CN104513925B

CN104513925B - Yttrium-nickel rare earth family hydrogen storage alloy, and secondary battery containing hydrogen storage alloy

Info

Publication number: CN104513925B
Application number: CN201410427281.9A
Authority: CN
Inventors: 闫慧忠; 李宝犬; 熊玮; 王利; 李金�
Original assignee: Baotou Rare Earth Research Institute; Ruike Rare Earth Metallurgy and Functional Materials National Engineering Research Center Co Ltd; Tianjin Baogang Rare Earth Research Institute Co Ltd
Current assignee: Baotou Rare Earth Research Institute; Ruike Rare Earth Metallurgy and Functional Materials National Engineering Research Center Co Ltd; Tianjin Baogang Rare Earth Research Institute Co Ltd
Priority date: 2014-08-28
Filing date: 2014-08-28
Publication date: 2017-05-03
Anticipated expiration: 2034-08-28
Also published as: CN104513925A

Abstract

The invention relates to a yttrium-nickel rare earth family hydrogen storage alloy, and a secondary battery containing the hydrogen storage alloy, and concretely relates to an AB3 type RExYyNiz-a-bMnaAlb hydrogen storage electrode alloy. The alloy has good activation performances, rate discharge ability, and charge and discharge or hydrogen adsorption desorption cycle stability, can be used in a wide temperature range, has small self discharge, and has a highest electrochemical capacity reaching above 360mAh.g＜-1＞. The alloy has better electrochemical performances and gas phase hydrogen adsorption and desorption performances than traditional LaNi5 type hydrogen storage alloy as a hydrogen storage electrode and a hydrogen storage material respectively, and contains no magnesium element; and the preparation method of the hydrogen storage electrode alloy is simpler and safer than the preparation method of rare earth-magnesium-nickel family AB3 hydrogen storage alloy.

Description

A kind of yttrium-nickel lanthanon hydrogen storage alloy and the secondary cell containing the hydrogen bearing alloy

Technical field

The present invention relates to a kind of AB₃Type RE-Y-NiMnAl hydrogen bearing alloy.

Background technology

Hydrogen bearing alloy is the functional material that the class for finding at the end of the sixties in last century has high storage hydrogen density, has hydrogen storage Alloy is broadly divided into six classes from composition：Rare Earth AB₅Type such as LaNi₅；Magnesium system such as Mg₂Ni、MgNi、La₂Mg₁₇；Rare-earth and Mg- Nickel system AB_3-4Type such as La₂MgNi₉, La₅Mg₂Ni₂₃, La₃MgNi₁₄；Titanium system AB type such as TiNi, TiFe；Zirconium, titanium system Laves phases AB₂ Type such as ZrNi₂；Vanadium system solid solution such as (V_0.9Ti_0.1)_1-xFe_x。

Now widely used hydrogen storage material is LaNi₅Type hydrogen storage alloy.The alloy is mainly used as metal hydride-nickel two The negative material of primary cell (MH/Ni), its theoretical electrochemistry capacity is 373mAhg^-1, the commodity negative material Mm of practical application (NiCoMnAl)₅The maximum capacity about 350mAhg of (wherein Mm is norium)^-1.In order to develop chemical property The bigger hydrogen bearing alloy of more preferable or hydrogen storage content, the research to magnesium base alloy gives the attention of height.Mg-base hydrogen-bearing alloy material Theoretical electrochemistry capacity it is high, especially RE-Mg-Ni system AB₃Type, A₂B₇Type, A₅B₁₉The research of type hydrogen storage alloy achieves weight It is in progress, and into the commercial application stage.Zirconium, titanium system and vanadium system hydrogen storage material are because activation is difficult, the too high original of cost Because not all being widely used.

Document《An electrochemical study of new La_1-xCe_xY₂Ni₉(0≤x≤1)hydrogen storage alloys》(Electrochimica Acta, 46 (2001)：2385-2393) and document《New ternary Intermetallic compounds belonging to the R-Y-Ni (R=La, Ce) system as negative electrodes for Ni-MH batteries》(Journal of Alloys and Compounds, 330-332 (2002)：782-786) report AB₃Type La-Y-Ni hydrogen bearing alloy, but Mn and Al elements, and hydrogen storage capability are not contained in alloy Highest only has 260mAhg^-1。

AB widely studied at present₃Mg elements are one of principal component in type RE-Mg-Ni materials base hydrogen storage alloy.Such as CN102660700A discloses a kind of AB₃Type hydrogen storage alloy and preparation method.AB₃The chemical formula of type hydrogen storage alloy is： La_0.35Pr_0.30Mg_xNi_2.90Al_0.30, wherein x=0.30～0.35.Y element is not contained in the proprietary alloy composition, but must be contained There are Mg elements, due to the vapour pressure height of active metal element magnesium so that manufacture difficulty increases, and alloying component is difficult to control to, while The fine magnesium powder of volatilization is inflammable and explosive and there is potential safety hazard.

The content of the invention

The present invention is intended to provide a kind of lanthanon hydrogen storage alloy for not containing Mg elements, with overcome it is of the prior art not Foot.

The present invention relates to a kind of formula is RE_xY_yNi_z-a-bMn_aAl_bLanthanon hydrogen storage alloy, wherein, RE=La, Ce, One or more elements in Pr, Nd, Sm, Gd, x ＞ 0, y >=0.5, x+y=3；9.5 ＞ z >=8.5 (are stoichiometry during z=9 Compare AB₃Type；It is non-stoichiometric AB during z ≠ 9₃Type), 3.5 >=a+b ＞ 0.

Further, the preferred content range of RE elements is 0.5～2.0；

Further, the preferred content range of Mn elements is 0.5～2.0；

Further, the preferred content range of Al elements is 0.2～1.0.

Alloy is prepared using high melt-quick quenching technique, its technical process is as described below：Each elemental metals or centre in composition The equal ＞ 99.0% of purity of alloy raw material, calculates according to chemical molecular formula proportioning and accurately weighs each raw material, and raw material is put successively Enter Al₂O₃Crucible, is evacuated to 3.0Pa, is filled with inert gas Ar to 0.055MPa.Intensification melting, rapid hardening after insulation about 6min. Rapid hardening copper roller linear velocity is 3.4m/s.Copper roller normal open cooling water, 25 DEG C of coolant water temperature.Easily scaling loss raw material need in right amount increase proportioning, Increase ratio such as following table：

Raw material	RE	Y	Mn	Al
					Increase ratio	2%	1%	5%	3%

In addition to above-mentioned preparation method, RE of the present invention_xY_yNi_z-a-bMn_aAl_bHydrogen bearing alloy can also adopt this area Other hydrogen bearing alloy preparation methods are prepared, for example：High melt casting method, mechanical alloying (MA) method, powder sintering, High melt-gas atomization, reduction-diffusion process, displacement diffusion method, conbustion synthesis (CS) method, self-propagating high-temperature synthesis (SHS) etc..

Present invention also offers a kind of by described RE_xY_yNi_z-a-bMn_aAl_bThe secondary electricity that type hydrogen storage alloy is prepared Pond.

RE of the present invention_xY_yNi_z-a-bMn_aAl_bHydrogen bearing alloy can also be multiple by different proportion with other hydrogen storage materials Close, prepare new hydrogen storage material.

RE of the present invention_xY_yNi_z-a-bMn_aAl_bType hydrogen storage alloy can improve its institutional framework using heat treatment method And performance, such as：Eliminate alloy structure stress and solute segregation, improve the discharge charge that hydrogen platform identity or alloy electrode are inhaled/put to alloy Electric platform identity, raising hydrogen-sucking amount and cycle life etc.；Various surface treatment methods can also be adopted to improve its performance, such as： Improve the suction of alloy/put hydrogen or charge/discharge dynamic performance, strengthen the oxidation resistance of alloy, improve the conductive and heat-conductive of alloy Performance etc..

AB of the present invention₃Type RE_xY_yNi_z-a-bMn_aAl_bHydrogen storage electrode alloy, with good activity function, multiplying power Hydrogen cyclical stability is put in discharge capability, discharge and recharge or suction, can use within the scope of wider temperature, and self discharge is little, its highest Electrochemistry capacitance is up to 360mAhg^-1More than.The alloy is as the chemical property of hydrogen-storage electrode and as hydrogen storage material Gas phase hydrogen storage property is better than tradition LaNi₅Type hydrogen storage alloy, does not contain magnesium elements, with RE-Mg-Ni system AB in its composition₃Type is stored up Hydrogen alloy is compared, and manufacture method is simple and safe.In addition, yttrium (Y) element is main component in hydrogen bearing alloy of the present invention One of, yttrium aboundresources in the rare earth mineral reserve of China, the use of the element is conducive to balancing the comprehensive utilization of China's rare earth resources.

Description of the drawings

Fig. 1 is LaY₂Ni₈Mn_0.5Al_0.5The XRD of hydrogen bearing alloy

Specific embodiment

AB described in embodiment 1～22 is prepared using preceding method₃Type RE_xY_yNi_z-a-bMn_aAl_bHydrogen bearing alloy.

Embodiment 13 and alloy described in embodiment 14 are using identical raw material than being obtained.Alloy described in embodiment 13 is using front State high melt-quick quenching technique to prepare, its technical process is：The equal ＞ of the purity of each elemental metals or intermediate alloy raw material in composition 99.0%, calculate according to chemical molecular formula proportioning and accurately weigh each raw material (easy scaling loss raw material need in right amount increase proportioning), by original Material is sequentially placed into Al₂O₃Crucible, is evacuated to 3.0Pa, is filled with inert gas Ar to 0.055MPa.Intensification melting, is incubated about 6min Rapid hardening afterwards.Rapid hardening copper roller linear velocity is 3.4m/s.Copper roller normal open cooling water, 25 DEG C of coolant water temperature.

Alloy described in embodiment 14 may also be employed high melt-quick quenching technique and prepare, and increase in its technical process at annealing heat Reason step, specially：The equal ＞ 99.0% of the purity of each elemental metals or intermediate alloy raw material, matches somebody with somebody according to chemical molecular formula in composition Than calculate and accurately weigh each raw material (easy scaling loss raw material need in right amount increase proportioning), raw material is sequentially placed into into Al₂O₃Crucible, takes out true Sky is filled with inert gas Ar to 0.055MPa to 3.0Pa.Intensification melting, rapid hardening after insulation about 6min.Rapid hardening copper roller linear velocity is 3.4m/s.Copper roller normal open cooling water, 25 DEG C of coolant water temperature.Rapid hardening alloy sheet is moved back under vacuum or inert gas shielding at 750 DEG C It is burning hot to process 8h.

M1 in embodiment 20 is lanthanum rich norium, is about wherein being about 64%, Ce containing La and being about 25%, Pr 3%th, Nd is about 8%.

The preparation method of test electrode is：The alloy Jing Mechanical Crushings of embodiment 1～22 into 200-300 mesh powder, alloy Powder is mixed with carbonyl nickel powder with 1: 4 mass ratio, is made under 16MPa pressureMH electrode slices, the electrode slice is put Between two panels nickel foam, while sandwiching the nickel strap as lug, make under 16MPa pressure again negative for the hydrogen storage of test Pole (MH electrodes), the close contact between electrode slice and nickel screen is ensured around electrode slice by spot welding.

In the electrode system of open type two of test chemical property, negative pole is MH electrodes, and positive pole adopts the burning of capacity excess Knot Ni (OH)₂/ NiOOH electrodes, electrolyte is 6molL^-1KOH solution, the battery for assembling shelves 24h, using LAND batteries Tester with galvanostatic method determine alloy electrode chemical property (activation number of times, peak capacity, high-rate discharge capacity HRD, Cyclical stability etc.), test environment temperature is 298K.Density of charging current 70mAg^-1, charging interval 6h, discharge current density 70mA·g^-1, electric discharge stopping potential is 1.0V, charge and discharge intermittent time 10min.

Table 1 below lists RE described in embodiment 1～22_xY_yNi_z-a-bMn_aAl_bHydrogen bearing alloy and its chemical property.

The RE of table 1_xY_yNi_z-a-bMn_aAl_bHydrogen bearing alloy and its chemical property

Note：A is the cycle-index that electrode activation needs；B is maximum discharge capacity；C be circulate 100 times capacity keep Rate；D be discharge current density Id be 350mAg-1 when multiplying power discharging ability；Discharge capacity when e is low temperature 243K keeps Rate；F is the capability retention (self-discharge characteristics) after depositing 72 hours.

As seen from Table 1, alloy LaY described in embodiment 13 and 14₂Ni₈Mn_0.5Al_0.5Chemical property compare, through annealing The electrochemistry capacitance of the alloy electrode of embodiment 14 of heat treatment increases, and cycle life, multiplying power discharging ability, low temperature discharge are special Property, self-discharge performance make moderate progress.

As shown in figure 1, analyzing LaY using x-ray diffractometer₂Ni₈Mn_0.5Al_0.5The institutional framework of alloy (embodiment 13), Alloy principal phase is YNi₃Phase or LaNi₃Phase.

Claims

1. a kind of lanthanon hydrogen storage alloy, it is characterised in that：Composition formula is RE_xY_yNi_z-a-bMn_aAl_b, wherein RE be La, Ce, One or more elements in Pr, Nd, Sm, Gd；X ＞ 0, y >=2, x+y=3；9.5 ＞ z >=8.5；3.5 >=a+b ＞ 0.

2. a kind of lanthanon hydrogen storage alloy as claimed in claim 1, it is characterised in that：1.0≥x≥0.5.

3. a kind of lanthanon hydrogen storage alloy as claimed in claim 1 or 2, it is characterised in that：2.0≥a≥0.5.

4. a kind of lanthanon hydrogen storage alloy as claimed in claim 1 or 2, it is characterised in that：1.0≥b≥0.2.

5. a kind of lanthanon hydrogen storage alloy as claimed in claim 1 or 2, it is characterised in that：Z=9.

6. a kind of lanthanon hydrogen storage alloy as claimed in claim 1, it is characterised in that：1.0 >=x >=0.5,2.0 >=a >=0.5, 1.0 >=b >=0.2, z=9.

7. a kind of preparation method of lanthanon hydrogen storage alloy as claimed in claim 1, it is characterised in that：According to chemical molecular formula Proportioning is calculated and accurately weighs each elemental metals raw material, and material purity is all higher than 99.0%；Raw material is put into into Al₂O₃Crucible, takes out true Sky is filled with inert gas Ar to 0.055MPa to 3.0Pa；Intensification melting, is incubated rapid hardening after 6min, and rapid hardening copper roller linear velocity is 3.4m/s, copper roller normal open cooling water, 25 DEG C of coolant water temperature.

8. a kind of preparation method of lanthanon hydrogen storage alloy as claimed in claim 7, it is characterised in that：Terminate in rapid hardening step Afterwards, alloy is under vacuum or inert gas shielding, annealing heat-treats 8h at 750 DEG C.

9. a kind of hydrogen-bearing alloy electrode, it is characterised in that made with the lanthanon hydrogen storage alloy any one of claim 1-6 For hydrogen storage media.

10. a kind of secondary cell, it is characterised in that containing the hydrogen-bearing alloy electrode described in claim 9.