CN102021363B - Hydrogen storage alloy and preparation method thereof as well as negative pole and battery using hydrogen storage alloy - Google Patents
Hydrogen storage alloy and preparation method thereof as well as negative pole and battery using hydrogen storage alloy Download PDFInfo
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Abstract
The invention belongs to the field of a hydrogen storage alloy and provides a hydrogen storage alloy. The hydrogen storage alloy is shown in the formula below: Ml1-a-bQaAlbNixCuyFezMnuRw, wherein Ml represents a mixed rare earth metal containing lanthanum, and the lanthanum in Ml accounts for 50-80 wt% of the total weight of the mixed rare earth metal; Q is Ca and/or Mg; R is one or two of Li andNa; and 0<a<=0.15, 0.03<=b<=0.18, 2.3<=x<=3.6, 0.5<=y<=1.2, 0.1<=z<=0.5, 0.5<u<=0.9, 0.1<=w<=0.6, and 4.6<=x+y+z+u+w<=5.7. The hydrogen storage alloy has fine electrochemical performance, the open battery produced from hydrogen storage alloy powder obtained by the invention has fine high-rate discharge performance, and favorable discharge capacity and cycle performance. The hydrogen storage alloyprepared by the invention can be widely used as the active material at the negative pole of a nickel-hydrogen secondary battery. The invention also provides a preparation method of the hydrogen storage alloy as well as a negative pole and a battery containing the hydrogen storage alloy.
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 receives extensive attention because of advantage such as energy is high, security is good, pollution-free, memory-less effect, is one of main supplying cell type of electronics.
As the negative electrode active material that uses for nickel-hydrogen battery is hydrogen-storage alloy, and the performance of hydrogen-storage alloy directly influences capacity and the cycle performance of the battery that adopts this hydrogen-storage alloy 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.To AB
5The research of type hydrogen-storage alloy mainly concentrates on the substituting of metallic element of A, B both sides, through substituting with the metallic element of other element to A, B both sides, thereby improves the activation performance of hydrogen-storage alloy.
At present, B side element generally adopts one or more part displacements Ni metallic element of Co in the transition metal, Al, Mn, Cr, Cu, Fe, Si and Ti etc.A side element generally adopts other REEs such as Ce, Pr, Nd etc. partly to substitute the La element, and perhaps the A side directly adopts mishmetal, perhaps adopts metallic element Ca, Ti, Zr etc. partly to replace the La element of A side.
Nickel, cobalt are elements indispensable in the storage alloy material for hydrogen, and wherein nickel is to the alloy heavy body, and high-rate charge-discharge capability plays an important role; Cobalt is to the chemical property of alloy, and especially the stable circulation performance plays key effect.So commercial AB
5In the type hydrogen-storage alloy, like hydrogen-storage alloy MmNi
3.55Co
0.75Mn
0.4Al
0.3, all contain higher cobalt, nickel, costing an arm and a leg of cobalt wherein though cobalt contents only about 10wt%, accounts for 40%～50% of raw materials cost, therefore reduced the cobalt contents in the storage alloy material for hydrogen, can reduce the alloy raw material cost greatly.
In order to reduce the content of high price cobalt in the hydrogen-storage alloy; The general partly or entirely alternative cobalt element of comparatively cheap metallic element that in alloy, adopts; Thereby reduced cost of alloy significantly, should keep the good initial stage activation performance of hydrogen-storage alloy, loading capacity performance and cycle performance simultaneously.The unit that is commonly used to alternative Co have Fe, Cu etc.But result of study shows; Along with the raising of Fe element add-on in the alloy, though suitable room temperature cyclical stability when hydrogen-storage alloy still keeps cobalt contents higher, the loading capacity of alloy descends; And alloy has the tendency of surface passivation, causes its high-rate discharge ability to reduce; Because the atomic radius of Cu greater than Ni, substitutes the increase of measuring with Cu, lattice constant and unit cell volume increase, and density reduces, and the volumetric expansion behind the suction hydrogen reduces, and hydrogenate stability improves, but platform pressure and hydrogen storage amount descend.In general; Cu substitutes Co in hydrogen-storage alloy, can make alloy have stable circulation performance preferably, but can make alloy surface in working cycle, generate the zone of oxidation of thicker Cu; Cause the high-rate discharge ability of alloy to reduce, and the electrochemistry capacitance of alloy is descended.
Cobalt contents reduces in the alloy though aforesaid method can make effectively, and the high-rate discharge ability of battery is not well improved.
Summary of the invention
The technical problem that the present invention will solve is the shortcoming of the high-rate discharge ability difference of existing nickel metal hydride battery, thereby a kind of high-rate discharge ability that can make nickel metal hydride battery good hydrogen-storage alloy and its preparation method is provided and contains the negative pole and the battery of this hydrogen-storage alloy.
The invention provides a kind of hydrogen-storage alloy, wherein, this hydrogen-storage alloy has formula
Ml
1-a-bQ
aAl
bNi
xCu
yFe
zMn
uR
wThe composition of expression,
In the formula, Ml representes to contain the norium of lanthanum, and the content of lanthanum is the 50-80 weight % of the gross weight of norium among the Ml, and Q is Ca and/or Mg, and R is one or more among Li, the Na;
Wherein, 0＜a≤0.15,0.03≤b≤0.18,2.3≤x≤3.6,0.5≤y≤1.2,0.1≤z≤0.5,0.5＜u≤0.9,0.1≤w≤0.6,4.6≤x+y+z+u+w≤5.7.
The invention provides a kind of hydrogen storage preparation method, this method is included under the shielding gas, and alloy raw material is carried out melting and cooled and solidified becomes ingot casting, and wherein, the ratio of said alloy raw material meets group of alloys accepted way of doing sth Ml
1-a-bQ
aAl
bNi
xCu
yFe
zMn
uR
wThe composition of expression,
In the formula, Ml representes to contain the norium of lanthanum, and the content of lanthanum is the 50-80 weight % of the gross weight of norium among the Ml, and Q is Ca and/or Mg, and R is one or more among Li, the Na;
Wherein, 0＜a≤0.15,0.03≤b≤0.18,2.3≤x≤3.6,0.5≤y≤1.2,0.1≤z≤0.5,0.5＜u≤0.9,0.1≤w≤0.6,4.6≤x+y+z+u+w≤5.7.
The present invention also provides a kind of hydrogen-storage alloy negative pole, this negative pole comprise collector with load on the negative material on the collector, said negative material contains negative electrode active material and tackiness agent, wherein, said 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 said electrode group and alkaline electrolyte are sealed in the battery container, and said electrode group comprises positive pole, negative pole and dividing plate; Wherein, said negative pole is a negative pole of the present invention.
Hydrogen-storage alloy of the present invention has excellent electrochemical properties, and the high-rate discharge ability of the open cell that the hydrogen-storage alloy powder that is obtained by the present invention is processed is good, and the loading capacity of this battery and cycle performance are also fine simultaneously.The hydrogen-storage alloy that the present invention makes can widespread use be the negative electrode active material of nickel-hydrogen secondary cell.Owing to do not contain cobalt element in the hydrogen-storage alloy of the present invention, thereby make the preparation cost of hydrogen-storage alloy reduce significantly.
Embodiment
The invention provides a kind of hydrogen-storage alloy, this hydrogen-storage alloy has formula
Ml
1-a-bQ
aAl
bNi
xCu
yFe
zMn
uR
wThe composition of expression,
In the formula, Ml representes to contain the norium of lanthanum, and the content of lanthanum is the 50-80 weight % of the gross weight of norium among the Ml, and Q is Ca and/or Mg, and R is one or more among Li, the Na;
Wherein, 0＜a≤0.15,0.03≤b≤0.18,2.3≤x≤3.6,0.5≤y≤1.2,0.1≤z≤0.5,0.5＜u≤0.9,0.1≤w≤0.6,4.6≤x+y+z+u+w≤5.7.
According to hydrogen-storage alloy provided by the invention, for the consumption that reduces nickel and guarantee that the viewpoint of activation performance, loading capacity and the cycle performance of hydrogen-storage alloy considers, under preferable case; 0.05＜a≤0.15,0.05≤b≤0.15,2.5≤x≤3.4; 0.6≤y≤1.0,0.1≤z≤0.3,0.6＜u≤0.8; 0.2≤w≤0.4,4.6≤x+y+z+u+w≤5.7.
In hydrogen-storage alloy provided by the invention, under preferable case, the content of lanthanum is preferably the 60-80 weight % of the gross weight of norium among the Ml, and the content of lanthanum can further improve electrochemical properties of hydrogen storage alloys in preferable range.
According to hydrogen-storage alloy provided by the invention; Said Ml is at least a elementary composition norium among La and Ce, Pr, Nd, Pm, Sm, Eu, Yb, Lu, the Y; Be preferably the norium of La and Ce, Pr and Nd; As long as the content of lanthanum is in said scope among the assurance Ml, the content of other rare earth metal can be any ratio among the Ml among the present invention, but the ratio of the atomicity of preferred Ce, Pr and Nd is 8-12: 1: 2-5; According to this preferred implementation, can further improve the loading capacity of hydrogen-storage alloy.
The present invention also provides a kind of hydrogen storage preparation method, and this method is included under the shielding gas, and alloy raw material is carried out melting and cooled and solidified becomes ingot casting, and wherein, the ratio of said alloy raw material meets group of alloys accepted way of doing sth Ml
1-a-bQ
aAl
bNi
xCu
yFe
zMn
uR
wThe composition of expression,
In the formula, Ml representes to contain the norium of lanthanum, and the content of lanthanum is the 50-80 weight % of the gross weight of norium among the Ml, and Q is Ca and/or Mg, and R is one or more among Li, the Na;
Wherein, 0＜a≤0.15,0.03≤b≤0.18,2.3≤x≤3.6,0.5≤y≤1.2,0.1≤z≤0.5,0.5＜u≤0.9,0.1≤w≤0.6,4.6≤x+y+z+u+w≤5.7.
According to hydrogen-storage alloy provided by the invention, for the consumption that reduces nickel and guarantee that the viewpoint of activation performance, loading capacity and the cycle performance of hydrogen-storage alloy considers, under preferable case; 0.05＜a≤0.15,0.05≤b≤0.15,2.5≤x≤3.4; 0.6≤y≤1.0,0.1≤z≤0.3,0.6＜u≤0.8; 0.2≤w≤0.4,4.6≤x+y+z+u+w≤5.7.
In hydrogen-storage alloy provided by the invention, under preferable case, the content of lanthanum is preferably the 60-80 weight % of the gross weight of norium among the Ml, and the content of lanthanum can further improve electrochemical properties of hydrogen storage alloys in preferable range.
According to hydrogen-storage alloy provided by the invention; Said Ml is at least a elementary composition norium among La and Ce, Pr, Nd, Pm, Sm, Eu, Yb, Lu, the Y; Be preferably the norium of La and Ce, Pr and Nd; As long as the content of lanthanum is in said scope among the assurance Ml, the content of other rare earth metal can be any ratio among the Ml among the present invention, but the ratio of the atomicity of preferred Ce, Pr and Nd is 8-12: 1: 2-5; According to this preferred implementation, can further improve the loading capacity of hydrogen-storage alloy.
According to hydrogen storage preparation method of the present invention; The method of said melting can be 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, said smelting temperature is preferably 1400-1700 ℃, and smelting time is preferably 0.5-4 hour.In fusion process, said shielding gas is helium and/or argon gas.
According to hydrogen storage preparation method provided by the invention, preferably, after melting finished, said cooled and solidified can adopt the method for cooling of various routines in this area, for example, can in the water-cooled copper crucible, cool off and be frozen into ingot casting.
As the hydrogen-storage alloy powder that is used for nickel-hydrogen battery negative pole, also need the hydrogen-storage alloy ingot casting that above-mentioned cooling obtains be heat-treated, said thermal treatment comprises said ingot casting 800-1100 ℃ of following insulation 6-12 hour.The hydrogen-storage alloy that the thermal treatment postcooling is obtained carries out just pulverizing, and under shielding gas, in the vacuum sphere grinding machine, further pulverizes then, and can sieve as required then obtains the hydrogen-storage alloy powder of prescribed level average particle diameter.General said sieving makes the average particle diameter of said hydrogen-storage alloy powder get final product for the 30-100 micron.
Hydrogen-storage alloy negative pole provided by the invention comprises collector and loads on the negative material on the collector that said negative material contains negative electrode active material and tackiness agent, and wherein, said 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 not special qualification to forming required other composition and the content of hydrogen-storage alloy negative pole, can be conventional composition and the content that uses in this area.For example; Said tackiness agent can be one or more in various hydrophilic adhesives, the hydrophobic adhesive, for example can be in CMC 99.5, Vltra tears, methylcellulose gum, ZX-I and the polytetrafluoroethylene (PTFE) one or more.The amount of said 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 said tackiness agent is 0.01-5 weight %, is preferably 0.02-3 weight %.The collector that forms said 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.
According to negative material provided by the invention; Under preferable case; Can also contain static eliminator; Said static eliminator can be nickel-hydrogen secondary battery negative electrode various static eliminators commonly used, like in graphite, graphitized carbon black, nickel powder, the cobalt powder etc. one or more, preferably uses graphitized carbon black to be static eliminator in the specific embodiment of the invention.The consumption of static eliminator gets final product for this area conventional amount used.For example, be benchmark with the weight of negative electrode active material, the content of said static eliminator is 0.01-5 weight %, is preferably 0.02-3 weight %.
Except using hydrogen-storage alloy provided by the invention; Preparing nickel-hydrogen secondary cell provided by the invention can be 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; For example; Comprise that hydrogen-storage alloy powder, static eliminator 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 said hydrogen-storage alloy negative pole.The solvent types and the consumption that form said binder solution are conventionally known to one of skill in the art.For example, said solvent can be selected from any solvent that can make said mixture form pasty state, is preferably water.The consumption of solvent can make said mashed prod be coated on the solid material and get final product.
Nickel-hydrogen secondary cell provided by the invention comprises electrode group and alkaline electrolyte, and said electrode group and alkaline electrolyte are sealed in the battery container, and said electrode group comprises positive pole, negative pole and dividing plate, and wherein, said negative pole is a negative pole of the present invention.
According to nickel-hydrogen secondary cell provided by the present invention, said dividing plate is arranged between positive pole and the negative pole, and it has electrical insulation capability and liquid retainability ability, and said electrode group and alkaline electrolyte are contained in the battery case together.Said dividing plate can be selected from various dividing plates used in the alkaline secondary cell, like polyolein fiber non-woven fabrics and the surperficial chip component of introducing hydrophilic fibre or handling through sulfonation.The position of said dividing plate, character and kind are conventionally known to one of skill in the art.
According to nickel-hydrogen secondary cell provided by the invention, said positive pole 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.Said anodal conducting base is a nickel-hydrogen secondary cell anodal conducting base commonly used, like matrix, perforated metal panel or the expanded metal of nickel foam substrate, felt piece structure.
The said positive electrode material of nickel-hydrogen secondary cell contains nickel hydroxide and tackiness agent, and said tackiness agent can adopt tackiness agent used in the negative pole.For example, be used for the said tackiness agent of anodal can be selected from CMC 99.5, Vltra tears, methylcellulose gum, ZX-I, tetrafluoroethylene and Z 150PH 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 said anodal tackiness agent is 0.01-5 weight %, is preferably 0.02-3 weight %.
According to nickel-hydrogen secondary cell provided by the invention, said anodal preparation method can adopt conventional preparation method.For example, said nickel hydroxide, tackiness agent and solvent are blended into pasty state, apply and/or be filled on the said conducting base, drying, pressing mold or pressing mold not can obtain said positive pole.Wherein, said solvent can be selected from any solvent that can make said mixture form pasty state, is preferably water.The consumption of solvent can make said mashed prod have viscosity, can be coated on the said conducting base to get final product.In general, the content of said 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.
According to nickel-hydrogen secondary cell provided by the invention, said electrolytic solution is the used electrolytic solution of alkaline secondary cell, like in potassium hydroxide aqueous solution, aqueous sodium hydroxide solution, the lithium hydroxide aqueous solution one or more.The IR 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 said negative material contained said hydrogen-storage alloy provided by the invention, other step was conventionally known to one of skill in the art.In general,, constitute an electrode group, this electrode group is contained in the battery container, inject electrolytic solution between said positive pole for preparing and the negative pole dividing plate being set, then that battery container is airtight, can obtain alkaline secondary cell provided by the invention.
Through embodiment the present invention is illustrated in greater detail below.
Embodiment 1
Present embodiment is explained hydrogen-storage alloy provided by the invention and preparation method thereof.
Mol ratio by the alloy composition shown in the embodiment in the table 11 takes by weighing each feed metal; And (electric furnace ltd in Jinzhou produces to place medium frequency induction melting furnace; Capacity is 500kg); Melting is 3 hours under 1450 ℃ of argon shields, and casting obtains alloy pig, then with this alloy pig in argon shield and 950 ℃ insulation 8 hours down.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 d of hydrogen-storage alloy powder
50It is 70 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.
Embodiment 2-12
Method according to embodiment 1 prepares hydrogen-storage alloy, and different is, the raw material for preparing said 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 2-12 in the table 1.Final warp is pulverized and is obtained the hydrogen-storage alloy powder that average particle diameter is 70 microns, with X-ray diffractometer these hydrogen-storage alloy powders is carried out respectively finding that the crystalline structure of these hydrogen-storage alloys is CaCu behind the X-ray diffraction analysis
5The type phase structure.
Comparative Examples 1-6
Method according to embodiment 1 prepares hydrogen-storage alloy; Different is; The raw material of preparation 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 1-6 in the table 1; Wherein final warp is pulverized and is obtained the hydrogen-storage alloy powder that average particle diameter is 70 microns, with X-ray diffractometer these hydrogen-storage alloy powders is carried out respectively finding that the crystalline structure of these hydrogen-storage alloys is CaCu behind the X-ray diffraction analysis
5The type phase structure.
Embodiment 12
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.
By weight 100: 2: 8: 20 take by weighing nickel hydroxide, 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 D1 of negative pole control capacity with SE (PVC) plate.
Embodiment 13-22
Method according to embodiment 12 prepares nickel-hydrogen secondary cell, and different is the hydrogen-storage alloy that said hydrogen-storage alloy powder obtains for embodiment 2-11.Finally make nickel-hydrogen secondary cell and be respectively D2-D11.
Comparative Examples 7-12
Method according to embodiment 12 prepares nickel-hydrogen secondary cell, and different is the hydrogen-storage alloy that said hydrogen-storage alloy powder obtains for Comparative Examples 1-6.Finally make nickel-hydrogen secondary cell and be respectively CD1-CD6.
< chemical property of nickel-hydrogen secondary cell >
(1) the activation number of times and the maximum discharge capacity of open cell
Adopt the test of DC-5 cell container tester, concrete test condition is following: under 25 ℃, battery D1-D11 and CD1-CD6 were charged 4.5 hours with 50mA, 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 peak open cell has reached active state, record reaches the described cycle index of this active state as the activation number of times, and the peak that writes down this loading capacity is as maximum discharge capacity.The result is as shown in table 2.
(2) capability retention of open cell
A, 1C discharge and recharge the discharge capacity of the cell conservation rate under the condition
After the nickel-hydrogen secondary cell activation; Use 50 milliamperes of constant current charges to volts lost-Δ V=10 millivolt at normal temperatures; Shelve after 15 minutes again with 150 milliamperes of constant current discharge to 0.9 volts; Repeat 3 times then at normal temperatures and above-mentionedly discharge and recharge operation, write down each loading capacity, and according to computes 1C discharge capacitance.The result is as shown in table 2.
MV/maximum discharge capacity * 100% of 1C discharge capacitance=3 time loading capacity
B, 5C discharge and recharge the discharge capacity of the cell conservation rate under the condition
After the nickel-hydrogen secondary cell activation; Use 50 milliamperes of constant current charges to volts lost-Δ V=10 millivolt at normal temperatures; Shelve after 15 minutes again with 750 milliamperes of constant current discharge to 0.8 volts; Repeat 3 times then at normal temperatures and above-mentionedly discharge and recharge operation, write down each loading capacity, and calculate the 5C discharge capacitance according to following formula.The result is as shown in table 2.
(3) capability retention of open cell after 300 circulations
Open cell continues to carry out cycle charge-discharge 300 times according to the method in the above-mentioned performance test (1) through after the above-mentioned test then, and writes down the loading capacity after the circulation 300 times, then according to the capability retention after 300 circulations of computes.The result is as shown in table 1.
Loading capacity after the capability retention=300 time circulation after 300 circulations/high discharge capacity * 100%
Test the chemical property of the hydrogen-storage alloy powder that is made by embodiment 1-11 and contrast 1-6 according to the method described above respectively, the result is as shown in table 2.
Table 1
| Numbering | A group of alloys accepted way of doing sth | The content of lanthanum among the Ml | x+y +z+ u+w |
| Embodiment 1 | Ml 0.8Ca 0.05Mg 0.1Al 0.05Ni 2.3Cu 1.0Fe 0.3Mn 0.8Li 0.2 | 50 | 4.6 |
| Embodiment 2 | Ml 0.82Ca 0.05Mg 0.1Al 0.03Ni 2.7Cu 1.0Fe 0.2Mn 0.6Li 0.3 | 75 | 4.8 |
| Embodiment 3 | Ml 0.8Ca 0.05Mg 0.1Al 0.05Ni 2.9Cu 0.8Fe 0.2Mn 0.9Li 0.3 | 75 | 5.1 |
| Embodiment 4 | Ml 0.8Ca 0.05Mg 0.1Al 0.05Ni 3.1Cu 1.0Fe 0.2Mn 0.6Li 0.2 | 70 | 5.1 |
| Embodiment 5 | Ml 0.8Ca 0.05Mg 0.1Al 0.05Ni 3.4Cu 0.7Fe 0.1Mn 0.5Li 0.4Na 0.2 | 80 | 5.3 |
| Embodiment 6 | Ml 0.8Ca 0.05Mg 0.1Al 0.05Ni 2.5Cu 1.0Fe 0.5Mn 0.6Li 0.1 | 60 | 4.7 |
| Embodiment 7 | Ml 0.8Ca 0.05Mg 0.1Al 0.05Ni 2.9Cu 0.9Fe 0.4Mn 0.7Li 0.15Na 0.05 | 70 | 5.1 |
| Embodiment 8 | Ml 0.8Ca 0.1Mg 0.05Al 0.05Ni 3.4Cu 0.6Fe 0.1Mn 0.6Li 0.3 | 70 | 5.0 |
| Embodiment 9 | Ml 0.81Mg 0.01Al 0.18Ni 3.1Cu 0.8Fe 0.2Mn 0.6Li 0.3 | 50 | 5.0 |
| Embodiment 10 | Ml 0.8Mg 0.05Al 0.15Ni 3.1Cu 0.5Fe 0.2Mn 0.6Li 0.1Na 0.1K 0.1 | 75 | 4.7 |
| Embodiment 11 | Ml 0.8Ca 0.05Mg 0.05Al 0.1Ni 3.1Cu 1.2Fe 0.2Mn 0.8Li 0.4 | 75 | 5.7 |
| Comparative example 1 | Ml 1.0Ni 3.8Co 0.1Cu 0.6Fe 0.2Mn 0.2 | 70 | 4.9 |
| Comparative Examples 2 | Ml 1.0Ni 3.1Cu 1.0Fe 0.1Mn 0.5 | 70 | 4.7 |
| Comparative Examples 3 | Ml 0.85Ca 0.05Mg 0.1Ni 3.1Cu 1.0Fe 0.1Mn 0.5 | 70 | 4.7 |
| Comparative Examples 4 | Ml 0.85Al 0.15Ni 3.1Cu 1.0Fe 0.1Mn 0.5Li 0.1 | 70 | 4.8 |
| Comparative Examples 5 | Ml 0.8Ca 0.05Mg 0.1Al 0.05Ni 2.2Cu 1.0Fe 0.2Mn 0.6Li 0.1 | 70 | 4.1 |
| Comparative Examples 6 | Ml 0.7Ca 0.05Al 0.25Ni 3.6Cu 1.0Fe 0.2Mn 0.8Li 0.4 | 70 | 5.8 |
Annotate: Ml is that La and Ce form
Table 2
| Sequence number | Maximum discharge capacity (mAh/g) | 1C discharge capacitance % | 5C discharge capacitance % | 300 circulation volume conservation rates (%) | The activation number of times |
| D1 | 310 | 89 | 72 | 93 | 3 |
| D2 | 318 | 88 | 75 | 96 | 4 |
| D3 | 324 | 86 | 73 | 96 | 4 |
| D4 | 320 | 86 | 75 | 95 | 3 |
| D5 | 331 | 87 | 72 | 95 | 3 |
| D6 | 327 | 87 | 76 | 94 | 2 |
| D7 | 330 | 87 | 75 | 94 | 2 |
| D8 | 310 | 86.9 | 72 | 93 | 3 |
| D9 | 306 | 88 | 74 | 92 | 3 |
| D10 | 312 | 85.6 | 73 | 92 | 2 |
| D11 | 322 | 89 | 77 | 95 | 3 |
| CD1 | 300 | 82 | 63 | 89 | 3 |
| CD2 | 270 | 78 | 56 | 81 | 5 |
| CD3 | 281 | 77 | 56 | 73 | 6 |
| CD4 | 262 | 75 | 52 | 73 | 6 |
| CD5 | 266 | 63 | 49 | 63 | 5 |
| CD6 | 253 | 58 | 32 | 51 | 5 |
Can find out from table 2; Adopt the nickel-hydrogen secondary cell D1-D11 of negative electrode active material of the present invention to reach respectively more than 85% and 70% at the capability retention of 1C discharge and the capability retention of 5C discharge; But respectively mostly all to below 80% and 60%, the nickel-hydrogen secondary cell D1-D2 height that the high-rate discharge ability that the nickel-hydrogen secondary cell for preparing with hydrogen-storage alloy of the present invention be described obviously makes than Comparative Examples 1-6 much at the capability retention of the capability retention of 1C discharge and 5C discharge for the nickel-hydrogen secondary cell CD1-CD6 of Comparative Examples.In addition, the capability retention of nickel-hydrogen secondary cell after 0.2C discharges and recharges the 300th circulation under the condition for preparing with hydrogen-storage alloy of the present invention reaches more than 90%, and the nickel-hydrogen secondary cell that the hydrogen-storage alloy for preparing with Comparative Examples 1-6 prepares is all below 90%.Therefore, method of the present invention can increase substantially the high-rate discharge ability and the cycle performance of battery.
Claims (11)
1. a hydrogen-storage alloy is characterized in that, this hydrogen-storage alloy has formula
Ml
1-a-bQ
aAl
bNi
xCu
yFe
zMn
uR
wThe composition of expression,
In the formula, Ml representes to contain the norium of lanthanum, and the content of lanthanum is the 50-80 weight % of the gross weight of norium among the Ml, and Q is Ca and/or Mg, and R is one or more among Li, the Na;
Wherein, 0＜a≤0.15,0.03≤b≤0.18,2.3≤x≤3.6,0.5≤y≤1.2,0.1≤z≤0.5,0.5＜u≤0.9,0.1≤w≤0.6,4.6≤x+y+z+u+w≤5.7.
2. alloy according to claim 1, wherein, 0.05＜a≤0.15,0.05≤b≤0.15,2.5≤x≤3.4,0.6≤y≤1.0,0.1≤z≤0.3,0.6＜u≤0.8,0.2≤w≤0.4, and 4.6≤x+y+z+u+w≤5.7.
3. alloy according to claim 1, wherein, the content of lanthanum is the 60-80 weight % of the gross weight of norium among the Ml.
4. according to any described alloy of claim 1-3, wherein, said Ml is at least a elementary composition norium among La and Ce, Pr, Nd, Pm, Sm, Eu, Yb, Lu, the Y.
5. the described hydrogen storage preparation method of claim 1 is characterized in that this method is included under the shielding gas, and alloy raw material is carried out melting and cooled and solidified becomes ingot casting, it is characterized in that the ratio of said alloy raw material meets group of alloys accepted way of doing sth Ml
1-a-bQ
aAl
bNi
xCu
yFe
zMn
uR
wThe composition of expression,
In the formula, Ml representes to contain the norium of lanthanum, and the content of lanthanum is the 50-80 weight % of the gross weight of norium among the Ml, and Q is Ca and/or Mg, and R is one or more among Li, the Na;
Wherein, 0＜a≤0.15,0.03≤b≤0.18,2.3≤x≤3.6,0.5≤y≤1.2,0.1≤z≤0.5,0.5＜u≤0.9,0.1≤w≤0.6,4.6≤x+y+z+u+w≤5.7;
The temperature of said melting is 1400-1700 ℃, and the time is 0.5-4 hour; Said cooled and solidified is for cooling in the water-cooled copper crucible and be frozen into ingot casting.
6. method according to claim 5, wherein, 0.05＜a≤0.15,0.05≤b≤0.15,2.5≤x≤3.4,0.6≤y≤1.0,0.1≤z≤0.3,0.6＜u≤0.8,0.2≤w≤0.4, and 4.6≤x+y+z+u+w≤5.7.
7. method according to claim 5, wherein, the content of lanthanum is the 60-80 weight % of the gross weight of norium among the Ml.
8. according to any described method of claim 5-7, wherein, said Ml is at least a elementary composition norium among La and Ce, Pr, Nd, Pm, Sm, Eu, Yb, Lu, the Y.
9. method according to claim 5, wherein, said shielding gas is helium and/or argon gas.
10. hydrogen-storage alloy negative pole; This negative pole comprises collector and loads on the negative material on the collector; Said negative material contains negative electrode active material and tackiness agent, it is characterized in that, said negative electrode active material is any described hydrogen-storage alloy among the claim 1-4.
11. nickel-hydrogen secondary cell; This battery comprises electrode group and alkaline electrolyte, and said electrode group and alkaline electrolyte are sealed in the battery container, and said electrode group comprises positive pole, negative pole and dividing plate; It is characterized in that said negative pole is the described negative pole of claim 10.
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