CN116043064A - Low-cost long-life pure phase 2H type A 2 B 7 Hydrogen storage alloy electrode material and preparation method thereof - Google Patents
Low-cost long-life pure phase 2H type A 2 B 7 Hydrogen storage alloy electrode material and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C19/00—Alloys based on nickel or cobalt
- C22C19/03—Alloys based on nickel or cobalt based on nickel
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/0005—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes
- C01B3/001—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes characterised by the uptaking medium; Treatment thereof
- C01B3/0031—Intermetallic compounds; Metal alloys; Treatment thereof
- C01B3/0047—Intermetallic compounds; Metal alloys; Treatment thereof containing a rare earth metal; Treatment thereof
- C01B3/0057—Intermetallic compounds; Metal alloys; Treatment thereof containing a rare earth metal; Treatment thereof also containing nickel
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
- C22C1/023—Alloys based on nickel
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C19/00—Alloys based on nickel or cobalt
- C22C19/007—Alloys based on nickel or cobalt with a light metal (alkali metal Li, Na, K, Rb, Cs; earth alkali metal Be, Mg, Ca, Sr, Ba, Al Ga, Ge, Ti) or B, Si, Zr, Hf, Sc, Y, lanthanides, actinides, as the next major constituent
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/02—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working in inert or controlled atmosphere or vacuum
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/10—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of nickel or cobalt or alloys based thereon
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/383—Hydrogen absorbing alloys
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C2202/00—Physical properties
- C22C2202/04—Hydrogen absorbing
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- 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
Abstract
The invention discloses a pure phase 2H type A with low cost and long service life 2 B 7 Electrode material of hydrogen storage alloy and preparation method thereof, wherein the hydrogen storage alloy can be prepared from La 1‑x‑y‑z‑w R w Sm z Y y Mg x Ni c‑a‑b Al a Fe b The expression is as follows: r represents at least one element selected from rare earth Ce and Zr, wherein x, y, z, w, a, b, c is represented by the formulaThe mol ratio is equal to or more than 0.12 and equal to or less than 0.18,0.02, y is equal to or less than 0.10,0.10 and equal to or less than 0.25, z is equal to or less than 0 and less than 0.10,0.10, w is equal to or less than 0.05,0.05 and less than a is equal to or less than 0.2, b is equal to or less than 0.15,3.3 and c is equal to or less than 3.5, the hydrogen storage alloy electrode material is prepared by adopting a method combining induction smelting and annealing treatment, and the crystal structure type of the prepared hydrogen storage alloy is pure-phase hexagonal system 2H type A 2 B 7 And a phase structure. The hydrogen storage alloy prepared by the invention has low cost, high discharge capacity and excellent electrochemical cycle life, the maximum discharge capacity is more than or equal to 380mAh/g, the capacity retention rate after 300 charge and discharge cycles is more than or equal to 75%, the preparation process is simple and stable, the process condition is easy to control, and the industrialized production and application are facilitated.
Description
Technical Field
The invention relates to the field of nickel-hydrogen batteries, in particular to a pure phase 2H type A with low cost and long service life 2 B 7 A hydrogen storage alloy electrode material and a preparation method thereof.
Background
In nickel-metal hydride (Ni/MH) batteries, the negative electrode material is critical in determining the physicochemical properties of the battery. The intensive research and development of novel high-performance and low-cost anode materials has important significance for the industrialized development of Ni/MH batteries. The current commercial Ni/MH battery cathode material is mainly rare earth series AB 5 Hydrogen storage alloys, however, have a low maximum discharge capacity of only 330mAh/g and are difficult to further improve. Therefore, the development of novel high-performance low-cost hydrogen storage alloys is a technical key.
The rare earth-magnesium-nickel (RE-Mg-Ni) hydrogen storage alloy developed in the early period of the century has the advantages of high capacity, easy activation and the like due to the special superlattice structure, and has gradually become a substitute for the traditional AB 5 Novel alloys of Ni/MH battery negative electrode materials. RE-Mg-Ni hydrogen storage alloy consists of [ AB ] 5 ]And [ A ] 2 B 4 ]Two kinds of sub-lattices are periodically stacked along the direction of the c-axis, wherein [ AB ] 5 ]And [ A ] 2 B 4 ]The two sublattices are stacked according to the ratio of 1:1, 2:1, 3:1 and 4:1 to form AB 3 、A 2 B 7 、A 5 B 19 And AB 4 Superlattice structures, and each superlattice structure is based on the [ a ] it contains 2 B 4 ]The difference in the types of the sub-lattices can be divided into two different crystalline isomorphous phases, namely a hexagonal 2H type and a trigonal 3R type. The special superlattice structure can make the discharge capacity of RE-Mg-Ni hydrogen storage alloy reach 410mAh/g at most, especially A 2 B 7 The hydrogen storage alloy has good comprehensive electrochemical performance, but the main problem facing the alloy at present is that the electrochemical life (cycle stability) can not meet the market application requirements.
From the current research results, alloy phase purity and element composition are key factors affecting the alloy. The RE-Mg-Ni intermetallic compound has small difference of different phase structure components and close formation temperature, 2H and 3R isomerism components of each phase structure are easy to convert, so that the alloy prepared at present is of a multiphase structure, when different phase structures coexist, the expansion rate of the volume of a sub-lattice is different, the increase of internal stress and serious pulverization of the alloy are caused, and finally, the service life of the alloy is poor, therefore, the heat treatment condition is required to be strictly controlled in the preparation process to eliminate heterogeneous phase, and the alloy phase structure is purified. However, the heat treatment conditions of the pure alloy phase structure are related not only to the alloy structure type but also to the alloy element composition. In addition, the alloy composition element not only affects the preparation condition of the pure phase, but also is a key for improving and optimizing the electrochemical performance of the alloy. The rare earth elements Pr and Nd on the A side have good corrosion resistance, which is beneficial to prolonging the cycle life of the alloy, increasing the pressure of a hydrogen releasing platform of the alloy and beneficial to the rate discharge performance of the alloy, but the price per kilogram is about 36 times of that of metal La at present, which also becomes the constraint cost. In addition, the B-side transition metal element Co can have beneficial effects on the discharge performance and the cycle stability of Jin Beilv, but the price of the B-side transition metal element Co is 1.4 times of that of the metal Ni at present. In addition, the price of metallic Ni is still higher in recent years, A is higher than B-side Ni 5 B 19 Alloy A 2 B 7 Alloy can beThe method has a certain advantage in cost, but how to improve the electrochemical cycling stability of the optimized alloy under the condition of low cost is still a key technical problem in the field, and the method is not only an important problem to be solved by the prior hydrogen storage alloy with the superlattice structure, but also has important significance for improving the market competitiveness of the nickel-hydrogen battery cathode material.
Disclosure of Invention
The invention aims to overcome the problems in the prior art and provides a pure phase 2H type A with low cost and long service life 2 B 7 A hydrogen storage alloy electrode material and a preparation method thereof.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a pure phase 2H type A with low cost and long service life 2 B 7 The chemical general formula of the hydrogen storage alloy electrode material is represented by La 1-x-y-z-w R w Sm z Y y Mg x Ni c-a-b Al a Fe b Wherein: r represents at least one element selected from rare earth Ce and Zr, wherein x, y, z, w, a, b, c represents a molar ratio of 0.12-0.18,0.02-0.05,0.10-0.25, 0-0.05,0.05-0.2, 0-0.15,3.3-3.5.
As one limitation of the present invention, the hydrogen storage alloy has a chemical composition of La 0.63 Sm 0.2 Y 0.05 Mg 0.12 Ni 3.25 Al 0.1 5 Fe 0.1 、La 0.5 Ce 0.05 Sm 0.25 Y 0.02 Mg 0.18 Ni 3.05 Al 0.1 Fe 0.15 、La 0.65 Zr 0.05 Sm 0.1 Y 0.05 Mg 0.15 Ni 3.15 Al 0.2 Fe 0.05 Or La (La) 0.65 Ce 0.025 Zr 0.025 Sm 0.15 Y 0.03 Mg 0.12 Ni 3.25 Al 0.05 Fe 0.15 One of them.
As a second limitation of the present invention, the type of crystal structure of the hydrogen occluding alloy is hexagonal system type 2H A 2 B 7 The phase structure and the phase content are 100wt%.
The hydrogen storage alloy prepared in the expression and the composition range of the constituent elements of the hydrogen storage alloy is pure phase 2H type A 2 B 7 The pure phase hydrogen storage alloy is used as the active material of the negative electrode material of the nickel-hydrogen battery, and has the characteristics of low cost, high discharge capacity and long cycle life.
Aiming at the problems of high cost and unsatisfactory cycle stability of the prior hydrogen storage alloy with the superlattice structure, the invention selects rare earth and transition metal elements with low price, utilizes corresponding elements to generate action on the specific phase structure of the alloy, controls, regulates and optimizes the volume of the superlattice structure unit cell of the alloy and the matching degree of the sub-lattice structure, combines the corrosion resistance and the oxidation resistance of the specific metal elements, and obtains the pure-phase hexagonal system 2H type A based on specific preparation conditions 2 B 7 The phase structure alloy can improve the cycle life of the superlattice structure hydrogen storage alloy under the conditions of low cost and high hydrogen storage discharge capacity.
As a result of extensive research in the present invention, it was found that Y tends to enter the superlattice structure [ A ] 2 B 4 ]The sub-lattice can co-act with Mg to reduce [ A ] 2 B 4 ]The volume of the sub-lattice, while the low cost B-side metallic elements Al and Fe tend to enter [ AB 5 ]The matching degree of the sub-lattices is regulated and controlled together, and the corrosion resistance of the alloy can be obviously improved by the Y and Al elements, and the chalk resistance of the alloy can be obviously improved by the Fe elements, so that the electrochemical cycle life of the alloy can be prolonged. In addition, compared with Sm with lower cost of Pr and Nd rare earth elements, sm also has the effect of improving the cycling stability of the alloy, and rare earth elements Ce and Zr with low cost further replace La by a small amount can make the superlattice structure hydrogen storage alloy more stable, and meanwhile, after La is replaced, the corrosion oxidation degree of the alloy can be reduced, so that 2H type A is realized on the basis of low cost 2 B 7 The superlattice phase structure has good structural stability, pulverization resistance and corrosion resistance, and improves the cycle life of the alloy.
The invention also provides a pure phase 2H type A with low cost and long service life 2 B 7 The preparation process of hydrogen storage alloy electrode material includes the following stepsSequentially carrying out the following steps:
(1) And (3) batching: selecting metal simple substances as raw materials, proportioning according to the chemical composition of the alloy, taking volatilization of corresponding metals in the smelting process into consideration, adding excessive corresponding metals to compensate burning loss during proportioning, and then placing other raw materials except Mg into a crucible of a vacuum induction smelting furnace, and placing the Mg into a charging bin;
(2) Smelting: preparing a target alloy by adopting an induction smelting method, wherein Mg is added in a secondary feeding mode, and then casting and cooling are carried out to obtain an alloy cast ingot;
(3) And (3) heat treatment: placing the alloy cast ingot obtained in the step (2) into a high-temperature resistant stainless steel annealing pot for sealing, placing the alloy cast ingot into a vacuum annealing furnace, and then carrying out heat treatment under inert gas or vacuum conditions, wherein the heat treatment is carried out sequentially according to the following steps,
a first temperature rising stage: heating to 600 ℃ from room temperature, and preserving heat for 0.5h;
a second temperature rising stage: heating from 600 ℃ to 920-950 ℃, and preserving heat for 12-20h;
and (3) a cooling stage: cooling to room temperature along with the furnace.
As one limitation of the preparation method of the invention, in the step (3), the heating rate of the first heating stage is 15-20 ℃/min, and the heating rate of the second heating stage is 2-5 ℃/min.
In the preparation process of the invention, because the melting point of other adopted metals is lower than that of Ni, the other adopted metals are easy to volatilize in the smelting process, and therefore, the excessive metering addition is needed in the batching process so as to ensure that the alloy obtained by smelting is in a preset proportion range. In addition, because the metal Mg has a larger melting point difference compared with other metals, the metal Mg is extremely volatile in the smelting process, and therefore, the magnesium loss is reduced by adopting a secondary feeding mode, and the alloy components are ensured to reach the expected target composition.
The heat treatment of the invention adopts two sections of heating and heat preserving processes and then naturally cooling and lowering the temperature, and the heat treatment process has close relation with the chemical composition and phase structure formation of the alloy, in particular:
in the first temperature raising and maintaining stage, there areThe rapid heating rate and the short heat preservation time are due to the fact that the alloy is low-Mg alloy, and Mg is balanced in the system while volatilization of Mg element is reduced. In the second stage, the temperature is raised and maintained to ensure that the chemical particles in the cast alloy structure are distributed from MgCu 4 Sn phase is fully dissociated and CaCu is separated 5 The form phase is subjected to peritectic reaction to form a specific product phase hexagonal system 2H type A 2 B 7 The method has the advantages that the crystal grains of the phase are shaped, the crystal grains are continuously grown in the heat preservation process, the temperature rising rate at the stage is not easy to be too high, or else insufficient reaction is possibly caused, and the nucleation rate of the crystal grains is low; while too slow a crystal secondary crystallization may occur, resulting in the formation of trigonal 3R form A in the product 2 B 7 A molding phase; while the heat treatment temperature is not preferably below 920 ℃ or above 950 ℃, otherwise phase structure transformation occurs: when the temperature is lower than 920 ℃, the 3R type A of the trigonal system in the cast alloy 5 B 19 The form phase is not completely and effectively eliminated by peritectic reaction, and above 950 ℃ the hexagonal form 2H form A is further transformed 5 B 19 And a model phase. And in the cooling process, the alloy is cooled, and the crystal growth is completed. Meanwhile, the heat treatment temperature of the invention needs to be matched with the heat preservation time of the invention to ensure the completion of peritectic reaction, ensure the complete growth of alloy grains and reduce lattice defects, which is a necessary condition for ensuring the alloy to have excellent electrochemical performance.
It should be noted that the control of the heat treatment procedure and the heat treatment temperature and time in the present invention is critical, and this is largely related to the elemental composition of the alloy and the crystalline form of the superlattice structure to be obtained, which directly determines whether the final alloy is pure phase 2H form a 2 B 7 The phase structure and ultimately the electrochemical properties, particularly the cycle life, of the hydrogen storage alloy.
By adopting the technical scheme, compared with the prior art, the invention has the following technical progress:
(1) The invention provides a pure phase 2H type A with low cost and long service life 2 B 7 The electrode material of hydrogen storage alloy has low cost, high discharge capacity and excellent electrochemical circulation stabilityAnd (3) qualitative property, wherein the maximum discharge capacity is more than or equal to 380mAh/g, and the capacity retention rate is more than or equal to 75% after 300 charge and discharge cycles.
(2) The invention provides a pure phase 2H type A 2 B 7 The hydrogen storage alloy electrode material is prepared by carrying out a specific heat treatment mode on the hydrogen storage alloy after induction smelting, has simple method, is easy to control, has short preparation period and is suitable for industrial production; in addition, the peritectic reaction of the internal hetero-phase structure of the alloy can be fully realized by the staged heat treatment in the preparation process, and the pure phase 2H type A can be stably formed 2 B 7 The alloy is excellent in electrochemical cycle life, and the purposes of refining grains and eliminating residual stress are achieved.
The invention is suitable for preparing pure phase 2H type A with low cost and long service life for nickel-hydrogen batteries 2 B 7 A hydrogen storage alloy electrode material.
The present invention will be described in further detail with reference to specific examples.
Drawings
FIG. 1 is a low cost long life pure phase 2H form A prepared in example 1 of the present invention 2 B 7 Rietveld full spectrum fitting map of hydrogen storage alloy.
FIG. 2 is a low cost long life pure phase 2H form A prepared according to example 2 of the present invention 2 B 7 Rietveld full spectrum fitting map of hydrogen storage alloy.
FIG. 3 is a low cost long life pure phase 2H form A prepared in example 3 of the present invention 2 B 7 Rietveld full spectrum fitting map of hydrogen storage alloy.
FIG. 4 is a low cost long life pure phase 2H form A prepared in example 4 of the present invention 2 B 7 Rietveld full spectrum fitting map of hydrogen storage alloy.
FIG. 5 shows a low cost long life pure phase 2H form A prepared according to examples 1-4 of the present invention 2 B 7 The discharge capacity of the hydrogen storage alloy electrode material changes with the cycle number.
FIG. 6 shows a low cost long life pure phase 2H form A prepared according to examples 1-4 of the present invention 2 B 7 Capacity retention curve of hydrogen storage alloy electrode material.
Detailed Description
The preparation methods and test methods used in the examples below were all conventional methods unless otherwise specified.
Example 1
This example prepares a low cost long life pure phase 2H type A 2 B 7 A hydrogen storage alloy with a chemical formula of La 0.63 Sm 0. 2 Y 0.05 Mg 0.12 Ni 3.25 Al 0.15 Fe 0.1 The preparation method sequentially comprises the following steps:
(11) And (3) batching: selecting metal simple substance La, sm, Y, mg, ni, al and Fe as raw materials, proportioning according to the designed chemical composition, taking volatilization of corresponding metals in the smelting process into consideration, adding excessive corresponding metals to compensate burning loss during proportioning, then putting other raw materials except Mg into a crucible of a vacuum induction smelting furnace, and putting Mg into a charging bin;
(12) Smelting: preparing a target alloy by adopting an induction smelting method, wherein Mg is added in a secondary feeding mode, and then casting and cooling are carried out to obtain an alloy cast ingot;
(13) And (3) heat treatment: placing the alloy cast ingot obtained in the step (12) into a high-temperature resistant stainless steel annealing pot for sealing, placing the alloy cast ingot into a vacuum annealing furnace, then carrying out heat treatment under inert gas or vacuum conditions, carrying out heat treatment procedures sequentially as follows,
a first temperature rising stage: heating to 600 ℃ from room temperature, and preserving heat for 0.5h;
a second temperature rising stage: heating from 600 ℃ to 930 ℃, and preserving heat for 12 hours;
and (3) a cooling stage: cooling to room temperature along with the furnace.
Wherein the heating rate of the first heating stage is 15 ℃/min, and the heating rate of the second heating stage is 2 ℃/min.
Grinding the obtained hydrogen storage alloy block to remove surface oxide layer, mechanically crushing, grinding into powder, sieving, collecting alloy powder with 400 mesh sieve, performing X-ray diffraction (XRD) test, and performing Rietve1d full spectrum fitting on the collected data for quantitative analysis, as shown in figure 1Analysis results show that the alloy is hexagonal system type 2H A 2 B 7 The content of the molding phase is 100wt%.
Example 2
This example prepares a low cost long life pure phase 2H type A 2 B 7 The chemical formula of the hydrogen storage alloy is La 0.5 Ce 0.05 Sm 0.25 Y 0.02 Mg 0.18 Ni 3.05 Al 0.1 Fe 0.15 The preparation method is sequentially carried out according to the following steps:
(21) And (3) batching: selecting metal simple substance La, ce, sm, Y, mg, ni, al and Fe as raw materials, proportioning according to the designed chemical composition, taking volatilization of corresponding metals in the smelting process into consideration, adding excessive corresponding metals to compensate burning loss during proportioning, then putting other raw materials except Mg into a crucible of a vacuum induction smelting furnace, and putting Mg into a charging bin;
(22) Smelting: preparing a target alloy by adopting an induction smelting method, wherein Mg is added in a secondary feeding mode, and then casting and cooling are carried out to obtain an alloy cast ingot;
(23) And (3) heat treatment: placing the alloy cast ingot obtained in the step (22) into a high-temperature resistant stainless steel annealing pot for sealing, placing the alloy cast ingot into a vacuum annealing furnace, then carrying out heat treatment under inert gas or vacuum conditions, carrying out heat treatment procedures sequentially as follows,
a first temperature rising stage: heating to 600 ℃ from room temperature, and preserving heat for 0.5h;
a second temperature rising stage: heating from 600 ℃ to 920 ℃, and preserving heat for 10 hours;
and (3) a cooling stage: cooling to room temperature along with the furnace.
Wherein the heating rate of the first heating stage is 20 ℃/min, and the heating rate of the second heating stage is 2 ℃/min.
Grinding the obtained hydrogen storage alloy block to remove surface oxide layer, mechanically crushing, grinding into powder, sieving, taking alloy powder with 400 mesh sieve, performing XRD test, and performing Rietve1d full spectrum fitting on the collected data for quantitative analysis, wherein as shown in figure 2, the analysis result shows that the alloy is hexagonal system 2H type A 2 B 7 A phase containingThe amount was 100wt%.
Example 3
The embodiment is a pure phase 2H type A with low cost and long service life 2 B 7 The chemical formula of the hydrogen storage alloy is La 0.65 Zr 0.05 Sm 0.1 Y 0.05 Mg 0.15 Ni 3.15 Al 0.2 Fe 0.05 The preparation method is sequentially carried out according to the following steps:
(31) And (3) batching: the metal simple substance La, zr, sm, Y, mg, ni, al and Fe are selected as raw materials, the ingredients are prepared according to the designed chemical composition, the volatilization of corresponding metals in the smelting process is considered, excessive corresponding metals are added during the ingredients to compensate burning loss, then other raw materials except Mg are put into a crucible of a vacuum induction smelting furnace, and Mg is put into a charging bin.
(32) Smelting: preparing a target alloy by adopting an induction smelting method, wherein Mg is added in a secondary feeding mode, and then casting and cooling are carried out to obtain an alloy cast ingot;
(33) And (3) heat treatment: placing the alloy cast ingot obtained in the step (32) into a high-temperature resistant stainless steel annealing pot for sealing, placing the alloy cast ingot into a vacuum annealing furnace, then carrying out heat treatment under inert gas or vacuum conditions, carrying out heat treatment procedures sequentially as follows,
a first temperature rising stage: heating to 600 ℃ from room temperature, and preserving heat for 0.5h;
a second temperature rising stage: heating from 600 ℃ to 925 ℃ and preserving heat for 20h;
and (3) a cooling stage: cooling to room temperature along with the furnace.
Wherein the heating rate of the first heating stage is 18 ℃/min, and the heating rate of the second heating stage is 5 ℃/min.
Grinding the obtained hydrogen storage alloy block to remove surface oxide layer, mechanically crushing, grinding into powder, sieving, taking alloy powder with 400 mesh sieve, performing XRD test, and performing Rietve1d full spectrum fitting on the collected data for quantitative analysis, wherein as shown in figure 3, the analysis result shows that the alloy is hexagonal system 2H type A 2 B 7 The content of the molding phase is 100wt%.
Example 4
The embodiment is a pure phase 2H type A with low cost and long service life 2 B 7 La of hydrogen storage alloy 0.65 Ce 0.025 Zr 0.025 Sm 0.1 5 Y 0.03 Mg 0.12 Ni 3.25 Al 0.05 Fe 0.15 The preparation method comprises the following steps:
(41) And (3) batching: the metal simple substance La, ce, zr, sm, Y, mg, ni, al and Fe are selected as raw materials, the ingredients are prepared according to the designed chemical composition, the volatilization of corresponding metals in the smelting process is considered, excessive corresponding metals are added during the ingredients to compensate burning loss, then other raw materials except Mg are put into a crucible of a vacuum induction smelting furnace, and Mg is put into a charging bin.
(42) Smelting: preparing a target alloy by adopting an induction smelting method, wherein Mg is added in a secondary feeding mode, and then casting and cooling are carried out to obtain an alloy cast ingot;
(43) And (3) heat treatment: placing the alloy ingot obtained in the step (42) into a high-temperature resistant stainless steel annealing pot for sealing, placing the stainless steel annealing pot into a vacuum annealing furnace, then performing heat treatment under inert gas or vacuum conditions, performing the heat treatment procedure sequentially as follows,
a first temperature rising stage: heating to 600 ℃ from room temperature, and preserving heat for 0.5h;
a second temperature rising stage: heating from 600 ℃ to 950 ℃ and preserving heat for 18h;
and (3) a cooling stage: cooling to room temperature along with the furnace.
Wherein the heating rate of the first heating stage is 20 ℃/min, and the heating rate of the second heating stage is 4 ℃/min.
Grinding the obtained hydrogen storage alloy block to remove surface oxide layer, mechanically crushing, grinding into powder, sieving, taking alloy powder with 400 mesh sieve, performing XRD test, and performing Rietve1d full spectrum fitting on the collected data for quantitative analysis, wherein as shown in figure 4, the analysis result shows that the alloy is hexagonal system 2H type A 2 B 7 The content of the molding phase is 100wt%.
Example 5 Low cost long life pure phase 2H form A 2 B 7 Performance test of hydrogen storage alloy electrode
Grinding the hydrogen storage alloy obtained in the examples 1-4 to remove a surface oxide layer, crushing, grinding to obtain powder, taking 200-400 mesh powder, cold pressing the powder and carbonyl nickel powder according to the mass ratio of 0.15g to 0.75g under the pressure of 15MPa to obtain electrode plates with the diameter of 10mm, and sintering Ni (OH) 2 The NiOOH is used as a counter electrode, the Hg/HgO is used as a reference electrode, and a 6mol/L KOH aqueous solution is assembled into a three-electrode battery test system, and the electrochemical performance of the battery system is tested by using a LANDA battery tester.
1. Maximum discharge capacity of alloy electrode
The testing system of the maximum discharge capacity of the alloy electrode is as follows: and charging and discharging the battery by adopting the current density of 60mA/g, charging for 8 hours, standing for 10 minutes, discharging to the cutoff potential of 1.0V, and performing charge/discharge circulation until the battery reaches the maximum discharge capacity.
As shown in FIG. 5, the low cost long life pure phase 2H form A prepared in examples 1-4 2 B 7 After electrochemical test, the maximum discharge capacity of the nickel-hydrogen battery assembled by the hydrogen storage alloy electrode material is 383mAh/g, 387mAh/g, 385mAh/g and 380mAh/g respectively.
2. Cycling stability of alloy electrodes
The test system of the cycling stability of the alloy electrode is as follows: after the alloy electrode is fully activated, charging for 1.6 hours by adopting a current density of 300mA/g, standing for 10 minutes, discharging to a cut-off potential of 1.0V by adopting a current density of 60mA/g, and recording the discharge capacity per week to 300 times, wherein the capacity retention rate of the alloy is the ratio of the discharge capacity per week to the maximum discharge capacity. The cycle life of the alloy electrode is characterized in this example by a capacity retention rate of 500 weeks.
As shown in FIG. 6, the low cost long life pure phase 2H form A prepared in examples 1-4 2 B 7 The nickel-hydrogen battery assembled by the hydrogen storage alloy electrode material is subjected to electrochemical test, and after 300 charge/discharge cycles, the capacity retention rates are 76.8%, 80.5%, 79.4% and 78.1%, respectively.
In conclusion, the low-cost long-life pure phase 2H type A provided by the invention 2 B 7 The hydrogen storage alloy electrode has cost as the negative electrode material of nickel-hydrogen batteryLow, high discharge capacity, and in particular, excellent electrochemical cycling stability.
Comparative example 6
The hydrogen storage alloy is prepared by the embodiment, and the specific chemical composition is as follows:
group A: la (La) 0.63 Sm 0.2 Y 0.05 Mg 0.12 Ni 3.25 Al 0.15 Fe 0.1 Example 1
Group B: la (La) 0.68 Sm 0.2 Mg 0.12 Ni 3.25 Al 0.15 Fe 0.1
Group C: la (La) 0.83 Y 0.05 Mg 0.12 Ni 3.25 Al 0.15 Fe 0.1
Group D: la (La) 0.63 Sm 0.2 Y 0.05 Mg 0.12 Ni 3.35 Al 0.15
Group E: la (La) 0.63 Sm 0.2 Y 0.05 Mg 0.12 Ni 3.4 Fe 0.1
The alloys prepared in the above groups were subjected to structural tests and assembled into nickel-hydrogen batteries in the same manner as in example 1, and electrochemical performance tests were performed thereon, with the specific results shown in table 1 below.
Table 1 comparative alloy crystal structure and electrochemical performance table
As can be seen from Table 1, although the same preparation method and conditions as in example 1 were employed, the phase structure of the prepared B and D gold combinations was incapable of forming pure phase 2H type A when the hydrogen storage alloy was used with different elemental compositions 2 B 7 The alloy has a model phase structure, no Y or Fe element exists in the alloy, and the cycle life of the finally obtained alloy is poor; furthermore, although groups C and E were prepared using the same preparation method and conditions, pure phase 2H form A could be obtained 2 B 7 The resulting alloy has a poor cycle life due to the absence of Sm or Al in the alloy.
Comparative example 7
The hydrogen storage alloy with a series of structures is prepared in the embodiment, and the specific chemical composition is as follows:
group A: la (La) 0.63 Sm 0.2 Y 0.05 Mg 0.12 Ni 3.25 Al 0.15 Fe 0.1 Example 1
Group B: la (La) 0.43 Sm 0.2 Y 0.20 Mg 0.12 Ni 3.25 Al 0.15 Fe 0.1
Group C: la (La) 0.53 Sm 0.3 Y 0.05 Mg 0.12 Ni 3.25 Al 0.15 Fe 0.1
Group D: la (La) 0.63 Sm 0.2 Y 0.05 Mg 0.12 Ni 3.25 Al 0.2 Fe 0.1
Group E: la (La) 0.63 Sm 0.2 Y 0.05 Mg 0.12 Ni 3.15 Al 0.15 Fe 0.2
Group F: la (La) 0.59 Sm 0.2 Y 0.05 Mg 0.08 Ni 3.25 Al 0.15 Fe 0.1
Group G: la (La) 0.53 Sm 0.2 Y 0.05 Mg 0.22 Ni 3.25 Al 0.15 Fe 0.1
Group H: la (La) 0.63 Sm 0.2 Y 0.05 Mg 0.12 Ni 2.95 Al 0.15 Fe 0.1
Group I: la (La) 0.63 Sm 0.2 Y 0.05 Mg 0.12 Ni 3.45 Al 0.15 Fe 0.1
The alloys prepared in the above groups were subjected to structural testing and assembled into nickel-hydrogen batteries in the same manner as in example 1, and electrochemical performance was tested, with the specific results shown in table 2 below.
Table 2 comparative alloy crystal structure and electrochemical performance table
As can be seen from Table 2, when the same kind of elements and the same preparation method and conditions as in example 1 were employed, the alloys were used with different contents of elemental components, although the prepared B-D group alloys were capable of obtaining pure phase 2H type A 2 B 7 The alloy has a phase structure, but the content of Y, sm and Al element in the alloy is too high, so that the discharge capacity of the alloy is obviously reduced, and A is caused 2 B 7 The shape alloy loses the advantage of high capacity; the prepared E-I gold composition can not obtain pure phase 2H type A under the same preparation method and conditions due to the change of the relative content of components 2 B 7 Alloy with phase structure, while generation of hetero-phase significantly reduces the cycle life of the alloy, and AB 5 The miscibility also significantly reduces the discharge capacity of the alloy.
Example 8 Effect of different heat treatment temperature increasing programs and conditions on superlattice Hydrogen storage alloy Structure and electrode Material Properties
The superlattice hydrogen storage alloys prepared under different heat treatment conditions were different in structure and performance, and different heat treatment temperature rise procedures were investigated in this example, wherein the chemical composition of the alloy was similar to that of example 1, except that: the heat treatment temperature rise program in the preparation process is different, and the specific steps are as follows:
group A: the heat treatment temperature-increasing program provided in this example 1;
group B: a stage of heat treatment temperature raising program, namely, directly raising the temperature from the room temperature to the end temperature of 930 ℃ and preserving the heat for 12 hours;
group C: the second stage heat treatment temperature raising program, that is, the first temperature raising stage is to raise the temperature from room temperature to 600 deg.c and to maintain the temperature for 0.5 hr; the second heating stage is to heat from 600 ℃ to 900 ℃ and keep the temperature for 12 hours.
Group D: the second stage heat treatment temperature raising program, that is, the first temperature raising stage is to raise the temperature from room temperature to 600 deg.c and to maintain the temperature for 0.5 hr; the second temperature rising stage is to rise from 600 ℃ to 980 ℃ and keep the temperature for 12 hours.
The alloy prepared above was subjected to phase structure test, and assembled into a nickel-hydrogen battery in the same manner as in example 1, and subjected to electrochemical performance test, and the results are shown in table 3.
TABLE 3 alloy Crystal Structure and electrochemical Property Meter for different Heat treatment Processes
As can be seen from Table 3, although the alloy elements are guaranteed to have the same composition, the annealing process, the temperature and the holding time are different, and pure phase type 2H A cannot be formed 2 B 7 And finally, the alloy discharge capacity is reduced and the cycle life is deteriorated.
Examples 1-4 are intended to be illustrative of the preferred embodiments of the present invention and not limiting in any way, and any person skilled in the art may make modifications or alterations to the equivalent embodiments using the above teachings. Simple modifications, equivalent changes and adaptations of the above embodiments do not depart from the technical spirit of the invention, and remain within the scope of the invention as defined by the appended claims.
Claims (5)
1. Low-cost long-life pure phase 2H type A 2 B 7 The hydrogen storage alloy electrode material is characterized in that the hydrogen storage alloy can be represented by a chemical general formula of La 1-x-y-z-w R w Sm z Y y Mg x Ni c-a-b Al a Fe b Wherein: r represents at least one element selected from rare earth Ce and Zr, wherein x, y, z, w, a, b, c represents a molar ratio of 0.12-0.18,0.02-0.05,0.10-0.25, 0-0.05,0.05-0.2, 0-0.15,3.3-3.5.
2. A low cost long life pure phase 2H type a according to claim 1 2 B 7 The hydrogen storage alloy electrode material is characterized in that the chemical composition of the hydrogen storage alloy is La 0.63 Sm 0.2 Y 0.05 Mg 0.12 Ni 3.25 Al 0.15 Fe 0.1 、La 0.5 Ce 0.05 Sm 0.25 Y 0.02 Mg 0.18 Ni 3.05 Al 0.1 Fe 0.15 、La 0.65 Zr 0.05 Sm 0.1 Y 0.05 Mg 0.15 Ni 3.15 Al 0.2 Fe 0.05 Or La (La) 0.65 Ce 0.025 Zr 0.025 Sm 0.1 5 Y 0.03 Mg 0.12 Ni 3.25 Al 0.05 Fe 0.15 One of them.
3. A low cost long life pure phase 2H type a according to claim 1 2 B 7 The hydrogen storage alloy electrode material is characterized in that the crystal structure type of the hydrogen storage alloy is hexagonal system 2H type A 2 B 7 The phase structure and the phase content are 100wt%.
4. A low cost long life pure phase 2H form a as claimed in any one of claims 1 to 3 2 B 7 The preparation method of the hydrogen storage alloy electrode material is characterized by sequentially carrying out the following steps:
(1) And (3) batching: selecting metal simple substances as raw materials, proportioning according to the chemical composition of the hydrogen storage alloy as claimed in claim 1, taking volatilization of corresponding metals in the smelting process into consideration, adding excessive corresponding metals to compensate burning loss during proportioning, and then placing other raw materials except Mg into a crucible of a vacuum induction smelting furnace, and placing Mg into a charging bin;
(2) Smelting: preparing a target alloy by adopting an induction smelting method, wherein Mg is added in a secondary feeding mode, and then casting and cooling are carried out to obtain an alloy cast ingot;
(3) And (3) heat treatment: placing the alloy cast ingot obtained in the step (2) into a high-temperature resistant stainless steel annealing pot for sealing, placing the alloy cast ingot into a vacuum annealing furnace, and then carrying out heat treatment under inert gas or vacuum conditions, wherein the heat treatment is carried out sequentially according to the following steps,
a first temperature rising stage: heating to 600 ℃ from room temperature, and preserving heat for 0.5h;
a second temperature rising stage: heating from 600 ℃ to 920-950 ℃, and preserving heat for 10-20h;
and (3) a cooling stage: cooling to room temperature along with the furnace.
5. A low cost long life pure phase 2H type a according to claim 4 2 B 7 The preparation method of the hydrogen storage alloy electrode material is characterized by comprising the following steps: in the step (3), the heating rate of the first heating stage is 15-20 ℃/min, and the heating rate of the second heating stage is 2-5 ℃/min.
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| CN114231794A (en) * | 2021-12-07 | 2022-03-25 | 江西江钨浩运科技有限公司 | A2B7 type hydrogen storage alloy for nickel-metal hydride battery and preparation method thereof |
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