CN101099258A - Nickel hydrogen storage battery and production method for its cathode - Google Patents
Nickel hydrogen storage battery and production method for its cathode Download PDFInfo
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- CN101099258A CN101099258A CNA2005800461098A CN200580046109A CN101099258A CN 101099258 A CN101099258 A CN 101099258A CN A2005800461098 A CNA2005800461098 A CN A2005800461098A CN 200580046109 A CN200580046109 A CN 200580046109A CN 101099258 A CN101099258 A CN 101099258A
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
A strip-form cathode (4) having a mixture layer consisting of hydrogen storage alloy disposed on a core material and a strip-form anode are wound spirally via a separator to constitute an electrode group, and this electrode group is housed in a bottomed cylindrical container with the cathode (4) forming the outer-most peripheral portion, wherein a portion corresponding to a cathode outer-most peripheral portion (5) is formed as a thin-walled portion and this thin-walled portion is curved in an arc shape in the winding direction of the electrode group in advance, whereby the cathode outer-most peripheral portion is prevented from separating from the electrode group when the spiral electrode group is formed and an inserting performance into the bottomed cylindrical container is improved.
Description
Technical field
The present invention relates to nickel-hydrogen accumulator, in more detail, relate to by improving negative pole structure and improve the electrode group to the insertion that the bottom tube-like container is arranged.
Background technology
Alkaline battery is widely used in portable machine with in the power supply as battery that can repeated charge.Wherein, use hydrogen bearing alloy as the nickel-hydrogen accumulator of negative electrode active material because the energy density height is also cleaner aspect environment, therefore just promoted as the various main power sources that carry machine.
The current collection method of nickel-hydrogen accumulator is: the bottom tube-like container is arranged as negative terminal with what accommodate the electrode group that constitutes by both positive and negative polarity, with the hush panel of its insulation as positive terminal.Anodal integrated by lead-in wire and hush panel, thus the current collection structure formed, and on the contrary, negative pole forms the current collection structure by its outermost perimembranous is linked to each other with the side inner walls that the bottom tube-like container is arranged.
From making the viewpoint of this nickel-hydrogen accumulator high capacity, following method has been proposed: make the thin thickness (for example specially permit No. 3056521 communique) of the thickness of the negative pole on the outermost perimembranous that is arranged on the spiral electrode group that constitutes by both positive and negative polarity and barrier film than other parts.
Be specifically described with reference to the conventional example of putting down in writing in Figure 11, No. 3056521 communique of 12 pairs of above-mentioned special permissions.The alkaline cell that also is suitable in nickel-hydrogen accumulator has following structure: the negative pole 101 and the strip-shaped positive electrode 102 of band shape are curled into helical form and constitute the electrode group across barrier film 103, accommodate this electrode group in the container 104 that bottom tube-like is arranged.The outermost perimembranous of above-mentioned electrode group is provided with above-mentioned negative pole 101, the outermost perimembranous 105 of this negative pole 101 forms following structure: contact with said vesse 104, the thickness of the outermost perimembranous 105 of negative pole 101 is than the thickness little (specifically being 50%～90%) of other parts 106 simultaneously.The length L of the outermost perimembranous 105 of above-mentioned negative pole 101 and the inner periphery of said vesse 104 are long basic identical, have formed boundary portion 107 between this outermost perimembranous 105 and other parts 106.
The outermost perimembranous of the negative pole of putting down in writing in the above-mentioned communique usually can be when reducing on collector body the coating cathode agent the anode mixture layer that forms with the thickness identical of thickness or prune with other parts or improve packed density and form.Yet, all there is following problem in all cases: because the influence of the thickness difference of the outermost perimembranous of negative pole and other parts, when constituting the electrode group positive pole being curled into helical form across barrier film, have only the outermost perimembranous not bend to helical form and come off from the electrode group, when being inserted into this electrode group in the bottom tube-like container, can be tangled, thereby generation is inserted bad.
This problem is thinner than inboard (central side of electrode group) at the mixture layer in the outside of negative pole outermost perimembranous (the inwall side that the bottom tube-like container is arranged), it is arranged under the situation in the outside especially remarkable when constituting the electrode group.Promptly, this is to produce curling character because the coating thing that has a different-thickness at the front and back of core has because of calendering produces stress deformation and becomes inboard mode according to a side of thin thickness, and negative pole oppositely curls with curl direction on the outermost perimembranous of electrode group.
The invention solves above-mentioned problem, its objective is when constituting the spiral electrode group, can suppress negative pole outermost perimembranous and come off, improve to the insertion that the bottom tube-like container is arranged from this electrode group.
Summary of the invention
In order to solve above-mentioned problem, the described nickel-hydrogen accumulator of claim 1 of the present invention is by the banded negative pole that will core be provided with the mixture layer that is made of hydrogen bearing alloy and bandedly anodally constitutes the electrode group across the barrier film curl that curls, and in the bottom tube-like container is arranged, accommodate this electrode group and constitute, wherein, the outermost perimembranous of above-mentioned electrode group is provided with above-mentioned negative pole, above-mentioned negative pole has the thickness thinner wall section littler than other position of above-mentioned mixture layer at the position corresponding with the outermost perimembranous of above-mentioned electrode group, above-mentioned thinner wall section bends to circular-arc along the curl direction of spiral electrode group in advance.
In foregoing invention, as described in claim 2, thinner wall section is preferably following formation: the front and back at core has different-thickness, and the face that the mixture layer thickness is little in the above-mentioned thinner wall section contacts with the inwall that the bottom tube-like container is arranged.
In order to realize claim 1 or 2 described negative pole structures, the described nickel-hydrogen accumulator of claim 3 of the present invention is the manufacture method that is used for the nickel-hydrogen accumulator of following nickel-hydrogen accumulator with the manufacture method of negative pole, above-mentioned nickel-hydrogen accumulator is by the banded negative pole that will core be provided with the mixture layer that is made of hydrogen bearing alloy and bandedly anodally constitutes the electrode group across the barrier film curl that curls, and in the bottom tube-like container is arranged, accommodate this electrode group and constitute, above-mentioned manufacture method comprises following operation: coating and the dry mixture that contains hydrogen bearing alloy are stuck with paste on core, thereby preparation has the 1st operation of the negative pole band (hoop) of mixture layer on the two sides; The pressurization and cut off above-mentioned negative pole band, obtain the 2nd operation of banded negative pole; At an end of the lengthwise side of above-mentioned banded negative pole, only from its part of simultaneously peeling off the mixture layer to form the 3rd operation of thinner wall section; And above-mentioned thinner wall section is passed through in the gap of hard roller and soft roller, thereby make it bend to the 4th circular-arc operation according to the mode that the little face of mixture layer thickness becomes the outside.
In addition, in order to realize claim 1 or 2 described negative pole structures, the described nickel-hydrogen accumulator of claim 6 of the present invention is the manufacture method that is used for the nickel-hydrogen accumulator of following nickel-hydrogen accumulator with the manufacture method of negative pole, above-mentioned nickel-hydrogen accumulator is by the banded negative pole that will core be provided with the mixture layer that is made of hydrogen bearing alloy and bandedly anodally constitutes the electrode group across the barrier film curl that curls, and in the bottom tube-like container is arranged, accommodate this electrode group and constitute, above-mentioned manufacture method comprises following operation: coating and the dry mixture that contains hydrogen bearing alloy are stuck with paste on core, thereby preparation has the mixture layer on the two sides, and form the 1st operation of the negative pole band of the little thinner wall section of mixture layer thickness in its part; The pressurization and cut off above-mentioned negative pole band, obtain the 2nd operation of banded negative pole; And above-mentioned thinner wall section is passed through in the gap of hard roller and soft roller, thereby make it bend to the 3rd circular-arc operation according to the mode that the little face of mixture layer thickness becomes the outside.
In order to realize claim 3,6 manufacture method, be preferably as follows formation: use metallic roll as hard roller, use the rubber rollers that on the metal shaft core, is coated with rubber as soft roller, and have can two-way rotation rubber roller drive division.
According to foregoing invention, circular-arc by negative pole outermost perimembranous is bent to along the curl direction of spiral electrode group in advance, can realize the electrode group to the smooth insertion that the bottom tube-like container is arranged, reduce insert bad.This effect can obtain significant especially effect under the original like that bending of the negative pole as claimed in claim 2 situation opposite with curl direction.
In order to solve above-mentioned problem, the described nickel-hydrogen accumulator of claim 10 of the present invention is by the banded negative pole that will core be provided with the mixture layer that is made of hydrogen bearing alloy and bandedly anodally constitutes the electrode group across the barrier film curl that curls, and in the bottom tube-like container is arranged, accommodate this electrode group and constitute, wherein, the outermost perimembranous of above-mentioned electrode group is provided with above-mentioned negative pole; Above-mentioned negative pole has thickness and packed density above-mentioned mixture layer than the common portion high thinner wall section littler than common portion of above-mentioned mixture layer at the position corresponding with the outermost perimembranous of above-mentioned electrode group; At the thickness setting with above-mentioned thinner wall section is A, and the departing from interval of center line separately of the thickness direction in the length direction cross section is set under the situation of B with above-mentioned thinner wall section and common portion, and B/A is below 0.15.
In foregoing invention, as described in claim 11, be preferably as follows formation: the center line of thinner wall section is partial to be curled into the central side of spiral helicine electrode group with respect to the center line of common portion.
Above-mentioned B/A is necessary for below 0.15, is preferably below 0.10.
In foregoing invention, as described in claim 12, be preferably as follows formation: be set at X in the packed density with the hydrogen bearing alloy in the mixture layer of above-mentioned thinner wall section, the packed density of the hydrogen bearing alloy in the mixture layer of common portion is set under the situation of Y, X/Y is in 1.03～1.15 scope.In addition, above-mentioned X/Y more preferably 1.07～1.11.
In addition, as making the method for this nickel-hydrogen accumulator with negative pole, the manufacture method of the negative pole of the described nickel-hydrogen accumulator of claim 13 of the present invention is nickel-hydrogen accumulator with the mixture layer that is made of the hydrogen bearing alloy manufacture method with negative pole, and it has following operation: in the two sided coatings anode mixture layer of the core that is made of two-dimentional porous body the 1st operation with preparation negative pole band; Evenly roll the 2nd operation of above-mentioned negative pole band; And in above-mentioned negative pole band, only the 3rd operation with the thickness that forms the mixture layer thinner wall section littler than common portion is rolled at the position corresponding with the outermost perimembranous of electrode group once more, and at the thickness setting with thinner wall section is A, the departing from interval of center line separately of the thickness direction in the length direction cross section is set under the situation of B with above-mentioned thinner wall section and common portion, and formation B/A is the thinner wall section below 0.15.
According to foregoing invention, approaching by the center line separately that makes the thickness direction in the length direction cross section in the thinner wall section and common portion of negative pole, and be arranged to symmetry substantially, and can reduce amount of crimp, reduce to the insertion that the bottom tube-like container is arranged bad significantly.
Being described more specifically aforesaid right requirement 13 described nickel-hydrogen accumulators is the described invention of claim 15 of the present invention with the 1st operation in the manufacture method of negative pole.This invention is in the 1st operation, cathode agent at the two sided coatings pasty state of the core that constitutes by two-dimentional porous body, and by making banded core on core, be coated with cathode agent with the mixture apparatus for coating of projection by having slit and broach shape centre pilot, then by the dry negative pole band for preparing, above-mentioned slit is used to determine the thickness of the anode mixture layer corresponding with the little thinner wall section of the big common portion of thickness and thickness, above-mentioned broach shape centre pilot with projection in the two sides of above-mentioned slit and be used to determine the position of the thickness direction of core.
In addition, in foregoing invention, as described in claim 16, be preferably as follows formation: at step (step) height setting with the coated face between the formation portion of the formation portion of the above-mentioned common portion of slit and above-mentioned thinner wall section is X, to be that the wide part in border is set at T1 with the step in the interval between the two sides of above-mentioned slit, narrow part is set at T2, to be that the thick part in border is set at t1 with the step in coating and the dried thickness of electrode, thin part is set at t2, to be defined as under the situation of t1/T1=t2/T2=α as the coating shrinkage of the function of the viscosity of coating speed and pasty state cathode agent, shoulder height is X=t1/ α-t2/ α.
Utilize the best approach of foregoing invention to make the shoulder height and the shape optimization of slit jaw, thereby cut off when finishing, can obtain the nickel-hydrogen accumulator negative pole that interior perimembranous, outermost perimembranous are expectation thickness at coating, calendering, veneer.In addition, behind electrode forming, need not to cut cathode agent, can solve fee of material loss, because the operating environment that causes of dust worsens, because the minute short circuit that dust adhesion causes, because the problems such as burning of the hydrogen bearing alloy of the cathode agent that frictional heat causes.
According to the present invention, the insertion that can reduce the electrode group is bad, can high production rate ground preparation high capacity type nickel-hydrogen accumulator.
Description of drawings
Fig. 1 is the three-dimensional skeleton diagram of negative pole bending apparatus of the present invention.
Fig. 2 is the cross section skeleton diagram of negative pole bending apparatus of the present invention.
Fig. 3 is the partial enlarged drawing of the electrode group of nickel-hydrogen accumulator of the present invention.
Fig. 4 be nickel-hydrogen accumulator of the present invention negative pole want portion's cross section enlarged drawing.
Fig. 5 is the skeleton diagram of manufacture method of the negative pole of expression nickel-hydrogen accumulator of the present invention.
Fig. 6 is the sectional view of the battery electrode manufacturing installation that uses among the present invention.
Fig. 7 is the A-A line amplification sectional view of Fig. 6 of expression loading hopper inside.
Fig. 8 is the reference sectional view along the loading hopper inside of the B-B line of Fig. 6.
Fig. 9 is the sectional view along the loading hopper inside of the B-B line of Fig. 6.
Figure 10 is the sectional view of negative pole that utilizes the slot coated of Fig. 9.
Figure 11 is the sectional view of the nickel-hydrogen accumulator of conventional example.
Figure 12 is the stereogram of the nickel-hydrogen accumulator of conventional example with negative pole.
Embodiment
Below, describe being used to implement embodiments of the present invention.
[the 1st execution mode]
The 1st execution mode is the nickel-hydrogen accumulator that contains the spiral electrode group in the bottom tube-like container is arranged, and it is characterized in that, the outermost perimembranous of the negative pole that will contact with the side inner walls that the bottom tube-like container is arranged bends to circular-arc along the curl direction of spiral electrode group in advance.
By making negative pole outermost perimembranous bend to circular-arc along the curl direction of spiral electrode group in advance, thereby when constituting the spiral electrode group, can suppress negative pole outermost perimembranous and come off from this electrode group, can improve the electrode group to the insertion that the bottom tube-like container is arranged, it is bad to reduce insertion.
Wherein, under the situation of the high capacity of considering nickel-hydrogen accumulator, it is the little thinner wall section of mixture layer thickness that the choosing of negative pole most peripheral quality award from the ministry is compared with other parts, from the angle of consideration with the molecular balance of positive pole, more preferably: in thinner wall section, the mixture layer thickness of the face relative with the inwall that the bottom tube-like container is arranged (promptly not relative with positive pole face) is littler than the mixture layer thickness of opposing face (promptly relative with positive pole face), under these circumstances, make the face that the mixture layer thickness is little in the thinner wall section become the outside, the curl direction along the spiral electrode group bends to circular-arc in advance.
For the equipment that is used to realize above-mentioned negative pole structure, use accompanying drawing to describe.Fig. 1 is the three-dimensional skeleton diagram of negative pole bending apparatus of the present invention.Fig. 2 is its cross section skeleton diagram.From be arranged with at crimped status as the metallic roll 1 of hard roller and as soft roller the metal shaft core is coated with the gap of device of rubber rollers 2 of rubber, the outermost perimembranous 5 of negative pole 4 is passed through, thereby prebend into circular-arc.Wherein, drive division 3 has the function of the two-way rotation of energy as the arrow among Fig. 1.That is, anticathode outermost perimembranous 5 is shaped in advance owing to utilize this only to install, and the other parts of negative pole 4 are not crooked, therefore drive division 3 required to have above-mentioned functions.
Here, making whole negative pole 4 bendings if be shaped in advance, then be difficult to conveyance negative pole 4 when coiled coil shape electrode group, is not preferred therefore.In addition, negative pole outermost perimembranous 5 is being made under the situation of thinner wall section, as shown in Figure 2, overlayed on metallic roll 1 by the face that the mixture layer thickness is big, can make thinner wall section according to the little face of mixture layer thickness become the outside mode bend to circular-arc, thereby constitute the spiral electrode group easily.
Wherein, littler by the diameter that makes metallic roll 1 than the diameter of rubber rollers 2, can make the operation that constitutes by this device stable.In addition, littler by the diameter that makes metallic roll 1 than the diameter of spiral electrode group, can be shaped in advance effectively.
Above-mentioned forming process is in advance carried out in the terminal stage of negative pole preparation.Specifically, under the mixture layer thickness of the negative pole outermost perimembranous situation identical with other parts, passing through coating and the dry mixture paste that contains hydrogen bearing alloy on core, thereby prepare the 1st operation and the pressurization of the negative pole band that has the mixture layer on the two sides of core and cut off this negative pole band, obtain after the 2nd operation of banded negative pole, as the 3rd operation, carry out above-mentioned forming process in advance.In addition, be under the situation of thinner wall section in negative pole outermost perimembranous, can from 2 kinds of following methods, select.The 1st kind is to pass through coating and the dry mixture paste that contains hydrogen bearing alloy on core, thereby preparation has this negative pole band of the 1st operation, pressurization and cut-out of the negative pole band of mixture layer on the two sides, obtain the 2nd operation of banded negative pole and a part of only simultaneously peeling off the mixture layer at an end of the lengthwise side of this band shape negative pole at it, thereby form after the 3rd operation of thinner wall section, as the 4th operation, carry out above-mentioned forming process in advance.The 2nd kind is to pass through coating and the dry mixture paste that contains hydrogen bearing alloy on core, thereby preparation have the mixture layer on the two sides and form in its part the little thinner wall section of mixture layer thickness the negative pole band the 1st operation and pressurization and cut off this negative pole band, obtain after the 2nd operation of banded negative pole, as the 3rd operation, carry out above-mentioned forming process in advance.In all cases, all can realize to bring into play the negative pole of effect of the present invention.
Wherein, negative pole prepares by the following method: use hydrogen bearing alloy as active material, add conductive agent, the tackifier such as (being designated hereinafter simply as CMC) of carboxymethyl cellulose as required and Styrene-Butadiene adhesives such as (being designated hereinafter simply as SBR) such as carbon black therein in right amount and form paste, after its coating or being filled on the cores such as perforated metal, it is carried out drying, calendering, cut-out.
Positive pole prepares by the following method: use nickel hydroxide as active material, add adhesives such as tackifier such as conductive agents such as cobalt hydroxide or metallic cobalt powder, CMC as required and polytetrafluoroethylene therein in right amount and form paste, after its coating or being filled on the core such as foaming nickel ternary porous body, it is carried out drying, calendering, cut-out.
Barrier film can use the nonwoven fabrics of olefine kind resins such as polypropylene.In addition, as required, can also carry out hydrophilic treated such as sulfonation to this nonwoven fabrics.
Electrolyte can use the suitable aqueous solution of having adjusted the ratio of KOH, NaOH, LiOH.
There is the bottom tube-like container can use and is material, and suitably carried out being used for the container of antirust nickel plating etc. with iron or stainless steel.
Below by enumerating embodiment, present embodiment is described in detail.
(embodiment 1)
Use is by MmNi
3.55Co
0.75Al
0.3Mn
0.4The hydrogen bearing alloy that constitutes, be ground into the particle diameter of 3～50 μ m with pulverizer after, impregnation process in the thermokalite aqueous solution.With respect to this hydrogen bearing alloy of 100 weight portions, add 0.2 weight portion CMC, 0.8 weight portion SBR and water as decentralized medium after, mixing and the preparation mixture is stuck with paste.Stick with paste carrying out on the perforated metal collector body of nickel plating this mixture of coating, after the drying, roll, cut into the shape, size of regulation and prepare negative pole.
As depicted in figs. 1 and 2, in the gap of the device of the rubber rollers (on the metal shaft core, being coated with the roller of rubber) of metallic roll that is provided with diameter 15mm with crimped status and diameter 60mm, the outermost perimembranous of this negative pole is passed through, thereby made it bend to circular-arc along the curl direction of spiral electrode group in advance.
Make the bending direction of outermost perimembranous of this negative pole consistent with curl direction, be curled into helical form across the barrier film that the polypropylene non-woven fabric by sulfonation constitutes to replace overlapping state with the positive pole that with the nickel hydroxide is the principal component formation then, thus the spiral electrode group of preparation diameter 15mm.Same with the conventional example shown in Figure 11,12, this electrode group is inserted into iron has been applied having in the bottom tube-like container of nickel plating, the preparation nickel-hydrogen accumulator.It is the battery of embodiment 1.
(embodiment 2)
Contrast in the battery of embodiment 1, before the outermost perimembranous of crooked negative pole, only peel off the part of mixture layer and form thinner wall section in the one side of outermost perimembranous, the face that the mixture layer thickness is big overlays on metallic roll, thereby make thinner wall section bend to circular-arc according to the mode that the little face of mixture layer thickness becomes the outside, in addition, preparation nickel-hydrogen accumulator similarly to Example 1.It is the battery of embodiment 2.
(embodiment 3)
Contrast in the battery of embodiment 1, when the coating cathode agent is stuck with paste on the perforated metal collector body, the mode that reduces according to the mixture layer thickness is coated with the position corresponding with the outermost perimembranous, thereby formation thinner wall section, the face that the mixture layer thickness is big overlays on metallic roll, it is circular-arc that thereby the mode that makes thinner wall section become the outside according to the little face of mixture layer thickness bends to, in addition, and similarly to Example 1 nickel-hydrogen accumulator of preparation.It is the battery of embodiment 3.
(embodiment 4)
Contrast in the battery of embodiment 2, it is circular-arc that the metallic roll of use diameter 23mm bends to negative pole outermost perimembranous, in addition, and preparation nickel-hydrogen accumulator similarly to Example 2.It is the battery of embodiment 4.
(embodiment 5)
Contrast in the battery of embodiment 2, it is circular-arc that the metallic roll of use diameter 60mm bends to negative pole outermost perimembranous, in addition, and preparation nickel-hydrogen accumulator similarly to Example 2.It is the battery of embodiment 5.
(comparative example 1)
Contrast in the battery of embodiment 1, it is circular-arc that the whole face of negative pole is bent to, in addition, and preparation nickel-hydrogen accumulator similarly to Example 1.It is the battery of comparative example 1.
(comparative example 2)
Contrast in the battery of embodiment 2, it is circular-arc that the whole face of negative pole is bent to, in addition, and preparation nickel-hydrogen accumulator similarly to Example 2.It is the battery of comparative example 2.
(comparative example 3)
Contrast in the battery of embodiment 1, negative pole outermost perimembranous is not bent to circular-arc, in addition, similarly to Example 1 nickel-hydrogen accumulator of preparation.It is the battery of comparative example 3.
(comparative example 4)
Contrast in the battery of embodiment 2, negative pole outermost perimembranous is not bent to circular-arc, in addition, similarly to Example 2 nickel-hydrogen accumulator of preparation.It is the battery of comparative example 4.
For the nickel-hydrogen accumulator of gained embodiment and comparative example, each prepares 1000 spiral helicine electrode groups, estimates the electrode group to the insertion of bottom tube-like container is arranged.As evaluation criterion, the battery that the electrode group can't be inserted in the time of will inserting the electrode group in the bottom tube-like container is arranged and negative pole outermost perimembranous taken place to fracture or folding state under the battery that inserts be designated as and insert badly, write down its quantity.The result is shown in (table 1).
Table 1
| Metallic roll (mm φ) | Rubber rollers (mm φ) | The diameter of roller compares Metal/rubber | The diameter ratio of metallic roll/electrode group | The thickness of outermost perimembranous | The formation of outermost perimembranous thinner wall section | Crooked position | Insert bad number in 1000 | |
| |
15 | 60 | 0.25 | 1 | Same with other position | - | The |
1 |
| |
15 | 60 | 0.25 | 1 | Thin-walled property | Peel off the one side of mixture layer | The |
2 |
| |
15 | 60 | 0.25 | 1 | Thin-walled property | The mixture coating thickness changes | The |
2 |
| |
23 | 60 | 0.38 | 1.5 | Thin-walled property | Peel off the one side of mixture layer | The |
4 |
| |
60 | 60 | 1 | 4 | Thin-walled property | Peel off the one side of mixture layer | The outermost perimembranous | 6 |
| Comparative example 1 | 15 | 60 | 0.25 | 1 | Same with other position | - | |
15 |
| Comparative example 2 | 15 | 60 | 0.25 | 1 | Thin-walled property | Peel off the one side of mixture layer | All | 35 |
| Comparative example 3 | - | - | - | - | - | - | - | 12 |
| Comparative example 4 | - | - | - | - | - | - | - | 57 |
As known from Table 1, with respect to the battery that in advance the outermost perimembranous of negative pole is not bent to circular-arc comparative example 3～4, it is bad that the battery of the embodiment of the invention 1～5 can significantly reduce insertion.Wherein, be under the situation of thinner wall section in negative pole outermost perimembranous, effect of the present invention become significantly (comparing embodiment 2～5 and comparative example 4).
Yet,, and the battery that whole face bends to circular-arc comparative example 1～2 less can be seen reducing inserts bad effect not only with the outermost perimembranous of negative pole.Its reason can be thought: owing to the bending of whole negative pole makes the conveyance reduction of when coiled coil shape electrode group negative pole, the position instability of negative pole in the electrode group, therefore the shape of electrode group is distorted easily, the result since with the essential factor of generation problem of the present invention different reason cause the insertion reduction of bottom tube-like container is arranged.
In addition, the insertion umber of defectives of the embodiment 4 that the diameter of metallic roll is bigger than the diameter of electrode group is higher slightly than embodiment 2.Its reason can be thought: because the degree of crook deficiency of negative pole outermost perimembranous, therefore effect of the present invention is insufficient.Equally, in the diameter of the metallic roll embodiment 5 bigger than the diameter of rubber rollers, it is remarkable that this tendency becomes.As can be known from the above results, preferably in advance with the nickel-hydrogen accumulator of the outermost perimembranous bending of negative pole with in the bending apparatus of negative pole, the diameter of metallic roll is littler than the diameter of rubber rollers, more preferably also the diameter than spiral electrode group is little.
[the 2nd execution mode]
Below, use accompanying drawing, the 2nd execution mode of the present invention is described.
Fig. 3 is the partial enlarged drawing of the electrode group of the 2nd execution mode nickel-hydrogen accumulator.Be curled into helical form with the common portion 12 of negative pole across the mode that barrier film 14 is arranged alternately according to anodal 13, be provided with the thinner wall section 11 of the thickness negative pole thinner in its outermost perimembranous than common portion 12.
Fig. 4 wants portion's cross section enlarged drawing around the border of thinner wall section 11 and portion 12 usually of negative pole of the above-mentioned nickel-hydrogen accumulator of expression.Thickness in thinner wall section 11 is A, when usually the thickness of portion 12 is C, by the thickness A of thinner wall section 11 and usually the thickness C of portion 12 derive thinner wall section 11 and usually the thickness direction of portion 12 in the length direction cross section center line depart from B at interval.Center line by making the thickness direction of thinner wall section 11 in the length direction cross section is approaching with the center line of the thickness direction of portion 2 in the length direction cross section usually, making B/A is below 0.15, that can avoid rolling the stress deformation that causes influences formation and reverse the curling of curl direction, therefore can reduce the friction when in the bottom tube-like container is arranged, inserting the electrode group, and significantly reduce the internal short-circuit (inserting bad) that the coiling dislocation of electrode group is produced.B/A and the proportional increase of difference at the coating thickness of the mixture layer of the front and back of core coating.Than above under 0.15 the situation,, therefore can't solve bad at this as the insertion of problem of the present invention because amount of crimp is significantly changed.
Wherein, the packed density of the hydrogen bearing alloy in the mixture layer of thinner wall section 11 is X, and usually the packed density of the hydrogen bearing alloy in the mixture layer of portion 12 is under the situation of Y, and X/Y is preferably in 1.03～1.15 scope.Under the situation of X/Y less than 1.03, the thickness of thinner wall section 11 does not have variation substantially with the thickness of common portion 12, and therefore the high power capacity design as the object of the invention is difficult to set up.On the contrary, under X/Y surpassed 1.15 situation, because the packed density of thinner wall section 11 is excessive, the oxygen absorbing function when utilizing overcharging that negative pole carries out reduced, so inner pressure of battery increases a little.
In order to realize above-mentioned negative pole, the method below preferred the employing.That is the manufacture method that, has following operation: at the two sided coatings anode mixture layer of the core that constitutes by two-dimentional porous body and prepare the 1st operation of negative pole band; The 2nd operation with the even calendering of negative pole band; And in the negative pole band, the 3rd operation that the position corresponding to the outermost perimembranous of electrode group is rolled once more only.Its concrete example shown in Figure 5.After will evenly rolling through 1 pair of stack of negative pole band 17 usefulness 15 of the 1st operation preparation, only privileged site is rolled once more with 1 pair of step forming roll 16 having given step.By on the direction vertical, cutting off this negative pole band 17, can prepare continuously negative pole with the thinner wall section corresponding 11 and the common portion 12 beyond it with electrode group outermost perimembranous with rolling direction.
In addition, can also enumerate the method lower: through behind the stack 15, cut off negative pole band 17, form the precursor of negative pole, the part of this negative pole precursor is exerted pressure with flat board, thereby form thinner wall section 11 with desired size with respect to said method productivity ratio.
In addition, behind the two sided coatings anode mixture layer of the core that constitutes by two-dimentional porous body,, make it compare less thick with other positions by the position corresponding of pruning with the outermost perimembranous of electrode group, this compares with the uniform situation of whole coating thickness, can more easily form thinner wall section 1.
Positive pole prepares by the following method: use nickel hydroxide as active material, add adhesives such as tackifier such as conductive agents such as cobalt hydroxide or metallic cobalt powder, CMC as required and polytetrafluoroethylene therein in right amount and form paste, after its coating or being filled on the core such as foaming nickel ternary porous body, be dried, roll, cut off.
Barrier film can use the nonwoven fabrics of olefine kind resins such as polypropylene.In addition, as required, can also carry out hydrophilic treated such as sulfonation to this nonwoven fabrics.
Electrolyte can use the suitable aqueous solution of having adjusted the ratio of KOH, NaOH, LiOH.
There is the bottom tube-like container can use and is material, and the container that suitably carried out being used for antirust nickel plating etc. with iron or stainless steel.
Below by the reference accompanying drawing and enumerate embodiment, present embodiment is described in detail.
(embodiment 6)
Use is by MmNi
3.55Co
0.75Al
0.3Mn
0.4The hydrogen bearing alloy that constitutes, be ground into the particle diameter of 3～50 μ m with pulverizer after, impregnation process in the thermokalite aqueous solution.With respect to this hydrogen bearing alloy of 100 weight portions, add after 0.2 weight portion CMC, 0.8 weight portion SBR, the water as dispersant, mixing and the preparation mixture is stuck with paste.Having carried out this mixture paste of coating on the perforated metal collector body of nickel plating, obtain negative pole band 17.For position corresponding to the thinner wall section 11 of this negative pole band 17, the mixture of the one side of pruning makes that the mixture of this face is 90 weight % with respect to the mixture of another side, by stack 15 packed density of the hydrogen bearing alloy of whole anode mixture layer is adjusted into 5.4g/ml (integral thickness 0.46mm) then.Then, only corresponding to the position of thinner wall section 1 again with the protuberance calendering of step forming roll 16, thereby the packed density of the hydrogen bearing alloy at this position is adjusted into 5.9g/ml (thickness 0.40mm).Wherein, the ratio B/A that departs from interval B of the center line of the thickness A of thinner wall section thickness direction in the length direction cross section with thinner wall section 1 and common portion 2 is 0.03.Vertically cut off with the negative pole band 17 after step forming roll 16 calendering to obtain negative pole with rolling direction, this negative pole is as the negative pole of embodiment 6.
(embodiment 7～8)
Contrast in the negative pole of embodiment 6, prune mixture with the one side of thinner wall section 11 corresponding positions, make that the mixture of this face is 80,60 weight % with respect to the mixture of another side, thereby the thickness that makes thinner wall section 11 is respectively 0.38,0.34mm; the thickness A of thinner wall section and thinner wall section 11 and usually the thickness direction of portion 12 in the length direction cross section center line depart from interval that the ratio B/A of B is 0.06,0.15; in addition, obtain negative pole similarly to Example 6.With these negative poles as embodiment 7～8.
(embodiment 9～12)
Contrast in the negative pole of embodiment 7, preparation thinner wall section 11 makes that the packed density of hydrogen bearing alloy of thinner wall section 11 is X/Y=1.02,1.04,1.15,1.17; thickness of thinner wall section 11 is respectively 0.41,0.40,0.36,0.35mm, in addition, and the negative pole that preparation and embodiment 7 are identical.With these negative poles as embodiment 9～12.
(embodiment 13)
Contrast in the negative pole of embodiment 6, do not prune mixture with the one side of thinner wall section 11 corresponding positions, the thickness that makes thinner wall section 11 is 0.42mm; the thickness A of thinner wall section and thinner wall section 11 and usually the thickness direction of portion 12 in the length direction cross section center line depart from interval that the ratio B/A of B is 0; in addition, the negative pole that preparation and embodiment 6 are identical.With its negative pole as embodiment 13.
(comparative example 5)
Contrast in the negative pole of embodiment 6, prune mixture with the one side of thinner wall section 11 corresponding positions, make that the mixture of this face is 40 weight % with respect to the mixture of another side, thereby the thickness that makes thinner wall section 11 is 0.30mm; the ratio B/A that departs from interval B of the center line of the thickness A of thinner wall section thickness direction in the length direction cross section with thinner wall section 11 and common portion 12 is 0.2; in addition, obtain negative pole similarly to Example 6.With its negative pole of 5 as a comparative example.
(comparative example 6)
Contrast in the negative pole of embodiment 6, except thinner wall section 11 further not being pressurizeed, preparation negative pole similarly to Example 6.With its negative pole of 6 as a comparative example.
With the negative pole of gained embodiment and comparative example and the banded positive pole 3 of in the nickel ternary porous body, having filled nickel hydroxide, be curled into helical form across the polypropylene system barrier film 4 that has carried out the sulfonation processing, thereby under the situation of the negative pole that uses embodiment 6, the preparation diameter is the electrode group of 17.2mm.This electrode group is inserted into internal diameter 17.8mm applying on the iron nickel plating the bottom tube-like container is arranged after, descend to show evaluation.The result is shown in (table 2).
(inserting fraction defective measures)
After in the bottom tube-like container is arranged, inserting the electrode group, by the shape of X ray viewed in transmittance electrode group.(specifically, because barrier film 14 dislocation produce the position that positive pole 13 and negative pole directly contact) battery is bad as insertion, writes down its quantity with the curling dislocation that produces the electrode group.In each example, observe 1000 batteries, the number of detected bad battery is shown with percentage in (table 2).
(inner pressure of battery mensuration)
Accommodating the electrolyte that injects ormal weight is arranged in the bottom tube-like container and sealing of electrode group, activate discharge and recharge (break-in charging-discharging) after, current charges to charge capacity with 1 hour rate is 110%, obtains the inner pressure of battery of this moment.The result is shown in (table 2).
Table 2
| B/A | Packed density (g/ml) | X/Y | Thinner wall section thickness (mm) | The thinner wall section mixture is pruned | Insert bad (%) | Inner pressure of battery (MPa) | |||
| Thinner wall section X | The common Y of portion | ||||||||
| Embodiment | 6 | 0.03 | 5.9 | 5.4 | 1.09 | 0.4 | Have | 0 | 0.75 |
| 7 | 0.06 | 5.9 | 5.4 | 1.09 | 0.38 | Have | 0 | 0.8 | |
| 8 | 0.15 | 5.9 | 5.4 | 1.09 | 0.34 | Have | 0 | 0.83 | |
| 9 | 0.06 | 5.5 | 5.4 | 1.02 | 0.41 | Have | 5 | 0.6 | |
| 10 | 0.06 | 5.6 | 5.4 | .104 | 0.4 | Have | 0 | 0.7 | |
| 11 | 0.06 | 6.2 | 5.4 | 1.15 | 0.36 | Have | 0 | 0.95 | |
| 12 | 0.06 | 6.3 | 5.4 | 1.17 | 0.35 | Have | 0 | 1.3 | |
| 13 | 0 | 5.9 | 5.4 | 1.09 | 0.42 | Do not have | 5 | 0.8 | |
| Comparative example | 5 | 0.2 | 5.9 | 5.4 | 1.09 | 0.3 | Have | 25 | 1 |
| 6 | 0.03 | 5.4 | 5.4 | 1.00 | 0.44 | Have | 15 | 0.8 | |
B/A is that embodiment 6～13 so little below 0.15 is with respect to departing from bigger comparative example 5 between the center line, because the amount of crimp in the thinner wall section 11 reduces the effect that produces, can improve the insertion in the bottom tube-like container is arranged, except embodiment 9 and 13, it is bad to thoroughly do away with insertion.In addition, insert bad reason a little as in embodiment 9 and 13, observing, can think because the thickness of thinner wall section 11 is excessive slightly, (measured value is the 17.2mm with respect to embodiment 6 to the diameter of electrode group greatly with respect to embodiment 6 changes, be 17.3mm), so cause and the friction that the bottom tube-like container is arranged.The insertion of comparative example 6 (the diameter 17.4mm of electrode group) is bad significantly also to be thought based on identical reason.Thus, in order to realize the high power capacity design, the thickness of thinner wall section 11 must clearly reduce with respect to common portion 12.
Wherein, the packed density of the hydrogen bearing alloy in the mixture layer of thinner wall section 11 is X, usually the packed density of the hydrogen bearing alloy in the mixture layer of portion 12 is under the situation of Y, with respect to the embodiment 6,10,11 of X/Y in 1.03～1.15 scope, X/Y surpasses 1.15 embodiment 12 because the packed density of thinner wall section 11 is excessive, oxygen absorbing function when utilizing overcharging that negative pole carries out reduces, and inner pressure of battery increases a little as a result.
[the 3rd execution mode]
Below, use accompanying drawing that the present invention's the 3rd execution mode is described.The 3rd execution mode relates to the 1st operation of the negative pole band for preparing the 2nd execution mode, and other formations are identical with the 2nd execution mode, therefore omits explanation.
Above-mentioned negative pole band uses the manufacturing installation manufacturing shown in Fig. 1～3.Its details below is shown.
Fig. 6 is the skeleton diagram of device.Fig. 7 is an A-A line amplification sectional view among Fig. 6 of loading hopper (mixture apparatus for coating).Fig. 8 is a B-B line sectional view among Fig. 6.In the drawings, the 21st, sheet metal stock roll (master roll), the 2nd, band metal thin plate (core that is made of two-dimentional porous body), the 23rd has the loading hopper of opening up, and its depth width is corresponding with the Width size of sheet metal 22.Under the inside of loading hopper 23 and loading hopper outlet, be provided with the rotary centre pilot roller 24 of seizing sheet metal 22 on both sides by the arms.The 25th, be housed in the paste (pasty state cathode agent), the 26th of loading hopper inside, the paste coating weight that is provided with below the upstanding portion 31 of loading hopper 23 is adjusted slit, the 27th, by the paste coated sheets (being coated with the core of cathode agent), the 28th of loading hopper 23, the passage drying oven, the 29th of drying coated paste 25, the dried coated sheets 27 of curling finish roller.Be provided with relative centre pilot usefulness projection 33 in the tapering part 32 in loading hopper 23, the thickness of the slit of this relative centre pilot usefulness projection 33 and the sheet metal 22 of shape shown in Figure 8 is basic identical.In addition, with the rate of finished products that improves active material with guarantee that weld is a purpose, spill to Width, be provided with a pair of sheet structure body 34 abreast with projection 33 with centre pilot in order to prevent that active material from sticking with paste.
After coating and drying, in order to obtain the only different electrode (negative pole) of thickness of a part, on this part of coating weight adjustment slit 26 step being set just can realize, but the thickness of electrode must be controlled respectively in interior perimembranous and most peripheral portion, decides the ratio of thickness separately according to above-mentioned shoulder height.Make separate mobile formula (separable-movable) slit so that it is difficult can changing shoulder height, because there are problems such as paste leakage, the durable shape of slit.Therefore, must set the shoulder height of the thickness of electrode that can obtain expectation.
Fig. 9 is the schematic diagram of the coating slit after the improvement for preparing in order to solve above-mentioned problem, and Figure 10 is coating and the dried sectional view that utilizes the electrode of this slot coated.
Promptly, above-mentioned slit shoulder height is being set at X, to be that the wide part in border is set at T1, narrow part is set at T2 with the step in the interval of above-mentioned slit, to be that the thick part in border is set at t1, thin part is set at t2 with the step in coating and the dried thickness of electrode, to be defined as under the situation of t1/T1=t2/T2=α as the coating shrinkage that coating speed and electrode composition are stuck with paste the function of viscosity, when shoulder height being set at X=t1/ α-t2/ α, then after coating, can obtain the thickness of electrode of expectation.
The embodiment of present embodiment below is shown.In addition, present embodiment relates to the nickel-hydrogen dattery negative pole, also can expand to nickel-cadmium accumulator or lithium rechargeable battery.
(embodiment 14)
Use is by formula M mNi
3.55Co
0.75Mn
0.4Al
0.3The hydrogen-bearing alloy powder of (Mm is the cerium alloy of light rare earth class mixture) expression, using ball mill in water it to be crushed to average grain diameter is 30 μ m, thereby obtains alloy.Use is as section's qin carbon black (Ketjen black) of conductive agent, as the CMC (carboxymethyl cellulose) of tackifier, mix this alloy powder as the SBR (styrene butadiene ribber) of adhesive with water as decentralized medium, the preparation active material is stuck with paste.
Use the device shown in Fig. 7, Fig. 9, this electrode composition of coating is stuck with paste and is dry on sheet metal.As sheet metal, the iron perforated metal of the nickel plating of used thickness 60 μ m, piercing aperture 1mm, percent opening 42%.Having obtained at coating speed according to prior research is that viscosity that 2cm/ second, electrode composition are stuck with paste is that shrinkage under the situation of 10000cps is 50%.Thickness of electrode target after calendering, the veneer processing is that interior perimembranous is that 0.46mm, outermost perimembranous are 0.26mm.Can make the thickness of electrode composition coated portion become 50% by calendering, therefore coating and dried thickness of electrode target are that interior perimembranous is that 0.86mm, outermost perimembranous are 0.46mm.Because the shrinkage that the electrode composition of trying to achieve is in advance stuck with paste is 50%, so the interval of slit is 1.66mm in interior perimembranous, is 0.86mm in the outermost perimembranous.That is, the step of protuberance is 0.8mm.So, the following setting of shape of coating slit.The width setup of coating slit is 200mm, step is set makes apart from slit end 70mm to becoming protuberance apart from the part between the slit end 150mm, and the size of this step is set at 0.8mm.Use the slit that does not have step having the relative side of the coating slit of step, the slit separation at both ends is set at 1.6mm is coated with this.After coating and drying, cut off the negative pole band with the length of 35mm in the longitudinal direction, from the flow direction with respect to coating is the direction at right angle, under large-sized state, roll with roller extruder, the part of 100mm on the Width of slit is cut off then, thereby the length of perimembranous is that the length of 60mm, outermost perimembranous is the hydrogen storage alloy negative (nickel-hydrogen accumulator negative pole) of 40mm in the preparation.With its negative pole as embodiment 14.
(embodiment 15～18)
Except the step with slit is set at 0.4mm, 0.6mm, 1.0mm, 1.2mm, prepare hydrogen storage alloy negative similarly to Example 14.With its negative pole as embodiment 15～18.
(comparative example 7)
Except using the two sides all not have the slit of step, prepare electrode similarly to Example 14 after, with among No. 80 the file beveled electrode length 100mm from the end to the part of 40mm, up to making thickness become 0.26mm, thereby prepare hydrogen storage alloy negative.With its negative pole of 7 as a comparative example.For the negative pole that makes, carry out following evaluation.
(thickness measurement)
The negative pole that respectively prepares 500 each embodiment and comparative example respectively from wherein selecting the thickness of perimembranous and outermost perimembranous in 30 mensuration, calculates mean value.
(minute short circuit fraction defective)
Constitute battery pack with 500 negative poles of above-mentioned preparation, corresponding positive pole and barrier film, calculate the minute short circuit fraction defective.
(life test)
Respectively select 5 batteries and carry out cycling life test in the battery of above-mentioned preparation, record becomes 60% period of initial capacity, notes the mean value of 5 batteries.
(Dust Capacity in operation place is measured)
In the operation that the use file of comparative example grinds, measure the Dust Capacity in the atmosphere in operation place in the operation process.Assay method uses common Dust Capacity analyzer.That is, use pump to attract a certain amount of atmosphere, judge the hydrogen bearing alloy amount by the nickel concentration of measuring in the foreign matter that adheres on the filter.This operation is not owing to existing in the operation of embodiment, therefore in order to compare the Dust Capacity in the atmosphere in the operation place of mensuration veneer cut-out operation.
(number on fire in the grinding operation)
Be recorded in battery lead plate number on fire in the operation that the use file of comparative example grinds.
In above result shown in the table 3.
Table 3
| Slit step mm | Interior perimembranous thickness mm | Outermost perimembranous thickness mm | Minute short circuit fraction defective % | Cycle life cycle | Dust Capacity mg/m 3 | On fire | |
| Embodiment | |||||||
| 14 | 0.8 | 0.47 | 0.26 | 0.0 | 578 | 0.01 the ※ veneer cuts off the atmosphere in the operation place of operation | - |
| |
0.4 | 0.46 | 0.37 | 0.8 | 550 | - | |
| |
0.6 | 0.47 | 0.30 | 0.2 | 563 | - | |
| |
1.0 | 0.46 | 0.21 | 0.0 | 505 | - | |
| Embodiment 18 | 1.2 | 0.45 | 0.17 | 0.0 | 441 | - | |
| Comparative example 7 | Do not have | 0.46 | 0.26 | 2.6 | 432 | 0.69 | 43 |
Perimembranous has identical thickness in each, and peripheral part is basic as the order target value.Shrinkage is 50%, further becomes 50% by calendering, therefore compares with the interval of slit, becomes about 25% thickness.The minute short circuit fraction defective is to compare with comparative example 7, and all embodiment all are greatly improved.This can think to grind the dust adhesion that is produced owing to reduced file.Yet, the minute short circuit fraction defective of embodiment 15,16 is many slightly, can think because the thickness of outermost perimembranous is thicker than target, so the diameter of battery pack surpasses the internal diameter of box, when being inserted into battery pack in the box, the dust the when electrode composition of most peripheral is pruned is caused.In the life test, the period of embodiment 14,15,16 is the longest, and identical.The period of embodiment 17,18 shortens successively, can think because the electrode composition amount of outermost perimembranous is few, so whole hydrogen bearing alloy amount is few caused.The period of comparative example 7 is the shortest, and this is because in the process of life test, and the minute short circuit that causes because of dust causes the capacity rapid deterioration of some samples.Thus, can be clear and definite be to abolish the file grinding step by step is set on slit, can significantly improve the quality of battery, wherein,, can further improve quality by the step of having considered shrinkage is set.
The Dust Capacity in the file grinding step operation place of comparative example 7 is compared with the veneer manufacturing procedure of embodiment 14, significantly increases.In addition, in this operation since frictional heat cause hydrogen bearing alloy in the electrode composition on fire have 43.That is, can be clear and definite be by abolishing the file grinding step, environment and secure context in the operation place can be greatly improved.
In addition, by abolishing the file grinding step, can significantly reduce the loss of material.
According to the present invention, the electrode group that can significantly reduce the high capacity type nickel-hydrogen accumulator is inserted not good, significantly improves the productivity ratio of this battery forms, so its utilizability and relate to effect and enlarge markedly.
Claims (16)
1, a kind of nickel-hydrogen accumulator, it is by the banded negative pole (4) that will core be provided with the mixture layer that is made of hydrogen bearing alloy and bandedly anodally constitutes the electrode group across the barrier film curl that curls, and in the bottom tube-like container is arranged, accommodate this electrode group and constitute, wherein, the outermost perimembranous of described electrode group is provided with described negative pole (4); Described negative pole (4) has the thickness thinner wall section littler than other position of described mixture layer at the position corresponding with the outermost perimembranous (5) of described electrode group; Described thinner wall section bends to circular-arc along the curl direction of spiral electrode group in advance.
2, nickel-hydrogen accumulator according to claim 1, wherein, the mixture layer of thinner wall section has different-thickness at the front and back of core, and the face that the mixture layer thickness is little in the described thinner wall section contacts with the inwall that the bottom tube-like container is arranged.
3, a kind of nickel-hydrogen accumulator manufacture method of negative pole, described nickel-hydrogen accumulator is by the banded negative pole (4) that will core be provided with the mixture layer that is made of hydrogen bearing alloy and bandedly anodally constitutes the electrode group across the barrier film curl that curls, and in the bottom tube-like container is arranged, accommodate this electrode group and constitute, described manufacture method comprises following operation: coating and the dry mixture that contains hydrogen bearing alloy are stuck with paste on core, thereby preparation has the 1st operation of the negative pole band of mixture layer on the two sides; The pressurization and cut off described negative pole band, obtain the 2nd operation of banded negative pole (4); At an end of the lengthwise side of described banded negative pole, only in its part of simultaneously peeling off the mixture layer to form the 3rd operation of thinner wall section; And described thinner wall section is passed through in the gap of hard roller (1) and soft roller (2), thereby make it bend to the 4th circular-arc operation according to the mode that the little face of mixture layer thickness becomes the outside.
4, the nickel-hydrogen accumulator according to claim 3 manufacture method of negative pole, wherein, use metallic roll (1) as hard roller, use the rubber rollers (2) that on the metal shaft core, is coated with rubber as soft roller, and the drive division (3) with energy described rubber rollers of two-way rotation (2).
5, the nickel-hydrogen accumulator according to claim 4 manufacture method of negative pole, wherein, the diameter of metallic roll (1) is littler than the diameter of rubber rollers (2).
6, a kind of nickel-hydrogen accumulator manufacture method of negative pole, described nickel-hydrogen accumulator is by the banded negative pole (4) that will core be provided with the mixture layer that is made of hydrogen bearing alloy and bandedly anodally constitutes the electrode group across the barrier film curl that curls, and in the bottom tube-like container is arranged, accommodate this electrode group and constitute, described manufacture method comprises following operation: coating and the dry mixture that contains hydrogen bearing alloy are stuck with paste on core, thereby preparation has the mixture layer and forms the 1st operation of the negative pole band of the little thinner wall section of mixture layer thickness in its part on the two sides; The pressurization and cut off described negative pole band, obtain the 2nd operation of banded negative pole (4); And described thinner wall section is passed through in the gap of hard roller (1) and soft roller (2), thereby make it bend to the 3rd circular-arc operation according to the mode that the little face of mixture layer thickness becomes the outside.
7, the nickel-hydrogen accumulator according to claim 6 manufacture method of negative pole, wherein, use metallic roll (1) as hard roller, use the rubber rollers (2) that on the metal shaft core, is coated with rubber as soft roller, and the drive division (3) with energy described rubber rollers of two-way rotation (2).
8, the nickel-hydrogen accumulator according to claim 7 manufacture method of negative pole, wherein, the diameter of metallic roll (1) is littler than the diameter of rubber rollers (2).
9, use the manufacture method of negative pole according to each described nickel-hydrogen accumulator in the claim 4,5,7 or 8, wherein, the diameter of metallic roll (1) is littler than the diameter that is curled into columnar electrode group.
10, a kind of nickel-hydrogen accumulator, it is to be curled into helical form by the banded negative pole that will core be provided with the mixture layer that is made of hydrogen bearing alloy and banded anodal (13) across barrier film (14) to constitute the electrode group, and in the bottom tube-like container is arranged, accommodate this electrode group and constitute, wherein, the outermost perimembranous of described electrode group is provided with described negative pole; Described negative pole has the thinner wall section (11) that thickness is littler than common portion (12) and packed density is higher than common portion (12) of described mixture layer at the position corresponding with the outermost perimembranous of described electrode group; At the thickness setting with described thinner wall section (11) is A, and the departing from interval of center line separately of the thickness direction in the length direction cross section is set under the situation of B with described thinner wall section (11) and common portion (12), and B/A is below 0.15.
11. nickel-hydrogen accumulator according to claim 10, wherein, the center line of thinner wall section (11) is partial to be curled into the central side of spiral helicine electrode group with respect to the center line of common portion (12).
12. according to claim 10 or 11 described nickel-hydrogen accumulators, wherein, be set at X in the packed density with the hydrogen bearing alloy in the mixture layer of described thinner wall section (11), the packed density of the hydrogen bearing alloy in the common portion (12) is set under the situation of Y, X/Y is in 1.03～1.15 scope.
13. the nickel-hydrogen accumulator manufacture method of negative pole, described nickel-hydrogen accumulator has the mixture layer that is made of hydrogen bearing alloy with negative pole, and described manufacture method has following operation: in the two sided coatings anode mixture layer of the core that is made of two-dimentional porous body the 1st operation with preparation negative pole band (17); Evenly roll the 2nd operation of described negative pole band (17); And in described negative pole band (17), only the 3rd operation with the thickness that forms the mixture layer thinner wall section (11) littler than common portion (12) is rolled at the position corresponding with the outermost perimembranous of electrode group once more, and at the thickness setting with thinner wall section (11) is A, the departing from interval of center line separately of the thickness direction in the length direction cross section is set under the situation of B with described thinner wall section (11) and common portion (12), and formation B/A is the thinner wall section (11) below 0.15.
14. nickel-hydrogen accumulator according to claim 13 wherein, replaces the 3rd operation with the manufacture method of negative pole, has the position corresponding with described electrode group outermost perimembranous of pruning so that its thickness is littler than other position, thereby forms the operation of thinner wall section (11).
15. the nickel-hydrogen accumulator according to claim 13 manufacture method of negative pole, wherein, in the 1st operation, cathode agent (25) at the two sided coatings pasty state of the core that constitutes by two-dimentional porous body (22), and by making banded core (22) go up coating cathode agent (25) with the mixture apparatus for coating of projection (33) is next at core (22) by having slit (26) and broach shape centre pilot, then by the dry negative pole band for preparing, described slit (26) is used to determine the thickness of the anode mixture layer corresponding with the little thinner wall section of the big common portion of thickness and thickness, described broach shape centre pilot with projection (33) in the two sides of described slit (26) and be used to determine the position of the thickness direction of core (22).
16. the nickel-hydrogen accumulator according to claim 15 manufacture method of negative pole, wherein, be set at X in shoulder height with the coated face between the formation portion of the formation portion of the described common portion of slit (26) and described thinner wall section, to be that the wide part in border is set at T1 with the step in the interval between the two sides of described slit (26), narrow part is set at T2, to be that the thick part in border is set at t1 with the step in coating and the dried thickness of electrode, thin part is set at t2, to be defined as under the situation of t1/T1=t2/T2=α as the coating shrinkage of the function of the viscosity of coating speed and pasty state cathode agent (25), shoulder height is X=t1/ α-t2/ α.
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| CN109728255A (en) * | 2017-10-31 | 2019-05-07 | 丰田自动车株式会社 | The manufacturing device and manufacturing method of band electrode |
| CN109728255B (en) * | 2017-10-31 | 2021-09-17 | 丰田自动车株式会社 | Apparatus and method for manufacturing strip-shaped electrode |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100555731C (en) | 2009-10-28 |
| CN101459261A (en) | 2009-06-17 |
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