CN1320671C - Amorphous rear-earth-magnesium-Nickel series hydrogen storage electrode material and producing method thereof - Google Patents

Amorphous rear-earth-magnesium-Nickel series hydrogen storage electrode material and producing method thereof Download PDF

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CN1320671C
CN1320671C CNB2005100969872A CN200510096987A CN1320671C CN 1320671 C CN1320671 C CN 1320671C CN B2005100969872 A CNB2005100969872 A CN B2005100969872A CN 200510096987 A CN200510096987 A CN 200510096987A CN 1320671 C CN1320671 C CN 1320671C
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electrode material
hydrogen storage
ball
powder
magnesium
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CN1741307A (en
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熊玮
闫慧忠
孔繁清
李宝犬
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Inner Mongolia Rare Earth Functional Materials Engineering Technology Research Center
Baotou Rare Earth Research Institute
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    • 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 relates to the amorphous hydrogen storing electrode material of rare earth-magnesium-nickel series and a preparing method thereof. The chemical composition of the hydrogen storing material is Ml2Mg17Ba A<b>+x wt. %Ni, wherein the A is one or more than one of the elements of fluorinated graphite (CFn), silicon (Si), sulfur (S), carbon (C), phosphorus (P), aluminum (Al), germanium (Ge), selenium (Se) or iodine (I); 0.01<=a<=3.0; 0<=b<=2.5; the x represents the percentage content of weight corresponding to the Ml2Mg17; 150<=x<=250. The hydrogen storing electrode material has the obvious advantages that initial electrochemical capacity is high, cycling stability for charging and discharging is good, the hydrogen storing electrode material can be used for the preparation of the amorphous hydrogen storing electrode materials of rare earth-magnesium-nickel series by using a continuous ball milling technology in a shorter time, and material preparing efficiency is greatly enhanced. The hydrogen storing electrode material can be used for the preparation of active materials for the negative electrodes of MH/Ni secondary cells.

Description

Amorphous Rare Earth-magnesium-nickel series Hydrogen-bearing Electrode Material And Preparation Method
Technical field
The present invention relates to a kind of Amorphous Rare Earth-magnesium-nickel series Hydrogen-bearing Electrode Material And Preparation Method.
Background technology
LaNi 5Type hydrogen storage alloy is the negative material of present widely used nickel-hydrogen secondary cell (MH/Ni), and its theoretical electrochemistry capacity (power-carrying) is 373mAh/g, the commodity negative material Mm (NiCoMnAl) of practical application 5The heap(ed) capacity of (wherein, Mm is a norium) is 310-320mAh/g, and the specific energy of such battery is compared with some high-energy secondary cell (as lithium ion battery) and had big gap.In recent years, in order to develop the high-performance hydrogen bearing alloy that is used for MH/Ni battery cathode active material, the research of magnesium base alloy has been given the attention of height.The theoretical electrochemistry capacity height of magnesium-base hydrogen storage material, low price promises to be MH/Ni battery a new generation high performance-price ratio storage hydrogen negative material most.La wherein 2Mg 17Theoretical capacity up to 1474mAh/g, be LaNi 5Four times, and the cost of Unit Weight approximately is LaNi at present 51/5.Amorphous state La by melting-mechanical lapping (MG) preparation 2Mg 17+ x wt.%Ni composite material (a-La 2Mg 17+ x wt.%Ni, x are that Ni is with respect to La 2Mg 17Addition), demonstrate higher actual measurement electrochemistry capacitance and good initial activation performance.Have the increase of the alloy of non crystalline structure owing to equilibrium hydrogen pressure, even at room temperature also can discharge the hydrogen of absorption, and non crystalline structure provides the passage that helps the hydrogen diffusion.
At document " Electrochemical properties of the ball-milled La 1.8Ca 0.2Mg 14Ni 3+ x wt%Nicomposites (x=0,50,100 and 200) " (ball milling La 1.8Ca 0.2Mg 14Ni 3The electrochemical properties of+x wt%Ni composite material (x=0,50,100 and 200)) Journal of Alloys and Compounds (alloy and compound) is among 354 (2003) 120-123, by the La of multi-element alloyed modification with the induction melting preparation 2Mg 17Type alloy La 1.8Ca 0.2Mg 14Ni 3With x wt.%Ni (x=0,50,100,200) mechanical ball milling, ratio of grinding media to material 2: 1, argon shield, 225 rev/mins of the speeds of mainshaft, ball milling time 50h.The composite structure of preparation is an amorphous state, and the Electrochemical results under 298K shows, La 1.8Ca 0.2Mg 14Ni 3The discharge capacity of+100wt.%Ni is pressed La 1.8Ca 0.2Mg 14Ni 3Mass Calculation reaches 1004mAh/g, and 10 times capacity attenuation about 60% circulates.This article thinks that the improvement of the composite material electrochemistry capacitance that ball milling prepares is that adding nickel is the key factor that forms non-crystaline amorphous metal in advance owing to formed non crystalline structure, and cyclical stability also is subjected to the influence of non-crystallization degree and nickel addition simultaneously.
Document " Electrochemical Hydrogen Storage of Nanocrystalline La 2Mg 17AlloyBallmilled with Ni Powders " (with the nanocrystalline La of Ni powder ball milling 2Mg 17The electrochemical hydrogen storage of alloy) Electrochemical and Solid-State Letters (electrochemistry and solid-state communication), 7 (2004): the A102-A104 report, by ball milling La 2Mg 17Alloy and Ni powder have prepared La 2Mg 17The base nanometer crystal alloy, the two is by weight 1: 2 ball milling, the initial capacity of product near 990mAh/g (with La 2Mg 17Calculate).Trace it to its cause, metal Ni particle high degree of dispersion is on the nanometer crystal alloy matrix, and the Ni that inlay on the surface not only becomes the electrochemical catalysis response location but also be that hydrogen absorbs the position, thereby has quickened the charge discharge process.
Hydrogen bearing alloy chemical formula among the patent CN1397658A " a kind of non-crystal rare-earht-Mg based hydrogen bearing alloy and manufacture method thereof " is Re 2-xM xMg 17-yN y, in the formula, 0≤x≤1,0≤y≤4; Re is a kind of among rare-earth metal La, Ce, Pr, Nd, Sm, cerium-rich mischmetal metal M m, the lanthanum rich norium Ml; M be metal Ca, Ti, V, Zr, in a kind of; N is a kind of among metal Ni, Co, Mn, the Cu.Predefined rare-earth and Mg base alloying component is made crystal alloy by melting, alloy at room temperature is ground into less than 200 powder materials, place the ball mill ball milling to form amorphous alloy with the aromatic organic compounds solvent powder again, promptly obtain solid amorphous attitude rare earth and magnesium-based hydrogen storage alloy except that after desolvating.
The subject matter that the magnesium-based hydrogen-storage electrode material exists is that capacity attenuation comparatively fast is the charge and discharge cycles poor stability.The reason of magnesium base hydrogen-storing electrode capacity decay be it is generally acknowledged: because the chemical activity of magnesium makes electrode material form Mg (OH) in alkaline electrolyte 2Passivation layer has hindered suction/put the hydrogen process so capacity attenuation; The efflorescence that the dissolving of alloying element in electrolyte in addition, electrode are being inhaled/put in the hydrogen process also is the reason that causes capacity attenuation.
For suppressing La 2Mg 17The research of+x wt.%Ni material capacity decay almost is blank.The present invention has developed a kind of poly modified a-Ml 2Mg 17+ x wt.%Ni (Ml represents lanthanum rich norium) magnesium-based hydrogen-storage electrode material and preparation method thereof.
Summary of the invention
The purpose of this invention is to provide a kind of Amorphous Rare Earth-magnesium-nickel series Hydrogen-bearing Electrode Material And Preparation Method, by the material modification technology, make this material have initial electrochemistry capacitance height on the one hand, the charge and discharge cycles stable properties, on the other hand, shorten the decrystallized ball milling time of material, improve the preparation efficiency of material.The magnesium-base hydrogen storage material of being invented can be used to prepare the negative material of MH/Ni secondary cell.
The objective of the invention is to realize by following mode:
A kind of non-crystal rare-earht-Mg-Nickel series hydrogen storage electrode material, chemical composition are Ml 2Mg 17B aA b+ x wt.%Ni, wherein, A is one or more in fluorographite (CFn), silicon (Si), sulphur (S), carbon (C), phosphorus (P), aluminium (Al), germanium (Ge), selenium (Se) or iodine (I) element; 0.01≤a≤3.0,0≤b≤2.5; X is with respect to Ml 2Mg 17Weight percentage, 150≤x≤250.
The preparation method of described non-crystal rare-earht-Mg-Nickel series hydrogen storage electrode material: at first adopt fusion technology to prepare Ml 2Mg 17Alloy, raw material are lanthanum rich norium and magnesium metal (99.9%) ingot bar.Melting is carried out in the vacuum induction shower furnace of argon shield, prepared Ml 2Mg 17Alloy cast ingot exists Organic solventIn be crushed to 100-500 order powder;
Adopting ball mill to prepare rare-earth and Mg-nickel by mechanical lapping under argon shield is hydrogen storage material, raw material Ml 2Mg 17Powder, nickel powder (Ni), boron powder (B) and A mix by stoichiometric proportion, with abrading-ball by ratio of grinding media to material 35～10: 1 puts into ball grinder seals, ball grinder is evacuated and feeds argon gas, under greater than 200 rev/mins rotational speed of ball-mill, with the mixture in the continuous ball milling method mechanical lapping jar, ball milling obtained non-crystal rare-earht-Mg-Nickel series hydrogen storage electrode material in 5～45 hours.The powder electrode material of preparation is thus made the Mg base hydrogen bearing alloy negative pole by the technology for preparing electrode of any MH/Ni battery.
The present invention has 2 points with the main distinction of prior art: the one, and material is formed different, and foundry alloy of the present invention is Ml 2Mg 17, Ml has substituted La with norium 2Mg 17In pure rare earth element La, help improving the resistance to chemical corrosion of material, improve the charge and discharge cycles stability of electrode material; The 2nd, at Ml 2Mg 17Boron (B), the fluorographite higher elements of electronegativity such as (CFn) have been added in+x wt.%Ni the material, improve the chemical property of material on the one hand, especially improved the stability of electrode material cycle charge-discharge, on the other hand, has the effect that the promotion material is decrystallized, suppress the material crystallization owing to add element, shorten the morphogenetic ball milling time of amorphous, improved development and production efficiency.
The effect of invention:
Material Ml of the present invention 2Mg 17B aA b+ x wt.%Ni has initial electrochemistry capacitance height, the characteristics of charge and discharge cycles good stability as hydrogen storage electrode material.Institute's invention material is by melting-mechanical lapping (MG) two steps preparation, the ball milling time of its MG technology and the Ml that does not add boron (B) and A 2Mg 17+ x wt.%Ni material is compared greatly and is shortened, and has improved the efficient of preparation non-crystal rare-earht-Mg-Nickel series hydrogen storage electrode material.The magnesium-base hydrogen storage material of being invented can be used to prepare the negative material of MH/Ni secondary cell.
At Ml 2Mg 17The boron (B) that adds in+x wt.%Ni the material, fluorographite (CFn), silicon (Si), sulphur (S), carbon (C), phosphorus (P), aluminium (Al), germanium (Ge), selenium (Se), iodine elements such as (I) all have higher electronegativity, can fetter the peripheral electron of the active Mg element of chemical property effectively, reduce the reproducibility of Mg element, thereby slow down the corrosion of Mg based hydrogen storage material in electrolyte, improved the electrochemistry cyclical stability of magnesium-based hydrogen-storage electrode material; On the other hand, these elements with nonmetal feature have promoted the decrystallized process of Mg based hydrogen storage material effectively, have shortened the ball milling time of preparation amorphous magnesium based hydrogen storage material, have improved material preparation efficient.In addition, shorten the ball milling time, also can increase the granularity of powder, also help the electrochemistry cyclical stability of electrode.
Embodiment
Embodiment 1
Primary raw material: battery grade mischmetal Ml, magnesium metal Mg, Mg content 〉=99.9, the easy prestige magnesium industry in Taiyuan Group Co.,Ltd produces.Analyze pure nickel powder Ni, Ni content 〉=99.9.
Ml 2Mg 17The melting preparation of alloy: Ml is the norium of La content 64.3%, and mean atomic weight 139.7 is calculated Ml by stoichiometric proportion 2Mg 17In the theoretical weight ratio of Ml and Mg be respectively 40.3% and 59.7%, excessive in 0.2% when the batching to the high element magnesium of vapour pressure under the high temperature guaranteeing to obtain to meet the composition of stoichiometric proportion, adopt the melting of vacuum magnetic suspension stove.Vacuumize before the melting, under argon shield, smelt Mm then 2Mg 17Hydrogen bearing alloy, remelting three times.Alloy pig is broken for-500 order powder after removing descale in benzinum.
Utilize high-energy ball milling to prepare a kind of non-crystal rare-earht-Mg-Nickel series hydrogen storage electrode material.The chemical formula of this hydrogen storage material is Ml 2Mg 17B+180wt.%Ni calculates Ml by this chemical formula 2Mg 17, B, Ni weight proportion be 100: 1.5: 180, by 30: 1 ratios of grinding media to material with abrading-ball and Ml 2Mg 17Alloyed powder, Ni powder, the B powder ball grinder of packing into charges into protection gas Ar gas after vacuumizing.The ball milling operation is carried out in the QM-1SP planetary ball mill, 450 rev/mins of drum'ss speed of rotation, and ball milling discharging in 40 hours continuously uses Philips-PW1700 type x-ray diffractometer to analyze the alloy organizing structure, and alloy powder all is an amorphous state.
The preparation method of test electrode is that ball milling alloy powder 0.07 gram mixes with conductive agent carbonyl Ni powder 0.35 gram (200 order), depresses to the disk of 10 millimeters of φ as negative pole at 40 tons/square centimeter pressure.Ni (OH) just very 2/ NiOOH, electrolyte are the 6M KOH aqueous solution, adopt the chemical property of DC-5 electro-chemical test system testing material, the 300mA/g 3.5h that charges, and 100mA/g is discharged to 1.0V, and the initial discharge capacity that records is by Ml 2Mg 17The weight of B is calculated as 860mAh/g, charge and discharge cycles 20 times, and capacity keeps more than 90%, and does not add the amorphous state Ml of boron 2Mg 17The initial capacity of+180wt.%Ni electrode material is 930mAh/g, charge and discharge cycles 20 times, and capacity keeps 75%.
Embodiment 2
Melting prepares Ml 2Mg 17Alloy materials and smelting technology are with embodiment 1.
Utilize high-energy ball milling to prepare a kind of non-crystal rare-earht-Mg-Nickel series hydrogen storage electrode material.The chemical formula of this hydrogen storage material is Ml 2Mg 17B (CFn) 0.2+ 180wt.%Ni calculates Ml by this chemical formula 2Mg 17, B, CFn, Ni weight proportion be 100: 1. 5: 0.9: 180, by 30: 1 ratios of grinding media to material with abrading-ball and Ml 2Mg 17Alloyed powder, Ni powder, B powder, the CFn powder ball grinder of packing into charges into protection gas Ar gas after vacuumizing.The ball milling operation is carried out in the QM-1SP planetary ball mill, 450 rev/mins of drum'ss speed of rotation, and ball milling discharging in 35 hours continuously uses Philips-PW1700 type x-ray diffractometer to analyze the alloy organizing structure, and alloy powder all is an amorphous state.
The preparation of test electrode and method of testing are with embodiment 1.The initial discharge capacity that records is by Ml 2Mg 17B (CFn) 0.2Weight be calculated as 750mAh/g, charge and discharge cycles 20 times, capacity keeps more than 93%.
Embodiment 3
Melting prepares Ml 2Mg 17Alloy materials and smelting technology are with embodiment 1.
Utilize high-energy ball milling to prepare a kind of non-crystal rare-earht-Mg-Nickel series hydrogen storage electrode material.The chemical formula of this hydrogen storage material is Ml 2Mg 17BAl 0.3+ 180wt.%Ni calculates Ml by this chemical formula 2Mg 17, B, CFn, Ni weight proportion be 100: 1.5: 1.2: 180, by 30: 1 ratios of grinding media to material with abrading-ball and Ml 2Mg 17Alloyed powder, Ni powder, B powder, the Al powder ball grinder of packing into charges into protection gas Ar gas after vacuumizing.The ball milling operation is carried out in the QM-1SP planetary ball mill, 450 rev/mins of drum'ss speed of rotation, and ball milling discharging in 45 hours continuously uses Philips-PW1700 type x-ray diffractometer to analyze the alloy organizing structure, and alloy powder all is an amorphous state.
The preparation of test electrode and method of testing are with embodiment 1.The initial discharge capacity that records is by Ml 2Mg 17B (CFn) 0.2Weight be calculated as 780mAh/g, charge and discharge cycles 20 times, capacity keeps more than 95%.

Claims (2)

1. non-crystal rare-earht-Mg-Nickel series hydrogen storage electrode material, it is characterized in that: the chemical composition of electrode material is Ml 2Mg 17B aA b+ x wt.%Ni, wherein, A is one or more in fluorographite (CFn), silicon (Si), sulphur (S), carbon (C), phosphorus (P), aluminium (Al), germanium (Ge), selenium (Se) or iodine (I) element; 0.01≤a≤3.0,0≤b≤2.5; X is with respect to Ml 2Mg 17Weight percentage, 150≤x≤250, Ml is a lanthanum rich norium.
2. the preparation method of non-crystal rare-earht-Mg-Nickel series hydrogen storage electrode material according to claim 1 is characterized in that: at first adopt fusion technology to prepare Ml 2Mg 17Alloy, raw material are lanthanum rich norium and magnesium metal ingot bar, and melting is carried out in the vacuum induction shower furnace of argon shield, prepared Ml 2Mg 17Alloy cast ingot is crushed to 100-500 order powder in organic solvent;
Adopting ball mill to prepare rare-earth and Mg-nickel by mechanical lapping under argon shield is hydrogen storage material, raw material Ml 2Mg 17Powder, nickel powder (Ni), boron powder (B) and A mix by stoichiometric proportion, with abrading-ball by ratio of grinding media to material 35～10: 1 puts into ball grinder seals, ball grinder is evacuated and feeds argon gas, under greater than 200 rev/mins rotational speed of ball-mill, with the mixture in the continuous ball milling method mechanical lapping jar, ball milling obtained non-crystal rare-earht-Mg-Nickel series hydrogen storage electrode material in 5～45 hours.
CNB2005100969872A 2005-08-30 2005-08-30 Amorphous rear-earth-magnesium-Nickel series hydrogen storage electrode material and producing method thereof Expired - Fee Related CN1320671C (en)

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CN109440150B (en) * 2018-12-10 2021-01-29 沈阳大学 Method for preparing aluminum-magnesium-lanthanum alloy film by room temperature electrodeposition
CN114645168B (en) * 2022-03-14 2023-07-28 上海交通大学 Hydrogen-storage magnesium alloy and preparation method thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4259110A (en) * 1978-07-07 1981-03-31 Agence Nationale De Valorisation De La Recherche (Anvar) Process for storing of hydrogen and the use thereof, particularly in engines
CN1397659A (en) * 2002-04-10 2003-02-19 浙江大学 Non-crystal rare-earth and Mg base hydrogen bearing alloy and its preparing process

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4259110A (en) * 1978-07-07 1981-03-31 Agence Nationale De Valorisation De La Recherche (Anvar) Process for storing of hydrogen and the use thereof, particularly in engines
CN1397659A (en) * 2002-04-10 2003-02-19 浙江大学 Non-crystal rare-earth and Mg base hydrogen bearing alloy and its preparing process

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
制备方法对La1.5Mg17Ni0.5储氢材料性能的影响 蒋利军等，稀有金属材料与工程，第33卷第8期 2004 *
制备方法对La1.5Mg17Ni0.5储氢材料性能的影响 蒋利军等，稀有金属材料与工程，第33卷第8期 2004;铸态及快淬态La2Mg(Ni0.85Co0.15)9B0.1贮氢合金 董小平等，电池，第34卷第5期 2004 *
铸态及快淬态La2Mg(Ni0.85Co0.15)9B0.1贮氢合金 董小平等，电池，第34卷第5期 2004 *

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