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 PDFInfo
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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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- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 48
- 239000001257 hydrogen Substances 0.000 title claims abstract description 48
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 239000007772 electrode material Substances 0.000 title claims abstract description 28
- 238000003860 storage Methods 0.000 title claims abstract description 24
- 238000000034 method Methods 0.000 title claims abstract description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 58
- 239000000956 alloy Substances 0.000 claims abstract description 30
- 239000000463 material Substances 0.000 claims abstract description 30
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 28
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 26
- 238000000498 ball milling Methods 0.000 claims abstract description 25
- 238000002360 preparation method Methods 0.000 claims abstract description 21
- 239000000126 substance Substances 0.000 claims abstract description 15
- 239000011232 storage material Substances 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 8
- 239000011669 selenium Substances 0.000 claims abstract description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 4
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims abstract description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 4
- 229910052732 germanium Inorganic materials 0.000 claims abstract description 4
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 4
- 239000011574 phosphorus Substances 0.000 claims abstract description 4
- 229910052711 selenium Inorganic materials 0.000 claims abstract description 4
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 4
- 239000010703 silicon Substances 0.000 claims abstract description 4
- OCVXZQOKBHXGRU-UHFFFAOYSA-N iodine(1+) Chemical compound [I+] OCVXZQOKBHXGRU-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000011777 magnesium Substances 0.000 claims description 73
- 239000000843 powder Substances 0.000 claims description 28
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 16
- 239000013078 crystal Substances 0.000 claims description 14
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 13
- 238000002844 melting Methods 0.000 claims description 9
- 230000008018 melting Effects 0.000 claims description 9
- 229910052786 argon Inorganic materials 0.000 claims description 8
- 238000005516 engineering process Methods 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 8
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 6
- 229910052746 lanthanum Inorganic materials 0.000 claims description 6
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 6
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 5
- 150000002910 rare earth metals Chemical class 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 claims description 4
- 239000005864 Sulphur Substances 0.000 claims description 3
- 239000004411 aluminium Substances 0.000 claims description 3
- 230000006698 induction Effects 0.000 claims description 3
- 230000004927 fusion Effects 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 abstract description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 5
- QLOAVXSYZAJECW-UHFFFAOYSA-N methane;molecular fluorine Chemical compound C.FF QLOAVXSYZAJECW-UHFFFAOYSA-N 0.000 abstract 1
- 239000007773 negative electrode material Substances 0.000 abstract 1
- 229910052717 sulfur Inorganic materials 0.000 abstract 1
- 239000011593 sulfur Substances 0.000 abstract 1
- 229910052749 magnesium Inorganic materials 0.000 description 12
- 230000005518 electrochemistry Effects 0.000 description 9
- 239000001996 bearing alloy Substances 0.000 description 5
- 229910052796 boron Inorganic materials 0.000 description 5
- 239000002131 composite material Substances 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000007599 discharging Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000000713 high-energy ball milling Methods 0.000 description 3
- 238000012856 packing Methods 0.000 description 3
- 229910052684 Cerium Inorganic materials 0.000 description 2
- 229910001122 Mischmetal Inorganic materials 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 2
- 238000005275 alloying Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 229910002640 NiOOH Inorganic materials 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- 241001062472 Stokellia anisodon Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 229910000808 amorphous metal alloy Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- -1 aromatic organic compounds Chemical class 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000006182 cathode active material Substances 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
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- 238000006253 efflorescence Methods 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000005300 metallic glass Substances 0.000 description 1
- 230000001002 morphogenetic effect Effects 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 206010037844 rash Diseases 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
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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
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- Battery Electrode And Active Subsutance (AREA)
Abstract
本发明涉及一种非晶态稀土-镁-镍系储氢电极材料及其制备方法。该储氢材料的化学组成为Ml2Mg17BaAb+xwt.%Ni，其中，A为氟化石墨(CFn)、硅(Si)、硫(S)、碳(C)、磷(P)、铝(Al)、锗(Ge)、硒(Se)或碘(I)元素中的一种或一种以上；0.01≤a≤3.0，0≤b≤2.5；x为相对于Ml2Mg17的重量百分含量，150≤x≤250。该储氢电极材料的突出优点是：初始电化学容量高，充放电循环稳定性好，可以应用连续球磨工艺在更短的时间内制备非晶态稀土-镁-镍系储氢合金电极材料，大大提高了材料制备效率。该储氢电极材料可用于制备MH/Ni二次电池负极活性材料。The invention relates to an amorphous rare earth-magnesium-nickel hydrogen storage electrode material and a preparation method thereof. The chemical composition of the hydrogen storage material is Ml 2 Mg 17 B a A b +xwt.%Ni, wherein, A is graphite fluoride (CFn), silicon (Si), sulfur (S), carbon (C), phosphorus ( One or more of P), aluminum (Al), germanium (Ge), selenium (Se) or iodine (I) elements; 0.01≤a≤3.0, 0≤b≤2.5; x is relative to Ml2 The weight percentage of Mg 17 , 150≤x≤250. The outstanding advantages of this hydrogen storage electrode material are: high initial electrochemical capacity, good charge-discharge cycle stability, continuous ball milling process can be used to prepare amorphous rare earth-magnesium-nickel hydrogen storage alloy electrode material in a shorter time, The efficiency of material preparation is greatly improved. The hydrogen storage electrode material can be used to prepare negative electrode active materials for MH/Ni secondary batteries.
Description
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.
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Citations (2)
| 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 |
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Patent Citations (2)
| 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)
| 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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