CN100347901C - Alkali storage battery and method of producing the same - Google Patents
Alkali storage battery and method of producing the same Download PDFInfo
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- CN100347901C CN100347901C CNB2004800016485A CN200480001648A CN100347901C CN 100347901 C CN100347901 C CN 100347901C CN B2004800016485 A CNB2004800016485 A CN B2004800016485A CN 200480001648 A CN200480001648 A CN 200480001648A CN 100347901 C CN100347901 C CN 100347901C
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- polyvinyl resin
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- alkaline battery
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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Abstract
An alkali storage battery comprising a positive electrode plate, a negative electrode plate, a separator interposed between the positive and negative electrode plates, and an alkali electrolytic solution, wherein the respective first ends of the positive and negative electrode plates serve as collector sections, and at at least the second end opposite to the first end of at least the positive electrode plate, an end surface and both sides therearound are coated with polyethylene resin, the polyethylene resin coating provided on the second end of the positive electrode plate being welded to the separators disposed on both sides.
Description
Technical field
The present invention relates generally to the end construction of the pole plate of alkaline battery.
Background technology
In the past, at the positive electrode of alkali accumulator plate following scheme has been proposed, be that appendix nickel hydroxide particle (for example opening clear 50-36935 communique (patent documentation 1) with reference to the spy) on about 95% the foaming nickel substrate promptly having as shown in Figure 13 dimension interconnected pores and porositys.Foaming nickel substrate is widely used as the core of high power capacity positive electrode of alkali accumulator plate at present.But if contain the battery repeated charge of this positive plate, then positive plate can expand at thickness direction and Width.Its reason is the nickel hydroxide generation volumetric expansion in the positive plate.If the positive active material of extruding at Width comes off, then the problem of Chan Shenging is that the active material that comes off contacts with opposed negative plate.In addition, in negative plate, also produce active material after active material comes off, comes off such problem that contacts with opposed positive plate sometimes.
The scheme of the 2 dimension structural core of use punch metal thin plate and metal lath (expandedmetal sheet) and so on has been proposed in recent years.The core of 2 dimension structures is made with mechanicalness punching operation usually, thereby is cheap.If adopt the core of 2 dimension structures, then can realize the high capacity of positive plate.In addition, if adopt the core that constitutes by the electrolysis paper tinsel, then can realize the slimming of pole plate.But in the core of 2 dimension structures, existing shortcoming is a little less than the confining force of active material.So, the someone proposed 2 the dimension structures the core solids be processed into 3 the dimension structures scheme (for example with reference to the spy open flat 7-130370 communique (patent documentation 2), the spy opens 2002-15741 communique (patent documentation 3)).
Fig. 2 is the stereogram of an example of expression core, and wherein said core is processed into 3 dimension structures by solid.In addition, Fig. 3 is the partial enlarged drawing of presentation graphs 2.This core 1 constitutes by having the sheet metal 3 that forms rectangular slit, and the rectangular segment between a pair of slit is outstanding alternately and form the 1st and the 2nd curved raised portion 4,7 at the positive and negative of core 1 along a direction X.The the 1st and the 2nd curved raised portion 4,7 is disposed in parallel to each other, forms along the protrusion of direction X capable 8.A plurality of protrusions capable 8 are the par 9 of preset width at interval, arranges along the other direction Y vertical with direction X.Direction Y is exactly the length direction of core 1, and direction X is exactly the Width of core 1.At edge part along core 1 length direction, residual the vegetarian noodles portion (plain part) 5 that does not form curved raised portion 4,7.In vegetarian noodles portion 5, the recess of many ditch shapes 15 forms ripple with the configuration that is parallel to each other.
But even when the core appendix shown in Fig. 2,3 active material, the active material confining force is also insufficient.For this reason, if because of repeated charge causes nickel hydroxide volumetric expansion in the positive plate, then positive plate expands at thickness direction and Width.Therefore, will produce and adopt the same problem of situation of foaming nickel substrate.
On the other hand, someone has proposed following scheme, promptly puncture the short circuit that barrier film causes owing to the burr of core, the end face of pole plate end and peripheral both sides thereof are covered (for example opening flat 5-190200 communique (patent documentation 4) with reference to the spy) with resin in order to prevent.The order of this motion is not preventing coming off of active material.Therefore, almost can't see the effect that inhibition comes off from the active material that is covered end face by resin.
Summary of the invention
Extruding active material at the Width of a side pole plate comes off, active material that perhaps comes off and opposed the opposing party's pole plate such problem that is short-circuited only can not be prevented with end face and the peripheral both sides thereof that resin covers plate end portion.This is to expand owing to active material is accompanied by carrying out repeatedly of discharging and recharging, and resin is extruded at Width with active material thus.
In addition, also consider to be provided with the exposed division of the electrode core that does not have active material, the porous metal layer is bonded on this exposed division, thereby utilizes this porous metal layer, end coming off of active material in the end of pole plate.But porous metal layer in that event is across barrier film and to electrode contraposition, and then electric current is just concentrated on the porous metal layer.And because carrying out repeatedly of charge and discharge cycles impels barrier film and the contacted part of porous metal layer to degenerate.
The present invention relates to alkaline battery, it is made of positive plate, negative plate, barrier film and alkaline electrolyte between positive plate and negative plate, and wherein, positive plate and negative plate the 1st end separately becomes curren-collecting part; At least at least the 2 end relative of positive plate, cover the both sides of end face and periphery thereof with polyvinyl resin with the 1st end; The filming of polyvinyl resin that is arranged on positive plate the 2nd end is deposited over the barrier film that is configured in its both sides.
In such structure, the both sides sidepiece of pole plate end face and periphery thereof is that polyvinyl resin covers with insulating material fully, and, thereby can prevent that polyvinyl resin from extruding at the Width of pole plate with active material because polyvinyl resin is deposited over barrier film.
In negative plate, consider from overcoming contact with the opposed positive plate angle of such defective of active material that active material comes off and come off, also, cover with polyvinyl resin in the both sides of its end face and periphery thereof preferably for the 2nd end of negative plate.
The fusing point of polyvinyl resin is preferably 120 ℃ or following, and this is because if the fusing point of polyvinyl resin at 120 ℃ or following, just can not cause damage to active material, and can cover the end of pole plate with polyvinyl resin.
The coating thickness of polyvinyl resin is preferably 5～50 μ m in (just on the direction perpendicular to the pole plate end face) on the end face of the 2nd end.
The active material layer on the electrode core is constituted by electrode core and appendix usually for positive plate and negative plate.So at least one side of positive plate and negative plate, also at least the 2 end of the pole plate that can cover with polyvinyl resin is set at the exposed division that does not have the electrode of active material layer core.Preferably engage the porous metal layer at electrode core exposed division.In such structure, also can obtain to prevent effects such as coming off of active material by the porous metal layer.
By the 2nd end portion thickness that the exposed division and the porous metal layer of electrode core constitutes, be preferably 50～100% of the electrode thickness that constitutes by electrode core and active material layer.
In at least one side of positive plate and negative plate, curren-collecting part is preferably set to the exposed division that does not have the electrode of active material layer core.At this moment, be preferably to cover around the border of curren-collecting part and active material layer at least with polyvinyl resin.
Electrode core exposed division at curren-collecting part can engage the porous metal layer.The part of porous metal layer preferably uses the end near the active material layer of described exposed division to cover.In such structure,, can block the electric current that flows into the porous metal layer by polyvinyl resin as insulating material.Therefore, can prevent electric current concentrating on the porous metal layer, thereby the part of the barrier film that inhibition contacts with the porous metal layer is degenerated.
In the electrode core, preferred metal forming or the sheet metal that carried out lath processing or punching processing that adopt.For example, metal forming or sheet metal form rectangular slit, with the rectangular segment between a pair of slit, form the 1st and the 2nd curved raised portion along a direction mutual the giving prominence to of positive and negative.
The invention still further relates to a kind of manufacture method of the alkaline battery that constitutes by positive plate, negative plate, barrier film between positive plate and negative plate and alkaline electrolyte.
Described manufacture method has following operation: (a) be produced on the positive plate that the 1st end has curren-collecting part, with the operation that has the negative plate of curren-collecting part in the 1st end, (b) at least at least the 2 end relative of positive plate with the 1st end, the operation that the both sides of end face and periphery thereof are covered with polyvinyl resin, (c) stacked or the reel positive plate separated by barrier film and the negative plate operation of making the pole plate group, and (d) appendix is had the 2nd end of polyvinyl resin to heat, make the operation of filming and being deposited over of polyvinyl resin with the barrier film that is configured in its both sides.
Operation (b) for example is made of following operation, promptly the aqueous dispersions of polyvinyl resin be coated in pole plate the 2nd end end face and the periphery both sides on.
At this, the operation that the aqueous dispersions of polyvinyl resin is coated in the both sides of described end face and periphery thereof preferably is made of following operation, promptly the aqueous dispersions of polyvinyl resin is offered the cylinder surface that is rotating continuously from a direction, and the operation of filming of predetermined thickness is set at cylinder surface; And the both sides of described end face and periphery thereof are contacted with described filming, make the operation that moves to the tangential direction of cylinder with respect to the pole plate of cylinder surface arranged perpendicular simultaneously.At this moment, make the same moved further of rotary speed of pole plate and cylinder, can form uniformly in the end of pole plate thus and film.
In the aqueous dispersions of polyvinyl resin, the preferred dissolution methylcellulose is with its antisettling agent as thickener and polyvinyl resin.Such aqueous dispersions longer-term storage demonstrates good storage stability, and has the viscosity that is suitable for the painter.
Operation (a) for example has following operation, and promptly along at least the 2 end relative with the 1st end of electrode core, coating contains the slurry of metal dust and thickener, and described slurry is carried out drying and sintering, thereby forms the operation of porous metal layer; And at least the 1 end and the 2nd end of reserving the electrode core, with the operation of active material layer appendix on the electrode core.
Operation (a) can further comprise following operation, and promptly the 1st end along the electrode core applies described slurry, and described slurry is carried out drying and sintering, thereby forms the porous metal layer.
According to the present invention,, just can effectively prevent coming off of short circuit between positive active material and the negative plate and active material by extremely simple method.Therefore, in the battery after carrying out charge and discharge cycles repeatedly, can effectively suppress the minute short circuit that is easy to generate.In addition, according to the present invention, can also prevent electric current the concentrating of curren-collecting part, thereby the part that can suppress barrier film is degenerated.
Description of drawings
Fig. 1 is the enlarged photograph of the major part of foaming nickel substrate.
Fig. 2 is the stereogram of an example of core, and wherein said core is processed into 3 dimension structures by solid.
Fig. 3 is the partial enlarged drawing of Fig. 2 core.
Fig. 4 is the plane graph of an example of expression positive plate.
Fig. 5 is that the I-I of Fig. 4 is to cutaway view.
Fig. 6 is the plane graph of an example of positive plate, and wherein said positive plate is provided with polyvinyl resin in the 2nd end and films.
Fig. 7 is that the I-I of Fig. 6 is to cutaway view.
Fig. 8 is the figure of an example of expression, and wherein this example has been enumerated a kind of method at pole plate end coating polyvinyl resin aqueous dispersions.
Fig. 9 is a cutaway view, is illustrated in the structure of the interior positive plate of pole plate group with a near example the end of polyvinyl resin covering.
Figure 10 is the longitudinal section of the another one example of positive plate.
Figure 11 is the longitudinal section of the another one example of positive plate, and wherein this positive plate is being provided with filming of polyvinyl resin in the 2nd end.
Figure 12 is a cutaway view, is illustrated in the structure of the interior positive plate of pole plate group with near the another one example the end of polyvinyl resin covering.
Figure 13 is the cutaway view of major part of an example of pole plate group, and wherein said pole plate group is being provided with filming of polyvinyl resin around the border of curren-collecting part and active material layer.
Figure 14 is the cutaway view of major part of the another one example of pole plate group, and wherein said pole plate group is being provided with filming of polyvinyl resin around the border of curren-collecting part and active material layer.
Figure 15 is the longitudinal section that launches the part of cylindrical nickel H accumulator of the present invention.
Figure 16 represents that each battery of embodiment and comparative example is in capacity sustainment rate after the placement and the relation between the charge and discharge cycles number of times.
Embodiment
Generally the active material layer on this electrode core constitutes alkaline storage battery pole plate by electrode core and appendix.Fig. 4 is the plane graph of an example of expression pole plate, and Fig. 5 is that the I-I of pole plate 30 of Fig. 4 is to cutaway view.In Fig. 4, the tow sides of the core 32 of 2 smooth dimension structures appendix separately active material layer 31.But, the present invention no matter adopt what kind of the electrode core can, and especially preferably be that the sheet metals of 3 dimension structures are used as positive plate with solid processing (distortion).
As solid processing (distortion) is the sheet metal of 3 dimension structures, as Fig. 2～shown in Figure 3, for example can use to have the capable core of protrusion (hereinafter referred to as core A), wherein said protrusion is capable of being constituted in the 1st and the 2nd outstanding alternately curved raised portion of the positive and negative of thin plate.In addition, the also preferred core (hereinafter referred to as core B) that adopts with following burr, wherein said burr form from the mutual punching of the tow sides of core, thereby alternatively highlight from the tow sides of core respectively.Before solid was processed as 3 dimension structures, the thickness of sheet metal was generally 10～80 μ m.
In addition, as the electrode core, can adopt also that to have 3 dimension interconnected pores and porositys be about 95% foaming nickel substrate.Foaming nickel substrate generally is used as the core of positive electrode of alkali accumulator.In addition, as the sheet metal that is used for anodal core, preferably adopt nickel foil or coating surface that the iron foil of nickel is arranged.
The electrode slip is coated on the electrode core, carries out drying and calendering then, just form active material layer thus.Specifically, as shown in Figure 4, after the curren-collecting part 33 that the exposed division of reserving by core constitutes, active material layer 31 is arranged on the tow sides of core 32.Curren-collecting part 33 forms a side (hereinafter referred to as the 1st end) of the end that is parallel to the core length direction, and makes it have predetermined width.The cropped as required size that becomes to be scheduled to of thin plate that is made of electrode core and active material layer that obtains so just obtains pole plate thus.
It is the positive active material and the binding agent of main component that the anodal slip that is used to form positive electrode active material layer contains with the nickel hydroxide, also can contain electric conducting material and thickener.Anodal electric conducting material preferably uses cobalt compounds such as cobalt hydroxide.
The negative pole slip that is used to form negative electrode active material layer contains predetermined negative electrode active material, also can contain binding agent, electric conducting material, thickener etc.
Positive active material preferably uses the solid solution hydrogen nickel oxide powder that contains cobalt, zinc etc.
Negative electrode active material can use hydrogen bearing alloy, zinc compound and cadmium compound etc.
Binding agent preferably uses polytetrafluoroethylene (hereinafter referred to as PTFE), polythene derivative and fluorubber etc.
Thickener preferably uses water-soluble cellulose derivative, water soluble acrylic resin's derivative and polyvinyl alcohol derivative etc.
Then as shown in Figure 6, cover the end face and the peripheral both sides thereof of at least the 2 end relative of gained pole plate with the 1st end with polyvinyl resin.Fig. 6 is that expression is provided with the film plane graph of an example of 34 pole plate of polyvinyl resin.In addition, Fig. 7 is that the I-I of pole plate 30 of Fig. 6 is to cutaway view.
For example the aqueous dispersions of polyvinyl resin is coated in the end face and the peripheral both sides thereof of the 2nd end of pole plate, heats the heating of filming afterwards, just form polyvinyl resin thus and film.In addition, also can consider under the state of heating and melting, to apply polyvinyl resin.But such method is difficult to form thin filming.In addition, the end beyond the 2nd end of pole plate, the same with the 2nd end, also can apply polyvinyl resin.
The aqueous dispersions of polyvinyl resin can adopt commercially available dispersion liquid.In the aqueous dispersions of commercially available polyvinyl resin, when the ratio of solid constituent is high (for example resin content be 60 weight % or when above), preferred water etc. dilutes.If use the high aqueous dispersions of solid constituent ratio at that, then be difficult to form filming of polyvinyl resin with the thickness of wanting.
When carrying out the dilution of aqueous dispersions, if adopt pure water, then polyvinyl resin tends to produce cohesion and precipitation.In order to prevent cohesion and precipitation, effective method is that the water-soluble resin that will have thickening effect adds in the dilution water.But if employing carboxymethyl cellulose etc. contain alkali-metal water-soluble resin, then effect is on the contrary, because it has further promoted the precipitation of polyvinyl resin.Therefore, preferably use the water-soluble resin of alkali-free metal, for example methylcellulose, polyvinyl alcohol etc. especially preferably use methylcellulose.
The content of polyvinyl resin is preferably 10～50 weight % in the polyvinyl resin aqueous dispersions.Polyvinyl resin contain quantity not sufficient 10 weight % the time, filming of polyvinyl resin is easy to generate defective, if surpass 50 weight %, then because the surface tension of aqueous dispersions increases, causes evenly coating difficulty.The content of polyvinyl resin can be adjusted at any time according to the difference of required coating thickness.
The content of water-soluble resin is preferably 2.5～5.0 weight % in the polyvinyl resin aqueous dispersions.If the content of water-soluble resin is too much, then polyvinyl resin become film after, water-soluble resin will sweeten off from film and become electrolyte.Therefore, polyvinyl resin is expected that the insulation effect that produces will reduce.On the other hand, if the content of water-soluble resin is very few, then be difficult to be filmed uniformly.
The polyvinyl resin that at least the 2 end of pole plate is covered is low density polyethylene (LDPE) preferably.In addition, the fusing point of polyvinyl resin is preferably 120 ℃ or following, more preferably 110 ℃ or following.This is because if the fusing point of polyvinyl resin surpasses 120 ℃, and when then making polyvinyl resin be deposited on the pole plate in the end of heating pole plate, active material will be degenerated, thereby reduce the utilance of active material.
In the molecule of polyvinyl resin, the residual of two keys arranged in manufacture process.The content that is included in the two keys in the polyvinyl resin is preferably low as much as possible.For example, if filming of polyvinyl resin is set on positive plate, then polyethylene is in the state of oxidation, is the decomposition that basic point carries out polyvinyl resin with two keys often.For this reason, if adopt the high polyvinyl resin of double bond content, then when carrying out the charge and discharge cycles of battery repeatedly, filming has the tendency that degeneration takes place.
Method at the aqueous dispersions of the both sides coating polyvinyl resin of the end face of at least the 2 end of pole plate and periphery thereof is not particularly limited.For example, according to following method, can access uniformly and film.
Describe below with reference to Fig. 8.In addition, Fig. 8 is conceptual description, and the size of each key element etc. are different with actual conditions.
At first, the aqueous dispersions 50 of polyvinyl resin is offered the surface of the cylinder 51 that is rotating continuously from a direction, and film 52 what described cylinder surface was provided with predetermined thickness.
For example, cylinder 51 is arranged on the liquid level of aqueous dispersions of polyvinyl resin and the position of intersecting perpendicular to the cylinder section of rotating shaft 53.Make cylinder 51 rotations with speed arbitrarily then.The rotating shaft 53 of cylinder or almost parallel parallel with liquid level.
When making the cylinder rotation with such configuration, cylinder surface moves under liquid level, and during this period, aqueous dispersions becomes films attached to cylinder surface.Being attached with cylinder surface that aqueous dispersions films moves on the liquid level along with the rotation of cylinder.For the aqueous dispersions with preferred thickness is filmed attached to cylinder surface, the rotary speed of cylinder needs to carry out suitable adjustment according to the viscosity of aqueous dispersions etc.
Secondly, the 2nd end 55 of pole plate 54 52 is contacted with filming attached to the aqueous dispersions of cylinder surface, the pole plate 54 with respect to the cylinder surface arranged perpendicular is moved to the tangential direction X of cylinder.By such operation,, can apply the aqueous dispersions 56 of polyvinyl resin in the both sides of the end face and the periphery thereof of the 2nd end 55 of pole plate 54.Be coated at aqueous dispersions under the situation of the 1st end of pole plate, also can use same operation to carry out polyvinyl resin.
The translational speed of pole plate should be carried out suitable adjustment according to the viscosity of aqueous dispersions, the rotary speed of cylinder etc.The moving direction of pole plate can be consistent with the moving direction of cylinder surface, also can be opposite direction.But, for being provided with uniform polyvinyl resin, the both sides at the end face of pole plate and periphery thereof film, and preferably with the speed synchronous, pole plate is moved towards the direction identical with the moving direction of cylinder surface with the rotary speed of cylinder.
The diameter of cylinder be preferably 150mm or more than.The diameter of cylinder is big more, the sagging that the aqueous dispersions that produces with regard to suppressing to be subjected to effect of surface tension is more filmed.Therefore, can thickness be set in the both sides of the end face of pole plate end and periphery thereof films uniformly.
After the aqueous dispersions of at least the 2 end of pole plate coating polyvinyl resin, the temperature of its end that raises is carried out drying and is made moisture evaporation, thereby polyvinyl resin is deposited on the pole plate.The temperature that polyvinyl resin is deposited on the pole plate is preferably 105～120 ℃.
Follow positive plate and negative plate stacked or that coiling is separated by barrier film and make the pole plate group.Fig. 9 is illustrated near the structure the 2nd end of the positive plate in the pole plate group with section.As shown in Figure 9, than the wideer barrier film 63 of positive plate 61 and negative plate 62 width between two-plate.In the both sides of the end face and the periphery thereof of the 2nd end 64 of positive plate 61, what be formed with polyvinyl resin films 65.Filming of polyvinyl resin is 65 adjacent with the barrier film 63 of both sides that is configured in positive plate 61.
The thickness that the polyvinyl resin that end face in the 2nd end of pole plate forms is filmed, promptly the thickness deltat k among Fig. 9 is preferably 5～50 μ m, more preferably 5～20 μ m.If the thickness deltat k less than 5 μ m that polyvinyl resin is filmed, the weakened of then filming perhaps produces defective in filming.Consequently film and to bear the expansion of pole plate, thereby be difficult to prevent the short circuit between positive plate and the negative plate.If the thickness deltat k that films surpasses 50 μ m, then when constituting the pole plate group, often produce problems such as winding position skew.
The both sides of the end face periphery of the 2nd end that the filming of polyvinyl resin also can be arranged on pole plate.The height (being the height Δ h among Fig. 9) that the polyvinyl resin of the end face periphery both sides of the 2nd end is filmed is preferably 0.3～1mm.Under the situation that the both sides of end face periphery polyvinyl resin of no use covers, by polyvinyl resin film and barrier film between deposited formed barrier film and pole plate between to engage be inadequate.
In such pole plate group, the position at 64 places, the 2nd end by heating cathode plate 61 is deposited over 65 barrier films 63 with the both sides that are configured in positive plate 61 of filming of polyvinyl resin.Make 65 temperature that are deposited over barrier film 63 of filming of polyvinyl resin, be preferably the temperature also higher 5～10 ℃ than the fusing point of polyvinyl resin.If exceed 5 ℃ of the temperature less thaies of fusing point, then filming of polyvinyl resin can not fully be deposited over barrier film.In addition, surpass 10 ℃ if exceed the temperature of fusing point, then polyvinyl resin is toward dirty, makes deposited between barrier film and the polyvinyl resin become inhomogeneous.
For filming of polyvinyl resin is deposited over barrier film, also can heat whole pole plate group.But, when the pole plate group is warmed up to too high temperature, then bring because of active material the low of caused utilance that degenerate.In addition, the temperature of pole plate group is preferably lowered the temperature when polyvinyl resin begins fusion at once.In case keep the molten condition of polyvinyl resin for a long time, then polyvinyl resin will be toward dirty, makes deposited between barrier film and the polyvinyl resin become inhomogeneous.
Barrier film can use the known barrier film that uses in the alkaline battery, not what special restriction.For example the nonwoven fabrics that can constitute with polypropylene system nonwoven fabrics, polyethylene system nonwoven fabrics, by polypropylene and poly compound etc. is as barrier film.These barrier films are preferably implemented hydrophilicity-imparting treatment such as sulfonation.
Expose with the side of helical structure at pole plate group end face the 1st end that becomes the positive plate curren-collecting part.On this curren-collecting part, welding anodal collector plate.Similarly, the curren-collecting part of negative plate is exposed with the end face of helical structure pole plate group the opposing party, the collector plate of itself and negative plate can be welded together.The pole plate group that obtains like this is housed in the housing with electrolyte,, just can obtains alkaline battery if the peristome of housing is sealed with the hush panel that safety valve is housed.
It is the aqueous alkali of main solute dissolving that electrolyte can use with potassium hydroxide.
In at least one side of positive plate and negative plate, the 2nd end of the pole plate that will cover with polyvinyl resin is set at the exposed division that does not have the electrode of active material layer core, and situation like this describes below.
Figure 10 is the longitudinal section that is not had the pole plate 90 that the exposed division of the electrode core of active material layer constitutes by the 2nd end.In Figure 10, in the tow sides of the core 92 of smooth 2 dimension structures, appendix active material 91 respectively.But in fact, core preferably adopts the sheet metal that is processed as 3 dimension structures by solid.
On the 1st end 93 of pole plate 90, the curren-collecting part that the exposed division by core constitutes is being set, on 2nd end 94 relative, the exposed division of core is being set also with the 1st end.Then, the exposed division with porous metal layer 95 and the 2nd end 94 is bonded together.By the 2nd end portion thickness that the exposed division and the porous metal layer of electrode core constitutes, be generally 50～100% of the electrode thickness that constitutes by electrode core and active material layer.
Along the 2nd end 94, coating contains the slurry of metal dust and thickener, and porous metal layer 95 can form by drying and the described slurry of sintering.In addition, when curren-collecting part is made of the exposed division of core, also can engage same porous metal layer at its exposed division.
The average primary particle diameter of metal dust is preferably 0.5～4 μ m, and primary particle preferably is connected to form 3 dimension structures with the form of chain.Can be with nickel powder, stainless steel powder, chromium powder, copper powder etc. as metal dust.
Secondly, active material layer in the 1st end of electrode core and the regional appendix beyond the 2nd end.And as shown in figure 11, in the end face and the peripheral both sides thereof of the 2nd end 94, what be provided with polyvinyl resin films 96.In the pole plate 100 that obtains like this, the porous metal layer has the effect that prevents that active material from coming off and so on.
Figure 12 represents near the structure the 2nd end of positive plate in the pole plate group with section, wherein said pole plate group adopts the positive plate of Figure 11 to be assembled into and forms.As shown in figure 12, positive plate 43 is made of anodal core 41 and the positive electrode active material layer 42 that is arranged on its two sides, than the wideer barrier film 45 of the width of positive plate 43 and negative plate 44 between two-plate.The exposed division of core is being set in the 2nd end of anodal core 41, and porous metal layer 46 is bonded together with this exposed division.Then, the 2nd end of the positive plate that is made of the exposed division and the porous metal layer of core 47 covers with filming of polyvinyl resin.Because polyvinyl resin is insulating material, so filming of polyvinyl resin 47 has the effect that prevents that electric current from concentrating at the porous metal layer.Its result can suppress the part of the barrier film that contacts with the porous metal layer and degenerate.
In addition, in the middle of the exposed division of core, because electric current concentrates on curren-collecting part especially, therefore around curren-collecting part and the border between the active material layer that the exposed division by core constitutes, it also is effective that filming of polyvinyl resin is set.
The cutaway view of the major part of Figure 13～14 expression pole plate groups, wherein said pole plate group is being provided with filming of polyvinyl resin around the border of curren-collecting part and active material layer.In Figure 13～14, the symbol same to common element annotation.Why an end face side pole plate group one side is provided with filming of polyvinyl resin, is the passage in order to ensure electrolyte.But,, be not limited to the situation shown in Figure 13～14 for the position that polyvinyl resin is filmed is set.
In the upper surface and the lower surface of pole plate group, disposing anodal collector plate 109 and negative pole collector plate 110 respectively.On anodal collector plate 109, connecting the curren-collecting part of the positive plate 103 that constitutes by anodal core 119 and the positive electrode active material layer 120 that is arranged on its two sides.The curren-collecting part of positive plate is made of with the porous metal layer 122 that is bonded on its two sides the exposed division 121 of anodal core.On the other hand, on negative pole collector plate 110, connecting the curren-collecting part of the negative plate 104 that constitutes by negative pole core 123 and the negative electrode active material layer 124 that is arranged on its two sides.The curren-collecting part of negative plate is made of with the porous metal layer 128 that is bonded on its two sides the exposed division 127 of negative pole core.Than the wideer barrier film 107 of the width of positive plate and negative plate between two-plate.
In Figure 13, the 2nd end of positive plate is not provided with the porous metal layer.Therefore, at the end face of the 2nd end, active material layer has revealed to come out.For this reason, the both sides of this end face and periphery thereof 130 coverings of filming that constitute by polyvinyl resin.And with the 1st end of the adjacent negative plate in the 2nd end of positive plate, what polyvinyl resin had been set around the border of porous metal layer 128 and negative electrode active material layer 124 films 140.
In Figure 14, the 2nd end at positive plate and negative plate is being provided with porous metal layer 133 and 134 respectively.Therefore, at the end face of the 2nd end of positive plate, porous metal layer 133 has revealed to come out.For this reason, this end face and peripheral both sides thereof 130 coverings of filming that constitute by polyvinyl resin.And with the 1st end of the adjacent negative plate in the 2nd end of positive plate, what polyvinyl resin had been set around the border of the porous metal layer 128 of negative pole curren-collecting part and negative electrode active material layer 124 films 140.
As an example of alkaline battery of the present invention, Figure 15 represents to launch the longitudinal section of the part of cylindrical nickel H accumulator.In the inside of the housing 74 of Figure 15, accommodating the pole plate group that forms by positive plate of separating by barrier film 73 71 and negative plate 72 rollbacks with the electrolyte (not shown).Hush panel 75 has positive terminal 76 and safety valve 77.Safety valve 77 is made of the rubber bodies that clogs hole 78, and hole 78 makes the inside and the external communications of housing 74.When inside battery generation gas, when causing internal pressure to rise, rubber bodies deforms, and gas is just discharged from enclosure interior and outside intercommunicating pore.Because the periphery of hush panel 75 is equipped with insulating washer 79, so positive terminal 76 insulate mutually with the housing 74 that has negative terminal concurrently.
In Figure 15, anodal collector plate 80 is welded on the upper end of pole plate group.On the one hand, the curren-collecting part of negative plate exposes in the lower end surface of pole plate group with helical structure, and itself and negative pole collector plate 81 weld together.Anodal collector plate 80 is connected inboard with the hush panel of positive terminal conducting by lead 82.On the other hand, negative pole collector plate 81 contacts with the inner bottom surface of metal shell, and the negative plate that is positioned at pole plate group outermost also contacts with the inner face of metallic housing.By these contacts, the current collection to negative terminal is carried out.
In above-mentioned alkaline battery, at least the 2nd end of positive plate by polyvinyl resin film cover, this is filmed and is deposited over the barrier film that is configured in the positive plate both sides.Therefore, even carry out discharging and recharging repeatedly, can prevent that also polyvinyl resin is extruded with the Width of positive active material at positive plate.Therefore, though discharge and recharge carry out repeatedly after, also be difficult to cause minute short circuit, even remain on charged state, be difficult for also causing that capacity reduces.And under the situation about constituting by the exposed division and the porous metal layer of electrode core in the 2nd end of pole plate, utilize the porous metal layer can prevent the generation of problems such as coming off of active material, utilize polyvinyl resin simultaneously, can prevent electric current concentrating on the porous metal layer.In addition, under the situation about covering with polyvinyl resin in the 2nd end of negative plate, also can prevent generation from problems such as coming off of the active material of negative plate.Moreover, in the 1st end of pole plate, when around the border that covers curren-collecting part and active material with polyvinyl resin, also can prevent electric current concentrated on curren-collecting part.
In addition, Fig. 2～15 are the illustration of embodiment of the present invention only, and no matter the present invention can use in the alkaline battery of which kind of scheme.
Embodiment 1
(1) making of core
The core of 1st and 2nd curved raised portion with rectangular shape of making shown in Fig. 2,3, wherein curved raised portion is outstanding alternately at the positive and negative of core respectively is convex.At the pure nickel paper tinsel that obtains by electro-plating method (thickness 20 μ m, 170g/m
2) on, form slit with the spacing of 0.5mm perpendicular to its length direction, the rectangular segment by the slit clamping is swelled alternately at tow sides, the making of this core is promptly accused and is finished thus.At the edge part along the core length direction, the vegetarian noodles portion that will not form curved raised portion gives over to curren-collecting part.In vegetarian noodles portion, the recess of many ditch shapes 15 forms ripple with the configuration that is parallel to each other.The apparent thickness of implementing the core after this processing is set at 500 μ m.Follow the core two sides after processing, the mixed slurry of coating carbonyl nickel powder (INCO corporate system #255) and methylated cellulose aqueous solution (SHIN-ETSU HANTOTAI's chemistry (strain) system SM400) carries out sintering after the drying, be 50g/m so that make the coating amount of carbonyl nickel powder
2Afterwards, in the reducing atmosphere that the mist by hydrogen that contains steam and nitrogen constitutes, the core that appendix is had a carbonyl nickel powder was 950 ℃ of following sintering 15 minutes.
(2) making of positive plate
The solid solution hydrogen nickel oxide powder of 100 weight portions, the cobalt hydroxide micropowder of 7 weight portions, carboxy methyl cellulose (CMC) aqueous solution (CMC concentration is 1%) of 21 weight portions and the rubber latex (Aflas 150 of Asahi Glass (strain) system) of 4 weight portions (solid constituent) are mixed, prepare anodal slip.
Utilize the mold pressing coating machine that described anodal slip is coated on the described core, the hot blast of following with 100 ℃ is dried 2 minutes, just forms active material layer thus.Then, adopt roller extruder, have the core of active material layer to roll to appendix, making its thickness is 400 μ m, be cut into the size of length 375mm * width 35mm after, just obtain positive plate.In addition, in the vegetarian noodles portion of the core that becomes anodal curren-collecting part, the residual part that the wide not appendix active material layer of 1mm is arranged.
(3) coating of polyvinyl resin
With fusing point is aqueous dispersions (Mitsui Chemicals (strain) system of 100 ℃ polyvinyl resin, solid constituent is 60 weight %), with methylated cellulose aqueous solution (SHIN-ETSU HANTOTAI's chemistry (strain) system SM400, methylcellulose concentration is 4 weight %) be that 1: 4 ratio is mixed with weight ratio, just make the dilution dispersion liquid of polyvinyl resin.
In container, fill the dilution dispersion liquid of polyvinyl resin, the cylinder that rotatable diameter is 300mm is set near its liquid level.Be configured cylinder this moment, makes perpendicular to 75% of the cylinder section of rotating shaft to be positioned under the liquid level.Then, make cylinder rotation, just be attached with the filming of dilution dispersion liquid of polyvinyl resin at cylinder surface.
Then vertically dispose positive plate with respect to cylinder surface, the end relative with the curren-collecting part of positive plate contacted with filming of aqueous dispersions attached to cylinder surface, the tangential direction to cylinder surface moves simultaneously.The moving direction of cylinder surface is identical with positive plate, and translational speed is set at 40mm/sec too.Its result, the dilution dispersion liquid of polyvinyl resin can evenly be coated in and the curren-collecting part opposing end faces of positive plate and the both sides of periphery thereof.
The positive plate that is coated with polyvinyl resin dilution dispersion liquid heated 1 minute under 110 ℃ temperature, and polyvinyl resin is deposited over positive plate.The coating thickness of the polyvinyl resin that forms at the end face of positive plate is 10 μ m like this.In addition, the sidepiece at the positive plate from its end face to distance end face height 0.5mm also is formed with filming of polyvinyl resin.
(4) making of negative plate
Coating surface there be the core of the iron foil (thickness 60 μ m) of nickel as negative pole.Is the cathode size that principal component contains in the coating of the two sides of this core with the hydrogen bearing alloy, after the dry also calendering, is cut into predetermined size, has just obtained negative plate.Side in the end parallel with the length direction of negative plate exposes the negative pole core, with its curren-collecting part as negative plate.
(5) making of battery
Positive plate and negative plate that coiling is separated by the polypropylene system barrier film of having implemented hydrophilic treated are just produced the pole plate group.At this moment, the curren-collecting part that makes the curren-collecting part of positive plate and negative plate exposes at a side's of pole plate group end face and the opposing party's end face respectively with helical structure.The pole plate group that obtains like this is warmed up to 110 ℃, kept 1 minute, the polyvinyl resin that just will cover the end relative with the curren-collecting part of positive plate is deposited over barrier film.Then, each curren-collecting part that the collector plate of nickel-clad steel plate system and each end face in the pole plate group are exposed welds together.The pole plate group that is welded with collector plate is inserted in the housing of SC size, to be that the lysigenous aqueous alkali of main solute is that electrolyte injects housing with 31 weight % potassium hydroxide, adopt hush panel that housing is sealed, just producing nominal capacity is the cylindrical nickel H accumulator of the embodiment 1 of 3300mAh.
Embodiment 2
(1) making of core
The core of 1st and 2nd curved raised portion with rectangular shape of making shown in Fig. 2,3, wherein curved raised portion is outstanding alternately at the positive and negative of core respectively is convex.At the pure nickel paper tinsel that obtains by electro-plating method (thickness 20 μ m, 170g/m
2) on, form slit with the spacing of 0.5mm perpendicular to its length direction, the rectangular segment by the slit clamping is swelled alternately at tow sides, the making of this core is promptly accused and is finished thus.In the two edges portion along the core length direction, the vegetarian noodles portion that will not form curved raised portion gives over to curren-collecting part and the 2nd end.In vegetarian noodles portion, the recess of many ditch shapes 15 forms ripple with the configuration that is parallel to each other.The apparent thickness of implementing the core after this processing is set at 500 μ m.Follow the core two sides after processing, the mixed slurry of coating carbonyl nickel powder (INCO corporate system #255) and methylated cellulose aqueous solution (SHIN-ETSU HANTOTAI's chemistry (strain) system SM400), the coating amount that makes carbonyl nickel powder after the drying is 50g/m
2
Moreover, with the mixed slurry of carbonyl nickel powder (INCO corporate system #255) and methylated cellulose aqueous solution (SHIN-ETSU HANTOTAI's chemistry (strain) system SM400) width with 1.0mm, be coated on the place that become anodal core the 2nd end with distributor, carry out drying then, making the thickness (thickness that comprises nickel foil) behind the sintering is 400 μ m.Afterwards, in the reducing atmosphere that the mist by hydrogen that contains steam and nitrogen constitutes, the core that appendix is had a carbonyl nickel powder was 950 ℃ of following sintering 15 minutes.
(2) making of positive plate
The solid solution hydrogen nickel oxide powder of 100 weight portions, the cobalt hydroxide micropowder of 7 weight portions, carboxy methyl cellulose (CMC) aqueous solution (CMC concentration is 1%) of 21 weight portions and the rubber latex (Aflas 150 of Asahi Glass (strain) system) of 4 weight portions (solid constituent) are mixed, prepare anodal slip.
Utilize the mold pressing coating machine that described anodal slip is coated on the described core, the hot blast of following with 100 ℃ is dried 2 minutes, just forms active material layer thus.Then, adopt roller extruder, have the core of active material layer to roll to appendix, making its thickness is 400 μ m, be cut into the size of length 375mm * width 35mm after, just obtain positive plate.In addition, in the vegetarian noodles portion of the core that becomes anodal curren-collecting part with become the vegetarian noodles portion of the 2nd end, the residual part that the wide not appendix active material layer of 1mm is arranged.
(3) coating of polyvinyl resin
With fusing point is aqueous dispersions (Mitsui Chemicals (strain) system of 100 ℃ polyvinyl resin, solid constituent is 60 weight %), with methylated cellulose aqueous solution (SHIN-ETSU HANTOTAI's chemistry (strain) system SM400, methylcellulose concentration is 4 weight %) be that 1: 4 ratio is mixed with weight ratio, just make the dilution dispersion liquid of polyvinyl resin.
In container, fill the dilution dispersion liquid of polyvinyl resin, the cylinder that rotatable diameter is 300mm is set near its liquid level.Be configured cylinder this moment, makes perpendicular to 75% of the cylinder section of rotating shaft to be positioned under the liquid level.Then, make cylinder rotation, just be attached with the filming of dilution dispersion liquid of polyvinyl resin at cylinder surface.
Then vertically dispose positive plate with respect to cylinder surface, 2nd end relative with the curren-collecting part of positive plate contacted with filming of aqueous dispersions attached to cylinder surface, the tangential direction to cylinder surface moves simultaneously.The moving direction of cylinder surface is identical with positive plate, and translational speed is set at 60mm/sec too.Its result, the dilution dispersion liquid of polyvinyl resin can evenly be coated in curren-collecting part end face relative, that expose the porous metal layer and the peripheral both sides thereof with positive plate.
The positive plate that is coated with polyvinyl resin dilution dispersion liquid heated 1 minute under 110 ℃ temperature, and polyvinyl resin is deposited over positive plate.The coating thickness of the polyvinyl resin that forms at the end face of positive plate is 10 μ m like this.In addition, the sidepiece at the positive plate from its end face to distance end face height 1.2mm also is formed with filming of polyvinyl resin.
(4) making of negative plate
Coating surface there be the core of the iron foil (thickness 60 μ m) of nickel as negative pole.Is the cathode size that principal component contains in the coating of the two sides of this core with the hydrogen bearing alloy, after the dry also calendering, is cut into predetermined size, has just obtained negative plate.Side in the end parallel with the length direction of negative plate exposes the negative pole core, with its curren-collecting part as negative plate.
(5) making of battery
Positive plate and negative plate that coiling is separated by the polypropylene system barrier film of having implemented hydrophilic treated are just produced the pole plate group.At this moment, the curren-collecting part that makes the curren-collecting part of positive plate and negative plate exposes at a side's of pole plate group end face and the opposing party's end face respectively with helical structure.The pole plate group that obtains like this is warmed up to 110 ℃, kept 1 minute, the polyvinyl resin that just will cover the end relative with the curren-collecting part of positive plate is deposited over barrier film.Then, each curren-collecting part that the collector plate of nickel-clad steel plate system and each end face in the pole plate group are exposed welds together.The pole plate group that is welded with collector plate is inserted in the housing of SC size, to be that the lysigenous aqueous alkali of main solute is that electrolyte injects housing with 31 weight % potassium hydroxide, adopt hush panel that housing is sealed, just producing nominal capacity is the cylindrical nickel H accumulator of the embodiment 2 of 3300mAh.
Comparative example 1
Cover the end relative with the curren-collecting part of positive plate without polyvinyl resin, in addition, other is the same with embodiment 1, makes the battery of comparative example 1.
Comparative example 2
Produce after the pole plate group, the operation that the polyvinyl resin that does not carry out covering the end relative with the curren-collecting part of positive plate is deposited over barrier film, in addition, other is the same with embodiment 1, makes the battery of comparative example 2.
Comparative example 3
Cover the end relative with the curren-collecting part of positive plate without polyvinyl resin, in addition, other is the same with embodiment 2, makes the battery of comparative example 3.
The evaluation of battery
For the battery of the embodiment that makes above and the battery of comparative example, implement the initial charge/discharge of following 2 circulations: promptly the charging rate with 0.1C charged 15 hours, discharged 4 hours with the velocity of discharge of 0.2C again.Afterwards, carry out 3 days burin-in process (promoting the activation of negative pole alloy) by a definite date at 45 ℃.
Afterwards, carry out common charge and discharge cycles repeatedly.In common charge and discharge cycles, after the control mode of using dT/dt (dT=1.5 ℃, dt=30 second) is charged with the charging rate of 1C, till being discharged to cell voltage and reaching 0.8V with the discharging current of 10A.
Wherein, 50 circulations of every experience just are charged to 120% (promptly 72 minutes) of nominal capacity with the charging rate of 1C, after placing 1 hour, till being discharged to cell voltage and reaching 1.0V with the velocity of discharge of 1C.At this moment the capacity that obtains is referred to as C-1h.
Then be charged to 120% of nominal capacity with the charging rate of 1C once more, after placing 72 hours, till being discharged to cell voltage and reaching 1.0V with the velocity of discharge of 1C.At this moment the capacity that obtains is referred to as C-72h.
At this, obtain the ratio (C-72h/C-1h) of C-72h with respect to C-1h with percentage.Capacity sustainment rate after below this value being referred to as to place.Capacity sustainment rate after Figure 16 represents to place and the relation between the period.
In Figure 16, the capacity sustainment rate (C after the battery of comparative example 1 is placed
1) and the battery of the comparative example 2 capacity sustainment rate (C after placing
2) 80～200 circulations of experience just reach 60% or below.On the other hand, the capacity sustainment rate (A) after the battery of embodiment 1 is placed is even surpass 450 circulations, still remain on 60% or more than.Moreover the capacity sustainment rate (B) after the battery of embodiment 2 is placed is even surpass 650 circulations, still remain on 60% or more than.
Why producing such difference, is because expanding appears along with carrying out repeatedly of discharging and recharging in pole plate.It is generally acknowledged that in comparative example 1 positive active material is extruded at the Width of pole plate, in comparative example 2, resin coating film is extruded with the Width of positive active material at pole plate.And in comparative example 1,2, it is generally acknowledged positive active material positive plate and and its opposed negative plate between cause short circuit.
Capacity sustainment rate (C after the battery of comparative example 3 is placed
3) just reduction significantly of 450 circulations of experience.It is generally acknowledged in the battery of comparative example 3, because the 2nd end of positive plate is subjected to the protection of firm porous metal layer, so, positive active material also can not occur and be extruded, produce such problem that comes off at Width even pole plate expands.On the other hand, the porous metal layer of positive plate is owing to mutually opposed with negative plate by barrier film, so electric current is concentrated on the porous metal layer easily.Therefore, it is generally acknowledged, promoted barrier film and the contacted part of porous metal layer to degenerate by carrying out charge and discharge cycles repeatedly.
Under the situation of the battery of embodiment 2, because the surface of porous metal layer is that polyvinyl resin is filmed and is covered with insulating material, so blocked the current path that flows to the porous metal layer.Therefore, electric current can not concentrated on the porous metal layer, even carry out charge and discharge cycles repeatedly, can suppress the degeneration of the membrane portions that contacts with the porous metal layer yet.It is generally acknowledged that the capacity sustainment rate that makes thus after the placement is improved.
According to the present invention, utilize simple method just can prevent coming off of short circuit between positive active material and the negative plate and active material effectively, so can provide high performance alkaline battery with low cost.
Claims (16)
1, a kind of alkaline battery, it is made of positive plate, negative plate, barrier film and alkaline electrolyte between described positive plate and negative plate, and wherein, described positive plate and negative plate the 1st end separately becomes curren-collecting part; At least at least the 2 end relative of positive plate, cover the both sides of end face and periphery thereof with polyvinyl resin with described the 1st end; The filming of polyvinyl resin that is arranged on described positive plate the 2nd end is deposited over the barrier film that is configured in its both sides.
2, alkaline battery as claimed in claim 1, wherein on described at least the 2nd end of described negative plate, the both sides of its end face and periphery thereof are covered by polyvinyl resin.
3, alkaline battery as claimed in claim 1, the fusing point of wherein said polyvinyl resin are 120 ℃ or following.
4, alkaline battery as claimed in claim 1, the coating thickness of wherein said polyvinyl resin are 5～50 μ m on described end face.
5, alkaline battery as claimed in claim 1, active material layer on described electrode core constitutes at least one side of wherein said positive plate and negative plate by electrode core and appendix, and described the 2nd end that covers with described polyvinyl resin is made of the exposed division of the described electrode core that does not have described active material layer.
6, alkaline battery as claimed in claim 5, wherein the porous metal layer is bonded on the electrode core exposed division of described the 2nd end, and described porous metal layer is covered by described polyvinyl resin.
7, alkaline battery as claimed in claim 6, described the 2nd end portion thickness that is made of the exposed division and the described porous metal layer of described electrode core wherein is 50～100% of the electrode thickness that is made of described electrode core and described active material layer.
8, alkaline battery as claimed in claim 5, wherein at least one side of described positive plate and negative plate, described curren-collecting part is made of the exposed division of the described electrode core that does not have described active material layer, and is to be covered by polyvinyl resin around the border of described curren-collecting part and described active material layer at least.
9, as claim 6 or 8 described alkaline batterys, wherein the porous metal layer is bonded on the exposed division of described electrode core of described curren-collecting part, and the part of described porous metal layer covers with the end near the described active material layer of described exposed division.
10, alkaline battery as claimed in claim 5, wherein said electrode core is made of the metal forming or the sheet metal that carried out lath processing or punching processing; Described metal forming or sheet metal have and form rectangular slit; With the rectangular segment between a pair of slit, outstanding alternately and form the 1st and the 2nd curved raised portion at positive and negative along the row or column of described matrix.
11, a kind of manufacture method of alkaline battery, wherein alkaline battery is by positive plate, negative plate, barrier film between described positive plate and negative plate and alkaline electrolyte constitute, described manufacture method has following operation: (a) be produced on the positive plate that the 1st end has curren-collecting part, with the operation that has the negative plate of curren-collecting part in the 1st end, (b) at least at least the 2 end relative of described positive plate with described the 1st end, the operation that the both sides of end face and periphery thereof are covered with polyvinyl resin, (c) stacked or the reel described positive plate separated by described barrier film and the negative plate operation of making the pole plate group, and (d) appendix is had the 2nd end of described polyvinyl resin to heat, make the operation of filming and being deposited over of described polyvinyl resin with the barrier film that is configured in its both sides.
12, the manufacture method of alkaline battery as claimed in claim 11, wherein said operation (b) is made of the operation on the both sides that the aqueous dispersions of polyvinyl resin are coated in described end face and periphery thereof.
13, the manufacture method of alkaline battery as claimed in claim 12, the operation that wherein aqueous dispersions of polyvinyl resin is coated in the both sides of described end face and periphery thereof is made of following operation: the aqueous dispersions of described polyvinyl resin is offered the cylinder surface that is rotating continuously from a direction, and the operation of filming of predetermined thickness is set at described cylinder surface; And the both sides of described end face and periphery thereof are contacted with described filming, make the operation that moves to the tangential direction of described cylinder with respect to the described pole plate of described cylinder surface arranged perpendicular simultaneously.
14, the manufacture method of alkaline battery as claimed in claim 12, wherein in the aqueous dispersions of described polyvinyl resin, the dissolving methylcellulose is with its antisettling agent as thickener and polyvinyl resin.
15, the manufacture method of alkaline battery as claimed in claim 11, wherein said operation (a) has following operation: along at least the 2 end relative with described the 1st end of the electrode core of described positive plate or described negative plate, coating contains the slurry of metal dust and thickener, and described slurry carried out drying and sintering, thereby form the operation of porous metal layer; And described at least the 1st end and the 2nd end of reserving described electrode core, with the operation of active material layer appendix on described electrode core.
16, the manufacture method of alkaline battery as claimed in claim 15, wherein said operation (a) has: the 1st end along the electrode core applies described slurry, and described slurry is carried out drying and sintering, thereby forms the operation of porous metal layer.
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| JP117231/2003 | 2003-04-22 | ||
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| TW200810199A (en) * | 2006-08-08 | 2008-02-16 | Matsushita Electric Ind Co Ltd | Accumulator and its manufacturing method |
| US8765299B2 (en) | 2010-01-15 | 2014-07-01 | Samsung Sdi Co., Ltd. | Electrode assembly and secondary battery including the same |
| CN102130320B (en) * | 2010-01-15 | 2015-04-01 | 三星Sdi株式会社 | Electrode assembly and secondary battery including the same |
| US20110177383A1 (en) * | 2010-01-19 | 2011-07-21 | Lightening Energy | Battery cell module for modular battery with interleaving separator |
| CN104810503B (en) * | 2011-01-28 | 2019-08-16 | 丰田自动车株式会社 | Secondary cell |
| CN103094619B (en) * | 2013-01-17 | 2015-02-04 | 北京好风光储能技术有限公司 | High-energy density lithium ion battery cell and preparation method thereof |
| CN108493398B (en) * | 2018-03-06 | 2020-05-26 | 深圳前海优容科技有限公司 | Battery cell, manufacturing method thereof, battery and electronic device |
| WO2019169557A1 (en) * | 2018-03-06 | 2019-09-12 | 深圳前海优容科技有限公司 | Cell and manufacturing method therefor, battery, and electronic device |
| CN108428854B (en) * | 2018-03-06 | 2024-01-16 | 深圳前海优容科技有限公司 | Battery cell, manufacturing method thereof, battery and electronic device |
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| JPH09171818A (en) * | 1994-12-26 | 1997-06-30 | Samsung Display Devices Co Ltd | Nickel-metal hydride storage battery and its preparation |
| CN1189925A (en) * | 1996-04-23 | 1998-08-05 | 住友电气工业株式会社 | Non-aqueous electrolyte cell |
| JP2001176506A (en) * | 1999-11-10 | 2001-06-29 | Alcatel | Non-sintered electrode having three-dimensional base for electrochemical secondary battery having alkaline electrolyte |
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2004
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09171818A (en) * | 1994-12-26 | 1997-06-30 | Samsung Display Devices Co Ltd | Nickel-metal hydride storage battery and its preparation |
| CN1189925A (en) * | 1996-04-23 | 1998-08-05 | 住友电气工业株式会社 | Non-aqueous electrolyte cell |
| JP2001176506A (en) * | 1999-11-10 | 2001-06-29 | Alcatel | Non-sintered electrode having three-dimensional base for electrochemical secondary battery having alkaline electrolyte |
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