CN1918740A - Lead storage battery - Google Patents
Lead storage battery Download PDFInfo
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- CN1918740A CN1918740A CNA2005800045463A CN200580004546A CN1918740A CN 1918740 A CN1918740 A CN 1918740A CN A2005800045463 A CNA2005800045463 A CN A2005800045463A CN 200580004546 A CN200580004546 A CN 200580004546A CN 1918740 A CN1918740 A CN 1918740A
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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
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- Y02E60/10—Energy storage using batteries
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Abstract
A lead storage battery comprising a plate group including a plurality of negative plates holding a negative electrode active material layer in a negative electrode grid, a plurality of positive plates holding a positive electrode active material layer in a positive electrode grid, and a plurality of separators for isolating the positive plates from the negative plates, positive electrode connection members connected with the respective positive plates in the plate group, and negative electrode connection members connected with the respective negative plates in the plate group. The positive electrode grid, the negative electrode grid, the positive electrode connection member and the negative electrode connection member are composed of a Pb alloy containing at least one of Ca and Sn, the negative electrode active material layer contains Sb, and the separator contains silica.
Description
Technical field
The present invention relates to lead accumulator, more particularly, the present invention relates to be used to be equipped with stop-lead accumulator of the vehicle of starting system (stop-and-go-system) and regeneration brake system useful life character improvement.
Background technology
Traditionally, lead accumulator has been used to pilot engine and the stand-by power supply of vehicle.In these purposes, the lead accumulator of piloting engine is except to the battery motor power supply that is used for piloting engine, also to the various electricity and the electronic installation power supply that are installed on the vehicle.After having started engine, charge to lead accumulator by alternating current generator.The output voltage and the output current of alternating current generator are set, thereby the SOC (charged state) that keeps lead accumulator is 90-100%.
Recent years, it seems that from environmental protection the demand that vehicle fuel efficiency improves increases day by day.For this demand, for instance, considered to install and stopped-vehicle of starting system and regeneration brake system.Stopping-starting system in, engine idle when vehicle stops, and in regeneration brake system, the kinetic energy of vehicle changes into electric energy when slowing down, and stores this electric energy.
Stop in installation-vehicle of starting system in, lead accumulator does not charge when vehicle stops in idle stop mode.In the time of in being in this state, lead accumulator is the device provisioning electric power in being installed in vehicle sometimes.Therefore, compare with traditional lead accumulator of piloting engine, the SOC of lead accumulator is step-down inevitably.In the vehicle of regeneration brake system is installed,,, be low to moderate about 50-90% so that the SOC of lead accumulator must be controlled to is lower because lead accumulator is wanted store electrical energy when regeneration (deceleration).
In any of these system, recharge and discharge (charge/discharge) continually under than lower in the past SOC scope.In addition, be accompanied by increasing vehicle part by power supply, dark current increases, lead accumulator discharge when vehicle stops for a long time, thus might over-discharge can.
Therefore, for the lead accumulator that the vehicle that these systems are installed uses, need to improve the useful life under the use pattern of frequent recharge/discharge under the lower SOC scope.
For the unfavorable factor of the lead accumulator under this use pattern, the chargeability that mainly can mention owing to lead accumulator reduces the undercharge that causes.Because the charging system of vehicle is controlled based on constant voltage, so when the chargeability of negative plate reduced, cathode voltage was increased to the predeterminated voltage value fast in reduction of charging starting stage and voltage, thereby has comparatively fast reduced electric current.Therefore, can not guarantee the charging of lead accumulator q.s, thereby make battery be in the state of undercharge.
In order to suppress this degeneration, advised on anodal screen (grid) surface of for example Pb-Ca-Sn alloy, forming the method (patent documentation 1) of the lead alloy layer that comprises Sn and Sb.Forming this layer will suppress the degeneration of positive active material and form passivation layer on the interface between positive active material and the negative pole screen.
In addition, the Sb that exists on the anodal screen surface is partly dissolved in the electrolyte, and deposits on the negative plate.The Sb that deposits on the negative electrode active material is with the electromotive force of rising negative plate when charging, and charging voltage will descend thus, thereby improve the chargeability of lead accumulator.As a result, suppressed because the degeneration of the caused lead accumulator of undercharge during the charge/discharge.
It is very effective that this method surpasses 90% o'clock engine start lead accumulator to use at SOC, and character will obviously be improved in useful life.
But, when using lead accumulator in the vehicle that is being equipped with above-mentioned stopping-starting system or regeneration brake system, promptly, when using lead accumulator in the pattern of recharge/discharge under low SOC scope, although the problem of in the fin (tab) of negative pole screen, corroding easily occurs to guarantee chargeability.When corrosion appearred in the fin of negative pole screen, because the reduction of fin thickness, the water catchment efficiency of negative plate descended, thereby has shortened useful life.
The reduction of negative pole screen fin thickness has also reduced the intensity of fin except reducing water catchment efficiency.Especially in the battery on being installed in vehicle, because when travelling, vehicle is often applied vibration and impact, so the distortion of negative pole screen fin causes the negative plate disengaging configuration, might internal short-circuit take place by produce contact between negative plate and positive plate.
Traditionally, about the corrosion of negative pole screen fin, known that negative pole attachment strap and fin welding portion are corroded, and cause disconnection because negative pole attachment strap (strap) and negative pole screen fin are exposed in the airborne oxygen from electrolyte.But, even negative pole attachment strap and negative pole screen fin are immersed in the electrolyte, because the Sb that comprises in the anodal screen and comprise that the Sb that comprises in the anodal connector of anodal attachment strap, anode bar and anodal connector dissolves in electrolyte, when very small amount of Sb deposited on the negative pole screen flap surface, negative pole screen fin also was corroded easily.
In patent documentation 2, advised a kind of lead accumulator, wherein form anodal screen, anodal connector, negative pole screen fin and anode connector, and in one of negative pole screen or negative electrode active material layer, comprise the very small amount of Sb that can not increase the electrolyte losses amount by Pb that does not contain Sb or Pb alloy.Based on this structure, shown to be dissolved in the electrolyte and Sb deposits on the negative pole screen fin by the Sb that suppresses to exist in the positive plate, can improve the chargeability and the useful life of battery deep discharge to a certain extent.
Patent documentation 1: TOHKEMY Hei 03-37962
Patent documentation 1: TOHKEMY Hei 2003-346888
Summary of the invention
The problem to be solved in the present invention
Therefore, the purpose of this invention is to provide, have the more lead accumulator of long life and high reliability by improving chargeability and suppressing the corrosion of negative pole screen and under the use pattern that is being in the heavy multiple charge/discharge of low scope time-frequency as SOC.
The method of dealing with problems
The present invention relates to lead accumulator, it comprises:
The electrode plate groups (pack) that comprises the barrier film of a plurality of negative plates, a plurality of positive plate and described positive plate of a plurality of isolation and described negative plate, each negative plate comprises negative pole screen with fin and the negative electrode active material layer that is kept by this negative pole screen, and each positive plate comprises anodal screen with fin and the positive electrode active material layer that is kept by this positive pole screen;
The anodal attachment strap and anode bar that provides on this positive pole attachment strap or the anodal connector that are connected with the fin of each positive plate of described electrode plate groups are provided anodal connector; And
The negative pole attachment strap and cathode rod that provides on this negative pole attachment strap or the negative pole connector that are connected with the fin of each negative plate of described electrode plate groups are provided anode connector,
Wherein said anodal screen, negative pole screen, anodal connector and anode connector comprise and contain Pb alloy at least a among Ca and the Sn,
Described negative electrode active material layer comprises Sb, and
Described barrier film comprises silicon dioxide.
In first preferred embodiment of barrier film, barrier film comprises micropore synthetic resin sheet and the silica dioxide granule that is dispersed in this micropore synthetic resin sheet, and comprises the silica dioxide granule of 40-85 quality %.
In second preferred embodiment of barrier film, the silica dioxide granule that barrier film comprises fibrage and kept by this fibrage, and comprise the silica dioxide granule of 10-40 quality %.
The Sb that comprises the 0.0002-0.006 mass parts in the preferred described negative electrode active material layer altogether among the negative electrode active material of 100 mass parts and the Sb.
Preferred described anodal screen has the lead alloy layer that contains Sn at least in the part on described positive electrode gate sheet frame surface.
Preferred described barrier film is bag shape and holds described negative plate.
Preferred described barrier film comprises the oil of 5-30 quality %.
The mass ratio of negative electrode active material and described positive active material is 0.7-1.3 described in the preferred described electrode plate groups.
Preferred described negative pole screen is a kind of expansion screen, it comprises the expanded mesh that keeps described negative electrode active material layer, at the upper rim frame that provides and the fin that is connected with described frame of described expanded mesh, and the ratio of the width of the height of described fin and frame is 2.2-15.0.
Effect of the present invention
According to the present invention, because improved chargeability and suppressed the corrosion of negative pole screen fin, so under the use pattern of frequent recharge/discharge under the lower SOC scope, can obtain to have the more lead accumulator of long life and high reliability.In addition, although battery has the possibility that is in over-discharge state under this use pattern, even under over-discharge state, also can suppress the corrosion of negative pole screen fin.
Description of drawings
The perspective view that the part of the lead accumulator of [Fig. 1] embodiment of the invention is cut open;
The front view of the positive plate of [Fig. 2] above-mentioned lead accumulator;
The front view of the negative plate of [Fig. 3] above-mentioned lead accumulator;
The diagrammatic sketch of the step of [Fig. 4] expansion substrate material piece;
[Fig. 5] obtains to be used for to produce the diagrammatic sketch of step of the composite sheet of grid body;
The longitudinal sectional view of the part of [Fig. 6] expression positive plate, described positive plate has used the positive electrode gate plate body that has the lead alloy layer on the surface of positive electrode gate plate body;
Embodiment
The present invention relates to be used to be equipped with and stop-lead accumulator of the vehicle of starting system and regeneration brake system.In the present invention, in anodal screen, anodal connector, negative pole screen and anode connector, use the Pb alloy that does not comprise the Sb that causes the corrosion of negative pole screen fin basically.In negative electrode active material, add Sb, and in barrier film, comprise silicon dioxide.Based on this battery, for the use pattern of the said system of frequent recharge/discharge under low SOC scope, useful life that can the significant prolongation battery.
Below, explain embodiment of the present invention in detail.Fig. 1 is the perspective view that lead accumulator of the present invention is partly cut open.
The battery case 12 of lead accumulator 1 is divided into a plurality of battery chambers 14 by dividing plate 13, and in each battery chamber 14 storage electrode plate group 11.Electrode plate groups 11 is inserted barrier film 4 therebetween and is constituted by piling up polylith positive plate 2 and negative plate 3.Positive plate 2 is connected with anodal connector 10 and negative plate 3 is connected with anode connector 9.
In electrode plate groups 11, the fin 22 of the anodal screen of positive plate 2 is connected with anodal attachment strap 6, and the fin 32 of the negative pole screen of negative plate 3 is connected with negative pole attachment strap 5.The anodal connector 8 that is connected with the anodal attachment strap 6 of electrode plate groups 11 in battery chamber 14 connects by the negative pole connector that is connected with the negative pole attachment strap of electrode plate groups 11 in the hole that provides on the dividing plate 13 and the adjacent cell compartment 14.Therefore, electrode plate groups 11 is connected in series with another electrode plate groups 11 in the adjacent cell compartment 14.On the anodal attachment strap of battery case 12 1 ends, form anode bar, and on the negative pole attachment strap 5 of battery case 12 other ends, form cathode rod 7.
Therefore, anodal attachment strap 6 and anode bar that provides on anodal attachment strap 6 or the anodal connector 8 that is connected with the fin 22 of anodal screen is provided anodal connector 10; And the negative pole attachment strap 5 that is connected with the fin 32 of negative pole screen and the cathode rod 7 that provides on negative pole attachment strap 5 or negative pole connector are provided anode connector 9.
The battery cover 15 that will have positive terminal 16 and negative terminals 17 is connected on the opening of battery case 12.Anode bar is connected with negative terminals 17 with positive terminal 16 respectively with cathode rod.In the liquid inlet that on battery cover 15, provides, be connected with abat-vent 18, be used for the gas that inside battery produces is discharged to the battery outside with ventilation orifice.
The front view that has shown positive plate 2 among Fig. 2.
For the Pb alloy, with regard to corrosion resistance and mechanical strength, can use the Pb-Sn alloy that comprises 0.05-3.0 quality %Sn, comprise the Pb-Ca alloy of 0.01-0.10 quality %Ca or comprise Ca and the Pb-Ca-Sn alloy of Sn.
Be used for anodal screen or anodal connector contain Ca and at least a Pb alloy of Sn is substantially free of Sb.But, can be used as impurity and comprise the Sb that consumption is approximately 0.001-0.002 quality %, make it can not be and battery performance is had the scope of adverse effect owing to the increase of electrolyte losses amount and self discharge.When the Sb content in anodal screen and the anodal connector was in above-mentioned scope, Sb can not move to negative plate.
In addition, in order to improve the corrosion resistance of anodal screen, the lead alloy of anodal screen can comprise the Ba of 0.01-0.08 quality % and the Ag of 0.001-0.05 quality %.When use contains the lead alloy of Ca,, can add the Al of about 0.001-0.05 quality % in order to suppress Ca oxidation and consumption from the lead alloy of fusion.In addition, can be used as the Bi that impurity comprises about 0.0005-0.005 quality %.This is harmless to effect of the present invention and is acceptable.
Fig. 3 has shown the front view of negative plate 3.
Can obtain positive plate 2 and negative plate 3 by following method.
Can in positive pole is stuck with paste, for instance raw material lead powder (mixture of lead and lead oxide), sulfuric acid, water etc. be mixed in the positive electrode gate plate body by the anodal unfashioned positive plate of acquisition of sticking with paste of filling, solidify then and drying.
In addition, can stick with paste and obtain unfashioned negative plate, in negative pole is stuck with paste, for instance the swelling agent of raw material lead powder (lead and lead oxide), sulfuric acid, water and for example lignin and barium sulfate is mixed in the negative electrode grid plate body, solidify then and dry by filling negative pole.For lignin, can use natural lignin (for example VANILLEX N that produces by Nippon Paper Chemicals) and synthetic lignin for instance, for example the bis-phenol sulphonic acid ester of Nong Suoing (for example VISPERSE P215 that produces by NipponPaper Chemicals).
Then, obtain above-mentioned positive plate 2 and negative plate 3 by forming unfashioned positive plate and negative plate.Can in the battery case of the lead accumulator that uses unfashioned positive plate and negative plate to make, form, perhaps when producing lead accumulator, form before the composition electrode plate groups.
Negative electrode active material layer 34 comprises Sb.By comprise the Sb that hydrogen overvoltage is lower than negative electrode active material in negative electrode active material layer, the charge potential of negative plate increases, thereby has significantly improved the chargeability of negative plate.In addition, because lead accumulator of the present invention has the structure that only comprises Sb in negative electrode active material layer,, and can suppress the corrosion of negative pole screen fin so Sb is not easy to dissolve in the electrolyte.
Especially, when the Sb content in the negative electrode active material layer for the negative electrode active material of 100 mass parts altogether and Sb in when being not less than 0.0002 mass parts, improved character in useful life.In addition, when the Sb content in the negative electrode active material layer for the negative electrode active material of 100 mass parts altogether and Sb in when being not less than 0.0004 mass parts, significantly improved character in useful life.On the other hand, when the Sb content in the negative electrode active material layer be that the corrosion of negative pole screen fin increases gradually when surpassing 0.006 mass parts among the negative electrode active material of 100 mass parts altogether and the Sb.
Therefore, the Sb content in the preferred negative electrode active material layer be to be the 0.0002-0.006 mass parts among the negative electrode active material of 100 mass parts altogether and the Sb.Sb content in the further preferred negative electrode active material layer be to be the 0.0004-0.006 mass parts among the negative electrode active material of 100 mass parts altogether and the Sb.
By when producing negative pole and stick with paste, with Sb or comprise the compound of Sb, for example in the addings negative poles pastes such as the oxide of Sb or sulfate, antimonite and Sb is added in the negative electrode active material layer.In addition, can for example comprise in the dilute sulfuric acid of antimony sulfate and antimonite electrolytic deposition Sb on negative electrode active material by negative plate is immersed the electrolyte that comprises the Sb ion that is used to electroplate.
In lead accumulator of the present invention, as mentioned above, suppose the battery over-discharge can, and frequent recharge/discharge under low SOC scope.Under this use pattern, only only in negative electrode active material layer, add the corrosion that Sb can not suppress negative pole screen fin fully by restriction.
Problem hereto, by in barrier film, comprising silicon dioxide, because the silicon dioxide in barrier film absorption Sb, in addition at Sb under this use pattern when negative electrode active material layer dissolves, also can suppress the corrosion of the negative pole screen that causes owing to the deposition of Sb on negative pole screen fin.
Therefore, improved and comprised the corrosion that silicon dioxide has suppressed negative pole screen fin in chargeability and the barrier film because comprise Sb in the negative plate, so under above-mentioned use pattern, will significantly improve the character in useful life of lead accumulator.
In first preferred embodiment of barrier film 4, barrier film comprises micropore synthetic resin sheet and the silica dioxide granule that is dispersed in this micropore synthetic resin sheet, and the content of silica dioxide granule is 40-85 quality % in the barrier film.When the content of silica dioxide granule in the barrier film that comprises the synthetic resin sheet that contains silica dioxide granule was lower than 40 quality %, the effect that suppresses the corrosion of negative pole screen fin slightly reduced.On the other hand, when the content of silica dioxide granule in the barrier film that comprises the synthetic resin sheet that contains silica dioxide granule surpasses 85 quality %, barrier film reduction degree and break easily and produce the hole, thus cause internal short-circuit of battery easily.
Because can obtain to suppress the remarkable effect of negative pole screen fin corrosion, and the effect that improves character in useful life, be 40-65 quality % so preferably comprise the content of silica dioxide granule in the barrier film of the synthetic resin sheet that contains silica dioxide granule.
For synthetic resin, can mention polyethylene and polypropylene for instance.In order to improve ionic conductivity, can in synthetic resin, comprise carbon.
For silica dioxide granule, in order to adsorb Sb easily in its surface, preferred use for example has the porous silica that average pore size is no more than 20 microns pore.In addition, also preferred the use has about 200m
2The porous silica of the bigger serface of/g.The particle diameter of preferred silicon dioxide is the 5-40 micron.
The micropore synthetic resin sheet has the pore of the electrolyte permeable of the about 0.01-1 micron in aperture.When the aperture surpassed 1 micron, active material passed through barrier film easily.For instance, add silica dioxide granule when comprising the micro pore sheet of synthetic resin in production and can obtain this barrier film.
In second preferred embodiment of barrier film 4, the silica dioxide granule that barrier film comprises fibrage and kept by this fibrage, and the silica dioxide granule content in the barrier film is 10-40 quality %.When the content of silica dioxide granule was lower than 10 quality % in comprising the fibrolaminar barrier film that keeps silica dioxide granule, the effect that suppresses the corrosion of negative pole screen fin slightly reduced.On the other hand, when the content of silica dioxide granule surpasses 40 quality % in comprising the fibrolaminar barrier film that keeps silica dioxide granule, since the reduction of the adhesion of fiber, the barrier film weakened, and because the internal resistance of cell increases, battery discharge voltage reduces.
For fiber, can use fibre diameter to be acrylic resin fiber of 1-10 micron etc. for instance as the glass fibre of 0.1-2 micron or fibre diameter.For instance, can obtain this barrier film by in paper technology, adding silica dioxide granule when the producd fibers layer.
Each battery comprises electrolyte.And anodal attachment strap, negative pole attachment strap and electrode plate groups all are immersed in the electrolyte.Because negative plate does not contact with air with the negative pole attachment strap, so they are not easy oxidation.Because negative electrode active material layer comprises the Sb that hydrogen overvoltage is lower than negative electrode active material, so the present invention can not be applied to absorb with negative plate the valve mode lead accumulator of oxygen.When the present invention was applied to valve mode lead accumulator, based on the gas of a small amount of generation, inner pressure of battery increased, and control valve keeps opening for a long time.As a result, air flow in the battery and negative plate oxidized, thereby make the easy variation of battery.
Preferred anodal screen 21 has the lead alloy layer that contains Sn in its surperficial part at least.This lead alloy layer has improved the chargeability of positive plate after deep discharge or the over-discharge can, and useful life character is improved.In addition, the interface that can be suppressed between positive active material and the anodal screen forms passivation layer.
When anodal screen comprised Sn, the Sn content in the preferred lead alloy layer was higher than the Sn content in the anodal screen.For instance, when comprising the Sn of 1.6 quality % in anodal screen, preferred lead alloy layer comprises the Sn that is not less than 1.6 quality % at least, and more preferably, the Sn content in the lead alloy layer is 3.0-6.0 quality %.When the Sn content in the lead alloy layer is lower than Sn content in the anodal screen and since anodal screen and positive active material have Sn content lead alloy still less at the interface, the effect of above-mentioned Sn weakens.
For instance, can obtain in its surperficial part at least, to have the anodal screen of the lead alloy layer that contains Sn according to the methods below.By roller between supply the base material sheet that comprises the Pb alloy with the lead alloy-foil that contains Sn, and this lead alloy-foil is pressed onto the composite sheet that obtains to comprise base material sheet and lead alloy layer on the base material sheet.At this moment, lead alloy-foil is adhered at least a portion base material sheet by compacting, promptly on the expanded mesh that forms by the expansion mentioned later.
Then, obtain anodal screen by the expansion composite sheet.The preferred thickness of substrate material layer is the 0.7-1.3 millimeter in the composite sheet, and the preferred thickness of lead alloy layer is the 1-20 micron.
Because negative plate is stored in a bag shape barrier film, even when the Sb in the negative electrode active material dissolves in the electrolyte, because bag shape barrier film has been captured the Sb of dissolving fast and reliably, can suppress because Sb deposits to the corrosion of the negative pole screen fin that causes on the negative pole screen fin.
The barrier film 4 that preferably comprises the synthetic resin sheet that contains silica dioxide granule further comprises the oil of 5-30 quality %.By in barrier film, comprising oil, further capture Sb reliably.In addition, improved the non-oxidizability of barrier film itself.For oil, can use by from oil, removing the mineral oil that volatility content, tar and bitumen content obtain.For this mineral oil, can use density to be 0.85-0.90g/cm for instance
3Alkyl mineral oil (straight chain saturation alkane).
For instance, can be by when producing the micropore synthetic resin sheet, adding the barrier film that oil obtains to comprise oil with silica dioxide granule.
Even the oil part flows out barrier film, the oil of outflow moves into place in the more top electrolytical liquid level of electrode plate groups, and because do not have oil between positive plate and negative plate and the electrolyte, so can adverse influence not arranged to battery performance.
When the oil content in the barrier film is lower than 5 quality %, the effect of capturing Sb by oil will become not enough.On the other hand, when the oil content in the barrier film was higher than 30 quality %, the ion permeability of barrier film reduced, and inner pressure of battery increases.In addition, the greasy dirt that flows out barrier film dyes the inwall of battery case, makes to be difficult to the electrolytical liquid level of visual examination.
Negative electrode active material (NAM) is 0.7-1.3 with the mass ratio (hereinafter to be referred as NAM/PAM) of positive active material (PAM) in the preferred electrode plate group 11.Based on this ratio, even when when charge/discharge cycle, carrying out deep discharge and over-discharge can, also can suppress the dissolving of Sb in the negative electrode active material layer, and can suppress because Sb deposits to the corrosion of the negative pole screen fin that causes on the negative pole screen fin.
When NAM/PAM less than 0.7 the time, the effect of Sb dissolving will weaken in the above-mentioned inhibition negative electrode active material layer.On the other hand, when NAM/PAM was higher than 1.3, positive plate is variation when overcharging, and made it to reduce behind the state of overcharging easily character in useful life.In addition, the amount of negative electrode active material increases and has increased the weight of battery, and this is unpractical.
More preferably NAM/PAM is 0.82-1.08.When NAM/PAM was not less than 0.82, the corrosion of negative pole screen fin was carried out hardly.When NAM/PAM was higher than 1.08, cycle life character slightly reduced after the over-discharge can.
At negative pole screen 31---in the expansion screen, the height (Lt) of the fin 32 of the negative pole screen shown in preferred Fig. 3 is 2.2-15.0 with the ratio (hereinafter to be referred as Lt/Lf) of the width (Lf) of frame 33.As shown in Figure 3, when the fin 32 with the negative pole screen integrally is welded on the negative pole attachment strap 5, the height Lt of the fin 32 of negative pole screen be the fin 32 of negative pole screen from the bottom that is connected with frame 33 to the length of the bottom of negative pole attachment strap 5.
When Lt/Lf was no more than 15.0, the Sb amount that deposits on the fin 32 of negative pole screen reduced, thereby can suppress the corrosion of the fin 32 of negative pole screen.But when Lt/Lf surpassed 15.0, the Sb that dissolves in the electrolyte deposited on the fin 32 of negative pole screen easily, thereby has increased the etching extent of the fin 32 of negative pole screen.
When Lt/Lf more hour, can suppress the corrosion of the fin 32 of negative pole screen more.But when in order to make Lt/Lf further littler, when the width Lf of frame broadened, the height of expanded mesh 35 became littler, and the amount of negative electrode active material reduces, thereby had reduced the capacity of battery.
In addition, when in order to make Lt/Lf littler, the height of negative pole screen fin becomes more hour, because the distance of 6 of distance between positive plate 2 and the negative pole attachment strap 5 and negative plate 3 and anodal attachment straps becomes shorter, becoming causes internal short-circuit easily.
In order to prevent the short circuit of positive plate and negative plate, between positive plate 2 and negative plate 3, insert barrier film 4, thereby make the upper end of barrier film 4 be higher than the upper end of positive plate 2 and negative plate 3.Therefore, the height Lt of negative pole screen fin can not be arranged to be shorter than the downside of negative pole attachment strap 6 and the distance between barrier film 4 upper ends.
Therefore, from preventing that short circuit be it seems between positive plate and negative plate, positive plate and negative pole attachment strap and negative plate and the anodal attachment strap, and the collateral security battery capacity it seems that the lower limit of preferred Lt/Lf is 2.2.More preferably Lt/Lf is 2.2-12.0.When Lt/Lf is in this scope, has greatly suppressed the corrosion of negative pole screen fin, and significantly improved character in useful life.
Although hereinbefore, made up and had the bag shape barrier film that wherein stores negative plate, except this structure, synthetic resin sheet or fibrage can be folded into two (letter U shapes), insert negative plate betwixt.
To explain embodiments of the invention below.
Embodiment 1
(1) manufacturing of bag shape barrier film
In the polyethylene of mean molecule quantity 8000000, add silica dioxide granule, mineral oil (Daphne Oil CP, by Idemitsu Kosan Co., Ltd. makes) and powdered carbon, mediate then.Behind the material that extrusion molding is mediated, remove mineral oil with for example solvent of hexane, obtain to comprise the polythene strip of silica dioxide granule, it has the aperture, and to be no more than 1 micron pore and thickness be 0.3 millimeter.The polythene strip that so obtains is folded into two, and the left end side by the thermal weld pleated sheet and right-hand member side only obtain to have on the part in the above the bag shape barrier film of opening.
For silica dioxide granule, use to have the porous particle (particle diameter: the 5-40 micron) that average pore size is no more than 20 microns pore.
(2) manufacturing of positive plate
The positive plate 2 that following manufacturing is shown in Figure 2.
Mediate raw material lead powder (mixture of lead and lead oxide), water and dilute sulfuric acid with 100: 15: 5 weight ratios, thereby obtain anodal the paste.
On the other hand, will be squeezed into 1.1 millimeters thick by the base material sheet that comprises the Pb alloy that contains 0.07 quality %Ca and 1.3 quality %Sn that obtains by casting.After being to form predetermined slit on the base material sheet 27, the expansion slit is with formation expanded mesh 25 (Fig. 4 (a)), thus the grid body (expansion process) that acquisition is expanded.The middle body of base material sheet 27 does not expand, because this part will be used for forming the fin 22 and the frame 23 of following anodal screen.
Positive pole is stuck with paste 24a be packed into (Fig. 4 (b)) in the expanded mesh 25, and cut and form the shape (Fig. 4 (c)) of the battery lead plate of fin 22 with anodal screen.Solidify and dry so cutting and the expansion screen that forms, thereby obtain unfashioned positive plate 2a (length: 115 millimeters, width: 137.5 millimeters).Then, the unfashioned positive plate 2a that in following battery case, is shaped, thus obtain the positive plate 2 that anodal screen 21 keeps positive electrode active material layer 24.
(3) manufacturing of negative plate
The negative plate 3 that following manufacturing is shown in Figure 3.
With 100: 15: 3.5: 2.5: 2.5 weight ratio mix and mediate raw material lead powder, water, dilute sulfuric acid, as the natural lignin's (VANILEX N is made by NIPPON PAPERCHEMICALS) and the barium sulfate of swelling agent, stick with paste thereby obtain negative pole.
Then, will be squeezed into 0.7 millimeters thick by the base material sheet that comprises the Pb alloy that contains 0.07 quality %Ca and 0.25 quality %Sn that obtains by casting, and expand according to method same as described above.Stick with paste to fill expanded mesh with negative pole, and obtain unfashioned negative plate (length: 115 millimeters, width: 137.5 millimeters) according to method same as described above.Then, the unfashioned negative plate that in following battery case, is shaped, thus obtain the negative plate 3 that negative pole screen 31 keeps negative electrode active material layer 34.
(4) manufacturing of lead accumulator
Make lead accumulator 1 shown in Figure 1 by following method.Fig. 1 is the perspective view that the part of lead accumulator is cut open.
In bag shape barrier film 4, store the negative plate 3 that obtains above six respectively.With five positive plates 2 barrier film 4 of stacking and storing negative plate 3 alternately, promptly pile up positive plate 2 and negative plate 3, and insert barrier film 4 betwixt, thereby obtain electrode plate groups 11.Subsequently, respectively that the fin 32 of the fin 22 of homopolarity and homopolarity is welded together, obtain anodal attachment strap 6 and negative pole attachment strap 5.Each electrode plate groups 11 is stored in six battery chambers 14 that separated by the dividing plate in the battery case 12 13.Connect with the negative pole connector that is connected with the negative pole attachment strap by the anodal connector 8 that will be connected with anodal attachment strap 6, adjacent electrode plate groups is connected in series.In the present embodiment, by the connection of carrying out in the through hole (not shown) that provides on the dividing plate 13 between the electrode plate groups.
Be arranged in the electrode plate groups that is connected in series at two ends, anode bar be connected with an electrode plate groups, and cathode rod 7 is connected with another electrode plate groups.Then, battery cover 15 is connected on the opening of battery case 12, simultaneously positive terminal 16 that will on battery cover 15, provide and negative terminals 17 and anode bar and cathode rod 7 welding.Subsequently, the sulfuric acid of pouring 700 ml concns from the liquid inlet that battery cover 15 provides into and be 34 quality % each battery is as electrolyte, and forms in battery case.After shaping, will have the abat-vent 18 that is used for the gas that inside battery produces is discharged to the ventilation hole of outside and be fixed in the liquid inlet, thereby obtain 55D23 type (12V-48Ah) lead accumulator (hereinafter to be referred as battery) of appointment in JIS D5301.After shaping, electrode plate groups 11, anodal attachment strap 6 and negative pole attachment strap 5 are immersed in the electrolyte fully.
In the manufacturing of above-mentioned barrier film, make the content of silica dioxide granule in the bag shape barrier film that comprises the polythene strip that contains silica dioxide granule become 0 quality %, 35 quality %, 40 quality %, 65 quality % or 85 quality %.
In producing above-mentioned negative pole paste, in negative pole is stuck with paste, add the sulfate of Sb, make to be shaped Sb content in the negative electrode active material layer of back for being 0 (in the detectability of 0.0001 quality %), 0.0002 quality %, 0.0004 quality %, 0.006 quality % or 0.007 quality % among the negative electrode active material of 100 mass parts altogether and the Sb.
For anodal connector and anode connector, use the Pb alloy that comprises the Pb alloy of 2.5 quality %Sn or comprise 2.5 quality %Sb.As the result that the Sb content quantitative is analyzed, the Sb content that comprises in the Pb alloy of 2.5 quality %Sn is lower than detectability (0.0001 quality %).
The width Lf of negative electrode grid sheet frame is arranged to 1.5 millimeters.The height Lt of the negative pole screen fin with negative pole screen fin and negative pole attachment strap after welded together is arranged to 18 millimeters.That is, Lt/Lf is arranged to 12.0.In addition, the width (Wf among Fig. 3) of battery lead plate is arranged to 137.5 millimeters, and the width (Wt among Fig. 3) of negative pole screen fin is arranged to 10.0 millimeters.
In addition, the negative electrode active material (NAM) and the ratio (NAM/PAM) of positive active material (PAM) are arranged to 1.08.
Then, shown in table 1 and 2, in various combinations, use the polythene strip comprise the silica dioxide granule that contains different amounts barrier film, have the negative plate that anodal connector that different-alloy forms and anode connector and maintenance have the negative electrode active material layer of different Sb content, prepare battery A1-A5, B1-B5, C1-C5, D1-D5, E1-E5, F1-F5, G1-G5, H1-H5, I1-I5 and J1-J5.
In table 1, battery B2-B5, C2-C5, D2-D5 and E2-E5 are the batteries of embodiment.Other battery in the table 1 is the battery of comparative example.The Pb alloy that table 1 has represented to comprise 2.5 quality %Sn is used for the situation of anodal connector of battery and anode connector, and the table 2 Pb alloy of having represented to comprise 2.5 quality %Sb is used for the situation of anodal connector of battery and anode connector.
[table 1]
| Battery number | Dioxide-containing silica in the barrier film (quality %) | Sb content (mass parts) in the negative electrode active material layer | The rate of corrosion (%) of negative pole screen fin | Cycle-index (cycle life) |
| A1 | 0 | 0(＜0.0001) | 2.1 | 22500 |
| A2 | 0 | 0.0002 | 78.9 | 23900 |
| A3 | 0 | 0.0004 | 78.5 | 24200 |
| A4 | 0 | 0.006 | 80.6 | 25500 |
| A5 | 0 | 0.007 | 80.9 | 29000 |
| | 35 | 0(＜0.0001) | 2.0 | 22100 |
| | 35 | 0.0002 | 2.4 | 36900 |
| | 35 | 0.0004 | 3.0 | 68500 |
| | 35 | 0.006 | 3.3 | 76800 |
| | 35 | 0.007 | 9.2 | 66500 |
| C1 | 40 | 0(＜0.0001) | 2.1 | 28200 |
| C2 | 40 | 0.0002 | 2.2 | 44300 |
| C3 | 40 | 0.0004 | 2.7 | 107000 |
| C4 | 40 | 0.006 | 2.9 | 107400 |
| C5 | 40 | 0.007 | 7.6 | 81000 |
| D1 | 65 | 0(＜0.0001) | 2.0 | 27200 |
| D2 | 65 | 0.0002 | 2.1 | 45200 |
| D3 | 65 | 0.0004 | 2.4 | 110400 |
| D4 | 65 | 0.006 | 2.6 | 113000 |
| D5 | 65 | 0.007 | 7.2 | 105000 |
| E1 | 85 | 0(＜0.0001) | 1.9 | 23900 |
| E2 | 85 | 0.0002 | 2.0 | 45900 |
| E3 | 85 | 0.0004 | 2.4 | 107200 |
| E4 | 85 | 0.006 | 2.5 | 107600 |
| E5 | 85 | 0.007 | 7.2 | 92100 |
[table 2]
| Battery number | Dioxide-containing silica in the barrier film (quality %) | Sb content (mass parts) in the negative electrode active material layer | The rate of corrosion (%) of negative pole screen fin | Cycle-index (cycle life) |
| F1 | 0 | 0(＜0.0001) | 84.1 | 22400 |
| F2 | 0 | 0.0002 | 84.5 | 22300 |
| F3 | 0 | 0.0004 | 85.8 | 21000 |
| F4 | 0 | 0.006 | 88.2 | 21200 |
| F5 | 0 | 0.007 | 87.2 | 20400 |
| | 35 | 0(＜0.0001) | 81.3 | 23900 |
| | 35 | 0.0002 | 82.3 | 21700 |
| | 35 | 0.0004 | 82.7 | 21800 |
| | 35 | 0.006 | 83.9 | 21500 |
| | 35 | 0.007 | 87.3 | 21500 |
| H1 | 40 | 0(＜0.0001) | 78.0 | 24400 |
| H2 | 40 | 0.0002 | 78.5 | 24500 |
| H3 | 40 | 0.0004 | 79.1 | 25200 |
| H4 | 40 | 0.006 | 80.2 | 25000 |
| H5 | 40 | 0.007 | 80.9 | 25900 |
| I1 | 65 | 0(＜0.0001) | 79.3 | 26800 |
| I2 | 65 | 0.0002 | 80.2 | 25400 |
| I3 | 65 | 0.0004 | 81.8 | 25200 |
| I4 | 65 | 0.006 | 83.3 | 25000 |
| I5 | 65 | 0.007 | 85.1 | 26800 |
| J1 | 85 | 0(＜0.0001) | 75.9 | 25500 |
| J2 | 85 | 0.0002 | 76.5 | 27400 |
| J3 | 85 | 0.0004 | 81.3 | 25900 |
| J4 | 85 | 0.006 | 82.2 | 27000 |
| J5 | 85 | 0.007 | 82.6 | 28100 |
As the quantitative analysis results of Sb content in anodal screen, positive electrode active material layer and the negative pole screen, find that the content of Sb is lower than detectability (0.0001 quality %) in any result.
Evaluation shown in below carrying out for each battery of acquisition like this.
(5) evaluation of cycle life character after the over-discharge can
Under 25 ℃ room temperature, battery discharges under the 10A electric current becomes 10.5V until cell voltage.Subsequently, connecting between the terminals under 12 watts the situation of bulb, battery left standstill 48 hours, made the battery over-discharge can.Then, under the constant voltage of 14.5V (maximum current 25A), made battery charge 8 hours.
Then, under the condition battery after the over-discharge can is carried out cycling life test below.
Before cycling life test, measure the weight of battery.For charge/discharge cycle, repeat under 25 ℃ room temperature electric current with 25A and make 20 seconds of battery discharge, then in the constant voltage (maximum charging current 25A) of the 14V step 7200 time in 40 seconds of charging down.Then, measure the weight of battery once more, and obtain the loss in weight (WL) before and after the charge/discharge cycle.Then, make 30 seconds of battery discharge with the electric current of 300A.Obtain the discharge voltage (being designated hereinafter simply as V30) in the 30th second, replenish the water of battery weight loss amount then.
Under each the 7200th time circulation, obtain V30, and when V30 is reduced to 7.0V, be set to the battery termination in useful life.Usually, the lead accumulator that is being used for piloting engine, carry out underloading test in useful life, wherein repeat under the electric current of 25A, to make battery discharge 4 minutes, then the step (stipulating in according to JISD5301) of charging 10 minutes down in constant voltage (maximum current 25A).But in this cycling life test, frequent charge/discharge is provided with experimental condition under the lower SOC comparing with test in underloading commonly used useful life by supposition.
Obtain the cycle-index of battery life according to the methods below.The V30 that (obtains charge/discharge cycles by 7200 * n) obtain when at the n time becomes 7.0V first or when following, V30 be made as Vn, and (n-1) V30 of front is made as Vn-1.Then, in that ordinate is set is that V30 and abscissa are among the figure of charge/discharge cycles, and coordinate (7200 (n-1), Vn-1) and coordinate (7200n, Vn) connect into straight line, and with the abscissa value at this straight line and V30=7.0 joining place as cycle-index (cycle life).
(6) measurement of negative pole screen fin rate of corrosion
Take the battery of finishing life test apart, and by measure negative pole screen fin the thickness of thin part obtain the rate of corrosion of negative pole screen fin.By cutting middle body at Width, and measure the thinnest part with microscope and obtain the thickness of thin part of negative pole screen fin.Then, be made as T, and the thickness of negative pole screen fin after the life test is made as TE, calculate the rate of corrosion (%) of negative pole screen fin with formula (T-TE)/T * 100 by thickness with reset condition negative pole screen fin.
Result of the test is illustrated in table 1 and the table 2.
As shown in table 2, when use comprised the Pb alloy of 2.5 quality %Sb, in any battery, the rate of corrosion of negative pole screen fin was high and cycle-index is 20000 to 30000 circulations.This may be because the Sb that comprises in anodal connector and the anode connector dissolves in the electrolyte, and the Sb of dissolving deposits on the negative pole screen fin.Take these batteries apart, and, find in negative pole screen fin, to exist the Sb of about 0.0006 quality % as the result of quantitative analysis.
As shown in table 1, in battery B2-B5 of the present invention, C2-C5, D2-D5 and E2-E5 (wherein used the anodal connector and the anode connector that comprise the Pb alloy that contains 2.5 quality %Sn, comprise the negative electrode active material layer of Sb and comprised the barrier film of the polythene strip that contains silica dioxide granule), compare with battery A1-A5, B1, C1, D1 and the E1 of comparative example, the rate of corrosion of negative pole screen fin reduces, and cycle-index increases.
The improvement of cycle life character may be based on the improvement of the chargeability of anticathode plate by comprise Sb in negative electrode active material layer.In addition, although take these batteries apart and, from negative pole screen fin, do not detect the Sb that is higher than detectability (0.0001 quality %) as the result of the quantitative analysis of Sb in the negative pole screen fin.
Because the silica dioxide granule that comprises in the barrier film has been captured the Sb ion that dissolves in the electrolyte, thereby suppressed near the diffusion of Sb ion negative pole screen fin, and suppressed the deposition of Sb on negative pole screen fin, so probably suppressed the corrosion of negative pole screen fin.
Because when battery charge, be adsorbed onto Sb ion deposition on the silica particles near the surface of the negative electrode active material the barrier film, so by in negative plate, comprising the improvement effect that Sb can obtain chargeability continuously.
In using the comparative example battery A2-A5 of barrier film that does not comprise silica dioxide granule and the negative electrode active material layer that comprises Sb, because the carrying out of negative pole screen fin corrosion, the rate of corrosion of negative pole screen fin significantly increases, and the afflux character of negative plate descends, so cycle-index (cycle life) is lower than 30000 circulations.This may be because dissolve the Sb that deposit on the negative pole screen fin and along with recharge/discharge from negative electrode active material layer owing to over-discharge can before battery life test, deposits to the corrosion that Sb on the negative pole screen fin has promoted negative pole screen fin.
Comprise the barrier film of silica dioxide granule and do not comprise among comparative example battery B1, C1, D1 and the E1 of negative electrode active material layer of Sb in use, although the corrosion of negative pole screen fin is carried out hardly, useful life, character reduced.When taking the battery of finishing the battery life test apart, find the lead sulfate accumulation of discharge generation.Therefore, confirmed that it is the reduction of chargeability that battery reaches the reason in its life-span.
When the Sb content in the negative electrode active material layer was 0.0002 mass parts in for the negative electrode active material of 100 mass parts altogether and Sb, useful life, character was improved.And when the Sb content in the negative electrode active material layer for the negative electrode active material of 100 mass parts altogether and Sb in when being not less than 0.0004 mass parts, useful life, character was significantly improved.But when the Sb content in the negative electrode active material layer was 0.007 mass parts in for the negative electrode active material of 100 mass parts altogether and Sb, the rate of corrosion of negative pole screen fin increased.Can obtain conclusion from above: the Sb content in the negative electrode active material layer is preferably among the negative electrode active material of 100 mass parts altogether and the Sb and is the 0.0002-0.006 mass parts.
When the content of the silica dioxide granule in the barrier film that comprises the polythene strip that contains silica dioxide granule was not less than 35 quality %, useful life, character was improved, and had suppressed the corrosion of negative pole screen fin.Especially when the content of the silica dioxide granule in the barrier film that comprises the polythene strip that contains silica dioxide granule is 40-85 quality %, the remarkable improvement of character in useful life and the inhibition of negative pole screen fin corrosion have been realized.When the content of the silica dioxide granule in the barrier film that comprises the polythene strip that contains silica dioxide granule was higher than 85 quality %, although the effect above having realized, the intensity of barrier film reduced, and the handling properties variation during making.Can reach a conclusion from above: the content that comprises the silica dioxide granule in the barrier film of the polythene strip that contains silica dioxide granule is preferably 40-85 quality %.
In the acidic aqueous solution that has disperseed silica dioxide granule,, obtain the glass layer of 1.0 millimeters thick of maintenance silica dioxide granule by the paper technology of glass fibre.Then, the glass layer that is obtained is folded into two layers, and prepares the bag shape barrier film that only has opening in the above by thermal weld left part and right part.At this moment, the content that will comprise the silica dioxide granule in the barrier film of the glass layer that keeps silica dioxide granule is arranged to 0 quality %, 5 quality %, 10 quality %, 40 quality % and 50 quality %.For silica dioxide granule, use with embodiment 1 in identical silica dioxide granule.
As shown in Tables 3 and 4, by combination have different silica dioxide granule content the barrier film that comprises the glass layer that keeps silica dioxide granule, have the negative electrode active material layer of different Sb content and have anodal connector and the anode connector that different-alloy is formed, prepare battery K1-K5, L1-L5, M1-M5, N1-N5, O1-O5, P1-P5, Q1-Q5, R1-R5, S1-S5 and T1-T5 according to the method identical with embodiment 1.
Battery L2-L5, M2-M5, N2-N5 and O2-O5 in the table 3 are the batteries of embodiment, and other battery in the table 3 and the battery in the table 4 all are the batteries of comparative example.The Pb alloy that battery in the table 3 has represented to comprise 2.5 quality %Sn is used for the situation of anodal connector and anode connector, and the Pb alloy of having represented to comprise 2.5 quality %Sb of the battery in the table 4 is used for the situation of anodal connector and anode connector.
[table 3]
| Battery number | Dioxide-containing silica in the barrier film (quality %) | Sb content (mass parts) in the negative electrode active material layer | The rate of corrosion (%) of negative pole screen fin | Cycle-index (cycle life) |
| K1 | 0 | 0(＜0.0001) | 2.1 | 19800 |
| K2 | 0 | 0.0002 | 81.7 | 20600 |
| K3 | 0 | 0.0004 | 81.2 | 21200 |
| K4 | 0 | 0.006 | 83.2 | 22800 |
| K5 | 0 | 0.007 | 82.3 | 23000 |
| | 5 | 0(＜0.0001) | 2.1 | 20600 |
| | 5 | 0.0002 | 2.3 | 53600 |
| | 5 | 0.0004 | 3.0 | 74300 |
| | 5 | 0.006 | 3.2 | 85400 |
| | 5 | 0.007 | 9.8 | 72600 |
| | 10 | 0(＜0.0001) | 2.1 | 22200 |
| | 10 | 0.0002 | 2.1 | 99100 |
| | 10 | 0.0004 | 2.6 | 102200 |
| | 10 | 0.006 | 2.9 | 119100 |
| | 10 | 0.007 | 7.8 | 128100 |
| N1 | 40 | 0(＜0.0001) | 2.0 | 24820 |
| N2 | 40 | 0.0002 | 2.0 | 112200 |
| N3 | 40 | 0.0004 | 2.4 | 129000 |
| N4 | 40 | 0.006 | 2.5 | 128700 |
| N5 | 40 | 0.007 | 7.2 | 123400 |
| O1 | 50 | 0(＜0.0001) | 1.9 | 17600 |
| O2 | 50 | 0.0002 | 2.1 | 63400 |
| O3 | 50 | 0.0004 | 2.3 | 108900 |
| O4 | 50 | 0.006 | 2.5 | 107500 |
| O5 | 50 | 0.007 | 7.0 | 82700 |
[table 4]
| Battery number | Dioxide-containing silica in the barrier film (quality %) | Sb content (mass parts) in the negative electrode active material layer | The rate of corrosion (%) of negative pole screen fin | Cycle-index (cycle life) |
| P1 | 0 | 0(＜0.0001) | 83.2 | 25800 |
| P2 | 0 | 0.0002 | 84.1 | 23700 |
| P3 | 0 | 0.0004 | 88.6 | 20300 |
| P4 | 0 | 0.006 | 84.3 | 22000 |
| P5 | 0 | 0.007 | 85.4 | 21600 |
| | 5 | 0(＜0.0001) | 78.3 | 23800 |
| | 5 | 0.0002 | 79.2 | 22350 |
| | 5 | 0.0004 | 82.8 | 20680 |
| | 5 | 0.006 | 83.7 | 21820 |
| | 5 | 0.007 | 89.5 | 21730 |
| | 10 | 0(＜0.0001) | 77.0 | 23600 |
| | 10 | 0.0002 | 77.5 | 25000 |
| | 10 | 0.0004 | 80.4 | 26040 |
| | 10 | 0.006 | 82.6 | 25700 |
| | 10 | 0.007 | 82.6 | 25960 |
| S 1 | 40 | 0(＜0.0001) | 79.2 | 26300 |
| S2 | 40 | 0.0002 | 80.9 | 25700 |
| S3 | 40 | 0.0004 | 81.5 | 25520 |
| S4 | 40 | 0.006 | 83.5 | 24640 |
| S5 | 40 | 0.007 | 87.7 | 26920 |
| T1 | 50 | 0(＜0.0001) | 76.1 | 27450 |
| T2 | 50 | 0.0002 | 78.6 | 28510 |
| T3 | 50 | 0.0004 | 76.4 | 25960 |
| T4 | 50 | 0.006 | 77.2 | 28240 |
| T5 | 50 | 0.007 | 79.7 | 28240 |
For each battery, the cycling life test after overcharging and under the experimental condition identical, measure the rate of corrosion of negative pole screen fin with embodiment 1.The result of these tests is illustrated in table 3 and 4.
As shown in table 4, when the Pb alloy that comprises 2.5 quality %Sb is used for anodal connector and anode connector, the rate of corrosion of negative pole screen fin is high, and cycle-index (cycle life) is less than about 30000 circulations greatly, and the corrosion of negative pole screen fin is carried out in any battery.With the same among the embodiment 1, this may be because the Sb that comprises in anodal connector and the anode connector dissolves in the electrolyte, and the Sb of dissolving deposits on the negative pole screen fin.When taking these batteries apart and carrying out quantitative analysis, find to find the Sb of about 0.0005 quality % at negative pole screen fin place for the Sb on the negative pole screen fin.
As shown in table 3, use comprise the Pb alloy that contains 2.5 quality %Sn anodal connector and anode connector, comprise the negative electrode active material layer of Sb and comprise among battery L2-L5 of the present invention, M2-M5, N2-N5 and the O2-O5 of barrier film of the glass layer that keeps silica dioxide granule, compare with battery K1-K5, L1, M1, N1 and the O1 of comparative example, the rate of corrosion of negative pole screen fin reduces, and cycle-index (cycle life) increases.When taking these batteries apart and carrying out quantitative analysis for the Sb on the negative pole screen fin, finding not have discovery to be higher than the Sb of detectability (0.0001 quality %) at negative pole screen fin place.
In using the comparative example battery K2-K5 of barrier film that does not comprise silica dioxide granule and the negative electrode active material layer that comprises Sb, based on carrying out owing to the corrosion of negative pole screen fin, the rate of corrosion of negative pole screen fin significantly increases and the afflux character of negative plate descends, so cycle-index (cycle life) is lower than 30000.
Comprise the barrier film of silica dioxide granule and do not comprise among comparative example battery L1, M1, N1 and the O1 of negative electrode active material layer of Sb in use, although the corrosion of negative pole screen fin is carried out hardly, because chargeability descends, useful life, character reduced.
When the content of the silica dioxide granule in the barrier film that comprises the glass layer that keeps silica dioxide granule was not less than 5 quality %, useful life, character was improved, and had suppressed the corrosion of negative pole screen fin.Especially when the content of the silica dioxide granule in the barrier film that comprises the glass layer that keeps silica dioxide granule is 10-40 quality %, significantly realized the inhibitory action of the corrosion of the improvement of character in useful life and negative pole screen fin.The content of the silica dioxide granule in the barrier film that comprises the glass layer that keeps silica dioxide granule is in the battery of 50 quality %, and the cycle-index during the battery life slightly reduces.Can reach a conclusion from above: the content that comprises the silica dioxide granule in the barrier film of the glass layer that keeps silica dioxide granule is preferably 10-40 quality %.
When the Sb content in the negative electrode active material layer for the negative electrode active material of 100 mass parts altogether and Sb in when being not less than 0.0002 mass parts, character improvement in useful life.Especially when the Sb content in the negative electrode active material layer for the negative electrode active material of 100 mass parts altogether and Sb in when being not less than 0.0004 mass parts, useful life, character was significantly improved.But when the Sb content in the negative electrode active material layer was 0.007 mass parts in for the negative electrode active material of 100 mass parts altogether and Sb, the rate of corrosion of negative pole screen fin increased.Can obtain conclusion from above: the Sb content in the negative electrode active material layer is for being preferably the 0.0002-0.006 mass parts among the negative electrode active material of 100 mass parts altogether and the Sb.
The battery of the present invention that comprises the barrier film of the polythene strip that contains silica dioxide granule with use among the embodiment 1 is compared, use the battery of the present invention of the barrier film that comprises the glass layer that keeps silica dioxide granule among the embodiment 2 even under a spot of silica dioxide granule, also realized the effect of bigger inhibition negative pole screen fin corrosion.
Can infer and following conclusion.In the barrier film that comprises the polythene strip that contains silica dioxide granule, silica dioxide granule is dispersed in the polythene strip.Therefore, a lot of silica dioxide granules are covered by polyethylene, and be capped this part can not adsorb the Sb ion.On the other hand, in the barrier film that comprises the glass layer that keeps silica dioxide granule, silica dioxide granule is dispersed on the surface of fiber.Therefore, the major part of silica particles can be adsorbed the Sb ion.
As shown in Figure 5, in the pressing step that anodal screen is made, between roller is to 45, supply base material sheet 27 and lead alloy-foil 27a, and push base material sheet 27 and lead alloy-foil 27a simultaneously by roller.By this pressing process, lead alloy-foil 27a adheres on the base material sheet 27, and obtains the composite sheet that has 20 micron thickness lead alloy layers on base material sheet one side in 1.1 millimeters thick.The Pb alloy that comprises 5.0 quality %Sn is used for lead alloy-foil 27a.The anodal screen identical with embodiment 1 is used for base material sheet 27.
Go up base material sheet 27 parts of lead alloy-foil 27a for extruding, only be squeezed in the part that will form expanded mesh and frame in the following expansion process, and lead alloy-foil is not expressed on the middle body of base material sheet 27 of the fin 22 that will form anodal screen, as shown in Figure 4.
Except composite sheet is carried out the expansion process, obtain positive plate according to the method identical with embodiment 1.As shown in Figure 6, anodal screen has the alloy-layer 25a that comprises the Pb alloy that contains 5 quality %Sn in the positive plate on a side of the expanded mesh 25 with lozenge shape cross-section.
Except using the positive plate that obtains above, make the battery C8 that has same structure with C3.
Except bag shape barrier film is stored positive plate rather than the negative plate, make the battery C7 that has same structure with C8.
Except bag shape barrier film is stored positive plate rather than the negative plate, make the battery C6 that has same structure with C3.
Except the barrier film that comprises the glass layer that keeps silica dioxide granule that uses battery M3 replaces the barrier film that comprises the polythene strip that contains silica dioxide granule of battery C3, make the battery M6-M8 that has same structure with battery C6-C8 respectively.
Result of the test is illustrated in the table 5.
[table 5]
| Battery number | Barrier film | The lip-deep lead alloy of anodal screen | The rate of corrosion of negative pole screen (%) | Cycle-index (cycle life) | |
| Composition material | The battery lead plate that stores | ||||
| C6 | Polyethylene | Anodal | Do not have | 79.6 | 25600 |
| C7 | Polyethylene | Anodal | Have | 81.1 | 26600 |
| C3 | Polyethylene | Negative pole | Do not have | 2.7 | 107000 |
| C8 | Polyethylene | Negative pole | Have | 2.8 | 153000 |
| M6 | Glass fibre | Anodal | Do not have | 80.0 | 20100 |
| M7 | Glass fibre | Anodal | Have | 82.6 | 22300 |
| M3 | Glass fibre | Negative pole | Do not have | 2.6 | 102200 |
| M8 | Glass fibre | Negative pole | Have | 2.7 | 144000 |
When on anodal screen one side lead alloy layer that comprises Sn being arranged, suppressed on the interface of anodal screen and active material, to form passivation layer, thereby improved the chargeability of positive plate, and increased cycle-index (cycle life).
In addition, because when storing negative plate rather than positive plate in bag shape barrier film, the diffusion of Sb more is suppressed, so because Sb deposits to the rate of corrosion of the negative pole screen fin that causes on the negative pole screen fin is low.
The positive pole that will fill is stuck with paste and the amount of negative pole paste except adjusting, and makes that the mass ratio (NAM/PAM) of negative electrode active material and positive active material satisfies outside the value as shown in table 6 in the electrode plate groups, produces the battery C9-C13 that has same structure with battery C3.
In addition, except the barrier film of the polythene strip that comprises silica dioxide granule of the barrier film replacement battery C3 that comprises the glass layer that keeps silica dioxide granule that uses battery M3, produce the battery M9-M13 that has same structure with battery C9-C13.
The result of the test of battery is as shown in table 6.
[table 6]
| Battery number | The composition material of barrier film | NAM/PAM | The rate of corrosion (%) of negative pole screen fin | Cycle-index (cycle life) |
| C9 | Polyethylene | 0.6 | 83.7 | 22200 |
| C10 | Polyethylene | 0.7 | 2.9 | 99300 |
| C11 | Polyethylene | 0.82 | 2.8 | 99900 |
| C3 | Polyethylene | 1.08 | 2.7 | 107000 |
| C12 | Polyethylene | 1.3 | 2.5 | 98000 |
| C13 | Polyethylene | 1.35 | 2.2 | 96900 |
| M9 | Glass fibre | 0.6 | 81.2 | 21200 |
| M10 | Glass fibre | 0.7 | 2.9 | 97600 |
| M11 | Glass fibre | 0.82 | 2.8 | 98300 |
| M3 | Glass fibre | 1.08 | 2.6 | 102200 |
| M12 | Glass fibre | 1.3 | 2.5 | 101000 |
| M13 | Glass fibre | 1.35 | 2.5 | 99000 |
When NAM/PAM is 0.7-1.3, obtain excellent character in useful life, suppressed the corrosion of negative pole screen fin simultaneously.Especially when NAM/PAM is 0.82-1.08, the inhibition of negative pole screen fin corrosion and the effect that useful life, character was improved have significantly been realized.
When NAM/PAM is 0.6, because the corrosion of negative pole screen fin is carried out and the afflux character of negative plate descends, so cycle-index (cycle life) drops to 20000-30000.This may be because deposit on the negative pole screen fin because of over-discharge can Sb of stripping from negative electrode active material layer before life test.
On the other hand, when NAM/PAM is 1.35, although the corrosion of negative pole screen fin is lower slightly, the few of improvement of character in useful life.This may be because because over-discharge can positive electrode capacity reduction.
With the various ratios shown in the table 7, comprise with battery 3 in comprise mineral oil (Daphne Oil CP, by Idemitsu KosanCo., Ltd. makes) in the barrier film of polythene strip of identical silica dioxide granule.Except using these barrier films, produce the battery C14-C17 that has same structure with battery C3 respectively.
Result of the test is represented as shown in table 7.
[table 7]
| Battery number | Oil content in the barrier film (quality %) | The corrosion (%) of negative pole screen fin | Cycle-index (cycle life) |
| C3 | 0 | 2.7 | 107000 |
| | 5 | 2.7 | 109000 |
| | 10 | 2.5 | 110100 |
| C16 | 30 | 2.2 | 99400 |
| C17 | 40 | 2.0 | 34500 |
When the oil content in the barrier film is 5-30 quality %, because oil has been captured the Sb of stripping from negative electrode active material layer, so further suppressed because the corrosion of the negative pole screen fin of Sb.When the oil content in the barrier film was higher than 30 quality %, although can obtain to capture the effect of Sb, because oil has stopped up the pore of barrier film, the ion permeability of barrier film reduced, and the internal resistance of battery increase, so useful life, character descended.
Embodiment 6
Except the fin that differently changes the negative pole screen and the size of frame, after making that the fin 33 of negative pole screen integrally is welded on the negative pole attachment strap, the ratio of the height Lt of the width Lf of the frame 33 in the negative pole screen and the fin 32 of negative pole screen satisfies outside the value as shown in table 8, produces the battery C18-C21 that has same structure with battery C3.
In addition, replace producing the battery M18-M21 that has same structure with C18-C21 the barrier film of battery C3 except the barrier film that uses battery M3.When the height to battery limits, produce these batteries that satisfy the Lt+Lf=30.0 millimeter.
In addition, except the width (Wt among Fig. 3) that makes negative pole screen fin is 15.0 millimeters, produce the battery C18 '-C21 ' and the M18 '-M21 ' that have same structure with battery C18-C21 and M18-M21.The result of the test of these batteries is illustrated in table 8 and 9.
[table 8]
| Battery number | The composition material of barrier film | Lt/Lf | The rate of corrosion (%) of negative pole screen fin | Cycle-index (cycle life) |
| C18 | Polyethylene | 2.2 | 2.6 | 96200 |
| C19 | Polyethylene | 7.5 | 2.8 | 96500 |
| C3 | Polyethylene | 12.0 | 2.7 | 107000 |
| C20 | Polyethylene | 15.0 | 2.9 | 97100 |
| C21 | Polyethylene | 20.0 | 83.2 | 24000 |
| M18 | Glass fibre | 2.2 | 2.6 | 95800 |
| M19 | Glass fibre | 7.5 | 2.6 | 96000 |
| M3 | Glass fibre | 12.0 | 2.6 | 102200 |
| M20 | Glass fibre | 15.0 | 3.2 | 98300 |
| M21 | Glass fibre | 20.0 | 80.3 | 23400 |
[table 9]
| Battery number | The composition material of barrier film | Lt/Lf | The rate of corrosion (%) of negative pole screen fin | Cycle-index (cycle life) |
| C18′ | Polyethylene | 2.2 | 2.7 | 96000 |
| C19′ | Polyethylene | 7.5 | 2.7 | 97200 |
| C3′ | Polyethylene | 12.0 | 2.7 | 103400 |
| C20′ | Polyethylene | 15.0 | 3.0 | 98200 |
| C21′ | Polyethylene | 20.0 | 82.9 | 24300 |
| M18′ | Glass fibre | 2.2 | 2.9 | 92600 |
| M19′ | Glass fibre | 7.5 | 3.0 | 93400 |
| M3′ | Glass fibre | 12.0 | 3.0 | 99300 |
| M20′ | Glass fibre | 15.0 | 4.2 | 97300 |
| M21′ | Glass fibre | 20.0 | 81.3 | 24700 |
When Lt/Lf was 2.2-15.0, the rate of corrosion of negative pole screen fin reduced, and had suppressed the corrosion of negative pole screen fin.In addition, increase cycle-index (cycle life), and improved character in useful life.Especially when Lt/Lf is no more than 12.0, suppressed the corrosion of negative pole screen fin.This trend is identical with any situation that is 10.0 millimeters and 15.0 millimeters when the width (Wt) of negative pole screen fin.Therefore, the width of finding negative pole screen fin influence hardly negative pole screen fin corrosion and useful life character.
Industrial applicability
Because lead accumulator of the present invention has the character in service life of excellence under the use pattern of recharge/discharge under the low SOC scope, so lead accumulator of the present invention is applicable to be equipped with the vehicle of stop-start system and regeneration brake system etc.
Claims (10)
1. lead accumulator, it comprises:
The electrode plate groups that comprises the barrier film of a plurality of negative plates, a plurality of positive plate and described positive plate of a plurality of isolation and described negative plate, wherein, each negative plate comprises negative pole screen with fin and the negative electrode active material layer that is kept by described negative pole screen, and each positive plate comprises anodal screen with fin and the positive electrode active material layer that is kept by described anodal screen;
The anodal attachment strap and anode bar that provides on described anodal attachment strap or the anodal connector that are connected with the described fin of each positive plate of described electrode plate groups are provided anodal connector; And
The negative pole attachment strap and cathode rod that provides on described negative pole attachment strap or the negative pole connector that are connected with the described fin of each negative plate of described electrode plate groups are provided anode connector,
Wherein said anodal screen, described negative pole screen, described anodal connector and described anode connector comprise and contain Pb alloy at least a among Ca and the Sn,
Described negative electrode active material layer comprises Sb, and
Described barrier film comprises silicon dioxide.
2. according to the lead accumulator of claim 1, wherein said barrier film comprises micropore synthetic resin sheet and the silica dioxide granule that is dispersed in the described micropore synthetic resin sheet, and comprises the described silica dioxide granule of 40-85 quality %.
3. according to the lead accumulator of claim 1, the silica dioxide granule that wherein said barrier film comprises fibrage and kept by described fibrage, and comprise the described silica dioxide granule of 10-40 quality %.
4. according to the lead accumulator of claim 1, in the wherein said negative electrode active material layer in the described negative electrode active material of 100 mass parts and the described Sb that Sb comprises the 0.0002-0.006 mass parts altogether.
5. according to the lead accumulator of claim 1, wherein said anodal screen has the lead alloy layer that contains Sn at least in its surperficial part.
6. according to the lead accumulator of claim 1, wherein said barrier film is the sack shape and holds described negative plate.
7. according to the lead accumulator of claim 2, wherein said barrier film comprises the oil of 5.0-30 quality %.
8. according to the lead accumulator of claim 1, the mass ratio of negative electrode active material and described positive active material described in the wherein said electrode plate groups is 0.7-1.3.
9. according to the lead accumulator of claim 1, wherein
Described negative pole screen is a kind of expansion screen, and it comprises the expanded mesh that keeps described negative electrode active material layer, at the upper rim frame that provides and the described fin that is connected with described frame of described expanded mesh, and
The ratio of the height of described fin and the width of described frame is 2.2-15.0.
10. lead accumulator, it comprises:
The electrode plate groups that comprises the barrier film of a plurality of negative plates, a plurality of positive plate and described positive plate of a plurality of isolation and described negative plate, wherein, each negative plate comprises negative pole screen with fin and the negative electrode active material layer that is kept by described negative pole screen, and each positive plate comprises anodal screen with fin and the positive electrode active material layer that is kept by described anodal screen;
The anodal attachment strap and anode bar that provides on described anodal attachment strap or the anodal connector that are connected with the described fin of each positive plate of described electrode plate groups are provided anodal connector; And
The negative pole attachment strap and cathode rod that provides on described negative pole attachment strap or the negative pole connector that are connected with the described fin of each negative plate of described electrode plate groups are provided anode connector,
Wherein said anodal screen, described negative pole screen, described anodal connector and described anode connector comprise and contain Pb alloy at least a among Ca and the Sn,
Described negative electrode active material layer comprises Sb,
Described barrier film comprises silicon dioxide, and
The mass ratio of negative electrode active material and described positive active material described in the described electrode plate groups is 0.7-1.3.
Applications Claiming Priority (9)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP109809/2004 | 2004-04-02 | ||
| JP2004109809A JP2005294142A (en) | 2004-04-02 | 2004-04-02 | Lead storage battery |
| JP111810/2004 | 2004-04-06 | ||
| JP248061/2004 | 2004-08-27 | ||
| JP302595/2004 | 2004-10-18 | ||
| JP302594/2004 | 2004-10-18 | ||
| JP328749/2004 | 2004-11-12 | ||
| JP328748/2004 | 2004-11-12 | ||
| JP340225/2004 | 2004-11-25 |
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| CN100583534C CN100583534C (en) | 2010-01-20 |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013031263A1 (en) * | 2011-09-01 | 2013-03-07 | 新神戸電機株式会社 | Lead storage cell |
| CN104067414A (en) * | 2012-12-21 | 2014-09-24 | 松下电器产业株式会社 | Lead storage battery |
| CN105895919A (en) * | 2015-02-12 | 2016-08-24 | 株式会社杰士汤浅国际 | Lead-acid battery, negative electrode plate thereof and method for producing lead-acid battery |
| CN105895911A (en) * | 2015-02-18 | 2016-08-24 | 株式会社杰士汤浅国际 | Lead-acid battery |
| CN114709552A (en) * | 2015-10-05 | 2022-07-05 | 达拉米克有限责任公司 | Functionalized lead acid battery separators, improved lead acid batteries, and related methods |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2847761B2 (en) * | 1989-06-12 | 1999-01-20 | 株式会社ユアサコーポレーション | Sealed lead-acid battery and method of manufacturing the same |
-
2004
- 2004-04-02 JP JP2004109809A patent/JP2005294142A/en active Pending
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2005
- 2005-04-01 CN CN200580004546A patent/CN100583534C/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013031263A1 (en) * | 2011-09-01 | 2013-03-07 | 新神戸電機株式会社 | Lead storage cell |
| CN104067414A (en) * | 2012-12-21 | 2014-09-24 | 松下电器产业株式会社 | Lead storage battery |
| CN104067414B (en) * | 2012-12-21 | 2016-07-06 | 松下知识产权经营株式会社 | Lead battery |
| CN105895919A (en) * | 2015-02-12 | 2016-08-24 | 株式会社杰士汤浅国际 | Lead-acid battery, negative electrode plate thereof and method for producing lead-acid battery |
| CN105895919B (en) * | 2015-02-12 | 2020-11-24 | 株式会社杰士汤浅国际 | Lead storage battery, negative plate thereof, and method for manufacturing lead storage battery |
| CN105895911A (en) * | 2015-02-18 | 2016-08-24 | 株式会社杰士汤浅国际 | Lead-acid battery |
| CN114709552A (en) * | 2015-10-05 | 2022-07-05 | 达拉米克有限责任公司 | Functionalized lead acid battery separators, improved lead acid batteries, and related methods |
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| Publication number | Publication date |
|---|---|
| JP2005294142A (en) | 2005-10-20 |
| CN100583534C (en) | 2010-01-20 |
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