CN104205430A

CN104205430A - Nickel-zinc rechargeable pencil battery

Info

Publication number: CN104205430A
Application number: CN201380014166.2A
Authority: CN
Inventors: J·菲利普斯; S·莫罕塔; C·马斯克
Original assignee: PowerGenix Systems Inc
Current assignee: PowerGenix Systems Inc
Priority date: 2012-02-07
Filing date: 2013-01-29
Publication date: 2014-12-10
Also published as: WO2013119422A1

Abstract

A rechargeable pencil battery has a hollow cylindrical positive electrode including nickel hydroxide; a gelled negative electrode comprising at least one of zinc and a zinc compound; a separator interposed between the hollow cylindrical positive electrode and the gelled negative electrode; and a negative electrode current collector inserted into the gelled negative electrode. Rechargeable batteries of the invention are capable of between about 50 and 1000 cycles from a fully charge state to a fully discharged state at a discharge rates of about 0.5C or greater, in some embodiments about 1C or greater. Batteries of the invention have a ratio of length to diameter of between about 1.5:1 and about 20:1, and therefore can be longer than typical commercially available batteries but also include batteries of commercial sizes e.g. AAAA, AAA, AA, C, D, sub-C and the like.

Description

Nickel zinc rechargeable pencil formula battery

The cross reference of related application

That the application requires is that on February 7th, 2012 submits to, application number is 61/595,955, title is the rights and interests of the U.S. Provisional Patent Application of " NICKEL-ZINC RECHARGEABLE PENCIL BATTERY " (act on behalf of case number for PWRGP038P2), by reference its full content is herein incorporated and for all objects at this.The application submits on October 12nd, 2010, application number is 12/903, 004, title is the part continuation application of the U.S. Patent application of " CYLINDRICAL NICKEL-ZINC CELL WITH POSITIVE CAN " (acting on behalf of case number is PWRGP041), it requires on October 13rd, 2009 to submit to, application number is 61/251, 222, title is the rights and interests of the U.S. Provisional Patent Application of " CYLINDRICAL NICKEL-ZINC CELL WITH POSITIVE CAN " (acting on behalf of case number is PWRGP041P), by reference their full content is herein incorporated and for all objects at this.

Background technology

The disclosure is about nickel-zinc cell.More particularly, about the composition for nickel zinc rechargeable battery, structure and manufacture method.

Recent economic trend shows the needs to high power and high-energy-density rechargeable battery, especially for the application such as motor vehicle and electric tool.Economic trend also shows the needs of the rechargeable battery to cheapness, quick charge.Adopt some aqueous batteries of nickel hydroxide positive electrode and zinc-base negative electrode to meet these needs.

The composition of nickel-zinc cell and manufacture method affect their business success.Need to reduce costs and simplified manufacturing technique is applicable to the nickel-zinc cell of motor vehicle (EV), plug-in hybrid electric vehicle (PHEV), consumption electronic products and other application to produce.

Summary of the invention

In one aspect, embodiment, about rechargeable pencil formula battery, is characterized in that herein: the hollow cylinder positive electrode that comprises nickel hydroxide; Comprise at least one the gelling negative electrode in zinc metal and zinc compound; Be inserted in the spacer between hollow cylinder positive electrode and gelling negative electrode; Negative electrode current collector in gelling negative electrode; Hold the battery can of cylindrical positive electrode, gelling negative electrode, spacer and negative electrode current collector, wherein battery can comprises first end and the second end of opening; And be fixed to the positive cover of the second end of battery can.In certain embodiments, the ratio of the length of rechargeable battery and the diameter of rechargeable battery is at least about 1.5:1, and is between about 2:1 and about 20:1 in certain embodiments, between about 1.5:1 and 10:1 or between about 1.5:1 and 5:1.In certain embodiments, cell diameter is between about 5mm and about 100mm.In certain embodiments, the ratio of battery length and cell diameter is greater than about 5:1 and diameter between about 10mm and 100mm.In other embodiments, the ratio of battery length and cell diameter is greater than about 5.5:1 and diameter between about 10mm and 50mm.The battery of this aspect is longer than commercially available battery in typical market, but embodiment herein also comprises the battery of commercial size, for example AAAA, AAA, AA, C, D, inferior C etc.In some implementations, the hollow diameter of cylindrical positive electrode and the ratio of cell diameter are (for example, between about 0.5-0.9, between about 0.6-0.85 or between about 0.6-0.7) between about 0.4-0.95.

In some implementations, hollow cylinder positive electrode is multiple stacking ring segments.In some instances, hollow cylinder positive electrode can comprise nickel hydroxide and cobalt metal and/or cobalt compound, and it can comprise the first conductive agent.The first conductive agent can comprise at least one in nickel, carbon, conducting polymer and conductivity ceramics.In certain embodiments, the first conductive agent adopts the form of powder, foam, fiber or their combination.Hollow cylinder positive electrode can comprise binding agent, and in certain embodiments, binding agent can comprise polytetrafluoroethylene (PTFE), cellulose, carboxymethyl cellulose (CMC) and Hydroxypropyl methylcellulose (HPMC).Further, hollow cylinder positive electrode can comprise irrigation, and in certain embodiments, irrigation comprises at least one in aluminium oxide, cellulose and water wetted material.In certain embodiments, the thickness of the ring of hollow cylinder positive electrode (that is, between the outer radius of ring and inner radial poor) is between about 1.5-2.5mm, or between about 2.1-2.5mm.

In some instances, gelling negative electrode can comprise the solid mixture, alkaline electrolyte and the second conductive agent that combine with gelling agent.Solid mixture can comprise zinc and zinc oxide.In some implementations, solid mixture comprises at least one in aluminium oxide, cellulose and newsprint.In a particular embodiment, solid mixture comprises the zinc oxide of weight between the zinc of weight between about 0%-30% and about 65%-100%.In some implementations, solid mixture comprises the cellulose between about 0.5-5%.Solid mixture can also comprise the aluminium oxide between about 0.5-5%.In certain embodiments, the second conductive agent can comprise at least one in carbon, titanium nitride and bismuth oxide.In some cases, the second conductive agent can occupy up to about 30% of gelling negative electrode volume.In one embodiment, solid mixture, gelling agent, alkaline electrolyte and the second conductive agent at spacer situ in conjunction with to form gelling negative electrode.In optional embodiment, solid mixture, gelling agent, alkaline electrolyte and the second conductive agent, in conjunction with to form gelling negative electrode, are then introduced gelling negative electrode in spacer.

In some implementations, spacer is tubulose substantially.Spacer can comprise double-layer lamination, and this double-layer lamination comprises barrier layer and wicking layer.In some implementations, barrier layer comprises the microporous barrier of thickness between about 25-75 μ m.In certain embodiments, the thickness of wicking layer is between about 25-200 μ m.Spacer will typically have the highest part.In some implementations, the highest part of spacer is above the highest part of hollow cylinder positive electrode, and the highest part of this hollow cylinder positive electrode is above the highest part of gelling negative electrode.In particular example, the highest part of spacer is above the highest part of hollow cylinder positive electrode between about 2-5mm, and the highest part of this hollow cylinder positive electrode is above the highest part of gelling negative electrode between about 1-5mm.

Negative electrode current collector can comprise at least one in brass, copper and steel, and can comprise liberation of hydrogen inhibitor alternatively.Liberation of hydrogen inhibitor can comprise at least one in tin, lead, bismuth, silver and indium.In some cases, negative electrode current collector can comprise that surface area strengthens geometric element, and these elements can comprise at least one in fin, grid, perforation, spiral, meander configuration, ridge, helix and their combination.In certain embodiments, there is the negative electrode terminal plate that is electrically connected to negative electrode current collector.In some cases, anode collector dish and gelling negative electrode electric connection, and anode collector dish is the smooth surface substantially of serving as the negative terminal of rechargeable battery.

Rechargeable battery can also comprise the identification label that identifies uniquely rechargeable battery and allow its charging of monitoring and/or discharge cycles quantity.In some cases, identification label is bar code.In some implementations, the second end of tank can comprise steam vent.Steam vent can also be arranged in positive cover.

In certain embodiments, rechargeable pencil formula battery comprises the hollow cylinder positive electrode of nickel hydroxide; Comprise at least one the gelling negative electrode in zinc and zinc compound; Be inserted in the spacer between hollow cylinder positive electrode and gelling negative electrode; And insert the negative electrode current collector in gelling negative electrode.Rechargeable battery can be with about 1C or larger discharge rate between approximately 50 from complete charged state to discharge condition completely and 1000 circulations.In certain embodiments, rechargeable battery can be with about 0.5C or larger discharge rate between approximately 50 from complete charged state to discharge condition completely and 1000 circulations.Note, battery described herein goes for the application of low discharge speed or the application of high discharge rate.For example, for low rate application (, about 1/10C is to the discharge rate between 1/3C), the battery of disclosed realization can be replaced more expensive " jellyroll " battery.The battery of this aspect (for example has between about 1.5:1 and about 20:1, between about 1.5:1 and 10:1, between about 1.5:1 and 5:1, be greater than about 5:1 or be greater than about 5.5:1) length and the ratio of diameter, and therefore can be longer than commercially available battery in typical market, but also comprise the battery of commercial size, for example AAAA, AAA, AA, C, D, inferior C etc.In some implementations, the hollow diameter of cylindrical positive electrode and the ratio of cell diameter are (for example, between about 0.5-0.9, between about 0.6-0.85 or between about 0.6-0.7) between about 0.4-0.95.

Another aspect of embodiment is rechargeable pencil formula battery herein, it is characterized in that: hollow cylinder positive electrode, comprise nickel hydroxide (comprising alternatively hydroxy nickel oxide), and cobalt metal and/or cobalt compound; Gelling negative electrode, comprise weight 0% and approximately the zinc between 30%, weight are zinc oxide (, not adding the percentage of the dry weight composition of electrolyte) between approximately 65% and 100%, gelling agent, alkaline electrolyte and at least one in carbon, cellulose, titanium nitride and aluminium oxide alternatively; Be inserted in the spacer of the tubulose substantially between hollow cylinder positive electrode and gelling negative electrode; And negative electrode current collector in gelling negative electrode.The rechargeable battery of this aspect can also be between approximately 25 of the discharge rate taking about 0.5C or larger (in certain embodiments as about 1C or larger) and 1000 full capacitys circulate.The battery of this aspect (for example has between about 1.5:1 and about 20:1, between about 1.5:1 and 10:1, between about 1.5:1 and 5:1, be greater than about 5:1 or be greater than about 5.5:1) length and the ratio of diameter, and therefore can be longer than commercially available battery in typical market, but also comprise the battery of commercial size, for example AAAA, AAA, AA, C, D, inferior C etc.In some implementations, the hollow diameter of cylindrical positive electrode and the ratio of cell diameter are (for example, between about 0.5-0.9, between about 0.6-0.85 or between about 0.6-0.7) between about 0.4-0.95.In certain embodiments, the thickness of ring (, between the outer radius of ring and inner radial poor) is between the thickness of about 1-3mm.In some implementations, hollow cylinder positive electrode can also comprise nickel and/or carbon.

Some aspect of embodiment provides the method for manufacturing rechargeable pencil formula battery herein.In some cases, manufacture method is similar to the manufacture method of conventional alkaline primary cell.In these methods, positive electrode is pressed onto in circlet shape sheet, then sheet is introduced in tank or container as stacking.Thereby barrier tube is placed on, chamber is inner to be formed, and introduces gelling negative electrode in barrier tube.With the method substituting, positive electrode is introduced in tank, then introducing before spacer or be pressed into hollow cylinder shape simultaneously.Current collector (for example brass, stainless steel or tin-plated brass structure) is introduced in gelling negative electrode.

In the nickel zinc pencil formula battery unit that can describe herein, adopt various current collector designs.In some this designs, current collector is supposed the shape of thin bar or " nail ".In some cases, current collector is soldered to closure member, and when for sealed cell, current-collector is placed at the center of its contiguous gelling negative electrode.In some implementations, form gelling negative electrode at spacer situ.In certain embodiments, negative electrode current collector can comprise that surface area strengthens geometric element, for example, and fin, grid, perforation, spiral, coil, helix, meander configuration, ridge and/or their combination.In certain embodiments, the highest part of barrier tube is above the highest part of hollow cylinder positive electrode, and the highest part of this hollow cylinder positive electrode is above the highest part of gelling negative electrode.In a particular embodiment, the highest part of barrier tube is above the highest part of hollow cylinder positive electrode between about 4-10mm, and the highest part of this hollow cylinder positive electrode is above the highest part of gelling negative electrode between about 1-10mm.In some implementations, negative electrode current collector is attached to for hermetically sealed can and completes the closure member that rechargeable battery fills.

Material, component, structure and method and further feature and the advantage of the manufacture of the battery of disclosed realization are further discussed with reference to associated drawings below.

Brief description of the drawings

Figure 1A has described the manufacture method of the battery of disclosed embodiment.

Figure 1B has presented the example with the positive battery unit cover of battery unit tank and the battery unit structure of negative pole bottom.

Fig. 2 has presented according to the battery unit tank of some embodiment and the viewgraph of cross-section of battery unit cover.

Fig. 3 A and 3B have schematically described the jar structure of strengthening.

Fig. 4 has described to have flat tank and the specific embodiment using together with additional reinforcing.

Fig. 5 has presented the technological process for the manufacture of rechargeable nickel-zinc cell unit according to some embodiment.

Fig. 6 has described for the loop-around data of 80 circulating batteries of disclosed embodiment and the ratio of charging capacity and discharge capacity.

Describe in detail

Embodiment described herein relates to the rechargeable battery that comprises pencil formula battery.It will be appreciated by those skilled in the art that following detailed description is illustrative and do not limit the range of application of disclosed rechargeable pencil formula battery.

Battery design

The present embodiment relates to rechargeable battery technology.For convenience's sake, because each assembly or the parts of the battery of disclosed realization are mentioned in following discussion, therefore when assembly or parts are referred or in unitary part time, describe and will concentrate on this assembly or parts to can provide more details in the situation that not disperseing senior description.

Nickel zinc rechargeable pencil formula battery

The rechargeable battery of some embodiment is nickel zinc " pencil formula " battery herein.Certain material, electrode component and the method for their manufacture are described below.

Conventionally follow battery unit structure and the necessary manufacture requirement of more complicated for the new component of high power density and high-energy-density rechargeable battery.Wherein the battery unit of these more complicated structure is accommodated in the battery structure of " pencil formula battery unit ", and the needs that meet consumption electronic products industry are very important.In addition,, due to cylinder form easily, therefore the pencil formula battery unit of non-traditional size is used in non-consumption and/or the application of special consumer.

The rechargeable battery of disclosed embodiment has the cylindrical geometry body that battery length is greater than its diameter; That is to say, the ratio of battery length and cell diameter is at least about 1.5:1, and is between about 1.5:1 and about 20:1 in certain embodiments.In embodiment more specifically, the ratio of battery length and cell diameter is between about 1.5:1 and 10:1.In other embodiments, the ratio of battery length and cell diameter is between about 1.5:1 to 5:1.In some implementations, cell diameter is between about 5mm and about 100mm.In certain embodiments, the ratio of battery length and cell diameter is greater than about 5.5:1 and diameter is between about 10mm and 50mm.In certain embodiments, battery is configured to size available on the market, for example AAAA, AAA, AA, C, D, inferior C etc.In other embodiments, battery (for example can have the diameter substantially the same with the battery unit available on the market of routine, on traditional market, can obtain battery diameter 1% in, or on conventional market, can obtain battery diameter 5% in), but longer.

Manufacture the method for nickel zinc pencil formula battery unit

As mentioned above, the secondary cell of embodiment is cylindrical battery or general cylindrical battery herein.Due to this geometry, in the time manufacturing the rechargeable battery of disclosed realization by outstanding component alternative as electrode and other assembly, the method for manufacturing primary cell is very suitable for manufacturing the secondary cell of disclosed realization.To the particular aspects of some assemblies be described in the unitary part after this part in more detail.

In certain embodiments, rechargeable battery has the hollow cylinder positive electrode that comprises nickel hydroxide; There is at least one the gelling negative electrode in zinc metal and zinc compound; Be inserted in the spacer between hollow cylinder positive electrode and gelling negative electrode; And insert the negative electrode current collector in gelling negative electrode.Negative electrode current collector can also be called negative pole currect collecting device, negative current collector, current collector or negative current collector nail.

Figure 1A described manufacture pencil formula battery (such as described herein those) a method.With reference to Figure 1A, positive electrode material (active material and add-on assemble) is formed as circlet shape sheet 10 and this sheet is introduced in tank 20 as lamination.In this example, barrier tube (fusing together to form pipe by pipe 30a and bottom 30b makes) thus be placed on that chamber is inner to be formed.Except two assemblings by describing, can also or be molded as single-piece by spacer extruding here.The assembling of sheet 10, tank 20 and spacer is depicted as assembly 40.Then, in barrier tube, introduce gelling negative electrode material.Gelling negative electrode material can be pre-formed and be introduced into barrier tube.Alternatively, the assembly of gelling negative electrode material can mix at spacer situ.In certain embodiments, the highest part of spacer is above the highest part of hollow cylinder positive electrode, and the highest part of this hollow cylinder positive electrode is above the highest part of gelling negative electrode.In other embodiments, the highest part of spacer above the highest part of hollow cylinder positive electrode between about 2mm and about 5mm (for example, about 3mm), the highest part of this hollow cylinder positive electrode is again for example, above the highest part of gelling negative electrode between about 0.5mm and about 2mm (, about 1mm).This layout helps prevent zinc creep and arrival positive electrode on spacer.

With alternative method, replace the stacking of sheet positive electrode material, positive electrode is introduced in tank, then before introducing spacer or be pressed into hollow cylinder shape simultaneously.This can be by for example by sacrificing, bar inserts in tank, then constrictor positive electrode material around removes bar and complete.In one example, during compression anode material, sacrifice bar and there is spacer thereon, once so that bar is removed, just realize efficiently assembly 40.In certain embodiments, positive electrode is the single preformed hollow cylinder main body of inserting in tank.

Refer again to Figure 1A, current collector 50 (for example brass, stainless steel or tin-plated brass structure) is introduced in gelling negative electrode.To the each side of current collector be described in unitary part below in more detail.In some cases, current collector 50 (for example " nail ") is fixed to closure member 60 (for example, by welding), and this closure member, when for sealed cell, is placed on nail at the center of gelling negative electrode.Once sealing, the assembling of battery 70 has just completed.After assembling, can form, charge, discharge and recharge.

Below various aspects are described, especially positive electrode, gelling negative electrode, spacer, negative electrode current collector, tank, battery unit polarity, structure etc. are together with forming and charging agreement and exemplary embodiment.

Positive electrode component and structure

Positive electrode material comprises the electro-chemical activity nickel hydroxide of type described herein.Term " nickel hydroxide " comprises, except nickel hydroxide, and the compound of other the nickeliferous oxygen existing during any charged state.This compound comprises hydroxy nickel oxide and nickel oxide.In addition, it can comprise that one or more additive is to promote manufacture, electronics transmission, wettability, mechanical performance etc.For example, positive electrode preparation can include or not mix the nickel hydroxide particle of cobalt hydroxide or cobalt oxide or hydroxy cobalt oxide, together with one or more in following: zinc oxide, cobalt oxide (CoO), cobalt metal, nickel metal and the flow control agent such as carboxymethyl cellulose (CMC).Note, metallic nickel and cobalt can be metal element or alloy.Can on identical particle, form nickel oxide particle and associated cobalt oxide or cobalt hydroxide, for example, process or by cobalt oxide or cobalt hydroxide are deposited on nickel oxide particle by co-precipitation.In certain embodiments, positive electrode has the component similar to component for manufacture nickel electrode at conventional nickel-cadmium cell or conventional nickel metal hydride battery.

Other material can be provided for positive electrode.The example that can improve the material of charge efficiency comprises strontium hydroxide (Sr (OH) ₂), barium monoxide (BaO), calcium hydroxide (Ca (OH) ₂), Fe ₃o ₄, calcirm-fluoride (CaF ₂) and yittrium oxide (Y ₂o ₃).The interpolation that has shown yittrium oxide and calcium compound is beneficial to the charge acceptance under higher temperature." Nickel Hydroxide Electrode:improvement of charge efficiency at high temperature " (the Hydrogen and Metal Hydride Batteries being compiled by T.Sakai and P.D.Bennett) referring to K.Ohta, K.Hyashi, H Matsuda, Y.Yoyoguchi and Mikoma in the volume 94-27 of The Electrochemical Society proceedings, its full content is incorporated herein by reference.

In certain embodiments, the positive electrode completing is included in cobalt metal powder between about 0-10 percetage by weight, for example, at the cobalt compound between about 0-10 percetage by weight (cobalt oxide, cobalt hydroxide or hydroxy cobalt oxide), at the nickel powder between about 0-10 percetage by weight, any one oxide and/or hydroxide in the zinc oxide between about 0-3 percetage by weight, cadmium between 0-1 percetage by weight, yttrium, calcium, barium, strontium, scandium, lanthanide series, bismuth, manganese, magnesium.

In addition, electrode can comprise a small amount of " flushing " agent, for example carboxymethyl cellulose (CMC), aluminium oxide, cellulose, alumina/silica compound and nylon fiber.In one embodiment, newsprint is used as irrigation.The concentration of irrigation (in the time existing) is between approximately 1% and approximately 6% weight, and in certain embodiments between approximately 2% and approximately 3% weight.Irrigation helps to keep positive electrode sufficiently moistening in cycle period.Because the thickness of electrode may hinder, during repetitive cycling, electrolyte is to the transmission in electrode interior region, and therefore the irrigation of sufficient amount is for guaranteeing that good long-term behaviour is sought after.Positive electrode also comprises binding agent alternatively, and concentration is for example about 0.1-2% weight (being generally the fluorinated polyolefin such as PTFE).

Further, positive electrode can comprise high conductive additive, for example nickel metal, carbon, conductivity ceramics, cobalt metal powder or cobalt compound and conducting polymer.With whole positive electrode material volumes approximately 2% and 8% between quantity interpolation (one or more) conductive additive.In positive electrode, the ultimate density of conductive additive is at least about 10% volume.In certain embodiments, the ultimate density of conductive additive is volume approximately 20%.Electric conducting material can adopt the form of powder, foam, fiber or its combination.Conductive additive is to keeping superperformance to need, especially for the relative thickness electrode described herein two-forty performance of (as compared with for example Jellyroll constructs).

The counterbalance (balance) of positive electrode material is nickel hydroxide (or nickel compound of modification).In certain embodiments, nickel hydroxide exists with the amount of about 60-95 percetage by weight.Note, all concentration and all dry weights based on positive electrode of quantity of positive electrode assembly of narration here, its not included in assembling and operating period impregnated electrode electrolyte.

In particular example, pasty state nickel hydroxide electrode component is made up of together with (PTFE) the Ni210 powder of the Co powder of from approximately 1% to approximately 5% weight, approximately 2% to approximately 10% weight and poly-(tetrafluoroethene) of approximately 0.4% sodium carboxymethyl cellulose to approximately 2% weight (CMC) and approximately 0.1% to approximately 2% weight.Nickel hydroxide powder forms counterbalance.

In the following files, described various positive electrode assemblies, each in these files is incorporated herein by reference: publication number is the PCT application (Ni (OH) of co-precipitation of WO 02/039534 (being applied for by J.Phillips) ₂, CoO and fine crushing cobalt metal), on July 26th, 2004 being applied for by J.Phillips of submitting to, publication number is the publication number applied for by J.Phillips in 2005-0003270 United States Patent (USP), on March 15th, 2002 United States Patent (USP) (fluoride additive) that is 20020192547, the U.S. Patent application 12/365 that on February 4th, 2009 submits to, the U.S. Patent application 12/432,639 that 658 (nickel hydroxide electrodes) and on April 29th, 2009 submit to.

For example, although other substrate-like precedent, as paillon foil, perforated sheet, conventionally in conductive substrates (nickel foam matrix), nickel hydroxide electrode is set, and expanding metal can also be for the manufacture of hollow cylinder positive electrode.In some implementations, nickel foam is provided by the Vale Canada Co., Ltd of Chinese Lyrun company or Toronto.In a particular embodiment, using density is from about 300-500g/m ²the nickel foam of scope.In another is realized, scope is at about 350-500g/m ²between.In one example, use and there is density for about 350g/m ²nickel foam.

The method of manufacturing the positive electrode of disclosed embodiment comprises wet processing and dry process.In the U.S. Patent application 10/921,062 of submitting on August 17th, 2004, describe wet processing and be incorporated herein by reference.For example, can use stable nickel hydroxide powder for example, to manufacture pasty state nickel hydroxide electrode together with the mixture of other positive electrode composition in slurry (, cobalt powder, nickel powder, CMC and PTFE).Active material slurry is pushed in nickel foam and press to form nickel electrode as above or ring.In other embodiments, manufacture positive electrode by the dry process that does not adopt large water gaging or other liquid.Referring to, for example on March 1st, 2006 submit to U.S. Patent application 11/367,028 and its be incorporated herein by reference.The composition material of nickel hydroxide, nickel powder and cobalt powder and suitable binding agent can be dry mixed and be combined and introduce in hopper.In one embodiment, dry mixture is used to form cathode sheets as above.In another embodiment, in the time that rotary brush is shifted dry substance onto in foam hole, suck continuous nickel foam bar through powder.Then, compression step can for example be pressed into foam ring segment as above.

That the positive electrode of realization herein has is hollow, columniform shape substantially.As mentioned, positive electrode can be individual construction, but in certain embodiments, positive electrode forms (it comprises active material and as other agent described herein) by the stacked rings of positive electrode material.As what describe in experimental example below, can be at the many thin rings of stacking middle use (, vertically symmetrical the very short ring of axle) to realize the electrode height of expectation.Alternatively, as described in Figure 1A, lesser amt can be used to form stacking compared with epipodium.

Important consideration for the manufacture of the width of the stacking ring of positive electrode.Once due to stacking ring, they will form occupied by negative electrode hollow, therefore this width may be important.Hollowly define the surface area that negative electrode electrically contacts with it by spacer.In addition the hollow maximum of determining available volume and therefore determine the negative electrode that can use together with spacer (it compares relative thin with anode) in battery unit.

The various preparations of positive electrode and negative electrode need specific anode ring thickness with the conductivity that they obtain, to realize negative pole to the desired balance of anodal electric connection surface area, this balance is determined the MAH (mAH) that every square centimeter of interface area can be used.Anodal thickness can be according to the expression that compares of hollow diameter and battery unit diameter.In one embodiment, comparing approximately 0.4 and approximately between 0.95 of hollow diameter and battery unit diameter.In another embodiment, comparing approximately 0.5 and approximately between 0.9 of hollow diameter and battery unit diameter.In another embodiment again, the comparing between approximately 0.6 and 0.85 of hollow diameter and battery unit diameter.In certain embodiments, battery unit has the diameter between about 5mm and 100mm.Therefore, in one example, for the high cycle life under high-energy-density with compared with high rate discharge, (diameter for example for AA battery unit, 14mm) cylindrical positive pole between about 1mm and about 3mm thickness (between the outer radius of annular electrode and inside radius poor) will be there is, in another example, AA battery unit will have the cylindrical positive pole of thickness between about 1.5mm and 2.5mm, in another example again, AA battery unit will have the cylindrical positive pole (the comparing approximately 0.6 and approximately 0.7 between of hollow diameter and battery unit diameter) of thickness between about 2.1mm and 2.5mm.Having in larger-diameter battery unit, for example D or non-traditional size, because interface area is higher, therefore anode can be thicker, but will have the compromise of power-energy.

Negative electrode component

Gelling negative electrode comprises alternatively with one or more and adds for example, one or more electroactive source in zinc or the zincate ion of material (conductivity reinforcing material as described below, corrosion inhibitor, wetting (or flushing) agent and gelling agent etc.) combination.In the time manufacturing electrode, it is characterized in that specific physics, chemistry and morphological feature, for example the chemical composition of Coulomb capacity, active zinc, porosity, tortuosity etc.

In certain embodiments, electro-chemical activity zinc source can comprise one or more in following ingredients: zinc oxide, zincic acid calcium, zinc metal and various kirsite.Any in all these materials can be provided during manufacture and/or produce any in all these materials in standard cell unit cycle period.As particular example, consideration can be by comprising the slurry of for example calcium oxide and zinc oxide or the zincic acid calcium that paste produces.

If employing kirsite, it can comprise bismuth and/or indium in certain embodiments.In certain embodiments, it can comprise up to about 20/1000000ths lead.It is available on the market that to meet kirsite source that this component requires be the PG101 being provided by Canadian Noranda company.Zinc active material can exist with the form of powder, granular component etc.

In one embodiment, gelling negative electrode comprises the solid mixture combining with gelling agent and alkaline electrolyte.Solid mixture comprises zinc and/or zinc oxide.In one implementation, solid mixture be included in 0% and approximately between 30% the zinc of weight and between approximately 65% and 100% the zinc oxide of weight.Except electro-chemical activity zinc composition, solid mixture can also comprise for example irrigation in a small amount as described below, binding agent etc.Solid mixture is combined to form gelling negative electrode with electrolyte and gelling agent.The negative electrode composition of all " by weight " concentration of not adding electrolyte described here is provided based on dry ingredients.

Except (one or more) electro-chemical activity zinc component, gelling negative electrode can comprise one or more interpolation material that promotes or otherwise affect some process in electrode, for example ion transport, electronics transmission are (for example, strengthen conductivity), wetability, porosity, structural intergrity (for example, caking property), foaming, active material solubility, barrier property (for example, reducing the zinc amount of leaving electrode), corrosion suppress etc.

Conductive agent can form gelling negative electrode volume nearly approximately 35% (in a particular embodiment for volume approximately 5% and 30% between).Can add negative electrode to and comprise the various electrode compatible materials with high intrinsic electron conduction with the example of the material of raising electron conduction.Certainly, definite concentration will depend on the performance of (one or more) selected additive.Conductive agent for gelling negative electrode comprises carbon, titanium nitride, conductivity ceramics, protoxide, bismuth, glass putty or the bismuth of for example titanium and the oxide of tin (it will be transformed into metal during forming).Electric conducting material can adopt the form of powder, foam, fiber or its combination.In certain embodiments, be used as conductive matrices with the copper foam that tin or zinc apply alternatively.The conductive additive of high concentration is for maintaining superperformance relatively, and the high rate discharge performance of relatively thick negative electrode especially described herein may be necessary.

As positive electrode, negative electrode can be benefited from the use of irrigation or wetting agent.In certain embodiments, the concentration of wetting agent, between approximately 1% and approximately 8% weight, is greater than 8% weight in certain embodiments.Irrigation helps to keep negative electrode sufficiently wetting in cycle period.Because the thickness of gelling negative electrode may hinder, during repetitive cycling, electrolyte is to the transmission in electrode interior region, and therefore the irrigation of q.s is for guaranteeing that good long-term behaviour needs.Can add negative electrode to and comprise that to improve the example of material of wetability cellulose, titanium oxide, aluminium oxide, silicon dioxide, aluminium oxide are together with silicon dioxide etc.Can provide this material with the form of fiber, particle, powder etc.Can be disclosed on November 2nd, 2004, be the United States Patent (USP) 6 of " Formulation of Zinc Negative Electrode for Rechargeable Cells Having an Alkaline Electrolyte " by Jeffrey Phillips application, title, 811, in 926, find the further discussion of this material, it is incorporated herein by reference for all objects.

Comprise carboxymethyl cellulose, the acid of cross-linking type branched p 0 lypropylene, natural gum, can obtain from the Noveon of Cleveland, OH for the gelling agent of gelling negative electrode etc..Note, although negative electrode is described as to " gelling " electrode herein, embodiment is not limited in this.Alternatively, can be using negative electrode as paste, slurry, solid mixture etc. provide.

In certain embodiments, negative electrode comprises the oxide such as bismuth oxide, indium oxide and/or aluminium oxide.Bismuth oxide and indium oxide can interact with zinc and reduce in the gas dissipation of electrode place.Can with approximately 1% of gelling negative electrode weight of formulation and approximately the concentration between 10% bismuth oxide is provided.Bismuth oxide, aluminium oxide and/or indium oxide can also promote the restructuring of oxygen.Indium oxide can with approximately 0.05% of gelling negative electrode weight of formulation and approximately the concentration between 0.2% exist.Can with approximately 1% of gelling negative electrode weight of formulation and approximately the concentration between 8% aluminium oxide is provided.

In certain embodiments, thus can comprise that one or more additive is to improve the corrosion resistance of zinc electroactive material and to contribute to long shelf life.Business success or the failure of shelf life to battery unit is most important.Recognize that battery is the equipment of chemically unstable in essence, can take steps to preserve battery cell assemblies (comprising negative electrode) with their chemically useful forms.When electrode material did not use and when corrosion occurring or degrading to significance degree, their value becomes and is limited to of short duration shelf life in several weeks or several months.

Can comprise that anion is to reduce the solubility of zinc in electrolyte, the particular example of this anion comprises phosphate, fluoride, borate, zincate, silicate, stearate etc.Conventionally, these anions can be present in negative electrode with the concentration of the negative electrode preparation up to approximately 5% weight.Should believe, at least some in these anions can be to reduce the solubility of zinc in battery unit cycle period enters solution.The example that comprises the electrode preparation of these materials is included in following patent and patent application, each in them is incorporated herein by reference for all objects: on September 28th, 2004 disclosed, that applied for by Jeffrey Phillips, that title is " Negative Electrode Formulation for a Low Toxicity Zinc Electrode Having Additives with Redox Potentials Negative to Zinc Potential " United States Patent (USP) 6,797,433; On December 28th, 2004 is disclosed, United States Patent (USP) 6 that applied for by Jeffrey Phillips, that title is " Negative Electrode Formulation for a Low Toxicity Zinc Electrode Having Additives with Redox Potentials Positive to Zinc Potential ", 835,499; On November 16th, 2004 is disclosed, United States Patent (USP) 6,818,350 that applied for by Jeffrey Phillips, that title is " Alkaline Cells Having Low Toxicity Rechargeable Zinc Electrodes "; And PCT/NZ02/00036 (publication number WO 02/075830) submission on March 15th, 2002, that applied for by people such as Hall.

For the object that bonds and disperse, can add various organic materials to negative electrode.Example comprises free acid form (HCMC), polytetrafluoroethylene (PTFE), poly styrene sulfonate (PSS), polyvinyl alcohol (PVA), nopcosperse dispersant (can obtain from the San Nopco Co., Ltd of kyoto, Japan) of hydroxyethylcellulose (HEC), carboxymethyl cellulose (CMC), carboxymethyl cellulose etc.

In the time limiting electrode component herein, be generally understood as and be applicable to the component as produced and may forming cycle period or the component of generation afterwards or for example, during using one or more charge-discharge cycles of (, in the time powering for portable dam) when battery unit or afterwards in manufacturing.In certain embodiments, rechargeable battery can be with about 1C or larger discharge rate approximately 50 and approximately 1000 circulations from complete charged state to complete discharge condition, or can be with about 1C or larger discharge rate approximately 100 and approximately 800 circulations from complete charged state to complete discharge condition, or can be with about 1C or larger discharge rate approximately 200 and approximately 500 circulations from complete charged state to complete discharge condition.In certain embodiments, realize these range of DOs by the battery that is discharged to complete discharge condition from complete charged state with about 0.5C or larger discharge rate.

In the following files, described various negative electrode compositions and mixture in the scope realizing herein, each in these files is incorporated herein by reference: the open WO 02/039534 (J.Phillips) of open WO 02/39521, PCT of open WO 02/039520 (J.Phillips), PCT of open WO02/39517 (J.Phillips), PCT of PCT and United States Patent (USP) disclose 2002182501.In the above referred-to references, negative electrode additive comprises fluoride, transition metal, heavy metal and the noble metal of for example silicon dioxide and various alkaline-earth metal.

Finally, although it should be noted that can be by some Material Additions to negative electrode to give particular characteristic, can introduce some in those materials or characteristic by the battery component except negative electrode.For example, can in electrolyte or spacer, be provided for reducing electrolyte in some material (have equally or do not offer negative electrode) of solubility of zinc.The example of this material includes, but are not limited to phosphate, fluoride, borate, zincate, silicate and stearate.Above-identified other additive for electrode that may provide in electrolyte and/or spacer includes, but are not limited to ion of surfactant, bismuth, lead, tin, calcium, indium etc.

Spacer

Conventionally, spacer will have aperture.In certain embodiments, spacer comprises multiple layers of lamination.Hole and/or laminar structure can for zinc dendritic crystal zigzag path is provided and therefore effectively prevent infiltration and by the short circuit of dendritic crystal.In one embodiment, porous spacer has in the tortuosity between approximately 1.5 and 10 or between approximately 2 and 5.Approximately 0.2 micron at most of average pore size, and in certain embodiments between approximately 0.02 and approximately 0.1 micron.And hole size is quite even in spacer.In a particular embodiment, spacer has the porosity between approximately 35% and 55%.In a realization of this embodiment, spacer material has approximately 45% porosity and the hole size of approximately 0.1 micron.

In certain embodiments, spacer comprises at least two layers (and in one embodiment just in time two layers)-stop the barrier layer of zinc infiltration and keep the wetting layer of battery unit wetability with electrolyte, thereby allows ionic current flow.Conventionally be not like this for nickel-cadmium cell cell cases, it only adopts single spacer material between adjacent electrode layer.

As indicated, can be by keeping the performance of electrode wetability boosting battery unit.Therefore, in certain embodiments, barrier layer is positioned near negative electrode and wetting layer is positioned near positive electrode.This layout contacts to improve cell performance by maintaining electrolyte with positive electrode.In other embodiments, wetting layer is placed near negative electrode and barrier layer is placed near positive electrode.This layout is by promoting via electrolyte, the oxygen transmission of negative electrode to be contributed to the restructuring of negative electrode place oxygen.

Barrier layer is microporous barrier normally.Can use any microporous barrier of ionic conduction.Conventionally have approximately 30% and approximately the porosity between 80% and the polyolefin with the average pore size between approximately 0.005 and approximately 0.3 micron will be suitable.In one embodiment, normally capillary polypropylene of barrier layer.The thickness on barrier layer is generally between approximately 10 μ m and approximately 100 μ m, and thickness is between approximately 25 μ m and approximately 75 μ m in some implementations.

Wetting (or wicking) layer can be made up of any suitable wettable spacer material.Conventionally wetting layer has relatively high porosity, for example, and between approximately 50% and approximately 85% porosity.Example comprises polyamide material, for example, based on polyethylene nylon and wettable and polypropylene material.In certain embodiments, the thickness of wetting layer is between approximately 25 μ m and approximately 250 μ m, or thickness is between approximately 25 μ m and approximately 200 μ m, or thickness is between approximately 75 μ m and approximately 150 μ m.The example that can be used as the material of wet material employing comprises NKK VL100 (the NKK company of Tokyo), FS2213E or Vilene FV4365 (Fei Dengbao of Germany) and Scimat 650/45 (Britain, the SciMAT Co., Ltd of Swidon).

Can adopt other spacer material as known in the art.As indicated, the material based on nylon and micropore polyolefin (for example, polyethylene and polypropylene) are normally suitable.

Whether another consideration in spacer design provides for example, assembly or spacer as multiple parts (manage and cover) of spacer whether to be formed as individual unit (for example, in pipe).In one embodiment, by making them be formed as tubulose to form spacer to microporous layer and the horizontal layering of wicking layer and via tube core or axle.If appropriate, can carry out heat seal with knitting layer to the structure producing.

Electrolyte

In some embodiment about nickel-zinc cell unit, the formation of dendritic crystal and other form of material redistribution in electrolyte component restriction zinc electrode.License to the example of having described suitable electrolytes in the United States Patent (USP) 5,215,836 of M.Eisenberg on June 1st, 1993, this patent is incorporated herein by reference.In some cases, electrolyte comprises (1) alkali metal or alkaline earth metal hydroxide, (2) water soluble alkali or alkali earth metal fluoride, and (3) borate, arsenate and/or phosphate (for example, potassium borate, potassium metaborate, Boratex, kodalk and/or sodium phosphate or potassium).In a particular embodiment, electrolyte comprises approximately 4.5 potassium hydroxide to approximately 10 equivalent/litres, approximately 2 boric acid to approximately 6 equivalent/litres or kodalk and approximately 0.01 potassium fluoride to approximately 1 equivalent/litre.Specific electrolyte for high discharge rate application comprises the boric acid of the hydroxide of approximately 8.5 equivalent/litres, approximately 4.5 equivalent/litres and the potassium fluoride of approximately 0.2 equivalent/litre.

Embodiment is not limited to the electrolyte component proposing in the patent of Eisenberg.Conventionally, the electrolyte component of any satisfied standard that application interested is specified is all enough.Suppose to need high power applications, electrolyte should have extraordinary conductivity so.Suppose to need long cycle life, electrolyte should be resisted dendritic crystal formation so.In many in existing realization, use the formation that contains the electrolytical borate of KOH and/or fluoride and reduced together with suitable partition layer dendritic crystal, realize thus electrokinetic cell unit firmer and that the life-span is long.

In a specific embodiment, electrolyte component comprises the hydroxide (for example, KOH, NaOH and/or LiOH) between excessive approximately 3 and approximately 5 equivalent/litres.This hypothesis negative electrode is Zinc oxide-base electrode.For zincic acid calcium negative electrode, alternative electrolyte preparation may be suitable.In an example, the suitable electrolyte of zincic acid calcium has following component: approximately 15% to the KOH of approximately 25% weight and approximately 0.5% LiOH to approximately 5.0% weight.

In some cases, electrolyte can comprise the phosphate ion of relative high concentration of discussing in the U.S. Patent application 11/346,861 as submitted on February 1st, 2006, and this patent application is incorporated herein by reference for all objects.

Negative electrode current collector

The rechargeable battery of disclosed realization has the negative electrode current collector that is arranged in gelling negative electrode.In considering manufacturing cost, consider to maximize water catchment efficiency.In one implementation, negative electrode current collector is made up of at least one alloy in brass, copper, steel and their combination.In certain embodiments, negative electrode current collector comprises liberation of hydrogen inhibitor alternatively.The liberation of hydrogen inhibitor of embodiment comprises at least one in tin, lead, bismuth, silver and indium herein.Some in the material using in current collector can only form face coat.In such an embodiment, can apply coating by plating (for example,, by electroplating and/or electroless plating), brushing, spraying etc.

Normally, but optionally, negative electrode current collector is configured to insert " nail " type structure of gelling negative electrode." nail " is narrow, columniform shape substantially, and selectively taper ground is towards the end of going deep into most gelling electrode.

Balance in gelling negative electrode between water catchment efficiency and active material amount is extremely important.In the time that the shape of current collector is essentially cylindrical, the diameter that in fact current collector contacts with gelling negative electrode and length have been determined the interface surface area between current collector and gelling negative electrode.In some implementations, the diameter of current collector is cell diameter approximately 5% and approximately between 20%, or be cell diameter approximately 10% and approximately between 15%, or be cell diameter approximately 10% and approximately between 12%.Therefore be important parameter with the length of the actual current collector contacting of gelling negative electrode.In certain embodiments, given current collector diameter as above, the length L of the gelling negative electrode in spacer (residing in hollow cylinder positive electrode) ¹be arranged in the corresponding length L of the part of gelling negative electrode with negative electrode current collector ²meet following relation: 0.5≤L ²/ L ¹≤ 0.95 or 0.6≤L ²/ L ¹≤ 0.9 or 0.75≤L ²/ L ¹≤ 0.85.

In other embodiments, thus expect that the shape that changes negative electrode current collector is to increase surface area and to improve current collector efficiency.In certain embodiments, negative electrode current collector comprises that surface area strengthens geometric element.Therefore, current collector can comprise fin, grid, perforation, spiral, coil, meander configuration, ridge and their combination.In one embodiment, current collector is perforated plate or cylindrical.In another embodiment, current collector is the rigid grid that becomes current collector to form metal or alloy mesh compression by for example.In another embodiment, current collector is on perforated metal surface and/or inner (in columniform situation) has perforated plate or cylindrical (so that rigidity to be provided) of grid or foam.Although utilize this embodiment that increases surface area, current collector diameter becomes less important, and the length of inserting the current collector of gelling electrode remains the variable of particular importance, in order to maximize the gelling electrode amount that can be used for charging, discharges and recharge.Therefore, may be less than above-mentionedly for the average diameter of those elements of columniform current collector substantially because surface area strengthens the average diameter of geometric element, therefore the surface area of current collector has increased (with respect to simple cylinder form).

Finally, the battery of disclosed realization can comprise the negative electrode terminal plate that is electrically connected to negative electrode current collector.As described with reference to Figure 1A, terminal board can be integrated in closure member 60.

Form and charging

The formation of battery unit relates to initial charge.Use the improvement battery of realizing can complete the formation of battery herein, for example, use U.S. Patent application 12/432 that submit to, that applied for by J.Phillips on April 29th, 2009, that title is " Nickel Hydroxide Electrode for Rechargeable Batteries ", the method of describing in 639, this patent application is incorporated herein by reference for all objects.

The charging of nickel-zinc cell can be according to the charging technique of previous report, the United States Patent (USP) 6 of for example being applied for by J.Phillips, title is " Charger for rechargeable nickel-zinc battery ", 801, those that describe in 017, this patent is incorporated herein by reference for all objects.

Alternatively, can use constant voltage phase place to charge to nickel-zinc cell, it can be constant current phase before and/or can be rear voltage-phase afterwards.The U.S. Patent application 12/442 that submit to, that applied for by J.Phillips on March 19th, 2009, title is " Charging methods for Nickel-Zinc Battery Packs ", in 096, described this method, this patent application is incorporated herein by reference for all objects.These methods comprise the two-stage or the three stage charging mechanisms that start with constant current phase, until battery unit reaches the voltage level of temperature-compensating.Therefrom, charging is to constant voltage phase transition.Those of ordinary skill in the art will understand, for as particular battery cell layout described herein, charging method can be suitable for the configuration of specific battery unit and component.

Polarity, tank and battery unit structure

Embodiment shown in Figure 1A has and the opposite polarity of finding in conventional pencil formula battery unit, and its middle cover is that negative pole and tank are anodal.In conventional electric power battery unit, the polarity of battery unit is that lid is anodal, and tank or container are negative poles.That is to say, the positive electrode of battery cell assemblies is electrically connected with lid, and the negative electrode of battery cell assemblies is electrically connected with the tank of preserving battery cell assemblies.Although in the embodiment describing with reference to Figure 1A, the polarity of battery unit and conventional batteries unit be contrary (, negative electrode is electrically connected with lid, and positive electrode is electrically connected with tank), should be appreciated that, in certain embodiments, polarity keeps identical with in conventional design (having positive cover).This is by for example, and amendment as the closure member 60 of describing with reference to Figure 1A are realized, so as it in the bottom of amendment jar with in imitating the shape of tank, the bottom of imitating tank.It will be apparent to one skilled in the art that also and can realize conventional polarity by other method, for example, exchange the position of positive electrode and gelling negative electrode, and use is used for the tank of negative electrode afflux etc.

Tank is to serve as the shell of final battery unit or the container of box.That in the conventional batteries unit of negative terminal, it is nickel-plated steel normally at tank.As noted, in the present embodiment, tank can be negative pole or positive terminal.Be in the embodiment of negative pole at tank, tank material can be to be similar to the component (for example steel) adopting in conventional nickel-cadmium cell---as long as material is coated with and the another kind of material of the electromotive force compatibility of zinc electrode.For example, cathode pot can apply such as the material of copper to prevent corrosion.Be that positive pole and lid are in the embodiment of negative pole at tank, tank can be to be similar to the component using in conventional nickel-cadmium cell unit, normally nickel-plated steel.

In certain embodiments, can recombinate with help hydrogen by coating material in the inside of tank.Can use any material of catalysis hydrogen restructuring.An example of this material is silver.

In Figure 1B, describe to have an example of the battery unit configuration at the bottom of positive cover and cathode pot.According to the disclosed embodiments, Figure 1B shows the decomposition view of nickel-zinc cell unit.Cylindrical electrode assembly 101 (sometimes also claiming assembly, cylindrical positive electrode assembly, positive electrode and negative electrode assembly or cylinder shape assembly) is positioned over tank 113 or other closed container inside.As mentioned above, assembly 101 comprises outside positive electrode and inner zinc electrode (for example, gelling electrode).Can be plated on tank inside to help conduction with for example tin.Once battery unit is assembled, negative electrode current collector dish 103 (for example copper is optionally coated with for example tin) be attached or otherwise with cylinder shape assembly 101 electric connections.In one embodiment, current-collector dish 103 is attached to be similar to the mode of closure member 60 nail-type current collector of describing as in Figure 1A context.Negative pole currect collecting device is folded the effect of outside negative terminal, and wherein anode collector dish is electrically connected to negative electrode.Positive electrode by with interior substrate and/or the side electric connection of tank.

A part for flexible gaskets 111 is shelved on anode collector dish top and a part is also shelved on the circumferential pearl 115 arranging along the circumference in tank 113 top parts.Packing ring 111 is used for anode collector dish 103 and tank 113 electricity isolation.

Insert positive and negative electrode assembly 101 in tank after, conventionally by using tank in the crimping processing of the part above pearl 115 and by inside the annular section of tank crimping and crimping above the circumferential section of packing ring 111 top sections and anode collector dish 103, by tank hermetically closing, thus by seal of vessel with by electrode and associated electrolyte and environment isolation.

Battery can 113 is to serve as the shell of final battery unit or the container of box.That in the conventional batteries unit of negative terminal, it is nickel-plated steel normally at tank.In conventional batteries unit, tank can or negative terminal or positive terminal.In the time that tank is positive pole, exhaust cap is on negative pole; In the time that tank is negative pole, exhaust cap on positive pole, that is, and the battery unit of normal polarity.That is to say, in conventional batteries unit, exhaust cap is a part for the assembly of hermetically sealed can openend normally.

The disclosed embodiments are utilized the exhaust cap at anodal tank and anodal place, thereby realize the battery unit of the normal polarity with anodal tank.Align fully with the hole being attached in the exhaust cap of tank substrate in hole in the substrate of tank.This structure maintains the steam vent on positive terminal, the maximum opposing spreading for the electrolyte more easily occurring at negative pole place compared with positive pole.As mentioned, electrode assemblie 101 is inserted in tank, and the negative terminal of battery unit is connected to the current collector dish of crimping, and intervenient packing ring will coil and the isolation of tank electricity at battery unit closed period.Can easily plate or coating disk with the material that suppresses liberation of hydrogen, and do not have and tank inside is evenly plated to the difficulty that this material is associated.This battery unit configuration and manufacture method thereof provide at least following advantages: 1) for example, because the surface area (tank inside) contacting with plated material is less, therefore the tendency of negative electrode exhaust reduces, 2) because steam vent is positioned on positive terminal, therefore the tendency that electrolyte is revealed by steam vent via creep mechanism reduces, 3) do not need to suppress material with hydrogen and electroplate tank inside, 4) because steam vent assembly is not subject to the impact of the pressure of crimping operation, therefore steam vent operation is more reproducible, 5) owing to using less material cost-saving (as explained in more detail below), and 6) due to more simply design and corresponding minimizing manufacture requirement and cost-saving.

An aspect of the present disclosure is rechargeable nickel-zinc cell unit, comprising: i) comprise nickel positive electrode, zinc negative electrode and be placed on nickel positive electrode and zinc negative electrode between the electrode assemblie of at least one partition layer; Ii) with the tank of nickel positive electrode electric connection, this tank comprises hole in the bases of tank; Iii) be fixed to the substrate of tank and the exhaust cap with tank electric connection, this exhaust cap is configured to from rechargeable nickel-zinc cell unit via hole Exhaust Gas; And iv) with zinc negative electrode electric connection and with the anode collector dish of tank electricity isolation, this anode collector dish is configured to the closure member of the openend of tank.

In this application, term " tank " refers to battery can, generally but must not be metal can, and for example steel or stainless steel.Conventionally, but not necessarily, electroplate tank with nickel.Other tank design will meet, and for example, in certain embodiments, the tank based on polymer that is coated with electric conducting material will be suitable.Further, term " substrate of tank " refers to " bottom " (although embodiment is not restricted to the constraint of any this directivity) of blind end (or exhaust end) in the time comprising hole or battery can.In one embodiment, tank is nickel-plated steel.

Referring again to Figure 1B, assembly is not as conventional rechargeable battery cells complexity.First, conventional rechargeable battery cells usually has the negative pole and the cathode collector dish that serve as internal terminal.Battery unit in Figure 1B only has the anode collector dish that serves as outside terminal.Because can directly contact between the substrate of positive electrode and tank and/or side, therefore not need anode collection device.Equally, do not need the lug of welding to carry out the electrical connection of the substrate from negative electrode to anode collector dish or tank yet.In Figure 1B, as directed battery component has the negative electrode substrate in formed by positive electrode substrate hollow.In this realization, the positive electrode of battery cell assemblies is electrically connected with lid, and the negative electrode of battery cell assemblies is connected with side or the bottom electrical of the tank of preserving battery cell assemblies.

Forward Fig. 2 to, tank 113 has hole 108 in the bases (being depicted as the bottom of tank here) of tank.Cylindrical anodal assembly 101 inserts in tank, and negative pole currect collecting device 103 is placed on the top of cylindrical positive electrode assembly in tank.In one embodiment, anode collector is the metal dish (for example copper or brass dish) applying with anti-liberation of hydrogen material.In one embodiment, anti-liberation of hydrogen material comprises at least one in metal, alloy and polymer.In another embodiment, anti-hydrogen material comprises at least one in tin, silver, bismuth, brass and lead.In another embodiment again, anti-hydrogen material comprises fluoridized polyolefin alternatively, in embodiment more specifically, and Teflon ^tM(E.I.Dupont de Nemours and Company, Wilmington Delaware is for the trade name of polytetrafluoroethylene).In another embodiment, as mentioned above, anode collector is nail.

Current collector 103 is configured to conventionally to carry out electric connection by nail or other negative pole currect collecting device and zinc negative electrode.In can adopting about any one embodiment in embodiment above, carry out electric connection by being in direct contact with between anode collector dish and zinc negative electrode between anode collector dish and negative pole currect collecting device.In a particular embodiment, negative electrode current collector directly contacts with anode collector dish.For example, applying with non-conducting material (anti-liberation of hydrogen material) in the embodiment of negative pole currect collecting device dish, nail or other current collector can be configured to pierce through non-conducting material on battery cell assemblies to set up electric connection.

Once cylindrical electrode assembly 101 is sealed in tank, negative pole currect collecting device dish 103 just serves as the closure elements of tank 113.For by negative pole currect collecting device and tank (owing to being anodal with the anodal substrate electric connection (in this example by directly contacting) of electrode assemblie) electricity isolation, close tank packing ring 111 is placed between tank and current collector before cylindrical electrode component sealing is in tank in crimping.

As mentioned above, in this example, positive electrode directly contacts with the end of the tank with hole 108.Before by cylindrical electrode component sealing in tank or after by tank sealing, electrolyte can be introduced in tank.Electrolyte can be introduced tank via hole 108.

Exhaust cap 109 attached (for example welding) is to the end of tank with hole 108.Aliging fully with the hole 112 in exhaust cap in hole 108, discharges with the hole that allows gas to pass through adjacency.Being described in more detail of exhaust cap that is suitable for disclosed realization is included in the specific part that steam vent changes below.

Exhaust cap

Although battery unit generally with respect to environmental sealing, can allow battery unit that the gas generating during charging and discharging is discharged from battery.Therefore, for example,, with reference to Figure 1B, lid 109 (although having carried out general description) are exhaust cap.Typical nickel-cadmium cell unit is to be approximately the pressure Exhaust Gas of 200 pounds/square inch (psi).In certain embodiments, nickel-zinc cell unit is designed to descend operation and do not need exhaust at this pressure and even higher pressure (for example, until about 300psi).This higher pressure exhaust can be encouraged in the inner any oxygen generating of battery unit and the restructuring of hydrogen.In certain embodiments, battery unit is constructed to maintain up to about 450psi or even up to the internal pressure of about 600psi.In other embodiments, nickel-zinc cell Unit Design becomes with relatively low pressure Exhaust Gas.While not needing them to recombinate in battery unit when designing encouragement hydrogen and/or Oxygen control release, this lower pressure exhaust can be suitable.

In following patent application, can find some details of exhaust cover structure, these patent applications are incorporated herein by reference for all objects: submit PCT/US2004/026859 (publication number WO 2005/020353A3) in the PCT/US2006/015807 that on April 25th, 2006 submits to and on August 17th, 2004.

Fig. 2 is the cross section that shows packing ring 111, negative pole currect collecting device 103, tank 113 and exhaust cap 109 with decomposition view.Battery unit will comprise these assemblies, together with cylindrical electrode assembly (not describing).As mentioned, many defects that these simple and exquisite designs have solved with more complex configurations is associated.The design component of describing in Fig. 2, together with cylindrical electrode assembly and electrolyte in conjunction with to manufacture improved rechargeable nickel-zinc cell unit.In order to assemble, cylindrical electrode assembly is introduced in tank 113, wherein negative electrode occupies the hollow space being limited by cylindrical positive electrode inside radius.Then, at cylindrical electrode assembly top, negative pole currect collecting device dish 103 is introduced in tank 113, wherein, be directly electrically connected with negative pole currect collecting device nail or be electrically connected with negative pole currect collecting device nail by the metal lug that is for example soldered to substrate.Above negative pole currect collecting device 103 or around introduce packing ring 111, afterwards at open end place, (for example, above circumferential notch 115) carries out crimping with hermetically sealed can to tank, simultaneously by insert packing ring 111 tank and negative pole currect collecting device dish 103 are insulated.Exhaust cap 109 attached (for example welding) is to tank 113 to have some overlappingly by the exhaust gear (being described below) of exhaust cap 109, gas to be discharged from tank allowing with hole 108 and 112.Can be before inserting cylindrical electrode assembly and hermetically sealed can attached exhaust cap 109, and in one embodiment, this is the order of assembling.

Fig. 2 has shown the more details of exhaust cap 109.Exhaust cap can comprise basal disc 109a and lid 109b, and their each freedom electric conducting material that discharge portion is described is in the above made.Lid 109b is fixed to basal disc 109a and holds dividing plate 109c, and this lid 109b is made up of elastomeric material, once assemble battery unit, this elastomeric material just allows gas to discharge via hole 108 and 112.In the time reaching sufficient pressure, gas between dividing plate 109c and basal disc 109a through and by one or more hole 109d (covering the side of 109b in this example) exhaust.According to the material for dividing plate and by the lid applied pressure of suppressing dividing plate, can maintain such as pressure and the suitably exhaust described in steam vent part in the above, and can transition do not reveal electrolyte, especially when battery unit is all the more so during in limited configuration as above.

Reinforce tank

Other power that the rigidity opposing deformation of in certain embodiments, battery can being reinforced to provide extra and battery unit suffer.In one embodiment, side thickness is compared in the substrate of tank.In some other embodiment, tank has sufficient thickness to stand to put on the power on tank, for example, and deformation and/or gas pressure.In a particular embodiment, suppose that exhaust do not open, tank can stand up to approximately 500 and even the pressure of 600psi so.In another embodiment, the substrate of tank is reinforced.Fig. 3 A has described an example of the battery can of strengthening.Tank 300 has annular ridge 302, and this annular ridge 302 is pressed into the material for constructing tank.It is longitudinally (as indicated by cutting M) cross section of tank 300 that top presents, and to present be the top view of looking down into from tank 300 in bottom.For example,, if steel, for tank, can be manufactured these ridges so as a part for the Sheet Metal Forming Technology of producing tank.In another example, if tank is made up of polymeric material, ridge can be constructed as a part for the blow mold process for the manufacture of tank so.Two piece can, in the scope of disclosed embodiment, that is to say, for example, the carinate bottom being made of metal can fuse to build the battery that is similar to 300 with polymer pipe.

Fig. 3 B has also described reinforcing tank 304.Tank 304 has ridge 306 in substrate.Upper left cross section has been described along the cutting of line N.It is the top view of looking down into from tank 304 that lower-left presents.These ridges are another structures for the substrate of tank being given to rigidity.It should be appreciated by those skilled in the art that in the scope that is combined in implementation herein of this structure.For example, ridge 306 can combine with one or more circular ridge (as the ridge 302 in tank 300).In another example, the substrate of tank has the ridge of comb mesh pattern etc.In this example, each being shown as in substrate in tank 300 and 304 has hole 301, but this is not restrictive (the same).

In one embodiment, as the ridge of the description about Fig. 3 A and 3B is combined with current collecting plates.In one embodiment, current collecting plates is metal foam.In one embodiment, current collecting plates is nickel foam.In this embodiment, nickel foam compresses to meet the shape of ridge, makes it can not occupy the more volume than necessity in fact.That is to say, because cylindrical electrode assembly leans against in the top of ridge, therefore foam occupies the space between ridge and does not have compressed.In one embodiment, ridge (no matter whether being combined with nickel foam current collector dish) is sharp at top place, to nip in cylindrical electrode assembly.In another embodiment, the bottom of ridge and/or tank is coated with nickel plating.

It should be appreciated by those skilled in the art that the ridge structure in Fig. 3 A and 3B allows exhaust cap to be attached to the bottom of tank, can not disturb exhaust gear simultaneously yet.For example,, as the exhaust cap of describing about Fig. 2 will work to tank 300.This is owing to there being the flat surfaces of enough areas to make and the dividing plate of exhaust cap and/or the base plate 109a of exhaust cap sealing on tank 300 bottoms.The place that ridge 306 forms groove in the bottom of tank 304 may need for blast pipe lid 109 uses exhaust structure, to guarantee that exhaust does not only occur by groove by exhaust gear.

In one embodiment, exhaust gear uses these grooves as the passage for exhaust.In the present embodiment, exhaust cap attached (for example spot welding) is to the bottom of tank 304.During this upper right at Fig. 3 B presents, describe, Fig. 3 B has only shown the base section of tank 304, and lid 109b (not shown) spots weld the flat surfaces on the bottom of the tank 304 between the groove for example being formed by ridge 306 in by tank substrate.Gas can be according to the discharge of being described by thick dashed line arrow.In other words, gas can be discharged by hole and between dividing plate 109c and the bottom of tank, then passes groove and discharges.

In other embodiments, although used the tank with flat bottom, stiffener is attached to the bottom (inside) of tank.Fig. 4 has described a this embodiment.Top cross section has been described along the cutting of line O.Tank 400 has stiffener 404, and its attached (for example welding) is to the inside bottom of tank.The lower-left of Fig. 4 presents and shows member 404 and have four arms and centre bore 406.Centre bore is configured to aim at the hole 402 in tank substrate so that gas can be discharged by it.The bottom right of Fig. 4 presents the top view that shows the tank 400 in tank substrate with member 404.The thickness of stiffener only needs the substrate that is enough to reinforce tank afford to stand the suprabasil power of tank, for example deformation of cylindrical electrode assembly and/or gas pressure before exhaust.Depend on material, member 404 can be as thin as one millimeter and thick in several millimeters.Member 404 does not need to have the structure shown in Fig. 4, and for example, it can be annular, have arm of varying number etc., the member in Fig. 4 be many may in a modification.Member has rigidity and main body relatively flat (to save volume in battery unit), and this main body is given reinforcing to the substrate of battery can.In the example illustrating, can be with for example, nickel foam occupies the region 408 between the arm of member.In one embodiment, be similar to the ridge in Fig. 3 A and 3B, member is combined with nickel foam, and nickel foam compresses between cylindrical electrode assembly and member 404, but packing space 408 and being clipped in these spaces between the substrate and electrode assemblie of tank.Preferably, member 404 is made up of rigid material and is conducted electricity.Member 404 can be for example made up of the steel that is coated with nickel or titanium.Exhaust gear described herein is soldered or be otherwise attached to the bottom of the tank that disposes so this stiffener.

Broadly, as what describe in the handling process 500 of Fig. 5, an embodiment is the method for manufacturing rechargeable nickel-zinc cell unit, the method comprises: 502) enclosed electrode assembly in tank, comprise nickel positive electrode, zinc negative electrode and be arranged on described nickel positive electrode and zinc negative electrode between at least one partition layer, make substrate and the main body electric connection of nickel positive electrode and tank, and the negative pole currect collecting device electric connection at the other end place of zinc negative electrode and tank and with tank electricity isolation; Negative pole currect collecting device is configured to the closure member of the open end to tank; 504) pierce through battery can in the bases of tank, thereby make to form hole in the substrate of tank; And 506) add exhaust cap in the bases of tank; Exhaust cap is configured to gas to discharge from rechargeable nickel-zinc cell unit via hole.Before sealing or after sealing, via hole, electrolyte is introduced in tank.Handling process element needn't be carried out according to the order of describing, the substrate that for example can pierce through tank, and exhaust cap is attached to tank, and then as described, electrode assemblie is sealed in tank.In another embodiment, electrode insertion assembly, hermetically sealed can, then pierces through tank to produce hole.An embodiment is battery component, comprises as electrode assemblie described herein, is sealed in battery can as described herein, does not wherein pierce through battery can, and for example there is no electrolyte or electrode assemblie in constrained state.This assembly be can store and/or transport for finally piercing through, electrolyte and attached steam vent assembly added, for example, as described herein.

Similarly, the inside of tank is for example plated in expectation (although dispensable) with nickel.As embodiment is described above, if cylindrical electrode component sealing in tank and pierce through subsequently tank to form hole, may exist the sub-fraction of the tank of the protection that there is no nickel at perforation position place.Equally, in some cases, be difficult to effectively plate the inside of tank.In the embodiment describing herein, therefore positive electrode, on the outside of cylindrical electrode assembly, and, for example, in the time that tank is steel, can not disturb the function of positive electrode significantly from the iron catabolite of tank.

But, in certain embodiments, expect to start from preformed hole tank, then use protective agent (for example nickel) to plate tank.By this way, do not exist not by the part in the hole 108 of nickel protection and wish not use the inside of the tank of nickel protection.In these embodiments, process operation 504 and will not be present in handling process.Therefore, another embodiment is the method for manufacturing rechargeable nickel-zinc cell unit, the method comprises: 502) enclosed electrode assembly in tank, comprise nickel positive electrode, zinc negative electrode and be arranged on described nickel positive electrode and zinc negative electrode between at least one partition layer, make substrate and the main body electric connection of nickel positive electrode and tank, and the negative pole currect collecting device electric connection at the other end place of zinc negative electrode and tank and with tank electricity isolation; Tank comprises the hole in the substrate of tank; Negative pole currect collecting device is configured to the closure member of the open end to tank; And 506) add exhaust cap in the bases of tank; Exhaust cap is configured to gas to discharge from rechargeable nickel-zinc cell unit via hole.Again, handling process operation 502 and 506 also can be carried out in reverse order.

In can be about any one embodiment who uses together in embodiment above, tank be the steel of nickel plating.In another embodiment, anode collector is the metal dish that is coated with anti-liberation of hydrogen material (for example, in metal, alloy and polymer at least one).Describe the particular example of these materials above and be included in embodiment herein.Anode collector can be for example at least one steel, brass or the copper being coated with in tin, silver, bismuth, brass, zinc and lead.In one embodiment, dish is brass or the copper that is coated with tin and/or silver.In one embodiment, at least a portion of dish is coated with polymer (for example Teflon).In another embodiment, anode collector is nail as above.

Rechargeable nickel-zinc cell in primary cell unit application

In certain embodiments, the nickel-zinc cell unit of describing type is herein for consumer electronics application or other application in leading market conventionally of primary cell unit.The example of this application comprises toy, photoflash lamp, some game etc.For this application, as rechargeable nickel-zinc cell described herein can be configured to operate as conventional primary cell unit.In a method, in the time that this battery unit discharges completely, it is put back to the recharging station relevant to the supplier of battery unit or another entity by its user.At recharging station place, secondary nickel-zinc cell is re-charged electricity and then sells to new application.For this application, must manufacture rechargeable nickel-zinc cell in relatively economical ground, for example, one dollar of about each battery unit or the order of magnitude still less.Further, battery unit must be able to recharge at least number of times of moderate amount.For example, the number of times of the charging and discharging circulation that battery can stand can be at least about 10 times, or at least about 20 times, or at least about 25 times, or at least about 50 times, or at least about 100 times.

In order to follow the tracks of the life-span of battery, thereby and follow the tracks of the number of times that it can recharge and resale, battery can be equipped with every primary cell and submit the identifier (for example bar code or RFID label) reading while recharging to.After battery has used the maximum allocated number of times of its charging cycle, it will be dropped.

The recharging station of battery can be automatic or manual.In the situation that automatically recharging operation, for user provides automatic vending machine or similar devices in order to their nickel-zinc cell of electric discharge is returned.This equipment can be configured to allow user to insert battery, so be preserved for recharging or automatically recharging in equipment.In some implementations, in the time that battery is inserted in equipment, equipment is bought for further battery user accounting.In some cases, equipment is configured to distribute new storage battery in the time inserting the cash of right quantity or credit.

In manual recharging station, recharging station is equipped with one or more responsible reception discharge batteries and places them in the employee in suitable recharging device.In manual and automatic system, system must determine before recharging whether battery will be dropped or recharge at every turn.For this function, system can check that the identifier of battery has stood the charge-discharge cycles of how many times to determine it.

In certain embodiments, adopted large-scale recharging device.This device may be able to recharge tens of or hundreds of nickel-zinc cells simultaneously.For example, recharge on a large scale and can in shunting means, complete, wherein, at 25 DEG C, voltage maintains between about 1.89-1.94V.

In certain embodiments, recharge algorithm for thering is the battery as described design herein.Having in the nickel-zinc cell of the design as presented, guarantee that quality transmission enough occurs to support that recharging fast of battery unit may be a challenge rapidly herein.This is to be positioned at the distance relatively far away apart from positive electrode material and vice versa due to some in negative electrode material.In order to solve this and/or other possible challenge, recharge algorithm and can utilize relax stage, wherein carrying out after the charging of a period of time, temporarily relaxing charged electric potential or electric current in order to allow time enough to be used for the quality transmission of proper level in electrode.This relaxation cycle can carry out once in battery charging process, twice, three times or more times.

In certain embodiments, nickel-zinc cell described herein recharge speed at about C/10 between C/2.

Experiment

By 70 thick positive electrode material rings of preformed 0.4mm being placed in tank and then, spacer is introduced in form by stacked rings hollow, thus the battery unit of manufacture time C size.Positive electrode material by 91% commercially available from CRI (the coating Co of (Changsha Research Institute, Yuelu, Changsha, Hunan, China) ³⁺ni (OH) ₂, 8% Ni, 0.13% PTFE make and all the other are CMC binding agent.Spacer is by being pre-formed the laminating system forming for poromerics layer and the wick material layer of tubulose.Negative pole gelling electrode material is placed in barrier tube.Negative material is the pregelatinised mixture by the double oxide of 60% ZnO powder, 30% Zn particle, 4% aluminium oxide, 4% PTFE and 2%.Be soldered to the top that brass nail on closure member is positioned at tank, with make nail (current collector) in negative pole gelling electrode material in the heart.Then with insulant, closure member is crimped to tank so that positive pole (tank) can not be contacted with negative electrode terminal.The battery forming is thus carried out to performance test.

Fig. 6 show according to embodiment herein for pencil formula battery loop-around data and the charge and discharge Capacity Ratio up to 80 circulations.Battery unit shown that charge and discharge Capacity Ratio is close to 1 (constant in 80 circulations), and soft short circuit never occurs in pilot cell unit.Charge rate is that 600mA and discharge rate are 400mA.

Conclusion

Although only having some implements all, for for the purpose of being described clearly and provide, can to implement various alternate design.Therefore, this example is considered to be illustrative and not restrictive, and this enforcement is not limited to details given here, but can revise within the scope of the invention.Obviously it is apparent, can realizing within the scope of the appended claims some change and amendment for the person of ordinary skill of the art.

Claims

1. a rechargeable battery, comprising:

A) comprise the hollow cylinder positive electrode of nickel hydroxide;

B) comprise at least one the gelling negative electrode in zinc and zinc compound;

C) be inserted in the spacer between inner surface and the described gelling negative electrode of described hollow cylinder positive electrode;

D) negative electrode current collector in described gelling negative electrode;

E) hold the battery can of described cylindrical positive electrode, described gelling negative electrode, described spacer and described negative electrode current collector, wherein said battery can comprise first end and the second end of opening; And

F) be fixed to the positive cover of the described the second end of described battery can.

2. rechargeable battery according to claim 1, wherein said hollow cylinder positive electrode comprises multiple stacking ring segments.

3. rechargeable battery according to claim 1, wherein said hollow cylinder positive electrode comprises nickel hydroxide and cobalt metal and/or cobalt compound.

4. rechargeable battery according to claim 3, wherein said hollow cylinder positive electrode comprises the first conductive agent.

5. rechargeable battery according to claim 4, wherein said the first conductive agent comprises at least one in nickel, carbon, conducting polymer and conductivity ceramics.

6. rechargeable battery according to claim 5, wherein said the first conductive agent is taked the form of powder, foam, fiber or their combination.

7. rechargeable battery according to claim 3, wherein said hollow cylinder positive electrode comprises binding agent.

8. rechargeable battery according to claim 7, wherein said binding agent comprises at least one in polytetrafluoroethylene PTFE, cellulose, carboxyl methyl cellulose and HPMC.

9. rechargeable battery according to claim 3, wherein said hollow cylinder positive electrode comprises irrigation.

10. rechargeable battery according to claim 7, wherein said irrigation comprises at least one in aluminium oxide, cellulose and water wetted material.

11. rechargeable batteries according to claim 1, wherein said gelling negative electrode comprises the solid mixture, alkaline electrolyte and the second conductive agent that combine with gelling agent.

12. rechargeable batteries according to claim 11, wherein said solid mixture comprises zinc and zinc oxide.

13. rechargeable batteries according to claim 12, wherein said solid mixture be included in 0% and approximately between 30% the zinc of weight and between approximately 65% and 100% the zinc oxide of weight.

14. rechargeable batteries according to claim 12, wherein said solid mixture also comprises at least one in aluminium oxide, cellulose and newsprint.

15. rechargeable batteries according to claim 14, wherein said solid mixture is included in approximately 0.5% and the about aluminium oxide between 5%.

16. rechargeable batteries according to claim 14, wherein said solid mixture is included in approximately 0.5% and the about cellulose between 5%.

17. rechargeable batteries according to claim 11, wherein said the second conductive agent comprises at least one in carbon, titanium nitride and bismuth oxide.

18. rechargeable batteries according to claim 11, wherein said spacer is tubulose substantially.

19. rechargeable batteries according to claim 18, wherein said the second conductive agent comprise described gelling negative electrode volume nearly 30%.

20. rechargeable batteries according to claim 11, wherein said solid mixture, described gelling agent, described alkaline electrolyte and described the second conductive agent at described spacer situ in conjunction with to form described gelling negative electrode.

21. rechargeable batteries according to claim 11, in conjunction with to form described gelling negative electrode, then introduce described solid mixture, described gelling agent, described alkaline electrolyte and described the second conductive agent in described spacer by described gelling negative electrode.

22. rechargeable batteries according to claim 11, wherein said spacer comprises double-layer lamination, described double-layer lamination comprises barrier layer and wicking layer.

23. rechargeable batteries according to claim 22, wherein said barrier layer comprises that thickness is the microporous barrier between approximately 25 μ m and 75 μ m.

24. rechargeable batteries according to claim 22, the thickness of wherein said wicking layer is between approximately 25 μ m and 200 μ m.

25. rechargeable batteries according to claim 11, the highest part of wherein said spacer is above the highest part of described hollow cylinder positive electrode, and the highest part of described hollow cylinder positive electrode is again above the highest part of described gelling negative electrode.

26. rechargeable batteries according to claim 25, the highest part of wherein said spacer is above the highest part of described hollow cylinder positive electrode between about 2mm and about 5mm, and the highest part of described hollow cylinder positive electrode is again above the highest part of described gelling negative electrode between about 1mm and about 5mm.

27. rechargeable batteries according to claim 1, wherein said negative electrode current collector comprises at least one in brass, copper and steel; Comprise alternatively liberation of hydrogen inhibitor.

28. rechargeable batteries according to claim 27, wherein said liberation of hydrogen inhibitor comprises at least one in tin, lead, bismuth, silver and indium.

29. rechargeable batteries according to claim 27, wherein said negative electrode current collector comprises that surface area strengthens geometric element.

30. rechargeable batteries according to claim 29, wherein said surface area strengthens geometric element and comprises at least one in fin, grid, perforation, spiral, meander configuration, ridge, helix and their combination.

31. rechargeable batteries according to claim 1, further comprise the negative electrode terminal plate that is electrically connected to described negative electrode current collector.

32. rechargeable batteries according to claim 1, the ratio of the length of wherein said rechargeable battery and the diameter of described rechargeable battery at about 1.5:1 between about 20:1.

33. rechargeable batteries according to claim 32, the ratio of the length of wherein said rechargeable battery and the diameter of described rechargeable battery is between about 1.5:1 and 10:1.

34. rechargeable batteries according to claim 32, the ratio of the length of wherein said rechargeable battery and the diameter of described rechargeable battery is between about 1.5:1 and 5:1.

35. rechargeable batteries according to claim 32, the ratio >5:1 of the length of wherein said rechargeable battery and the diameter of described rechargeable battery and described diameter are between about 10mm and 100mm.

36. rechargeable batteries according to claim 35, the ratio >5.5:1 of the length of wherein said rechargeable battery and the diameter of described rechargeable battery and described diameter are between about 10mm and 50mm.

37. rechargeable batteries according to claim 1, wherein said battery can has the shape factor that meets following size and dimension, and described size and dimension is the size and dimension of the standard cell size selected of the group from being made up of AAA, AA, C, D and inferior C.

38. rechargeable batteries according to claim 1, further comprise the identification label that identifies uniquely described rechargeable battery and allow the quantity of its charging of monitoring or discharge cycles.

39. according to the rechargeable battery described in claim 38, and wherein said identification label is bar code.

40. rechargeable batteries according to claim 1, the described the second end of wherein said tank comprises steam vent.

41. rechargeable batteries according to claim 1, further comprise with the anode collector dish of described gelling negative electrode electric connection and have substantially smooth surface and serve as negative terminal for described rechargeable battery.

42. rechargeable batteries according to claim 1, wherein said positive cover comprises steam vent.

43. according to the rechargeable battery described in claim 35 or 36, and the relative ratios of the hollow diameter of wherein said hollow cylinder positive electrode and the diameter of described rechargeable battery is approximately 0.4 and approximately between 0.95.

44. according to the rechargeable battery described in claim 35 or 36, and the relative ratios of the hollow diameter of wherein said hollow cylinder positive electrode and the diameter of described rechargeable battery is approximately 0.5 and approximately between 0.9.

45. according to the rechargeable battery described in claim 35 or 36, and the relative ratios of the hollow diameter of wherein said hollow cylinder positive electrode and the diameter of described rechargeable battery is approximately 0.6 and approximately between 0.85.

46. according to the rechargeable battery described in claim 35 or 36, and the relative ratios of the hollow diameter of wherein said hollow cylinder positive electrode and the diameter of described rechargeable battery is approximately 0.6 and approximately between 0.7.

47. according to the rechargeable battery described in claim 45, and the annular thickness of wherein said hollow cylinder positive electrode is between about 1.5mm and 2.5mm.

48. according to the rechargeable battery described in claim 45, and the annular thickness of wherein said hollow cylinder positive electrode is between about 2.1mm and 2.5mm.

49. 1 kinds of rechargeable batteries, comprising:

A) hollow cylinder positive electrode, comprises (i) nickel hydroxide and/or hydroxy nickel oxide, and (ii) cobalt metal and/or cobalt compound;

B) gelling negative electrode, comprises weight 0% and approximately the zinc between 30%, weight are at least one in zinc oxide, gelling agent, alkaline electrolyte and optional carbon, cellulose, titanium nitride and the aluminium oxide between approximately 65% and 100%;

C) be inserted in the spacer of the tubulose substantially between described hollow cylinder positive electrode and described gelling negative electrode; And

Wherein said rechargeable battery can be with about 0.5C or larger discharge rate have an appointment from complete charged state to complete discharge condition 25 and 1000 circulations.

50. according to the rechargeable battery described in claim 49, and the ratio of the length of wherein said rechargeable battery and the diameter of described rechargeable battery is between about 1.5:1 and 10:1.

51. according to the rechargeable battery described in claim 49, and the ratio of the length of wherein said rechargeable battery and the diameter of described rechargeable battery is between about 1.5:1 and 5:1.

52. according to the rechargeable battery described in claim 51, further comprises and is configured to the size available on the market selected the group from being made up of AAA, AA, C, D and inferior C.

53. according to the rechargeable battery described in claim 52, is configured to described size AA available on the market.

54. according to the rechargeable battery described in claim 53, and the annular thickness of wherein said hollow cylinder positive electrode is between about 1mm and about 3mm.

55. according to the rechargeable battery described in claim 49, and wherein said hollow cylinder positive electrode further comprises nickel and/or carbon.

Manufacture the method for rechargeable battery assembly for 56. 1 kinds, described method comprises:

A) the hollow cylinder positive electrode that comprises nickel hydroxide is incorporated in tank;

B) barrier tube is incorporated in described hollow cylinder positive electrode hollow;

C) at least one the gelling negative electrode having in zinc and zinc compound is incorporated in described barrier tube; And

D) insert the negative electrode current collector being inserted in described gelling negative electrode.

57. according to the method described in claim 56, wherein forms described gelling negative electrode at described spacer situ.

58. according to the method described in claim 56, and wherein said hollow cylinder electrode mixture comprises the stacking of ring segment.

59. according to the method described in claim 56, and the highest part of wherein said barrier tube is above the highest part of described hollow cylinder positive electrode, and the highest part of described hollow cylinder positive electrode is again above the highest part of described gelling negative electrode.

60. according to the method described in claim 59, the highest part of wherein said barrier tube is above the highest part of described hollow cylinder positive electrode between about 4mm and about 10mm, and the highest part of described hollow cylinder positive electrode is again above the highest part of described gelling negative electrode between about 1mm and about 10mm.

61. according to the method described in claim 56, and wherein said negative electrode current collector is attached to for sealing described tank and the closure member that completes described rechargeable battery assembly.