CN102738470B - Lead accumulator grid, positive plate, pole plate group, lead accumulator and manufacture method thereof - Google Patents
Lead accumulator grid, positive plate, pole plate group, lead accumulator and manufacture method thereof Download PDFInfo
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- CN102738470B CN102738470B CN201110085830.5A CN201110085830A CN102738470B CN 102738470 B CN102738470 B CN 102738470B CN 201110085830 A CN201110085830 A CN 201110085830A CN 102738470 B CN102738470 B CN 102738470B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/70—Carriers or collectors characterised by shape or form
- H01M4/72—Grids
- H01M4/73—Grids for lead-acid accumulators, e.g. frame plates
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/70—Carriers or collectors characterised by shape or form
- H01M4/72—Grids
- H01M4/74—Meshes or woven material; Expanded metal
- H01M4/745—Expanded metal
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2220/00—Batteries for particular applications
- H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
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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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- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Cell Electrode Carriers And Collectors (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a kind of lead accumulator grid, use the positive plate of this grid, pole plate group and lead accumulator, and the manufacture method of above-mentioned lead accumulator.Described grid cuts by reciprocating the grid that draws in the net that daraf(reciprocal of farad) makes, the described grid that draws in the net has and to be interlocked the mesh formed by many ruled line, it is characterized in that, when drawing in the net described in setting that the ruling width of grid is W, grating thickness is T, representing ratio T/W=1.50 ~ 1.90 of grid tortuosity.Lead accumulator of the present invention has excellent high rate discharging cycle characteristics, is applicable to such as electric bicycle and so repeatedly carries out the charging/discharging apparatus of deep discharge.
Description
Technical field
The present invention relates to lead accumulator grid, employ the positive plate of this grid, the manufacture method of pole plate group, lead accumulator and lead accumulator.
Background technology
Lead accumulator has cheap, stable output, is suitable for the advantages such as heavy-current discharge, has a wide range of applications in the field such as main power source, stand-by power supply of vehicle launch, electric motor car or electric tool always.Lead accumulator mainly comprises open liquid formula lead accumulator and the valve-regulated lead-acid battery of sealed type, and wherein valve-regulated lead-acid battery has non-maintaining advantage, therefore applies more extensive.Valve-regulated lead-acid battery is by positive plate, negative plate, barrier film, electrolyte, form with the part such as shell of safety valve, and positive/negative plate all adopts grid type plate, is filled in by active material on special alloy grid and makes.
About lead accumulator grid, according to the difference of its manufacture method, roughly can be divided into casting grid and draw in the net grid two kinds.Compared with the casting grid obtained by casting method, the draw in the net grid (expand grid) obtained by Qie Lafa not only can save material cost, and the grid weight difference drawn out is little, and production efficiency significantly improves.Therefore, tend at present adopt and draw in the net grid and replace traditional casting grid gradually.
Drawing in the net the manufacture method of grid there will be a known and rotaryly cut daraf(reciprocal of farad) and reciprocatingly cut daraf(reciprocal of farad).Rotary daraf(reciprocal of farad) of cutting metallic plate feeding is had discoideus cutter and does to carry out cutting between a pair roller of continuous rotation to draw processing, due to grid be subject in joint-cutting and stretching step twice heavily stressed, therefore the ruling of Nodes easily ruptures, and have impact on the life performance of battery.Reciprocating cut daraf(reciprocal of farad) be metallic plate is sent into off and on there is pair of plate-shaped cutter mould in, by pumping of tabular cutter, process the slit of broad ways intermittent arrangement on a metal plate line upon line, this slit is stretched vertically downward by tabular cutter simultaneously, thus forms mesh.Because the reciprocating Nodes cutting daraf(reciprocal of farad) basic checks not match grid is in process of production exerted pressure, and ruling is not twisted, and therefore, the grid as accumulator plate can show good life performance.But traditional reciprocating shortcoming of cutting daraf(reciprocal of farad) is that speed of production is lower, in order to overcome this problem, Patent Document 1 discloses and a kind of reciprocatingly cut drawing process, by multiple tabular cutter is superimposed as V-arrangement shape at predetermined intervals, thus the oblique joint-cutting of multiple row can be formed along its length by a punching press, the method is reciprocatingly cut compared with daraf(reciprocal of farad) with traditional, can have the extension net slice of microgrid with high production efficiency manufacture.
For the lead accumulator for needing in equipment such as electric bicycle (E-Bike) repeatedly carrying out deep discharge etc., even if depth of charge (SOC) is very shallow sometimes, also need high rate discharging, under such service condition, easily produce overdischarge.During in order to suppress overdischarge, the sharply decline of cathode voltage, is necessary the electrical collector suitably reducing positive pole.
Drawing in the net the edge of grid does not exist outside frame usually, and thus compared with casting grid, electrical collector is relatively low, but active material easily overflows from grid edge, and loading is restricted.Therefore, draw in the net grid if all adopted in the positive plate and negative plate of lead accumulator, then there is battery capacity difference, active material easily overflows and cause the problems such as internal short-circuit of battery.
In order to solve the problem, propose in patent documentation 2 only to use in positive pole draw in the net grid and in negative pole, use the scheme of casting grid, thus voltage when can improve high rate discharging reduces.In addition, in patent documentation 3, causing internal short-circuit of battery to prevent active material from overflowing from positive pole grid, it is also proposed the technical scheme using in positive pole and draw in the net grid, use casting grid in negative pole.
On the other hand, the grid of alloy mainly plays a supportive role and current collection effect to active material.If between grid with active material bonding not, then easily produce the problem that active material comes off in charge and discharge process, or uneven owing to producing electrical collector in the inside of active material, the active material far away apart from grid produces the problem of easily deterioration when overdischarge.
For this reason, in patent documentation 4 ~ 7, various optimal design is done for the ruling width of grid, ruling thickness, node cross section, grating thickness and shape of a mesh etc., thus effectively prevent the corrosion fracture of ruling, improve the adhesiveness of active material, and improve the life characteristic of battery to a certain extent, but still insufficient for the cycle characteristics under high rate discharging condition.
List of references
Patent documentation 1: Chinese patent application CN1229282A
Patent documentation 2: Japanese Unexamined Patent Publication 10-321237
Patent documentation 3: Japanese Unexamined Patent Publication 10-334940
Patent documentation 4: Chinese patent application CN1420576A
Patent documentation 5: Japanese Laid-Open Patent Publication 58-5969
Patent documentation 6: Japanese Patent Publication 1-45710
Patent documentation 7: Japanese Patent Publication 1-42115
Summary of the invention
The object of the present invention is to provide a kind of lead accumulator, even if it repeats high rate discharging under shallow depth of charge (SOC), also can have good cycle life.
The present inventors find under study for action, when adopt just very draw in the net grid, negative pole be the combination of casting grid time, because the electrical collector of grid of drawing in the net of positive pole suitably declines, the overdischarge of active material during high rate discharging can be avoided to a certain extent, therefore be with positive pole, negative pole compared with the situation of drawing in the net grid or casting grid, the life-span of battery can extend a little, but still can not reach desired level.
Therefore, the present inventors are conceived to the design improvement of positive pole grid further, for how to improve active material and grid cementability and and then the high rate discharging characteristic improving battery carried out repeatedly studying, result obtains following opinion.
In the past, when employing draw in the net grid as pole plate grid time, for the ease of carrying out follow-up painting cream operation, usually to carry out Shape correction to the net slice cutting pull-shaped one-tenth.Such as in patent documentation 5, after cutting and drawing operation to terminate, net slice is pressed into the thin slice also thinner than original. g., lead tape, thus reduces grating thickness, avoid the near nodal of positive plate grid to corrode.Draw the slit gap in operation to set less owing to cutting, the ruling width of the net slice cut out is also less, and grating thickness is more ironed, therefore, in order to obtain thinner net slice, in technology in the past, what generally adopt is the scheme as far as possible reducing slit gap.Such as in patent documentation 6 and patent documentation 7, in order to make grid lightweight further, slit gap is controlled below. g., lead tape thickness.
But the present inventors find, draw in operation reciprocating cutting, need the ratio adjusting slit gap and the. g., lead tape thickness that. g., lead tape Width is formed, thus obtain suitable ruling flakiness ratio; And then, to cut draw the net slice obtained to carry out Shape correction in, if net slice is not pressed too thin, but control suitable condition, make the tortuosity of grid of drawing in the net after shaping be certain limit, excellent lead plaster coating (below sometimes referred to as " being coated with cream ") can be obtained.In addition, in follow-up lead plaster filling work procedure, by using the grid that draws in the net with above-mentioned tortuosity, easily obtain suitable lead plaster and cross filling rate, the pole plate being like this excessively filled with lead plaster is used for the positive plate of lead accumulator, even if repeat high rate discharging under shallow depth of charge, lead plaster is also not easy deterioration, can obtain excellent high rate discharging cycle characteristics.This is the effect never found in research in the past.
Based on above-mentioned opinion, the invention provides a kind of lead accumulator grid, it cuts by reciprocating the grid that draws in the net that daraf(reciprocal of farad) makes, the described grid that draws in the net has and to be interlocked the mesh formed by many ruled line, it is characterized in that, when drawing in the net described in setting that the ruling width of grid is W, grating thickness is T, represent ratio T/W=1.50 ~ 1.90 of grid tortuosity, preferred ratio T/W=1.60 ~ 1.80.
More preferably, when draw in the net described in setting the ruling thickness of grid be t time, represent ratio W/t=1.25 ~ 1.60 of ruling flakiness ratio.
In addition, the invention provides a kind of lead accumulator positive plate, it comprises above-mentioned grid and the lead plaster as positive active material that draws in the net on grid described in being filled in of drawing in the net.
Preferably, when the electrode thickness that setting is filled with the positive plate of described lead plaster is P, represent that lead plaster crosses ratio P/T=1.10 ~ 1.40 of filling rate, preferred ratio P/T=1.14 ~ 1.30.
In addition, the invention provides a kind of lead accumulator pole plate group, it comprises above-mentioned positive plate, negative plate, barrier film between described positive plate and negative plate and electrolyte.The wherein casting grid made preferably by casting method of the grid of negative plate.
And then the present invention also provides a kind of lead accumulator, it comprises above-mentioned pole plate group.
In addition, the present invention also provides a kind of manufacture method of lead accumulator, and it at least comprises the following operation for the manufacture of positive plate:
(1) cut and draw operation: use reciprocating punching mould repeatedly to carry out punching press to. g., lead tape, while forming multiple slit along the length direction of. g., lead tape, this slit is launched along the direction vertical with. g., lead tape surface, thus formation to be interlocked the net slice formed by many ruled line;
(2) trimming: utilize the pair of rolls of shaping mould to carry out shaping to described net slice, obtain drawing in the net grid,
(3) lead plaster filling work procedure: what obtain after shaping draws in the net on grid, the length direction along grid fills the lead plaster as positive active material;
(4) severing operation: the positive plate grid being filled with lead plaster being cut to given size,
Wherein, the slit gap drawing in operation and adjust described reciprocating punching mould and formed in. g., lead tape is cut described, and in described trimming, adjust roller spacing and the roll-in of described pair of rolls, make when set to obtain after shaping described in draw in the net that the ruling width of grid is W, grating thickness is T time, described in draw in the net grid tortuosity T/W=1.50 ~ 1.90 of grid.
Preferably, draw in operation described cutting, corresponding to the thickness of described. g., lead tape, adjust the slit gap that described reciprocating punching mould is formed in. g., lead tape, make when set to obtain after shaping described in draw in the net the ruling thickness of grid be t time, described in draw in the net ruling flakiness ratio W/t=1.25 ~ 1.60 of grid.
More preferably, in described lead plaster filling work procedure, adjust the coating weight of described lead plaster, make, when the electrode thickness that setting is filled with described lead plaster is P, to represent that lead plaster crosses ratio P/T=1.10 ~ 1.40 of filling rate.
According to the present invention, can provide a kind of tortuosity larger draw in the net grid, it has good painting cream, by grid filling positive active material with suitable filling rate of crossing such drawing in the net, even if the lead accumulator repeating high rate discharging under shallow depth of charge (SOC), also there is good cycle life can be obtained, be particularly useful for the purposes in electric bicycle.
Accompanying drawing explanation
Fig. 1. (a) schematically shows the front view drawing in the net grid of the present invention; B () above-mentioned draws in the net the close-up schematic view of grid; The cutaway view drawing in the net the online A-A place of grid of (c) Fig. 1 (b).
Fig. 2. (a) schematically shows the front view of positive plate of the present invention; The end view of (b) above-mentioned positive plate; C partial sectional view that () above-mentioned positive plate through-thickness cuts.
Fig. 3. schematically show the stereogram after a part for lead accumulator of the present invention being excised.
Embodiment
Below, each inscape of the present invention is described in detail.
(grid)
The effect of grid in pole plate supports active material and conduction current between active material and terminal.Common grill designs is rectangle, has a lug to be used for being connected with bus-bar.The casting grid utilizing casting method to make has thick outside frame and tiny inside ruling in length and breadth, and the grid that draws in the net utilizing Qie Lafa to make is the mesh-shape thin slice using diel to cut out slit after-drawing in. g., lead tape and formed.Drawing in the net grid has lighter quality relative to casting grid, and consistency is good, and therefore productivity is more superior.
Grid of the present invention. g., lead tape is cut by reciprocating daraf(reciprocal of farad) of cutting the grid that draws in the net drawn.As the. g., lead tape of raw material, can adopt the lead alloy-foil that this area is conventional, such as, Pb Alloy Foil containing at least one in Ca and Sn, with regard to corrosion resistance and mechanical strength, is preferably made up of Pb-Ca-Sn ternary alloy three-partalloy.When use has the. g., lead tape of such alloy composition, the cycle life characteristics of lead accumulator easily improves.
Of the present inventionly cut the reciprocating punching mould drawing in operation and have employed and there is a pair dynamic model and quiet mould.Dynamic model (patrix) has multiple continuous print blade part, and these blade parts to be in the shape of the letter V arrangement along the throughput direction (i.e. length direction) of. g., lead tape, but do not arrange blade part on the position of central portion corresponding to. g., lead tape thickness direction.Quiet mould (counterdie) has multiple continuous print prismatic portion, and the prismatic face in prismatic portion corresponds to the position at the blade part place of patrix.Quiet mould is fixed by external equipment, and control dynamic model from top to bottom punching press. g., lead tape, when the crest line of blade part between adjacent prismatic portion of dynamic model,. g., lead tape is cut into multiple interrupted slit, downward punching press is continued in the front end of blade part simultaneously, is launched by this slit along prismatic face in the direction perpendicular to. g., lead tape surface.The length direction conveying. g., lead tape of one edge. g., lead tape, repeatedly carries out above-mentioned punching course, thus. g., lead tape is processed into the net slice with multiple mesh.In addition, the blade part position on adjustment dynamic model, makes the middle body of. g., lead tape Width become the blank parts not having mesh, and this part forms upper side frame and the lug of grid by processing of cutting described later.
Under normal circumstances, cut the thickness fluctuation drawing the net slice after just terminating large, and out-of-shape, therefore, in ensuing trimming, need to utilize the pair of rolls of shaping mould to carry out shaping to above-mentioned net slice, after shaping, obtain drawing in the net grid.
In trimming in the past, general employing diameter stack that is comparatively large, Heavy Weight carries out shaping to net slice, and due to comparatively large to net slice applied pressure, therefore the height at ruling intersection point (hereinafter referred to as node) place is compressed, the integral thickness of grid is thinning, and tortuous reduces.The present inventors find, if excessive to net slice applied pressure during shaping, although then the integral thickness of grid can thinning, intensity become greatly, Nodes is subject to stress and easily corrodes, and has harmful effect to the life-span of battery.Therefore, have employed little and lightweight a pair stack of diameter in the present invention, by controlling spacing between this pair of rolls and roll-in, less pressure being applied to Nodes, the height of Nodes is not almost compressed, and after shaping, grid still keeps larger tortuous.Now, owing to almost not applying pressure to Nodes, therefore Nodes can keep high strength, and corrosion resistance is good, and the size distortion of grid is little, and the thickness deviation of grid etc. also can decrease.
Fig. 1 represents the schematic diagram drawing in the net grid 1 of the present invention obtained by said method.As shown in Fig. 1 (a), drawing in the net grid 1 has the mesh of the near-rhombic formed that to be interlocked by many ruled line g, and each mesh i is surrounded by 4 ruling g, is interconnected between each mesh i by node f.Drawing in the net grid 1 is the blank parts not forming mesh at the central portion of Width, only illustrates and draw in the net grid 1 from this central portion to the part of downside in Fig. 1 (a), because second half is the shape of full symmetric, thus omits its diagram.
. g., lead tape forms the ruling g with one fixed width and thickness after cutting the slit expansion of drawing and being cut out in operation, the width of ruling g corresponds to the gap of adjacent slots on. g., lead tape Width (hereinafter referred to as slit gap), and the thickness of ruling g corresponds to the thickness (hereinafter referred to as. g., lead tape thickness) as the. g., lead tape of raw material.In this specification, term " ruling width ", " ruling thickness " and following " grating thickness " all have usual the had implication in this area, and specifically, as shown in the schematic diagram of Fig. 1 (b), ruling width is W, and ruling thickness is t.Here, although it is pointed out that in Fig. 1 (b) of the present invention, be expressed as paper for simplicity and by the plane at ruling place, in a practical situation, the plane at ruling g place and paper have certain angle of inclination.When cutting open along the cutting line A-A in Fig. 1 (b), as shown in Fig. 1 (c), width is that the ruling of W forms tortuous zigzag fashion, at two, node f place, ruling g overlaps, the length of this lap is 2 times of ruling width W, and the thickness of the lap thickness of dash area (in the figure) is ruling thickness t.In addition, the overall maximum height (i.e. node f height in a thickness direction) in a thickness direction of grid is grating thickness T, in this specification, defines grid tortuosity with the ratio T/W of grating thickness T dative line width W.T/W is larger for this ratio, shows that grid tortuosity is larger.
The present inventors find, when cut draw in operation suitably adjust slit gap and in trimming, suitably adjust roller spacing and roll-in thus grid tortuosity T/W is controlled in the scope of 1.50 ~ 1.90 time, in follow-up filling work procedure, fillibility as the lead plaster of active material becomes good, not only successfully the lead plaster as active material can be applied in each mesh of grid, but also can lead plaster be filled higher than grid surface.Like this, more active material can be held in positive pole grid, obtain high battery capacity.By this phenomenon " cross and fill (over paste) " referred to as lead plaster in this specification.
In the present invention, by the grid tortuosity T/W suitably adding haul seine grid compared with the past, good lead plaster coating can be obtained, its reason can be thought, relative to the pole plate of per unit area, the tortuosity of grid is larger, contact area between grid and active material is more, and the distance of active material surface and grid is nearer, thus the cementability between active material and grid can not only be improved, and in active material layer everywhere with the distance of grid relatively, the difference of electrical collector reduces, and is thus conducive to obtaining good high rate discharging characteristic.
Under normal conditions, there is no the support of outside frame owing to drawing in the net the edge of grid, overflow in order to avoid active material from grid edge, the amount of filled active material must be limited.If the active material layer thickness of coating is excessively thin, then battery capacity is restricted, and the electrical collector relative surplus of grid, easily cause the deterioration of active material.If but coat activated material blocked uply, then the superficies distance grid of active material is excessively far away, and not, and in active material, electrical collector is uneven for its cementability with grid, easily comes off latter stage discharging, causes the deterioration of battery cycle life.What thus need control lead plaster crosses filling rate in suitable scope.
When the above-mentioned grid tortuosity T/W of control is in OK range, becomes good owing to being coated with cream, therefore can increase and be coated with cream amount, easily obtain suitable lead plaster and cross filling rate, thus improve the high-rate discharge property of battery.From this viewpoint, grid tortuosity T/W is preferably the scope of 1.50 ~ 1.90, is more preferably the scope of 1.60 ~ 1.80, is particularly preferably the scope of 1.65 ~ 1.75.When grid tortuosity is too small, the reactive substance adheres on lead plaster surface is poor, coming off, causing the cycle life of battery short when repeatedly carrying out deep discharge with regard to easily producing; If but grid tortuosity is excessive, then likely causes electrical collector superfluous, increased the weight of the deterioration of active material during overdischarge on the contrary, caused the shortening of battery cycle life.
The grid with above-mentioned tortuosity can use reciprocating punching mould to produce when not destroying grid node.The feature of reciprocating punching technique is that the node of basic checks not match grid compresses, thus can the larger net slice of production tortuosity.In addition, owing to have employed in follow-up trimming, the little shaping mould of pressure is applied to grid Nodes, therefore obtain after shaping to draw in the net the tortuosity of grid larger, and Nodes is not under pressure substantially, high strength can be kept, not perishable, this is also a major reason of longer cell life.
In the present invention, the size of grid tortuosity T/W is determined by grating thickness T and ruling width W two factors, and grating thickness T mainly with net slice in net slice thickness before calendering and trimming before calendering after Thickness Ratio relevant, the thickness of net slice depends on the factor such as width of mesh and ruling width.Therefore, can by drawing in operation and trimming suitably Controlling Technology condition to obtain desired grid tortuosity cutting.Such as, the downward stroke size of the dynamic model of suitably adjustment reciprocating punching mould or slit length can be drawn in operation to control formed width of mesh cutting, or the distance adjusted between the spacing in prismatic face of quiet mould and the blade part of dynamic model is to adjust the slit gap in. g., lead tape.In addition, the pressing force etc. of the roller spacing to a pair stack that net slice rolls, roller can be adjusted in trimming, control thus net slice before calendering after Thickness Ratio.
Wish in the present invention to obtain larger grid tortuosity, therefore need slit gap also to set larger cutting to draw in operation.But according to the difference of used. g., lead tape thickness (i.e. ruling thickness), also there is certain preferable range in slit gap (i.e. ruling width).Specifically, relative to certain. g., lead tape thickness, if slit gap excessive (ruling width is wide), then the grating thickness made is blocked up, overall weight becomes large, not easily realizes the high capacity of battery.If slit gap too small (ruling width is meticulous), then easy because of corrosion cause fracture, cause the decline of battery high rate life characteristic.In this manual, define the flakiness ratio W/t of ruling with the ratio of ruling width W and ruling thickness t, in the present invention, preferably the flakiness ratio W/t of ruling is controlled the scope 1.20 ~ 1.65.If draw in the net the ratio of the ruling width W of grid and ruling thickness t more than 1.20 after shaping, then easily increase grating thickness T, make the filling of crossing of lead plaster become easy.If the ratio of ruling width W and ruling thickness t below 1.65, then can obtain the lightweight of grid.The flakiness ratio W/t of ruling is more preferably 1.25 ~ 1.60, and more preferably 1.30 ~ 1.50, be particularly preferably 1.30 ~ 1.40.
(positive plate)
Using the grid that draws in the net obtained above as positive pole grid, lead plaster filling work procedure is carried out to it, namely drawing in the net grid fills the lead plaster as positive active material along the length direction of grid.Lead plaster as positive active material is in the lead powder be made up of the lead oxide of 60 ~ 90 quality % and the metallic lead of 40 ~ 10 quality %, adds water and sulfuric acid carries out mixing.In addition, as required, the additive that this area is conventional can also be added in anode diachylon.Lead plaster can be filled from the one side of net slice, also can fill from the tow sides of net slice.
Then, in severing operation, the grid being filled with lead plaster is cut to given size, forms the pole plate shape with lug, slaking, dry rear formation positive plate of the present invention.As shown in Figure 2, positive plate 4 of the present invention comprises and draws in the net grid 1 and be filled in the lead plaster 3 as positive active material drawn in the net in grid 1 as above with lug 2.
In this specification, " electrode thickness " has usual the had implication in this area, refers to the gross thickness of the pole plate comprising lead plaster.Specifically, as shown in Fig. 2 (b), electrode thickness P is the upper and lower surface difference in height in a thickness direction of the lead plaster be filled in grid.The coating weight of lead plaster is larger, then electrode thickness P is larger.
In addition, as shown in Fig. 2 (c), the ratio of electrode thickness P and grating thickness T is adopted to define the filling rate excessively of lead plaster.Starting point of the present invention manufactures the grid with suitable tortuosity, and then fill lead plaster with certain filling rate of crossing on grid, thus reach excellent high rate discharging cycle characteristics.Therefore, the relation excessively filling rate and high rate discharging cycle characteristics between of the present inventors to lead plaster is studied, and found that, when the mistake filling rate P/T of lead plaster is the particular range of 1.10 ~ 1.40, can obtain excellent high rate discharging characteristic.
Its reason is presumed as follows: when the mistake filling rate of lead plaster is less than 1.10, the loading of lead plaster is closely similar to the loading scope in usual grid, the improvement DeGrain to high rate discharging characteristic that the present invention is obtained by the crossing filling of lead plaster, when the mistake filling rate of lead plaster is greater than 1.40, the thickness of the active material layer of filling is blocked up, the lead plaster being in outmost surface easily comes off, and thus can cause the decline of high-rate discharge property on the contrary.The above-mentioned ratio P/T of preferred control, in the scope of 1.10 ~ 1.40, is more preferably the scope of 1.14 ~ 1.30, is particularly preferably the scope of 1.16 ~ 1.26.
The present inventors also find, for the effect improving high-rate discharge property, it is all effective for controlling grid tortuosity, the flakiness ratio of ruling and the filling rate excessively of lead plaster, but first will ensure that grid tortuosity T/W is within preferable range.Such as, even if the filling rate P/T of crossing of lead plaster is arbitrary numerical value in 1.10 ~ 1.40, if but the tortuosity T/W of grid outside preferable range (1.50 ~ 1.90), then the cycle life characteristics of battery is still likely insufficient.
Its reason is presumed as follows: if the grid that draws in the net of positive pole meets tortuosity T/W=1.50 ~ 1.90, then the fillingization excessively of lead plaster is easy, and positive pole grid is suitable to the electrical collector of lead plaster, consequently when high rate discharging, lead plaster does not produce deterioration, and battery life is long.If grid tortuosity ratio is not in above-mentioned scope, even if then lead plaster was in occupied state, but the possibility insufficient with the cementability of grid, electrical collector is not enough or superfluous is comparatively large, thus can not obtain effect of the present invention.
(negative plate)
Negative plate of the present invention comprises negative pole grid and is filled in the lead plaster as negative electrode active material in described negative pole grid.
Lead plaster as negative electrode active material is in the lead powder be made up of the lead oxide of 60 ~ 90 quality % and the metallic lead of 40 ~ 10 quality %, adds water and sulfuric acid carries out mixing.In addition, as required, the additive that this area is conventional can also be added in cathode lead plaster.Lead plaster can be filled from the one side of negative pole grid, also can fill from the tow sides of negative pole grid.To the slaking of negative pole grid, the drying of lead plaster be filled with, form negative plate of the present invention.
Negative pole grid can adopt any one of drawing in the net in grid or casting grid, when adopt draw in the net the grid of grid as negative plate time, need the pole plate shape becoming to have lug by its processing of cutting.But from the view point of improving battery capacity and preventing internal short-circuit of battery, preferred negative plate of the present invention is casting grid.
(pole plate group)
Pole plate group of the present invention comprises positive plate, negative plate, barrier film between positive plate and negative plate and electrolyte.
Barrier film is used for isolating adjacent positive and negative pole plate, has enough porositys simultaneously, and the acid in electrolyte can be moved into or move out pole plate.The pocket type dividing plate that the form of barrier film can adopt sheet-like separator or be wrapped by negative or positive electrode.About the material of barrier film, material conventional in lead accumulator field can be adopted, have no particular limits.Main body such as can be adopted to be the barrier film, polyalkene diaphragm, sintering PVC barrier film etc. of glass fibre.
When comprising multi-disc positive plate and multi-disc negative plate in a pole plate group, the lug set of same polarity being welded together, forming bus-bar.Such pole plate group forms a monocell (cell).
In pole plate group of the present invention, preferably adopt casting grid at negative plate, adopt at positive plate and draw in the net grid.Effect acquired by such combination is: do not have horizontal edge bone because positive pole draws in the net grid, therefore the electrical collector of positive pole relatively declines, thus the overdischarge of positive active material when avoiding high rate discharging, the effect of battery long lifetime can be obtained.
(lead accumulator)
As shown in Figure 3, lead accumulator 11 of the present invention is included in battery case 8 and is isolated the separated multiple monocell groove of plate.A pole plate group (monocell) is accommodated with in each monocell groove.Pole plate group is by multi-disc positive plate 4, multi-disc negative plate 5 and the multi-disc barrier film 6 between positive plate and negative plate is alternately laminated forms.The lug of same polarity is welded together, and forms bus-bar 7.Each cells in series directly or cross division board via pole and weld with the bus-bar 7 of the negative side of adjacent monocell, thus connects by the bus-bar 7 of the side of the positive electrode of each monocell.At the opening part of battery case, the middle cover of battery 9 being built-in with safety valve is installed, the positive terminal of the both side ends of battery case and negative terminal are connected with the positive terminal be located on middle cover of battery and negative terminal respectively, and battery case 8 and middle cover 9 are sealed with binding agent fixing.Then in battery case 8, inject electrolyte (not shown), after fluid injection, cell cover 10 and middle cover 9 are sealed fixing, thus forms lead accumulator 11 of the present invention.
Electrolyte can adopt sulfuric acid solution conventional in lead accumulator field, has no particular limits, such as, for mass fraction is the dilute sulfuric acid of 1.1-1.4g/ml.For valve-regulated lead-acid battery, such as, can adopt adsorbing electrolyte, be adsorbed in the barrier film based on glass fibre, or adopt the colloidal electrolyte of gelation.
Lead accumulator of the present invention draws in the net grid owing to adopting in positive plate, and the filling rate of crossing of the flakiness ratio of grid tortuosity, ruling and lead plaster is controlled in suitable scope, therefore the electrical collector of positive pole suitably declines, active material and grid cementability good, and there is uniform electrical collector, thus the overdischarge of positive active material when avoiding high rate discharging, be applicable to the charging/discharging apparatus such as electric bicycle (EB) repeatedly carrying out deep discharge, the effect of battery long lifetime can be obtained.
(manufacture method of lead accumulator)
Lead accumulator of the present invention can adopt the common manufacture method in this area to manufacture, but wherein at least comprises the following operation for the manufacture of positive plate:
(1) cut and draw operation: use reciprocating punching mould repeatedly to carry out punching press to. g., lead tape, while forming multiple slit along the length direction of. g., lead tape, this slit is launched along the direction vertical with. g., lead tape surface, thus formation has the net slice of the mesh formed that to be interlocked by many ruled line;
(2) trimming: utilize the pair of rolls of shaping mould to carry out shaping to described net slice, obtain drawing in the net grid;
(3) lead plaster filling work procedure: grid fills lead plaster along the length direction of grid described drawing in the net;
(4) severing operation: the grid that draws in the net being filled with lead plaster is cut to the positive plate of given size,
Wherein, described cut to draw in operation adjust the gap of described slit on. g., lead tape Width, and in described trimming, adjust roller spacing and the roll-in of described pair of rolls, make when drawing in the net described in setting that the ruling width of grid is W, grating thickness is T, described in draw in the net grid tortuosity T/W=1.50 ~ 1.90 of grid.
Draw in operation described cutting, preferably correspond to the thickness of described. g., lead tape and adjust the gap of described slit on. g., lead tape Width, make when draw in the net described in setting the ruling thickness of grid be t time, described in draw in the net ruling flakiness ratio W/t=1.25 ~ 1.60 of grid.
More preferably, in described lead plaster filling work procedure, adjust the coating weight of described lead plaster, make, when the electrode thickness that setting is filled with the positive plate of described lead plaster is P, to represent that lead plaster crosses ratio P/T=1.10 ~ 1.40 of filling rate.
Easily can obtain the lead accumulator with excellent high rate discharging cycle characteristics according to the manufacture method of lead accumulator of the present invention, be applicable to the charging/discharging apparatus such as electric bicycle repeatedly carrying out deep discharge, the effect of battery long lifetime can be obtained.
Embodiment
Below, utilize embodiment and comparative example to describe the present invention in detail, but the present invention is not limited to these object lessons.In addition, the numerical value such as the relevant ruling width W occurred in this specification, ruling thickness t, grating thickness T, all refers to the mean value obtained after taking multiple measurements at random the different parts of determination object.In addition, the present invention also comprises and the situation about changing different along with position such as the size of each mesh in grid or ruling width.In the case, above-mentioned mean value measures the mean value of the numerical value obtained after referring to and choose multiple position with uniform spacing on grid.
Embodiment 1:
(making of positive plate)
The. g., lead tape be made up of Pb-Ca-Sn ternary alloy three-partalloy thin slice is sent in foregoing reciprocating punching mould and carries out cutting drawing processing, multiple interrupted slit is cut into along the length direction of. g., lead tape after each punching press, the plurality of slit arranged askew in the direction of the width, each other there is certain interval, dynamic model continues downward punching press simultaneously, this slit is launched in the direction perpendicular to. g., lead tape surface, after repeated multiple times punching press, namely obtains having the net slice of the mesh formed of being interlocked by many ruled line.In addition, adjustment is arranged at the position of the blade part on dynamic model, makes the middle body of. g., lead tape become the blank parts not having mesh.Then, utilize the pair of rolls of shaping mould to carry out shaping to net slice obtained above, thus obtain positive pole of the present invention and draw in the net grid.
Now, the slit gap that adjustment. g., lead tape is formed, and adjust roller spacing and the roll-in of a pair stack, thus the ruling width of the grid obtained through above-mentioned operation, ruling thickness and grating thickness are controlled in desired scope, in the present embodiment, measuring the grating thickness T obtained is 2.2mm, and ruling width is 1.4mm, and ruling thickness is 1.05mm.
In addition, raw material lead powder (powder that brown lead oxide and metallic lead mix with mass ratio 70: 30) and water, sulfuric acid added with the ratio of weight ratio 100: 15: 10 and mixes, obtaining anode diachylon.Grid after shaping fills 87.9g anode diachylon along the length direction of grid.Then, the grid being filled with lead plaster is cut to the size and dimension of regulation, obtains the positive plate do not changed into after slaking drying (vertical: 139mm, horizontal: 64mm).The electrode thickness P measured is 2.9mm.
(making of negative plate)
Adopt the casting grid obtained by casting method as negative pole grid (vertical: 142mm, horizontal: 65mm, thick: 1.5mm).In addition, above-mentioned raw materials lead powder and water, sulfuric acid added with the ratio of weight ratio 100: 5: 10 and mixes, obtaining cathode lead plaster.After this, after be filled with 59.6g cathode lead plaster in negative pole grid, carry out slaking drying, obtain the negative plate do not changed into.The electrode thickness P measured after dry is 1.70mm.
(making of lead accumulator)
By positive plate obtained above and negative plate alternatively stacked across the barrier film based on glass fibre, the ear of the pole plate of same polarity is carried out joint welding respectively, formed bus-bar.Then, pole plate group is accommodated in respectively seriatim in 6 the monocell grooves marked off by division board of battery case, in the present embodiment, being connected in series by carrying out without the welding of pole bus-bar between pole plate group.
After this, in each monocell, injecting 170ml as the concentration of electrolyte is the sulfuric acid of 1.242g/ml, then installs middle cover and upper cover at the peristome of battery case and seals, obtaining the lead accumulator that battery capacity is 20Ah after changing into process.
Embodiment 2:
In the making of positive plate, adjust the roller spacing of a pair stack and roll-in and lead plaster coating weight, make obtained grating thickness T be 2.3mm, electrode thickness is 2.9mm.In addition, make positive plate identically with embodiment 1, and make negative plate and lead accumulator according to the method identical with embodiment 1.
Embodiment 3:
In the making of positive plate, adjust the roller spacing of a pair stack and roll-in and lead plaster coating weight, make obtained grating thickness T be 2.4mm, electrode thickness is 2.9mm.In addition, make positive plate identically with embodiment 1, and make negative plate and lead accumulator according to the method identical with embodiment 1.
Embodiment 4:
In the making of positive plate, adjust the roller spacing of a pair stack and roll-in and lead plaster coating weight, make obtained grating thickness T be 2.5mm, electrode thickness is 2.9mm.In addition, make positive plate identically with embodiment 1, and make negative plate and lead accumulator according to the method identical with embodiment 1.
Embodiment 5:
In the making of positive plate, adjust the roller spacing of a pair stack and roll-in and lead plaster coating weight, make obtained grating thickness T be 2.6mm, electrode thickness is 2.9mm.In addition, make positive plate identically with embodiment 1, and make negative plate and lead accumulator according to the method identical with embodiment 1.
Embodiment 6:
The method identical with embodiment 3 is utilized to make positive plate.But in the making of negative plate, adopt identical with the positive pole grid grid that draws in the net to substitute and cast grid, and the thickness of grid of drawing in the net adjusting negative pole is 1.6mm.In addition, lead accumulator has been made according to the method identical with embodiment 3.
Comparative example 1:
In the making of positive plate, adjust the roller spacing of a pair stack and roll-in and lead plaster coating weight, make obtained grating thickness T be 2.0mm, electrode thickness is 2.9mm.In addition, make positive plate identically with embodiment 1, and make negative plate and lead accumulator according to the method identical with embodiment 1.
Comparative example 2:
In the making of positive plate, adjust the roller spacing of a pair stack and roll-in and lead plaster coating weight, make obtained grating thickness T be 2.7mm, electrode thickness is 2.9mm.In addition, make positive plate identically with embodiment 1, and make negative plate and lead accumulator according to the method identical with embodiment 1.
Comparative example 3:
In the making of positive plate, change the. g., lead tape thickness used, and adjust the slit gap in Qie Lajia man-hour, the ruling thickness of grid of drawing in the net obtained after making shaping becomes 1.25mm, ruling width becomes 1.7mm, and adjust the roller spacing of a pair stack and roll-in and lead plaster coating weight, make obtained grating thickness T be 2.4mm, electrode thickness is 2.9mm.In addition, make positive plate identically with embodiment 1, and make negative plate and lead accumulator according to the method identical with embodiment 1.
Comparative example 4:
In the making of positive plate, substitute and draw in the net grid and adopt grating thickness to be the casting grid of 2.0mm, in addition, make positive plate identically with embodiment 1, and made negative plate and lead accumulator according to the method identical with embodiment 1.
Embodiment 7
In the making of positive plate, change the. g., lead tape thickness that uses, the ruling thickness of grid of drawing in the net obtained after making shaping is 1.15mm, in addition, make positive plate identically with embodiment 1, and make negative plate and lead accumulator according to the method identical with embodiment 1.
Embodiment 8
In the making of positive plate, adjust the. g., lead tape thickness that uses, the ruling thickness of grid of drawing in the net obtained after making shaping is 1.10mm, in addition, make positive plate identically with embodiment 1, and make negative plate and lead accumulator according to the method identical with embodiment 1.
Embodiment 9
In the making of positive plate, adjust the. g., lead tape thickness that uses, the ruling thickness of grid of drawing in the net obtained after making shaping is 0.90mm, in addition, make positive plate identically with embodiment 1, and make negative plate and lead accumulator according to the method identical with embodiment 1.
Embodiment 10
In the making of positive plate, adjust the. g., lead tape thickness that uses, the ruling thickness of grid of drawing in the net obtained after making shaping is 0.85mm, in addition, make positive plate identically with embodiment 1, and make negative plate and lead accumulator according to the method identical with embodiment 1.
To each lead accumulator obtained in above-described embodiment 1 ~ 10, comparative example 1 ~ 4, carry out following performance test.
(test of high rate discharging cycle life)
The each lead accumulator obtained in embodiment 1 ~ 10, comparative example 1 ~ 4 is carried out high rate discharging cycling life test under condition shown below.
Battery specifications: 12V, 20Ah
Charge condition: 14.7V constant voltage charges, maximum 16 hours
Discharging condition: 30A (1.5C) constant current discharge, until voltage is down to 9.6V
Repeatedly carry out above-mentioned charge and discharge cycles, terminate test when the discharge capacity of battery is reduced to 80% of the discharge capacity of the 1st circulation, calculate the period of the charge and discharge cycles of carrying out, charge to table 1.
Evaluate according to the high rate discharging cycle characteristics of following level to battery.
◎: period is more than 500
Zero: period is 400 ~ 500
△: period is 200 ~ 400
×: period is lower than 200
××: period is lower than 100
In the lead accumulator of embodiments of the invention 1 ~ 10, period is all greater than 300, and in the battery of comparative example 1 ~ 4, period, all lower than 150, can obviously be found out, lead accumulator of the present invention has the battery cycle life under excellent high rate discharging.
(the deterioration evaluation of anode diachylon)
Each storage battery after above-mentioned cycling life test is decomposed and takes apart, the situation of lead plaster on visualization positive plate.To find that lead plaster is peeled off from grid or the cell evaluation of obscission is " anode diachylon deterioration ".
In the lead accumulator of embodiments of the invention 1 ~ 10, all do not find lead plaster deterioration.And in the battery of comparative example 1 ~ 4, lead plaster all there occurs deterioration, wherein, in the battery of comparative example 1,4, anode diachylon deterioration is serious, and cause the high rate discharging cycle life of battery extremely short, period is lower than 100.
The test of the parameters of above-mentioned each storage battery and battery performance, evaluation result are shown in following table 1 after gathering.
According to the result of table 1, in the lead accumulator of comparative example 1, due to the filling rate excessive (1.45) excessively of lead plaster, the thickness of lead plaster layer becomes blocked up, and therefore repeatedly carrying out deep discharge circulation time, lead plaster there occurs serious coming off.And in the lead accumulator of comparative example 2, due to filling rate deficiency (1.07) excessively of lead plaster, cause the electrical collector of positive pole grid superfluous, therefore when repeatedly carrying out deep discharge circulation time, lead plaster there occurs deterioration.In the lead accumulator of comparative example 3, although lead plaster has suitable filling rate excessively, the grid tortuosity (1.41) of positive pole grid is not in preferable range of the present invention, and thus lead plaster electrical collector is everywhere uneven, lead plaster is easily deteriorated, equally also can not get effect of the present invention.In the lead accumulator of comparative example 4, because positive plate have employed casting grid, therefore the electrical collector of grid is superfluous, and the mistake filling rate of lead plaster is excessive, and therefore the deterioration of lead plaster is serious.
In contrast, be arranged in the scope of 1.50 ~ 1.90 and lead plaster crosses the lead accumulator of the present invention that filling rate P/T is positioned at the scope of 1.10 ~ 1.40 at employing grid tortuosity T/W, all obtain good lead plaster coating and excellent high rate discharging life-span.And, from the comparative result of embodiment 3,8,9 and embodiment 7,10, although have identical grid tortuosity and lead plaster crosses filling rate, the battery of flakiness ratio W/t in the scope of 1.25 ~ 1.60 of ruling obtains the more excellent high rate discharging life-span.In addition, from comparative result with embodiment 6, comparative example 4 of embodiment 3, positive plate adopts and draws in the net grid, negative plate and adopt the combination of casting grid to have more excellent high rate discharging cycle life characteristics than the grid combination of other types.
Claims (10)
1. a pole plate group for lead accumulator, comprises positive plate, negative plate, barrier film between described positive plate and negative plate and electrolyte,
In described positive plate, cut drawing in the net that daraf(reciprocal of farad) makes and be filled with the positive active material formed by lead plaster by reciprocating in grid,
When draw in the net described in setting the ruling width of grid be W, described in draw in the net the thickness of grid be T time, T/W is the scope of 1.5 ~ 1.9, wherein, the mean value that obtains after referring to and the different parts of determination object being taken multiple measurements at random of the value of described ruling width W, described thickness T
In described negative plate, in the casting grid made by casting method, be filled with the negative electrode active material formed by lead plaster.
2. the pole plate group of lead accumulator according to claim 1, wherein, T/W is the scope of 1.6 ~ 1.8.
3. the pole plate group of lead accumulator according to claim 1 and 2, wherein, when draw in the net described in setting the ruling thickness of grid be t time, W/t is the scope of 1.25 ~ 1.60, wherein, the mean value that obtains after referring to and the different parts of determination object being taken multiple measurements at random of the value of described ruling thickness t.
4. the pole plate group of lead accumulator according to claim 1, wherein, when the thickness setting described positive plate is P, P/T is the scope of 1.1 ~ 1.4, wherein, the mean value that obtains after referring to and the different parts of determination object being taken multiple measurements at random of the value of described thickness P.
5. the pole plate group of lead accumulator according to claim 4, wherein, P/T is the scope of 1.14 ~ 1.30.
6. a lead accumulator, it comprises the pole plate group according to any one of Claims 1 to 5.
7. an electric bicycle, it possesses lead accumulator according to claim 6.
8. a manufacture method for the pole plate group of lead accumulator, it is the manufacture method of the pole plate group of lead accumulator according to claim 1, and comprise positive plate and the negative plate operation across barrier film interaction cascading, described positive plate is manufactured by following operation:
(1) while. g., lead tape is formed multiple slit on the direction vertical with this. g., lead tape, the vertical direction of this slit along. g., lead tape is launched, thus cut the net slice drawing and be processed as and there is the mesh formed that to be interlocked by many ruled line;
(2) utilize pair of rolls to be shaped as by described net slice to draw in the net the operation of grid;
(3) in described operation of drawing in the net to fill in grid the positive active material formed by lead plaster;
(4) grid that draws in the net being filled with described positive active material is cut to the operation of the positive plate of given size, wherein, the adjustment gap of described slit on. g., lead tape Width in described operation (1), and in described operation (2), adjust roller spacing and the roll-in of described pair of rolls, making when drawing in the net the ruling width of grid described in setting is W, when the described thickness drawing in the net grid is T, T/W becomes the scope of 1.5 ~ 1.9, wherein, described ruling width W, the mean value that the value of described thickness T obtains after referring to and taking multiple measurements at random the different parts of determination object.
9. the manufacture method of the pole plate group of lead accumulator according to claim 8, wherein: in described operation (1), thickness corresponding to described. g., lead tape adjusts the gap of described slit on the Width of this. g., lead tape, make when draw in the net described in setting the ruling thickness of grid be t time, W/t becomes the scope of 1.25 ~ 1.60, wherein, the mean value that obtains after referring to and the different parts of determination object being taken multiple measurements at random of the value of described ruling thickness t.
10. the manufacture method of the pole plate group of lead accumulator according to claim 8 or claim 9, wherein: in described operation (3), adjust the coating weight of described lead plaster, make when the electrode thickness setting described positive plate is P, P/T becomes the scope of 1.1 ~ 1.4, wherein, the mean value that obtains after referring to and the different parts of determination object being taken multiple measurements at random of the value of described thickness P.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110085830.5A CN102738470B (en) | 2011-03-31 | 2011-03-31 | Lead accumulator grid, positive plate, pole plate group, lead accumulator and manufacture method thereof |
| JP2012535477A JP5230845B2 (en) | 2011-03-31 | 2012-04-02 | Electrode plate group for lead-acid battery, lead-acid battery, and method for producing electrode plate group for lead-acid battery |
| PCT/JP2012/002286 WO2012132476A1 (en) | 2011-03-31 | 2012-04-02 | Grid for lead storage battery, positive plate using grid, plate group, lead storage battery, and method for manufacturing positive plate for lead storage battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110085830.5A CN102738470B (en) | 2011-03-31 | 2011-03-31 | Lead accumulator grid, positive plate, pole plate group, lead accumulator and manufacture method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102738470A CN102738470A (en) | 2012-10-17 |
| CN102738470B true CN102738470B (en) | 2015-07-29 |
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| CN201110085830.5A Active CN102738470B (en) | 2011-03-31 | 2011-03-31 | Lead accumulator grid, positive plate, pole plate group, lead accumulator and manufacture method thereof |
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| Country | Link |
|---|---|
| JP (1) | JP5230845B2 (en) |
| CN (1) | CN102738470B (en) |
| WO (1) | WO2012132476A1 (en) |
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| CN103715397B (en) * | 2013-12-07 | 2016-01-13 | 河南超威电源有限公司 | A kind of grid surface leaching mucus and polar plate solidification process |
| CN104752643B (en) * | 2013-12-27 | 2019-03-15 | 松下蓄电池(沈阳)有限公司 | Lead storage battery |
| CN106025383B (en) * | 2016-05-24 | 2020-01-07 | 淄博火炬能源有限责任公司 | Valve-regulated lead-acid storage battery and preparation method thereof |
| JP6456537B1 (en) * | 2018-02-28 | 2019-01-23 | 古河電池株式会社 | Positive electrode grid for lead acid battery and lead acid battery |
| CN116833263B (en) * | 2023-09-01 | 2023-10-31 | 太原科技大学 | Roll-punching composite forming process and precision regulating and controlling method for metal bipolar plate of fuel cell |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5582936A (en) * | 1994-11-16 | 1996-12-10 | Globe-Union, Inc. | Lead-acid batteries with optimum current collection at grid lugs |
| CN1279824A (en) * | 1997-11-26 | 2001-01-10 | 约翰逊控制技术公司 | Stamped battery grid |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS56114282A (en) * | 1980-02-14 | 1981-09-08 | Yuasa Battery Co Ltd | Pasted lead acid battery |
| JPS56149772A (en) * | 1980-04-18 | 1981-11-19 | Yuasa Battery Co Ltd | Grid for lead battery |
| JPS56159065A (en) * | 1980-05-13 | 1981-12-08 | Yuasa Battery Co Ltd | Grid for lead acid battery |
| JPS585969A (en) * | 1981-07-02 | 1983-01-13 | Japan Storage Battery Co Ltd | Lead battery |
| JP3658834B2 (en) * | 1996-02-19 | 2005-06-08 | 松下電器産業株式会社 | Sealed lead acid battery |
| JP4092817B2 (en) * | 1999-06-18 | 2008-05-28 | 松下電器産業株式会社 | Method for producing expanded grid for lead-acid battery |
-
2011
- 2011-03-31 CN CN201110085830.5A patent/CN102738470B/en active Active
-
2012
- 2012-04-02 WO PCT/JP2012/002286 patent/WO2012132476A1/en active Application Filing
- 2012-04-02 JP JP2012535477A patent/JP5230845B2/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5582936A (en) * | 1994-11-16 | 1996-12-10 | Globe-Union, Inc. | Lead-acid batteries with optimum current collection at grid lugs |
| CN1279824A (en) * | 1997-11-26 | 2001-01-10 | 约翰逊控制技术公司 | Stamped battery grid |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102738470A (en) | 2012-10-17 |
| JPWO2012132476A1 (en) | 2014-07-24 |
| JP5230845B2 (en) | 2013-07-10 |
| WO2012132476A1 (en) | 2012-10-04 |
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Effective date of registration: 20170913 Address after: Liaoning, Shenyang economic and Technological Development Zone, Kunming Lake Street, No. 51 Co-patentee after: GS Yuasa International Corporation Patentee after: Panasonic Storage Battery (Shenyang) Co., Ltd. Address before: 110141 Shenyang economic and Technological Development Zone, Kunming, Lake Street, No. 51, No. Co-patentee before: Matsushita Electric Industrial Co., Ltd. Patentee before: Panasonic Storage Battery (Shenyang) Co., Ltd. |
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