CN101633985A - Preparation method of RE-Fe-B part hydrogen storage alloy - Google Patents

Preparation method of RE-Fe-B part hydrogen storage alloy Download PDF

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CN101633985A
CN101633985A CN200910145266A CN200910145266A CN101633985A CN 101633985 A CN101633985 A CN 101633985A CN 200910145266 A CN200910145266 A CN 200910145266A CN 200910145266 A CN200910145266 A CN 200910145266A CN 101633985 A CN101633985 A CN 101633985A
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alloy
hydrogen storage
storage alloy
preparation
part hydrogen
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闫慧忠
孔繁清
熊玮
李金�
李宝犬
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Baotou Rare Earth Research Institute
Ruike Rare Earth Metallurgy and Functional Materials National Engineering Research Center Co Ltd
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Baotou Rare Earth Research Institute
Ruike Rare Earth Metallurgy and Functional Materials National Engineering Research Center Co Ltd
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Priority to PCT/CN2009/001301 priority patent/WO2010057367A1/en
Priority to JP2011536727A priority patent/JP5773878B2/en
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Abstract

The invention relates to a preparation method of an RE-Fe-B part hydrogen storage alloy, which is characterized by comprising the following materials: RE contained in the RE-Fe-B part hydrogen storage alloy, a replaced element of the RE, B, a replaced element of the B, an RE-Fe alloy, a B-Fe alloy, a B-Ni alloy, an RE-Fe-B alloy, a LaNi5 type alloy and other preliminary alloys containing composition elements, wherein two or more materials are selected to be prepared according to a chemical composition formula of the RE-Fe-B part hydrogen storage alloy; one of a high-temperature smelting casting method, a high-temperature smelting-quick-quenching method, a high-temperature smelting-gas atomization method and a powder sintering method or a mechanical alloying method is adopted to manufacture the RE-Fe-B part hydrogen storage alloy; and the preparation process needs to be carried out under the protection of inert gas or a vacuum environment. The RE-Fe-B part hydrogen storage alloy is in a multiphase structure and comprises a LaNi5 phase, a La3Ni13B2 phase, a rich Fe or rich Ni phase, and the like. The prepared RE-Fe-B part hydrogen storage alloy has good activation property due to the special composition and structure, large current discharge capability, low-temperature electrochemistry property and charge/discharge or hydriding/dehydriding circulating stability, the maximum discharge capacity of the RE-Fe-B part hydrogen storage alloy can reach 400mAh.g<-1>, and the cost of the RE-Fe-B part hydrogen storage alloy is lower than that of other known hydrogen storage alloys; and in addition, the prepared RE-Fe-B part hydrogen storage alloy is used for battery negative pole materials, gaseous phase hydrogen storage materials and heat pump materials.

Description

The preparation method of RE-Fe-B base hydrogen storage alloy
Technical field:
The present invention relates to a kind of preparation method of RE-Fe-B base hydrogen storage alloy, belong to the hydrogen storage material field.
Background technology:
Earlier 1990s, high-performance, free of contamination LaNi 5Type hydrogen storage alloy replaces deleterious cadmium cathode in cadmium nickel (Cd/Ni) battery, develops environment-friendly metal hydride-nickel (MH/Ni) secondary cell, the application market of having captured portion C d/Ni battery.But because commodity LaNi 5Contain valuable higher metallic element Co in the type alloy and cost is higher, make the MH/Ni battery can't replace the Cd/Ni battery fully.
China is the manufacturing center and the maximum export State of global Cd/Ni battery, and Cd/Ni battery ultimate production reached 2,000,000,000 in 2004, and the volume of production and marketing of Cd/Ni battery was suitable with the MH/Ni battery in recent years, all had tens00000000 every year.Because contain the heavy metal cadmium of serious harm HUMAN HEALTH in the Cd/Ni battery, national governments have put into effect the restrictive policy about the electronic product pollutent successively, make the production of Cd/Ni battery and use be subjected to very big influence.Yet,, be still the main power supply in fields such as power tool, emergency light, shaving apparatus, cordless telephone and toy because the price comparison of Cd/Ni battery is cheap.
Under this background, all press for the substitute products of a kind of cost performance of exploitation to market near Cd/Ni battery, environmentally safe from battery producer.
RE (rare earth)-Fe-B base hydrogen storage alloy is the novel rare-earth functional materials of a class " green " environmental protection, with traditional LaNi 5Type alloy phase ratio, cost reduces about 40%, heavy-current discharge performance and low temperature electrochemical performance obviously improve, can develop the various hydrogen storage electrode materials that satisfy the different demands of battery, thereby further substitute the Cd negative pole in the Cd/Ni battery, produce a new generation's low cost, high-performance environment protection type MH/Ni secondary cell, satisfy the product transformation and the market requirement of Cd/Ni battery production producer.
RE-Fe-B is that hydrogen storage material also can replace the LaNi in the existing MH/Ni secondary cell 5The type hydrogen storage electrode alloy significantly reduces the MH/Ni battery cost, strengthens the market competitiveness of MH/Ni battery.
The inventor declares the binomial national inventing patent in October, 2008: " RE-Fe-B base hydrogen storage alloy ", application number: 200810176872.8, " La 15Fe 77B 8Type hydrogen storage alloy and uses thereof ", application number: 200810176873.2.But do not relate to the starting material of alloy preparation, do not propose preparation technology's specific requirement yet.
Summary of the invention:
The preparation method who the purpose of this invention is to provide a kind of RE-Fe-B base hydrogen storage alloy, can develop the novel hydrogen storage material of meeting the need of market with present method, this hydrogen storage material can be used for preparing the negative material of battery, as low-cost hydrogen storage material, high power type hydrogen storage material, high temperature/low temperature modification hydrogen storage material etc., also can be used for gas phase and inhale/put hydrogen hydrogen storage material.
The chemical constitution formula of the RE-Fe-B base hydrogen storage alloy for preparing mainly comprises RE 19Fe 68B 68, RE 17Fe 76B 7, RE 15Fe 77B 8, RE 8Fe 86B 6, RE 8Fe 27B 24, RE 8Fe 28B 24, RE 5Fe 18B 18, RE 5Fe 2B 6, RE 2Fe 23B 3, RE 2FeB 3, RE 2Fe 14B.Wherein, RE can be one or more in rare-earth elements of lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), lutetium (Lu), scandium (Sc) and the yttrium (Y), and, RE can by in the periodic table of chemical element can with magnesium (Mg), calcium (Ca), zirconium (Zr), titanium (Ti), all or part of replacement of vanadium (V) element of hydrogen evolution hydride; Fe (iron) can be by the transition metal nickel (Ni) in the periodic table of chemical element, manganese (Mn), aluminium (Al), cobalt (Co), copper (Cu), zirconium (Zr), titanium (Ti), vanadium (V), zinc (Zn), chromium (Cr), tungsten (W) and nontransition metal element gallium (Ga), tin (Sn), plumbous (Pb) all or part of replacement; B (boron) can be by metallic elements of ferrum (Fe), nickel (Ni), manganese (Mn), aluminium (Al), cobalt (Co), copper (Cu), zirconium (Zr), titanium (Ti), vanadium (V), zinc (Zn), chromium (Cr), tungsten (W), gallium (Ga), tin (Sn), plumbous (Pb) and metallic element silicon (Si), sulphur (S), carbon (C), all or part of replacement of phosphorus (P); Each atoms of elements is than adjusting in 50% scope in the RE-Fe-B base hydrogen storage alloy of being invented.As Nd 8Fe 27B 24The adjustable atomic ratio scope of alloy is 4-12: 14-40: 12-36.
The preparation method of described RE-Fe-B base hydrogen storage alloy comprises following content:
1) starting material are RE (rare earth) in the alloy composition and substitute element, Fe and substitute element thereof, B and substitute element thereof, RE-Fe alloy, B-Fe alloy, B-Ni alloy, RE-Fe-B alloy, LaNi 5Type alloy and other contain the master alloy of component, select wherein the chemical constitution formula preparation of two or more raw material according to alloy;
2) a kind of processing method manufacturing in employing high melt casting, high melt-quick quenching technique, high melt-gas atomization, powder sintering or the mechanical alloying method, preparation process need be carried out under protection of inert gas or under vacuum environment;
3) prepared RE-Fe-B base hydrogen storage alloy can further adopt heat treating method to improve its weave construction and performance;
4) prepared RE-Fe-B base hydrogen storage alloy and heat treatable alloy adopt a kind of in airflow milling, ball milling, sledge mill or the high temperature atomising method to prepare particle or the powder that granularity is 0.3～10mm;
5) particle of prepared RE-Fe-B base hydrogen storage alloy and heat treatable alloy or powder can adopt one or more methods in physics, chemistry or the mechanical means to unite to carry out surface treatment to improve its performance.
The key distinction of the present invention and prior art: the preparation raw material of RE-Fe-B base hydrogen storage alloy of the present invention can be the simple substance form of component, also can be the master alloy that contains component.RE-Fe-B base hydrogen storage alloy by described preparation method's preparation has better electrochemistry charge/discharge performance and gas phase suction/hydrogen discharging performance.
The effect of invention:
The RE-Fe-B base hydrogen storage alloy of the present invention's preparation is a heterogeneous structure, comprises LaNi 5Phase, La 3Ni 13B 2Phase, rich Fe or rich Ni equate.Prepared RE-Fe-B base hydrogen storage alloy is owing to distinctive The Nomenclature Composition and Structure of Complexes, and its hydrogen-bearing alloy electrode has good activation performance, large current discharging capability and low temperature electrochemical performance, and maximum discharge capacity can reach 400mAhg -1, cost is lower than known other hydrogen storage alloy.Prepared RE-Fe-B base hydrogen storage alloy has excellent corrosion resisting performance and the hydrogen-expansion rate is put in less suction, thereby has good charge/discharge or suction/put hydrogen cyclical stability.Prepared RE-Fe-B base hydrogen storage alloy has excellent gas phase and inhales/put reversible hydrogen, and the lag-effect of pressure-composition isothermal (P-c-I) curve is obviously less, and the hydrogen-storage amount under usual conditions is greater than 1.0wt.%.Prepared RE-Fe-B base hydrogen storage alloy can be used for cell negative electrode material, gas phase seasoning hydrogen material and heat pump material.
Description of drawings:
Fig. 1 is RE 15(FeNiMn) 77(BMnAl) 8The XRD figure spectrum of hydrogen storage alloy, alloy is a heterogeneous structure as can be seen.；
Fig. 2 is RE 15(FeNiMn) 77(BMnAl) 8The P-c-I curve of hydrogen storage alloy, alloy has good platform identity as can be seen, and lag-effect is very little.
Embodiment:
Embodiment 1.
Prepared alloy composition is RE 19(FeNiMn) 68(BMnAl) 68, RE 17(FeNiMn) 76(BMnAl) 7, RE 15(FeNiMn) 77(BMnAl) 8, RE 15(FeNiMnCu) 77(BMnAl) 8, RE 15(FeNiMnCu) 77(BMnAlSi) 8, RE 8(FeNiMn) 86(BMnAl) 6, RE 8(FeNiMn) 27(BMnAl) 24, RE 8(FeNiMn) 28(BMnAl) 24, RE 5(FeNiMn) 18(BMnAl) 18, RE 5(FeNiMn) 2(BMnAl) 6, RE 2(FeNiMn) 23(BMnAl) 3, RE 2(FeNiMn) (BMnAl) 3, RE 2(FeNiMn) 14(BMnAl).According to the stoichiometric ratio of prepared alloy, with RE-Fe alloy, RE-Fe-B alloy, LaNi 5Type alloy, B-Fe alloy, B-Ni alloy are raw material, are the raw material of equilibrium composition with other element simple substance RE, Fe, Ni, Mn, Cu, Mn, Al, Si in the alloy composition simultaneously, consider La, Mn wherein, the melting scaling loss of Al element.Calculate and the various raw materials of weighing (purity is all greater than 99.0%).Adopt Medium frequency induction melting-rapid quenching technique that starting material are made the RE-Fe-B alloy sheet under the Ar gas shiled.Prepared alloy sheet is heat-treated under vacuum or protection of inert gas, and heat-treat condition is: 850-1050 ℃ is incubated 2-5 hour, then 450-850 ℃ of insulation 2-5 hour.Thin slice after the thermal treatment is directly used in gas phase inhales/puts hydrogen test (measuring the P-c-I curve).The powder that thin slice after the thermal treatment is made 50-150 μ m through ball milling carries out the charge discharge performance test.The preparation method of test electrode is, prepared hydrogen storing alloy powder mixes with the mass ratio of carbonyl nickel powder with 1: 4, under 16MPa pressure, make the MH electrode slice of φ 15mm, this electrode slice is placed between two nickel foam, sandwich nickel strap simultaneously as lug, under 16MPa pressure, make the storage hydrogen negative pole (MH electrode) that is used to test once more, guarantee tight contact the between electrode slice and the nickel screen by spot welding around the electrode slice.Negative pole in open type two electrode systems of test chemical property is the MH electrode, the sintering Ni (OH) of anodal employing capacity surplus 2/ NiOOH electrode, electrolytic solution are 6molL -1KOH solution, the battery that assembles is shelved 24h, use the chemical property (activation number of times, peak capacity, high-rate discharge capacity HRD, cyclical stability etc.) of LAND cell tester with galvanostatic method mensuration alloy electrode, the test environment temperature is 298K, density of charging current 70mAg -1, duration of charging 6h, discharge current density 70mAg -1, the discharge stopping potential is 1.0V, charge and discharge intermittent time 10min.The alloy part test result sees Table 1 among the embodiment.
The performance of alloy part among table 1 embodiment
Figure G2009101452664D00031
Figure G2009101452664D00041
Annotate: a is the cycle index that electrode activation needs; B is a maximum discharge capacity; C is 100 times a capability retention of circulation; D is discharge current density I dBe 350mAg -1The time the multiplying power discharging ability.
Embodiment 2.
Prepared alloy composition is RE 15(FeNiMn) 77(BMnAl) 8According to RE 15(FeNiMn) 77(BMnAl) 8The stoichiometric ratio of alloy is a raw material with metal La, metal Ni, metal M n, metal A l and La-Fe, the B-Fe alloy of simple substance, considers La, Mn wherein, the melting scaling loss of Al element simultaneously, calculates and the various raw materials of weighing (purity is all greater than 99.0%).Melting preparation technology, heat treating method, milling method and performance test methods are with embodiment 1.Test result sees Table 2.
Table 2RE 15(FeNiMn) 77(BMnAl) 8The performance of hydrogen storage alloy
Figure G2009101452664D00042
Embodiment 3.
Prepared alloy composition and starting material are with embodiment 2.Adopt high melt casting, high melt-gas atomization, powder sintering preparation respectively.Preparation process is carried out under the Ar gas shiled, and heat treating method, milling method and performance test methods are with embodiment 1.Test result sees Table 3.
Table 3RE 15(FeNiMn) 77(BMnAl) 8The different preparation methods' of hydrogen storage alloy performance relatively
Figure G2009101452664D00043

Claims (4)

1, a kind of preparation method of RE-Fe-B base hydrogen storage alloy is characterized in that: starting material are RE in the alloy composition and substitute element, Fe and substitute element thereof, the substitute element of B, RE-Fe alloy, B-Fe alloy, B-Ni alloy, RE-Fe-B alloy, LaNi 5Type alloy and other contain the master alloy of component, select wherein the chemical constitution formula preparation of two or more raw material according to alloy; Adopt a kind of processing method manufacturing in high melt casting, high melt-quick quenching technique, high melt-gas atomization, powder sintering or the mechanical alloying method, preparation process need be carried out under protection of inert gas or under vacuum environment.
2, the preparation method of RE-Fe-B base hydrogen storage alloy according to claim 1 is characterized in that: prepared RE-Fe-B base hydrogen storage alloy adopts heat treating method to improve its weave construction and performance.
3, the preparation method of RE-Fe-B base hydrogen storage alloy according to claim 1 and 2 is characterized in that: prepared RE-Fe-B base hydrogen storage alloy adopts a kind of in airflow milling, ball milling, sledge mill or the high temperature atomising method to prepare particle or the powder that granularity is 0.3～10mm.
4, the preparation method of RE-Fe-B base hydrogen storage alloy according to claim 3 is characterized in that: prepared RE-Fe-B base hydrogen storage alloy particle or powder adopt one or more methods in physics, chemistry or the mechanical means to unite to carry out surface treatment to improve its performance.
CN200910145266A 2008-11-21 2009-05-21 Preparation method of RE-Fe-B part hydrogen storage alloy Pending CN101633985A (en)

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PCT/CN2009/001301 WO2010057367A1 (en) 2008-11-21 2009-11-23 RE-Fe-B SERIES HYDROGEN STORAGE ALLOY AND USE THEREOF
JP2011536727A JP5773878B2 (en) 2008-11-21 2009-11-23 RE-Fe-B hydrogen storage alloy and use thereof

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102694157A (en) * 2012-06-21 2012-09-26 广西大学 Rare earth hydrogen storage alloy electrode material and preparation method thereof
CN102709535A (en) * 2012-06-21 2012-10-03 广西大学 Fe-based hydrogen storage alloy electrode material and preparation method thereof
CN102952988A (en) * 2011-08-16 2013-03-06 中国科学院金属研究所 High activity and high hydrogen-induced disproportionation resisting hydrogen storage isotope Sc-Cr-Mn alloy
CN103949651A (en) * 2014-04-30 2014-07-30 浙江旭德新材料有限公司 Preparation method for unleaded abrasion resistant and corrosion resistant alloy powder material
CN106111997A (en) * 2016-06-28 2016-11-16 湘潭大学 A kind of preparation method of porous nickel alloy electrolysis liberation of hydrogen composite cathode material
CN111961908A (en) * 2020-08-27 2020-11-20 昆明理工大学 Preparation method for in-situ generation of binary boride reinforced noble metal high-temperature alloy

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102952988A (en) * 2011-08-16 2013-03-06 中国科学院金属研究所 High activity and high hydrogen-induced disproportionation resisting hydrogen storage isotope Sc-Cr-Mn alloy
CN102952988B (en) * 2011-08-16 2014-10-15 中国科学院金属研究所 High activity and high hydrogen-induced disproportionation resisting hydrogen storage isotope Sc-Cr-Mn alloy
CN102694157A (en) * 2012-06-21 2012-09-26 广西大学 Rare earth hydrogen storage alloy electrode material and preparation method thereof
CN102709535A (en) * 2012-06-21 2012-10-03 广西大学 Fe-based hydrogen storage alloy electrode material and preparation method thereof
CN102694157B (en) * 2012-06-21 2014-11-05 广西大学 Rare earth hydrogen storage alloy electrode material and preparation method thereof
CN102709535B (en) * 2012-06-21 2015-05-27 广西大学 Fe-based hydrogen storage alloy electrode material and preparation method thereof
CN103949651A (en) * 2014-04-30 2014-07-30 浙江旭德新材料有限公司 Preparation method for unleaded abrasion resistant and corrosion resistant alloy powder material
CN103949651B (en) * 2014-04-30 2016-01-20 浙江旭德新材料有限公司 A kind of preparation method of unleaded antifriction anticorrosion alloy dusty material
CN106111997A (en) * 2016-06-28 2016-11-16 湘潭大学 A kind of preparation method of porous nickel alloy electrolysis liberation of hydrogen composite cathode material
CN111961908A (en) * 2020-08-27 2020-11-20 昆明理工大学 Preparation method for in-situ generation of binary boride reinforced noble metal high-temperature alloy
CN111961908B (en) * 2020-08-27 2021-12-28 昆明理工大学 Preparation method for in-situ generation of binary boride reinforced noble metal high-temperature alloy

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