CN1361311A - Foamed nickel material with superhigh binding force and its prepn - Google Patents
Foamed nickel material with superhigh binding force and its prepn Download PDFInfo
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- CN1361311A CN1361311A CN00126771A CN00126771A CN1361311A CN 1361311 A CN1361311 A CN 1361311A CN 00126771 A CN00126771 A CN 00126771A CN 00126771 A CN00126771 A CN 00126771A CN 1361311 A CN1361311 A CN 1361311A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The preparation process of foamed nickel material with superhigh binding force includes: preparation of conducting mold core through chemical nickel plating, painting conducting glue or vacuum filming; composite electric deposition and heat treatment in vacuum or protecting hydrogen atmosphere. The process of the present invention can raise the tensile strength and the adhesion strength of the foamed nickel material as well as the performance of cell. The material of the present invention is one ideal kind of positive and negative electrode material for high quality alkali cell and NiH power cell.
Description
The present invention relates to a kind of type material and preparation method thereof, be specifically related to a kind of novel foam nickel material that is different from regular foam nickel and preparation method thereof.
Regular foam nickel material such as spongy foam nickel material are for having mushy metallic nickel web plate, can be used as the collector of the positive and negative pole plate of battery and the carrier of active substance, when making the high tension battery battery lead plate, utilize these holes, plate active material is fully used, reduce the internal resistance of cell, the augmenting response area improves battery performance.The stretched state of the area density of foam nickel material and the hole count on the unit length and roll off mode, the course of processing all has a significant impact the tensile strength of this material.The regular foam nickel material is observed at enough magnification microscopicallies and is the smooth surface shape, rib surface is smooth, roughness is not enough, and when therefore making battery pole plates, the real surface of electrode active material contact is long-pending few, poorly conductive, internal resistance of cell height, active material utilization is on the low side, and the capacity of battery also may be on the low side, discharging current is difficult to be improved, so, influence battery performance, particularly cell size and nickel foam pole plate smooth surface bonding force are poor, electrode active material comes off from the nickel foam substrate surface easily, influence battery life, keep enough bonding forces, must increase caking agent as making smooth surface, reduce active substance, cause cell container to reduce.Therefore tensile strength, roughness, bonding force and the accepted product percentage of regular foam nickel all the utmost point wait to improve.
The present invention's purpose aims to provide a kind of nickel foam surface and the rib roughness is good, the long-pending adhesion strength of greatly, effectively improving electrode active material and foamed nickel substrate of real surface, improve cell container, reduction internal resistance, extending battery life, be specially adapted to high-quality alkaline cell and foamed nickel material with superhigh binding force and preparation method thereof of electric current Ni-MH power cell greatly.
Technical solution of the present invention is: this superhigh binding force type nickel foam is prepared from by following production technique: the thermal treatment under core rod conductionization-galvanic deposit-vacuumize or the nitrogen atmosphere protection; Described core rod conduction metallization processes can be (1) chemical nickel plating, (2) coated conductive resin, conducting medium can be a nickel powder, also can be graphite, carbon black, acetylene black etc., the granularity of conducting medium should be about 50 nanometers (nm) to 100 (the μ m), (3) vacuum plating, the metal of lining are nickel; Can to be that serialization is zonal work continuously in described galvanic deposit, also can be the block operation that is interrupted, and the major technique measure of making higher roughness in the nickel foam rib surface is a composite electrodeposition; Described thermal treatment be vacuumize or the atmosphere of hydrogen shield under carry out, thermal treatment temp is between 400-1300 ℃.
The present invention is a kind of type material that is different from regular foam nickel; the novel process of being heat-treated down by core rod conductionization-galvanic deposit-vacuumize or nitrogen atmosphere protection is prepared from; stretched state by the hole count on choose reasonable area density, the unit length, roll off mode, the course of processing etc.; effectively improve the vertical or horizontal tensile strength 4-40% of this material, the present invention doubly realizes superpower bonding force by the surface-area 3-10 that the roughness that improves the nickel foam rib surface significantly increases rib.Therefore, superhigh binding force type nickel foam of the present invention not only can reduce the slurry broken belt rate, make percent defective descend about 5%, and can effectively improve the adhesion strength of electrode active material and foamed nickel substrate, improve cell container 2.5%, reduce internal resistance more than 1%, improve battery life 25%, being specially adapted to heavy-current discharge, is Ni-MH power cell ideal positive electrode substrate and negative electrode substrate material.Outstanding substantive distinguishing features of the present invention and unusual effect are also relatively proved by following accompanying drawing:
Fig. 1 is conventional nickel foam rib metallographic enlarged view,
Fig. 2 is a superhigh binding force type nickel foam rib metallographic enlarged view of the present invention,
Fig. 3 is a coventional type nickel foam metallographic enlarged view
Fig. 4 is a superhigh binding force type nickel foam metallographic enlarged view of the present invention.
Can find out obviously that from above-mentioned accompanying drawing conventional nickel foam rib is smooth bright, poor with cell size and electrode active material bonding force, real surface is long-pending few, and rib roughness height of the present invention, bonding force is strong, simultaneously choose reasonable the hole count on area density and the unit length, effectively improve tensile strength.
Below the present invention is described in further detail:
The process for producing of this superhigh binding force type nickel foam is: the thermal treatment under core rod conductionization-galvanic deposit-vacuumize or the nitrogen atmosphere protection.
One, core rod conduction metallization processes can be (1) chemical nickel plating; (2) coated conductive resin, conducting medium can be nickel powders, also can be graphite, carbon black, acetylene black etc., the granularity of conducting medium should be about 50 nanometers (nm) about 100 microns (μ m); (3) vacuum plating, the metal of plating are nickel.
1, core rod can be a urethane, polyester type or polyether-type, this material is to have the macromolecular compound that contains many multiple-NH-C-O-group on main chain that forms behind the polyester polyol of two above hydroxyls or polyether glycol and vulcabond, water, tensio-active agent, catalyzer and other additive polymerization reaction take places by end, is commonly called as polyurethane sponge.Core rod also can be the Web materials of man-made fiber such as nylon, polypropylene or cotton fibre textiles.Core rod can be above-mentioned sponge or net material individual layer, also bilayer or the multilayer that can be made up of them, for example net material-sponge-net material, or sponge-net material-sponge.
2, the chemical nickel plating in the core rod conduction metallization processes:
Core rod must degrease, alligatoring, hydrophilic, sensitization, activation etc. handle in earlier stage before chemical nickel plating, and the quality with the protection chemical nickel plating can be carried out subsequent technique smoothly.
Degrease: can be undertaken by the general technology that metal or nonmetallic surface are handled, treatment agent of selecting and concentration can be for following several: hydrogen sodium hydride 10-50g/L, yellow soda ash 10-50g/L, tertiary sodium phosphate 4-25g/L and water glass 2-15g/L, tensio-active agent OP emulsifying agent 1-5g/L.
Alligatoring: be the important procedure step of the core surface state being carried out modification, can adopt acidic medium to handle, as chromic anhydride 2-50g/L, hydrogen peroxide 2-30g/L, potassium permanganate 1-100g/L, Neutral ammonium fluoride 1g/L and the phosphoric acid below the 10g/L, sulfuric acid, acetic acid, hydrochloric acid.
Hydrophilic: hydrophilic treatment can be carried out synchronously with alligatoring, also can carry out separately, the core rod of selection after to alligatoring has the cats product of excellent hydrophilic to handle, as the alkylamine salt below the 30g/L, amino alcohol lipid acid, polyamines lipid acid pyridine, and amphoterics, as L-Ala, glycine, nonionic surface active agent such as polyoxyethylene glycol etc.
Sensitization: be that hydrochloric acid mixed solution with tin protochloride below the 20g/L and 100mL/L (37%) continues to handle.
Activation: activation separates subtype and colloidal palladium type, and ionic divides silver ions type, palladium ion type and gold ion type again.Silver ions type: handle with Silver Nitrate below the 100g/L and the ammonia water mixture of 120mL/L (25%); The palladium ion type is that the following acid organism complexing agent of the following Palladous chloride of 0.5g/L, the following hydrochloric acid of 20mL/L, the following boric acid of 30g/L and 5g/L is handled; The gold ion type is the above hydrochloro-auric acid (HAuCL of 1g/L
4.4H
2O) and the following hydrochloric acid mixed solution of 10g/L handle, the working temperature of above-mentioned ionic activation solution is all below 50 ℃, the treatment time is below 20 minutes.
The colloidal palladium type is that sensitization and activation procedure are merged into a procedure, thereby improves the adhesive ability of palladium ion to working-surface.
Colloidal palladium solution is prepared with following method:
1.5g/L following Palladous chloride (PdCl
2), the tin protochloride (SnCl that 10g/L is following
2.2H
2O), the hydrochloric acid (HCl) that 350ml/L is following, the sodium stannate (Na that 10g/L is following
2SnO
3.3H
2O), temperature is below 50 ℃, treatment time 1-30min; Or
The Palladous chloride that 1g/L is following, the following tin protochloride of 50g/L, the hydrochloric acid of 350ml/L, temperature is below 60 ℃, treatment time 1-10min; Or
Stoste is the following Palladous chloride of 0.5g/L, the tin protochloride that 10g/L is following, 200ml/L hydrochloric acid, 250g/L sodium-chlor (NaCl), 50g/L urea (CO (NH
2)
2), 1g/L sodium stannate, 2g/L Resorcinol (C
6H
6O
2), temperature is handled 1-10min below 50 ℃.Additional liquid is the 1g/L Palladous chloride, 10g/L tin protochloride, 100ml/L hydrochloric acid, 200g/L sodium-chlor and 50g/L urea.
Core rod after above-mentioned operation is handled carries out chemical nickel plating to be handled, because the core rod of selecting for use mostly is organic materials, for preventing high temperature deformation, chemical nickel plating is often selected middle subzero treatment solution for use.The common chemical nickel plating solution is the following single nickel salt (NiSO of 30g/L
4.7H
2O), the following inferior sodium phosphate (NaH of 25g/L
2PO
2.H
2O), the following Trisodium Citrate (Na of 60g/L
3C
6H
5O
7.2H
2O), temperature is below 50 ℃, treatment time 1-10min.
3, the coated conductive resin in the core rod conduction metallization processes:
Core rod also can adopt the mode conduction processing of coated conductive resin, conductive resin is by conducting medium, binding agent and solvent composition, conducting medium is used electrically conductive graphite, acetylene black nickel powder always, binding agent is Synolac, acrylic resin, polypropylene, polyurethane adhesive etc., and solvent is acetone, ethanol, trichloromethane etc.
The coated mode of conductive resin can be dip-coating, also can be spraying, and the core rod of coated conductive resin needs to dry in 30 ℃ of-60 ℃ of temperature environments.
Core rod is the coated conductive resin directly, also can carry out aforesaid roughening treatment before being coated with conductive resin.
4, the vacuum plating in the core rod conduction metallization processes:
Core rod also can adopt the mode conduction processing of vacuum plating, and vacuum plating can directly be carried out in core surface, also can carry out after core rod is carried out aforesaid roughening process.
Vacuum plating divides thermal evaporation plating, cathode sputtering and ion plating; Cathode sputtering divides two kinds of radio-frequency sputtering and magnetron sputterings again; Ion plating divides direct-current ion plating (DC method), hallow cathode deposition, HCD (HCD method), high frequency ion plating (RF method), atomic ion plating and arc discharge ion plating again.
The configuration of surface complexity of core rod in this patent, its conductionization processing can realize by the spirally wound continuous magnetron sputtering, also can realize by arc ion plating.
When selecting spirally wound continuous magnetron sputtering technique for vacuum coating for use, equipment adopts two chamber systems, vacuum time variable control, constant tension winding, efficient cooling, the workpiece fabric width 1200mm that rectifies a deviation automatically, thickness 0.5-2.5mm, workpiece walking speed 0.5-10 rice/min.Vacuum system realizes working vacuum degree 6 * 10 by lobe pump, oil diffusion pump and sliding vane rotary pump
-3-5 * 10
-4Holder, final vacuum 10
-6Holder recovers vacuum time≤20min.For reducing the influence of volatile gases that core rod may exist to coating equipment vacuum tightness, before carrying out magnetron sputtering, core rod will carry out the degasification of long period, and special-purpose degasifying device is made up of diffusion pump stage, injection pump stage, topping-up pump, maintenance pump, gas ballast rotary pump and bypass duct.
When selecting electric arc vacuum ion plating membrane process for use, select to be generally between the 200-1000mm than bigger workpiece of magnetron sputtering and the distance between the nickel target, the vacuum tightness of coating chamber is on the low side relatively, and vacuum tightness is 5 * 10
-2-8 * 10
-3Holder.The general selection of nickel palladium is a plurality of, and the nickel dam quality of arc ion plating is all superior than magnetron sputtering at the aspects such as adhesive ability of covering power, surface resistivity and square resistance, coating and matrix.But energy consumption may be bigger.
The technical process of magnetron sputtering and arc ion plating is as follows:
Prepare in (degreasing or alligatoring) → deaerating chamber let off roll degasification → dress roller before the plating and adjust let off roll and go into vacuum film coating chamber → vacuumize → enter argon gas → moving-mould-core tape transport → magnetron sputtering or arc ion plating → stop sputter → the enter encapsulation of atmosphere → taking-up wind-up roll → conductionization core rod.
Two, electrodeposition technology: the core rod through chemical nickel plating, after being coated with conductive resin and the processing of vacuum plating conductionization will carry out electroforming in special galvanic deposit mode, form superhigh binding force type nickel foam.
The galvanic deposit mode can be the zonal mode of working continuously of serialization, also can be the block mode of operation that is interrupted, and the major technique measure that forms higher roughness in the nickel foam rib surface is a composite electrodeposition.
Special-purpose electrodeposition apparatus and conventional serialization strip foaming nickel are similar, conventional equipment such as Chinese patent 98230333.5 described " the whole plating tank of serialization strip foaming nickel ".Galvanic deposit specific equipment of the present invention need be equipped with pneumatic blending and mechanical stirring device on the high Lower tank in conventional equipment, in the systemic circulation process of solution matrix material is suspended in the nickel plating solution equably.
The processing parameter of galvanic deposit tank liquor of the present invention is as follows:
1, sulfamate type:
Nickel sulfamic acid (Ni (NH
2SO
3)
2.4H
2O) 250-600g/L
Nickelous chloride (NiCl
2.6H
2O) 5-20g/L
Sodium Fluoride (NaF) 1-5g/L
Boric acid (H
3BO
3) 20-50g/L
Composite particles amount 30-150g/L
Particle size 50nm-100um
PH： 3-3.5
Temperature: 40-50 ℃
Fraction of particle 1-5% (quality) 1-10% (volume) in the coating
2, sulfate type
Single nickel salt (NiSO
4.7H
2O) 200-300g/L
Nickelous chloride (NiCl
2.6H
2O) 15-45g/L
Boric acid (H
3BO
3) 30-50g/L
Composite particles amount 30-150g/L
Particle size 50nm-100um
PH： 3-4.4
Temperature: 40-50 ℃
Fraction of particle 1-5% (quality) 1-20% (volume) in the coating
Except that nickel, also comprise other metals and non-metal particle in the above-mentioned composite electrodeposition layer of the present invention, the granularity of these particulates in 50 nanometers (nm) between 100 microns (μ m).The kind of metal particle comprise oxide compound, the nickel of nickel, nickel oxycarbide, cobalt, cobalt oxide compound and can be at the organic fine particles that is gasified totally below 500 ℃.This particulate both can form composite deposite with nickel, can not produce electrolytic solution again and pollute, as powders such as tetrafluoroethylene, PVC, polypropylene.
Three, thermal treatment process: this technological process should be vacuumize or the atmosphere of hydrogen shield under carry out, between thermal treatment temp 400-1300 ℃, burn core rod, make foamed nickel material with superhigh binding force.
Claims (9)
1, a kind of foamed nickel material with superhigh binding force and preparation method thereof is characterized in that being prepared from by following production technique: the thermal treatment under core rod conductionization-galvanic deposit-vacuumize or the nitrogen atmosphere protection; Described core rod conduction metallization processes can be (1) chemical nickel plating; (2) coated conductive resin, conducting medium can be nickel powders, also can be graphite, carbon black, acetylene black, the granularity of conducting medium should be about 50 nanometers (nm) about 100 microns (μ m); (3) vacuum plating, the metal of plating are nickel; Can to be that serialization is zonal work continuously in described galvanic deposit, also can be the block operation that is interrupted, and the major technique measure of making higher roughness in the nickel foam rib surface is a composite electrodeposition; Described thermal treatment be vacuumize or the atmosphere of hydrogen shield under carry out, thermal treatment temp is between 400-1300 ℃.
2, foamed nickel material with superhigh binding force according to claim 1 and preparation method thereof, it is characterized in that core rod can be urethane, polyester type or polyether-type, this material is polyester polyol or polyether glycol and the vulcabond ester that is had two above hydroxyls by end, water, tensio-active agent, the macromolecular compound that on main chain, contains many multiple-NH-C-O-group that forms behind catalyzer and other additive polymerization reaction take places, be commonly called as polyurethane sponge, core rod also can be a nylon, the Web materials of man-made fiber such as polypropylene or cotton fibre textiles.Core rod can be above-mentioned sponge or net material individual layer, also bilayer or the multilayer that can be made up of them.
3, foamed nickel material with superhigh binding force according to claim 1 and preparation method thereof, it is characterized in that in the described core rod conduction metallization processes, core rod is before chemical nickel plating, must degrease, alligatoring, hydrophilic, sensitization, activation treatment, alligatoring can adopt acidic medium to handle, these acidic mediums have chromic anhydride, hydrogen peroxide, potassium permanganate, Neutral ammonium fluoride and phosphoric acid, sulfuric acid, acetic acid, hydrochloric acid, hydrophilic treatment can be carried out synchronously with alligatoring, also can carry out separately, the core rod of selection after to alligatoring has the cats product of good hydrophilicity to handle, sensitization is to handle with tin protochloride and hydrochloric acid mixed solution, activation separates subtype and colloidal palladium type, ionic divides the silver ions type again, palladium ion type and gold ion type, the silver ions type adopts Silver Nitrate and ammonia water mixture, the palladium ion type is a Palladous chloride, hydrochloric acid, boric acid and acid organism complexing agent, the gold ion type is a hydrochloro-auric acid, hydrochloric acid mixed solution, the working temperature of above-mentioned ionic activation solution is all below 50 ℃, and the treatment time is below 20 minutes; The colloidal palladium type is sensitization and activation procedure to be merged into a procedure handle.
4, foamed nickel material with superhigh binding force according to claim 3 and preparation method thereof, it is characterized in that colloidal palladium solution can be prepared by following manner in the preceding activation treatment of described core rod chemical nickel plating: Palladous chloride, tin protochloride, hydrochloric acid sodium stannate or Palladous chloride, tin protochloride, hydrochloric acid or stoste are Palladous chloride, tin protochloride, hydrochloric acid, sodium-chlor, urea, sodium stannate, Resorcinol, and additional liquid is Palladous chloride, tin protochloride, hydrochloric acid, sodium-chlor and urea.
5, foamed nickel material with superhigh binding force according to claim 1 and preparation method thereof is characterized in that the chemical nickel plating in the core rod conduction metallization processes is selected middle subzero treatment solution for use, and solution compolision is the following single nickel salt (NiSO of 30g/L
4.7H
2O), the following inferior sodium phosphate (NaH of 25g/L
2PO
2.H
2O), the following Trisodium Citrate (Na of 60g/L
3C
6H
5O
7.2H
2O), temperature is below 50 ℃, treatment time 1-10min.
6, foamed nickel material with superhigh binding force according to claim 1 and preparation method thereof, it is characterized in that the coated conductive resin in the core rod conduction metallization processes, conductive resin is by conducting medium, binding agent and solvent composition, conducting medium can be a nickel powder, also can be graphite, carbon black, acetylene black, binding agent is the alkyd resin, acrylic resin, polypropylene, polyurethane adhesive, solvent is an acetone, ethanol, trichloromethane, the coated mode of conductive resin can be dip-coating, also can be spraying, the core rod of coated conductive resin needs to dry in 30 ℃ of-60 ℃ of temperature environments.
7, foamed nickel material with superhigh binding force according to claim 1 and preparation method thereof is characterized in that described vacuum plating divides thermal evaporation plating, cathode sputtering and ion plating; Cathode sputtering divides two kinds of radio-frequency sputtering and magnetron sputterings again; Ion plating divides direct-current ion plating (DC method), hallow cathode deposition, HCD (HCD method), high frequency ion plating (RF method), atomic ion plating and arc discharge ion plating again; When selecting spirally wound continuous magnetron sputtering technique for vacuum coating for use, equipment adopts two chamber systems, the vacuum time variable control, constant tension winding, efficient cooling, the workpiece fabric width 1200mm that rectifies a deviation automatically is before carrying out magnetron sputtering, core rod will carry out the degasification of long period, and special-purpose degasifying device is made up of diffusion pump stage, injection pump stage, topping-up pump, maintenance pump, gas ballast rotary pump and bypass duct; When selecting electric arc vacuum ion plating membrane process for use, select to be generally between the 200-1000mm than bigger workpiece of magnetron sputtering and the distance between the nickel target, vacuum tightness is 5 * 10
-2-8 * 10
-3Holder.It is a plurality of that the nickel palladium is selected, and the technical process of above-mentioned magnetron sputtering and arc ion plating is as follows: prepare in (degreasing or alligatoring) → deaerating chamber let off roll degasification → dress roller before the plating and adjust let off roll and go into vacuum film coating chamber → vacuumize → enter argon gas → moving-mould-core tape transport → magnetron sputtering or arc ion plating → stop sputter → the enter encapsulation of atmosphere → taking-up wind-up roll → conductionization core rod.
8, foamed nickel material with superhigh binding force according to claim 1 and preparation method thereof, it is characterized in that described galvanic deposit is a composite electrodeposition, its specific equipment is equipped with pneumatic blending and mechanical stirring device on high Lower tank, the processing parameter of galvanic deposit tank liquor is as follows:
(1), sulfamate type:
Nickel sulfamic acid (Ni (NH
2SO
3)
2.4H
2O) 250-600g/L
Nickelous chloride (NiCl
2.6H
2O) 5-20g/L
Sodium Fluoride (NaF) 1-5g/L
Boric acid (H
3BO
3) 20-50g/L
Composite particles amount 30-150g/L
Particle size 50nm-100um
PH： 3-3.5
Temperature: 40-50 ℃
Fraction of particle 1-5% (quality) 1-10% (volume) in the coating
(2), sulfate type
Single nickel salt (NiSO
4.7H
2O) 200-300g/L
Nickelous chloride (NiCl
2.6H
2O) 15-45g/L
Boric acid (H3BO3) 30-50g/L
Composite particles amount 30-150g/L
Particle size 50nm-100um
PH： 3-4.4
Temperature: 40-50 ℃
Fraction of particle 1-5% (quality) 1-20% (volume) in the coating
9, foamed nickel material with superhigh binding force according to claim 1 and preparation method thereof, it is characterized in that in the described electrodeposition technology, except that nickel, also comprise other metals and non-metal particle in the composite electrodeposition layer, the kind of metal particle comprise oxide compound, the nickel of nickel, nickel oxycarbide, cobalt, cobalt oxide compound and can be at the organic fine particles that is gasified totally below 500 ℃, as tetrafluoroethylene, PVC, polypropylene powder.
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|---|---|---|---|
| CNB00126771XA CN1152159C (en) | 2000-12-28 | 2000-12-28 | Foamed nickel material with superhigh binding force and its prepn |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB00126771XA CN1152159C (en) | 2000-12-28 | 2000-12-28 | Foamed nickel material with superhigh binding force and its prepn |
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|---|---|
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| CN1152159C CN1152159C (en) | 2004-06-02 |
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ID=4592061
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2000
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