CN202839873U - Sealed lead storage battery - Google Patents
Sealed lead storage battery Download PDFInfo
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- CN202839873U CN202839873U CN2012205045626U CN201220504562U CN202839873U CN 202839873 U CN202839873 U CN 202839873U CN 2012205045626 U CN2012205045626 U CN 2012205045626U CN 201220504562 U CN201220504562 U CN 201220504562U CN 202839873 U CN202839873 U CN 202839873U
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- lead accumulator
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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Abstract
The utility model provides a sealed lead storage battery which comprises a polar plate group, an electrolyte and a trough for receiving the polar plate group and the electrolyte. The polar plate group comprises an anode plate, a cathode plate and a diaphragm between the anode plate and the cathode plate. The anode plate comprises an anode grid and an anode lead plaster coated on the anode grid. The cathode plate comprises a cathode grid and a cathode lead plaster coated on the cathode grid. The sealed lead storage battery is characterized in that at least one of the anode grid and the cathode grid is a hauling grid. In the hauling grid, the thickness of the upper grid close to a lug is greater than that of the lower grid far from the lug. A reinforcing rib is arranged on the inner surface of the bottom of the trough, so that a liquid storage space for storing the dissociative electrolyte is formed between the bottom end of the polar plate group and the inner surface at the bottom of the trough.
Description
Technical field
The utility model relates to a kind of sealed type lead accumulator, specifically, relates to the design improved by grid and electric groove, thereby has improved the sealed type lead accumulator of discharge capacity, battery life and vibration proof.
Background technology
That lead accumulator has is cheap, stable output, be suitable for the advantage such as heavy-current discharge, therefore has widely purposes as the main power source of vehicle launch, electric motor car or portable dam, stand-by power supply etc. always.Wherein, the sealed type lead accumulator for example analysing valve control type lead-acid accumulator battery (VRLA) since have non-maintaining, without the advantage of leakage, become just gradually main flow.
The sealed type lead accumulator mainly is comprised of battery case, pole plate group and sulfuric acid electrolyte, the pole plate group is clipped barrier film and is laminated by positive plate, negative plate, and battery case comprises be used to the rectangle electricity groove that holds this pole plate group and electrolyte and the lid with safety valve that the peristome of this electricity groove is sealed.Positive and negative pole plate all adopts grid type plate, lead plaster (active material) is filled on the alloy grid of being made by lead alloy and obtains.About the alloy grid that uses in the lead accumulator, tend at present adopt and draw in the net grid and replace gradually traditional casting grid.
Drawing in the net grid is to cut the net that daraf(reciprocal of farad) is made by reciprocating type, is provided with lug on the frame at an upper portion thereof, and the lug of identical polar welds together by bus-bar, is connected on lead accumulator and the pole that outside terminal links to each other.Because drawing in the net grid is to carry out current collection by the lug that is arranged on the top frame, the therefore bottom of more past grid, current density is lower, and the reaction of battery is difficulty comparatively.In order to improve the utilization ratio of active material, hope is taked and the proportional plumbous amount of current density at the different parts of grid, thereby reduce the consumption of the lead alloy in the grid integral body, need to take the grill designs structure of top thicker (being that lead content is more), bottom thinner (being that lead content is less) this moment.
But above-mentioned such top grill designs thicker, that the bottom is thinner (being designated hereinafter simply as " upper thick and lower thin ") is used in open flooded batteries, for example automobile SLI battery usually.In the sealed type lead accumulator, owing to there is electrolyte stratification phenomenon as described below, the grill designs of this " upper thick and lower thin " is not widely adopted always.
In the sealed type lead accumulator, usually adopt sulfuric acid as electrolyte, according to the difference of using state, be divided into absorption electrolyte in the barrier film that is adsorbed on take glass fibre as main body and the colloidal electrolyte of gelation.
Absorption electrolyte is to insert the barrier film of being made by fine glass fibre between positive plate and negative plate, has not only isolated positive and negative pole plate, and has kept the necessary sulfuric acid electrolyte amount of discharge.In such hermetic lead accumulator, the diffusion velocity of sulfuric acid is very fast, is the main flow of hermetic lead accumulator.But in this battery, be accompanied by the carrying out that discharges and recharges, the proportion of electrolyte can be in vertical direction generation deviation, and hyperbaric electrolyte is because Action of Gravity Field is accumulated in the bottom of electric groove, and the proportion of the electrolyte on top is lower, namely occurs easily so-called " stratification phenomena of electrolyte ".
Thereby colloidal electrolyte is to make the immobilising mode of electrolyte with adding gelating agent in the electrolyte, and electrolyte stratification this moment phenomenon is difficult for occuring, but compares with absorption electrolyte, and battery performance and battery life are relatively poor.
In the flooded batteries such as SLI, the amount of electrolyte is more, and the degree of freedom that circulates in electric groove is high, and the vibration of automobile is so that disturbance often occurs the electrolyte of inside battery, and therefore the sulfuric acid proportion in electric groove upper and lower part becomes even easily.
And the normally fixing use state of sealed type lead accumulator is affected by gravity, and the proportion of the electrolyte of electric groove bottom raises easily, the proportion of the electrolyte on electric groove top reduces easily, so the stratification phenomena of electrolyte is particularly remarkable.
If the sulfuric acid proportion of electric groove bottom uprises, the easy corrosion in bottom of the especially anodal grid in grid bottom then, and negative plate is difficult to be recharged, along with the carrying out that discharges and recharges, the discharging product that generates active material in the bottom of negative plate is lead sulfate, cause deteriorated, the grid fracture of negative plate etc., cause thus shorten the useful life of battery, the fast-descending of discharge capacity.Usually do not adopt the reason of the grill designs of " upper thick and lower thin " in Here it is the sealed type lead accumulator.
Above-mentioned electrolyte stratification phenomenon has also limited the scope of operable electrolyte density in the sealed type lead accumulator, thereby has limited battery capacity.At present, as the method that prevents electrolyte stratification phenomenon, mainly be to strengthen confining force to electrolyte etc. by the improvement of barrier film.For example, thus disclose in the patent documentation 1 and a kind ofly at pole plate raised line be set and compress the method that fibreglass diaphragm between the positive/negative plate improves the confining force of electrolyte.But this method needs specially to form raised line at pole plate, thereby the making of battery is comparatively complicated.
On the other hand, about the design of electric groove in the sealed type lead accumulator, for preventing the purposes such as short circuit or alleviation swelling stress, proposed between pole plate group and electric trench bottom, to be provided with space part in the past.For example, disclose in the patent documentation 2 in order to prevent that negative plate and positive plate from internal short-circuit occuring and in electric groove inside edge reinforcement is set in the bottom of pole plate group, is overlapped on this reinforcement the bottom of negative plate.Disclose in the patent documentation 3 between the bottom of electric trench bottom and pole plate group space part has been set, assimilated the pressure that the expansion by positive plate brings by this space part.
But the pole plate group of sealed type lead accumulator mainly is parts such as the bus-bar, pole of top section and being fixed in the electric groove, because electrolyte is few, shortage is to the cushioning effect of vibration, if in the bottom of electric groove space part as described above is set, then when carrying or installation, easier because of vibration so that lug occurs damagedly, cause current collection decline, be electrically connected the situations such as bad.In order to improve the vibration proof of battery, the outer surface that discloses in the patent documentation 4 at electric trench bottom arranges rubber blanket to prevent from vibrating the infringement that battery is brought.
But, still do not have in the prior art to propose to carry out the technical scheme that design improved improves battery life, discharge capacity and vibration resistance simultaneously by grid and electric groove to the sealed type lead accumulator.
List of references
Patent documentation 1: Japanese kokai publication hei 6-124725
Patent documentation 2: Japanese kokai publication sho 59-91675
Patent documentation 3: Japanese kokai publication sho 59-217963
Patent documentation 4: Chinese utility model patent CN201156563Y
The utility model content
In order to address the above problem, the utility model provides a kind of sealed type lead accumulator, and it can access good discharge capacity and life-span and vibration resistance by the grid of lead accumulator and the design of electric groove are improved.
Specifically, the electric groove that sealed type lead accumulator of the present utility model comprises pole plate group, electrolyte and holds this pole plate group and electrolyte, described pole plate group comprises positive plate, negative plate and the barrier film between positive plate and negative plate, described positive plate comprises anodal grid and is coated on anode diachylon on the described anodal grid, described negative plate comprises the negative pole grid and is coated on cathode lead plaster on the described negative pole grid, it is characterized in that
In described anodal grid and the described negative pole grid at least one be for drawing in the net grid, draw in the net in the grid described, near the thickness of the upper grid of lug greater than the thickness away from the bottom grid of lug,
Bottom interior surface at described electric groove is provided with reinforcement, thereby is formed with the liquid storage space that stores free electrolyte between the bottom interior surface of the bottom of described pole plate group and described electric groove.
Preferably, described reinforcement extends into cross-like since four summits along diagonal on the bottom interior surface of described electric groove, and its top contacts with the bottom of described pole plate group.
Preferably, draw in the net in the grid described, consist of the width of rib of described upper grid greater than the width of the rib that consists of described bottom grid.
Preferably, draw in the net in the grid described, when regulation is that upper area, 30%～60% zone are central region, 60%～100% zone when being lower area from begin 0～30% zone near the top frame of lug, the width of the rib in this Three regions reduces in accordance with the order from top to bottom successively.
Preferably, the ratio of the rib width of described upper area and the rib width of described lower area is counted the scope of 101%-140%, the more preferably scope of 103%-130% with percentage.
Preferably, the height of described reinforcement, be that the distance of described reinforcement from the top to the bottom interior surface of described electric groove is 2mm～8mm, more preferably 3mm～7mm.
Preferably, the height of described reinforcement is 3mm～7mm at place, described four summits, and begins to reduce gradually towards described cornerwise crosspoint from described four summits, and its top forms arcuation.
Preferably, the height of described reinforcement at place, described cornerwise crosspoint be place, described summit height 30%～80%.
Preferably, described reinforcement is to arrange continuously or discontinuously.
Preferably, described electrolyte is that proportion is the above sulfuric acid electrolyte of 1.34g.
Preferably, when the height of described reinforcement was 3mm～7mm, the proportion of described sulfuric acid electrolyte was 1.34g/cm
3～1.38g/cm
3
Preferably, described anodal grid and described negative pole grid are the above-mentioned grid that draws in the net.
Preferably, described barrier film is fibreglass diaphragm.
According to sealed type lead accumulator of the present utility model, by at electric trench bottom reinforcement being set, form the liquid storage space between pole plate group and the electric trench bottom inner surface, avoided the stratification phenomena of electrolyte to the adverse effect of battery performance, thereby can adopt the grill designs of " upper thick and lower thin ", therefore effectively improved the utilization ratio of lead in the grid, the electrolyte of high specific weight can be adopted simultaneously, therefore the lead accumulator that possesses simultaneously good discharge capacity, life-span and vibration resistance can be accessed.
Description of drawings
Fig. 1. the employed schematic diagram that draws in the net grid in the sealed type lead accumulator of the present utility model, (a) front view, (b) end view.
Fig. 2 .(a) schematically expression utilizes diel to make the figure that draws in the net the operating state during grid of the present utility model, (b) schematically represents the vertical view of dynamic model in the above-mentioned diel (upper sword) and the position relationship of quiet mould (lower sword).
Fig. 3. the top is the vertical view that schematically represents to be provided with of the present utility model electric groove unit (E-1), (E-2) and the polycrystalline substance (E-3) of reinforcement, and the below is the end view of each reinforcement.
Fig. 4. schematically the end view of the element cell of above-mentioned electric groove unit (E-1) has been used in expression.
Fig. 5. expression possesses the schematic diagram of the electric groove of a plurality of electric grooves unit (E-1), (a) vertical view; (b) stereogram.
Fig. 6. expression possesses the schematic diagram of the electric groove of a plurality of electric grooves unit (E-2), (a) vertical view; (b) stereogram.
Fig. 7. schematically represent the end view of the structure of the element cell in the comparative example.
Embodiment
Below, with reference to accompanying drawing, sealed type lead accumulator of the present utility model is elaborated.
(draw in the net grid)
Draw in the net the lug operated by rotary motion of grid on top frame (curren-collecting part), when lead accumulator is discharged and recharged, current density by grid is larger in the close upper grid of lug, on the contrary, less in the current density in the bottom grid of lug away from, electric current is larger when particularly discharging, this effect is remarkable, therefore wish to use and the proportional plumbous amount of current density at the different parts of grid, namely adopt the thickness of upper grid greater than the grill designs of the what is called " upper thick and lower thin " of the thickness of bottom grid, to reduce use amount plumbous in the grid integral body, improve the utilization ratio of active material.
In the exploitation of automobile with the SLI flooded batteries, owing to need large electric current to pass through during the engine start of automobile, therefore especially need the grid of this design shape.And the developing history of sealed type lead accumulator (VRLA) is shorter than SLI battery, and original mainly as the stand-by power supply use, does not imagine large electric current and passes through, so seldom consider the grill designs that employing is such.Along with the sealed type lead accumulator is increased gradually in the requirement aspect the heavy-current discharge characteristic, hope is also adopted such grill designs in the batteries such as VRLA battery, but as aforementioned, because the peculiar electrolyte stratification of sealed type lead accumulator phenomenon, the grill designs of " upper thick and lower thin " is considered to that battery performance is had adverse influence, can greatly shorten battery life, so this design does not obtain actual utilization.
Of the present utility model being characterised in that adopted the grill designs of " upper thick and lower thin " in the grid of sealed type lead accumulator." upper thick and lower thin " refers near the thickness of the upper grid of lug greater than the thickness away from the bottom grid of lug.More specifically, if consist of near the rib of the upper grid of lug thicker, grid integral thickness thickening then, consumption of lead is many in the grid; If formation is thinner away from the rib of the bottom grid of lug, then the grid integral thickness is thinner, and consumption of lead is few in the grid.In the production process of grid, because it is consistent being used to form the thickness of the plumbous band of raw material of rib, therefore the thickness of rib is also basic identical, the principal element that affects the rib thickness is to cut the rib width that forms when drawing, therefore, the fineness that can represent with " rib width " rib, and then the thickness of expression grid.That is, in the grid of " upper thick and lower thin ", the width of the rib of formation upper grid is greater than the width of the rib that consists of the bottom grid.
As shown in Figure 1, drawing in the net in the front view of grid 1 shown in Fig. 1 (a), top frame 3 is the widest, is provided with lug 2 on it, and in addition, bottom frame 4 is also wider, with intensity and the planarization of guaranteeing grid integral body.For the rib 5 in the zone in addition, taked the grill designs of " upper thick and lower thin ", that is to say that the rib width of upper grid is greater than the rib width of bottom grid.Like this, can use at the different parts of grid and the proportional plumbous amount of current density, reduce use amount plumbous in the grid integral body, and improve the utilization ratio of active material.
Particularly, when regulation is that upper area (A), 30%～60% zone are that central region (B), 60%～100% zone are when being lower area (C) from begin 0～30% zone near the top frame of lug, shown in the end view of Fig. 1 (b), the width of top rib is represented as d
A, the width of middle part rib is represented as d
B, the width of the rib of bottom is represented as d
COf the present utility model being characterised in that, the rib width d of upper grid
ARib width d greater than the bottom grid
CMore preferably, this trizonal rib width reduces successively according to the order to C from A to B.
In above-mentioned A, B, each zone of C, the rib width can be respectively identical value, and namely the width of each rib in each zone is d
A, d
BOr d
C, the rib width in each zone can be not identical yet, for example takes rib width d
A, d
BOr d
CRespectively from top to bottom stepped minimizing or the mode that reduces continuously in zone separately.In this case, with the mean value of rib width in each zone as this regional rib width d
A, d
BOr d
C
In the utility model, the rib width d of the upper area of grid (A)
ARib width d with lower area (C)
CThe i.e. " d of ratio
A/ d
C" be controlled in percentage in 101%～140% the scope.If be lower than 101%, then the utility model is difficult to embody by the obtained effect of the grill designs of " upper thick and lower thin ", if be higher than 140%, the then productivity of grid difficulty, and rib is corrosion or fracture easily, causes the reduction of battery life and discharge capacity.Preferably be controlled in 103%～130% the scope, more preferably in 105%～125% scope, most preferably in 110%～120% scope.
As long as the ratio of the rib width of upper area and lower area is not then done any restriction to the concrete numerical value of each regional rib width in above-mentioned scope, can be according to the type of the general knowledge of this area and lead accumulator and suitably selection.As a preferred concrete example, for upper area (A), rib width d
ABe preferably 1.5 ± 0.4mm, if wide, then rib might expose the surface of lead plaster, contacts with sulfuric acid, makes easily the grid corrosion, causes shorter battery life; If narrow, then have large electric current by the time fuse easily and problem that active material is difficult to change into.The rib width d of central region (B)
BAs long as between upper area and lower area, be preferably 1.4 ± 0.4mm, the rib width d of lower area (C)
CBe preferably 1.3 ± 0.4mm, if wide, then the productivity of grid is difficult, if narrow, the then perishable fracture of grid, and active material is difficult to change into.
Above-mentioned grill designs can be applied in any of anodal grid and negative pole grid.Because the performance of lead accumulator mainly by positive plate control, therefore, preferably adopts the design of this " upper thick and lower thin " in positive plate.On the other hand, the generation of lead sulfate causes the volumetric expansion of negative pole grid lower end easily on the negative pole, might cause electric groove stressed excessive and break.From this angle, the preferred negative pole plate adopts the structure of " upper thick and lower thin ".The grid of further preferred positive plate and negative plate is all selected the grill designs of above-mentioned " upper thick and lower thin ".
The manufacture method of grid (draw in the net)
The grid that draws in the net of the present utility model can utilize diel to make by the common drawing process of cutting.Operable diel comprises the dynamic model with sword on a plurality of dentations and the quiet mould with sword under a plurality of prism-shaped in the utility model, by adjusting the spacing between each adjacent cut surface in dynamic model and the quiet mould, just can obtain the grid that draws in the net of " upper thick and lower thin " of the present utility model.
Lead band as raw material can adopt this area lead alloy-foil commonly used, for example contains the Pb Alloy Foil of at least a metal among Ca and the Sn, with regard to corrosion resistance and mechanical strength, preferably is made of the Pb-Ca-Sn ternary alloy three-partalloy.When use had the lead band of such alloy composition, the life characteristic of lead accumulator improved easily.
Fig. 2 (a) has schematically represented to utilize diel to make operating state during grid of drawing in the net of " upper thick and lower thin " of the present utility model.With raw material lead with 6 along its length (the horizontal direction of arrow among the figure) send between dynamic model 7 and the quiet mould 8 and carry out punching press, when the upper sword 9 of dynamic model 7 moves both vertically with respect to the lower sword 10 of quiet mould 8 and is with 6 to carry out punching press to lead, be with 6 to form many slits at lead, and launch downwards by the continuation campaign of dynamic model 7.After this punching press finishes, make lead be with 6 to move forward along its length predetermined distance, repeat above-mentioned step, thereby be with a plurality of diamond-mesh of formation at lead.The middle body of the plumbous band of raw material is not stamped, and is processed into lug in the operation described later cutting.
Shown in Fig. 2 (a), dynamic model 7 in the drawings on first of right side sword 9 be shaped as trapezoidal, with respect to the lower sword of quiet mould 8 vertically (arrow of above-below direction among the figure) move downward, at lead with the slit that forms first row.Owing to be in the edge of plumbous band, so this slit expansion amplitude is less, forms the bottom frame of grid.The upper sword 9 of second beginning from the right side is triangle, be with formation second row slit by cutting at lead, form rib between first row slit and the second row slit, the distance of two rows between the slits is the width of rib, and sword and second gap of going up between the sword are corresponding on first of this width and right side.
Shown in the vertical view of Fig. 2 (b), dynamic model 7 forms cut surface 11 with quiet mould 8 relative motions, and the gap between adjacent upper sword 9 or the adjacent lower sword 10 namely is two spacings between the adjacent cut surface 11.As can be seen from the figure, the spacing d between the adjacent cut surface in left side in figure
aBe greater than the spacing d between the adjacent cut surface on right side in figure
c, thus one, draw in the net in the grid rib width d of upper area what form
ABe greater than the rib width d of lower area
C
Employed diel is characterised in that in the utility model, and the spacing between each adjacent cut surface is not equally spaced, but from left to right reduces gradually, therewith accordingly, is tapered from top to the bottom by the formed rib width of this diel.Thus, by the spacing between the adjacent cut surface of control diel, just can have the net of different rib width with forming at lead, thereby obtain the grid that draws in the net of " upper thick and lower thin " of the present utility model.
(electric groove)
The utility model has reached and has reduced plumbous consumption by adopting the grill designs of " upper thick and lower thin ", improves the initial purpose of active material utilization.But the problem that this design brings is exactly the easy corrosion in lower end of grid.Problem for fear of the grid lower end corrosion that the stratification phenomena by electrolyte causes, the present inventors are provided with reinforcement at the electric trench bottom of lead accumulator, thereby Integral lifting the pole plate group, avoid contacting of grid bottom and the hyperbaric electrolyte that is stored in electric trench bottom.
As shown in Figure 3, the present inventors are provided with reinforcement 14 with three kinds of different designs respectively on the bottom interior surface of electric groove unit (E-1), (E-2) and (E-3), wherein, (E-1) reinforcement adopts is often that adopt and an arrangement mode that the base is parallel electric groove in the SLI battery, this arrangement mode is fairly simple, the bottom of pole plate group can stably be overlapped on the top upper surface of reinforcement, thereby forms certain liquid storage space between the bottom of pole plate group and electric trench bottom inner surface.But in this case, can only be with the pole plate group to pack into the orthogonal direction of reinforcement, the degree of freedom of electric groove design is lower.
And in (E-2) and design (E-3), reinforcement 14 is that four summits from electric trench bottom begin to extend ground along diagonal to the centre cross shaped head that forms is set.This design is compared with the design of above-mentioned (E-1) has obvious advantage, not only the stability of reinforcement is eager to excel, save material usage, and design freedom improves greatly, no matter how the pole plate group packs into, can stably be overlapped on the reinforcement, thereby solve the restriction of directivity of the placement of electrode.
In above-mentioned any design, reinforcement 14 can arrange continuously at its length direction, also can arrange discontinuously, when arranging continuously, stability is stronger, and is beneficial to the vibration resistance of battery, when interruption arranges, the degree of freedom of free electrolyte convection current that is stored in electric trench bottom is larger, to the uniformity of electrode reaction, to improve battery capacity beneficial.
The height of reinforcement is that decide according to the size of employed pole plate group and electric groove to the distance of the bottom interior surface of electric groove on the top of reinforcement, for common employed VRLA, for example is suitably 2mm～8mm.Balance angle from battery capacity and battery life is preferably 3mm～7mm.If reinforcement is too high, then the pole plate group reduces with the contact area of the sulfuric acid that is stored in electric trench bottom, the electrolyte content that causes being adsorbed in the pole plate group reduces, be unfavorable on the contrary battery capacity and life characteristic, if it is low that the height of reinforcement is spent, then can not stably contact with the bottom of pole plate group the anti-vibration performance variation of battery.
Shown in the end view of the below among Fig. 3, in (E-1) and design (E-2), the top of reinforcement 14 is the horizontal linear shape, shows that the height of reinforcement equates everywhere.But the height of reinforcement can not be to equate also everywhere, for example shown in (E-3), the height of reinforcement begins towards cornerwise crosspoint and gradually reduction from four summits of described electric groove, its top forms arcuation, at this moment, as long as the height of its highest point (place, summit) is defined as 2mm～8mm, is preferably 3mm～7mm.In this design, the convection current of free electrolyte that is stored in electric trench bottom is comparatively favourable, and the proportion of electrolyte is even easily, to the uniformity of electrode reaction, to improve battery capacity beneficial, therefore more preferred.More preferably, the height of described reinforcement at place, cornerwise crosspoint is at 30%～80% of the height at place, described summit, can take into account like this convection current of electrolyte and the stability of pole plate group.
In addition, owing to form certain liquid storage space by reinforcement is set at electric trench bottom, the free sulfuric acid in this part space can fully be adsorbed by the pole plate group, therefore not only is conducive to extending battery life, can also improve battery capacity.
In addition, the lead accumulator of sealed type is compared with liquid formula storage battery, because electrolyte is less, so vibration resistance is relatively poor.The utility model is overlapped on this reinforcement the bottom of pole plate group by between pole plate group bottom and electric trench bottom inner surface reinforcement being set, and forms certain liquid storage space at electric trench bottom, therefore, the vibration resistance of battery is improved.
In the example of the concrete set-up mode of above-mentioned reinforcement, be illustrated as an example of rectangular electric groove example, but the utility model is not limited to this.As long as can form certain liquid storage space at electric trench bottom by reinforcement is set, just be included in the scope of the present utility model.The electricity groove shape also can be other shapes beyond rectangle or the square, and need to suitably adjust this moment to the set-up mode of reinforcement.
(electrolyte)
The electrolyte of sealed type lead accumulator of the present utility model can adopt sulfuric acid solution commonly used in the lead accumulator field, has no particular limits.Usually adopting proportion in the valve-regulated lead-acid battery is 1.30～1.33g/cm
3Sulfuric acid.The present inventors find, by reinforcement is set, can effectively avoid the etching problem of grid bottom, and therefore, the utility model can adopt the higher sulfuric acid of proportion than in the past.Specifically, in the utility model, by at electric trench bottom reinforcement being set, can adopt proportion is 1.33g/cm
3Above sulfuric acid, preferably adopting proportion is 1.34g/cm
3Therefore above sulfuric acid improved the discharge capacity characteristics of battery greatly.On the other hand, too high sulfuric acid proportion can increase the corrosion to grid, therefore, preferably with the sulfuric acid specific gravity control at 1.40g/cm
3Below.
The present inventors find to have certain equilibrium relation between the height of reinforcement, sulfuric acid proportion and battery capacity, the life characteristic.Particularly, when the height of reinforcement was 3mm～7mm, preferably using proportion was 1.34～1.38g/cm
3Sulfuric acid, can reach the optimal balance point of battery life and capacity this moment.Preferred sulfuric acid specific gravity range is 1.35～1.37g/cm
3
The reason that causes above-mentioned phenomenon also is not very clear, but by inference, can think height by suitable adjustment reinforcement, so that the thicker frame of grid bottom contacts with the denseer electrolyte of electric trench bottom just, because frame is more not perishable, hyperbaric sulfuric acid has improved the current density at grid frame place simultaneously, thereby can improve battery capacity, so, battery life and battery capacity can reach preferably balance.
That is to say, the present inventors have overcome traditional prejudice that " stratification phenomena of electrolyte " in the sealed type lead accumulator can bring to battery performance adverse effect, by reinforcement is set, effectively utilized this phenomenon, not only can adopt upper thick and lower thin grill designs, and can and use the electrolyte of high specific weight, thereby under the prerequisite that does not reduce battery life, further improved battery capacity.
Particularly, by between pole plate group and electric trench bottom, reinforcement being set, promoted the height of pole plate group, the problems such as the grid lower end that caused by electrolyte stratification phenomenon is perishable, the negative plate bottom expands have been avoided, therefore can adopt upper thick and lower thin grill designs, reduced plumbous use amount, and guaranteed that battery life does not reduce.And then, owing to be formed with the liquid storage space at electric trench bottom, the sulfuric acid that proportion is high does not directly contact with pole plate group bottom, therefore can adopt the sulfuric acid of high specific weight as electrolyte, in the battery use procedure, the electrolyte in this space is replenished the supply to the pole plate group simultaneously, therefore further improved the capacity of battery.In addition, by being arranged on the reinforcement of electric trench bottom, also improve the vibration resistance of battery, obtained possessing simultaneously the sealed type lead accumulator of good discharge capacity, battery life and vibration resistance.
(lead accumulator)
Sealed type lead accumulator of the present utility model mainly is comprised of battery case, pole plate group, sulfuric acid electrolyte, the pole plate group is clipped barrier film and is laminated by positive plate, negative plate, and battery case comprises the electric groove that holds this pole plate group and electrolyte and the lid with safety valve that the peristome of this electricity groove is sealed.Positive/negative plate all adopts grid type plate, lead plaster (active material) is filled on the alloy grid that lead alloy makes and obtains.
Except adopting grid of the present utility model, electric groove, sealing-type lead-acid battery of the present utility model can prepare by manufacture method in the past commonly used.Specifically, at first, fill at the above-mentioned enterprising quadrat cream of grid that draws in the net of the present utility model.Be in the lead powder that the metallic lead by the lead oxide of 60 ~ 90 quality % and 40 ~ 10 quality % consists of as the lead plaster of active material, add entry and sulfuric acid and carry out mixing forming.Lead plaster can be filled from the one side of net, also can fill from the tow sides of net, forms pole plate of the present utility model after slaking, drying.
As shown in Figure 4, the pole plate group 12 that a plurality of positive plates, a plurality of negative plate are laminated across fibreglass diaphragm is put into an electric groove unit 13, the bottom of pole plate group 12 is overlapped on the reinforcement 14 of electric trench bottom, form an element cell.In Fig. 4, reinforcement 14 has adopted the arrangement mode of (E-1), can certainly take (E-2) or arrangement mode (E-3).Fig. 5 and Fig. 6 show respectively the schematic diagram of the electric groove that possesses a plurality of electric grooves unit 13.Reinforcement 14 adopts the arrangement mode of (E-1) among Fig. 5, and reinforcement 14 adopts (E-2) or arrangement mode (E-3) among Fig. 6.
At first, in each illustrated electric groove unit, place the pole plate group, then, opening part on electric groove top is installed the middle cover of battery that is built-in with safety valve, with the positive terminal of the both side ends of electric groove and negative terminal respectively be located at middle cover of battery on positive terminal and negative terminal be connected, and electric groove and middle cover are bondd with binding agent.Then in electric groove, inject electrolyte, after the fluid injection that cell cover and electric groove and middle cover sealing is fixing, thus form lead accumulator of the present utility model.
Lead accumulator of the present utility model is owing to adopted upper thick and lower thin design in the pole plate grid, and be provided with reinforcement at electric trench bottom, therefore can adopt the sulfuric acid electrolyte of high concentration, avoided the corrosion of electrolyte stratification phenomenon to the grid bottom, not only cell integrated vibration proof increase, and obtained good discharge capacity and life characteristic.
Embodiment
Below, utilize embodiment and comparative example to describe the utility model in detail, but the utility model is not limited to these object lessons.
Embodiment 1:
The plumbous band of raw material is sent in the diel of the present utility model, and the plumbous band of punching press is made net slice repeatedly up and down, then the net slice that obtains is carried out shaping, and fills anode diachylon or cathode lead plaster.The net that is filled with lead plaster is cut to the shape and size of regulation, form after the slaking drying positive plate of the present utility model (vertical: 121mm, horizontal stroke: 139mm, thick: 3.3mm) and negative plate (indulge: 119mm, horizontal stroke: 139mm, thick: 2.1mm).
In above-mentioned stamping procedure, adjust the spacing between each adjacent cut surface of diel, thereby will draw in the net the rib width of grid in zones of different is set as suitable value.In the present embodiment, the rib width on anodal grid top is 1.5mm, and the bottom is 1.3mm, the width ratio of top and bottom is 115%, the rib width on negative pole grid top is 1.0mm, and the rib width of bottom grid is 0.85mm, and the width ratio of top and bottom is 118%.
Then, 8 positive plates and 7 negative plates are alternatively stacked across the barrier film take glass fibre as main body, form the pole plate group.Then, the pole plate group is accommodated in each electric groove unit, so that the bottom of pole plate group just in time is overlapped on the reinforcement of electric trench bottom setting.In the present embodiment, the bottom of electric groove unit is provided with the reinforcement of E-2 type, and the height of reinforcement is 2mm.
After this, inject an amount of electrolyte in the electric groove, then middle cover and loam cake are installed and are sealed at the peristome of electric groove, obtain the VRLA type lead accumulator that battery capacity is 100Ah after changing into processing.This moment, the proportion of sulfuric acid was 1.360g/cm
3, be by resolving the numerical value of actual measurement.
Embodiment 2:
Except the height with reinforcement changes 3mm into, make in the same manner VRLA type lead accumulator with embodiment 1.
Embodiment 3:
Except the height with reinforcement changes 4mm into, make in the same manner VRLA type lead accumulator with embodiment 1.
Embodiment 4:
Except the height with reinforcement changes 5mm into, make in the same manner VRLA type lead accumulator with embodiment 1.
Embodiment 5:
Except the height with reinforcement changes 6mm into, make in the same manner VRLA type lead accumulator with embodiment 1.
Embodiment 6
Except the height with reinforcement changes 7mm into, make in the same manner VRLA type lead accumulator with embodiment 1.
Embodiment 7
Except the height with reinforcement changes 8mm into, make in the same manner VRLA type lead accumulator with embodiment 1.
Embodiment 8
Except the height with reinforcement changes 5mm into and changes the proportion of sulfuric acid into 1.33g/cm
3In addition, make in the same manner VRLA type lead accumulator with embodiment 1.
Embodiment 9
Except the height with reinforcement changes 5mm into and changes the proportion of sulfuric acid into 1.34g/cm
3In addition, make in the same manner VRLA type lead accumulator with embodiment 1.
Embodiment 10
Except the height with reinforcement changes 5mm into and changes the proportion of sulfuric acid into 1.35g/cm
3In addition, make in the same manner VRLA type lead accumulator with embodiment 1.
Embodiment 11
Except the height with reinforcement changes 5mm into and changes the proportion of sulfuric acid into 1.37g/cm
3In addition, make in the same manner VRLA type lead accumulator with embodiment 1.
Except the height with reinforcement changes 5mm into and changes the proportion of sulfuric acid into 1.38g/cm
3In addition, make in the same manner VRLA type lead accumulator with embodiment 1.
Except the height with reinforcement changes 5mm into and changes the proportion of sulfuric acid into 1.39g/cm
3In addition, make in the same manner VRLA type lead accumulator with embodiment 1.
Except the bottom in electric groove unit arranges the reinforcement of E-3 type and the height of reinforcement is changed into the 5mm, make in the same manner VRLA type lead accumulator with embodiment 1.
Except the bottom in electric groove unit arranges the reinforcement of E-1 type and the height of reinforcement is changed into the 5mm, make in the same manner VRLA type lead accumulator with embodiment 1.
Embodiment 16
Adjusting the spacing between the adjacent cut surface in the diel, is 1.45mm thereby make the rib width of anodal grid middle and upper part, and the bottom is 1.41mm, and the width ratio of top and bottom is 103%; The rib width that makes negative pole grid middle and upper part is 0.95mm, and the bottom is 0.92mm, and the width ratio of top and bottom is 103%.In addition, change the height of reinforcement into 5mm, in addition, make in the same manner VRLA type lead accumulator with embodiment 1.
Embodiment 17
Adjusting the spacing between the adjacent cut surface in the diel, is 1.5mm thereby make the rib width of anodal grid middle and upper part, and the bottom is 1.15mm, and the width ratio of top and bottom is 130%; The rib width that makes negative pole grid middle and upper part is 0.95mm, and the bottom is 0.73mm, and the width ratio of top and bottom is 130%.In addition, change the height of reinforcement into 5mm, in addition, make in the same manner VRLA type lead accumulator with embodiment 1.
Embodiment 18
Adjusting the spacing between the adjacent cut surface in the diel, is 1.5mm thereby make the rib width of anodal grid middle and upper part, and the bottom is 1.49mm, and the width ratio of top and bottom is 101%; The rib width that makes negative pole grid middle and upper part is 0.95mm, and the bottom is 0.94mm, and the width ratio of top and bottom is 101%.In addition, change the height of reinforcement into 5mm, in addition, make in the same manner VRLA type lead accumulator with embodiment 1.
Embodiment 19
Adjusting the spacing between the adjacent cut surface in the diel, is 1.5mm thereby make the rib width of anodal grid middle and upper part, and the bottom is 1.1mm, and the width ratio of top and bottom is 135%; The rib width that makes negative pole grid middle and upper part is 0.95mm, and the bottom is 0.7mm, and the width ratio of top and bottom is 135%.In addition, change the height of reinforcement into 5mm, in addition, make in the same manner VRLA type lead accumulator with embodiment 1.
Comparative example 1
Except the bottom that at electric trench bottom reinforcement is not set, makes the pole plate group directly with electric trench bottom contacts, made in the same manner VRLA type lead accumulator with embodiment 1.Wherein, the design of electric groove is referring to Fig. 7 (A).
Comparative example 2
Except reinforcement not being set, element cell is arranged in the electric groove (referring to Fig. 7 (B)) apart from the mode of the unsettled 5mm of electric trench bottom inner surface with the bottom of pole plate group at electric trench bottom, made in the same manner VRLA type lead accumulator with embodiment 1.
Comparative example 3
Except reinforcement not being set, PVC cushion block 15(being set referring to Fig. 7 (C) in the bottom of pole plate group at electric trench bottom), VRLA type lead accumulator made in the same manner with embodiment 1.
Comparative example 4
Adjusting the spacing between the adjacent cut surface in the diel, is 1.4mm thereby make the rib width of anodal grid middle and upper part, and the bottom is 1.4mm, and the width ratio of top and bottom is 100%; The rib width that makes negative pole grid middle and upper part is 0.95mm, and the bottom is 0.95mm, and the width ratio of top and bottom is 100%.In addition, change the height of reinforcement into 5mm, in addition, make in the same manner VRLA type lead accumulator with embodiment 1.
To each lead accumulator that obtains in above-described embodiment 1～19, the comparative example 1～4, carried out under the following conditions the evaluation test of battery performance.
(1) evaluation of discharge capacity
Battery to fully charged state, under 25 ± 2 ℃ ambient temperature, carry out the constant-current discharge that discharging current is 0.25C, be the 10.5V/cell(monocell at final discharging voltage) time finish discharge, record the discharge time (unit for minute) of each battery, according to discharge time, estimate the discharge capacity of battery with following standard.
◎: more than 220 minutes
Zero-◎: 210～220 minutes
Zero: 200～210 minutes
Zero-△: 190～200 minutes
△: 180～190 minutes
*: below 180 minutes
(2) evaluation of battery life:
(1) initial capacity C
0Mensuration:
At first, to the battery of fully charged state, under 25 ± 2 ℃ ambient temperature, carry out the constant-current discharge that discharging current is 0.25C, when final discharging voltage is 1.75V/cell, finish discharge, h discharge time of record battery
0, obtain as follows initial capacity C
0:
Initial capacity C
0=discharging current (I) * discharge time (h
0)
(2) recover charging:
To the battery behind the said determination, under 25 ± 2 ℃ ambient temperature, carry out the constant voltage charge that charging voltage is 2.275V/cell, maximum charging current is 0.4C, charges 6～16 hours, reaches fully charged state.
(3) high temperature trickle charge:
Put above-mentioned battery into 60 ± 2 ℃ insulating box, carry out the constant voltage charge that charging voltage is 2.275V/cell, continue 3 weeks of charging.
(4) mensuration of discharge capacity C:
Above-mentioned battery is taken out from insulating box, after placing 12～25 hours under 25 ± 2 ℃ the environment, carry out with (1) the same terms under discharge, measure h discharge time of this moment, obtain as follows discharge capacity C, with this process as a charge and discharge cycles.
Discharge capacity C=discharging current (I) * discharge time (h)
(5) repeatedly carry out the step of above-mentioned (2)～(4), when the discharge capacity C that calculates is lower than initial capacity C
050% the time, finish test, estimate the life characteristic of battery according to the charge and discharge cycles number of times that carries out.
◎: more than 13 times
Zero-◎: 12 times
Zero: 11 time
Zero-△: 10 times
△: 9 times
*: below 8 times
(3) evaluation of vibration patience
(1) experimental subjects and environment:
To at 30 days above-mentioned new product batteries with interior manufacturing, do not having in the specially appointed situation, 15～35 ℃ of temperature, estimate under the condition of relative humidity 25～75%.
(2) experimental procedure:
To above-mentioned battery charging, measure its static characteristic, the mensuration project comprises open circuit voltage, internal resistance, quality.Then, utilize vibration rig under following condition, battery to be applied vibration, again measure the static characteristic of battery after the end, comprise that terminal voltage, judgement have or not short circuit, open circuit, and the outward appearance of observing battery, confirm to have or not distortion, breakage or leakage, then measure discharge capacity according to above-mentioned identical method.
The condition of vibration:
(a), direction of vibration horizontal and vertical
(b), double amplitude 4mm
(c), vibration number 16.7Hz
(d), time of vibration is continuous 1 hour
(e), the posture erectility of battery
(3) evaluation criterion
◎: be that outward appearance is unchanged more than 220 minutes discharge time.
Zero-◎: be that outward appearance is unchanged more than 210～220 minutes discharge time
Zero: be 200～210 minutes discharge time, and outward appearance is unchanged.
Zero-△: be 190～200 minutes discharge time, and outward appearance is unchanged
△: be 180～190 minutes discharge time, and outward appearance is unchanged
*: be that outward appearance deforms below 180 minutes discharge time, leakage, short circuit occur or opens circuit
Be shown in following table 1 after the parameters of each storage battery obtained above and every test result gathered.
Table 1
According to the result of table 1 as can be known, in comparative example 1, although adopted the grill designs of " upper thick and lower thin ", but be not provided with reinforcement at electric trench bottom, the bottom of pole plate group directly contacts with electric groove bottom, the sulfuric acid of the high concentration of electric trench bottom has corrosion to grid at this moment, so the life characteristic of battery is relatively poor.In comparative example 2, also to adopt the grill designs of " upper thick and lower thin ", but be not provided with reinforcement at electric trench bottom, pole plate group bottom is unsettled and contact with electric groove bottom, and the life characteristic of battery is better at this moment, but vibration resistance is poor.In comparative example 3, also to have adopted the grill designs of " upper thick and lower thin ", and in the bottom of pole plate group cushion block has been set, this moment, the vibration resistance of battery was better, but life characteristic is relatively poor.In comparative example 4, although be provided with reinforcement at electric trench bottom, do not have to adopt the grill designs of " upper thick and lower thin ", so the discharge capacity of battery and life characteristic are undesirable.
Compare with comparative example 1～4, the grill designs that has adopted " upper thick and lower thin " of the present utility model and be provided with the battery of the embodiment 1～19 of reinforcement at electric trench bottom is all obtaining significant raising aspect discharge capacity, life characteristic and the vibration resistance.Especially, adopt embodiment 1～14,16～19 embodiment 15 with respect to the electric groove design of having adopted E-1 of the electric groove design of E-2 and E-3, aspect design freedom, also had superiority.
In addition, be 1.34～1.38g/cm in that the reinforcement height is defined as 3～7mm and has adopted proportion
3The embodiment 2～6,9～12,14～17 battery of sulfuric acid obtaining good balance aspect discharge capacity, the life characteristic, and having good vibration resistance.
Claims (15)
1. sealed type lead accumulator, the electric groove that it comprises pole plate group, electrolyte and holds this pole plate group and electrolyte, described pole plate group comprises positive plate, negative plate and the barrier film between positive plate and negative plate, described positive plate comprises anodal grid and is coated on anode diachylon on the described anodal grid, described negative plate comprises the negative pole grid and is coated on cathode lead plaster on the described negative pole grid, it is characterized in that
In described anodal grid and the described negative pole grid at least one be for drawing in the net grid, draw in the net in the grid described, near the thickness of the upper grid of lug greater than the thickness away from the bottom grid of lug,
Bottom interior surface at described electric groove is provided with reinforcement, thereby is formed with the liquid storage space that stores free electrolyte between the bottom interior surface of the bottom of described pole plate group and described electric groove.
2. sealed type lead accumulator according to claim 1 is characterized in that, described reinforcement extends into cross-like since four summits along diagonal on the bottom interior surface of described electric groove, and its top contacts with the bottom of described pole plate group.
3. sealed type lead accumulator according to claim 1 and 2 is characterized in that, draws in the net in the grid described, consists of the width of rib of described upper grid greater than the width of the rib that consists of described bottom grid.
4. sealed type lead accumulator according to claim 3, it is characterized in that, draw in the net in the grid described, when regulation is that upper area, 30%～60% zone are central region, 60%～100% zone when being lower area from begin 0～30% zone near the top frame of lug, the width of the rib in this Three regions reduces in accordance with the order from top to bottom successively.
5. sealed type lead accumulator according to claim 4 is characterized in that, the rib width of described upper area and the ratio of the rib width of described lower area are counted the scope of 101%-140% with percentage.
6. sealed type lead accumulator according to claim 4 is characterized in that, the rib width of described upper area and the ratio of the rib width of described lower area are counted the scope of 103%-130% with percentage.
7. sealed type lead accumulator according to claim 1 and 2 is characterized in that, the height of described reinforcement is 2mm～8mm.
8. sealed type lead accumulator according to claim 1 and 2 is characterized in that, the height of described reinforcement is 3mm～7mm.
9. sealed type lead accumulator according to claim 1 and 2, it is characterized in that, the height of described reinforcement is 3mm～7mm at place, described four summits, and begins to reduce gradually towards described cornerwise crosspoint from described four summits, and its top forms arcuation.
10. sealed type lead accumulator according to claim 7 is characterized in that, the height of described reinforcement at place, described cornerwise crosspoint be place, described summit height 30%～80%.
11. sealed type lead accumulator according to claim 1 and 2 is characterized in that, described reinforcement is to arrange continuously or discontinuously.
12. sealed type lead accumulator according to claim 1 and 2 is characterized in that, described electrolyte is that proportion is the above sulfuric acid electrolyte of 1.34g.
13. sealed type lead accumulator according to claim 8 is characterized in that, the proportion of described sulfuric acid electrolyte is 1.34g/cm
3～1.38g/cm
3
14. sealed type lead accumulator according to claim 1 and 2 is characterized in that, described anodal grid and described negative pole grid are the grid that draws in the net described in the claim 1.
15. sealed type lead accumulator according to claim 1 and 2 is characterized in that, described barrier film is fibreglass diaphragm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012205045626U CN202839873U (en) | 2012-09-28 | 2012-09-28 | Sealed lead storage battery |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012205045626U CN202839873U (en) | 2012-09-28 | 2012-09-28 | Sealed lead storage battery |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102903966A (en) * | 2012-09-28 | 2013-01-30 | 松下蓄电池(沈阳)有限公司 | Sealed-type lead storage battery |
| CN103456907A (en) * | 2013-08-19 | 2013-12-18 | 浙江吉利汽车研究院有限公司 | Reinforcing and fixing structure for battery pack |
| CN105470584A (en) * | 2014-09-30 | 2016-04-06 | 古河电池株式会社 | Lead storage battery |
| CN117790699A (en) * | 2024-02-23 | 2024-03-29 | 昆明理工恒达科技股份有限公司 | Full-automatic assembly equipment of aluminium base lead alloy composite electrode |
-
2012
- 2012-09-28 CN CN2012205045626U patent/CN202839873U/en not_active Expired - Lifetime
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102903966A (en) * | 2012-09-28 | 2013-01-30 | 松下蓄电池(沈阳)有限公司 | Sealed-type lead storage battery |
| CN102903966B (en) * | 2012-09-28 | 2018-02-27 | 松下蓄电池(沈阳)有限公司 | Sealed lead accumulator |
| CN103456907A (en) * | 2013-08-19 | 2013-12-18 | 浙江吉利汽车研究院有限公司 | Reinforcing and fixing structure for battery pack |
| CN105470584A (en) * | 2014-09-30 | 2016-04-06 | 古河电池株式会社 | Lead storage battery |
| CN105470584B (en) * | 2014-09-30 | 2017-09-29 | 古河电池株式会社 | Lead accumulator |
| CN117790699A (en) * | 2024-02-23 | 2024-03-29 | 昆明理工恒达科技股份有限公司 | Full-automatic assembly equipment of aluminium base lead alloy composite electrode |
| CN117790699B (en) * | 2024-02-23 | 2024-04-26 | 昆明理工恒达科技股份有限公司 | Full-automatic assembly equipment of aluminium base lead alloy composite electrode |
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