CN1272462C - Non crystal state hydrogen storage composite materal and its producing method - Google Patents
Non crystal state hydrogen storage composite materal and its producing method Download PDFInfo
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- CN1272462C CN1272462C CNB2003101228286A CN200310122828A CN1272462C CN 1272462 C CN1272462 C CN 1272462C CN B2003101228286 A CNB2003101228286 A CN B2003101228286A CN 200310122828 A CN200310122828 A CN 200310122828A CN 1272462 C CN1272462 C CN 1272462C
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- hydrogen storage
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- 239000001257 hydrogen Substances 0.000 title claims abstract description 33
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 33
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 238000003860 storage Methods 0.000 title claims abstract description 31
- 239000002131 composite material Substances 0.000 title claims abstract description 26
- 238000000034 method Methods 0.000 title claims description 10
- 239000013078 crystal Substances 0.000 title claims description 5
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 36
- 239000000956 alloy Substances 0.000 claims abstract description 36
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 13
- 229910052751 metal Inorganic materials 0.000 claims abstract description 12
- 239000000126 substance Substances 0.000 claims abstract description 12
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 11
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 11
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 9
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 9
- 238000004519 manufacturing process Methods 0.000 claims abstract description 8
- 229910052987 metal hydride Inorganic materials 0.000 claims abstract description 7
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 7
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 6
- 229910001122 Mischmetal Inorganic materials 0.000 claims abstract description 4
- 150000004681 metal hydrides Chemical class 0.000 claims abstract description 4
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 4
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 4
- 229910052779 Neodymium Inorganic materials 0.000 claims abstract description 3
- 229910052777 Praseodymium Inorganic materials 0.000 claims abstract description 3
- 229910052772 Samarium Inorganic materials 0.000 claims abstract description 3
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052742 iron Inorganic materials 0.000 claims abstract description 3
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims abstract description 3
- 230000007704 transition Effects 0.000 claims abstract description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 44
- 238000000498 ball milling Methods 0.000 claims description 15
- 239000011159 matrix material Substances 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 230000006698 induction Effects 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 abstract 1
- 229910052726 zirconium Inorganic materials 0.000 abstract 1
- 239000011777 magnesium Substances 0.000 description 41
- 239000011575 calcium Substances 0.000 description 15
- 229910052749 magnesium Inorganic materials 0.000 description 15
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 8
- 239000002585 base Substances 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 4
- 239000007773 negative electrode material Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- -1 nickel metal hydride Chemical class 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000000840 electrochemical analysis Methods 0.000 description 2
- 230000005518 electrochemistry Effects 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229910000861 Mg alloy Inorganic materials 0.000 description 1
- 229910019083 Mg-Ni Inorganic materials 0.000 description 1
- 229910019403 Mg—Ni Inorganic materials 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- 229910002640 NiOOH Inorganic materials 0.000 description 1
- 241001417490 Sillaginidae Species 0.000 description 1
- 241001062472 Stokellia anisodon Species 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 239000001996 bearing alloy Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 229910001068 laves phase Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000005551 mechanical alloying Methods 0.000 description 1
- 238000003701 mechanical milling Methods 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
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
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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- Battery Electrode And Active Subsutance (AREA)
- Powder Metallurgy (AREA)
Abstract
The present invention relates to an amorphous hydrogen storage composite material and a production method thereof. The composite material is characterized in that the chemical general formula of the composite material is Re2-xMxMg17-yNy+zNi, wherein x is 0 to 0.5, and y is 0 to 3; Re is one or a plurality of rare earth metals containing La, Ce, Pr, Nd and Sm, a rich cerium misch metal Mm and a rich lanthanum misch metal MI; M is one of the metallic elements of Ca, Ti, V and Zr, wherein the metallic elements can react with hydrogen to generate metal hydrides; N is one of the transition elements of Y, Ni, Co, Fe and Cr; z is 0.5 to 1.5, and z is the weight ratio of Ni to Re2-xMxMg17-yNy. Compared with the existing hydrogen storage electrode alloys, the composite material of the present invention has the obvious advantage that the electrochemical hydrogen storage is realized at the room temperature; electrodes made from the composite material of the present invention have abnormally high discharge capacity, and are especially suitable for high specific energy nickel-hydrogen batteries.
Description
Technical field:
The present invention relates to a kind of is the alkaline secondary cell negative electrode active substance of main component with magnesium, rare earth metal and nickel, particularly a kind of non-crystalline state composite for hydrogen storage and manufacture method thereof.
Background technology:
Nickel one metal hydride (Ni/MH) battery is with the heavy body alkaline secondary cell of hydrogen storage electrode alloy as negative electrode active material, has realized extensive industrialization so far.At present, the negative electrode active material of nearly all commodity nickel metal hydride battery is AB with rare earth all
5The type hydrogen storage electrode alloy, they all are at typical binary LaNi
5The multicomponent alloy that grows up on the alloy basis.LaNi
5The theoretical electrochemistry capacity be 372mAhg
-1, and commercially available practical AB
5The polynary hydrogen storage electrode alloy loading capacity of type is 280～320mAhg only
-1, be about LaNi
575～85% of theoretical loading capacity.
Because the developing rapidly and popularizing of electronic product such as computer, communication equipment, audio and video equipment and electric vehicle, requirements at the higher level have been proposed for heavy body, miniaturization and the lightweight of secondary cell.Some new improvement materials are suggested, and the some of them titanium is AB
2Type Laves phase electrode metal loading capacity reaches 380～420mAhg
-1, and the electrode metal loading capacity of vanadium base solid solution type also can reach 350～420mAhg
-1, be AB all apparently higher than rare earth
5The type multicomponent alloy.
Pure magnesium and Mg base hydrogen bearing alloy are the highest classes of unit weight hydrogen-storage density in all kinds of hydrogen storage alloys that occurred at present, and pure magnesium reaches 7.6%; Mg
2The Ni alloy is 3.6%; And the rare earth and magnesium-based alloy that rare earth and magnesium are formed is (as typical C eMg
12, La
2Mg
17) the weight hydrogen-storage density is then between pure magnesium and Mg
2Between the Ni, being 4.5～6.0%, is AB far above rare earth
5The gas-solid reaction hydrogen storage capability of type alloy 1.4%.But all ordinary methods prepare and all can't at room temperature realize gas-solid reaction reversible hydrogen storage or electrochemical reversible storage hydrogen without pure magnesium or magnesium alloy that any modification is handled.For this reason, various improvement technology have been studied and have proposed, wherein, effective means is that Magnuminium is prepared into non-crystal structure, for example document [1] utilizes the mechanical alloying method that the Mg-Ni alloy is prepared into amorphous, thereby realized the electrochemical hydrogen storage under the room temperature, document [2,3] then provides a kind of milled Mg of passing through
2The mixture of Ni and Ni is prepared into amorphous, has also realized the electrochemical hydrogen storage under the room temperature.
Summary of the invention:
The object of the present invention is to provide a kind of at room temperature matrix material and the manufacture method thereof of a large amount of electrochemical hydrogen storages, this matrix material is specially adapted to the negative electrode active material as the high-energy-density nickel metal hydride battery.Composite for hydrogen storage of the present invention is by a kind of binary or 2: 17 shaped metal compounds of polybasic crystalline state rare earth-magnesium base hydrogenous alloy and the nickel powder non-crystalline state composite for hydrogen storage that ball milling forms that is mixed, the high hydrogen storage capability that it had both kept former crystalline structure rare earth-magnesium base alloy to be had has overcome the shortcoming that former crystal alloy can't at room temperature carry out electrochemical hydrogenation and dehydrogenation again.Therefore, replacing rare earth with this new composite for hydrogen storage is AB
5The type electrode metal can make the battery rated capacity of same volume increase substantially as the negative electrode active material of nickel metal hydride battery, and the battery volume of same rated capacity is reduced significantly.
A kind of non-crystalline state composite for hydrogen storage is characterized in that: the chemical general formula of this matrix material is RE
2-xM
xMg
17-yN
y+ zNi, 0≤x in the formula≤0.5,0≤y≤3, RE is one or more among rare-earth metal La, Ce, Pr, Nd, Sm, cerium-rich mischmetal metal M m, the lanthanum rich norium Ml, M is for generating a kind of among metallic element Ca, Ti, V, the Zr of metal hydride with H-H reaction, N is a kind of among transition element Y, Ni, Co, Fe, Mn, the Cr, 0.5≤z≤1.5, and z is Ni weight and RE
2-xM
xMg
17-yN
yThe ratio of weight.
A kind of manufacture method of non-crystalline state composite for hydrogen storage is characterized in that adopting following steps:
A) according to chemical formula RE
2-xM
xMg
17-yN
yIn composition and the weight percent of composition batching, place the vacuum induction furnace of argon shield to be smelted into the crystal alloy ingot, alloy pig is broken into the alloy powder of granularity less than 75 μ m;
B) 0.5～1.5 times nickel powder of above-mentioned alloy powder and alloy powder weight is packed into together ball milling in the ball mill spherical tank, ratio of grinding media to material is 20: 1, ball milling is 30～50 hours continuously, obtains the non-crystalline state composite for hydrogen storage; The granularity of nickel powder is less than 75 μ m.
Rare earth-magnesium base hydrogenous alloy and the nickel powder of forming composite hydrogen storage material of the present invention all are easy decrystallized materials, particularly the two is mixed together ball milling and has played the decrystallized effect of mutually promoting, and matrix material amorphous degree is high more, and promptly the shared high more then matrix material of the ratio electrochemistry capacitance at room temperature of non-crystalline state is high more in the matrix material.Mechanical milling process is a kind of mechanical mill process, it is crucial to the non-crystalline state that crystalline state rare earth-magnesium base alloy is converted into tiny high specific area, and the participation ball milling of nickel powder is absolutely necessary, because the existence of nickel powder has changed transmission ofenergy and distribution in the process of lapping system, thereby makes rare earth-magnesium base alloying pellet and nickel powder itself can obtain tiny amorphous rather than nanocrystalline in the shorter time.The nickel powder increase makes ball milling become the amorphous time to shorten, and the non-crystallization degree of matrix material is high more; And rare earth-magnesium base alloy ratio in amorphous composite increases, and the electrochemical hydrogen storage capacity of the amorphous composite of gained increases, so can obtain high electrochemical hydrogen storage capability guaranteeing to obtain under the situation of whole amorphous composites the minimum nickel powder amount of employing.When this tiny amorphous composite is made electrode sample in three-electrode system with 50mAhg
-1Continuous current carries out the loading capacity test, and under 25 ℃ of temperature, the actual measurement loading capacity is up to 1000～1100mAhg (RE
2-xM
xMg
17-yN
y)
-1, for present commercially available rare earth is 2～3 times of electrode metal, supporting electrode is Ni (OH) during test
2/ NiOOH, reference electrode are Hg/HgO, and alkali lye is 6MKOH, and the discharge stopping potential is-0.55V (with respect to the HgO/Hg electrode).
Embodiment 1:
A kind of non-crystalline state composite for hydrogen storage, its chemical general formula are RE
2-xM
xMg
17-yN
y+ zNi, RE is La in the formula, x=0, y=0, z are 0.75, promptly Ni grain weight amount is La
2Mg
1775% of weight is pressed chemical formula La
2Mg
17Calculate the weight proportion of La and Mg, La is the lanthanoid metal of purity 98% in the starting material, and Mg is the MAGNESIUM METAL of purity 99%, smelts in the vacuum induction furnace of argon shield is arranged then, obtains crystalline state La
2Mg
17Alloy pig is broken for the spherical tank that places ball mill less than the alloy powder ， And of 75 μ m with alloy pig, adds La again
2Mg
1775% nickel powder of weight is 20: 1 an abrading-ball ball milling with ratio of grinding media to material, and the nickel powder granularity is less than 75 μ m, and the ball mill speed of mainshaft is 225 rev/mins, and ball milling promptly obtains tiny amorphous composite after 50 hours continuously.The matrix material of gained is made electrode, in alkaline three-electrode system with 50mAhg
-1Continuous current carries out the loading capacity test, and probe temperature is 25 ℃, and the discharge stopping potential is-0.55V, and is real that loading capacity is 1060mAhg (La
2Mg
17)
-1
Embodiment 2:
Preferred chemical general formula RE
2-xM
xMg
17-yN
yAmong+the zNi, RE is La, and x=0.2, M are Ca, and N is Ni, and y=3, z are 1.5, promptly constitute La
1.8Ca
0.2Mg
14Ni
3+ 1.5Ni alloy.Press chemical formula La
1.8Ca
0.2Mg
14Ni
3Calculate the weight proportion of La, Ca, Mg, Ni, Ca is the calcium metal of purity 98% in the starting material, and Ni is the electrolytic nickel of purity 99%, and other material purities are smelted in the vacuum induction furnace of argon shield is arranged with embodiment 1, gets crystalline state La
1.8Ca
0.2Mg
14Ni
3Alloy pig is broken for the alloy powder less than 75 μ m then, is 150% nickel powder ball milling of alloy powder amount again with weight, the nickel powder granularity is less than 75 μ m, ball-milling technology is with embodiment 1, and continuous ball milling compound changed amorphous composite into through 40 hours, and the loading capacity that records is 1004mAhg (La
1.8Ca
0.2Mg
14Ni
3)
-1Electro-chemical test mode and parameter are with embodiment 1.
Embodiment 3:
Preferred chemical general formula RE
2-xM
xMg
17-yN
yAmong+the zNi, RE is La, and x=0.2, M are Ca, and N is Y, y=1, and Z=1.5 constitutes La
1.8Ca
0.2Mg
16The Y+1.0Ni mixing material is pressed chemical formula La
1.8Ca
0.2Mg
16Y calculates the weight proportion of La, Ca, Mg and Y, and Y is the metallic yttrium of purity 99% in the starting material, and other material purities are with embodiment 2, smelt and ball-milling technology with embodiment 1, nickel powder weight and La
1.8Ca
0.2Mg
16The Y weight ratio is 1.5, and the ball milling time is 40 hours, and the loading capacity of the amorphous composite of making is 1100mAhg (La
1.8Ca
0.2Mg
16Y)
-1Electro-chemical test mode and parameter are with embodiment 1.
Document [1]: Chinese invention patent CN 1044175C
Document [2]: J.Alloys and Compounds, 1998 Vol.267, pp76-78
Document [3]: J.Alloys and Compounds, 1998, Vol.270, pp142-144
Claims (3)
1. non-crystalline state composite for hydrogen storage, it is characterized in that: the chemical general formula of this matrix material is RE
2-xM
xMg
17-yN
Y+ZNi, in the formula, 0≤x≤0.5; 0≤y≤3; RE is one or more among rare-earth metal La, Ce, Pr, Nd, Sm, cerium-rich mischmetal metal M m, the lanthanum rich norium Ml, M is for generating a kind of among metallic element Ca, Ti, V, the Zr of metal hydride with H-H reaction, N is a kind of among transition element Y, Ni, Co, Fe, Mn, the Cr, 0.5≤z≤1.5, z is Ni weight and RE
2-xM
xMg
17-yN
yThe ratio of weight.
2. manufacture method of implementing the described non-crystalline state composite for hydrogen storage of claim 1 is characterized in that adopting following steps:
A) according to chemical formula RE
2-xM
xMg
17-yN
yIn composition and the weight percent of composition batching, place the vacuum induction furnace of argon shield to be smelted into the crystal alloy ingot, alloy pig is broken into the alloy powder of granularity less than 75 μ m;
B) 0.5～1.5 times nickel powder of above-mentioned alloy powder and this alloy powder weight is packed into together ball milling in the ball mill spherical tank, ratio of grinding media to material is 20: 1, ball milling is 30～50 hours continuously, obtains the non-crystalline state composite for hydrogen storage.
3. manufacture method according to claim 2, it is characterized in that: Ni refers in particular to nickel powder in the chemical formula, and the granularity of used nickel powder is less than 75 μ m in the manufacturing processed.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2003101228286A CN1272462C (en) | 2003-12-21 | 2003-12-21 | Non crystal state hydrogen storage composite materal and its producing method |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2003101228286A CN1272462C (en) | 2003-12-21 | 2003-12-21 | Non crystal state hydrogen storage composite materal and its producing method |
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|---|---|
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| CN1272462C true CN1272462C (en) | 2006-08-30 |
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| CN101289576B (en) * | 2007-04-20 | 2010-08-25 | 中国科学院大连化学物理研究所 | Composite material of conducting high polymers/alloy for nickel-hydrogen battery and preparation thereof |
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