CN1185735C - Plate of nickel cell and preparation method thereof - Google Patents
Plate of nickel cell and preparation method thereof Download PDFInfo
- Publication number
- CN1185735C CN1185735C CNB021007357A CN02100735A CN1185735C CN 1185735 C CN1185735 C CN 1185735C CN B021007357 A CNB021007357 A CN B021007357A CN 02100735 A CN02100735 A CN 02100735A CN 1185735 C CN1185735 C CN 1185735C
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- CN
- China
- Prior art keywords
- nickel
- battery
- polar plate
- foaming
- plate material
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- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 183
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 93
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000000463 material Substances 0.000 claims abstract description 44
- 238000005187 foaming Methods 0.000 claims abstract description 35
- 238000000034 method Methods 0.000 claims abstract description 22
- 229910000990 Ni alloy Inorganic materials 0.000 claims abstract description 18
- 230000008569 process Effects 0.000 claims abstract description 8
- 238000004070 electrodeposition Methods 0.000 claims abstract description 7
- 239000000956 alloy Substances 0.000 claims description 27
- 229910045601 alloy Inorganic materials 0.000 claims description 22
- 229910000831 Steel Inorganic materials 0.000 claims description 21
- 239000010959 steel Substances 0.000 claims description 21
- 239000004033 plastic Substances 0.000 claims description 19
- 229920003023 plastic Polymers 0.000 claims description 19
- 238000004519 manufacturing process Methods 0.000 claims description 16
- 229910052802 copper Inorganic materials 0.000 claims description 11
- 239000010949 copper Substances 0.000 claims description 11
- 239000010936 titanium Substances 0.000 claims description 11
- 229910052719 titanium Inorganic materials 0.000 claims description 11
- 229910052751 metal Inorganic materials 0.000 claims description 10
- 229910001069 Ti alloy Inorganic materials 0.000 claims description 9
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 9
- 239000011701 zinc Substances 0.000 claims description 8
- 229910052725 zinc Inorganic materials 0.000 claims description 8
- 230000011218 segmentation Effects 0.000 claims description 7
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- 239000006260 foam Substances 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 238000000137 annealing Methods 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 4
- -1 nickel aluminum titanium Chemical compound 0.000 claims description 4
- JGEPRYWSGIOOSM-UHFFFAOYSA-N [Ni].[Ti].[Zn] Chemical compound [Ni].[Ti].[Zn] JGEPRYWSGIOOSM-UHFFFAOYSA-N 0.000 claims description 3
- 150000003841 chloride salts Chemical class 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims 1
- 238000000151 deposition Methods 0.000 claims 1
- 230000008021 deposition Effects 0.000 claims 1
- 239000011148 porous material Substances 0.000 claims 1
- 238000009713 electroplating Methods 0.000 abstract description 5
- 230000007547 defect Effects 0.000 abstract 1
- 230000002349 favourable effect Effects 0.000 abstract 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 13
- 239000000243 solution Substances 0.000 description 13
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 7
- 229910052742 iron Inorganic materials 0.000 description 7
- 238000007747 plating Methods 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 230000007797 corrosion Effects 0.000 description 6
- 238000005260 corrosion Methods 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 6
- 241000080590 Niso Species 0.000 description 5
- 238000003860 storage Methods 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 229910003307 Ni-Cd Inorganic materials 0.000 description 4
- 229910018095 Ni-MH Inorganic materials 0.000 description 4
- 229910018477 Ni—MH Inorganic materials 0.000 description 4
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 230000018109 developmental process Effects 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 150000002815 nickel Chemical class 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- QELJHCBNGDEXLD-UHFFFAOYSA-N nickel zinc Chemical compound [Ni].[Zn] QELJHCBNGDEXLD-UHFFFAOYSA-N 0.000 description 3
- 238000004080 punching Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000006399 behavior Effects 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 229960001484 edetic acid Drugs 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000010295 mobile communication Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 description 1
- 208000032953 Device battery issue Diseases 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- RGHNJXZEOKUKBD-SQOUGZDYSA-N Gluconic acid Natural products OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 229910018487 Ni—Cr Inorganic materials 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- VNNRSPGTAMTISX-UHFFFAOYSA-N chromium nickel Chemical compound [Cr].[Ni] VNNRSPGTAMTISX-UHFFFAOYSA-N 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- CEYULKASIQJZGP-UHFFFAOYSA-L disodium;2-(carboxymethyl)-2-hydroxybutanedioate Chemical compound [Na+].[Na+].[O-]C(=O)CC(O)(C(=O)O)CC([O-])=O CEYULKASIQJZGP-UHFFFAOYSA-L 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000000174 gluconic acid Substances 0.000 description 1
- 235000012208 gluconic acid Nutrition 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000007788 roughening Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
Landscapes
- Cell Electrode Carriers And Collectors (AREA)
Abstract
The present invention relates to material of a polar plate of a nickel battery and a preparation method thereof. The material of the polar plate of the nickel battery is made of foaming nickel alloy. The nickel alloy contains 5% to 50% of nickel. Based on the existing electrodeposition process, the method of the material of the polar plate of the nickel battery adopts a segment voltage boosting electroplating method. The polar plate of the nickel battery, which is provided by the present invention, greatly reduces the cost of the polar plate and simultaneously keeps the original good performance of the nickel polar plate. In addition, the present invention improves the defect of poor resistance to high temperature of the original nickel polar plate and increases mechanical properties and electric conductive performance of the polar plate. The segment voltage boosting electroplating method of the preparation method which is provided by the present invention provides reliable assurance for obtaining the foaming nickel alloy with uniform tissue and contents, effectively reduces the cost of the nickel battery and makes contribution to the popularization of the green energy resource which is favorable to environment protection.
Description
Technical field
The present invention relates to the battery material field, relate in particular to plate material of a kind of nickel-based battery and preparation method thereof.
Back of the body amount technology
Storage battery is a kind of very ancient power source, and it is outstanding widely-used as power three with steam, gasoline at the 19th-century end, even also is applied in the driving of vehicle.From the environmental protection aspect, battery has bigger superiority than other two kinds of power sources, still, because the problem of storage battery itself is treated coldly it gradually in competition.The reason of storage battery failure in competing with the energy of other type is hanged down except specific energy (energy that Unit Weight or volume provide) and specific power (power that Unit Weight or volume provide) is low reaches the weak point in useful life, and a very important problem costs an arm and a leg exactly.Along with the constant growth of productivity, the energy resource structure based on gasoline has produced ill effect to environment now, and people have rediscovered storage battery when seeking substitute.
Storage battery roughly can be divided into four kinds: the most ancient lead-acid battery and the nickel series rechargeable battery that comprises NI-G, ni-mh, nickel zinc etc. also have lithium battery and fuel cell in addition.
Nickel such as NI-G, ni-mh, nickel zinc series rechargeable battery is as typical case's representative of chemical energy source, has characteristics such as small-sized, high energy, zero discharge.Since the 1980s, at first,, the mobile communication industry development provides the energy and power for entering huge numbers of families as the energy of mobile communication, and the mankind have entered communication and information age thus.Since middle 1990s, scientist and enterpriser make joint efforts, and have developed batteries such as super high power ni-mh jointly, as the drive energy of the vehicles such as automobile, motorcycle, have obtained tremendous development.
Although lithium ion battery, fuel cell launch in countries in the world as the research of automobile batteries, but nickel series batteries such as ni-mh, nickel zinc are pollution-free with it, high-performance, long-life, advantage such as be fit to composite characteristic such as heavy-current discharge and technology is ripe relatively, price is low, fail safe is good will be the commercialization main flow of automobile batteries in the period of quite growing from now on.
Yet, the development of world's nickel-based battery is faced with a major challenge, its performance of market demands that Here it is expands on the one hand day by day improves constantly, increasingly competitive market trend but requires the market price of nickel-based battery to reduce significantly simultaneously, and how balance quality improves the bottleneck problem that the contradiction that reduces with price becomes the nickel-based battery development.
Decision battery manufacturing cost is mainly two big factors: the cost of battery material, the manufacturing process of battery and scale.Wherein, the cost of battery material is particularly important.
Main four parts of the material of battery: positive electrode, negative material, plate material and diaphragm material, wherein plate material shared cost ratio maximum in entire cell.Therefore, plate material is the focus that reduces the battery cost study.
Plate material is the carrier (skeleton) of cell active materials and discharges and recharges collector.As the pole plate of electrokinetic cell, require to have following performance:
Conductivity: resistance is the smaller the better, with internal resistance, the reduction in-fighting that reduces battery.
Fillibility: the filling active material is The more the better, helps making the heap(ed) capacity battery.
Volume: pole plate does not increase battery capacity, under battery size one stable condition, requires the pole plate volume the smaller the better, promptly gets over Bao Yuehao.
In history, nickel is that multiple pole plate was successively used in the production of battery:
Before 1985, nickel be battery mainly with sintering method production, bipolar pole plate mainly adopts the porous steel strip of punching.
After 1985, it is battery that the two bubble formula methods of PANASONIC invention are produced nickel, make the two poles of the earth pole plate with foaming nickel, realized that nickel is the miniature and high power capacity ratio of battery, but this pole plate price is too high, and high-temperature behavior is poor, be not suitable for the production of macrocell, the plate materials such as foaming nickel of commercialization not only do not possess the required heavy-current discharge performance of electrokinetic cell, and account for more than 20% of battery cost, do not meet the road of the cost degradation of battery manufacturing.
After 1997, it is the negative plate of battery as nickel that PANASONIC at first utilizes porous steel strip, but positive pole nickel occurs and be single bubble production technology of battery, and use till today always still with foaming nickel, and for world's nickel be Battery Plant's extensive use.This technology has not only reduced manufacturing cost, and part has improved the high-power charge-discharge performance of battery., also developed plate materials such as nickel strap, nickel felt, copper strips therebetween,, do not become the market mainstream eventually because of cost and property relationship.Therefore, nickel is that the plate material of battery has formed positive pole-foaming nickel, the market mainstream of negative pole-porous steel strip.
Table
1The Cost And Performance characteristics of multiple commercially available plate material have been enumerated
Table
1Various plate material prices
| Plate material | Price (unit/m2) | Design feature | High-temperature behavior | Fillibility | Use |
| Foaming nickel | The block 70-80 of continuous 90-100 | Three-dimensional | Generally | Fabulous | Ni-MH Ni-Cd just/the negative pole band |
| The nickel felt | 150-180 | Two dimension is between the three-dimensional | Generally | Very | Ni-MH Ni-Cd just/the negative pole band |
| Nickel strap | 0.06mm thick 70-80 | Two dimension | Good | Better | Ni-MH Ni-Cd negative pole band |
| Copper strips | 0.02-0.04mm thick 30-40 | Two dimension | Generally | Better | Lithium |
| Punching steel strip | 0.06mm thick 20-25 | Two dimension | Excellent | Better | Ni-MH Ni-Cd negative pole band |
By above-mentioned contrast as can be known, the good really plate material of foaming nickel, but its cost is too high, and resistance to elevated temperatures is poor, and it is made powerful electrokinetic cell and also has defective.
Summary of the invention
The objective of the invention is to improve the deficiencies in the prior art, provide a kind of and have equal good fillibility and chemical property such as discharge and recharge, but cost reduces significantly, have the nickel-based battery plate material of resistance to elevated temperatures preferably simultaneously with foaming nickel; Another object of the present invention provides the preparation method of above-mentioned plate material.
The object of the present invention is achieved like this:
Nickel-based battery plate material provided by the invention is the nickel-containing alloys of foaming or claims the foaming nickel alloy that wherein the content of nickel is in 5.0～50% (percetages by weight).
The voidage of described foaming nickel alloy material is preferably in more than 90%.
Described nickel alloy can be the nickel-containing alloys steel, also can be nickel aluminum titanium alloy steel or nickel zinc titanium alloy steel or ambrose alloy titanium alloy steel.
Metal is the power battery plate body of material owing to have good conductivity.In all metals, iron and steel has least cost, therefore select for use iron and steel to make pole plate, carry out structural design, crystal inside tissue and surface modification, make it the conductivity, resistance to elevated temperatures except that fillibility, Punching steel strip with foaming nickel, also have excellent mechanical property and chemical property, can reduce the plate material price significantly.But general iron and steel decay resistance is relatively poor, can not directly be used for battery pole plates.Nickel is why selected to be exactly that it has excellent corrosion resistance as plate material, but learn according to production experience in the past, obtain outstanding corrosion resistance, it is not certain pure nickel of using, a large amount of nickeliferous alloy in the prior art, all have good corrosion resistance such as nickel and stainless steel and nickel chromium stainless steel etc., adapt to the residing corrosive atmosphere of battery pole plates fully.But general nickel and stainless steel its not possess the most important characteristic of pole plate be fillibility, but they are carried out structural change, make it to have the high voidage as foaming nickel, its fillibility just can improve.
Iron is the stock element of material of the present invention, adds nickel and makes dilval, makes it possess Corrosion Protection.The content of nickel is high more, and corrosion resistance is strong more, but cost is also high more, therefore, needs only the corrosion of ability nickel-based battery environment, should control the content of nickel as far as possible.
The zone of reasonableness of the content of nickel in this nickel-based battery plate material is 5.0～50%, and optimum value is 10～20%.
For intensity, ductility and the conductivity that improves dilval, can add a certain amount of other metallic element, as metals such as Ti, Cu, Al.
The adding of titanium can improve the intensity of alloy.The content of titanium in this nickel-based battery plate material preferably is controlled in 1%, so that this plate material keeps cheap cost when having enough intensity.
The adding of Cu, Zn, Al can improve its ductility and conductivity.Cu, Zn, Al can add respectively also can add wherein any two kinds simultaneously.Also can add above-mentioned three kinds of metallic elements simultaneously.Described Cu, Zn, every kind of addition of Al can be 1.0～10%, and the best is 5～10%.
The preparation technology of the foaming nickel alloy as the nickel-based battery plate material of the present invention is similar with the preparation technology of foaming nickel, and the preparation method of the nickel that foams in the prior art has sintering process, foaming, vacuum phase sedimentation and electrodeposition process.The preparation technology of foaming nickel-containing alloys of the present invention uses for reference electrodeposition process.Its main process is: prepare a conductive layer earlier on Foam Plastic Surface, be placed on then in the solution of the sulfate of metals such as Fe, Ni or chloride salt and carry out electro-deposition, take off aforesaid foamed plastics and finished product foaming nickel-containing alloys of the present invention is just made in annealing through burning again.
Processing stainless steel foams of the present invention, alloying element is more in the electroplate liquid in plating, if the electro-plating method with prior art adopts one section of constant voltage, the constant current plating of boosting at the very start, so, some metal will preferentially be attached on the matrix, consequently makes the electrodeposited coating composition everywhere that obtains inconsistent.Will preferentially adhere to as the ferro element in the electroplate liquid of the present invention, nickel to adhere to speed then slack-off.The characteristics of processing method provided by the invention are to adopt the segmentation electro-plating method that boosts, and can prevent the appearance of the problems referred to above so effectively.Institute's segments is preferably three sections in the described segmentation step-up method.
The pole plate of nickel-based battery provided by the invention becomes the nickel-containing alloys of pure nickel into foaming, when having kept the original superperformance of nickel pole plate, greatly reduce the cost of pole plate, in addition, owing in pole plate, added more iron, improved the low defective of original nickel pole plate resistance to elevated temperatures.Further, in this pole plate, add mechanical performance and the conductivity that some metallic elements have improved this pole plate in addition.The manufacture method of above-mentioned pole plate provided by the invention; especially wherein segmentation is boosted, and galvanoplastic are organized acquisition and the nickel-containing alloys of the uniform foaming of content provides reliable assurance; for reducing the cost of nickel-based battery effectively, make this popularization that helps the green energy resource of environmental protection make contribution.
Description of drawings
Fig. 1 is the sectional structure schematic diagram of the nickel-containing alloys pole plate of foaming provided by the invention
Embodiment
Embodiment 1:
Nickel-based battery plate material 1 provided by the invention is the nickel-containing alloys of foaming, and wherein the content of nickel is in 10～20% (percetages by weight).
Battery electrode 1 inside has many holes 2, and its voidage is preferably in 95%.
Described nickel alloy is the nickel-containing alloys steel,
The concrete steps of its manufacturing are as follows:
A, foamed plastics is carried out roughening treatment
Foamed plastics is that the three-dimensional structure of the high hole in the foaming nickel-containing alloys in the future produces the source, and obtain the good plate material of porous nickel, mechanical property and chemical property will carry out degreasing, de-oiling to foam, be beneficial to the plating of subsequent handling.
A, compound concentration are that the potassium permanganate solution and the concentration of 1.2-1.5 grams per liter is every liter of sulfuric acid solution that contains concentrated sulfuric acid 5-6 milliliter, with above-mentioned two kinds of aqueous solution;
B, the raw material foamed plastics was soaked 5-10 minute in above-mentioned mixed solution, take out then;
C, be oxalic acid (or other weak acid such as acetic acid, phosphoric acid) reduction 1-30 minute of 1-3 grams per liter with the foamed plastics concentration in preceding step;
D, after above-mentioned coarsening process is finished, can also carry out the secondary alligatoring again, remove the grease on the Foam Plastic Surface more up hill and dale;
E, compound concentration are the chromic anhydride aqueous solution and every liter of sulfuric acid solution that contains concentrated sulfuric acid 1-5 milliliter of 1.0-3.0 grams per liter, and the chromic anhydride aqueous solution and sulfuric acid solution are mixed;
F, will place above-mentioned solution to soak 10-20 hour, take out then through the foamed plastics of an alligatoring;
G, be that 2 milliliters/liter hydrochloric acid solution washed 1-2 minute with the foamed plastics concentration in preceding step.
B, foamed plastics is carried out sensitization handle
A, compound concentration are the SnCl of 30 ± 5 grams per liters
22H
2The O aqueous solution;
B, place above-mentioned solution to soak 5-15 minute the foamed plastics in preceding step, take out then;
C, water washed 5-10 minute the foamed plastics in preceding step;
C, foamed plastics is carried out chemical plating handle
A, preparation NiSO
47H
2O5-10g/L, natrium citricum 5-10g/L NH
4Cl20-30g/L, inferior sodium phosphate 20-30g/L, FeSO
47H
2O15-30g/L is heated to 40 ± 5 ℃ again with its mixing then, makes its PH at 8.3-8.5;
B, place above-mentioned mixed solution to soak 20-30 minute the foamed plastics in preceding step, take out then.
D, electro-deposition
Adopt the mixing electroplate liquid of metallic iron and nickel to electroplate, typical solution is as follows:
NiSO
4·7H
2O 10-20g/L
FeSO
4·7H
2O 100-200g/L
NiCl
2·6H
2O 5-10g/L
FeCl
2·6H
2O 50-100g/L
NaCl 30-35g/L
NH
4Cl 30-40g/L
H
3BO
3 30-50g/L
Citric acid 15-25g/L
Gluconic acid 10-30g/L
EDTA (ethylenediamine tetra-acetic acid) 1-5g/L
Above-mentioned substance is made into electrolyte, and adjusting its pH value is 4.5～6.0, and keeps its temperature at 40～60 ℃.To place above-mentioned electrolyte to carry out the segmentation plating of boosting by the intermediate that chemical plating is handled, the described segmentation process of boosting is divided three sections at least.
Electrolyte with regard to above-mentioned prescription can take branch to boost for four sections when electroplating:
Its system of boosting is: 1.3V 20-25 minute
2.6V 15 minutes
3.9V 10 minutes
4.12V constant current (500-600A)
The PH=4.5-6.0 of electroplate liquid during plating, temperature is at 40-60 ℃.
E, burning
Carry out continuous burning on meshbeltfurnace, the speed of service of material piece is controlled at 3-5 rice/minute be advisable.
F, annealing
Carry out continuous annealing on meshbeltfurnace, impose the Buchholz protection measure to prevent the plate material oxidation, protective gas can be nitrogen and hydrogen, and annealing temperature is controlled at 900-1100 ℃ and is advisable, and mean residence time was at 2 hours.
Embodiment 2:
Nickel-based battery plate material provided by the invention is the nickel-containing alloys of foaming or claims the foaming nickel alloy that wherein the content of nickel is in 12～18% (percetages by weight).
The voidage of described foaming nickel alloy material is preferably in more than 90%.
Described nickel alloy is a nickel aluminum titanium alloy steel, and wherein the content of aluminium is 6-8% (WT), and the content of titanium is 5-7% (WT).
Its manufacture method is identical with embodiment 1 basically, has just added the sulfate liquor of aluminium and the chloride solution of titanium in the electrolyte.Its content is respectively:
NiSO
4 50-110g/L
Al
2(SO
4)
3 10-20g/L
TiCl
4 10-20g/L
Embodiment 3:
Nickel-based battery plate material provided by the invention is the nickel-containing alloys of foaming or claims the foaming nickel alloy that wherein the content of nickel is in 12～18% (percetages by weight).
The voidage of described foaming nickel alloy material is preferably in more than 90%.
Described nickel alloy is a nickel zinc titanium alloy steel, and wherein the content of zinc is 6-8% (WT), and the content of titanium is 5-7% (WT).
Its manufacture method is identical with embodiment 1 basically, has just added the chloride solution of zinc and the chloride solution of titanium in the electrolyte.Its content is respectively:
NiSO
4 50-110g/L
ZnCl
2 10-20g/L
TiCl
4 10-20g/L
Embodiment 4:
Nickel-based battery plate material provided by the invention is the nickel-containing alloys of foaming or claims the foaming nickel alloy, wherein the content of nickel 12～18% (?) (percetage by weight).
The voidage of described foaming nickel alloy material is preferably in more than 90%.
Described nickel alloy is an ambrose alloy titanium alloy steel, wherein the content of copper be 6-8% (?), the content of titanium be 5-7% (?).
Its manufacture method is identical with embodiment 1 basically, has just added the sulfate liquor of copper and the chloride solution of titanium in the electrolyte.Its content is respectively:
NiSO
4 50-110g/L
CuSO
4 10-20g/L
TiCl
4 10-20g/L
Claims (5)
1, a kind of plate material of nickel-based battery is characterized in that: be the nickel-containing alloys of foaming, wherein the content of nickel is 10～20%; Described nickel-containing alloys is the nickel-containing alloys steel; In described nickel-containing alloys steel, add Ti, Cu, Al, Zn metallic element formation nickel aluminum titanium alloy steel or nickel zinc titanium alloy steel or ambrose alloy titanium alloy steel; The content of described titanium is in 1%; Described Cu, Zn, every kind of addition of Al are 1.0～10%.
2, nickel-based battery plate material according to claim 1 is characterized in that: described Cu, Zn, every kind of addition of Al are 5～10%.
3, the plate material of nickel-based battery according to claim 1 is characterized in that: the voidage of described foaming nickel alloy material is more than 90%.
4, a kind of method of making nickel-based battery plate material as claimed in claim 1 is:
A, on Foam Plastic Surface the preparation one conductive layer;
B, the foamed plastics that will have a conductive layer place the sulfate of the metal that constitutes the nickel-based battery pole plate or the solution of chloride salt to carry out electro-deposition, and the segmentation galvanoplastic of boosting are adopted in described electro-deposition;
C, the foamed plastics that previous step is obtained deposition layer are removed aforesaid foamed plastics through burning;
D, the remaining material with multi-pore structure is made annealing in process to taking off foamed plastics through burning.
5, manufacture method according to claim 4 is characterized in that: institute's segments is at least three sections in the described segmentation step-up method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021007357A CN1185735C (en) | 2002-01-21 | 2002-01-21 | Plate of nickel cell and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021007357A CN1185735C (en) | 2002-01-21 | 2002-01-21 | Plate of nickel cell and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1434528A CN1434528A (en) | 2003-08-06 |
| CN1185735C true CN1185735C (en) | 2005-01-19 |
Family
ID=27627228
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB021007357A Expired - Lifetime CN1185735C (en) | 2002-01-21 | 2002-01-21 | Plate of nickel cell and preparation method thereof |
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| CN (1) | CN1185735C (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102321893A (en) * | 2011-09-06 | 2012-01-18 | 中国第一汽车股份有限公司 | Preparation process of foam metal carrier for post-treatment |
| CN102623759B (en) * | 2012-04-17 | 2014-11-05 | 河南创力新能源科技有限公司 | Iron-nickel storage battery adopting foamed-type iron electrode as cathode and preparation method of iron-nickel storage battery |
| CN102623758B (en) * | 2012-04-17 | 2014-07-09 | 河南创力新能源科技有限公司 | Iron-nickel storage battery adopting foamed nickel or iron-type iron electrode as cathode and preparation method of iron-nickel storage battery |
| CN102623710B (en) * | 2012-04-17 | 2014-07-23 | 河南创力新能源科技有限公司 | Foamed iron electrode and preparation method thereof |
| CN104087975A (en) * | 2013-12-19 | 2014-10-08 | 浙江工商大学 | Preparation method of foamed copper |
| CN104195608A (en) * | 2014-09-22 | 2014-12-10 | 常德力元新材料有限责任公司 | Method for preparing cathode substrate material, foamed nickel of vehicle-mounted power batteries |
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2002
- 2002-01-21 CN CNB021007357A patent/CN1185735C/en not_active Expired - Lifetime
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| CN1434528A (en) | 2003-08-06 |
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