaction, metal lead emits electrons and changes to lead sulfate, and in a charging reaction, lead sulfate obtains electrons and changes to metal lead. Lead sulfate generated at the time of discharge is an insulating substance having neither ionic conductivity nor electronic conductivity. Further, the solubility of lead sulfate in lead ions is extremely small. As described above, in addition to the low conductivity of electrons and ions, lead sulfate also has poor solubility in lead ions, so the reaction rate from lead sulfate to metallic lead is slow, and the high-rate charging characteristics are low. It is.

[0005] As a countermeasure against these problems, for example, the amount of carbon added to the negative electrode active material is optimized (Japanese Patent Laid-Open No.
Attempts have been made to improve the charging performance by using metallic tin in the negative electrode active material (JP-A-5-89873).

[0006]

In order to improve the high rate charging characteristics, it is necessary to improve the characteristics of lead sulfate.
The first is to improve the conductivity of lead sulfate, and the second is to increase the solubility of lead sulfate in lead. JP-A-9-
As seen in JP-A-213336, it is possible to improve the electronic conductivity and ionic conductivity of lead sulfate by adding an optimum amount of carbon. However, carbon cannot improve the solubility of lead sulfate in lead. Similarly, when metal tin is contained, the conductivity of lead sulfate can be improved, but the solubility of lead sulfate in lead cannot be improved.

SUMMARY OF THE INVENTION An object of the present invention is to improve the conductivity of lead sulfate and, in addition, to improve the solubility of lead sulfate in lead, so that the charging reaction of the negative electrode active material can proceed smoothly to achieve a high rate of charge. An object of the present invention is to provide a lead-acid battery having excellent performance and a novel carbon material having excellent charge acceptability.

[0008]

Lead-acid battery of the present invention the first SUMMARY OF THE INVENTION The desulfurization catalyze the anode, or, characterized in that the addition of carbon powder containing a simple substance and or compounds of SO _x oxidation catalysis. As the carbon material for a lead storage battery of the present invention, wherein the desulfurization catalyst activity, or a carbon powder containing a simple substance and or compounds of SO _x oxidation catalysis. By using the above carbon powder,
The high rate charging performance of the lead storage battery is improved. In particular, when carbon containing a simple substance and / or a compound having a hydrodesulfurization catalytic action is added, a remarkable effect is obtained in the high-rate charging performance of the lead storage battery.

As the simple substance and / or compound having the desulfurization catalytic action, a main component constituting a desulfurization catalyst or a deodorization catalyst among petroleum refining catalysts, heavy oil desulfurization catalysts, gas production catalysts, or pollution prevention catalysts. By including at least one component, the high rate charging performance of the lead storage battery can be further improved.

The above components include Co, Mo, Ni, Z
It is preferable to include at least one of a simple substance selected from n, Cu, and Mn, or an oxide, a sulfate, or a hydroxide.

[0011] alone with the SO _x oxidation catalysis, and or as a compound, also by including at least one main component constituting the sulfuric acid production catalyst, it can improve the high rate charge performance of lead-acid battery. Particularly, those capable of being sulfated are preferable.

The above-mentioned components include a simple substance selected from alkali metals, alkaline earth metals, V, Mn, and rare earth elements;
Alternatively, it is desirable to include at least one of an oxide and a sulfate.

Second, the lead storage battery of the present invention is characterized in that the following carrier is added to the negative electrode. That is, Hf,
Nb, Ta, W, Ag, Zn, Ni, Co, Mo, C
u, V, Mn, Ba, K, Cs, Rb, Sr, Na, desirably Ni, Co, Mo, Cu, V, Mn, Ba,
Simple substance or oxide of K, Cs, Rb, Sr, Na,
Alternatively, a carrier in which at least one of a sulfate, a hydroxide, and a carbide is supported on carbon powder is added. By using these carriers, the high-rate charging performance of the lead storage battery is improved.

The above-mentioned atomic species are used in a weight ratio of 1 per element.
0 ppm or more, 5000 ppm or less, preferably 50 pp
By adding to the carbon in the range of not less than m and not more than 1000 ppm, the high-rate charging performance of the lead storage battery can be further improved.

The carbon used in the present invention includes carbon black, acetylene black, natural graphite, artificial graphite,
Pyrolytic carbon, coke, isotropic graphite, mesophase carbon, pitch-based carbon fiber, vapor-grown carbon fiber, carbon fluoride, nanocarbon, activated carbon, activated carbon fiber, PAN
By using at least one of the carbon fibers, excellent high-rate charging performance can be exhibited. Some of these carbons have various primary particle diameters, various specific surface areas, oil absorptions obtained with various dibutyl phthalates, and various apparent densities, but they can be applied to any carbon. It is.

The average primary particle size of the simple substance or the compound supported on the support is 0.1 nm or more and 1000 nm or more.
It is desirable to be within the following range. The average primary particle size used herein is an average value of primary particle sizes obtained by observation using a transmission electron microscope. In the case of the carrier, the size of the primary particle size obtained varies depending on the firing conditions such as the firing temperature and the firing atmosphere. For example, 30 in air
Around 0 ° C, around 350 ° C in nitrogen, and 370 in hydrogen
In the vicinity of ° C., a carrier having an average primary particle size in the above range is obtained.

Third, the lead storage battery of the present invention is characterized in that the following activated carbon and / or carbon black is added to the negative electrode. That is, Cu, Ni, Zn, Mn, Al,
Activated carbon containing at least one of Si, K, and Mg alone or a compound is added. The carbon powder added to the lead storage battery of the present invention includes Cu, Ni, Zn,
Activated carbon containing at least one kind or a compound of Mn, Al, Si, K, and Mg, and / or carbon black. Activated carbon and carbon black have a complicated pore structure. These pores contain various impurity elements. Among them, in particular, by using activated carbon or carbon black containing at least one kind or a compound of at least one of Cu, Ni, Zn, Mn, Al, Si, K, and Mg as an impurity element, a high-rate charge of a lead storage battery is achieved. Performance can be improved.

As such activated carbon, it is preferable to use activated carbon having a Cu content of more than 5 ppm by weight and less than 15,000 ppm. Since activated carbon is a natural product, the raw material of which is used as a raw material, Cu, Mn, Al, Si, and K derived from natural products are included in a large amount. In particular, in a region where the content of Cu is more than 5 ppm by weight and less than 15000 ppm, high-rate charging performance and charge acceptability of the negative electrode of the lead battery can be significantly improved.

Examples of such carbon black include N
It is desirable to use furnace black in which the total content of i, Cu, Zn, and Mn is greater than 1 ppm by weight and less than 1000 ppm. Furnace black is made from heavy oil, which contains many impurities, and thus contains a large amount of Ni, Cu, Zn, and Mn derived from the raw material. In particular, in the region where the total content of Ni and Cu is more than 1 ppm by weight and less than 1000 ppm, high-rate charging performance and charge acceptability of the negative electrode of the lead battery can be significantly improved.

Finally, the carbon material for a lead storage battery according to the present invention comprises Hf, Nb, Ta, W, Ag, Zn, Ni, Co,
Mo, Cu, V, Mn, Ba, K, Cs, Rb, Sr,
It is a carbon powder containing or carrying a simple substance selected from at least one of Na, an oxide, a sulfate, a hydroxide, or a carbide. The carbon powder may be added to the electrolyte solution of the lead-acid battery or to the electrode surface. In either case, the effect of promoting the start of charging is obtained. As a method for containing the simple substance, oxide, sulfate, hydroxide, or carbide, a wet supporting method is preferable.

According to the present invention, energy loss due to gas generation is small even at a large current charge of 2 C or more, and the high-efficiency charge performance of a lead storage battery can be improved. Here, 2C is a current value required to discharge the entire discharge capacity of the battery in 0.5 hours, and 1C is a current value required to discharge the entire discharge capacity of the battery in 1 hour.

A feature of the present invention is that these catalysts have an interaction with sulfur (S) which is common to them, that is, at least one of them has a strong adsorptivity between the element in the catalyst and sulfur (S). This is the characteristic that is used. For example, in desulfurization of crude oil and the like, desulfurization of thiophenes is generally well known. In the benzothiophene, S in the benzothiophene is adsorbed on the active site of the catalyst, and is simultaneously hydrogenated and eliminated as H ₂ S, whereby the desulfurization reaction proceeds. This also applies to the reaction of dissociation of lead sulfate into lead ions, which is the elementary charge reaction of the negative electrode of a lead-acid battery, and the sulfate groups in the lead sulfate are adsorbed on the active sites of the catalyst and are simultaneously hydrogenated. than it is released into the electrolytic solution as ^- HSO ₄ Te. For lead-acid battery, for sulfuric acid concentrations in the electrolyte and high 30 vol%, SO ₄ ^2-
In can not be dissociated, mostly, HSO ₄ ^- dissociates as. This also, HSO ₄ ^- be dissipated can be said to play an important role in improving the solubility of lead sulfate as.

On the other hand, elements which can be sulfated in order in ipecac in the molecule are used primarily the SO _x in the sulfuric acid production catalyst. Sulfates such as V ₂ O ₅ and Rb, K, Cs are SO _x
It is known that VOSO ₄ or Me ₂ S ₂ O ₇ (Me is Rb, K, Cs) is taken into the molecule by incorporation into the molecule. This also applies to the reaction in which lead sulfate, which is the elementary charge reaction of the negative electrode of a lead-acid battery, dissociates into sulfate ions and lead ions, and the above-described oxide or sulfate dissociates sulfate ions in the molecule. Incorporation can promote dissolution.

The negative electrode of the present invention has, for example, a desulfurization catalytic action,
It is characterized by adding carbon containing a simple substance or various compounds having a specific catalytic action such as an SO _x oxidation catalytic action or a sulfuric acid production catalytic action. Carbon is a substance that is indispensable to enhance the conductivity of lead sulfate, but cannot provide sufficient charging performance by itself. Therefore, it is necessary to provide a simple substance having a specific catalytic action or various compounds. Conversely, if only a simple substance having a specific catalytic action or only various compounds is added, a conductive effect such as carbon cannot be obtained, so that a sufficiently high rate charging performance cannot be obtained.

In order to make the catalytic action more effective, it is desirable to disperse a simple substance or various compounds having a catalytic action on carbon as particles having a fine particle diameter.

Activated carbon having a complex pore structure, that is, a porous structure, a microstructure, a mesopore structure, a micropore structure, a submicropore structure, a macropore structure, a structure having an internal surface, a structure having a high specific surface area, etc. Some carbon blacks
Some of the pores contain the above-mentioned catalytic element or various compounds in trace amounts. This is advantageous for further exerting the catalytic action.
Activated carbon and carbon black have the function of adsorbing various molecules and ions to their complicated pores. That is,
During the reaction of dissociation of lead sulfate, which is a charge element reaction of a negative electrode of a lead storage battery, into sulfate ions and lead ions, sulfate ions are easily adsorbed to the pores of the activated carbon. The pore part, due to the presence of single or various compounds having a catalytic action of the above, readily sulfate ions HSO ₄ ^- dissociation as, or is incorporated into the oxide or sulfate, The charging reaction proceeds smoothly. As described above, carbons made from natural products such as activated carbon and carbon black, and heavy oils, etc., often contain a large amount of catalytically simple substances or various compounds from the beginning. If the carbon is adjusted to an optimum concentration range, excellent high-rate charging performance can be obtained without carrying.

Further, since the carbon powder of the present invention contains the above-mentioned specific element or compound having a high catalytic action,
If added to the electrolyte or electrode surface of a lead storage battery, the start of charging can be promoted. Since the carbon can be adsorbed at the reaction interface of the active material, passivation of lead sulfate called sulfation can be suppressed, and even when a complete discharge is performed, passivation does not progress. The charge acceptance is greatly improved.

As described above, when the negative electrode of the present invention is used,
Lead-acid batteries applicable to industrial batteries that require high input and output characteristics such as electric vehicles, parallel hybrid electric vehicles, simple hybrid vehicles, power storage systems, elevators, power tools, uninterruptible power supplies, and distributed power supplies can get.

[0029]

DESCRIPTION OF THE PREFERRED EMBODIMENTS (Examples) The present invention will be described in more detail with reference to specific examples, but the present invention is not limited to the examples unless it exceeds the gist of the invention. Also,
An example to which the present invention is applied will be described in detail while comparing with a lead storage battery (comparative example) manufactured to confirm the effect of the example.

First, a method for manufacturing the lead storage batteries of the respective examples and comparative examples will be described. Note that, in the examples following Example 2 and Comparative Examples 1 and 2, the description of the same manufacturing method as in Example 1 is omitted, and different parts will be described.

(Example 1) (Preparation of simple substance and / or compound-supporting carbon) In preparing simple substance and / or compound-supporting carbon, first, aqueous solutions of nickel nitrate having various concentrations were prepared, and acetylene black was added thereto as carbon powder. 10 g and 0.1 g of a surfactant were added, and the mixture was stirred in a water bath at 40 ° C. Sodium hydroxide was added dropwise until the pH reached 7, the solution was filtered, and the obtained precipitate was washed with distilled water, dried at 120 ° C for 2 hours, and then in air, nitrogen or hydrogen. , 300-
It was baked at 500 ° C. for 30 minutes to produce nickel-supported carbon. From XRD (X-raydiffraction),
It was found that NiO was generated by firing in air, Ni by firing in hydrogen, and a mixture of NiO and Ni by firing in nitrogen. Here, the X-ray diffraction method is a test method used for crystal structure analysis, in which the intensity of a diffraction line is measured while changing the diffraction angle of the X-ray, and the angle and the intensity are analyzed. For the measurement of X-ray diffraction of the present invention, a normal powder diffraction method is applied,
CuKα radiation was used as the radiation source.

Table 1 shows an ICP analysis (Inductively coupled).
This shows the Ni content in carbon determined by plasma spectrometry (inductively coupled high frequency plasma spectroscopy). here,
ICP analysis is a test method that can detect and quantify multiple elements simultaneously with high sensitivity. The sample was placed in an acidic solution such as hydrochloric acid or nitric acid boiled at 100 ° C. or higher, and boiled for 2 to 3 hours to dissolve the metal, and the solution was measured.

[0033]

[Table 1]

(Preparation of Negative Electrode Plate) In preparing a negative electrode plate, first, 0.3% by weight of lignin and 0.2% by weight of barium sulfate or strontium sulfate based on lead powder and the above-mentioned present invention are used. Of a simple substance and / or a compound-supporting carbon powder in an amount of 0.2 to 1.0% by weight,
A mixture obtained by kneading the mixture was prepared. Next, lead powder and 13% by weight of dilute sulfuric acid (specific gravity 1.26, 20 ° C.) with respect to the lead powder,
A negative electrode active material paste is prepared by kneading 12% by weight of water with respect to the lead powder, and 73 g of the negative electrode active material paste is filled in a current collector made of a lattice of a lead-calcium alloy.
After aging for 18 hours at a temperature of 50 ° C. and a humidity of 95%, the product was left at a temperature of 110 ° C. for 2 hours and dried to produce an unformed negative electrode.

(Preparation of Positive Electrode Plate) In preparing the positive electrode plate, first, lead powder, 13% by weight of dilute sulfuric acid (specific gravity 1.26, 20 ° C.) based on lead powder and 12% by weight based on lead powder % Of water was mixed to prepare a positive electrode active material paste. next,
After filling 85 g of the positive electrode active material paste into a current collector made of a lattice of a Pb-calcium alloy, the mixture was left to stand at a temperature of 50 ° C. and a humidity of 95% for 18 hours to be aged.
It was left to dry at 2 ° C. for 2 hours to produce an unformed positive electrode plate.

FIG. 1 is a view showing an embodiment of the present invention. Six unformed negative electrode plates 1 and five unformed positive electrode plates 2 were laminated with a glass fiber separator 3 interposed therebetween, and electrode plates having the same polarity were connected to each other with a strap to prepare an electrode plate group 4. . 5 is a positive electrode strap, and 6 is a negative electrode strap. Further, the electrode group 4 is placed in the battery case 7 for 18 minutes.
After being connected and arranged in series, a dilute sulfuric acid electrolyte having a specific gravity of 1.05 (20 ° C.) was injected to produce an unformed battery. After the unformed battery was formed at 9A for 42 hours, the electrolyte was discharged,
A diluted sulfuric acid electrolyte having a specific gravity of 1.28 (20 ° C.) was injected again. A lid 10 having a positive electrode terminal 8 and a negative electrode terminal 9 welded together and having an exhaust valve
To complete the lead-acid battery. The capacity of the obtained battery is 18 Ah, and the average discharge voltage is 36 V.

Here, the discharge voltage is 36 V and the charge voltage is 4
The battery of 2V is referred to as a 42V battery, but the present invention is not limited to this voltage range. A predetermined voltage can be obtained by connecting a plurality of single batteries in series. In the embodiment of the present invention, a 42V battery is manufactured, and various characteristics of the present invention do not change in this voltage range.

In the high-rate charging characteristic test, first, the obtained lead-acid battery was charged at a constant current and a constant voltage for 16 hours at a charging current of 6 A and an upper limit voltage of 44.1 V, and then charged at a discharging current of 4 A.
Discharge was performed until the voltage reached 1.5 V, and the discharge capacity was confirmed. Again, after 16 hours of constant current and constant voltage charging at a charging current of 6 A and an upper limit voltage of 44.1 V, 10% of the previously obtained discharge capacity was discharged at a discharging current of 4 A, and a depth of charge (SOC) of 90% was obtained.
%. From this state, the charging voltage Vc when charging at a charging current of 40 A for 30 seconds was obtained.

As the charging reaction proceeds, the charging voltage Vc increases, and hydrogen gas is generated from the negative electrode by electrolysis of water. The amount of generated hydrogen gas increases with an increase in the charging voltage Vc, and eventually becomes depleted of water and reaches the end of its life.
Therefore, the charging voltage Vc naturally has an upper limit during charging, and it is necessary to suppress the voltage to a voltage lower than the upper limit. In this battery, the upper limit voltage at which the gas generation amount reaches the permissible limit is 45 V, and the upper limit voltage at which gas generation does not occur is 43.2 V. Therefore, these batteries were evaluated based on these values. In other words, the evaluation criterion is preferably such that the charging voltage is lower.

FIG. 2 shows the relationship between the Ni content (ppm) of acetylene black supported on nickel fired in air and the charging voltage Vc. Regardless of the Ni content, it was lower than the upper limit voltage of 45 V which reached the allowable limit value of the gas generation amount, and showed good characteristics in high rate charging performance. In particular, when the Ni content was 5000 ppm or less and 10 ppm or more, the charging voltage Vc was lower than 43.2 V, showing remarkably good characteristics in high-rate charging performance. In addition, the Ni content is 1
In the range of 000 ppm or less and 50 ppm or more, the charging voltage Vc was 43 V or less, and further excellent high-rate charging characteristics were exhibited.

FIG. 3 shows the relationship between the firing temperature of nickel-supported acetylene black fired in nitrogen and the charging voltage Vc.
At any temperature, the charging voltage Vc was lower than 45 V, indicating good characteristics in high-rate charging performance.
In particular, the charging voltage Vc was lower than 43.2 V when the firing temperature was in the range of 350 ° C. or more and 400 ° C. or less, and further excellent high-rate charging performance was exhibited. The average primary particle size of NiO or metallic Ni obtained by TEM of the support fired at 350 ° C. or more and 400 ° C. or less was in the range of 0.1 to 1000 nm.

FIG. 4 shows the relationship between the calcination temperature of nickel-supported acetylene black fired in hydrogen and the charging voltage Vc.
At any temperature, the charging voltage Vc was lower than 45 V, indicating good characteristics in high-rate charging performance.
Particularly, when the firing temperature is around 450 ° C., the charging voltage Vc is 43.
It was lower than 2 V, and further excellent high rate charging performance was exhibited. The average primary particle size of Ni obtained by TEM of the support baked at around 450 ° C. was in the range of 0.1 to 1000 nm.

(Comparative Example 1) A lead-acid battery was prepared in the same manner as in Example 1 using acetylene black which does not support a single substance or a compound, and high-rate charging performance was evaluated. The Ni content of acetylene black alone and / or acetylene black not carrying a compound was less than 1 ppm by ICP analysis, which was below the detection limit. It was found that the charging voltage Vc increased to 48 V, which was higher than the upper limit voltage of 45 V, and the high-rate charging performance was inferior.

(Example 2) In the production of simple substance and / or compound-supporting carbon, nickel-supporting carbon was produced in the same manner as in Example 1 by using various carbons shown in Table 2 as carbon powder.

A lead-acid battery was fabricated in the same manner as in Example 1,
The high rate charging performance was evaluated. Table 2 shows the charging voltage Vc.
In any of the carbons, the charging voltage Vc was lower than 45 V, and good characteristics were exhibited in high-rate charging performance. Also in the mixed system of these carbons, similarly, the charging voltage Vc was lower than 45 V, and it was confirmed that good characteristics were exhibited in the high-rate charging performance.

[0046]

[Table 2]

(Comparative Example 2) Ni content was measured by ICP for various carbons shown in Table 3 which did not support a simple substance and / or a compound. Ni content was 1
It was below the detection limit at less than ppm. A lead-acid battery was produced in the same manner as in Example 1 except that these were used alone or in place of the compound-supporting carbon, and high-rate charging performance was evaluated. It was found that the charging voltage Vc was higher than 45 V, and the high rate charging performance was inferior.

[0048]

[Table 3]

Example 3 Various activated carbons were used as carbon. Table 4 shows that the results of ICP analysis show that copper, nickel,
Indicates the content of manganese, aluminum, silicon, potassium, and magnesium. Example 1 using activated carbon of various impurities in place of simple substance and / or compound-supported carbon
A lead-acid battery was produced in the same manner as in Example 1 and the high-rate charging performance was evaluated. Table 4 shows the charging voltage Vc. Both are charging voltage Vc
Was lower than 45 V, showing good characteristics in high-rate charging performance.

[0050]

[Table 4]

(Example 4) Activated carbon was used as carbon. The raw material of activated carbon is washed with 1N (1N: 1 mol / l) hydrochloric acid for the time shown in Table 5, washed with water until the pH becomes 7, dried, and calcined. Activated carbon was produced. Table 5 shows the Cu content obtained from the results of the ICP analysis. A lead-acid battery was produced in the same manner as in Example 1, except that various types of coconut activated carbon having a Cu content were used alone or in place of the compound-supporting carbon, and high-rate charging performance was evaluated. Table 5 shows the charging voltage Vc. At any Cu content, the charging voltage Vc was lower than 45 V, indicating good characteristics in high-rate charging performance. Further, when the Cu content is more than 5 ppm,
The charging voltage Vc was lower than 43.2 V in a smaller region, and further excellent characteristics in high-rate charging performance were exhibited.

[0052]

[Table 5]

(Example 5) As a simple substance and / or a compound-supported carbon-supported material, instead of nickel of Example 1,
Various simple substances and / or compounds shown in Table 6 were supported on various carbon blacks shown in Table 3. As shown in Table 6, the form of the carried material was a single substance, an oxide, a sulfate, a hydroxide, or a carbide, or a mixture of these, and was analyzed by X-ray diffraction. More confirmed. A lead-acid battery was produced in the same manner as in Example 1, and high-rate charging performance was evaluated. FIG. 5 shows the relationship between the content of the supported element and the charging voltage Vc. All showed good characteristics in high rate charging performance. In particular, the charging voltage Vc was lower than 43.2 V when the content of the supported element was 5000 ppm or less and 10 ppm or more, showing remarkably good characteristics in high-rate charging performance. When the content was 1,000 ppm or less and 50 ppm or more, the charging voltage Vc was 43 V or less, and further excellent high-rate charging characteristics were exhibited. Similarly, even in a system in which a plurality of these supported simple substances and / or compounds are mixed, the charging voltage Vc is also 4
It was lower than 5 V, and it was confirmed that good characteristics were exhibited in the high rate charging performance.

[0054]

[Table 6]

(Example 6) Various substances and / or compounds shown in Table 7 were substituted for the substances and / or compounds of Example 5 as a carrier for carbon supported on the substance and / or compound.
On carbon black of the type shown in Table 1. As shown in Table 7, the form of the supported material was a single substance, an oxide, a sulfate, a hydroxide, or a carbide, or a mixture thereof. More confirmed. A lead-acid battery was produced in the same manner as in Example 1, and high-rate charging performance was evaluated. Table 7 shows the charging voltage Vc. All were lower than 45 V and showed good characteristics in high-rate charging performance. Also, in a system in which a plurality of these supported simple substances and / or compounds were mixed, similarly, the charging voltage Vc was lower than 45 V, and it was confirmed that good characteristics were exhibited in high-rate charging performance.

[0056]

[Table 7]

Example 7 In the production of carbon containing a simple substance and / or a compound having a catalytic action for desulfurization or catalytic action for SO _x oxidation, first, 1 wt% of a catalyst shown in Table 8 was sampled, added to acetylene black and mortared. And mixed well. A lead-acid battery was produced in the same manner as in Example 1, and high-rate charging performance was evaluated. All were lower than 45 V and showed good characteristics in high rate charging performance. Particularly, by using a desulfurization catalyst, a deodorization catalyst, or a sulfuric acid production catalyst of a petroleum refining catalyst, a heavy oil desulfurization catalyst, a gas production catalyst, a pollution control catalyst, the charging voltage Vc becomes lower than 43.2 V, and a high rate of charge is achieved. It showed remarkably good characteristics in performance. In addition, Co, Mo, Ni, Z are used in desulfurization catalysts and deodorization catalysts for petroleum refining catalysts, heavy oil desulfurization catalysts, gas production catalysts, pollution control catalysts, and the like.
n, Cu, Mn simple substance or compound, and alkali metal, alkaline earth metal, V, M
In the case of n or a rare earth element alone or a compound, the charging voltage Vc was 43 V or less, and further excellent high-rate charging characteristics were exhibited. In addition, it was also confirmed that, in a system in which a plurality of these supported simple substances and / or compounds were mixed, good characteristics were similarly exhibited in high-rate charging performance. In addition, it was confirmed that the system using carbon of the type shown in Table 3 as the carbon powder also exhibited good characteristics with high rate charging performance.

[0058]

[Table 8]

In addition to elements such as Ni, Co, Mo, and Cu, which have a low hydrogen overvoltage, hydrogen generation occurs simultaneously with the charging reaction. FIG. 6 shows a model of the reaction mechanism. Water molecules in the electrolytic solution dissociate on the above elements, and hydrogen ions are once adsorbed. Sulfate ions dissociated from lead sulfate are also adsorbed there and combined with hydrogen ions to be released as HSO ₄ ^- ions into the electrolyte. On the other hand, lead ions transfer electrons from carbon and precipitate as metallic lead. In this way, the charging reaction easily proceeds, and as a result, the high-rate charging performance of the lead storage battery is improved. Accordingly, in addition to those shown here, a simple substance or a compound having a catalytic action for desulfurization causes the reaction to proceed by the same mechanism, and thus the lead storage battery similarly has a high rate of charge performance.

In addition to V, Mn, an alkali metal, an alkaline earth metal, a rare earth element, and the like, in the case of a simple substance or a compound which is easily sulphated, the sulphation proceeds even in the battery. FIG. 7 shows a model of the reaction mechanism. Sulfate ions dissociated from lead sulfate are adsorbed on the surface of the element and easily incorporated into the element alone or into a compound. On the other hand, lead ions transfer electrons from carbon and precipitate as metallic lead. In this way, the charging reaction easily proceeds, and as a result, the high-rate charging performance of the lead storage battery is improved. Thus, where in addition to those shown in, since the reaction proceeds in a similar mechanism by itself or a compound of SO _x oxidation catalysis, high rate charging performance is improved in the lead-acid battery in the same way.

(Example 8) (Evaluation of monopolarity) Using various simple substances shown in Table 9, or oxides, sulfates, hydroxides, or carbides, acetylene black of 4000 to 5000 was used.
Various carbon powders added or supported so as to have an addition amount in the range of ppm were produced. This was added to lead powder in an amount of 0.5% by weight, and then pressed and used as a working electrode. A cyclic voltammogram was measured using a platinum net as a counter electrode, a silver / silver chloride electrode as a reference electrode, and dilute sulfuric acid having a specific gravity of 1.26 (20 ° C.) as an electrolyte. The scanning speed was 50 mV / min and the scanning potential was -800 mV (silver /
The range is from -200 mV (based on silver / silver chloride electrode) to silver chloride electrode (based on silver chloride electrode). Before the test, -1400 mV (silver /
A reduction treatment was performed for 5 minutes using a silver chloride electrode (based on a silver chloride electrode). Regarding the current-potential characteristics studied here, the current density on the vertical axis was evaluated by the absolute value (log | I |) of the log scale. The minimum value of log | I | represents the charge start potential and the discharge start potential. The charge start potential is indicated by Ec, and the discharge start potential is indicated by Ed.

FIG. 8 shows an electrode added with Ni-added carbon,
4 shows the current-potential characteristics of an electrode to which carbon is added and undoped carbon. When the charge start potential is expressed as Ec and the discharge start potential is expressed as Ed, when the magnitude relation between Ec and Ed is compared for Ni-added carbon, it is expressed as Ec> Ed. This indicates that the start of charging was accelerated, and even when the battery was completely discharged, passivation of lead sulfate did not progress, and charge acceptability was significantly improved. On the other hand, for non-added carbon, the magnitude relationship between Ec and Ed is expressed as Ec <Ed, which is opposite to the case for Ni-added carbon. In other words, it indicates that when the start of charging is slow and complete discharge is performed, passivation progresses and the charge acceptability is significantly reduced.

Table 9 shows the evaluation results of the magnitude relation between Ec and Ed of carbon to which various simple substances or compounds are added or supported. Those having a tendency of Ec> Ed have an improved charge acceptability, and thus the evaluation is indicated by ○, and those having a tendency of Ec <Ed are inferior in the charge acceptability, and the evaluation is indicated by x. Hf,
Nb, Ta, W, Ag, Zn, Ni, Co, Mo, C
u, V, Mn, Ba, K, Cs, Rb, Sr, and Na alone or a compound.

[0064]

[Table 9]

Table 1 shows the relationship between the content of impurities such as Cu contained in the carbon black and the charging voltage showing high rate charging performance when various carbon blacks were used for carbon.
0 is shown. Table 10 shows the contents of copper, nickel, manganese, aluminum, silicon, potassium, and zinc from the results of the ICP analysis. A lead-acid battery was prepared in the same manner as in Example 1, except that carbon black having various amounts of impurities was used alone or in place of the compound-supporting carbon, and high-rate charging performance was evaluated. The charging voltage Vc in Table 10 indicates high rate charging performance. In each case, the charging voltage Vc was lower than 45 V, indicating good characteristics in high-rate charging performance. In particular, in furnace black where the total content of Ni, Cu, Zn, and Mn is more than 1 ppm and less than 1000 ppm, the charging voltage Vc is lower than 43.2 V, and further excellent characteristics in high-rate charging performance are exhibited. ing.

[0066]

[Table 10]

[0067]

As described above, according to the present invention, a lead-acid battery excellent in high-rate charging performance can be obtained by using a simple substance having a catalytic action or carbon to which a compound is added or supported. In addition, a carbon material for a lead storage battery having remarkable improvement in charge acceptability can be obtained.

[Brief description of the drawings]

FIG. 1 is a diagram showing an embodiment of the present invention.

FIG. 2 is a characteristic diagram showing the relationship between the Ni content (ppm) of acetylene black fired in air in air and the charging voltage Vc in Example 1 of the present invention.

FIG. 3 is a characteristic diagram showing a relationship between a sintering temperature of nickel-supported acetylene black fired in nitrogen and a charging voltage Vc in Example 1 of the present invention.

FIG. 4 is a characteristic diagram showing a relationship between a firing temperature of nickel-supported acetylene black fired in hydrogen and a charging voltage Vc in Example 1 of the present invention.

FIG. 5 is a characteristic diagram showing a relationship between a supported amount of a supported element and a charging voltage Vc in Example 5 of the present invention.

FIG. 6 is a model diagram showing a desulfurization catalytic action in Example 7 of the present invention.

FIG. 7 is a model diagram showing an SO _x oxidation catalytic action in Example 7 of the present invention.

FIG. 8 is a diagram showing current-potential characteristics in Example 8 of the present invention.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 1 ... negative electrode plate, 2 ... positive electrode plate, 3 ... separator, 4 ... electrode plate group, 5 ... positive electrode strap, 6 ... negative electrode strap, 7 ... battery case, 8 ... positive electrode terminal, 9 ... negative electrode terminal, 10 ... lid.

Continued on the front page (72) Inventor Eiji Hoshi 7-1-1, Omika-cho, Hitachi City, Ibaraki Prefecture Inside Hitachi Research Laboratory, Hitachi, Ltd. (72) Inventor Ren Muranaka 7-1-1, Omika-cho, Hitachi City, Ibaraki Prefecture No. Hitachi, Ltd. Hitachi Research Laboratories (72) Inventor Toroshi Takeuchi 1-1-1, Omika-cho, Hitachi City, Ibaraki Prefecture F-term in Hitachi Research Laboratories Hitachi Research Laboratories 5H050 AA02 BA09 CA06 CB15 DA09 EA01 EA02 EA03 EA04 EA06 EA07 EA08 EA09 EA10 EA12 FA16 FA17 HA01 HA05

Claims (17)

[Claims] 1. A lead-acid battery comprising a negative electrode and the positive electrode and the electrolyte solution, that the negative electrode of carbon containing elemental and / or compound of desulfurization catalytic or SO _x oxidation catalysis has been added Characteristic lead storage battery. 2. The above-mentioned simple substance and / or compound according to claim 1 is a component constituting a desulfurization catalyst or a deodorization catalyst among petroleum refining catalysts, heavy oil desulfurization catalysts, gas production catalysts, or pollution prevention catalysts. A lead-acid battery comprising at least one of the following. 3. The composition according to claim 2, wherein the component is Co, M
A lead-acid battery comprising at least one of a simple substance selected from the group consisting of o, Ni, Zn, Cu, and Mn, an oxide, a sulfate, and a hydroxide. 4. The lead-acid battery according to claim 1, wherein said simple substance and / or compound contains at least one main component constituting a sulfuric acid production catalyst. 5. The composition according to claim 4, wherein the component contains at least one of a simple substance selected from alkali metals, alkaline earth metals, V, Mn, and rare earth elements, oxides and sulfates. Lead-acid battery. 6. A lead storage battery comprising a negative electrode, a positive electrode and an electrolyte, wherein the negative electrode comprises Hf, Nb, Ta, W, Ag, Z
n, Ni, Co, Mo, Cu, V, Mn, Ba, K, C
A lead-acid battery characterized by adding a carrier in which at least one of s, Rb, Sr, and Na, an oxide, a sulfate, a hydroxide, or a carbide is carried on carbon. 7. A lead storage battery comprising a negative electrode, a positive electrode and an electrolyte, wherein the negative electrode comprises Ni, Co, Mo, Cu, V, M
A lead-acid battery characterized by adding a carrier in which at least one of n, Ba, K, Cs, Rb and Sr, an oxide, a sulfate, a hydroxide or a carbide is carried on carbon. 8. The method according to claim 6, wherein the atomic species of the simple substance is not less than 10 ppm and not more than 5000 ppm by weight per one element.
A lead-acid battery comprising the following amount in the carbon. 9. The method according to claim 6, wherein the atomic species of said simple substance is 50 ppm or more and 1000 ppm by weight per one element.
A lead-acid battery comprising the following amount in the carbon. 10. The method according to claim 1, wherein said carbon is carbon black, acetylene black, natural graphite, artificial graphite, pyrolytic carbon, coke, isotropic graphite, mesophase carbon, pitch. A lead-acid battery including at least one of carbon fibers, vapor grown carbon fibers, carbon fluoride, nanocarbon, activated carbon, activated carbon fibers, and PAN-based carbon fibers. 11. The method according to claim 6, wherein the simple substance or the compound has an average primary particle size of 0.1 n.
A lead-acid battery having a range of not less than m and not more than 1000 nm. 12. A lead-acid battery comprising a positive electrode, a negative electrode and an electrolyte, wherein the negative electrode comprises Cu, Ni, Zn, Mn, A
A lead-acid battery, wherein activated carbon or carbon black or both activated carbon and carbon black containing at least one kind or compound of at least one of l, Si, K and Mg are added. 13. A lead-acid battery according to claim 12, wherein said activated carbon contains activated carbon having a Cu content of more than 5 ppm by weight and less than 15,000 ppm. 14. The carbon black according to claim 12, wherein the content of Ni, Cu, Zn and Mn is 1 by weight.
A lead-acid battery containing more than 1000 ppm and less than 1000 ppm of furnace black. 15. A carbon powder added to a lead storage battery, wherein Hf, Nb, Ta, W, Ag, Zn, Ni, C
o, Mo, Cu, V, Mn, Ba, K, Cs, Rb, S
A carbon material for a lead-acid battery, containing or carrying a simple substance, oxide, sulfate, hydroxide or carbide selected from at least one of r and Na. 16. A carbon powder added to the lead-acid battery, a carbon material for a lead storage battery, which comprises elemental and / or compound of desulfurization catalytic or SO _x oxidation catalysis. 17. The carbon powder added to a lead storage battery, wherein Cu, Ni, Zn, Mn, Al, Si, K, Mg
Activated carbon and / or carbon black containing at least one kind or compound thereof among the above.