CN114242927B - 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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- CN114242927B CN114242927B CN202111580230.6A CN202111580230A CN114242927B CN 114242927 B CN114242927 B CN 114242927B CN 202111580230 A CN202111580230 A CN 202111580230A CN 114242927 B CN114242927 B CN 114242927B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/04—Construction or manufacture in general
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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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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- 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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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention discloses a positive electrode material and a magnesium secondary battery containing the positive electrode material, wherein the positive electrode material has an annular three-dimensional covalent organic framework structure, so that the positive electrode material can adapt to the volume expansion of magnesium ion deintercalation in the circulating process and is not dissolved in electrolyte; meanwhile, the COF has the semiconductor characteristic, solves the problem of poor electronic conductivity of the organic electronic material, and can be grown on the carbon nano tube to further improve the conductivity of the carbon nano tube, thereby solving the problem that the traditional small molecular material structure cannot conduct electricity and cannot exert capacity; the positive electrode material is of a frame type three-dimensional structure, so that a large amount of magnesium ions can be stored between layers; meanwhile, the anode material is also an organic crystal material, can adapt to volume expansion in the circulation process so as to adapt to the intercalation and deintercalation of magnesium ions, further improves the circulation performance of the magnesium battery, and has the excellent characteristics of high coulomb efficiency, high mass 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 increasing decrease of fossil fuel reserves represented by coal, petroleum and natural gas, chemical power sources have paid great attention to development and utilization of high-tech devices, green low-energy transportation, renewable energy sources and the like. Among the existing primary and secondary batteries, the magnesium battery has the greatest energy density and thus is widely studied and used. However, due to the high activity of magnesium metal, the reliability and safety of magnesium batteries are difficult to ensure, and in particular, large-sized power magnesium secondary batteries still have a number of potential safety hazards. Therefore, conventional toxic and low capacity lead-acid or silver-cadmium batteries are still employed in practical power sources. With the continuous emphasis on the energy, resource and environmental fields, people begin to develop novel, high-performance and low-cost green chemical power supplies while improving the existing batteries.
Magnesium secondary batteries are widely regarded as one of green chemical power sources by researchers. However, magnesium secondary batteries are still under preliminary research, and thus there are still many technical problems to be solved. The synthesis of a novel positive electrode material and the research of electrochemical performance of the novel positive electrode material in a magnesium battery system are one of important directions of the research of magnesium secondary batteries. Relative to Li + For Mg, mg 2+ Since the charge density is high and the solvation is more serious, most of positive electrode materials that can be used for lithium secondary batteries cannot be directly applied to magnesium secondary batteries. Up to now, research on embeddable materials such as inorganic transition metal oxides, sulfides, borides, NASICON-structured transition metal phosphates, and the like has been focused mainly on magnesium secondary batteries. The above-mentioned embeddable material requires a large amount of calcination during the production of the magnesium secondary battery, and thus consumes a large amount of energy.
Disclosure of Invention
In order to solve the technical problems, the invention provides an organic material serving as a magnesium secondary battery anode material (COF), which is more energy-saving and environment-friendly, has an annular covalent organic framework structure, can adapt to volume expansion of magnesium ion deintercalation in a circulating process, and is insoluble in electrolyte; meanwhile, the COF has semiconductor characteristics, and solves the problem of poor electronic conductivity of the organic electronic material. The material provided by the invention has the characteristic of a semiconductor structure, so that the material can be grown 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, so that the capacity of the material cannot be exerted; the positive electrode material is of a frame type three-dimensional structure, so that a large amount of magnesium ions can be stored between layers; in addition, the anode material is also an organic crystal material, and can adapt to volume expansion in the circulation process so as to adapt to the intercalation and deintercalation of magnesium ions, thereby improving the circulation performance of the magnesium battery. The positive electrode material also has the excellent characteristics of low capacity loss rate in a cyclic test, high coulombic efficiency, high mass specific capacity and the like.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
the invention provides a positive electrode material, which has a cyclic three-dimensional covalent organic framework structure.
According to the invention, the positive electrode material is a two-dimensional planar macromolecular compound-carbon nanotube composite material or an aromatic ring compound-carbon nanotube composite material, and the composite material has a cyclic 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 compound forms a two-dimensional planar compound through hydrogen bonding, and then 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 present invention, the two-dimensional planar macromolecular compound has, for example, a structural fragment represented by formula I or formula II:
in formula I, R', equal 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 from 0 to 6; the dashed lines represent the links between the structural fragments;
in formula II, R 1 、R 2 The same OR a different one of the above, independently of one another, from-OH, -OR, -C (=O) R OR-O-Si (R') 3 R is selected from alkyl, R' are the same or different and are independently selected from alkyl; r' and n are as defined for formula I; the broken lines represent the links between the structural fragments.
According to the invention, R' in formula I and formula II, identical or different, are selected independently of one another from C 2-6 Alkenyl, -C (=o) H or-C (=o) R, R being selected from C 1-4 Alkyl groups such as methyl, ethyl, propyl, isopropyl, tert-butyl; n is the same or different and is selected from 0, 1, 2, 3, 4 independently of each other;
in formula II, R 1 、R 2 Identical OR different, independently of one another, from the group-OR, -C (=O) R OR-O-Si (R') 3 R is selected from C 1-4 Alkyl groups such as methyl, ethyl, propyl, isopropyl, tert-butyl; r' are identical or different and are selected independently of one another from C 1-4 Alkyl groups are, 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 formula IIa, R 1 And R is 2 Is the same and is selected from-O-Si (CH) 3 )(CH 3 ) (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', equal 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 from 0 to 6;
in formula IV, R 1 、R 2 The same OR a different one of the above, independently of one another, from-OH, -OR, -C (=O) R OR-O-Si (R') 3 R is selected from alkyl, R' are the same or different and are independently selected from alkyl; r' and n are as defined for formula III.
According to the invention, R' in formula III and formula IV, identical or different, are selected independently of one another from C 2-6 Alkenyl, -C (=o) H or-C (=o) R, R being selected from C 1-4 Alkyl groups such as methyl, ethyl, propyl, isopropyl, tert-butyl; n is the same or different and is selected from 0, 1, 2, 3, 4 independently of each other;
in formula IV, R 1 、R 2 Identical OR different, independently of one another, from the group-OR, -C (=O) R OR-O-Si (R') 3 R is selected from C 1-4 Alkyl groups such as methyl, ethyl, propyl, isopropyl, tert-butyl; r' are identical or different and are selected independently of one another from C 1-4 Alkyl groups are, for example, methyl, ethyl, propyl, isopropyl, tert-butyl.
According to the invention, the aromatic ring compound has, for example, a structure represented by 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 nano tube is 1 (0.5-2), and the mass ratio is 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 electrode sheet 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 invention, the active material layer further comprises 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 exemplary examples are 6:1:1, 7:13:1, 8:7:1, 8:1:1, 8:13:1, and 9:1:1.
The invention also provides a magnesium secondary battery, which comprises the positive electrode 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, APC, mg (HMDS) may be used for the electrolyte 2 /THF、Mg(TFSI) 2 At least one of the DME systems.
The beneficial effects of the invention are as follows:
the invention provides an organic material as a magnesium secondary battery anode material, which 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, and has semiconductor characteristic, is an organic crystal, and can store a large amount of magnesium ions between layers. The positive electrode material is based on a redox enolization mechanism when magnesium ions are stored, and two carbonyl groups are on one benzene ring, so that the deintercalation of the magnesium ions is facilitated. The positive electrode material of the invention is beneficial to Mg 2+ The rapid release and the embedding in the positive electrode greatly improve the rapid charge and discharge performance of the magnesium secondary battery. The concrete steps are as follows:
(1) The magnesium secondary battery prepared from the positive electrode material provided by the invention has the mass specific capacity of 180mAh/g under the current density of 10C, has the capacity retention rate of 80% after 200 cycles, and has the advantage of no dendrite, so that the magnesium secondary battery can be used as the positive electrode material of the magnesium secondary battery for quick charge.
(2) The COF of the present invention is a semiconductor without compounding carbon nanotubes (its conductivity is 2×10 -10 S/cm or less), and the conductivity after compounding the carbon nano-tube is up to 2 multiplied by 10 -4 S/cm, thus facilitating the conduction of magnesium ions.
(3) The initial specific capacity of the positive electrode material can reach 320mAh/g, and exceeds the mass specific capacity of the current 98% of magnesium secondary battery positive electrode material.
(4) The positive electrode material of the present invention has no problem of dissolution in the electrolyte during the cycle, and thus can be cycled 400 times at a 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 a battery shell.
(6) The electrolyte of the positive electrode 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 a cathode material of example 1
Fig. 2 is a cycle performance chart of the magnesium secondary batteries manufactured in examples 1 to 4.
Detailed Description
The invention also provides a preparation method of the positive electrode 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 in a formula V and/or at least one compound shown in a formula VI into the mixed system of the step S1;
in the formula V and the formula VI, R' and n are defined as before;
R 3 、R 4 identical or different, independently of one another, from H, unsubstituted or optionally substituted by one or more R a A substituted boronic acid group; r is R a Identical or different, independently of one another, from H, C 1-6 Alkyl groups such as H, methyl, ethyl, propyl, isopropyl, tert-butyl;
in formula VI, R 1 And R is 2 Is as defined above;
s3: and stirring and reacting in an argon atmosphere to obtain the positive electrode material.
According to an exemplary embodiment of the present invention, the compound of formula V and the compound of formula VI are, for example, selected from the group consisting of
At least one of them.
According to the invention, in the step S1, the dosage ratio of the carbon nano tube to the mixed solvent is 100mg (20-40 ml), and the dosage ratio is 100 mg/20 ml, 100 mg/30 ml and 100 mg/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 exemplary mixing ratios are 1:0.5, 1:1 and 1:2.
According to the invention, the mass ratio of the carbon nano tube 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 present invention, in step S3, the temperature of the reaction is 60 to 100 ℃, illustratively 60 ℃, 70 ℃, 80 ℃,85 ℃, 90 ℃, 100 ℃; the reaction time is 60 to 80 hours, and exemplary are 60 hours, 70 hours, 75 hours and 80 hours.
According to the invention, the preparation method of the positive electrode material further comprises the following steps:
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 employ means known in the art, such as centrifugation.
According to an embodiment of the present invention, step S4 further comprises: and washing the reaction product obtained by solid-liquid separation. For example, the washing solvent may be acetone.
According to an embodiment of the invention, step S4 further comprises drying the washed reaction product. For example, the drying is performed under vacuum. For example, the drying temperature is 140 to 160 ℃, and is exemplified by 140 ℃, 150 ℃, 160 ℃.
The invention also provides application of the positive electrode material as a magnesium secondary battery positive electrode material.
The invention also provides a preparation method of the positive plate, which comprises the steps of uniformly dispersing the positive electrode material, the conductive agent and the adhesive in a solvent, coating the positive electrode material, the conductive agent and the adhesive on a current collector, and then vacuum drying the current collector to prepare the positive electrode film.
The invention also provides a preparation method of the magnesium secondary battery, which comprises the following steps: the magnesium secondary battery is obtained by separating the positive electrode plate and the negative electrode plate by a diaphragm, injecting electrolyte and assembling.
For a further understanding of the present invention, preferred embodiments of the invention are described below in conjunction with the examples, but it is to be understood that these descriptions are merely intended to illustrate further the features and advantages of the invention and are not limiting of the invention.
The invention is further illustrated by the following examples.
The testing method comprises the following steps:
conductivity test: and (3) conducting conductivity test on the surface of the positive electrode material by using a high-temperature four-probe tester HEST-800 instrument.
Battery cycle number test: after the battery is assembled, a LAND blue battery test system is used for carrying out cycle performance test under the condition of 0.3-2.4V charge-discharge voltage according to the charge-discharge current of 1C/1C.
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 dispersing by ultrasonic;
s2: 100mg of a compound [ (7-Borono-4, 5-diox-pyren-2-yl) boronic Acid ] of the formula was added to the above solvent;
s3: stirring at 85 ℃ for 75 hours under argon atmosphere;
s4: the product was collected by centrifugation, washed with acetone, and dried under vacuum at 150 ℃ to obtain the positive electrode material of the present invention.
Preparing a positive electrode plate and a battery:
uniformly dispersing the positive electrode material (450 mg), the conductive agent Super-P (50 mg) and the binder PVDF (50 mg) in a solvent NMP, coating the mixture on a carbon fiber paper current collector, and carrying 21mg/cm of positive electrode 2 Then vacuum drying to prepare an anode 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) 2 THF, assembled 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 dispersing by ultrasonic;
s2: 100mg of a compound of Pyrene-4,5-dione (Pyrene-4, 5-dione) represented by the following formula was added to the above solvent;
s3: stirring at 85 ℃ for 75 hours under argon atmosphere;
s4: the product was collected by centrifugation, washed with acetone, and dried under vacuum at 150 ℃ to obtain the positive electrode material of the present invention.
Preparing a positive electrode plate and a battery:
uniformly dispersing the positive electrode material (450 mg), the conductive agent Super-P (50 mg) and the binder PVDF (50 mg) in a solvent NMP, coating the mixture on a carbon fiber paper current collector, and carrying 21mg/cm of positive electrode 2 Then vacuum drying to prepare an anode 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) 2 THF, assembled toTo 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 dispersing by ultrasonic;
s2: 100mg of a compound (4, 5-Tetramethyl-1,3, 2-dioxabilian-2-yl) -4,5-bis (tert-butyl methyl) pyridine) represented by the following formula was added to the above solvent;
s3: stirring at 85 ℃ for 75 hours under argon atmosphere;
s4: the product was collected by centrifugation, washed with acetone, and dried under vacuum at 150 ℃ to obtain the positive electrode material of the present invention.
Preparing a positive electrode plate and a battery:
uniformly dispersing the positive electrode material (450 mg), the conductive agent Super-P (50 mg) and the binder PVDF (50 mg) in a solvent NMP, coating the mixture on a carbon fiber paper current collector, and carrying 21mg/cm of positive electrode 2 Then vacuum drying to prepare an anode 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) 2 THF, assembled 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 dispersing by ultrasonic;
s2: 100mg of a compound 4, 5-bis- (t-butyldimethylsilyloxy) -pyrene (tert-butyldimethylsilyloxy) -pyrene represented by the following formula was added to the above solvent;
s3: stirring at 85 ℃ for 75 hours under argon atmosphere;
s4: the product was collected by centrifugation, washed with acetone, and dried under vacuum at 150 ℃ to obtain the positive electrode material of the present invention.
Preparing a positive electrode plate and a battery:
uniformly dispersing the pool anode material (450 mg), the conductive agent Super-P (50 mg) and the binder PVDF (50 mg) in a solvent NMP, coating the mixture on a carbon fiber paper current collector, and carrying 21mg/cm anode 2 Then vacuum drying to prepare an anode 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) 2 THF, assembled to obtain the magnesium secondary battery.
Fig. 2 is a cycle performance chart of the magnesium secondary batteries manufactured in examples 1 to 4. As can be seen from the figures: the organic positive electrode material has good cycling stability, gram capacity performance and high electrode conductivity. Wherein the performance of example 1 was optimal, and the capacity retention rate was maintained at 80% after 400 cycles, thus showing a higher Ca content 2+ 、Al 3+ The cycle performance advantage of the plasma multivalent ion battery is more remarkable.
The positive electrode conductivities, the initial capacities, and the capacity retention rates of the magnesium secondary batteries prepared in examples 1 to 4 were tested, and specific test results are shown in table 1.
TABLE 1
While the foregoing is directed to the preferred embodiments of the present invention, it will be appreciated by those skilled in the art that various modifications and adaptations can be made without departing from the principles of the present invention, and such modifications and adaptations are intended to be comprehended within the scope of the present invention.
Claims (8)
1. The positive electrode material is characterized by having a cyclic three-dimensional covalent organic framework structure, and being a two-dimensional planar macromolecular compound-carbon nanotube composite material or an aromatic ring compound-carbon nanotube composite material;
the two-dimensional planar macromolecular compound has a structural fragment shown in a formula I or a formula II:
i is a kind of
II (II)
In formula I, R', equal 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 to 6; the dashed lines represent the links between the structural fragments;
in formula II, R 1 、R 2 The same OR a different one of the above, independently of one another, from-OH, -OR, -C (=O) R OR-O-Si (R') 3 R is selected from alkyl, R' are the same or different and are independently selected from alkyl; r' and n are as defined for formula I; the dashed lines represent the links between the structural fragments;
the aromatic ring compound has a structure shown in a formula III or a formula IV:
formula III->IV (IV)
In formula III, R', equal 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 from 0 to 6;
in formula IV, R 1 、R 2 The same OR a different one of the above, independently of one another, from-OH, -OR, -C (=O) R OR-O-Si (R') 3 R is selected from alkyl, R' are the same or different and are independently selected from alkyl; r' and n are as defined for formula III.
2. The positive electrode material according to claim 1, wherein in the composite material of the two-dimensional planar macromolecular compound and the carbon nanotubes, the two-dimensional planar macromolecular compound is laid on the surface of the carbon nanotubes through 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 compound forms a two-dimensional planar compound through hydrogen bonding, and then is paved on the surface of the carbon nano tube through hydrogen bonding to form a ring-shaped three-dimensional covalent organic framework structure.
3. The positive electrode material of claim 1, wherein the two-dimensional planar macromolecular compound has a structural fragment according to formula Ia or formula IIa:
formula Ia
IIa
In formula IIa, R 1 And R is 2 Is the same and is selected from-O-Si (CH) 3 )(CH 3 ) (tert-butyl).
4. The positive electrode material of claim 1, wherein the aromatic ring compound has a structure of formula IIIa or formula IVa:
formula IIIa->Formula IVa.
5. The positive electrode material according to any one of claims 1 to 4, wherein the mass ratio of the two-dimensional planar macromolecular compound or aromatic ring compound to the carbon nanotubes in the composite material is 1 (0.5 to 2).
6. A positive electrode sheet comprising the positive electrode material according to any one of claims 1 to 5.
7. The positive electrode sheet according to claim 6, wherein the positive electrode sheet comprises a current collector and an active material layer on at least one side surface of the current collector, the active material layer comprising the above 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.
8. A magnesium secondary battery characterized in that it comprises the positive electrode material according to any one of claims 1 to 5; alternatively, a positive electrode sheet according to claim 6 or 7 is included.
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