CN101376941A - Hydrogen storage alloy, preparation thereof, and cathode and battery using the hydrogen storage alloy - Google Patents
Hydrogen storage alloy, preparation thereof, and cathode and battery using the hydrogen storage alloy Download PDFInfo
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- 239000000956 alloy Substances 0.000 title claims abstract description 145
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- 239000001257 hydrogen Substances 0.000 title claims abstract description 26
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 10
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 29
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 18
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- 239000002184 metal Substances 0.000 abstract description 7
- 239000004615 ingredient Substances 0.000 abstract 1
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- 239000011572 manganese Substances 0.000 description 47
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 46
- 239000010949 copper Substances 0.000 description 46
- 239000000843 powder Substances 0.000 description 30
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 19
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- 239000010941 cobalt Substances 0.000 description 18
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- 229910004247 CaCu Inorganic materials 0.000 description 8
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- 239000006258 conductive agent Substances 0.000 description 8
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 8
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- 238000002441 X-ray diffraction Methods 0.000 description 7
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- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
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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
- Y02E60/10—Energy storage using batteries
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- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to a hydrogen storage alloy which is characterized by comprising the ingredients shown in a formula LaaM(l-a)NixCuyFezCouMnvAlw, wherein, M refers to at least two types of raw earth metal other than lanthanum; a, x, y, z, u, v and w are respectively the molar fraction of La, Ni, Cu, Fe, Co, Mn and Al, wherein, a is more than or equal to 0.4 and less than or equal to 0.9, x is more than or equal to 2.5 and less than or equal to 3.6, y is more than or equal to 0.4 and less than or equal to 1.0, z is more than or equal to 0 and less than or equal to 0.2, u is more than or equal to 0 and less than or equal to 0.2, v is more than or equal to 0.4 and less than or equal to 0.7, w is more than or equal to 0.2 and less than or equal to 0.4, and x+y+z+u+v+w is more than or equal to 4.8 and less than or equal to 5.3. In addition, the invention also provides a preparation method of the hydrogen storage alloy, and a cathode containing the hydrogen storage alloy and a ni-mh secondary battery. The hydrogen storage alloy has low cost and excellent electro chemical performance.
Description
Technical field
The present invention relates to a kind of hydrogen-storage alloy and preparation method thereof and the negative pole and the battery that adopt this hydrogen-storage alloy.
Background technology
In recent years, because the development of mobile electronic device and the revolution of traffic power source, the research and development of the high tension battery energy have become the focus of countries in the world academia and Industrial Revolution.Nickel metal hydride battery is subjected to extensive attention because of advantage such as energy height, security are good, pollution-free, memory-less effect, is one of main supplying cell type of electronics.
In nickel metal hydride battery, negative electrode active material is generally hydrogen-storage alloy, and the performance of hydrogen-storage alloy directly influences the capacity of the battery that adopts this hydrogen-storage alloy and cycle performance etc.What at present, research was more is with LaNi
5AB for the basis
5The type hydrogen-storage alloy, AB
5The type hydrogen-storage alloy is because platform is pressed moderately, and chemical property is good, as the negative electrode active material practicability of nickel metal hydride battery.For AB
5The metallic element that the research of type hydrogen-storage alloy mainly concentrates on A, B both sides substitutes, by substituting with the metallic element of other element to A, B both sides, thus activation performance, loading capacity and the cycle performance etc. of raising hydrogen-storage alloy.
At present, B side element substitution generally adopts one or more part displacements Ni metallic element among transition metal Co, Al, Mn, the Cr etc., and wherein the adding of Co can improve the cycle performance of hydrogen-storage alloy, and therefore, present hydrogen-storage alloy all adds usually cobalt.A side element substitution generally adopts other rare earth elements such as Ce, Pr, Nd etc. partly to substitute the La element, and perhaps the A side directly adopts mishmetal, also has and adopts metallic element Ca, Ti, Zr etc. partly to replace the La element of A side.
For example, CN 1567619A discloses a kind of rich lanthanum hydrogen-storage alloy powder, and its chemical general formula is MlNi
5-x-y-z-vCo
xMn
yAl
zQ
v, it is characterized in that Ml is a lanthanum rich mischmetal, Q is W, V, Zr free element or its complex element, 0.64≤x≤0.86,0.27≤y≤0.39,0.2＜z≤0.3,0.001≤v≤0.01.
In addition, CN 1143837A discloses a kind of metal oxide-metal hydride battery of alkalescence, and its positive pole contains metal oxide, and its negative pole is to be made of hydrogen-storage alloy, wherein except cerium mischmetal, also comprises nickel and cobalt element, and has CaCu
5The crystalline structure of type is characterized in that the part cobalt in this alloy is replaced by iron and/or copper, and has following chemical constitution: MmNi
vAl
wMn
xCo
yM
z, wherein Mm is a cerium mischmetal, and M is Fe and/or Cu, and other parameter is 0.2≤x≤0.4,0.1＜z≤0.4,0.2≤y≤0.4,0.3≤w≤0.5,4.9≤v+w+x+y+z≤5.1.
The loading capacity of above-mentioned disclosed hydrogen-storage alloy and cycle performance are all better, because the content of nickel, cobalt is all very high in the above-mentioned hydrogen-storage alloy.Nickel, cobalt are elements indispensable in the hydrogen-storage alloy, and wherein nickel plays an important role to alloy heavy body, high-rate charge-discharge capability; Cobalt is to the chemical property of alloy, and especially cycle performance plays key effect.So commercial AB
5All contain higher cobalt, nickel in the type hydrogen-storage alloy.The content that reduces nickel, cobalt can cause the hydrogen-storage alloy chemical property to descend.But the costing an arm and a leg of nickel and cobalt, especially cobalt are though cobalt contents accounts for the 40-50% of raw materials cost generally only about 10 weight % in the hydrogen-storage alloy.
Therefore, under the prerequisite that does not influence chemical properties such as hydrogen-storage alloy loading capacity and cycle performance, the content that reduces nickel, cobalt in the hydrogen-storage alloy is the key that reduces the hydrogen-storage alloy preparation cost.
Summary of the invention
The objective of the invention is in order to overcome the high shortcoming of hydrogen-storage alloy preparation cost in the prior art, provide a kind of preparation cost low and have a hydrogen-storage alloy and preparation method thereof and the negative pole and the battery that adopt this hydrogen-storage alloy of good activation performance, loading capacity and cycle performance.
The invention provides a kind of hydrogen-storage alloy, wherein, this hydrogen-storage alloy has formula La
aM
(1-a)Ni
xCu
yFe
zCo
uMn
vAl
wThe composition of expression, in the formula, M represents at least two kinds in the rare earth metal except that lanthanum, and a, x, y, z, u, v, w are respectively the molar fraction of La, Ni, Cu, Fe, Co, Mn and Al, 0.4≤a≤0.9,2.5≤x≤3.6,0.4≤y≤1.0,0≤z≤0.2,0＜u≤0.2,0.4≤v≤0.7,0.2≤w≤0.4,4.8≤x+y+z+u+v+w≤5.3.
The present invention also provides a kind of hydrogen storage preparation method, and this method is included under the shielding gas, alloy raw material is carried out melting and cooled and solidified becomes ingot casting, and wherein, the ratio of described alloy raw material meets group of alloys accepted way of doing sth La
aM
(1-a)Ni
xCu
yFe
zCo
uMn
vAl
wIn the formula, M represents at least two kinds in the rare earth metal except that lanthanum, and a, x, y, z, u, v, w are respectively the molar fraction of La, Ni, Cu, Fe, Co, Mn and Al, 0.4≤a≤0.9,2.5≤x≤3.6,0.4≤y≤1.0,0≤z≤0.2,0＜u≤0.2,0.4≤v≤0.7,0.2≤w≤0.4,4.8≤x+y+z+u+v+w≤5.3.
The present invention also provides a kind of hydrogen-storage alloy negative pole, and this negative pole comprises collector and the negative material that loads on the collector, and described negative material comprises negative electrode active material and binding agent, and wherein, described negative electrode active material is a hydrogen-storage alloy of the present invention.
The present invention also provides a kind of nickel-hydrogen secondary cell, this battery comprises electrode group and alkaline electrolyte, and described electrode group and alkaline electrolyte are sealed in the battery container, and described electrode group comprises positive pole, negative pole and dividing plate, wherein, described negative pole is a negative pole of the present invention.
The hydrogen-storage alloy that the present invention makes has excellent electrochemical properties, the loading capacity and the cycle performance of the open cell that the hydrogen-storage alloy powder that is obtained by the present invention is made are all good, and it is few to reach the required cycle index of active state, therefore, the hydrogen-storage alloy that makes of the present invention is suitable as the negative electrode active material of nickel-hydrogen secondary cell.Simultaneously, the content of the cobalt element in the hydrogen-storage alloy of the present invention is less than 2.8 weight %, and therefore the content of nickel and cobalt element reduces greatly in the hydrogen-storage alloy of the present invention, thereby makes the preparation cost of hydrogen-storage alloy reduce significantly.
Embodiment
Hydrogen-storage alloy of the present invention has formula La
aM
(1-a)Ni
xCu
yFe
zCo
uMn
vAl
wThe composition of expression, in the formula, M represents at least two kinds in the rare earth metal except that lanthanum, and a, x, y, z, u, v, w are respectively the molar fraction of La, Ni, Cu, Fe, Co, Mn and Al, 0.4≤a≤0.9,2.5≤x≤3.6,0.4≤y≤1.0,0≤z≤0.2,0＜u≤0.2,0.4≤v≤0.7,0.2≤w≤0.4,4.8≤x+y+z+u+v+w≤5.3.
Contain the rare earth element more than three kinds in the alloy of the present invention, wherein, described a represents the molar fraction of lanthanum, and the content that suitably improves lanthanum described in the alloy can improve the loading capacity of hydrogen-storage alloy, and the scope of described a is preferably 0.5≤a≤0.8.In addition, described M is preferably among Ce, Pr, Nd, Pm, Sm, Eu, Yb, Lu and the Y at least two kinds.The content of the various rare earth elements among the M can be any ratio.
In addition, consider from the viewpoint of the consumption that reduces nickel and cobalt and the activation performance, loading capacity and the cycle performance that guarantee hydrogen-storage alloy, the scope of the molar fraction of nickel, copper, iron, cobalt, manganese and aluminium is preferably following scope: 2.6≤x≤3.2 respectively, 0.5≤y≤0.9,0.1≤z≤0.2,0.05≤u≤0.1,0.4≤v≤0.6.
The crystalline structure of hydrogen-storage alloy of the present invention is CaCu
5The type phase structure, described CaCu
5The type phase structure can obtain by the X-ray diffraction analysis test.Be in the collection of illustrative plates that behind X-ray diffraction analysis, obtains of hydrogen-storage alloy of the present invention, have typical C aCu
5The type characteristic peak, and do not have other assorted peaks, can show that so described alloy is CaCu
5The type phase structure.Described X-ray diffraction method is conventionally known to one of skill in the art.For example can carry out diffraction analysis to hydrogen-storage alloy by X-ray diffractometer.
Hydrogen storage preparation method of the present invention is included under the shielding gas, alloy raw material is carried out melting and cooled and solidified becomes ingot casting, and wherein, the ratio of described alloy raw material meets group of alloys accepted way of doing sth La
aM
(1-a)Ni
xCu
yFe
zCo
uMn
vAl
wIn the formula, M represents at least two kinds in the rare earth metal except that lanthanum, and a, x, y, z, u, v, w are respectively the molar fraction of La, Ni, Cu, Fe, Co, Mn and Al, 0.4≤a≤0.9,2.5≤x≤3.6,0.4≤y≤1.0,0≤z≤0.2,0＜u≤0.2,0.4≤v≤0.7,0.2≤w≤0.4,4.8≤x+y+z+u+v+w≤5.3.
From activation performance, loading capacity and the cycle performance of hydrogen-storage alloy and the angle consideration that reduces the hydrogen-storage alloy preparation cost, above-mentioned composition formula La
aM
(1-a)Ni
xCu
yFe
zCo
uMn
vAl
wIn the scope of each composition be preferably: 0.5≤a≤0.8,2.6≤x≤3.2,0.5≤y≤0.9,0.1≤z≤0.2,0.05≤u≤0.1,0.4≤v≤0.6.In addition, described M is preferably among Ce, Pr, Nd, Pm, Sm, Eu, Yb, Lu and the Y at least two kinds.The content of the various rare earth elements among the M can be any ratio.
The method of described melting is the melting method of various routines in this area, as long as with the abundant fusion of alloy raw material, for example can in medium frequency induction melting furnace, carry out melting, smelting temperature and smelting time are along with used alloy raw material different have some variations, among the present invention, described smelting temperature is preferably 1400-1700 ℃, and smelting time is preferably 0.5-4 hour.
In order to make each metallic element uniform distribution in the alloy, the process of described melting, cooled and solidified preferably repeats 2-4 time.
In fusion process, described shielding gas is one or more in neutral element rare gas element and the nitrogen.
After melting finished, described cooled and solidified can adopt the method for cooling of various routines in this area, for example, can cool off and be frozen into ingot casting in the water-cooled copper crucible.
As the hydrogen-storage alloy powder that is used for nickel-hydrogen battery negative pole, the hydrogen-storage alloy ingot casting that also needs above-mentioned cooling is obtained is heat-treated, and described thermal treatment comprises described ingot casting 900-1100 ℃ of following insulation 8-12 hour.The hydrogen-storage alloy that the thermal treatment postcooling is obtained carries out just pulverizing, and further pulverizes in the vacuum sphere grinding machine under shielding gas then, and can sieve as required then obtains the hydrogen-storage alloy powder of prescribed level average particle diameter.General described sieving makes the average particle diameter of described hydrogen-storage alloy powder get final product for the 10-50 micron.
Hydrogen-storage alloy negative pole of the present invention comprises collector and the negative material that loads on the collector, and described negative material comprises negative electrode active material and binding agent, and wherein, described negative electrode active material is a hydrogen-storage alloy of the present invention.
Because the present invention only relates to the improvement to hydrogen-storage alloy, therefore there is no particular limitation to forming other required compositions of hydrogen-storage alloy negative pole and content, can be conventional composition and the content that uses in this area.For example, the collector that forms described hydrogen-storage alloy negative pole can be the conducting base that this area routine is used for nickel-hydrogen secondary battery negative electrode, for example can be matrix, perforated metal panel or the expanded metal of nickel foam substrate, felt piece structure.
Described negative material preferably also comprises tackiness agent and conductive agent.Described tackiness agent for example can be one or more in various hydrophilic adhesives, the hydrophobic adhesive, for example can be in carboxymethyl cellulose, Vltra tears, methylcellulose gum, sodium polyacrylate and the polytetrafluoroethylene (PTFE) one or more.The amount of described tackiness agent gets final product for this area conventional amount used, for example, is benchmark with the weight of negative electrode active material, and the content of described tackiness agent is 0.01-5 weight %, is preferably 0.02-3 weight %.
Described conductive agent can be nickel-hydrogen secondary battery negative electrode various conductive agents commonly used, as in graphite, graphitized carbon black, nickel powder, the cobalt powder etc. one or more, preferably uses graphitized carbon black to be conductive agent in the specific embodiment of the invention.The consumption of conductive agent gets final product for this area conventional amount used.For example, be benchmark with the weight of negative electrode active material, the content of described conductive agent is 0.01-5 weight %, is preferably 0.02-3 weight %.
Except using hydrogen-storage alloy provided by the invention, it is identical with the method for hydrogen-storage alloy negative pole with the conventional nickel-hydrogen secondary cell of preparation with the concrete operation method of hydrogen-storage alloy negative pole to prepare nickel-hydrogen secondary cell provided by the invention, for example, comprise that hydrogen-storage alloy powder, conductive agent are carried out dry powder blend is even, then dry powder is joined in the binder solution, obtain behind the uniform slurry with the slurry uniform loading on the collector, dry, calendering or do not roll, punching press, get final product after cutting described hydrogen-storage alloy negative pole.The solvent types and the consumption that form described binder solution are conventionally known to one of skill in the art.For example, described solvent can be selected from any solvent that can make described mixture form pasty state, is preferably water.The consumption of solvent can make described mashed prod have viscosity, can be coated on the solid material to get final product.
In addition, nickel-hydrogen secondary cell provided by the invention comprises electrode group and alkaline electrolyte, and described electrode group and alkaline electrolyte are sealed in the battery container, and described electrode group comprises positive pole, negative pole and dividing plate, and wherein, described negative pole is a negative pole of the present invention.
According to nickel-hydrogen secondary cell provided by the present invention, described dividing plate is arranged between positive pole and the negative pole, and it has electrical insulation capability and liquid retainability energy, and described electrode group and alkaline electrolyte are contained in the battery case together.Described dividing plate can be selected from various dividing plates used in the alkaline secondary cell, as polyolein fiber non-woven fabrics and the surperficial chip component of introducing hydrophilic fibre or handling through sulfonation.The position of described dividing plate, character and kind are conventionally known to one of skill in the art.
Anode can be selected from the used positive pole of various nickel-hydrogen secondary cells, and it can commercially obtain, and also can adopt existing method preparation.Described anodal conducting base is a nickel-hydrogen secondary cell anodal conducting base commonly used, as matrix, perforated metal panel or the expanded metal of nickel foam substrate, felt piece structure.
The described positive electrode material of nickel-hydrogen secondary cell contains nickel hydroxide and tackiness agent, and described tackiness agent can adopt tackiness agent used in the negative pole.For example, describedly can be selected from carboxymethyl cellulose, Vltra tears, methylcellulose gum, sodium polyacrylate, tetrafluoroethylene and the polyvinyl alcohol one or more.The content of tackiness agent is conventionally known to one of skill in the art, is benchmark with the positive active material nickel hydroxide generally, and the content of described anodal tackiness agent is 0.01-5 weight %, is preferably 0.02-3 weight %.
Described anodal preparation method can adopt conventional preparation method.For example, described nickel hydroxide, tackiness agent and solvent are blended into pasty state, apply and/or be filled on the described conducting base, drying, pressing mold or pressing mold not can obtain described positive pole.Wherein, described solvent can be selected from any solvent that can make described mixture form pasty state, is preferably water.The consumption of solvent can make described mashed prod have viscosity, can be coated on the described conducting base to get final product.In general, the content of described solvent is the 15-40 weight % of nickel hydroxide, is preferably 20-35 weight %.Wherein, drying, the method for pressing mold and condition are conventionally known to one of skill in the art.
Described electrolytic solution is the used electrolytic solution of alkaline secondary cell, as in potassium hydroxide aqueous solution, aqueous sodium hydroxide solution, the lithium hydroxide aqueous solution one or more.The injection rate of electrolytic solution is generally 0.9-1.6g/Ah, the concentration of electrolytic solution be generally 6-8 rub/liter.
According to the preparation method of nickel-hydrogen secondary cell provided by the invention, except described negative material contained described hydrogen-storage alloy provided by the invention, other step was conventionally known to one of skill in the art.In general, will between described positive pole for preparing and the negative pole dividing plate be set, constitute an electrode group, this electrode group is contained in the battery container, inject electrolytic solution, then that battery container is airtight, can obtain alkaline secondary cell provided by the invention.
Below by embodiment the present invention is illustrated in greater detail.
Embodiment 1
Present embodiment illustrates hydrogen-storage alloy provided by the invention and preparation method thereof.
Mol ratio by the group of alloys accepted way of doing sth shown in the embodiment in the table 11 takes by weighing each feed metal, and places medium frequency induction melting furnace (electric furnace company limited in Jinzhou produces, and capacity is 500kg), and 1450 ℃ of following meltings 3 hours, casting obtained alloy pig.And then carry out melting according to the method described above and cool off obtaining alloy pig.Ultimate analysis shows, gained hydrogen-storage alloy piece consist of the group of alloys accepted way of doing sth shown in the table 1.With this hydrogen-storage alloy piece mechanical disintegration, screening under the argon gas atmosphere protection; obtain hydrogen-storage alloy powder; use BT-9300S laser particle size distribution instrument (hundred special Instr Ltd. produce) to measure the size-grade distribution of hydrogen-storage alloy powder, the average particle diameter of hydrogen-storage alloy powder is 40 microns.
Hydrogen-storage alloy powder is carried out finding behind the X-ray diffraction analysis with Japan Ricoh D/MAX200PC type X-ray diffractometer the crystalline structure of this hydrogen-storage alloy is CaCu
5The type phase structure.
Test the chemical property of this hydrogen-storage alloy powder below.
The making of＜open cell 〉
Get the hydrogen-storage alloy powder that 0.5 gram embodiment 1 makes, mix with the Ni powder of 1.5 grams, with 20Mpa pressure on tabletting machine, be pressed into radius be the disk of 12.5mm as the open cell negative pole, then with the spot welding nickel strap as negative wire, and on negative pole parcel nylon felt diaphragm paper.
100:2:8:20 takes by weighing nickel hydroxide by weight, concentration is the PTFE emulsion of 60 weight %, the Vltra tears aqueous solution and the deionized water of 2 weight % concentration, obtain slurry after fully mixing, it is in 95% the foaming nickel porous insert that this slurry is filled in vesicularity, oven dry, roll-in then, cut and make 25 millimeters * 25 millimeters * 0.65 millimeter positive plate, wherein, the content of nickel hydroxide is about 1 gram.
The negative pole of parcel nylon felt diaphragm paper is clipped in the middle with above-mentioned two positive poles, fixes, immerse in the KOH electrolytic solution of 7mol/L, constitute the open cell system of negative pole control capacity with polyvinyl chloride (PVC) plate.
＜electrochemical properties of hydrogen storage alloys 〉
(1) the activation number of times of open cell and high discharge capacity
Adopt the test of DC-5 cell container tester, concrete test condition is as follows: under 25 ℃, with 50mA charging 4.5 hours, placed 30 minutes, be discharged to 1.0V with 30mA, placed 30 minutes, repeat above-mentioned charge and discharge process then.Write down each loading capacity, show that when loading capacity reaches maximum value open cell has reached active state, record reaches the described cycle index of this active state as the activation number of times, and the maximum value that writes down this loading capacity is as high discharge capacity.The result is as shown in table 1.
(2) capability retention of open cell after 300 circulations
Described open cell continues to carry out cycle charge-discharge 300 times according to the method in the above-mentioned performance test (1) after reaching active state then, and writes down the loading capacity after the circulation 300 times, calculates the capability retention after the circulation 300 times according to following formula then.The result is as shown in table 1.
Loading capacity after the capability retention=300 time circulation after 300 circulations/high discharge capacity * 100%
Embodiment 2-21
Method according to embodiment 1 prepares hydrogen-storage alloy, and different is, the raw material for preparing described hydrogen-storage alloy is respectively according to the preparation alloy pig that feeds intake of the group of alloys accepted way of doing sth shown in the embodiment 2-21 in the table 1.Finally obtain the hydrogen-storage alloy powder that average particle diameter is 40 microns, these hydrogen-storage alloy powders are carried out respectively finding that the crystalline structure of these hydrogen-storage alloys is CaCu behind the X-ray diffraction analysis with X-ray diffractometer through pulverizing
5The type phase structure.
Test the chemical property of these hydrogen-storage alloy powders then respectively according to the method for embodiment 1, the result is as shown in table 1.
Embodiment 22
Method according to embodiment 1 prepares hydrogen-storage alloy, and different is that the raw material for preparing described hydrogen-storage alloy fed intake 2 hours according to the group of alloys accepted way of doing sth shown in the embodiment in the table 1 22 respectively.And described melting, process of cooling are carried out 3 times repeatedly, obtain alloy pig.Finally obtain the hydrogen-storage alloy powder that average particle diameter is 20 microns, hydrogen-storage alloy powder is carried out finding that the crystalline structure of this hydrogen-storage alloy is CaCu behind the X-ray diffraction analysis with X-ray diffractometer through pulverizing
5The type phase structure.
Test the chemical property of the hydrogen-storage alloy powder that makes then according to the method for embodiment 1, the result is as shown in table 1.
Comparative Examples 1-11
Method according to embodiment 1 prepares hydrogen-storage alloy, and different is, the raw material for preparing described hydrogen-storage alloy is respectively according to the preparation alloy pig that feeds intake of the group of alloys accepted way of doing sth shown in the Comparative Examples 1-11 in the table 1.Finally obtain the hydrogen-storage alloy powder that average particle diameter is 40 microns, these hydrogen-storage alloy powders are carried out respectively finding that the crystalline structure of these hydrogen-storage alloys is CaCu behind the X-ray diffraction analysis with X-ray diffractometer through pulverizing
5The type phase structure.
Test the chemical property of these hydrogen-storage alloy powders then respectively according to the method for embodiment 1, the result is as shown in table 1.
Table 1
| Numbering | A group of alloys accepted way of doing sth | Activation number of times (inferior) | High discharge capacity (mAh/g) | 300 circulation back capability retentions (%) |
| Comparative Examples 1 | La 0.2Ce 0.5Pr 0.1Nd 0.2Ni 3.3Cu 0.6Fe 0.1Co 0.1Mn 0.6Al 0.3 | 5 | 272 | 96 |
| Comparative Examples 2 | La 0.35Ce 0.25Pr 0.2Nd 0.2Ni 3.3Cu 0.6Fe 0.1Co 0.1Mn 0.6Al 0.3 | 5 | 285 | 95 |
| Embodiment 1 | La 0.4Ce 0.3Pr 0.1Nd 0.2Ni 3.3Cu 0.6Fe 0.1Co 0.1Mn 0.6Al 0.3 | 5 | 304 | 95 |
| Embodiment 2 | La 0.6Ce 0.2Pr 0.1Nd 0.1Ni 3.3Cu 0.6Fe 0.1Co 0.1Mn 0.6Al 0.3 | 5 | 310 | 92 |
| Embodiment 3 | La 0.8Ce 0.1Pr 0.05Nd 0.05Ni 3.3Cu 0.6Fe 0.1Co 0.1Mn 0.6Al 0.3 | 5 | 320 | 90 |
| Comparative Examples 3 | LaNi 3.3Cu 0.6Fe 0.1Co 0.1Mn 0.6Al 0.3 | 5 | 324 | 79 |
| Comparative Examples 4 | La 0.6Ce 0.2Pr 0.1Nd 0.1Ni 3.7Cu 0.2Fe 0.1Co 0.1Mn 0.6Al 0.3 | 5 | 326 | 72 |
| Embodiment 4 | La 0.6Ce 0.2Pr 0.1Nd 0.1Ni 3.5Cu 0.4Fe 0.1Co 0.1Mn 0.6Al 0.3 | 4 | 323 | 90 |
| Embodiment 5 | La 0.6Ce 0.2Pr 0.1Nd 0.1Ni 3.4Cu 0.5Fe 0.1Co 0.1Mn 0.6Al 0.3 | 4 | 315 | 93 |
| Embodiment 6 | La 0.6Ce 0.2Pr 0.1Nd 0.1Ni 3.1Cu 0.9Fe 0.1Co 0.1Mn 0.6Al 0.3 | 4 | 308 | 95 |
| Embodiment 7 | La 0.6Ce 0.2Pr 0.1Nd 0.1Ni 3.0Cu 1.0Fe 0.1Co 0.1Mn 0.6Al 0.3 | 4 | 307 | 96 |
| Comparative Examples 5 | La 0.6Ce 0.2Pr 0.1Nd 0.1Ni 2.8Cu 1.2Fe 0.1Co 0.1Mn 0.6Al 0.3 | 5 | 273 | 97 |
| Embodiment 8 | La 0.6Ce 0.2Pr 0.1Nd 0.1Ni 3.3Cu 0.6Co 0.1Mn 0.6Al 0.3 | 5 | 312 | 93 |
| Embodiment 9 | La 0.6Ce 0.2Pr 0.1Nd 0.1Ni 3.3Cu 0.6Fe 0.1Co 0.1Mn 0.6Al 0.3 | 4 | 310 | 94 |
| Embodiment 10 | La 0.6Ce 0.2Pr 0.1Nd 0.1Ni 3.3Cu 0.6Fe 0.2Co 0.1Mn 0.6Al 0.3 | 4 | 308 | 95 |
| Comparative Examples 6 | La 0.6Ce 0.2Pr 0.1Nd 0.1Ni 3.3Cu 0.6Fe 0.3Co 0.1Mn 0.6Al 0.3 | 5 | 275 | 96 |
| Comparative Examples 7 | La 0.6Ce 0.2Pr 0.1Nd 0.1Ni 3.4Cu 0.6Fe 0.1Mn 0.6Al 0.3 | 5 | 310 | 77 |
| Embodiment 11 | La 0.6Ce 0.2Pr 0.1Nd 0.1Ni 3.35Cu 0.6Fe 0.1Co 0.05Mn 0.6Al 0.3 | 4 | 310 | 90 |
| Embodiment 12 | La 0.6Ce 0.2Pr 0.1Nd 0.1Ni 3.3Cu 0.6Fe 0.1Co 0.1Mn 0.6Al 0.3 | 4 | 312 | 93 |
| Embodiment 13 | La 0.6Ce 0.2Pr 0.1Nd 0.1Ni 3.2Cu 0.6Fe 0.1Co 0.2Mn 0.6Al 0.3 | 4 | 311 | 95 |
| Comparative Examples 8 | La 0.6Ce 0.2Pr 0.1Nd 0.1Ni 3.7Cu 0.6Fe 0.1Co 0.1Mn 0.2Al 0.3 | 5 | 275 | 80 |
| Embodiment 14 | La 0.6Ce 0.2Pr 0.1Nd 0.1Ni 3.5Cu 0.6Fe 0.1Co 0.1Mn 0.4Al 0.3 | 4 | 308 | 90 |
| Embodiment 15 | La 0.6Ce 0.2Pr 0.1Nd 0.1Ni 3.2Cu 0.6Fe 0.1Co 0.1Mn 0.7Al 0.3 | 4 | 310 | 91 |
| Comparative Examples 9 | La 0.6Ce 0.2Pr 0.1Nd 0.1Ni 3.1Cu 0.6Fe 0.1Co 0.1Mn 0.8Al 0.3 | 5 | 298 | 80 |
| Comparative Examples 10 | La 0.6Ce 0.2Pr 0.1Nd 0.1Ni 3.5Cu 0.6Fe 0.1Co 0.1Mn 0.6Al 0.1 | 5 | 276 | 89 |
| Embodiment 16 | La 0.6Ce 0.2Pr 0.1Nd 0.1Ni 3.4Cu 0.6Fe 0.1Co 0.1Mn 0.6Al 0.2 | 4 | 308 | 90 |
| Embodiment 17 | La 0.6Ce 0.2Pr 0.1Nd 0.1Ni 3.2Cu 0.6Fe 0.1Co 0.1Mn 0.6Al 0.4 | 4 | 310 | 90 |
| Comparative Examples 11 | La 0.6Ce 0.2Pr 0.1Nd 0.1Ni 3.0Cu 0.6Fe 0.1Co 0.1Mn 0.6Al 0.6 | 5 | 298 | 74 |
| Embodiment 18 | La 0.6Ce 0.2Pr 0.1Nd 0.05Pm 0.05Ni 3.2Cu 0.6Fe 0.1Co 0.1Mn 0.5Al 0.3 | 4 | 315 | 91 |
| Embodiment 19 | La 0.6Ce 0.2Pr 0.2Ni 3.3Cu 0.6Fe 0.1Co 0.1Mn 0.5Al 0.3 | 4 | 308 | 95 |
| Embodiment 20 | La 0.6Ce 0.2Pr 0.1Sm 0.1Ni 3.3Cu 0.7Fe 0.1Co 0.1Mn 0.6Al 0.3 | 4 | 310 | 95 |
| Embodiment 21 | La 0.6Ce 0.2Pr 0.1Y 0.1Ni 3.3Cu 0.7Fe 0.15Co 0.1Mn 0.6Al 0.35 | 4 | 310 | 96 |
| Embodiment 22 | La 0.6Ce 0.2Pr 0.1Nd 0.1Ni 3.4Cu 0.7Fe 0.1Co 0.2Mn 0.6Al 0.3 | 4 | 310 | 96 |
| Comparative Examples 12 | La 0.6Ce 0.4Ni 4.0Co 0.4Mn 0.6Al 0.3 | 4 | 316 | 96 |
From shown in the table 1, the open cell that the hydrogen-storage alloy that is obtained by Comparative Examples 1-11 is made can't have excellent discharge capacity and cycle performance simultaneously, and chemical property is relatively poor.The hydrogen-storage alloy powder that embodiment of the invention 1-22 obtains compares the hydrogen-storage alloy powder that ratio 12 obtains and is more or less the same on chemical property, the open cell of making possesses good loading capacity and cycle performance, and it is few to reach the required cycle index of active state, therefore, the hydrogen-storage alloy that makes of the present invention is suitable as the negative electrode active material of nickel-hydrogen secondary cell.Simultaneously, the content of the cobalt element in the hydrogen-storage alloy of the present invention is less than 2.8 weight %, and therefore the content of nickel and cobalt element reduces greatly in the hydrogen-storage alloy of the present invention, thereby makes the preparation cost of hydrogen-storage alloy reduce significantly.
Embodiment 23
Present embodiment illustrates hydrogen-storage alloy negative pole provided by the invention and nickel-hydrogen secondary cell.
Taking by weighing hydrogen-storage alloy powder, the concentration that embodiment 1 obtains by weight 100:1:10:0.5 is the PTFE emulsion of 60 weight %, the Vltra tears aqueous solution and the conductive agent carbon black of 2 weight % concentration, obtain the heavy-gravity slurry after fully mixing, again this slurry is coated on the perforation nickel plated steel strip of 0.06 mm thick, dry back compacting, cut, obtain the hydrogen-storage alloy negative pole of long 145 millimeters, wide 44 millimeters, thick 0.3 millimeter H-AA2100 (MAH), the content of hydrogen-storage alloy powder is 10.5 grams on this negative pole.
100:2:8:20 takes by weighing nickel hydroxide by weight, concentration is the PTFE emulsion of 60 weight %, the Vltra tears aqueous solution and the deionized water of 2 weight % concentration, obtain slurry after fully mixing, it is in 95% the foaming nickel porous insert that this slurry is filled in vesicularity, oven dry, roll-in then, cut to make and be of a size of 109 millimeters * 44 millimeters * 0.65 millimeter positive plate, wherein, the content of nickel hydroxide is about 8.3 grams.
Above-mentioned hydrogen-storage alloy negative pole, nylon felt barrier film and nickel positive pole are stacked gradually the electrode group that is wound into scroll, are installed in the battery case, and inject with the amount of 1.5g/Ah 7 rub/liter KOH electrolytic solution, seal, obtain H-AA2100 (MAH) battery A1.
＜battery performance test 〉
(1) loading capacity
Press the initial discharge capacity (MAH) of the method test battery A1 of IEC61951 regulation, the result is as shown in table 2.
(2) cycle performance test
After battery A1 activation, pacify constant current charges to volts lost-△ V=10 millivolt with 2.1 at normal temperatures, shelve after 20 minutes again with 2.1 peace constant current discharge to 1.0 volts, repeat at normal temperatures then above-mentionedly to discharge and recharge operation and carry out cycle performance test, cycle index when the record cell container is reduced to initial capacity 80%, the result is as shown in table 2.
Embodiment 24-29
According to embodiment 23 preparation batteries, different is the hydrogen-storage alloy powder that the active substance of the negative pole of battery adopts embodiment 2, embodiment 18-22 to make respectively.Finally obtain battery A2-A7.
Performance according to the method test battery A2-A7 of embodiment 23.The result is as shown in table 2.
Comparative Examples 13
According to embodiment 23 preparation batteries, different is the hydrogen-storage alloy powder that the active substance Comparative Examples 12 of the negative pole of battery makes.Finally obtain battery D1.
Performance according to the method test battery D1 of embodiment 23.The result is as shown in table 2.
Table 2
| The battery source | Initial capacity (mAh) | Cycle index (inferior) |
| Embodiment 23 | 2140 | 676 |
| Embodiment 24 | 2141 | 679 |
| Embodiment 25 | 2143 | 679 |
| Embodiment 26 | 2142 | 680 |
| Embodiment 27 | 2140 | 675 |
| Embodiment 28 | 2145 | 676 |
| Embodiment 29 | 2140 | 678 |
| Comparative Examples 13 | 2150 | 689 |
As can be seen from Table 2, the initial capacity of the battery D1-D7 that embodiment 23-29 makes all reaches more than 2140 MAHs, and the cycle index of cell container when reducing to initial capacity 80% be more than 670 times, and initial capacity and the cycle performance of the battery D1 that makes with Comparative Examples 13 are basic identical.
Claims (10)
1, a kind of hydrogen-storage alloy is characterized in that, this hydrogen-storage alloy has formula La
aM
(1-a)Ni
xCu
yFe
zCo
uMn
vAl
wThe composition of expression, in the formula, M represents at least two kinds in the rare earth metal except that lanthanum, and a, x, y, z, u, v, w are respectively the molar fraction of La, Ni, Cu, Fe, Co, Mn and Al, 0.4≤a≤0.9,2.5≤x≤3.6,0.4≤y≤1.0,0≤z≤0.2,0＜u≤0.2,0.4≤v≤0.7,0.2≤w≤0.4,4.8≤x+y+z+u+v+w≤5.3.
2, alloy according to claim 1, wherein, 0.5≤a≤0.8,2.6≤x≤3.2,0.5≤y≤0.9,0.1≤z≤0.2,0.05≤u≤0.1,0.4≤v≤0.6.
3, alloy according to claim 1, wherein, described M is at least two kinds among Ce, Pr, Nd, Pm, Sm, Eu, Yb, Lu and the Y.
4, the described hydrogen storage preparation method of claim 1, this method is included under the shielding gas, alloy raw material is carried out melting and cooled and solidified becomes ingot casting, it is characterized in that the ratio of described alloy raw material meets group of alloys accepted way of doing sth La
aM
(1-a)Ni
xCu
yFe
zCo
uMn
vAl
wIn the formula, M represents at least two kinds in the rare earth metal except that lanthanum, and a, x, y, z, u, v, w are respectively the molar fraction of La, Ni, Cu, Fe, Co, Mn and Al, 0.4≤a≤0.9,2.5≤x≤3.6,0.4≤y≤1.0,0≤z≤0.2,0＜u≤0.2,0.4≤v≤0.7,0.2≤w≤0.4,4.8≤x+y+z+u+v+w≤5.3.
5, method according to claim 4, wherein, described M is at least two kinds among Ce, Pr, Nd, Pm, Sm, Eu, Yb, Lu and the Y, 0.5≤a≤0.8,2.6≤x≤3.2,0.5≤y≤0.9,0.1≤z≤0.2,0.05≤u≤0.1,0.4≤v≤0.6.
6, method according to claim 4, wherein, the temperature of described melting is 1400-1700 ℃, the time is 0.5-4 hour.
7, method according to claim 4, wherein, described melting, refrigerative process repeat 2-4 time.
8, method according to claim 4, wherein, described shielding gas is one or more in neutral element rare gas element and the nitrogen.
9, a kind of hydrogen-storage alloy negative pole, this negative pole comprises collector and the negative material that loads on the collector, described negative material comprises negative electrode active material and binding agent, it is characterized in that, described negative electrode active material is any described hydrogen-storage alloy among the claim 1-3.
10, a kind of nickel-hydrogen secondary cell, this battery comprises electrode group and alkaline electrolyte, and described electrode group and alkaline electrolyte are sealed in the battery container, and described electrode group comprises positive pole, negative pole and dividing plate, it is characterized in that described negative pole is the described negative pole of claim 9.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102230111A (en) * | 2011-05-31 | 2011-11-02 | 四川宝生实业发展有限公司 | High iron hydrogen storage electrode alloy, preparation method thereof and nickel-hydrogen battery cathode material |
| CN101994030B (en) * | 2009-08-10 | 2013-01-30 | 北京有色金属研究总院 | Low-cost high-performance AB5 type hydrogen storage alloy and preparation method thereof |
| CN105463256A (en) * | 2015-12-03 | 2016-04-06 | 内蒙古稀奥科贮氢合金有限公司 | Hydrogen storage alloy for nickel-metal hydride battery and manufacturing method of hydrogen storage alloy |
| CN111118345A (en) * | 2019-11-28 | 2020-05-08 | 包头稀土研究院 | Multi-element samarium-nickel hydrogen storage material, negative electrode, battery and preparation method |
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Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2000239769A (en) * | 1998-12-22 | 2000-09-05 | Shin Etsu Chem Co Ltd | Rare earth hydrogen storage alloy and electrode using it |
| JP2000192177A (en) * | 1998-12-22 | 2000-07-11 | Shin Etsu Chem Co Ltd | Hydrogen storage alloy and nickel-hydrogen secondary battery |
| JP2001294958A (en) * | 2000-04-11 | 2001-10-26 | Sumitomo Metal Ind Ltd | Hydrogen storage alloy for nickel-hydrogen secondary battery and its producing method |
| WO2005014871A1 (en) * | 2003-08-08 | 2005-02-17 | Mitsui Mining & Smelting Co., Ltd. | LOW Co HYDROGEN OCCLUSION ALLOY |
| CN1790777A (en) * | 2004-12-17 | 2006-06-21 | 比亚迪股份有限公司 | Nickel-hydrogen battery negative pole and battery using same and preparing method |
| CN1319196C (en) * | 2005-09-09 | 2007-05-30 | 珠海金峰航电源科技有限公司 | AB5 type negative pole hydrogen-storage material |
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| CN101994030B (en) * | 2009-08-10 | 2013-01-30 | 北京有色金属研究总院 | Low-cost high-performance AB5 type hydrogen storage alloy and preparation method thereof |
| CN102230111A (en) * | 2011-05-31 | 2011-11-02 | 四川宝生实业发展有限公司 | High iron hydrogen storage electrode alloy, preparation method thereof and nickel-hydrogen battery cathode material |
| CN102230111B (en) * | 2011-05-31 | 2015-12-09 | 四川宝生实业发展有限公司 | High ferro hydrogen-storing alloy as electrode and nickel-hydrogen battery negative pole material |
| CN105463256A (en) * | 2015-12-03 | 2016-04-06 | 内蒙古稀奥科贮氢合金有限公司 | Hydrogen storage alloy for nickel-metal hydride battery and manufacturing method of hydrogen storage alloy |
| CN111118345A (en) * | 2019-11-28 | 2020-05-08 | 包头稀土研究院 | Multi-element samarium-nickel hydrogen storage material, negative electrode, battery and preparation method |
| CN112259726A (en) * | 2020-10-15 | 2021-01-22 | 湘潭大学 | Application of AlCuCo quasicrystal material |
| CN112259726B (en) * | 2020-10-15 | 2022-01-18 | 湘潭大学 | Application of AlCuCo quasicrystal material |
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