CN1914751A - Alkaline cells having high capacity - Google Patents

Abstract

A high capacity electrochemical cell has a cathode containing an oxide of copper as an active material, as well as an anode, an electrolyte, and separators for use with the cathodes of the invention in an alkaline electrochemical cell.

Description

Alkaline cells having high capacity

The cross reference of related application

The priority of U.S. Provisional Patent Application 60/528414 that the application requires to submit on August 8th, 2003 U.S. Provisional Patent Application was submitted at December 10 in 60/493695,2003 and the U.S. Provisional Patent Application of submitting on June 4th, 2,004 60/577292, its each disclosed whole content is incorporated herein by reference.

About the research of federal government's patronage or the statement of exploitation

Inapplicable.

Background technology

Alkali electrochemical battery is set to long cylinder battery (for example AA-, AAA-, C-and D-size cell) or flat cell (for example prismatic cell and button cell) usually.The basis alkaline battery comprises negative pole (anode), anodal (negative electrode), electrolyte, dividing plate, positive current-collector and negative current-collector.The negative electrode of conventional basic alkali electrochemical battery comprises manganese dioxide (MnO in the mixture wetting by the aqueous alkaline electrolyte of for example potassium hydroxide ₂) and being generally the conduction carbonaceous material of graphite, described graphite this as field are known for example to be synthetic, natural or expanded graphite or its mixture.In cylindrical battery, be pressed into cathode mix in the annular ring and be stacked in the battery case, maybe mixture directly can be expressed in the shell, this shell is as positive current-collector.

The anode of basis alkaline battery generally includes zinc or the zinc alloy granules with various sizes and shape, and its other additive with the gelling agent of for example carboxymethyl cellulose (CMC) and for example surfactant is set in the alkaline electrolyte of potassium hydroxide for example.To bear current-collector, normally brass pin or nail are arranged to electrically contact with the gelling anode.Be arranged on dividing plate between the electrode can be between negative electrode and anode transfer ions and do not comprise electronics, stop material to be in direct contact with one another simultaneously and produce electrical short.Usually, dividing plate is with wetting porous, nonwoven, the fiber material of electrolyte.Usually dividing plate is arranged on the radially inner side of negative electrode.The others of conventional batteries also are known.

Along with the continuous commercialization of these primary cells on market, researched and developed new method continuously with battery design to be the voltage characteristic that has long working life, acceptable storage life and operate common portable unit.

Yet, the low-density of manganese bioxide material and its water consumption (needing the designer that necessary water is provided) during the exoelectrical reaction of conventional zinc-manganese dioxide alkali electrochemical battery has limited the amount of space (it has determined working life) that zinc anode can be used, and causes low relatively volume energy density thus.Have recognized that alternative cathode material is a cupric oxide, it has high density of material, consume water not in 2 electron discharges reactions, small volumetric expansion when having smooth discharge curve, high volume energy density and discharge.Although it shows is the good candidate of long service live battery,, the operating voltage with conventional batteries of zinc anode and copper oxide cathode is not higher than about 1.05V, described brownout and can not reasonably operate modern electronics under the power consumption.Under any basic device power consumption, it may significantly be reduced to below the 1V, makes device can not operate basically.

It is known that the compound of use sulphur improves the operating voltage with CuO negative electrode.Yet this area recognizes that the solvable sulfur material antianode performance and the storage life that produce all are disadvantageous when having alkaline electrolyte.Therefore commercial the application is restricted.

In addition, nearest method discloses the battery that uses expanded graphite and/or gnf and CuO manufacturing to have long service live.Yet the operating voltage in this system is generally about 0.7V.It should be noted that many existing methods fail to mention may antianode disadvantageous soluble copper material, the method that alleviates this problem is not provided, fail to recognize that active site is to the importance of battery discharge voltage and performance on the surface area of CuO particle or the particle.So disclosed technology does not produce the gratifying battery with reasonable storage life.

Summary of the invention

According to a scheme of the present invention, a kind of electrochemical cell is provided, it has anode; Negative electrode, it comprises active material of cathode; And one deck dividing plate at least, it is between described anode and described negative electrode.Alkaline aqueous main body electrolyte is communicated with described anode and cathode fluid, and whole basically described fluids are communicated with by described dividing plate.Described dividing plate has and is at least 50% eliminating value.

According to another scheme, a kind of electrochemical cell is provided, it comprises the anode with active material of positive electrode.Negative electrode is provided, and it comprises the soluble substance of active material of cathode and at least a obstruction anode.At least one deck dividing plate is between described negative electrode and anode.Alkaline aqueous main body electrolyte is communicated with described anode and cathode fluid.Substantially whole described fluids are communicated with by described dividing plate.The soluble substance that described dividing plate is suitable for effectively limiting at least a obstruction anode arrives described anode from described cathodic migration by described dividing plate.

According to another scheme, comprise anode, negative electrode, the dividing plate between described anode and negative electrode in a kind of elongated cylindrical electrochemical cell.The alkaline aqueous electrolyte of main body be communicated with described anode and cathode fluid and described negative electrode in contain soluble substance.Substantially whole described fluids are communicated with by described dividing plate.Described dividing plate effectively limits the soluble substance that hinders anode and arrives described anode from described cathodic migration by described dividing plate.

According to another scheme, a kind of electrochemical cell is provided, it comprises zinc anode; And negative electrode, it comprises the oxide and the CuS of copper.Dividing plate is between described anode and negative electrode.Alkaline aqueous electrolyte is communicated with described anode and cathode fluid.Described dividing plate 1) comprise polyvinyl alcohol film, and 2) be configured to effectively to limit the soluble copper material and solvable sulfur material is moved to described anode.

Another kind of form provides a kind of dividing plate that is used for electrochemical cell according to the present invention.Described dividing plate comprises the polymer film with opposite flank, and described polymer film can effectively limit the soluble copper material is moved to described polymer film from a side of described polymer film opposite side.

According to another kind of form, a kind of dividing plate that is used for electrochemical cell is provided, described dividing plate comprises the polymer film with opposite flank, and described polymer film can effectively limit solvable sulfur material is moved to described polymer film from a side of described polymer film opposite side.

According to another kind of form, a kind of dividing plate that is used for electrochemical cell is provided, described dividing plate comprises the polymer film with opposite flank, and described polymer film can effectively limit soluble copper material, solvable silver material and solvable sulfur material are moved to described polymer film from a side of described polymer film opposite side.

When below reading to each embodiment specify and during in conjunction with appended claims, others and advantage will be obviously, and will be further understood that the variation and the physical attribute of concrete adjustment, component.

Description of drawings

Fig. 1 is the side cross-sectional view of cylindrical electrochemical cell;

Fig. 2 is illustrated in 357 button cells under the state that uses jet grinding CuO, 34-2 electrolyte and 5mA discharge EMD/CuO and the independent CuO physical/mechanical mixed performance to Zn;

Fig. 3 is illustrated in overflow-type (flooded) half-cell in the chemical synthesis Cu/Mn mixed oxide that is increased in the cathode material Cu to the influence of the ratio of pure CuO under using 5mA continuous discharge, the electrolytical state of 28-2;

Fig. 4 is illustrated in the overflow-type half-cell chemical synthesis CuO+MnO under the state that uses the 5mA discharge ₂The performance of negative electrode;

Fig. 5 is illustrated under the 5mA discharge condition by mechanical mixture and chemical synthesis/CuO is deposited to the MnO that market obtains ₂The level and smooth performance that the EMD/CuO of the combination (EMD) changes;

Fig. 6 is illustrated in the half-cell pure CuO and various CuO/CuS mixture to the figure of the discharge performance of Hg/HgO reference electrode;

Fig. 7 is illustrated in and uses the more influence of high surface CuO under its discharge voltage;

Fig. 8 is illustrated in the overflow-type half-cell CuS particle size to the influence of the rated capacity of jet grinding CuO/CuS negative electrode, wherein electric current step progressively between 5mA and 35mA;

Fig. 9 is illustrated in to use under jet grinding CuO, 66%BIP screening anode, 34-2 electrolyte and pre-wetting electrolyte of 25-0 and the 5mA discharge condition and comprises (EMD) MnO ₂The discharge performance of the layering negative electrode of+CuO;

Figure 10 illustrates three examples of electrode structure of the flat negative electrode of button cell;

Figure 11 illustrates two examples of cylindrical electrode structure;

Figure 12 illustrates the particle size distribution of screening Zn alloy anode particle;

Figure 13 illustrates the battery performance of the electrochemical cell that comprises CuO, and wherein first power brick is contained in the low electrolyte concentration Zn of screening down, and second battery comprises conventional Zn that distributes and higher electrolyte concentration;

Figure 14 is illustrated in the variation of the solubility of CuO in the KOH electrolyte with electrolyte concentration and storage time;

Figure 15 illustrates the EMD that changes than with electrolyte concentration, the wettability of CuO;

Figure 16 illustrates the migration by various separator materials in 4 hours of KOH and water;

Figure 17 is to use the abundant weld side seam of ultra-sonic welded technology to the PVA film;

Figure 18 illustrates the cylindrical partition component of the joint seal with the sealed end that utilizes the pulse heat seal device;

Figure 19 illustrate be formed the battery container bottom shape and will be inserted into wherein joint seal and the bottom of the PVA dividing plate pipe of end sealing;

Figure 20 illustrates the open circuit voltage of a plurality of batteries of a plurality of CuO of having negative electrodes and various dividing plates;

Figure 21 illustrates the discharge curve of a plurality of batteries with CuO/CuS negative electrode and various dividing plate and combination;

Figure 22 illustrates the discharge curve of a pair of battery with CuO/CuS negative electrode and various dividing plates;

Figure 23 illustrates the discharge curve of a pair of battery with CuO/CuS negative electrode to be illustrated in the influence that comprises PVA in the negative electrode;

Figure 24 illustrates the discharge curve of a pair of battery with CuO/CuS negative electrode and various dividing plates;

Figure 25 illustrates the discharge curve of a pair of battery with CuO/CuS negative electrode and various dividing plates;

Figure 26 has compared the initial moisture absorption of various separator materials; And

Figure 27 illustrates the fusion curve and the corresponding fusing point of various separator materials.

Embodiment

The present invention relates to a kind of alkali electrochemical battery and building block thereof.Typical conventional cylindrical battery shown in Figure 1, but the technical staff be appreciated that the present invention be not limited to shown in battery, and can be used for other cylindrical battery structure and other non-cylindrical battery, for example plane battery (prismatic cell and button cell).At first with reference to figure 1, axially extended cylindrical battery 18 has positive terminal 21, negative terminal 23 and not plate the positive current-collector that cylindrical steel container 20 forms form.Near anodal end 25 beginnings of container 20 its positive terminal 21 are closed, and near its end negative terminal 23 opens, thereby the negative pole end of container is curling with closed battery 18, understand as the technical staff is common.

At least one or more cylindrical annular cathode loops 24 are pressed into positive current-collector, form this ring like this, make they outer peripheral sidewall external diameter be a bit larger tham the internal diameter of positive current-collector 20.The coating 22 that is preferably carbon can be applied to the inner radial surface of container 20, to strengthen electrically contacting between cathode loop 24 and the container.The installation formation of cathode loop 24 contacts with the pressure of coating 22.Negative electrode 24 also has such inner surface 27, and it limits the space that is positioned at the center in cylindrical battery, be provided with anode 26 in described space.

Between anode 26 and negative electrode 24, dividing plate 32 is set.The anode 26 that is placed in cathode loop 24 inside is generally cylindrical, and has the outer surface that engages with the inner surface of dividing plate 32, according at least one scheme of the present invention, comprises gelling zinc.Dividing plate be set to and negative electrode 24 and anode 26 between inwall 27 adjacent.The alkaline aqueous electrolyte that generally includes potassium hydroxide and water is to the wetting anode 26 of small part, negative electrode 24 and dividing plate 32.

Near negative pole end 41, packing ring (bead) 30 is involved in container to support seal disc 34.Seal disc 34 has the negative current-collector 36 that extends through it, and is placed in the open end of container 20, and contacts with packing ring 30.The negative pole open end 41 of container 20 curls on seal disc 34, thus it is pressed between curling and the packing ring 30 with sealing and sealed cell.The insulation spacer 38 that will have centre bore is arranged on the curled ends of battery, makes the end protrusion of negative current-collector 36 pass the hole.Contact spring 40 is appended to the end of negative current-collector 36.Negative terminal cap 42 and positive terminal cap 44 are arranged to respectively contact with positive current-collector 20 with contact spring 40, around battery 18 insulated tube 46 and box hat 48 are set, and are curled so that the terminal cap is remained on the appropriate location in its end.Be to be understood that and save box hat 48 and insulated tube 46 to increase the internal cell volume that active component takies.Described this set in the United States Patent (USP) 5814419 that transfers Rayovac Corporation, it openly is incorporated herein by reference, with technical information as a setting.

In embodiment widely, battery of the present invention comprises negative electrode, and it comprises the oxide as the copper of active material of cathode.The suitable oxide that comprises copper is cupric oxide (II) or mixed oxide, and it comprises copper and another kind of at least metal, and wherein another kind of metal has reducible oxidation state.This negative electrode can comprise the physical mixture of the two, or the two or the chemical synthesis composite oxides of multielement more.The present invention also can relate to negative electrode, anode, dividing plate and electrolytical other composition, these compositions can mix on demand with the discharge with raising produced according to the invention and useful life feature.This not the others of specifically described battery of the present invention can be conventional.

The invention still further relates to the method for manufacture and use thereof of negative electrode, anode, electrolyte, dividing plate/baffle plate, dividing plate/baffle plate sealing and alkali electrochemical battery.

Cathode material and design

Negative electrode at first is discussed, and a scheme of the present invention recognizes, cupric oxide be considered to high power capacity (for example, for 1 electron reduction, about 337mA/g; For 2 electron reductions, about 674mA/g) cathode material, but to compare with the alkaline battery that present market obtains, it can significantly improve working life.Yet several problems make the technical staff that cupric oxide is reduced to minimum as the possibility of the cathode material of conventional Zn gelling anode alkaline battery usually.One of them problem causes that so promptly for requiring open circuit voltage requiring the application of closed circuit voltage more than 1.0V more than the 1.1V or under rational power consumption, the operating voltage of cupric oxide is too low.Various forms of the present invention can make the operating voltage of the battery that comprises cupric oxide improve.

Another problem is the solubility from the copper that contains cathode in the alkaline electrolyte.Particularly, arrive anode if be allowed to pass through dividing plate from the soluble substance of these materials, may be harmful to the electric power storage and the discharge of the gelling zinc anode of alkaline battery.Various scheme of the present invention discloses the method that alleviates and/or address this problem, and makes battery have the working life and the storage life of raising.Also there are similar problem in silver, nickel, iodate and/or sulfur-bearing cathode material.

Various forms of the present invention provides physics and chemical method the work discharge voltage that comprises the battery of metal oxide, particularly Cu oxide in negative electrode to be brought up to the value that is higher than when only CuO being arranged.Be not limited under the situation of theory of the present invention, thinking that the thermodynamics and kinetics factor supports disclosed method.Replenish CuO, for example EMD, CMD, NiO, NiOOH, Cu (OH) by the other active material of cathode that is higher than cupric oxide with at least a operating voltage ₂, cobalt oxide, PbO ₂, AgO, Ag ₂O, AgCuO ₂, Cu ₂Mn ₂O ₄, Cu ₂Ag ₂O ₄And Cu ₂Ag ₂O ₃, can improve the operating voltage of negative electrode.Therefore the combination of CuO and additive also has the operating voltage that is higher than CuO.

Optionally, replenish CuO, can improve the discharge voltage of negative electrode by the additive that is lower than cupric oxide with at least a discharge voltage.Yet when with suitable additive and cupric oxide combination, this combination has than independent additive or the higher discharge voltage of CuO.Certainly, can come to determine the open circuit and the discharge voltage of the combination of CuO, additive and CuO and additive by experiment by those skilled in the art.Optionally, the inventor recognizes, can need not test and select suitable additive by sieving multiple alternative materials, at first estimate the variation of composition, utilize the Gibbs free energy formula to determine the open circuit voltage of reduction reaction then the Gibbs free energy of Zn.Particularly, when bigger, then can determine suitable additive to the variation of the Gibbs free energy of the reduction reaction of Zn than arbitrary single composition to the variation of the Gibbs free energy of the reduction reaction of Zn when composition.Certainly, can replace the possibility of going up the Zn anode to the battery with different anodes, this can be understood by those of ordinary skills.Though open circuit voltage is a thermodynamic characteristics, because the thermodynamics factor, high value does not always produce high operating voltage, the alternative additives that it is suitable that high open circuit voltage expresses possibility.In case selected alternative materials according to the variation of calculating Gibbs free energy, person of skill in the art will appreciate that, can simply test to determine the discharge voltage of its composition.Carry out the discussion of this respect below with reference to the CuO/CuS mixture.

A scheme of the present invention provides a kind of negative electrode with such active material, and the discharge voltage of this material is higher than CuO, and battery service life is 60% of CuO electrode at least simultaneously.Compatibly, comprise that negative electrode as described below adds the discharge voltage of the battery of material, under the current density of 5mA/g, on 5% time that begins at least in battery discharge cycle (meaning is battery continuous discharge is reduced to the total length of time of 0.8V up to operating voltage beginning 5%), generation is higher than the discharge voltage of 1.05V, described negative electrode adds material and has 1) the higher discharge voltage or 2 than first active material of cathode) compare the lower discharge voltage of first active material of cathode, but when making up, produce composition with the discharge voltage that is higher than first active material of cathode with first active material of cathode.Therefore, the negative electrode that constitutes according to the solution of the present invention has obtained the discharge voltage higher than prior art battery, and the battery of described prior art comprises that copper oxide cathode active material, its discharge voltage are not high enough to the operation modem devices.

A kind of method provides a kind of active material of cathode, and it comprises the oxide of copper and the physical mixture of another kind of metal oxide.Second method comprises chemical combination or compound multiple composition with synthetic new active material of cathode, and described material comprises copper and another kind of at least metal or nonmetal.The third usual way provides a kind of negative electrode, it has in every way and at least a other material mixing or the cupric oxide that combines, make and the Gibbs free energy of Zn overall reaction owing at (for example) CuO with improve as the displacement reaction between the other material of copper sulfide (CuS) in addition.Recognize that also the various combinations that can use described conventional method are to improve required result.

In first method, use standard treatment methods known to a person of ordinary skill in the art, can become homogeneous with having the chemical composition physical mixed that is used for the required physical features of negative electrode (for example particle size, surface area etc.).In use, this physics cathode mix is converted to the discharge performance of Cu oxide from the discharge performance of higher oxide.Can select to add to the additive metal oxide of Cu oxide from the group of generally well-known positive electrode, these positive electrodes initially provide higher operating voltage to Zn separately than Cu oxide in discharge.The suitable example of positive electrode can include, but not limited to MnO ₂(EMD or CMD), NiO, NiOOH, Cu (OH) ₂, cobalt oxide, PbO ₂, AgO, Ag ₂O, Ag ₂Cu ₂O ₃, CuAgO ₂, CuMnO ₂And suitable combination.

At this Mn is used as an example, because it is the most widely used active material of cathode of current quilt.Thereby Mn is used for improving with the combination of Cu the initial part of CuO discharge curve, and the long working life that keeps CuO to have.Use other element of for example Ni, Co, Pb, Ag etc., can utilize similar method to improve voltage in the discharge curve initial part as required.Usually, the oxidation state of active material is high more, and discharge voltage is high more.

For example, has an amount of EMD MnO ₂The negative electrode of (such as 5-60%), it has initial high operating voltage, but discharge curve quite tilts, and can mix with CuO to produce the mixing negative electrode, and described mixing negative electrode has MnO ₂Higher initialization voltage and the working life of the prolongation of the more feature of CuO under～1V.MnO ₂At first discharge, CuO discharge then has rapider transformation between it.Can predict, by adding about 20% MnO ₂, can obtain (to be much higher than MnO with CuO discharge capacity much at one ₂Itself), and discharge had the advantage of the high working voltage of manganese oxide in first 6 hours, as shown in Figure 2, it shows the raising when EMD operating voltage during with various ratios and CuO physical mixed.As a reference, also show the performance of EMD, it was discharged into 0.8V after about 25 hours.The simple electromotive force that mixes cathode material of this example explanation, it can discharge high at least 50% capacity than EMD itself.Can under range of proportions, provide two kinds of compositions to meet required discharge characteristic.Can use the compound with other element equally, for example Ni, Co, Ag, Pb etc.

MnO ₂Be very different with the discharge mechanism of CuO.Zn/MnO in standard ₂In the battery, MnO ₂Density with 4.5g/cc, every mole of MnO2 consumes 1 mole of water, and proton is incorporated in its structure to generate MnOOH (bad electric conductor and low density material).The amount of the active material (for example zinc) that cathode reaction needs water to limit can be used in the battery, this has caused low relatively volume energy density.Negative electrode also has the discharge curve of inclination and is lower than the low capacity of 1V.On the other hand, cupric oxide (CuO) with about 6.3g/cc density, only consume half mole of water (having small size expands) for the every mole of CuO that is used for first electron discharge, and have very smooth discharge curve, high volume energy density is provided in battery.

In the negative electrode of the physical mixture that comprises the two, the performance that shows negative electrode CuO part is with MnO ₂The raising of content and variation, this may be owing to following reason.In this negative electrode, at MnO ₂Carry out the CuO exoelectrical reaction after discharging its first electronics.Yet, there are not enough electrolyte to be used for effecting reaction for CuO, produce the mass transport polarization.MnO at interdischarge interval ₂Volumetric expansion may separate with itself the CuO particle with the electric conducting material that provides usually (for example synthetic or expanded graphite) in negative electrode.This has increased the Ohmic resistance in the negative electrode, causes the further loss of voltage.In addition, anode partial discharge is used for cell voltage with anode polarization when CuO discharge beginning.Think that the clean influence of these processes is that the CuO material is worked under than the lower voltage of the voltage under other situation, cause being lower than required cell voltage, shown in 2.

Specified scheme of the present invention (being 40 weight % of CuO 〉=active material of cathode) is also by being provided at multiple active material of cathode alternatively (or in can comprising the layer that separates of oxide mixture) in the layer or piece grain separately in battery, feasible operating voltage with battery of zinc anode and negative electrode of the present invention is higher than the Zn/CuO battery, thereby manages to reduce the adverse effect of discharge performance inequality.

In second kind of conventional method, solution phase chemistry chemical combination by utilizing solvable cation element or synthesize is created in one mutually or the mixed oxidization compound or the compound that exist in heterogeneous, can obtain than higher operating voltage of pure CuO and the transformation more level and smooth and more continuous than preceding method.The element that is fit to can include, but not limited to Mn, Ni, Co, Fe, Sn, V, Mo, Pb or Ag, or its combination.Be readily appreciated that as those skilled in the art, under suitable temperature, also can produce the oxidized compound of this mixing by solid-state reaction.

According to the program of the present invention, the general formula of copper based mixed oxide material of the present invention is M _xCu _yO _z(wherein M is any as noted suitable element, and 1≤x≤5,1≤y≤5 and 1≤z≤20).Can also be with AM _xCu _yO _zFor the compound design of general formula (wherein A for example can be Li, Na, K, Rb, Cs, Ca, Mg, Sr and Ba) as active material of cathode.

An example that is used to prepare the technology of mixed oxide active material of cathode comprises and complexing agent and reducing agent (tetrahydro boron sodium (NaBH for example ₄), sodium formate, formic acid, formaldehyde, fumaric acid or hydrazine) electronation mixing salt solution together, comprise the compound of metal with generation.When in this reduction step, adding the 3rd slaine, can the preparation form be AM also as precursor _xCu _yComplex chemical compound.Can use oxidant (for example hydrogen peroxide, potassium permanganate, potassium peroxydisulfate or potassium chlorate) under acid condition with the products therefrom oxidation, to form the copper based mixed oxide.

For example, confirm that by X-ray diffraction (XRD) analysis the Cu/Mn compound of preparation is the mixed copper Mn oxide of cenotype by this way.Although do not have the ASTM card corresponding to this oxide, its diffraction pattern and Cu ₂Mn ₃O ₈Similar.When the pH value that makes hydrogen peroxide during oxidation processes more is partial to acidity, also detect for example independent or with the Cu of CuO combination ₂Mn ₂O ₅Other compound.The crystal structure of oxidizing condition appreciable impact copper based mixed oxide.

It is also envisioned that and at for example alkaline solution or to have the oxidation of carrying out in the solution of pH neutral the Cu/Mn compound.Can use organic or inorganic acid (or base) to regulate the pH of oxidizing solution.And, before chemical oxidation, can at first heat-treat compound.In addition, mixing with electric conducting material before forming negative electrode and can carry out heat treatment earlier mixed oxide.

Known mechanical alloy processing method that can also be by utilizing high-energy ball milling or by in stove directly high temperature melting prepare compound.Further can predict,, follow thermal precipitation thing under proper condition, can optionally make M by the mixture of co-precipitation metal salt solution _xCu _yO _z-or AM _xCu _yO _z-copper based mixed oxide material.

Fig. 3 illustrates the performance of this mixed oxide material, and the influence that increases Cu content in the cathode material in synthetic overflow-type (flooded) electrolyte half-cell.Usually the new cathode material of test in overflow-type half-cell fixture has wherein been removed the complexity from other technology in order only to pay close attention to negative electrode.In this fixture, have excessive electrolyte, and anode is the high surface area inert electrode, as the Ni net.Record is for the voltage of reference electrode, and as known to those skilled in the art, described reference electrode comprises the Hg/HgO reference electrode for alkaline system.As shown in Figure 3, the existence of Mn has improved initial discharge voltage, and along with the raising of the ratio of Cu in the material, discharge capacity also improves, and initial high voltage is had minimum adverse effect.Therefore, form, can obtain required discharge characteristic, comprise high initial voltage and long service live by regulating.

Another technology that is used for preparing mixed-metal oxides comprises: by solvable first slaine of the potassium permanganate oxidation of aqueous slkali, and copper (I or II) salt (for example Schweinfurt green) for example.Higher oxidation state is arrived in first burning, and the Mn in the permanganate-reducing.The performance of the Cu/Mn negative electrode that Fig. 4 will prepare in this way and CuO negative electrode relatively prove the required initial voltage that can obtain to be higher than CuO.Fig. 4 also is illustrated in about 90% the discharge capacity that has kept CuO in the activated cathode.Can predict,, can adjust these character by in synthetic, regulating the relative scale of Cu and Mn.In addition, the flat of discharge curve illustrates average voltage than the high 30mV of CuO material that obtains on the market.The surface activity and the surface area of active material also play effect to performance at this.Think that the form (morphology) and the surface area of deposition materials also are favourable for higher voltage discharge.

Can use another kind of technology to synthesize more high-tension cupric cathode material.Particularly use AgNO ₃And Cu (NO ₃) ₂3H ₂The Cu of O synthetic+3 attitudes in silver compound uses K under the situation that KOH participates in ₂S ₂O ₈The oxidation mixed solution.Yet the oxide among this KOH can produce copper and the silver material that stops up anode.Therefore the present invention also provides a kind of system for partition wall, and it has overcome this difficulty, and obtains to have the available battery of acceptable storage life, will specifically describe below.

In relevant embodiment, can obtain active material of cathode with combining of chemical synthesis by physical mixed.This is combined on the surface of manganese oxide cupric oxide is provided, and this helps the phase of each compound and the level and smooth transformation between the discharge curve.Use this combination, can obtain voltage curve shown in Figure 5.Its direction process also can be used, thereby can be with MnO ₂Or other material is arranged on the CuO surface.

According to the embodiment of this method, under the situation that EMD participates in alkaline media respectively from CuSO ₄And AgNO ₃Be settled out CuO and Ag ₂O.About 1% the Ag that cathode material for example can comprise 64% CuO, 35% EMD and add as the conduction reinforcing agent ₂O.Ag ₂O at first discharges, and produces high-conductive metal silver in negative electrode.Synthetic, natural or expanded graphite well known in the art provides sufficient conductivity and globality to negative electrode.The gained negative electrode, as shown in Figure 5, initial voltage significantly improves, and provides simultaneously obviously greater than MnO ₂Discharge capacity.The flat of discharge is also than the about 45mV of voltage mean height that has only CuO.Among Fig. 5 from MnO ₂Characteristic is also milder than the transformation among Fig. 2 to the transformation of CuO characteristic.An advantage of the invention is that the discharge capacity of battery is higher than conventional batteries on the scope of certain discharge rate.

In the third conventional method, can from such element or compound, select the supplemented by additives that is used to make up, described element or compound have the discharge voltage lower than CuO, but produce the discharge voltage higher than any separate constituent when making up with CuO.When reaction power was suitably fast, the discharge voltage of these combinations also had the variation tendency identical with open circuit voltage.The example of these materials can include, but not limited to elementary sulfur, selenium, tellurium, sulfide, selenides, tellurides and iodate, for example CuS, Ag ₂S, ZnS, B ₂S ₃, SnS, FeS, Fe ₂S ₃, CoS, NiS, CuSe, CuTe, CuAgS, CuAg ₃S and suitable compound thereof and mixture.For example think that as result's (being that CuS has the discharge voltage that is lower than CuO) of CuO and CuS displacement reaction, discharge voltage is unexpectedly high for the situation of CuO/CuS combination.Therefore, although pure CuS itself has the lower discharge voltage to zinc (0.7V is to Zn), the voltage discharge down that CuS is higher than the voltage of arbitrary material self with being combined in of CuO.Illustrate below for the theoretical open circuit voltage of correlated response with aid illustration CuO/CuS system:

Copper oxide reduction reaction: (reaction 1)

ΔG＝-50.2 K cal

Theoretical OCV:1.089V vs.Zn

Copper sulfide reduction reaction: (reaction 2)

ΔG＝-32.6 K cal

Theoretical OCV:0.708V vs.Zn

Cupric oxide/copper sulfide mixture reduction reaction: (reaction 3)

ΔG＝-54.6 K cal

Theoretical OCV:1.183V vs.Zn

In order to determine the variation on free energy and the top open circuit voltage, used anode reaction is:

Find that the experiment OCV value that is obtained has reflected theoretical value well.Determined that reaction power is enough fast, caused the discharge voltage of CuO/CuS combination to be higher than CuO or CuS separately to the discharge voltage of zinc.Calculate the variation of Gibbs free energy from the free energy that forms reactant and product, the free energy of described reactant and product can be from " The oxidation states of the elements and theirpotentials in aqueous solutions ", second edition, Wenell M.Latimer, Prentice Hall, Inc, 1952 obtain, it openly is incorporated herein by reference, and has wherein discussed to be used to form at this and has described the reactant of type and the free energy of product.Utilize formula Δ G=-hFE to calculate open circuit voltage, as readily understood by the skilled person, wherein Δ G represents the Gibbs free of reacting, and n represents to participate in the electron number of reaction, and F is Faraday constant (96500 coulombs/mole), and E is to be the voltage of unit with V.

Think that the ratio of CuO and CuS defines discharge voltage profile.For example, excessive CuS will make reaction carry out in two steps in the CuO/CuS mixture, wherein at first approximately reacting 3 under the 1.18V, be consumed up to CuS, follow at about 1.09V reacting 1 under the zinc.Because cupric oxide/copper sulfide mixture reduction reaction consumes the CuO and the CuS of equimolar amounts, the mixture that use comprises the CuO of 1: 1 mol ratio and CuS provides the discharge curve of about 1.1V for all told, as mentioned above, when CuO is excessive, do not observe the steady part of lower discharge.1: 1 mol ratio represents that the weight ratio of mixture C uO/CuS is 45/55.The cathode mix of CuO/CuS that Fig. 6 is illustrated in pure CuO in the half-cell and comprises various mol ratios is to the discharge performance of Hg/HgO reference electrode.What deserves to be mentioned is that operating voltage is apparently higher than independent pure CuO.The present invention also provides has ratio such as MnO ₂More smooth and with the cathode material of the more similar voltage curve of CuO.

Various forms of the present invention is included in 0.5: 1 to 1: 1.5 the interior CuO/CuS of scope, and 1/10th increments of CuO are between 0.5: 1 to 1.5: 1, and suitable mol ratio is approximately 1: 1.

Table 1 illustrates the theoretical capacity of Hg/HgO reference electrode to-0.9V, and it can obtain from the negative electrode that comprises various CuO/CuS mixed in molar ratio.

Table 1

Cathode mix	At 5mA, to-0.3V theoretical capacity to the Hg/HgO reference electrode
		CuS: CuO mol ratio	mAh/gm
1∶1	306
		0.9∶1	292
0.8∶1	275
		0.6∶1	235

For cylindrical battery (AAA, AA, C, D), wherein in ex situ or form ring-shaped cylinder shape negative electrode in position, have been found that the characteristic of the uniqueness that can influence the CuS material, with the unexistent fritter of alkaline battery (tablet) density on allowing to obtain at present.Negative electrode in the alkaline battery in the market has the density of about 3.2g/cc cathode volume.By suitable selection CuO, CuS (for example about 97%), conductive carbon (for example about 3% or KS4 and/or expanded graphite) and treatment conditions (for example using standard hydraulic pressure or ball to press (pelletting press)), can obtain the cathode density that about 3.5g/cc arrives about 4.5g/cc cathode volume.The variation that those skilled in the art will appreciate that these percentages also can produce described cathode density.In this battery that allows will significantly more active material to pack into so that the at present known working life of the service life as compared of battery longer.Can make the AA battery that the release capacity reaches 4Ah, this has improved the release capacity that is approximately 2.5-2.8Ah that alkaline battery had in the market greatly.

The inventor also recognizes, CuO jet grinding available on the market to reduce particle size and to increase surface area, has been caused higher operating voltage.Surface area plays an important role to the operating voltage of reaction power and battery.The present invention recognizes that the electric current that applies to negative electrode has produced the stress that distributes on the whole surf zone of negative electrode.Therefore, as shown in Figure 7, the negative electrode with large surface area carries out better than the negative electrode that those have small surface area.

Except mechanical friction and air jet grinding, also can increase the surface area of CuO by adjusting process condition during synthetic CuO, if particularly use solution-treated.(from Sigma/Aldrich, be positioned at St.Louis, jet grinding MO) demonstrates to have from～1.27m the former state CuO that market is obtained ²/ g is to 5.57m ²The BET surface area that is higher than twice of/g.Can obtain the synthetic CuO of solution, its surface area is obviously higher, thereby provides lower polarization to electrode.The known method of determining the surface area of powder is the BET method, and it uses the principle of particle surface GAS ABSORPTION to come the estimated statement area.Use Tristar 3000 analysis by absorption of gases agent available on the market and by being positioned at Norcross, the Smart prep Degasser that the Micromeretics Corp. of GA makes is used for analyzing.After the degassing 2 hours, use 1 gram sample.The results are shown in Table 2.

Table 2

CuO and source	Average particle size particle size, micron (um)	Particle size range um	BET surface area m 2/g
				As Recd is from Aldrich 99+% ACS level,＜5 microns	9.6	1-25	1.3
Jet grinding Aldrich	1.9	0.7-3.5	5.6
				Taixing, Jiangsu (China)	4.5	0.2-60	10.5
Nano(NanoScale Corp.)	22.3	1.0-60	39.6
CuS and source
				Alfa Aesar, No. 200 powder of 99.8% (Metal Substrate)	24	0.1-100	1.2

The one-tenth piece nanometer CuO of chemical synthesis also can be used for negative electrode.Can be from NanoScaleMaterials, Inc.1310 Research Park Drive, Manhattan, KS 66502 USA obtain this material.According to a scheme of the present invention, in the particle size scope below: its lower end and comprises 1 micron and 10 microns between 1 micron and 10 microns; Its upper end and comprises 50 microns and 150 microns between 50 microns and 150 microns.According to another aspect of the present invention, in the surface area of the CuO scope below: its lower end is at 0.5m ²/ g, 1m ²/ g and 5m ²Between/the g, and comprise 0.5m ²/ g, 1m ²/ g and 5m ²/ g; Its upper end is at 20m ²/ g, 30m ²/ g, 60m ²/ g, 70m ²/ g and 100m ²Between/the g, and comprise 20m ²/ g, 30m ²/ g, 60m ²/ g, 70m ²/ g and 100m ²/ g.

The particle size of CuS, particle store distribution (PSD) and Brunauer, Emmett and Teller (BET) surface area and are considered to have important effect to obtaining required negative electrode packaging density and globality and discharge voltage feature.It will be understood by those skilled in the art that the relevant PSD of CuO and CuS also is considered to form the key factor of mixture.

Fig. 8 is illustrated in the overflow-type half-cell CuS particle size to the influence of the rated capacity of jet grinding CuO/CuS negative electrode, electric current step progressively between 5mA and 35mA in described battery.Under 20mA and higher electric current, comprise that particle size shows than comprising the negative electrode significantly lower polarization (higher voltage) of diameter greater than 25 microns CuS particle less than the electrode of 25 microns CuS.Because the smaller particles size provides bigger surface area than the larger particles of equal in quality, so this result shows that the CuS of bigger surface area has current-carrying capacity (rated capacity) preferably in comprising the negative electrode of CuO/CuS.Those skilled in the art will appreciate that the physical features that needs to optimize all material that comprises negative electrode, to obtain required physical strength and discharge characteristic in the battery.CuS available on the market generally has from about 0.5m ²/ g is to about 1.2m ²The BET surface area of/g.Increase surface area and help electrode structure and performance.Think, surface area is increased to 50 or 100m ²/ g will provide required advantage in electrochemical cell.Can increase surface area by a plurality of conventional methods of for example air jet grinding.Those skilled in the art also will recognize, also can increase surface area by suitably control synthesis condition during making the CuS material.Find that in addition the platy structure of CuS makes material shearing strain under suitable treatment conditions (shear), thus provide the surface area of increase and smaller particles size and with the better mixing and the combination of other composition of negative electrode.

According to a scheme of the present invention, in the CuS particle size scope below: its lower end and comprises 0.1 micron and 10 microns between 0.1 micron and 10 microns; Its upper end and comprises 50 microns and 150 microns between 50 microns and 150 microns.According to another aspect of the present invention, in the surface area of the CuS scope below: its lower end is at 0.5m ²/ g, 1m ²/ g and 5m ²Between/the g, and comprise 0.5m ²/ g, 1m ²/ g and 5m ²/ g; Its upper end is at 20m ²/ g, 30m ²/ g, 60m ²/ g, 70m ²/ g and 100m ²Between/the g, and comprise 20m ²/ g, 30m ²/ g, 60m ²/ g, 70m ²/ g and 100m ²/ g.

A problem that has the mixture of sulfur-bearing or sulfide in the negative electrode is, sulfur material in alkaline electrolyte (for example KOH) solubility and they to the migration of zinc anode, wherein they can hinder and influence the reaction of anode and cause passivation, self discharge or other restrains the unwanted situation of anode voltage according to condition.Therefore need to hinder, fetter or slow down the process that material produces and moves, so that make available battery with suitable storage life.Various scheme of the present invention has proposed the use of special separator material and has been prepared method with the seal diaphragm seam, so that allow to utilize high working voltage and make the battery with suitable storage life.

Various forms of the present invention is recognized excellent lubricating properties and the high conductivity of CuS in the practice.Therefore in mixture, use CuS to allow in negative electrode, to reduce or remove conductive carbon, and be the space of the extra 5-7wt.% of active material raising, further improved battery capacity thus.In relevant scheme, can utilize conduction and the conductive carbon coating 22 (referring to Fig. 1) of greasy property of CuS to use on the alternative inner casing surface in alkaline battery at present.

By comprising other high voltage active material of cathode, for example MnO ₂, NiO, NiOOH, CuAg ₂O ₄Deng, can further improve the initial voltage of CuO/CuS combination.But, if each material characteristics is not suitably to mate, so before the discharge, among or any afterwards not matching will cause that the performance of discharge material afterwards is inferior to its normal discharge performance, as shown in Figure 2.If particularly the time have under the situation of the discharging product that tangible volume or variable density, consume water or electrolyte or generation have poor conductivity in discharge at first discharge material.When this happens, second discharge material no longer has desirable discharging condition, so the overall performance of battery is damaged, and has offset the advantage of mixing two kinds of materials.

Though this discusses in the example of Fig. 2, by further example explanation, in described situation, soluble sulfur material or sulfide are present in and MnO under these circumstances for it ₂Mixture in, and sulfur material shows and hinders MnO ₂Proton insert, thereby reduced MnO ₂The operating voltage of part.Think, if MnO ₂Separate with the mixture of CuO and CuS, perhaps stop sulfur material contact MnO ₂, will minimize this adverse effect.Therefore,, provide a kind of method, different active materials has not been mixed by it in order to stop the reduction of the operating voltage that causes owing to any above-mentioned reason (physics and/or chemistry).And then, will exist unmatched independent active material to remain in separately the layer or piece grain, thereby make a kind of material only influence the performance of second kind of discharge material tinily.

Every layer or piece grain comprise different active material of cathode or are suitable for being used in the physical mixture of the material in the combination of the present invention.Specifically considered to be provided with the cathode layer that separates or the position of piece grain, one deck or piece grain can comprise the physical mixture of cupric oxide and another kind of additive (for example metal oxide or sulfide) at least, and another layer or piece grain can comprise the compound of mixing.Equally, one deck or piece grain can comprise the oxide of mixing and the physical mixture of additive (for example another kind of metal oxide or sulfide).

Such setting under the situation of CuO and MnO2 has been shown among Fig. 9.Particularly, show the uniform physical mixture of EMD and CuO, wherein also show, after initial EMD discharge and changing, be starkly lower than generation CuO discharge under the discharge voltage of pure CuO.The use of layering negative electrode, wherein as shown in figure 10, EMD and CuO have significantly relaxed the problem that is caused by the interaction between EMD and the CuO in the layer that separates on top each other.

Negative electrode is in the button cell of dish therein, and active material can be in the layer of one deck on another layer, perhaps as a center circle (dish) in another, as shown in figure 10.Active material can be the form that is changed to semi-circular portion respect to one another.

For the long cylinder battery structure, it uses cylindrical cathode in shell, itself or be pressed into and inserted from the outside, perhaps in shell, made by original position, can use identical being provided with to make material separately, as shown in figure 11.Though material keeps in touch, do not mix or be entrained in together.

Have recognized that compare with the negative electrode that only comprises CuO, CuO in the negative electrode and the mixture of CuS can improve the operating voltage of negative electrode in alkaline solution.Yet when having been found that in being stored in alkaline solution, the mixture of CuO and CuS can react, and produces soluble sulfur material, if described sulfur material can attentively not moved to anode, may produce adverse influence to the performance of zinc anode.For the purpose of this paper, the material that will have a negative impact to the performance of zinc anode is called anode and hinders material.The example that anode hinders material is known to those skilled in the art, comprises various Cu, Ag, S, Fe, Ni and Sb material.

For example, have recognized that, when negative electrode comprises sulphur, trend towards moving to one or more sulfur materials that anode hinders anode, for example sulfide, sulfate, sulphite or thiosulfate thereby can produce.In these cases, need provide the additive that reduces sulfur material obstruction anode ability in addition.Additive-package can be contained in anode, negative electrode, electrolyte or the dividing plate, its work in produce anode hinder the position of material, obstruction material on the dividing plate will move the position passed through or anode hinder material from the migration of negative electrode anode by dividing plate after but in anode obstruction material and anode reaction and before hindering anode.Additive can be worked like this: by be bound on the sulfur material or with sulfur material chemical reaction (for example by oxidation, reduction, compound, coordination etc.) to form the product that does not hinder anode, for example have reduction solubility metal sulfide or do not hinder the sulfate of anode.In addition, described additive can reduce the influence of the soluble substance that hinders anode by regulating the ion concentration of local hydroxide in the electrode.Precipitation is a kind of method of removing soluble substance from solution by reducing its solubility.Solubility is by their K _SpValue representation.Can determine that the low solubility product of the product between the soluble substance of additive and obstruction anode is favourable.Have been found that so favourable solubility product is less than or equal to 2 * 10 ^-25Disproportionated reaction between the various sulfur materials in all right catalysis alkaline electrolyte of additive they are converted to the material of less obstruction anode, hinders thereby reduce.Therefore be appreciated that described additive by limiting sulphur effectively from the cathodic migration to the anode, and/or with the sulfur material reaction and form the harmless product or the product of less obstruction, can alleviate anode and hinder.Various forms of the present invention recognizes that suitable additive comprises, but is not limited to bismuth oxide (Bi ₂O ₃), bismuth hydroxide (Bi (OH) ₃) and zinc oxide (ZnO).For example Xia Mian example 9 has been described the effect of ZnO additive in the CuO/CuS negative electrode.When adding the sulfur-bearing negative electrode to, each that has been found that these chemical substances by with the sulfur material reaction or limit effectively the sulfur material migration by dividing plate to anode, can reduce the ability that sulfur material hinders anode.Those skilled in the art recognizes that the additive of carrying out similar functions can be a target with the soluble copper material that hinders anode.For example the complexing agent of EDTA (ethylenediamine tetra-acetic acid), monoethanolamine, oxalic acid or citric acid reacts with metal ion in solution.

Anode:

Also be provided for the formula of the high power capacity anode in the alkaline battery.As mentioned above, the negative electrode of conventional alkaline battery, for example its cathode activity composition is MnO ₂Negative electrode, the more water that produces by anode reaction (being zinc anode and electrolytical reaction) by the cathode reaction consumption rate.Therefore the represented following consume water of total cell reaction, and therefore be called as " water consumption ":

Therefore usually the zinc anode of conventional alkaline battery is restricted to zinc concentration in the anode below 70 weight %, higher zinc load can not effectively be discharged, because anode comprises the electrolyte of q.s suitably to keep the water consumption reaction in negative electrode.In addition, the high zinc load with conventional granulates distribution of sizes causes higher mass transfer polarization, because the low porousness of these anodes causes early stage anodic passivity and initial failure.

The anode that provides according to embodiment can be used for electrochemical cell, and the negative electrode of described battery is than conventional alkaline manganese dioxide battery consumption water still less, and obtains higher discharging efficiency than conventional batteries.Because the low water consumption of the cupric oxide active material of the cupric oxide of negative electrode and mixing, the electrolytical amount that needs in the anode reduces with respect to conventional zinc-manganese dioxide alkaline battery.Low water consumption reaction advantageously allows the zinc load in the anode to improve, thereby helps longer battery service life.

Determined, contained copper oxide cathode and be a example than the negative electrode of alkaline manganese dioxide battery consumption water still less.Zinc/air cell negative electrode is an example, wherein reacts not consume water, and anode in the anode zinc load for effectively worked to 76 weight % with respect to 68 weight % of anode total weight (comprising electrolyte), this is much higher than conventional alkaline manganese battery.

Therefore more " do " than conventional electrochemical cell according to the anode of embodiment formation, promptly anode has higher zinc particulate load, and described anode can discharge under the electrolyte concentration that reduces effectively by following anode cell reaction:

In conventional alkaline battery, during the continuous discharge speed of medium and height (for example for the battery of AA size greater than 250mA), the loss of hydroxyl ion will become significantly, and in these cases, described loss reduces owing to the anode fault causes battery performance.And as the zincate Zn (OH) of electrolyte to generating in reacting in the above ₄ ^2-When saturated, the zincate precipitation is to form zinc oxide, and zinc oxide makes the zinc anode passivation again, thereby reduces battery performance.Conventional zinc powder comprise have from several microns to about 1000 microns wide particle size distribution particle, the scope of most particle size distribution between 25 microns to 500 microns.Therefore, in order to obtain the suitable discharge of this routine zinc powder, also use about 34% KOH concentration usually necessarily.

The inventor finds that the narrow particle size distribution that following mask body is described allows to use the electrolyte concentration that is significantly less than conventional alkaline battery.This helps lower Cu solubility, cathode surface in the electrolyte better wetting and help the discharging efficiency of negative electrode again.

Particularly, utilize principle of the present invention, and avoid the early stage anodic passivity that in conventional batteries, takes place, need be less than the KOH concentration of 36% (for example KOH concentration is between 25% to 34%).

Various scheme of the present invention knows that the particle size distribution of zinc (" PSD ") plays an important role to the discharging efficiency that improves in the low zinc load anode, and this will specifically describe below.Particularly, determined several PSD, it allows to use lower electrolyte concentration and provide necessary anode porousness for effectively discharging under high zinc load.

The inventor has realized that the physically modifying of antianode also can improve battery service life, and described physically modifying can carry out separately or combine with above-mentioned chemical modification carrying out.For example, by reducing the diffusional resistance of hydroxyl ion,, can discharge effectively to the battery that in electrolyte, has advantageously lower hydroxide ion concentration than the conventional batteries of using.For example this can finish with the narrow distribution that similar zinc particle size is provided to anode by adjusting the zinc particle size distribution, and the transmission for hydroxyl ion provides porousness (the evolving path) thus.Except the migration that in the gelling anode substrate, improves the quality, particle size distribution of the present invention also provides the porousness that strengthens, its permission less precipitates ZnO at the zinc particle surface, therefore compares with the particle size distribution that has usually in conventional batteries, has postponed anodic passivity.This method can be used in each scheme of the present invention effectively, can use separately or be used in combination with other improvement disclosed herein.

Equally, suitable zinc particle size distribution is: the particle at least about 70% has the standard screen size particle size in 100 micron-scale scopes, and the mode that distributes is between about 100 microns to 300 microns.Preferred 70% distribution of particles in addition be narrower than 100 microns distribution of sizes scope, for example 50 microns or even 40 microns or littler.

Suitable gelling anode described here comprises metal alloy powders (preferred alloy zinc powder), gelling agent and alkaline electrolyte.Those skilled in the art selects suitable zinc powder (with the alloy of In, Bi, Ca, Al, Pb etc.) easily.Here used " zinc " is meant and can comprises the zinc particle that well known to a person skilled in the art kirsite.Another scheme of electrochemical cell described herein is, anode can comprise seldom or do not have mercury (for example less than about 0.025 weight %).Notice that the known gelling agent except required Sodium Polyacrylate gelling agent is suitable for each scheme of the present invention.These gelling agents comprise carboxymethyl cellulose, the acid of cross-linking type branched p 0 lypropylene, natural rubber etc.

The inventor recognizes that another factor of control battery performance is relevant with the surface area of anode.Particularly, the surface area of increase active anode electrode provides and kept the required enough active reaction positions of cathode reaction under high discharge rate.Therefore, the battery of the zinc particle (can be the form of zinc or kirsite) with the scheduled volume that adds anode gel to is provided.According to one embodiment of present invention, consideration is less than the zinc particle of about 75 microns (No. 200 sizes), the amount that promptly in anode, has a particle by 200 screen size sizes with respect to the zinc in the anode (comprising the crude zinc particle) total amount less than about 10 weight %, preferably in 1% to 10% scope, alternatively in 1% to 8% scope, or alternatively in 4% to 8% scope; Be appreciated that littler particle further increases the effective surface area of anode.At this scope of screen size size with the regulation particle size proposed.For example-No. 200 expression is less than 75 microns particle, and+No. 200 expressions are greater than 75 micron particles.Optionally, use also can obtain required result greater than the zinc attritive powder of 10% amount, and have the zinc particle of diameter between 75 to 105 microns (+75 and-No. 140 sizes) can account for total zinc weight in the anode 1% to 50% between any percentage, and be more suitable for accounting for total zinc weight in the anode 10% to 40% between any percentage.

Various scheme of the present invention is known, diameter comprise between 75 to 105 microns less than 105 microns (No. 140 sizes) (+200 and-No. 140 sizes) a plurality of scopes the zinc particle and can be used to improve battery performance less than the zinc attritive powder of 75 microns (No. 200 sizes).For example, anode can comprise the zinc particle between 75 to 105 microns, when anode gel have less than 30%, alternatively during the electrolyte between 20% and 30% (KOH) concentration, it has the advantage that improves battery performance.When the zinc attritive powder has size in (+625 and-200 screen sizes) between 20 to 75 microns, preferably between 38 to 75 microns when (+400 and-200 screen sizes), when KOH concentration 30% between 40% the time, preferably 33% between 38% the time, battery performance has special raising.Another suitable scope is between 20% to 34%, alternatively between 25% to 33%, and alternatively between 25% to 30%." low KOH concentration " of using in the disclosure refers to KOH concentration in above-mentioned scope or be lower than any above-mentioned scope.

Although the low KOH concentration of known combination ground uses the zinc attritive powder can improve battery performance, those skilled in the art should also be clear that the benefit of the KOH concentration of independent use zinc attritive powder and reduction.

Although special needs improve battery operated voltage in containing the battery of CuO, and this battery is relevant with lower cell voltage potential usually, but be appreciated that, specified scheme of the present invention provides the negative electrode that contains the oxide that comprises copper, but wherein negative electrode does not just comprise CuO, but the CuO that combines with other oxide, sulfide or mixed oxidization copper product.In a particular embodiment, negative electrode can be than the more water of other scheme consumption.According to the composition of negative electrode, those skilled in the art can determine to revise corresponding to the acceptable anode of the water consumption that reduces this negative electrode.

In order to improve reaction power, reduce copper ion dissolving (moving to anode thus) and to obtain high operating voltage, in comprising the system of CuO, need lower electrolyte concentration.Think that the electrolyte (with respect to the electrolyte concentration in the anode) that uses low concentration comes pre-wetting negative electrode that performance is improved, this is because of in the cathode wet lubricant nature of raising.To the lower copper ion migration of zinc reduced self discharge and between the storage life gas release (gassing) of anode, this causes storage life of improving.Low anode polarization also helps to obtain required closed circuit voltage in battery.

When with at common Zn/MnO ₂When the conventional anode that uses in the alkaline battery compared, various forms of anodes described here had many improvement in the art.These improvement comprise:

1, utilizes than conventional Zn/MnO ₂The higher zinc load of the low water consumption negative electrode of alkaline battery.If in conventional alkaline battery, improve the zinc load, can cause usually can getting still less electrolyte (water still less) at negative electrode, therefore hindered the discharge performance of negative electrode.Therefore the chemical reaction of high water consumption has limited the overall cell design in the conventional batteries.In addition, the high power capacity of CuO and/or density allow than MnO ₂The more jumbo negative electrode of packing in the littler volume of negative electrode, thus allow in battery, to place the more anode of volume, and keep the required electrolyte level of battery.Compare with conventional alkaline battery, this ratio with anode capacity and volume (Ah/cc) improves significantly to the former unavailable scope of thinking.For example, the alkaline battery on the conventional market is limited to～anode capacity/internal cell volume ratio of 0.5Ah/cc, this is based on the zinc capacity of 820mAh/g and the MnO of 400mAh/g ₂Capacity, it is based on MnO ₂1.33 electronics reduce.Obtained＞anode capacity/internal cell volume ratio of 0.5Ah/cc according to the battery of various forecast scheme configurations of the present invention, it is between 0.55 to 0.9Ah/cc, further between 0.55 to 0.7Ah/cc.PSD of the present invention, grain shape and electrolyte concentration make high zinc load anode efficient discharge.This causes higher battery capacity.

2, the suitable selection of zinc powder PSD of the present invention makes it possible to use lower electrolyte concentration and can not be created in the conventional alkaline battery the early stage passivation of using conventional powder to take place.Particularly, in electrochemical cell, when anode reaction generated zinc oxide, zinc oxide had covered the zinc that is left in the anode, thereby prevention KOH contacts with the zinc that is left and reacts, thereby described passivation takes place.Known, when using lower electrolyte concentration, the conventional MnO2 alkaline battery anode with conventional PSD can early stage passivation.Conventional anode particle size distribution between the 45-500 micron, from but in 455 microns wide region, rather than inventor's imagination in 100 to 150 microns close limit.

According to optional embodiment, can be distributed in 200 microns and be in 150 microns the close limit alternatively at this preferred disclosed zinc PSD, promptly, weight 90% to 95% between and comprise 90% to 95% and up to 100% particle size in 150 or 200 microns scope, particularly basically with about 100 microns, 175 microns, 250 microns and 300 microns be the center closely distribute (promptly between 90% to 95% and comprise 90% to 95%, zinc particle up to 100% has specifically to be of a size of the particle size at center).Those skilled in the art recognizes, can use ASTM Designation:B214-99 to determine corresponding to the screen size of these particle sizes.The PSD has here improved the porousness of zinc anode, thereby has reduced passivation.It is for example shown in Figure 12 that to have with about 100 microns be the zinc powder of the PSD closely at center.As mentioned above, the present invention includes with about 175 microns and 250 microns is the similar distribution at center.Zinc powder shown in Figure 12 comprises additive, and it comprises bismuth, indium and lead that those skilled in the art can expect.

3. the PSD when combining with low electrolyte concentration causes higher battery operated voltage usually.Particularly, Figure 13 shows following battery performance: 1) the first control battery, it has the zinc oxide concentration of 37% electrolyte concentration (with respect to the weight concentration of the KOH of electrolyte mixture) and 2% in anode, and the conventional anode that distributes, and 2) second battery, it is according at the principles of construction of this discussion, and it has the electrolyte concentration of concentration of 30 weight %KOH and the zinc oxide concentration of 2 weight % in anode, and anode distribution described here.Therefore Figure 13 illustrates the raising of operating voltage when anode described here is used in the Zn-CuO battery.Should be appreciated that before battery discharge, the initial oxidation zinc concentration can be between 0.5 weight % and 6 weight % in the anode, because the solubility of ZnO is according to the KOH change in concentration, so the oxidation zinc concentration changes according to electrolyte concentration.Particularly, along with the reduction of electrolyte concentration, the oxidation zinc concentration raises, and vice versa.

4, lower electrolyte concentration has been considered to reduce the solubility of copper ion, causes the lower copper ion migration of anode.With reference now to Figure 14,, 1) under the room temperature and 2) under 60 ℃ be that the electrolyte of the KOH of 30% KOH and 35% mixes with CuO with concentration.In both cases, along with the raising of KOH concentration, the solubility of CuO in KOH improves.The reduction of balance KOH concentration will reduce the solubility of copper ion in negative electrode in battery.Be not limited to this theory, think that the reduction of copper ion solubility and migration causes lower self discharge of anode and gas release, this has been considered to improve the storage life of battery.

5, lower electrolyte concentration has also improved the wetability that contains the CuO negative electrode, and this is considered to cause better reaction power.As can be seen from Figure 15, CuO is than EMD MnO ₂Have more hydrophobicity, the wetability of using lower pre-wetting KOH concentration to improve negative electrode improves the performance of CuO/Zn battery.

Dividing plate

A form of suitable separator material has the main polymer chain that is formed by straight chain, side chain or its variant.The example that has been found that the material with this main chain that suitable dividing plate is provided comprises polyvinyl alcohol, (PVA), poly-(mixing or the co-extrusion pressure (co-extrusions) of these of the material of the copolymer of ethene-altogether-vinyl alcohol-EVOH), polystyrene, for example polyethylene, polypropylene, polystyrene and above-mentioned variant or materials similar.Other suitable separator material comprises the cellulose membrane of cellophane for example and variant thereof.Yet not every these polymer all are fit to.But the polymer that is fit to keeps the electrolyte in the dividing plate, and wherein in dividing plate, the electrolyte of maintenance has be lower than the electrolytical pH value of the main body of finding in negative electrode and anode.The electrolyte that dividing plate keeps preferably has the 0.5 pH value to 3pH unit, and it is lower than the electrolytical pH value of main body.Keep the electrolytical pH scope of electrolytical scope and maintenance can be different from the main body electrolyte in dividing plate, it can be by the polymer pendant groups adjustment that is provided with on the main chain.The ethanol side group is suitable, and its scope to the more complicated side chain that comprises at least one pure fragment, comprises straight line, ring-type and a side chain that can comprise carbon, nitrogen, oxygen, sulphur, silicon etc. from simple hydroxyl.Can on dividing plate, provide for example other side group of carbonic acid functional group, with electrolytical confining force or pH in enhancing or the prevention dividing plate.As in conventional batteries, dividing plate is by the alkaline aqueous electrolyte hydration of main body, but the electrolyte that remains in the hydration dividing plate has the electrolytical feature pH of the main body of being lower than.

Dividing plate can be a film, preferably it is formed on the negative electrode during the battery manufacturing or inserts in the battery.Particularly suitable film has the very little section thickness of reality, the machinability of keep making simultaneously (for example flexibility, mechanical stability, the globality under treatment temperature and the globality in battery etc.), enough electrolyte absorption and at the advantageous property of this proposition.Suitable build is usually in about 10 to 250 microns scope.The inventor recognizes, according to the electrolytical pH value of main body with remain on the poor of electrolytical pH value in the dividing plate, the thickness that can optionally optimize the film dividing plate hinders the migration of the soluble substance of anode with restriction effectively.

A kind of form of the present invention comprises the system for partition wall of the sealing that is used for electrochemical cell, and it is set between the gelling zinc anode and the above-mentioned negative electrode that comprises copper, sulphur or the soluble substance of the two of the above-mentioned type.Thereby be appreciated that, term " system for partition wall of sealing " is used herein to and limits such structure, described structure with galvanic anode and negative electrode physics separately, make hydroxyl ion and water except that by material itself, utilize migration that seam and bottom seal, also for example limit effectively that the dividing plate that passes through of other soluble substance of copper, silver, nickel, iodate and sulfur material moves from the negative electrode to the anode in migration between anode and the negative electrode, restriction.

By the baffle plate-system for partition wall of improvement is set in battery, this system limits the soluble substance that hinders anode allows hydroxyl ion simultaneously from the cathodic migration to the anode part migration effectively, can improve the use of the alkali electrochemical battery that constitutes according to the principle of the invention greatly.Utilize the particular cathode material, for example CuO, CuAg ₂O ₄And Cu ₂Ag ₂O ₃, it is favourable using this system for partition wall: it uses the migration of soluble substance of for example Cu, Ag that barrier material prevents to produce, S etc., and (migration has reduced about 50% at least; Alternatively about at least 60%; At least reduce 70% in the described at last test here).This barrier material can comprise the combination or synthetic mixing of the stacked or non-lamination of PVA (polyvinyl alcohol) film, modification or crosslinked PVA (polyvinyl alcohol) film, EVOH (ethyl vinyl alcohol), cellulose type film and these films.According to the solution of the present invention, these materials make a large amount of various oxides, sulfide and metal composite can be used as active material of cathode, have the battery of the storage life of raising with manufacturing.

Dividing plate can also comprise structure and conductivity enhancer therein.Dividing plate can be the conformal dividing plate that is used for electrochemical cell, its median septum include imitate restriction (promptly about at least 50%, alternatively about at least 60%; At least about 70%; At last about at least 90%) soluble substance is from its material that passes.

Negative electrode of the present invention also can have such additive, and it is by reacting to each other with soluble substance, and the soluble substance of effectively restriction obstruction anode moves from the negative electrode anode.For example the additive of the silicate of polyvinyl alcohol, active carbon, natural or synthesis of clay and for example Laponite etc. shows the ability that absorbs or hinder ionic species.

Therefore the solution of the present invention has overcome the several difficulties relevant with have solvable cathode material in negative electrode at least.These difficulties comprise:

1. trend towards spreading and move to anode-side from the soluble copper of negative electrode or silver material and, may cause that bridge short circuit, anodic gas discharge or anodic passivity with the form deposition of metal.When for example material of zinc oxide, copper or silver deposits and passes dividing plate, when forming bridge between anode and negative electrode, the bridge short circuit will take place, thereby shorten battery life.Anodic passivity may cause in various degree anode hinder, from rising (internal resistance the battery is higher thus) the stopping fully of anode resistance to anode reaction.

Sulfur material may dissolve from the sulfur-containing compound of sulphur compounds additive or other existence with the solvable sulfur material of formation in additive or in other sulfur-containing compound that exists, and forms solvable sulfur material in alkaline electrolyte.These materials can further react each other and with other ionic reaction that is dissolved in the electrolyte, in dividing plate or at dividing plate, to electrode interface, be settled out, hinder the electrolyte between negative electrode and the anode thus or cause the bridge short circuit.

2. comprise as sulfide or during when negative electrode as the sulphur of the sulphur that mixes with metal oxide, sulfide and sulphur can react to form sulfide, polysulfide, thiosulfate and sulphite in solution with alkali and alkaline earth hydroxide, they can spread and/or move to the anode-side of battery, thereby make anodic passivity and influence exoelectrical reaction and the storage life.

3. above-mentioned substance can react each other and be dissolved in ionic reaction in the electrolyte with other, is settled out to electrode interface in dividing plate or at dividing plate, thereby hinders required ion and electrolyte between negative electrode and the anode.

4. even when separator material limits soluble copper material, silver material, sulfide, polysulfide, thiosulfate, sulphite, iodate effectively or similarly hinder the migration of soluble substance of anode, should be appreciated that, the cylindrical battery dividing plate has the seam one or more ends and the side of cylindrical battery dividing plate (particularly along), if inappropriate sealing then may provide path for these materials still spread and move to anode.Conventional cylindrical battery dividing plate can not suitably limit these soluble substances moves to anode part.Here " side seams " is defined as the seam of the overlapped ends (or electromotive force adjacent end portion) that is positioned at cylindrical dividing plate.Here " end joint " is defined as the seam of an openend that is arranged on the cylindrical battery dividing plate.Therefore should be appreciated that term " anode " and " negative terminal " refer to after dividing plate is installed in the battery, be separately positioned on the end of the anode and near the dividing plate the negative terminal of cylindrical battery.Here " peripheral ends seam " is defined as when being installed to button or prismatic cell the outer rim of wanting sealed flat and circle, pros or rectangular clapboard.

Various scheme of the present invention provides such dividing plate combination and structure, and it has overcome the many above-mentioned difficulties that have or generate the electrochemical cell of various anodes obstruction materials, for example copper, silver and sulphur.

Separator material and combination:

Can overcome a difficulty 1,2 and 3 by selecting suitable separator material or combination of materials.

According to various schemes of the present invention, the combination that has been found that different materials and material is effective for the alkaline battery that has the gelling zinc anode and have copper, silver and a sulphion in negative electrode.Further these materials of assessment limit the migration of the soluble substance that hinders anode effectively to determine which kind of material character.

Determined that the high relatively physics porousness that the cathode side from the anode-side of dividing plate to dividing plate extends through the open-cellular form of dividing plate is unwanted dividing plate.For example, illustrate and describe, wish cellophane, PVA, EVOH, filling TiO as following reference example 1-3 ₂High molecular weight polyethylene (HMWPE) film etc.From being positioned at Billerica, the Advanced Membrane Systems of MA obtains the HMWPE sample, and it is can enough TiO ₂Fill the perforated membrane that reduces porousness and improve the flexibility in dividing plate hole.

Determine in addition, if porousness is minimized or eliminates, described as following reference example 6, with the polymer-coated of for example PVA, EVA and EVOH (its each can be crosslinked) or the PVA film or the fabric of dipping, here it is defined as by " mixing dividing plate ", the migration that restriction is hindered the soluble substance of anode is effective.

Although is effectively with the suitable polymer-coated of for example PVA or EVA or the adhesive-bonded fabric substrate of dipping to restriction Cu, Ag and S migration, need to reduce the thickness of material and use these materials to form impervious relatively film.In this respect, the PVA film directly can be cast in the substrate from group water solution, peel off dry film easily from described substrate.The 10%PVA solution of in the Mylar substrate, pouring into a mould (from Celanese Ltd., Dallas, Celvol grade 350 PVA of TX)/at 70 ℃ of demouldings.The experiment of " getting rid of test " method according to the rules shows that film has required barrier properties to the transport of copper, silver and sulfur material.Also estimated PVA film available on the market, it has showed similar trend.An example of the manufacturer of this PVA film is to be positioned at Portage, the MonodolLLC of IN.Estimated the several samples from Monosol, some comprise handles auxiliary agent and/or plasticizer.Also measured the resistance of the film in the KOH that concentrates, the raising that hinders the ability of material migration along with effective restriction anode is shown, ion resistance increases.Usually, the PVA membrane sample that comprises a large amount of plasticizer keeps acceptable low ion resistance to have relatively poor effect to the migration of restriction soluble substance simultaneously.Those skilled in the art will appreciate that character, comprise chemical composition, molecular weight, molecular weight distribution, additive and, can obtain effective restriction the soluble substance migration by suitable crosslinked by selective polymer.

It will be appreciated by those skilled in the art that, when when having zinc anode and comprising the dividing plate of electrochemical cell of negative electrode of the soluble substance that hinders anode, can also use other polymer solution to apply or flood nonwoven or cellophane dividing plate and obtain to use the shown similar effect of PVA.Optionally, polymer solution is coated anode or negative electrode directly, thereby the conformal dividing plate is provided.Therefore should be appreciated that, when forming the part of mixing dividing plate (for example with polymer-coated or dipping adhesive-bonded fabric dividing plate), the multiple polymers solution of discussing below can optionally be applied directly to inner cathode surface or outer cathode surface, and the conformal dividing plate that allows the hydroxyl ion migration effectively to limit the migration of soluble copper, silver and sulfur material simultaneously is provided.This dividing plate can also minimize the demand to independent side seams and end sealing.

Other such polymer is ethane-acetic acid ethyenyl ester (EVA) emulsion (it comprises the vinylacetate monomer), vinylacetate-ethylene copolymer and vinyl acetic acid ester polymer, can or be impregnated on the nonwoven dividing plate its coating with for example migration of the soluble substance of the obstruction anode of copper, silver, sulfide, polysulfide, thiosulfate, sulphite, iodate, iodide, phosphate, silicate or carbonate of effective restriction, as described in following example 7.Another kind of suitable polymers is EVOH.

The organic or inorganic material, for example Laponite, Bentonite or terre verte, perhaps material such as clay also can be added into polymer solution with by structure being provided or improving the ion migration or ionic conductivity further improves the performance of the dividing plate of coated polymer.Following example 8 illustrates and has described the performance that Laponite is added the dividing plate of the nonwoven F3T23 dividing plate that applies crosslinked PVA in 357 size cell.

Find in addition, dividing plate can comprise first group of (group I) separator material (for example cellophane, fill TiO ₂HMWPE etc.) and second group of (group II) separator material (PVA film or on the nonwoven dividing plate, apply or the PVA film or the PVA of dipping for example, have or do not have crosslinked) combination, first group of material effectively limited and hindered the soluble copper of anode and the migration of silver material, and second group of material effectively limited the migration that hinders the solvable sulfur material of anode.This combination has effectively limited soluble copper, silver and sulfur material.Therefore the dividing plate that comprises group I and II combination is effective to discussed above difficult 1,2 and 3 minimize.In example 5 and 6, this dividing plate is tested below.Two kinds of separator materials can stacked, the stacked or coating with various combinations.For example, can group I coated materials to surface (or layer of suitable nonwoven dividing plate) in the face of the nonwoven dividing plate of the group II of anode or faces cathode, or optionally be arranged between the adjacent layer of the nonwoven dividing plate that applies with PVA or the suitably combination of nonwoven dividing plate.

The measurement of applicability of dividing plate of migration that effective restriction is hindered the soluble substance of anode is the measurement to the air permeability of dividing plate.Those skilled in the art will appreciate that and to measure air permeability second with Gurley.Because the air of Gurley thermometrically predetermined is by the required time span of dividing plate, than the long low air permeability of time measurement value representation.Have been found that the Gurley air permeability is that 500Gurley second or higher dividing plate are applicable to above-mentioned electrochemical cell, and overcome difficulty 1,2 and 3.Use available on the marketly from being positioned at Troy, the model 4150N of the GurleyPrecision Instruments of N.Y. carries out Gurley and measures, and shifts the 10cc air by 1 area in square inches under the pressure drop of 12.2 inches water.The Gurley air permeability is high more good more.Those skilled in the art recognizes, the film dividing plate with higher Gurley air permeability has perforate seldom, if having.

Should be appreciated that when using the electrolyte that contains the soluble substance that hinders negative electrode wetting, air permeability is not necessarily represented the permeability of dividing plate exactly.Therefore, the more direct measurement of dividing plate applicability of migration that effective restriction is hindered the soluble substance of anode is to use the result of the direct Measurement and analysis of for example " getting rid of test " that describes below.

Dividing plate and various negative electrode, anode, the variant of electrolyte structure and chemical composition and improvement are compatible, but find, to having the battery advantageous particularly of the negative electrode that comprises one or more active material of cathode, above-mentioned active material of cathode comprises monobasic metal oxide or sulfide at least, binary metal oxide or sulfide, ternary metal oxide or sulfide or quaternary metallic oxide or sulfide a kind of, wherein metal is selected from manganese, copper, nickel, iron and silver, they can dissolve to form the soluble substance that one or more hinder anode, include but not limited to, ionic metal material and sulfur material, they can with the liquid of negative electrode and anode circulation in unfriendly the cathodic migration from the main body electrolytic liquid to anode.Here used " binary ", " ternary " and " quaternary " refer to and comprise two, three or four kind of predetermined substance.Find to include but not limited to manganese dioxide, copper sulfide, cupric oxide, Kocide SD, hydroxy nickel oxide, silver oxide, cupric iodate, nickelous iodate, copper fluoride, copper chloride, copper bromide, cupric iodide, copper silver oxide and copper Mn oxide and combination thereof as the example of active material of cathode.The combination of active material of cathode can be provided in as mixture or the negative electrode as body separately.

In various schemes of the present invention, sealing comprises that the fluid communication path between negative electrode and anode of dividing plate seam to minimize or to eliminate except the fluid connection (for example main body is electrolytical) by separator material, is provided with one deck separator material at least.And, need will be all basically the main body electrolyte in the anode bar quality guarantee cathode side that is held in dividing plate do not move to anode.Therefore dividing plate is relevant with " eliminating value ", and " eliminating value " refers to be prevented from moving to by dividing plate from negative electrode the percentage of the soluble substance of anode." used basically " is intended to represent that dividing plate has about 50% eliminating value at least; Be chosen as about at least 60%; Be chosen as about at least 70%; Be chosen as about at least 80%; Be chosen as about at least 85%; Be chosen as about at least 90%; Be chosen as about at least 95%; Be chosen as about at least 97%; Last basis is in the method for testing of this research and description optional about at least 99%.

Yet the active material of positive electrode that is appreciated that battery is allowed soluble substance to a certain degree, and battery can allow that the soluble substance that hinders anode passes through some migrations of dividing plate.So, if usually dividing plate by can allow than active material of positive electrode and the material still less that do not hindered, so the dividing plate of Shi Heing has limited the migration of the soluble substance of obstruction anode effectively.Yet, wish that the amount of soluble substance is fully few.

In addition, the most of electrolyte that in dividing plate, keeps, for example about at least 50%, with main polymer chain or its side group associate (common non-covalent association).To the suitable measurement of this association is to obtain with the temperature that the water of determining to remain in the dividing plate dissolves after freezing by analyzing separator material.Yet Free water remains in the dividing plate, but does not associate with its physics, and polymer dissolves at about 0 ℃, and lower melting temperature is represented and polymer associate, thus the dividing plate that expression is wished.Be used for determining that the suitable method that water that dividing plate keeps is transformed into the temperature of liquid phase is to use simple differential scanning calorimetry (DSC) test.With the sample of the suitable dimension of separator material swelling one hour in water, be immersed into then in the liquid nitrogen up to freezing.The sample that will freeze (can be from TAInstruments (Newark on the market in low temperature DSC device, Delaware) obtain) dissolve with the speed of 2 ℃ of per minutes, observe melting temperature and be low to moderate approximately-30 ℃ at least in about 20 ℃ scope (referring to Figure 16).

Suitable separator material also needs water and hydroxyl ion more than hydroxyl ion are moved to soluble substance in the battery.Appended Figure 16 shows by the water of various alternative separator materials migrations and the relative quantity of KOH, and the balance electrolysis OH again in battery discharge as water and KOH is shown ^-And H ₂During O concentration, dividing plate described here passes through water and KOH migration the relative ability of seal diaphragm material.This has represented " infiltration " migration.

Diaphragm structure and seam and end sealing

Solve above-mentioned the 4th difficulty (relating to ion permeability) by following method and corresponding device thereof by bulkhead sides and/or abutted seam.

The dividing plate of sealing though be applicable to all battery systems, is found to be specially adapted to system for example described herein, wherein may move to another electrode from the soluble substance of an electrode, reduces performance and storage life thus.These are commonly referred to the soluble substance that hinders anode.In this case, emphasize that separately separator material is not enough, because soluble substance can be along the end migration of seam or dividing plate, unless have impervious substantially sealing.

As mentioned above, it is desirable for by seal diaphragm and make anode and negative electrode be isolated by liquid substantially, minimize or eliminate being communicated with along the fluid of the path of dividing plate between negative electrode and the anode except path by dividing plate.Can obtain the method for seal diaphragm material by known method, comprise be bonded and sealed, heat seal, ultrasonic sealing etc.The dividing plate of Xing Chenging can adopt the shape of the pipe with blind end like this.For water-soluble separator material, it comprises polyvinyl alcohol, by with limited amount water softening material, then by heating or pressurization or the two seals simultaneously, can form sealing.This design needs, because the dividing plate that dissolves sealing has limited the possibility of the unwanted passage of the direct fluid connection between negative electrode and anode usually.

In button or square planar battery, the sealing that can obtain hinders the soluble substance of anode along the dividing plate seepage, because dividing plate is pressed in the plane (for example dish or square-shaped electrode) by the relative parts of for example insulated enclosure circle with effective restriction usually.Yet in cylindrical battery, the sealing that is not easy to obtain, because for the reason of difficulty, speed and the cost made, generally the pipe that dividing plate is placed (cross-placed) as coiling, screw winding, intersection is inserted in the chamber, thereby is difficult to sealing joints.

Cylindrical dividing plate with periphery and first and second end can be provided.Can be during dividing plate be made (promptly by extruding, melt jet etc.) make near the dividing plate end that is arranged on the battery positive terminal not have seam, perhaps pass through chemistry or physical method and seal, with the migration of the soluble substance of effective restriction obstruction anode.Chemical means comprises uses the adhesive that comprises or do not comprise chemical bond.The physical seal method comprises heating (welding), vibration (for example ultrasonic bonds) and working pressure or its combination.According to the selection of material, also can use the various combinations of chemistry and/or physical seal method, for example, the PVA film is attached to itself, use heat, water and/or pressure to produce effective seal/connection.

In chemical means, a kind of method that forms sealing comprises uses cross-linked polymer and crosslinking agent joint seal and end sealing at least to be provided and top sealing (after the gelling anode is incorporated into the dividing plate cavity) preferably also is provided.

Can externally make the diaphragm structure of the joint seal and end sealing, be inserted in the battery then, or can original position manufacturing after dividing plate pipe screw winding, that reel or that intersection is placed is inserted the battery cavity.

Crosslinked polymeric lock is fixed on the position and produces the complete sealing run through battery life.Polymer simply condense or the precipitation in high pH environment produces spawn usually, its during operation or during physics in normal process or transportation or the mechanical oscillation by expanding or shrink and can move or be shifted, thereby the infringement sealing.Can use does not have crosslinked adhesive polymer yet, certainly, wish that the entire cell life-span that is sealed in that forms is stable upward in cell electrolyte, and described sealing does not allow anode obstruction material than separator material itself more moving to be arranged in seam and end sealing place.

By suitably selecting material, crosslinked all is effective with condensing.The example of two kinds of suitable separator materials as the ex situ sealing proposed.A kind of material is a cellophane, and another kind is to comprise the mixing dividing plate that applies adhesive-bonded fabric with PVA, and it uses crosslinking agent to carry out crosslinked.Abundant load to PVA is necessary (＞5g/m ²) so that make the non-woven paper of impermeable air basically, make Gurley air permeability＞500 second.Low air permeability guarantees in battery when polymer absorbed electrolyte swelling, do not have path to be used to hinder the soluble substance migration of anode by this material basically.In order to make joint seal, with two surface engagement to applying one deck viscosity PVA solution (for example 2-10 weight % in the water) near the seam together, then apply the skim crosslinking agent, for example Boratex or other material well known in the art.Sealing area is crosslinked immediately, and two surfaces also are bonded together simultaneously.The simple test of soaking 5 days in concentrating the KOH electrolyte shows that seam is intact, can not be torn by physics, has shown the works fine characteristic in battery.Can use eliminating described herein to test the effect of sealing that effective restriction hinders the soluble substance of anode.Be fit to or include but not limited to polyethylene glycol, polyvinyl butyral resin and polyvinylpyrrolidone as other cross-linked polymer that is fit to of adhesive.

In order to form end sealing, it is folding to form cap on the dish shape piece of identical or other dividing plate of placing on the mandrel end face, the cross-linked polymer that then drips (for example PVA) to have an end of at least some overlapping coiling dividing plate pipes interlayer (the inside has mandrel (mandrel)).When adding enough crosslinking agents, form crosslinked, bonding complex wrapping bottom, it has effectively limited the migration that hinders the soluble substance of anode.Utilize tubular baffle to make battery in a conventional manner then.

Though the sealing of above-mentioned ex situ is very effective, see that from the viewpoint of battery design and performance it does not wish most, because between the pipe of sealing and negative electrode cavity, often have the gap.This space produces relatively poor wetting interface between anode and negative electrode, cause bad battery performance, is particularly passing through long battery storage after the phase.A solution of this problem is to use the dividing plate of remarkable swelling when absorbed electrolyte, thereby is filled in dry pipe and the space between the negative electrode.Also can use the folded tubular baffle that after insertion, can expand.Another solution of this problem is that original position forms this sealing after inserting the pipe of (for example) screw winding, as the situation of the nonwoven dividing plate of the coating cross-linked polymer described below.The special advantage of original position scheme is that after the dividing plate of unencapsulated screw winding pipe or intersection placement inserted cavity, it can expand in the available volume and reduce itself and the gap of cathode material, so that the generation good interface.The situation of this pipe that also helps to reel is in removing the technology of inserting mandrel, because also not sealing of seam, by the slight reverse twist or the gas blowing of control, so that allow or make dividing plate expand to cavity.

Therefore in alternate preferred embodiment, in order to obtain the original position sealing, can apply the nonwoven dividing plate with the cross-linked polymer (for example PVA) of abundant load and the mixture of crosslinking agent (for example borate derivative), so that its impermeabilisation (Gurley air permeability＞500 second) basically.Select crosslinking agent like this, make its not crosslinked immediately PVA (promptly keeping resting state) up to suitably being triggered.An example of this borate derivative crosslinking agent is a boric acid.In this instantiation, behind (KOH) electrolyte contact dividing plate, be increased to 7 crosslinking agents of triggering when above as pH in the battery, thereby will take place crosslinked.Reel to apply the dividing plate (as present alkaline battery manufacturing) of dry basically PVA/ boric acid along mandrel, make to have between the layer that at least some are overlapping.At the bottom of one end is folded to form cap cover shape, and pipe is inserted into the negative electrode cavity.As mentioned above, then will comprise in the chassis insertion tube of identical or other separator material that applies with cross-linked polymer and crosslinking agent, so that remain on the inside of the foldable bottom of coiling dividing plate pipe.When electrolyte that will penetrate is in advance introduced in the dividing plate pipe or added when comprising electrolytical Zn gel, to cause crosslinked to PVA under the situation of boric acid existing, simultaneously also between the adjacent layer of dividing plate, the seam crossing of between chassis and the pipe and overlay region forms sealing or engages.

Another method that realizes identical purpose is to begin with non-woven paper, and it has the cross-linked polymer of coating q.s thereon, and PVA (but not having crosslinking agent) for example is so that its impermeabilisation (Gurley air permeability＞500 second) basically.As mentioned above, form folding bottom and it is inserted in the negative electrode cavity, then insert with PVA and apply or the end cap of dipping.Then crosslinking agent (for example Boratex) is applied to the dividing plate pipe of insertion, thus the adjacent layer of crosslinked simultaneously and seal diaphragm pipe, the end cap and overlapping seaming zone on earth.Have been found that then this crosslinking process becomes more effective if water is pre-wetting or spray dividing plate before applying crosslinking agent.Should be appreciated that, should optimize correct processing step and condition according to the characteristic of cross-linked polymer and crosslinking agent.

Can use other polymer and/or crosslinking agent to obtain identical final result.As limiting examples, as on PVA or modified PVA, applying or stacked regenerated cellulose, carboxyl can be introduced among the PVA and with glutaraldehyde cross-linking to improve the characteristic of film.Can be with PVA and acrylic acid copolymer with remarkable reduction ion resistance.Can be with polyacrylic acid modified acetylation PVA film.Also can use acrylic acid-or methacrylic acid-grafting PVA.Equally, the grafting methacrylic acid on polyethylene or polypropylene screen also is suitable as dividing plate.

In another scheme, can also use the combination of ex situ and in-situ process.For example, can earlier PVA be applied to the dividing plate seam of coiling and the bottom of suitable separator material, be inserted into the battery cavity then.Then the Boratex of necessary amount (or other) crosslinking agent is applied in the pipe, makes assembly crosslinked and seal on the throne.

The other scheme of the present invention is will conduct electricity during polymer-coated technology and structure enhancing filler, and for example Laponite, pyrogenic silica, Bentonite etc. optionally add in the dividing plate.Because require than the higher PVA load of conventional batteries so that the nonwoven layers impermeabilisation, this may increase the resistance of dividing plate.Add the flash-over characteristic that suitable filler can be brought up to conductivity acceptable value and improve battery.

Second kind of conventional method of making seal diaphragm is physical method, uses heat sealable macromolecular material, for example PVA, polyethylene, polypropylene, nylon etc.Provide one deck macromolecular material by form, and this layer is inserted into the zone (for example being installed to the periphery of the dividing plate of AA size cell) that will seal, to form sealing with continuous film or porous fibre film.Under the control heating that applies or do not apply air pressure, dividing plate can form sealing then.Also heat sealable macromolecule layer can be applied to a surface (can maybe cannot seal) of carrier ring, then be wound as cylinder, make the overlay region will comprise the salable macromolecular material that one deck contacts with another carrier ring.Thereby therefore heat sealable macromolecular material at the condition lower seal of control heating to other carrier ring.Before dividing plate is formed into cylinder, macromolecular material can also be positioned periphery or interior Zhou Xianglin with cylindrical dividing plate.Optionally, macromolecular material can be applied to the interface (otherwise it can not be engaged with each other) of two overlapping ends of cylindrical dividing plate.Thereby polymeric seal is bonded together two ends under the condition of control heating, and forms sealing.Can also be with the macromolecule layer of suitable shape stacked or be coated on any side of dividing plate so that be installed in the button cell, thus the periphery of macromolecular material seal diaphragm during the control heating condition.

Have been found that using ultrasonic vibration is effective with material melts one-tenth itself or another kind of material to make good sealing in (for example) PVA film.

The third method that forms sealing is that hot wax or epoxy resin or other glue type sealant are applied to seam.Importantly, material used herein (wax or epoxy resin) should tolerate the high alkalinity environment of battery and keep their sealing characteristics.

Optionally, can use the no seam dividing plate pipe that utilizes various polymer treatment methods, for example extruding of these methods, injection moulding or blowing/blown film.Equally, can prepare no seamed pipe like this, for example use the polymer of suitable formation dividing plate, for example regenerated cellulose applies the joint filler such as fiber material fully, makes that seam is not to be arranged in dividing plate, but is arranged in following material.Should be appreciated that diaphragm structure described herein can comprise any amount of above-mentioned material layer, so that the migration of the soluble substance of more effectively restriction obstruction anode.

Another possibility is to apply or be laminated on for example cellulosic dividing plate in conjunction with heat seal and crosslinked polymer by the cross-linked polymer that will have crosslinking agent.Can use conventional laying method that dividing plate is in place.Separately or the electrolytical introducing in anode with cross-linked polymer to form seal diaphragm.

The mode that the soluble substance that the positive and negative end that be also to be understood that dividing plate also should be preferably hinders anode with fully effective restriction be moved to anode seals.Usually cylindrical battery comprises ring spacer, and it is set near the battery cathode terminal, axially or radially is pressed on negative electrode and the dividing plate to stop anode to overflow.By at negative terminal with polymer distribution to the periphery of dividing plate, and at the polymer of control heating condition lower seal by sealing ring, the negative terminal that can make dividing plate is by sealing ring and sealing.Comprise that crosslinked chemical bond can be used to form sealing.Also can use the negative terminal of the mechanical seal dividing plates such as sealing ring of dividing plate fixture with suitable design.Optionally, physical seal can be used for the upper end of zinc anode so that the soluble substance of effectively restriction obstruction anode is moved to anode.By using the dish-shaped cap that applies with cross-linked polymer also can seal negative terminal, the cylindrical dividing plate pipe that described cross-linked polymer seals sealing joints and bottom when crosslinked polymer.Optionally, can be by the upper surface and the edge of suitable cross-linked polymer or polymer gel covered cathode, so that the migration of the soluble substance of effectively restriction obstruction anode.Optionally, can cover the upper surface of anode by suitable cross-linked polymer or polymer gel, so that effectively restriction hinders the soluble substance of anode from cathodic migration.

In the 4th kind of method, can use mandrel and hoop (shoe) device, and molten material is made side seal to form side (seam) sealing ultrasonically.The PVA film of a slice cutting is kept static around the mandrel coiling and by hoop.Keep enough films to cross coiling being used for processing intent, and it is overlapping to reach the sealing of about 3mm.Mandrel/hoop means is arranged on the programmable slide block of speed, and it is installed to again on the plate of spring loaded.Then slide block and plate are placed under the ultra-sonic welded arm (horn), need work between the 40kHz at 20kHz.The spring that has different coefficient of elasticity by use can regulating arm and plate applies between the PVA film on the mandrel power (expectation 3-10lb _f, be chosen as 4-7lb _f, or be chosen as 5-6lb _f).The quality of seam of welding depends on the moisture content/temperature of film during the speed, film of slide block are with respect to the amplitude of the pressure of arm, welding machine and welding procedure.Moisture content under 21 ℃ wishes to be 1-25%, is chosen as 3-10% and is chosen as 5-7%.When welding was finished, final pipe should be continuously the cylinder of sealing, did not have origin to come from insufficient heating of ultra-sonic welded or porousness (surpassing basal lamina material) that the transition heating causes (Figure 17) basically.Can dismiss too much overlapping from cylindrical tube.

For the dividing plate pipe that forms sealing or bag, should seal at least a portion of end of the cylinder of complete side seal.Use pulse apparatus for heat sealing (Fuji FS-315), with the end seal in being substantially perpendicular to the line of side seal (Figure 18) of at least a portion cylinder.The end of fold seals then, and form cylindrically by several different methods, making the maximization of inner bag volume, described pipe has the shape (Figure 19) of its shell that is inserted into subsequently bottom.As mentioned above, can use any other suitable end seal method, comprise ultrasonic technique, adhesive seal etc., move to anode as long as it can limit the soluble substance that hinders anode effectively.

For suitable battery is provided, need to form leak free substantially sealed tube.Utilize quality test and determine airtight quality in the following manner.External diameter (OD) size is littler by about 0.005 than PVA bag internal diameter (ID) " hollow tube be connected to source of the gas (preferred argon gas or nitrogen).The PVA bag of being longer than the cylindrical battery desired height is greatly inserted in the hollow tube, make the total height that is installed in the bag in the battery still be lower than the bottom of hollow tube.By this way elasticity O shape ring is placed on the PVA bag, makes by the hollow tube sealing bag.The air pressure of 2-3psig is provided to pipe, and making has time enough to the bag blanketing gas and reach the final air pressure of 2-3psig.In case with bag inflation (the PVA bag is without any size distortion), (95.2%, Fisher Scientific is positioned at Pittsburg, in pond PA), occurs representing that by the bubble of EtOH sealing bag leaks that the expression bag can not be used to be inserted into EtOH.

At last, when suitable dividing plate being set, can effectively limit the diffusion of the soluble substance that hinders anode according to the description here.Can directly in button cell or other testing apparatus, simply test sieving various specimen materials, and monitoring open circuit voltage (OCV) in time.The decay of OCV is the indicating device that the surface of an electrode changes, and most probably hinders the result of the soluble substance migration of anode, because other component of all in the cells known does not generally cause the OCV decay.Separator material for greater number sieves and selects and estimate improvement and/or the modification that concrete material is carried out, and more need " outside the battery " in specially designed structure test (eliminating test for example described herein).The following applicability of getting rid of test with definite separator material, or the effect of definite sealing.

A kind of glass tube is provided, and it is tightly connected by two L shaped O rings and is divided into first end (A side) and second end (B side), and the O ring is of a size of-112, and (Ace Glass is positioned at Vineland, NL).Between central authorities, the O ring that the seam of the sealing of dividing plate or dividing plate sample is placed on pipe is tightly connected.A side with the KOH filling glass pipe of the 34wt.% of the mixture that comprises 0.25g CuO and 0.25g CuS of 10mL.This has guaranteed to have the constant supply of soluble copper and sulfur material in main body solution, described solution approaches equilibrium concentration under these conditions substantially at experimental session.The B side is filled with the KOH of the 34wt.% of 10mL, does not have the mixture of CuO, CuS or CuO and CuS basically.For the known concentration of using soluble copper and sulfur material in the A side, select to use CuO and CuS particle, because imitated the essential condition in the battery that in electrolyte, comprises the solid state cathode material so more approx.Get rid of experiment for silver, use the AgO of 0.25g in the A side.The A side provides the eliminating value to the difference between the material concentration on the B side, and it is that dividing plate is effectively limited the measurement that the soluble substance that hinders anode passes through the ability of dividing plate.When from the KOH of the A side that places glass tube such as CuO or CuS powder dissolved material does not begin the time, experiment is also represented from the solubility of the soluble substance of molten material not.The KOH (for example 34wt.%) that needs high concentration dissolves to guarantee the quick and significant of soluble substance that hinders anode.Above-mentioned experiment was carried out under 60 ℃ 5 days.

A. button cell experiment:

The button cell of 357 sizes that comprise the dividing plate that will test is provided.Negative electrode comprises 92% active material, 5% graphite, 2.5% electrolyte and 0.5% polyethylene adhesive.Anode comprises the gelling agent of 68% screening zinc, 31.25% 34-2 electrolyte and 0.75% and the combination of resist.With battery storage in 60 ℃ stove.Open circuit voltage (OCV), impedance and the cell expansion of monitoring battery.Frequency of utilization response analyzer (for example from Schlumberger Inc. Model 12) is measured battery impedance.The electromotive force that the reduction of OCV means one or two electrode is degenerated from its thermodynamics value, and the expression soluble substance that hinders anode is moving and passes through dividing plate.The increase of resistance between two electrodes is represented in the raising of battery impedance, and it also can be caused by the obstruction of dividing plate or the passivation that hinders the zinc anode surface of the diffusion of material or migration owing to anode.Cell expansion is that if copper ion migration contacts by dividing plate and with zinc anode, this also is an expected result owing to produce the tired signal of interior hematocrit of gas.Can measure expansion with respect to the rising of time by the external height of monitoring assembled battery.Therefore, monitor these features for understanding and estimating effect or its airtight quality of concrete separator material or sieve several alternative materials or combination is that directive significance is arranged very much.

B. get rid of test:

A kind of quantitative methods more comprises that the anode on the either side of the dividing plate that direct measurement is studied hinders the concentration of material.To install under 60 ℃ in stove and store 5 days, evaporate with limit electrolysis matter at the sealed glass tube top.As described here, analyze the concentration of the electrolytical specific ion in both sides then.

When the particular ion concentration of B side during, think that dividing plate or sealing have effectively limited the migration that hinders the soluble substance of anode less than A side concentration.The result of table 4 represents to get rid of the result of test, in these specific descriptions.

The inductively coupled plasma of use standard (ICP) analytical technology, (Waltham, the Thermo Iris Intrepid II (radius unit) that MA) provides analyze the soluble copper material among the KOH to utilize Thermo ElectronCorporation.Usually, before analysis, use prepares sample with the 1g electrolyte sample that 10% salpeter solution is diluted to 50ml.Checking curve comprises three kinds of solution: sky, 0.5ppm and 1ppm, wherein all solution are 10% nitric acid.Use the Spex standard of 1000ppm to come verification copper.Utilize the copper that on average carries out of four wavelength (223.0,224.7,324.7,327.3) to measure.Each sample and standard (20ppm) that the Scandium internal standard is used to measure.

The inductively coupled plasma of use standard (ICP) analytical technology, utilize Thermo ElectronCorporation (Waltham, the Thermo Iris Intrepid II (radius unit) that MA) provides, AnalyzeKOH In solvable sulfur material.Usually, use prepares sample with the 1g electrolyte sample that 10% salpeter solution is diluted to 50ml.Usually carry out the dilution of other 5: 50 or 10: 50, its measured volume is to provide suitable result in this technology.Checking curve comprises three kinds of solution: sky, 0.5ppm and 1ppm, wherein all solution are 10% nitric acid.Use is from Spex SO ₄(K ₂SO ₄Initial source) the standard verification sulphur of standard fabrication.Utilize the sulphur that on average carries out of two wavelength (180.7,182.0) to measure.Each sample and standard (20ppm) that the Scandium internal standard is used for measuring.

Be also noted that, when as the dividing plate in the battery, be used in the plasticizer in the film manufacturing or handle auxiliary agent, polyvinyl alcohol for example, may adverse effect be arranged to the ability of film that effective restriction hinders the soluble substance of anode, like this, be undesirable with the film of a large amount of one or more plasticizer preparations.Wishing that film dividing plate used according to the invention comprises is less than about 15 weight %, is chosen as the plasticizer that is less than about 10 weight % or is less than about 5 weight %.Particularly suitable film dividing plate comprises the plasticizer smaller or equal to about 3 weight %.

A kind of possible dividing plate is to be insoluble to cold water, noncrosslinking polyvinyl alcohol film dividing plate, and it comprises the plasticizer that is less than about 3 weight %.Two kinds of so suitable polyvinyl alcohol films are M-1000 and M-2000 (Monosol).

Although can dividing plate of the present invention be set by above-mentioned, dividing plate can be selected to engage (for example stacked or bonding) in pairs with conventional nonwoven fabric layer with other usual manner.

Below case description various embodiment of the present invention.For considering the explanation of the present invention described here or the technical staff of enforcement, can expect other embodiment in the appended claims scope.The present invention is intended to, and specifies with example only to be used for explanation, and scope and spirit of the present invention are by pointing out at example following claim book.

Example

Example 1

This is that the example of effect of ability that various dividing plates effectively limit the migration of the soluble substance that hinders anode is shown.For 357 batteries that the various dividing plates of a plurality of usefulness are made, compare at beginning and the OCV after 1 day room temperature storage.Negative electrode is CuO (can obtain from Aldrich market), and galvanic anode is conventional alkaline Zn gel anode, and it has conventional zinc and electrolyte concentration.

In most of the cases, in battery, use two-layer dividing plate, a faces cathode (" cathode side separator "), another is in the face of anode (" anode side baffle ").Below the OCV data shown in the table 3 comprise the average of two batteries that provide battery types.Should be appreciated that the soluble copper material that the reduction of OCV represents to hinder anode is moved to the increase of anode.

Table 3

The cathode side separator type	Model	Anode side baffle	OCV, V (beginning)	OCV, V (after 1 day)
					Cellophane	350P00	FS2213	1.115	1.098
SC-216	F3T23	1.116	1.095
				SC-216		SC-216	1.299	1.163
SC216	Do not have	1.115	1.101
				SF-586		F3T23	1.107	1.018
SF-586	Do not have	1.250	1.169
				The FAS microporous barrier		A	F3T23	1.118	1.096
B	F3T23	1.116	1.108
					C	F3T23	1.116	1.107
D	F3T23	1.130	1.091
					E	Do not have	1.268	1.138
Microporous barrier	F	F3T23	1.088						0.554
				G	F3T23	1.095	0.736
	Celgard 3407	F3T23	1.118					0.856

Annotate:

350P00: can obtain Inc.UK from the market from UCB Film

SC-216 and SF-586: can obtain from Viskase Corporation from the market, IL

FAS microporous barrier sample is by Advanced Membrane System, and MA provides

Sample F is by W.L.Gore.﹠amp; Associates, INC., MD provides

Sample G is by Aporous, and MA provides

Celgard 3407: can obtain from the market, from Hoechst Celanese Corporation, NC

FS2213: can obtain from the market, from Freudenberg, Germany

F3T23: can obtain from the market, from Kuraray Co.LTD., Osaka, Japan

As shown in table 3, based on the OCV variation, as can be seen, fill cellophane and TiO ₂HMWPE (High molecular weight polyethylene) film be better than pore type film (Celgard 3407 PE for example, B10ab nylon and Excellerator alkalescence PTEE etc.), it is more effective to show that they hinder the migration of copper material of anode to restriction.

Example 2

This is various dividing plates to be shown effectively limit the example of ability that anode hinders the migration of material.As described in addition, the A side of glass tube device is filled with the 34%KOH of the copper ion with known concentration, and adds the electrolyte of no copper ion to the B part.At room temperature measure the concentration of B side complex copper ion after 1 week.

With reference now to table 4,, on various dividing plates, gets rid of test to determine to store the eliminating value of the soluble copper in back, silver and sulfur material 60 ℃ of temperature.A side with 34%KOH solution filling glass device with the 0.25g CuO (cupric oxide) that produces soluble copper shown in secondary series and the 4th row and sulfur material concentration and 0.25g CuS powder.Eliminating is determined for silver, and the A side that 0.25g AgO is used in device is to produce the silver concentration shown in the 6th row.List the result of summary in the table 4 below.

Show after 4:54 days under 60 ℃ the eliminating test result of soluble copper, silver and sulfur material.

Separator membrane (1 layer is shown unless annotate)	A side copper ion (ppm)	B side copper ion (ppm)	A side sulphur (ppm)	B side sulphur (ppm)	A side silver (ppm)	B side silver (ppm)	The eliminating value (%) of Cu	The eliminating value (%) of S	The eliminating value (%) of Ag
										SC-216 (Viskase)	166	47	358	192	31	＜1	72	46	＞97
SC-216,2 layers (Viskase)	129	22	410	100	--	--	83	76	--
										1 layer of SF-586	157	58	--	--	--	--	63.0	--	--
Hybrid #33	123	86	277	174	--	--	30	37	--
										Hybrid #33/SC216 /Hyb#33	115	34	313	156	--	--	70	50	--
In-house PVA (film #3) *	115	22	362	38	--	--	81	90	--
										Monosol PVA M1030	136	69	321	162	--	--	49	50	--
Monosol PVA M1000	133	18	377	83	32	＜1	87	78	＞97
										Monosol PVA M2000	136	23	348	61	33	＜1	83	83	＞97

Condition: every side of film is 10mL 34%KOH, and copper is from 0.25g CuO, and sulphur is from 0.25gCuS, and is silver-colored in 0.25g AgO, 60 ℃ of storages in 5 days

* from 10.6%PVA solution (Celvol 350) cast PVA film

Above the result of table 4 illustrate: for the migration of restriction soluble copper and sulfur material, multilayer insulating panel is more effective than the identical separator material of individual layer under 60 ℃.The result also shows the PVA film for the applicability of getting rid of soluble copper, silver and sulfur material.

Example 3

This is to be illustrated in the button cell of 357 sizes of storage the example of application of migration that effectively restriction hinders the soluble substance of anode.With reference now to Figure 20,, four batteries with CuO negative electrode at room temperature store 5 days, then store down up to battery failure (OCV, impedance and expansion by previous discussion are determined) at 60 ℃.From store first day to each battery continuous measurement OCV.Figure 20 illustrates, and for the battery that contains the CuO negative electrode, the cellophane dividing plate is better than FAS 350Z dividing plate.And thicker cellophane dividing plate (SF-586,3mil is thick) surpasses thin cellophane dividing plate (350P00 and SC216 are that 1mil is thick), has confirmed to get rid of the result of test experiments.

Example 4

This is the example that the application of the battery of being made by material of the present invention is shown.With reference now to Figure 21,, provides two pairs of batteries.Every pair of battery comprises: 1) battery, and its dividing plate comprises one deck Viskase cellophane (SC-216), and is included in the mixing dividing plate of the crosslinked PVA on the F3T23 adhesive-bonded fabric in conjunction with one deck; And 2) second battery, its dividing plate comprises two-layer Viskase cellophane.First pair of battery (battery 541 and 543) discharging under 5mA after the battery manufacturing immediately.Second pair of battery (battery 540 and 542) discharged under 5mA after 17 hours.

Figure 21 illustrates the battery made from 2 layers of Viskase cellophane dividing plate (SC-216), if it discharges immediately, can discharge into all told, if but discharge after placing 17 hours, it has very short capacity.With one deck Viskase cellophane dividing plate and one deck mixing dividing plate (applying crosslinked PVA on the F3T23) even the battery separator of making still discharges into all told after placing 17 hours.Those skilled in the art will readily understand that although separator material can show suitable eliminating value, the sealing in the battery of for example button cell can influence the ability of the soluble substance migration of its effectively restriction obstruction negative electrode.

Thereby example 4 illustrates, and the combination of cellophane and mixing dividing plate is more effective than 2 layers of SC216 cellophane for the migration of restriction soluble copper and sulfur material.

Should be appreciated that used mixing carrier ring above making by 2%PVA in the crosslinked aqueous solution on the surface of F3T23 nonwoven dividing plate and 5% dobell's solution.The PVA of load is about 10g/m in mixing dividing plate ², and under drying regime, have the 1800Gurley air permeability of second.Mixed layer is arranged on the anode gel side of diaphragm structure.Use above-mentioned Gurley accuracy test instrument to determine air permeability.

Example 5

This is the example that the application of the dividing plate of each scheme of use the present invention and the battery that cathode material is made is shown.With reference now to Figure 22,, a pair of electrochemical cell is provided, it has the negative electrode that comprises CuO and CuS.With battery discharge after placing 17 hours.First battery has and comprises that one deck is arranged on the dividing plate of the Viskase cellophane between the two-layer mixing dividing plate.Therefore mixed layer towards outside, promptly towards anode and negative electrode.Be similar to Figure 21, Figure 22 illustrates: for the mixture of CuO and CuS, the combination of cellophane dividing plate and mixing dividing plate (applying crosslinked PVA on F3T23) is than only 2 layers of cellophane are more effective.

Example 6

This is the example that the application of the battery of representing a scheme of the present invention is shown.With reference to Figure 23, a pair of battery was discharged under 5mA after 5 days.Each battery comprises the negative electrodes that comprise CuO and CuS with 2 layers of mixing dividing plate (applying crosslinked PVA on F3T23).A battery comprises the PVA adhesive in negative electrode, and another battery does not comprise.Figure 23 illustrates the battery with the negative electrode that comprises the CuO/CuS mixture, and dividing plate hindered the soluble copper of anode to restriction after 5 days and the migration of sulfur material is still effectively even 2 layers are mixed, thereby allowed battery discharge to all told.In addition, the PVA that adds 0.2wt% to negative electrode shows that it makes and utilize cathode capacities better, thereby has prolonged discharge capacity of the cell.

Example 7:

This is the example that the application of dividing plate described here and cathode material is shown.With reference now to Figure 24,, provides a pair of 357 size cell.Negative electrode uses the CuO and the CuS mixture of 1 to 1 mol ratio to make.First battery has the dividing plate that comprises a pair of mixed layer (applying crosslinked PVA on F3T23).Another battery has one deck the EVA emulsion that applies on the F3R23 (but obtain on the market, from Kuraray).First battery was discharged under 5mA after 5 days.Second battery was discharged under 5mA after 4 days.Figure 24 illustrates, even increase by one day before test after, the crosslinked PVA that applies on F3T23 still is better than applying the F3R23 of EVA.Also show, the F3R23 dividing plate that applies EVA does not have the performance deficiency of the previous 2 layers of SC216 cellophane (example 6) that propose.

Example 8

This is the example that is illustrated in according to the effect of the migration of restriction anode obstruction material in the battery of various schemes manufacturings according to the present invention.With reference now to Figure 25,, a pair of battery is provided, each has the CuO that comprises 1 to 1 mol ratio and the negative electrode of CuS.First battery has the mixing dividing plate of one deck with the Laponite dipping.Second battery has one deck and is clipped in Viskase cellophane between the two-layer mixing (applying crosslinked PVA on the F3T23).First battery was discharged under 5mA after 4 days.Second battery was discharged under 5mA after 1 day.Figure 25 illustrates, and moves to anode for solvable sulphur of restriction and copper material, and two kinds of dividing plates all are effective.

Example 9

This example be illustrated in use ZnO for example in the negative electrode additive to reduce the effect that copper and sulfur material hinder the ability of anode.Construct the button cell of two 357 sizes in a similar fashion, but the negative electrode of a button cell comprises 2% the ZnO that mixes with negative electrode.Cathode mix is from 1: the jet grinding CuO of 1M ratio and make by mixing the CuS that is obtained with KS4 graphite and ZnO additives dry makes negative electrode form to be 95% activating agent, 3% graphite and 2% ZnO.There is not the negative electrode of the battery of ZnO additive to form to be 95% activating agent and 5% KS4 graphite.Anode is made of the BIP anode of 68% screening, and dividing plate is the simple folding of M2000PVA film.Two batteries are all discharged after 7 days in room temperature storage.Two batteries were all carried out 1 hour with the test mode at intermittence that comprises the 12.5mA electric current, then carry out open test, repeat every day 4 times.Below the result shown in the table 5 show, to have the discharge capability of the battery output 240mA/g of 2%ZnO than being the control battery that does not have ZnO of 100mAh/g only.The result has shown and has added the favourable aspect of ZnO for the battery storage phase.

Table 5

Negative electrode	Arrive the discharge capacity mAh/g of the battery of 0.7V
		95％1∶1 M CuO/CuS+5％KS4	100
95％1∶1 M CuO/CuS，3％KS4， 2％ZnO	240

Example 10

With reference to Figure 26, this example show be used for determining free and at the dividing plate sample in conjunction with the method for the relative quantity of water.The preparation diameter is 0.11 " sample and (＜1% relative humidity) preliminary treatment 24 hours under dry atmospheric condition of separator material.Then sample is immersed in the deionized water 1 hour, under the atmosphere of＜1% relative humidity, shifts out, and blot with Kimwipe.Under the atmosphere of＜1% relative humidity sample disc is weighed, the sample with preparation is inserted in the sample disc then.Then to the preparation samples weighing and write down weight.Then sample is covered crimping to dish.Shuttle is immersed any water to freeze to exist in the sample in the liquid nitrogen immediately.Use differential scanning calorimetry meter (from TA Instruments of NewCastle, DE obtains, model Q100) to come assess sample.The oblique line that system is programmed for 2 ℃ of per minutes rises, and the scanning temperature range is from-80 ℃ to 50 ℃.By the heat flow curve of evaluation generation with by determining to be positioned at the curve and the ratio that is positioned at the part more than-1 ℃ below-1 ℃, determine amount in conjunction with water.When the fusion curve of material shows melting capacity (J/g) greater than 50% below-1 ℃ the time, it is more than Free water in conjunction with water to determine that so material has in dividing plate.Have in conjunction with water than Free water the brighter material of multilist be suitable for being provided for the desired dividing plate characteristic of migration that effectively restriction hinders the soluble substance of anode.

Example 11

This is the example that the method for the relative fusing point that is used for definite PVA dividing plate sample is shown.The preparation diameter is 0.11 " the sample of separator material, and preliminary treatment 24 hours under the atmospheric condition of 50% relative humidity.Under 50% relative humidity atmosphere sample disc is weighed, the sample with preparation inserts in the sample disc then.Then to the preparation samples weighing and write down weight.Then sample is covered crimping to dish.Shuttle is inserted in the differential scanning calorimetry meter (from TA Instruments ofNew Castle, DE obtains, model Q100) that is used for assess sample.The oblique line that system is programmed for 5 ℃ of per minutes rises, and the scanning temperature range is from 30 ℃ to 300 ℃.Those skilled in the art will appreciate that the fusing point (seeing Figure 27) of determining material by the first tangible peak of heat flow curve (W/g).When the fusion curve indication fusing point of material is higher than 215 ℃, determine that the PVA material is the suitable material that is used for the migration of effectively restriction anode obstruction described here material.

Example 12

This is the example that the method for the electrolytical relative pH value that is used for determining remaining on dividing plate is shown.With (＜1%RH) minimum 24 hours of the preliminary treatment under dry atmospheric condition of the sample of separator material.To samples weighing, be close to 0.0001g.Monosol M2000, M1000 and M1030 PVA film were soaked 24 hours in the 34-0KOH at 10ml under 23 ℃.After soaking, film is dipped in the methyl alcohol removing the KOH and the water on surface, and cleans to remove remaining solvent with carrene.Allow the carrene of sample of KOH with absorption then by keeping coming in 5 minutes evaporation residue down at 23 ℃, with weight record to 0.0001g.In the deionized water at 25mL under 70 ℃, dissolve this film then, up to dissolving.During measuring, write down pH and solution temperature together.Use the standard chemical computational methods, utilize pH value of solution and temperature data to calculate the pH of electrolyte under 23 ℃ that keeps in each film.The test material that utilization is duplicated experimentizes to control sample, only is in 7 the deionized water solution but they are exposed to pH.Variation from corresponding sample compensation (adding deduct) from pH 7 is to obtain to remain on the electrolytical standard pH the sample dividing plate.Table 6 is illustrated in the dividing plate with suitable eliminating value, and the electrolytical pH value that keeps in these dividing plates is lower than the pH value in the main body electrolyte.

Table 6

Dividing plate	The electrolytical pH value that keeps	Poor to the electrolytical pH value of main body
			M1000	13.7	1.8
M2000	13.7	1.8

The 34-0 main body electrolyte of standard has 15.5 pH value

In view of foregoing, several advantages of obtaining of the present invention and other favourable outcome of acquisition as can be seen.Without departing from the scope of the invention, can carry out various changes to top technology and composition, the present invention is intended to, and all are contained in the above description and content illustrated in the accompanying drawings all is interpreted as illustrative and not restrictive.

Claims (74)

1. electrochemical cell comprises:

Anode;

Negative electrode, it comprises active material of cathode;

At least one deck dividing plate, it is between described anode and described negative electrode;

Alkaline aqueous main body electrolyte, it is communicated with described anode and cathode fluid, and whole basically described fluids are communicated with by described dividing plate;

Wherein said dividing plate has and is at least 50% eliminating value.

2. electrochemical cell as claimed in claim 1, wherein said battery is a cylindrical battery.

3. electrochemical cell as claimed in claim 1, wherein said battery is a flat cell.

4. electrochemical cell as claimed in claim 1, wherein said active material of cathode are the oxides of metal.

5. electrochemical cell as claimed in claim 4, wherein said metal are selected from least a in manganese, copper, nickel, iron and the silver.

6. electrochemical cell as claimed in claim 4, wherein said active material of cathode is selected from manganese dioxide, cupric oxide and composition thereof.

7. electrochemical cell as claimed in claim 1, wherein said active material of cathode comprises the sulfide of metal.

8. electrochemical cell as claimed in claim 7, wherein said metal are selected from least a in manganese, copper, nickel, iron and the silver.

9. electrochemical cell as claimed in claim 1, wherein said active material of cathode are selected from manganese dioxide, copper sulfide, cupric oxide, Kocide SD, hydroxy nickel oxide, silver oxide, cupric iodate, nickelous iodate, copper fluoride, copper chloride, copper bromide, cupric iodide, copper silver oxide, copper Mn oxide and combination in any thereof.

10. electrochemical cell as claimed in claim 1, wherein said negative electrode comprises soluble substance, described soluble substance is got rid of from described anode to small part by described dividing plate.

11. electrochemical cell as claimed in claim 10, wherein said soluble substance is a metallics.

12. electrochemical cell as claimed in claim 11, wherein said metallics are the oxides of metal.

13. electrochemical cell as claimed in claim 11, wherein said metallics are the sulfide of metal.

14. electrochemical cell as claimed in claim 1, wherein said negative electrode comprises soluble substance, and described soluble substance is selected from copper material, sulfur material, nickel material, iron substance and silver material.

15. electrochemical cell as claimed in claim 1, wherein said polymeric separator plates material comprise polymeric material and the alkaline aqueous electrolyte that is maintained at wherein.

16. electrochemical cell as claimed in claim 15, wherein said dividing plate comprise main polymer chain and are coupled to the electrolytical side group of maintenance of described main chain.

17. having, electrochemical cell as claimed in claim 16, wherein said maintained electrolyte be lower than the electrolytical pH value of described main body.

18. electrochemical cell as claimed in claim 16, the electrolytical side group of wherein said maintenance are regulated described maintained electrolyte with respect to the electrolytical pH value of described main body.

19. electrochemical cell as claimed in claim 16, the electrolytical side group of wherein said maintenance are selected from pure fragment, line style side chain, go back shape side chain and side-chain branching, wherein said side chain comprises at least one pure fragment.

20. electrochemical cell as claimed in claim 16, wherein said main polymer chain are selected from straight chain polymer main chain and branched polymer main chain.

21. comprising, electrochemical cell as claimed in claim 15, wherein said polymeric separator plates material be selected from following polymer: polyvinyl alcohol, ethyl vinyl alcohol and cellophane.

22. electrochemical cell as claimed in claim 21, wherein in the differential scanning calorimetry test, the water that is maintained in the described separator material dissolves in the temperature that is lower than 0 ℃.

23. electrochemical cell as claimed in claim 22, the water at least about 50% that wherein is maintained in the described separator material is coupled to described polymeric separator plates material.

24. electrochemical cell as claimed in claim 22, wherein said dividing plate have about 10 and about 250 microns between dried section thickness.

25. electrochemical cell as claimed in claim 15, wherein said separator material is a film.

26. electrochemical cell as claimed in claim 25, wherein said separator material are joined to the adhesive-bonded fabric of film in pairs.

27. electrochemical cell as claimed in claim 25, wherein said separator material comprises the plasticizer that is not more than about 15 weight %.

28. electrochemical cell as claimed in claim 25, wherein said separator material comprises the plasticizer that is not more than about 10 weight %.

29. electrochemical cell as claimed in claim 25, wherein said separator material comprises the plasticizer that is not more than about 5 weight %.

30. electrochemical cell as claimed in claim 25, wherein said separator material comprises the plasticizer that is not more than about 3 weight %.

31. electrochemical cell as claimed in claim 25, wherein said separator material comprises the plasticizer that is not more than about 1 weight %.

32. electrochemical cell as claimed in claim 25, wherein said dividing plate also comprises adhesive-bonded fabric.

33. electrochemical cell as claimed in claim 32, wherein said fabric is joined to described film in pairs.

34. electrochemical cell as claimed in claim 32, wherein said fabric is laminated to described film.

35. electrochemical cell as claimed in claim 32, wherein said fabric is adhered to described film.

36. electrochemical cell as claimed in claim 32, wherein said film be formed on described fabric to small part.

37. electrochemical cell as claimed in claim 15, wherein said main body electrolyte and described maintained electrolyte comprise potassium hydroxide.

38. electrochemical cell as claimed in claim 15, wherein said maintained electrolytical pH value 0.5 and 3pH unit between, be lower than the electrolytical pH value of described main body.

39. having, electrochemical cell as claimed in claim 1, wherein said dividing plate be at least 75% eliminating value.

40. having, electrochemical cell as claimed in claim 1, wherein said dividing plate be at least 80% eliminating value.

41. having, electrochemical cell as claimed in claim 1, wherein said dividing plate be at least 90% eliminating value.

42. having, electrochemical cell as claimed in claim 1, wherein said dividing plate be at least 95% eliminating value.

43. having, electrochemical cell as claimed in claim 1, wherein said dividing plate be at least 97% eliminating value.

44. having, electrochemical cell as claimed in claim 1, wherein said dividing plate be at least 99% eliminating value.

45. electrochemical cell as claimed in claim 1 also comprises the dividing plate sealing, it prevents described main body electrolyte except that being communicated with by the fluid between described negative electrode and anode the described dividing plate.

46. what electrochemical cell as claimed in claim 45, wherein said dividing plate sealed is to heat or welded seal to small part.

47. electrochemical cell as claimed in claim 45, the sealing of wherein said dividing plate to small part be adhesive seal.

48. electrochemical cell as claimed in claim 1, wherein said dividing plate is migration water and hydroxyl ion breezily.

49. electrochemical cell as claimed in claim 1, wherein with respect to the soluble electrode material, described dividing plate preferentially allows the diffusion of water and hydroxyl ion.

50. electrochemical cell as claimed in claim 1, wherein said active material of cathode has voltage, described negative electrode also comprises such additive, described additive has the voltage of the voltage that is lower than described active material, and the combination of wherein said active material and additive has higher voltage than arbitrary independent described active material or additive.

51. electrochemical cell as claimed in claim 50, wherein said additive is selected from elementary sulfur, selenium, tellurium and compound thereof.

52. electrochemical cell as claimed in claim 51, wherein said additive comprises the sulfide of copper.

53. electrochemical cell as claimed in claim 1, wherein said negative electrode also comprises the oxide of copper.

54. an electrochemical cell comprises:

Anode, it comprises active material of positive electrode;

Negative electrode, it comprises the soluble substance of active material of cathode and at least a obstruction anode;

At least one deck dividing plate, it is between described negative electrode and anode;

Alkaline aqueous main body electrolyte, it is communicated with described anode and cathode fluid, substantially whole described fluids are communicated with by described dividing plate, and the soluble substance that described dividing plate is suitable for effectively limiting at least a obstruction anode arrives described anode from described cathodic migration by described dividing plate.

55. electrochemical cell as claimed in claim 54, wherein said active material of cathode is selected from iodate, Ag ₂Cu ₂O ₄And Ag ₂Cu ₂O ₃

56. electrochemical cell as claimed in claim 54, wherein said dividing plate comprises straight chain polymer, described straight chain polymer has main chain and is coupled to the electrolytical pure side group of maintenance of described main chain, and described maintained alkaline aqueous electrolyte has and is lower than the electrolytical pH value of described main body.

57. electrochemical cell as claimed in claim 56, wherein said polymer is a polyvinyl alcohol.

58. electrochemical cell as claimed in claim 57, wherein said separator material comprises the plasticizer that is not more than about 15 weight %.

59. electrochemical cell as claimed in claim 57, wherein said separator material comprises the plasticizer that is not more than about 10 weight %.

60. electrochemical cell as claimed in claim 57, wherein said separator material comprises the plasticizer that is not more than about 5 weight %.

61. electrochemical cell as claimed in claim 57, wherein said separator material comprises the plasticizer that is not more than about 3 weight %.

62. electrochemical cell as claimed in claim 56 also is included in welding or heated sealant on the described dividing plate.

63. electrochemical cell as claimed in claim 54, wherein said active material of cathode comprises the oxide of copper.

64. in the elongated cylindrical electrochemical cell, described battery comprises anode, negative electrode, at the dividing plate between described anode and the negative electrode, the alkaline aqueous electrolyte of main body and the soluble substance in described negative electrode that are communicated with described anode and cathode fluid, comprise following improvement:

Described dividing plate effectively limits the soluble substance that hinders anode and arrives described anode from described cathodic migration by described dividing plate, and whole substantially described fluids are communicated with by described dividing plate.

65. as the described electrochemical cell of claim 64, described dividing plate comprises such polymer, described polymer has main chain and is coupled to the electrolytical side group of maintenance of described main chain, and described maintained alkaline aqueous electrolyte has and is lower than the electrolytical pH value of described main body.

66. as the described electrochemical cell of claim 64, wherein said dividing plate comprises sealing.

67. as the described electrochemical cell of claim 66, wherein said sealing to small part be the heating or welded seal.

68. as the described electrochemical cell of claim 66, wherein said sealing to small part be adhesive seal.

69. an electrochemical cell comprises:

Zinc anode;

Negative electrode, it comprises the oxide and the CuS of copper;

Dividing plate, it is between described anode and negative electrode; And

Alkaline aqueous electrolyte, it is communicated with described anode and cathode fluid,

Described dividing plate (i) comprises polyvinyl alcohol film, and (ii) is configured to effectively to limit the soluble copper material and solvable sulfur material is moved to described anode.

70. as the described electrochemical cell of claim 69, wherein the described electrolytical pH value in described dividing plate is lower than the described electrolytical pH value in described anode and negative electrode.

71. as the described electrochemical cell of claim 69, wherein whole substantially described fluids are communicated with by described dividing plate.

72. one kind is applicable to the dividing plate in the electrochemical cell, described dividing plate comprises:

Polymer film with opposite flank, described polymer film can effectively limit the soluble copper material is moved to described polymer film from a side of described polymer film opposite side.

73. one kind is applicable to the dividing plate in the electrochemical cell, described dividing plate comprises:

Polymer film with opposite flank, described polymer film can effectively limit solvable sulfur material is moved to described polymer film from a side of described polymer film opposite side.

74. one kind is applicable to the dividing plate in the electrochemical cell, described dividing plate comprises:

Polymer film with opposite flank, described polymer film can effectively limit soluble copper material, solvable silver material and solvable sulfur material are moved to described polymer film from a side of described polymer film opposite side.

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