CN116200627B - Long-cycle life pure-phase 2H-A2B7 hydrogen storage alloy electrode material and preparation method thereof - Google Patents
Long-cycle life pure-phase 2H-A2B7 hydrogen storage alloy electrode material and preparation method thereof Download PDFInfo
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- CN116200627B CN116200627B CN202310052855.8A CN202310052855A CN116200627B CN 116200627 B CN116200627 B CN 116200627B CN 202310052855 A CN202310052855 A CN 202310052855A CN 116200627 B CN116200627 B CN 116200627B
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- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 6
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- 229910052751 metal Inorganic materials 0.000 claims description 29
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- 239000011261 inert gas Substances 0.000 claims description 8
- 238000007789 sealing Methods 0.000 claims description 8
- 239000010935 stainless steel Substances 0.000 claims description 8
- 229910001220 stainless steel Inorganic materials 0.000 claims description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 230000014759 maintenance of location Effects 0.000 abstract description 7
- 239000011777 magnesium Substances 0.000 description 44
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 25
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- 238000007599 discharging Methods 0.000 description 3
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- 229910002059 quaternary alloy Inorganic materials 0.000 description 2
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- 230000003442 weekly effect Effects 0.000 description 2
- 229910004247 CaCu Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910002640 NiOOH Inorganic materials 0.000 description 1
- RZJQYRCNDBMIAG-UHFFFAOYSA-N [Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Zn].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn] Chemical class [Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Zn].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn] RZJQYRCNDBMIAG-UHFFFAOYSA-N 0.000 description 1
- OWXLRKWPEIAGAT-UHFFFAOYSA-N [Mg].[Cu] Chemical compound [Mg].[Cu] OWXLRKWPEIAGAT-UHFFFAOYSA-N 0.000 description 1
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- 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
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- 229910052749 magnesium Inorganic materials 0.000 description 1
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Classifications
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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
-
- 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
-
- 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
-
- 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
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- Mechanical Engineering (AREA)
- Metallurgy (AREA)
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- Thermal Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a long-cycle life pure phase 2H-A 2 B 7 Electrode material of hydrogen storage alloy and preparation method thereof, the hydrogen storage alloy can be prepared from Sm 2‑a‑b‑c La c M b Mg a Ni z‑x‑y Al x N y The expression is as follows: m represents at least one element selected from rare earth Ce, pr, nd, gd and Y, N represents at least one element selected from Mn or Co, wherein a, b, c, x, Y, z represents a molar ratio of 0.32-0.4, 0-0.1,0.4-0.6,0.2-x-0.4, 0-0.1,6.8-z-7. The alloy is prepared by the steps of proportioning, induction smelting and heat treatment in sequence, and the prepared alloy has a crystal structure of 2H-A 2 B 7 The superlattice structure has the phase content of 100wt%, and the alloy has high discharge capacity and ultra-long electrochemical cycle stability, the maximum discharge capacity is more than or equal to 350mAh/g, the capacity retention rate is more than or equal to 70% after 500 charge-discharge cycles, the preparation process is simple, and the process is easy to control.
Description
Technical Field
The invention relates to the field of nickel-hydrogen batteries, in particular to a long-cycle life pure phase 2H-A 2 B 7 An electrode material of hydrogen storage alloy and a preparation method thereof.
Background
The nickel-metal hydride battery (Ni/MH) can be widely applied to the fields of hybrid electric vehicle power batteries, standby power supplies, mobile energy storage systems and the like due to the technical characteristics of safety, rapid charge and discharge and the like. The Ni/MH adopts the hydrogen storage alloy as the negative electrode material, optimizes the electrochemical performance of the hydrogen storage alloy and perfects the preparation technology thereof to improve the market competitiveness of the Ni/MH and promote the development thereofHas important significance. At present AB 5 The hydrogen storage alloy has been applied in industrialization, but the hydrogen storage capacity of the alloy is low, and the market demand of high energy density is gradually difficult to meet.
In recent years, rare earth hydrogen storage alloys have been developed which have a superlattice structure, namely rare earth-magnesium-nickel (RE-Mg-Ni) hydrogen storage alloys, which contain similar AB 2 Alloy and AB 5 The alloy structure has high hydrogen storage capacity and fast hydrogen absorption and desorption capacity, and thus becomes a substitute for AB 5 Ni/MH new type negative electrode material of hydrogen storage alloy. RE-Mg-Ni based alloy according to its structure [ A ] 2 B 4 ]And [ AB 5 ]The AB can be formed by the periodical stacking proportion of the sub-lattices along the direction of the c-axis 3 、A 2 B 7 、A 5 B 19 And AB 4 Superlattice structure, and when [ A ] 2 B 4 ]When the types of the superlattice are different, each superlattice structure can be further divided into P6 3 A mmc space group structure (type 2H) and an R-3m space group structure (type 3R). It was found that for such superlattice alloys, as the structure [ AB ] 5 ]The increase of the subcell content reduces the discharge capacity of the alloy, and improves the high rate discharge performance and the cycle stability (Journal of Power Sources (2015) 77-86). Wherein A is 2 B 7 Alloy not only with AB 3 The alloy has the advantage of high capacity, and the maximum discharge capacity can reach 380 mAh/g-410 mAh/g (which is far higher than commercial AB) 5 Hydrogen storage alloy) and compared with AB 3 The type alloy has better cycle stability and also becomes the earliest industrialized superlattice structure alloy type. However, A 2 B 7 The electrochemical cycle life of the shaped alloy is still not ideal, and the industrialized preparation technology of the shaped alloy still has a barrier.
Current research shows that the cycling stability of the RE-Mg-Ni superlattice structure alloy depends on the alloy element composition and the purity of the crystal structure phase thereof, and the element composition of the alloy has a significant influence on the preparation condition of the pure phase alloy. On the one hand, compared with rare earth La, ce, pr, nd, sm, gd, Y and other A side elements, the rare earth La, ce, pr, nd, sm, gd, Y and other A side elements have the advantages thatThe small atomic radius and the larger electronegativity are beneficial to reducing the strain of the crystal structure in the hydrogen absorption and desorption process, have better anti-powdering performance, and meanwhile, the stronger corrosion resistance is beneficial to prolonging the cycle life of the alloy; the B-side element Al can also adjust the unit cell volume and has good corrosion resistance, the cycle life of the alloy can be obviously prolonged, and the Co and Mn elements can improve the structural stability of the alloy, enhance the reversibility of hydrogen absorption/desorption reactions and be beneficial to the improvement of the cycle life of the alloy. On the other hand, the RE-Mg-Ni series alloy has different phase structures with the generation temperature close to that of each phase structure, and 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, the different phase structures have different volume expansion rates in the hydrogen absorption and desorption processes, so that the internal stress of the alloy is obviously increased, the pulverization is serious, the service life of the alloy is finally poor, and the impurity phases are eliminated by controlling the heat treatment conditions, so that the cycle life of the alloy can be obviously prolonged by purifying the alloy phase structure. For example, when La 0.78 Mg 0.22 Ni 3.45 The alloy is completely converted into 2H type A from three-phase coexistence 2 B 7 In phase, the capacity retention of the alloy can be increased by 6% (Journal of Materials Chemistry A3 (2015) 13679-13690). However, the heat treatment conditions of the pure alloy phase structure are not only related to the alloy structure type but also to the alloy element composition. For example, type 3R AB 3 The heat treatment temperature of the pure phase La-Nd-Mg-Ni quaternary alloy is 950 ℃ (Journal of the Electrochemical Society 162 (10) (2015) A2218-A2226), and the 2H type A under the same constituent elements 2 B 7 The heat treatment temperature of the La-Nd-Mg-Ni quaternary alloy of type 975 ℃ (Journal of Alloys and Compounds 861 (2021) 158469) but in type 2H A 2 B 7 After the low-melting Al component is added into the alloy, the heat treatment temperature of the pure phase is reduced to 950 ℃. From this, it can be seen that a novel long cycle life A was developed 2 B 7 It has become critical to produce hydrogen storage alloys and to achieve efficient commercial processes.
Disclosure of Invention
The invention aims to overcome the problems in the background art and provide a pure phase 2H-A with long cycle life for the application field of nickel-hydrogen batteries 2 B 7 An electrode material of hydrogen storage alloy and a preparation method thereof.
In order to achieve the above purpose, the technical scheme provided by the invention is as follows:
the invention provides a long-cycle life pure phase 2H-A 2 B 7 The chemical general formula of the hydrogen storage alloy electrode material is Sm 2-a-b-c La c M b Mg a Ni z-x-y Al x N y Wherein: m represents at least one element selected from rare earth Ce, pr, nd, gd and Y, N represents at least one element selected from Mn or Co, wherein a, b, c, x, Y, z represents a molar ratio of 0.32-0.4, 0-0.1,0.4-0.6,0.2-x-0.4, 0-0.1,6.8-z-7.
As one limitation of the present invention, the hydrogen storage alloy has the chemical composition Sm 1.18 La 0.4 Y 0.1 Mg 0.32 Ni 6.6 Al 0.2 Mn 0.1 、Sm 1.05 La 0.56 Ce 0.05 Mg 0.34 Ni 6.4 Al 0.35 Co 0.05 、SmLa 0.56 Nd 0.08 Mg 0.36 Ni 6.52 Al 0.38 Mn 0.04 Co 0.06 、SmPr 0.08 La 0.6 Mg 0.32 Ni 6.6 Al 0.4 Or Sm 1.06 Gd 0.1 La 0.5 Mg 0.34 Ni 6.6 Al 0.4 One of them.
As a second limitation of the present invention, the hydrogen occluding alloy has a crystal structure of 2H-A 2 B 7 Superlattice structure, and phase content of 100wt%.
The hydrogen storage alloy prepared in the chemical composition range of the invention is pure phase 2H-A 2 B 7 The pure-phase hydrogen storage alloy is used as an active substance of a nickel-hydrogen battery negative electrode material, and has the advantages of higher discharge capacity and super-long cycle life.
The invention aims at the current A 2 B 7 The hydrogen storage alloy with superlattice structure has the problem of poor cycle life, and the rare earth Sm has relatively low price and obviously reduced atomic radius compared with LaLow atomic radius and large electronegativity, and effectively reduces A by largely substituting La to form Sm-Mg-Ni-based alloy with high Sm content 2 B 7 In superlattice structure [ A ] 2 B 4 ]The superlattice is unstable, and meanwhile, the superlattice structure unit cell volume is regulated and controlled together with the B side Al element, so that the [ A ] is improved 2 B 4 ]And [ AB 5 ]The matching degree of the sub-lattice structure reduces deformation energy and stress in the process of absorbing and releasing hydrogen of the alloy. Furthermore, based on specific preparation conditions, pure-phase hexagonal system 2H-A is obtained 2 B 7 The alloy with the superlattice phase structure eliminates alloy stress aggregation caused by inconsistent structural changes of different superlattice phase structures in the hydrogen absorption and desorption process, thereby prolonging the cycle life of the hydrogen storage alloy with the superlattice structure.
The invention also provides a long-cycle life pure phase 2H-A 2 B 7 The preparation method of the hydrogen storage alloy electrode material comprises the following steps in sequence:
s1, batching
Selecting metal simple substances as raw materials, proportioning according to the chemical composition of the hydrogen storage alloy, considering volatilization of corresponding metals in the smelting process, 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;
s2, induction smelting alloy
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;
s3, alloy heat treatment
The alloy cast ingot obtained in the step S2 is put into a high temperature resistant stainless steel annealing pot for sealing, then is put into a vacuum annealing furnace for heat treatment under inert gas or vacuum condition, the heat treatment procedure is as follows,
a first temperature rising stage: heating to 600 ℃ from room temperature, and preserving heat for 1h;
a second temperature rising stage: heating from 600 ℃ to 985-1010 ℃ and preserving heat for 10-18h;
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 S3, the heating rate of the first heating stage is 10-15 ℃/min, and the heating rate of the second heating stage is 1-2 ℃/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 a two-stage heating and heat preservation process, and then naturally cooling and lowering the temperature, and the invention is specific:
in the first heating stage, setting a faster heating rate, reducing volatilization of Mg element, and keeping the temperature for 1h to balance Mg in the system; 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 phase of the shaped phase is subjected to peritectic reaction to form a specific product phase 2H-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, leading to the formation of A in the product 5 B 19 A molding phase; while the heat treatment temperature is not preferably lower than 985 ℃ or higher than 1010 ℃, otherwise phase structure transformation occurs: at a temperature below 985 ℃, 3R-A in the as-cast alloy 5 B 19 The form phase is not completely efficiently eliminated by peritectic reaction, but is further converted into A at a temperature higher than 1010 DEG C 5 B 19 The phase is even decomposed into AB 5 And a model phase.
And in the cooling process, the alloy is cooled, and the crystal growth is completed.
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 reduceLattice defects, which are necessary conditions to ensure good electrochemical performance of the alloy. It should be noted that the heat treatment procedure and the control of the heat treatment temperature and time of the present invention are critical, which is mainly 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-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 long-cycle life pure phase 2H-A 2 B 7 The hydrogen storage alloy electrode material has higher discharge capacity, particularly has ultra-long electrochemical cycling stability, and has the maximum discharge capacity of more than or equal to 350mAh/g and the capacity retention rate of more than or equal to 70 percent after 500 charge and discharge cycles.
2. The invention provides a pure phase 2H-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 and stably formed into pure phase 2H-A through staged heat treatment in the preparation process 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 the ultra-long cycle life pure phase 2H-A for the nickel-hydrogen battery 2 B 7 And a shaped electrode material.
The present invention will be described in further detail with reference to specific examples.
Drawings
FIG. 1 shows a pure phase 2H-A with an ultra-long cycle life prepared in example 1 of the present invention 2 B 7 Rietveld full spectrum fitting map of hydrogen storage alloy.
FIG. 2 is a pure phase 2H-A with an ultra-long cycle life prepared in example 2 of the present invention 2 B 7 Rietveld full spectrum fitting map of hydrogen storage alloy.
FIG. 3 is a pure phase 2H-A with an ultra-long cycle life prepared in example 3 of the present invention 2 B 7 Rietveld full spectrum fitting map of hydrogen storage alloy.
FIG. 4 shows a long-life pure phase 2H-A prepared in examples 1-3 of the present invention 2 B 7 The discharge capacity of the hydrogen storage alloy electrode material changes with the cycle number.
FIG. 5 shows a long-life pure phase 2H-A prepared in examples 1-3 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
Pure phase 2H-A with long cycle life 2 B 7 SmLa hydrogen storage alloy 0.6 Mg 0.4 Ni 6.6 Al 0.4 The preparation method comprises the following steps:
s11, proportioning: the metal simple substance Sm, la, mg, ni and Al 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.
S12 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;
s13, heat treatment: the alloy ingot obtained in the step S12 is put into a high temperature resistant stainless steel annealing pot for sealing, then is put into a vacuum annealing furnace for heat treatment under inert gas or vacuum condition, the heat treatment procedure is as follows,
a first temperature rising stage: heating to 600 ℃ from room temperature according to a heating rate of 10 ℃/min, and preserving heat for 1h;
a second temperature rising stage: heating from 600 ℃ to 985 ℃ according to the heating rate of 1 ℃/min, and preserving heat for 10 hours;
and (3) a cooling stage: cooling to room temperature along with the furnace.
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 X-ray diffraction (XRD) test, and performing quantitative analysis on collected data by Rietve1d full spectrum fitting, as shown in FIG. 1 and Table 1, wherein the analysis result shows that the alloy is 2H-A 2 B 7 The content of the shaped phase structure is 100wt%.
Example 2
Pure phase 2H-A with long cycle life 2 B 7 Hydrogen storage alloy Sm 1.18 La 0.4 Y 0.1 Mg 0.32 Ni 6.6 Al 0.2 Mn 0.1 The preparation method comprises the following steps:
s21, proportioning: the metal simple substance Sm, la, Y, mg, ni, al and Mn 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.
S22, 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;
s23, heat treatment: the alloy ingot obtained in the step S22 is put into a high temperature resistant stainless steel annealing pot for sealing, then is put into a vacuum annealing furnace for heat treatment under inert gas or vacuum condition, the heat treatment procedure is as follows,
a first temperature rising stage: heating to 600 ℃ from room temperature according to a heating rate of 15 ℃/min, and preserving heat for 1h;
a second temperature rising stage: heating from 600 ℃ to 995 ℃ according to the heating rate of 1 ℃/min, and preserving heat for 12 hours;
and (3) a cooling stage: cooling to room temperature along with the furnace.
Grinding the obtained hydrogen storage alloy block to remove surface oxide layer, mechanically crushing, grinding into powder, sieving, and collecting alloy powder with 400 mesh sieveXRD test was not performed, and Rietve1d full spectrum fitting was performed on the collected data for quantitative analysis, as shown in FIG. 2 and Table 1, the analysis results showed that the alloy was 2H-A 2 B 7 The content of the shaped phase structure is 100wt%.
Example 3
Pure phase 2H-A with long cycle life 2 B 7 Hydrogen storage alloy Sm 1.05 La 0.56 Ce 0.05 Mg 0.34 Ni 6.4 Al 0.35 Co 0.05 The preparation method comprises the following steps:
s31, proportioning: the method comprises the steps of selecting metal simple substances Sm, la, ce, mg, ni, al and Co as raw materials, carrying out batching 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 batching, then putting other raw materials except Mg into a crucible of a vacuum induction smelting furnace, and putting the Mg into a charging bin.
S32 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;
s33, heat treatment: the alloy ingot obtained in the step S32 is put into a high temperature resistant stainless steel annealing pot for sealing, then is put into a vacuum annealing furnace for heat treatment under inert gas or vacuum condition, the heat treatment procedure is as follows,
a first temperature rising stage: heating to 600 ℃ from room temperature according to a heating rate of 15 ℃/min, and preserving heat for 1h;
a second temperature rising stage: heating from 600 ℃ to 990 ℃ according to a heating rate of 2 ℃/min, and preserving heat for 10 hours;
and (3) a cooling stage: cooling to room temperature along with the furnace.
Grinding the obtained hydrogen storage alloy block to remove surface oxide layer, mechanically crushing, grinding into powder, sieving, taking 400 mesh alloy powder for XRD test, and quantitatively analyzing the collected data by Rietve1d full spectrum fitting, as shown in figure 3 and table 1, the analysis result shows that the alloy is 2H-A 2 B 7 The content of the shaped phase structure is 100wt%.
Example 4
Pure phase 2H-A with long cycle life 2 B 7 SmLa hydrogen storage alloy 0.56 Nd 0.08 Mg 0.36 Ni 6.52 Al 0.38 Mn 0.04 Co 0. 06 The preparation method comprises the following steps:
s41, batching: the method comprises the steps of selecting metal simple substances Sm, la, nd, mg, ni, al, mn and Co as raw materials, carrying out batching 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 batching, then putting other raw materials except Mg into a crucible of a vacuum induction smelting furnace, and putting the Mg into a charging bin.
S42 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;
s43, heat treatment: the alloy ingot obtained in the step S42 is put into a high temperature resistant stainless steel annealing pot for sealing, then is put into a vacuum annealing furnace for heat treatment under inert gas or vacuum condition, the heat treatment procedure is as follows,
a first temperature rising stage: heating to 600 ℃ from room temperature according to a heating rate of 10 ℃/min, and preserving heat for 1h;
a second temperature rising stage: heating from 600 ℃ to 1010 ℃ according to the heating rate of 1 ℃/min, and preserving heat for 14h;
and (3) a cooling stage: cooling to room temperature along with the furnace.
Grinding the obtained hydrogen storage alloy block to remove surface oxide layer, mechanically crushing, grinding into powder, sieving, taking alloy powder passing through a 400-mesh sieve, performing XRD test, and performing quantitative analysis on the collected data by Rietve1d full spectrum fitting, wherein the analysis result shows that the alloy is 2H-A 2 B 7 The content of the shaped phase structure is 100wt%.
Example 5
Pure phase 2H-A with long cycle life 2 B 7 SmPr hydrogen storage alloy 0.08 La 0.6 Mg 0.32 Ni 6.6 Al 0.4 The preparation method comprises the following steps:
s51, proportioning: the metal simple substance Sm, pr, la, mg, ni and Al 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.
S52 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;
s53 heat treatment: the alloy ingot obtained in the step S52 is put into a high temperature resistant stainless steel annealing pot for sealing, then is put into a vacuum annealing furnace for heat treatment under inert gas or vacuum condition, the heat treatment procedure is as follows,
a first temperature rising stage: heating to 600 ℃ from room temperature according to a heating rate of 12 ℃/min, and preserving heat for 1h;
a second temperature rising stage: heating from 600 ℃ to 1010 ℃ according to the heating rate of 1 ℃/min, and preserving heat for 16h;
and (3) a cooling stage: cooling to room temperature along with the furnace.
Grinding the obtained hydrogen storage alloy block to remove surface oxide layer, mechanically crushing, grinding into powder, sieving, taking alloy powder passing through a 400-mesh sieve, performing XRD test, and performing quantitative analysis on the collected data by Rietve1d full spectrum fitting, wherein the analysis result shows that the alloy is 2H-A 2 B 7 The content of the shaped phase structure is 100wt%.
Example 6
Pure phase 2H-A with long cycle life 2 B 7 Hydrogen storage alloy and Sm 1.06 Gd 0.1 La 0.5 Mg 0.34 Ni 6.6 Al 0.4 The preparation method comprises the following steps:
s61, proportioning: the metal simple substance Sm, gd, la, mg, ni and Al 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.
S62 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;
s63 heat treatment: the alloy ingot obtained in the step S62 is put into a high temperature resistant stainless steel annealing pot for sealing, then is put into a vacuum annealing furnace, and is subjected to heat treatment under inert gas or vacuum conditions, wherein the heat treatment procedure is as follows,
a first temperature rising stage: heating to 600 ℃ from room temperature according to a heating rate of 10 ℃/min, and preserving heat for 1h;
a second temperature rising stage: heating from 600 ℃ to 1005 ℃ according to a heating rate of 1 ℃/min, and preserving heat for 18h;
and (3) a cooling stage: cooling to room temperature along with the furnace.
Grinding the obtained hydrogen storage alloy block to remove surface oxide layer, mechanically crushing, grinding into powder, sieving, taking alloy powder passing through a 400-mesh sieve, performing XRD test, and performing quantitative analysis on the collected data by Rietve1d full spectrum fitting, wherein the analysis result shows that the alloy is 2H-A 2 B 7 The content of the shaped phase structure is 100wt%.
EXAMPLE 7 ultra long cycle life pure phase 2H-A 2 B 7 Performance test of hydrogen storage alloy
Grinding the alloy obtained in the examples 1-6 to remove the surface oxide layer, crushing, grinding and pulverizing, taking 200-400 mesh powder, and mixing the powder with carbonyl nickel powder according to the mass ratio of 0.15g:0.75g of electrode plate with the diameter of 10mm is cold-pressed under the pressure of 15MPa, and sintered 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 figure 4 and in table 1,pure phase 2H-A with very long cycle life prepared in examples 1-6 2 B 7 The maximum discharge capacity of the nickel-hydrogen battery assembled by the hydrogen storage alloy electrode is 358mAh/g, 351mAh/g, 356mAh/g, 354mAh/g, 357mAh/g and 353mAh/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 weekly discharge capacity to 500 weeks, wherein the capacity retention rate of the alloy is the ratio of the weekly discharge capacity 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. 5 and Table 1, the ultra-long cycle life pure phase 2H-A prepared in examples 1-6 2 B 7 After 500 weeks of charge/discharge cycles, the capacity retention rates of the nickel-hydrogen battery assembled with the hydrogen storage alloy electrode were 70.7%, 72.5%, 74.8%, 78.2%, 76.4% and 77.3%, respectively.
Table 1 example alloy crystal structure and electrochemical performance table
In conclusion, the pure phase 2H-A provided by the invention 2 B 7 The hydrogen storage alloy electrode as the nickel-hydrogen battery cathode material shows high discharge capacity and is compared with the prior A 2 B 7 The superlattice structure hydrogen storage alloy has an ultra-long electrochemical life.
Comparative example 8
This example separately prepares A 2 B 7 The hydrogen storage alloy with superlattice structure comprises the following chemical components:
group a: smLa 0.6 Mg 0.4 Ni 6.6 Al 0.4 Example 1
Group b: sm (Sm) 1.5 La 0.1 Mg 0.4 Ni 6.6 Al 0.4
Group c: sm (Sm) 0.7 La 0.9 Mg 0.4 Ni 6.6 Al 0.4
d group: smLa 0.6 Mg 0.4 Ni 6.6 Al 0.6
Group e: smLa 0.6 Mg 0.4 Ni 6.9 Al 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, although the same preparation method and conditions as in example 1 were employed and the same kind of elements were employed, when Sm or Al content in the alloy was too high, the phase structure of the prepared b and d gold compositions could not form pure phase 2H-A 2 B 7 The discharge capacity of the finally obtained alloy is too low; furthermore, although groups c and e were prepared using the same preparation method and conditions, pure phase 2H-A could be obtained 2 B 7 The shape phase structure, however, when the Sm or Al content in the alloy is too low, the cycle life of the finally obtained alloy becomes poor.
Comparative example 9 Effect of different heat treatment temperature increasing programs and conditions on superlattice Hydrogen storage alloy Structure and electrode Material Performance
In a great deal of experimental study, the heat treatment condition is found to have an important influence on the structure and performance of the superlattice structure hydrogen storage alloy, and the embodiment researches different heat treatment temperature rise procedures, wherein the chemical composition of the alloy is similar to that of the embodiment 1, and the only difference is 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 985 ℃, and preserving the heat for 10 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 maintain the temperature for 1 hr; the second temperature rising stage is to rise from 600 ℃ to 980 ℃ and keep the temperature for 10 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 maintain the temperature for 1 hr; the second heating stage is to heat from 600 ℃ to 1020 ℃ and keep the temperature for 10 hours.
Group E: 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 maintain the temperature for 1 hr; the second heating stage is to heat from 600 ℃ to 985 ℃ and keep the temperature for 6h.
Group F: 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 maintain the temperature for 1 hr; the second heating stage is to heat from 600 ℃ to 985 ℃ and keep the temperature for 24 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 2H-A cannot be formed 2 B 7 A type superlattice structure and eventually lead to an alloy with too low discharge capacity or poor cycle life.
Examples 1-6 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 (3)
1. Pure phase 2H-A with long cycle life 2 B 7 The hydrogen storage alloy electrode material is characterized in that the hydrogen storage alloy can be represented by the chemical general formula Sm 2-a-b-c La c M b Mg a Ni z-x-y Al x N y The expression is as follows: m represents at least one element selected from rare earth Ce, pr, nd, gd and Y, N represents at least one element selected from Mn or Co, wherein a, b, c, x, Y, z represents a molar ratio of 0.32-0.4, 0-0.1,0.4-0.6,0.2-x-0.4, 0-0.1,6.8-z-7;
the crystal structure of the alloy is 2H-A 2 B 7 A superlattice structure and a phase content of 100wt%;
the long cycle life pure phase 2H-A 2 B 7 The preparation method of the hydrogen storage alloy electrode material is carried out sequentially according to the following steps:
s1, batching
Selecting metal simple substances as raw materials, proportioning according to the chemical composition of the hydrogen storage 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 Mg into a charging bin;
s2, induction smelting alloy
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;
s3, alloy heat treatment
The alloy cast ingot obtained in the step S2 is put into a high temperature resistant stainless steel annealing pot for sealing, then is put into a vacuum annealing furnace for heat treatment under inert gas or vacuum condition, the heat treatment procedure is as follows,
a first temperature rising stage: heating to 600 ℃ from room temperature, and preserving heat for 1h;
a second temperature rising stage: heating from 600 ℃ to 985-1010 ℃ and preserving heat for 10-18h;
and (3) a cooling stage: cooling to room temperature along with the furnace.
2. A long cycle life pure phase 2H-a according to claim 1 2 B 7 The hydrogen storage alloy electrode material is characterized in that the hydrogen storage alloy has the chemical composition Sm 1.18 La 0.4 Y 0.1 Mg 0.32 Ni 6.6 Al 0.2 Mn 0.1 、Sm 1.05 La 0.56 Ce 0.05 Mg 0.34 Ni 6. 4 Al 0.35 Co 0.05 、SmLa 0.56 Nd 0.08 Mg 0.36 Ni 6.52 Al 0.38 Mn 0.04 Co 0.06 、SmPr 0.08 La 0.6 Mg 0.32 Ni 6.6 Al 0.4 Or Sm 1.0 6 Gd 0.1 La 0.5 Mg 0.34 Ni 6.6 Al 0.4 One of them.
3. A long cycle life pure phase 2H-a according to claim 1 2 B 7 The hydrogen storage alloy electrode material is characterized in that: in the step S3, the temperature rising rate of the first temperature rising stage is 10-15 ℃/min, and the temperature rising rate of the second temperature rising stage is 1-2 ℃/min.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090169995A1 (en) * | 2007-12-27 | 2009-07-02 | Sanyo Electric Co., Ltd. | Hydrogen storage alloy and alkaline storage battery employing hydrogen storage alloy as negative electrode active material |
| CN104294087A (en) * | 2014-09-09 | 2015-01-21 | 上海纳米技术及应用国家工程研究中心有限公司 | Method for preparing superlattice hydrogen storing alloy |
| CN108493436A (en) * | 2018-03-09 | 2018-09-04 | 燕山大学 | Ni-based quaternary hydrogen-storing alloy electrode material of a kind of super stacking provisions lanthanum-M-magnesium-of 2H types A5B19 and preparation method thereof |
| CN112877567A (en) * | 2021-01-11 | 2021-06-01 | 包头中科轩达新能源科技有限公司 | Hydrogen storage alloy suitable for low-pressure solid hydrogen storage and preparation method thereof |
| 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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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090169995A1 (en) * | 2007-12-27 | 2009-07-02 | Sanyo Electric Co., Ltd. | Hydrogen storage alloy and alkaline storage battery employing hydrogen storage alloy as negative electrode active material |
| CN104294087A (en) * | 2014-09-09 | 2015-01-21 | 上海纳米技术及应用国家工程研究中心有限公司 | Method for preparing superlattice hydrogen storing alloy |
| CN108493436A (en) * | 2018-03-09 | 2018-09-04 | 燕山大学 | Ni-based quaternary hydrogen-storing alloy electrode material of a kind of super stacking provisions lanthanum-M-magnesium-of 2H types A5B19 and preparation method thereof |
| CN112877567A (en) * | 2021-01-11 | 2021-06-01 | 包头中科轩达新能源科技有限公司 | Hydrogen storage alloy suitable for low-pressure solid hydrogen storage and preparation method thereof |
| 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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