CN1106079A - Metallic porous sheet and method for manufacturing same - Google Patents
Metallic porous sheet and method for manufacturing same Download PDFInfo
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- CN1106079A CN1106079A CN 94113727 CN94113727A CN1106079A CN 1106079 A CN1106079 A CN 1106079A CN 94113727 CN94113727 CN 94113727 CN 94113727 A CN94113727 A CN 94113727A CN 1106079 A CN1106079 A CN 1106079A
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Abstract
Process of imparting conductivity to a three-dimensional net-shaped porous sheet can be performed efficiently before carrying out electroplating process. Fine metallic powders are applied to the porous sheet made of a foamed sheet, a nonwoven sheet, a mesh sheet or a plurality of sheets layered one on the other, so that a conductive metallic layer is formed on the porous sheet. Then, an electroplated layer is formed on the surface of the conductive metallic layer. The conductive metallic layer remains when the porous sheet burned out. Consequently, a metallic layer of the conductive metallic layer and the electroplated layer forms the metallic framework of the metallic porous sheet.
Description
The present invention relates to metallic porous sheet and manufacture method thereof, specifically, relate to the method for utilizing three-dimensional netted porous layer to make metallic porous sheet, this three-dimensional netted porous layer is by a foam layer, a nonwoven layers, one stratum reticulare constitutes, or by at least two types layer in the three types above-mentioned layer is mutually combined, the multilayer that is laminated into constitutes a lamination one deck.Reactive powder is inserted in the hole of metallic porous sheet, available this metallic porous sheet is as nickel-cadmium cell, nickel metal hydride battery, lithium cell, the cell panel that the battery lead plate of fuel cell or automobile are used.
The applicant once applied for the battery lead plate of metallic porous sheet as battery.Porous layer in the application is by a foam layer, a nonwoven layers, and a stratum reticulare constitutes, or by at least two types layer in the above-mentioned three types layer is mutually combined, the multilayer formation that is laminated into a lamination one deck.This porous layer is electroplated, made a kind of metallic porous sheet (Japanese Patent discloses 1-290792 and 3-130393).
If foam materials as the solid support material (body material) of metallic porous sheet, nonwoven layers or stratum reticulare by the organic substance of for example synthetic resins, natural fiber, Mierocrystalline cellulose, paper or analogue or for example the inorganic substance of glass or analogue form, then need to make carrier to have electroconductibility.Even carrier is made of metal, preferably also to make this carrier have electroconductibility.
As making carrier have the method for electroconductibility, carbon is coated onto on the surface of solid support material, or with electroless plating or vapor plating with electro-conductive material for example metal be plated on the surface of porous layer.
There is following point in the traditional method that makes solid support material have electroconductibility:
(a) vapour plating
Vapour plating must carry out in vacuum apparatus.When transfer passage is carried porous layer continuously, because, to porous layer, be unsettled with the metal vapour plating at the import and export generation air leaking of vacuum apparatus.Therefore, be difficult to keep vacuum state.In addition, the big equipment of essential outfit, and manufacturing expense height make porous layer have electroconductibility and consume the plenty of time.
(b) electroless plating method
The operation of carrying out the electroless plating needs is many, needs to use a large amount of chemicals.Especially, prepare the equipment cost height that disposes waste liquid.In addition, the cost height of chemical substance.
(c) be coated with the carbon method
Although the cost of this method ratio vapourization plating method and electroless plating method is low, there is a large amount of carbon to stay on the surface of solid support material as impurity.The resistance of the conductive layer that forms on solid support material in addition, is up to 100～200 Ω/cm.Therefore, be difficult to carry out electroplating technology with big electric current.In order to obtain big electric current, must for example hang down with the production line of low-speed control delivery vehicles material by 0.1～0.5m/ minute, to prevent that solid support material from being burnt.
In above-mentioned three kinds of methods, the main employing is coated with the carbon method, because it is lower than other two kinds of method costs to implement this method.
Yet this method has the low shortcoming of travelling speed of the production line of the resistance height of conductive layer thereby delivery vehicles material.
Therefore,, must reduce to the resistance of conductive layer and be lower than 30 Ω/cm, so that obtain big electric current in the plating step of carrying out to the step that makes solid support material have electroconductibility thereafter for the production line that makes the delivery vehicles material runs at high speed increase output.
In addition, be coated onto its carbon with electroconductibility is not removed fully by the metal that burn off carbon and resin and sintering are plated on the carbon, also have small amount of carbon to stay on the surface of solid support material.
The solid support material that comprises resin layer in utilization forms in the process of metallic porous sheet, and electrolytic coating must have the total metal content of requirement.So, the current consumption height, and the plated conductive metal level need be with for a long time.Therefore, can not be with high productivity and the low-cost metallic porous sheet of making.
Therefore, the purpose of this invention is to provide a kind of method of giving electroconductibility of novelty and a kind of metallic porous sheet made from this method.
According to method of the present invention, metal fine powder is coated onto on the surface of solid support material and makes the hole of porous layer have electroconductibility, so that form conductive metal layer.The resistance of this metal fine powder is low, thereby obtains big electric current in the plating step of carrying out to the step that makes solid support material have electroconductibility thereafter.Thereafter in the process of the burn off resin that carries out to plating step, conductive metal layer bears high temperature, remains as the composition material of the structure of metallic porous sheet.On conductive metal layer form thin electrolytic coating thereafter.
In addition, when utilizing caking agent to be coated onto metal fine powder on the porous layer surface, can on the surface of porous layer, form conductive metal layer, need not plate electrolytic coating at conductive layer surface with the total metal content that requires.
In order to realize these and other objects of the present invention, first type metallic porous sheet is provided, it has tridimensional network to this metallic porous sheet around the hole, and this structure comprises conductive metal layer that is made of metal fine powder and the metal plating that forms on conductive metal layer.
Second type metallic porous sheet is provided, and this metallic porous sheet has tridimensional network around the hole, and this structure comprises the conductive metal layer that is made of metal fine powder.
The granularity of metal fine powder is less than 6.0 μ m.
Metal fine powder is by Ni, and NiO, Cu, Ag, Al, Fe, Zn, Sn, Au, In, at least a micro mist among P and the Cr form or be made up of their two or more mixture.
Metal fine powder immersed contain in the metal ion solution, so that adsorption of metal ions is gone forward side by side on the surface of micro mist in the micro mist.Metal ion is by Ni, Cu, Ag, Fe, Zn, Sn, at least a composition in Au and the In ion.
Before being coated onto metal fine powder on the porous layer, the porous layer of the solid support material by will being used as metallic porous sheet carries out activation treatment and/or replacement Treatment, makes metal fine powder have electroconductibility.Can after being coated onto metal fine powder on the porous layer,, make metal fine powder have electroconductibility by porous layer is carried out activation treatment and/or replacement Treatment.
In order to improve the electroconductibility of metal fine powder, preferably will put into the metal fine powder and the Au of ball mill, Ag, the mixture of metal-powder such as Cu and In stirs, so that under pressure with soft, that have electroconductibility and be difficult for oxidized Au, Ag, the metal-powder of Cu or In is coated onto on the surface of metal fine powder.
If metal fine powder is made up of with regard to not needing good Cu of electroconductibility or Ag it is activated and/or replacement Treatment.Preferably use under pressure its surface to scribble the oxidized Au that is difficult for of satisfactory electrical conductivity, Ag, the Ni of a kind of metal-powder among Cu and the In, NiO, Cu, Ag, Al, Fe, Zn, Sn, the mixture of two or more of at least a metal fine powder among P and the Cr or they.
Preferably use a kind of in flaky metal powder submicron metal and the granulated metal powder as metal fine powder, wherein the thickness of flaky metal powder is 0.02～2.0 μ m, the outward appearance length of longer sides is 0.2～10.0 μ m, the diameter of submicron metal is 0.02～1.0 μ m, and the diameter of granulated metal powder is 1.0～6.0 μ m.Preferably use the metal fine powder of forming by at least two kinds of mixtures in above-mentioned three kinds of metal-powders.
Best two-layer at least in the metal level of the flaky metal powder by stacked flaky metal powder, submicron metal and granulated metal powder, another layer of a lamination constitutes metal level.Preferably also can be by the stacked metal level of forming by the mixture of above-mentioned three kinds of metal-powders with by a kind of metal level of forming in three kinds of metal-powders, another layer of a lamination constitutes metal level.
Preferably the metal level of flaky metal powder or the hybrid metal that comprises flaky metal powder are placed on the outside of the metal level that a plurality of metal levels of being laminated into by another layer of lamination ground form.
On the surface of the structure of three-dimensional netted porous layer by the conductive metal layer of forming by metal fine powder, three-dimensional netted porous layer is by a foam layer, one nonwoven layers, one stratum reticulare constitutes or by making foam layer, nonwoven layers, two-layer at least mutually combining in the stratum reticulare, the multilayer that another layer of lamination ground is laminated into constitutes.That is, it is such that the following method of facing this metallic porous sheet of manufacturing will be described in detail, after metal fine powder being coated onto on the three-dimensional netted porous layer surface of (and metal level needs to electroplate), and burn off porous layer from the metal level of metal fine powder.Porous layer can be without burn off.
A kind of active substance is inserted in the hole, so that utilize porous plate of the present invention as a kind of cell panel.
Make the first method that has the metallic porous sheet of tridimensional network on every side in hole of the present invention, on all surfaces of the three-dimensional netted porous layer of the body structure surface that comprises the following steps: to utilize tackiness agent metal fine powder to be coated onto the hole that comprises qualification, form a conductive metal layer; The surface of plated conductive metal level forms a metal plating on conductive metal layer.Preferably heating has formed the porous layer of conductive metal layer and metal plating thereon, so as from formed metal level burn off porous layer and tackiness agent; And after having formed conductive metal layer and metal plating, sintering conductive metal layer and metal plating.Also can be after conductive metal layer form, heating burn off porous layer and tackiness agent, metallizing on conductive metal layer, sintering conductive metal layer and metal plating then.In addition can be behind sintering, metallizing on metal coating surface again.
Be manufactured on the hole around have a metallic porous sheet of tridimensional network all surfaces of the second method three-dimensional netted porous layer that comprises the following steps: to utilize tackiness agent metal fine powder to be coated onto the body structure surface that comprises limiting hole on, the heating porous layer so as from formed conductive layer burn off porous layer and tackiness agent; And burn off porous layer and tackiness agent; And sintering conductive metal layer.
Used three-dimensional netted porous layer is by a foam layer in first kind and second method, a nonwoven layers, and a stratum reticulare constitutes, or by making foam layer, nonwoven layers, two-layer at least the mutually combining in the stratum reticulare, the multilayer that is laminated into formation a lamination one deck.
Foam layer is made of polyurethane(s) sponge plastics etc.Preferably its thickness is 0.5～5.0mm, and the diameter in hole is 50～500 μ m, and 50～99% hole is arranged on the foam layer.
Nonwoven layers and stratum reticulare be by for example synthetic resins of polyester, polypropylene, polyurethane(s) and analogue, the organic materials of natural fiber, Mierocrystalline cellulose, paper and analogue, and for example the inorganic materials of metal, glass, carbon and analogue constitutes.
Stratum reticulare has by braiding warp and the reticulated structure that weaves parallel or be made of one or more threads that are woven into linear structure.Has the most suitable application of 2～200 purpose stratum reticulares.
The thread of stratum reticulare and nonwoven layers is made of fiber, and the diameter of fiber is 0.01～1.0mm, and thread has 40～99% hole.When carrying along transfer passage when being shaped as the porous layer of successive layer, conductive metal layer and metal plating have been formed.
Conductive metal layer forms by organic binder bond being coated onto then metal fine powder is coated onto on the organic binder bond on the porous layer.Metal fine powder is sprayed to porous layer to be scribbled on the surface of organic binder bond, utilize vibrator and/or air scraper plate to make metal fine powder enter porous plate then, make metal fine powder equably on all surfaces attached to the body structure surface of surface that comprises porous layer and limiting hole in the porous layer thickness direction.
Conductive metal layer is that all surfaces by the body structure surface that will be coated onto the surface that comprises porous layer and limiting hole by the slurries that mutual blended metal fine powder and organic binder bond are formed forms.
By spraying slurries, being coated onto on the porous layer.
By the roller that is immersed in the slurries slurries are coated onto on the porous layer.
The roller that has the slurries of supply by its surface is coated onto slurries on the porous layer.
Slurries are coated onto on the porous layer for the net on the circumferential surface of the roller that slurries are arranged by being contained in.
The slurries of forming with tackiness agent and metal fine powder and/or by mutual blended metal fine powder and tackiness agent are coated onto on the porous layer from the two sides of porous layer.In addition, the slurries of being made up of mutual blended metal fine powder, tackiness agent and ion adsorbent can be coated onto on the surface of porous layer.
Before the plated conductive metal level, tackiness agent is coated onto on the conductive metal layer.
Utilize method of the present invention that metal fine powder is coated onto on the porous layer when forming conductive metal layer, the resistance of conductive metal layer is low to reach 1-8 Ω/cm, and the upper limit 30 Ω/cm of needed resistance is low during than the plated conductive metal level.Therefore, can adopt big electric current that conductive metal layer is electroplated.Like this, after forming conductive metal layer, can be by pre-determined thickness high speed electrodeposition conductive metal layer.In this manner, adopt method of the present invention can make metallic porous sheet efficiently.
According to the conventional method, with the conduction carbon or conductive agent be coated onto porous layer the surface on so that the surface of porous layer has electroconductibility.Yet when heating burn off porous layer, conductive agent is removed.Therefore, according to the conventional method, electrolytic coating must have desired total metal content.Recently, on metallic porous sheet, form a large amount of holes and need insert a large amount of reactive powders, therefore, require to reduce the amount that is plated to the metal on the conductive metal layer.Recently, attached to the metal level of porous layer from 600g/m
2Become 420g/m
2It is believed that, be 100g/m attached to the amount of the conductive metal layer on the porous layer
2, the amount that is plated in the metal on the conductive metal layer is 320g/m
2, be 600g/m
2Half about.According to method of the present invention, the amount that is plated to the metal on the conductive metal layer can reduce, even because conductive metal layer is heated, and burn off resin or solid support material, and be sintered, conductive metal layer still remains as the structure of three-dimensional netted metallic porous sheet.Therefore, the predetermined total amount of the plating amount of electrolytic coating being adjusted to the metal level that forms from the surface at porous layer deducts the resulting difference of amount of conductive metal layer.So, can adopt less current intensity to finish plating in the short period of time.Therefore, can adopt high productivity and the low-cost metallic porous sheet of making.
On porous layer, can amount on request form a metal level, need not form electrolytic coating.That is, the processing of giving electroconductibility to metal fine powder only relates on request amount and is formed on metal level on the porous layer.Therefore, owing to do not need to electroplate, can adopt very low cost and high productivity to make metallic porous sheet.
Select to adopt and metal fine powder to be coated onto method on the porous layer still to adopt the method that porous layer is immersed tackiness agent to depend on the kind of solid support material, solid support material is a foam layer by porous layer, one nonwoven layers, one stratum reticulare constitutes, or by making foam layer, nonwoven layers, two-layer at least the mutually combining in the stratum reticulare, the multilayer that is laminated into constitutes a lamination one deck.When being coated with the slurries that contain metal fine powder and tackiness agent, regulate the viscosity of slurries, so that on all surfaces of the porous layer of the body structure surface of upper and lower surface that comprises porous layer and limiting hole, form metal level reliably.
By traditional method, when the heating porous layer, when burn off resin or solid support material, and when carrying out sintering, the carbon that is used to traditionally to make metal porous layer have electroconductibility is stayed the surface of metallic porous sheet as impurity, yet,, do not have impurity to stay on the structure of metallic porous sheet according to method of the present invention.Therefore, adopt the quality height of the metallic porous sheet of method manufacturing of the present invention, so can be used as the advanced battery plate.
These and other objects of the present invention and advantage are from reference to the accompanying drawings in conjunction with becoming clearer, wherein the description of preferred embodiment:
Fig. 1 is a schema, and the step of metallic porous sheet is made in expression according to first embodiment of the invention;
Fig. 2 is a synoptic diagram, and expression is made the process of metallic porous sheet according to first embodiment and a used device in first embodiment;
Fig. 3 is a local amplification sectional view, and expression utilizes the metallic porous sheet of making according to the method for first embodiment;
Fig. 4 is a synoptic diagram, and expression is coated onto used on a porous layer device according to first embodiment with tackiness agent;
Fig. 5 is a synoptic diagram, and expression sprays to device used on the porous layer according to first embodiment with metal fine powder;
Fig. 6 is a partial enlarged drawing, the device shown in the presentation graphs 5;
Fig. 7 is a schematic section, and expression makes metal fine powder have a used device of electroconductibility;
Fig. 8 is a synoptic diagram, and the method for the resistance of conductive metal layer is measured in expression;
Fig. 9 is a synoptic diagram, and expression sprays to used on a porous layer device according to an embodiment with metal fine powder;
Figure 10 is a schema, and the step of metallic porous sheet is made in expression according to second embodiment of the present invention;
Figure 11 is a synoptic diagram, and expression is coated onto used on a porous layer device according to second embodiment with slurries;
Figure 12 A is a diagrammatic side view, and expression is coated onto another used on porous layer device with slurries;
Figure 12 B is a schematic front view, the device shown in the presentation graphs 12A;
Figure 13 A is a diagrammatic side view, and expression is coated onto another used on porous layer device with slurries;
Figure 13 B is a partial enlarged drawing, the device shown in the presentation graphs 13A;
Figure 14 is a side-view, and expression will be coated with slurries and be coated onto used on a porous layer device;
Figure 15 is a schema, and the step of metallic porous sheet is made in expression according to the 3rd embodiment of the present invention;
Figure 16 is a schema, and the step of metallic porous sheet is made in expression according to the 4th embodiment of the present invention;
Figure 17 is a synoptic diagram, and expression is made the process of metallic porous sheet and used device in the 4th embodiment according to the 4th embodiment of the present invention;
Figure 18 is a local amplification sectional view, and expression utilizes the metallic porous sheet according to the manufacturing of the method for the 4th embodiment;
Figure 19 is a schema, and the step of metallic porous sheet is made in expression according to the 5th embodiment of the present invention;
Figure 20 is a schema, and the step of metallic porous sheet is made in expression according to the 6th embodiment of the present invention;
Figure 21 is a synoptic diagram, represents used in the present invention metal fine powder;
Figure 22 is a sectional view, the example that the expression metal fine powder distributes;
Figure 23 A, 23B and 23C are sectional views, another example that the expression metal fine powder distributes;
Figure 24 A, 24B, 24C and 24D are sectional views, another example that the expression metal fine powder distributes;
Figure 25 A and 25B are sectional views, the 4th example that the expression metal fine powder distributes;
Figure 26 is a chart, and the Overall Steps of metallic porous sheet is made in expression according to the present invention.
Before beginning to describe the present invention, notice that identical part is represented with identical label in whole accompanying drawings.
Below, referring to figs. 1 through 9 a kind of metallic porous sheets of describing according to a first embodiment of the invention.
Expression shown in the schema of Fig. 1 is according to the manufacturing step of first embodiment, the manufacturing step of schematically representing first embodiment shown in Fig. 2 and used device.The body material that cuts of metallic porous sheet is made of three-dimensional netted porous layer 1, three-dimensional netted porous layer 1 is by a foam layer, a nonwoven layers, and a stratum reticulare constitutes, or by at least two types layer in the above-mentioned three types layer is mutually combined, the multilayer that is laminated into constitutes a lamination one deck.Porous layer 1 is a successive, therefore can be transferred and carry out the successive art breading.
In the process of carrying porous layer 1, at first, in the step of Fig. 1
#1, in a tackiness agent groove 11 that contains organic binder bond 2, organic binder bond 2 is coated onto on the body structure surface of porous layer 1 of the upper and lower surface of porous layer 1 and limiting hole, these holes will encyclopaedize in the back.
Then, in step
#2, granularity is sprayed on the organic binder bond 2 from the powderject device 12 along the transfer passage setting of porous layer less than the metal fine powder 4 of 6.0 μ m.The granularity of metal fine powder is preferably less than 1.0 μ m.After on the upper surface that metal fine powder 4 is sprayed to porous layer 1, on the porous plate transfer passage, porous layer 1 is turned over, so that metal fine powder is sprayed on the lower surface of porous layer 1.Preferably adopt Ni, NiO, Cu, Ag, Al, Fe, Zn, Sn, Au, In, the mixture of two or more of the micro mist of P and Cr or they is as metal fine powder.
Only utilize powderject device 12 that metal fine powder 4 is sprayed to and cause metal fine powder inhomogeneous on the porous layer 1, and non-desired distribution enters the body structure surface of the porous layer 1 of the limiting hole 1C that forms in the inside of porous layer 1 in the surface arrangement of porous layer.Therefore, in step
#3, utilize a vibration machine 13 to make porous layer 1 produce vibration, make metal fine powder 4 uniform distribution on the surface of porous layer 1, and unnecessary metal fine powder 4 is fallen from porous layer 1.Then, in step
#4, utilize air scraper plate 14 that metal fine powder is entered in the porous layer 1 at the thickness direction of porous layer 1, the metal fine powder 4 that may be blocked in the hole is fallen.Adopt this mode, metal fine powder 4 is adhered on the organic binder bond 2 on the body structure surface that is coated in limiting hole equably.Adopt this mode, on the surface of porous layer 1, form a conductive metal layer 5.
In step
#2 to step
#Employed method is carried out one to three time on demand in 4, like this, is approximately 1/2 of the metal level total amount that will form in the amount of the conductive metal layer 5 that forms on the surface of porous layer 1 on the surface of porous layer 1.Though it is the amount of conductive metal layer 5 is not limited in 1/2 of the predetermined total amount of metal level, fixed to 1/2 in first embodiment.
Form by a kind of metal rather than form as if metal fine powder 4, porous layer 1 immersion that has formed conductive metal layer 5 is in its surface filled in the groove 15 of activated solution, so that metal fine powder 4 activation by easy oxidized Cu or the Ag in surface.
Then, in step
#6, if the resistivity of metal fine powder 4 is big, porous layer 1 immersion is filled in the groove 16 of substitutional solution, so that carry out replacement Treatment.
In step
#7 finish drying step after, in step
#8 are coated onto organic binder bond 6 on the upper surface of conductive metal layer 5.To organic binder bond 2 is coated onto on the porous layer 1 similar, porous layer 1 is transported to the groove 17 that fills tackiness agent 6, so that organic binder bond 6 is coated onto on the upper surface of conductive metal layer 5.
After organic binder bond 6 being coated onto on the upper surface of conductive metal layer 5, in step
#9, utilize electroplanting device 18 plated conductive metal levels 5, so that form electrolytic coating 7.The plating amount of electrolytic coating 7 deducts the resulting difference of amount of conductive metal layer 5 to the predetermined total amount of the metal level that will form from the surface at porous layer 1 surely.
Behind the plated conductive metal level 5, utilize a heating unit 19 to heat porous layer 1 within the predetermined time, so that burn off formation porous layer 1 is not the solid support material that is made of metal from formed metal level by predetermined temperature.
Then, in step
#11, utilize a heating unit 20 under reducing atmosphere by predetermined temperature heating of metal layer within the predetermined time, so that the metal level that sintering is made of the electrolytic coating 7 of conductive metal layer 5.
In step
#12, allow metallic porous sheet 8 by a pair of skin-pass roller 21, so that it is adjusted to pre-determined thickness.
Adopt this mode, pass through step
#1 to step
#12 step just can produce a kind of metallic porous sheet, and this porous plate has conductive metal layer 5 and the electrolytic coating 7 that is layered in above the conductive metal layer 5 around the hole, as shown in Figure 3.
In being used for as shown in Figure 2 tackiness agent 2 is coated onto a device on the porous layer 1, with tackiness agent for example acrylic adhesives store in tackiness agent groove 11; Be installed in the tackiness agent groove 11 by liquid roller 22, it is contacted with tackiness agent 2; Applicator roll 23 contacts with the top that is subjected to liquid roller 22; Help roll 24 is installed in the top of applicator roll 23, and porous layer is sandwiched in the middle of them.
In adopting this device of method of roll coating, tackiness agent in the tackiness agent groove 11 2 is coated onto on the porous layer 1, so that simultaneously by being subjected to liquid roller 22, applicator roll 23 and help roll 24, make porous layer 1 be subjected to the pressure of applicator roll 23 and help roll 24, allow tackiness agent infiltrate porous layer 1.
Adopt a device as shown in Figure 4 to replace the device shown in Fig. 2 that tackiness agent 2 is coated onto on the porous layer 1.In this device, a plurality of roller 25A and 25B are installed in the tackiness agent groove 11, allow their contact adhesives 2; Porous layer 1 is transported in the adhesive slot 11 along roller 25A and 25B, porous layer 1 is immersed in the tackiness agent 2; Allow porous layer 1 pass through, so that remove unnecessary tackiness agent 2 from porous layer 1 by pressurizeing to porous layer near pair of rolls 26A the channel outlet above the tackiness agent groove 11 and the gap between the 26B.
According to Fig. 2 and 4 tackiness agent 2 is coated onto these used on the porous layer 1 methods, porous layer 1 passes through the gap between roller, makes porous layer 1 be subjected to the pressure of roller.After constituting porous layer 1 and from roller, pass through by foam layer, flexibly return to its original shape, i.e. its original depth.
When porous layer 1 is made of a nonwoven layers, it from roller by after do not return to its original depth.Therefore, it is suitable utilizing method rather than employing aforesaid method that tackiness agent 2 is sprayed on the porous layer 1.Adopt the method for spraying, vaporific tackiness agent is ejected on the porous layer 1 from an injector, and unnecessary tackiness agent siphons away with vacuum, so that with homogeneous thickness tackiness agent 2 is coated onto on the porous layer 1.
When porous layer was made of a stratum reticulare, it all was reliable adopting above-mentioned two kinds of methods.
As shown in Figure 2, in step
#2, utilize two powderject devices 12 that metal fine powder is sprayed on the porous layer 1, this is by porous layer 1 is turned over, realize on the upper and lower surface that metal fine powder 4 is sprayed to it.As shown in FIG. 2, powderject device 12 is positioned at the top of the porous layer of flatly being carried 1, so that powderject device 12 is ejected into metal fine powder 4 downwards on the porous layer 1.
Referring to Fig. 5 and 6, be set at the rotor hole 28a of housing 28 and be contained in rotor at the outlet 27a of the lower end of metal fine powder 4 being supplied with a used powder funnel 27 of powderject device 12 and roll between the circumferential surface of rotor 29 of tolerance amount of powder of 28a inside.
As shown in Figure 6, the rotor 29 of the tolerance amount of powder blade 29a that separates by fixed intervals that has that inner circumferential surface at rotor tilts.When the rotor 29 of tolerance amount of powder rotates, admit the metal fine powder 4 that falls into the gap between the blade 29a from outlet 27a, the metal fine powder of predetermined amount is maintained between the contiguous blade 29a.
Not only utilize the powderject device 12 on the top shown in Fig. 5 and 6 metal fine powder 4 to be ejected on the upper surface of porous layer 1, and by porous layer 1 is turned over along transfer passage, utilize the powderject device 12 of bottom that metal-powder 4 is ejected on the lower surface of porous layer 1, as shown in Figure 2.
Utilize powderject device 12 metal injection micro mist 4 above porous layer 1 to cause the metal fine powder skewness, in addition, metal fine powder stops up the hole of porous layer 1.Therefore, behind metal injection micro mist 4 above the porous layer 1, utilization is positioned at the vibration machine 13 vibration porous layers 1 below the porous layer 1, metal fine powder 4 is scattered, and vibrate the unnecessary metal fine powder 4 that to be blocked in the hole.Adopt this mode, metal fine powder 4 adheres on the lip-deep tackiness agent 2 of the upper surface that is coated onto porous layer 1 and limiting hole equably.
Do not adhere on the tackiness agent 2 and vibrated the metal fine powder 4 that by vibration machine 13 and be collected in together so that recycle.
Therefore, in the housing 28 of sealing, utilize powderject device 12 metal injection micro mists 4 and utilize vibration machine 13 vibration metal fine powders 4.
Behind vibration porous layer 1, utilize air scraper plate 14 that high-pressure air is blown on the porous layer 1, so that make the lip-deep metal fine powder 4 that sprays to porous layer 1 in its thickness direction enters porous layer 1, promptly enter the hole of porous layer 1, like this, metal fine powder 4 is coated onto on the hole wall securely, and the metal fine powder 4 that is blocked in the hole is blown down.
Metal injection micro mist 4 above porous layer 1, vibration porous layer 1 utilizes the air scraper plate that metal fine powder 4 is entered in the hole of porous layer 1, and above-mentioned steps can repeat.
If porous layer 1 is thin, 4 of metal fine powders can be ejected on its upper surface or lower surface.
In step
#1 to step
#After forming conductive metal layer in 4 steps that will finish, respectively in step
#5 and step
#6 carry out activation treatment and replacement Treatment.If metal fine powder 4 is made up of Cu with electroconductibility or Ag, then needn't carry out these processing.If metal fine powder 4 is to be made of the easy oxidized metal in its surface, if promptly they do not have electroconductibility, in step
#5 should carry out activation treatment.If form the resistivity height of the metal of metal fine powder 4, be in step
#6 carry out replacement Treatment, so that its resistivity is reduced to less than 30 Ω/cm.
Before being coated onto metal fine powder 4 on the porous layer 1, can in order it be immersed in activated solution and the substitutional solution, then, utilize powderject device 12, above porous layer 1, spray metal fine powder 4 activated and that replacement Treatment is crossed.
In order to improve the electroconductibility of metal fine powder 4, be preferably in immerse metal fine powder 4 in activation and the substitutional solution before, or metal fine powder 4 is not immersed in activation and the substitutional solution, better conductivity, its hardness ratio form the hardness of metal of metal fine powder 4 low and be difficult for oxidation such as Au, Ag, a kind of powder in the such metal of Cu and In is put into ball mill with metal fine powder 4, and their mixture is stirred.
More particularly, as shown in Figure 7, the inner barrel 80a of ball mill 80 and its outer cylinder body 80b continue to rotate a preset time, nickel metal fine powder 4 and zirconia ball 81 are arranged, so that nickel metal fine powder 4 uniform distribution in ball mill 80 in the ball mill 80.Then, Ag is put into ball mill 80, allow inner core 80a and urceolus 80b continue to relatively rotate a scheduled time, like this, under pressure, nickel metal fine powder 4 is coated onto on the soft Ag powder.
Acryloid cement (acrylic resin: 45%; Water, alcohol or solvent: 55%) put into tackiness agent groove 11, the porous layer of being made by nonwoven layers 1 adopts method shown in Figure 4 to carry, that is, be maintained in the tackiness agent groove 11 and be transferred along with being immersed in porous layer 1 in the tackiness agent 2.Unnecessary tackiness agent 2 is inhaled under near the vacuum 11 outlets of tackiness agent groove to be gone.
Its size is less than 1.0 μ m, the fine nickel powder end be sprayed onto on the porous plate 1 by powder spraying device 12; Make porous layer 1 vibration; The fine nickel powder end is infiltrated in the hole of porous layer 1 by air scraper plate 14; Then, porous layer 1 heated one minute down at 150 ℃.The upper and lower surface of porous layer 1 is once sprayed at its fine nickel powder end respectively as shown in Figure 2.
The weight of the fine metal powder 4 of the conductive metal layer 5 that forms on porous layer 1 in above-mentioned operation is 130g/m
2
The porous layer 1 that has formed conductive metal layer 5 on its porous layer 1 at room temperature immersed in the 2N salpeter solution one minute, with activation fine metal powder 4.
The resistance of the conductive metal layer 5 of activated processing is 4800 Ω/cm.In order to measure its resistance, a pair of probe 33 is arranged on the surface of the porous layer 1 that forms conductive metal layer 5 on its porous plate 1, is spaced apart 10mm between its probe 33, and lead is connected with a meter with probe 33, as shown in Figure 8.
After the activated processing, its porous layer 1 at room temperature immerses 30 seconds in the Ag substitutional solution that pH value is 4-5, and its Ag substitutional solution is mixed and forms with ammonia, (second) aldehyde, sodium hypophosphite and stablizer as reductive agent by 5-10 gram/litre Silver Nitrate.
The resistance of its conductive metal layer 5 is 8.0 Ω/cm, and 30 Ω/cm is little than required plating upper limit resistance for it.
If porous layer 1 is immersed in chemical nickel (reaction) plating liquor rather than in the silver-colored substitutional solution, be 22g/m so that on conductive metal layer 5, form value
2 Electrolytic coating 7, the resistance of its conductive metal layer 5 is 6.0 Ω/cm so.
After replacement Treatment, the organic binder bond 6 that is similar to the organic binder bond 2 of splendid attire in tackiness agent groove 11 sprays to the whole surface of conductive metal layer 5, to electroplate its conductive metal layer 5.
One plating tank is furnished with the single nickel salt through blended 360 gram/litres, the boric acid of the nickelous chloride of 60 gram/litres and 42 gram/litres, and the temperature of its groove is set to 65 ℃.
Its nickel layer 7 is formed on the surface of conductive metal layer 5 in the electroplating process, and the amount of formed nickel layer 7 is 290g/m in the plating
2, like this, comprise conductive metal layer 5(130g/m
2With the total amount of the metal level of electrolytic coating 7 be 420g/m
2(130+290).
After the plating, its nonwoven layers by to its porous layer 1 800 ℃ of down heating three minutes and being burnouted, thereby the metal level that comprises conductive metal layer 5 and electroless nickel layer is by decomposing in the ammonia environments heat-agglomerating 10 minutes to it at 1000 ℃.
As shown in Figure 9, in first embodiment, its fine metal powder 4 is sprayed onto on the porous layer 1 by powder spraying device 12, sprays its lip-deep fine metal powder 4 but can fully scatter with scraper 35, so that form preset thickness in its surface.
After being assigned to the upper surface of porous layer 1 equably by scraper 35 its fine metal powders 4, make the fine metal powder vibration, then, the air scraper plate that its fine metal powder 4 usefulness are similar to first embodiment puts on its body structure surface in the hole that limits porous plate 1.
The metallic porous sheet of second embodiment is described below with reference to Figure 10 to 14.Figure 10 is a process flow sheet, and it shows the manufacturing process of second embodiment of the invention, and it is not the first embodiment step
#1 to
#3 formed various operations, but in the step of this second embodiment
#The slurries that will contain tackiness agent 2 and fine metal powder 4 intermingling in 1 are added on the porous layer 1.The step of second embodiment
#2 to
#10 each operation and the first embodiment steps that form
#4 to
#12 each operation that forms are identical.
Step at second embodiment
#1 ' in, contain tackiness agent 2 and fine metal powder 4 composite slurries 40 are added on the whole surface of porous layer 1 and infiltrate and be limited on its body structure surface of hole that forms on the porous layer 1, so that slurry 40 injection porous layers 1, as shown in figure 11.
In the device shown in Figure 11, adopted method of roll coating, the groove 41 that receives roller 42 to place slurries 40 are housed, receive the lower section of roller 42 to be dipped in the slurries 40, one is coated with roller 43 is disposed at and receives on the roller 42 and be in contact with it, one help roll 44 places and is coated with on the roller 43, and its porous layer 1 is clipped in and is coated with between roller 43 and the help roll 44.
In this device, its slurries 40 are coated with on the roller 43 by receiving roller 42 to be transported to, and are coated with roller 43 and help roll 44 relative extruding by its porous layer 1, and its slurries 40 put on the porous layer 1.
The amount that puts on the slurries 40 on the porous layer 1 can be controlled by the gap width that adjusting is coated with between roller 43 and the help roll 44.In a second embodiment, the gap width that is coated with between roller 43 and the help roll 44 is set to 1/3 of porous layer 1 thickness, so that the inside of its porous layer 1 can be dipped into slurries 40 reliably.
In this device, put on be coated with porous layer 1 lower surface that roller 43 contacts on the amount of slurries 40 will be more than the amount of the slurries 40 that put on the upper surface that contacts with help roll 44.Therefore preferably porous layer 1 is turned, adopt to be similar to device shown in Figure 11, be coated with for the upper surface of porous layer 1 to add slurries 40 by being coated with roller 43, in the method, the slurries that put on porous layer 1 upper and lower surface have homogeneous thickness.
Also can be coated with slurries 40 and be added on the porous layer 1 i.e. employing rotation sieve method by the device shown in Figure 12 A and the 12B.Its slurries 40 enter in the roller, the circular surfaces of each roller that constitutes by a sieve and slurries 40 will be added on the porous layer 1.This device comprises that have a following structure a pair of is coated with the rotating screen 46 that roller by silk screen made at 48: and is installed in advance on the tubular circle wall, and it is contained between the side panel 45 that is disposed at the device both sides; Hole 45a is formed on the center of each side panel 45, and slurries supply-pipe 47 is along the axis configuration of tubular sieve 46; The both sides patchhole 45a of its slurry supply-pipe 47, its slurries spout 47a is formed on the slurries supply-pipe 47 every a segment distance, and it is coated with roller 48 and can clamps porous layer 1 ground configuration.
These slurries 40 are supplied in the slurries supply-pipe 47, and pipe 47 is configured in the inside that is coated with roller 48, is sprayed onto on the porous layer 1 by sieving 46 from slurries spray orifice 47a, so that porous layer 1 is infiltrated by slurries 40.
It is uniform being coated with the thickness that is added on the porous layer 1 towards the slurries 40 of ejection of porous layer 1 by sieve.
The rotation sieve method also can adopt the device shown in Figure 13 A and the 13B, is similar to Figure 12 A and 12B shown device, and its porous layer 1 is clamped in a pair of being coated with between the roller 50.Be similar to and be coated with roller 48 shown in Figure 12 A and the 13B, the sieve of being made by silk screen 51 is loaded on each circular surfaces that is coated with roller 50.Supplied to by spumescence slurries 40 that generate along the pipe (not shown) that is coated with roller 50 axis configurations and to discharge element 52,2-3 is atmospheric to be coated with in the roller 50 this arrangements of components having.
The discharge element of being supplied with by foamed slurries 40 52 has a discharge outlet 52a, and this discharge outlet is positioned at and porous layer 1 an opposed side.When slurries 40 supply on the porous layer 1 from discharge outlet 52a by its sieve 51, slurries 40 are in the atmosphere, consequently, because the differential pressure action of the pressure of normal atmosphere and spumescence slurry 40, its spumescence slurries 40 ejections also return to original state, therefore be the state of viscosity, be coated with to be added on the porous layer 1 and have homogeneous thickness.
In the device shown in Figure 11,12 and 13, the gap width that the ratio of the thickness setting of porous layer 1 is coated with between roller is big, porous layer 1 by being coated with roller the gap and during by relative roller extruding, its slurry is coated with and is added on the porous layer 1, and the pressure that is coated with roller makes slurries 40 inject porous layer 1 in the porous layer thickness direction.
At this moment, the porous layer of being made up of foam layer or stratum reticulare 1 is by flexibly getting back to its original thickness after being coated with roller.If porous layer 1 is made up of nonwoven layers, its porous layer 1 can not got back to its original thickness after by roller.
Like this, preferably adopt as shown in figure 14 an immersion system that nonwoven layers is immersed in the slurries 40, promptly be coated with roller 56A up and down and 56B is arranged in the groove 55 that slurries 40 are housed parallel to each other, the position of a pair of extrusion roll 57A and 57B configured slot 55 tops many.
Also can adopt the method that slurries 40 is sprayed onto porous layer 1 surface.In addition, can adopt scraper that slurries 40 are assigned on the surface of porous layer 1 with complete homogeneous thickness, and infiltrate at its thickness direction.
In step according to the method described above
#1 ' its slurries 40 are coated with to be added on the porous layer 1 with after infiltrating porous layer 1, is similar to first embodiment, in step
#2 usefulness air scraper plates 14 are coated with the slurries 40 that are added on porous layer 1 and infiltrate at thickness direction, and the slurries 40 that then adhere in porous layer 1 hole are blown away, and like this, slurries 40 have been attached on the whole surface of porous layer 1 and on the surface of the thickness structure that is limited to.
Can replace the air scraper plate or adopt vibrator simultaneously and the air scraper plate with vibrator.
Step
#After 2, porous layer 1 is dried, and then is similar to first embodiment, in step
#3 activation fine metal powders 4 are in step
#Finish replacement Treatment in 4.
Before slurries 40 utilize fine metal powder 4 and the preparation of organic binder bond intermingling, can activate or replacement Treatment.
Be similar among first embodiment by activation treatment of carrying out and replacement Treatment at second embodiment, so it describes omission.In addition, step
#5 arrive
#9 processing of carrying out are similar among first embodiment, so it describes also omission.
Preparation comprises that also slurries 40 are coated with the method that is added to porous layer has produced a problem when slurries 40 viscosity are big for organic binder bond and fine metal powder 4, the surface of its porous layer 1 becomes coarse, promptly, slurries 40 viscosity are big, the slurries 40 that are attached to porous layer 1 surface are spherical, consequently porous layer 1 surface imperfection.
If the water content in the increase slurries 40 needs dry slurries 40 for a long time to reduce the viscosity of slurries 40.
To this, preferably with the viscosity controller of its slurries 40 at 2000cps between the 15000cps.
If the mixture ratio of the tackiness agent 2 that contains in the slurries 40 is little, the resistance of its conductive metal layer 5 is just little, and its mixture ratio is big, its resistance is just big, therefore, it is little by the mixture ratio that contains tackiness agent 2 to be preferably in slurries 40, considers the minimum demand that tackiness agent 2 and fine metal powder adhere to, and preferably the weight percent of the tackiness agent 2 that contains in its slurries 40 is between 3-20.
The amount of utilizing slurries 40 to be attached to the conductive metal layer 5 that forms on the porous layer 1 is the 50-95% of the predetermined total amount of metal level, and the amount of electrolytic coating 7 is its 5-50%.
If the required thickness of conductive metal layer 5 is big, the operation that preferably utilizes slurries 40 to be attached to porous layer 1 surface and form conductive metal layer 5 is carried out several times, if and its slurries 40 are attached to and carry out once in the operation on porous layer 1 surface when forming thick conductive metal layer 5, so just cause the surface irregularity of porous plate 1.Therefore, will be coated with the slurries 40 that add at last and will be divided into several sections, preferably the amount of the tackiness agent that contains in the slurries 40 is few as much as possible, and is low with the resistance of the conductive metal layer 5 that forms, thereby can electroplate under high electric current.
90 portions of epoxy resin binders (epoxy resin binder: 10%, 90%), the mixing (thing) of 600 parts of fine nickel powder ends, 480 parts of water and 1 part of dispersion agent puts into the high speed rotating agitator and make slurries 40 water:, the viscosity of its slurries is 4200cps.
The thick foam layer of the 1.6mm that is made by polyurethanes foam material is as porous layer 1, be coated with 0.2mm thick gap roller 48 between of this porous layer 1 by as shown in figure 12, it is coated with the upper and lower surface that roller 48 is coated with slurries 40 to be added to porous layer 1 and infiltrates slurries 40.
Then infiltrate porous layer by its slurries 40 of an air scraper plate at its thickness direction, then, porous layer 1 is following dry one minute at 150 ℃.
The amount that is attached to the conductive metal layer 5 on the porous layer 1 is 85g/m
2, 85g/m
2Weight comprised the weight of tackiness agent 2.The weight of whole fine metal powder is 76.5g/m
2 Conductive metal layer 5 goes up in smoke with after removing organic binder bond, and the weight of its fine metal powder 4 is through measuring.
Be coated with the slurries 40 that are added on porous layer 1 and be dried the resistance of the measured conductive metal layer 5 in back up to 970000 Ω/cm.
The resistance of activated conductive metal layer 5 drops to 850 Ω/cm from 970000 Ω/cm.Then activated fine metal powder 4 is handled to improve the electroconductibility of fine metal powder 4 by carry out chemical reaction with silver powder, and consequently the resistance of conductive metal layer 5 is reduced to 7.5/ Ω/cm.
The MC solution of 140 portions of acryloid cements, 4,680 parts of water of 400 parts thin nickel metal powders, 2 parts of dispersion agents and 40 part 5% mixes to be put into the high speed rotating agitator and forms slurries 40, and the viscosity of its slurries 40 is 6200cps.
The thick foam layer of the 1.7mm that is made by the polyurethane foam materials is as porous layer.This porous layer 1 is coated with the upper and lower surface that is added to 1 porous layer 1 to slurries 40 and makes slurries 40 inject porous layer 1 so that be coated with roller 50 by being coated with the 0.2mm gap between the roller 50 as shown in figure 13.
Then, slurries 40 immerse its porous layer 1 by the air scraper plate in the porous layer thickness direction, and then, porous layer 1 is following dry one minute at 150 ℃.
The amount that is attached to the conductive metal layer 5 of porous layer 1 is 125g/m
2, and the weight of fine metal powder 4 is 112.5g/m
2
Because slurries 40 are coated with the result who is added on porous layer 1 for the second time, the amount that is attached to the conductive metal layer 5 of porous layer 1 is 250g/m
2Because slurries 40 are coated with and are added on porous plate 1 for the third time, the amount that is attached to the conductive metal layer of porous layer 1 is 375g/m
2
After porous layer 1 drying, fine metal powder 4 usefulness 2N nitric acid carry out activation in 30 seconds, advance replacement Treatment with silver then, and consequently the resistance of conductive metal layer 5 is reduced to 7 Ω/cm.
Then, conductive metal layer 5 is at 50A/dm
2Under electroplated for 35 seconds be 45g/m so that on conductive metal layer 5, form value
2Nickel fine powder end layer.
This porous layer 1 heated 3 minutes down at 800 ℃, with foam layer and the tackiness agent of burnouting, then, the metal level that comprises conductive metal layer 5 and electrolytic coating sintering 30 minutes under 1000 ℃ of reduced states, then, the gap of 1.5mm between porous layer 1 rolls by a pair of surface skin dress rolling, thus the thick metallic porous sheet of 1.55mm 8 obtained.
Before the sintering, the width of metallic porous sheet 8 is 200mm, and behind the sintering, the thickness of metallic porous sheet 8 is reduced to 194mm, the also attenuation of the thickness of metallic porous sheet 8.
The reason that its thickness reduces is because when sintering, the tackiness agent in the slurries 40 has been burnt, and has formed the nickel metal construction in addition.Hole (mesh) to this metallic porous sheet 8 has also dwindled.
During as battery pole plates, little hole has caused the problem that a large amount of activating substances can not be injected at metallic porous sheet 8.
To this, find that if the diameter in its hole passes through customary way, the bore dia of making big approximately (supposing that the bore dia that adopts customary way to make is 200-500 μ φ) so just can not produce above-mentioned problem at 10% o'clock.
37 portions of acryloid cements, 500 parts of nickel by powder, 550 parts of water, 1 part of dispersion agent and 25 parts of MC solution mixing are put into the high speed rotating agitator and are made slurries 40, and the viscosity of these slurries 40 is 3800cps.
The nonwoven layers of the 2.5mm thickness of being made by the polyester foam materials is as porous layer 1, three to each external diameter be 80mm be coated with roller 56A and 56B is dipped in the slurries 40, in its slurries 40, its slurries 40 be loaded in the groove of immersion system shown in Figure 14, be coated with the gap of rolling between 56A and the 56B and be set to 2.3m, be configured in a pair of extrusion roll 57A of groove top and the gap between the 57B and be set to 2.0mm.
Its nonwoven layers is by three pairs of gap and extrusion roll 57A and 57B gaps that are coated with roller 56A and 56B, and then, slurries 40 usefulness air scraper plates immerse porous plate 1 at its thickness direction, and then, porous layer heated 1 minute down at 150 ℃, thereby obtains the plate of 2mm thickness.
The amount that is attached to porous layer 1 conductive metal layer 5 is 54g/m
2, and the weight of fine metal powder 4 is 48.6g/m
2
The resistance of conductive metal layer 5 is 900000 Ω/cm.
Activation conductive metal layer 5, its resistance is reduced to 820 Ω/cm as a result.
Then, carry out chemical reaction and activate conductive metal layer 5 with silver powder, thereby the resistance of its conductive metal layer 5 is reduced to 8.6 Ω/cm.
The method that nonwoven layers and tackiness agent operation and sintering circuit are similar to experiment 1 is removed in electroplating work procedure, utilization burning.
Because nonwoven layers is made by staple fibre, the distribution of fiber is uneven, that is, fiber concentrates on a zone or forms the gap in another zone, and therefore, nonwoven layers can not immerse slurries 40 equably.
To this, the mixture ratio of the fine metal powder in the nonwoven layers is littler by 20% than the mixture ratio of the fine metal powder in the foam layer, so that the viscosity of slurries 40 is reduced to 3000-4000cps, promptly so that make slurries 40 thinning.Therefore, nonwoven layers can be immersed by slurries 40 soon.
75 portions of acryloid cements, 500 parts of fine nickel powder ends, 360 parts of water, 1 part of dispersion agent and 25 parts of 5%MC solution mixing are put into the high speed rotating agitator and are made slurries 40, and the viscosity of its slurries 40 is 9000cps.
90 1 stratum reticulares of being made by alkyd resin adopt immersion system shown in Figure 14 as porous plate 1.
Be similar to experiment 4, its slurries 40 are coated with and are added on the stratum reticulare, and then, slurries 40 immerse stratum reticulare by the air scraper plate at its thickness direction, and then, this stratum reticulare heated one minute down at 150 ℃.
The amount that is attached to the conductive metal layer 5 on the porous layer 1 is 32g/m
2, and the weight of fine metal powder 4 is 18g/m
2
The resistance of conductive metal layer 5 is 97000 Ω/cm.
Activation conductive metal layer 5, thus its resistance is reduced to 520 Ω/cm.
Then, carry out chemical reaction activation conductive metal layer 5 with silver powder, the result is that the resistance of conductive metal layer 5 is reduced to 6.2 Ω/cm.
Make slurries when the departure direction as the stratum reticulare of porous layer blows open with the air scraper plate, the viscosity of its slurries is preferably up to 7000-9000cps, so that slurries 40 can not be blown stratum reticulare fully.
The metallic porous sheet of the 3rd embodiment below will be described with reference to Figure 15.The difference of the 3rd embodiment and second embodiment is, does not carry out the second embodiment step
#The operation of burning solid support material in 8 promptly, is not burnt from the structure that comprises conductive metal layer 5 and electrolytic coating 7 by foam layer, nonwoven layers, stratum reticulare (as the solid support material of metal porous laminate) that polyurethane foam materials or analogue are formed.In first implementation step
#Burning the operation of solid support material in 10 does not carry out in the 3rd embodiment yet.
If stratum reticulare is made up of knit wire, do not need from metal porous plate structure, to burn stratum reticulare.
In the above-described embodiments, the porous layer that is used as the solid support material of metallic porous sheet comprises foam layer, nonwoven layers or stratum reticulare.Can it one and another stack constitute superimposed layer as solid support material, as, foam layer and one of stratum reticulare be placed on another or nonwoven layers be clipped in the middle of the stratum reticulare.Superimposed layer is being formed in the process of metallic porous sheet, the porous plate that comprises superimposed layer they go to be coated with add tackiness agent before or go to be put in another to one before affixed mutually, and be coated with before adding tackiness agent directly affixed mutually.
The metallic porous sheet of the 4th embodiment is described below with reference to Figure 16 and 17.Figure 16 shows the schema of the manufacturing process of the 4th embodiment.Figure 17 shows the schematic representation of apparatus of the manufacturing process that is used for the 4th embodiment.
In the 4th embodiment, do not electroplate, that is, metallic porous sheet only is made up of the conductive metal layer 5 that comprises fine metal powder 4.
Be similar to first to the 3rd embodiment, the solid support material of metallic porous sheet comprises three-dimensional net form porous layer 1, and its porous layer is made or stacked on one deck by the two-layer mutual combination in the above-mentioned at least layer many layers of another layer and makes by foam layer, nonwoven layers, stratum reticulare.Its porous layer 1 is a successive, therefore can handle ground and carry in continuous processing.
When porous layer 1 operation, Figure 16 step originally
#Be placed with the slurries 40 that contain organic tackiness agent 2 and fine metal powder 4 in 1 the tackiness agent groove 11, slurries 40 are coated with the upper and lower surface that is added to porous layer 1 and immerse by on the body structure surface that limits, and its details is described later on.
According to step
#1 slurries of being implemented are coated with addition, and its porous layer 1 of the whole bag of tricks by first embodiment is dipped into slurries 40.
After slurries 40 are coated with and are added to porous layer 1, slurries 40 on the porous layer 1 are applied on the surface of the pore structure that limits porous plate 1 by air doctor blade 14, the slurries 40 that are attached in the hole are blown away, so that slurries 40 are attached on the surface of porous layer 1 with homogeneous thickness and on the surface of limiting hole structure.
Can replace the air scraper plate or can make air scraper plate and vibrator simultaneously with vibrator.
Step
#After 2 operations of carrying out were finished, slurries 40 were dried, step then
#Activation fine metal powder 4 in 3 is then in step
#4 carry out replacement Treatment.
The activation treatment of fine metal powder 4 and replacement Treatment can be carried out after organic binder bond 2 and fine metal powder 4 intermingling are made slurries 40.
That is to say, if fine metal powder 4 by except outside the Cu of the very easy oxidation in its surface or the metal the Ag are formed, the porous layer 1 that has formed conductive metal layer 5 on porous layer 1 immerses in the groove 15 that activated solution is housed so that activation fine metal powder 4.
In the step 4 after connecing, if the resistivity height of fine metal powder 4, porous layer 1 is dipped in the groove 16 that substitutional solution is housed so, to carry out replacement Treatment.
In step
#After its slurries 40 were dried in 5, its porous layer 1 was in step
#Under required temperature, heat a predetermined for some time by heating unit 19 in 6, be not solid support material that be made of metal, composition porous layer 1 so that from the structure of forming conductive metal layer 5, burn.
Then in step
#In 7, in reducing environment, make its porous layer 1 be heated required for some time with sintering fine metal powder 4 with required temperature by heating unit 20.
In step
#In 8, porous layer 1 rolls 21 its thickness by a pair of skin-pass and adjusts to preset value.
As shown in figure 18, metallic porous sheet 8 is by step
#1 arrives
#8 operation manufacturing, this porous plate 8 comprise around the tridimensional network in the hole of being made up of conductive metal layer 5.
Implement 6
140 portions of acryloid cements (acryloid cement: 30%, 70%), 4, the 680 parts of water in 400 parts of fine nickel powder ends, 2 parts of dispersion agents and 40 parts of 5%MC solution mix and put into the high speed rotating agitator to make slurries 40 water:.The viscosity of its slurries 40 is 6200cps.
The thick foam layer of the 1.7mm that is made by the polyurethane foam materials is as porous layer, and as shown in figure 17, its porous layer 1 passes the 0.5mm gap that is coated with between roller 23 and 24, and it is coated with roller 23 and 24 makes slurries 40 be coated with the downside that is added to porous layer 1.Owing to be coated with and roll 23 and be coated with roller 23 and 24 extruding so that porous layer 1 is relative be provided with little of 24 gap, be coated with the slurries 40 that are added to porous layer 1 downside and upwards immerse, therefore there are enough slurries 40 to be infiltrated up to the upside of porous layer 1.
Then, immerse porous layer 1 by air scraper plate slurries 40 in the porous layer thickness direction, then, porous layer 1 was dried under 150 ℃ one minute.
The amount that is attached to the conductive metal layer 5 on the porous layer 1 is 125g/m
2, and the weight of fine metal powder 4 is 112.5g/m
2, because weight 125g/m
2The weight that has comprised organic binder bond 2.After its conductive metal layer 5 was sintered, the weight of fine metal powder 4 was measured.
For the second time be coated with when adding slurries 40, porous layer 1 is turned over, and slurries 40 is coated with is added to the upside that immerses the porous layer 1 in the groove 11.
For the second time slurries 40 are coated be added on the porous layer 1 after, the amount that is attached to the conductive metal layer 5 on the porous layer 1 is 266g/m
2
For the third time slurries 40 be coated be added on the porous layer 1 after, the amount that is attached to the conductive metal layer 5 of porous layer 1 is 480g/m
2The weight of fine metal powder 4 is 432g/m
2, it is greater than the predetermined total amount 420g/m of the metal level of not electroplating fine metal powder 4
2
Then, conductive metal layer 5 sintering 30 minutes in 1000 ℃ of reducing environments.
Then, porous layer 1 passes the gap that a pair of skin-pass rolls 1.5mm, thereby heavily arrives the thick metallic porous sheet of 1.55mm 8.
Metallic porous sheet 8 width before carrying out sintering is 200mm, and the width of metallic porous sheet 8 is reduced to 180mm behind the sintering, and the also attenuation of its thickness is also shunk little with regard to the hole (mesh) of this metallic porous sheet 8.
If metallic porous sheet 8 is as battery pole plates, the problem that aperture brings is that a large amount of activating substances can not be received in the aperture.
This is found,, just can not cause the problems referred to above if the diameter in its hole is bigger by 10% than the bore dia that adopts customary way to make (supposing that the bore dia that adopts conventional process to make is 200-500 μ φ).
110 portions of acryloid cements (acryloid cement: 30%, 70%), 800 parts of fine nickel powder ends, 680 parts of water water:, 1 part of dispersant is put into the high speed rotating agitator and is made slurries 40, and its viscosity is 3600cps.
The thick nonwoven layers of the 2.2mm that is made by the polyester form material is that be coated with roller 56A and the 56B of 80mm is immersed in the slurries 40 in the groove of immersion system shown in Figure 14 as 1, two pair of external diameter of porous layer.The gap that is coated with roller 56A and 56B is decided to be 2.0mm, is configured in a pair of extrusion roll 57A of groove top and the gap of 57B and is set at 1.9mm.
Nonwoven layers is passed two pairs and is coated with the gap of roller 56A and 56B and the gap of extrusion roll 57A and 57B, and rear slurry 40 immerses its porous layer 1 by the air scraper plate at its porous layer thickness direction, and then porous layer 1 is heated 1.2 minutes under 200 ℃.
Above-mentioned technology triplicate, the total amount that causes being attached to the conductive metal layer 5 on the porous layer 1 is 426g/m
2
When implementing above-mentioned technology for the second time, 1.9mm is transferred in the gap that is coated with roller 56A and 56B, and 1.8mm is transferred in the gap of a pair of extrusion roll 57A and 57B.When implementing above-mentioned technology for the third time, 1.8mm is transferred in the gap that is coated with roller 56A and 56B, and the gap of a pair of extrusion roll 57A and 57B is adjusted to 1.7mm.Then, porous layer 1 800 ℃ down heating then fine nickel powder end 4 was sintered 30 minutes under 1000 ℃ of reduced states to burn nonwoven layers in 3 minutes, then, porous layer 1 passes gap that skin-pass rolls so that the thickness of porous layer 1 is adjusted to 1 to 1.4mm.
The shrinking percentage of the metallic porous sheet width that the employing nonwoven layers is made is 7%, and it is less than the shrinkage in width per-cent of the metallic porous sheet 8 that adopts foam materials to make.
Metallic porous sheet 8 can bear the pulling force that acts on the 2.1kg/20mm on it when carrying.
Its metallic porous sheet 8 can 360 ° of bendings, can not cause breaking of its surface, this means that it can be used as battery electrode plate reliably.
Because nonwoven layers is made by staple fibre, its Fiber Distribution is uneven, that is, fiber concentrates on a zone or forms the gap in another zone, so slurries 40 can not immerse nonwoven layers equably.
To this, the mixture ratio of the relative tackiness agent of fine metal powder is littler by 20% than the mixture ratio of the relative tackiness agent of fine metal powder in foam layer in nonwoven layers, so that the viscosity of slurries 40 is reduced to 3000-4000cps, that is, so that make its slurries 40 thinning.The result is that slurries 40 immerse nonwoven layers easily.
200 portions of acryloid cements (acryloid cement: 30%, 70%), 1000 parts of fine nickel powder ends, 680 parts of water, 3 parts of dispersion agents and 40 parts of 5%MC solution put into the high speed rotating agitator and make slurries 40 water:, the viscosity of its slurries 40 is 9000cps.
The 90-stratum reticulare of being made by vibrin is as porous layer 1, and adopts immersion system shown in Figure 14.
Be similar to 3 the method for implementing that adopts, slurries 40 are coated with to be added on the stratum reticulare, then, is immersed in the stratum reticulare by the thickness direction of air scraper plate slurries 40 at its stratum reticulare, then stratum reticulare is heated 1 minute under 150 ℃, and the amount that is attached to the conductive metal layer 5 on the porous layer 1 is 253g/m
2
Then, porous layer 1 is heated 1 minute to burn stratum reticulare and slurries 40 under 800 ℃, and then, the fine nickel powder end is sintered 30 minutes under 900 ℃ of reduced states.
Can bear the pulling force of the 4.8kg/20mm that is applied to it when carrying with the metallic porous sheet 8 of twine manufacturing, when it is can 360 ° crooked do not break in its surface.
Below will describe the metallic porous sheet of the 4th embodiment with reference to Figure 19, Figure 19 shows the schema of the 4th embodiment production technique.In step
#In 1, the slurries 40 that contain fine metal powder are coated with and are added on the porous layer 1 step
#In 2, porous layer 1 is heated to burn solid support material and tackiness agent, step
#3 electroplate thin metal level, step
#4 sintering, step
#The thin layer of 5 roll-in sintering.
Much less, the 4th embodiment step
#2 arrive
#Each operation of 5 operations can be in the 5th embodiment step if need
#1 He
#Carry out between 2.
The metal multi-platen of the 6th embodiment is described below with reference to Figure 20, and Figure 20 shows the schema of the 6th embodiment production technique.Step
#1, the slurries 40 that contain fine metal powder are coated with and are added to porous layer 1, step
#2, porous layer 1 is immersed in and contains to some extent in the identical metal ion solution of the fine metal powder that adopts, so that its ionic adsorption is to fine metal powder, and is coated onto on the surface of fine metal powder and immerses fine metal powder.Step
#3, porous layer 1 is heated burns solid support material and tackiness agent, step from structure
#The conductive metal layer that is formed by fine metal powder in 4 is sintered, roll-in agglomerating metal-powder in the step 5 then.
Much less, in step
#Burning the technology of solid support material and tackiness agent in 3 can omit.
Much less, if need be in the 4th embodiment step
#2 arrive
#Each operation of 5 operations can be in the step of the 6th embodiment
#1 He
#Carry out between 2.
Metallic porous sheet of the present invention can be by the whole bag of tricks manufacturing shown in Figure 26, that is, 16 kinds of methods can be used for making metallic porous sheet of the present invention.
According to the present invention, adopted three kinds of different fine metal powders of its shape and size in the above-described embodiments, that is, depend on machining to scatter metal-powder to form flaky metal powder, its thickness is 0.02-2.0 μ m, and the outward appearance length on its long limit is 0.2-10.0 μ m.Metal-powder forms submicron metal through chemical treatment, and its diameter is 0.02-1.0 μ m.Metal-powder forms the powdered metal-powder through mechanical mill, and its diameter is 1.0-6.0 μ m.Three kinds of fine metal powders can suitably be combined to form the high-density metal layer mutually.It has formed three-dimensional netted honeycomb sandwich.
Particularly as first example, its three-dimensional netted honeycomb sandwich is by at least three kinds of metal-powders, that is, flaky metal powder, super-fine metal powder is in forming with two kinds of metal levels that mix at granulated metal end.
As second example, three-dimensional netted honeycomb sandwich is made up of the metal level that one deck is superimposed as on another layer, and its metal level comprises two metal layers at least, and its one deck is made up of any of three kinds of metal-powders.
As the 3rd example, three-dimensional netted honeycomb sandwich is the metal level that one deck is superimposed as on another layer, and a metal level comprises two kinds of three kinds of metal-powder intermingling at least, and a metal level perhaps each layer of many metal levels comprises any of three kinds of metal-powders.
Preferably metal of being made up of flaky metal powder or the metal level that contains flaky metal powder are formed at the outside of the metal level that is formed by many metal level one stacked one decks.
Much less comprise on the layer on surface of metal of above-mentioned metal-powder and can be electroplated.
As described in above-mentioned embodiment, the above-mentioned metal-powder that is slurry condition is coated with and is added on the porous layer surface or sticking being coated onto on the porous layer surface, and two kinds of methods all can make metal-powder be attached on the surface that limits the porous layer internal pore structure.
Can make its size and dimension different two or three flaky metal powder, submicron metal and granulated metal powder mutually the metal-powder of combination be attached on the highdensity layer of carrier material.
For example, the super-fine metal powder intermingling of large diameter powder metal powder and minor diameter, consequently the powder of minor diameter is seeped in the gap of major diameter powder, and like this, the metal level that contains mixed powder can be attached on the solid support material of high desnity metal porous plate.
If it is smooth that layer on surface of metal needs, the metal level that contains flaky metal powder is formed on the outside of metal level.
Thick metal layers if desired preferably is clipped in the granulated metal powder and contains submicron metal or flaky metal powder and be configured between the metal level on formed its metal level both sides.
Two or three metal-powder of combination has been because the advantage of another kind of metal-powder has compensated a kind of shortcoming of metal-powder, thereby the metal level that is suitable for using is provided.
And the combination of three kinds of metal-powders can easily realize.
That is, two or three metal-powder and tackiness agent intermingling are added on the solid support material so that formed mixture is coated with.
At two kinds (three kinds) when metal level makes up mutually, the mixture of first kind of metal-powder and tackiness agent be coated be added to form metal level on the solid support material after, the mixture of second kind of metal-powder and tackiness agent is coated with on the upper surface that is added to its metal level again.
After tackiness agent is coated with and is added on the surfaces of carrier materials, two or three metal powder mixture or a kind of metal-powder will be added on the tackiness agent.
The embodiment of three kinds of metal-powders is described below.
Figure 21 shows flaky metal powder 100, submicron metal 200 and granulated metal powder 300.
The thickness of flaky metal powder 100 is 0.02-2.0 μ m, and the outward appearance length on its long limit is 0.2-10.0 μ m.Flaky metal powder 100 has a big surface region or and is flaky.The diameter of submicron metal 200 is 0.02-1.0 μ m.The diameter of granulated metal powder 300 is 1.0-6.0 μ m.
Ceramic Balls is best suited for, and ball also can adopt zirconium (oxygen) soil, aluminium (oxygen) soil or iron to make, and the diameter of ball is decided to be about 10mm.
In the method for above-mentioned manufacturing flaky metal powder 100, the globular metallic powder in the container contacts with Ceramic Balls under pressure, little by little is unfolded or expands.Its metal-powder mixes the back with water and solution processed under the wet environment of container.Prevented to break when therefore metal-powder contacts with ball, can expand reliably like this.
Promptly, ionized metal ion and salt ion in the water-soluble solution of the crystalline powder of metal-salt, then, metal ion is reduced by the reductive agent that is added in the aqueous solution, therefore separated out as submicron metal, its diameter is 0.02-1.0 μ m, and mixture is stirred in processing, metal ion and negatively charged ion combination in reduction reaction, thus diameter is 0.02-1.0 μ m submicron metal salting out along with its edge.Its mixture prevents by high-speed stirring owing to stir ultrafine powder and interosculate, and can prevent that therefore them from gathering agglomeratingly, is 0.02-1.0 μ m and keep its diameter.
Diameter is that the granulated metal powder 300 of 1.0-6.0 μ m is to adopt mechanical means processing commonly used.
As mentioned above, three kinds of metal-powders make up mutually aptly and mix the formation mixture with tackiness agent and become slurries.Adopt rolling method, sieve to be coated with method, spraying method, spread coating or similar method and slurries are coated onto on the surface of three-dimensional netted porous layer, its porous layer is made up of foam layer, nonwoven layers, stratum reticulare or is made up of many layers of the two-layer at least mutual combination one lamination one deck in above-mentioned three types of layers.
Then, porous layer and tackiness agent are removed by the way of burning, and the conductive layer that contains fine metal powder is sintered and forms three-dimensional netted perforated plate construction.
For example shown in Figure 22, comprise in the metal level of flaky metal powder 100 and ultrafine powder 200 intermingling in formation, porous layer 10 is transported in the groove 41 that is placed with tackiness agent, flaky metal powder 100 and submicron metal 200 intermingling, and adopt method of roll coating shown in Figure 14 that slurries 40 are coated with on upper and lower surface that is added to porous layer 10 and the surface that limits porous layer 10 pore structures.
Then adopt the foregoing description and make metallic porous sheet 8 by method shown in Figure 26, its metallic porous sheet 8 comprises flaky metal powder 100 that laminates mutually and the submicron metal 200 that immerses the gap between the flaky metal powder 100, as shown in figure 22.Like this, metal-powder can be attached on the surface of porous layer 10.
With reference to Figure 23 A, earlier flaky metal powder 100 is coated with the upper and lower surface that is added to porous layer 10, then, the mixture of submicron metal 200 and granulated metal powder 300 is coated onto on the flaky metal powder 100, and then flaky metal powder 100 is coated onto on the mixture of submicron metal 200 and granulated metal powder 300 again.Burn porous layer 10 from mixture, the upper and lower surface of the metal level of combination all has flaky metal powder.
With reference to Figure 23 B, flaky metal powder 100 is coated onto the upper and lower surface of porous layer 10, then, the mixture of submicron metal 200 and granulated metal powder 300 is coated onto on the flaky metal powder 100, burn porous layer 10 from mixture, the metal level of its combination has flaky metal powder 100 being limited on the porous layer 10 pore structure surfaces.
The setting of Figure 23 C metal level is opposite with Figure 23 B.
The diameter of granulated metal powder 300 is big, therefore, preferably adopt granulated metal powder 300 in order to form thick metal level, but between granulated metal powder 300, can form the gap, to this, preferably by aforesaid granulated metal powder 300 and submicron metal 200 intermingling, because submicron metal 200 can be seeped in the gap of granulated metal powder 300.
The metal that Figure 24 A shows lamination one deck of being made up of flaky metal powder 100 and submicron metal 200 to 24D constitutes the example of metal sheet.
Figure 25 A shows the metal level be made up of flaky metal powder 100 and the example of the metal sheet that is made of metal level one lamination one deck that granulated metal powder 300 is formed to 25B.
Though do not illustrate on the figure, metal sheet can be made up of the metal level that submicron metal 200 and granulated metal powder 300 constitute.
Preferably submicron metal 200, granulated metal powder 300 and tackiness agent are pressed 10-99%, 1-90% and 5-50% mixing respectively.
600 parts extra-fine nickel powder end, 400 parts of powdery nickel by powder, 140 portions of acryloid cements, 680 parts of H
2The mixture intermingling of O, 40 parts of 5%MC solution and 2 parts of dispersion agents forms slurries, and its viscosity is 6200cps.Foam layer passes the gap that is coated with roller, then with the air scraper plate made slurries is coated onto to limit on the foam layer pore structure surface.Foam layer 150 ℃ dry 1 minute down, thereby the weight that obtains the conductive layer of the slurries that contain nickel dam and be attached to cystose is 125g/m
2, burning-off slurries then, the weight of residuum (nickel) is 112.5g/m
2, be similar to and for the first time be coated with the technology that adds slurries are coated onto on the foam layer for the second time, consequently, the amount that is attached to the conductive metal layer on the foam layer is 266g/m
2, be similar to be coated with for the first time and add its slurries of technology and be coated with for the third time and be added on the foam layer, consequently, the amount of adhering to the conductive metal layer 5 on the porous layer 1 is 480g/m
2, and the weight of nickel by powder is 432g/m
2
Porous layer is that foam layer is heated 3 minutes to burn it under 800 ℃, sintering 30 minutes under 1000 ℃ of reduced states then, and porous layer passes the 1.55mm gap of skin-pass roller, thereby obtains the metallic porous sheet that thickness is 1.55mm.
The metallic porous sheet that contains the nickel fine powder end can be electroplated.At this moment, the metal that plates on nickel dam is 10% of predetermined total metal level.
As mentioned above, fine metal powder can be attached on the highdensity solid support material, its metal sheet can be made up mutually and be made by the different flaky metal powder of size and dimension, submicron metal and granulated metal powder.
For example, the submicron metal intermingling of large diameter granulated metal powder and minor diameter, thereby submicron metal is seeped in the gap of its major diameter granular powder, and the metal level of being made up of mixed powder can be attached on the highdensity solid support material like this.
If need slick layer on surface of metal, the metal level that contains flaky metal powder is configurable to formed metal level outside.
If need thick metal level, preferably the granulated metal powder be clipped in by containing submicron metal or flaky metal powder and being configured between the metal level on formed its metal level both sides.
Two or three metal-powder of combination has been because the advantage of another kind of metal-powder has compensated a kind of shortcoming of metal-powder, thereby the metal level that is suitable for using is provided.
And the combination of three kinds of metal-powders can easily realize.
That is, two or three metal-powder and tackiness agent intermingling are coated onto on its solid support material.
At two kinds (three kinds) when metal level makes up mutually, after the mixture of first kind of metal-powder and tackiness agent was coated onto and forms metal level on the solid support material, the mixture of second kind of metal-powder and tackiness agent was coated onto on the upper surface of its metal level again.
After tackiness agent was coated with and is added on the surfaces of carrier materials, the mixture of two or three metal-powder or a kind of metal-powder were coated with and are added on the tackiness agent.
Though described the present invention with reference to accompanying drawing and most preferred embodiment are complete, but can notice that be conspicuous to the those skilled in the art to its variations and modifications, can be understood as these variations and modification be included in do not break away from of the present invention by in the scope of the present invention that claim limited of enclosing.
Claims (34)
1, a kind of metallic porous sheet has tridimensional network around the hole, it is characterized in that, this structure comprises a conductive metal layer and an electrolytic coating that forms that is made of metal fine powder on this conductive metal layer.
2, a kind of metallic porous sheet has tridimensional network around the hole, it is characterized in that, this structure comprises a conductive metal layer that is made of metal fine powder.
According to the metallic porous sheet of claim 1 or 2, it is characterized in that 3, the granularity of metal fine powder is less than 6.0 μ m.
By the metallic porous sheet one of in the claim 1 to 3, it is characterized in that 4, metal fine powder is by Ni, NiO, Cu, Ag, Al, Fe, Zn, Sn, Au, In, P, a kind of micro mist among the Cr is formed, or is made up of two or more the mixture of these metals.
5, by the metallic porous sheet one of in the claim 1 to 4, it is characterized in that,, and make metal ion enter conductive metal layer at the surperficial matel coated ion of conductive metal layer.
6, by the metallic porous sheet of claim 5, it is characterized in that, from by Ni, Cu, Ag, Fe, Zn, Sn selects at least a in the group that Au and In form or more than one are as metal ion.
7, by the metallic porous sheet one of in the claim 1 to 6, it is characterized in that metal fine powder is by Ni, NiO, Cu, Ag, Al, Fe, Zn, Sn, P, the micro mist of one or more among the Cr is formed, and is coated with on metal fine powder from Au, Ag, select in the group of Cu and In, have good electroconductibility and be difficult for oxidized metal.
8, by the metallic porous sheet one of in the claim 1 to 7, it is characterized in that, as the metal of electrodeposition of metals by Ni, Cu, Ag, Fe, Zn, Sn, one or more compositions among Au and the In.
9, by the metallic porous sheet one of in the claim 1 to 8, it is characterized in that metal fine powder is made up of flaky metal powder, its thickness is 0.02～2.0 μ m, and the outward appearance length on its long limit is 0.2～10.0 μ m.
10, by the metallic porous sheet one of in the claim 1 to 8, it is characterized in that metal fine powder is made up of submicron metal, its diameter is 0.02～1.0 μ m.
11, by the metallic porous sheet one of in the claim 1 to 8, it is characterized in that metal fine powder is by the granulated metal powder constituent, its diameter is 1.0～6.0 μ m.
12, by the metallic porous sheet one of in the claim 1 to 8, it is characterized in that, metal fine powder is by flaky metal powder, at least two kinds mixture in submicron metal and the granulated metal powder is formed, wherein, the thickness of flaky metal powder is 0.02～2.0 μ m, and the outward appearance length on its long limit is 0.02～10.0 μ m, the diameter of ultrafine metallic micropowder is 0.02～1.0 μ m, and the diameter of granulated metal micro mist is 1.0～6.0 μ m.
13, by the metallic porous sheet one of in the claim 1 to 8, it is characterized in that, the conductive metal layer of metal fine powder is by a sheet metal powder layer, two-layer at least in one a submicron metal layer and the granulated metal powder bed, the metal level that is laminated into constitutes one lamination one deck, wherein, the thickness of flaky metal powder is 0.02～2.0 μ m, the outward appearance length on its long limit is 0.02～10.0 μ m, the diameter of submicron metal is 0.02～1.0 μ m, and the diameter of granulated metal powder is 1.0～6.0 μ m.
14, by the metallic porous sheet one of in the claim 1 to 8, it is characterized in that, the conductive metal layer of metal fine powder is by flaky metal powder, the mixolimnion that at least two kinds mixture in submicron metal and the granulated metal powder constitutes, one sheet metal powder layer, an one submicron metal layer or a granulated metal powder bed, the metal level that builds up constitutes one lamination one deck, wherein, the thickness of flaky metal powder is 0.02～2.0 μ m, the outward appearance length on its long limit is 0.2～10.0 μ m, and the diameter of submicron metal is 0.02～1.0 μ m, and the diameter of granulated metal powder is 1.0～6.0 μ m.
15, by claim 13 or 14 metallic porous sheet, it is characterized in that flaky metal powder layer or comprise the outside of hybrid metal layer metal level of stacked a plurality of metal levels formation of flaky metal powder on lamination one deck ground.
16, by the metallic porous sheet one of in the claim 1 to 15, it is characterized in that conductive metal layer is made of the agglomerating metal-powder.
17, by the metallic porous sheet one of in the claim 1 to 16, it is characterized in that, the conductive metal layer that is made of metal fine powder is on the surface of the structure of three-dimensional netted porous layer, this three-dimensional netted porous layer is by a foam layer, a nonwoven layers, and a stratum reticulare constitutes, or by making foam layer, nonwoven layers, two-layer at least the mutually combining in the stratum reticulare, the multilayer that is laminated into constitutes a lamination one deck.
18, by the metallic porous sheet one of in the claim 1 to 17, it is characterized in that porous layer is a successive, and in the hole, insert activating substance, so that become the battery lead plate of battery.
19, a kind of method that has the metallic porous sheet of tridimensional network on every side of manufacturing hole comprises the following steps:
Utilize tackiness agent metal fine powder to be coated onto on all surfaces of three-dimensional netted porous layer on the surface that comprises limiting hole, form one deck electric metal layer; With
The surface of plated conductive metal level forms an electrodeposition of metals thereon.
20, press the method for the manufacturing metallic porous sheet of claim 19, it is characterized in that, burn conductive metal layer and electrodeposition of metals, so that burn off porous layer and tackiness agent, sintering conductive metal layer and electrodeposition of metals subsequently.
21, by the method for the manufacturing metallic porous sheet of claim 20, it is characterized in that, behind said first sintering, electroplate the surface of electroplated metal layer again, subsequently sintering metal electrolytic coating for the second time.
22, press the method for the manufacturing metallic porous sheet of claim 19, it is characterized in that, after forming conductive metal layer, burn conductive metal layer, so that burn off porous layer and tackiness agent are electroplated subsequently, form electrodeposition of metals, last sintering conductive metal layer and electrodeposition of metals.
23, a kind of method that has the metallic porous sheet of tridimensional network on every side of manufacturing hole comprises on all surfaces of the three-dimensional netted porous layer that utilizes tackiness agent metal fine powder to be coated onto the surface that comprises limiting hole, forms the step of one deck electric metal layer.
24, press the method for the manufacturing metallic porous sheet of claim 23, it is characterized in that, burn conductive metal layer, subsequently the sintering conductive metal layer with porous layer.
25, by claim 19, the method for the manufacturing metallic porous sheet one of in 20,21,23,24 is characterized in that, conductive metal layer is immersed contain in the metal ion solution, makes adsorption of metal ions to metal fine powder.
26, a kind of method that has the metallic porous sheet of tridimensional network on every side of manufacturing hole comprises the following steps:
Utilize tackiness agent metal fine powder to be coated onto on all surfaces of tridimensional network porous layer on the surface that comprises limiting hole, form a conductive metal layer;
Burn off has formed the porous layer and the tackiness agent of conductive metal layer thereon;
The conductive metal layer immersion is contained in the metal ion solution, make adsorption of metal ions to metal fine powder; With
The sintering conductive metal layer.
27, a kind of method that has the metallic porous sheet of tridimensional network on every side of manufacturing hole comprises the following steps:
Utilize tackiness agent metal fine powder to be coated onto on all surfaces of three-dimensional netted porous layer on the surface that comprises limiting hole, form a conductive metal layer;
Burn off has formed the porous layer and the tackiness agent of a conductive metal layer thereon;
The conductive metal layer immersion is contained in the metal ion solution, make adsorption of metal ions to metal fine powder;
The surface of plated conductive metal level; Form an electrodeposition of metals thereon;
Sintering conductive metal layer and electrodeposition of metals.
28, a kind of method that has the metallic porous sheet of tridimensional network on every side of manufacturing hole comprises the following steps:
Utilize tackiness agent metal fine powder to be coated onto on all surfaces of three-dimensional netted porous layer on the surface that comprises limiting hole, form a conductive metal layer;
The porous layer immersion that has formed conductive metal layer on it is contained in the metal ion solution, make adsorption of metal ions to metal fine powder;
The surface of plated conductive metal level forms an electrodeposition of metals thereon;
Burn off has formed the porous layer and the tackiness agent of a conductive metal layer and electrolytic coating thereon; With
Sintering conductive metal layer and electrodeposition of metals.
29, a kind of method that has the metallic porous sheet of tridimensional network on every side of manufacturing hole comprises the following steps:
Utilize tackiness agent metal fine powder to be coated onto on all surfaces of three-dimensional netted porous layer on the surface that comprises limiting hole, form a conductive metal layer;
The porous layer immersion that has formed a conductive metal layer on it is contained in the metal ion solution, make adsorption of metal ions to metal fine powder;
Burn off has formed the porous layer and the tackiness agent of a conductive metal layer on it;
The sintering conductive metal layer.
30, by the method for the manufacturing metallic porous sheet one of in the claim 19 to 29, it is characterized in that three-dimensional netted porous layer is by a foam layer, one does not have anti-layer, and a stratum reticulare constitutes, or by foam layer, nonwoven layers, two-layer at least the mutually combining in the stratum reticulare, the multilayer that is laminated into constitutes a lamination one deck.
31, by the method for the manufacturing metallic porous sheet one of in the claim 19 to 30, it is characterized in that, before or after being coated onto metal fine powder on the porous layer, metal fine powder is activated and replacement Treatment.
32, by the method for the manufacturing metallic porous sheet one of in the claim 19 to 31, it is characterized in that,, metal-powder is coated onto forms conductive metal layer on the organic binder bond by organic binder bond is coated onto on the porous layer.
33, by the method for the manufacturing metallic porous sheet one of in the claim 19 to 31, it is characterized in that, on interior all surfaces, form conductive metal layer by all surfaces that will be coated onto the porous layer on the surface that comprises limiting hole by the slurries that mutual blended metal fine powder and organic binder bond are formed.
34, by the method for the manufacturing metallic porous sheet one of in the claim 19 to 31, by will be by mutual blended metal fine powder, the slurries that organic binder bond and ion adsorbent are formed be coated onto on all surfaces on the surface that comprises porous layer and form conductive metal layer.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP229284/93 | 1993-09-14 | ||
| JP229283/93 | 1993-09-14 | ||
| JP22928393 | 1993-09-14 | ||
| JP26759193A JP3483600B2 (en) | 1993-10-26 | 1993-10-26 | Porous metal body and method for producing the metal porous body |
| JP267591/93 | 1993-10-26 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1106079A true CN1106079A (en) | 1995-08-02 |
Family
ID=26528726
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 94113727 Pending CN1106079A (en) | 1993-09-14 | 1994-09-14 | Metallic porous sheet and method for manufacturing same |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1106079A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103443333A (en) * | 2011-04-08 | 2013-12-11 | 三井金属矿业株式会社 | Composite metal foil and production method therefor |
| CN104436867A (en) * | 2014-09-30 | 2015-03-25 | 成都易态科技有限公司 | Process for fabricating inorganic porous filtering element through asymmetric sintering |
| CN106159191A (en) * | 2011-02-28 | 2016-11-23 | 应用材料公司 | The method forming porous three-dimensional electrode microstructure |
| CN106521563A (en) * | 2016-10-31 | 2017-03-22 | 无锡职业技术学院 | Electric casting manufacturing device and process of carbon fiber reinforced metal |
| CN109628963A (en) * | 2019-01-22 | 2019-04-16 | 浙江工贸职业技术学院 | Galvanoplastic prepare the device and its processing technology of foam metal |
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1994
- 1994-09-14 CN CN 94113727 patent/CN1106079A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106159191A (en) * | 2011-02-28 | 2016-11-23 | 应用材料公司 | The method forming porous three-dimensional electrode microstructure |
| CN103443333A (en) * | 2011-04-08 | 2013-12-11 | 三井金属矿业株式会社 | Composite metal foil and production method therefor |
| CN103443333B (en) * | 2011-04-08 | 2016-08-03 | 三井金属矿业株式会社 | Composite metallic material and manufacture method thereof |
| CN104436867A (en) * | 2014-09-30 | 2015-03-25 | 成都易态科技有限公司 | Process for fabricating inorganic porous filtering element through asymmetric sintering |
| CN104436867B (en) * | 2014-09-30 | 2016-05-18 | 成都易态科技有限公司 | The preparation technology of the inorganic porous filter element of asymmetric sintering |
| CN106521563A (en) * | 2016-10-31 | 2017-03-22 | 无锡职业技术学院 | Electric casting manufacturing device and process of carbon fiber reinforced metal |
| CN106521563B (en) * | 2016-10-31 | 2018-12-28 | 无锡职业技术学院 | The electroforming manufacturing device and technique of carbon fiber reinforced metal |
| CN109628963A (en) * | 2019-01-22 | 2019-04-16 | 浙江工贸职业技术学院 | Galvanoplastic prepare the device and its processing technology of foam metal |
| CN109628963B (en) * | 2019-01-22 | 2020-01-07 | 浙江工贸职业技术学院 | Device for preparing foam metal by electroplating method and processing technology thereof |
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