CN1289700C - Novel anticorrosion zinc-base rare earth aluminium-magnesium alloy negative electrode material - Google Patents
Novel anticorrosion zinc-base rare earth aluminium-magnesium alloy negative electrode material Download PDFInfo
- Publication number
- CN1289700C CN1289700C CNB031039014A CN03103901A CN1289700C CN 1289700 C CN1289700 C CN 1289700C CN B031039014 A CNB031039014 A CN B031039014A CN 03103901 A CN03103901 A CN 03103901A CN 1289700 C CN1289700 C CN 1289700C
- Authority
- CN
- China
- Prior art keywords
- zinc
- rare earth
- mishmetal
- aluminium
- negative electrode
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
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
Abstract
The present invention provides a new anticorrosion zinc-base rare earth-Al-Mg alloy negative electrode material. The new anticorrosion Zn-base rear earth-Al-Mg alloy negative electrode material comprise the following chemical components: 0.07 to 0.15 wt% of rare earth, 0.1 to 0.7 wt% of Al, 0.01 to 0.1 wt% of Mg and Zn as the rest, wherein the rare earth comprises ordinary mixed rare earth and new La-Pr-Ce mixed rare earth whose Ce and Nd are extracted. The alloy can be used as an additive of a Zn negative electrode or can be used for partially or completely taking the place of Znpowder in order to refine tissues, reducing the corrosion of Zn poles, reducing the dissolvability of ZnO and extending the service life of Zn cells.
Description
Affiliated technical field
The present invention relates in the chemical power source zinc-base material as negative pole.
Background technology
Excellent characteristics such as zinc is low with its aboundresources, equilibrium potential, good reversibility, energy density height and environmental nonpollution are widely used as the negative material of chemical power source, as zinc-manganese (MnO
2) battery, zinc-Yin (Ag
2O) battery etc.Because nickel-zinc battery operating voltage higher (1.6V) but, nontoxic fast charging and discharging, operating temperature range wide (20-60 ℃), and be considered to a kind of comparatively ideal green power cell.But zinc electrode exists problems such as burn into inerting, distortion, dendrite, makes that zinc battery circulation volume decay is fast, self discharge is serious, cycle life is short, does not reach actual requirement.One of important channel that addresses these problems is the preferred of zinc electrode material, to suppress the inerting of zinc electrode burn into, distortion and liberation of hydrogen, the capacity and the life-span of realizing improving zinc battery.
Summary of the invention
The purpose of this invention is to provide a kind of corrosion resistant zinc base rare earth aluminium magnesium alloy material, the zinc powder in order to part or all of replacement zinc battery negative electrode is used with corrosion resistance nature that improves negative pole and the distortion that reduces negative pole, prolongs shelf-lifeing and cycle life of zinc battery.Zinc battery comprises once or secondary zinc nickle battery, zinc manganese dioxide battery, zinc-silver oxide cell, zinc-air battery.
The present invention realizes that the technical scheme of above-mentioned purpose has provided a kind of zinc base rare earth aluminium magnesium alloy material, this alloy material is made up of rare earth, aluminium, magnesium, zinc element, and each element atom weight percent is: rare earth 0.07-0.15, aluminium 0.1-0.7, magnesium 0.01-0.1, Yu Weixin.In fact rare earth, aluminium, magnesium are the additive of zinc or are called inhibiter.Zinc is main component, and the purity of its zinc needs more than 99.995%.Rare earth is with common light rare earths Mm or carry lpc rare-earth mixture LPC after cerium is carried neodymium.Their prescription is:
Mm: lanthanum/mishmetal 25-32%
Praseodymium/mishmetal 3-7%
Cerium/mishmetal 45-52%
Neodymium/mishmetal 9-17%
LPC: lanthanum/mishmetal＞80%
Praseodymium/mishmetal 3-10%
Cerium/mishmetal 5-12%.
Feature of the present invention has two:
1, the chemically reactive of rare earth metal is very strong, has to remove the effect of quickening zinc negative pole corrosive impurity such as sulphur, iron etc., and corrosion speed is reduced; Rare earth can form intermetallic compound with Zn, Al, Mg etc. again, the crystallization nucleus increases, structure refinement, evenly, reduce zinc electrode surface unevenness, reduce the difference of surperficial each point electrochemical activity, just reduced forming microbattery based on each point chemically reactive difference (some zone becomes the anode of corrosion microbattery because of current potential is lower, the other zone is its negative electrode) number, thereby reduce the corrosion certainly of zinc electrode.The corrosion of zinc electrode has not only consumed active substance, reduces capacity of negative plates, and the generation of gas may cause that inner pressure of battery increases, and electrode expands, and work-ing life is low.Experimental result shows that this corrosion resistant zinc base rare earth aluminium magnesium alloy improves 1-3 doubly than the corrosion resistance of metallic zinc.
When 2, zinc base rare earth aluminium magnesium alloy negative electrode discharges, forming Zn (OH)
2The time, also can form Mg (OH)
2, Al (OH)
3And RE (OH)
3, these three kinds of oxyhydroxide by with Zn (OH)
2Effect forms Mg (OH)
22Zn (OH)
3, Al (OH)
32Zn (OH)
2, RE (OH)
22Zn (OH)
3Compound, they can reduce the solubleness of ZnO in electrolytic solution, this and added Ca (OH) in the electrode in the past
2Form Ca (OH)
22Zn (OH)
22H
2The situation of O compound is similar, thereby reduces the distortion of zinc, increases the service life.
Embodiment
The zinc base rare earth aluminium magnesium alloy negative electrode material that the present invention proposes, available two kinds of mishmetal Mm (common light rare earths) or LPC (mishmetal) add the zinc alloy melting that contains aluminium, magnesium and form.
Illustrate the preparation of alloy material: each 2Kg of industrial KCl, NaCl is mixed, be heated to 800 ℃ of fusings in the aluminum oxide of packing into the pincers pot, aluminium block 3Kg is added in the above-mentioned fused salt in three batches, and every batch adds second batch after molten again, and molten fully back is incubated half an hour in 700 ℃ of-750 ℃ of scopes.The aluminum basketry that 0.5Kg rare earth (Mm) and 0.25Kg magnesium are housed is sunk to rotation at leisure in the molten aluminum pot, make whole fusings, form aluminium alloy, cast aluminium, magnesium, the little ingot of rare earth intermediate alloy.Pack into the zinc liquid (the graphite pincers pot of zinc ingot metal is housed with the resistance furnace heating) of putting into 400 ℃ of-460 ℃ of 500Kg 99.999% in the aluminium basket of little ingot is slowly rotated master alloy and zinc alloy are melted, form required zinc base rare earth aluminium magnesium alloy.
The zinc base rare earth aluminium magnesium alloy that makes is tested its performance with two kinds of methods.
Performance test 1. usefulness linear time base sweep methods are measured zinc and the weak polarization curve of zinc base rare earth aluminium magnesium alloy in 0.5%NaCl solution, record characteristic parameter Ec (corrosion potential), ic (corrosion current) and the ba (electrode dissolving slope) that estimates corrosion resistance nature by it, be shown in following table:
RE represents rare earth
As seen from the above table: after adding rare earth, aluminium, magnesium, Ec all shuffle to some extent (illustrating that corrosion reaction is by retardation); Ic obviously reduces, and is best with the effect of adding rare earth especially; Ba also descends at double, illustrates that corrosion speed is slowed down.
The corrosive nature of performance test 2. zinc and zinc base rare earth aluminium magnesium alloy coating relatively.Zinc and zinc base rare earth aluminium magnesium alloy hot dipping on the steel body, are immersed in the 3%NaCl solution, and the corrosion weight loss amount with each sample of analytical balance weighing calculates the average weight loss (* 10 on the unit surface
-6G/mm
2), the result is as follows:
| Kind | 24 hours | 48 hours | 96 hours | 144 hours | 200 hours |
| Zn | 3.50 | 3.94 | 5.14 | 8.56 | 12.01 |
| Zn-Al | 3.10 | 3.80 | 4.67 | 7.53 | 10.81 |
| Zn-Al-Mm | 2.46 | 3.31 | 3.72 | 4.14 | 5.42 |
| Zn-Al-LPC | 2.40 | 3.13 | 3.64 | 4.10 | 5.40 |
As seen, a small amount of rare earth of interpolation and aluminium are greatly improved to the coating corrosion resistance nature in zinc, and is remarkable with the effect of adding common light rare earths Mm or lpc rare-earth mixture LPC especially.Zn-Al-LPC is better slightly than Zn-Al-Mm, and the price of LPC is lower than Mm, and stronger competitive capacity is arranged.
Find out from the sample macro morphology that soaks after 240 hours: the corrosion of zinc layer begins to the periphery diffusion from matrix border, and seriously corroded exposes matrix; And the corrosion of Zn-Al-Mm and Zn-Al-LPC coating is low more than pure zinc coating to the speed of periphery diffusion; Zn-Al coating has exposes matrix, and the corrosion of Zn-Al-Mm and Zn-Al-LPC is more even, and local heavy corrosion phenomenon does not take place.
Rare earth is a surfactant, tissue to zinc has refining effect: rare earth and zinc, aluminium, magnesium form intermetallic compound and are distributed in the effect of playing the pinning crystal boundary on the crystal boundary, hindering crystal boundary migration with the disperse form, thereby make that zinc granule attenuates, homogeneous microstructure, zinc layer each point electrochemical activity difference diminish, thereby reduced the corrosion of zinc.
Find out from X-ray spectrum, contain small amounts of Pb in the pure zinc coating
4SO
7, CrO
3Materials such as (Al, Fe, Si) H; And behind the adding rare earth, impurity obviously reduces mutually, and illustrating in the rare earth adding zinc has the effect of the impurity of purification, and these impurity have the bad influence of the zinc of acceleration corrosive.
Claims (3)
1. corrosion resistant zinc base rare earth aluminium magnesium alloy material, it is characterized in that this alloy material is made up of rare earth, aluminium, magnesium, zinc element, the proportional range of each element is pressed the atomic wts percentage calculation, be respectively: rare earth 0.07-0.15, aluminium 0.1-0.7, magnesium 0.01-0.1, Yu Weixin, its middle-weight rare earths is common light rare earths Mm or carries lpc rare-earth mixture LPC after cerium is carried neodymium that their rare earth formula is respectively:
Mm: lanthanum/mishmetal 25-32%
Praseodymium/mishmetal 3-7%
Cerium/mishmetal 45-52%
Neodymium/mishmetal 9-17%
LPC: lanthanum/mishmetal＞80%
Praseodymium/mishmetal 3-10%
Cerium/mishmetal 5-12%.
2. according to using zinc as a kind of raw material in the described corrosion resistant zinc base rare earth aluminium magnesium alloy material of claim 1, the zinc material purity is＞99.995%.
3. according to the described corrosion resistant zinc base rare earth aluminium magnesium alloy material of claim 1, this alloy material is used as once or the negative electrode active material of secondary zinc-manganese battery, zinc-air battery, nickel-zinc battery or zinc-silver oxide cell.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031039014A CN1289700C (en) | 2003-01-30 | 2003-01-30 | Novel anticorrosion zinc-base rare earth aluminium-magnesium alloy negative electrode material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031039014A CN1289700C (en) | 2003-01-30 | 2003-01-30 | Novel anticorrosion zinc-base rare earth aluminium-magnesium alloy negative electrode material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1521282A CN1521282A (en) | 2004-08-18 |
| CN1289700C true CN1289700C (en) | 2006-12-13 |
Family
ID=34282111
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB031039014A Expired - Fee Related CN1289700C (en) | 2003-01-30 | 2003-01-30 | Novel anticorrosion zinc-base rare earth aluminium-magnesium alloy negative electrode material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1289700C (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014062385A1 (en) * | 2012-10-18 | 2014-04-24 | Fluidic, Inc. | Degenerate doping of metallic anodes |
| US11450847B2 (en) * | 2019-01-23 | 2022-09-20 | Energizer Brands, Llc | Alkaline electrochemical cells comprising increased zinc oxide levels |
| CN110669962B (en) * | 2019-11-11 | 2021-03-09 | 湘潭大学 | Degradable biomedical Zn-Al-Mg-Nd zinc alloy and preparation method thereof |
-
2003
- 2003-01-30 CN CNB031039014A patent/CN1289700C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN1521282A (en) | 2004-08-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101638786B (en) | High-potential sacrificial magnesium alloy anode and manufacturing method thereof | |
| CN103199263B (en) | A kind of process for positive slab lattice of lead-acid accumulator Alloy And Preparation Method | |
| CN101656312B (en) | Alloy material for high-energy accumulator grid and preparation method thereof | |
| CN101084594B (en) | Non-aqueous electrolyte battery | |
| Zhong et al. | Evaluation of lead—calcium—tin—aluminium grid alloys for valve-regulated lead/acid batteries | |
| CN101510609A (en) | Alloy material for accumulator positive slab lattice and preparation method thereof | |
| CN102820472A (en) | Manganese-aluminum containing anode material and preparation method thereof, as well as air cell prepared by using anode material | |
| CN101388457A (en) | Aluminum alloy anode material for battery | |
| CN109694964A (en) | A kind of preparation method of aluminium-air cell anode material | |
| CN111916766A (en) | Mg-Bi-Ca-In alloy as negative electrode material of magnesium air battery and preparation method thereof | |
| CN111793760A (en) | Anode alloy material for magnesium air battery, preparation method thereof and battery | |
| CN107881356A (en) | A kind of lead-acid accumulator silver alloy anode plate grid and preparation method thereof | |
| US7838158B2 (en) | Sheet anodes based on zinc-aluminum alloys and zinc-air batteries containing the same | |
| CN1289700C (en) | Novel anticorrosion zinc-base rare earth aluminium-magnesium alloy negative electrode material | |
| CA1086988A (en) | Magnesium-lithium alloy | |
| CN111575563A (en) | Magnesium alloy and preparation method and application thereof | |
| CN110042278A (en) | A kind of aluminium-air cell anode material and preparation method thereof | |
| JP7078185B2 (en) | Ni-plated steel sheet and its manufacturing method | |
| EP0945908B1 (en) | Zinc alloy powder as anode material for use in alkaline manganese cells and process for producing the same | |
| CN110380045A (en) | A kind of magnesium-alloy anode material and its preparation method and application, magnesium air battery | |
| CN116043077B (en) | High-cube-texture-content high-electrochemical-activity aluminum alloy negative electrode material and heat treatment method thereof | |
| CN114438388B (en) | Magnesium alloy anode material with novel product morphology for magnesium seawater fuel cell and preparation method thereof | |
| CN1462080A (en) | Novel corrosion-resistant zinc-based rare earth aluminum magnesium alloy negative electrode material | |
| CN100414744C (en) | Lead-free environment-friendly zinc-manganese dry battery | |
| CN1271734C (en) | Metal negative electrode material for nickel-hydrogen battery and preparing process |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| ASS | Succession or assignment of patent right |
Owner name: JIANGSU HAISIDA POWER CO., LTD. Free format text: FORMER OWNER: JIANGSU HAISIDA GROUP CO., LTD. Effective date: 20080104 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20080104 Address after: No. 1018, Renmin West Road, Jiangsu, Qidong Patentee after: Jiangsu Highstar Battery Manufacturing Co., Ltd. Address before: No. 1018, Renmin West Road, Jiangsu, Qidong Patentee before: Jiangsu Haisida Group Co., Ltd. |
|
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20061213 Termination date: 20100130 |