CN106207193B

CN106207193B - The high-tension battery group and packaging method of a kind of bipolar plate-shaped unit high-energy lead-acid battery and its composition

Info

Publication number: CN106207193B
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: 2019-04-09
Anticipated expiration: 2035-05-08
Also published as: CN106207193A

Abstract

The present invention relates to lead-acid accumulator, the packaging method of the high-tension battery group and battery pack of specifically a kind of bipolar plate-shaped unit high-energy lead-acid battery and its composition.Unit high-energy lead-acid battery includes electronic conductor bipolar plates, and the anode and cathode active materials layer that two sides is respectively coated is the same active material prepared based on lead sulfate, wherein re-lays battery separator on active material layer on one side.Height easy to accomplish forces down internal resistance long circulation life battery after carrying out the cell package of series stack using invention unit battery, while simplifying the production technology of battery, reduces production cost.

Description

The high-tension battery group and envelope of a kind of bipolar plate-shaped unit high-energy lead-acid battery and its composition Dress method

Technical field

The present invention relates to lead-acid accumulator, high pressure that specifically a kind of bipolar plate-shaped unit high-energy lead-acid battery is composed in series The compact package method of battery pack and battery pack.

Background technique

Since French scientist Pulan spy's invention lead-acid battery in 1859, lead-acid battery industry is had been subjected to 154 years Industry development history.Although lead-acid battery is cheap, performance is stablized, operational safety.But it there are also many fatal to lack Point, such as specific energy is small, specific power is low, the service life is short.The expansion of application field is severely impacted.

In existing lead-acid battery technology, the structure used substantially is: supporting positive and negative anodes active respectively by positive and negative anodes " grid " Material connects multiple " grids " by " tab " being fixed on grid by " busbar connector ", then is drawn by " pole " of " busbar connector " Out to outside battery case, " interpolar connecting line " completes the cascade by element cell to battery pack.Between positive and negative anodes in element cell There is " partition " isolation, to prevent short circuit between positive and negative anodes, fills electrolyte~dilution heat of sulfuric acid therebetween.

In existing lead-acid battery technology, two kinds of lead are used, one kind is " nonactive lead ", is exactly above-mentioned " grid ", " converges Stream row ", " tab ", " pole ", lead and metal included in " connecting line between grade "." nonactive lead " not directly participate in fill, Electrochemical reaction involved in discharging, therefore it does not make any contribution to " charge storage ability " of battery.Another kind is " active lead ", It is exactly " lead sponge " on negative plate and " lead oxide " on positive plate, it is the electrochemical reaction for participating in charge and discharge.

But not all " active lead " can contribute to " charge storage ability ", because there are also the " living of significant proportion Property lead " undertaken in electrochemical reaction " electrical path " and support bigger serface reaction structure " logistics " effect.Because being positive Active material on negative plate generates nonconducting " lead sulfate ", if active material is completely anti-during exoelectrical reaction It should all generate nonconducting " lead sulfate ", without conductive path when charging, electrochemical reaction cannot be carried out.Equal to electricity Pond is entirely ineffective.

The reason of one of fatal defects of existing lead-acid battery " specific energy is small ", is that the ratio of " nonactive lead " accounts for entirely 50% or more of portion's consumption of lead occupies almost half weight and biggish volume of prior art lead-acid battery.In addition, due to Exoelectrical reaction product PbSO₄Insoluble in dilute sulfuric acid, crystallization is also non-conductive in the surface of active material, and electrochemical reaction institute Required electric path will be undertaken by active material itself, i.e., really for " the active lead " of power storage utilization rate not yet To 50%.Lead in lead-acid battery existing in this way only has the electrochemical reaction that the ratio less than 25% takes part in charge and discharge.In this way The specific energy of existing lead-acid battery cannot also reach the 1/4 of its theoretical specific energy (174wh/kg)；Only on the left side 35wh/kg It is right.

Two " service life is short " of existing lead-acid battery fatal defects.The phenomenon that most common cell damage is positive electrode active materials It falls off, cathode irreversible sulfation occurs and loses activity.

Positive electrode active materials~" brown lead oxide " is there are two types of crystalline form, α lead oxide and beta-oxidation lead, about why designing two When the reason of lead oxide of kind crystalline form is used for positive electrode active materials, explain in the prior art: α lead oxide mechanical strength is good, changes Learn that reactivity is low, and beta-oxidation lead chemical reactivity height is 3 times of α lead oxide, but bad mechanical strength, when two kinds of ingredients When matching position 1:1.25, reaction efficiency highest.It is generated in electrochemical reaction without each crystalline form component is explained further Effect.

α lead oxide is responsible for the active material reaction structure for maintaining support high-specific surface area and the work for taking on electric path in fact With, because its reactivity is low, it does not participate in reaction substantially, and beta-oxidation lead is only and really carries out energy storage in anode The active principle of charge and discharge.Charge and discharge energy storage reaction can really be participated in by only having half in brown lead oxide.If β oxygen in exoelectrical reaction Change lead it is completely depleted when because compare activity with beta-oxidation lead too low for α lead oxide, reaction almost stops, and is because of α lead oxide It is generated under alkaline environment, acidic electrolysis bath environment cannot generate α lead oxide, so the ratio of two kinds of crystalline forms of α, β generates change A possibility that change, is smaller, so, the reaction structure stability of the bigger serface of positive electrode material brown lead oxide is relatively high, It is biggish " lead sulfate " piece not allow volume easily generated, therefore seldom occurs irreversible sulfation on anode plate grid.

However, reaction is not participated in completely not equal to it although the expression activitiy of α lead oxide is poor, once α lead oxide is participated in After reaction generates lead sulfate, during the charging process, lead sulfate cannot be reduced into α lead oxide and can only go back under acidic environment Original is at beta-oxidation lead.It increased although making the capacity of battery, since activity improves, the amount for the lead sulfate that when electric discharge is converted into is just It will increase, the volume of the volume ratio brown lead oxide of lead sulfate is big very much, and active material structure will be destroyed because of volume expansion. So positive plate service life short phenomenon mainly because on grid caused by swelling stress active material fall off.

In contrast, negative electrode material " lead sponge " only has a kind of crystalline form, serves as conductive path and energy storage electrochemical reaction It is same material, uninevitable boundary line therebetween, it is easy to because current density is uneven, local overdischarge is generated, it is raw At the biggish lead sulfate of volume, block diameter biggish " lead sulfate " is and non-conductive because being insoluble in dilute sulfuric acid, thus just in charging It cannot be reduced into " lead sponge ", electro-chemical activity is lost and generate " irreversible sulfation ".Although in cathode lead sponge It is mixed with barium sulfate impurity, since its crystal form is identical as lead sulfate, makes newly generated lead sulfate crystallization on barium sulfate, utilizes knot Brilliant power eliminates " passivation " automatically, but is not able to maintain the stabilization of reaction structure.This be also why lead-acid battery cathode grid The damage always basic reason as caused by " irreversible sulfation ".

Why traditional lead-acid battery has to sacrifice a certain amount of active material to do conductive path and support reality The upper part active material for directly participating in discharge and recharge reaction? the designer of early stage lead-acid battery wants in limited polar plate area On produce the battery of as far as possible big " ampere-hour capacity ".Therefore thicker active material is coated on grid.But actually due to putting Electric reaction product " lead sulfate " is not dissolved in electrolyte, is attached to the surface of active material and generates passivation, for prevent can not The frequent generation of inverse sulfation.It only envisions in anode using two kinds of crystalline structures of α lead oxide and beta-oxidation lead, sacrifices α oxygen Change the energy storage effect of lead, to support the bigger serface reaction structure of three-dimensional.And be to use inorganic expansion agents barium sulfate in cathode, Organic expander lignosulfonic acid usually guarantees to form three-dimensional bigger serface reaction structure, just can solve real under finite volume The now original design intention of big " ampere-hour capacity ".What actually control exoelectrical reaction ended is to utilize positive electrode active materials α lead oxide and β Lead oxide chemical reactivity differs three times, once beta-oxidation lead is depleted, reaction speed sharp fall, to prevent not It can depth overdischarge.But α lead oxide activity is low and is two concepts without activity, low activity will also participate in reaction, only not It is very slow to cross speed.And α lead oxide generates under alkaline condition, and a small amount of α lead oxide generates lead sulfate once reacting, Beta-oxidation lead can only be returned to when charging.Even if that is actually α lead oxide is also to exist always in the reaction of " non-over-discharge " Consumption, so positive electrode active materials three-dimensional Large ratio surface reaction structure just in cycle charge-discharge, constantly fails and loses Effect.And then the active material solid Large ratio surface reaction structure for influencing anode is also constantly be generated in cycle charge-discharge and declines The phenomenon that moving back.Therefore, the service life it is short be lead-acid battery active material structure essential problem.

Why short the positive and negative pole plate service life is, and there are one common reasons from ancient, not yet changed so far The cascade side of " cathode grid-tab-busbar connector-pole-grade conjuncted-pole-busbar connector-tab-anode grid " Formula, there are following several problems for this cascade system:

1. cascade average path it is long, cascade path sectional area it is small caused by cascade resistance it is big, cause entire battery pack No matter during being charged or discharged, battery pack is made to affect electricity because cascading the additional fever of resistance, due to added losses increase The performance of pond group.

2. the confluence that electrochemistry generates electric current exports on the tab in grid one end very little region for grid.This Resulted in the uneven of entire grid current density distribution, the difference of current density results in temperature gradient, at tab most Height is gradually reduced to screen distal end.Electrochemical reaction rates are the functions of temperature, the close regional Electronic circulation path away from tab The cation assembled on the short active material that can neutralize pole plate connection in time, ion concentration polarization is weak, is conducive to electrochemical reaction It carries out, the region remote apart from tab, electron flow path path length, cannot neutralize and assemble just on the active material of pole plate connection in time Ion, ion concentration polarization is strong, reduces electrochemical reaction progress, and two factors of temperature and concentration polarization have resulted on grid Active material electrochemical reaction rates are inconsistent, and " expansion drop of anode grid active material " above-mentioned and " cathode grid is living Property material irreversible sulfation " very big a part is the reason is that because what this cascade structure generated.In repeated charge During, electrochemical reaction depth disparity, is continually repeated caused by this cascade structure causes weak current density unevenness to weigh, Constantly the result for causing lead-acid battery short-lived is damaged in part caused by accumulation first.

Grid is bent 3. the reason of generally all pole plate falls off in the prior art is attributed to thermal overload, this thermal overload A part of reason is also caused by cascade internal resistance is excessive.Since lead or brown lead oxide combine the sulphur in electrolyte in exoelectrical reaction Acid group and when generating lead sulfate, the stress that volume expansion generates causes other active materials to fall off and is only the underlying cause.

Because traditional lead acid batteries are easy with gassing (hydrogen is precipitated in positive precipitated oxygen, cathode) in charging, not only cause Battery dehydration needs often to carry out moisturizing maintenance.It is also easy to the corrosion for making pole plate by oxygen and the raised sulfuric acid of concentration, is reduced The service life of battery.Hydrogen, the oxygen being precipitated simultaneously converge to be easy explosion and constitutes insecurity factor in air.So occurring Valve-control sealed lead acid battery technology, it is higher than the deposition potential in positive oxygen using the deposition potential of cathode hydrogen, will be electrolysed Gas passage is established in liquid and diaphragm, the oxygen that anode is first precipitated is directed into cathode, is reacted with the lead of cathode deposition, oxidation is generated Sub- lead, due to electrode surface lead monoxide presence it is prevented that hydrogen precipitation, simultaneous oxidation Asia lead generates with effect of sulfuric acid Lead sulfate and water, this prevents the generations of phenomenon of losing water.So the sealed lead acid battery in " floating charging " operating condition is almost The maintenance work that need not carry out moisturizing, facilitates the use of battery.Lead-acid battery colloidal electrolyte technology utilizes the silicon of molecular level Glue network, the relatively fixed micro-structure of active material, makes it to stabilizing active material reaction structure, extends lead-acid battery Service life has played certain effect.But the gas passage between two-plate is manufactured in electrolyte and partition and needs to pass through centainly After service life, the dry and cracked formation air flue of silica gel.

Grid corrosion is prevented as those, the effort of Lai Zengchang battery life has no actual progressive meaning.Because they The deadly defect in this structure is not found out.

Lead fabric grid horizon battery starts to challenge to the ancient structure based on grid, but he challenge it is only all One of mostly unreasonable structure.By tab by the concentration confluence of traditional grid, the section work for changing into entire lead fabric grid converges. Compared with traditional cascade structure, although increasing the sectional area in cascade path, averagely cascade road is not changed fundamentally The length of diameter, therefore the actual distribution of current density or non-uniform on entire grid.

Hydrogen-oxygen fuel cell is used for reference, the cascade bipolar plates concept in succinct inside in solid electrolyte fuel cell also has People proposes bipolar plates lead-acid battery.Maiden attempt that radical change is carried out to the ancient structure of lead-acid battery is begun with.These Due to the limitation of bipolar plate material selection in technical measures, positive and negative anodes active material structure is still identical as ancient structure, electricity Service life short situation in pond is not improved, and is widely applied so this innovation there is no.

From the significant improvement that " winding type lead-acid battery " of American invention is to traditional lead acid batteries structure.It uses The structure of thin plate grid and thin active material reduces the ratio of nonactive lead.Though some improve, plate is based on without radical departure The ancient technology of the lead-acid battery of grid structure, due to the lead of winding grid be from each pole plate it is distributed draw alleviate pole The non-uniform situation of ear formula grid current density.Still there are opening grid on thin plate grid used in it as traditional grid Lattice are to increase the contact strength of active material, while active material has still used matching for traditional " lead sponge "-" lead oxide " To active material.The traditional problem of bigger serface active material structure in this way still remains, and does not obtain basic solution.

Meanwhile in lead-acid battery 154 years industry history, the work of refining lead, casting lead, high energy ball milling lead powder is continued to use always Skill.Not only energy consumption is huge, and lead contamination is serious, is unfavorable for environmental protection.Positive and negative electrode grid form is different, positive and negative anodes activity material Material is different, and no matter technological innovation has carried out how many times, uses nonactive lead production busbar connector, pole, tab, grade in power battery Between line structure and anode do not changed always using brown lead oxide, cathode using total pattern that lead sponge makees active material structure Become.Complex process, production efficiency are low.

However, for the industry why lead-acid battery can undergo 154 years survive lasting reason where, the present invention Think in all chemical cells, lead-acid battery is one of classic chemical design.Classic feature is as follows:

1. positive and negative anodes reaction product is all identical chemical substance~" lead sulfate ", just so-called " bis sulfonate ".This It is unexistent in all chemical cells so far, do not know why this outstanding feature is never paid attention to, Just it is not utilized.

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

3. the design of automatic " depassivation " mechanism, this automatic " depassivation " dexterously selects barium sulfate as depassivation work Matter, it not only has identical crystal structure with lead sulfate, but also does not participate in the discharge and recharge reaction of lead-acid battery, has quite high Chemical stability.Identical crystal structure makes the sulfuric acid lead molecule generated in exoelectrical reaction by the force of crystallization of same crystal structure It draws and forms eutectic with barium sulfate around barium sulfate, not only prevent it from forming polycrystalline passivation layer on active material, but also try Figure all three-dimensional bigger serface structure of reforming activity material in exoelectrical reaction each time.

Application No. is in 200910171743.4 Chinese patent background technique, review in the recent period much about bipolar plates lead The public technology of sour battery illustrates that the problem is all organic mostly in bipolar plates lead-acid battery technical background in the patent The patent of the ion Insulation Problems and Publication No. CN101202356A that cause between substrate and metal insert there are gap Also in that the sealing problem of element cell, causes cycle life unstable.To improve between organic substrate and metal insert Ion sealing problem and bipolar plates lead-acid battery existing for grid corrosion, sulfation problem, active material and plastic grid Binding force problem and it is so-called in the prior art to active material single side do work problem, propose that improved measure is: 1. will be organic Hydrophobic treatment is made on the surface of plate and metal insert；It lives 2. then the felt for pasting Electolyte-absorptive on substrate is arranged on felt surface Property material layer, makes active material two sides that can participate in reaction, here it is the so-called surface work doings of the inventor；3. in each battery Unit opens stomata upwards, and the shared gas chamber of each venthole of connection is arranged when necessary, and pressure reducing valve is arranged on sharing gas chamber.

1. it is the repellency by material for measure, prevents aqueous electrolyte between metal insert and organic substrate Slit in circulation to improving ion resistance.This method is feasible.But the bipolar plates that structure basis originally uses are too Thickness, since the dosage of bipolar plates is very big, weight and volume is all an impediment to battery pack overall weight specific energy and energy density per unit volume Raising.2. measure is to increase the felt cloth setting of Electolyte-absorptive between active material layer and organic substrate, make active material Expect that inside and outside two sides all touches electrolyte, i.e., so-called surface work doing can thus elongate the length of electrochemical reaction conductive path Degree, this will not only consume the specific gravity for voluntarily taking on conductive path active material, further decrease active material utilization, heavier Be that cannot be laid with direction along active material in active material to form very long conductive path, this is because the activity of lead-acid battery Material is lead oxide and lead sponge, all generates lead sulfate in their exoelectrical reactions, and lead sulfate be it is nonconducting, undertake conductive logical Exoelectrical reaction once has occurred in the active material in road, will nip off conductive path necessary to the electrochemical reaction of distal end, and Irreversible sulfation is more readily formed.Even if not setting the felt of Electolyte-absorptive overleaf, electrolyte can be existing by capillary As immersing active material, this measure is not only to draw a snake and add feet to it, and the combination in more unfavorable bipolar plates face and active material.Measure 3. being that the upward venthole of adding unit battery and foundation share gas chamber installation pressure reducing valve, this measure is electric in the unit of the invention New meaning is had no under the conditions of pond thickness is biggish, because being all by multiple unit plumbic acids in the traditional lead acid batteries of all 4V or more Battery is connected in series, wherein each lead-acid battery has upward outlet passageway, also there is public gas chamber and pressure reducing valve.If The element cell of bipolar plates lead-acid battery is thin to close to millimeter or lower, and this problem is only a technological difficulties.Even this Sample, the inventor do not speak of at all, and what is gone out from air hole may be the electrolyte that gas is also likely to be expanded by heating, if it is Electrolyte can form ion short-channel few in public passage, influence the normal discharge and recharge reaction of battery.So It is just feasible to there is provision of mutually isolated electrolyte memory space between each unit battery in public gas chamber.

Application No. is 201210115319.X, entitled film composite material bipolar cell and bipolar plates matrix should When illustrating current bipolar plates lead-acid battery problem in technical background, the patent that the U.S. and China have disclosed is listed, and summarize 4 problems existing for bipolar plates battery are had, 1. the sealing problem between neighboring unit cell；2. power caused by contact resistance Loss problem；3. the problem of electrolyte causes bipolar plates to be corroded；4. whether the complexity of manufacture craft is conducive to advise greatly The problem of mould produces.It is to be added using acidproof thermosetting or thermoplastics type's high molecular material to the solution of the above problem in this application Enter the conductive particle composing base of some dot matrixs, it is desirable that if 1.1~1.4 times of the partial size substrate thickness of conductive particle, base The two sides of plate coated with lead foil hot pressing, ultimately forms film composite material pole plate again, and then the two sides of this pole plate is respectively applied Anode diachylon and cathode lead plaster, just at bipolar plates.Between bipolar plates place perfusion sulfuric acid electrolyte ultra-fine fibre glass every Both ends after these element stacks are respectively added a positive unipolar plate and negative unipolar plate by film, are drawn respectively by the pole of oneself, at For a bipolar plates battery, bipolar plates matrix is film composite material.And 1. enumerated in the technical background of the patent is asked Whether topic seems to be not directed to, solve the problems, such as 2., 3., 4., also responds without front, only describes " this hair in the description Bright prepared bipolar film composite material lead-acid battery has many advantages, such as that corrosion resistance and good, light weight and cost are cheap, and full The extensive manufacturing condition of foot " is given and is handed over.Solution described in the patent, skill actually known in bipolar plates lead-acid battery The reprint for wearing metal needle of described plastic plate rectangular in art, it is desirable that the length of needle is had to than plate thickness, so as to electrically Connect two sides active material layer.The preceding part of the solution of the patent and above-mentioned technology and indistinction.Rear portion attempts to lead to Cross the combination that hot pressing solves two sides lead foil and conductive particle, the combination of lead foil and plastic base.And say 150 degree of precompressed temperature, heat 250 degree of temperature of pressure.And the fusing point of lead is 328 degrees Celsius, does not have theories integration that can pass through in existing technology far from fusing point Pressure, can be by two metal bondings together, if this is the fact in 15 minutes, and welding technique will exit history dance Platform.Further more, without 50 microns of thick lead foils of theories integration.It can be combined together with plastics by 250 ° of high temperature.From 250 Depanning after the temperature hot pressing of degree, returns to room temperature, nearly 200 ° of the temperature difference, and inventor does not illustrate whether plastics and lead foil have together The thermal expansion coefficient of sample, usually understands, the line of plastics is swollen, and temperature coefficient is greater than lead.After returning to room temperature, thermal stress can make lead foil It is separated with plastics.

Further more, solution is all " nonactive lead " in all background technology documents of existing bipolar plates lead-acid battery Problem, specific manifestation they be all using the different active material in the two poles of the earth of existing lead-acid battery technology and apply cream technique.No Take into account in the prior art, there are also close to half inside active material, does not participate in the electrochemical reaction of charge and discharge at all, and only It is to have done " logistic work " --- the fact that serve as current channel necessary to electrochemical reaction and structural support.

Summary of the invention

It is an object of that present invention to provide a kind of high-tension battery group that bipolar plate-shaped unit high-energy lead-acid battery is constituted and batteries The compact package method of group.

The technical solution adopted by the present invention to achieve the above object are as follows:

A kind of bipolar plate-shaped unit high-energy lead-acid battery, unit high-energy lead-acid battery include electronic conductor bipolar plates 15, Two sides is respectively coated same using lead sulfate as the active material layer 20 of positive and negative anodes primary active material, wherein activity on one side Battery separator 19 is re-layed in material layer.

The bipolar plate-shaped unit high-energy lead-acid battery, the work for being respectively coated on 15 two sides of electronic conductor bipolar plates Property layer thickness be 0.15-0.3mm, preferred thickness 0.2mm.

Active material layer is made of lead sulfate, additive and lead-acid battery colloidal electrolyte, and wherein additive is known lead (the composition additive of such as barium sulfate, humic acid and the mixture of acetylene black and PP staple fiber mixes sour cell negative electrode material additive The additional amount for closing object is 1wt%~1.3wt%, and the additional amount of PP staple fiber is 0.5wt%；Wherein barium sulfate, humic acid and second Weight fraction ratio between the mixture of acetylene black is 5:4:2).Colloidal electrolyte is the electrolyte of existing known colloid lead-acid battery (dilute sulfuric acid plus nano silica), the weight ratio of colloidal electrolyte and lead sulfate are 1 ︰ 10.

The electronic conductor bipolar plates 15 are thermally treated again by lead plating " stainless steel fibre cloth " dipping pure lead of fused solution Rolling and manufactured composite thin plate；Lamella thickness is 0.02-0.04mm, preferred thickness 0.03mm, lead in thin plate (including Lead plating and dipping lead) it with the preferred volume ratio of stainless steel fibre is 4:6.

The active material layer is coated on the centre of electronic conductor bipolar plates 15 with uniform thickness, double to electronic conductor The uncoated region of pole plate 15 carries out hydrophobic treatment using the prior art.

The rectangular area that the active material layer 20 is coated with is less than the rectangular area of bipolar plates 15, active layer edge with it is bipolar The vertical range at plate sides aligned parallel, edge and 15 edge of electronic conductor bipolar plates is 0.4-3mm；It is preferred that active material layer 20 Three edges of the rectangle of coating and the vertical range at 15 edge of electronic conductor bipolar plates are 0.5mm, another vertical range is 2mm, vertical range are that the side of 2mm corresponds to " upper surface " of battery pile, and gas relief cavity is installed on herein.

The battery separator 19 is the AGM diaphragm after the immersion of lead-acid battery colloidal electrolyte, and its rectangular dimension Identical as the size of electronic conductor bipolar plates 15, wherein membrane thicknesses are 0.2-0.4mm, preferred thickness 0.2mm.

A kind of series connection bipolar plates lead-acid battery group 25, is the battery pack of 2NV for output voltage, and the battery pack includes N- 1 bipolar series connection of plate-shaped unit high-energy lead-acid battery 18 is piled up, and it is any two adjacent bipolar plates that battery pack, which piles up sequence, One side of the type unit high-energy lead-acid battery 18 with diaphragm 19 is with another bipolar plates element cell 18 without the active material of diaphragm Bed of material face 20 is adjacent to realization series connection, and all 18 4 side of element cell alignment install gas relief cavity 26 in " upper surface ", then again The output polar plate group of "+number ", "-number " 24 is referred to as into battery pack with 2.Two output pole plates all one side coating active materials Layer 20, coating size and marginal dimension with element cell as.Only "-number " output pole plate 24 will also stick on one on active layer Open partition 19.Tab and " upper surface " for exporting pole plate are equidirectional.

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

1) battery pack 25 that the described series connection is formed is clamped using tooth holder 27, fixture contact be "+number " 22, "- Number " 24 output pole plate, fixture optimizes clamping force 1kg/cm², after clamping, use the two sides of acidproof insulated paint spraying battery pack With bottom surface (i.e. the face opposite with the end face for setting gas relief cavity), insulated paint has filled active material layer 20 in each element cell Space of the edge to 15 edge of electronic conductor bipolar plates.Thickness of the insulated paint outside pole plate edge should reach 0.5mm, so that each Element cell sealing is connected, and forms the pre-sealed of element cell；

2) after pre-sealed solidification, it is attached to the face for being coated with insulated paint with high strength fibre cloth, then uses strap by gas Body protective shell (26.c) of releasing is fixed on " upper surface "；

3) the tooth mouth (29) for passing through tooth holder will include that output electrode plate exists using commercially available high strength fibre bandlet (32) Interior battery pile carries out multiple tracks and ties up, will tense per winding together, heat and take envelope, can still maintain after removing fixture Pressure between battery pack internal polar plate；

4) using speckling with the high-intensity fiber of uncured resin, along the direction of strap the region of not strap uniformly around Tight battery pack forms smooth, smooth high-intensitive shell and reinforcing high strength fibre cloth after resin solidification and is used to protect together Pre-sealed insulating lacquer layer；

5) to above-mentioned steps 4) processing after battery pack output draw tab and gas relief cavity protective cover outlet carry out work After dress protection, by battery pack mass-impregnation resin and solidify.The tooling protection for dismantling above-mentioned after solidification, is protected in gas relief cavity Cover outlet installation pressure-limiting safety valve, that is, realize the encapsulation of battery pack.The resin is well known epoxy resin, carbon chopped fiber And flame retardant of magnesium hydroxide；Wherein, the additional amount of carbon chopped fiber and flame retardant of magnesium hydroxide is respectively the 5wt% of epoxy resin.

Gas relief cavity surface is through hydrophobic treatment, the interior element cell number (n-1) for being equipped with battery pack of gas relief cavity A isolation board, each isolation board are equipped with position-stopping plate, between the bipolar plates of position-stopping plate partial insertion battery below, position-stopping plate For limiting, bipolar plates edge is pushed against.The externally-arranged protective shell of gas relief cavity, protective shell are fixed on gas by strap and let out It puts outside chamber, and is sealed by the whole resin that immerses.

The present invention will be also described further:

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

The cathode and anode of battery of the present invention are all used as primary active material using same " lead sulfate ".Use colloid Electrolyte by lead sulfate mix at paste after, be coated on the two sides of bipolar plates (15), in advance without positive and negative electrode point.Only exist After charging, positive and negative anodes can be just separated.Because in the pole plate plate face corresponding to the anode of charge power supply, being generated just after charging Pole active material " lead oxide "；And negative electrode active material " lead sponge " is generated in the corresponding pole plate plate face of power cathode.Such as If " lead sulfate " coated on fruit positive/negative plate is absolutely consistent and equivalent, the conversion ratio of this active material is up to 100%.

The active material structure of high-energy lead-acid battery of the present invention after charging are as follows:

1) charge after positive electrode active materials " lead oxide " in there is no to active material play a supportive role " alpha-crystal form Lead oxide ", because " alpha-crystal form lead oxide " can only generate under alkaline solution environment.It is generated in the case where acidic electrolysis bath It can only be " beta crystal lead oxide ", it has very high electro-chemical activity, is the active material for being able to achieve effective positive charge and discharge Material.In the present invention, bipolar plates (15) instead of support " beta crystal lead oxide " and undertake " the alpha-crystal form oxygen of electrochemistry conductive path Change lead ".Illustrate that the active material of the anode in lead-acid battery of the invention can be utilized with 100%.

2) negative electrode active material " lead sponge " after charging is identical as conventional batteries in form, and the difference is that 0.2mm is thick Active material in, actually without as " logical as the conduction for undertaking electrochemical reaction in aforementioned existing plumbic acid technology Support construction of the road " without participating in energy storage reaction.It can accomplish to make " lead sponge " 100% on pole plate to convert in exoelectrical reaction At " lead sulfate ", and do not have to worry irreversible " sulfation " occur.

3) so-called " lead sulfate " is slightly soluble in dilute sulfuric acid and refers under conditions of no electric field force, when " lead sulfate " is placed in forceful electric power When under field intensity, its solubility in dilute sulfuric acid just be will increase, and go on smoothly charging reaction." irreversible sulfation " is Refer to that exoelectrical reaction generation sulfuric acid salt block diameter is too big, each element cell charging voltage 2.4V or so, electric field strength is removed equal to voltage Distance, if fruit block diameter is too big, it is exactly above-mentioned distance, be applied in this way sulfate it is fast on electric field strength will be lower than dissolving Threshold value, without dissolving, but when discharging, the lead sulfate that generates can also be deposited preferentially on it, increased block diameter, just formed Irreversible sulfation.Only has 0.2mm in view of the thickness of the active material applied on pole plate, bipolar plate structure ensure that uniformly Current density distribution.The use of lead-acid battery colloidal electrolyte, secures active material micro-structure, will not in exoelectrical reaction There is the aggregation of " lead sulfate ".The thickness of " lead sulfate " from anywhere in therefore, in polar plate area does not exceed 0.2mm. And " lead sulfate " of this thickness can fully dissolve under the action of the electric field strength that charging voltage converts.The present invention is from pole plate In the mechanism of structure, the appearance of irreversible " sulfation " is prevented, the service life of battery is effectively extended.

The present invention selects the reasons why " lead sulfate " active material common as the two poles of the earth: the originally classic electricity of lead-acid battery One of the characteristics of chemical design is exactly that identical reaction product-" lead sulfate " is generated in positive/negative plate exoelectrical reaction.And " sulphur The density of lead plumbate " had both been less than the density of positive electrode material " lead oxide ", and again smaller than the density of negative electrode active material " lead sponge ", this is just The volume of traditional lead acid batteries pole plate in exoelectrical reaction can expand as much as to say, and active material structure can be made because expanding stress And it falls off.This can be attributed to the fatal error of original chemical design.The product of the exoelectrical reaction of any battery also all can be because dividing The variation of minor structure expands.But we around and row strategy, be by after volume expansion " lead sulfate " as live Property material.After charging to it, when positive and negative anodes plate face is converted into " lead oxide " and " lead sponge " respectively, the body of active material Product reduces, and the space of " apt " should have just been reserved for the anti-product that discharges, the present invention is again from the selection of active material On, the structure mechanism for fundamentally preventing pole plate expansion drop is established, is made that beneficial contribution to extend the service life of battery.

The present invention is also added into traditional lead acid batteries additive used in active material in lead sulfate.It is led as increased Electrical carbon black, acetylene black prevent active material hardened and keep as micro barium sulfate and the lignosulfonic acid element of swelling agent It is fluffy.Existing lead-acid battery technology only uses inorganic expansion agents barium sulfate in negative electrode active material, and the present invention is living at the two poles of the earth Property material in make swelling agent using barium sulfate, when exoelectrical reaction generates lead sulfate, because there is the presence of barium sulfate that can prevent The formation of even polycrystalline passivation layer.

The present invention why " lead sulfate " be positive and negative anodes common active material another reason for be, compared with prior art Eliminate " lead powder processed " technique of high pollution.Complete wet processing extracting sulfuric acid lead in the solution.It improves resource utilization, letter Chemical industry skill reduces pollution, reduces manufacturing cost.

2. the selection of plate material

In traditional lead acid batteries, the corrosion of grid be also influence the service life an important factor for one of.It is used in primitive technology Pure stereotype grid it is corrosion-resistant, but mechanical strength is inadequate.Alloy grid meets strength demand but not corrosion-resistant.It is bipolar in the present invention Plate material is " pure lead base stainless steel fibre cloth composite material ".Its preparation method: first will be micro- with a thickness of 15 using well-known technique Lead plating after stainless steel fibre cloth (its fiber string diameter is 6 microns) surface treated of rice, after drying under inert gas protection, leaching Enter after pulling out cooling in molten state liquid pure lead, is flattened through rolling, thickness is only 0.03mm.To bipolar plate surfaces, also using tool There is " polyaniline " coating of high conductivity to carry out preservative treatment, can exceed that its corrosion resistance in the electrolytic solution 10 years.

Ultra-thin bipolar plates (15) not only act as the supporting role of " the nonactive lead " of existing lead-acid battery to active material, It has also acted as in " the active lead " of existing lead-acid battery and has taken on the effect of " logistics " conductive path, and therefore eliminated in existing lead In technic acid, those do not participate in the nonactive and active lead of charge and discharge electrochemical reaction directly, to improve lead most possibly Utilization rate.Bipolar plates also act as the inside cascade of element cell in battery pack.So that " cascade path length " is 0.03mm, " cascade path sectional area " is the area of pole plate.Compared with existing lead-acid battery, it will be reduced because of electronics internal resistance caused by cascade Millions of times.Due to the two poles of the earth active material and diaphragm thickness all only have 0.2mm, ultrashort cascade path prevent jointly from The generation of sub- concentration polarization.So the internal resistance for the lead-acid battery that the present invention is constructed is far below traditional lead acid batteries.

The present invention improves the mechanical strength of pole plate, and the chemistry without changing pure lead using chemically stable stainless steel fibre The hydrogen-evolution overpotential of property, pure Plante-type plate is improved, in addition the sealed colloid electrolyte battery technology that we inherit totally, energy The appearance of harmful " gassing " phenomenon is prevented well.

3. element cell and battery pack structure:

" unit lead-acid battery " of the invention is to be coated with equivalent amount of active material on bipolar plates two sides, then be superimposed one layer and be saturated with glue The AGM diaphragm of the 0.2mm thickness of body electrolyte.It is equal to a four-layer structure, and bipolar plates and diaphragm area have identical dimensioning Very little, 3 edges of the active material layer in 4 side of bipolar plates have been reserved at a distance from 0.3~0.8mm wide, preferred size 0.5mm, Element cell seal isolation space has been reserved along bipolar plate end face；The distance of 3mm~5mm has been reserved at a remaining edge, this Place has been bonded gas overflowing cofferdam.Constitute the unit lead-acid battery that an overall thickness is 0.63mm.Lead-out wire is not cascaded, only There is an electrode plate.

When constituting battery pack, only need to by above-mentioned element cell, successively series aiding connection is stacked, and made using lead plating copper sheet For the extraction pole at battery pack both ends, battery pack is just constituted.

4. the encapsulating structure of battery pack:

1. element cell isolating seal

Must all have sealing well with each of existing battery technology element cell, the present invention is necessary The compact sealing of element cell is realized between the element cell of High Density Packaging.

It is sequentially connected in series several element cells stacked and constitutes a battery pack, in addition to two output pad-faces, there are also 4 A heap face, it is reserved that high-grade acid-proof insulated paint is filled to each element cell bipolar plates edge and active material layer edge In the sealed airspace and side of gas overflowing cofferdam, it is pre-sealed to carry out element cell.

2. battery pack fastening method

Using high-strength hot blown fibre baling strips, multiple tracks is done to battery pile by prestressing force stiffening plate and ties up dozen envelope, So as to keep suitable pole plate between pressure.Using insulated paint be adhesive will reinforce enhancing high strength fibre cloth be bonded in rear end and Two sides.

3. gas relief cavity protective cover and safety valve is arranged in

Gas relief cavity protective cover is seated in the outside of element cell gas overflowing cofferdam group and is fixed on battery pack Front end.

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

The high-intensity fiber of epoxy resin-impregnated slurry is uniformly around protection location cell sealing layer after solidifying outside battery pack.

5. battery pack entirety mass-impregnation composite resin.It include alumina short fibre and magnesium hydroxide flame retardant in resin Agent forms firm battery pack shell after solidification.

Divider wall configured with electrolyte between element cell in gas relief cavity prevents ion short-circuit.Leave divider wall Between gap be used to discharge the gassing that is likely to occur and may spilling a small amount of electrolyte.

In this way, battery pack side, bottom surface, the insulated paint of bipolar plates two sides active material outer edge 0.5mm wide is just constituted In each element cell, the reliable isolation of positive and negative anodes active material is also prevented from the ion in electrolyte on edge, around bipolar Plate short circuit.

Encapsulation compact in this way can reduce in traditional lead acid batteries structure, because of battery case to battery weight specific energy and The influence of energy density per unit volume.

5. the selection of battery pack output voltage.

The voltage of traditional commodities lead-acid battery group is lower, and the electric current under same output power is larger, and the electronics of external circuit Element and output loop can all cause excessive loss because of high current, reduce the energy utilization rate of system.List in the present invention The thickness of first battery only has 0.63mm.The output voltage of the battery pack of 63mm thickness is as high as 200V, under same output power, because Voltage greatly improves, and electric current will be fallen too low, while be reduced in exoelectrical reaction, internal resistance caused by polarizing because of ion concentration Loss.Not only the exoelectrical reaction efficiency of battery improves, but also the energy conversion efficiency of external circuit is also because of the raising of voltage and electric current Reduction and be improved.I.e. the selection of high output voltage is made that contribution to the cost for proposing entire application system.

Invention unit battery one layer plane active material of very thin tiling on pole plate.Using pole plate as the electricity of active material The support of the conductive path and active material of chemical reaction.Electric discharge can all exhaust the active material on pole plate every time, be produced The thickness of raw lead sulfate will not also form " irreversible sulfation ".Response area and view are essentially identical in area.So that single Response area in the volume of position is instead far more than traditional lead acid batteries.Storage capacity in unit volume simultaneously, will be far more than biography System lead-acid battery technology.Especially, this big response area in unit volume by structural system of the invention it is fixed under Come, will not fail with the lengthening of charge and discharge cycles, will not be destroyed because of overdischarge for the moment or overcharge.It is theoretical On, the bipolar plates corrosion resistant service life is exactly the service life of battery." polyaniline, graphene composite wood if can be directly used from now on " conductive plastic film makees bipolar plates to material, and the theoretical service life can be to more than many decades.

Beneficial effects of the present invention:

The present invention inherit traditional lead acid batteries it is outstanding chemical reaction design, and lead-acid battery colloidal electrolyte, Active material additive and the technological improvements such as maintenance-free method of gassing in charging process are prevented, but fundamentally changes plumbic acid The structure of battery eliminates the nonactive lead in traditional lead acid batteries, and does not play energy storage directly and only undertake electrochemistry and lead The active lead material of electric pathway, using battery of the present invention structure compared with prior art, at the same capacity, the use of battery Lead amount reduces 3/4 or more；Gravimetric specific energy is increased to close to 135wh/kg；(prior art 35wh/kg, existing LiFePO4 electricity Pond 100wh/kg) gravimetric specific power raising about 220w/kg；(prior art 45w/kg) deep-cycle service life is about 2000 times；It is (existing Having technology 200 times) active material only has 0.2mm thickness, and the extremely low internal resistance of cell allows high current quick charge, without damaging electricity Pond.Production cost than equivalent capability traditional lead acid batteries reduces by 20%.It is secured in mechanical structure big in unit volume The active structure of surface area keeps it steady in a long-term.Using the ultra-thin lead composite material bipolar plates with a thickness of 0.03mm, so that charge and discharge The uniform current density of electric electrochemical reaction, the generation of the irreversible sulfation fundamentally prevented.Lead sulfate is used simultaneously As the active material at the two poles of the earth, prevent the generation for causing active material obscission because of expansion, extends following for lead-acid battery The ring service life reaches 2000 times or more.Element cell immerses the shell of resin after there is no shell, battery pack that fiber is integrally used to wind Packaging technology improves energy density per unit volume.

Internal resistance, long circulation life, high power are forced down using monomer height easy to accomplish after the configuration of the present invention is simple and cell package Rate charge-discharge battery, while the production technology of battery is simplified, reduce production cost.

Detailed description of the invention

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

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

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

Fig. 9 is-number output electrode structural schematic diagram；

Figure 10 is that battery pack " central part " structure and gas release and cavity configuration and is fit into the shape of battery center part State schematic diagram；

Figure 11 is that battery pack gas is released box structure schematic diagram；

Figure 12 is that the first procedure of encapsulation implements battery pack clamping process explanatory diagram；

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

Figure 14 is that encapsulation third procedure implements the reinforcing of high strength fibre cloth side end face and installation protective cover procedure declaration figure, Positional diagram of Figure 14 .1 between gas relief cavity protective shell and relief cavity；

Figure 15 is that encapsulation the 4th procedure implementation multiple tracks strap ties up procedure declaration figure；

Figure 16 is stained with resin high-intensity fiber winding battery formation composite material shell process for encapsulation five processes implementation and says Bright figure；

Figure 17 is that the 6th procedure of encapsulation implements battery pack mass-impregnation alumina short fibre and flame retardant of magnesium hydroxide is multiple Resin packaging process explanatory diagram；

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

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

Figure 20 is that gas of the present invention is released cavity plate installation condition schematic diagram.

Specific embodiment

It elaborates with reference to the accompanying drawing to implementation process of the present invention:

It should be pointed out that in the absence of conflict, the embodiment of the present patent application and the various skills in embodiment It is a variety of not in the embodiment of description of the invention that art feature and its deriving method can combine composition, but these are all of the invention real The embodiment of matter spirit is also all constituted to protection scope of the present invention.The illustrating of the present embodiment is not formed can to other Can embodiment limitation, put up with below with reference to attached drawing and do specific explanations in conjunction with the embodiments.

In order to understand that the present invention is intended to the improvement of traditional lead acid batteries, traditional lead acid batteries are first illustrated with Fig. 1-Fig. 5 Structure.The structure of the lead-acid battery of the prior art as seen from Figure 1, (1) are the shell of lead-acid battery, and (6) are negative electrode grid, (7) For negative electrode active material " lead sponge ", it is attached on (6)；It (11) is the outlet tab of negative plate gate current, (12) are pair Multiple negative electrode grids carry out negative bus-bar in parallel, and (13) are the negative terminals that cathodal current is drawn to capsul (1), and (14) are With the concatenated cascade conducting wire of adjacent cell anode in battery pack, (10) are anode plate grid, and (9) are positive electrode active materials " oxidation Lead ", it is attached on (10)；It (3) is the outlet tab of positive plate gate current；It (4) is that parallel connection is carried out to multiple anode plate grids Positive bus, (5) be by positive electrode current draw capsul (1) positive terminal；(2) it is and adjacent cell cathode in battery pack Concatenated cascade conducting wire.(8) partition between positive and negative anodes active material in lead-acid battery.Dilute sulfuric acid electrolysis is filled in battery Liquid.Described current density unevenly refers to that active material is attached to anode plate grid (10) and negative electrode grid (6) in background technique On, it is different in the action process of the nethermost active material of grid and the uppermost active material charge and discharge of grid, because There is provided redox ability is the electric current of external circuit, and electric current is transmitted on active material by grid, under grid The current path in face will be grown；And will be short in current path above, therefore current density slight difference is caused, repeatedly filled Electric discharge will be such that this small difference constantly accumulates, will be on the top of negative electrode grid because path is short, resistance is small, current density Greatly, it causes part " overdischarge " and generates " irreversible sulfation ", and on the top of anode plate grid due to part " overcharge " Generate the oxidation corrosion of grid.

Once thering is one small " irreversible sulfation " to generate, as long as electric discharge carries out, on negative electrode grid, around it Newly-generated lead sulfate will be selected first in the upper surface of it " implantation crystallization ", this is inexorable law when substance is precipitated.In this way " nucleus " of " irreversible sulfation " will promptly grow up.Not only active material is made to fail, and due to " irreversible sulfuric acid Other active materials are squeezed in the expansion of salinization crystal " broken to fall off from grid.

As can be seen from Figure 1 positive and negative anode grid (6), (10), plate railings of anode and cathode tab (3), (11) are multiple positive and negative The busbar connector (4) of pole plate grid parallel connection, (12), by the positive and negative electrode pole (5) except electric current guidance unit battery, (13), battery Group cascade conducting wire (2), (14), these are all lead and metal manufactured goods.They are without " electrochemistry is living required for energy storage Property ", these are " nonactive lead ", and the weight ratio of they and active material is almost 1 ︰ 1.

By Fig. 4 a prior art lead-acid battery after charging active material localized micro structure schematic diagram as it can be seen that charging after " lead oxide " (7) are depended on anode plate grid (6), wherein " alpha-crystal form " lead oxide (7.1), it " electro-chemical activity is low, mechanical Intensity is good ", it does not participate in the chemical reaction of charge and discharge directly, only plays to " beta crystal " lead oxide with " electro-chemical activity " (7.2) make the effect of bracket and conductive path." lead sponge " (9) have been depended on negative electrode grid (10) after the visible charging of Fig. 4 b, with Positive electrode active materials are distinguished there are two types of crystalline form, and negative electrode active material only has a kind of crystal form.And after the visible electric discharge of Fig. 5 a, original " β Crystal form " lead oxide (7.2) all becomes " lead sulfate " (7.3)；It is expanded because combining sulfate radical volume.When (7.2) are whole After being converted to lead sulfate, positive electrode active materials only have " alpha-crystal form " lead oxide (7.1), its chemical activity is compared with " beta crystal " lead oxide (7.2) much lower, so discharge current falls sharply rapidly, therefore it not only controls positive electrochemical reaction and also controls cathode Electrochemical reaction.The electrochemical reaction of entire battery is set substantially to stop.Fig. 5 b, since negative electrode active material only has one kind Crystal form, therefore, the lead sulfate of generation and the active material for undertaking electric path do not have apparent boundary, the big place of current density The lead sulfate of generation wants thick, and the small place of current density is just thinner.

The embodiment of bipolar plates

As shown in fig. 6, the substrate (17) of bipolar plates is that 6 strand of 316 Stainless Steel fiber that diameter is 6 microns is spun into line, then with The line is made into plain cloth.By the stainless steel plain cloth after alkali cleaning, pickling, washing, drying, it is electroplated pure lead (16), it is micro- to 35 Rice, then it is spare to be cut into band volume for tempering and hot rolling after being densified to 30 microns.It is coated with active material (20).

Active material prepares embodiment

800 mesh lead sulfates are several, and it is (such as mixed with 5:4:2 ratio that additive known in the lead-acid battery of 1.0~1.3wt% is added The barium sulfate of conjunction, humic acid, acetylene black) and 0.5wt% PP staple fiber.The colloid sulfuric acid of 2.5ml/L is added after mixing Solution be sufficiently stirred make pole plate coating it is spare.

Shutter embodiment

Using AGM battery 0.2~0.4mm of block board thickness, the preferred thickness 0.2mm of the prior art, colloid electrolysis is impregnated Liquid fills all gaps of AGM partition, and solidifies.Battery separator (19) as preliminary filling electrolyte.

Element cell embodiment

As shown in fig. 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 with lead sulfate active material layer as main component (20), wherein active material on one side Battery separator (19) are re-layed on layer.

The active material layer for being respectively coated on electronic conductor bipolar plates (15) two sides is with a thickness of 0.2mm；Active material Layer is made of lead sulfate, additive and lead-acid battery colloidal electrolyte, wherein additive component and existing lead-acid battery cathode material Feed additives are identical, and colloidal electrolyte component is identical as the electrolyte component of existing colloid lead-acid battery.The active material layer It is coated on the centre of electronic conductor bipolar plates (15), the uncoated region of electronic conductor bipolar plates (15) is through well known hydrophobic Processing.

The vertical range at active material layer (20) edge and electronic conductor bipolar plates (15) edge is 0.5mm, wherein The distance for pasting one side of gas overflowing cofferdam partition (26.1) is 2mm.This side of bipolar plates (15) is known as element cell (18) " upper surface ".

Export pole plate embodiment

It is as shown in Figure 8, Figure 9 to export pole plate, including "+number output pole plate " (22) and "-number output pole plate " (24).Output stage The pole plate (23) of plate is the lead plating copper sheet of 2mm thickness, and there is a tab in end, "+number " tab (23.1), "-number " tab (23.2). "+number " output pole plate (22) is in the single side towards tab, active material layer (20) after being coated with 0.2mm, coated form and list First battery is identical；"-number " pole plate (24) are exported in the single side towards tab, it is coated with the active material layer of 0.2mm thickness (20) after, and one layer of AGM diaphragm (19) for being saturated with colloidal electrolyte is covered on active material layer, Edge Distance requires and unit Battery is identical.

Battery embodiment

Referring to Fig. 8-11, the constructive method for bipolar plates lead-acid battery group of connecting: battery assembly sequence ligand is: any two are double Polar plate type unit high-energy lead-acid battery (18) series connection method is a unit in any two adjacent bipolar plates element cells The septate one side of battery band and another adjacent element cell are without one face contact of diaphragm, and two adjacent unit electricity " upper surface " in pond is aligned.The output voltage of corresponding 2nV, battery pack will include the n-1 bipolar plate-shaped unit high-energy lead-acids Battery (18) series connection is piled up (25), then one "+number " output pole plate (22) and one "-number " are exported pole plate (24) and are mounted on list First battery pile (25) both ends composition.Wherein, the bipolar plate-shaped unit high-energy lead-acid electricity of edge series connection direction one end of battery pack (25) Pond (18) is coated with the one side of active material layer (20) and is in close contact with the diaphragm face (19) of "-number " output pole plate (24)；Battery pack (25) one side of bipolar plate-shaped unit high-energy lead-acid battery (18) membrane layer (19) of the other end and "+number " output pole plate (22) Active level (20) be in close contact；Tab and " upper surface " for exporting pole plate are equidirectional.

Gas relief cavity is packed on the end face of the n-1 bipolar plate-shaped unit high-energy lead-acid batteries piled up of connecting (26)。

As shown in figure 9, collector plate (23) is divided into two parts, tab (23.2) and doab (23.1), "-number " marking exist The two sides of tab.

As shown in Figure 10, the battery pack gas relief cavity (26) has a position-stopping plate (26.2), when installation, position-stopping plate patch To the end face of battery pile, the edge of electronic conductor bipolar plates (15) is pushed against, from the blown-up partial detail of Figure 10, it can be seen that every It in the following length of position-stopping plate (26.2) is 2mm from plate (26.1), the lead sulfate active material in thickness and element cell (18) Layer (20) thickness is mutually all 0.2, after isolation board (26.1) is inserted into battery pile (25), is just filled with institute on battery pile (25) end face There is gap of interior lead sulfate active material layer (20) edge of element cell (18) to electronic conductor bipolar plates (15) edge.Sub- chamber every It is just clipped between diaphragm (19) and bipolar plates (15) from plate (26.1).Electrolyte or gas can pass through air-and water-permeable diaphragm (19), into sub- chamber (referring to Figure 10).Gas relief cavity (26) also serves as electrolyte breathing box simultaneously, the gas relief cavity (26) tool Have a n sub- chambers (26.5), the corresponding element cell (18) of each sub- chamber (26.5), sub- chamber by partition (26.1) pin (26.4) it is inserted into internal battery pack, is close to the electronic conductor bipolar plates (15) of element cell, each element cell is kept apart, by Hydrophobic treatment is all made in the surface at gas relief cavity (26) and electronic conductor bipolar plates (15) edge, the repellency on surface makes son Chamber isolation board (26.1) can prevent electrolyte from flowing between adjacent-cell battery.Therefore sub- chamber (26.5) lower part can accommodate swollen The liquid electrolyte of expansion, top allow gas to overflow (referring to Figure 11) from overfall (26.3).

Gas relief cavity second embodiment

The design of above-mentioned gas relief cavity (26) can also as follows, as Figure 19 is used with edge (26.b) The partition (26') of monolithic, it is by sub- chamber partition (26.1'), position-stopping plate (26.2'), gas outlet (26.3'), pin (26.4') group At；As shown in figure 20, during piling up battery pack using element cell, each a piece of partition of element cell (26'), monolithic The pin (26.4') of partition (26') pushes against the edge of the active material layer (20) of element cell, the stop bit of single partition (26') Plate (26.2') abuts against the edge of element cell partition (19), and single partition (26') is sticked to the electricity of element cell with acidproof glue On sub- conductor plates (15).After battery pile (25) heap is good, there are 4 notches (26.a) on the edge (26.b) of every partition Through being aligned, wherein being put into diameter is 0.5mm plastic wire, single partition group is auxiliarily fixed.Then in battery unit package Gas outlet (26.3') is covered when two procedures, also to monolithic when carrying out pre-sealed to element cell using acidproof insulated paint Partition group is sealed.Sealing paint will cover the gas relief cavity that single partition group becomes an entirety.Embodiment 2 mentions It is to adapt to the deviation that the thickness of active material layer (20) and battery separator (19) is likely to occur out.When side is installed simultaneously Just.

Above-mentioned battery pack can be implemented under two ways, i.e. high-tension battery group and A-battery group；Specifically:

High voltage-small current battery pack

The thickness of the element cell is only 0.63mm, so the thickness of 250 series units, which adds, is encapsulated as 160mm, i.e., There can be the operating voltage of 500V.Such battery pack is uncommon in conventional batteries technology.It is high under same output power The output electric current of piezoelectric battery can be proportional because of the raising of output voltage reduction, low output electric current will reduce electricity both ways The loss in pond, ion diffusion concentration difference and the polarization pressure drop caused by circuit in battery of electrolyte in electrochemical reaction, because of electricity The reduction of stream and reduce.Pressure drop caused by battery cascade resistance equally can also reduce.

Currently, often needing the supply voltage of 500V or more in electric car.It is returned with reducing the cost of automatically controlled device with electrical The loss on road, so bipolar plates lead-acid battery of the invention is very suitable to the application of electric vehicle.

Low-voltage, high-current battery pack (40) (by taking the 48V that electric bicycle uses as an example)

The element cell of bipolar plates lead-acid battery realizes that the output voltage of 48V only needs 1.44cm's with a thickness of 0.63mm Heap is thick, and active goods and materials layer 0.2mm is thick, and only there are about 0.02Ah/cm for the capacity of unit area², to obtain higher ampere-hour capacity, It just must be by concatenated battery pack further (traditional lead acid batteries technology is connected after elder generation is in parallel in fact) in parallel. Figure 18 is by the schematic diagram of 3 48V battery pack core parallel connections.It is to be completed in mode in parallel after first connecting in this embodiment 's.3 series-connected cells (47) are connected in parallel.Confluence pole plate (41) is the anode of the 1st battery.Confluence pole plate (42) be The cathode of first series-connected cell and second series-connected cell.Confluence pole plate (46) is second series-connected cell and third series connection The anode of battery.Confluence pole plate (44) is the cathode of third series-connected cell.Positive output pole (45) by three series-connected cells just Confluence pole plate (41), (46) are linked together, negative output pole (43), by the negative confluence pole plate (42) of three series-connected cells, (44) it is linked together.

Battery unit package embodiment

The encapsulation for bipolar plates lead-acid battery group of connecting:

The first procedure (referring to Figure 12) of encapsulation, be adjacent to dentation fixture (27), (28) from upper and lower surface+,-number output Pole plate clamps the assembled battery pack in battery embodiment.Use 0.8kg/cm²~1.2kg/cm²Pressure battery pile is pressed from both sides Tightly, preferred pressure 1kg/cm²。

The second operation work (referring to Figure 13) of encapsulation, in the state of clamp, using acid-proof insulated paint (30) along electricity The stacking side of Chi Dui (25) sprays, and the electronic conductor for making insulated paint filling enter each bipolar plate unit lead-acid battery (18) is double In pole plate (15) edge and the space of active material layer (20) border 0.5mm, due to the edge of electronic conductor polar plate two-sided It is all first to have done hydrophobic treatment, therefore the affine wellability of this position and organic material is just high, insulated paint passes through infiltration surface Capillary phenomenon, the narrow slit for element cell sealing can be entered sufficiently into, while also being wanted in the outside of battery pile heap face 0.5mm millimeters of thick lacquer painting is formed, so as to integral, the realization pair by the sealing paint connection in each and every one element cell edge narrow slit Each element cell is reliable " pre-sealed " in battery pile.This process also includes the front end face for being equipped with gas relief cavity, The position-stopping plate of relief cavity is embedded in insulated paint.

The third procedure of encapsulation, using insulated paint as adhesive, uses high strength reinforcement fibre in the state of clamp Wei Bu (31) is attached to two sides and without then using gas relief cavity protective shell (26.c) on the rear end face of gas relief cavity Strap (32) is fixed in front end face.Packaging band shackle (26.6) detailed construction is also shown in Figure 14.Wherein lock Tight pin (26.7) is locked strap (32) on lock (26.6) (referring to Figure 14) using frictional resistance.

The shell (26.c) that wherein protective cover is installed as protective cover is pressed on the position-stopping plate (26.2) of gas relief cavity (26), The safety valve installing port (26.8) of gas discharge outlet (26.3) alignment protective cover (26.c) of gas relief cavity (26), battery pile is defeated The tab (23.1) of cylinder manifold (23) is in the following, be mounted with two limited screws (26.e) to protective cover out.

4th procedure of encapsulation connects high-intensitive packing fiber bandlet using heat-fusible in the state of clamp (33) pass through dentation fixture (27), (28) tooth mouth (29), battery pile is done into multiple tracks along long side side and is tied up, per pass be banded in by Hot melt takes envelope (33.1) after fiber flat (33) band tenses.After ensuring that fixture (27), (28) are removed, still make the pole in battery pile Pressure when holding jig clamps between plate (referring to Figure 15).

The five processes of encapsulation open tooth holder (27), (28) up and down.Use the high-strength fibre for speckling with uncured resin Dimension, along strapping direction in the region of not bundling belt to battery pack uniform winding, because containing curing agent in resin, by several points Clock resin is formed by curing the composite material shell (34) of smooth fairing automatically, internal to the pre-sealed of a element cell with protection (30) (referring to Figure 16).

Figure 17 is the 6th procedure of encapsulation, protects cladding tab (23.1) and gas to release using easy-to-dismount technique The battery pack for completing five processes is integrally immersed by the pressure-limiting safety valve installing port (26.8) of the protective shell (26.c) of chamber Composite resin (35) including alumina short fibre and flame retardant of magnesium hydroxide, resin impregnable (35) thickness are about 0.7mm.These resins are also added to curing agent, after cured, remove the limit of the protective shell of tab (23.1) and gas relief cavity The protection process sleeve for pressing safety valve installing port (26.8), installs pressure-limiting safety valve (26.9) (referring to Figure 17).So far, work is encapsulated Sequence terminates.Since pressure-limiting safety valve uses the safety valve of the prior art, which is not described herein again.

Subsequently it is necessary to carry out pole plate chemical conversion and several charge and discharge recycled to it on product test frame, make same It is the active material of lead sulfate, high activity β type lead oxide is reduced into anode, in cathodic reduction at lead sponge.It will when charging Charge power supply electrode line is connected in "+number " output pole plate (22), and the negative line of charge power supply is connected to "-number " output pole plate (24) On.

Before uncharged after finalization of the manufacture, without the positive and negative anodes that electrochemistry is specified, only after charging, with charge power supply The connected output electrode of anode is just at the anode of battery pack, and the output electrode being connected with power cathode, just at battery The cathode of group.For safety easy to use, when charging the electrode line of charger should be connected to battery pack of the present invention+number output stage On the tab of plate, and charge power supply negative line be connected to-number output pole plate tab on.

Claims

1. a kind of bipolar plate-shaped unit high-energy lead-acid battery, it is characterised in that: unit high-energy lead-acid battery includes that electronic conductor is double Pole plate (15), the positive and negative electrode primary active material layer (20) that two sides is respectively coated are the same activity based on lead sulfate Material, wherein battery separator (19) are re-layed on active material layer on one side；

The active material layer (20) of electronic conductor bipolar plates (15) two sides is with a thickness of 0.15-0.3mm；Active material layer (20) It is made of lead sulfate, additive, with lead-acid battery colloidal electrolyte by active material mix at cream；

The electronic conductor bipolar plates (15) are that the pure lead of fused solution thermally treated roller again is impregnated by lead plating " stainless steel fibre cloth " It rolls and manufactured composite thin plate；Lamella thickness is 0.02-0.04mm, and the volume ratio of lead and stainless steel fibre is 4 in thin plate: 6。

2. bipolar plate-shaped unit high-energy lead-acid battery according to claim 1, it is characterised in that: the active material is with equal Even thickness is coated on the centre of electronic conductor bipolar plates (15), to electronic conductor bipolar plates (15) uncoated active material Hydrophobic treatment is made in region.

3. bipolar plate-shaped unit high-energy lead-acid battery according to claim 2, it is characterised in that: the active material layer (20) area being coated with is less than the area of electronic conductor bipolar plates (15), and edge hangs down with electronic conductor bipolar plates (15) edge Straight distance is 0.4-3mm.

4. bipolar plate-shaped unit high-energy lead-acid battery according to claim 2, it is characterised in that: the battery separator (19) For the AGM diaphragm after the immersion of lead-acid battery colloidal electrolyte, and its rectangular dimension and electronic conductor bipolar plates (15) Size is identical, and wherein membrane thicknesses are 0.2-0.4mm.

5. a kind of series connection bipolar plates lead-acid battery group, it is characterised in that: it is the battery pack (25) of 2NV for output voltage, it is described Battery pack includes that N-1 bipolar plate-shaped unit high-energy lead-acid battery series connection as claimed in claim 4 are piled up, and battery pack is piled up suitable Sequence is the one side and another bipolar plates list in any two adjacent bipolar template unit high-energy lead-acid battery, with AGM diaphragm First battery is now connected without active material layer (20) face paste consolidation of diaphragm, and all four side of element cell alignment are filled in upper surface Upper gas relief cavity (26) is then referred to as the output polar plate group of "+number " (22), "-number " (24) into battery pack with 2 again.

6. the packaging method of series connection bipolar plates lead-acid battery group described in a kind of claim 5, it is characterised in that:

1) clamped using the battery pack (25) that tooth holder (27) form series connection, fixture (27) contact be "+number " (22), "- Number " the output pole plate of (24), after clamping, using the two sides and bottom surface of acidproof insulated paint spraying battery pack, insulated paint is full Active material layer (20) edge makes each unit battery to the space at electronic conductor bipolar plates (15) edge in each element cell Sealed insulation paint is connected, and forms the pre-sealed of element cell；

2) after pre-sealed solidification, it is attached to the face for being coated with insulated paint with high strength fibre cloth, is then let out gas using strap Protective shell (26.c) is put to be fixed on upper surface；

3) by the tooth mouth (29) of tooth holder, using high strength fibre strap (32) by the electricity including output electrode plate Chi Dui carries out multiple tracks and ties up, and will tense per winding together, heat and take envelope, battery pack can be still maintained after removing fixture Pressure between internal polar plate；

4) using the high-intensity fiber for speckling with uncured resin, electricity is uniformly taken up in the region of not strap along the direction of strap Pond group, smooth, smooth high-intensitive shell is formed after resin solidification and reinforce high strength fibre cloth be used to protect together it is pre- close The insulating lacquer layer of envelope；

5) to above-mentioned steps 4) processing after battery pack output draw tab and gas relief cavity protective cover outlet carry out tooling guarantor After shield, by battery pack mass-impregnation resin and solidify, the tooling protection for dismantling above-mentioned after solidification goes out in gas relief cavity protective cover Mouth installation pressure-limiting safety valve, that is, realize the encapsulation of battery pack.

7. the packaging method of series connection bipolar plates lead-acid battery group according to claim 6, it is characterised in that: the gas is let out Chamber surface is put through hydrophobic treatment, a isolation board of the interior element cell number (n-1) equipped with battery pack of gas relief cavity, each isolation Plate is equipped with position-stopping plate, and between the bipolar plates of position-stopping plate partial insertion battery below, position-stopping plate pushes against bipolar plates for limiting Edge, the externally-arranged protective shell of gas relief cavity, protective shell is fixed on outside gas relief cavity by strap, and passes through entirety Resin is immersed to be sealed.