CN114242927A - Positive electrode material and magnesium secondary battery containing same - Google Patents
Positive electrode material and magnesium secondary battery containing same Download PDFInfo
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- CN114242927A CN114242927A CN202111580230.6A CN202111580230A CN114242927A CN 114242927 A CN114242927 A CN 114242927A CN 202111580230 A CN202111580230 A CN 202111580230A CN 114242927 A CN114242927 A CN 114242927A
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H—ELECTRICITY
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
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- H—ELECTRICITY
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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
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Abstract
The invention discloses a positive electrode material and a magnesium secondary battery containing the same, wherein the positive electrode material has a ring-shaped three-dimensional covalent organic framework structure, so that the positive electrode material can adapt to volume expansion of magnesium ion deintercalation in a circulation process and is insoluble in electrolyte; meanwhile, the COF has the semiconductor characteristic, the problem of poor electronic conductivity of the organic electrode material is solved, the COF can be grown on the carbon nano tube to further improve the conductivity of the carbon nano tube, and the problem that the traditional small molecular material structure cannot conduct electricity and cannot exert capacity is solved; the anode material is in a frame type three-dimensional structure, so that a large amount of magnesium ions can be stored between layers; meanwhile, the cathode material is also an organic crystal material, can adapt to volume expansion in the circulation process so as to adapt to the embedding and the separation of magnesium ions, further improves the circulation performance of the magnesium battery, and has the excellent characteristics of high coulomb efficiency, high-quality specific capacity and the like.
Description
Technical Field
The invention belongs to the technical field of battery electrode materials, and particularly relates to a positive electrode material, a preparation method thereof and a magnesium secondary battery containing the positive electrode material.
Background
With the decreasing reserves of fossil fuels represented by three major energy sources of coal, petroleum and natural gas, chemical power sources have gained great attention in the aspects of high-tech devices, green transportation with low energy consumption, development and utilization of renewable energy sources and the like. Among the existing primary and secondary batteries, the magnesium battery has the greatest energy density, and thus has been widely studied and applied. However, due to the high activity of magnesium metal, the reliability and safety of magnesium batteries are difficult to ensure, and especially large-scale power magnesium secondary batteries still have many potential safety hazards. Therefore, conventional toxic and low capacity lead-acid or silver-cadmium batteries are still used in practical power sources. With the continuous attention paid to the fields of energy, resources and environment, people begin to research and develop novel, high-performance and low-cost green chemical power sources while improving the problems of the existing batteries.
The magnesium secondary battery is one of green chemical power sources and is widely regarded by researchers. However, the magnesium secondary battery is still in the initial stage of research, and thus there are still many technical problems to be solved. Among them, the synthesis of new positive electrode materials and the study of their electrochemical properties in magnesium battery systems are one of the important directions in the study of magnesium secondary batteries. Relative to Li+In particular, Mg2+Has a large charge density and is more severely solvated, and thus most of the positive electrode materials that can be used for lithium secondary batteries cannot be directly applied to magnesium secondary batteries. So far, the magnesium secondary battery positive electrode has mainly focused on embeddableThe research of materials, such as inorganic transition metal oxides, sulfides, borides, NASICON structure transition metal phosphates, and the like. The above-mentioned intercalatable material is subjected to a large amount of calcination in the production process of a magnesium secondary battery, and thus consumes a large amount of energy.
Disclosure of Invention
In order to improve the technical problems, the invention provides an organic material as a magnesium secondary battery positive electrode material (COF), the positive electrode material is more energy-saving and environment-friendly, has a cyclic covalent organic framework structure, can adapt to volume expansion of magnesium ion deintercalation in a circulation process, and is insoluble in an electrolyte; meanwhile, the COF has the semiconductor characteristic, and the problem of poor electronic conductivity of the organic electrode material is solved. The material of the invention has the characteristics of a semiconductor structure, so the material can also grow on the carbon nano tube to further improve the conductivity of the carbon nano tube, and further solve the problem that the traditional small molecular material structure cannot conduct electricity and cannot exert capacity; the anode material is in a frame type three-dimensional structure, so that a large amount of magnesium ions can be stored between layers; in addition, the cathode material is also an organic crystal material, can adapt to volume expansion in the circulation process so as to adapt to the embedding and the separation of magnesium ions, and further improves the circulation performance of the magnesium battery. The positive electrode material disclosed by the invention also has the excellent characteristics of low capacity loss rate in a cycle test, high coulombic efficiency, high quality-capacity specific capacity and the like.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a positive electrode material which has a ring-shaped three-dimensional covalent organic framework structure.
According to the invention, the cathode material is a composite material of a two-dimensional planar macromolecular compound and a carbon nano tube, or a composite material of an aromatic ring compound and a carbon nano tube, and the composite material has a ring-shaped three-dimensional covalent organic framework structure.
According to the invention, in the composite material of the two-dimensional planar macromolecular compound and the carbon nano tube, the two-dimensional planar macromolecular compound is paved on the surface of the carbon nano tube through hydrogen bonding to form a ring-shaped three-dimensional covalent organic framework structure.
According to the invention, in the composite material of the aromatic ring compound and the carbon nano tube, the aromatic ring compounds form a two-dimensional planar compound through hydrogen bonding, and then the two-dimensional planar compound is paved on the surface of the carbon nano tube through the hydrogen bonding, so that a ring-shaped three-dimensional covalent organic framework structure is formed.
According to the invention, the two-dimensional planar macromolecular compound has, for example, a structural fragment of formula I or formula II:
in formula I, R', which are identical OR different, are independently selected from alkenyl, alcohol, phenol, -OR, -C (═ O) H OR-C (═ O) R, R being selected from alkyl; n is the same or different and is independently selected from integers of 0-6; the dotted lines represent the links between the structural segments;
in the formula II, R1、R2Identical OR different, independently of one another, from the group consisting of-OH, -OR, -C (═ O) R OR-O-Si (R')3R is selected from alkyl, R' are identical or different and are independently selected from alkyl; r' and n are as defined for formula I; the dashed lines represent the bonds between the structural segments.
According to the invention, R' in the formulae I and II, which are identical or different, are selected independently of one another from C2-6Alkenyl, -C (═ O) H or-C (═ O) R, R being selected from C1-4Alkyl, such as methyl, ethyl, propyl, isopropyl, tert-butyl; n are identical or different and are independently selected from 0, 1, 2, 3, 4;
in the formula II, R1、R2Identical OR different, independently of one another, from the group-OR, -C (═ O) R OR-O-Si (R')3R is selected from C1-4Alkyl, such as methyl, ethyl, propyl, isopropyl, tert-butyl; r' are identical or different and are independently selected from C1-4Alkyl is, for example, methyl, ethyl, propyl, isopropyl, tert-butyl.
According to the invention, the two-dimensional planar macromolecular compound has, for example, a structural fragment of the formula Ia or IIa:
in the formula IIa, R1And R2Same, selected from-O-Si (CH)3)(CH3) (tert-butyl).
According to the invention, the aromatic ring compound has, for example, a structure represented by formula III or formula IV:
in formula III, R', which are identical OR different, are independently selected from alkenyl, alcohol, phenol, -OR, -C (═ O) H OR-C (═ O) R, R being selected from alkyl; n is an integer of 0 to 6;
in the formula IV, R1、R2Identical OR different, independently of one another, from the group consisting of-OH, -OR, -C (═ O) R OR-O-Si (R')3R is selected from alkyl, R' are identical or different and are independently selected from alkyl; r' and n are as defined for formula III.
According to the invention, R' in the formulae III and IV, which are identical or different, are selected independently of one another from C2-6Alkenyl, -C (═ O) H or-C (═ O) R, R being selected from C1-4Alkyl, such as methyl, ethyl, propyl, isopropyl, tert-butyl; n are identical or different and are independently selected from 0, 1, 2, 3, 4;
in the formula IV, R1、R2Identical OR different, independently of one another, from the group-OR, -C (═ O) R OR-O-Si (R')3R is selected from C1-4Alkyl, such as methyl, ethyl, propyl, isopropyl, tert-butyl; r' are identical or different and are independently selected from C1-4Alkyl is, for example, methyl, ethyl, propyl, isopropyl, tert-butyl.
According to the invention, the aromatic ring compound has, for example, a structure according to formula IIIa or formula IVa:
according to the invention, in the composite material, the mass ratio of the two-dimensional planar macromolecular compound or aromatic ring compound to the carbon nanotube is 1 (0.5-2), and is exemplarily 1:0.5, 1:1, 1:1.5 or 1: 2.
The invention also provides a positive plate which comprises the positive electrode material.
According to the invention, the positive plate comprises a current collector and an active material layer positioned on at least one side surface of the current collector, wherein the active material layer comprises the positive electrode material.
According to the present invention, the active material layer further includes a conductive agent and a binder. Preferably, the mass ratio of the positive electrode material to the conductive agent to the binder is (6-9): 1-13): 1, and is exemplarily 6:1:1, 7:13:1, 8:7:1, 8:1:1, 8:13:1, 9:1: 1.
The invention also provides a magnesium secondary battery, which comprises the cathode material; alternatively, the positive electrode sheet is included.
According to the present invention, the magnesium secondary battery further includes a negative electrode sheet. For example, the negative electrode sheet is a magnesium sheet.
According to the present invention, the magnesium secondary battery further includes a separator.
According to the present invention, the magnesium secondary battery further includes an electrolyte. For example, the electrolyte may be APC, Mg (HMDS)2/THF、Mg(TFSI)2At least one of the DME systems.
The invention has the following beneficial effects:
the invention provides an organic material as a magnesium secondary battery anode material, the anode material has a ring-shaped three-dimensional covalent organic framework structure, can adapt to the volume expansion of magnesium ion deintercalation in the circulation process, is insoluble in electrolyte, has semiconductor characteristics and is a COF (chip on film) material with semiconductor characteristicsOrganic crystals, and thus can store a large amount of magnesium ions between layers. The anode material is based on a redox enolization mechanism when storing magnesium ions, and two carbonyl groups are on one benzene ring, so that the de-intercalation of the magnesium ions is facilitated. The positive electrode material of the present invention is advantageous for Mg2+The rapid de-intercalation in the positive electrode greatly improves the rapid charge and discharge performance of the magnesium secondary battery. The concrete expression is as follows:
(1) the magnesium secondary battery prepared from the cathode material can achieve the specific capacity of 180mAh/g under the current density of 10C, still has 80% capacity retention rate after 200 cycles, and has the advantage of no dendritic crystal, so the cathode material can be used as the cathode material of the magnesium secondary battery for quick charging.
(2) The COF of the present invention is a semiconductor (the conductivity thereof is 2X 10) without compounding carbon nanotubes-10Less than S/cm), and the conductivity of the composite carbon nanotube is as high as 2 x 10-4S/cm, thus contributing to the conduction of magnesium ions.
(3) The initial specific capacity of the anode material can reach 320mAh/g, which exceeds the mass specific capacity of the current 98 percent of the anode material of the magnesium secondary battery.
(4) The positive electrode material of the invention has no problem of being dissolved in electrolyte in the circulating process, so that the positive electrode material can be circulated for 400 circles under the current density of 1C.
(5) The cathode material of the invention can be matched with magnesium electrolyte without chloride ions, thereby being beneficial to environmental protection and reducing the requirement on battery shells.
(6) The electrolyte of the anode material has wide adaptation range and can be matched with various electrolytes for use.
Drawings
FIG. 1 is a schematic view of the preparation process of the positive electrode material of example 1
FIG. 2 is a graph showing cycle characteristics of the magnesium secondary batteries obtained in examples 1 to 4.
Detailed Description
The invention also provides a preparation method of the cathode material, which comprises the following steps:
s1: adding the carbon nano tube into a mixed solvent of 1, 4-dioxane and mesitylene, and completely dispersing by ultrasonic;
s2: adding at least one compound shown as a formula V and/or at least one compound shown as a formula VI into the mixed system of the step S1;
in formula V and formula VI, R' and n are as defined above;
R3、R4identical or different, independently of one another, from H, unsubstituted or optionally substituted by one or more RaA substituted boronic acid group; raSame or different, independently from each other selected from H, C1-6Alkyl, such as H, methyl, ethyl, propyl, isopropyl, tert-butyl;
in the formula VI, R1And R2The definition of (1) is as before;
s3: and stirring and reacting under the argon atmosphere to obtain the cathode material.
According to an exemplary embodiment of the invention, the compounds of formula V and VI are selected, for example, from
At least one of (1).
According to the invention, in step S1, the dosage ratio of the carbon nanotube to the mixed solvent is 100mg (20-40) ml, and the exemplary dosage ratio is 100mg:20ml, 100mg:30ml and 100mg:40 ml.
According to the invention, the mixing ratio of the 1, 4-dioxane and the mesitylene in the mixed solvent is 1 (0.5-2), and the mixing ratio is 1:0.5, 1:1 and 1: 2.
According to the invention, the mass ratio of the carbon nanotube to the compound shown in the formula V or the compound shown in the formula VI is 1 (0.5-2), and the mass ratio is 1:0.5, 1:1 and 1: 2.
According to the invention, in step S3, the temperature of the reaction is 60-100 ℃, exemplary 60 ℃, 70 ℃, 80 ℃, 85 ℃, 90 ℃, 100 ℃; the reaction time is 60-80 h, and 60h, 70h, 75h and 80h are exemplified.
According to the present invention, the method for preparing the positive electrode material further comprises the steps of:
s4: after the reaction is finished, carrying out solid-liquid separation on the reaction system to obtain a reaction product.
For example, the solid-liquid separation may be by means known in the art, such as centrifugation.
According to an embodiment of the present invention, step S4 further includes: washing the reaction product obtained by solid-liquid separation. For example, the washing solvent may be acetone.
According to an embodiment of the present invention, step S4 further includes drying the washed reaction product. For example, the drying is performed under vacuum conditions. For example, the drying temperature is 140 to 160 ℃, and the exemplary temperatures are 140 ℃, 150 ℃ and 160 ℃.
The invention also provides application of the cathode material as a cathode material of a magnesium secondary battery.
The invention also provides a preparation method of the positive plate, which comprises the steps of uniformly dispersing the positive material, the conductive agent and the adhesive in a solvent, coating the solution on a current collector, and then drying the solution in vacuum to prepare a positive electrode film.
The invention also provides a preparation method of the magnesium secondary battery, which comprises the following steps: the method comprises the steps of separating the positive plate and the negative plate by a diaphragm, injecting electrolyte, and assembling to obtain the magnesium secondary battery.
For a further understanding of the invention, reference will now be made to the preferred embodiments of the invention in conjunction with the following examples, but it will be understood that the description is intended to illustrate the features and advantages of the invention further, and not to limit the invention.
The invention is further illustrated by the following specific examples.
The test method comprises the following steps:
and (3) conductivity test: and (3) carrying out conductivity test on the surface of the anode material by using a Hua-testing high-temperature four-probe tester HEST-800 instrument.
And (3) testing the cycle number of the battery: after the battery is assembled, a LAND blue battery test system is used for carrying out cycle performance test under the conditions of 1C/1C charge-discharge current and 0.3V-2.4V charge-discharge voltage.
Example 1
Preparing a positive electrode material:
s1: adding 100mg of carbon nano tube into a mixed solvent of 15ml of 1, 4-dioxane and 15ml of mesitylene, and completely performing ultrasonic dispersion;
s2: 100mg of a compound represented by the following formula [ (7-Borono-4, 5-dioxopyren-2-yl) boronic Acid ] was added to the above solvent;
s3: stirring for 75 hours at 85 ℃ under the argon atmosphere;
s4: the product was collected by centrifugation, washed with acetone, and vacuum-dried at 150 ℃ to collect the product, to obtain a positive electrode material of the present invention.
Preparing a positive pole piece and a battery:
uniformly dispersing the positive electrode material (450mg), the conductive agent Super-P (50mg) and the binder PVDF (50mg) in a solvent NMP, coating the mixture on a carbon fiber paper current collector, and coating the carbon fiber paper current collector with the positive electrode loading of 21mg/cm2Then vacuum drying to prepare a positive electrode film; separating the positive electrode film and the negative electrode material (polished metal magnesium) by Celgard 3000 diaphragm, and injecting electrolyte 0.25M Mg (HMDS)2THF, assembling to obtain the magnesium secondary battery.
Example 2
Preparing a positive electrode material:
s1: adding 100mg of carbon nano tube into a mixed solvent of 15ml of 1, 4-dioxane and 15ml of mesitylene, and completely performing ultrasonic dispersion;
s2: adding 100mg of Pyrene-4,5-dione (Pyrene-4,5-dione) represented by the following formula into the above solvent;
s3: stirring for 75 hours at 85 ℃ under the argon atmosphere;
s4: the product was collected by centrifugation, washed with acetone, and vacuum-dried at 150 ℃ to collect the product, to obtain a positive electrode material of the present invention.
Preparing a positive pole piece and a battery:
uniformly dispersing the positive electrode material (450mg), the conductive agent Super-P (50mg) and the binder PVDF (50mg) in a solvent NMP, coating the mixture on a carbon fiber paper current collector, and coating the carbon fiber paper current collector with the positive electrode loading of 21mg/cm2Then vacuum drying to prepare a positive electrode film; separating the positive electrode film and the negative electrode material (polished metal magnesium) by Celgard 3000 diaphragm, and injecting electrolyte 0.25M Mg (HMDS)2THF, assembling to obtain the magnesium secondary battery.
Example 3
Preparing a positive electrode material:
s1: adding 100mg of carbon nano tube into a mixed solvent of 15ml of 1, 4-dioxane and 15ml of mesitylene, and completely performing ultrasonic dispersion;
s2: 100mg of a compound represented by the following formula (2,7-bis (4,4,5, 5-tetramethylol-1, 3,2-dioxaborolan-2-yl) -4,5-bis (tert-butylmethyliminox) pyrene) was added to the above solvent;
s3: stirring for 75 hours at 85 ℃ under the argon atmosphere;
s4: the product was collected by centrifugation, washed with acetone, and vacuum-dried at 150 ℃ to collect the product, to obtain a positive electrode material of the present invention.
Preparing a positive pole piece and a battery:
uniformly dispersing the positive electrode material (450mg), the conductive agent Super-P (50mg) and the binder PVDF (50mg) in a solvent NMP, coating the mixture on a carbon fiber paper current collector, and coating the carbon fiber paper current collector with the positive electrode loading of 21mg/cm2Then vacuum drying to prepare a positive electrode film; separating the positive electrode film and the negative electrode material (polished metal magnesium) by a Celgard 3000 diaphragm, and injecting electrolyte 0.25M Mg(HMDS)2THF, assembling to obtain the magnesium secondary battery.
Example 4
Preparing a positive electrode material:
s1: adding 100mg of carbon nano tube into a mixed solvent of 15ml of 1, 4-dioxane and 15ml of mesitylene, and completely performing ultrasonic dispersion;
s2: 100mg of 4, 5-bis- (t-butyldimethylsilyloxy) -pyrene (4,5-bis (tert-butyldimethylsilyloxy) -pyrene) represented by the following formula was added to the above solvent;
s3: stirring for 75 hours at 85 ℃ under the argon atmosphere;
s4: the product was collected by centrifugation, washed with acetone, and vacuum-dried at 150 ℃ to collect the product, to obtain a positive electrode material of the present invention.
Preparing a positive pole piece and a battery:
uniformly dispersing the above-mentioned cell positive electrode material (450mg), conductive agent Super-P (50mg) and binder PVDF (50mg) in solvent NMP, coating on carbon fiber paper current collector, and making positive electrode load be 21mg/cm2Then vacuum drying to prepare a positive electrode film; separating the positive electrode film and the negative electrode material (polished metal magnesium) by Celgard 3000 diaphragm, and injecting electrolyte 0.25M Mg (HMDS)2THF, assembling to obtain the magnesium secondary battery.
FIG. 2 is a graph showing cycle characteristics of the magnesium secondary batteries obtained in examples 1 to 4. As can be seen from the figure: the organic anode material has good cycling stability and gram capacity exertion performance, and has high electrode conductivity. Among them, example 1 has the best performance, and the capacity retention rate can be kept at 80% after 400 cycles, thereby showing that compared with Ca2+、Al3+The plasma multi-valence ion battery has more remarkable cycle performance advantages.
The positive electrode of the magnesium secondary batteries obtained in examples 1 to 4 was tested for conductivity, initial capacity and capacity retention rate, and the specific test results are shown in table 1.
TABLE 1
While the foregoing is directed to the preferred embodiment of the present invention, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (10)
1. The positive electrode material is characterized by having a ring-shaped three-dimensional covalent organic framework structure, and being a composite material of a two-dimensional planar macromolecular compound and a carbon nano tube or a composite material of an aromatic ring compound and the carbon nano tube.
2. The positive electrode material according to claim 1, wherein in the composite material of the two-dimensional planar macromolecular compound and the carbon nanotube, the two-dimensional planar macromolecular compound is spread on the surface of the carbon nanotube by hydrogen bonding to form a ring-shaped three-dimensional covalent organic framework structure;
and/or in the composite material of the aromatic ring compound and the carbon nano tube, the aromatic ring compounds form a two-dimensional planar compound through hydrogen bonding, and then the two-dimensional planar compound is paved on the surface of the carbon nano tube through the hydrogen bonding to form a ring-shaped three-dimensional covalent organic framework structure.
3. The positive electrode material according to claim 1, wherein the two-dimensional planar macromolecular compound has a structural fragment represented by formula I or formula II:
in formula I, R', which are identical OR different, are independently selected from alkenyl, alcohol, phenol, -OR, -C (═ O) H OR-C (═ O) R, R being selected from alkyl; n is the same or different and is independently selected from integers of 0-6; the dotted lines represent the links between the structural segments;
in the formula II, R1、R2Identical OR different, independently of one another, from the group consisting of-OH, -OR, -C (═ O) R OR-O-Si (R')3R is selected from alkyl, R' are identical or different and are independently selected from alkyl; r' and n are as defined for formula I; the dashed lines represent the bonds between the structural segments.
4. The positive electrode material according to claim 3, wherein the two-dimensional planar macromolecular compound has a structural fragment represented by formula Ia or IIa:
in the formula IIa, R1And R2Same, selected from-O-Si (CH)3)(CH3) (tert-butyl).
5. The positive electrode material according to claim 1, wherein the aromatic ring compound has a structure represented by formula III or formula IV:
in formula III, R', which are identical OR different, are independently selected from alkenyl, alcohol, phenol, -OR, -C (═ O) H OR-C (═ O) R, R being selected from alkyl; n is an integer of 0 to 6;
in the formula IV, R1、R2Identical OR different, independently of one another, from the group consisting of-OH, -OR, -C (═ O) R OR-O-Si (R')3R is selected from alkyl, R' is the same or differentAnd, independently of one another, are selected from alkyl; r' and n are as defined for formula III.
6. The positive electrode material according to claim 5, wherein the aromatic ring compound has a structure represented by formula IIIa or formula IVa:
7. the positive electrode material according to any one of claims 1 to 6, wherein the mass ratio of the two-dimensional planar macromolecular compound or aromatic ring compound to the carbon nanotube in the composite material is 1 (0.5 to 2).
8. A positive electrode sheet, characterized by comprising the positive electrode material according to any one of claims 1 to 7.
9. The positive electrode sheet according to claim 8, comprising a current collector and an active material layer on at least one surface of the current collector, the active material layer comprising the positive electrode material;
the active material layer also comprises a conductive agent and a binder; the mass ratio of the positive electrode material to the conductive agent to the adhesive is (6-9): 1-13): 1.
10. A magnesium secondary battery, characterized by comprising the positive electrode material according to any one of claims 1 to 7; alternatively, the positive electrode sheet according to claim 8 or 9 is included.
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