JP4899378B2 - Lead acid battery and negative electrode for lead acid battery - Google Patents

Description

  The present invention relates to an improvement of a lead-acid battery, and more particularly to an improvement of the negative electrode.

In recent years, the demand for lead-acid batteries has been increasing as a power source for portable electronic devices, emergency power supply devices or electric vehicles, and high capacity is desired, and various attempts have been made. Increased capacity of the lead-acid battery is made porous by reducing the positive and negative electrode plates to increase the number of electrode plates, and reducing the density of the active material filled in the lattice, as disclosed in Patent Document 2. Or means such as disclosed in Patent Document 1 to improve the charge acceptance performance of the negative electrode by adding carbon or the like to the negative electrode active material to improve the utilization rate of the negative electrode active material. Has been done by.
JP 2001-332264 A Japanese Patent Laid-Open No. 10-040907

  Increasing the number of electrode plates by thinning the positive and negative plates described above has a problem that the lattice body must also be thinned, and the strength of the lattice body is lowered early due to corrosion. Reducing the density of the active material that fills the body to make it porous has the problem that the active material is likely to soften or fall off due to repeated charge / discharge and vibration, both of which reduce the life performance of lead-acid batteries. Had a cause to do. Moreover, adding carbon powder to the negative electrode active material to improve the utilization rate of the negative electrode active material and improving the charge acceptance performance of the negative electrode leads to a problem that the amount of the active material is reduced and a large current of 1 CA or more. However, there is a problem that a sufficient effect cannot be obtained for charging, and there is a limit to increasing the capacity.

  In view of the above problems, the inventor disclosed in Japanese Patent Application No. 2004-329958, a quinone substance having a quinone structure, or a quinone polymer obtained by polymerizing the quinone substance (the quinone substances include benzoquinone, anthraquinone, naphthoquinone or the like). It has been proposed that the life performance of lead-acid batteries can be improved without reducing the amount of active material by adding a derivative of the above) to the lead powder. It is.

  In the above-mentioned Japanese Patent Application No. 2004-329958, the life performance of a lead storage battery was improved by adding naphthoquinone or a functional group such as amino group or chloro group introduced into naphthoquinone to lead powder. This is because the solubility of lead sulfate is improved by such a functional group. On the other hand, in the present invention, when a functional group having a hydrophilic group such as a sulfone group, a carboxyl group or a hydroxyl group is introduced into the naphthoquinone, the naphthoquinone is uniformly dispersed in the negative electrode active material by the hydrophilic group. A quinone substance having a functional group introduced therein is contained in the negative electrode, and the functional group is at least one selected from a sulfone group, a carboxyl group, and a hydroxyl group, and the quinone substance is a naphthoquinone or a naphthoquinone derivative. A lead-acid battery characterized in that it contains a quinone substance into which a functional group is introduced, and the functional group is at least one selected from a sulfone group, a carboxyl group, and a hydroxyl group; The quinone substance is naphthoquinone, and is a negative electrode for a lead storage battery (Claim 2). 1% by mass or more and 0.04% by mass or less (Claim 3), and a quinone substance into which a functional group is introduced is contained, and the functional group is at least one selected from a sulfone group, a carboxyl group, and a hydroxyl group The quinone substance is a naphthoquinone derivative, and is a negative electrode for a lead storage battery (Claim 4), and the naphthoquinone derivative is added in an amount of 0.05% by mass to 0.5% by mass with respect to the lead powder (Claim 5) The naphthoquinone derivative is menaquinone and a derivative thereof or phylloquinone and a derivative thereof (Claim 6), respectively.

  According to the present invention, naphthoquinone or a naphthoquinone derivative is uniformly dispersed in a negative electrode active material by containing a naphthoquinone or a naphthoquinone derivative having a hydrophilic functional group such as a sulfone group, a carboxyl group, or a hydroxyl group. In addition, the oxygen atom of the quinone material is adsorbed on the surface of the negative electrode active material, and the negative electrode active material can be prevented from shrinking, that is, the specific surface area can be reduced by repeating charge and discharge. In addition, according to the present invention, since the negative electrode active material described above is used for a lead storage battery, it contributes to obtaining a high capacity lead storage battery without reducing the amount of active material and the life performance. it can. In addition, as long as the above-described effects can be obtained, such a quinone material does not necessarily need to be contained in the negative electrode active material, and various ways of inclusion such as application to the surface of the lattice constituting the negative electrode can be used. It can be selected appropriately.

  Hereinafter, the present invention will be described based on the embodiments.

A negative electrode active material for a lead-acid battery was prepared as follows. That is, as a quinone substance, naphthoquinone A (the functional group X shown in Chemical Formula 1 is hydrogen H), the naphthoquinones C whose functional group X is a sulfone group —SO ₃ H, and the functional group X is carboxyl A naphthoquinone D which is a group —COOH, a naphthoquinone E whose functional group X is a hydroxyl group —OH, menaquinone H which is a kind of naphthoquinone derivatives (the first isoprenoid side chain is introduced into the basic structure of naphthoquinone shown in Chemical Formula 1) In which the functional group X is a hydrogen H), the functional group X is a sulfone group —SO ₃ H, and the functional group X is a carboxyl group. Menaquinones J which are —COOH and menaquinol K which is a kind of menaquinone derivative (C—O double bond of the basic structure of naphthoquinone shown in Chemical Formula 1 is represented by C—O, respectively. And a functional group X having a structure shown in Chemical Formula 3 in which the first isoprenoid side chain is introduced and the functional group X is hydrogen H). Is a sulfone group —SO ₃ H, phylloquinone M, which is a kind of naphthoquinone derivative (in which a second isoprenoid side chain is introduced instead of the first isoprenoid side chain of menaquinone H shown in Chemical Formula 2, Phylloquinones N having a structure shown in Chemical formula 4 and the functional group X being hydrogen H), and the functional group X being a sulfone group —SO ₃ H, and phylochromenol being a kind of phylloquinone derivative O (in place of the first isoprenoid side chain of menaquinol K shown in Chemical Formula 3, the second isoprenoid side chain of phylloquinone M is introduced, and one O—H single bond O is replaced with the second isoprenoid side chain. It is a single bond to C C = C double bond portion in the maytansinoid side chains of relative functional group X are hydrogen H) shown in 5, the functional group X is sulfone group -SO ₃ H A certain phylochromenol P was prepared. And, to the lead powder produced by a known method, barium sulfate, 1.0% by mass with respect to the lead powder, polypropylene fiber short fibers (average length of 2 to 5 mm) as an active material reinforcing material, 0.03 mass% with respect to the lead powder, the naphthoquinones C, D, and E are 0.005 mass%, 0.01 mass%, 0.02 mass%, and 0.03 mass with respect to the lead powder, respectively. %, 0.04% by mass and 0.05% by mass of negative electrode active material, menaquinones I, J, menaquinols L, phylloquinones N, phylochromemenols P with respect to the lead powder 30 kinds of negative electrode active materials added with 0.02% by mass, 0.05% by mass, 0.1% by mass, 0.3% by mass, 0.5% by mass and 0.6% by mass, respectively, according to the present invention. It was produced as a product. In addition to these, naphthoquinone A in the examples of the Japanese Patent Application No. 2004-329958, naphthoquinones B in which an amino group -NH ₂ is introduced into the functional group X, and a methyl group -CH ₃ in the functional group X. The introduced naphthoquinones F and naphthoquinones G having a methoxy group —OCH ₃ introduced into the functional group X thereof are 0.005% by mass, 0.01% by mass, 0.02% by mass, and 0.0. 24 kinds of negative electrode active materials added with 03% by mass, 0.04% by mass and 0.05% by mass, menaquinone H, menaquinol K, phylloquinone M, phylochromenol O in the examples of the aforementioned Japanese Patent Application No. 2004-329958 Types of negative electrode actives in which 0.02 mass%, 0.05 mass%, 0.1 mass%, 0.3 mass%, 0.5 mass% and 0.6 mass% were added to lead powder, respectively. object And, it was prepared as reference materials.

  Similarly, 0.25% by mass of the lignin having the basic structure shown in Chemical Formula 6 with respect to the lead powder, 1.0% by mass of barium sulfate, and 0.03% by mass of the active material reinforcing material were added. A negative electrode active material to which 1.0% by mass of barium sulfate and 0.03% by mass of the above active material reinforcing material were added was used as a comparative product.

  Next, to these negative electrode active materials, dilute sulfuric acid and water were added and kneaded by a conventional method to prepare negative electrode active material pastes.

  Next, each of the negative electrode active material pastes described above is filled in an expanded lattice produced from a Pb-0.07 wt% Ca-1.5 wt% Sn alloy, and aged and dried to produce an unformed negative electrode plate. did. Then, four unformed negative electrode plates and three unformed paste-type positive electrode plates prepared by a known method are prepared and laminated with a separator made of polyethylene interposed between the positive and negative electrode plates. A group of plates was used. Each electrode plate group is placed in a polypropylene battery case, and an electrolytic solution made of dilute sulfuric acid having a specific gravity of 1.28 at 20 ° C. is injected into the battery case, and the battery case is formed under known conditions. , Naphthoquinones C, D, E, menaquinones I, J, menaquinols L, phylloquinones N, phylochromemenols P, lead-acid batteries of the present invention products c, d, e, Each of i, j, l, n, and p was completed by changing the addition amount as described above. Reference products a, b, f, g, h of lead acid batteries using negative electrodes according to reference examples including naphthoquinone A, naphthoquinones B, F, G, menaquinone H, menaquinol K, phylloquinone M, phylochromenol O , K, m, and o were each completed by changing the addition amount as described above. Further, a conventional lead storage battery using a conventional negative electrode active material for the negative electrode and a comparative lead storage battery using a comparative negative electrode active material for the negative electrode were completed one by one. The obtained lead storage battery had a nominal capacity of 27 Ah, and the positive and negative electrode plate dimensions were 115 mm in length, 103 mm in width, and 1.5 mm in thickness.

  Next, the present invention product, reference product, conventional product, and comparative product of the lead storage battery described above were subjected to a cycle life test, and the results are shown in FIGS. FIG. 1 shows the relationship between the amount of naphthoquinone A, naphthoquinones B, C, D, E, F, and G and the number of cycle lives. FIG. 2 shows menaquinone H, menaquinones I, J, menaquinol K, menaquinols L. , Phylloquinone M, phylloquinones N, phyllochromenol O, phylochromenols P, and the relationship between the number of cycles and the number of cycles. The test conditions were those in which the ambient temperature in the light load life test specified in JIS D 5301 was changed from 40 ° C. to 25 ° C., and discharge was performed for 4 minutes at a constant current of 25 A under the ambient temperature. After that, the battery is charged for 10 minutes with a constant voltage of 14.4 V and a maximum charging current of 25 A, and then discharged with a constant current of 272 A. The life at the point where the voltage at 30 seconds falls below 7.2 V It is a thing. FIG. 1 and FIG. 2 show the number of cycles that can be repeated until the end of the life in this way as 100, and the number of cycles that can be repeated with a conventional lead-acid battery as 100.

  From the results shown in FIG. 1, the products c, d and e of the lead-acid battery have a life performance in the range where the addition amount of naphthoquinones C, D and E is 0.01 mass% or more and 0.03 mass% or less. Compared to conventional lead-acid batteries, the lead-acid battery reference products a and b to which naphthoquinone A and naphthoquinones B are added have a life performance level of 0.04% by mass. On the other hand, in the case of naphthoquinones C, D and E, even if the addition amount is 0.04% by mass, no significant decrease in the life performance is observed. This is because naphthoquinones C, D and E are more effective in improving the dispersibility of the active material than naphthoquinone A and naphthoquinones B. When naphthoquinone A and naphthoquinones B are added in a larger amount, this is unevenly distributed in the active material. This is considered to be the cause of hindering charging and discharging. From this, the present invention products c, d and e of the lead storage battery are more than the reference product a of the lead storage battery to which the naphthoquinone A is added or the reference product b of the lead storage battery to which the naphthoquinones B having an amino group introduced into the naphthoquinone A are added. It can be said that there is an effect. The lead-acid battery reference products f and g are functional groups that are not hydrophilic groups such as sulfone groups, carboxyl groups, and hydroxyl groups such as naphthoquinones F and G in naphthoquinones C, D, and E (methyl groups, It is considered that the methoxy group) could not contribute to the improvement of the life performance.

  In addition, from the results of FIG. 2, the products i, j, l, n, and p of the lead storage battery according to the present invention had an addition amount of menaquinones I, J, menaquinols L, phylloquinones N, phylochromemenols P of 0. In the range of 05% by mass or more and 0.5% by mass or less, the life performance is improved as compared with the conventional lead acid battery, and the lead acid battery to which menaquinone H, menaquinol K, phylloquinone M, phylochromenol O is added. It can be seen that the life performance is greatly improved as compared with the reference products h, k, m and o. Therefore, as in the case of the naphthoquinones C, D, and E described above, the sulfone group introduced into the menaquinones I, menaquinols L, phylloquinones N, and phylochromemenols P and menaquinones J were introduced. It is considered that a hydrophilic group such as a carboxyl group contributes to the improvement of the life performance.

  Next, after the end of the cycle life test described above, all the batteries were disassembled, the specific surface area was analyzed by the BET method with each negative electrode plate, the average value was calculated for each battery, and the results are shown in FIG. Table 1 and Table 2 show the cycle life performance ratio shown in FIG. Tables 1 and 2 show the life performance of the conventional lead-acid battery and the maximum value of the specific surface area of the conventional product as 100.

  From the results in Table 1, the specific surface area of the negative electrode plate in the lead-acid battery products c (c-1 to c-6), d (d-1 to d-6), and e (e-1 to e-6) of the present invention. Is relative to the specific surface area of the negative electrode plate in the conventional product of the lead acid battery and the specific surface area of the negative electrode plate in the reference products a (a-1 to a-6) and b (b-1 to b-6) of the lead acid battery. You can see that it is getting bigger. Moreover, from the result of Table 2, this invention product i (i-1 to i-6), j (j-1 to j-6), l (l-1 to 1-6), n (n) of lead acid battery -1 to n-6) and the specific surface area of the negative electrode plate in p (p-1 to p-6), the specific surface area of the negative electrode plate in the conventional lead acid battery, and the reference product h (h-1 to lead acid battery). h-6), k (k-1 to k-6), m (m-1 to m-6), and o (o-1 to o-6) are larger than the specific surface area of the negative electrode plate. I understand that. From this, naphthoquinones C, D, E, menaquinones I, J, menaquinols L, phylloquinones N, phylochromemenols P are introduced into the negative electrode by hydrophilic groups such as sulfone groups, carboxyl groups, and hydroxyl groups. It is considered that the shrinkage of the active material is suppressed and the decrease in the specific surface area is suppressed. In addition, the specific surface area of the negative electrode plate in the reference products f (f-1 to f-6) and g (g-1 to g-6) of the lead storage battery in Table 1 is the specific surface area of the negative electrode plate in the conventional product of the lead storage battery. The reason is that the functional groups of naphthoquinones F and G added to the negative electrode active material are not hydrophilic and do not contribute to an increase in the specific surface area of the negative electrode plate. It is done.

  The naphthoquinones C, D, and E are naphthoquinones in which one of hydrophilic groups such as a sulfone group, a carboxyl group, and a hydroxyl group is introduced into naphthoquinone A, but an amino group is introduced into naphthoquinone A. The above-described hydrophilic group may be introduced into naphthoquinones in which a chloroquinone or an alkyl group is introduced into naphthoquinone A in B or Japanese Patent Application No. 2004-329958. Similarly, menaquinones J have one carboxyl group introduced into menaquinone H as a hydrophilic group, and menaquinones I, menaquinols L, phylloquinones N, and phylochromemenols P are menaquinone H, menaquinol K, phylloquinone M, Menoroquinones, menaquinols, and phylloquinones in which a chloro group or an alkyl group is introduced into menaquinone H described in Japanese Patent Application No. 2004-329958. The above-described hydrophilic group may be introduced into phyllochromenols. In the naphthoquinone derivatives of the above-described examples, only examples in which a hydrophilic functional group X is introduced into the basic structure of naphthoquinone are shown. However, a hydrophilic functional group is present in the illustrated first or second isoprenoid side chain. X may be introduced, and the number and type thereof are not limited. Menaquinone derivatives include menachromenol and menachromanol in addition to the above menaquinol, and phylloquinone derivatives include phyloquinol and phytochromanol in addition to the above phylochromenol. The type or the position and number where it is introduced can be arbitrarily selected. Furthermore, preferably, in order to improve the mixing of the naphthoquinone or naphthoquinone derivative and the negative electrode active material, naphthoquinone or naphthoquinone derivative is introduced into a solution in which Na, K, Ca, Mg, etc. are dissolved. Thus, a salt obtained by adding Na, K, Ca, Mg or the like to the functional group X may be used.

  Although the above-described embodiment is for a liquid type lead acid battery used for an automobile battery or the like, similar results were obtained for a control valve type lead acid battery used for consumer use or stationary use. That is, as a control valve type lead-acid battery, a battery of 2V, 7Ah was subjected to a float charge life test at an ambient temperature of 65 ° C., then disassembled and analyzed for the specific surface area of the negative electrode plate. Thus, it was found that the decrease in specific surface area was suppressed. From this, also in the control valve type lead-acid battery, it is considered that the shrinkage of the negative electrode active material is suppressed by adding naphthoquinone and naphthoquinone derivatives having various functional groups. As described above, the present invention can exert its effect regardless of the type and form of the lead storage battery. In addition, the test method shown by the above-mentioned Example is not limited to this, You may use methods other than embodiment.

  As described above, the present invention can contribute to providing a long-life lead-acid battery capable of suppressing the shrinkage of the negative electrode active material, and therefore has great industrial applicability.

The figure which showed the relationship between the addition amount of naphthoquinone A, naphthoquinones B, C, D, E, F, and G, and the cycle life number. The figure which showed the relationship between the addition amount of menaquinone H, menaquinones I and J, menaquinol K, menaquinols L, phylloquinone M, phylloquinones N, phylochromenol O, phylochromenols P, and the cycle life number.

Claims (6)

The negative electrode contains a quinone substance having a functional group introduced therein , wherein the functional group is at least one selected from a sulfone group, a carboxyl group, and a hydroxyl group, and the quinone substance is naphthoquinone or a naphthoquinone derivative. Lead acid battery. A negative electrode for a lead storage battery , comprising a quinone substance into which a functional group is introduced , wherein the functional group is at least one selected from a sulfone group, a carboxyl group, and a hydroxyl group, and the quinone substance is naphthoquinone . The negative electrode for lead acid batteries according to claim 2, wherein the amount of naphthoquinone added is 0.01% by mass or more and 0.04% by mass or less with respect to the lead powder. A negative electrode for a lead storage battery , comprising a quinone substance into which a functional group is introduced, wherein the functional group is at least one selected from a sulfone group, a carboxyl group, and a hydroxyl group, and the quinone substance is a naphthoquinone derivative . 5. The negative electrode for a lead storage battery according to claim 4, wherein the naphthoquinone derivative is added in an amount of 0.05% by mass to 0.5% by mass with respect to the lead powder. The negative electrode for lead acid batteries according to claim 5, wherein the naphthoquinone derivative is menaquinone and a derivative thereof or phylloquinone and a derivative thereof.

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