CN117185253A - Surface treatment method of hydrogen storage alloy and application thereof - Google Patents
Surface treatment method of hydrogen storage alloy and application thereof Download PDFInfo
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- CN117185253A CN117185253A CN202311144343.0A CN202311144343A CN117185253A CN 117185253 A CN117185253 A CN 117185253A CN 202311144343 A CN202311144343 A CN 202311144343A CN 117185253 A CN117185253 A CN 117185253A
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- 239000000956 alloy Substances 0.000 title claims abstract description 111
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 110
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 88
- 239000001257 hydrogen Substances 0.000 title claims abstract description 88
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 81
- 238000003860 storage Methods 0.000 title claims abstract description 62
- 238000000034 method Methods 0.000 title claims abstract description 27
- 238000004381 surface treatment Methods 0.000 title claims description 16
- 238000010438 heat treatment Methods 0.000 claims abstract description 49
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000004321 preservation Methods 0.000 claims description 28
- 238000001816 cooling Methods 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- 239000010405 anode material Substances 0.000 claims 1
- 239000006260 foam Substances 0.000 claims 1
- 238000003825 pressing Methods 0.000 claims 1
- 230000000630 rising effect Effects 0.000 claims 1
- 239000000758 substrate Substances 0.000 claims 1
- 238000003466 welding Methods 0.000 claims 1
- 230000005415 magnetization Effects 0.000 abstract description 10
- 239000002344 surface layer Substances 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 3
- 229910052987 metal hydride Inorganic materials 0.000 abstract description 2
- 238000007254 oxidation reaction Methods 0.000 abstract description 2
- 229910052761 rare earth metal Inorganic materials 0.000 abstract 1
- 150000002910 rare earth metals Chemical class 0.000 abstract 1
- 239000002994 raw material Substances 0.000 description 14
- 238000012360 testing method Methods 0.000 description 7
- 238000005530 etching Methods 0.000 description 5
- 238000010998 test method Methods 0.000 description 5
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 230000008859 change Effects 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 229910017488 Cu K Inorganic materials 0.000 description 1
- 229910017541 Cu-K Inorganic materials 0.000 description 1
- 229910019566 Re—Mg—Ni Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- -1 comprises reduction Substances 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 238000004451 qualitative analysis Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention relates to the technical field of rare earth hydrogen storage alloy electrodes, and provides a method for modifying the surface of a hydrogen storage alloy through low-temperature heat treatment. The method comprises the following steps: the hydrogen storage alloy is placed in a muffle furnace for low-temperature short-time heat treatment, and micro-oxidation is carried out on the surface layer of the alloy to form nano nickel, so that the saturation magnetization intensity of the alloy is improved, and the charge-discharge rate performance of the alloy is greatly improved on the premise of ensuring the discharge capacity of the alloy. The invention has simple process conditions, is environment-friendly and low in cost, and can obviously improve the charge-discharge rate performance of the nickel-metal hydride battery.
Description
Technical Field
The invention relates to the technical field of nickel-hydrogen battery electrode treatment, in particular to a surface treatment method of hydrogen storage alloy and application thereof.
Background
As a secondary battery for early commercialization application, a nickel-metal hydride (Ni-MH) battery has the characteristics of high energy density, good overcharge and overdischarge resistance, high safety performance, environmental protection and the like, and has irreplaceable positions in some application fields. The nickel-hydrogen battery still has a large improvement space in the aspects of output power, cycle life, low-temperature performance and the like, and the key for improving the performance of the nickel-hydrogen battery is to improve the cathode material of the nickel-hydrogen battery. After the hydrogen storage alloy powder is manufactured to obtain a battery electrode, the corrosion pulverization of the alloy powder can lead to the gradual reduction of the battery performance in the process of repeatedly charging and discharging in alkaline electrolyte. Therefore, the activity of the alloy surface needs to be optimized by a surface modification technology, so that the intercalation and deintercalation of hydrogen on the surface of the hydrogen storage alloy powder are easier, and the aim of optimizing the performance of the alloy electrode is fulfilled.
The surface treatment method of the hydrogen storage alloy powder mainly comprises reduction, coating, alkali solution, acid solution and the like. The Ni-rich layer formed on the surface of the alloy after the heat alkali treatment has good catalytic activity and corrosion resistance, but the too high Ni content can cause difficult hydrogen atom transmission and reduced hydrogen storage capacity. And the alkali treatment process needs to use a large amount of strong alkali solution and clear water for cleaning the alloy surface, and has long treatment time, thus causing a certain environmental protection problem. Therefore, providing an environment-friendly and efficient hydrogen storage alloy surface treatment method is a problem to be solved at present.
Disclosure of Invention
In order to solve the problems, the invention aims to provide a surface treatment method of a hydrogen storage alloy and application thereof, wherein the treatment method carries out low-temperature heat treatment on the hydrogen storage alloy in a muffle furnace, and the method has the advantages of simple operation and equipment, high safety factor, low energy consumption, mild condition, stable and easily controlled reaction process and convenient large-scale industrial production and use.
In order to achieve the above object, the present invention adopts the following technical scheme:
a surface treatment method of a hydrogen occluding alloy, comprising the steps of:
and carrying out low-temperature heat treatment on the hydrogen storage alloy to obtain the treated hydrogen storage alloy.
Preferably, as a preferred embodiment, the hydrogen storage alloy has a particle size of 200 to 400 mesh.
Preferably, as a preferred embodiment, the hydrogen storage alloy has a mass of 2g.
Preferably, as a preferred embodiment, the heat treatment may be performed in a tube furnace or a muffle furnace.
Preferably, as a preferred embodiment, the temperature rise rate of the low-temperature heat treatment is 5 ℃/min, the heat treatment heat preservation temperature is 80-240 ℃, and the heat treatment heat preservation time is 10-60min.
Preferably, as a preferred embodiment, after the treatment, an oxide layer with a certain thickness is formed on the surface of the alloy, and the alloy has a certain content of nickel, and the higher the heat treatment holding temperature is, the higher the saturation magnetization degree of the hydrogen storage alloy is.
Preferably, as a preferred embodiment, the hydrogen storage alloy is A 2 B 7 Form and AB 5 Hydrogen storage alloys, e.g. Re-Mg-Ni based and LaNi 5 And the base alloy needs to contain Ni or Co elements.
Another object of the present invention is to provide a hydrogen occluding alloy obtained by the surface treatment method.
Another object of the invention is to provide a use of the hydrogen storage alloy in a negative electrode material of a nickel-hydrogen battery.
Compared with the prior art, the invention has the beneficial effects that:
the invention provides a surface treatment method of hydrogen storage alloy, which is characterized in that the hydrogen storage alloy is subjected to low-temperature heat treatment in a muffle furnace, so that the operation and equipment are simple, the safety coefficient is high, the energy consumption is low, the condition is mild, the reaction process is stable and easy to control, and the method is convenient for large-scale industrial production and use. The hydrogen storage alloy obtained by the invention obtains a surface with high activity on the premise of ensuring the discharge capacity. The maximum discharge capacity of the hydrogen storage alloy electrode obtained by different heat treatment time and temperature is 350-360mAh/g, and the capacity retention rate S after 100 charge and discharge cycles 100 Between 80-82%. By the surface treatment method, the discharge performance HRD of the hydrogen storage alloy is realized under the current density of 1200mA/g 1200 From 71.77% to 87.14% of original alloy, HRD 1500 From 67.54% to 84.47% of the original alloy, and at the same time, the saturation magnetization of the alloy is raised to the highest from 0.097emu/g of the original alloy
1.898emu/g, and the Ni content of the alloy surface is greatly improved.
The low-temperature heat treatment mode adopted by the invention has low cost and excellent electrochemical performance, and can be widely used as a new material for the nickel-hydrogen battery cathode with high capacity, long service life and high current discharge performance
Drawings
FIG. 1 is a graph showing the saturation magnetization of samples treated in examples 1-6 of the present invention compared to the original alloy; the results show that the saturation magnetization after sample treatment is improved.
FIG. 2 is an XRD pattern of samples treated in examples 1-6 of the present invention; the results showed no change in bulk structure of the treated samples.
FIG. 3 is a graph showing the high rate discharge performance of the samples treated in examples 1-6 of the present invention;
FIG. 4 is a graph showing the comparison of XPS multi-layer etching fine spectra of Ni elements of a sample of a hydrogen storage alloy material of the present invention and a sample treated in example 6; the results show that the metal Ni content of the sample surface layer after treatment is increased.
FIG. 5 is a graph showing the high rate discharge performance of the treated sample of example 7 of the present invention.
Detailed Description
1. Example 1
La with particle size of 200-400 meshes 0.32 Sm 0.56 Mg 0.12 Zr 0.0024 (Ni 0.96 Al 0.04 ) 3.53 Placing the hydrogen storage alloy raw material into a magnetic boat, placing the magnetic boat into a muffle furnace for low-temperature heat treatment, wherein the heating rate is 5 ℃/min, the heat treatment heat preservation temperature is 200 ℃, the heat treatment heat preservation time is 10min, and after the heat preservation time is over, cooling the sample to room temperature along with the furnace to obtain the treated hydrogen storage alloy.
The resulting hydrogen storage alloy was subjected to an X-ray powder diffraction (XRD, PANalytical Empyrean) test under the following conditions: the Cu-K alpha rays are adopted, the power is 45KV multiplied by 40mA, the step length is 0.02 DEG, and the testing range is 20-60 deg. XRD qualitative analysis was performed on the obtained hydrogen absorbing alloy and hydrogen absorbing alloy raw material, and the obtained results are shown in FIG. 2.
0.1g of the hydrogen occluding alloy treated in this example and 0.1g of the hydrogen occluding alloy raw material were weighed and analyzed by a vibrating sample magnetometer VSM, respectively, to obtain a saturated magnetization of the hydrogen occluding alloy treated in this example under a magnetic field of 5000Oe of 0.946emu/g and a magnetization of the hydrogen occluding alloy raw material of 0.097emu/g, and the obtained results are shown in FIG. 1.
The hydrogen storage alloy and Ni powder obtained after the treatment of the embodiment have the mass ratio of 1:4, uniformly mixing the materials in a proportion, taking 0.1g of mixed powder, and maintaining the pressure at 20MPa for 30s to obtain a round hydrogen storage alloy electrode plate with the diameter of 10cm and the thickness of about 1 mm; the test is carried out by adopting a three-electrode system at the temperature of 25 ℃ in an incubator, wherein the negative electrode is a hydrogen storage electrode, the positive electrode is a Ni (OH) 2 electrode, the reference electrode is a Hg/HgO electrode, and the electrolyte is a potassium hydroxide solution of 6 mol/L. And (3) standing the test electrode in a KOH solution with the concentration of 6mol/L for 1h, charging for 7.5h with the concentration of 60mA/g, standing for 5min, discharging to the cut-off potential of-0.6V (vs. Hg/HgO) with the concentration of 60mA/g, standing for 5min, and performing the next circulation. The high-rate discharge performance test is that the electrode is charged for 7.5 hours at a current density of 60mA/g, and then is discharged at current densities of 300, 600, 900, 1200 and 1500mA/g respectively, the discharge cut-off voltage is-0.6V (vs. Hg/HgO), and the discharge capacity of the alloy electrode under different discharge current densities is recorded.
Other conditions are controlled unchanged, and the hydrogen storage alloy treated in the embodiment is replaced by a hydrogen storage alloy raw material and alloy powder subjected to low-temperature heat treatment respectively. The highest specific discharge capacity and charge-discharge cycle performance were tested, and the results obtained are shown in Table 1, wherein C max Refers to the highest specific discharge capacity of the alloy, S 100 Refers to the ratio of the discharge capacity of the alloy after 100 circles of circulation to the highest discharge specific capacity; the high rate discharge performance was tested and the results obtained are shown in fig. 3.
2. Example 2
Mixing La with 200-400 mesh particle size 0.32 Sm 0.56 Mg 0.12 Zr 0.0024 (Ni 0.96 Al 0.04 ) 3.53 Placing the hydrogen storage alloy raw material into a magnetic boat, placing the magnetic boat into a muffle furnace for low-temperature heat treatment, wherein the heating rate is 5 ℃/min, the heat treatment heat preservation temperature is 180 ℃, the heat treatment heat preservation time is 10min, and after the heat preservation time is over, cooling the sample to room temperature along with the furnace to obtain the treated hydrogen storage alloy.
The hydrogen occluding alloy treated in example 2 was tested in the same test method as in example 1, and the results obtained are shown in table 1 and fig. 1 to 3.
3. Example 3
Mixing La with 200-400 mesh particle size 0.32 Sm 0.56 Mg 0.12 Zr 0.0024 (Ni 0.96 Al 0.04 ) 3.53 Placing the hydrogen storage alloy raw material into a magnetic boat, placing the magnetic boat into a muffle furnace for low-temperature heat treatment, wherein the heating rate is 5 ℃/min, the heat treatment heat preservation temperature is 220 ℃, the heat treatment heat preservation time is 10min, and after the heat preservation time is over, cooling the sample to room temperature along with the furnace to obtain the treated hydrogen storage alloy.
The hydrogen occluding alloy treated in example 3 was tested in the same test method as in example 1, and the results obtained are shown in table 1 and fig. 1 to 3.
4. Example 4
Mixing La with 200-400 mesh particle size 0.32 Sm 0.56 Mg 0.12 Zr 0.0024 (Ni 0.96 Al 0.04 ) 3.53 Placing the hydrogen storage alloy raw material into a magnetic boat, placing the magnetic boat into a muffle furnace for low-temperature heat treatment, wherein the heating rate is 5 ℃/min, the heat treatment heat preservation temperature is 240 ℃, the heat treatment heat preservation time is 10min, and after the heat preservation time is over, cooling the sample to room temperature along with the furnace to obtain the treated hydrogen storage alloy.
The hydrogen occluding alloy treated in example 4 was tested in the same test method as in example 1, and the results obtained are shown in table 1 and fig. 1 to 3.
5. Example 5
Mixing La with 200-400 mesh particle size 0.32 Sm 0.56 Mg 0.12 Zr 0.0024 (Ni 0.96 Al 0.04 ) 3.53 Placing the hydrogen storage alloy raw material into a magnetic boat, placing the magnetic boat into a muffle furnace for low-temperature heat treatment, wherein the heating rate is 5 ℃/min, the heat treatment heat preservation temperature is 200 ℃, the heat treatment heat preservation time is 30min, and after the heat preservation time is over, cooling the sample to room temperature along with the furnace to obtain the treated hydrogen storage alloy.
The hydrogen occluding alloy treated in example 5 was tested in the same test method as in example 1, and the results obtained are shown in table 1 and fig. 1 to 3.
6. Example 6
Mixing La with 200-400 mesh particle size 0.32 Sm 0.56 Mg 0.12 Zr 0.0024 (Ni 0.96 Al 0.04 ) 3.53 Placing the hydrogen storage alloy raw material into a magnetic boat, placing the magnetic boat into a muffle furnace for low-temperature heat treatment, wherein the heating rate is 5 ℃/min, the heat treatment heat preservation temperature is 200 ℃, the heat treatment heat preservation time is 60min, and after the heat preservation time is over, cooling the sample to room temperature along with the furnace to obtain the treated hydrogen storage alloy.
XPS test is carried out on the hydrogen storage alloy obtained after the treatment of the example 6 and the hydrogen storage alloy raw material, the test result is shown in figure 4, the left graph shows the XPS spectrogram of Ni element of the hydrogen storage alloy raw material with different etching thickness, and the alloy Ni increases with the etching thickness 2+ The metal Ni is reduced, the metal Ni is increased, and the thickness of the surface layer is about 10-15nm; the right graph shows the XPS spectrogram of the sample with different etching thickness after treatment, and compared with the hydrogen storage alloy raw material, the alloy Ni with the increase of the etching thickness 2+ The Ni content in the surface layer of the hydrogen storage alloy is increased by 10-15nm after low temperature treatment compared with the hydrogen storage alloy raw material, wherein the thickness of the surface layer is about 5 nm.
The hydrogen occluding alloy treated in example 6 was tested in the same test method as in example 1, and the results obtained are shown in table 1 and fig. 1 to 3.
TABLE 1 Performance results of alloy samples obtained in examples 1-6
As can be seen from table 1, as the temperature of the low-temperature heat treatment is raised, the magnetization intensity of the alloy sample is gradually raised, the change of the highest discharge specific capacity of the alloy is smaller, and the charge-discharge cycle performance is more stable; along with the extension of the low-temperature heat treatment heat preservation time, the magnetization intensity of the alloy sample is gradually improved, the change of the highest discharge specific capacity of the alloy is smaller, and the charge-discharge cycle performance is relatively stable. The treated hydrogen storage alloy has a Ni-rich layer formed on the surface, so that the saturation magnetization is enhanced, the electrocatalytic property and the surface conductivity of the alloy powder are improved, and oxidation and pulverization are inhibited.
As can be seen from fig. 1, the phase structure of the treated sample was not changed.
As can be seen from fig. 4, the high-rate discharge performance of the alloy sample is gradually enhanced with the increase of the holding temperature of the low-temperature heat treatment; along with the extension of the low-temperature heat treatment heat preservation time, the high-rate discharge performance of the alloy sample is gradually weakened.
7. Example 7
In order to verify the universality of the method, AB is selected 5 La is the gold sample of the hydrogen storage alloy 0.658 Ce o.213 Sm 0.104 Zr 0.026 Ni 4.32 Co 0.166 Mn 0.25 Al 0.35 Testing AB 5 Placing the magnetic boat in a muffle furnace for low-temperature heat treatment, wherein the heating rate is 5 ℃/min, the heat preservation temperature of the heat treatment is 200 ℃ and 240 ℃, the heat preservation time of the heat treatment at 200 ℃ is 10min and 30min, the heat preservation time at 240 ℃ is 10min, and after the heat preservation time is over, the sample is cooled to room temperature along with the furnace, so that the treated hydrogen storage alloy is obtained.
The sample obtained in example 7 was tested for high rate discharge performance, and the results obtained are shown in fig. 5. It can be seen from fig. 5 that the high rate discharge performance of the alloy changes in the same manner as in fig. 3, which means that the method of the present invention is also applicable to other hydrogen storage alloys.
Claims (6)
1. A method for surface treatment of a hydrogen occluding alloy, comprising the steps of:
carrying out low-temperature heat treatment on the hydrogen storage alloy to obtain the treated hydrogen storage alloy;
the heat treatment and heat preservation temperature is 180-240 ℃;
the low-temperature heat treatment and the heat preservation time are 10-60min;
the temperature rising rate of the low-temperature heat treatment is 5 ℃/min, and the cooling mode is furnace-following cooling.
2. As claimed inThe surface treatment method according to 1, wherein the hydrogen absorbing alloy is A 2 B 7 Or AB 5 Hydrogen storage alloy.
3. The surface treatment method according to claim 1, wherein the particle diameter of the hydrogen absorbing alloy is 200 to 400 mesh, and the mass of the hydrogen absorbing alloy is 2g.
4. A method for preparing a hydrogen storage alloy electrode, comprising the steps of:
the hydrogen storage alloy treated by the surface treatment method of claim 1 and Ni powder are mixed according to the following ratio of 1:4, uniformly mixing, cold pressing into electrode plates under the pressure of 20MPa, coating the electrode plates in a foam nickel substrate, and performing spot welding by using nickel strips to prepare the hydrogen storage alloy electrode.
5. The hydrogen occluding alloy prepared by the surface treatment method of claim 1.
6. The use of the hydrogen storage alloy treated by the surface treatment method according to claim 1 in a nickel-hydrogen battery anode material.
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