CN112397690A - Method for in-situ construction of surface coating layer based on metal-organic framework material - Google Patents
Method for in-situ construction of surface coating layer based on metal-organic framework material Download PDFInfo
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Abstract
The invention provides a method for constructing a surface coating layer in situ based on a metal-organic network framework material, which comprises the following steps of regulating and controlling the dynamic process of a metal-organic network framework structure: nucleation and growth promote the in-situ growth of the nano particles on the surface of the core structure, thereby achieving the purpose of constructing a uniform coating layer on the surface of the core. By adopting the method, a coating layer based on the metal-organic network framework material can be constructed on the surface of the conventional anode material, and the prepared anode material can effectively inhibit the side reaction of the electrode material and the electrolyte, slow down the generation of surface SEI, reduce the impedance of a surface film and the impedance of charge transfer and improve the reaction kinetic process of lithium ions; but also can inhibit the dissolution of transition metal ions, effectively relieve the collapse of a lattice structure in the circulation process of the electrode material and obviously improve the circulation stability and the rate capability of the anode material.
Description
Technical Field
The invention belongs to the field of lithium ion battery electrode materials, and relates to a method for constructing surface coating layers in situ on different substrates based on a metal-organic framework material.
Background
The updating speed of portable electronic equipment, transportation modes and power grids puts higher requirements on the technical development of batteries, and the development direction of lithium ion batteries is high energy density and long cycle life. High specific capacity and high operating voltage are effective measures for improving energy density. Therefore, the design and development of high specific volume and high voltage electrode materials are the focus of attention of battery material researchers.
The development of high specific energy battery materials is accompanied by a series of problems of structural stability and safety, so that new materials need to be designed to simultaneously satisfy the characteristics of high specific energy and long cycle stability. The core-shell structure composite material has important functions in the aspects of biology, catalysis, energy storage, energy conversion and the like as a special novel functional material, and the composite structure can play the role of a protective layer on the surface of the material and can endow the core material with new characteristics. The uniform coating layer construction (namely the core-shell structure composite material) on the surface of the positive electrode material can keep the specific capacity of the electrode material, and simultaneously form a physical protection barrier on the surface of the electrode material, thereby effectively inhibiting the side reaction of the electrode material and acidic substances (HF, HCl and the like) generated by the decomposition of electrolyte and slowing down the dissolution of transition metal ions. Secondly, the surface coating layer effectively slows down the conversion from a layered structure to a spinel structure to a rock salt phase structure generated by electrochemical cycle, inhibits the rapid formation of SEI on the surface of the electrode material, avoids the damage of the crystal structure of the electrode material, accelerates the transmission of lithium ions, and improves the reaction kinetics of the lithium ions. The surface coating solves the series of safety problems such as battery short circuit induced by the precipitation of oxygen in the circulation process, and plays an irreplaceable role in the commercial application of lithium ions.
Conventional coating methods include atomic layer deposition, dry powder methods, and wet chemical methods. The complex process of atomic layer deposition and the high cost-benefit characteristic of the dry powder method limit the large-scale application of the method, and the characteristics of uniform mixing, simple operation and the like of the wet chemical method are widely concerned by people. In the traditional wet chemical method, a coating precursor and a core structure are dispersed in a solvent at the same time to form turbid liquid, the coating precursor is formed on the surface of a core through adsorption force, and then the solvent is evaporated to dryness so as to form a coating layer on the surface of the core structure. However, this method has disadvantages that the thickness uniformity and continuity of the clad layer are poor and the thickness of the clad layer cannot be precisely controlled. Therefore, it is necessary to develop a method capable of achieving uniform coating instead of this method.
Disclosure of Invention
In order to remedy the disadvantages of the prior art, it is an object of the present invention to provide a method for the in situ construction of surface coating layers on different substrates based on metal-organic framework Materials (MOFs). The method utilizes a solvent atomic layer deposition method, and adjusts two kinetic processes of nucleation and growth of the coating layer through selection of solvent polarity, so that uniform and continuous growth of the coating layer on different substrates is realized, and uniform coating layers are successfully constructed. The coated electrode material prepared by the coating method can effectively inhibit side reactions between the electrode material and electrolyte, improve the interface stability of the electrode material-electrolyte, and maintain the interface electronic and ionic conductivities in the circulating process, thereby exerting the high capacity retention rate and high rate characteristics of the core-shell composite material.
The purpose of the invention is realized by the following technical scheme:
a method for in-situ construction of a surface coating based on a metal-organic network framework material, the method comprising:
(1) mixing the core particles, metal salt and metal complexing agent in a polar solvent, and reacting to prepare the coated particles with the core-shell structure, wherein the core particles are used as cores, and the metal-organic network framework material is used as a shell.
According to the invention, in the step (1), the core particles are selected from one or a mixture of several of metal materials, metal oxide materials, inorganic silicon materials, inorganic carbon materials, semiconductor materials, organic materials or anode materials.
The metal material can be one or a mixture of more of gold, silver, copper and the like, and the average particle size of the metal material is 5-100 nm.
The metal oxide material can be tin dioxide particles, titanium dioxide particles, silver oxide particles, cerium dioxide particles, cobaltosic oxide particles, cobalt oxide particles, manganese dioxide particles, manganomanganic oxide particles and the like, and the average particle size of the metal oxide material is 40-55 nm.
Wherein, the inorganic silicon material can be silicon dioxide particles with the particle size range of 300-450 nm.
The inorganic carbon material may be carbon nanotube (such as multi-walled carbon nanotube), graphene oxide, polymer carbonized bead, or the like.
The semiconductor material can be silicon (with an average particle size of 50-150nm), germanium and the like.
The organic matter can be highly polymerized organic matter, and the highly polymerized organic matter particles can be styrene spheres (with an average particle size of 400-500nm), phenolic resin spheres (with an average particle size of 200-300nm), and the like.
The positive electrode material can be lithium nickel manganese oxide, lithium cobaltate, lithium nickel oxide, lithium manganese oxide, lithium nickel manganese aluminum oxide and lithium nickel cobalt manganese oxide. Illustratively, the lithium nickel cobalt manganese oxide is, for example, LiNi0.4Co0.4Mn0.2O2、LiNi0.6Co0.2Mn0.2O2、LiNi0.8Co0.1Mn0.1O2、LiNi0.5Co0.2Mn0.3O2、LiNi0.33Co0.33Mn0.33O2And LiNi0.9Co0.05Mn0.05O2。
According to the present invention, in the step (1), the polar solvent is selected from the group consisting of methanol, absolute ethanol, propanol, isopropanol, 1, 3-propanediol, ethylene glycol, acetonitrile, acetone, N-dimethylformamide, N-dimethylacetamide, tetrahydrofuran, tetraethylene glycol, pyridine, diethyl ether, cyclohexane, hexane, octane, pentane, glacial acetic acid, cyclohexanone, methylcyclohexanone, N-methylpyrrolidone, and a mixed solvent of two or more of these solvents. For example, the solvent mixture of N, N-dimethylformamide and other solvents (such as absolute ethanol, methanol, propanol, ethylene glycol, tetrahydrofuran, etc.) is (0.5-10):1, for example, (0.5-5): 1.
According to the invention, in the step (1), the metal salt can be at least one of chloride, nitrate, sulfate, acetate, alkoxide or organic acid salt (such as oxalate) of metal; the metal is selected from any one of Al, Nb, Ta, Zr, Zn, W, La, Ti and Mg.
According to the present invention, in the step (1), the metal complexing agent may be 1, 3-phthalic acid, 1, 4-phthalic acid, 1,3, 5-isophthalic acid, naphthalenedicarboxylic acid, aminoterephthalic acid, 2-iodo-1, 4-phthalic acid, 2-bromoterephthalic acid, 2,3,5, 6-tetraiodo-1, 4-phthalic acid, 2, 5-dihydroxyterephthalic acid, biphenyl-4, 4 '-dicarboxylic acid, 4, 4' -benzene-1, 3, 5-triyltriphenylformate, 1,3, 5-tris (4-carboxyphenyl) benzene, benzene-1, 3, 5-tricarboxylic acid ester, 1,3, 5-trimethyl-2, 4, 6-tris (4-carboxyphenyl) benzene, or a mixture thereof, 4,4 '- (benzene-1, 3, 5-triyltris (ethynylethane-2, 1-diyl) benzoate, 4, 4' -nitrilotribenzoate, 2 ', 3', 5 ', 6' -tetramethylterphenyl-4, 4 '-dicarboxylic acid, pyridine-2, 6-dicarboxylic acid, biphenyl-3, 4', 5-tricarboxylic acid, 5-tetrazolylisophthalic acid, 2-biquinoline-4, 4-dicarboxylic acid, 2,4, 6-triisopiperazinoic acid-1, 3, 5-triazine, 1, 10-azobenzene-3, 30,5, 50-tetracarboxylate, 9, 10-anthracenedicarboxylate, azobenzene-3, 30,5, 50-tetracarboxylate, 5,50- (9, 10-anthracenediyl) diisobutyrate, 1, 3-bis (3, 5-dicarboxyphenylethynyl) benzene, biphenyl-3, 40, 5-tricarboxylate, 4, 40-dicarboxylide, 3, 6-bis (4-pyridyl) -1,2,4, 5-tetrazine, 1, 10-biphenyl-3, 30,5, 50-tetracarboxylate, 2, 20-bipyridine-5, 50-dicarboxylate, 4, 40-bipyridine-2, 6,20, 60-tetracarboxylate, 2-bromobenzene-1, 4-dicarboxylic acid, 4-carboxyurethane, 1, 2-dihydrocyclobutene-3, 6-dicarboxylate, 2, 5-dioxy-1, 4-phthalate, Naphthalenedicarboxylic acid ester, methyl tetraphenyl formate, nitrobiphenyl-3, 5-dicarboxylic acid, naphthalene-1, 4,5, 8-tetracarboxylic acid salt.
According to the invention, in the step (1), the metal complexing agent and the metal salt react to form the metal-organic network framework material and coat the outer surface of the core particle. The metal-organic network framework material can be calcined to prepare a cladding material with a core-shell structure or a material with a hollow structure.
According to the invention, in the step (1), the concentration of the core particles in the mixed system is 0.1g/L-100 g/L.
According to the invention, in step (1), the core particle: metal salt: the mass mol ratio of the metal coordination agent is (0.01-10g) to (0.01-20 mmol): (0.005-20mmol), further optimized as (0.01-10g): 0.1-2 mmol): (0.05-1.8 mmol).
According to the invention, in step (1), the temperature of the reaction is 60 ℃ to 160 ℃.
According to the invention, in the step (1), the reaction time is 1-72 h.
According to the present invention, in the step (1), the coating layer of the resulting coated particle has a thickness of 1 to 10nm, for example, 1nm, 2nm, 3nm, 4nm, 5nm, 6nm, 7nm, 8nm, 9nm, 10 nm.
According to the invention, the method further comprises the steps of:
(2) and (2) calcining the coated particles obtained in the step (1) at high temperature to prepare the material with the core-shell structure or the hollow structure.
According to the invention, in the step (2), the temperature of the high-temperature calcination is 400-1000 ℃.
According to the invention, in the step (2), the high-temperature calcination time is 1-20 h.
According to the invention, in the step (2), the atmosphere of the high-temperature calcination is oxygen or air.
The invention also provides a composite material with a core-shell structure, which is prepared by the following method:
(1) mixing the core particles, metal salt and metal complexing agent in a polar solvent, and reacting to prepare coated particles which take the core particles as cores and take metal-organic network framework materials as shells and have a core-shell structure;
(2) calcining the coated particles obtained in the step (1) at high temperature to prepare a material with a core-shell structure;
the core particles are selected from one or a mixture of several of metal materials, metal oxide materials, semiconductor materials, inorganic silicon materials or anode materials.
The invention also provides a composite material with a hollow structure, which is prepared by the following method:
(1) mixing the core particles, metal salt and metal complexing agent in a polar solvent, and reacting to prepare coated particles which take the core particles as cores and take metal-organic network framework materials as shells and have a core-shell structure;
(2) calcining the coated particles obtained in the step (1) at high temperature to prepare the composite material with a hollow structure;
wherein, the core particle is selected from one or a mixture of several of inorganic carbon materials and organic matters.
The invention also provides a positive electrode material which comprises the composite material with the core-shell structure, wherein the core particles are the positive electrode material.
The invention also provides a high-energy type energy storage device which takes the anode material as an electrode.
According to the present invention, the high energy type lithium storage device is a lithium ion battery or a lithium battery.
The invention has the beneficial effects that:
the invention provides a method for constructing a surface coating layer in situ based on a metal-organic network framework material, which comprises the following steps of regulating and controlling the dynamic process of a metal-organic network framework structure: nucleation and growth promote the in-situ growth of the nano particles on the surface of the core structure, thereby achieving the purpose of constructing a uniform coating layer on the surface of the core. The method has mild action conditions, simple preparation method, easy large-scale production and preparation and higher potential in the industrial application of the composite material with the core-shell structure of the cathode material.
By adopting the method, a coating layer based on the metal-organic network framework material can be constructed on the surface of the conventional anode material, and the prepared anode material can effectively inhibit the side reaction of the electrode material and the electrolyte, slow down the generation of surface SEI, reduce the impedance of a surface film and the impedance of charge transfer and improve the reaction kinetic process of lithium ions; but also can inhibit the dissolution of transition metal ions, effectively relieve the collapse of a lattice structure in the circulation process of the electrode material and obviously improve the circulation stability and the rate capability of the anode material.
Drawings
FIG. 1 is TEM and EDS images of Al-MOF structure-coated silica spheres of example 1.
FIG. 2 is a TEM image of Al-MOF structure coated tin dioxide pellets of example 2.
FIG. 3 is a TEM image of Al-MOF structure coated phenolic resin beads of example 3.
FIG. 4 is a TEM image of Al-MOF structure coated nanosized silicon spheres of example 4.
FIG. 5 is a TEM image of Al-MOF structure coated multi-walled carbon nanotubes of example 5.
FIG. 6 is LiNi after treatment of example 60.6Co0.2Mn0.2O2TEM and EDS of (a).
FIG. 7 shows LiNi before and after treatment in example 60.6Co0.2Mn0.2O2SEM analysis of images.
FIG. 8 shows LiNi before and after treatment in example 60.6Co0.2Mn0.2O2XRD spectrum of (1).
FIG. 9 shows LiNi before and after treatment in example 60.6Co0.2Mn0.2O2Cycling performance images at 0.2C magnification, 40mA/g current density.
FIG. 10 shows LiNi before and after treatment in example 60.6Co0.2Mn0.2O2Cycling performance images at 2C magnification, 400mA/g current density.
Detailed Description
The preparation method of the present invention will be described in further detail with reference to specific examples. It is to be understood that the following examples are only illustrative and explanatory of the present invention and should not be construed as limiting the scope of the present invention. All the technologies realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.
The experimental methods used in the following examples are all conventional methods unless otherwise specified; reagents, materials and the like used in the following examples are commercially available unless otherwise specified.
The invention is further illustrated by the following specific examples. The addition amounts of the organic coordination agent and the solvent can be adjusted according to actual conditions, so that controllable synthesis of the metal-organic network framework material on the coating layer of the surface (core particle) of the micro-nano particle is realized. The invention is not limited by these examples.
The transmission electron microscope used in the following examples was tested under an electron microscope model JEM-2100F and the accelerating voltage was 200 kV.
Example 1
Firstly, preparing silicon dioxide pellets (SiO) coated with Al-MOF structure2)
Mixing 100mg of SiO2Dispersing the small balls, 166mg of aluminum sulfate octadecahydrate and 75mg of isophthalic acid into 15ml of N, N-dimethylformamide solution and 5ml of absolute ethanol solution, and performing ultrasonic treatment and uniform dispersion; and carrying out reflux reaction at 80 ℃ for 24h, and centrifuging, washing and drying to obtain the silica with the core-shell structure based on the Al-MOF structure coating.
Secondly, carrying out structural and morphological characterization on the processed material
The silica coated based on Al-MOF structure prepared in the above scheme has a typical core-shell structure, and its transmission electron microscope is shown in FIG. 1. The core material is silica spheres with an average particle size of 414nm, the shell material is an Al-MOF structure with a thickness of 30nm, and the Al-MOF is uniformly distributed on the surface of the silica.
Example 2
Firstly, preparing tin dioxide pellets (SnO) coated with Al-MOF structure2)
Will 100mg SnO2Dispersing small balls (the average particle size is 50nm), 166mg of aluminum sulfate octadecahydrate and 75mg of isophthalic acid into 15ml of N, N-dimethylformamide solution and 5ml of absolute ethanol solution, and performing ultrasonic treatment and uniform dispersion; and carrying out reflux reaction at 80 ℃ for 24h, and centrifuging, washing and drying to obtain the tin dioxide coated on the basis of the Al-MOF structure and having the core-shell structure.
Secondly, carrying out structural and morphological characterization on the processed material
The tin dioxide coated based on the Al-MOF structure prepared in the scheme has a typical core-shell structure, and a transmission electron microscope of the tin dioxide is shown in FIG. 2. The core material is tin dioxide spheres with the average particle diameter of 50nm, the shell material is an Al-MOF structure with the thickness of 15nm, and the Al-MOF is uniformly distributed on the surface of the tin dioxide.
Example 3
Firstly, preparing phenolic resin balls (Carbon Spheres) coated with Al-MOF structures
Dispersing 30mg of phenolic resin balls, 44mg of aluminum sulfate octadecahydrate and 20mg of isophthalic acid into a mixed solution of 15ml of N, N-dimethylformamide solution and 5ml of absolute ethyl alcohol, and carrying out ultrasonic treatment and uniform dispersion; and carrying out reflux reaction at 80 ℃ for 24h, and centrifuging, washing and drying to obtain the phenolic resin ball with the core-shell structure based on the Al-MOF structure coating.
Secondly, carrying out structural and morphological characterization on the processed material
The phenolic resin spheres coated based on the Al-MOF structure prepared in the scheme have a typical core-shell structure, and a transmission electron microscope of the phenolic resin spheres is shown in FIG. 3. The core material is phenolic resin carbon spheres with the particle size of 200nm, the shell material is an Al-MOF structure with the thickness of 8nm, and the Al-MOF is uniformly distributed on the surfaces of the phenolic resin carbon spheres.
Example 4
Firstly, preparing silicon pellets (Si) coated with Al-MOF structure
Dispersing 50mg of Si balls (the average particle size is 110nm), 166mg of aluminum sulfate octadecahydrate and 75mg of isophthalic acid into 15ml of N, N-dimethylformamide solution and 5ml of absolute ethanol solution, and performing ultrasonic treatment and uniform dispersion; and carrying out reflux reaction at 80 ℃ for 24h, and centrifuging, washing and drying to obtain the silicon with the Al-MOF structure coated and the core-shell structure.
Secondly, carrying out structural and morphological characterization on the processed material
The Al-MOF structure-based coated silicon spheres prepared in the above scheme have a typical core-shell structure, and a transmission electron microscope thereof is shown in FIG. 4. The core material is silicon globule with the particle diameter of 110nm, the shell material is Al-MOF structure with the thickness of 10nm, and the Al-MOF is uniformly distributed on the surface of the silicon nano-particle.
Example 5
First, preparing Al-MOF structure coated carbon nano-tube (CNT)
Dispersing 50mg of multi-walled Carbon Nanotubes (CNT), 166mg of aluminum sulfate octadecahydrate and 75mg of isophthalic acid into 15ml of N, N-dimethylformamide solution and 5ml of absolute ethanol solution, and performing ultrasonic treatment and uniform dispersion; and carrying out reflux reaction at 80 ℃ for 24h, and centrifuging, washing and drying to obtain the Al-MOF structure-coated multi-wall carbon nano tube with the core-shell structure.
Secondly, carrying out structural and morphological characterization on the processed material
The Al-MOF structure-based coated multi-walled carbon nanotubes prepared in the above scheme have a typical core-shell structure, and a transmission electron microscope thereof is shown in FIG. 5. The core material is a multi-wall carbon nano tube with the average diameter of 50nm, the shell material is an Al-MOF structure with the thickness of 3nm, and the Al-MOF structure is uniformly distributed on the surface of the multi-wall carbon nano tube.
Example 6
Firstly, preparing aluminum oxide coated high nickel ternary positive electrode composite material LiNi0.6Co0.2Mn0.2O2
500mg of high nickel ternary positive electrode composite material (LiNi)0.6Co0.2Mn0.2O2Marked as NCM622), 11mg of aluminum sulfate octadecahydrate and 5mg of isophthalic acid are dispersed into 15ml of N, N-dimethylformamide solution and 5ml of absolute ethanol solution, and the ultrasonic treatment and the uniform dispersion are carried out; carrying out reflux reaction for 24h at 80 ℃, centrifuging, washing and drying to obtain the Al-MOF structure coated high-nickel ternary positive electrode composite material LiNi0.6Co0.2Mn0.2O2。
Calcining the prepared core-shell structure composite material for 2 hours at the high temperature of 700 ℃ to prepare the aluminum oxide coated high-nickel ternary cathode composite material LiNi0.6Co0.2Mn0.2O2(denoted as Al @ NCM 622).
Secondly, preparing the electrode of the alumina coated high nickel ternary anode composite material
Uniformly mixing and coating the prepared alumina-coated high-nickel ternary positive electrode composite material Al @ NCM622, conductive additive acetylene black (Super P) and binder (PVDF) on a current collector aluminum foil according to the mass ratio of 8:1:1, placing the current collector aluminum foil on a vacuum drying oven at 80 ℃ for drying for 12 hours, and finally filling the dried electrode with sheets.
Assembly of button cell
Taking the prepared aluminum oxide-coated ternary cathode composite material electrode as a cathode and a lithium sheet as a cathode, and placing the cathode in a glove box (O) protected by argon atmosphere2<0.01ppm，H2O<0.01ppm) were assembled to obtain a coin cell. Electrolyte selection LiPF6(concentration is 1M) and the solvent ratio is DMC: DEC: MC: 1:1: 1. Fourth, battery test
Constant current charging and discharging are carried out by a Wuhan blue electricity system, the voltage interval of charging and discharging is 3-4.5V, and the testing temperature is 25 ℃ of constant temperature. The active material and specific capacity of the battery are high nickel ternary positive electrode material (LiNi)0.6Co0.2Mn0.2O2) And (4) calculating.
Comparative example 1
The other example is the same as example 6 except that step one is omitted and the alumina-coated high nickel ternary positive electrode composite material of example 6 is replaced with equal mass of NCM 622.
FIG. 6 is LiNi after treatment of example 60.6Co0.2Mn0.2O2TEM and EDS of (a). FIG. 7 shows LiNi before and after treatment in example 60.6Co0.2Mn0.2O2SEM analysis of images. FIG. 8 shows LiNi before and after treatment in example 60.6Co0.2Mn0.2O2XRD spectrum of (1).
As can be seen from fig. 6 to 8, the electrode material still maintains a layered structure after being coated, and has good crystallinity, and structural damage is not generated to the electrode material. The shape of the coated material and the size of the particles are unchanged compared to the uncoated electrode material.
FIG. 9 shows LiNi before and after treatment in example 60.6Co0.2Mn0.2O2Cycling performance images at 0.2C magnification, 40mA/g current density. FIG. 10 shows LiNi before and after treatment in example 60.6Co0.2Mn0.2O2Cycling performance images at 2C magnification, 400mA/g current density.
From fig. 9-10, it can be seen that the specific capacity of the high nickel ternary material after coating treatment is not substantially changed at low current density (40mA/g) and high current density (400mA/g), and the high nickel ternary material shows superior cycling stability compared with the untreated material.
The above results show that: the coating of the electrode material does not generate important damage to the crystal structure and the appearance, namely, the lossless coating of the electrode material can be realized. The coated electrode material shows electrochemical performance superior to that of an untreated material in the processes of low-current and high-current charge and discharge. The improvement of the electrochemical performance is attributed to the fact that the protective layer on the surface of the electrode material reduces the interface side reaction of the electrolyte and the anode material, inhibits the rapid increase of impedance, and improves the kinetic process of lithium ions.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A method for in-situ construction of a surface coating based on a metal-organic network framework material, wherein the method comprises:
(1) mixing the core particles, metal salt and metal complexing agent in a polar solvent, and reacting to prepare the coated particles with the core-shell structure, wherein the core particles are used as cores, and the metal-organic network framework material is used as a shell.
2. The method according to claim 1, wherein in the step (1), the core particles are selected from one or more of a metal material, a metal oxide material, an inorganic silicon material, an inorganic carbon material, a semiconductor material, an organic material or a positive electrode material.
Preferably, the metal material can be one or a mixture of several of gold, silver, copper and the like, and the average particle size of the metal material is 5-100 nm.
Preferably, the metal oxide material may be tin dioxide particles, titanium dioxide particles, silver oxide particles, cerium dioxide particles, tricobalt tetraoxide particles, cobalt oxide particles, manganese dioxide particles, trimanganese tetraoxide particles, etc., and the metal oxide material has an average particle size of 40-55 nm.
Preferably, the inorganic silicon material can be silica particles with an average particle size of 300-450 nm.
Preferably, the inorganic carbon material may be carbon nanotubes (e.g., multi-walled carbon nanotubes), graphene oxide, polymer carbonized beads, and the like.
Preferably, the semiconductor material can be silicon (with an average particle size of 50-150nm), germanium, and the like.
Preferably, the organic matter can be a highly polymerized organic matter, and the highly polymerized organic matter particles can be styrene beads (with an average particle size of 400-500nm), phenolic resin beads (with an average particle size of 200-300nm), and the like.
Preferably, the positive electrode material may be lithium nickel manganese oxide, lithium cobaltate, lithium nickel oxide, lithium manganese oxide, lithium nickel manganese aluminum oxide, or lithium nickel manganese oxide. Illustratively, the lithium nickel cobalt manganese oxide is, for example, LiNi0.4Co0.4Mn0.2O2、LiNi0.6Co0.2Mn0.2O2、LiNi0.8Co0.1Mn0.1O2、LiNi0.5Co0.2Mn0.3O2、LiNi0.33Co0.33Mn0.33O2And LiNi0.9Co0.05Mn0.05O2。
3. The process according to claim 1 or 2, wherein in the step (1), the polar solvent is selected from the group consisting of methanol, absolute ethanol, propanol, isopropanol, 1, 3-propanediol, ethylene glycol, acetonitrile, acetone, N-dimethylformamide, N-dimethylacetamide, tetrahydrofuran, tetraethylene glycol, pyridine, diethyl ether, cyclohexane, hexane, octane, pentane, glacial acetic acid, cyclohexanone, methylcyclohexanone, N-methylpyrrolidone, and a mixed solvent of two or more of these solvents. For example, the solvent mixture of N, N-dimethylformamide and other solvents (such as absolute ethanol, methanol, propanol, ethylene glycol, tetrahydrofuran, etc.) is (0.5-10):1, for example, (0.5-5): 1.
Preferably, in the step (1), the metal salt may be at least one of a chloride, nitrate, sulfate, acetate, alkoxide or organic acid salt (e.g. oxalate) of the metal; the metal is selected from any one of Al, Nb, Ta, Zr, Zn, W, La, Ti and Mg.
Preferably, in the step (1), the metal complexing agent may be 1, 3-phthalic acid, 1, 4-phthalic acid, 1,3, 5-isophthalic acid, naphthalenedicarboxylic acid, aminoterephthalic acid, 2-iodo-1, 4-phthalic acid, 2-bromoterephthalic acid, 2,3,5, 6-tetraiodo-1, 4-phthalic acid, 2, 5-dihydroxyterephthalic acid, biphenyl-4, 4 '-dicarboxylic acid, 4, 4' -benzene-1, 3, 5-triyltriphenylate, 1,3, 5-tris (4-carboxyphenyl) benzene, benzene-1, 3, 5-tricarboxylic acid ester, 1,3, 5-trimethyl-2, 4, 6-tris (4-carboxyphenyl) benzene, benzene-1, 3, 5-tricarboxylic acid ester, 4,4 '- (benzene-1, 3, 5-triyltris (ethynylethane-2, 1-diyl) benzoate, 4, 4' -nitrilotribenzoate, 2 ', 3', 5 ', 6' -tetramethylterphenyl-4, 4 '-dicarboxylic acid, pyridine-2, 6-dicarboxylic acid, biphenyl-3, 4', 5-tricarboxylic acid, 5-tetrazolylisophthalic acid, 2-biquinoline-4, 4-dicarboxylic acid, 2,4, 6-triisopiperazinoic acid-1, 3, 5-triazine, 1, 10-azobenzene-3, 30,5, 50-tetracarboxylate, 9, 10-anthracenedicarboxylate, azobenzene-3, 30,5, 50-tetracarboxylate, 5,50- (9, 10-anthracenediyl) diisobutyrate, 1, 3-bis (3, 5-dicarboxyphenylethynyl) benzene, biphenyl-3, 40, 5-tricarboxylate, 4, 40-dicarboxylide, 3, 6-bis (4-pyridyl) -1,2,4, 5-tetrazine, 1, 10-biphenyl-3, 30,5, 50-tetracarboxylate, 2, 20-bipyridine-5, 50-dicarboxylate, 4, 40-bipyridine-2, 6,20, 60-tetracarboxylate, 2-bromobenzene-1, 4-dicarboxylic acid, 4-carboxyurethane, 1, 2-dihydrocyclobutene-3, 6-dicarboxylate, 2, 5-dioxy-1, 4-phthalate, Naphthalenedicarboxylic acid ester, methyl tetraphenyl formate, nitrobiphenyl-3, 5-dicarboxylic acid, naphthalene-1, 4,5, 8-tetracarboxylic acid salt.
4. The method according to any one of claims 1 to 3, wherein, in the step (1), the concentration of the core particles in the mixed system is from 0.1g/L to 100 g/L.
Preferably, in step (1), the core particle: metal salt: the mass mol ratio of the metal coordination agent is (0.01-10g) to (0.01-20 mmol): (0.005-20mmol), further optimized as (0.01-10g): 0.1-2 mmol): (0.05-1.8 mmol).
Preferably, in step (1), the temperature of the reaction is 60 ℃ to 160 ℃.
Preferably, in the step (1), the reaction time is 1-72 h.
Preferably, in the step (1), the coating layer of the coated particle obtained is 1 to 10nm thick.
5. The method according to any one of claims 1-4, wherein the method further comprises the step of:
(2) and (2) calcining the coated particles obtained in the step (1) at high temperature to prepare the material with the core-shell structure or the hollow structure.
6. The process according to any one of claims 1 to 5, wherein the high-temperature calcination in step (2) is carried out at a temperature of 400 ℃ to 1000 ℃.
Preferably, in the step (2), the high-temperature calcination time is 1-20 h.
Preferably, in the step (2), the atmosphere of the high-temperature calcination is oxygen or air.
7. A composite material with a core-shell structure is prepared by the following steps:
(1) mixing the core particles, metal salt and metal complexing agent in a polar solvent, and reacting to prepare coated particles which take the core particles as cores and take metal-organic network framework materials as shells and have a core-shell structure;
(2) calcining the coated particles obtained in the step (1) at high temperature to prepare a material with a core-shell structure;
the core particles are selected from one or a mixture of several of metal materials, metal oxide materials, semiconductor materials, inorganic silicon materials or anode materials.
8. A composite material with a hollow structure is prepared by the following method:
(1) mixing the core particles, metal salt and metal complexing agent in a polar solvent, and reacting to prepare coated particles which take the core particles as cores and take metal-organic network framework materials as shells and have a core-shell structure;
(2) calcining the coated particles obtained in the step (1) at high temperature to prepare the composite material with a hollow structure;
wherein, the core particle is selected from one or a mixture of several of inorganic carbon materials and organic matters.
9. A positive electrode material comprising the core-shell structured composite material according to claim 7, wherein the core particle is a positive electrode material.
10. A high energy type energy storage device, which is a high energy type energy storage device having the positive electrode material according to claim 9 as an electrode.
Preferably, the high energy type lithium storage device is a lithium ion battery or a lithium battery.
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