CN1735987A - Optimised alkaline electrochemical cells - Google Patents

Abstract

Alkaline electrochemical cells with substantially increased performance characteristics have a porous anode, with a porosity equal to or greater than 69%, and a porous cathode, comprising manganese dioxide and having a porosity equal to or greater than 26%.

Description

Optimised alkaline electrochemical cells

The present invention relates to alkali electrochemical battery, it has porous cathode, and this negative electrode comprises manganese dioxide.

Alkali electrochemical battery was coming out more than 20 year on the market.In the middle of many modern Application, it is far better that alkaline battery is compared performance with traditional zinc-carbon cell, therefore is the battery that is subjected to the most consumers favor.

Though in order to produce best alkaline battery, all exist keen competition, the still old many restrictive conditions of pendulum in face of people, the size of especially any given battery always.

The stock size of alkaline primary cell comprises AAA, AA, C, D and 9V (being respectively LR03, LR6, LR14, LR20 and 6LR61), and has all stipulated standard size at all these types.Therefore, no matter select which kind of battery, all necessary volume up to specification has so just limited the maximum addition of various compositions in any given battery.

At these restrictive conditions, utilize the inner volume of battery for optimization, battery manufacturers have been taked various measures, such as the thickness that significantly reduces cell wall, reduce the thickness of seal and the identification method that changes battery.

Because it is not-so-practical further improving the volume of battery component, so battery manufacturers all assign to further strengthen the property and extending battery life by strengthening and/or change the one-tenth that is adopted attempting, but finally all limited.

The another kind of method of improving cell discharge performance is to improve the utilization ratio of active material in discharge process.If battery (ohmic load that is device is very low, electric current leak (current drain) very high and power consumption when very high) under the very low condition of discharging efficiency uses, and is exactly the most effective.Because by battery-driven device battery has been proposed more and more higher requirement, has become more and more important so this has become.

United States Patent (USP) 5,283,139 (are designated hereinafter simply as ' 139 or US ' 139) are openly arrived, and improve the density of anode and negative electrode and the consumption that need not improve aqueous potassium hydroxide electrolyte just can improve the performance of battery.If can not improve the volume of given active component, so logically, improve density and improve the most direct method of discharge capacity of the cell exactly.

However, still be desirable to provide the electrochemical cell that performance is become better and better.

In International Patent Application WO 01/99214, we show, wondrous and opposite be with desired, by optimizing the ratio of water, this is opposite with US ' 139, can significantly strengthen the performance of battery thus, its performance is far super press those batteries that US ' 139 prepares, and the highlyest improves 15% or higher.

Before ' 139, US-A-5,489,493 disclose alkali electrochemical battery, and it comprises negative electrode, and this negative electrode comprises manganese dioxide, and wherein negative electrode is to be made of the mixture of a small amount of high porosity manganese dioxide with a large amount of low porosity manganese dioxide.This high porosity manganese dioxide is example with chemical manganese bioxide (CMD), and is distributed in the whole negative electrode, so that provide the evolving path by negative electrode for ion.But CMD under any circumstance can both meet the demands, because the peroxidating degree of CMD is lower and its density is lower than electrolytic manganese dioxide (EMD).Therefore be that the theoretical capacity of CMD is lower than EMD in volume.

The feasibility of utilizing semi-solid cathode material is disclosed in WO 00/30193.The porosity of this semisolid material is very high and its electrolyte content is very high, and it mainly acts on is the polarity effect that reduces negative electrode.The shortcoming of this structure comprises that battery capacity significantly reduces and MnO ₂: the C ratio is very low, the more important thing is, this cathode material is difficult to operation, and it is not-so-practical therefore utilizing the battery that conventional manufacture method and equipment manufacturing are contained this class material.Compare with US ' 139, the capacity and the performance of this class battery are also had a greatly reduced quality.

WO 98/50969 discloses the purposes of uniform zinc particle in anode, when the porosity of anode up to and when surpassing 80%, can improve performance.So porosity is easy to make the zinc particle to separate and improves impedance, particularly in 1 meter drop test.The disclosure content is told us, improves porosity and just can improve performance, and prerequisite is that what to be adopted is sheet zinc.High porosity is easy to obtain, even also be so under relative higher density, because the density of zinc is very high, and does not have the upper limit, can obtain good result though test data shows when porosity is 75～80%.

The battery industry standard adopts constant resistance to test to define the battery performance grade at common application traditionally.Along with the improvement of battery-operated device, and the appearance of more complicated testing equipment, begun to comprise gradually and decided current testing, in the recent period since in addition comprise and decide power test.What more and more pay attention to now is not only will obtain battery performance under heavier load and improve effect, and will decide electric current and decide to be discharged under the power-type discharging condition higher voltage terminal point under heavier load.These trend also more and more require battery can show good performance in niche area, such as heavy duty, decide electric current (A), decide power (W), continuously and intermittent discharge, and combination.

Voltage when improving battery discharge can improve the discharge capacity when heavily leaking discharge (heavy draindischarge), when particularly being discharged to the higher voltage terminal point.In alkaline battery, theoretically, the working voltage elevating agents is such as Ag ₂O and ferrate are very noticeable, but the problem that exists comprises cost, operability and unsteadiness.Therefore, reducing internal resistance is to improve the unique feasible approach of battery-operated voltage.In order to improve the high discharge performance of deciding under the power, always all in the conductivity of being devoted to improve anode and negative electrode, but the obtained success of these behaves is very little or basic just do not achieve success, and improves effect because will offset these when other parameter being done necessary variation.

Known dry cell is made with mercury at first, contains mercury cell in a large number and can cause potential destruction to environment but abandon, and has received close concern in this respect.Therefore, the mercury content in the dry cell has been reduced to the degree of not adding mercury in most of user's batteries on the market now.Exist the mercury of trace in the zinc, but its content in ppm is.

The consumption that reduces mercury is not a lead-pipe cinch so, especially its phenomenon (gassing) that can prevent to give vent to anger.Have the fact to show, by otherwise reducing the phenomenon of giving vent to anger, it is possible removing mercury, such as the purity of improving various electrodes and electrolyte components and add various additives, such as the ammonium derivative that replaces.

Remove after the mercury, also have the fact to show the consumption that must improve zinc, because mercury also helps the conductivity of anode.Remove the electronic efficiency that mercury can reduce anode zinc, therefore have to improve the consumption of zinc.In order in whole discharge process, to make conductivity keep sufficiently high level, generally need excessive zinc.The zinc capacity was generally about 1.33: 1 with the ratio of cathode capacities.But what excessive zinc rose is the function of conductor, and the function of non-active material, has therefore just limited the amount of the active material that can charge in battery.Another shortcoming is that when battery ran out, any residual zinc might react with the water of any remnants and produce hydrogen.

Anode: the negative electrode ratio be 1.33: 1 very common, very common at least to a certain extent because exist secondary electron reaction, Mn ^III→ Mn ^IIThough this reaction is primary reaction Mn ^IV→ Mn ^IIISecondary reaction, but it is believed that at present it occupies very significant status in total discharge capacity of battery.The secondary electron reaction is what to carry out in suitable center in solution, and these center majorities are graphite, and adopting the purpose of graphite in the negative electrode is in order to obtain conductivity.Graphite is not active material, therefore generally all reduces its consumption as far as possible, and activated manganese dioxide: the ratio of graphite generally was at least 20: 1.In order to improve the content of active material to greatest extent, keep conductivity simultaneously, people are taking various measures to improve activated manganese dioxide always: the ratio of graphite.

But the consumption that reduces graphite can reduce the required activated centre of generation secondary reaction, thereby can reduce the efficient of this secondary electron reaction.Therefore, can reduce the consumption of zinc like this, thus will remaining a part of zinc after battery uses up, produce gas thus.This effect can cause is bringing leakage problem through after the deep discharge.Compensate because if reduce the consumption of zinc, will reduce the discharge capacity of battery, so better choice is to guarantee that battery can be because of tired exhaust or the leakage problem of producing of hematocrit in typical under non-exceptional condition.

Surprisingly, we find, the porosity of negative electrode and anode is not only important, and porosity separately all exists maximum, and be easy to obtain, it is very little or just do not have to surpass benefit that this value obtained, and by the two is made up at all, in fact the performance of the battery of manufacturing even better than the battery performance that is obtained by US ' 139 disclosures although reduced the consumption of active material in order to obtain higher porosity.

Therefore, the invention provides the electrochemical cell that comprises aqueous alkaline electrolyte, porous cathode and porous anode, wherein negative electrode comprises manganese dioxide, the porosity of negative electrode is equal to or greater than 26%, anode comprises and is insoluble to this electrolyte electrochemical active material, and the porosity of anode is more than or equal to 69%.

Term used herein " porosity " refers to bulking value non-solid in the relevant electrode.Solid is an insoluble composition under the common condition in the battery of assembling.In anode, solid generally only comprises zinc and indium hydroxide, if present.Other anode component generally dissolves in electrolyte solution, comprises gelling agent.When calculating porosity, will not dissolve in electrolytical component and be considered as solid.If the part of composition is insoluble,, when calculating the electrode porosity, will this soluble part not be included among the solid so such as when electrolyte is saturated; The total amount of this composition all will be got rid of.Under any circumstance, the consumption of gelling agent is generally all very little in the anode, thereby in fact can it not counted when calculating porosity.In negative electrode, solid generally in fact only comprises MnO ₂And carbon (generally being graphite).With regard to actual conditions, though the negative electrode binding agent generally is insoluble, therefore can be calculated as solid, the amount of any binding agent is generally all very little, therefore has no significant effect calculating porosity.Because it (is respectively MnO that negative electrode and anode all contain insoluble active material ₂With preferred zinc), therefore in electrochemical cell of the present invention, the porosity of male or female all can not be 100%.

The present invention is further illustrated with reference to the accompanying drawing of appendix, wherein:

Fig. 1 is by its anode porosity of battery of embodiment of the present invention manufacturing and the curve chart of anode efficiency;

Fig. 2 is by its negative electrode porosity of battery of embodiment of the present invention manufacturing and the curve chart of cathode efficiency;

Fig. 3 is by its anode porosity of battery of embodiment of the present invention manufacturing and the curve chart of zinc metal sheet (zincflake) consumption; And

Fig. 4 is by its maximum total zinc bulk density of battery of embodiment of the present invention manufacturing and the curve chart of anode porosity relation.

Battery by manufacturing of the present invention has the negative electrode of high porosity and the anode of high porosity. Just be easy to observe Performance Characteristics and strengthen effect although improve the porosity of one of them electrode, improving effect when only having the two porosity all to be in floor level of the present invention at least just can be remarkable. When being in these levels, battery performance will rapidly be improved immediately, all has electrode discharge efficient and discharge time significantly to raise. What can know is, improves the porosity of one of them electrode, and the capacity of this electrode must descend, and supposes the constant volume of electrode. But when being higher than minimum level of the present invention, the loss on the raising meeting compensation capacity of battery performance but also have a surplus. As if as if the raising of porosity can improve the efficient of relevant electrode, and with the improving combination of effects and can make electrochemical cell reactions carry out more freely of two electrodes together, the loss that has compensated thus electrode capacity is also had a surplus. Improve the known high-rate discharge characteristic of improving of electrode conductivuty, if but the porosity of electrode is lower than level of the present invention, just can not see the beneficial effect that improves electrode conductivuty, and perhaps this effect has been masked.

Therefore, be at least 26% and the anode porosity is at least 69% by its negative electrode porosity of battery of manufacturing of the present invention.

If the porosity of negative electrode and anode all is in the optimum efficiency level, thereby if being carried out suitable selection, zinc make anode keep enough electric conductivity, the factor of electric conductivity will produce unusual Beneficial Effect to the battery performance of deciding power (W) when discharge in the impact so, particularly when high power discharge. The granularity that the zinc particle has in the anode and shape must be so that zinc can form electric conductivity matrix, even zinc is very low with respect to the consumption of anode volume. Otherwise the zinc particle will be separated, and is distributed in by spells in the conductive matrices of anode. If the zinc particle has these shapes and granularity, the bulk density of zinc is quite low.

Therefore, one embodiment of the invention provide alkali electrochemical battery, and it comprises manganese dioxide base negative electrode and zinc-base anode, and the porosity of this negative electrode is equal to or greater than 27%, the porosity of anode is equal to or greater than 69%, and anode zinc is made of the zinc of total calculating bulk density less than 3.2g/cc.

" manganese dioxide base " and " zinc-base " refer to manganese dioxide and zinc is respectively main active electrode material in negative electrode and anode.

By the porosity of further raising anode and negative electrode one or both of, can obtain further to improve effect, and the preferred battery of institute is that the anode porosity is at least 70% and the negative electrode porosity is at least 28%.

Though high porosity anode and height porosity negative electrode suit, improving the anode porosity to surpassing at 76% o'clock, institute obtains additionally to improve effect and seems very little or just do not have at all.Need not further to improve again the porosity of anode, improve any problem of bringing afterwards with regard to having avoided carrying out this type of thus, also reduce thereupon such as consumption that reduces material and capacity.The influence that negative electrode produced does not have so remarkable, but from the negative electrode porosity being increased to the angle that surpasses the overall performance that was obtained at 36% o'clock, influence still has slightly.

Surpass certain a bit, the additional beneficial effect that is obtained can not have very little or at all, and such point depends on the overall characteristic of battery.But as if with regard to negative electrode, this point generally is between 71～74%.Be higher than at about 71% o'clock, the influence that reduces anode capacity will become very remarkable, and along with the further raising of anode porosity, performance platform will occur and progressively reduce then.

The porosity of anode relation general and battery target purposes is little.But the negative electrode porosity is bigger to the influence of discharge performance, and therefore preferred negative electrode porosity also depends on the target purposes of battery to a certain extent.Generally speaking, when the negative electrode porosity was at least 30%, the high rate discharge performance will be better, and when the negative electrode porosity was at least 31%, its performance even meeting were better.The negative electrode porosity preferably is no more than 34%.

If the porosity of battery of the present invention is generally than being considered as preferred battery porosity height, these batteries also comprise in the present invention so, though this class battery is compared with the prior art battery, its performance is only suitable even performance is lower than the battery of prior art, it is available that but their performance still is regarded as, the content of its active component reduces greatly simultaneously, therefore helps reducing manufacturing cost.

Electrode capacity used herein refers to the theoretical capacity electrode, represents with ampere-hour (Ah).Unless point out in addition or existing expressing that specific volume value used herein is 0.285Ah/g with regard to the manganese dioxide of 1 electron discharge, and is 0.820Ah/g with regard to zinc.

Generally speaking, when calculating cathode capacities according to the 1 electronics rule of this paper the following stated, the cathode capacities of battery of the present invention: the preferred 0.42～0.49Ah/cm of ratio of battery volume ³On the contrary, when adopting regular that US ' 139 provides, this ratio is about 0.54～0.63Ah/cm ³

An embodiment preferred, the battery of the present invention that provides, when calculating cathode capacities according to 1 electronics rule, cathode capacities: the ratio of battery volume is 0.42～0.49Ah/cm ³

Therefore with regard to AA or LR6 battery, when cathode capacities was equal to or greater than 2.6Ah, advantage of the present invention will be clearly.When being lower than this value, performance is often only suitable with prior art, though can see the advantage that the active component consumption reduces.When reaching or be higher than 2.9Ah, the ratio of the combined effect of raising electrode porosity and raising capacity and reduction A: C can be worked in coordination with and be played a role, the battery that is provided not only decides to have excellent performance under electric current (the continuous high drainconstant current) condition continuous high the leakage, and also has excellent performance in low leakage interrupted (lowerdrain intermittent) test.

Therefore, in preferred embodiments, provide LR6 battery of the present invention, its cathode capacities is at least 2.6Ah.

Equally, with regard to the LR6 battery, can obtain effect of the present invention to capacity and be up to about 3.2Ah.When being higher than this value, satisfy the requirement that improves density and will make available space reduce too much, and these advantages will progressively being lost.But it is quite difficult making cathode capacities surpass 2.9Ah.Generally speaking, when being in 2.6～3.0Ah scope, will strengthen the LR6 battery quite significantly and leak the performance of using in (high drain applications), and this being particularly preferred at height.

Battery of the present invention is particularly useful for high the leakage in the application, such as the PDA (personal digital assistant) and the miscellaneous equipment that need continuous discharge or frequent discharge, and digital camera, video camera and photoflash equipment.Be particularly preferred for battery by the approximate equipment of deciding the power mode discharge, such as the MP3 player.For low leakage was used, though the influence that the capacity reduction is produced because of the raising porosity is bigger, the present invention still showed advantage, thereby must correspondingly take in this factor when providing battery at such application.

As previously mentioned, the final goal purposes of battery is influential to the selection of battery parameter.Such as, if battery at be that the purposes of (continuous dischargeconstant power drain situation) under the power leakage condition is decided in continuous discharge, wish that the negative electrode porosity surpasses 30%, preferred 30～36%, more preferably 32～34%, particularly about 33%.It all is useful that porosity reaches any anode of at least 69%, such as aforesaid 71%.For LR6 (AA) battery, cathode capacities this class continuous power leak (continuous power drain) use in preferred about 2.7～2.9Ah (comprising end value), and preferred independently 20: 1～25: 1 of EMD: C.

Just as was expected, and with regard to intermittently deciding the power discharge condition, battery capacity has just become more significant factor, thereby the balance between negative electrode porosity and the capacity is taken a turn for the worse.For AA or LR6 battery, negative electrode porosity preferably about 28～30% (comprising end value), and the preferred 2.9～3.0Ah of cathode capacities (comprising end value).Preferred independently 20: 1～23: 1 of EMD: C.In fact this embodiment can both obtain excellent result in currently used most of power tests, if not all, and has constituted particularly preferred embodiment of the present invention.According to the rule of defined before, be applicable to any battery types know this embodiment, all other embodiments as herein described also are so, express unless have in addition.

Particularly preferably be, when depth of discharge is an electronics, that is, battery is discharged to by the following stated after the level of 1 electronics, and the KOH calculating concentration of any battery is about 50%w/w.Surpass at 50% o'clock, KOH will promptly crystallize out, and reduces basicity and water content thus, because each KOH divides the crystallization water of two molecules of subband.Therefore, the final calculating concentration of KOH substantially exceeds at 50% o'clock, and battery will soon lose efficacy.

The final calculating concentration of KOH was significantly less than 50% o'clock, the general efficient of the battery that is obtained is all very low, because water has occupied the space that should be occupied by active component.In addition, if KOH too dilutes, this inefficiencies will further be aggravated so, as detailed below.But within being in porosity ranges of the present invention and when adopting the electrolyte concentration that prior art adopts, the KOH ultimate density can be reduced to and be lower than 50% and not necessarily can wasting space.Though this class battery generally is also included among the present invention, but find that this class battery can't be by maximal efficiency work, although electrolyte has only occupied the unserviceable space of active component, only, the KOH ultimate density could obtain optimum efficiency 50% the time approximately when being calculated as.

We find that if the anode porosity of battery has reached peak efficiency, the KOH ultimate density can cause voltage to descend less than 50% o'clock, thereby make battery " inefficacy " in advance.In other words, such as in long run test, battery reaches 1V and expects that the time of failpoint will be 50% battery faster than 1 electronics KOH ultimate density.In fact also notice that final KOH also shows the phenomenon that the zinc passivation shifts to an earlier date less than 50% battery.

In the anode porosity battery lower than the present invention, improve KOH concentration, no matter be during when beginning or by 1 electron discharge, all can obtained performance improve effect.But this performance can not surpass performance of the present invention forever, and because porosity is lower, must improve the consumption of active material.Therefore, porosity of the present invention makes the consumption of remarkable reduction active material become possibility, and the performance characteristics of enhancing but can be provided.

Bound by theory is not now thought when the anode porosity is low, improve KOH concentration reaction scheme shown below (I) is pushed ahead, thereby otherwise low porosity can limit the carrying out that ion motion hinders this reaction.But, when being in porosity of the present invention, in case this inhibition significantly and also the anode porosity reach about 70 or at 71% o'clock, this cell reaction is exactly to be decided by negative electrode.

In the cell reaction process, when electric current flowed, the concentration of KOH obviously raise in the negative electrode, then reduced in the anode.If the anode porosity is too low, compensate the necessary ion exchange of this effect and just can't enough carry out apace, make concentration effect increase the weight of.If any one KOH concentration is reduced to 0% in the anode, passivation takes place in zinc in so should the zone possibly, seriously weakens its performance.

Generally speaking, when the anode porosity is lower than approximately 70% the time, as if negative electrode is subjected to the influence of various variations bigger, and can think that battery performance is decided by negative electrode.As if when being higher than this scope, the effect of anode begins to become important.Bound by theory not, why the KOH ultimate density most preferably 50%, and seemingly because KOH can be in negative electrode but not crystallized out in anode, and when the anode porosity was higher than 70%, negative electrode was a decisive factor.The anode porosity is lower than at 70% o'clock, and higher KOH can partly compensate porosity and reduce the influence produced, thus partial offset anticathode adverse effect.When the anode porosity was higher than 70%, this influenced still clearly, but anticathode influence begins to become even more important, so the crystallization behavior of KOH in negative electrode determined the highest ultimate density of KOH.

Therefore, the present invention further provides the battery of aforementioned definitions, it comprises the electrolyte that contains KOH, and this battery selected KOH concentration before discharge will make that the KOH calculating concentration of battery after being discharged to the 1 electron discharge degree of depth is about 50%w/w.Preferred amount of electrolyte will make the calculating 1 electron discharge level that is in manganese dioxide the time, the calculating concentration of KOH is 49.5～51.5% (w/w solution).

Because the complexity that uncertainty presented of every kind of composition and another composition relation can't at large be collected various information from the data that test cell obtained, in the past such as the influence of porosity change.Particularly, what only can determine in the past is have enough water to exist, and its form is KOH solution (in this article with industrial all be called " electrolyte "), thereby makes electrochemical reaction to carry out.Referring to US ' 139, the various measures of being taked in this article all are in order to improve the amount of " activity " composition to greatest extent, and not to the in addition any specific concern of electrolytical amount.

We notice now, and it is about 50% very important that the ultimate density of KOH is no more than, and no matter which kind of degree this battery is intended to be discharged to, and perhaps discharge rate how, and this rule all is suitable for.Can produce very significantly influence to battery performance with this rule generation deviation, and can twist,, even can't obtain significant conclusion if it is not observed by changing the result of the test that other parameter obtains.

The KOH ultimate density should be 50% after 1 electron discharge, and this is found to be the standardization electrochemical cell strict criterion is provided, and just might set up various relations this moment between all other compositions of electrochemical cell.In the equation group that constitutes electrochemical cell, now just can establish its variate-value, prerequisite is the benchmark that can obtain to fix now, benchmark just can be determined other amount thus.

Do not recognize that the KOH ultimate density is in 50% scope is very crucial for the performance that improves any given battery to greatest extent in the past, the porosity that changes negative electrode or anode will inevitably change the ultimate density of KOH, thereby the final performance of battery is not only relevant with selected porosity but also relevant with the ultimate density of KOH.Therefore, these results are all without any meaning, and can't determine desirable negative electrode or anode porosity.

But if battery is to make according to the rule that KOH ultimate density after 1 electron discharge should be in 50% scope, so with desired opposite, just might determine that negative electrode and anode all exist the desirable porosity that is easy to obtain this moment.If the two one of porosity be significantly less than this ideal value, performance will significantly descend so, and if the two one of porosity substantially exceed this ideal value, will make performance produce reduction again owing to lacking active material so.

Generally speaking, battery of the present invention does not preferably contain and adds mercury and comprise moisture KOH electrolyte, contain zinc anode and contain manganese dioxide cathodes.

Though for the present invention not necessarily, before the preferred discharge in the electrolyte concentration of KOH be about 34～37% (w/w solution)." before the discharge " refers to have passed through to be in after all manufacturing steps for the user and uses battery under the ready state.Manufacture process may comprise a spot of discharge, such as in the electrical testing process.But general even more important considering is that ultimate density is within 50% scope, suitably selects initial concentration to obtain this result.

What need know is that the amount of manganese dioxide and zinc generally all maintains certain capacity than within the scope, thereby change one of them another is changed thereupon.This ratio can be that given manufacturer wishes any value of adopting, and the ratio of anode and negative electrode (A: C than) was generally about 1.2: 1～about 1.4: 1.In this article, when describing, suppose that the population proportion of anode capacity and cathode capacities remains unchanged with regard to the parameter that changes one of them electrode.

In the past, the amount that reduces zinc just means the volume ratio that makes anode and negative electrode and remains unchanged and improve the porosity of anode, perhaps reduces the volume of anode.In the previous case, must will can't obtain the cathode capacities reinforced effects, and under latter event,, thereby battery performance be affected adversely because the amount of electrolyte (major part of anode) too reduces.This is because anode is more much bigger than the porosity of negative electrode, and therefore the measure of any reduction anode dimension all can reduce electrolytical amount usable.As following more specify, the final too low subject matter that produces of electrolyte level is that the concentration of KOH can be increased to and be much higher than 50% after 1 electron discharge.What need know is to be exactly that this discovery makes battery technology stride forward major step.

By improving the porosity of negative electrode and anode, the current size that just might reduce anode but can keep electrolytical cumulative volume capacity.Therefore, by improving the porosity of two electrodes, just can introduce enough electrolyte before using in battery, thereby it is about 50% that the concentration of KOH is no more than, more specifically explanation as follows.

The present invention is by reducing the ratio of A: C, reduces deep discharge thus and leaks (deep dischargeleakage) and can not reduce the low discharge period when leaking intermittent discharge.In fact, reduce after this ratio, can improve continuous high the leakage by the content that improves manganese dioxide in the negative electrode and decide current capability (continuous high drain constant current performance).

Anode efficiency also is very important feature.Although the prior art to outstanding explanation is in the present invention optimized, anode efficiency seldom surpasses 26%.Therefore, if A: the ratio of C is reduced to and is lower than about 1.1.5: 1, and performance is reduced, improve effect because can't see desired anode efficiency, thereby make anode efficiency become the limiting factor of performance in these batteries.

As if anode efficiency very close with the relation of initial KOH concentration.In the present invention, the ultimate density of KOH must be about 50% behind 1 electron discharge.But initial KOH concentration changes with the capacity and the electrolytical total amount of manganese dioxide.If electrolytical content is very high, the concentration of so initial KOH will be higher, because the water that is consumed in the cell reaction has concentrated effect slightly to KOH, but this concentration still must end at 50%.

Corollary is, initial electrolytical amount is few more, and needed KOH concentration is just low more, because the dehydrating effect of cell reaction is much higher.With regard to same water consumption, KOH concentration raises highly more, and initial concentration just must be low more, so that ultimate density still is in about 50%.

This can influence anode efficiency because KOH concentration the efficient of high anode is just high more more.As empirical law, we find, the every raising of initial KOH concentration is about 1%, and anode efficiency improves about 0.5%.Because higher initial KOH concentration depends on the more initial content of polyelectrolyte, therefore, what know is that anode efficiency can reduce with the reduction of anode dimension, because the porosity of anode is higher than negative electrode, be bound to reduce electrolytical initial content thereby reduce anode dimension.Therefore, though can improve the amount of cathode material, finally can reduce offseting with the anode efficiency that causes because of the reduction anode dimension.

Can improve the porosity of arbitrary electrode by any suitable mode.With regard to anode,, the content of zinc is remained unchanged in order to realize that this purpose such as the interior diameter that can improve negative electrode, improves the volume of anode thus.If do not improve anode volume, so just must reduce the amount of zinc, the consumption of corresponding thus reduction cathode material is so that reduce the porosity of anode, unless change A through the careful consideration decision: the C ratio.What know is to an advantage of the invention is when reducing the active electrode material total amount and can improve battery performance.

Must suitably select used zinc in the anode, thereby make anode keep enough conductivity.Even in the amount of zinc for anode under the quite few situation, the particle that this zinc is included, its shape and size also must can reach this effect.To contain the zinc particle can keep conductivity matrix under lower concentration in order to make, its bulk density is very low.When porosity is higher than approximately 66% the time, anode preferably comprises non-particulate shape zinc.This zinc can be any type of zinc simply, and powdered zinc commonly used wants high in its surface area ratio battery.

When the anode porosity more than or equal to 69% the time, in the battery of making by the present invention, total bulk density of the zinc that is adopted is preferably less than 3.2g/cc.Generally speaking, along with the raising of anode porosity, must reduce the bulk density of zinc.For the lower anode of porosity, when the anode porosity is higher than 69%, the every raising 1% of porosity, preferred maximum bulk density just reduces 0.06g/cc.More preferably, when the anode porosity was 69%, total bulk density of zinc was no more than 3.13g/cc, and for the lower anode of porosity, when the anode porosity is higher than 69%, the every raising 1% of porosity, total bulk density reduces 0.085g/cc.When the anode porosity is about 71% the time, the preferred total bulk density of zinc is 2.83～2.96g/cc (comprising end value).

A kind of method of controlling total bulk density is to adopt the mixture of high and low-density zinc.Such as, the low-density zinc particle of common high density zinc powder in irregular shape and shape homogeneous is mixed, thereby obtain required total bulk density.This class mixture also has processing or cost advantage.

" the zinc particle of shape homogeneous " refers to single zinc particle consistent basically shape.This is different from typical zinc powder, and the latter does not from start to finish have the shape of rule, and is nearly all not alike each other.In order to have uniform shape, what each coating of particles factor must be to all other particles is similar basically.So such as, if this homogeneous shape is a sheet, so all particles all must be sheets.In order to produce the particle of shape homogeneous, must control to guarantee to obtain required consistent grain shape moulding or classification process.Can determine the zinc coating of particles by mode with the sem observation particle.

Total bulk density of zinc is to be obtained as calculated by the measurement bulk density of dissimilar zinc contained in the anode.Total bulk density equals 100/ ∑ (d _n/ w _n), d wherein _nBe the bulk density of n type zinc, and w _nBe the percetage by weight of n type zinc, based on the total amount of zinc particle in the anode.If what adopt is the zinc of single type, then total bulk density then equals the measurement bulk density of sample zinc.

Sheet is useful shape, and it has relatively low bulk density, but in order to reduce total bulk density of zinc in the anode, also can adopt other 2 peacekeepings, 3 dimension shapes.This zinc can overcome when the anode porosity is higher separates the zinc conductive path loss problem that causes because of the zinc particle.Zinc metal sheet is the preferred form of the low-density zinc institute of shape homogeneous, and generally all refers to this zinc in this article, even so, know when mentioning zinc metal sheet, also comprise other form of low-density zinc, unless otherwise noted or existing expressing.

When height leaked constant-current discharge, the zinc metal sheet content that accounts for the about 5%w/w of zinc total amount just was enough to compensate the conductive path loss, and the porosity of this moment reaches as high as about 73%.Generally speaking, when anode surpassed 66%, porosity per 1% improved, and it is exactly enough that the sheet body burden increases 1%w/w, even so, know that the one skilled in the art can adopt more zinc metal sheet as required.As required, no matter how much zinc in the anode reduced, and can compensate it with other anode composition.Surprisingly, decide under the current condition in the height leakage, efficient is high especially when zinc metal sheet is 70～73% for about 5～7% anode porositys, and performance can improve several percentage points.

Decide power discharge in order to improve high the leakage, the preferred use than this many slightly zinc metal sheet.Generally speaking, when anode surpasses 67%, the every raising 1% of porosity, it is exactly enough that the content of zinc metal sheet in overall zinc increases about 1.5%w/w, even so, know that the one skilled in the art can adopt more zinc metal sheet as required.More preferably when anode surpasses 67%, the every raising 1% of porosity, zinc metal sheet content increases about 2%w/w.Though surpassing this value also is acceptable, generally can obtain further performance improvement effect hardly, the high more just difficult more operation of zinc metal sheet content, and zinc metal sheet is comparatively expensive.More particularly,,, find that it can be used in combination with about 71% anode porosity based on the total amount of zinc particle in the anode when zinc metal sheet content is about 8～11% the time, such as the zinc metal sheet of content about 8% not only have commercially available and also from actual easily.

Such as, zinc can be mixture, and it comprises the low-density zinc particle of at least 4 weight %, shape homogeneous, and its bulk density is less than 2.5g/cc.

Anode can manufacture porous form according to multiple mode.A kind of art methods has adopted CMD.When cell cathode contains CMD, to compare with the battery that only contains EMD, this battery leaks in the long run test at height and generally shows very poor performance.But surprisingly, this moment, we found, if adopt CMD in the present invention, cooperated porous anode, just can alleviate the various shortcoming of CMD.Though contain the battery of CMD, its performance is not good as otherwise porosity being increased to the battery of its peer-level, only exists little difference between them.It should be noted that especially and can give negative electrode very high additional strength that this is a very big advantage when assembling.

Also can adopt other method to prepare porous cathode.Preferable methods is to form generally those of structure uniformly.Amount by manganese dioxide or carbon in the reduction cathode mix generally just can realize this purpose.But, when manganese dioxide compresses inadequately, can have problems, because the structural intergrity of negative electrode is impaired easily, unless in addition it is compensated.Equally, the amount that reduces carbon not only can reduce structural intergrity, and can cause conductivity to reduce.

The amount that reduces manganese dioxide can reduce capacity, and if when forming negative electrode, adopted less material, so also must reduce the density of negative electrode.This may have problems during fabrication, and is easier to be cracked such as lamellar body.Can overcome it by variety of way, such as in manufacture process, adopting trash ice or solid KOH, or improve the consumption of manganese dioxide to greatest extent and reduce the content of carbon, such as adopting carbon black.Under all these situations, still negative electrode can be compressed to conventional limit, but can make more porous of negative electrode.

If what adopt is solid KOH, make electrolyte reach required level even add water or KOH solution subsequently, be surprisingly found out that and also can too do not generate heat, and can obtain tough lamellar body.The lamellar body intensity that carbon black obtained is high but have good electrical conductivity, but wonderful discovery, if its electrolyte with about 5～30% is pre-mixed, what suit is about 10～15% electrolyte, will form tough lamellar body.All these methods all are preferred, and every kind of method all helps to provide the sufficiently high cathode material of solid degree of making used in battery by compression.

Generally make the content of carbon keep minimum, thereby must reduce the consumption of manganese dioxide, to obtain higher porosity with respect to the volume of negative electrode.Generally speaking, manganese dioxide: carbon weight ratio preferably at least 20: 1.Under the prerequisite of the conductivity of considering negative electrode, higher ratio is possible.

Though it is very big to have found to improve the influence of anode conducting, finds that also cathodic conductivity has remarkable influence to the performance of battery of the present invention in power test.

By the content of suitable selection carbon, can strengthen the conductivity of negative electrode.In the prior art, generally make the content of carbon keep minimum, thereby must make the amount of manganese dioxide reduce as far as possible,, make conductivity remain on enough levels simultaneously to reduce the content of non-active ingredient in the negative electrode.This also is applicable to other battery types, but in the present invention, find manganese dioxide: the ratio of carbon weight preferably is no more than about 26: 1.Preferred ratio is 20: 1～25: 1, particularly 22: 1～24: 1, and such as when adopting Superior GA17 graphite and GHU EMD, preferred about 23: 1 of this moment.When adopting the manganese dioxide of other carbon source or graphite and/or other brand, can change these ratios, and the one skilled in the art is easy to definite those suitable ratios.

Generally speaking, the alkaline battery reaction scheme is as follows:

(I)

Though manganese compound is expressed as manganese dioxide, this is with regard to conventional, and the one skilled in the art knows that manganese dioxide is non-stoichiometric, and the practical structure formula is approximately MnO _1.96Therefore, the actual number electron approximation that participates in this reaction is 0.925.Also be referred to as " 1 electronics " in this article routinely, or 1e.

Reaction scheme shown in aforementioned (I) generally is referred to as " primary electron reaction ", and it is the reaction of unique generation not necessarily, and can be attended by the secondary electron reaction, and MnOOH changes into Mn (OH) therein ₂This secondary reaction generally only just becomes remarkable at battery consumption totally the time.It as if to 1e discharge (primary electron reaction) afterwards the KOH ultimate density be that 50% requirement does not influence, perhaps influence is very little, and be that the battery table that 50% this requirement is optimized reveals more performance according to KOH after the 1e, no matter whether these batteries proceed to the secondary electron stage of reaction.Therefore in this article, only consider first electron reaction.No matter when mention " terminal point " herein and all refer to the primary electron reaction, perhaps from stoichiometry angle 0.925 electronics, this point when finishing (, Mn ^{+ 3.925}Be reduced into Mn ^{+ 3.0}).

For example, on discharge curve, ampere-hour is measured under discharge lines, is example with manganese dioxide, originally in most cases can form sizable shoulder, sharply glides from platform then, has crossed this point and can see losing of second electronics once in a while afterwards.The binding site that 1 electron discharge begins corresponding to shoulder bottom and platform.Though this platform is to produce under than the also low voltage of the voltage that is considered as losing efficacy with regard to most of batteries, and is generally all very steep with the pressure drop that this point is a terminal point, and can not influence 1 electronics result of calculation of the present invention.

Can see from aforementioned equation, must have enough water, thereby reaction can be carried out fully, so visual be discharge fully.The previous reaction scheme is carried out in the presence of strong base solution, and KOH solution is that institute is preferred at present for battery manufacturers.

From as can be known aforementioned, should be appreciated that KOH " ultimate density " (when being primary electron discharge end) is a calculated value.But the reaction scheme of application of aforementioned (I) is easy to calculate the ultimate density of KOH in battery is overall, and prerequisite is that the initial concentration of KOH is known.

In fact,, the KOH ultimate density calculated just mean and need not make battery discharge 1 electronics, also need not measure the ultimate density of KOH based on this principle, no matter at be anode or negative electrode, perhaps the two is taken into account.

Therefore, be easy to design and produce preferred battery,, thereby when 1 electron discharge, make KOH reach suitable final calculating concentration because be easy to by assembly and the initial amount of adjusting active material.

As previously mentioned, the ultimate density of KOH has very large influence to battery performance.Wish especially that when reaction end the KOH concentration of calculating with regard to entire cell should not surpass about 51.5%.More preferably, its value should be greater than 51%, and about 50.6% is optimum value.Value less than 50.6% is an acceptable, comprise about 49.5%, but as described below,, the possibility that obtains reinforced effects is reduced if should value too small.

As previously mentioned, " porosity " refers to the relative quantity of the relevant electrode that is not regarded as solid, v/v.The solids content that in volume is is generally than the easier calculating of non-solid content, but also because porosity comprises the air of carrying secretly such as any, so the computing formula of porosity generally is expressed as

[(V _∑-V _S)/V _∑]*100

V wherein _∑Be the measurement cumulative volume of electrode, and V _SIt is the volume of solid constituent.

The general volume of directly not measuring solid constituent, but it is calculated to be the merchant of weight and density.When calculating porosity, know that given solid matter has very likely had porosity to a certain degree, may be such as the porosity of chemical manganese bioxide (CMD) above 50%.

Therefore, in order to calculate the porosity of electrode more reliably, adopt the theoretical porosity of this material.During calculating based on molecular structure and 3-D array, and any porosity of not considering manufacture method and being produced.For this reason, EMD is regarded as identical solid density with CMD.If in the process of calculating porosity, adopted the actual apparent density of material, the electrode porosity result of calculation that is obtained so just not will consider the porosity that solid is brought into, this can cause misleading with regard to best situation, and this is skimble-skamble with regard to the worst situation.

In the supposition solid density of electrode of the present invention as follows:

Negative electrode

Component	Solid density	The weight of every 100g	The volume of every 100g
				EMD	4.53(d 1)	w 1	v 1＝w 1/4.53
CMD	4.53(d 2)	w 2	v 2＝w 2/4.53
				Graphite	2.25(d 3)	w 3	v 3＝w 3/2.25
Coathylene 	0.92(d 4)	w 4	v 4＝w 4/0.92
				40％KOH	1.39(d 5)	w 5	v 5＝w 5/1.39
Other component	d 6Deng	w 6Deng	v 6＝w 6/d 6Deng
						∑＝100

Coatylene ^It is polyethylene

Anode

Component	Type	Solid density	The weight of every 100g	The volume of every 100g
					Zinc +	Solid	7.14(d 7)	w 7	?v 7＝w 7/7.14
Carbopol?940	Liquid	1.41(d 8)	w 8	?v 8＝w 8/1.41
					Indium hydroxide	Solid	4.60(d 9)	w 9	?v 9＝w 9/4.60
ZnO	Liquid	5.61(d 10)	w l0	?v 10＝w 10/5.61
					36％KOH	Liquid	1.35(d 11)	w 11	?v 11＝w 11/1.35
Component x	？	D 12	w 12	?v 12＝w 12/d 12Deng

Wherein ' x ', '? ' and ' etc. ' refer to and can also comprise any further component, can be solid or liquid.

Therefore, the theoretical volume of negative electrode is the summation=V of all the components _∑=∑ (v ₁: v ₆)=(v ₁+ v ₂+ v ₃+ v ₅+ v ₆Deng).

Equally, the theoretical volume=V of anode _T=v ₇+ v ₈+ v ₉+ v ₁₀+ v ₁₁+ v ₁₂

With regard to negative electrode, its theoretical volume is substantially the same with actual volume, therefore there is no need to introduce compensating factor.But the actual volume of negative electrode is but different with calculated value, and porosity has accounted for very big proportion in the negative electrode of reality.

For fear of leading to misunderstanding, try to achieve the interior diameter and the overall diameter (being respectively ID and OD) of negative electrode (H) height and negative electrode, just can calculate the actual volume of negative electrode.In the present invention, preferably adopt a folded cathode sheets when making battery, so the height of H=negative electrode lamination.

In concrete example, only for usefulness for example, the negative electrode diameter is as follows for this example:

	As prepare the lamellar body of state	Canned
			Negative electrode OD	?1.345＝OD p	1.335＝OD c
Negative electrode ID	?0.900＝ID p	0.885＝ID c

Therefore,

And

Under afore-mentioned, no matter cathode sheets is loose attitude or " canned " (in can), OD ²-ID ²Difference all be 0.999.This is because under such situation, and this also is preferred for this invention, and lamellar body has passed through compression.Because this can not influence volume,,, thereby volume is remained unchanged with the reduction of compensation overall diameter so interior diameter also must decrease.

In negative electrode, theoretical volume solid=V _S=v ₁+ v ₂+ v ₃+ v ₄

Therefore,

And the present invention paid close attention to is exactly this porosity.

In anode, V _L=liquid volume=v ₈+ v ₁₀+ v ₁₁, V _S=solid volume=v ₇+ v ₉, therefore theoretical

And what constitute the anode lotion is exactly this theory porosity, and the present invention paid close attention to also is it.

With regard to anode, the difference between theoretical volume and the actual volume is often very big, and this is somewhat dependent upon the method that is adopted when filling the anode basket.In the embodiment of the following stated, this basket comprises slider, and it is to be placed in the anode cavities that is in the negative electrode.

The method that is adopted when filling the anode basket generally has two kinds.First method is the top completion method, and second method is the bottom completion method.The former relates to generally from the position dropping anode lotion near the basket top.The latter relates generally to insert distributing pipe in basket, then with move back the speed injection anode lotion that pipe speed equates, generally the strength that can extrude from pipe by means of lotion wholly or in part withdraws from pipe.

When adopting the top completion method, the air of being carried secretly in the anode is often more than the bottom completion method.No matter when, entrapped air or anode dead volume generally are at least 5%v/v, and are up to about 17% at any position.When adopting the bottom completion method, dummy section is about 5%～10%, and when adopting the top completion method, dummy section is about 8%～17%.

The porosity of anode of the present invention and the dead volume of anode are irrelevant, and the simple core of anode has just been represented the porosity that anode had basically.Therefore, porosity of the present invention at be the anode lotion of putting into before the battery.

In " ready-made (off the shelf) " battery, exist foregoing anode dead volume, and be generally about 10%.According to the present invention, in order to determine the porosity of anode, the most accurate method is to obtain core, and analyzes according to the following stated method.But rough, the anode dead volume that records in most of batteries is about 10%.Any and the porosity that deviation obtained this value are within the test error scope mostly, because be to compare with the negative electrode dead volume, when the anode dead volume is about 10% the time, can make that the anode porosity is overall to improve about 3% at 0% o'clock.Therefore, if the dead volume of supposition anode is about 10%, and in manufacturing equipment, adopt the standard bottom completion method, the anode dead volume that is obtained is about 9%, and when adopting standard top completion method in this equipment, the anode dead volume that is obtained is about 12% or 13%, so clearly, suppose that dead volume is at about 10% o'clock, the porosity broadband content that is obtained is about 1%.

When making battery of the present invention, at first calculate the theoretical volume of the overall component middle-jiao yang, function of the spleen and stomach of every 100g utmost point component.Obtain the volume of anode basket then, it is different from interior body space, and the latter is that the volume according to used spacer material is defined by negative electrode.To subtract 10% under this volume then, with adjustment anode dead volume, and the volume of Here it is used anode lotion.

Therefore, if only with porosity as the tolerance of total solid in the basket with respect to volume, the anode apparent porosity that is obtained so approximates [theoretical porosity/(100-10)] * 100, supposes that dead volume is 10%.In other words, apparent porosity approximates (theoretical porosity+about 11%).Rough, the actual porosity of anode approximates apparent porosity divided by 1.11 in the ready-made battery.But as previously mentioned, this will depend on the dead volume of battery.As previously mentioned, the porosity that the present invention paid close attention to is the porosity of anode itself, is not anode porosity+dead volume.

In this example, although the packing volume of anode has been reduced 10%, general its packed height of anode lotion that obtains is general, and still the overhead height with cathode sheets is identical.What know is according to the difference of the anode fill method that the one skilled in the art adopted, must do the variation with 10% on consumption.In fact, dead volume is filled by electrolyte, and this electrolyte enters after no matter filling, and has still existed in basket before filling, and has all constituted the required overall electrolytical part of battery of the present invention.No matter when, the anode dead volume is all occupied by electrolyte, is perhaps directly occupied, perhaps after driving away air and occupy.

Under any circumstance, the consumption of anode lotion should be approximate with high with cathode material.If highly different, if particularly anode is lower than negative electrode, so high leakage performance will be adversely affected.Therefore, for the height of negative electrode, wish that the tolerance of difference in height is not more than 2.5%.If the difference of truly having, preferred anodes is than negative electrode height so, and still only preferred difference is very little, and preferably is no more than 2.5%.

What know is, after adjusting through 10%, the amount of anode lotion must contain an amount of zinc, thus holding anode: the ratio of negative electrode Ah, suppose that in this example this ratio is 1.33.If what adopt is other ratio, just must do with suitable adjustment, but principle of the present invention still remains unchanged to volume.

In " existing shape " battery, porosity is easy to measure.Substantially, must at first measure the volume of electrode, measure its solids content then.When measuring KOH content, earlier each component of battery is analyzed, merge these results then and get final product.

Adopt modified form Dean﹠amp; The Stark method can be measured the amount of water.These equipment are such as can be from Quickfit﹠amp; Quarz Ltd. obtains.Cover sample with the toluene of drying, the 45min that refluxes then guarantees that thus most condensation processes carry out in water-cooled condenser.Access graduated cylinder or the cuvette that effluent uses below the condenser and collect water to be placed on.The improved form of this method is to blast carbon dioxide to the toluene that seethes with excitement, thereby make KOH change into K ₂CO ₃, otherwise can't collect whole water,, a part of water forms the crystallization water because can being held back by KOH.

Extract each component with the independent Soxhlet of water and obtain to contain the solution of KOH and water, so just be easy to measure OH ^-Amount.Merge all samples, gather into known volume, then by standard method titration OH ^-Such as, can adopt the known HCl of molar concentration, with phenolphthalein as indicator.In the method, suppose all OH ^-All be KOH, and correspondingly calculate its weight.

The amount (calculating according to the following stated) that the volume and the manganese dioxide of water have been arranged, the one skilled in the art just can determine whether given battery satisfies standard-required of the present invention.

Return the electrode porosity, and as previously mentioned, can calculate it according to following formula basically:

[(cumulative volume-solid volume)/(cumulative volume)] * 100

More specifically, can measure the volume of electrode according to any suitable mode.Preferably obtain volume by on the spot mode, and preferably utilize x-ray method to obtain this volume, it can make explanation, the particularly height of anode and negative electrode and width clearly with regard to the endosome size of battery.For this reason, can cut battery earlier, separate each electrode then.

Such as with regard to the described battery of appendix embodiment, the general discovery only needs to consider zinc in the anode when determining porosity, and only need in the negative electrode to consider manganese dioxide (EMD and CMD, if present) and carbon (generally being graphite).Other component is not that amount is few, and the not too high and amount of compactness also seldom perhaps forms an electrolytical part, even therefore considered these components, has been fallen among the error burst by the deviation of its generation yet.

Therefore, in anode:

● measure the inner volume size of anode basket

● the height of anode from the X ray outcome measurement basket of battery

● remove all anode materials, then with water washing zinc, to remove gelling agent and electrolyte

● wash with ammonia spirit, only stay zinc

● the zinc of weighing

● zinc volume=zinc weight/7.14

● porosity [(0.9* basket volume-zinc volume)/(0.9* basket volume)] * 100

What know is that 0.9 refers to 10% dead volume.As required, remove the gelatine electrolyte, measure the residual volume of anode then, so just can calculate dead volume by careful washing anode strip.

In negative electrode:

● from the size of X ray and observed result measurement negative electrode, from valve jacket, take out negative electrode (negative electrode OD, negative electrode ID, negative electrode are measured height) then

● with the water washing negative electrode, stay EMD/CMD, graphite and binding agent.Binding agent can be ignored, and it is the volume (less than measure error) of accessory constituent and not appreciable impact negative electrode

● solid is weighed

● the mixture with the moisture HCl of 50%w/v dissolves manganese dioxide from solid, residue graphite residue

● graphite is weighed

● manganese dioxide weight=solid weight-graphite weight

● manganese dioxide volume=manganese dioxide weight/4.53

● graphite volume=graphite weight/2.25

● negative electrode porosity=[(cathode volume-manganese dioxide volume-carbon volume)/cathode volume] * 100

What know is, can adopt more complicated chemistry or mechanical means as required, and this be the one skilled in the art can accomplish.

Clearly, the component (powder and sheet) of zinc ratio of component as comprising more than one, manganese dioxide also is (EMD and CMD) like this, but this does not have substantial influence to measurement method of porosity.

What also will know is, the density of KOH solution, and perhaps electrolytical density can change according to the difference of KOH content.But the density of KOH solution is of no significance for the invention.Generally speaking, the density of compound can be referring to Handbook of Chemistry ﹠amp; Physics.

The battery of the present invention of the following stated supposes that its volume is 6.2ml, and is the AA battery, unless otherwise noted.But what know is, the present invention is applicable to all batteries, comprise such as AAAA, AAA, AA, C, D and 9V, and the battery of other type, what also will know is to do with suitable adjustment capacity.But no matter be the battery of which kind of type, principle of the present invention all remains unchanged.

Such as, adopt identical negative electrode anode volume ratio, the present invention is equally applicable to other known standard or non-standard battery size, effective inner volume such as AAAA is about 1.35ml, effective inner volume of AAA is about 2.65ml, effective inner volume of C is about 20.4ml, and effective inner volume of D is about 43.7ml.

The present invention should adopt the manganese dioxide of LITHIUM BATTERY, and it can be from chemistry, electrolysis or natural prodcuts, and most preferably electrolytic production is the chemical method product then.Manganese dioxide has many different crystal structures, is commonly referred to as " α ", " β ", " γ ", " δ " etc.Preferred employing γ form, and any herein calculating relevant with manganese dioxide is all to use this form to be starting point.If what adopt is other crystal structure of manganese dioxide, need calculate reaction end based on different assumed condition, particularly relevant with " 1 electronics ".Particularly, main discharge curve and voltage are exactly terminal point less than the binding site between 1.0 o'clock formed platforms.If what adopt is γ type manganese dioxide, all manganese all is Mn when calculating this terminal point ^{+ 3.0}

If exist other material or reaction (such as helping negative electrode) in the battery, they are consume water in discharge process, so just must consider these materials or the water that reaction consumed.Carrying out this class when calculating, can not consider that those participate in the but material of consume water not of cell reactions.

Similarly considerations also is applicable to the battery discharge initial concentration of KOH before.Reaction scheme I (seing before) shows that the every consumption 2 molecule manganese dioxide of electrode reaction just consume 1 molecular water.But, when KOH 36% the time, different reactions will take place far below about.

KOH was far below about 36% o'clock, and reaction scheme becomes

(II)

Therefore, rise to 36% until the amount of KOH, this reaction just cannot not become significantly, because consumed the water yield out of necessity, thereby terminal point 50.6% is arrived too in advance, and perhaps the water yield that exists in the battery has occupied the share that belongs to other active component originally thus out of required.The former is generally more harmful than the latter, because can't reach complete discharge effect.

Once in battery, introduce zinc peroxide (ZnO) in the past, can in electrolyte, introduce it, but not too effective, perhaps in negative electrode, introduce it, because find that the main effect of ZnO in anode is to form plated film on current-collector, thus it is played a protective role.Suitable is the zinc oxide that adds about 3%w/w in entire cell.But more effectively be, only add it in the anode, add about 0.05%w/w in the anode this moment and just can obtain similar result.

When considering the initial concentration of KOH, generally supposition herein, the zinc oxide concentration of battery in negative electrode the most at the beginning is 0%.But, having found that zinc oxide influences the initial concentration of KOH, the result reaches about 50% if still wish ultimate density, just must improve the initial concentration of KOH.Therefore, if adopted the zinc oxide (introducing) that accounts for entire cell 3%w/w with electrolyte, the preferably about 37%w/w solution of the initial concentration of KOH so, if 2%w/w, so preferred 36～37%w/w solution, and if 1%, the solution of preferred 35-37%w/w.

As previously mentioned, KOH concentration will effectively be ended when KOH just surpasses 50.6% with raising the useful life of battery, and after this battery will lose efficacy rapidly.The water that exists in the battery is many more, and the initial concentration of KOH is just high more, supposes that terminal point is 50.6%.If reduced the amount of water when initial,, so also must reduce the concentration of KOH if do not wish that terminal point surpasses 50.6%.

To calculate final KOH according to the starting characteristic of battery.If battery is when constructing for the first time, below is known:

The weight w of manganese dioxide in the battery ₁

Electrolytical starting weight w in the battery ₂

The average initial concentration z of KOH in the battery ₁%

Calculating K OH ultimate density (after promptly 1 electron discharge finishes), based on this hypothesis, promptly all manganese dioxide all discharges and forms MnOOH.Whether really so unimportant, because found just can obtain these advantages as long as battery designs for about 50% according to the KOH ultimate density, and no matter how many final depth of discharges of battery is.

The average initial concentration which cell reaction will depend on KOH takes place:

(I)

(II)

This paper supposes as initial OH when calculating ^-During＞8N, reaction (I) 100% takes place, and as initial OH ^-During＜6N, reaction (II) 100% takes place.What also will know is, as the benchmark that 8N and 6N calculate, the definite initial concentration of KOH also depends on and dissolved which kind of other material among the KOH, such as zinc oxide or silicate.

Such as, under the identical situation of other condition, when the zinc oxide in the anode is 0.05w/w, OH ^-＞8N is equivalent to KOH initial concentration＞36%, and＜6N then is equivalent to＜and 29%; If dissolved 3% zinc oxide in the entire cell in KOH,＞8N is equivalent to KOH initial concentration＞38%, and＜6N then is equivalent to KOH initial concentration＜31%; Yet, if electrolyte does not dissolve other material in (only referring to KOH), OH so ^-＞8N is equivalent to＞34% KOH initial concentration, and＜6N then is equivalent to KOH initial concentration＜27%.

Suppose OH at 6-8N ^-Between arbitrary pH value down, be linear transitions from reaction (I) to reacting (II).

Therefore, the ultimate density of calculating K OH like this.

100% reaction (I), 0% reaction (II)＞8N OH ^-

Reaction (I) percentage=a%=100%

Reaction (II) percentage=(100-a) %=0%

0% reaction (I), 100% reaction (II)＜6N OH ^-

Reaction (I) percentage=a%=0%

Reaction (II) percentage=(100-a) %=100%

50% reaction (I), 50% reaction (II) 7N OH ^-

Reaction (I) percentage=a%=50%

Reaction (II) percentage=(100-a) %=50%

Weight=[electron number] * (a/100) * (molal weight of 0.5 * water) of reaction (I) institute water consumption]/(molal weight of manganese dioxide) * w ₁=w ₃

Weight=[electron number] of reaction (II) institute water consumption * ((100-a)/100] * [(molal weight of 1.0 * water)/(molal weight of manganese dioxide) * w ₁]=w ₄

Aforesaid equation is an empirical formula, but the result generally is consistent with these equations.

Electron number=0.925

The molal weight of water=18

The molal weight of manganese dioxide=86.93

Electrolytical final weight=w ₂-w ₃-w ₄=w ₅

Weight=the z of KOH solid ₁/ 100 * w ₂=w ₆

Ultimate density=w of KOH ₆/ w ₅* 100

Surprisingly, need not consider the secondary electron reaction.This reaction is generally carried out after the primary electron reaction, and can make battery produce extra energy.But, in order to optimize battery, it should be apparent that this moment, need not consider this secondary electron reaction.

Find that useful especially for the present invention slider can adopt the slider that comprises following copolymer:

(1) ethylenically unsaturated carboxylic acids of structural formula (I):

(R wherein ¹, R ²And R ³Be same to each other or different to each other, and each represents the alkyl of hydrogen atom, 1～10 carbon atom, perhaps aryl; And A represents direct key or the highest alkylidene group that contains 8 carbon atoms) or its salt or ester; And

(2) aromatic compound of structural formula (II):

(R wherein ⁴, R ⁵And R ⁶Be same to each other or different to each other, and each represents the alkyl of hydrogen atom, 1～10 carbon atom, perhaps aryl; And R ⁷Represent sulfonate or carboxylate groups and balance cation), perhaps this slider can comprise the homopolymers of the described aromatic compound of structural formula (II).Generally speaking, the preferred directly key of A and R ¹-R ⁷All be hydrogen.

This copolymer can directly be used as slider, and preferably utilize it to form slider on the spot this moment in battery, perhaps it is coated on (such as the separating tissue of routine) in the porous substrate, just can adopt thin paper and/or layer still less this moment.

Particularly preferred copolymer is the copolymer that comprises acrylic or methacrylic acid and styrene sulfonate, and most preferred copolymer is the copolymer of acrylic acid and styrene sulfonate, this copolymer is optional to comprise one or more other monomers, but does not preferably adopt this class monomer.Most preferred copolymer is the copolymer of acrylic acid and Sodium styrene sulfonate.Perhaps, can adopt the homopolymers of Sodium styrene sulfonate.

If separately with copolymer or homopolymers as slider, preferably the form with solution or dispersion is sprayed it on the spot in battery.Therefore, first part assembled battery is inserted one of anode and negative electrode in the battery cover.Use the solution or the dispersion of copolymer or homopolymers then on anode or the negative electrode,, then make its drying, with in another insertion battery in negative electrode and the anode, finish battery thus then such as by spray-on process.

Perhaps as used among this paper embodiment, copolymer or homopolymers are carried in that class porous substrate that is commonly used for slider in the electrochemical cell technology, are also referred to as separating tissue herein, though this substrate not necessarily really is a paper.Copolymer or homopolymers can be used on one or both sides and formed coating, but, preferably only be applied on the side, it is immersed among substrate for the ease of using.Perhaps, use it, carry out drying (desolvating) then, generally realize it, perhaps make it to solidify according to preceding method by the steamdrum seasoning such as removing by evaporation with the form of solution or dispersion.

Coating can be the coating apparatus of any routine with equipment, and various ways all is commercially available in this kind equipment.Equipment used herein is Dixon Pilot Coater, by T.H.Dixon﹠amp; Co.Ltd., Letchworth, Herts, England makes, and when enforcement is of the present invention, can adopt the commercial scale type or the suitable therewith commercial size unit of this equipment.

The advantage of such chorista especially is, is to be to avoid the unique essential slider of short circuit when being formed with the battery of usefulness through the individual layer separating tissue of copolymer or homopolymers coating or dipping.Prior art has adopted double-deck slider, and particularly in the less battery of size, it has occupied the expensive real estate that should give active material.

The present invention can adopt any suitable or conventional spacer material.The example of appropriate materials comprises the mixture of polyvinyl alcohol (vinylon) and mercerising hardwood fiber VLZ75 and VLZ105 (thickness is respectively about 75 and 105 μ m), the latter two Nippon Kodoshi Corporation (NKK) sell, the similar material that Hollingsworth and Vose sells, and lyocell staple fibre, vinal, matrix fiber and Freudenberg sell the mixture of binder fibre.

Therefore, in preferred embodiments, the invention provides the electrochemical cell that comprises the individual layer separating tissue, this paper is coated with and/or is impregnated with the copolymer or the homopolymers of above definition.

What know is when group structure alkali electrochemical battery, must consider many factors.In the present invention, suppose that battery meets battery generally and makes principle, and expect that negative electrode is a solid property, but not semisolid.Can use any standard analysis in the battery of the present invention, such as comprising binding agent and antigassing additive.The embodiment of appendix does not add binding agent when allotment.

By following examples the present invention is further detailed.Unless point out in addition, the battery among the embodiment is as follows: the initial concentration of KOH is 36～42%, but its ultimate density is 50.6% after 1 electron discharge by selecting to make.Equally, Ah herein and no matter when mention Ah (ampere-hour), all based on this supposition, promptly 1 electron reaction is carried out (0.925e) fully but the secondary electron reaction is not taken place, thereby only comes the expection capacity from elementary main reaction when calculating.Unless point out in addition, Ah is relevant with the capacity of negative electrode.Used slider is to scribble acrylic acid and Sodium styrene sulfonate (ratio is 20: 80w/w) one deck VLZ75 paper of copolymer, coating weight is 30gsm, perhaps double-deck VLZ105 paper.Used manganese dioxide is GHU EMD, and graphite is Superior GA17.

In these embodiments, a part of battery is tested by following, employing be ArbinInstruments, 3206 Longmire Drive, College Station, TX77845, No.BT2043 type standard testing machine and the software MITS 97 of USA, it is also from ArbinInstruments.

1A/ continuously/1V0

In this test, electrochemical cell is being decided continuous discharge under the electric current 1A, until reaching end point voltage 1V.The result is with minute (m) expression.

43R0/4h/1d/0V9

In this test, electrochemical cell is being decided resistance 43 Ω following every day of continuous discharge 4h, is being had a rest and put 20h then, until reaching end point voltage 0.9V.The result is with hour (h) expression.

10R0/1h/1d/0V9

In this test, electrochemical cell is had a rest then and is put 23h, until reaching end point voltage 0.9V deciding resistance 10 Ω following every day of continuous discharge 1h.The result is with hour (h) expression.

3R9/1h/1d/0V8

In this test, electrochemical cell is had a rest then and is put 23h, until reaching end point voltage 0.8V deciding resistance 3.9 Ω following every day of continuous discharge 1h.The result is with minute (m) expression.

1W/ continuously/1V0

In this test, electrochemical cell is with the speed continuous discharge of 1.0W, until reaching end point voltage 1.0V.The result is with minute (m) expression.

1W/30m/12h/1V0

Test cell leaked electricity 30 minutes with the speed of 1.0W, made its no-load leave standstill 11.5h then.Repeat this circulation, reach terminal point 1.0V until battery.

1W5/3s/7s/1h/1d/1V0

Test cell makes its no-load leave standstill 7s with the speed electric leakage 3s of 1.5W then.Repeat this circulation 1h continuously.Make the battery no-load leave standstill 23h then.Repeat whole circulation then, reach terminal point 1.0V until battery.

In following embodiment, manufacturing be LR6 (AA size cylinder shape alkali zinc/manganese dioxide) battery, and it is tested estimating the influence of negative electrode and anode porosity, and other battery behavior.Used valve jacket is the steel valve jacket, and inner surface scribbles graphite, to reduce the internal impedance between negative electrode and the valve jacket to greatest extent.The nominal inner volume of finished product battery is 6.33cm ³, and the nominal volume of each composition (anode, negative electrode and electrolyte) is 6.20cm ³

Generally speaking, the battery of embodiment 1-4 is to make according to anode, negative electrode and electrolyte formula and other important battery characteristics that table 1 provides, comprises calculated performance, unless point out in addition in this article.In table 1, percentage is percetage by weight, and except the porosity, it is based on volume.

Table 1

Cathode mix
					EMD	％	95.23
Graphite	％	3.17
					40％KOH	％	1.60
					Cathode sheets
Weight	g	2.69
					Highly	cm	1.080
The negative electrode external diameter	cm	1.345
					The negative electrode internal diameter	cm	0.900
The sheet number		4
					Negative electrode internal diameter in the valve jacket	cm	0.885
					Slider
The number of plies		1
					Type		VLZ75/AA：SSA
					Anode cream
Zinc	％	68.300
					Carbopol	％	0.400
In(OH) 3	％	0.015
					ZnO	％	0.034
Electrolyte	％	31.250
					KOH concentration	％	38
The percentage of sheet zinc	％		5
						Anode cream weight	g	6.94
					Electrolyte adds
Electrolyte concentration	％	38
					Add earlier	g	1.36
Add the back	g	0.36
Computational item
					Negative electrode Ah			Ah	2.92
The negative electrode porosity			％	28.8
					EMD: C ratio				30
Anode A h			Ah	3.89
					The anode porosity			％	70.7
Anode: negative electrode Ah ratio				1.33
					Final KOH concentration			％	50-51
Negative electrode Ah/ composition Vol ratio				0.471

Embodiment 1

Table 2 has gathered the discharge period (" 1A " row) that many important battery characteristics and 1A continuous discharge are represented with min when testing to 1.0V.

Table 2

Negative electrode				Initial		Anode
											Porosity (%)	Ah	EMD∶C	ID (nm)	KOH (wt％)	Slider	Lamellar body (wt%)	Porosity (%)	1A	Cathode efficiency %	Anode efficiency %
＞27	2.6-2.9						70-76
											28.8	2.9	30	8.85	38	1xVLZ/AA：SS	3	70.7	56	32.0	24.0
31.3	2.8	26	8.85	40	1xVLZ/AA：SS	5	72.2	56	33.3	25.1
											31.3	2.7	23	9.05	40	2xVLZ105	5	71.7	55	34.3	25.8
31.3	2.7	23	9.05	40	1xVLZ/AA：SS	8	74.3	54	33.7	25.3
											33.8	2.7	23	8.85	40	2xVLZ105	3	70.3	55	34.5	25.9
33.8	2.7	23	8.58	40	1xVLZ/AA：SS	7	73.4	56	35.1	26.4
											33.8	2.6	23	9.05	41	2xVLZ105	6	72.8	55	35.8	26.9
33.8	2.6	23	9.05	41	1xVLZ/AA：SS	10	75.5	54	35.2	26.4
											36.3	2.7	20	8.58	40	1xVLZ/AA：SS	5	72.2	54	34.0	25.5
＞27	2.4-2.6						＞76
											28.8	2.6	26	9.40	40	1xVLZ/AA：SS	12	76.7	51	32.7	24.6
31.3	2.5	26	9.40	41	1xVLZ/AA：SS	13	77.7	51	34.0	25.6
											33.8	2.4	23	8.85	42	1xVLZ/AA：SS	15	78.8	50	34.7	26.1
＜27	2.6-2.9						70-76
											25.8	2.9	30	9.05	40	1xVLZ/AA：SS	5	72.2	53	30.5	22.9
22.3	2.8	26	9.40	39	1xVLZ/AA：SS	10	75.3	49	29.2	21.9
											25.8	2.8	20	9.05	39	1xVLZ/AA：SS	6	73.0	52	31.0	23.3
25.8	2.7	20	9.40	40	1xVLZ/AA：SS	13	77.2	52	32.1	24.1
											26.9	2.8	26	9.16	40	1xVLZ/AA：SS	8	74.2	53	32.0	24.1
＞27	2.6-2.9						＜70
											28.8	2.9	30	8.85	38	1xVLZ/AA：SS	0	70.7	53	30.3	22.7
33.8	2.8	23	8.85	40	2xVLZ105	0	67.5	52	31.0	23.3
											36.3	2.8	20	8.05	40	1xVLZ/AA：SS	0	65.9	52	31.0	23.3
36.3	2.8	26	8.85	40	2xVLZ105	1	69.0	53	31.5	23.7
											＞27	＞2.9						＜70
31.3	3.0	30	8.65	37	1xVLZ/AA：SS	1	69.1	54	30.0	22.6
											33.5	3.1	20	8.05	36	2xVLZ105	0	57.8	44	23.9	18.0
＜27	＞2.9						70-76
											22.1	3.0	26	8.85	36	1xVLZ/AA：SS	4	71.1	50	27.8	20.9
＜27	＞2.9						＜70
											26.9	3.1	26	8.65	36	2xVLZ105	0	63.6	46	25.0	18.8
26.9	3.1	26	8.65	36	1xVLZ/AA：SS	0	67.4	51	27.7	20.8
											28.8	3.1	30	8.65	36	1xVLZ/AA：SS	0	65.4	51	27.7	20.8
25.8	3.0	30	8.85	37	1xVLZ/AA：SS	2	69.5	53	29.4	22.1
											22.1	3.0	26	8.85	36	2xVLZ105	0	67.5	44	24.4	18.4

Table 2 is divided into 7 intervals:

Negative electrode porosity negative electrode Ah anode porosity

Interval 1＞27% 2.6-2.9 70-76%

Preferable range of the present invention is done place change

Interval 2＞27% 2.4-2.6＞76%

Interval 3＜27% 2.6-2.9 70-76%

Interval 4＞27% 2.6-2.9＜70%

Preferable range of the present invention is done the change of at least 2 places

Interval 5＞27%＞2.9＜70%

Interval 6＜27%＞2.9 70-76%

Interval 7＜27%＞2.9＜70%

1 result has highlighted the present invention and has leaked the many advantages of using the battery that designs for height in the interval.Negative electrode and anode porosity are within the scope of the invention.The result is very good for the 1Amp long run test.These results accompany by high efficient.

Result in interval 2 shows that along with increasing of anode porosity, efficient is kept.But the porosity of negative electrode is more and more higher can to consume additional space, thereby makes the cathode capacities reduction and make performance impaired thereupon.1A result is than interval 1 short at least 3min.

Result in interval 3 shows that when negative electrode porosity reduction value was lower than 27%, cathode efficiency can be corresponding impaired.Best result is observed when optimizing other parameter in this interval, and such as when cathode capacities is very high, perhaps porosity reaches at 27% o'clock.

Result in interval 4 shows that the result of anode and cathode type are seemingly.Therefore, when the anode porosity less than 70% the time, anode efficiency will be corresponding impaired and performance also can be impaired.

In the interval 5-7 of table 2, battery efficiency is greater than 2.9Ah.Under this level, the cumulative volume of composition is 6.2ml in addition, is difficult to design the battery that anode and negative electrode porosity satisfy requirement of the present invention.Battery in these intervals, its shortcoming are that cathode efficiency and anode efficiency are all very low.Cathode capacities is high more, and the performance that is obtained is just good more to a certain extent, reduces the influence that is produced but can't compensate porosity.

Embodiment 2

The influence that table 3 expression improves zinc metal sheet content.For the ease of contrast, the data in table 2 first interval in table 3 second interval, have been repeated to list.

Table 3

Negative electrode				Initial		Anode
											Porosity (%)	Ah	EMD∶C	ID	KOH (wt％)	Slider	Lamellar body (wt%)	Porosity (%)	1A	Cathode efficiency %	Anode efficiency %
＞27	2.6-2.9						70-76
											28.8	2.9	30	8.85	38	1xVLZ/AA：SS	5	70.7	59	33.7％	25.3％
32.6	2.9	25	8.65	39	1xVLZ/AA：SS	5	70.7	59	34.4％	25.9％
											33.8	2.8	23	8.58	39	1xVLZ/AA：SS	5	70.3	60	35.8％	26.9％
33.8	2.8	23	8.58	39	1xVLZ/AA：SS	8	70.3	59	35.2％	26.5％
											36.3	2.7	20	8.58	40	1xVLZ/AA：SS	8	71.8	58	36.5％	27.4％
＞27	2.6-2.9						70-76
											28.8	2.9	30	8.85	38	1xVLZ/AA：SS	3	70.7	56	32.0	24.0
31.3	2.8	26	8.85	40	1xVLZ/AA：SS	5	72.2	56	33.3	25.1
											31.3	2.7	23	9.05	40	2xVLZ105	5	71.7	55	34.3	25.8
31.3	2.7	23	9.05	40	1xVLZ/AA：SS	8	74.3	54	33.7	25.3
											33.8	2.7	23	8.85	40	2xVLZ105	3	70.3	55	34.5	25.9
33.8	2.7	23	8.58	40	1xVLZ/AA：SS	7	73.4	56	35.1	26.4
											33.8	2.6	23	9.05	41	2xVLZ105	6	72.8	55	35.8	26.9
33.8	2.6	23	9.05	41	1xVLZ/AA：SS	10	75.5	54	35.2	26.4
											36.3	2.7	20	8.58	40	1xVLZ/AA：SS	5	72.2	54	34.0	25.5

Table 3 shows, improves the content of zinc metal sheet a little, just can significantly improve anode efficiency and battery performance.But,, when carrying out 1A continuous discharge test, just can not obtain any further performance reinforced effects when zinc metal sheet content is increased to when surpassing 5%.

Embodiment 3

Accompanying drawing 1 expression be influence (the negative electrode porosity is higher than 28%) in 1Amp continuous discharge anode porosity antianode efficient to the test of 1.0V, be influence (the about 70-71% of anode porosity) and Fig. 2 represents in 1Amp continuous discharge negative electrode porosity target efficient to the test of 1.0V.Can be clear that when the anode porosity is about 71% the time, anode efficiency is platform basically.But, just offset as previously mentioned, by capacitance loss along with cathode efficiency continues to rise to about 28%.

Embodiment 4

In following table 4, expression be of the influence of KOH concentration to performance and efficient.

Table 4

Negative electrode				A: C Ah ratio	KOH		Anode		The continuous 1V0 of 1A/
												Porosity %	Negative electrode Ah	EMD: C weight ratio	ID mm	Initial (wt%)	Finally (wt%)	Lamellar body (wt%)	Porosity %	Performance m	Cathode efficiency % %	Anode efficiency % %
25.8	3.3	20	8.20		1.33	34	61	0	60	42	21.2												15.9
				25.8								3.3	20	8.20	1.33	36	55	0	60	45	22.7	17.1
25.8	3.3	20	8.20		1.33	38	57	0	60	49	24.7												18.6
				25.8								3.3	20	8.20	1.33	40	60	0	60	50	25.3	19.0
25.8	3.0	20	8.65		1.33	34	54	2	68	42	23.3												17.5
				25.8								3.0	20	8.65	1.33	36	50	2	68	45	25.0	18.8
25.8	3.0	20	8.65		1.33	38	52	2	68	49	27.2												20.5
				25.8								3.0	20	8.65	1.33	40	55	2	68	50	28.3	21.3
25.8	2.8	20	9.05		1.33	34	50	7	73	46	27.3												20.6
				25.8								2.8	20	9.05	1.33	36	48	7	73	49	29.2	21.9
25.8	2.8	20	9.05		1.33	38	50	7	73	52	30.9												23.3
				25.8								2.8	20	9.05	1.33	39	51	7	73	52	30.9	23.3
25.8	2.8	20	9.05		1.33	40	52	7	73	49	29.2												21.9
				25.8								2.7	20	9.40	1.33	34	47	13	77	47	29.0	21.8
25.8	2.7	20	9.40		1.33	36	46	13	77	50	30.9												23.2
				25.8								2.7	20	9.40	1.33	38	48	13	77	51	31.5	23.7
25.8	2.7	20	9.40		1.33	40	50	13	77	52	32.1												24.1
				28.8								2.92	30	8.85	1.33	36	48	5	71	56	32.2	24.2
28.8	2.92	30	8.85		1.33	38	50	5	71	60	34.5												25.9
				33.8								2.79	23	8.65	1.33	36	47	5	71	58	34.6	26.0
33.8	2.79	23	8.65		1.33	39	50	5	71	61	36.4												27.3
				36.6								2.64	20	8.65	1.33	36	45	7	72	55	34.7	26.1
36.6	2.64	20	8.65		1.33	40	51	7	72	58	36.6												27.5
				33.8								2.92	30	8.85	1.33	38	50	3	71	56	31.9	24.0
33.8	2.79	23	8.65		1.33	39	50	3	71	56	33.5												25.2
				36.6								2.64	20	8.65	1.33	41	51	5	72	54	34.1	25.6

In last table 4, can be clear that when the anode porosity is lower than 70%, improves KOH concentration and can raise the efficiency and performance, but be 70% and during Geng Gao in the anode porosity, the raising degree that is obtained is different.Can also be clear that, the best ultimate density of KOH is about 50% at 70% o'clock, and be significantly less than approximately 70% the time when the anode porosity that situation is really not so.

Embodiment 5-7

What adopt among following examples 5-7 is and the similar LR6 battery of embodiment 1-4 that just their prescription and feature are as shown in table 5, unless point out in addition.Percentage is percetage by weight, and except the porosity, it is based on volume.The control cell of embodiment 5 is that the change part sees Table 5 according to the preparation of the method for international publication number W001/99214.

Table 5

		The comparative example 5	Embodiment 6	Embodiment 7
					Cathode mix
EMD	％	94.76	95.23	95.23
					Graphite	％	3.64	3.17	3.17
40％KOH	％	1.60	1.60	1.60
					Cathode sheets
Weight	g	2.84	2.69	2.83
					Highly	cm	1.080	1.080	1.080
The negative electrode external diameter	cm	1.345	1.345	1.345
					The negative electrode internal diameter	cm	0.900	0.900	0.873
The sheet number		4	4	4
					Negative electrode internal diameter in the valve jacket	cm	0.885	0.885	0.858
Slider		2 *VLZ105	VLZ75/AA：SS	VLZ75/AA：SS
					Anode cream
Zinc	％	73.200	68.300	68.500
					Carbopol?940	％	0.340	0.400	0.390
In(OH) 3	％	0.017	0.015	0.016
					ZnO	％	0.036	0.034	0.034
Electrolyte	％	26.407	31.251	31.060
					KOH concentration	％		36	38	37
The percentage of sheet zinc	％		0	5							5
					Anode cream weight	g	6.80	6.94	6.51
Electrolyte adds
					Electrolyte concentration	％		36	38	37
Add earlier	g	1.33	1.36	1.39
					Add the back	g	0.35	0.36	0.32
Computational item
					Negative electrode Ah	Ah	3.07	2.92	3.07
The negative electrode porosity	％	24.5	28.8	28.5
					EMD: C ratio		26	30	30
Anode	Ah	4.08	3.89	3.66
					The anode porosity	％	66.0	70.7	70.7
A: C Ah ratio		1.33	1.33	1.19
					The KOH ultimate density	％	50-51	50-51	50-51
Negative electrode Ah/ composition Vol ratio		0.495	0.471	0.495

In 4 aforesaid discharge tests, the battery of embodiment 5-7 is tested.The results are summarized in the table 6.

Table 6

		The comparative example 5	Embodiment 6	Embodiment 7
					ANSI/IEC
43R0/4h/0V9	h	95	91	95
					10R0/1h/0V9	h	21.5	20.5	21.9
3R9/1h/0V8	m	486	474	506
					1A/ is continuous
1A/ continuously/1V0	m	46	59	56

Three tests in the table 6 are that the industrial standard of simulating ultralow leakage equipment is intermittently tested.The battery of embodiment 5 shows good performance in these trials.The battery of embodiment 6 shows more much betterly than embodiment 5 in 1A (high continuously the leakage) test, but its discharge performance is impaired slightly in slow-speed test.Embodiment 7 batteries not only show excellent discharge performance in 1A continuous discharge test, and their discharge performances of in slow-speed test, being showed also the battery with embodiment 5 is the same good at least.

Embodiment 8

The LR6 battery is similar to Example 7, further represents A: C comparison high rate discharge Effect on Performance.The result of the test of important battery parameter and 1A continuous discharge test is summarised in the table 7.In all batteries, the ultimate density of KOH is 50-51%.Concentration

Table 7

Negative electrode				A∶C	Initial KOH concentration (wt%)	Anode			1A	Cathode efficiency %	Anode efficiency %
												Porosity (%)	Ah	EMD∶C	ID mm	Lamellar body (wt%)	Porosity (%)	Ah
28.6	3.07	30	8.58			1.19	37	5											70.7	3.65	56	30.4	25.5
				26.5	3.07				20	8.58	1.19	37	5	70.7	3.65	53	28.8	24.2
26.5	3.07	26	8.58			1.17	37	5											70.7	3.59	54	29.3	25.1
				26.5	3.07				30	8.75	1.24	37	5	70.7	3.81	57	30.9	25.0
26.5	3.07	30	8.75			1.19	37	7											70.7	3.65	53	28.8	24.2
				28.6	3.07				30	8.58	1.19	37	0	70.7	3.65	50	27.1	22.8
27.7	3.07	25	8.58			1.19	37	0											70.7	3.65	50	27.1	22.8
				26.5	3.07				20	8.58	1.19	37	0	70.7	3.65	50	27.1	22.8
26.5	3.07	26	8.58			1.17	37	2											70.7	3.59	51	27.7	23.7
				30.6	3.20				25	8.58	1.00	36	5	70.7		48	25.0	25.0

Table 7 shows as a result, and in 1A continuous discharge test, anode efficiency can't surpass 25.5% forever.As A: when C was lower than 1.15: 1, cell discharge performance reduced, because anode is limited by low A: the C ratio.The A of embodiment 8 batteries: the C ratio is 1.15: 1～1.25: 1, and it shows much better 1A discharge performance than the control cell of embodiment 5.

What embodiment 9-13 adopted is and the similar LR6 battery of embodiment 1-8 that just its prescription and feature see Table 8, unless point out in addition.Percentage is percetage by weight, and except the porosity, it is based on volume.

Table 8

Cathode mix
					EMD	％	94.30
Graphite	％	4.10
					40％KOH	％	1.60
Cathode sheets
					Weight	g	2.70
Highly	cm	1.080
					The negative electrode external diameter	cm	1.345
The negative electrode internal diameter	cm	0.890
					The sheet number		4
Negative electrode internal diameter in the valve jacket	cm	0.885
					Slider
The number of plies		1
					Type		VLZ75/AA：SSA
Anode cream
					Zinc	％	68.00
Carbopol	％	0.400
					In(OH) 3	％	0.015
ZnO	％	0.034
					Electrolyte	％	31.55
KOH concentration	％	38.5
					The percentage of sheet zinc	％		10
Anode cream weight	g	6.90
					Electrolyte adds
Electrolyte concentration	％	38.5
					Add earlier	g	1.49
Add the back	g	0.21
					Computational item
Negative electrode Ah			Ah	2.90
					The negative electrode porosity			％	29.2
EMD: C ratio				23
					Anode A h			Ah	3.86
The anode porosity			％	70.9
					Anode: negative electrode Ah ratio				1.33
Final KOH concentration			％	50-51
					Negative electrode Ah/ composition Vol ratio				0.468

Embodiment 9

The battery that just meets requirement of the present invention in others is measured the influence to it of zinc bulk density and sheet body burden.The results are shown in following table 9.Total bulk density is by described calculating before.Measure the bulk density of every type zinc according to following steps, but also can adopt any proper method known to the one skilled in the art, that can obtain identical result:

● the empty graduated cylinder of weighing 5ml band scale

● in graduated cylinder, add zinc and carry out weighing once more

● with rubber stopper flicking graduated cylinder, be stabilized in certain level until zinc

● read the volume of zinc from cylinder scale

● with the net weight of zinc in the compacted volume removal graduated cylinder of viewed zinc, obtain the bulk density of zinc thus

Table 9

The negative electrode porosity	Negative electrode Ah	The anode porosity	Sheet body burden (wt%)	Zinc bulk density g/cc	A: C ratio	The continuous 1V0 of 1A/ (min.)	The continuous 1V0 of 1W/ (min.)	Difference (min.)
									28％	3.1	71％	0％	3.40	1.19	51	55	4
28％	3.1	71％	5％	3.11	1.19	56	61	5
									28％	3.1	71％	8％	2.96	1.19	55	62	7
28％	3.1	71％	11％	2.83	1.19	54	63	9
									29％	2.9	71％	0％	3.40	1.33	53	57	4
29％	2.9	71％	3％	3.22	1.33	56	62	6
									29％	2.9	71％	5％	3.11	1.33	59	66	7
29％	2.9	71％	8％	2.96	1.33	58	66	8

Can see, reduce total bulk density of zinc, can improve the performance of 1A long run test and 1W long run test.In order to reduce total bulk density of zinc, can adopt the mixture of zinc powder and zinc metal sheet.The bulk density of zinc powder is generally about 3.2～3.7g/cc.Zinc powder used in the present embodiment is barium-indium-aluminium alloy, and by Brussels, the Union Miniere of Belgium is commercially available, and its bulk density is 3.4g/cc.The production code member of zinc metal sheet is 5454.3, from Columbus, and Ohio, the Transmet Corp. of USA, its bulk density are 1.2g/cc.When total bulk density was 3.11g/cc, being equivalent to the sheet body burden was 5%, and based on the total weight of zinc, the performance of 1A long run test is best, and in the 1W long run test, surpassed 5% later performance improvement effect still continuing, and found no the sign of decline.In addition, the higher battery of negative electrode porosity also shows result preferably in two tests, highlighted the importance that improves cathode efficiency to greatest extent thus.

Embodiment 10

Measured EMD: the influence of C ratio, the battery that is adopted is: negative electrode porosity＞28%, the porosity that contains the zinc anode lotion are 71%, and wherein zinc comprises the lamellar body of 8 weight %, and A: the C ratio is 1.33.Total bulk density of zinc is 2.96g/cc.Discharge test the results are shown in following table 10.

Table 10

Negative electrode (Ah)	EMD: C (weight ratio)	1A/ continuously/1V0 (min.)	1W/ continuously/1V0 (min.)	Difference (min.)
					2.7	15∶1	54	65	11
2.8	20∶1	56	66	10
					2.8	23∶1	58	68	10
2.9	25∶1	58	68	10
					2.9	30∶1	59	64	5

As can be seen from Table 10, discharge capacity of the cell is mostly with EMD: the increase of C ratio improves.Along with EMD: the raising of C ratio, continuous performance of 1A such as expection and improve, cathode capacities also increases.But 1W continuous discharge performance but fails to show identical relation, when EMD: C ratio is 23-25: in the time of 1, its performance the best.Therefore, though the continuous performance of 1A depends primarily on capacity, the continuous performance of 1W is relevant with capacity to a certain extent, and the conductivity of negative electrode is an important factor.

Embodiment 11

Expression is the influence that changes various battery parameters in the following table 11.In each case, the porosity of anode is 71%.

Table 11

Negative electrode porosity (%)	Negative electrode Ah	EMD∶C	A: C ratio	Lamellar body (wt%)	Zinc bulk density (g/cc)	The continuous 1V0 of 1W0/ (minute)
							＞30％	2.7-2.9	＜26	＞1.25
33	2.9	25	1.33	8	2.96	69
							36	2.7	20	1.33	11	2.83	68
36	2.7	20	1.33	8	2.96	67
							34	2.8	23	1.33	8	2.96	67
＜30％	2.7-2.9	＜26	＞1.25
							29	2.9	20	1.33	8	2.96	66
29	2.9	23	1.33	8	2.96	64
							28	2.9	20	1.33	10	2.87	65
28	2.7	15	1.33	8	2.96	65
							＞30％	＜2.7	＜26	＞1.25
34	2.6	23	1.33	8	2.96	62
							＜30％	2.7-2.9	＞26	＞1.25
29	2.9	30	1.33	8	2.96	65
							＞30％	＞2.9	＜26	＜1.25
30	3.0	25	1.22	8	2.96	64
							＜30％	＞2.9	＜26	＞1.25
28	3.0	20	1.26	8	2.96	63
							＜30％	＞2.9	＜26	＜1.25
29	3.0	23	1.24	8	2.96	60
							28	3.1	25	1.19	11	2.83	64
28	3.1	25	1.19	8	2.96	62
							28	3.0	20	1.22	8	2.96	62
＞30％	＞2.9	＞26	＜1.25
							29	3.1	3D	1.19	11	2.83	62
＜30％	＞2.9	＞26	＜1.25
							28	3.1	30	1.18	8	2.96	61

For convenience of explanation, will go up table 11 and be divided into 9 intervals.

Interval 1 represents with regard to overall preferred range with regard to the battery of 1W continuous application:

Negative electrode porosity negative electrode Ah EMD: C A: C ratio

Interval 1＞30% 2.7-2.9＜26＞1.25

Do place change to interval 1:

Interval 2＜30% 2.7-2.9＜26＞1.25

Interval 3＞30%＜2.7＜26＞1.25

Do the change of 2 places to interval 1:

Interval 4＜30% 2.7-2.9＞26＞1.25

Interval 5＞30%＞2.9＜26＜1.25

Interval 6＜30%＞2.9＜26＞1.25

Do the change of 3 places to interval 1:

Interval 7＜30%＞2.9＜26＜1.25

Interval 8＞30%＞2.9＞26＜1.25

Interval 9＜30%＞2.9＞26＜1.25

From last table 11, can see, when averaging out between capacity, efficient and the conductivity, can obtain the best power of deciding continuously and leak result of the test.This is opposite with the battery of using at continuous constant-current discharge, and the latter only need average out between capacity and efficient.Can see, be not ideal value if any one component is arranged, and another excessively a little just can be compensated, such as when the negative electrode porosity is 33%.Rising at 36% o'clock, improving efficient is cost with the capacity, but can recently partly compensate it by improving EMD: C.

Embodiment 12

The antianode porosity is the influence of 71% battery when measure changing some parameter.The results are shown in following table 12.

Table 12

Negative electrode porosity (%)	Negative electrode Ah	EMD∶C	A: C ratio	Lamellar body (wt%)	Zinc bulk density (g/cc)	1W5/3s/7s 1h/1d/1V0 (minute)
							＞28％	＞2.9	＜24	＞1.25
29	2.9	23	1.33	8	2.96	43
							29	2.9	20	1.33	10	2.87	43
28	2.9	20	1.33	10	2.87	43
							28	3.0	20	1.26	8	2.96	43
＞28％	＞2.9	＜24	＜1.25
							29	3.0	23	1.24	8	2.96	41
28	3.0	20	1.22	8	2.96	39
							28	2.9	15	1.24	8	2.96	38
＞28％	＞2.9	＞24	＞1.25
							28	3.0	25	1.26	8	2.96	37
29	2.9	30	1.33	9	2.92	34
							＞28％	＜2.9	＜24	＞1.25
34	2.8	23	1.33	8	2.96	32
							＞28％	＞2.9	＞24	＜1.25
30	3.0	25	1.22	8	2.96	37
							28	3.1	25	1.19	9	2.92	34
28	3.1	30	1.18	8	2.96	36
							＜28％	＞2.9	＜24	＞1.25
26	3.1	20	1.19	9	2.92	33

To go up table 12 and be divided into 7 intervals.Interval 1 is overall preferred range with regard to the test shown in the table 12.

Negative electrode porosity negative electrode Ah EMD: C A: C ratio

Interval 1＞28%＞2.9＜24＞1.25

Do the change of 1 place to interval 1:

Interval 2＞28%＞2.9＜24＜1.25

Interval 3＞28%＞2.9＞24＞1.25

Interval 4＞28%＜2.9＜24＞1.25

Do the change of 2 places to interval 1:

Interval 5＞28%＞2.9＞24＜1.25

Interval 6＜28%＞2.9＜24＜1.25

Intermittently leak in the power test at 1W5/3s/7s/1h/1d/1V0, negative electrode Ah＞2.9, EMD: C than＜24 and A: C than＞1.25 combination condition under, can obtain the best performance.

Embodiment 13

In this embodiment, 3 data of deciding power test have been contrasted.In each case, the porosity of anode is 71%.With 3 test for data additions, and it is expressed as the percentage of battery objective result summation, and the negative electrode porosity of this battery is 28%, cathode capacities is 2.7Ah, A: the C ratio is 1.33, the anode porosity is 69%, the zinc bulk density is 3.40g/cc and does not add zinc metal sheet.The results are shown in following table 13.

Table 13

Negative electrode porosity (%)	Negative electrode Ah	EMD∶C	Negative electrode ID (mm)	A: C ratio	Lamellar body (wt%)	Zinc bulk density (g/cc)	1W/ continuously/1V0 (minute)	1W0/30m/ 12h/1V0 (minute)	1W5/3s/7s/ 1h/1d/1V0 (minute)	The percentage of target summation
											Target							37	37	18	100％
28-30	2.9-3.0	＜24		＞1.25
											29	2.9	23	8.90	1.33	8	2.96	64	64	43	195％
29	2.9	20	8.90	1.33	10	2.87	66	58	43	191％
											28	2.9	20	9.00	1.33	10	2.87	64	57	43	189％
28	3.0	20	8.73	1.26	8	2.96	63	57	43	188％
											28-30	2.9-3.0	＜24		＜1.25
29	3.0	23	8.73	1.24	8	2.96	60	57	41	181％
											28	3.0	20	8.73	1.22	8	2.96	61	57	39	179％
28-30	2.9-3.0	＞24		＞1.25
											29	3.0	30	9.00	1.33	8	2.96	64	58	34	173％
28-30	2.9-3.0	＞24		＜1.25
											29	3.0	25	8.73	1.22	8	2.96	65	57	39	182％
30	3.0	25	8.73	1.23	8	2.96	63	60	37	179％
											＞30	＜2.9	＜24		＞1.25
34	2.8	23	8.73	1.29	8	2.96	67	58	34	175％
											36	2.7	20	8.73	1.33	8	2.96	68	58	34	176％
28-30	＞3.0	＞24		＜1.25
											29	3.1	30	8.73	1.18	8	2.96	61	57	36	174％
28	3.1	25	8.73	1.19	8	2.96	63	57	34	171％
											＜28	＞3.0	＜24		＜1.25
26	3.1	20	8.73	1.19	9	2.92	61	57	33	171％

Table 13 is divided into 7 intervals.Interval 1 is with regard to overall preferred range with regard to the battery of all three assay optimization:

Negative electrode porosity negative electrode Ah EMD: C A: C ratio

Interval 1 28-30% 2.9-3.0＜24＞1.25

Do the change of 1 place to interval 1:

Interval 2 28-30% 2.9-3.0＜24＜1.25

Interval 3 28-30% 2.9-3.0＞24＞1.25

Do the change of 2 places to interval 1:

Interval 428-30% 2.9-3.0＜24＜1.25

Interval 5＞30%＜2.9＜24＞1.25

Do the change of 3 places to interval 1:

Interval 6 28-30%＞3.0＜24＜1.25

Interval 7＜28%＞3.0＜24＜1.25

Though can see that each result who is obtained is all fine when the negative electrode porosity is higher, but in general, when the negative electrode porosity ranges is 28-30%, EMD in addition: the C ratio is lower than 24%, total zinc bulk density is that 2.96g/cc and zinc metal sheet content are about 8%, based on the total weight of zinc, the battery that is obtained is in all 3 performances of deciding all to show in the power test excellence of embodiment 13.

Embodiment 14

Accompanying drawing 3 has illustrated the approximate influence of zinc metal sheet under the different situation of battery target purposes.What provide in the figure, is that [constant impedance (resistance), decide electric current (electric current) and decide power (power)] is for obtaining the required zinc metal sheet percetage by weight of the highest discharge performance and the functional relation of anode porosity under three kinds of different discharge modes.Such as, when the anode porosity is 71%,, so only need considerably less zinc metal sheet just can produce beneficial effect if battery is intended to be used for the purposes of industrial standard (ANSI/IEC) constant impedance type discharge test representative, generally be no more than 1～2%.When battery was intended to be used for deciding electric current leakage condition, the desired contents of zinc metal sheet was about 4 weight % zinc.This total bulk density that is equivalent to zinc is 3.1g/cc.But when battery was intended to be used for deciding the power demand occasion, desirable zinc metal sheet content was about 8% (total bulk density of zinc is about 2.96).

Which kind of final goal purposes no matter what is interesting is, be, Fig. 3 curve all clearly illustrates that, adds zinc metal sheet and can't produce any advantage, unless the porosity of anode is above 67% or about this value.

Equally, Fig. 4 curve representation total bulk density of zinc and the relation of anode porosity.When the anode porosity is 71%, even the total bulk density of zinc in deciding resistance test almost can not damage performance up to 3.3g/cc yet, and for constant-current discharge, best performance is when bulk density is no more than about 3.1g/cc, for deciding power discharge, maximum total bulk density of zinc is about 2.96g/cc.

Claims (28)

1. electrochemical cell, it comprises aqueous alkaline electrolyte, porous cathode and porous anode, and wherein negative electrode comprises manganese dioxide, and the porosity of negative electrode is more than or equal to 26%, anode comprises and is insoluble to the electrolyte electrochemical active material, and the porosity of anode is equal to or greater than 69%.

2. the battery of claim 1, it also comprises the electrolyte that contains KOH, by selecting the concentration of KOH before the discharge, makes battery by discharge the manganese in the manganese dioxide is being reduced into Mn ^{+ 3.0}Afterwards, the calculating concentration of KOH is about 50w/w.

3. the battery of claim 2, wherein the manganese of KOH in manganese dioxide is reduced into Mn ^{+ 3.0}Final calculating concentration afterwards is 49.5～51.5% (w/w solution).

4. any one battery of aforementioned claim, wherein the porosity of negative electrode is at least 27%.

5. any one battery of aforementioned claim, wherein the negative electrode porosity is equal to or greater than 27%, and anode comprises zinc, and this zinc is to constitute by calculating the zinc of total bulk density less than 3.2g/cc.

6. the battery of claim 5, wherein when the anode porosity was 69%, the total bulk density of the max calculation of zinc was 3.19g/cc, and also when the anode porosity surpasses 69%, the every increase by 1% of porosity, this total bulk density just reduces 0.06g/cc.

7. the battery of claim 6, wherein when the anode porosity was 69%, the total bulk density of the max calculation of zinc was 3.13g/cc, and also when the anode porosity surpasses 69%, the every increase by 1% of porosity, this total bulk density just reduces 0.085g/cc.

8. any one battery of claim 5-7, wherein total bulk density of zinc is 2.83～2.96g/cc (comprising end value), and the porosity of anode is about 71%.

9. any one battery of claim 5-8, wherein zinc comprises the low-density zinc particle of at least 4 weight % shape homogeneous, and its bulk density is less than 2.5g/cc.

10. any one battery of aforementioned claim, wherein the porosity of negative electrode is at least 28%.

11. the battery that aforementioned claim is any, wherein the porosity of negative electrode is no more than 36%.

12. the battery of claim 11, wherein the porosity of negative electrode is no more than 34%.

13. the battery that aforementioned claim is any, wherein the porosity of anode is at least 70%.

14. the battery that aforementioned claim is any, wherein the porosity of anode is no more than 76%.

15. the battery that claim 9-14 is any, wherein the low-density zinc of shape homogeneous is zinc metal sheet, and the thickness of this zinc metal sheet than the length of zinc metal sheet and width to when young 10 times.

16. the battery of claim 15, wherein when the anode porosity surpasses 66%, the every raising 1% of porosity, the zinc metal sheet content in the zinc is 1%w/w at least.

17. the battery of claim 16, wherein when the anode porosity surpasses 67%, per 1% porosity, the low-density zinc of shape homogeneous forms 1.5%w/w at least.

18. the battery of claim 17, wherein when the anode porosity surpasses 67%, per 1% porosity, the low-density zinc of shape homogeneous forms 2%w/w at least.

19. the battery of claim 13, wherein anode comprises zinc, and the zinc metal sheet content of this zinc is about 5～11 weight %, and the porosity of anode is 70～73%.

20. the battery of claim 19, the zinc of wherein about 8～11 weight % is zinc metal sheet.

21. the battery that aforementioned claim is any, wherein the Capacity Ratio of anode and negative electrode is 1.15: 1～1.25: 1.

22. the battery that aforementioned claim is any, wherein negative electrode further comprises carbon, and the ratio of manganese dioxide and carbon is no more than about 26: 1.

23. the battery of claim 22, wherein manganese dioxide is 20: 1～25: 1 with the ratio of carbon.

24. the battery of claim 23, wherein manganese dioxide is 22: 1～24: 1 with the ratio of carbon.

25. the battery of claim 24, wherein manganese dioxide is about 23: 1 with the ratio of carbon.

26. the battery of claim 23, wherein the porosity of negative electrode was 28～30% (comprising end value), and the ratio of manganese dioxide and carbon is 20: 1～23: 1.

27. the battery of claim 23, wherein the porosity of negative electrode surpasses 30%.

28. the battery that aforementioned claim is any, wherein cathode capacities: the ratio of battery volume is 0.42～0.49Ah/cm ³, all be reduced into Mn based on manganese all in the manganese dioxide when calculating cathode capacities ^{+ 3.0}This supposition.

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