CN114023927B - Hydrogen storage alloy negative electrode for metal-organic framework compound in-situ coated nickel-metal hydride battery and preparation method thereof - Google Patents
Hydrogen storage alloy negative electrode for metal-organic framework compound in-situ coated nickel-metal hydride battery and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a hydrogen storage alloy negative electrode for a nickel-hydrogen battery coated with a metal organic framework compound in situ and a preparation method thereof, and relates to the technical field of negative electrode materials of nickel-hydrogen batteries. The invention adopts a stirring method to uniformly coat the metal organic framework compound on the surface of the rare earth hydrogen storage alloy in situ, and directly obtains the hydrogen storage alloy cathode for the nickel-hydrogen battery coated with the metal organic framework compound in situ. The La-Y-Ni based rare earth hydrogen storage alloy material coated by the uniform metal organic framework compound in situ is obtained by the method. The experimental results show that: the rare earth hydrogen storage alloy material coated with the surface metal organic framework compound in situ can effectively prevent pulverization of the rare earth hydrogen storage alloy material and corrosion of electrolyte to the material, relieves capacity attenuation, and has better cycle stability and rate capability than the uncoated material.
Description
Technical Field
The invention belongs to the field of nickel-hydrogen battery negative electrode materials, and particularly relates to a hydrogen storage alloy negative electrode for a nickel-hydrogen battery coated with a metal organic framework compound in situ and a preparation method thereof.
Background
In recent years, the hydrogen storage alloy is an important functional material in the field of hydrogen energy development and application, and is widely applied to the fields of nickel-hydrogen battery cathode materials, hydrogen compression, solid-state hydrogen storage, heat storage and the like due to high safety and good reversibility of hydrogen absorption and desorption. As the main application field of the hydrogen storage alloy, the nickel-hydrogen battery has the advantages of excellent wide temperature performance, good dynamic performance, environmental protection, high safety and the like, and is widely applied to the fields of electric automobiles, large-scale energy storage, coal illumination, ice and snow industry and the like.
The hydrogen storage alloy used as the negative electrode of the nickel-hydrogen battery mainly comprises AB 5 A is a 2 Type B, AB 2 A is a 2 B 7 Materials such as vanadium-based solid solution, A 2 Type B, AB 2 The solid solution based on vanadium and vanadium is difficult to absorb and release hydrogen at normal temperature, and cannot be applied to the field of batteries. Since commercialization in 1989, the negative electrode material of nickel-hydrogen batteries was mainly LaNi 5 The hydrogen storage alloy has the characteristics of long cycle life, mature technology, environmental friendliness and the like. Currently, the LaNi is commercialized 5 The maximum discharge capacity of the hydrogen storage alloy can reach 350mAh/g -1 Has approached the theoretical value (372 mAh.g -1 ) Meanwhile, the problems of poor high-rate discharge performance, high cost and the like still exist. Therefore, research into novel hydrogen storage alloys is being pursued to develop nickel-hydrogen batteries with high specific energy. In recent years, A with high capacity 2 B 7 The La-Y-Ni based rare earth hydrogen storage alloy material is widely paid attention to, but poor oxidation resistance leads to poor cycle performance and rate capability, which severely limits practical application. Research shows that the surface components, microstructure, electrocatalytic activity and other characteristics of the alloy have important influence on the performance of the nickel-hydrogen battery. The surface characteristics of the alloy can be changed through surface coating modification treatment, the electrode performance of the alloy is improved, and the popularization and application processes of the alloy are accelerated.
The surface modification treatment of the hydrogen storage alloy particles and the electrode material is an effective way for improving the performance of alloy electrodes and batteries. The method aims to change the surface state of the hydrogen storage alloy under the condition of maintaining the integral property of the original hydrogen storage alloy, so as to improve the electrochemical performance and the dynamic performance of the alloy. The common alloy surface modification treatment methods are as follows: alkaline, acidic solution treatment, surface coating metal film treatment, surface macromolecule modification and the like. Wherein, the acid-base treatment possibly causes excessive corrosion of alloy, loss of effective capacity and reduction of circulation stability. And the surface is coated with a metal film, so that a symbiotic phase is not formed between the coating layer and the alloy, and the coating layer is easy to fall off, so that the failure is caused. The surface macromolecule modification can lead the surface of the material to form a micro space, and H can be regulated and controlled by the selection of different surface groups 2 Preventing the material from falling off and improving the utilization rate. Improve the cycling stability of the nickel-hydrogen battery cathode material, thereby realizing the aim of commercial application. The current patent focuses mainly on optimizing the alloy material composition, has less research on surface coating, and is not easy for industrial practical production applications, such as: the preparation method of the PAN-based porous carbon-magnesium alloy supported Zr-based MOFs hydrogen storage alloy material by adopting the methods of reflux, calcination, ball milling and the like in the patent CN110835091A has high energy consumption in industrial production, and is difficult to produce in a large scale by adopting the reflux, heat treatment and ball milling method, so that the practical application of the material is limited. Thus, development is performed without changing the existing A 2 B 7 The method for carrying out surface coating modification on the premise of the production flow and equipment of the La-Y-Ni-based rare earth hydrogen storage alloy material has important application significance, is convenient for large-scale production, and greatly improves A 2 B 7 The electrochemical performance of the La-Y-Ni based rare earth hydrogen storage alloy material can well meet the current social development requirement.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides the hydrogen storage alloy cathode for the nickel-metal-organic framework compound in-situ coated nickel-metal hydride battery and the preparation method thereof, and the obtained La-Y-Ni-based rare earth hydrogen storage alloy material can effectively relieve material pulverization and has excellent cycle stability and rate capability.
In order to achieve the technical purpose and the technical effect, the invention is realized by the following technical scheme:
the invention firstly provides a preparation method of a hydrogen storage alloy anode for a nickel-hydrogen battery coated with a metal organic framework compound in situ, which comprises the following steps:
step one: la-Y-Ni based rare earth hydrogen storage alloy material and Co (NO) 3 ) 2 ·6H 2 Dispersing O into deionized water solution, and uniformly stirring to obtain mixed solution;
step two: c is C 4 H 6 N 2 Dissolving in deionized water solution, and stirring to obtain C 4 H 6 N 2 A solution;
step three: c obtained in the second step 4 H 6 N 2 Mixing the solution with the mixed solution in the first step, stirring and standing to obtain a mixture;
step four: and (3) centrifuging, washing and vacuum drying the mixture obtained in the step (III) to obtain the hydrogen storage alloy cathode for the nickel-hydrogen battery coated with the metal organic framework compound in situ.
Preferably, the La-Y-Ni based rare earth hydrogen storage alloy material in the step one is LaY 2 Ni 9.7 Mn 0.5 Al 0.3 The grain diameter is 200-400 meshes.
Preferably, co (NO 3 ) 2 ·6H 2 The concentration of O is 0.01-0.1 mol/L.
Preferably, the Co (NO 3 ) 2 ·6H 2 The mass ratio of O to La-Y-Ni based rare earth hydrogen storage alloy material is 0.2-0.8: 1.
preferably, the stirring time in the first step is 0.1 to 1 hour.
Preferably, C in the second step 4 H 6 N 2 The concentration of (C) is 0.1-1.0 mol/L.
Preferably, the stirring time in the second step is 0.1 to 1 hour.
Preferably, in the third step, the stirring time is 0.1-1 h, and the standing time is 2-12 h.
Preferably, the solvent for centrifugation and washing in the fourth step is deionized water solution and ethanol solution, the temperature for vacuum drying is 40-60 ℃, and the heat preservation time is 5-15 h.
The invention also provides a hydrogen storage alloy cathode for the nickel-hydrogen battery, which is coated by the metal organic framework compound in situ and is prepared by the preparation method.
The beneficial effects of the invention are that
The invention provides a hydrogen storage alloy negative electrode for a nickel-metal hydride battery with an in-situ cladding metal organic framework compound and a preparation method thereof. The method is simple and easy to operate and convenient to popularize and apply.
The experimental results show that: the hydrogen storage alloy cathode for the nickel-metal hydride battery, which is coated with the metal organic framework compound in situ, is prepared by the method, the alloy structure is well maintained, and the metal organic framework compound is uniformly coated on the alloy surface in situ. Example 1 La-Y-Ni based rare earth hydrogen storage alloy material surface in-situ coated Co-MOF negative electrode material prepared by the method has discharge capacity of 258.3mAh g after being cycled for 350 circles under 1C current density under the voltage range of 0.8-16V -1 . Even under the high-multiplying power current density of 5C discharge rate, the specific discharge capacity can reach 234.2mAh g -1 Shows better cycle stability and rate performance than uncoated metal organic framework compounds.
Therefore, the hydrogen storage alloy cathode for the nickel-hydrogen battery, which is coated with the metal organic framework compound in situ and prepared by the method, has excellent charge-discharge cycle stability and high-rate discharge performance, can be widely applied to cathode materials of the nickel-hydrogen battery, and is suitable for popularization and application.
Drawings
FIG. 1 is a schematic illustration of an embodiment of the present inventionSEM pictures of the materials obtained in example 1 and comparative example 1. Wherein FIG. 1a is LaY of an uncoated metal organic framework compound 2 Ni 9.7 Mn 0.5 Al 0.3 Rare earth hydrogen storage alloy material, FIG. 1b shows LaY coated in situ with metal organic framework compound 2 Ni 9.7 Mn 0.5 Al 0.3 Rare earth hydrogen storage alloy material.
FIG. 2 discharge graphs of the materials obtained in example 1 and comparative example 1 of the present invention, which were mixed with nickel carbonyl powder to prepare a negative electrode, using sintered alpha-nickel hydroxide as a positive electrode, a sulfonated polypropylene graft film as a separator, were activated for 10 cycles at a current density of 0.2C in a voltage interval of 0.8 to 1.6V, and cycled at a current density of 1C.
Fig. 3 is an SEM image of two materials after 50 cycles. Wherein FIG. 3a is LaY of an uncoated metal organic framework compound 2 Ni 9.7 Mn 0.5 Al 0.3 Rare earth hydrogen storage alloy material, FIG. 3b shows LaY coated in situ with metal organic framework compound 2 Ni 9.7 Mn 0.5 Al 0.3 Rare earth hydrogen storage alloy material.
Fig. 4 is a graph showing the rate discharge performance of the assembled batteries of example 1 and comparative example 1 at 0.2C, 0.5C, 1C, 2C, 5C, and 0.2C.
Detailed Description
The invention provides a preparation method of a hydrogen storage alloy anode for a metal organic framework compound in-situ coated nickel-metal hydride battery, which comprises the following steps:
step one: la-Y-Ni based rare earth hydrogen storage alloy material and Co (NO) 3 ) 2 ·6H 2 Dispersing O into deionized water solution, and uniformly stirring for 0.1-1 h to obtain mixed solution;
the La-Y-Ni based rare earth hydrogen storage alloy material is preferably LaY 2 Ni 9.7 Mn 0.5 Al 0.3 The grain diameter is 200-400 meshes;
said Co (NO 3 ) 2 ·6H 2 The concentration of O is preferably 0.01 to 0.1mol/L, co (NO) 3 ) 2 ·6H 2 O and La-Y-Ni based rare earth hydrogen storage alloy materialThe preferred weight ratio is 0.2-0.8: 1, a step of;
step two: c is C 4 H 6 N 2 Dissolving in deionized water solution, stirring uniformly for 0.1-1 h to obtain C 4 H 6 N 2 A solution; the C is 4 H 6 N 2 The concentration of (C) is preferably 0.1 to 1.0mol/L;
step three: c obtained in the second step 4 H 6 N 2 Mixing the solution with the mixed solution in the first step, stirring and standing, wherein the stirring time is preferably 0.1-1 h, and the standing time is preferably 2-12 h; the mixture obtained;
the mixing sequence is C 4 H 6 N 2 Pouring the solution into the mixed solution rapidly;
step four: centrifuging, washing and vacuum drying the mixture obtained in the step three to obtain a hydrogen storage alloy anode for the nickel-hydrogen battery, wherein the nickel-hydrogen battery is coated with the metal organic framework compound in situ; the centrifugal and washing solvents are deionized water solution and ethanol solution, the temperature of vacuum drying is preferably 40-60 ℃, and the heat preservation time is preferably 5-15 h.
The invention also provides a hydrogen storage alloy cathode for the nickel-hydrogen battery, which is coated by the metal organic framework compound in situ and is prepared by the preparation method.
The following detailed description of the invention, which is a part of this specification, illustrates the principles of the invention by way of example, and other aspects, features, and advantages of the invention will become apparent from the detailed description. But this example does not limit the invention.
Example 1
1) Will LaY 2 Ni 9.7 Mn 0.5 Al 0.3 The rare earth hydrogen storage alloy material is fully ground and sieved in a mortar, and alloy powder with the grain diameter of 200-400 meshes is selected.
2) Weigh 2g LaY 2 Ni 9.7 Mn 0.5 Al 0.3 Rare earth hydrogen storage alloy material and 1.164g Co (NO) 3 ) 2 ·6H 2 O is dissolved in 80mL deionized water solution and stirred for 30min to obtain mixed solutionAnd (3) liquid.
3) Weigh 2.64gC 4 H 6 N 2 Dissolving in 80mL deionized water solution, stirring for 30min to obtain C 4 H 6 N 2 A solution.
4) C is C 4 H 6 N 2 And (3) rapidly pouring the solution into the mixed solution, stirring for 30min, standing for 2h, centrifuging, washing three times with deionized water and absolute ethyl alcohol respectively, and vacuum drying in a vacuum drying oven at 60 ℃ for 12h to obtain the hydrogen storage alloy cathode for the nickel-hydrogen battery coated with the metal organic framework compound in situ.
SEM test results of the hydrogen storage alloy negative electrode for the nickel-metal hydride battery with the in-situ coated metal-organic framework compound obtained in example 1 are shown in fig. 1b, and the surface of the negative electrode is uniformly coated with the metal-organic framework compound in-situ.
Comparative example 1
1) Will LaY 2 Ni 9.7 Mn 0.5 Al 0.3 The rare earth hydrogen storage alloy material is fully ground in a mortar, and alloy powder with the grain diameter of 200-400 meshes is selected.
LaY obtained in comparative example 1 2 Ni 9.7 Mn 0.5 Al 0.3 SEM test results of the rare earth hydrogen storage alloy material are shown in fig. 1a, and the surface of the rare earth hydrogen storage alloy material is smoother.
Application example 1
LaY prepared in example 1 and comparative example 1 2 Ni 9.7 Mn 0.5 Al 0.3 The rare earth hydrogen storage alloy material is subjected to electrochemical performance test. The method comprises the following specific steps:
mixing the anode active material and carbonyl nickel powder according to the mass ratio of 1:5, tabletting under 15MPa, wrapping with foam nickel, and welding the electrode lugs. The loading of the active material of the obtained pole piece is about 150mg. The positive electrode adopts sintered a-nickel hydroxide, a polypropylene grafted membrane treated by sulfonation is used as a diaphragm, an electrolyte is 6M KOH solution, and electrochemical performance test is carried out in a voltage range of 0.8-1.6V.
LaY obtained in example 1 and comparative example 1 2 Ni 9.7 Mn 0.5 Al 0.3 Preparation of rare earth Hydrogen storage alloy Material Battery activation at 0.2C Current Density and 1C Current Density in the Voltage interval of 0.8-1.6VThe discharge cycle performance of (2) is shown in fig. 2, and it can be seen that: laY 2 Ni 9.7 Mn 0.5 Al 0.3 The maximum discharge capacity of the rare earth hydrogen storage alloy material under the current density of 0.2C is 375.5mAh g -1 LaY coated in situ with metal organic framework compound 2 Ni 9.7 Mn 0.5 Al 0.3 The maximum discharge capacity of the rare earth hydrogen storage alloy material under the current density of 0.2C is 388.3mAh g -1 LaY after 350 cycles 2 Ni 9.7 Mn 0.5 Al 0.3 LaY coated in situ by rare earth hydrogen storage alloy material and metal organic framework compound 2 Ni 9.7 Mn 0.5 Al 0.3 The discharge capacity of the rare earth hydrogen storage alloy material is 216.5mAh g -1 And 258.3mAh g -1 。
LaY obtained in example 1 and comparative example 1 2 Ni 9.7 Mn 0.5 Al 0.3 SEM images of the rare earth hydrogen storage alloy material prepared cell after activation at 0.2C current density and 50 cycles at 1C current density in the voltage interval of 0.8-1.6V are shown in fig. 3, and it can be seen that: laY after 50 cycles of charge and discharge 2 Ni 9.7 Mn 0.5 Al 0.3 Surface of rare earth hydrogen storage alloy material is broken, while LaY coated by metal organic framework compound in situ 2 Ni 9.7 Mn 0.5 Al 0.3 After the appearance of the rare earth hydrogen storage alloy material is maintained, no cracking phenomenon is found, and the metal organic framework compound in-situ coating layer can effectively prevent the material from being pulverized and prevent the electrolyte from corroding the material.
LaY obtained in example 1 and comparative example 1 2 Ni 9.7 Mn 0.5 Al 0.3 The rate discharge cycle performance of the rare earth hydrogen storage alloy material prepared battery under different current densities in the voltage range of 0.8-1.6V is shown in figure 4, and can be seen as LaY coated with the metal organic framework compound in situ 2 Ni 9.7 Mn 0.5 Al 0.3 The rare earth hydrogen storage alloy material has better multiplying power discharge performance than that of an uncoated material, and has discharge capacities of 341.8 and 234.2mAh g respectively under the current densities of 2C and 5C -1 While uncoated LaY 2 Ni 9.7 Mn 0.5 Al 0.3 The discharge capacity of the rare earth hydrogen storage alloy material is only 323 and 74.9mAh g -1 After the current density was returned to 0.2C, the metal-organic framework compound was coated and uncoated LaY in situ 2 Ni 9.7 Mn 0.5 Al 0.3 The discharge capacity of the rare earth hydrogen storage alloy material is 361.9mAh g -1 And 348.2mAh g -1 。
The above results can be seen that the metal organic framework compound coats LaY in situ 2 Ni 9.7 Mn 0.5 Al 0.3 The cycling stability and the high-current discharge performance of the rare earth hydrogen storage alloy material are obviously better than those of the uncoated LaY 2 Ni 9.7 Mn 0.5 Al 0.3 The rare earth hydrogen storage alloy material fully proves that the metal organic framework compound in-situ cladding plays a role in stabilizing LaY 2 Ni 9.7 Mn 0.5 Al 0.3 The rare earth hydrogen storage alloy material has the function of surface structure, effectively prevents pulverization of the material and corrosion of electrolyte, and further greatly improves the cycle performance under high current density, so that the invention has more commercial popularization superiority.
The invention includes, but is not limited to, the above embodiments, any equivalent or partial modification made under the principle of the spirit of the invention, shall be considered as being within the scope of the invention.
Claims (10)
1. The preparation method of the hydrogen storage alloy cathode for the metal-organic framework compound in-situ coated nickel-metal hydride battery is characterized by comprising the following steps of:
step one: la-Y-Ni based rare earth hydrogen storage alloy material and Co (NO) 3 ) 2 •6H 2 Dispersing O into deionized water solution, and uniformly stirring to obtain mixed solution;
step two: c is C 4 H 6 N 2 Dissolving in deionized water solution, and stirring to obtain C 4 H 6 N 2 A solution;
step three: c obtained in the second step 4 H 6 N 2 Mixing the solution with the mixed solution obtained in the step one, stirring and standing to obtainA mixture obtained;
step four: and (3) centrifuging, washing and vacuum drying the mixture obtained in the step (III) to obtain a hydrogen storage alloy anode active material for the nickel-hydrogen battery, which is coated with the metal-organic framework compound in situ, mixing the anode active material and carbonyl nickel powder according to the mass ratio of 1:5, tabletting under 15MPa, and coating with foam nickel to obtain the hydrogen storage alloy anode for the nickel-hydrogen battery, which is coated with the metal-organic framework compound in situ.
2. The method for preparing a hydrogen storage alloy negative electrode for a metal-organic framework compound in-situ coated nickel-metal hydride battery as claimed in claim 1, wherein the La-Y-Ni based rare earth hydrogen storage alloy material in the first step is LaY 2 Ni 9.7 Mn 0.5 Al 0.3 The grain diameter is 200-400 meshes.
3. The method for preparing a hydrogen storage alloy anode for a metal-organic framework compound in-situ coated nickel-metal hydride battery as claimed in claim 1, wherein in the step one, co (NO 3 ) 2 •6H 2 The concentration of O is 0.01-0.1 mol/L.
4. The method for preparing a hydrogen storage alloy anode for a metal-organic framework compound in-situ coated nickel-metal hydride battery as claimed in claim 1, wherein the Co (NO 3 ) 2 •6H 2 The mass ratio of O to La-Y-Ni based rare earth hydrogen storage alloy material is 0.2-0.8: 1.
5. the method for preparing a hydrogen storage alloy negative electrode for a metal-organic framework compound in-situ coated nickel-metal hydride battery according to claim 1, wherein the stirring time in the first step is 0.1-1 h.
6. The method for preparing a hydrogen storage alloy anode for a metal-organic framework compound in-situ coated nickel-metal hydride battery as claimed in claim 1, wherein C in the second step is as follows 4 H 6 N 2 The concentration of (C) is 0.1-1.0 mol/L.
7. The method for preparing a hydrogen storage alloy negative electrode for a metal-organic framework compound in-situ coated nickel-metal hydride battery according to claim 1, wherein the stirring time in the second step is 0.1-1 h.
8. The method for preparing a hydrogen storage alloy negative electrode for a metal-organic framework compound in-situ coated nickel-metal hydride battery according to claim 1, wherein in the third step, stirring time is 0.1-1 h, and standing time is 2-12 h.
9. The method for preparing the hydrogen storage alloy negative electrode for the nickel-metal hydride battery coated with the metal-organic framework compound in situ according to claim 1, wherein the solvent for centrifugation and washing in the fourth step is deionized water solution and ethanol solution, the temperature for vacuum drying is 40-60 ℃, and the heat preservation time is 5-15 h.
10. The hydrogen storage alloy negative electrode for the nickel-hydrogen battery, which is coated with the metal-organic framework compound in situ and is obtained by the preparation method of claim 1.
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