CN103361517B - High-capacity hydrogen storage alloy electrode material and production method thereof - Google Patents
High-capacity hydrogen storage alloy electrode material and production method thereof Download PDFInfo
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Abstract
The invention discloses a kind of High-capacity hydrogen storage alloy electrode material, its chemical composition is in percentage by weight, including ML1 x ySmxMgyNizAlwCouMnv, wherein 0 < x < 0.62,0 < y < 0.4,3 < z < 4,0.03 < w < 0.15,0.03 <u < 0.15,0.03 < v < 0.15, elementary composition relation is 3.1 < z+w+u+v < 4.2；ML is lanthanum rich norium, and composition is: La 42%～45%, Nd 29%～35%, Ce 2%～5%, Pr 8%～11%；Described High-capacity hydrogen storage alloy electrode material is the alloy powder of 300～400 mesh.The invention also discloses the production method of a kind of High-capacity hydrogen storage alloy electrode material.The High-capacity hydrogen storage alloy electrode material that the present invention relates to, its specific discharge capacity and tradition AB5Type hydrogen storage alloy is compared and is exceeded 20%～30%, and has preferable high-rate discharge ability.
Description
Technical field
The present invention relates to a kind of material technology, specifically, relate to a kind of high capacity hydrogen storage alloy electrode
Material and production method thereof.
Background technology
Lanthanon hydrogen storage alloy starts from the 1980s for nickel-hydrogen battery negative pole material,
Just nickel-hydrogen battery negative pole material uses AB5Type hydrogen storage alloy, and table in the most numerous secondary cells
Reveal excellent specific energy and cycle life.However as the development of society and entering of battery industry
Step, with AB5Type hydrogen storage alloy is that the Ni-MH battery of negative material can not meet people gradually to battery
The requirement of specific energy.
As Chinese patent CN1075380A discloses a kind of store hydrogen alloy electrode material, have
Preferably cyclical stability, its specific discharge capacity is about 280mAh/g；Chinese patent CN1078268A
Disclose a kind of hydrogen-storage alloy for hydrogen electrode and capacity method thereof, the alloy prepared have antioxygen and
Noxious water performance is good, is stable and easy to the lanthanon hydrogen storage alloy of activation in alkaline medium, its electric discharge
Specific capacity is about 270mAh/g.
Along with the further investigation to lanthanon hydrogen storage alloy, it has been found that one has a super large structure cell
The alloy of structure, its chemical formula is expressed as A2B7, such hydrogen bearing alloy has relatively as electrode material
High specific discharge capacity, is the most promising novel hydrogen storage material of one.In the research in past,
A2B7Rare earth element in hydrogen bearing alloy is mainly based on neodymium (Nd), and along with the development in market,
The price of Nd element goes up day by day, and this is to A2B7The market application of type hydrogen storage alloy causes obstruction.
Summary of the invention
Technical problem solved by the invention is to provide a kind of High-capacity hydrogen storage alloy electrode material, its
Specific discharge capacity and tradition AB5Type hydrogen storage alloy is compared and is exceeded 20%～30%, and has preferably
High-rate discharge ability.
Technical scheme is as follows:
A kind of High-capacity hydrogen storage alloy electrode material, its chemical composition in percentage by weight, is wrapped
Include ML1-x-ySmxMgyNizAlwCouMnv, wherein 0 < x < 0.62,0 < y < 0.4,3 < z < 4,
0.03 < w < 0.15,0.03 <u < 0.15,0.03 < v < 0.15, elementary composition relation is 3.1 < z+w+u+v < 4.2；
ML is lanthanum rich norium, and composition is: La 42%～45%, Nd 29%～35%, Ce
2%～5%, Pr 8%～11%；Described High-capacity hydrogen storage alloy electrode material is 300～400 mesh
Alloy powder.
Further: its constituent is ML0.27Sm0.62Mg0.11Ni3.37Al0.06Co0.08。
Further: its constituent is ML0.57Sm0.22Mg0.21Ni3.07Al0.12Co0.08Mn0.2。
Another technical problem solved by the invention is to provide a kind of high capacity hydrogen storage alloy electrode
The production method of material, obtains High-capacity hydrogen storage alloy electrode material, its specific discharge capacity and tradition
AB5Type hydrogen storage alloy is compared and is exceeded 20%～30%, and has preferable high-rate discharge ability.
Technical scheme is as follows:
The production method of a kind of High-capacity hydrogen storage alloy electrode material, prepares with vacuum induction melting furnace
Obtain High-capacity hydrogen storage alloy electrode material, including charging, fusing, refine, casting and annealed
Journey, the chemical composition of the High-capacity hydrogen storage alloy electrode material obtained in percentage by weight, is wrapped
Include ML1-x-ySmxMgyNizAlwCouMnv, wherein 0 < x < 0.62,0 < y < 0.4,3 < z < 4,
0.03 < w < 0.15,0.03 <u < 0.15,0.03 < v < 0.15, elementary composition relation is 3.1 < z+w+u+v < 4.2；
ML is lanthanum rich norium, and composition is: La 42%～45%, Nd 29%～35%, Ce
2%～5%, Pr 8%～11%；The alloy pig obtained is used vibrator after surface cleaning
Wear into the alloy powder of 300～400 mesh.
Further: to prepare High-capacity hydrogen storage alloy electrode material with vacuum induction melting furnace and obtain
Constituent is ML0.27Sm0.62Mg0.11Ni3.37Al0.06Co0.08。
Further: in described charging process, the raw material weighed up by design composition is loaded vacuum induction
In the melting kettle of smelting furnace, charging sequence is: lanthanum rich norium, metal Sm, gold
Belong to Co, W metal, metal Al, described lanthanum rich norium, metal Sm, metal Co,
W metal, the percentage by weight of metal Al are followed successively by 11.2%, 27.6%, 1.4%, 58.5%, 0.5%；
In described fusion process, before melting, first it is evacuated to 1 × below 10-2MPa, is re-filled with appropriate
Argon makes vacuum be maintained at 0.06MPa；First progressively it is warmed up to 1200 DEG C～1350 DEG C during melting, protects
Hold power 3 minutes, make raw material gradually melt；
In described refine and casting cycle, it is continuously heating to 1400 DEG C～1500 DEG C, under argon shield
Vacuum degree control, in 0.06Mpa, refine 3 minutes, next reduces power, keeps the temperature at
1000 DEG C～1300 DEG C, Mg is added when just starting to crust by melt liquid level by secondary charging bucket；So
After be warming up to 1400 DEG C～1500 DEG C, vacuum 0.06Mpa, keep 1～2 minute, finally reduce temperature
Spend to 1300 DEG C～1400 DEG C, vacuum 0.06MPa, cast；
In described annealing process, at 800～1300 DEG C, at the heat that carries out under 0.5atm ar gas environment annealing
Reason 10～20h, obtains the uniform alloy of composition.
Further: prepare the group of High-capacity hydrogen storage alloy electrode material with vacuum induction melting furnace
One-tenth composition is ML0.57Sm0.22Mg0.21Ni3.07Al0.12Co0.08Mn0.2。
Further: in described charging process, the raw material weighed up by design composition is loaded vacuum induction
In the melting kettle of smelting furnace, charging sequence is: lanthanum rich norium, metal Sm, gold
Belong to Mn, metal Co, W metal, metal Al, described lanthanum rich norium, metal Sm,
Metal Mn, metal Co, W metal, the percentage by weight of metal Al be followed successively by 25.2%, 10.4%,
3.5%, 1.5%, 56.8%, 1.0%；
In described fusion process, before melting, first it is evacuated to 1 × below 10-2MPa, is re-filled with appropriate
Argon makes vacuum be maintained at about 0.06MPa.First 1200 DEG C～1350 progressively it are warmed up to during melting
DEG C, keep power 3 minutes, make raw material gradually melt.
In described refine and casting cycle, it is continuously heating to 1400 DEG C～1500 DEG C, under argon shield
Vacuum degree control, in 0.06MPa, refine 3 minutes, next reduces power, keeps the temperature at
1000 DEG C～1300 DEG C, Mg is added when just starting to crust by melt liquid level by secondary charging bucket；So
After be brought rapidly up to 1400 DEG C～1500 DEG C, vacuum 0.06MPa, keep 1～2 minute, finally drop
Low temperature to 1300 DEG C～1400 DEG C, vacuum 0.06MPa, cast；
In described annealing process, at 800～1300 DEG C, at the heat that carries out under 0.5atm ar gas environment annealing
Reason 10～20h, obtains the uniform alloy of composition.
The present invention compared with prior art has the advantage that
1, the High-capacity hydrogen storage alloy electrode material that the present invention relates to, its specific discharge capacity and tradition
AB5Type hydrogen storage alloy is compared and is exceeded 20%～30%, and has preferable high-rate discharge ability.
2, the High-capacity hydrogen storage alloy electrode material of present invention design, its cost of raw material is low, preparation
Technique and equipment are simple, and energy resource consumption is few, it is easy to industrialization and popularization.
Detailed description of the invention
It is an object of the invention to provide the relatively inexpensive Samarium Nitrate of a kind of employing (Sm) to substitute
The A that Nd prepares2B7Type hydrogen storage alloy.The present invention can significantly reduce this base hydrogen storage alloy
The cost of raw material, and the hydrogen bearing alloy prepared has good high-rate discharge ability and higher
Specific discharge capacity.
The present invention provides a kind of High-capacity hydrogen storage alloy electrode material, and its chemical composition is according to weight hundred
Proportion by subtraction meter, including:
ML1-x-ySmxMgyNizAlwCouMnv, wherein 0 < x < 0.62；0<y<0.4；3<z<4；
0.03<w<0.15；0.03<u<0.15；0.03<v<0.15.Upper each elementary composition relation is
3.1<z+w+u+v<4.2。
ML is lanthanum rich norium, and composition is: La 42%～45%, Nd 29%～35%,
Ce 2%～5%, Pr 8%～11%.
The High-capacity hydrogen storage alloy electrode material of heterogeneity ratio is prepared with vacuum induction melting furnace
Time, parameter used is identical, elaborates the preparation process of material below by two embodiments.
Embodiment 1
Preparing composition with vacuum induction melting furnace is ML0.27Sm0.62Mg0.11Ni3.37Al0.06Co0.08
Alloy pig, the parameter of fusion process and employing is as follows:
Step 11: charging；
The raw material weighed up by design composition is loaded in the melting kettle of vacuum induction melting furnace, charging
Order is: lanthanum rich norium → metal Sm → metal Co → W metal → metal Al, rich
La mixed rare earth metal, metal Sm, metal Co, W metal, the percentage by weight of metal Al
It is followed successively by 11.2%, 27.6%, 1.4%, 58.5%, 0.5%.
Step 12: fusing；
1 × 10 first it is evacuated to before melting-2Below MPa, is re-filled with appropriate argon and makes vacuum keep
At about 0.06MPa.First progressively it is warmed up to 1200 DEG C～1350 DEG C during melting, keeps power 3 minutes,
Raw material is made gradually to melt.
Step 13: refine and casting；
Then proceeding to be warming up to 1400 DEG C～1500 DEG C, the vacuum degree control under argon shield is 0.06
MPa, refine 3 minutes, next reduce power, keep the temperature at 1000 DEG C～1300 DEG C, molten
Body fluid face has just started crust and has been advisable, then is added by secondary charging bucket by Mg.Then it is brought rapidly up
To 1400 DEG C～1500 DEG C, vacuum 0.06MPa, keep 1～2 minute, finally reduce temperature to 1300
DEG C～1400 DEG C, vacuum 0.06MPa, carry out casting.
Step 14: annealing.
By it at 800～1300 DEG C after melting, carry out under 0.5atm ar gas environment anneal heat treatment 10～
20h, obtains the uniform alloy of composition.
Wear into the alloy powder of 300～400 mesh with vibrator after being purified by alloy surface.It is surveyed
The results are shown in Table 1 for the electrochemistry capacitance that examination obtains.
Table 1 ML0.27Sm0.62Mg0.11Ni3.37Al0.06Co0.08Alloy half-cell test result
| Discharge-rate | 1C | 2C | 3C |
| Discharge capacity (mAh/g) | 348.8 | 312.5 | 302.3 |
Embodiment 2
Preparing composition with vacuum induction melting furnace is
ML0.57Sm0.22Mg0.21Ni3.07Al0.12Co0.08Mn0.2Alloy pig.The parameter of fusion process and employing is such as
Under:
Step 21: charging；
First the raw material weighed up by design composition is loaded in the melting kettle of vacuum induction melting furnace,
Charging sequence is: lanthanum rich norium → metal Sm → metal Mn → metal Co → metal
Ni → metal Al, lanthanum rich norium, metal Sm, metal Mn, metal Co, metal
Ni, the percentage by weight of metal Al be followed successively by 25.2%, 10.4%, 3.5%, 1.5%, 56.8%,
1.0%.
Step 21: fusing；
1 × 10 first it is evacuated to before melting-2Below MPa, is re-filled with appropriate argon and makes vacuum keep
At about 0.06MPa.First progressively it is warmed up to 1200 DEG C～1350 DEG C during melting, keeps power 3 minutes,
Raw material is made gradually to melt.
Step 23: refine and casting；
Then proceeding to be warming up to 1400 DEG C～1500 DEG C, the vacuum degree control under argon shield exists
0.06Mpa, refine 3 minutes, next reduce power, keep the temperature at 1000 DEG C～1300 DEG C,
Melt liquid level has just started crust and has been advisable, then is added by secondary charging bucket by Mg.Rise the most rapidly
Warm to 1400 DEG C～1500 DEG C, vacuum 0.06MPa, keep 1～2 minute, finally reduce temperature extremely
1300 DEG C～1400 DEG C, vacuum 0.06MPa, carry out casting.
Step 24: annealing.
By it at 800～1300 DEG C after melting, carry out under 0.5atm ar gas environment anneal heat treatment 10～
20h, obtains the uniform alloy of composition.
The alloy powder of 300～400 mesh will be worn into vibrator after its surface cleaning.Its test
The results are shown in Table 2 for the electrochemistry capacitance obtained.
Table 2 ML0.57Sm0.22Mg0.21Ni3.07Al0.12Co0.08Mn0.2Alloy half-cell test result
| Discharge-rate | 1C | 2C | 3C |
| Discharge capacity (mAh/g) | 357.5 | 303.5 | 287.5 |
Claims (4)
1. a High-capacity hydrogen storage alloy electrode material, it is characterised in that: its chemical composition is according to weight
Amount percentages, including ML1-x-ySmxMgyNizAlwCouMnv, wherein 0 < x < 0.62,0 < y < 0.4,
3 < z < 4,0.03 < w < 0.15,0.03 <u < 0.15,0.03 < v < 0.15, elementary composition relation is
3.1<z+w+u+v<4.2；ML is lanthanum rich norium, and composition is: La 42%～45%, Nd
29%～35%, Ce 2%～5%, Pr 8%～11%, remaining is impurity；Described high capacity hydrogen storage closes
Gold electrode material is the alloy powder of 300～400 mesh.
2. High-capacity hydrogen storage alloy electrode material as claimed in claim 1, it is characterised in that: its group
One-tenth composition is ML0.27Sm0.62Mg0.11Ni3.37Al0.06Co0.08。
3. High-capacity hydrogen storage alloy electrode material as claimed in claim 1, it is characterised in that: its group
One-tenth composition is ML0.57Sm0.22Mg0.21Ni3.07Al0.12Co0.08Mn0.2。
4. a production method for High-capacity hydrogen storage alloy electrode material, uses vacuum induction melting furnace system
For obtaining High-capacity hydrogen storage alloy electrode material, including charging, fusing, refine, casting and annealing process,
It is characterized in that: in described charging process, the raw material weighed up by design composition is loaded vacuum induction melting
In the melting kettle of stove, charging sequence is: lanthanum rich norium, metal Sm, metal Co, gold
Belong to Ni, metal Al, described lanthanum rich norium, metal Sm, metal Co, W metal, gold
The percentage by weight belonging to Al is followed successively by 11.2%, 27.6%, 1.4%, 58.5%, 0.5%；Described fusing
During, first it is evacuated to 1 × 10 before melting-2Below MPa, is re-filled with appropriate argon and makes vacuum protect
Hold at 0.06MPa；First progressively it is warmed up to 1200 DEG C～1350 DEG C during melting, keeps power 3 minutes, make
Raw material gradually melts；In described refine and casting cycle, it is continuously heating to 1400 DEG C～1500 DEG C, argon
Vacuum degree control under Bao Hu, in 0.06Mpa, refine 3 minutes, next reduces power, makes temperature protect
Holding at 1000 DEG C～1300 DEG C, Mg is added when just starting to crust by melt liquid level by secondary charging bucket；
Then heat to 1400 DEG C～1500 DEG C, vacuum 0.06Mpa, keep 1～2 minute, finally reduce temperature
Spend to 1300 DEG C～1400 DEG C, vacuum 0.06Mpa, cast；In described annealing process, 800～
1300 DEG C, carry out heat treatment 10～20h of annealing under 0.5atm ar gas environment, obtain the uniform alloy of composition；
Prepare High-capacity hydrogen storage alloy electrode material with vacuum induction melting furnace and obtain constituent and be
ML0.27Sm0.62Mg0.11Ni3.37Al0.06Co0.08；ML is lanthanum rich norium, and composition is: La 42
%～45%, Nd 29%～35%, Ce 2%～5%, Pr 8%～11%, remaining is impurity；Will
The alloy pig obtained wears into the alloy powder of 300～400 mesh after surface cleaning with vibrator.
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