CN1695260A - positive plate for lead-acid battery and lead-acid battery - Google Patents

Abstract

A positive plate for a lead storage battery, having a high ratio of utilization of the positive plate active material, prevented from lowering in life performance of itself, and excellent in discharge performance and life performance. The positive plate includes a positive plate grid made of a lead alloy containing 1.2 weight% or more of tin and a paste that is prepared by kneading a positive plate active material stock mainly containing a lead powder and red lead with dilute sulfuric acid and is applied to the grid. The positive active material stock contains 5 or more and 50 or less weight% of red lead. The porosity of the positive active material after formation is 58% or more. A lead storage battery is also disclosed.

Description

The positive pole of lead acid accumulator and lead acid accumulator

Technical field

The present invention relates to the improvement of positive electrode active materials utilance, the raising of lead acid accumulator self-discharge characteristics and the deterioration of avoiding the lead acid accumulator cycle life performance.

Background technology

The improvement of the utilance of active material in the positive pole of lead acid accumulator, the especially improvement during high rate discharge are that reduction battery weight and size are necessary, and it have been done a lot of trials up to now.

These attempt mainly attempting to improve the porosity of positive electrode active materials.

Improve the porosity of positive electrode active materials and brought fabulous effect, but the life performance of lead acid accumulator is had opposite influence.Therefore, the raising of porosity is restricted, and up to the present, from practical standpoint, the upper limit of porosity is about 60%.

This is due to the fact that when porosity increases, adhesion between active material diminishes, and with the decline gradually of active material conductivity, only causing, near the active material grid is discharged, therefore cause the accumulation of lead sulfate around grid, described lead sulfate has extremely low conductivity.

Especially, in recent years, the tin that contains the 1 weight % that has an appointment in the lead alloy of grid is able to extensive use, to improve the corrosion resistance of anodal grid.Yet when the proportion of composing of tin rose, the binding ability of active material and grid was with deterioration.

This is because formed the tin-oxide film at grid surface during wet setting in producing anodal step, has damaged the adhesive property of active material and grid.

When the positive electrode active materials porosity increased, anodal life performance compared in the past deterioration more, hindered the improvement of lead acid accumulator performance, so this was very disadvantageous.

Now worked out the present invention to address the above problem, and its this problem (purpose) is to provide anodal for lead acid accumulator, by utilance that improves positive electrode active materials and the deterioration that prevents anodal life performance, described positive pole helps to improve the flash-over characteristic and the life characteristic of lead acid accumulator.

Summary of the invention

To achieve these goals, present invention is described in following (1) to (8) item.

(1) a kind of positive pole of lead acid accumulator comprises:

The anodal grid of making more than or equal to the lead alloy of 1.2 weight % by tin content and

Be filled in lead plaster wherein, described lead plaster is mediated as the anodal activated feedstock of main component and dilute sulfuric acid and is obtained by containing lead powder and red lead powder,

The content of red lead composition is 5 weight %～50 weight % in the wherein said anodal activated feedstock, and the positive pole of the lead acid accumulator of the lead plaster preparation made from anodal activated feedstock thus has the positive electrode active materials porosity more than or equal to 58% after changing into.

(2) positive pole of the lead acid accumulator described in (1) item, the content of the red lead composition in the wherein said anodal activated feedstock is more than or equal to 5 weight % and less than 30 weight %, and the positive pole of the lead acid accumulator of the lead plaster preparation made from anodal activated feedstock thus has the positive electrode active materials porosity more than or equal to 58% after changing into.

(3) positive pole of the lead acid accumulator described in (1) item, the content of the red lead composition in the wherein said anodal activated feedstock is 12 weight %～42 weight %, the content of the metallic lead composition in the described lead powder is 31 weight %～40 weight %, and the positive pole of the lead acid accumulator of the lead plaster preparation made from anodal activated feedstock thus has the positive electrode active materials porosity more than or equal to 58% after changing into.

(4) positive pole of the lead acid accumulator described in (3) item, wherein in described anodal activated feedstock, also contain metal lead powder, become to assign to calculate by the metallic lead in the metal lead powder of described lead powder and therefore interpolation, the content of the metallic lead composition in the described anodal activated feedstock be more than or equal to 19 weight % to less than 26 weight %, and the positive pole of the lead acid accumulator for preparing with the lead plaster that anodal activated feedstock is thus made has the positive electrode active materials porosity more than or equal to 58% after changing into.

(5) positive pole of the lead acid accumulator described in (1) item, the content of the red lead composition in the wherein said anodal activated feedstock is 10 weight %～50 weight %, and the average grain diameter of described red lead powder is less than or equal to 2.2 times of described lead powder average grain diameter.

(6) positive pole of the lead acid accumulator described in (1), wherein said lead powder are that the lead alloy of 0.005 weight %～0.1 weight % is made by its antimony content.

(7) as the positive pole of each described lead acid accumulator in (1) to (6), wherein said anodal grid is the hauling type grid.

(8) lead acid accumulator, this lead acid accumulator contain the positive pole that arrives each described lead acid accumulator in (7) item just like (1) item.

Description of drawings

Fig. 1 is the curve chart that the explanation initial capacity changes with the variation of red lead composition.

Fig. 2 curve chart that to be explanation change with the variation of red lead composition at the 5th cyclic discharge capacity.

Fig. 3 is the curve chart that explanation Capacity Ratio (B/A) changes with the variation of red lead composition.

Fig. 4 is the curve chart of explanation along with the relation of the variation tin content of red lead composition and active material adhesion amount.

Fig. 5 is explanation along with the curve chart of the relation of the discharge capacity of the 5th circulation of the variation of red lead composition and metallic lead composition.

Fig. 6 is the curve chart of explanation along with the relation of the variation initial capacity of red lead composition and metallic lead composition.

Fig. 7 is explanation along with the curve chart of the relation of the discharge capacity of the 5th circulation of the variation of red lead composition and metallic lead composition.

Fig. 8 is the curve chart of explanation along with the relation of the variation Capacity Ratio of red lead composition and metallic lead composition.

Fig. 9 is the curve chart of explanation to the test result of the cycle life performance of valve-regulated lead-acid battery.

Figure 10 is the curve chart of explanation valve-regulated lead-acid battery volume change in 60 ℃ of floating tests.

Figure 11 is the curve chart of explanation red lead particle size distribution.

Figure 12 is the curve chart that the explanation self-discharge rate changes with the variation of red lead composition.

Figure 13 is the curve chart that the variation of the percetage by weight of antimony during explanation cycle life in different red lead compositions compares with lead alloy changes.

Embodiment

First execution mode

In the first embodiment, anodal activated feedstock is mixed with the red lead predetermined amounts, even the porosity of positive electrode active materials, also can improve anodal life performance more than or equal to 58%.

First execution mode will be further described hereinafter.

Contain 0.05 weight % calcium and contain the lead alloy of 1.5 weight % tin by expansion, preparation height is 72mm, the wide 45mm of being and thickly is the grid of 2.9mm.

Then, filling positive electrode active materials lead plaster to the thickness for preparing according to prescription listed in the table 1 to these grids separately is 3.0mm, to prepare sample respectively the 1st to No. 12, for these samples prepare a plurality of pole plates separately.

Subsequently, be that 50 ℃, humidity are to place 72 hours so that with its slaking in 90 the atmosphere with these samples in temperature.Select 3 pole plates separately arbitrarily from these samples, carry out the drop shutter test of active material then, this test relates to the falling naturally from the 90cm eminence of repetition 20 times.Measure the adhesion amount of active material on grid surface then.

Select 9 pole plates from above-mentioned sample independently, total charge volume of each personal 20Ah carries out anodization (changing into) then, to form positive pole, carries out one time 24 hours discharge comprising the dilute sulfuric acid that in concentration is 28%.

Employed red lead powder has the purity more than or equal to 95%.

Subsequently, from these positive poles, select 6 pole plates.By mercury osmosis (mercurypenetration method) porosity of the positive electrode active materials of 3 electrodes in 6 utmost point electrodes is tested then, changing into the PbO of back other 3 electrodes by iodometry ₂Percentage by weight measure.

So the adhesion amount of the active material of measuring, change into back PbO ₂Percentage by weight and porosity be the mean value of per three electrodes.The results are shown in the table 1.

In the preparation that is used in common positive pole, the amount of employed metallic lead composition is 25 weight %～30 weight % in the lead powder in the present embodiment.

Dilute sulfuric acid is represented with the amount of the anodal activated feedstock of every 10kg.

Table 1

Sample number into spectrum	Lead plaster			After the active material drop shutter test, the adhesion amount (mg) of active material on the positive pole that does not change into	Positive pole after changing into
							Lead powder (weight %)	Red lead composition (weight %)	Dilute sulfuric acid proportion-volume (l)	The % porosity	??PbO 2(weight %)
	??1	??100	??0		??1.14-1.5	??450						??54	??91.3
??2				??100			??0	??1.16-1.7	??290	??56	??91.5
	??3	??100	??0		??1.16-1.9	??252						??58	??91.9
??4				??100			??0	??1.16-2.2	??223	??62	??92.5
	??5	??100	??0		??1.16-2.4	??191						??64	??93.6
??6				??97.5			??2.5	??1.16-2.2	??268	??62	??93.0
	??7	??95	??5		??1.16-2.2	??506						??62	??93.5
??8				??88			??12	??1.16-2.2	??621	??62	??94.5
	??9	??82	??18		??1.16-2.2	??653						??63	??94.8
??10				??76			??24	??1.16-2.2	??640	??63	??95.6
	??11	??70	??30		??1.16-2.2	??643						??63	??95.8
??12				??64			??36	??1.16-2.2	??638	??64	??96.1

Subsequently, other three positive poles are joined to contain excessive concentration be 40% dilute sulfuric acid and have in three batteries as the Plante-type plate of counterelectrode.Make these battery discharges then.Measure the initial capacity A and the discharge capacity B of these batteries then in the 5th circulation.

About measuring condition, discharging current is the constant current of 0.7A, and final discharging voltage with respect to the lead plaster type electrode of independent preparation be-500mV, and this lead plaster type electrode is by being to flood brown lead oxide in 40% the dilute sulfuric acid and lead alloy is made in concentration.

Initial capacity A is changing into back shown heap(ed) capacity in 3 discharge cycles.The discharge capacity of the 5th circulation is, serves as zero circulation with the discharge of above-mentioned demonstration initial capacity, shown discharge capacity when carrying out the 5th circulation discharge.The discharge capacity B of these results and the 5th circulation is listed in the table 2 with the ratio (Capacity Ratio B/A) of initial capacity A.

Table 2

Sample number into spectrum	Initial capacity A (Ah)	The discharge capacity B (Ah) of the 5th circulation	Capacity Ratio B/A
				??1	??2.34	??2.41	??1.030
??2	??2.45	??2.40	??0.980
				??3	??2.59	??2.48	??0.957
??4	??2.78	??2.25	??0.809
				??5	??2.82	??1.84	??0.651
??6	??2.77	??2.37	??0.856
				??7	??2.76	??2.70	??0.978
??8	??2.81	??2.78	??0.989
				??9	??2.80	??2.76	??0.986
??10	??2.81	??2.75	??0.979
				??11	??2.86	??2.56	??0.895
??12	??2.83	??2.36	??0.830

Subsequently, except the positive electrode active materials lead plaster is prepared by the anodal activated feedstock that contains 12 weight % red lead compositions according to the listed various prescriptions of table 3, beyond being filled in these anodal activated feedstock lead plasters in the above-mentioned grid equally then, use with table 2 in contain 100 weight % lead powder the identical mode of 1,2 and 3 sample that is numbered prepare the sample that is numbered 1a, 2a and 3a respectively.

In addition, according to the listed various prescriptions of table 3 by preparing the positive electrode active materials lead plaster by the anodal activated feedstock that contains 18 weight % red lead compositions, equally these positive electrode active materials lead plasters are filled in the above-mentioned grid then, preparation is numbered the sample of 1b, 2b and 3b respectively.

In addition, according to the listed various prescriptions of table 3 by preparing the positive electrode active materials lead plaster by the anodal activated feedstock that contains 24 weight % red lead compositions, equally these positive electrode active materials lead plasters are filled in the above-mentioned grid then, preparation is numbered the sample of 1c, 2c and 3c respectively.

In addition, according to the listed various prescriptions of table 3 by preparing the positive electrode active materials lead plaster by the anodal activated feedstock that contains 27 weight % red lead compositions, equally these positive electrode active materials lead plasters are filled in the above-mentioned grid then, preparation is numbered the sample of 1d, 2d and 3d respectively.

In addition, according to the listed various prescriptions of table 3 by preparing the positive electrode active materials lead plaster by the anodal activated feedstock that contains 30 weight % red lead compositions, equally these positive electrode active materials lead plasters are filled in the above-mentioned grid then, preparation is numbered the sample of 1e, 2e and 3e respectively.

In addition, according to the listed various prescriptions of table 3 by preparing the positive electrode active materials lead plaster by the anodal activated feedstock that contains 36 weight % red lead compositions, equally these positive electrode active materials lead plasters are filled in the above-mentioned grid then, preparation is numbered the sample of 1f, 2f and 3f respectively.

In addition, according to the listed various prescriptions of table 3 by preparing the positive electrode active materials lead plaster by the anodal activated feedstock that contains 42 weight % red lead compositions, equally these positive electrode active materials lead plasters are filled in the above-mentioned grid then, preparation is numbered the sample of 1g, 2g and 3g respectively.

Then under these conditions to carrying out slaking and anodization (changing into) in these samples separately to form positive pole.Changing into the back to each anodal PbO then ₂Percentage by weight and porosity are measured.Then other 3 positive poles are used to prepare above-mentioned battery.Ratio (B/A) to the discharge capacity B of the discharge capacity of the initial capacity of these batteries, the 5th circulation and the 5th circulation and initial capacity A carries out same mensuration separately then.The results are shown in the table 3.

The change that change that the discharge capacity of the change that initial capacity changes with the red lead composition, the 5th circulation changes with the red lead composition and ratio (B/A) change with the red lead composition is respectively shown in Fig. 1,2 and 3.

The ratio of above-mentioned (B/A) has provided the index of anodal life performance.

Table 3

Sample number into spectrum	Lead plaster			Positive pole after changing into		Initial capacity A (Ah)	The discharge capacity B (Ah) of the 5th circulation	Capacity Ratio B/A
									Lead powder (weight %)	Red lead composition (weight %)	Dilute sulfuric acid proportion-volume (l)	The % porosity	??PbO 2(weight %)
	??1a	??88％	??12％	??1.14-1.5	??55									??91.8	??2.39	??2.46	??1.029
??2a						??88％	??12％	??1.16-1.7	??57	??91.9	??2.49	??2.55	??1.024
	??3a	??88％	??12％	??1.16-1.9	??58									??92.5	??2.61	??2.66	??1.019
??1b						??82％	??18％	??1.14-1.5	??55	??91.9	??2.40	??2.50	??1.042
	??2b	??82％	??18％	??1.16-1.7	??57									??92.3	??2.52	??2.55	??1.012
??3b						??82％	??18％	??1.16-1.9	??59	??92.9	??2.62	??2.72	??1.038
	??1c	??76％	??24％	??1.14-1.5	??54									??92.1	??2.40	??2.52	??1.050
??2c						??76％	??24％	??1.16-1.7	??57	??92.8	??2.53	??2.60	??1.028
	??3c	??76％	??24％	??1.16-1.9	??59									??93.8	??2.69	??2.79	??1.037
??1d						??73％	??27％	??1.14-1.5	??54	??92.1	??2.41	??2.52	??1.046
	??2d	??73％	??27％	??1.16-1.7	??57									??92.9	??2.54	??2.61	??1.028
??3d						??73％	??27％	??1.16-1.9	??59	??93.8	??2.73	??2.83	??1.037
	??1e	??70％	??30％	??1.14-1.5	??55									??92.3	??2.43	??2.54	??1.045
??2e						??70％	??30％	??1.16-1.7	??56	??92.9	??2.54	??2.62	??1.031
	??3e	??70％	??30％	??1.16-1.9	??59									??94.0	??2.77	??2.83	??1.022
??1f						??64％	??36％	??1.14-1.5	??55	??92.8	??2.42	??2.51	??1.037
	??2f	??64％	??36％	??1.16-1.7	??56									??93.1	??2.53	??2.63	??1.039
??3f						??64％	??36％	??1.16-1.9	??59	??94.2	??2.82	??2.81	??0.996
	??1g	??58％	??42％	??1.14-1.5	??55									??93.2	??2.44	??2.46	??1.088
??2g						??58％	??42％	??1.16-1.7	??57	??93.6	??2.55	??2.52	??0.988
	??3g	??58％	??42％	??1.16-1.9	??59									??94.2	??2.83	??2.75	??0.972

According to Fig. 1 and table 3, have with table 1 in sample 1 essentially identical porosity (54%～55%) be numbered all samples of 1a to 1g, have with table 1 in sample 2 essentially identical porositys (56～57%) be numbered all samples of 2a to 2g, have with table 1 in sample 3 essentially identical porositys (58～59%) be numbered all samples of 3a to 3g, compare with the initial capacity of sample in the table 21, demonstrate initial capacity along with red lead composition in the anodal activated feedstock from 12 weight % to 42 weight % increase and improve.

Especially, sample 3a to 3g (58%～59%) demonstrate initial capacity along with red lead composition in the anodal activated feedstock from 24 weight % to 36 weight % increase and be significantly improved.

On the other hand, in Fig. 1 and table 3 as can be seen, as long as porosity is in 54%～57% scope, when red lead composition in the anodal activated feedstock increases, these samples have shown the raising of initial capacity, but with porosity is that 58%～59% sample is compared, and not only itself demonstrates littler initial capacity value, but also demonstrates littler initial capacity growth rate.

Similarly, as long as porosity is in 62%～64% scope, when red lead composition in the anodal activated feedstock increased, these samples had shown the raising of initial capacity, but were that 58%～59% sample is compared with porosity, itself demonstrated littler initial capacity value.

Therefore, can expect to need only porosity more than or equal to 58%, when red lead composition in the anodal activated feedstock increased, then initial capacity improved.

This may be because when red lead composition in the anodal activated feedstock increases, and changes into back PbO ₂Percentage by weight increase, cause the raising of initial capacity.

In addition, according to Fig. 2 and table 3, have with table 1 in sample 1 essentially identical porosity (54%～55%) be numbered all samples of 1a to 1g, have with table 1 in sample 2 essentially identical porositys (56～57%) be numbered all samples of 2a to 2g, have with table 1 in sample 3 essentially identical porositys (58～59%) be numbered all samples of 3a to 3g, compare with the discharge capacity that the 5th of sample in the table 21 circulates, demonstrate along with red lead composition in the anodal activated feedstock increases to 30 weight % the raising of the discharge capacity of the 5th circulation.

Especially, sample 3a demonstrates along with red lead composition in the anodal activated feedstock increases to 30 weight % to 3g (porosity=58～59%), being significantly improved of the discharge capacity of the 5th circulation.On the other hand, from Fig. 2 and table 3 as can be seen, as long as porosity is in 54%～57% scope, when red lead composition in the anodal activated feedstock increases, these samples have shown the raising of the discharge capacity of the 5th circulation, but with porosity is that 58%～59% sample is compared, and not only itself demonstrates the discharge capacity value of littler the 5th circulation, but also demonstrates the discharge capacity growth rate of littler the 5th circulation.

In addition, as long as porosity is in 62%～64% scope, when red lead composition in the anodal activated feedstock when 5 weight % increase to 30 weight %, the discharge capacity of the 5th circulation is increased sharply.When the red lead composition when being 5 weight %～24 weight % this trend particularly remarkable.

Therefore, can expect to need only porosity more than or equal to 58%, when red lead composition in the anodal activated feedstock increased, then the discharge capacity of the 5th circulation improved.

In addition, according to Fig. 3 and table 3, have with table 1 in sample 1 essentially identical porosity (54%～55%) be numbered all samples of 1a to 1g, have with table 1 in sample 2 essentially identical porositys (56～57%) be numbered all samples of 2a to 2g, have with table 1 in sample 3 essentially identical porositys (58～59%) be numbered all samples of 3a to 3g, compare with the Capacity Ratio (B/A) of sample in the table 21, demonstrate along with red lead composition in the anodal activated feedstock increases to 27 weight % from 5 weight % the raising of Capacity Ratio (B/A).

And find that among sample 11,12 in table 1 and sample 1e to 3e, the 1f to 3f and 1g to 3g in the table 3, after the mensuration of the discharge capacity that the 5th circulates, positive electrode active materials is accumulated in the battery.

This may be because excessive red lead composition causes the reduction of positive electrode active materials adhesion, along with the carrying out of charge and discharge cycles, has destroyed the interparticle conductive path of positive electrode active materials.

Therefore, when anodal activated feedstock comprises more than or equal to 5 weight % to the red lead powder less than 30 weight %, and the positive electrode active materials porosity is greater than or equal to 58%, be preferably at 58%～62% o'clock, can obtain to estimate the positive pole of the lead acid accumulator that the discharge capacity of initial capacity and the 5th circulation can be improved.

Sample 4 and sample 6～11 from table 1 can find out obviously that when the weight of red lead powder in the anodal activated feedstock increased, the active material adhesion amount increased.

Even this be because use by tin content be the lead alloy of 1.5 weight % make grid the time, this grid can form the tin-oxide film at grid surface, reduced the bond properties of grid and positive electrode active materials, the existence of red lead composition still can improve the bond properties of grid and positive electrode active materials.

In order to confirm this mechanism,, this lead plaster is filled in the grid that tin content is respectively 1.2 weight %, 1.1 weight % and 1.0 weight % according to the formulation positive electrode active materials lead plaster identical with sample 4 and sample 6～11 in the table 1.Then the adhesion amount of active material on these grids carried out same research.The results are shown among Fig. 4.

As can be seen from Figure 4, even the weight of the red lead powder that is contained in the anodal activated feedstock increases, tin content is the growth rate that the grid of 1.0 weight % and 1.1 weight % still demonstrates less active material adhesion amount, and when red lead powder that anodal activated feedstock contained during more than or equal to 5 weight %, tin content is the phenomenal growth that the grid of 1.2 weight % and 1.5 weight % demonstrates the active material adhesion amount.

Can think that this helps to improve life performance.

Therefore, in the time will being filled to tin content, can obtain to estimate the positive pole of the lead acid accumulator that the discharge capacity of initial capacity and the 5th circulation can be improved by the positive electrode active materials lead plaster of the anodal activated feedstock preparation that contains 5 weight %～30 weight % red lead compositions more than or equal to the grid of 1.2 weight %.

Second execution mode

Second execution mode relates to, and the positive pole that provides according to above-mentioned first execution mode is provided, wherein the configuration more than or equal to 30 weight % improves to the red lead composition of life performance deficiency, even so that its porosity is more than or equal to 58%, the gained positive pole also can be not second to first execution mode.

The prerequisite of the lead powder of first execution mode is that the amount of its metallic lead composition of supposition is 25 weight %～30 weight %.Yet when the metallic lead composition in the lead powder during greater than 30 weight %, the effect in first execution mode weakens possibly.

The purpose of second execution mode is effectively to utilize lead powder, even the content of its above-mentioned metallic lead composition greater than 30 weight %, always needs a large amount of equipment investments because produce the lead powder with stabilised quality.

In other words, second execution mode has such purpose: even in this lead powder, be predefined for more than or equal to 30 weight % by the amount that makes the red lead composition, also can obtain the positive pole not second to first execution mode.

In the above-described first embodiment, when anodal activated feedstock and red lead powder, help to improve anodal life performance.Yet when red lead component content during more than or equal to 30 weight %, the adhesion between active material reduces, so the increase of red lead composition is limited, and to give full play to the effect that prolongs anodal life performance be impossible by containing the red lead powder.In second execution mode, this problem is solved by the content of metallic lead in the lead powder of adjusting anodal activated feedstock.

Second execution mode will be further described hereinafter.

Contain 0.05 weight % calcium and contain the lead alloy of 1.5 weight % tin by expansion, preparation height is 72mm, the wide 45mm of being and thickly is the grid of 2.9mm.

Filling positive electrode active materials lead plaster to the thickness for preparing according to prescription listed in the table 4 to these grids separately is 3.0mm, with listed sample in the table 4 respectively, for these samples prepare a plurality of pole plates separately.

With the slaking under the condition identical with first execution mode of these samples, total charge volume of each personal 20Ah carries out anodization (changing into) then, carries out one time 24 hours discharge comprising the dilute sulfuric acid that in concentration is 28%, to form positive pole.

The purity of employed red lead powder is 95%.

(evaluation test 1)

Then to different positive pole according to the listed formulation of table 4, under the condition identical with first execution mode to the PbO after changing into ₂Weight percent contains than testing separately with porosity.The results are shown in Table 4.

Table 4

Sample number into spectrum	Lead plaster				Positive pole after changing into
							Lead powder (weight %)	Red lead composition (weight %)	Metallic lead in the lead powder (weight %)	Dilute sulfuric acid proportion-volume (l)	??PbO 2(weight %)	The % porosity
	??A-1	??100	??0	??26	??1.16-2.2	??92.5							??62
??A-2							??88	??12	??26	??1.16-2.2	??94.5	??62
	??A-3	??82	??18	??26	??1.16-2.2	??94.8							??63
??A-4							??76	??24	??26	??1.16-2.2	??95.6	??63
	??A-5	??73	??27	??26	??1.16-2.2	??95.6							??63
??A-6							??70	??30	??26	??1.16-2.2	??95.8	??63
	??A-7	??64	??36	??26	??1.16-2.2	??96.1							??64
??A-8							??58	??42	??26	??1.16-2.2	??96.8	??64
	??A-2′	??88	??12	??35	??1.16-2.2	??94.5							??62
??A-3′							??82	??18	??35	??1.15-2.2	??94.8	??62
	??A-4′	??76	??24	??35	??1.16-2.2	??95.6							??63
??A-5′							??73	??27	??35	??1.16-2.2	??95.6	??63
	??A-6′	??70	??30	??35	??1.16-2.2	??95.8							??63
??A-7′							??64	??36	??35	??1.16-2.2	??96.1	??63
	??A-8′	??58	??42	??35	??1.16-2.2	??96.2							??62
??A-2″							??88	??12	??40	??1.16-2.2	??93.5	??62
	??A-3″	??82	??18	??40	??1.16-2.2	??94.0							??62
??A-4″							??76	??24	??40	??1.16-2.2	??95.0	??63
	??A-5″	??73	??27	??40	??1.16-2.2	??95.4							??62
??A-6″							??70	??30	??40	??1.16-2.2	??95.9	??64
	??A-7″	??64	??36	??40	??1-16-2.2	??95.7							??63
??A-8″							??58	??42	??40	??1.16-2.2	??96.0	??64
	??A-6???	??70	??30	??28	??1.16-2.2	??96.2							??63
??A-7							??64	??36	??28	??1.16-2.2	??96.2	??64
	??A-8	??58	??42	??28	??1.16-2.2	??96.5							??64
??A-6′							??70	??30	??31	??1.16-2.2	??95.8	??62
	??A-7′	??64	??36	??31	??1.16-2.2	??96.1							??63
??A-8′							??58	??42	??31	??1.16-2.2	??96.3	??63

(evaluation test 2)

Under the condition identical with first execution mode, to be different from the evaluation test 1 with corresponding other three positive poles of each sample number into spectrum, carry out the measurement of the discharge capacity B of initial capacity A and the 5th circulation separately.The discharge capacity of its result and the 5th circulation is listed in the table 5 with the result (Capacity Ratio B/A) of the ratio of initial capacity A.

Fig. 5 has shown that for every kind of different metallic lead composition the discharge capacity of the 5th circulation changes with the change of red lead composition.

Table 5

Sample number into spectrum	Initial capacity A (Ah)	The discharge capacity (Ah) of the 5th circulation	Capacity Ratio B/A
				??A-1	??2.78	??2.25	??0.809
??A-2	??2.81	??2.78	??0.989
				??A-3	??2.80	??2.76	??0.986
??A-4	??2.81	??2.75	??0.979
				??A-5	??2.82	??2.69	??0.954
??A-6	??2.86	??2.56	??0.896
				??A-7	??2.83	??2.35	??0.830
??A-8	??2.80	??2.20	??0.786
				??A-2′	??2.79	??2.77	??0.993
??A-3′	??2.79	??2.76	??0.989
				??A-4′	??2.79	??2.76	??0.989
??A-5′	??2.82	??2.72	??0.965
				??A-6′	??2.85	??2.69	??0.944
??A-7′	??2.81	??2.61	??0.929
				??A-8′	??2.83	??2.59	??0.915
??A-2″	??2.77	??2.77	??1.000
				??A-3″	??2.77	??2.75	??0.993
??A-4″	??2.80	??2.77	??0.989
				??A-5″	??2.84	??2.79	??0.982
??A-6″	??2.84	??2.74	??0.965
				??A-7″	??2.80	??2.69	??0.957
??A-8″	??2.84	??2.60	??0.915
				??A-6	??2.83	??2.59	??0.916
??A-7	??2.85	??2.51	??0.882
				??A-8	??2.84	??2.44	??0.860
??A-6′	??2.86	??2.68	??0.936
				??A-7′	??2.86	??2.62	??0.914
??A-8′	??2.85	??2.57	??0.902

In above-mentioned evaluation test 2, the discharge capacity of measured the 5th circulation uses the variation for the red lead composition in the lead powder of every kind of metallic lead composition to show in Fig. 5.

From Fig. 5 and table 4 and table 5 as can be seen, A-2～A-5 compares with sample, sample A-1 and sample A-6～A-8 obviously have lower discharge capacity and Capacity Ratio (B/A) in the 5th circulation, wherein, in sample A-1, with the metallic lead composition is the main component of the lead powder of 26 weight % as anodal activated feedstock, and wherein mix the red lead powder is arranged, in sample A-6～A-8, with the metallic lead composition is the main component of the lead powder of 26 weight % as anodal activated feedstock, and the wherein mixed red lead composition that has more than or equal to 30 weight %, in sample A-2～A-5, with the metallic lead composition is the main component of the lead powder of 26 weight % as anodal activated feedstock, and the wherein mixed red lead composition that 12 weight %～27 weight % are arranged.

Yet, A-2～A-8 compares with sample, sample A-2 '～A-8 ' (particularly sample A-6 '～A-8 ') has demonstrated the discharge capacity of the 5th circulation and the raising of Capacity Ratio (B/A) respectively, wherein, in sample A-2 '～A-8 ', with the metallic lead composition is the main component of the lead powder of 35 weight % as anodal activated feedstock, and the wherein mixed red lead powder that 12 weight %～42 weight % are arranged.

Also having observed this trend in sample A-2 "～A-8 ", in sample A-2 "～A-8 ", is the main component of the lead powder of 40 weight % as anodal activated feedstock with the metallic lead composition, and the same mixed red lead powder that has.

This may be owing to the following fact: have excessive red lead composition in the anodal activated feedstock of sample A-6～A-8, has lower adhesion between the active material particles after therefore changing into, simultaneously in sample A-6 '～A-8 ' and sample A-6 "～A-8 ", increase to 35 weight % or 40 weight % as metallic lead composition in the lead powder of anodal activated feedstock main component, make in maturing process the red lead composition can with metallic lead composition generation chemical reaction, this has strengthened interparticle adhesion.

In addition, by Fig. 5 studies show that to the best of breed scope of red lead composition in the lead powder and metallic lead composition, A-6～A-8 compares with sample, sample A-6 ～A-8 and sample A-6 '～A-8 ' show the discharge capacity of the 5th circulation of raising, therefore improved Capacity Ratio (B/A), sample A-6 ～A-8 and sample A-6 '～A-8 ' comprise the lead powder that the metallic lead composition is 28 weight % and 31 weight % respectively, and sample A-6～A-8 comprises the lead powder that the metallic lead composition is 26 weight %.

Can think according to this fact to have a flex point, be that Capacity Ratio (B/A) or life performance show violent variation at this flex point place between 28 weight % and the 26 weight % at the metallic lead composition.

Because the metallic lead composition in the employed lead powder is 25 weight %～30 weight % in the production of common positive pole, therefore second execution mode is not given full play to the effect of the life performance of the positive pole that improvement prepares as anodal activated feedstock by this lead powder, overcome the effect that is difficult to prepare following positive pole but brought into play: described positive pole is by making as anodal activated feedstock with the lead powder of red lead powder, and the red lead content in the powder of described red lead is more than or equal to 30 weight %.

In other words, in second execution mode, even when using the containing metal lead composition more than or equal to the lead powder of 31 weight %, by the red lead composition being predefined for more than or equal to 30 weight %, can obtain Capacity Ratio (B/A) as calculated more than or equal to 0.9 positive pole, therefore help to improve lead powder output with good life performance.

Especially, when the applied metal lead composition is the lead powder of 35 weight %～40 weight %, can obtain to have better life performance, promptly Capacity Ratio (B/A) is more than or equal to 0.91 positive pole.

On the other hand, even when using the metallic lead composition to be the lead powder of 25 weight %～30 weight %, as long as the metallic lead composition just can obtain to have the positive pole of high power capacity than (B/A) in the lead powder as in sample A-6 in the scope of 28 weight %～30 weight %.

Above-mentioned evaluation test 1 and evaluation test 2 are about at 62% o'clock in anodal porosity and make.This is because by seeing among Fig. 2 and Fig. 3, when the red lead composition surpasses 30 weight %, attempt to prevent to have the positive pole of this porosity in the discharge capacity of the 5th circulation and the deterioration aspect the Capacity Ratio (B/A).Certainly, do not use so high lead powder of metallic lead component content, also can make porosity be lower than 62% just have a good life performance.

In addition, when the metallic lead composition in the lead powder was 31 weight %～40 weight %, even the red lead composition is less than or equal to 30%, preferred 12 weight %～30 weight % also can produce same effect.

The metallic lead composition is worthless more than or equal to 40 weight % in the lead powder, because the lead powder particle diameter that can cause producing thus as the use of the ball milling type lead-power machine of main modern lead powder production equipment becomes big, this not only exerts an influence to the performance of positive pole, and improved the oxidation rate of metallic lead, therefore brought the problem of undesirable lead powder storage.

Above-mentioned evaluation test 1 and evaluation test 2 are all based on the metallic lead composition in the lead powder.Yet,, therefore need to reduce the metallic lead composition in the lead powder because feasible being difficult in process of production of the increase of metallic lead composition controlled condition in the lead powder.

Therefore, contain lead powder and red lead powder and can also contain the metallic lead powder, rather than increase the metallic lead composition in the lead powder as the anodal activated feedstock of main component.

For this is confirmed, carry out following evaluation test.

(evaluation test 3)

The positive electrode active materials lead plaster is prepared by anodal activated feedstock under the condition identical with second execution mode, and described anodal activated feedstock is by being that the lead powder of 26 weight % mixes according to listed prescription in the table 6 with red lead powder and metallic lead powder and prepares with the metallic lead component content.The anodal activated feedstock lead plaster that will so prepare then be filled into second execution mode in the employed identical grid, to thickness be the sample of 3.0mm with institute's column number in the preparation table 6.For these samples prepare a plurality of pole plates separately.

With the slaking under the condition identical with second execution mode of these samples, total charge volume of each personal 20Ah carries out anodization (changing into) then, carries out one time 24 hours discharge comprising the dilute sulfuric acid that in concentration is 28%, to form positive pole.

The purity of employed red lead powder is 95%.

Under the condition identical, measure the PbO after these positive poles change into separately then with first execution mode ₂Percentage by weight and porosity.The results are shown in Table 6.

Table 6

Sample number into spectrum	The raw material of positive electrode active materials				Positive pole after changing into
							Lead powder (weight %)	Red lead composition (weight %)	Metallic lead powder (weight %)	Metallic lead composition (%)	??PbO 2(weight %)	The % porosity
	??A-1	??100.0	??0.0	??0.0	??26.0	??92.5							??62
??A-2							??88.0	??12.0	??0.0	??22.3	??94.5	??62
	??A-3	??82.0	??18.0	??0.0	??21.3	??94.8							??63
??A-4							??76.0	??24.0	??0.0	??19.8	??95.6	??63
	??A-5	??73.0	??27.0	??0.0	??19.0	??95.6							??63
??A-6							??70.0	??30.0	??0.0	??18.2	??95.8	??63
	??A-7	??64.0	??36.0	??0.0	??16.6	??96.1							??64
??A-8							??58.0	??42.0	??0.0	??15.1	??96.8	??64
	??a-4′	??75.5	??24.0	??0.5	??20.1	??95.5							??63
??a-5′							??72.0	??27.0	??1.0	??19.7	??95.5	??63
	??a-6′	??68.0	??30.0	??2.0	??19.7	??95.3							??62
??a-7′							??60.0	??36.0	??4,0	??19.6	??94.1	??62
	??a-8′	??52.0	??42.0	??6.0	??19.5	??93.5							??62
??a-2″							??85.0	??12.0	??3.0	??25.1	??94.5	??62
	??a-3″	??77.0	??18.0	??5.0	??25.0	??95.2							??62
??a-4″							??68.0	??24.0	??8.0	??25.7	??95.0	??62
	??a-5″	??64.5	??27.0	??8.5	??25.3	??93.6							??61
??a-6″							??60.5	??30.0	??9.5	??25.2	??92.8	??62
	??a-7″	??52.5	??36.0	??11.5	??25.2	??89.8							??61
??a-8″							??44.5	??42.0	??13.5	??25.1	??88.2	??61
	??a-2	??78.0	??12.0	??10.0	??30.5	??85.3							??61
??a-3							??70.0	??18.0	??12.0	??30.2	??83.0	??60
	??a-4	??62.0	??24.0	??14.0	??30.1	??80.5							??59
??a-9′							??47.5	??45.0	??7.5	??19.6	??93.8	??62
	??a-10′	??43.2	??48.0	??8.8	??20.0	??93.7							??62

(evaluation test 4)

Under the condition identical with second execution mode, to be different from the evaluation test 3 with corresponding other three positive poles of each numbering, carry out the measurement of the discharge capacity B of initial capacity A and the 5th circulation separately.The discharge capacity of its result and the 5th circulation is listed in the table 7 with the result (Capacity Ratio B/A) of the ratio of initial capacity A.

Fig. 6 has shown along with the variation of the metallic lead composition at containing metal lead powder end and along with the variation of red lead composition, the variation of initial capacity, Fig. 7 has shown the variation of the discharge capacity of the 5th circulation under condition same as described above, and Fig. 8 has shown the variation of Capacity Ratio under condition same as described above (B/A).

Selecting the metallic lead component content in above-mentioned evaluation test 3 and the evaluation test 4 is that the reason of 26% sample is that in the evaluation test 2 formerly of this lead powder, along with the increase of red lead composition, the discharge capacity of the 5th circulation has demonstrated significant reduction.

Table 7

Sample number into spectrum	Initial capacity A (Ah)	The discharge capacity B (Ah) of the 5th circulation	Capacity Ratio B/A
				??A-1	??2.78	??2.25	??0.809
??A-2	??2.81	??2.78	??0.989
				??A-3	??2.80	??2.76	??0.986
??A-4	??2.81	??2.75	??0.979
				??A-5	??2.82	??2.69	??0.954
??A-6	??2.86	??2.56	??0.895
				??A-7	??2.83	??2.35	??0.830
??A-8	??2.80	??2.20	??0.786
				??a-4′	??2.80	??2.70	??0.964
??a-5′	??2.80	??2.74	??0.979
				??a-6′	??2.81	??2.67	??0.950
??a-7′	??2.75	??2.60	??0.945
				??a-8′	??2.71	??2.58	??0.952
??a-2″	??2.71	??2.68	??0.989
				??a-3″	??2.76	??2.70	??0.978
??a-4″	??2.76	??2.73	??0.989
				??a-5″	??2.72	??2.64	??0.971
??a-6″	??2.65	??2.60	??0.981
				??a-7″	??2.49	??2.45	??0.984
??a-8″	??2.41	??2.46	??1.021

??a-2	??2.39	??-	??-
				??a-3	??2.11	??-	??-
??a-4	??1.99	??-	??-
				??a-9′	??2.61	??2.50	??0.958
??a-10′	??2.52	??2.25	??0.893

As in Fig. 6～Fig. 8 and table 6 and the table 7 as can be seen, the lead powder that when the metallic lead component content as main component is 26 weight % mixes with the metallic lead powder, and and then during with the red lead powder, the percentage of metallic lead composition reduces with the increase of red lead composition in the anodal activated feedstock, but when containing the metallic lead powder and remedy this loss, its content can improve.

The result can see that the discharge capacity of the 5th circulation improves.

For example, the red lead component content is that to contain the metallic lead composition be 18.2 weight % to the sample A-6 (identical with sample A-6 in the table 5) of 30.0 weight %, when mixing the content that makes the metallic lead powder with the metallic lead powder and reach 2.0 weight %, sample a-6 ' contains the metallic lead composition of 19.7 weight % simultaneously.

In addition, when mixing the content that makes the metallic lead powder with the metallic lead powder and reach 9.5 weight %, sample a-6 " the metallic lead composition that contains 25.2 weight %.Under any circumstance, all can improve the percentage by weight of metallic lead composition in the anodal activated feedstock.

As a result, compare with the situation that does not contain the metallic lead powder, the discharge capacity of the 5th circulation is improved.

Yet, the red lead component content is the metallic lead composition that the sample A-7 (identical with the sample A-7 in the table 5) of 36.0 weight % and sample A-8 (identical with the sample A-8 in the table 5) that the red lead component content is 42.0 weight % contain 16.6 weight % and 15.1 weight % respectively, when mixing the content that makes the metallic lead powder with the metallic lead powder and reach 4.0 weight % and 6.0 weight % respectively, sample a-7 ' and sample a-8 ' contain the metallic lead composition of 19.6 weight % and 19.5 weight % respectively simultaneously.

In addition, when mixing the content that makes the metallic lead powder with the metallic lead powder and reach 11.5 weight % and 13.5 weight % respectively, sample a-7 " and sample a-8 " contains the metallic lead composition of 25.2 weight % and 25.1 weight % respectively.

Found that, can improve the percentage by weight of metallic lead composition in the anodal activated feedstock, and compare with the situation that does not contain the metallic lead powder, can also improve the discharge capacity of the 5th circulation, but initial capacity reduces among sample a-7 " and sample a-8 " and the sample a-2 ～sample a-4 .

This may be because the following fact: compare with sample A-8 with sample A-7, sample a-7 " and sample a-8 " has demonstrated and has changed into back PbO ₂The reduction of percentage by weight.

This may be because the following fact: when the content of metallic lead powder surpassed 10 weight %, metallic lead powder and red lead powder reacted, and except strengthening the intergranular adhesion of positive electrode active materials, had also produced the effect that reduces anodal formation efficiency.

This will be clearly by the following fact: the initial capacity of sample a-2 ～sample a-4 descends, and these samples contain the metallic lead powder that makes the metallic lead composition surpass 30.0 weight %.

In addition, can obviously find out from Fig. 6～Fig. 8 and table 6 and table 7, it is the lead powder of 26 weight % that sample a-9 ' and sample a-10 ' contain the metallic lead composition as main component that mixes with the metallic lead powder, and and then make the content of its red lead composition be respectively 45.0 weight % and 48 weight % with the red lead powder, the discharge capacity of the 5th circulation of described sample has demonstrated significant reduction.

Can obviously find out from above-mentioned introduction, using the metallic lead component content is under the situation of lead powder as anodal activated feedstock of 26 weight %, when the red lead composition is predefined for 30 weight %～42 weight %, and contain when making the metallic lead composition be the metallic lead powder of 19 weight %～26 weight %, can improve the discharge capacity of initial capacity and the 5th circulation.

Especially, when the metallic lead powder that is contained is less than or equal to 10 weight %, as among sample a-4 '～a-8 ' and the a-2 "～a-6 ", then can significantly produce above-mentioned effect.

Even make to contain in the lead powder and be predefined for more than or equal to 19 weight % to situation less than the metallic lead composition of 26 weight % by containing the metallic lead powder, the red lead composition is predefined for is less than or equal to 30 weight %, preferred 12 weight %～30 weight %, above-mentioned to produce as Fig. 6～same effect shown in Figure 8.

About technology effective range of the present invention, its spirit is, and is on the basis of above-mentioned first and second execution modes and evaluation test 1～evaluation experimental 4, with the configuration as the main component of anodal activated feedstock of lead powder and red lead powder, preferred:

1. in the positive pole of lead acid accumulator, contain the anodal grid that is filled with lead plaster in the described positive pole, described lead plaster obtains by the anodal activated feedstock and the dilute sulfuric acid kneading that will mainly contain lead powder and red lead powder, red lead composition in the above-mentioned anodal activated feedstock be more than or equal to 5 weight % to less than 30 weight %, preferred 5 weight %～24 weight %;

2. the red lead component content is 12 weight %～42 weight % in the above-mentioned anodal activated feedstock, and the metallic lead composition in the lead powder is 31 weight %～40 weight %;

3. above-mentioned anodal activated feedstock also contains the metallic lead powder, and the red lead composition is 12 weight %～42 weight % in the raw material, and the metallic lead composition is extremely less than 26 weight % more than or equal to 19 weight % in the raw material; With

4. in addition, in the raw material content of metallic lead powder less than 10 weight %.

The 3rd execution mode

The 3rd execution mode relates to such configuration: by the average grain diameter of restriction red lead powder, even contain a large amount of red lead powder in the lead powder, also can improve self-discharge characteristics, and can not harm the cycle life performance of lead acid accumulator according to the lead acid battery positive electrode of first and second execution modes.

By contain the red lead powder in lead powder, described lead powder can improve the self-discharge characteristics of lead acid accumulator by utilizing Tianjin, island type ball mill or the production of Burton type lead-power machine.Yet, when containing a large amount of red leads powder, the generation lead sulfate that reacts of the sulfuric acid in red lead powder and the electrolyte, described lead sulfate grows to subsequently greater than the hole in the positive pole, therefore the destruction that causes the active material integrated structure reduced anodal life performance, and this is disadvantageous.

In the 3rd execution mode, the particle size distribution of red lead powder is predefined for suitable scope with respect to the lead powder particle size distribution, even like this when the red lead powder in the lead powder to be included in (main component of positive electrode active materials) and sulfuric acid reaction generate lead sulfate, the particle diameter of lead sulfate with respect to the average grain diameter of lead powder also can not increase too many.

In this configuration, can prevent that the integrated structure of active material is damaged, make and can bring into play by containing the effect of the raising self-discharge characteristics that the red lead powder produced, and do not reduce the service life of lead accumulator performance.

The 3rd execution mode will be further described hereinafter.

Employed lead powder is produced with Tianjin, island type ball mill in this execution mode, and the content of its average grain diameter and metallic lead composition is respectively 2.3 μ m and 25 weight %～30 weight %.

The average grain diameter of red lead powder is about 2.2 μ m.

The mixture and the dilute sulfuric acid of lead powder and red lead powder are mediated, with preparation positive electrode active materials lead plaster.

The positive electrode active materials lead plaster of preparation like this is filled in hauling type grid and the casting grid slaking under the condition identical with first execution mode then.

In the present embodiment, lead powder and red lead powder are dispersed in the mixed solvent of 3: 1 cyclohexanol and methyl alcohol, measure its sinking speed simultaneously and calculate average grain diameter.

Table 8 listed during mediating and slaking after be the lead plaster density of the anodal activated feedstock preparation of 0 weight %～50 weight % by the red lead component content.

The reason that the content of red lead composition is limited in 50 weight % is, even surpass 50 weight % when the content of red lead composition, also can following cycle life performance do not exerted an influence (referring to table 10).

By with the red lead component content the lead powder that changes below the 50 weight % and the mixture of red lead powder mix with dilute sulfuric acid the anodal active lead plaster density of making mediating during, after slaking and the drying almost all with not contain the anodal active lead plaster density that the red lead prepares identical.

The fact can be thought thus, in the step of mediating anodal active lead plaster, dilute sulfuric acid and red lead powder etc., and the reactivity of lead powder and red lead powder and dilute sulfuric acid and much at one.

Here the proportion of employed dilute sulfuric acid is 1.16, and mixed proportion is 2.0 liters of the anodal activated feedstocks that every 10kg mainly contains lead powder and red lead powder.

Table 8

Red lead content (weight %)	Lead plaster density (g/cm during the kneading 3)	Slaking and dried lead plaster density (g/cm 3)	Remarks
				??0	??4.02	??3.44	Comparative Examples
??10	??4.03	??3.43	Embodiment 1
				??20	??4.04	??3.45	Embodiment 2
??30	??4.02	??3.47	Embodiment 3
				??40	??4.03	??3.45	Embodiment 4
??50	??4.02	??3.45	Embodiment 5

The 40kg/dm that is producing by piling up ²Pressure under, formed positive pole, negative pole and the meticulous glass film plates retainer capacity of being installed to are equivalent on the valve-regulated lead-acid battery of 7AH (20 hour rate), described positive pole is that 1.10 dilute sulfuric acid carries out so-called slot type and changes into and prepare by slaking listed in the his-and-hers watches 8 and dried positive pole (comprising the casting grid) with proportion, described negative pole by much at one technology by changing into and drying prepares.

The electrolyte that has been injected in the valve-regulated lead-acid battery is that proportion is 1.300 dilute sulfuric acid.

So the valve-regulated lead-acid battery of preparation is comparative example and embodiment 1～embodiment 5.The electric current of each 10 hour rate of using by oneself carries out about 150% auxiliary charging to these valve-regulated lead-acid batteries, places 30 days at 40 ℃, detects self-discharge characteristics then.

Similarly, the 40kg/dm that is producing by piling up ²Pressure under, listed slaking and dried positive pole (comprising the hauling type grid) in the his-and-hers watches 8, carry out slaking and dried negative pole and meticulous glass film plates retainer by technology much at one and assemble, carry out so-called box changing into then, be equivalent to the valve-regulated lead-acid battery of 7AH (20 hour rate) with the preparation capacity.

As electrolyte, can use proportion is 1.225～1.245 dilute sulfuric acid, so that make its proportion reach 1.300 box changing into when finishing.

Like this Zhi Bei valve-regulated lead-acid battery also as a comparative example with corresponding with the red lead composition respectively embodiment 1～embodiment 5, placed 30 days at 40 ℃, similarly detect self-discharge characteristics then.

In order to measure self-discharge characteristics, the difference of the mean value of three discharge cycles after the discharge of circulation is for the first time charged with 10 hour rate currents of using 8.4AH after 30 days with placement is divided by 30.Quotient be multiply by 100 draw self-discharge rate.Table 9 has shown the result.

Table 9

Anodal type	Self-discharge rate (%/sky)
			Slot type changes into the battery of preparation	The box battery that changes into preparation
	Comparative example	??2.5			??2.1
Embodiment 1			??2.0	??1.6
	Embodiment 2	??1.4			??1.0
Embodiment 3			??1.2	??0.9
	Embodiment 4	??1.2			??0.8
Embodiment 5			??1.1	??0.8

As can be seen from Table 9, change into all to demonstrate along with the increase of red lead composition by slot type and reduce with the box self-discharge rate that changes into the sample of preparation.

When red lead composition during more than or equal to 30 weight %, the reduction of self-discharge rate is slack-off slightly.

In addition, contain the absolute value of self-discharge rate of the valve-regulated lead-acid battery by the box positive pole that changes into preparation less than containing the self-discharge rate of valve-regulated lead-acid battery that changes into the positive pole of preparation by slot type.

Subsequently, carried out the valve-regulated lead-acid battery that slot type changes into carry out the cycle life performance test under the following condition according to JISC8702 above-mentioned, probe temperature is 25 ℃ ± 2 ℃.

Discharge 0.25CA 2 hours

Charging 0.1CA 6 hours

By per 25 circulations with the discharging current that is equivalent to 0.25CA from complete charged state to final voltage for the 1.7V/ battery discharges, carry out the affirmation of capacity.It is cycle life that battery is demonstrated descended 50% or cycle criterion when lower of initial capacity of capacity.

These results are as shown in table 9.

As can be seen, the battery of embodiment 5 (the red lead composition that contains 50 weight %) also has the cycle life performance identical with Comparative Examples in table 9.

The volume test result in floating charge is used of floating charge Comparative Examples and embodiment 1～embodiment 5 as shown in figure 10.The capacity of the battery of embodiment 3 (the red lead composition that contains 30 weight %) descends minimum.

For floating test, by 60 ℃, under the condition of 2.275V/ battery, quicken floating test, carried out the affirmation of capacity in every month.

The affirmation of capacity is carried out under the condition identical with above-mentioned cycle life performance test.60% or the lower point that capacity are dropped to initial capacity are judged to be float life.

The average grain diameter peak value of listed red lead powder is about 2.2 μ m and (is about 1.0 times of lead powder average grain diameter in the table 8; Hereinafter be called " red lead A ").Lead acid accumulator is about 5.0 μ m respectively by the average grain diameter peak value and (is about 2.2 times of lead powder average grain diameter; Hereinafter referred to as " red lead B "), be about 10.5 μ m and (be about 4.6 times of lead powder average grain diameter; Hereinafter referred to as " red lead C ") and be about 14.9 μ m and (be about 6.5 times of lead powder average grain diameter; Hereinafter referred to as " red lead D ") the red lead powder preparation.

The results are shown in Table 10 to the acceleration floating charge test of self discharge test that these batteries carried out, cycle performance test and 60 ℃ under the condition identical with the 3rd execution mode.

The particle size distribution of red lead A～red lead D as shown in figure 11.

The average grain diameter of lead powder is 2.3 μ m.

Table 10

Red lead grain diameter of components ratio		(1.0 red lead A)	(2.2 red lead B)	(4.6 red lead C)	(6.5 red lead D)
						40% self-discharge rate [%/sky]	0 weight %	??2.5	??-	??-	??-
10 weight %	??2.0	??2.5	??2.7	??2.9
					20 weight %		??1.4	??1.6	??2.6	??3.0
30 weight %	??1.2	??1.3	??2.6	??3.2
					40 weight %		??1.2	??1.3	??2.9	??3.2
50 weight %	??1.1	??1.2	??3.0	??3.2
					Cycle life		0 weight %	300 circulations	??-	??-	??-
10 weight %	310 circulations	310 circulations	290 circulations	280 circulations
						20 weight %	320 circulations	320 circulations	280 circulations	270 circulations
30 weight %	340 circulations	330 circulations	270 circulations	260 circulations
						40 weight %	320 circulations	310 circulations	270 circulations	250 circulations
50 weight %	310 circulations	300 circulations	270 circulations	240 circulations
						60 ℃ of float life	0 weight %	12.5 month	??-	??-	??-
10 weight %	13.2 month	13.2 month	12.5 month	11.0 month
					20 weight %		14.2 month	14.2 month	11.8 month	10.2 month
30 weight %	15.3 month	15.0 month	10.7 month	9.8 month
					40 weight %		14.8 month	14.4 month	10.2 month	9.7 month
50 weight %	14.4 month	14.4 month	9.9 month	9.3 month

In table 10 as can be seen, when red lead composition percentage by weight is identical, by the cycle life of the lead acid accumulator of red lead C and red lead D preparation than short by the lead acid accumulator of red lead A and red lead B preparation.

This may be because when the average grain diameter of red lead powder surpasses 2.2 times of lead powder average grain diameter, by decompose the particle diameter increase of the lead sulfate crystal that the red lead powder generates with dilute sulfuric acid, has destroyed the integrated structure of positive electrode active materials.

This also may be because the lead sulfate productive rate reduces, and has increased in the self discharge test process to measure with the red lead of sulfuric acid reaction.As a result of, 60 ℃ of floating currents that quicken the floating charge test period increase, and have quickened the rate of corrosion of anodal grid, have therefore reduced float life.

In Figure 12, can see, when the red lead composition increases, as long as the average grain diameter of red lead powder is less than or equal to 2.2 times of the lead powder average grain diameter, then 40 ℃ discharge rate will reduce, when the red lead composition increases, as long as the average grain diameter of red lead powder is more than or equal to 2.2 times of the lead powder average grain diameter, then 40 ℃ discharge rate will raise.

No matter can obviously find out from this fact, be battery to be carried out slot type changes into or box changing into, and helps to reduce self-discharge rate by comprising the effect that the red lead powder produced.

Judge that according to foregoing description for 40 ℃ self-discharge rate, preferred red lead composition is 2.2 times that the average grain diameter of 20 weight %～50 weight % and red lead powder is less than or equal to the lead powder average grain diameter.Preferred red lead composition is that 30 weight %～50 weight % and red lead powder average grain diameter are 1.0 times of lead powder average grain diameter.

In addition, for cycle life, preferred red lead composition is 2.2 times that 10 weight %～50 weight % and red lead powder average grain diameter are less than or equal to the lead powder average grain diameter.

Preferred red lead composition is 2.2 times that 20 weight %～40 weight % and red lead powder average grain diameter are less than or equal to the lead powder average grain diameter.

In addition, for 60 ℃ of cycle lives, preferred red lead composition is 2.2 times that 10 weight %～50 weight % and red lead powder average grain diameter are less than or equal to the lead powder average grain diameter.

Preferred red lead composition is 2.2 times that 20 weight %～40 weight % and red lead powder average grain diameter are less than or equal to the lead powder average grain diameter.

In addition, the 3rd execution mode is described with reference to the lead acid accumulator that comprises meticulous glass film plates retainer.Because this lead acid accumulator is under the pressure,, also can brings into play the effect that comprises the red lead powder and can not cause coming off of active material even the red lead composition is 50 weight %.

The 4th execution mode

The 4th execution mode is the positive pole according to the lead acid accumulator of above-mentioned first to the 3rd execution mode, wherein use the lead powder of producing by the lead alloy that contains scheduled volume antimony (Sb), even thus when the red lead composition increases, the early stage deterioration that also can suppress anodal cycle life performance, suppress simultaneously because the softening caused discharge capacity of positive electrode active materials reduces, thereby the lead acid accumulator with excellent cycle life performance is provided.

When positive pole when making as the red lead powder of anodal activated feedstock and lead powder end, the binding ability of active material and grid strengthens.Yet, when lead powder is made by the lead alloy that contains antimony, strengthened the binding ability of active material particle by the cooperative effect that combination produced of lead powder and red lead powder.

Particularly, when the red lead composition based on anodal activated feedstock was 5 weight %～50 weight %, the binding ability of positive electrode active materials and grid strengthened.In addition, when use by antimony (Sb) content based on the weight of lead be the lead alloy of 0.005 weight %～0.1 weight % make lead powder the time, can suppress the softening of positive electrode active materials, significantly improve anodal life performance.

The 4th execution mode will be further described hereinafter.

The Pb-Sb alloy that has different antimony (Sb) content with the ball mill processing is to produce lead powder.

These lead powder are made by 7 kinds of lead alloys, and described lead alloy contains the metallic lead composition of 25 weight %～30 weight % and antimony (Sb) composition that is respectively 0.001 weight %, 0.005 weight %, 0.01 weight %, 0.05 weight %, 0.1 weight %, 0.5 weight % and 1 weight % based on plumbous weight.

In addition, also use the lead powder (antimony content of making by pure lead: 0 weight %).

Then above-mentioned various lead powder being mixed makes red lead content be respectively 3 weight %, 5 weight %, 10 weight %, 20 weight %, 30 weight %, 45 weight %, 50 weight % and 75 weight % based on anodal activated feedstock, with preparation positive electrode active materials lead plaster, mediating back lead plaster density is 3.85g/cm ³

Subsequently, above-mentioned lead plaster is filled into separately to contain Ca content be that 0.08 weight %, Sn content are in the hauling type grid of Pb alloy of 1.5 weight %, slaking and dry under the condition identical with first execution mode then is the positive pole that does not change into of 1.6mm with preparation thickness.

This positive pole that does not change into shows that lead plaster density is 4.02g/cm ³, and porosity is 59%.

Preparation is used for being filled to these positive electrode active materials in the grid, makes that plumbous mole is identical in different formulations.

In addition, as mentioned above, when the addition of tin increased, anodal grid showed that corrosion resistance improves, but when the addition of tin during more than or equal to 1.2 weight %, the active material that does not change into weakens with combining of grid.

Therefore, consider that from conventional experience the range of application of present embodiment is that tin content is the lead alloy of 1.5 weight %, its mainly cause active material with by mixing the problem that combines of the grid that tin prepares.

Rated capacity is that 36Ah (5 hour rate) and voltage are the lead acid accumulator of 2V, is prepared by 6 positive poles, 7 thick the using with the 3rd execution mode same procedure for the negative pole of 1.3mm and polyethylene separator by the method preparation identical with the 3rd execution mode.

In addition, make similar lead acid accumulator by positive pole, this positive pole contains the positive electrode active materials lead plaster of being made by lead powder, and described lead powder does not contain the lead alloy production of red lead powder and produced by pure lead by containing antimony (Sb).

Various lead acid accumulator cycle life performances are tested, and comparing with the capacity reduction that causes owing to active material is softening owing to active material on the grid peels off the capacity reduction that causes, the result as shown in figure 13.

Cycle life performance test is carried out under the following conditions: ambient temperature is 40 ℃, with the current discharge of 20A 1 hour, with the constant current charge of 5A 5 hours (discharge capacity 125%).

For the affirmation capacity, discharge electric current with 20A under 40 ℃ ambient temperature of the 25th circulation is carried out.After voltage reaches 1.7V, measure discharge capacity.

During the affirmation of cycle life test or capacity, be less than or equal to 50% of rated capacity when confirming that discharge capacity drops to, and when the capacity of display no longer raises in discharge subsequently, determine the life-span of battery.

Pure plumbous preparation lead powder by not containing the end, red lead prepares the positive electrode active materials lead plaster by this lead powder, is 100% with the period of the lead acid accumulator that comprises this positive electrode active materials lead plaster, and the cycle life among Figure 13 is than the value of expression with respect to this period.

Can see that in Figure 13 the life-span that comprises the lead acid accumulator of the positive pole of being made by positive electrode active materials lead plaster (by the lead powder preparation of the pure plumbous preparation that does not contain the red lead powder) stopped in the starting stage of cycle life performance test.

When taking this lead acid accumulator apart and check, find that positive electrode active materials peels off the decline that has caused positive electrode capacity from the grid, has therefore limited the capacity of battery.

On the other hand, the lead acid accumulator that comprises the positive pole of making by the positive electrode active materials lead plaster, wherein said positive electrode active materials lead plaster is made more than or equal to the anodal activated feedstock of 5 weight % by the red lead content of powder, no matter lead powder is by pure lead or by the lead alloy production that contains antimony, its life-span did not all stop in the starting stage of cycle life performance test.Therefore, obtained confirmation by containing red lead powder raising cycle life performance.

Therefore can confirm no matter lead powder is by pure lead or lead alloy production, the battery that wherein contains the red lead powder all can prevent the reduction of its capacity, and prevents that its life-span from stopping in the starting stage of cycle life performance test.

It is believed that by pure plumbous that produce and red lead component content and in the cycle life performance test, have the effect that prevents that initial capacity from reducing greater than the prepared lead acid accumulator of the lead powder of 30 weight %.Yet, have now found that lead acid accumulator by a kind of lead powder preparation that contains the production of antimony (Sb) lead alloy does not have by another kind and contain the effect that the lead acid accumulator of the lead powder preparation of antimony (Sb) lead alloy production is approved.

This is owing to the following fact: the 4th execution mode is the lead acid accumulator of malcompression, along with the carrying out of charge-discharge circulation, experiences the softening of positive electrode active materials and peels off process.Yet, can think that by following description this is because the lead powder by containing the production of antimony (Sb) lead alloy and the cooperative effect that combination produced of red lead powder.

In addition, compare with the lead acid accumulator with higher red lead component content, the lead acid accumulator that contains 3 weight % red lead compositions demonstrates bigger capacity in the starting stage of cycle life performance test to be reduced.This trend is similar with the trend of the lead acid accumulator that is prepared by the pure plumbous lead powder of producing.

This may be because the percentage by weight of red lead composition is very little, has limited the effect of red lead composition.

Following effect is proved: compare with the lead acid accumulator that is prepared by the pure plumbous lead powder of producing, by the lead acid accumulator that contains the lead powder preparation that antimony (Sb) lead alloy produces in the cycle life performance test, and in the red lead composition surpasses the scope of 30 weight %, demonstrate littler capacity and reduce.Yet, in the scope of red lead composition, by using the effect that does not almost have or obtain to improve the life-span by the lead powder of antimonial lead alloy production above 50 weight %.

Can judge that from The above results red lead composition percentage by weight is preferably 5 weight %～50 weight % based on anodal activated feedstock.

Hereinafter the condition that will play one's part to the full to the antimony that is included in the lead powder is described.

As shown in figure 13, when the content of red lead composition is 5 weight %～50 weight %, with compare by the lead acid accumulator of pure plumbous lead powder preparation of producing, can find that by the antimony content based on lead be the cycle life performance that the lead acid accumulator of lead powder preparation of the lead alloy production of 0.005 weight %～0.1 weight % has raising.

When checking after the end-of-life, confirm that these lead acid accumulators have the capacity of the positive limited of being subjected to.

Yet, have been found that when the lead powder that uses antimony content to produce more than or equal to the lead alloy of 0.5 weight % of lead, opposite with above-mentioned situation, the cycle life performance deterioration.

As the result of overhaul after the end-of-life, find that above-mentioned phenomenon is caused by following mechanism: negative pole is faster than anodal deterioration, and this has limited discharge capacity.

Therefore, obviously, when anodal activated feedstock contains the red lead powder of 5 weight %～50 weight %, and be the lead alloy of 0.005 weight %～0.1 weight % when producing based on the content of plumbous weight by antimony (Sb), can give full play to effect to cycle life performance.

In all above-mentioned execution modes, used grid by drawing in the net to produce.Because this grid is by in blocks with the lead alloy roll-in, cutting on sheet draws in the net the groove of this sheet to produce, so the grid that obtains has than the more smooth surface of grid by Foundry Production.

Therefore, positive electrode active materials is low with the binding ability of casting grid with the binding ability ratio of grid.Therefore, increase the further deterioration that the positive electrode active materials porosity causes the binding ability of positive electrode active materials and grid.Yet, when anodal activated feedstock contains the red lead powder, can overcome the deterioration of binding ability, making becomes possibility by having the lead acid accumulator that excellent productive hauling type grid obtains to have excellent cycle life characteristics.

Therefore, the present invention also can be applied to and contain in the storage battery of casting grid.

Industrial applicibility

As mentioned above, according to the present invention, as long as anodal grid is made more than or equal to the metal of 1.2 % by weight by tin content, then the maturation stage in the production process of positive pole produces the tin-oxide film, weakened the binding ability of active material and anodal grid, but the binding ability of anodal active grille and active material can be not weakened by the red lead powder that comprises scheduled volume in anodal activated feedstock.

In addition, contain at anodal activated feedstock in the situation of red lead powder, the adhesion between active material is deteriorated. Yet, by the metallic lead composition in the predetermined lead powder in anodal activated feedstock or raw material and metallic lead powder is mixed, can be in maturation stage or the redox reaction that changes into step acceleration red lead and metallic lead subsequently, so that changing into the deteriorated possibility that becomes that suppresses adhesion when step finishes, obtain thus the positive pole that can use for a long time.

Therefore, the present invention has made very huge industry contribution.

Claims (8)

1. the positive pole of a lead acid accumulator, this positive pole comprises:

The anodal grid of making more than or equal to the lead alloy of 1.2 weight % by tin content and

Be filled in lead plaster wherein, described lead plaster is mediated as the anodal activated feedstock of main component and dilute sulfuric acid and is obtained by containing lead powder and red lead powder, the content of red lead composition is 5 weight %～50 weight % in the wherein said anodal activated feedstock, and the positive pole of the lead acid accumulator of the lead plaster preparation made from anodal activated feedstock thus has the positive electrode active materials porosity more than or equal to 58% after changing into.

2. the positive pole of lead acid accumulator as claimed in claim 1, the content of the red lead composition in the wherein said anodal activated feedstock is more than or equal to 5 weight % and less than 30 weight %, and the positive pole of the lead acid accumulator of the lead plaster preparation made from anodal activated feedstock thus has the positive electrode active materials porosity more than or equal to 58% after changing into.

3. the positive pole of lead acid accumulator as claimed in claim 1, the content of the red lead composition in the wherein said anodal activated feedstock is 12 weight %～42 weight %, the content of the metallic lead composition in the described lead powder is 31 weight %～40 weight %, and the positive pole of the lead acid accumulator of the lead plaster preparation made from anodal activated feedstock thus has the positive electrode active materials porosity more than or equal to 58% after changing into.

4. the positive pole of lead acid accumulator as claimed in claim 3, wherein in described anodal activated feedstock, also contain metal lead powder, become to assign to calculate by the metallic lead in the metal lead powder of described lead powder and therefore interpolation, the content of the metallic lead composition in the described anodal activated feedstock is more than or equal to 19 weight % or less than 26 weight %, and the positive pole of the lead acid accumulator of the lead plaster preparation made from anodal activated feedstock thus has the positive electrode active materials porosity more than or equal to 58% after changing into.

5. the positive pole of lead acid accumulator as claimed in claim 1, the content of the red lead composition in the wherein said anodal activated feedstock is 10 weight %～50 weight %, and the average grain diameter of described red lead powder is less than or equal to 2.2 times of described lead powder average grain diameter.

6. the positive pole of lead acid accumulator as claimed in claim 1, wherein said lead powder are that the lead alloy of 0.005 weight %～0.1 weight % is made by its antimony content.

7. as the positive pole of each described lead acid accumulator in the claim 1～6, wherein said anodal grid is the hauling type grid.

8. lead acid accumulator, this lead acid accumulator contains the positive pole just like each described lead acid accumulator in the claim 1～7.

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