CN105762422A

CN105762422A - Valve control-type lead storage battery

Info

Publication number: CN105762422A
Application number: CN201510833695.6A
Authority: CN
Inventors: 松村朋子
Original assignee: GS Yuasa International Ltd
Current assignee: GS Yuasa International Ltd
Priority date: 2015-01-05
Filing date: 2015-11-25
Publication date: 2016-07-13
Anticipated expiration: 2035-11-25
Also published as: JP6548139B2; JP2016126924A; CN105762422B

Abstract

The invention relates to a valve control-type lead storage batter. In a positive pole casting grating, grain boundary corrosion, grain boundary breaking acceleration caused by the generating of the local stress extended along with the corrosion can be relieved to inhibit the breaking of the longitudinal frame close to the tab and the grating of the upper horizontal frame, and therefore the valve control-type lead storage battery having the long service lifetime can be provided. The use of the valve control-type lead storage battery is characterized in that the ratio a/b between the cross section area a of the longitudinal frame close to one side of the tab and the cross section area b of the thickest frame of the horizontal inner frame can be more than 1.3 or lower than 2.7, and preferably lower than 2.5, and in addition, the width of the tab is X, and the foot frame is disposed on the position out of a range having a distance to the center of the tab lower than 1.5 X. Preferably, the positive pole casting grating is provided with a cone-shaped part, which is expanded toward the tab part from the shoulder part of the upper horizontal frame away from the tab.

Description

Valve-regulated lead-acid battery

Technical field

The present invention relates to valve-regulated lead-acid battery, cast grid particularly to its positive pole.

Background technology

Valve-regulated lead-acid battery considers to be used for maintaining static purposes etc. from the easiness of its maintenance, and the collector body of positive plate generally uses casting grid.

Positive pole casting grid generally includes the multiple horizontal internal skeleton in the frame bone being made up of upper lower transverse frame bone and left right vertical frame bone, above-mentioned frame bone and multiple vertical internal skeleton, is arranged at the current collection ear of upper transverse frame bone and is arranged at the foot bone of lower transverse frame bone, and horizontal internal skeleton is made up of thick bone and thin bone.

In such positive plate, the corrosion that can produce grid because of life-time service extends, but owing to the upper weld of lug is in the terminal being fixed on electro bath-lid, so lug portion deforms because corrosion extends, and negative plate contact short circuit, and there is life-span shorter situation.Therefore, up to now, when positive plate bottom occurs corrosion to extend, it is advanced through deformation and the foot bone shape of extension can be absorbed.

In following patent documentation 1, describe following content: cast in grid at the positive pole maintaining static lead battery, the foot under lug is not made to be placed in saddle, even if thus producing corrosion at positive plate to extend, also extending under lug is made to move below such that it is able to prevent the short circuit that the local buckling of pole plate causes.

In following patent documentation 2, describe following content: by making the shape being shaped so as to extend along with the corrosion extension of pole plate, rupture of the foot of positive pole casting grid bottom, thus absorbing the extension of above-below direction, it is prevented that short circuit, it is provided that the lead battery lasted a long time.

In following patent documentation 3, describe following lead battery: the upper ledge bone being used in having the lead alloy plate expanding mesh is provided with the current collection ear of disalignment, and being provided with from above-mentioned current collection ear to the positive pole flase floor of the rake reduced from lug portion end height size farther out, this lead battery prevents the corrosion-deformation of positive pole flase floor and active substance from coming off.

Patent documentation 1: No. 3313275 publications of Japanese Patent No.

Patent documentation 2: No. 4092124 publications of Japanese Patent No.

Patent documentation 3: No. 4461697 publications of Japanese Patent No.

Like this, the past implements the various methods that the corrosion of the above-below direction for absorbing positive pole grid extends, and the problem of the short circuit that the deformation of grid causes is improved.

But, in recent years, in the positive pole casting grid of the valve-regulated lead-acid battery at high temperature used, at the vertical bone of lug bottom, upper transverse frame bone produces the grain boundary attack of local, break in grain boundary, produces the new problem of grid fracture etc.

Summary of the invention

It is an object of the invention to provide a kind of valve-regulated lead-acid battery that can solve the problem that above-mentioned problem.The purpose of other problems of the present invention is in that to provide a kind of valve-regulated lead-acid battery lasted a long time.

The present invention to achieve these goals, has following structure.

(1) a kind of valve-regulated lead-acid battery, it is made up of Pb-Ca-Sn alloy or Pb-Ca alloy,

Use the positive plate with positive pole casting grid, wherein this positive pole casting grid there is the multiple horizontal internal skeleton in the frame bone being made up of the vertical frame bone of upper and lower horizontal frame bone and left and right, above-mentioned frame bone and multiple vertical internal skeleton, the foot bone under off-centered lug and above-mentioned lower transverse frame bone on above-mentioned upper transverse frame bone

In described valve-regulated lead-acid battery,

The sectional area (a) of above-mentioned vertical frame bone of the side close to lug of above-mentioned positive pole casting grid is less than more than 1.3 2.7 with ratio (a)/(b) of the sectional area (b) of the thickest bone in above-mentioned horizontal internal skeleton,

If lug width is X, above-mentioned foot bone be positioned at except from lug center less than the position except the scope of 1.5X.

(2) on the basis of the valve-regulated lead-acid battery of above-mentioned (1), the sectional area (a) of above-mentioned vertical frame bone of the side close to lug of above-mentioned positive pole casting grid is less than more than 1.3 2.5 with (a)/(b) of the sectional area (b) of the thickest bone in above-mentioned horizontal internal skeleton.

(3) on the basis of the valve-regulated lead-acid battery described in above-mentioned (1) or (2), above-mentioned upper transverse frame bone has tapered portion, and the shoulder that this tapered portion is handed over from the above-mentioned vertical frame bone photo with the side away from lug extends to the position that above-mentioned lug erects.

(4) on the basis of the valve-regulated lead-acid battery of above-mentioned (3), the angle of above-mentioned tapered portion is more than 1.4 ° less than 4 °.

The present invention has said structure, thus casts in grid at positive pole, it is possible to suppress the situation producing the grain boundary attack of local at frame bone, break and cause grid to rupture in grain boundary such that it is able to provide the valve-regulated lead-acid battery of a kind of life-span length.

Accompanying drawing explanation

Fig. 1 represents positive pole casting grid involved in the present invention.

Fig. 2 represents the position of the shoulder of the present invention.

Fig. 3～Figure 11 represents the grille-like A involved by embodiments of the invention and comparative example～F, F ', G, H respectively.

Figure 12, Figure 13 represent (a)/(b) in grille-like A and grille-like B and grain boundary fracture pole plate number and the moon in life-span number relation.

Figure 14, Figure 15 represent (a)/(b) in grille-like C and grille-like D and grain boundary fracture pole plate number and the moon in life-span number relation.

Figure 16, Figure 17 represent (a)/(b) in grille-like A and grille-like C and grain boundary fracture pole plate number and the moon in life-span number relation.

Figure 18, Figure 19 represent (a)/(b) in grille-like B and grille-like D and grain boundary fracture pole plate number and the moon in life-span number relation.

Figure 20, Figure 21 represent with (a)/(b) be variable, the starting point of tapered portion in grille-like D, grille-like E and the pole plate number of grain boundary fracture and the moon in life-span number relation.

Figure 22, Figure 23 represent with (a)/(b) be variable, the position of foot bone in grille-like C, grille-like D and grille-like F and the pole plate number of quantity and grain boundary fracture and the moon in life-span number relation.

Figure 24, Figure 25 represent with (a)/(b) be variable, the position of foot bone in grille-like C, grille-like D, grille-like F and grille-like F ' and the pole plate number of quantity and grain boundary fracture and the moon in life-span number relation.

Figure 26, Figure 27 represent with (a)/(b) be variable, the pole plate number of tapered portion angle in grille-like D and grain boundary fracture and the moon in life-span number relation.

Figure 28, Figure 29 represent tapered portion angle in grille-like D, grille-like E, grille-like H and grain boundary fracture pole plate number and the moon in life-span number relation.

Detailed description of the invention

The positive pole casting grid of the present invention is common with existing positive pole casting grid in following: material is Pb-Ca-Sn alloy or Pb-Ca alloy, has a upper lower transverse frame bone and multiple horizontal internal skeleton in the frame bone that left right vertical frame bone is constituted, above-mentioned frame bone and multiple vertical internal skeleton, the foot bone under the lug of offset from center and above-mentioned pubic bone frame on above-mentioned upper transverse frame bone.

The present inventor be realised that situations below by generation is brought out the reason of the local stress that positive pole casts the local grain boundary corrosion of grid, break in grain boundary carried out investigating further, that is: extend along with the corrosion of positive pole grid, vertical bone and upper transverse frame bone to lug bottom apply stress, producing, in local, the part that corrosion is accelerated, therefore grid ruptures partly.It addition, also know: positive pole grille-like particularly vertical bone and the strength balance of transversum, the position of foot bone and the tapered portion shape of upper transverse frame bone are bigger on the generation impact of the burn into stress of local.

Casting in grid at existing positive pole, horizontal internal skeleton is made up of thick bone and thin bone.If the increasing number of thick bone, then cutting down vertical bone weight to suppress grid weight, life performance reduces, and therefore general thick bone is 2～3, remaining as thin bone.The specific surface area of thin bone is bigger, it is easy to be corroded, therefore easily horizontal expansion, and the specific surface area of thick bone is less, it is difficult to be corroded, and therefore horizontal extension is less.Therefore, producing stress at the thick bone of horizontal internal skeleton with the near intersections of vertical frame bone, grain boundary attack is accelerated.

If although it is believed that the quantity of the thick bone of horizontal internal skeleton is more, then horizontal corrosion extends evenly, and grain boundary is broken less, but from the viewpoint of grid weight, accelerates and there is the limit.

Additionally, when there is foot bone immediately below the lug of positive plate, at the vertical bone between them, the corrosion of flase floor is extended, it is difficult to be absorbed because of the restriction of tab welding structure up, it is difficult to because of the existence of foot bone in lower section be absorbed, therefore applies excessive stress, become grain boundary and break Producing reason.

Additionally, foot bone has the function of support grid, refer to and battery bottom or be arranged at the saddle of battery bottom and contact.

And know: in upper transverse frame bone, put on, because the corrosion of above-below direction extends the stress produced, the part that the intensity of upper transverse frame bone is relatively low, thus breaking and occur partly in grain boundary attack, grain boundary.

Therefore, present inventor have discovered that as shown in Figure 1, (following by casting, at positive pole, the vertical frame bone making the side close to lug in grid, be called " lug lower frame bone ") sectional area (a) and horizontal internal skeleton in the thickest bone (following, be called " horizontal in thick bone ") the ratio of sectional area (b) be that (a)/(b) is in prescribed limit, the stress that the intersection point of thick bone and vertical frame bone produces in horizontal stroke because corrosion extends can be relaxed, and by making the position that arranges of foot bone separate more than the specific length relevant to lug width immediately below lug, it is able to ensure that under lug the corrosion elongation of vertical bone, relax stress.

And, the present inventors have additionally discovered that: upper transverse frame bone can improve the mechanical strength of upper transverse frame bone by arranging the shoulder handed over from the vertical frame bone photo with the side away from lug towards the tapered portion of the position extension that lug erects, and by enabling the homogeneous current distribution of flase floor entirety to suppress to break the fracture of the grid caused because of the grain boundary attack of local of two frame bones in length and breadth, grain boundary.

If tapered portion angle is about 1 °, then mechanical strength is insufficient with the improvement of CURRENT DISTRIBUTION, if but more than 5 °, pore is easily formed during grid casting in tapered portion portion, intensity, corrosion resistance reduce.Preferred tapered portion angle range for 1.4 °～4.0 °.

If it addition, the midway with upper transverse frame bone arranges tapered portion for starting point, then easily the starting point of tapered portion being applied around stress because extending along with the grid of corrosion, grain boundary attack, grain boundary are broken acceleration.It is therefore preferable that the shoulder that the starting point of tapered portion is the side away from lug.

Additionally, as in figure 2 it is shown, shoulder refers to the scope from the starting point in grid inner arc portion to horizontal frame epiphysis.

The valve-regulated lead-acid battery lasted a long time can be provided by above cooperative effect.

[embodiment]

Following presentation embodiment.Furthermore, it is possible to be combined as all or part of of embodiment.

(example 1)

(positive pole casting grid and the making of battery)

Casting Pb-Ca-Sn alloy, makes the positive pole casting grid of the grille-like B shown in the grille-like A shown in Fig. 3 and Fig. 4,8 positive plates and 9 negative plates that use this grid is combined, makes valve-regulated lead-acid battery No.1～16 of 2V, specified 200Ah.

It addition, cast grid as positive pole, as shown in figs.5 and 6, except being except horizontal frame bone is provided with the grille-like C and grille-like D of the tapered portion started from shoulder, in the way of identical with grille-like A and B, make battery No.17～32.

Thick ratio (a)/(b) of sectional area (b) of bone, tapered portion angle, lug width are that the foot bone of the X distance from lug center is as shown in table 1 to the sectional area (a) of the lug lower frame bone of the positive pole grid that each battery uses with in horizontal stroke.

(accelerating overcharge test and evaluation methodology)

60 DEG C, the floating charge of 2.23V when carry out the quick float life test of high temperature, evaluated by the following method.

(1) at eight month, battery is disintegrated, takes out 8 positive plates, respectively the number producing in bone vertical under upper transverse frame bone (upper box bone), lug and a battery unit to rupture grain boundary has been confirmed.

(2) each month 25 DEG C, carry out the capacity validation test before 1.75V under 0.2CA, the time before 80% that is reduced to by capability retention is judged to the life-span.

In each battery, under upper transverse frame bone (upper box bone), lug, vertical bone and a battery unit produce respectively the pole plate number of grain boundary fracture, the moon in life-span number result as shown in table 1, grain boundary fracture in a battery unit produces the result of number and life performance such as shown in Figure 12～Figure 19.

[table 1]

Relative to battery No.1～8 that the position of foot bone is grille-like A immediately below lug, under the lug of battery No.9～16 of the grille-like B of the positional distance lug center 2X of foot bone, the fracture number of vertical bone reduces, it is known that particularly (a)/(b) be 1.3～2.7 scope in effectively.It addition, from Figure 12, Figure 13 it can be seen that the moon in life-span number extend, and, particularly when (a)/(b) is less than 2.0, additionally it is possible to suppress upper transverse frame bone fracture.

When having tapered portion, relative to battery No.17～24 that the position of foot bone is grille-like C immediately below lug, battery No.25～32 of the grille-like D of distance lug center 2X are when (a)/(b) is 1.3～2.7, it is also possible to suppress the fracture number based on bone vertical under the lug of grille-like D.It addition, can suppress the fracture of upper transverse frame bone by tapered portion, therefore as shown in Figure 14, Figure 15, the suppression and the life performance effect that rupture based on the grain boundary of foot bone position show with becoming apparent from.

In addition, be the battery of grille-like A immediately below lug in foot bone position with in the battery of grille-like C, according to Figure 16, Figure 17, in there is the battery of grille-like C of tapered portion, although the life-span somewhat extends, but by the braking effect of bone vertical under lug, the number of grain boundary fracture is constant, has not therefore given play to the effect arranging tapered portion.

On the other hand, it is located away from the battery of grille-like B and the battery of grille-like D at lug center in foot bone, according to Figure 18, Figure 19, there is the battery of grille-like D of tapered portion compared with the battery of grille-like B, a ()/(b) is the scope of 1.3～2.7, can suppress to produce the number of grain boundary fracture, the number prolongation of the moon in life-span.

Therefore, foot bone position and specifying when having the grille-like of tapered portion of (a)/(b) are particularly effective.

(example 2)

In order to confirm the effect of the shape of tapered portion, except cast grid use (a)/(b) as positive pole be 1.3,2.0,2.5, tapered portion do not arrive except the grille-like E shown in Fig. 7 of shoulder of horizontal frame bone, in the way of same as Example 1, be made for battery No.33～35.

Shown in the result such as table 2 and Figure 20, Figure 21 contrasted with the battery of grille-like D.

[table 2]

The tapered portion of upper transverse frame bone does not arrive battery No.33～35 of the grille-like E of shoulder compared with battery No.26,29,31 of the grille-like D of tapered portion arrival shoulder, the number of upper transverse frame bone fracture is more, according to Figure 20, Figure 21, in one battery unit grain boundary fracture number more, the moon in life-span number shorter.

Therefore, it is known that if the tapered portion of upper transverse frame bone arrives shoulder, then better effects if.

(example 3)

The impact of position and quantity in order to confirm foot bone, it is 1.3 except with (a)/(b), 2.0, 2.5, 1 grille-like C being located closely adjacent to immediately below lug in 2 foot bone, 1 root distance in 2 foot bone is from the grille-like D of lug center 1X～5X, the position of 1 foot bone and foot bone is 2X from lug center, grid construction F shown in Fig. 8 of 3X, and the position of 1 foot bone and foot bone be located remotely from lug side vertical frame bone lower section (bottom) the grille-like F ' shown in Fig. 9 positive pole casting grid beyond, battery No.36～53 are made in the way of same as Example 1.Shown in result such as table 3 and Figure 22～Figure 25.

[table 3]

Figure 22, Figure 23 indicate that the figure on the impact that rupture in grain boundary and life performance causes of the pole plate of battery of foot bone position and foot bone quantity that foot bone position is the grille-like C immediately below lug, the distance grille-like D (foot bone 2) of lug center 2X, grille-like F (foot bone 1).A ()/(b) is the scope of 1.3～2.5, regardless of the quantity of foot bone, all can manifest suppression, life performance effect that the grain boundary fracture brought because foot bone is located away from lug center produces.

It addition, Figure 24, Figure 25 indicate that foot bone is 2 and to be the grille-like C immediately below lug, foot bone be in foot bone position 2 and foot bone position is the grille-like D of 1X～3X, foot bone is 1 and the foot bone position grille-like F from lug center 3X and foot bone is 1 and grille-like F ' that foot bone position the is lower end figure on the impact that rupture in grain boundary and life performance causes of the pole plate of battery.Known: (a)/(b) is the scope of 1.3～2.5, quantity regardless of foot bone, when for the grille-like of foot bone positional distance lug center more than 1.5X, the grain boundary fracture caused because of the grain boundary attack of local, the generation broken of grain boundary is all inhibited, thus obtains the effect that life performance is excellent.

(example 4)

In order to confirm the impact of tapered portion angle, foot bone position from lug center 2X, (a)/(b) respectively 1.3,2.0,2.5 grille-like D in, except tapered portion angle is 1 °～5 °, in the way of same as Example 1, make battery No.54～68.

Additionally, in order to confirm the impact of the tapered portion angle in different grille-like, it is common in 2.0 in foot bone position from lug center 2X, (a)/(b), although the starting point of tapered portion is not shoulder for the starting point of the grille-like E of shoulder and tapered portion but lug is located off indulging in the grille-like H shown in Figure 11 of the position on frame bone, except respective tapered portion angle is 1 °～5 °, mode same as Example 1 is respectively prepared battery No.69～73, battery No.74～79.Shown in result such as table 4 and Figure 26～Figure 29.

[table 4]

Figure 26, Figure 27 indicate that the figure of the impact of the tapered portion angle in grille-like D.If the grille-like of the scope that known tapered portion angle is 1.4 °～4.0 °, then the fracture of upper transverse frame bone can be suppressed to produce.Therefore, a ()/(b) is the scope of 1.3～2.5, foot bone position is the distance from lug center 2X, thus the situation that the fracture of vertical bone is nearly free from under lug interacts, the grain boundary fracture in a battery unit can be suppressed to produce, make the battery that life performance is excellent.

Figure 28, Figure 29 are the figure impact of the tapered portion angle in grille-like E, grille-like H illustrated together with the situation of grille-like D.Battery No.69～73 of grille-like E that tapered portion is started from the midway of horizontal frame bone, 34, except the situation that tapered portion angle is 1 °, the effect arranging tapered portion is less.On the other hand, be starting point in tapered portion with shoulder, the lug not grille-like H on vertical frame bone, in battery No.75～78 of the scope that tapered portion angle is 1.4 °～4.0 °, play roughly the same effect with the situation of grille-like D.Therefore, known when lug portion is not on vertical frame bone, as long as the grille-like that the tapered portion of upper transverse frame bone starts from shoulder, then tapered portion angle is the scope of 1.4 °～4.0 °, the generation that grain boundary can be suppressed to rupture, makes the battery that life performance is excellent.

In addition, in order to confirm the foot bone position relative to grille-like H, also be made for using as shown in Figure 10 except foot bone position be immediately below lug except the battery of the grille-like G identical with grille-like H, but the battery of use grille-like A, grille-like C is too, the main grain boundary fracture producing vertical bone under lug.

[industrial utilizes probability]

A kind of valve-regulated lead-acid battery being suitable to maintain static purposes etc. can be provided.

Claims

1. a valve-regulated lead-acid battery, it is made up of Pb-Ca-Sn alloy or Pb-Ca alloy,

The positive pole casting grid used has the multiple horizontal internal skeleton in the frame bone being made up of the vertical frame bone of upper and lower horizontal frame bone and left and right, described frame bone and multiple vertical internal skeleton, the foot bone under off-centered lug and described lower transverse frame bone on described upper transverse frame bone,

Described valve-regulated lead-acid battery is characterised by,

The ratio a/b of the sectional area a and the sectional area b of the thickest bone in described horizontal internal skeleton of the described vertical frame bone of the side close to described lug of described positive pole casting grid is less than more than 1.3 2.7,

If the width of described lug is X, described foot bone is positioned at except the center from described lug is less than the position except the scope of 1.5X.

2. valve-regulated lead-acid battery according to claim 1, it is characterised in that

The ratio a/b of the sectional area a and the sectional area b of the thickest bone in described horizontal internal skeleton of the described vertical frame bone of the side close to described lug of described positive pole casting grid is less than more than 1.3 2.5.

3. valve-regulated lead-acid battery according to claim 1 and 2, it is characterised in that

Described upper transverse frame bone has tapered portion, and the shoulder that this tapered portion is handed over from the described vertical frame bone photo with the side away from described lug extends to the position that described lug erects.

4. valve-regulated lead-acid battery according to claim 3, it is characterised in that

The angle of described tapered portion is more than 1.4 ° less than 4 °.