CN101202355A - Long life high capacity bipolar-type pole plate lead acid battery for electric automobile - Google Patents

Long life high capacity bipolar-type pole plate lead acid battery for electric automobile Download PDF

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CN101202355A
CN101202355A CNA2006101713016A CN200610171301A CN101202355A CN 101202355 A CN101202355 A CN 101202355A CN A2006101713016 A CNA2006101713016 A CN A2006101713016A CN 200610171301 A CN200610171301 A CN 200610171301A CN 101202355 A CN101202355 A CN 101202355A
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pole plate
lead
conductive
battery
bipolar
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夏振明
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    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50Manufacturing or production processes characterised by the final manufactured product
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02TCLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00Road transport of goods or passengers
    • Y02T10/60Other road transportation technologies with climate change mitigation effect
    • Y02T10/70Energy storage systems for electromobility, e.g. batteries

Abstract

The invention provides a dual-pole polar plate lead-acid accumulator with long service life and high capacity used for an electric vehicle. A polar plate group consists of a dual-pole polar plate, an upper end polar plate, a lower end polar plate and a clapboard; the polar plate group is arranged in a battery frame which presses the polar plate group and gives a suitable pressure to active matter. The invention is technically characterized in that one surface of an anode of a baseplate of the dual-pole polar plate is provided with a conductive needle and one surface of a cathode is provided with a conductive column; furthermore, electrode modification is carried out for the baseplate and the conductive needle. After the modification, the specific capacity of the battery is 45-50Wh/kg, which is improved by 20%-30% compared with the existing normal battery. The design service life is 3-8 years, which is improved 2-3 times compared with the normal battery. The battery is mainly used for electric vehicles, electric bicycles, etc., as power supplies, and can be also used for all sites where the existing normal lead-acid batteries are applied.

Description

Long life high capacity bipolar-type pole plate lead acid battery for electric automobile
Technical field:
The present invention relates to a kind of lead acid accumulator, mainly be used as the electrical source of power of electric motor cars such as electric automobile, electric bicycle, electric motorcycle.
Background technology:
Since the automobile invention, car has just become people's main individual walking-replacing tool, but the high pollution of fuel automobile, the exhaustion of whole world petroleum resources, force the mankind to seek a kind of new walking-replacing tool of environment amenable sustainable development, so electric automobile becomes first-selection, by present development, it has been to fire trend that electric automobile replacement fuel-engined vehicle becomes city, the big city main riding instrument of individual.Vehicle body in the electric automobile four big parts, motor and control system, quick charging system three technology partly is all ripe, has only the technology of the 4th part storage battery not reach a standard.The used for electric vehicle battery technology is the key of restriction electric automobile development.
The storage battery that meets the requirement of used for electric vehicle storage battery will possess following three performances: the firstth, and high power capacity, the secondth, the long-life, the 3rd is low-cost.The main kind that is selected as the used for electric vehicle storage battery at present has Ni-MH battery, lithium ion battery, lead-acid battery, preceding two kinds of batteries can be accomplished the high power capacity of battery specific energy 60-120WH/kg, the life-span soprano can reach 1000 to 2000 dark circulations, realized that battery life and electric automobile life-span are synchronous, this binomial performance meets the requirement of used for electric vehicle accumulator property fully, but limited by the battery raw material cost, more than two production cost of cells high, the photocell cost will surpass the fuel-engined vehicle price, and the electric automobile that is disposed is unable to be competed with fuel-engined vehicle.The manufacturing cost of lead-acid battery has only 1/5th of above-mentioned two battery, but its capacity has only the 30-40WH/kg life-span to have only 350-500 dark circulation, and the electric automobile of configuration is also unable to be competed with fuel-engined vehicle.But the theoretical capacity of lead-acid battery reaches 12-15 the designed life of tubular type lead-acid battery up to 175WH/kg, and dark cycle-index surpasses 2000 times, so the room for promotion of lead-acid battery capacity and life performance is very big.If can increase substantially the capacity and the life-span of lead-acid battery, the lead-acid battery electric automobile is to be expected to become the vehicle of eliminating fuel-engined vehicle most.
For improving the capacity and the life-span of lead-acid battery, with respect to the plain edition lead-acid battery, people have developed the light-type grid lead-acid battery, second generation new products such as spirally wound lead acid battery and bipolar-type pole plate lead acid battery, and the present invention is the correction to existing bipolar-type pole plate lead acid battery.
U.S. Pat P5916709 discloses a kind of bipolar-type pole plate lead acid accumulator, and this battery improves 20~25% than the specific capacity of conventional batteries.Life-span prolongs 40~50%, is fit to quick charge, becomes the founder of bipolar-type pole plate storage battery.Thereafter the bipolar-type pole plate technology has all obtained application in lithium ion battery, lead-acid battery and Ni-MH battery field.China's patent disclosure two sections of bipolar-type pole plate lead acid accumulators, the first " flat lead-acid accumulator ", patent publication No.: CN1331500, content is a kind of flat lead-acid battery, comprise housing, dividing plate, positive/negative plate, positive/negative plate is made up of substrate and positive negative active material, positive negative active material layer is respectively attached to a side and the opposite side of substrate, dividing plate places in the middle of the positive/negative plate, sealing between each battery unit is to be provided with framework, total shell adopts covered plastics layer, and the relative United States Patent (USP) of this patent is not seen substantial novelty.Second is " horizontal bipolar type lead acid accumulator and bipolar plates thereof " patent No.: 200410014945.5, see figure one, feature is: wear the volume lead-sheathing on the employing plastic plate and mould core compound wire or lead coated carbon fibre core compound wire replacement titanium plate or the corrosion resistant plate conduction central layer as bipolar plates, and at conduction central layer surrounding frame arranged outside elastic sealing ring, each element cell has been realized elastic packing, has improved the reliability of galvanic circle.U.S. Pat P5916709 has the novelty on the progressive meaning relatively.
But there is following shortcoming in existing bipolar-type pole plate:
1. the anodal one side oxide etch of substrate (or claim central layer): be used in the titanium plate of making substrate or corrosion resistant plate in the battery use, the surface forms mixed oxides such as titanium oxide or chromium oxide easily, further developing the resistance that can make contact-making surface between substrate and the positive electrode active material layer increases, can form insulating barrier when serious, battery is scrapped; Volume expands behind titanium plate, the corrosion resistant plate surface oxidation simultaneously, and the jack-up positive active material disengages active material and substrate, when serious active material is come off.If adopt stereotype or lead-sheathing lead to make substrate, the metallic lead of an anodal substrate is oxidized to various plumbous derivatives, becomes the β-PbO that duplicates in positive active material at last 2Mixture can not form insulating barrier according to many materials between substrate and active material, but because of the inconsistency of its oxide etch at substrate surface, also can the jack-up positive electrode active material layer, and it is come off; Behind the seriously corroded, substrate is attenuation gradually, because substrate surface simultaneously produces oxidation reaction, one side produces reduction reaction, and substrate can not bored a hole in theory, but after the sulfation of reduction one side some areas, in the time of can not producing reduction reaction, the substrate leakage of also boring a hole makes battery short circuit and lost efficacy.
2. in existing bipolar-type pole plate lead acid battery system, battery cathode is velvet-like sponge lead, and substrate is a metallic object, and electric conductivity is good, and anode is β-PbO 2Multiple lead oxide mixture in the majority is a kind of semi-conducting material; Produce lead sulfate micro-crystallization layer respectively on anodal and negative electrode active material surface during battery discharge, form five-layer structure.When the battery heavy current is discharged, the active material on anodal surface should produce electric current with sulfuric acid reaction, bear the migration of the electric current that faces the battery unit generation mutually again and carry, its anodal surface discharge current density ratio plain edition pole plate is big, and the electrode overpotential increases, the lead sulfate crystal that causes being produced attenuates, the lead sulfate crystal layer is fine and close to be arranged, and resistance increases, and causes positive electrode active material utilization to reduce, also might make the battery heating, can produce the multiple sequelae of battery thus.In addition at the charging initial stage, if with the heavy current charging, electric current must be through two lead sulfate insulating barriers, and a semiconductor layer, battery generate heat even high heat easily, so heavy current charging and discharging when five-layer structure is unfavorable for discharging and during initial charge.
3. behind the battery discharge, form one deck fine crystal sulfuric acid lead layer in battery cathode and positive active material surface, lead sulfate is an insulator, when battery charging and discharging, stop electronics to flow, so when battery charge, electronics passes micro-crystallization sulfuric acid lead layer by electrolyte permeability and contacts just with active material and transmitted.When micro-crystallization sulfuric acid lead layer after producing recrystallization under a certain environment, sealed the electrolyte permeability path, then the electrode charge and discharge ability loses fully, battery failure.This is the ubiquitous sulfation phenomenon of common batteries.When but existing bipolar-type pole plate is produced three layers clearly demarcated, five layers of clearly demarcated structure during use, do not address this problem, on the contrary, because the bipolar-type pole plate battery is the series circuit assembling, when a battery unit wherein produces the sulfation phenomenon, entire cell will be scrapped, so the sulfation waste battery problem of existing bipolar-type pole plate lead acid battery is more serious than common lead-acid battery.
4. in battery discharge procedure, because the inconsistency of environment in each element cell system, may make a certain element cell at first form high resistance, such high resistance, stop other battery unit discharge, the entire cell capacity is reduced, also might make this battery unit that high heat takes place, damage entire cell.
5. battery for electric automobile requires that the long life-span is arranged, and in the best and same life-span of electric automobile, this just requires electric vehicle battery to satisfy the life cycle of 3-8.In very long process, since be subjected to the lead-acid battery electrode liberation of hydrogen, analyse that the air pressure that oxygen causes impacts, heat release is impacted and the existence of inevitable local sulfation phenomenon, make dehydration in the battery unit system, to lose sour phenomenon inevitable, so state-of-the-art maintenance-free lead-acid battery also will carry out full maintenance every half a year, implementation adds water and the charging of desulfuration hydrochlorate, will add acid balance electrolyte sometimes.No matter be the USP5916709 patented technology of the U.S., or Chinese patent: CN1331500 and application number 200410014945.5 all can not add water and add acid and safeguard, add acid if must add water, then must take each battery unit apart, ressemble.
Summary of the invention:
The objective of the invention is: a kind of bipolar-type pole plate lead acid accumulator is provided, make it have the power capacity higher than existing bipolar-type pole plate lead acid battery, longer useful life, better charge-discharge performance, keep the cheap advantage of lead-acid battery stable performance simultaneously, thereby replacement lithium ion battery, Ni-MH battery become the major impetus power supply of electric automobile.
Technical scheme of the present invention is: lead acid accumulator of the present invention is by battery frame, two external terminals, the pole plate group, the glass dividing plate is formed, the pole plate group comprises a upper end pole plate, lower end pole plate and polylith bipolar-type pole plate, can form the 4V-100V battery according to the battery nominal voltage, the quantity of bipolar-type pole plate is the 1-49 piece, usually the lower end pole plate adopts the single face positive active material to be coated with the cream layer, the upper end pole plate adopts the single face negative electrode active material to be coated with the cream layer, the upper end of bipolar-type pole plate scribbles positive electrode active material layer, the lower end scribbles negative electrode active material layer, but also can be provided with on the contrary, but bipolar-type pole plate on, the polarity of lower end active material layer must be opposite.Lower end pole plate, glass dividing plate, bipolar-type pole plate, glass dividing plate, bipolar-type pole plate,,,,,,, glass dividing plate, upper end pole plate arrange overlapping composition pole plate group in order, glass dividing plate is wherein inhaled electrolyte, and with the negative electrode active material of an end, the positive active material of the other end is formed a battery unit, produce the nominal voltage of 2V, in each battery unit, also be provided with the sealed type liquid filling hole that repeatedly to open.The pole plate group is fixed on the battery frame, give the both positive and negative polarity active material in the pole plate group a suitable pressure by the pressure transmission on the framework, the fluid sealant fixing seal is adopted in the slit between each pole plate, also can adopt the rubber seal elastic packing, two external terminals are drawn by upper end pole plate and lower end pole plate respectively, as positive-negative output end of battery.
The structure of above-mentioned bipolar-type pole plate is as follows: the anodal one side at the bipolar-type pole plate substrate is set up the numerous conductive pin of radical, conductive pin is perpendicular to substrate, peace requires to be clouded in the anodal surface of bipolar plates, and its length and positive active material are coated with the cream layer thickness and equate or grow a little a bit; Simultaneously set up a conductive pole at the negative pole of substrate, the cream layer thickness that is coated with of the length of conductive pole and negative electrode active material equates or grows a little a bit; Substrate adopts the metal manufacturing, and the material of recommendation has: titanium, stainless steel, lead and titanium alloy, lead alloy, also can adopt other metal species.Make the technology of substrate, conductive pin and conductive pole and recommend to adopt disposable die casting global formation, perhaps conductive pin separates die cast, and for example conductive pin is made with titanium silk or stainless steel wire, is cast into integral body with lead or stainless steel or titanium again in mould.The diameter of conductive pin and distribution density on substrate and positive active material be coated with the cream layer thickness, the utilance of triadic relation's scalable positive active material, the technology of recommending is, the conductive pin diameter is run business into particular one in the technology allowed band as far as possible, when being coated with the cream layer thickness when thicker, the conductive pin radical use multiple spot, distribution density is got big value, be coated with the cream layer thickness when thin, the conductive pin radical use few point, distribution density is got low value, but the sectional area of conductive pin radical summation should be able to satisfy the impact of the high charge-discharge electric current of entire cell, can not make its heating or burns.Below bipolar-type pole plate is carried out anti-corrosion treatment, make substrate and conductive pin have the technological design life-span of 3-8.Adopt the electrode modification principle that the substrate of the anodal one side of bipolar-type pole plate and conductive pin are plated one deck and conduct electricity inorganic decorative layer, as conductivity ceramics, conductive oxide etc., the material of recommendation has: SnO 2+ Sb 2O 3Or SnO 2+ SbO x+ I rO 3Coating also can adopt the Ti with China's independent intellectual property right 3SiC 2Be that conductivity ceramics and rare earth infiltrate the titanate conductivity ceramics.Be coated with last layer organic conductive coating with the electrode modification method again outside inorganic layer, the material of recommendation has poly-stupid amine (PAn) conduction high polymer or PAn and the compound conductive plastics of other material, also can adopt other organic conductive material.When organic coating is not dried, the β-PbO through screening in the spraying 2Particle or plumbous particle make the some of particle diameter enter coating and solidify on it, and another partly exposes and is coated with the cream layer with positive active material outside and combines closely.If substrate and conductive pole are cast by non-lead metal, then simultaneously electroplate one deck lead at the base plate strip conductive pole, itself and lead plaster can be combined closely, and the back is coated positive and negative pole lead paste respectively on the two sides of bipolar-type pole plate again, through promptly making ambipolar green plate behind pickling, slaking, the oven dry supervisor.
Anticorrosion only also can the employing of anodal substrate of above-mentioned bipolar-type pole plate and conductive pin modified electrode with one or more layers organic conductive coating, for example anodal one side of substrate and the conductive pin on it are modified poly-stupid amine conduction high polymer or PAn and the compound conductive plastics of other material, and then the identical organic conductive layers of modification one deck thin layer, when coating is not dried, β-PbO in the spraying 2Particle or plumbous particle make the some of particle diameter enter coating, solidify on it, and another partly exposes outside, are coated with the cream layer with positive active material and combine.
Above-mentioned lower end pole plate is formed by substrate with perpendicular to the conductive pin of substrate and topped anode diachylon on conductive pin thereof, the substrate and the conductive pin that need be coated with the cream one side are modified through inorganic conductive layer and organic conductive layers bilayer, also available organic conductive layers single or multiple lift is modified, and implants β-PbO on organic coating 2Particle or plumbous particle are coated the anode diachylon layer again, through pickling, slaking, oven dry.
Above-mentioned upper end pole plate is formed by substrate with perpendicular to conductive pole of substrate and topped cathode lead plaster on conductive pole and substrate thereof, if substrate and conductive pole are formed by non-lead metal die casting, then need on the substrate of conductive pole one side, to modify lead-coat, coat cathode lead plaster again after pickling, slaking, oven dry.
A kind of sealing means of battery unit is in the above-mentioned pole plate group: on metal bipolar-type pole plate substrate four limits compound on plastic frame, the plastic frame thickness of bipolar plates negative pole one side and cathode lead plaster thickness maintain an equal level or are lower slightly, the plastic frame thickness of anodal one side and anode diachylon layer and block board thickness sum maintain an equal level, and the sealed type liquid injection hole that can repeatedly open is set on one side at anodal plastic frame, on plastic frame of negative or positive electrode, lay the thixotropic fluid sealant again, pressure by the battery frame transmission, compressed together the plastic frame of the anodal one side of bipolar-type pole plate facing to the plastic frame of the negative pole one side of another bipolar-type pole plate, wait the glued hard back of sealing to form fixing seal.The said fixing sealing also can change makees elastic packing; Negative pole at plastic frame simultaneously is provided with perforation groove all around, and the elastic washer that acid-proof rubber is done is set in groove, by the pressure that battery frame transmits, realizes elastic packing.
Above-mentioned battery frame is made up of frame container and framework lid, and the frame container wall is with holes, is convenient to the eliminating of the gas that may escape in battery heat radiation and the battery.Frame container and lid are made with plastics, and external terminal is made with copper or other high conductivity metal alloy, and two external terminals are embossed in respectively on frame container bottom and the lid.The pole plate group that will arrange during assembling packs in the frame container, and on battery assembling special hot pressing machine, simultaneously behind the heating and melting, two interface relatively hots force together, and are integrator after the cooling frame container interface and cap interface.
The hot pressing of above-mentioned battery frame will be held the pressure limit of hot press, after the butt joint cooling, makes battery frame press the pole plate group, and this pressure is passed to each both positive and negative polarity active material in the pole plate group, gives active material certain initial pressure.
Because there is error in every electrode thickness when producing, be difficult to guarantee that battery frame is hot-forming after, give the consistency of the pressure that every battery transmits.The pressure micromatic setting is set on the external terminal of said frame lid for this reason, and this device is mainly by spring with regulate contact and forms, and is used for guaranteeing the consistency of the initial pressure of every inside battery active material.
Sealed type liquid injection hole in the above-mentioned pole plate group is arranged at the same side of battery.
Storage battery of the present invention adopts battery to change into mode, after the battery assembling, inject excessive rare electrolyte, adopt the common formation charging mode of common batteries, change into end after, with the unnecessary electrolyte of certain vacuum degree sucking-off, adjust charging again, to set up " oxygen cycle " system of inside battery, seal again after finishing, the sealing-type lead-acid battery.
Storage battery of the present invention is safeguarded once every half a year, it is excessive to electrolyte to open sealing filling pure water (distilled water) when safeguarding, after carrying out common maintenance charging, measure each battery unit electrolyte inside density, and be adjusted to standard, with the unnecessary electrolyte of certain vacuum degree sucking-off, adjust charging again, to set up " oxygen cycle " system of inside battery, seal again after finishing.
The good effect that the present invention has has:
1. by the electrode modification on the anodal surface of bipolar-type pole plate is handled, effectively improved the anti-corrosion capability of an anodal substrate and conductive pin, adopt different electrode modification modes, can make the antiseptic power of electrode base board and conductive pin reach the requirement in useful life of 3-8.
2. owing to be provided with conductive pin and conductive pole on electrode base board, when battery charge, electric charge enters each battery unit by conductive pin and conductive pole, is uniformly distributed in every polar board surface, is beneficial to carry out large current charge when initial charge, shortens the charging interval.When battery discharge, the electric current that faces battery unit mutually and produced can transmit along separate routes by conductive pin and conductive pole, and need not through the electrode surface in the five-layer structure: as two layers of lead sulfate insulating barrier and one deck lead oxide semiconductor layer, reduced the electrode surface discharge current density, reduce the generation probability of electrode sulfation, reduced the possibility of electrode heating.Fundamentally solved the single battery cell resistance and increased and influence the discharge of other battery unit, and single battery unit sulfation is scrapped the problem of entire cell.
3. because conductive pin is uniformly clouded in the positive active material, increased the conductance of positive active material, the corresponding utilance that improves positive active material.Have again, conductive pin and conductive pole can make electrode surface uniform charging and evenly discharge, particularly evenly discharge, reduced the electrode surface discharge current density, can improve the depth of discharge of electrode under the heavy-current discharge environment, also improve positive electrode active material utilization, also have, conductive pin and conductive pole can make each battery unit fully discharge, and can not keep.All of these factors taken together all makes bipolar-type pole plate lead acid battery of the present invention than existing homotype battery higher capacity be arranged.
4. the present invention has applied an initial pressure by battery frame to the both positive and negative polarity active material of pole plate, this pressure has stoped the expansion in the active material course of work, stop and delay the formation and the collapse of coralliform structure in the active material, make the active material of dull and stereotyped paste spread type positive plate have the operational environment that is equal to tubular type positive plate active material, make the useful life of positive active material of the present invention, near the useful life of tubular plate positive active material, reach the requirement of battery life 3-8.
5. battery of the present invention has been realized hermetically sealed, but can be the same with common completely-sealed lead-acid battery can periodic maintenance, guaranteed the dependability of battery of the present invention.
Description of drawings:
Fig. 1 is China's patent, application number: 200410014945.5 schematic diagram.
Fig. 2 is a bipolar-type pole plate structure chart of the present invention.11 substrates, 12 positive electrode active material layers, 13 negative electrode active material layers, 14 conductive poles, 15 plastic frames, 16 liquid injection holes among the figure.
Fig. 3 is the mansion view of Fig. 2, and 17 mould reinforced hole again among the figure.
Fig. 4 is an A portion enlarged drawing among Fig. 2 of the present invention.18 conductive pins among the figure.
Fig. 5 is lower end electrode plate structure figure of the present invention.
Fig. 6 is the present invention upper end electrode plate structure figure.
Fig. 7 is a lead-acid battery installation diagram of the present invention.2 lower end pole plates, 3 upper end pole plates, 4 dividing plates, 5 frame container, 6 framework lids, 7 docking ports, 8 external terminals, 9 battery frames, 10 bipolar-type pole plates among the figure.
Fig. 8 is a B portion enlarged drawing among Fig. 7,19 rubber stoppers among the figure.
Fig. 9 is Fig. 7 C of the present invention portion amplification assumption diagram.81 regulate contact, 82 springs, 83 fixed covers, 84 motion bars, 85 contact base plates among the figure.
Describe embodiment in detail below in conjunction with embodiment.
Embodiment one: bipolar-type pole plate (10)
See Fig. 2, Fig. 3, Fig. 4, bipolar-type pole plate (10) is made up of substrate (11), conductive pin (18), conductive pole (14), positive electrode active material layer (12), negative electrode active material layer (13) and plastic frame (15).
Once the property extrusion has the part in addition of conductive pin (18), conductive pole (14), substrate (11) disjunctor on die casting machine, for ease of composite plastic frame (15) around substrate (11), sets up a plurality of reinforced holes (17) of moulding again around substrate (11).The thickness of substrate (11) is done thin under technology allows as far as possible, and the thickness of recommendation is 1-0.1mm, and the material of substrate (11) can adopt all metals with conductive capability and forming ability, recommends to adopt lead, titanium, stainless steel and lead alloy, titanium alloy material.For adapting to the corrosive environment of these materials in electrolyte, adopt the electrode modification principle that material surface is carried out preservative treatment.At first, with inorganic conductive material electrode modification is carried out on the surface with conductive pin (18) one side of substrate (11), inorganic conductive material recommends to adopt SnO 2+ 5b 2O 3Or SnO 2+ SbO x+ I rO 3, also can adopt Ti with China's independent intellectual property right 3SiC 2Be that conductivity ceramics or rare earth infiltrate the titanate conductivity ceramics, the second, outside the inorganic conductive material layer, modify one deck organic conductive layers again, the material of recommendation has: PAn conduction high polymer or PAn and the compound conductive plastics of other material.If substrate (11) is non-lead metal casting, then have the negative pole one side lead plating of conductive pole (14) at substrate (11), be convenient to substrate (11) surface and combine for a long time with negative electrode active material layer (13) from now on.The 3rd, at the compound plastic frame (15) of going up of substrate (11) four limits periphery, show as Fig. 2, plastic frame (15) is bigger at positive pole one face thickness that substrate (11) has conductive pin (18), and a liquid injection hole (16) is set thereon, and the 4th, modify last layer thin PAn conduction high polymer or PAn conductive plastics in the anodal one side of substrate (11) band conductive pin (18) again, when coating is not dried, β-PbO in the spraying 2Particle or plumbous particle make the some of grain diameter enter organic conductive layers, and dry after coagulation is on it, and another partly exposes outside organic conductive layers with the lead plaster layer of coated from now on and combines.The back has a coated positive active material of the positive pole lead plaster layer (12) of conductive pin (18) at substrate (11) again, at substrate (11) band (14) coated negative electrode active material layers of conductive pole (13), by pickling, slaking, oven dry, promptly make bipolar-type pole plate (10) green plate again.
Embodiment two: bipolar-type pole plate (10).
Second embodiment of bipolar-type pole plate (10) is: conductive pin (18) is independent to be made, and material is got titanium or titanium alloy, stainless steel, also other metals such as desirable copper, aluminium.Conductive pin (18) is placed in the mould, with motlten metal die casting substrate (11) and conductive pole (14), conductive pin (18), substrate (11) and conductive pole (14) are cast into integral body, and motlten metal is recommended with lead, titanium or their alloy and stainless steel, and implementation process is with embodiment one thereafter.
Embodiment three: bipolar-type pole plate (10)
The 3rd embodiment of bipolar-type pole plate (10) is: after the anodal one side of substrate (11) band conductive pin (18) is modified inorganic conductive layer is composite plastic frame (15), and comparative examples one has been cancelled the trim of one deck organic conductive layers.Other implementation process is identical with embodiment one.
Embodiment four: bipolar-type pole plate (10)
Comparative examples one, the embodiment of the invention have been cancelled the inorganic conductive decorative layer of the anodal one side of substrate (11) band conductive pin (18), promptly only with one or more layers organic conductive decorative layer the anodal one side of substrate (11) band conductive pin (18) are modified.Implementation process is: after obtaining to have substrate (11), conductive pin (18), conductive pole (14) integral die-cast part, anodal one side to substrate (11) band conductive pin (18) is coated with last layer PAn conduction high polymer or PAn conductive plastics in the modified electrode mode, again to substrate (11) composite plastic frame (15) all around.Thereafter implementation process is identical with embodiment one.
Embodiment five: upper end pole plate (3).
Upper end pole plate (3) is made up of substrate (11), conductive pole (14), negative electrode active material layer (13), plastic frame (15).Substrate (11) and conductive pole (14) join together, by the die cast metal moulding.The material of recommending has: lead, titanium, stainless steel, also available other metal.The substrate (11) of substrate (11) contrast bipolar-type pole plate (10) increases certain thickness, and the thickness of recommendation is 1-3mm.If substrate (11) is non-lead material casting with the material of conductive pole (14), then electroplates and go up lead-coat in substrate (11) band conductive pole (14) one side.Back negative electrode active material layer (13) lead plaster on (14) coateds of substrate (11) band conductive pole again, through pickling, slaking, oven dry upper end pole plate (3) green plate.
Embodiment six: lower end pole plate (2).
Lower end pole plate (2) is made up of the liquid injection hole (16) on substrate (11), guide pin (18), positive electrode active material layer (12), plastic frame (15) and the plastic frame (15).Substrate (11) and the whole continuous casting of conductive pin (18) form or conductive pin (18) is put in the mould and is cast into integral body with substrate (11).The substrate of recommending during continuous casting (11), conductive pin (18) material lead, titanium and their alloy thereof, also available stainless steel.The material of conductive pin (18) is recommended with titanium, stainless steel during the branch casting, the material of substrate (11) lead, titanium and their alloy thereof, stainless steel.Substrate (11) thickness of lower end pole plate (2) is got 1-3mm.Comparative examples one, embodiment three, embodiment four, when the anodal one side of bipolar-type pole plate (10) adopted that a kind of electrode modification mode, the anodal one side of substrate (11) the band conductive pin (18) of lower end pole plate (2) also adopted the sort of modification mode, must be synchronously.After finishing electrode modification, at the compound all around plastic frame (15) of going up of substrate (11), and liquid injection hole (16) is set on plastic frame (15), the back has positive electrode active material layer (12) on (18) coateds of conductive pin at substrate (11) again, through pickling, slaking, oven dry lower end pole plate (2) green plate.
Embodiment seven: battery frame (9).
Battery frame (9) is made up of frame container (5), container lid (6), docking port (7) and two external terminals (8) of being fixed on the battery frame (9).An external terminal (8) is fixed on the mould, frame container (5) is made in injection moulding in mould, again another external terminal (8) is fixed on the mould, framework lid (6) is made in injection moulding in mould, on frame container (5) and framework lid (6), be respectively equipped with the docking port (7) of a protrusion, be used for frame container (5) and dock, form battery frame (9) with the hot pressing of framework lid (6).
Embodiment eight: external terminal (8).
The external terminal (8) of frame container (5) bottom adopts fixed, and the external terminal (8) of framework lid (6) upper end adopts movable composition micromatic setting.Structure such as Fig. 9 of movable external terminal (8) show that external terminal (8) is made up of adjusting contact (81), spring (82), fixed cover (83), motion bar (84), contact base plate (85).Be fixed on the container lid (6) during fixed cover (83) injection moulding, motion bar (84) microcephaly is inserted fixed cover (83) to be screwed on the contact base plate (85), in motion bar (84), put into spring (82), adjusting contact (81) is screwed on the fixed cover (83) promptly finishes assembling again.The effective length scalable of motion bar during work (84) and remedy pole plate group height error, regulating contact (81) rotates when moving downward or upward, pressure by spring (82) with contact base plate (85) and the pole plate group is applied or reduce pressure, thereby metering needle is to the initial pressure of active material.
Embodiment nine: lead-acid battery.
See Fig. 7, on a plastic frame of positive pole (15) edge of lower end pole plate (2) and every bipolar-type pole plate (10), evenly smear fluid sealant, again lower end pole plate (2), glass dividing plate (4), bipolar-type pole plate (10), glass dividing plate (4), bipolar-type pole plate (10), glass dividing plate (4), upper end pole plate (3) is arranged overlapping composition pole plate group in order, again the pole plate group is packed in the frame container (5), on battery assembling special hot pressing machine, behind docking port (7) heating and melting of docking port of frame container (5) (7) and framework lid (6), two docking ports (7) relatively hot forces together, and is integrator after the cooling.The pressure limit that the hot pressing of battery frame (9) will be held hot press, and this pressure passed to each positive electrode active material layer (12) in the pole plate group by in type battery frame (9), give positive active material (12) suitable initial pressures.Because when producing each piece pole plate, there is error in electrode thickness, cause pole plate group's overall error height bigger, be provided with micromatic setting in the external terminal (8) on framework lid (6) for this reason and see Fig. 9: pole plate group's height error is by the automatic revisal of effective length of motion bar (84), and hypertonia that hot press transmits or mistake low pass overwinding modulation joint contact (81) give revisal.When need sealing, each battery unit on liquid injection hole (16), fills in rubber stopper (19), can inject warm modification adhesive in rubber stopper (19) bottom surface all around in case of necessity, when temperature is lower than 60 ℃, adhesive has adhesive action, adhesive loses adhesive action when being higher than 60 ℃, rubber stopper (19) just can be opened, the purpose that realization can open repeatedly and seal.The present embodiment lead-acid battery adopts the cassette assembling when the assemble group, save the connection electric wire, can vertically install, and also can install sidewards.
Embodiment ten: lead-acid battery.
On a plastic frame of negative pole (15) of upper end pole plate (3) and every bipolar-type pole plate (10), open perforation groove all around, in groove, place the O type packing ring made from acid-resisting rubber, again lower end pole plate (2), glass dividing plate (4), bipolar-type pole plate (10), glass dividing plate (4), bipolar-type pole plate (10), glass dividing plate (4), upper end pole plate (3) is arranged overlapping composition pole plate group in order, the pole plate group is packed in the frame container (5), hot pressing upper frame lid (6), battery frame (9) is gone up the pressure that transmits and was both provided elastic packing for each battery unit, for each positive electrode active material layer (12) in the pole plate group provides certain initial pressure, implementation process thereafter is identical with embodiment nine again.

Claims (11)

1. bipolar-type pole plate lead acid accumulator, by the upper end pole plate, bipolar-type pole plate, the lower end pole plate, the glass dividing plate is formed the pole plate group, the pole plate group is installed in the battery frame, positive-negative output end of an external terminal as battery respectively is set at the two ends of battery frame, its critical component bipolar-type pole plate is made up of substrate and the positive electrode active material layer and the negative electrode active material layer that are attached to the substrate two sides, its technical characterictic is: the anodal one side of lower end pole plate and the anodal one side of bipolar-type pole plate are provided with conductive pin, the negative pole one side of upper end pole plate and the negative pole of bipolar-type pole plate simultaneously are provided with conductive pole, and battery frame presses the pole plate group, and positive active material in the pole plate group has been applied initial pressure.
2. lead-acid battery according to claim 1 is characterized in that: conductive pin is uniformly clouded in the anodal one side of lower end pole plate and the anodal one side of bipolar-type pole plate perpendicular to substrate, and conductive pin length equates with positive active material lead plaster layer, also can grow a bit; Value range 0.1mm-0.5mm, the diameter of conductive pin fill in process conditions and are permitted to run business into particular one down as far as possible, and value range is got 0.01mm-5mm; The conductive pin distribution density is got high value as far as possible under the situation that guarantees the positive active material capacity, value range is got every square centimeter 1 to 100.
3. lead-acid battery according to claim 1, its technical characterictic is: conductive pole is perpendicular to substrate, be arranged at the negative pole one side of upper end pole plate and the negative pole one side of bipolar-type pole plate, the conductive pole height equates with negative electrode active material lead plaster layer thickness, also can grow a bit, value range 0.1mm-0.5mm, conductive pole diameter span is 0.1mm-5mm.
4. lead-acid battery according to claim 1, it is characterized in that: in the anodal one side of lower end pole plate and the anodal one side of bipolar-type pole plate, with the electrode modification method substrate and conductive pin are modified the last layer inorganic conductive layer, decorative material is got conductivity ceramics or conductive oxide.
5. lead-acid battery according to claim 1, its technical characterictic is: modify the last layer organic conductive layers with the electrode modification method again outside inorganic conductive layer, decorative material is got conduction high polymer or conductive plastics.
6. lead-acid battery according to claim 1 is characterized in that: when organic conductive layers is not dried, and β-PbO in the spraying 2Particle or plumbous particle make the some of particle diameter enter organic conductive layers, fix after the drying on it, and another partly exposes outside, combine with the positive active material lead plaster.
7. lead-acid battery according to claim 1, its technical characterictic is: battery frame is made up of frame container and framework lid, frame container bottom, framework lid top portion are not provided with an external terminal, the pole plate group is installed in the frame container, become whole with the heat smelting crimp connection of framework lid docking port by frame container, when frame container and the heat seal of framework lid, hot press passes to battery frame to pressure, battery frame presses positive electrode active material layer, gives positive active material an initial pressure.
8. lead-acid battery according to claim 1, its technical characterictic is: the external terminal of framework cap top is made up of adjusting contact, spring, motion bar, fixed cover, contact base plate, be fixed on during the fixed cover injection moulding on the framework lid, motion bar passes fixed cover and is screwed on the contact base plate, in motion bar, place spring, be screwed on the fixed cover regulating contact, regulating contact rotates when moving downward or upward, pass to pole plate group by motion bar to the contact base plate by spring handle pressure, implement pressurization or step-down, give positive active material a suitable pressure.
9. lead-acid battery according to claim 1, its technical characterictic is: the effective length of motion bar is used for regulating the electrode thickness error, and its length is with the change of pole plate piece number, and value range is 5mm-50mm.
10. lead-acid battery according to claim 1, its technical characterictic is: run through answering of substrate in substrate setting all around and mould enhancing hole, aperture φ 1-φ 10, the mm of unit.
11. lead-acid battery according to claim 1, its technical characterictic is: respectively open a liquid injection hole in anodal one side of each bipolar-type pole plate plastic frame and the anodal one side of lower end pole plate plastic frame, dispose rubber stopper on the liquid injection hole, after rubber stopper clogs liquid injection hole, around warm modification adhesive sealing rubber stopper base, realize the repeatedly unlatching and the sealing of each battery unit.
CNA2006101713016A 2006-12-15 2006-12-15 Long life high capacity bipolar-type pole plate lead acid battery for electric automobile Pending CN101202355A (en)

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