CN101532102A - Rare-earth series hydrogen storage alloy - Google Patents

Rare-earth series hydrogen storage alloy Download PDF

Info

Publication number
CN101532102A
CN101532102A CN200910064627A CN200910064627A CN101532102A CN 101532102 A CN101532102 A CN 101532102A CN 200910064627 A CN200910064627 A CN 200910064627A CN 200910064627 A CN200910064627 A CN 200910064627A CN 101532102 A CN101532102 A CN 101532102A
Authority
CN
China
Prior art keywords
alloy
hydrogen storage
storage alloy
less
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.)
Granted
Application number
CN200910064627A
Other languages
Chinese (zh)
Other versions
CN101532102B (en
Inventor
李全安
李克杰
李守英
张兴渊
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henan University of Science and Technology
Original Assignee
Henan University of Science and Technology
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Henan University of Science and Technology filed Critical Henan University of Science and Technology
Priority to CN2009100646272A priority Critical patent/CN101532102B/en
Publication of CN101532102A publication Critical patent/CN101532102A/en
Application granted granted Critical
Publication of CN101532102B publication Critical patent/CN101532102B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

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

  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention discloses a rare-earth series hydrogen storage alloy. The chemical formula of the alloy has the following general formula: Ml1-xDyx(NiaCobAlcMndCueFefSngCrhZni), wherein x is more than 0 and less than 0.3; a is more than 2 and less than 4; b is more than 0 and less than 0.3; c is more than 0.2 and less than 0.4; d is more than 0.2 and less than 0.5; e is more than 0 and less than 0.2; f is more than 0 and less than 0.25; g is more than 0 and less than 0.22; h is more than or equal to 0 and less than 0.18; and i is more than 0 and less than 0.28; and Ml is mixed rare earth. The alloy uses Cu, Cr, Zn, Fe and Sn to replace Co element in the rare earth series hydrogen storage alloy, can obviously improve the circulation stability of the hydrogen storage alloy, reduces the content of Co in the hydrogen storage alloy by over 60 percent compared with commercial hydrogen storage alloy MlNi3.55Co0.75Mn0.4Al0.3, and greatly reduces the production cost.

Description

A kind of lanthanon hydrogen storage alloy
Technical field
The present invention relates to a kind of lanthanon hydrogen storage alloy.
Background technology
In recent ten years, because the fast development of products such as PC, mobile telephone, power tool and electromobile, promoted the development of supporting with it secondary cell, make the research and the development of Ni-MH battery have realistic meaning, yet one of its gordian technique is exactly the research of negative material hydrogen storage alloy.Rare earth is AB 5The type hydrogen storage electrode alloy is with LaNi 5, MmNi 5Rich Ce mishmetal), MlNi (Mm: 5Rich La mishmetal) etc. (Ml: be the lanthanon hydrogen storage alloy of representative, its maximum hydrogen-storage density is 14% (quality), even the oxide compound of rare earth oxide that it is surperficial and surperficial lower floor/Ni interface at room temperature also has hydrogen molecule dissociative initial stage activation characteristic, so the electrochemistry cycle life performance is very superior.
Rare earth is AB 5Type hydrogen storage alloy has obtained a large amount of research and application widely as the main raw material(s) of MH-Ni battery cathode, it has characteristics such as activation is easy, high-rate discharge ability is good, the P-C-T platform is smooth, electro catalytic activity is good, be widely used in the battery industry of Japan and China, the manufacturer of alloy powder also concentrates on this two countries substantially.As power cell, to compare with Ni-Cd battery, lithium ion battery, the Ni-MH battery is taken all factors into consideration from economy, performance and application prospect etc., has certain advantage.At present typical commercialization AB 5The type hydrogen storage alloy composition is MlNi 3.55Co 0.75Mn 0.4Al 0.3, wherein Elements C o plays effect of crucial importance to the chemical property of lanthanon hydrogen storage alloy, and its effect is as follows: the volume change when 1. reducing alloy hydrogen absorption and desorption, suppress the efflorescence of alloy; 2. during charge and discharge cycles, form protective membrane, suppress the corrosion of alloy, improve alloy life at alloy surface; 3. play katalysis in surface of metal particles, improve alloy activation performance and fast charging and discharging ability.But the Co element costs an arm and a leg, and less than the Co of 10wt% content, its cost but accounts for the about 50% of alloy raw material cost in the alloy, and production cost is higher.
At present, utilizing multicomponent alloy optimization is an above-mentioned production cost higher effective approach of solution that improves the alloy hydrogen storage property, reduces cost of alloy.By adopting the Co element of B side in the different element difference part instead of alloy, and other rare earth element instead of alloy of employing A side, hydrogen storage alloy is reduced cost, make it have suitable platform hydrogen pressure, and platform is grown and is put down, make alloy that bigger hydrogen be arranged, the lower absorption hydrogen coefficient of expansion, high resistance to corrosion etc.But can have much for the alloying element of considering employing, and the synergy between its each component is very big to the alloy performance impact, the selection to substitute element when the preparation hydrogen storage alloy has very big difficulty.
Summary of the invention
The purpose of this invention is to provide a kind of lower lanthanon hydrogen storage alloy of cobalt amount that contains, to reduce the production cost of hydrogen storage alloy.
In order to realize above purpose, the technical solution adopted in the present invention is: a kind of lanthanon hydrogen storage alloy, the chemical formula of this alloy has following general formula: Ml 1-xDy x(Ni aCo bAl cMn dCu eFe fSn gCr hZn i), 0＜x＜0.3,2＜a＜4,0＜b＜0.3,0.2＜c＜0.4,0.2＜d＜0.5,0＜e＜0.2,0＜f＜0.25,0＜g＜0.22,0≤h＜0.18,0＜i＜0.28 wherein, Ml is a mishmetal.
Described a+b+c+d+e+f+g+h+i is 5.
Described hydrogen storage alloy is by Dy, Ni, and Co, Al, Mn, Cu, Fe, Sn, Cr, Zn and Ml form for the raw material melting.
Described raw material Dy, Ni, Co, Al, Mn, Cu, Fe, Sn, Cr, the purity of Zn is all more than 99.5%.
Described mishmetal Ml comprises La, reaches the arbitrary combination of a kind of or three among Ce, Pr, the Nd.
Lanthanon hydrogen storage alloy of the present invention adopts cheap Dy instead of alloy A side element, adopts Cu, Cr, and Zn, Fe, the Co element of Sn instead of alloy B side is to reduce the production cost of hydrogen storage alloy.Because Cu and Co be residing position relation in the periodic table of chemical element, determine the similarity of its chemical property, can improve the cyclical stability and the fast charging and discharging performance of alloy; Because Cr can form fine and close oxide film at alloy surface, prevents the further oxidation of alloy, and the effect that reduces the alloy microhardness is arranged; Zn can improve the cell container of unit mass, reduces and inhales hydrogen platform pressure, and stable discharging voltage improves the multiplying power discharging ability; The Fe of trace mixes and can improve the loading capacity of alloy; The adding of Sn can reduce equilibrium pressure, strengthens oxide compound stability, reduces lag-effect, improves alloy loading capacity and cyclical stability.
The present invention utilizes Cu, Cr, Zn, Fe, the Co element of Sn instead of alloy B side can significantly improve the cyclical stability of hydrogen storage alloy, its cyclical stability is the highest can to improve 2.5 times, and with commercial hydrogen storage alloy MlNi 3.55Co 0.75Mn 0.4Al 0.3Compare, reduced in the hydrogen storage alloy Co content more than 60%, big senior general has reduced production cost.
Description of drawings
Fig. 1 is the loading capacity curve of electrode S, A, B, C;
Fig. 2 is the loading capacity curve of electrode S, D, E.
Embodiment
Each raw metal that embodiments of the invention are involved and mishmetal raw material are commercially available, and its purity is more than 99.5%.
Embodiment 1
The chemical formula of the lanthanon hydrogen storage alloy of present embodiment is:
Ml 0.98Dy 0.02Ni 3.6Co 0.25Al 0.25Mn 0.4Cu 0.1Fe 0.1Sn 0.1Cr 0.1Zn 0.1(alloy A).
The mishmetal Ml that is wherein adopted comprises following component by mass percent: La 80%, and Pr 7%, and Ce 8%, and Nd 5%.
The preparation method of the lanthanon hydrogen storage alloy of present embodiment is as follows:
According to said ratio dysprosium (Dy), mishmetal Ml and nickel (Ni), cobalt (Co), aluminium (Al), manganese (Mn), copper (Cu), iron (Fe), zinc (Zn), chromium (Cr), tin (Sn) are inserted in the vacuum non-consumable arc furnace; under argon shield, carry out melting; melt back 5 times is after the hydrogen storage alloy ingot is made in the cooling of water-cooled copper ingot mould.
The preparation of present embodiment hydrogen-bearing alloy electrode:
The alloy pig of making is carried out crossing 200 mesh sieves after mechanical disintegration is also ground obtain powdered alloy; Get during powdered alloy 200g and Cu powder pack transfer mold after mixing into by weight 1:2, use the 300KN universal hydraulic testing machine, under 35MPa, keep 1min to be cold-pressed into the disk sample of Φ 11mm, make electrode A.
The concrete steps of the electrochemical property test of present embodiment hydrogen storage alloy and parameter:
Adopt open type three electrode test systems, supporting electrode is sintered type nickel hydroxide (Ni (OH) 2/ NiOOH) electrode, reference electrode is mercuric oxide electrode (Hg/HgO), electrolytic solution is the KOH aqueous solution of 6mol/L.Testing tool adopts DC-5 auto charge and discharge record instrument, measures 25 ℃ of temperature.Charge and discharge activation performance, maximum discharge capacity and the cyclical stability of beta alloy with the 22mA continuous current, charging 3.5h, stopping potential are fixed on-0.6V (Hg/HgO electrode relatively).
Embodiment 2
The chemical formula of the lanthanon hydrogen storage alloy of present embodiment is:
Ml 0.95Dy 0.05Ni 3.8Co 0.15Al 0.35Mn 0.45Cu 0.05Fe 0.05Sn 0.05Cr 0.05Zn 0.05(alloy B).
The mishmetal Ml that is wherein adopted comprises following component by mass percent: La 90%, and Pr 4%, and Ce 4%, and Nd 2%.
The preparation method of present embodiment lanthanon hydrogen storage alloy and electrode and chemical property detection method are with embodiment 1, and the resulting hydrogen-bearing alloy electrode of present embodiment is labeled as electrode B.
Embodiment 3
The chemical formula of the lanthanon hydrogen storage alloy of present embodiment is:
Ml 0.88Dy 0.12Ni 3.6Co 0.1Al 0.3Mn 0.25Cu 0.15Fe 0.15Sn 0.15Cr 0.15Zn 0.15(alloy C).
The mishmetal Ml that is wherein adopted comprises following component by mass percent: La 84%, and Pr 10%, and Ce 4%, and Nd 2%.
The preparation method of present embodiment lanthanon hydrogen storage alloy and electrode and chemical property detection method are with embodiment 1, and the resulting hydrogen-bearing alloy electrode of present embodiment is labeled as electrode C.
Embodiment 4
The chemical formula of the lanthanon hydrogen storage alloy of present embodiment is:
Ml 0.8Dy 0.2Ni 3.4Co 0.2Al 0.22Mn 0.3Cu 0.19Fe 0.24Sn 0.2Zn 0.25(alloy D).
The mishmetal Ml that is wherein adopted comprises following component by mass percent: La 90%, and Ce 10%.
The preparation method of present embodiment lanthanon hydrogen storage alloy and electrode and chemical property detection method are with embodiment 1, and the resulting hydrogen-bearing alloy electrode of present embodiment is labeled as electrode D.
Embodiment 5
The chemical formula of the lanthanon hydrogen storage alloy of present embodiment is:
Ml 0.75Dy 0.25Ni 2.82Co 0.28Al 0.39Mn 0.49Cu 0.19Fe 0.23Sn 0.2Cr 0.15Zn 0.25(alloy E).
The mishmetal Ml that is wherein adopted comprises following component by mass percent: La 90%, and Pr 7%, and Nd 3%.
The preparation method of present embodiment lanthanon hydrogen storage alloy and electrode and chemical property detection method are with embodiment 1, and the resulting hydrogen-bearing alloy electrode of present embodiment is labeled as electrode E.
Respectively the alloy in the foregoing description 1～5 is carried out chemical property and detect, the comparison electrode that is adopted (electrode S) is commercial hydrogen storage alloy: MlNi 3.55Co 0.75Mn 0.4Al 0.3(alloy S).
The result that chemical property detects is as follows:
Table 1: the chemical property of each embodiment interalloy and alloy S
The alloy code name Maximum discharge capacity C max(mAh/g) The activation frequency n (C max—C i)/(n i—n max)
S 299 16 0.63
A 266 38 0.36
B 257 38 0.37
C 242 38 0.25
D 277 11 0.35
E 269 5 0.30
By table 1 as seen, S compares with the standard high cobalt alloy, adds the low cobalt hydrogen storage alloy evident characteristic of Dy to be: low cobalt alloy A, and B, C, cobalt contents reduces more than 60% among D and the E, and cost is low; Though capacity decreases, but still satisfy practical requirement; Cyclical stability increases substantially, and wherein cyclical stability is up to alloy C, has reached 2.5 times of alloy S.
The loading capacity of each electrode and the relation that discharges and recharges number of times are as shown in Figure 1, 2.Fig. 1,2 shows that alloy still has higher electrochemistry capacitance behind the polynary Co of falling, and outstanding feature is that cyclical stability increases substantially, and along with the increase that discharges and recharges number of times, loading capacity reduces slowly.After charge and discharge cycles 70 times, the loading capacity of alloy A begins apparently higher than the loading capacity of alloy S.
It should be noted last that, above example only is illustrative rather than definitive thereof technical scheme of the present invention, although the present invention is had been described in detail with reference to the foregoing description, those of ordinary skill in the art is to be understood that, still can make amendment or be equal to replacement the present invention, and not breaking away from any modification or partial replacement of the spirit and scope of the present invention, it all should be encompassed in the middle of the claim scope of the present invention.

Claims (5)

1, a kind of lanthanon hydrogen storage alloy is characterized in that: the chemical formula of this alloy has following general formula: M1 1-xDy x(Ni aCo bAl cMn dCu eFe fSn gCr hZn i), 0＜x＜0.3,2＜a＜4,0＜b＜0.3,0.2＜c＜0.4,0.2＜d＜0.5,0＜e＜0.2,0＜f＜0.25,0＜g＜0.22,0≤h＜0.18,0＜i＜0.28 wherein, M1 is a mishmetal.
2, lanthanon hydrogen storage alloy according to claim 1 is characterized in that: described a+b+c+d+e+f+g+h+i is 5.
3, lanthanon hydrogen storage alloy according to claim 1 is characterized in that: described hydrogen storage alloy is by Dy, Ni, and Co, Al, Mn, Cu, Fe, Sn, Cr, Zn and M1 form for the raw material melting.
4, lanthanon hydrogen storage alloy according to claim 3 is characterized in that: described raw material Dy, and Ni, Co, Al, Mn, Cu, Fe, Sn, Cr, the purity of Zn is all more than 99.5%.
5, according to arbitrary described lanthanon hydrogen storage alloy of claim 1-4, it is characterized in that: described mishmetal M1 comprises La, reaches the arbitrary combination of a kind of or three among Ce, Pr, the Nd.
CN2009100646272A 2009-04-13 2009-04-13 Rare-earth series hydrogen storage alloy Expired - Fee Related CN101532102B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN2009100646272A CN101532102B (en) 2009-04-13 2009-04-13 Rare-earth series hydrogen storage alloy

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN2009100646272A CN101532102B (en) 2009-04-13 2009-04-13 Rare-earth series hydrogen storage alloy

Publications (2)

Publication Number Publication Date
CN101532102A true CN101532102A (en) 2009-09-16
CN101532102B CN101532102B (en) 2010-12-29

Family

ID=41102961

Family Applications (1)

Application Number Title Priority Date Filing Date
CN2009100646272A Expired - Fee Related CN101532102B (en) 2009-04-13 2009-04-13 Rare-earth series hydrogen storage alloy

Country Status (1)

Country Link
CN (1) CN101532102B (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107574363A (en) * 2017-09-01 2018-01-12 桂林电子科技大学 A kind of ferromagnetic Fe Dy hydrogen storage materials and preparation method thereof
WO2020224589A1 (en) * 2019-05-06 2020-11-12 中国石油化工股份有限公司 Organic hydrogen storage raw material dehydrogenation catalyst, carrier of catalyst, hydrogen storage alloy, and method for providing high-purity hydrogen gas

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107574363A (en) * 2017-09-01 2018-01-12 桂林电子科技大学 A kind of ferromagnetic Fe Dy hydrogen storage materials and preparation method thereof
CN107574363B (en) * 2017-09-01 2019-08-23 桂林电子科技大学 A kind of ferromagnetic Fe-Dy hydrogen storage material and preparation method thereof
WO2020224589A1 (en) * 2019-05-06 2020-11-12 中国石油化工股份有限公司 Organic hydrogen storage raw material dehydrogenation catalyst, carrier of catalyst, hydrogen storage alloy, and method for providing high-purity hydrogen gas
WO2020224586A1 (en) * 2019-05-06 2020-11-12 中国石油化工股份有限公司 Organic hydrogen storage raw material dehydrogenation catalyst, carrier of the catalyst, hydrogen storage alloy, and method for providing high-purity hydrogen

Also Published As

Publication number Publication date
CN101532102B (en) 2010-12-29

Similar Documents

Publication Publication Date Title
JP2771592B2 (en) Hydrogen storage alloy electrode for alkaline storage batteries
CN111471895B (en) Hydrogen storage alloy containing gadolinium and nickel, cathode, battery and preparation method
JP2680669B2 (en) Hydrogen storage alloy electrode for alkaline storage battery
CN103456927A (en) Oxygen-containing vanadium titanium based hydrogen storage electrode alloy and preparation method thereof
CN101320801A (en) Hydrogen storage alloy for low temperature Ni-MH power cell
CN111118342B (en) A2B7 type RE-Sm-Ni series hydrogen storage alloy, negative electrode, battery and preparation method
CN101532102B (en) Rare-earth series hydrogen storage alloy
JP7311507B2 (en) Large-capacity and long-life La-Mg-Ni type negative electrode hydrogen storage material for secondary chargeable nickel-metal hydride battery and method for producing the same
JP3381264B2 (en) Hydrogen storage alloy electrode
JPH0821379B2 (en) Hydrogen storage electrode
KR100218835B1 (en) Mish metal for ni/mh secondary cell and nickel-series alloy storing hydrogen
CN102054982A (en) La-Mg-Ni type negative-pole hydrogen storage material for low-temperature nickel-hydrogen battery
CN1173055C (en) New-type hydrogen-storing RE electrode alloy for secondary Ni-metal oxide battery
JP2595967B2 (en) Hydrogen storage electrode
CN111118345B (en) Multi-element samarium-nickel hydrogen storage material, negative electrode, battery and preparation method
CN111224092B (en) Zirconium or titanium doped samarium-containing hydrogen storage alloy, negative electrode, battery and preparation method
CN111411262B (en) A5B19 type gadolinium-containing hydrogen storage alloy, negative electrode and preparation method
JP2004285406A (en) Hydrogen storage alloy and electrode for nickel-hydrogen battery using the same
CN100372157C (en) AB5 type negative pole hydrogen-storage material
KR100398709B1 (en) Manufacturing method of hydrogen storage alloy electrode and hydrogen storage alloy electrode
CN111118346B (en) Zirconium or titanium containing A2B7 type hydrogen storage alloy, negative electrode, battery and preparation method
CN204102994U (en) Nickel-hydrogen secondary cell
CN103094531B (en) A kind of power-type La-Mg-Ni negative hydrogen storage material for nickel-hydrogen batteries
CN1294664C (en) Negative hydrogen storage material for high-temperature nickel hydrogen battery
JPS61168870A (en) Metal-hydrogen alkaline storage battery

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
C17 Cessation of patent right
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20101229

Termination date: 20130413