CN106207193A

CN106207193A - A kind of bipolar plate-shaped unit high-energy lead-acid battery and the high-tension battery group of composition thereof and method for packing

Info

Publication number: CN106207193A
Application number: CN201510233558.9A
Authority: CN
Inventors: 曾碚凯; 曾培龙
Original assignee: Individual
Current assignee: Individual
Priority date: 2015-05-08
Filing date: 2015-05-08
Publication date: 2016-12-07
Anticipated expiration: 2035-05-08
Also published as: CN106207193B

Abstract

The present invention relates to lead-acid accumulator, a kind of bipolar plate-shaped unit high-energy lead-acid battery and the high-tension battery group of composition thereof and the method for packing of set of cells.Unit high-energy lead-acid battery includes electronic conductor bipolar plates, the anode and cathode active materials layer that its two sides is respectively coated be same with the active material that lead sulfate is main preparation, wherein, one side active material layer on re-lay battery separator.Use invention unit battery easily to realize height after carrying out the cell package of series stack and force down internal resistance long circulation life battery, simplify the production technology of battery simultaneously, reduce production cost.

Description

A kind of bipolar plate-shaped unit high-energy lead-acid battery and the high-tension battery group of composition thereof and method for packing

Technical field

The present invention relates to lead-acid accumulator, high-tension battery group that a kind of bipolar plate-shaped unit high-energy lead-acid battery is composed in series and the compact package method of set of cells.

Background technology

Since French scientist Pulan spy's invention lead-acid battery in 1859, lead-acid battery industry has been subjected to the industry development history of 154 years.Although lead-acid battery is cheap, stable performance, runs safety.But it also has the most fatal shortcoming, such as specific energy is little, specific power is low, the life-span is short.Severely impact the expansion of application.

In existing lead-acid battery technology, the structure of basic employing is: supported both positive and negative polarity active material respectively by both positive and negative polarity " grid ", multiple " grid " is connected by " lug " being fixed on grid by " bus-bar ", being drawn out to outside battery case by " pole " of " bus-bar ", " interpolar connecting line " completes by the cascade of element cell to set of cells again.There is " dividing plate " to isolate between both positive and negative polarity in element cell, to prevent short circuit between both positive and negative polarity, fill electrolyte～dilution heat of sulfuric acid therebetween.

In existing lead-acid battery technology, employing two kinds of lead, one is " nonactive lead ", it is simply that the lead included in above-mentioned " grid ", " bus-bar ", " lug ", " pole ", " inter-stage connecting line " and metal." nonactive lead " the most directly participates in the electrochemical reaction involved by charge and discharge, and therefore " charge storage ability " of battery is not made any contribution by it.Another kind is " activity lead ", it is simply that " lead sponge " on negative plate and " lead oxide " on positive plate, and it is used to the electrochemical reaction of participation charge and discharge.

But " charge storage ability " can be contributed by not all " activity lead ", because also " the activity lead " of significant proportion undertakes " electrical path " in electrochemical reaction and supports " logistics " effect of bigger serface reaction structure.Because the active material on positive/negative plate is during exoelectrical reaction, generating nonconducting " lead sulfate ", if active material reacts completely all generates nonconducting " lead sulfate ", without conductive path during charging, electrochemical reaction cannot be carried out.Equal to complete cell failure.

The reason of one of fatal defects of existing lead-acid battery " specific energy is little ", is that the ratio of " nonactive lead " account for more than the 50% of whole consumption of lead, occupy prior art lead-acid battery almost half weight and bigger volume.Further, since exoelectrical reaction product PbSO₄Insoluble in dilute sulfuric acid, crystallize the surface in active material, the most non-conductive, and electric path necessary to electrochemical reaction to be undertaken by active material self, the utilization rate of " the activity lead " that the most really stores for electric energy is also less than 50%.Lead in the most existing lead-acid battery only has the ratio less than 25% and take part in the electrochemical reaction of discharge and recharge.The specific energy of the most existing lead-acid battery also cannot reach the 1/4 of its theoretical specific energy (174wh/kg)；Only at about 35wh/kg.

Two " life-span is short " of existing lead-acid battery fatal defects.The phenomenon of modal cell damage is that positive electrode active materials comes off, and negative pole occurs that irreversible sulfation loses activity.

Positive electrode active materials～" Lead oxide brown " have two kinds of crystal forms, α lead oxide and beta-oxidation lead, about why to design the lead oxide of two kinds of crystal forms for the reason of positive electrode active materials time, prior art is explained: α lead oxide mechanical strength is good, chemical reactivity is low, and beta-oxidation lead chemical reactivity height is 3 times of α lead oxide, but bad mechanical strength, as the proportioning position 1:1.25 of two kinds of compositions, reaction efficiency is the highest.And effect that each crystal form component in electrochemical reaction produce is not explained further.

α lead oxide is responsible for maintaining the active material reaction structure supporting high-specific surface area and the effect taking on electric path in fact, because its reactivity is low, therefore, it does not the most participate in reaction, and beta-oxidation lead is only the real active substance carrying out energy storage discharge and recharge at positive pole.Lead oxide brown only has the participation discharge and recharge energy storage reaction that half can be real.If beta-oxidation lead is completely depleted in exoelectrical reaction, because α lead oxide and beta-oxidation lead phase specific activity are the lowest, reaction almost stops, again because α lead oxide generates under alkaline environment, acidic electrolysis bath environment can not generate α lead oxide, so the probability that the ratio of two kinds of crystal forms of α, β produces change is smaller, so, the reaction structure stability of the bigger serface of positive electrode material Lead oxide brown is of a relatively high, also it is not easy to generate " lead sulfate " piece that volume is bigger, therefore irreversible sulfation seldom occurs on anode plate grid.

But, although the specific activity of α lead oxide is poor, but it is not equal to it and does not the most participate in reaction, after once α lead oxide participates in reaction generation lead sulfate, in charging process, under sour environment, lead sulfate cannot be reduced into α lead oxide and can only be reduced into beta-oxidation lead.Although the capacity making battery increased, owing to activity improves, the amount of the lead sulfate being converted into during electric discharge will increase, and the volume of the volume ratio Lead oxide brown of lead sulfate is big a lot, and active material structure will be destroyed because of volumetric expansion.So active material comes off on the grid that mainly causes because of swelling stress of positive plate life-span short phenomenon.

By contrast, a kind of crystal form of negative material " lead sponge ", serve as conductive path and energy storage electrochemical reaction is commaterial, does not has therebetween the boundary line of certainty, it is easy to because electric current density is uneven, produce local overdischarge, generating the lead sulfate that volume is bigger, bigger " lead sulfate " in block footpath is because being insoluble in dilute sulfuric acid and non-conductive, thus " lead sponge " cannot be reduced into when charging, lose electro-chemical activity and produce " irreversible sulfation ".Although negative pole lead sponge is mixed with barium sulfate impurity, owing to its crystal formation is identical with lead sulfate, make newly generated lead sulfate crystallize on barium sulfate, utilize force of crystallization automatically to eliminate " passivation ", but stablizing of reaction structure can not be kept.This is also the basic reason that the damage of why lead-acid battery cathode grid is always caused by " irreversible sulfation ".

The most traditional lead-acid battery must sacrifice a certain amount of active material to do conductive path and to support the part active material of the most directly participation discharge and recharge reaction？The designer of lead-acid battery wants to produce as far as possible big " ampere-hour capacity " battery on limited polar plate area in early days.Therefore thicker active material it is coated with on grid.But actually it is not dissolved in electrolyte due to exoelectrical reaction product " lead sulfate ", is attached to the surface of active material and produces passivation, for preventing the frequent generation of irreversible sulfation.Only envision and use α lead oxide and two kinds of crystalline structures of beta-oxidation lead at positive pole, sacrifice the energy storage effect of α lead oxide, support the bigger serface reaction structure of three-dimensional.And be to use inorganic expansive agent barium sulfate at negative pole, organic expander lignosulfonic acid usually ensures to be formed three-dimensional bigger serface reaction structure, could solve to realize the design original intention of big " ampere-hour capacity " under finite volume.Actually control that exoelectrical reaction ends is to utilize positive electrode active materials α lead oxide and beta-oxidation lead chemical reactivity to differ three times, and once beta-oxidation lead is depleted, and response speed significantly declines, thus prevent can not degree of depth overdischarge.But α lead oxide activity is low and not have activity be two concepts, and SA reaction to be participated in, only speed is the slowest.And α lead oxide generates in the basic conditions, a small amount of α lead oxide once reacts generation lead sulfate, can only return to beta-oxidation lead when charging.Even if the most actually α lead oxide is also to consume in the reaction of " non-mistake is put " always, so positive electrode active materials three-dimensional Large ratio surface reaction structure is just in cycle charge-discharge, constantly decline and ineffective.And then the active material solid Large ratio surface reaction structure having influence on positive pole is also constantly be generated the phenomenon of decline in cycle charge-discharge.Therefore, the life-span is short is the essential problem of lead-acid battery active material structure.

The positive and negative pole plate life-span is the shortest, a common reason is also had to come from ancient, the cascade system of " the minus plate grid ear bus-bar pole level conjuncted pole bus-bar lug anode grid " that the most not yet changed, there is following several problem in this cascade system:

1. cascade average path is long, and the sectional area in cascade path is little and the cascade resistance that causes big, causes whole set of cells no matter in charging or discharge process, makes set of cells have impact on the performance of set of cells because of the cascade additional heating of resistance, added losses increasing.

2., for grid, electrochemistry produces and exports on the lug of grid one end very zonule confluxing of electric current.This has resulted in the uneven of whole grid electric current distribution, and the difference of electric current density results in thermograde, with the highest at lug, gradually reduces to screen far-end.Electrochemical reaction rates is the function of temperature, the cation assembled on the short active substance that can neutralize pole plate connection in time of the regional Electronic circulation path that lug is near, ion concentration polarization is weak, electrochemical reaction is conducive to carry out, the region that distance lug is remote, electron flow path path length, the cation assembled on the active substance that pole plate connects can not be neutralized in time, ion concentration polarization is strong, reduce electrochemical reaction to carry out, it is inconsistent that temperature and two factors of concentration polarization have resulted in active material electrochemical reaction rates on grid, a part of reason that aforesaid " expansion drop of anode grid active material " is the biggest with " the irreversible sulfation of negative electrode grid active material " is because what this cascade structure produced.During repeated charge, this cascade structure causes the caused electrochemical reaction depth disparity of weak current density unevenness weighing apparatus, is continually repeated, and constantly accumulates the local caused and first damages the result causing lead-acid battery short-lived.

3. typically all the reason that pole plate comes off being attributed to thermal overload in prior art makes grid bend, and a part of reason of this thermal overload also cascades that internal resistance is excessive to be caused.Due in exoelectrical reaction lead or Lead oxide brown combine the sulfate radical in electrolyte and when generating lead sulfate, the stress that volumetric expansion produces, cause other active materials to come off and be only the underlying cause.

Because to traditional lead acid batteries easy gassing (positive pole precipitated oxygen, negative pole separates out hydrogen) when charging, not only causing battery dehydration, need often to carry out moisturizing maintenance.Corroding of the sulphuric acid being also easy to make pole plate be raised by oxygen and concentration, reduces the life-span of battery.The hydrogen, the oxygen that separate out converge in atmosphere easily blast and constitute unsafe factor simultaneously.So occurring in that valve-control sealed lead acid battery technology, it utilizes the deposition potential of negative pole hydrogen higher than the deposition potential at positive pole oxygen, gas passage will be set up in electrolyte and barrier film, the oxygen first separated out by positive pole directs into negative pole, react with the lead of cathode deposition, generate lead monoxide, owing to the existence of electrode surface lead monoxide is it is prevented that the precipitation of hydrogen, simultaneous oxidation Asia lead and effect of sulfuric acid generate lead sulfate and water, this prevents the generation of phenomenon of losing water.So, it is in the sealed lead acid battery of " floating charging " operating mode almost without the maintenance work of moisturizing must be carried out, facilitates the use of battery.Lead-acid battery colloidal electrolyte technology utilizes the silica gel network of molecular level, has been relatively fixed the micro structure of active material so that it is to stabilizing active material reaction structure, the life-span extending lead-acid battery has played certain effect.But the gas passage manufactured between two-plate in electrolyte and dividing plate needs after certain use cycle, silica gel dry and cracked formation air flue.

Prevent grid corrosion as those, increase the effort of battery life, there is no the progressive meaning of reality.Because they do not find out the deadly defect in this structure.

Lead fabric grid horizon battery starts to challenge the ancient structure based on grid, but only one of many unreasonable structures of his challenge.Make to conflux by the concentration confluence of tradition grid, the section changing into whole lead fabric grid by lug.Compared with tradition cascade structure, although increase the sectional area in cascade path, but the most fundamentally change the average length cascading path, the actual distribution of electric current density or uneven on the most whole grid.

Use for reference hydrogen-oxygen fuel cell, the bipolar plates concept of the succinct internal cascade in solid electrolyte fuel cell, bipolar plates lead-acid battery is also proposed.Begin with structure ancient to lead-acid battery and carry out maiden attempt of radical change.The restriction selected due to bipolar plate material in these technical measures, both positive and negative polarity active material structure is still identical with ancient structure, and the short situation of battery is not improved, so this innovation there is no and is widely applied.

It is a significant improvement to traditional lead acid batteries structure from " winding type lead-acid battery " of American invention.Employ thin plate grid and the structure of thin active material, decrease the ratio of nonactive lead.Though some is progressive, but there is no the ancient technology of radical departure lead-acid battery based on grid structure, due to the lead-in wire of winding grid be from each pole plate distributed extraction alleviate the situation that lug formula grid electric current density is uneven.Still to have grill openings as tradition grid to increase the contact strength of active material on the thin plate grid wherein used, active material still employs the pairing active material of traditional " lead sponge " " lead oxide " simultaneously.So traditional problem of bigger serface active material structure still exists, and does not obtain basic solution.

Meanwhile, in the lead-acid battery industry history of 154 years, continue to use refining lead, casting lead, the technique of high energy ball milling Hydrocerussitum (Ceruse) always.Not only energy consumption is huge, and lead contamination is serious, is unfavorable for environmental conservation.Positive and negative electrode grid form is different, both positive and negative polarity active material is different, no matter technological innovation has carried out how many times, and the total general layout using nonactive lead making bus-bar, pole, lug, the structure of inter-stage line and positive pole to use Lead oxide brown, negative pole to use lead sponge to make active material structure in electrokinetic cell does not the most change.Complex process, production efficiency is low.

But, the industry that why can experience 154 years for lead-acid battery survive unfailing reason where, it is considered herein that in all of chemical cell, lead-acid battery is one of classic chemical design.Classic feature is as follows:

1. both positive and negative polarity reaction product is all identical chemical substance～" lead sulfate ", positive so-called " bis sulfonate ".This is unexistent in all chemical cells up to now, does not knows why this outstanding feature is never paid attention to, and is not the most utilized.

2. discharge product " lead sulfate " is slightly soluble in electrolyte～dilute sulfuric acid, and non-conductive, does not pollute electrolyte.

3. the design that " depassivation " is machine-processed automatically, this " depassivation " automatically selects barium sulfate as depassivation working medium dexterously, it had both had identical crystal structure with lead sulfate, does not the most participate in the discharge and recharge reaction of lead-acid battery, has at a relatively high chemical stability.Identical crystal structure makes the lead sulfate molecule generated in exoelectrical reaction be moved to form eutectic with barium sulfate around barium sulfate by the force of crystallization of same crystal structure, not only prevent it from forming polycrystalline passivation layer on active material, but also attempt the three-dimensional bigger serface structure of all reforming activity materials in exoelectrical reaction each time.

In the Chinese patent background technology of Application No. 200910171743.4, review the public technology the most much about bipolar plates lead-acid battery, this patent illustrating, in bipolar plates lead-acid battery technical background, produced problem is the most all to there is the ion Insulation Problems that gap is caused between organic substrate and metal insert, and the patent of Publication No. CN101202356A is also in that the sealing problem of element cell, causes cycle life unstable.For problem of in the ion sealing problem between improvement organic substrate and metal insert and the adhesion problem of grid corrosion, sulfation problem, active substance and the plastic grid of the existence of bipolar plates lead-acid battery and so-called prior art doing work active substance one side, the measure of proposition improvement is: 1. the surface of organic plates and metal insert is made hydrophobic treatment；2. paste the felt of Electolyte-absorptive on substrate then at felt surface configuration active material layer, make active substance two sides can participate in reaction, here it is the so-called surface work doing of this inventor；3. upwards open pore at each battery unit, the shared air chamber of each passage of UNICOM is set if desired, shared air chamber arranges air relief valve.

1. measure is made by the repellency of material, stops circulation in aqueous electrolyte slit between metal insert and organic substrate thus improve ion resistance.This way is feasible.But the bipolar plates that architecture basics originally uses is the thickest, owing to the consumption of bipolar plates is very big, its weight and volume is all an impediment to set of cells overall weight specific energy and the raising of energy density per unit volume.2. measure is that the felt cloth increasing Electolyte-absorptive is arranged between active material layer and organic substrate, two sides inside and outside active material is made all to touch electrolyte, the most so-called surface work doing, thus can elongate the length of electrochemical reaction conductive path, this not only to consume the proportion taking on conductive path active substance voluntarily, active material utilization is made to reduce further, heavier is can not to lay direction along active material in active material to form the longest conductive path, this is because the active material of lead-acid battery is lead oxide and lead sponge, they exoelectrical reactions all generate lead sulfate, and lead sulfate is nonconducting, the active substance undertaking conductive channel once there occurs exoelectrical reaction, conductive path necessary to far-end electrochemical reaction will be nipped off, and it is more readily formed irreversible sulfation.Even if setting the felt of Electolyte-absorptive the most overleaf, electrolyte can immerse active material by capillarity, and this measure is not only and is drawn a snake and add feet to it, and more unfavorable bipolar plates face and the combination of active material.3. measure is to increase element cell venthole upwards and sets up shared air chamber installation air relief valve, this measure there is no new meaning under conditions of the element cell thickness of this invention is relatively big, because being all to be in series by multiple unit lead-acid batteries in the traditional lead acid batteries of all of more than 4V, the most each lead-acid battery has outlet passageway upwards, also has public air chamber and air relief valve.If the element cell of bipolar plates lead-acid battery is thin to close to millimeter or lower, this problem is only technological difficulties.Even if so, this inventor does not speaks of at all, and the gas that is probably gone out from air-vent is also likely to be the electrolyte of expanded by heating, if electrolyte, even if seldom can form ion short-channel in public passage, affects battery normal discharge and recharge reaction yet.So it is the most feasible to there is provision of electrolyte memory space mutually isolated between unit battery in public air chamber.

Application No. 201210115319.X, invention entitled film composite material bipolar cell and bipolar plates matrix, when this technical background illustrates current bipolar plates lead-acid battery problem, list the U.S. and China's disclosed patent, and sum up 4 problems that existing bipolar plates battery exists, the 1. sealing problem between neighboring unit cell；2. the power loss problem that contact resistance causes；3. electrolyte causes the problem that bipolar plates occurs corrosion；4. the problem that whether complexity of processing technology is conducive to large-scale production.In this application, the solution to the problems referred to above is the conductive particle composing base using acidproof thermosetting or thermoplastics type's macromolecular material to add some dot matrixs, if requiring 1.1～1.4 times of the particle diameter substrate thickness of conductive particle, the two sides of substrate is again coated with lead foil hot pressing, ultimately form film composite material pole plate, then the two sides of this pole plate is respectively applied anode diachylon and cathode lead plaster, just becomes bipolar plates.The ultra-fine fibre glass barrier film of perfusion sulfuric acid electrolyte is placed between bipolar plates, by two ends after these element stack respectively plus a positive unipolar plate and negative unipolar plate, being drawn by the pole of oneself respectively, become a bipolar plates battery, its bipolar plates matrix is film composite material.And the technical background of this patent is enumerated 1. problem seem to be not directed to, 2. whether it solve, 3., 4. problem, front is not had to respond yet, describe " the bipolar film composite material lead-acid battery prepared by the present invention has corrosion resistance and good, the advantage such as lightweight, with low cost, and meets extensive manufacturing condition " the most in the description to hand over.The reprint wearing metal needle of plastic plate rectangular described in the solution described in this patent, actually bipolar plates lead-acid battery known technology, it is desirable to the length of pin must compare thickness of slab, in order to is electrically connecting two sides active material layer.The forward part of the solution of this patent and above-mentioned technology indistinction.Rear portion attempts to be solved the combination of two sides lead foil and conductive particle, lead foil and the combination of plastic base by hot pressing.And say precompressed temperature 150 degree, hot pressing temperature 250 degree.And the fusing point of lead is 328 degrees Celsius, not having theories integration can pass through pressure away from fusing point, can be combined by two metals in 15 minutes in existing technology, if this is true, solder technology will step down from the stage of history.Further, there is no 50 microns of thick lead foils of theories integration.Just can combine with plastics through the high temperature of 250 °.Depanning after the temperature hot pressing of 250 degree, returns to room temperature, the temperature difference of nearly 200 °, inventor do not illustrate plastics whether have with lead foil as thermal coefficient of expansion, usually understand, the swollen temperature coefficient of line of plastics be more than lead.After returning to room temperature, thermal stress can make lead foil separate with plastics.

Further, in all background technology documents of existing bipolar plates lead-acid battery, solution is all " nonactive lead " problem, concrete manifestation they be all to use the different active material in the two poles of the earth of existing lead-acid battery technology and be coated with cream technique.Do not account in prior art, also have close to half inside active material, do not participate in the electrochemical reaction of discharge and recharge at all, and be only to have done " logistic work " to serve as current channel necessary to electrochemical reaction and the fact that structure supports.

Summary of the invention

Present invention aim at a kind of high-tension battery group and the compact package method of set of cells providing bipolar plate-shaped unit high-energy lead-acid battery to constitute.

The technical solution used in the present invention is for achieving the above object:

A kind of bipolar plate-shaped unit high-energy lead-acid battery, unit high-energy lead-acid battery includes electronic conductor bipolar plates 15, its two sides is respectively coated the active material layer 20 that same is both positive and negative polarity primary active material with lead sulfate, wherein, the active material layer of one side re-lays battery separator 19.

Described bipolar plate-shaped unit high-energy lead-acid battery, described in be respectively coated the active material layer thickness in electronic conductor bipolar plates 15 both sides be 0.15-0.3mm, preferred thickness is 0.2mm.

Active material layer is made up of lead sulfate, additive and lead-acid battery colloidal electrolyte, wherein additive is known lead-acid battery cathode meterial additive (mixture and the composition additive of PP chopped fiber such as barium sulfate, humic acid and acetylene black, the addition of mixture is 1wt%～1.3wt%, and the addition of PP chopped fiber is 0.5wt%；Wherein the ratio of weight and number between barium sulfate, humic acid and the mixture of acetylene black is 5:4:2).Colloidal electrolyte is the electrolyte (dilute sulfuric acid plus nano silicon dioxide) of existing known colloid lead-acid battery, and colloidal electrolyte is 1 10 with the part by weight of lead sulfate.

Described electronic conductor bipolar plates 15 is the composite thin plate being made up of lead plating " stainless steel fibre cloth " the dipping fused solution the most thermally treated rolling of pure lead；Lamella thickness is 0.02-0.04mm, and preferred thickness is 0.03mm, and in thin plate, lead (including lead plating and dipping lead) is 4:6 with the preferred volume ratio of stainless steel fibre.

Described active material layer coats the centre of electronic conductor bipolar plates 15 with uniform thickness, uses prior art to carry out hydrophobic treatment in the region that electronic conductor bipolar plates 15 is uncoated.

The rectangular area of described active material layer 20 coating is 0.4-3mm less than the rectangular area of bipolar plates 15, active layer edge and bipolar plates sides aligned parallel, its edge with the vertical dimension at electronic conductor bipolar plates 15 edge；Preferably, three edges of rectangle of active material layer 20 coating are 0.5mm with the vertical dimension at electronic conductor bipolar plates 15 edge, another vertical dimension is 2mm, and vertical dimension is " upper surface " of the limit correspondence battery pile of 2mm, and gas relief cavity is installed on herein.

Described battery separator 19 is the AGM barrier film after lead-acid battery colloidal electrolyte soaks, and its rectangular dimension and electronic conductor bipolar plates 15 is equivalently-sized, and wherein membrane thicknesses is 0.2-0.4mm, and preferred thickness is 0.2mm.

A kind of series connection bipolar plates lead-acid battery group 25, it is the set of cells of 2NV for output voltage, described set of cells includes that N-1 described bipolar plate-shaped unit high-energy lead-acid battery 18 series connection is piled up, set of cells piles up order, and to be any two adjacent bipolar template unit high-energy lead-acid battery 18 be adjacent to realize connecting without the active material aspect 20 of barrier film with another bipolar plates element cell 18 with the one side of barrier film 19, align in all element cell 18 4 limits, in " upper surface ", gas relief cavity 26 is installed, the most again with 2 are called "+number ", the output pole plate composition set of cells of "-number " 24.Two output pole plate all single spreading active material layers 20, as coating size and marginal dimension are with element cell.Simply a dividing plate 19 also to be sticked on active layer by "-number " output pole plate 24.The lug of output pole plate is equidirectional with " upper surface ".

A kind of method for packing of bipolar plates lead-acid battery group of connecting, it is characterised in that:

1) using tooth holder 27 set of cells 25 that described series connection is formed to be clamped, holder contacts is "+number " 22, the output pole plate of "-number " 24, and fixture optimizes clamping force 1kg/cm², after clamping, using the acidproof insullac spraying two sides of set of cells and bottom surface (i.e. relative with the end face setting gas relief cavity face), insullac has filled in each element cell active material layer 20 edge to the space at electronic conductor bipolar plates 15 edge.Insullac thickness outside pole plate edge should reach 0.5mm, so that unit cell sealing is connected, forms the pre-sealed of element cell；

2) after pre-sealed solidification, it is attached to the face being coated with insullac with high strength fibre cloth, then uses strap containment vessel (26.c) of being released by gas to be fixed on " upper surface "；

3) by the tooth mouth (29) of tooth holder, use commercially available high strength fibre bandlet (32) by the battery pile including output electrode plate, carry out multiple tracks tie up, every be wound around together will strain, hot melt takes envelope, still can maintain the pressure between set of cells internal polar plate after removing fixture；

4) use speckles with the high-intensity fiber of uncured resin; set of cells is uniformly taken up in the region not having strap in direction along strap, forms smooth, smooth high intensity shell together with reinforcing high strength fibre cloth for protecting pre-sealed insulating lacquer layer after resin solidifies；

5) to above-mentioned steps 4) process after the output of set of cells draw after the outlet of lug and gas relief cavity protective cover carries out frock protection, by set of cells mass-impregnation resin and solidify.The frock protection dismantling above-mentioned after solidification, installs pressure-limiting safety valve in the outlet of gas relief cavity protective cover, i.e. realizes the encapsulation of set of cells.Described resin is known epoxy resin, carbon chopped fiber and flame retardant of magnesium hydroxide；Wherein, the addition of carbon chopped fiber and flame retardant of magnesium hydroxide is respectively the 5wt% of epoxy resin.

Described gas relief cavity surface is through hydrophobic treatment, being provided with the division board that the element cell number (n-1) of set of cells is individual in gas relief cavity, each division board is provided with position-stopping plate, between the bipolar plates of the partial insertion battery below position-stopping plate, position-stopping plate, for spacing, pushes against bipolar plates edge.The externally-arranged containment vessel of gas relief cavity, containment vessel is fixed on outside gas relief cavity by strap, and is sealed by the overall resin that immerses.

The present invention to be also described further:

1. the selection of lead-acid battery active material:

The negative pole of battery of the present invention and positive pole, all use same " lead sulfate " as primary active material.After using colloidal electrolyte that lead sulfate mix is become paste, it is coated on the two sides of bipolar plates (15), there is no dividing of positive and negative electrode in advance.The most after charging, both positive and negative polarity can just be separated.Because after Chong electricity, on the pole plate plate face corresponding to the positive pole of charge power supply, generate positive electrode active materials " lead oxide "；And generate negative active core-shell material " lead sponge " on the pole plate plate face that power cathode is corresponding.If " lead sulfate " of coating is absolute one to make peace if equivalent on positive/negative plate, the conversion ratio of this active material is up to 100%.

High-energy lead-acid battery of the present invention active material structure after charging is:

1) positive electrode active materials " lead oxide " after charging no longer there is passive to active material " lead oxide of alpha-crystal form ", because " alpha-crystal form lead oxide " can only generate under alkaline solution environment.Generate in the case of acidic electrolysis bath can only be " beta crystal lead oxide ", and it has the highest electro-chemical activity, is the active material that can realize effective positive pole discharge and recharge.In the present invention, bipolar plates (15) instead of support " beta crystal lead oxide " and undertakes " the alpha-crystal form lead oxide " of electrochemistry conductive path.Illustrate that the active material of the positive pole in the lead-acid battery of the present invention can utilize with 100%.

2) negative active core-shell material " lead sponge " after charging is the most identical with conventional batteries, and in except for the difference that thick for 0.2mm active material, there is no not participate in the supporting construction of energy storage reaction as " conductive path as undertaking electrochemical reaction " in aforementioned existing plumbic acid technology.Exoelectrical reaction can be accomplished make " lead sponge " 100% on pole plate change into " lead sulfate ", and not worry that irreversible " sulfation " occurs.

3) so-called " lead sulfate " being slightly soluble in dilute sulfuric acid and refer under conditions of without electric field force, when " lead sulfate " is placed under highfield intensity, its dissolubility in dilute sulfuric acid will increase, and is smoothed out charging reaction.It is the biggest that " irreversible sulfation " refers to that exoelectrical reaction generates sulphuric acid salt block footpath, about each element cell charging voltage 2.4V, electric field intensity removes distance equal to voltage, if block footpath is too big, it is exactly above-mentioned distance, be so applied to sulfate fast on electric field intensity will be lower than the threshold value dissolved, and do not dissolve, but the lead sulfate generated during electric discharge also can deposit the most thereon, makes block footpath increase, just forms irreversible sulfation.In view of on pole plate, the thickness of the active material of coating only has 0.2mm, bipolar plate structure ensure that uniform electric current distribution.The use of lead-acid battery colloidal electrolyte, secures active material micro structure, in exoelectrical reaction, does not haves the gathering of " lead sulfate ".Therefore, the thickness of " lead sulfate " Anywhere in polar plate area is not over 0.2mm.And can dissolve fully under " lead sulfate " of this thickness effect of electric field intensity of converting in charging voltage.The present invention, from the mechanism of electrode plate structure, has prevented the appearance of irreversible " sulfation ", has effectively extended the life-span of battery.

The present invention selects " lead sulfate " as the reason of the common active material in the two poles of the earth: one of feature that originally the classic electrochemistry of lead-acid battery designs is exactly to generate identical reaction product-" lead sulfate " in positive/negative plate exoelectrical reaction.And the density of " lead sulfate " is both less than the density of positive electrode material " lead oxide ", density again smaller than negative active core-shell material " lead sponge ", this is equal to traditional lead acid batteries volume of pole plate in exoelectrical reaction and can expand, and active material structure can be made to come off because expanding stress.This can be attributed to the fatal error of original chemical design.The product of the exoelectrical reaction of any battery the most all can expand because of the change of molecular structure.But we around and row strategy, using " lead sulfate " after volumetric expansion as active material.After it is charged, when being converted into " lead oxide " and " lead sponge " respectively in positive/negative plate face, the volume-diminished of active material, the space of " apt " just should have been reserved for the anti-product that discharges, the present invention is again from the selection of active material, establish the structure mechanism fundamentally preventing pole plate expansion drop, be made that useful contribution for extending the life-span of battery.

The present invention is also added into the additive that traditional lead acid batteries uses in active material in lead sulfate.As increased the white carbon black of electric conductivity, acetylene black, as the barium sulfate of trace and the lignosulfonic acid element of extender, prevent active material from hardening and keep fluffy.Existing lead-acid battery technology only uses inorganic expansive agent barium sulfate in negative active core-shell material, and the present invention all uses barium sulfate to make extender in the active material of the two poles of the earth, when exoelectrical reaction generates lead sulfate, because there being the existence of barium sulfate just can prevent the formation of uniform polycrystalline passivation layer.

The present invention Another reason why " lead sulfate " is both positive and negative polarity common active material is compared with prior art to eliminate " Hydrocerussitum (Ceruse) processed " technique of high pollution.Wet processing extracting sulfuric acid lead in the solution completely.Improve resource utilization, Simplified flowsheet, reduce and pollute, reduce manufacturing cost.

2. the selection of plate material

In traditional lead acid batteries, the corrosion of grid is also one of key factor affecting the life-span.The pure stereotype grid used in primitive technology are corrosion-resistant, but mechanical strength is inadequate.Alloy grid meets strength demand but the most corrosion-resistant.In the present invention, bipolar plate material is " pure lead base stainless steel fibre cloth composite ".Its preparation method: first use known technology by lead plating after stainless steel fibre cloth (its fiber string diameter is 6 microns) surface treated that thickness is 15 microns; dried under inert gas shielding; immerse after molten state liquid pure lead pulls out cooling; flattening through rolling, thickness is only 0.03mm.To bipolar plate surfaces, also use " polyaniline " coating with high conductivity to carry out preservative treatment so that it is in the electrolytic solution corrosion resistance can exceed that 10 years.

Ultra-thin bipolar plates (15) not only act as " the nonactive lead " of existing lead-acid battery supporting role to active material, also act as the effect taking on " logistics " conductive path in " the activity lead " of existing lead-acid battery, and therefore eliminate in existing plumbic acid technology, those the most directly participate in the nonactive and active lead of discharge and recharge chemical reaction, to improving the utilization rate of lead most possibly.Bipolar plates also acts as the inside cascade of element cell in set of cells.Making " cascade path " is 0.03mm, and " cascade path sectional area " is the area of pole plate.Compared with existing lead-acid battery, the electronics internal resistance caused because of cascade is reduced millions of times.Owing to the active material at the two poles of the earth and the thickness of barrier film all only have 0.2mm, the generation that ultrashort cascade path prevents ion concentration to polarize jointly.So the internal resistance of lead-acid battery that the present invention is constructed is far below traditional lead acid batteries.

The present invention uses chemically stable stainless steel fibre to improve the mechanical strength of pole plate, the most do not change the chemical property of pure lead, the hydrogen-evolution overpotential of pure Plante-type plate is improved, the sealed colloid electrolyte battery technology totally inherited plus us, just can prevent the appearance of " gassing " phenomenon being harmful to well.

3. element cell and battery pack structure:

" the unit lead-acid battery " of the present invention is to scribble equivalent amount of active material on bipolar plates two sides, then superposition one layer is saturated with the AGM barrier film thick for 0.2mm of colloidal electrolyte.It is equal to a four-layer structure, bipolar plates and diaphragm area have identical physical dimension, active material layer has reserved 0.3～0.8mm wide distance with 3 edges in bipolar plates 4 limit, and preferred size is 0.5mm, has reserved element cell seal isolation space along bipolar plates end face；The distance of 3mm～5mm has been reserved at a remaining edge, the most bonding gas overflowing cofferdam.Constitute the unit lead-acid battery that gross thickness is 0.63mm.Do not cascade lead-out wire, only a battery lead plate.

When constituting set of cells, only above-mentioned element cell successively series aiding connection need to be stacked, and use lead plating copper coin as the extraction pole at set of cells two ends, just constitute set of cells.

4. the encapsulating structure of set of cells:

1.. element cell isolating seal

Must have with each element cell in existing battery technology as sealing well, the present invention must realize the compact sealing of element cell between the element cell of High Density Packaging.

It is sequentially connected in series several element cells stacked and constitutes a set of cells, in addition to two output pad-faces, also have 4 heap faces, high-grade acid-proof insullac is filled in the sealed airspace that each element cell bipolar plates edge and active material layer edge are reserved and the side of gas overflowing cofferdam, carries out element cell pre-sealed.

2.. set of cells fastening method

Use high-strength hot blown fibre baling strips, by prestressing force reinforcing plate, battery pile is done multiple tracks and tie up dozen envelope, in order to keep pressure between the pole plate being suitable for.Using insullac is that binding agent is bonded in rear end and two sides by reinforcing the high strength fibre cloth strengthened.

3.. gas relief cavity protective cover and relief valve are set

Gas relief cavity protective cover is seated in the outside of element cell gas overflowing cofferdam group and is fixed on set of cells front end.

4.. the preparation pre-sealed protective layer of fiber reinforcement.

The high-intensity fiber of epoxy resin-impregnated slurry is uniformly around protected location cell sealing layer after solidification outside set of cells.

5. set of cells entirety mass-impregnation composite resin.Resin comprises alumina short fibre and flame retardant of magnesium hydroxide, after solidification, forms firm set of cells shell.

Gas relief cavity is configured with the divider wall of electrolyte between element cell, prevents ion short circuit.Leave the gassing that the space between divider wall is likely to occur and a small amount of electrolyte that may overflow for release.

So, set of cells side, bottom surface, insullac wide for bipolar plates two sides active material outward flange 0.5mm just constitutes in each element cell, the reliable isolation of both positive and negative polarity active material, and the ion being also prevented from electrolyte, on edge, walks around bipolar plates short circuit.

The compactest encapsulation just can reduce in traditional lead acid batteries structure, because battery case is on battery weight specific energy and the impact of energy density per unit volume.

5. the selection of set of cells output voltage.

The voltage of traditional commodities lead-acid battery group is relatively low, and the electric current under equal output is relatively big, and the electronic component of external circuit and output loop all can cause excessive loss because of big electric current, reduce the energy utilization rate of system.The thickness of the element cell in the present invention only has 0.63mm.The output voltage the most up to 200V of the set of cells that 63mm is thick, under equal output, because voltage is greatly improved, electric current will fall too low, and reduces in exoelectrical reaction simultaneously, the internal resistance loss caused because of ion concentration polarization.Not only the exoelectrical reaction efficiency of battery improves, and the energy conversion efficiency of external circuit is also improved because of the raising of voltage and the reduction of electric current.The i.e. selection of high output voltage is made that contribution to the cost putting forward whole application system.

Invention unit battery is very thin tiling one layer plane active material on pole plate.Using pole plate as conductive path and the support of active material of the electrochemical reaction of active material.Electric discharge can all exhaust the active material on pole plate every time, and the thickness of produced lead sulfate also will not form " irreversible sulfation ".Response area is essentially identical with apparent area.The response area in unit volume is made to exceed well over traditional lead acid batteries on the contrary.Storage capacitance in unit volume, will exceed well over traditional lead acid batteries technology simultaneously.Particularly, this big response area in unit volume is fixed up by the structural system of the present invention, will not fail with the lengthening of charge and discharge cycles, also will not be destroyed because of overdischarge for the moment or overcharge.In theory, the bipolar plates corrosion resistant life-span is exactly the life-span of battery.If can directly use " polyaniline, graphene composite material " conductive plastic film to make bipolar plates from now on, the theoretical life-span can be to more than many decades.

Beneficial effects of the present invention:

The present invention inherits the chemical reaction design that traditional lead acid batteries is outstanding, and at lead-acid battery colloidal electrolyte, active material additive with prevent the technological improvement such as maintenance-free method of gassing in charging process, but fundamentally change the structure of lead-acid battery, eliminate the nonactive lead in traditional lead acid batteries, and the most directly play energy storage effect and only undertake the active lead material of electrochemistry conductive path, use the structure of battery of the present invention compared with prior art, under equivalent capability, the consumption of lead of battery reduces more than 3/4；Gravimetric specific energy brings up to close to 135wh/kg；(prior art 35wh/kg, existing ferric phosphate lithium cell 100wh/kg) gravimetric specific power improves about 220w/kg；(prior art 45w/kg) deep-cycle life-span is about 2000 times；It is thick that (prior art 200 times) active material only has 0.2mm, and the extremely low internal resistance of cell allows big electric current quick charge, without damaging battery.20% is reduced than the production cost of equivalent capability traditional lead acid batteries.Frame for movement secures the active structure of high surface area in unit volume so that it is steady in a long-term.The ultra-thin lead composite material bipolar plates using thickness to be 0.03mm so that the uniform current density of discharge and recharge electrochemical reaction, the generation of the irreversible sulfation fundamentally stopped.Using lead sulfate as the active material at the two poles of the earth simultaneously, stopped to cause because of expansion the generation of active material obscission, the cycle life extending lead-acid battery reaches more than 2000 times.Element cell does not has shell, and the shell packaging technology that set of cells entirety uses fiber to immerse resin after being wound around improves energy density per unit volume.

Use present configuration simple and easily realize monomer height after cell package and force down internal resistance, long circulation life, high power charging-discharging battery, simplify the production technology of battery simultaneously, reduce production cost.

Accompanying drawing explanation

Fig. 1 shows the structure chart sketch of prior art lead-acid battery；

Fig. 2 shows prior art lead-acid battery anode plate grid and the schematic diagram of active material structure；

Fig. 3 shows prior art lead-acid battery cathode grid and the schematic diagram of active material structure；

Fig. 4 a, Fig. 4 b are respectively microstructure schematic diagram after the charging of prior art lead-acid battery anode and cathode active materials；

Fig. 5 a, Fig. 5 b are respectively microstructure schematic diagram after the electric discharge of prior art lead-acid battery anode and cathode active materials；

Fig. 6 is the electronic conductor electrode plate structure schematic diagram of bipolar plates plumbic acid element cell of the present invention；

Fig. 7 is bipolar plates plumbic acid unit cell structure schematic diagram of the present invention；

Fig. 8 is+number output electrode structural representation；

Fig. 9 is-number output electrode structural representation；

Figure 10 is set of cells " core " structure and gas relief cavity structure and the view being fit into battery center part；

Figure 11 is that set of cells gas is released box structural representation；

Figure 12 implements set of cells clamping process explanatory diagram for encapsulation first operation；

Figure 13 is encapsulation second operation work implementation unit battery pre-sealed procedure declaration figure；

Figure 14 implements high strength fibre cloth side end face for encapsulation three process and reinforces and install protective cover procedure declaration figure, and Figure 14 .1 is the position relationship schematic diagram between gas relief cavity containment vessel and relief cavity；

Figure 15 implements multiple tracks strap for encapsulation the 4th procedure and ties up procedure declaration figure；

Figure 16 implements to be stained with resin high-intensity fiber for encapsulation five processes and is wound around battery formation composite shell procedure declaration figure；

Figure 17 implements set of cells mass-impregnation alumina short fibre and flame retardant of magnesium hydroxide composite resin packaging process explanatory diagram for encapsulation the 6th procedure；

Figure 18 is second embodiment of the invention, formation low-voltage, high-current battery pack structure schematic diagram in parallel；

Figure 19 is the second embodiment of gas relief cavity of the present invention～gas is released cavity plate schematic diagram；

Figure 20 is that gas of the present invention is released cavity plate installment state schematic diagram.

Detailed description of the invention

Below in conjunction with the accompanying drawings implementation process of the present invention is elaborated:

It is to be noted; in the case of not conflicting; it is multiple not in the embodiment of description of the invention that various technical characteristics in the embodiment of the present patent application and embodiment and deriving method thereof can combine composition; but these are all the embodiments of true spirit, the most all constitute protection scope of the present invention.The present embodiment illustrate and be formed without to other may the restriction of embodiments, put up with below with reference to accompanying drawing and do specific explanations in conjunction with the embodiments.

In order to understand that the improvement of traditional lead acid batteries is intended to by the present invention, the structure of traditional lead acid batteries is first described with Fig. 1-Fig. 5.The structure of the lead-acid battery of prior art as seen from Figure 1, (1) is the shell of lead-acid battery, and (6) are negative electrode grid, and (7) are negative active core-shell material " lead sponge ", and it is attached on (6)；(11) it is the outlet lug of negative electrode grid electric current, (12) it is the negative bus-bar that multiple negative electrode grids are carried out parallel connection, (13) it is the negative terminal that cathodal current is drawn capsul (1), (14) be anode adjacent with in set of cells series connection cascade wire, (10) it is anode plate grid, (9) being positive electrode active materials " lead oxide ", it is attached on (10)；(3) it is the outlet lug of anode plate grid electric current；(4) being the positive bus that multiple anode plate grids carry out parallel connection, (5) are the positive terminals that positive pole electric current is drawn capsul (1)；(2) be battery cathode adjacent with in set of cells series connection cascade wire.(8) it is dividing plate between both positive and negative polarity active material in lead-acid battery.Dilute sulfuric acid electrolyte it is filled with in battery.Electric current density described in background technology is uneven refers to that active material is attached on anode plate grid (10) and negative electrode grid (6), different at the action process of the nethermost active material of grid and grid uppermost active material discharge and recharge, because provide redox ability is the electric current of external circuit, and electric current is delivered on active material by grid, the current path below grid will be grown；And superincumbent current path will be short, thus result in electric current density slightly difference, discharge and recharge will make this small difference constantly accumulate repeatedly, will be on the top of negative electrode grid because path is short, resistance is little, electric current density is big, cause local " overdischarge " to produce " irreversible sulfation ", and produce the oxide etch of grid on the top of anode plate grid because of local " overcharge ".

Once having small " an irreversible sulfation " to generate, as long as electric discharge is carried out, on negative electrode grid, first lead sulfate newly-generated around it will select on it " implantation crystallization ", and this is inexorable law during material precipitation.So " nucleus " of " irreversible sulfation " will promptly be grown up.Not only make active material lose efficacy, and broken come off from grid owing to other active materials are squeezed by the expansion of " irreversible sulfation crystal ".

The most positive and negative anode grid (6), (10), plate railings of anode and cathode lug (3), (11), the bus-bar (4) of multiple plate railings of anode and cathode parallel connection, (12), by the positive and negative electrode pole (5) outside electric current guidance unit battery, (13), set of cells cascade wire (2), (14), these are all lead and metal manufactured goods.They do not have " electro-chemical activity " required for energy storage, and these are " nonactive lead ", and they are almost 11 with the weight ratio of active material.

Schematic diagram from Fig. 4 a prior art lead-acid battery active material localized micro structure after charging, depended on " lead oxide " (7) on anode plate grid (6) after charging, wherein " alpha-crystal form " lead oxide (7.1), its " electro-chemical activity is low; mechanical strength is good ", it the most directly participates in the chemical reaction of discharge and recharge, only plays the effect making support and conductive path to " beta crystal " lead oxide (7.2) with " electro-chemical activity ".Depend on " lead sponge " (9) on negative electrode grid (10) after the visible charging of Fig. 4 b, had two kinds of crystal forms to distinguish with positive electrode active materials, a kind of crystal formation of negative active core-shell material.And after the visible electric discharge of Fig. 5 a, former " beta crystal " lead oxide (7.2) all become " lead sulfate " (7.3)；Expand because combining sulfate radical volume.After (7.2) are completely converted into lead sulfate, positive electrode active materials only has " alpha-crystal form " lead oxide (7.1), its chemism relatively " beta crystal " lead oxide (7.2) is much lower, so discharge current falls sharply rapidly, therefore it not only controls the electrochemical reaction of positive pole and also controls the electrochemical reaction of negative pole.The electrochemical reaction making whole battery is substantially stopped.Fig. 5 b, due to a kind of crystal formation of negative active core-shell material, therefore, the lead sulfate of generation and the active material undertaking electric path do not have obvious boundary, and the local lead sulfate generated that electric current density is big wants thickness, and the place that electric current density is little is the most thinner.

The embodiment of bipolar plates

As shown in Figure 6,6 strand of 316 Stainless Steel fiber that base material (17) is a diameter of 6 microns of bipolar plates is spun into line, then is made into plain with this line.By this rustless steel plain after alkali cleaning, pickling, washing, dry, electroplating pure lead (16), to 35 microns, then to be cut into band volume after being densified to 30 microns standby for temper hot rolling.Coat activated material (20).

Embodiment prepared by active material

800 mesh lead sulfates are some, add additive (such as the barium sulfate mixed with 5:4:2 ratio, humic acid, acetylene black) and the PP chopped fiber of 0.5wt% known in the lead-acid battery of 1.0～1.3wt%.Adding the colloid sulfuric acid solution of 2.5ml/L after mix homogeneously, to be sufficiently stirred for making pole plate coating standby.

Shutter embodiment

Using the AGM battery block board thickness 0.2～0.4mm of prior art, preferred thickness is 0.2mm, impregnates all spaces of colloidal electrolyte filling AGM dividing plate, and solidifies.Become the battery separator (19) of preliminary filling electrolyte.

Element cell embodiment

As shown in Figure 7, bipolar plate-shaped unit high-energy lead-acid battery (18) includes electronic conductor bipolar plates (15), electronic conductor bipolar plates (15) two sides is respectively coated the active material layer (20) with lead sulfate as main component, wherein, the active material layer of one side re-lays battery separator (19).

The described active material layer thickness being respectively coated in electronic conductor bipolar plates (15) both sides is 0.2mm；Active material layer is made up of lead sulfate, additive and lead-acid battery colloidal electrolyte, and wherein additive component is identical with existing lead-acid battery cathode meterial additive, and colloidal electrolyte component is identical with the electrolyte component of existing colloid lead-acid battery.Described active material layer coats the centre of electronic conductor bipolar plates (15), and the uncoated region of electronic conductor bipolar plates (15) is through known hydrophobic treatment.

The vertical dimension at described active material layer (20) edge and electronic conductor bipolar plates (15) edge is 0.5mm, wherein paste gas overflowing cofferdam dividing plate (26.1) distance be 2mm.This limit of bipolar plates (15) is referred to as " upper surface " of element cell (18).

Output pole plate embodiment

Export pole plate as shown in Figure 8, Figure 9, including "+number output pole plate " (22) and "-number output pole plate " (24).The pole plate (23) of output pole plate is lead plating copper coin thick for 2mm, and there is a lug end, "+number " lug (23.1), "-number " lug (23.2)."+number " output pole plate (22), at the one side towards lug, are coated with the active material layer after 0.2mm (20), and coated form is identical with element cell；"-number " export pole plate (24) at the one side towards lug, after being coated with the thick active material layer (20) of 0.2mm, one layer of AGM barrier film (19) being saturated with colloidal electrolyte in active material layer overlying again, Edge Distance requires identical with element cell.

Battery embodiment

See Fig. 8-11, the constructive method of series connection bipolar plates lead-acid battery group: set of cells assemble sequence is: any two bipolar plate-shaped unit high-energy lead-acid battery (18) series connection method is in the bipolar plates element cell that any two is adjacent, one septate one side of element cell band contacts without barrier film one side with another adjacent element cell, and " upper surface " alignment of two adjacent element cells.The output voltage of corresponding 2nV, set of cells will include that the series connection of n-1 described bipolar plate-shaped unit high-energy lead-acid battery (18) is piled up (25), then "+number " output pole plate (22) and one "-number " output pole plate (24) is arranged on element cell heap (25) two ends and is formed.Wherein, the one side of bipolar plate-shaped unit high-energy lead-acid battery (18) coat activated material floor (20) along series connection one end, direction of set of cells (25) is in close contact with the barrier film face (19) of "-number " output pole plate (24)；The one side of bipolar plate-shaped unit high-energy lead-acid battery (18) membrane layer (19) of the other end of set of cells (25) is in close contact with the active aspect (20) of "+number " output pole plate (22)；The lug of output pole plate is equidirectional with " upper surface ".

Gas relief cavity (26) is loaded on the end face of the n-1 that described series connection is piled up a described bipolar plate-shaped unit high-energy lead-acid battery.

As it is shown in figure 9, collector plate (23) is divided into two parts, lug (23.2) and doab (23.1), "-number " marking is on the two sides of lug.

As shown in Figure 10, described set of cells gas relief cavity (26) has a position-stopping plate (26.2), during installation, position-stopping plate is attached to the end face of battery pile, push against the edge of electronic conductor bipolar plates (15), from the blown-up partial detail of Figure 10, it can be seen that division board (26.1) is at the following a length of 2mm of position-stopping plate (26.2), thickness is all 0.2 mutually with lead sulfate active material layer (20) thickness in element cell (18), after division board (26.1) inserts battery pile (25), just it is filled with on battery pile (25) end face all element cells (18) interior lead sulfate active material layer (20) edge to the space at electronic conductor bipolar plates (15) edge.Sub-chamber division board (26.1) is just clipped between barrier film (19) and bipolar plates (15).Electrolyte or gas can pass through air-and water-permeable barrier film (19), enter sub-chamber (seeing Figure 10).Gas relief cavity (26) also serves as electrolyte breathing box simultaneously, this gas relief cavity (26) has n sub-chamber (26.5), each the corresponding element cell (18) in sub-chamber (26.5), internal battery pack is inserted by the pin (26.4) of dividing plate (26.1) in sub-chamber, it is close to the electronic conductor bipolar plates (15) of element cell, each element cell is kept apart, owing to hydrophobic treatment has all been made on the surface of gas relief cavity (26) and electronic conductor bipolar plates (15) edge, the repellency on surface makes sub-chamber division board (26.1) that electrolyte can be stoped to flow between adjacent-cell battery.The most sub-chamber (26.5) bottom can accommodate the liquid electrolyte expanding, and top allows gas to overflow (seeing Figure 11) from overfall (26.3).

Gas relief cavity the second embodiment

The design of above-mentioned gas relief cavity (26) also can be as follows, as Figure 19 uses the dividing plate (26') of the monolithic with edge (26.b), it is made up of sub-chamber dividing plate (26.1'), position-stopping plate (26.2'), gas outlet (26.3'), pin (26.4')；As shown in figure 20, during using element cell to pile up set of cells, the a piece of dividing plate of each element cell (26'), the pin (26.4') of single partition (26') pushes against the edge of the active material layer (20) of element cell, the position-stopping plate (26.2') of single partition (26') abuts against the edge of element cell dividing plate (19), is bonded on the electronic conductor pole plate (15) of element cell by single partition (26') with acidproof glue.Battery pile (25) heap well after, the edge (26.b) of every dividing plate has 4 notches (26.a) alignd, wherein puts into a diameter of 0.5mm plastic wire, single partition group is carried out auxiliary fixing.Then when battery unit package second operation work, gas outlet (26.3') is covered, use acidproof insullac also single partition group to be sealed when carrying out pre-sealed to element cell.Seal paint single partition group to be covered and become an overall gas relief cavity.The deviation that the thickness being proposed to adaptation active material layer (20) and battery separator (19) of embodiment 2 is likely to occur.Simultaneously more convenient during installation.

Above-mentioned set of cells can be implemented under two ways, i.e. high-tension battery group and low tension battery group；Particularly as follows:

High voltage-small current set of cells

The thickness of described element cell is only 0.63mm, so the thickness of 250 series units is plus being encapsulated as 160mm, can have the running voltage of 500V.Such set of cells is uncommon in conventional batteries technology.The reduction that the output electric current of high-tension battery can be proportional because of the raising of output voltage under equal output, low output electric current will reduce the loss of battery both ways, in electrochemical reaction, the ion of electrolyte spreads concentration difference and is polarized in the pressure drop that battery internal circuit is caused, and reduces because of the reduction of electric current.The pressure drop that battery cascade resistance is caused the most also can reduce.

At present, electric automobile often needs the supply voltage of more than 500V.To reduce cost and the loss of electric loop of automatically controlled device, so the bipolar plates lead-acid battery of the present invention is especially suitable for the application of electric motor car.

Low-voltage, high-current set of cells (40) (as a example by the 48V that electric bicycle uses)

The element cell thickness of bipolar plates lead-acid battery is 0.63mm, it is achieved the output voltage of 48V only needs the heap thickness of 1.44cm, and activity goods and materials layer 0.2mm is thick, and the capacity of unit are only there are about 0.02Ah/cm², for obtaining higher ampere-hour capacity, it is necessary for the set of cells being concatenated in parallel to (connecting after traditional lead acid batteries technology is all first parallel connection in fact) further.Figure 18 is by schematic diagram in parallel for 3 48V battery core assemblies.It is to complete in the way of parallel connection after first connecting in this embodiment.3 series-connected cells (47) are connected in parallel.The pole plate that confluxes (41) is the positive pole of the 1st battery.The pole plate that confluxes (42) is first series-connected cell and the negative pole of second series-connected cell.The pole plate that confluxes (46) is second series-connected cell and the positive pole of the 3rd series-connected cell.The pole plate that confluxes (44) is the negative pole of the 3rd series-connected cell.Just confluxed by three series-connected cells pole plate (41), (46) of positive output pole (45) are linked together, the negative pole plate that confluxes (42) of three series-connected cells, (44) are linked together by negative output pole (43).

Battery unit package embodiment

The encapsulation of series connection bipolar plates lead-acid battery group:

Encapsulation first operation (seeing Figure 12), with dentation fixture (27), (28) from upper and lower surface be adjacent to+,-number output stage a plate holder stay in the set of cells assembled battery embodiment.Use 0.8kg/cm²～1.2kg/cm²Pressure by battery pile clamp, preferred pressure is 1kg/cm²。

nullThe second operation work (seeing Figure 13) of encapsulation，When clamp，Acid-proof insullac (30) is used to spray along the stacking side of battery pile (25)，Insullac filling is made to enter in electronic conductor bipolar plates (15) edge of each bipolar plates unit lead-acid battery (18) and the space of active material layer (20) border 0.5mm，Owing to the edge of electronic conductor polar plate two-sided is all first to have done hydrophobic treatment，Therefore this position is the highest with the affine wellability of organic material，Insullac is by infiltrating the capillarity on surface，Just can enter sufficiently into the narrow slit sealed for element cell，Simultaneously at the thick lacquer painting of outside 0.5mm to be formed millimeter of battery pile heap face，So that the sealing paint in each and every one element cell edge narrow slit is connected into entirety，Realize to element cell each in battery pile reliably " pre-sealed ".This process also includes the front end face being provided with gas relief cavity, is embedded in insullac by the position-stopping plate of relief cavity.

The three process of encapsulation; when clamp; with insullac as binding agent; use high strength reinforcement fiber cloth (31) be attached to two sides and there is no gas relief cavity rear end face on, then by gas relief cavity containment vessel (26.c) use strap (32) be fixed in front end face.Figure 14 also show packaging band shackle (26.6) detailed construction.Wherein locking pin (26.7) utilizes frictional resistance by locked for strap (32) upper (seeing Figure 14) at snap close (26.6).

Wherein protective cover is installed as the shell (26.c) of protective cover and is pressed on the position-stopping plate (26.2) of gas relief cavity (26); the relief valve installing port (26.8) of the gas discharge outlet (26.3) alignment protective cover (26.c) of gas relief cavity (26); the lug (23.1) of battery pile output cylinder manifold (23) below, is mounted with two limited screws to protective cover (26.e).

4th procedure of encapsulation, when clamp, use thermal welding high intensity packing fiber bandlet (33) can pass dentation fixture (27), the tooth mouth (29) of (28), along long side face, battery pile being done multiple tracks to tie up, per pass is banded in thermal welding after being strained by flat for fiber (33) band and beats envelope (33.1).After guaranteeing that fixture (27), (28) are removed, still make to keep between the pole plate in battery pile the pressure (seeing Figure 15) during clamp.

The five processes of encapsulation, opens upper and lower tooth holder (27), (28).Use the high-intensity fiber speckling with uncured resin; the region of bundling belt is not being had to set of cells uniform winding along strapping tape direction; because resin contains firming agent; automatically the composite shell (34) of smooth fairing it is solidify to form, with internal pre-sealed (30) (the seeing Figure 16) to individual element cell of protection through several minutes resin.

Figure 17 is the 6th procedure of encapsulation; use the pressure-limiting safety valve installing port (26.8) of the containment vessel (26.c) of easy-to-dismount technique protection cladding lug (23.1) and gas relief cavity; the set of cells entirety completing five processes is immersed the composite resin (35) including alumina short fibre and flame retardant of magnesium hydroxide, and resin impregnable (35) thickness is about 0.7mm.These resins also with the addition of firming agent; after cured; remove the protection process sleeve of the pressure-limiting safety valve installing port (26.8) of the containment vessel of lug (23.1) and gas relief cavity, install pressure-limiting safety valve (26.9) (seeing Figure 17).So far, packaging process terminates.Owing to pressure-limiting safety valve uses the relief valve of prior art, repeat no more here.

Subsequent it is necessary to it is carried out pole plate chemical conversion and the discharge and recharge of several circulations on product test frame, making is the active material of lead sulfate equally, is reduced into high activity β type lead oxide at positive pole, becomes lead sponge at cathodic reduction.Charge power supply electrode line is received during charging on "+number " output pole plate (22), and the negative line of charge power supply is received in "-number " output pole plate (24).

Before the most uncharged, not having a both positive and negative polarity that electrochemistry is specified, the most after charging, the output electrode being connected with charge power supply positive pole has just become the positive pole of set of cells, and the output electrode being connected with power cathode, just become the negative pole of set of cells.For ease of use safety, the electrode line of charger should be received during charging set of cells of the present invention+number output pole plate lug on, and charge power supply negative line receive-number output pole plate lug on.

Claims

1. a bipolar plate-shaped unit high-energy lead-acid battery, it is characterised in that: unit high energy lead Acid battery includes electronic conductor bipolar plates (15), and the positive and negative electrode that its two sides is respectively coated mainly is lived Property material layer (20) be the active material that same is with lead sulfate, wherein, one side active material Battery separator (19) is re-layed on the bed of material.

2. the bipolar plate-shaped unit high-energy lead-acid battery as described in claim 1, it is characterised in that: Active material layer (20) thickness of described electronic conductor bipolar plates (15) both sides is 0.15-0.3mm； Active material layer (20) is made up of lead sulfate, additive, will live with lead-acid battery colloidal electrolyte Property material mix becomes cream.

3. bipolar plate-shaped unit high-energy lead-acid battery (18) as described in claim 1, its feature It is: described electronic conductor bipolar plates (15) is for melted by lead plating " stainless steel fibre cloth " dipping The most thermally treated rolling of the pure lead of liquid and the composite thin plate made；Lamella thickness is 0.02-0.04mm, lead in thin plate (including lead plating and dipping lead) is preferred with stainless steel fibre Volume ratio is 4:6.

4. bipolar plate-shaped unit high-energy lead-acid battery (18) as described in claim 1, its feature It is: described active material coats the central part of electronic conductor bipolar plates (15) with uniform thickness Position, has made hydrophobic treatment to the region of electronic conductor bipolar plates (15) uncoated active material.

5. bipolar plate-shaped unit high-energy lead-acid battery (18) as described in claim 4, it is special Levy and be: the area that described active material layer (20) is coated with is less than the area of bipolar plates (15), its Edge is 0.4-3mm with the vertical dimension at electronic conductor bipolar plates (15) edge.

6. bipolar plate-shaped unit high-energy lead-acid battery (18) as described in claim 1, it is special Levy and be: described battery separator (19) be through lead-acid battery colloidal electrolyte soak after AGM every Film, and its rectangular dimension and electronic conductor bipolar plates (15) is equivalently-sized, wherein every Film thickness is 0.2-0.4mm.

7. a series connection bipolar plates lead-acid battery group, it is characterised in that: for output voltage be The set of cells (25) of 2NV, described set of cells includes N-1 described bipolar plate-shaped unit high energy Lead-acid battery (18) series connection is piled up, and it is any two adjacent bipolar template list that set of cells piles up order In unit's high-energy lead-acid battery (18), with one side and another bipolar plates unit electricity of barrier film (19) Pond (18) is adjacent to realize series connection, all element cells without active material layer (20) face of barrier film Four limits alignment, load onto gas relief cavity (26) in upper surface, the most again with 2 be called "+ Number " (22), the output pole plate composition set of cells of "-number " (24).

8. the method for packing of a bipolar plates lead-acid battery group of connecting, it is characterised in that:

1) using set of cells (25) clamping that series connection is formed by tooth holder (27), fixture (7) connects Touch is "+number " (22), the output pole plate of "-number " (24), after clamping, uses acidproof insulation The two sides of paint spraying set of cells and bottom surface (i.e. relative with the end face setting gas relief cavity face), It is bipolar to electronic conductor that insullac has filled active material layer (20) edge in each element cell The space at plate (15) edge, makes unit cell sealing insullac be connected, and forms unit Battery pre-sealed；

2), after pre-sealed solidification, the face being coated with insullac it is attached to high strength fibre cloth, so Rear use strap containment vessel (26.c) of being released by gas is fixed on upper surface；

3) by the tooth mouth (29) of tooth holder, high strength fibre strap (32) is used to wrap Include output electrode plate in interior battery pile, carry out multiple tracks tie up, every be wound around together will strain, Hot melt takes envelope, still can maintain the pressure between set of cells internal polar plate after removing fixture；

4) use speckles with the high-intensity fiber of uncured resin, and the direction along baling strips is being beaten Set of cells is uniformly taken up in the region of band, forms smooth, smooth high intensity after resin solidifies Shell is used for protecting pre-sealed insulating lacquer layer together with reinforcing high strength fibre cloth；

5) to above-mentioned steps 4) process after the output of set of cells draw lug and gas relief cavity and protect After guard shield outlet carries out frock protection, by set of cells mass-impregnation resin and solidify, tear open after solidification Fall above-mentioned frock protection, in the outlet of gas relief cavity protective cover, pressure-limiting safety valve is installed, the most in fact The encapsulation of existing set of cells.

9. the method for packing of the series connection bipolar plates lead-acid battery group as described in claim 8, its It is characterised by: described gas relief cavity surface is provided with battery in hydrophobic treatment, gas relief cavity The individual division board of element cell number (n-1) of group, each division board is provided with position-stopping plate, only Between the bipolar plates of the partial insertion battery below the plate of position, position-stopping plate pushes against bipolar plates for spacing Edge.The externally-arranged containment vessel of gas relief cavity, containment vessel is fixed on gas by strap and lets out Put outside chamber, and sealed by the overall resin that immerses.