Electrode material based on intrinsic double-conduction heterogeneous layer coating, preparation method thereof and battery device

Abstract

The invention discloses an electrode material based on intrinsic double-conduction heterogeneous layer coating, a preparation method thereof and a battery device, and belongs to the technical field of battery electrode materials. According to the specific scheme, the electrode material comprises an electrode material base body and an intrinsic double-conduction heterogeneous layer wrapping the surface of the electrode material base body, and the intrinsic double-conduction heterogeneous layer is composed of an intrinsic double-conduction heterogeneous material with molecular-level topological design. An electron conduction phase and an ion conduction phase in the microstructure of the intrinsic double-conduction heterogeneous material form parallel transmission channels which are spatially heterogeneous and are uniformly distributed through chemical bonding. Compared with a traditional composite coating material, the intrinsic double-conduction heterogeneous layer has the advantages that the electronic conductivity is improved by 3-5 times under the same proportion, the ion diffusion coefficient is improved by 1-2 orders of magnitude, and the electrode polarization voltage is reduced by 40% or above. The method is suitable for high-energy-density lithium ion batteries and solid-state battery systems.

Description

Technical Field

[0001] The present invention belongs to the technical field of battery electrode materials, and specifically relates to an electrode material based on intrinsic dual-conducting heterogeneous layer coating, a preparation method thereof, and a battery device. Background Art

[0002] Surface coating of electrode material particles is a key strategy to improve battery energy density and cycle stability. Taking silicon-based negative electrode materials as an example, as high-capacity lithium-ion battery negative electrode materials, they have become a current research hotspot by using surface coatings to buffer the volume expansion of silicon (~300%) and improve the overall electrical conductivity and ion conductivity. However, traditional coating materials still face key challenges. Existing dual-conducting composite coatings (such as mechanical mixing systems of conductive carbon and solid electrolytes, and physical composite layers of sulfonated polyaniline and metal oxides) are only physically mixed in the electron / ion conducting phases, forming a high impedance barrier at the interface between the two phases, resulting in a cooperative transmission efficiency far lower than the theoretical value. In addition, the heterogeneous phase interface peels off due to stress concentration during the cycle, accelerating capacity decay.

[0003] The negative electrode material is the key to determining the performance of lithium batteries. Current mainstream improvement methods such as gradient coating design, metal oxide modification, and electronic / ionic conductor composite coating all have inherent limitations. The high interface impedance and uneven spatial distribution of the composite dual-conducting coating layer lead to tortuous ion diffusion paths and significant local concentration polarization, and the actual rate performance is less than 40% of the nominal value. The above defects make it difficult for existing technologies to simultaneously achieve high initial efficiency, long cycle time, and fast charging performance of batteries, which seriously restricts the practical application of various negative electrodes. Summary of the Invention

[0004] In response to the problems of interface instability, electron / ion conduction imbalance, etc. in the charge and discharge process of electrode materials, the present invention provides an electrode material based on intrinsic dual-conducting heterogeneous layer coating, its preparation method and battery device.

[0005] In order to achieve the above object, the present invention adopts the following technical solutions:

[0006] An electrode material coated with an intrinsic dual-conducting heterogeneous layer comprises an electrode material substrate and an intrinsic dual-conducting heterogeneous layer coated on the surface of the electrode material substrate. The intrinsic dual-conducting heterogeneous layer is composed of an intrinsic dual-conducting heterogeneous material with a molecular-level topological design. In the microstructure of the intrinsic dual-conducting heterogeneous material, an electron-conducting phase and an ion-conducting phase are chemically bonded to form spatially heterogeneous and uniformly distributed parallel transmission channels. Ion transport is synergistically enhanced by the conductive phase and its own pores and / or interlayer gap structure. The electron-conducting phase is a combination of one or both of a π-π conjugated skeleton and a metal d orbital network, and the ion-conducting phase is a combination of one or both of a dynamic coordination site and a dissociated functional group.

[0007] Furthermore, the mass ratio of the electrode material matrix to the intrinsic dual-conducting heterogeneous material is 1g:(5-200)mg, and the thickness of the intrinsic dual-conducting heterogeneous layer is 1-100nm.

[0008] Furthermore, the intrinsic dual-conducting heterogeneous material includes one or a combination of self-microporous polymer materials, metal-Salen based conjugated coordination polymer materials, covalent organic framework materials, and metal organic framework materials.

[0009] Furthermore, the self-microporous polymer material has ionic groups and conjugated groups, the ionic groups are one or more of sulfonic acid groups, phosphate groups, quaternary ammonium cations, and imidazolium cations, and the conjugated groups are one or more of the conjugated structural units of thiophene rings, benzene rings, and spirobifluorene derivatives; the metal-salen-based conjugated coordination polymer material is , wherein 2≤n≤1000, a three-dimensional network structure is formed by cross-linking the [M(Salen)] units through conjugated ligands, the metal center M forms an electron conduction network through d-π hybridization, and its unsaturated coordination sites participate in ion transport as dynamic coordination sites, M is at least one element selected from Ni, Fe, Mn, Co, Cu, Zn, Ti, Mo, Al, Mg, Ca, Sn, and lanthanide metals, the Salen ligand contains one of a sulfonic acid group and a phosphoric acid group; L is one of a phenanthroline and a salicylaldimine derivative, and is connected to the [M(Salen)] unit through a coordination bond; the covalent organic framework material The material comprises an ion-conducting phase and a π-π conjugated transport skeleton, wherein the ion-conducting phase includes one or more of sulfonic acid groups and phosphonic acid groups; the metal-organic framework material is formed by a metal ion M and an organic ligand K containing a nitrogen / oxygen chelate group connected by a coordination bond, and has a π-π conjugated skeleton structure and an ion-conducting phase, wherein M is at least one element selected from Ni, Fe, Mn, Co, Cu, Zn, Ti, Mo, Al, Mg, Ca, Sn, and lanthanide metals; the ion-conducting phase is a dynamic ion transport channel formed by the metal coordination site, or / and one or more of the sulfonic acid group, phosphonic acid group, carboxyl group, and quaternary ammonium salt group modified on the ligand K.

[0010] Furthermore, the preparation method of the metal organic framework material comprises the following steps:

[0011] (1) Ligand synthesis: a. Aromatic ether compounds are subjected to a halomethylation reaction to generate halomethyl derivatives; b. The halomethyl derivatives are subjected to an aldehyde reaction; c. A chelating group is introduced through a coupling reaction to synthesize an organic ligand K containing a nitrogen / oxygen chelating group; (2) MOF synthesis: a. Metal salts and organic ligands K are subjected to coordination self-assembly in a mixed solvent at a certain molar ratio, wherein the mixed solvent contains an electrolyte; b. The reaction is carried out under an inert atmosphere, and the product is separated to obtain a metal organic framework material M(K)_n·mS having a π-π conjugated skeleton and an ion conductive phase, where n is the coordination ratio of ligand K to metal ion M, ranging from 1 to 3; m is the number of solvent molecules, ranging from 1 to 3; and S is a solvent molecule.

[0012] Preferably, the method for preparing the metal organic framework material specifically comprises the following steps:

[0013] (1) Ligand synthesis:

[0014] a. halogenating one of aromatic ether compounds such as 1,4-dimethoxybenzene, 1,3-dimethoxybenzene, 1,3,5-trimethoxybenzene, and 4,4'-dimethoxybiphenyl to form a halomethyl derivative;

[0015] b. converting the halomethyl derivative into an aldehyde intermediate by Sommelet reaction;

[0016] c. introducing a substituent group into the aldehyde intermediate via a Suzuki coupling reaction to synthesize a salicylaldimine ligand K containing a nitrogen / oxygen chelating group;

[0017] (2) MOF synthesis:

[0018] a The metal salt and the organic ligand K in a molar ratio of 1: (1-3) is dissolved in a mixed solvent, the mixed solvent consisting of N, N- dimethylformamide and ethanol in a volume ratio (2-5): 1 composition, and to the mixed solvent is added or Electrolyte, wherein the volume ratio of the mixed solvent to the electrolyte is (8-12):1;

[0019] b. Separating the product under an inert atmosphere to obtain a metal-organic framework material M(K)_n·mS (n is the coordination ratio of ligand K to metal ion M, ranging from 1 to 3; m is the number of solvent molecules, ranging from 1 to 3; S is the number of solvent molecules) with a π-π conjugated skeleton and an ion-conducting phase.

[0020] Furthermore, the electrode material matrix includes positive electrode materials or negative electrode materials in secondary batteries such as lithium ion batteries, sodium ion batteries, and potassium ion batteries.

[0021] Furthermore, the lithium-ion battery positive electrode material includes lithium cobalt oxide ( ), nickel-cobalt-manganese ternary materials ( , where 0.3≤x≤0.8, 0.1≤y≤0.3, 0.1≤z≤0.4, and x+y+z=1), lithium nickel cobalt aluminum oxide ( )、Lithium Iron Phosphate( )、Lithium manganate( ), lithium-rich manganese-based materials ( , 0.3≤x≤0.7), sulfur-based composite materials (sulfur / lithium sulfide-carbon composites, sulfide polyacrylonitrile), iodine-based materials (iodine-carbon composites), metal oxides (vanadium-based oxides, manganese-based oxides), metal sulfides (iron-based sulfides, molybdenum-based sulfides, copper-based sulfides) or more; lithium-ion battery negative electrode materials include nano-silicon, silicon dioxide ( , 0.8≤x≤1.2), silicon-carbon composite materials, graphite (natural graphite, artificial graphite), hard carbon, soft carbon, lithium titanate ( ), one or more of lithium metal, lithium alloy (lithium magnesium alloy, lithium aluminum alloy); sodium ion battery positive electrode materials include layered oxides ( or , the range of x in both molecular formulas is 0.5≤x≤0.7), polyanionic compounds ( 、 , where 1.0≤x≤2.0), Prussian blue analogues ( , 0.1≤x≤1.2), sulfur-based materials (sulfur / sodium sulfide-carbon composites), metal oxides (vanadium-based oxides, cobalt-based oxides) or more; the negative electrode material of sodium ion batteries is hard carbon, soft carbon, sodium titanate ( ), tin-based materials (Sn, ), phosphorus-based materials (red phosphorus, black phosphorus), antimony-based alloy materials, sodium metal, sodium alloys; potassium ion battery positive electrode materials include layered oxides (manganese-based oxides, cobalt-based oxides), polyanionic compounds ( (1.0≤x≤2.0), K x FeSO4F (1.0≤x≤1.7)), Prussian blue analogues ( , 0.1≤x≤1.2), one or more of organic electrode materials (perylenetetracarboxylic dianhydride PTCDA), sulfur-based materials (sulfur / potassium sulfide-carbon composite); potassium ion battery negative electrode materials include graphite, soft carbon, transition metal sulfide ( 、 )、Potassium titanate( ), one or more of potassium metal and potassium alloy.

[0022] A method for preparing an electrode material coated with an intrinsic dual-conducting heterogeneous layer comprises the following steps:

[0023] Step 1: Dispersing the electrode material matrix and the intrinsic dual-conducting isomer material in a solvent and a dispersant to form a homogeneous slurry, wherein the amount of the dispersant added is 0.1-5wt% of the solvent mass, and the solid content of the slurry is 5-60wt%. The solvent includes one or more of water, ethanol, N-methylpyrrolidone, and tetrahydrofuran; the dispersant includes one or more of polyvinylpyrrolidone, sodium lauryl sulfate, and polyacrylic acid;

[0024] Step 2: Spray drying and forming, spray the slurry into the drying chamber through a centrifugal atomizer, control the centrifugal atomizer speed to 10,000-50,000 rpm, the atomizing disk porosity to 30%-60%, the atomization pressure to 0.1-0.5 MPa, the feed rate to 5-50 mL / min, and the atomized particle size to 10-100 μm; set the drying chamber inlet temperature to 80-200°C and the outlet temperature to 40-100°C, ensuring that the final mass ratio of the electrode material matrix to the intrinsic dual-conducting isomerized material is 1:(0.005-0.2);

[0025] Step 3: Post-treatment strengthening: the spray-dried product is heated to 40-400°C at 1-5°C / min under an inert atmosphere, kept warm for 1-3 hours for low-temperature heat treatment, and then chemically cross-linked or surface passivated to obtain an electrode material coated with an intrinsic dual-conducting heterogeneous layer.

[0026] A battery device comprises the electrode material coated with the intrinsic dual-conducting heterogeneous layer or the electrode material coated with the intrinsic dual-conducting heterogeneous layer prepared by the preparation method.

[0027] Compared with the prior art, the present invention has the following beneficial effects:

[0028] The electrode material based on intrinsic dual-conducting heterogeneous layer coating, its preparation method, and battery device provided by the present invention integrate the electronic conduction phase (π-π conjugated skeleton, metal d orbital network) and the ion conduction phase (dynamic coordination sites, dissociated functional groups) into a single material by chemical bonding through molecular-level topological design, forming spatially heterogeneous and uniformly distributed parallel transmission channels. In addition, the ordered pores and interlayer gap structure of the material body serve as the main path for directional ion transmission. Its low tortuosity and high uniformity significantly shorten the traditional random pore ion transmission path, and synergistically with the ion conduction phase, greatly improving the ion diffusion rate. Batteries assembled based on this electrode have high safety and long life characteristics, and have broad market application prospects in the field of battery electrode material technology. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] Figure 1Schematic diagram of the electrode material structure based on intrinsic dual-conducting heterogeneous layer coating;

[0030] Figure 2 yes Figure 1 Schematic diagram of the structural formula of the intrinsic dual-conducting heterogeneous layer;

[0031] Figure 3 This is the SEM of the Si@intrinsic dual-conductive coating layer-1 negative electrode material of Example 1 of the present invention;

[0032] Figure 4 This is the rate performance curve of the Si@intrinsic dual-conductive coating layer-1 negative electrode material of Example 1 of the present invention;

[0033] Figure 5 This is the 1C cycle curve of the Si@intrinsic dual-conductive coating layer-1 negative electrode material of Example 1 of the present invention;

[0034] Figure 6 This is the rate performance curve of the Si@intrinsic dual-conductive coating layer-2 negative electrode material of Example 2 of the present invention;

[0035] Figure 7 This is the 1C cycle curve of the Si@intrinsic dual-conductive coating layer-2 negative electrode material of Example 2 of the present invention. DETAILED DESCRIPTION

[0036] The technical solutions of the present invention will be clearly and completely described below in conjunction with the accompanying drawings and embodiments. Obviously, the described embodiments are only part of the embodiments of the invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of the present invention.

[0037] Example 1:

[0038] A method for preparing an electrode material coated with an intrinsic dual-conducting heterogeneous layer is carried out according to the following steps:

[0039] Step 1: Preparation of intrinsic biconductive isomers: 10 mmol of 1,4-dimethoxybenzene and 20 mmol of chloromethyl methyl ether were dissolved in 50 mL of dichloromethane, and 10 mL of concentrated sulfuric acid was added dropwise at 0°C. The mixture was reacted at room temperature for 12 hours to generate a chloromethylated intermediate. The intermediate was refluxed with 15 mmol of hexamethylenetetramine in toluene at 80°C for 6 hours, and an aldehyde compound was generated via a Sommelet reaction. The aldehyde compound was reacted with 5 mmol of 4-aminophenylboronic acid at 10°C. The salicylaldimine ligand K1 was prepared by Suzuki coupling reaction under catalysis. ), after three times of ethanol recrystallization and vacuum sublimation purification, HPLC purity ≥ 99.5%. 10 mmol of ligand K1 was dissolved in 50 mL of mixed solvent (DMF: ethanol: 1M = 8:3:1, volume ratio), under argon protection, stirred at 120°C for 48 hours; the product was separated by centrifugation, washed three times with DMF and ethanol in sequence, and dried in vacuo at 80°C for 24 hours to obtain red crystalline Ni-MOF-1.

[0040] Step 2: Prepare the precursor solution. Disperse 15 g of a silicon-carbon composite material (silicon content 50%) prepared by porous carbon CVD vapor phase silicon deposition and 1.5 g of Ni-MOF-1 in 100 mL of tetrahydrofuran solvent (density 0.889 g / mL). Add 0.8 g of sodium dodecyl sulfate as a dispersant and sonicate for 2 hours to form a homogeneous slurry with a solid content of 16.29 wt%.

[0041] Step 3: spray drying and forming. The slurry is passed through a centrifugal atomizer with a controlled rotation speed of 30,000 rpm and an atomizing disk aperture of 45%. The slurry is sprayed into the drying chamber at a feed rate of 25 mL / min. The atomization pressure is controlled at 0.3 MPa, the inlet air temperature is 150°C, the outlet air temperature is 70°C, and the atomized particle size D50 is 50 μm. The core-shell structure precursor powder is collected.

[0042] Step 4: Post-treatment strengthening: Place the precursor powder in a tube furnace, heat it to 300°C at 3°C / min under an argon atmosphere, and keep it at that temperature for 2 hours for low-temperature heat treatment; then immerse it in an ethanol solution containing 3 vol% KH-550 silane coupling agent for 30 minutes. After drying, the final product is obtained, which is recorded as Si@intrinsic dual-conductive coating layer-1 and can be used as a negative electrode material.

[0043] The SEM image of the Si@intrinsic dual-conductive coating layer-1 negative electrode material prepared in this embodiment is shown in FIG. Figure 3 As shown, a continuous and uniform coating layer (thickness 80±10nm) is formed on the surface of the material, and the silicon carbon core is Complete coverage with no exposed silicon particles.

[0044] The charge and discharge curves of the Si@C vs. Li half-cell assembled using the Si@intrinsic dual-conductive coating layer-1 negative electrode material at 0.1-3C rates are shown in Figure 2. Figure 4 As shown, the discharge capacity at the first cycle of 0.1C reaches 2650mAh / g, the capacity at 3C rate is 2173mAh / g, the capacity retention rate is 82%, and the polarization voltage difference is <0.12V.

[0045] The performance of the half-cell assembled with the Si@intrinsic dual-conductive coating layer-1 negative electrode material after 500 cycles at 1C is as follows: Figure 5 As shown, the capacity retention rate is 94.2% (2496.3mAh / g), the volume expansion rate is ≤110%, and the interface impedance is 55Ω·cm².

[0046] Example 2:

[0047] A method for preparing an electrode material coated with an intrinsic dual-conducting heterogeneous layer is carried out according to the following steps:

[0048] Step 1: Preparation of intrinsic biconductive isomers: 10 mmol of 3-sulfonic acid thiophene and 15 mmol of benzothiadiazole were dissolved in 50 mL of anhydrous N-methylpyrrolidone, and 0.5 mmol of azobisisobutyronitrile was added as an initiator. Under argon protection, the reaction was stirred at 80 ° C for 24 hours to generate a conjugated polymer precursor containing sulfonic acid groups, which was recorded as Then 5g of With 2g spirocyclic fluorene diamine in supercritical The product was washed with ethanol and dried under vacuum at 60°C to obtain a self-microporous polymer, which was recorded as .

[0049] Step 2: Preparation of precursor solution: 20g of nano-silicon particles and 3g of The product was dispersed in 100 ml of tetrahydrofuran (0.889 g / mL), 1.2 g of polyvinyl pyrrolidone was added as a dispersant, and ultrasonic treatment was performed for 2 h to obtain a homogeneous slurry with a solid content of 21.39 wt%.

[0050] Step 3: Spray drying and forming: the slurry is passed through a centrifugal atomizer, the speed is set to 35000 rpm, the atomizing disk opening rate is 40%, and the feed rate is sprayed into the drying chamber at 20 mL / min. The atomization pressure is controlled to be 0.35 MPa, the inlet air temperature is 170 ° C, the outlet air temperature is 75 ° C, and the atomized particle size D50 is 45 μm. The core-shell structure precursor powder is collected;

[0051] Step 4: Post-treatment strengthening: Place the precursor powder in a tube furnace, raise the temperature to 250°C at 2°C / min under an argon atmosphere, and keep it at this temperature for 3 hours for low-temperature heat treatment; then immerse it in an ethanol solution containing 3 vol% KH-550 silane coupling agent for 20 minutes. After drying, the final product is obtained, which is recorded as Si@intrinsic dual-conductive coating layer-2 and can be used as a negative electrode material.

[0052] The charge-discharge curves of the Si vs. Li half-cell assembled using the Si@intrinsic dual-conductive coating layer-2 negative electrode material at 0.1-3C rates are shown in FIG. Figure 6 As shown, the first cycle discharge capacity at 0.1C reaches 3150 mAh / g, the capacity at 3C rate is 2520 mAh / g, the capacity retention rate is 80%, and the polarization voltage difference is <0.15V.

[0053] The performance of the half-cell assembled using the Si@intrinsic dual-conductive coating layer-2 negative electrode material at 1C cycle 500 times is as follows Figure 7 As shown, the capacity retention rate is 90.4% (2847.6mAh / g), the volume expansion rate is ≤120%, and the interface impedance is 70Ω·cm².

[0054] Comparative Example 1:

[0055] Step 1: Liquid phase mixing: 10 g of nano-silicon particles with a particle size of 100-200 nm, 3 g of polyacrylic acid, and 1 g of conductive carbon black are dispersed in 100 mL of N-methylpyrrolidone, and magnetic stirring is performed for 6 h at a speed of 500 rpm to obtain a viscous slurry;

[0056] Step 2, spray drying: using the same process parameters as in Example 2 (atomization pressure 0.35 MPa, air inlet temperature 170°C, air outlet temperature 75°C, atomized particle size D50 = 45 μm), a silicon-based composite coating material Si@PAA-SP was obtained;

[0057] Si@PAA-SP prepared using the method of Comparative Example 1 was assembled with a lithium sheet into a button cell. At a 1C rate, the initial discharge capacity was 2840 mAh / g. After 100 cycles, the capacity plummeted to 1368.9 mAh / g, with a retention rate of 48.2%. At rates of 0.2C, 0.5C, 1C, and 2C, the capacity retention rates were 88%, 62%, 52%, and 35%, respectively. Complete failure occurred at 5C.

[0058] The kinetic performance test of the Si vs. Li half-cell assembled with the Si@intrinsic dual-conductive coating layer-2 negative electrode material obtained in Example 2 and the Si@PAA-SP obtained in Comparative Example 1 was performed. The results are shown in the following table:

[0059]

[0060] Test method:

[0061] Electronic conductivity: Four-probe method (GB / T 24521-2020);

[0062] Ion diffusion coefficient: constant potentiostatic intermittent titration (GITT);

[0063] Polarization voltage difference: the median voltage difference of the 0.5C charge and discharge platform.

[0064] Compared to conventional composite coating materials at the same ratio, the intrinsic dual-conducting heterogeneous layer of this invention increases electronic conductivity by 3-5 times, improves ion diffusion coefficient by 1-2 orders of magnitude, and reduces electrode polarization voltage by more than 40%. It is suitable for high-energy-density lithium-ion batteries and solid-state battery systems.

[0065] The electrode material prepared by the present invention, based on the intrinsic dual-conducting heterogeneous layer coating, significantly outperforms traditional carbon coating, polymer coating, or composite dual-conducting material coating systems in terms of cycle stability, volume expansion suppression, and interfacial dynamics. The material's performance has been significantly improved thanks to the synergistic effect of the intrinsic electronic and ion-conducting phases in the coating layer, as well as the ion-conducting phase and the bulk structure of the material. The material of the present invention combines high energy density with long cycle life, and its comprehensive performance fully meets the technical requirements for electrode materials in high-energy-density lithium-ion batteries, showing broad application prospects in electric vehicles, portable electronic devices, energy storage systems, and other fields.

[0066] In addition, it should be understood that although this specification is described in terms of implementation methods, not every implementation method contains only one independent technical solution. This narrative method of the specification is only for the sake of clarity. Those skilled in the art should regard the specification as a whole. The technical solutions in each embodiment can also be appropriately combined to form other implementation methods that can be understood by those skilled in the art.

Claims

1. An electrode material based on an intrinsic dual-conducting heterogeneous layer coating, characterized by: The invention comprises an electrode material matrix and an intrinsic dual-conducting heterogeneous layer coated on the surface of the electrode material matrix. The intrinsic dual-conducting heterogeneous layer is composed of an intrinsic dual-conducting heterogeneous material with a molecular-level topological design. In the microstructure of the intrinsic dual-conducting heterogeneous material, the electron-conducting phase and the ion-conducting phase are chemically bonded to form spatially heterogeneous and uniformly distributed parallel transmission channels. The electron-conducting phase is a combination of one or both of a π-π conjugated skeleton and a metal d orbital network, and the ion-conducting phase is a combination of one or both of a dynamic coordination site and a dissociated functional group.

2. The electrode material based on the intrinsic dual-conducting heterogeneous layer coating according to claim 1, characterized in that: The mass ratio of the electrode material matrix to the intrinsic dual-conducting heterogeneous material is 1g:(5-200)mg, and the thickness of the intrinsic dual-conducting heterogeneous layer is 1-100nm.

3. The electrode material based on the intrinsic dual-conducting heterogeneous layer coating according to claim 1, characterized in that: The intrinsic dual-conducting heterogeneous material includes one or a combination of self-microporous polymer materials, metal-Salen based conjugated coordination polymer materials, covalent organic framework materials, and metal organic framework materials.

4. The electrode material based on the intrinsic dual-conducting heterogeneous layer coating according to claim 3, characterized in that: The self-microporous polymer material has ionic groups and conjugated groups, wherein the ionic groups are one or more of sulfonic acid groups, phosphate groups, quaternary ammonium cations, and imidazolium cations, and the conjugated groups are one or more of the conjugated structural units of thiophene rings, benzene rings, and spirobifluorene derivatives; the metal-salen-based conjugated coordination polymer material is , wherein 2≤n≤1000, a three-dimensional network structure is formed by cross-linking [M(Salen)] units through conjugated ligands, the metal center M forms an electron conduction network through d-π hybridization, and its unsaturated coordination sites participate in ion transport as dynamic coordination sites, M is at least one element selected from Ni, Fe, Mn, Co, Cu, Zn, Ti, Mo, Al, Mg, Ca, Sn, and lanthanide metals, the Salen ligand contains one of a sulfonic acid group and a phosphoric acid group; L is one of a phenanthroline and a salicylaldimine derivative, and is connected to the [M(Salen)] unit through a coordination bond; the covalent organic framework material The invention comprises an ion-conducting phase and a π-π conjugated transport skeleton, wherein the ion-conducting phase includes one or more of sulfonic acid groups and phosphonic acid groups; the metal-organic framework material is formed by connecting a metal ion M and an organic ligand K containing a nitrogen / oxygen chelate group through a coordination bond, and has a π-π conjugated skeleton structure and an ion-conducting phase, wherein M is at least one element selected from Ni, Fe, Mn, Co, Cu, Zn, Ti, Mo, Al, Mg, Ca, Sn, and lanthanide metals; the ion-conducting phase is a dynamic ion transport channel formed by the metal coordination site, or / and one or more of the sulfonic acid groups, phosphonic acid groups, carboxyl groups, and quaternary ammonium salt groups modified on the ligand K.

5. The electrode material based on the intrinsic dual-conducting heterogeneous layer coating according to claim 3 or 4, characterized in that: The preparation method of the metal organic framework material comprises the following steps: (1) Ligand synthesis: a. Aromatic ether compounds are subjected to a halomethylation reaction to generate halomethyl derivatives; b. The halomethyl derivatives are subjected to an aldehyde reaction; c. A chelating group is introduced through a coupling reaction to synthesize an organic ligand K containing a nitrogen / oxygen chelating group; (2) MOF synthesis: a. Metal salts and organic ligands K are coordinated and self-assembled in a mixed solvent at a certain molar ratio, and the mixed solvent contains an electrolyte; b. The products are reacted and separated under an inert atmosphere to obtain a metal organic framework material M(K)_n·mS with a π-π conjugated skeleton and an ion conductive phase, where n is the coordination ratio of ligand K to metal ion M, ranging from 1 to 3; m is the number of solvent molecules, ranging from 1 to 3; and S is a solvent molecule.

6. The electrode material based on intrinsic dual-conducting heterogeneous layer coating according to claim 1, characterized in that: The electrode material matrix includes a positive electrode material or a negative electrode material of a lithium ion battery, a sodium ion battery or a potassium ion battery.

7. The electrode material based on the intrinsic dual-conducting heterogeneous layer coating according to claim 6, characterized in that: The positive electrode material of the lithium ion battery includes one or more of lithium cobalt oxide, nickel cobalt manganese ternary material, lithium nickel cobalt aluminum oxide, lithium iron phosphate, lithium manganese oxide, lithium-rich manganese-based material, sulfur-based composite material, iodine-based material, metal oxide, and metal sulfide; the negative electrode material of the lithium ion battery includes one or more of nano silicon, silicon oxide, silicon-carbon composite material, graphite, hard carbon, soft carbon, lithium titanate, lithium metal, and lithium alloy; the positive electrode material of the sodium ion battery includes one or more of layered oxide, polyanionic compound, Prussian blue analogue, sulfur-based material, and metal oxide; the negative electrode material of the sodium ion battery includes one or more of hard carbon, soft carbon, sodium titanate, tin-based material, phosphorus-based material, antimony-based material, sodium metal, and sodium alloy; the positive electrode material of the potassium ion battery includes one or more of layered oxide, polyanionic compound, Prussian blue analogue, organic electrode material, and sulfur-based material; the negative electrode material of the potassium ion battery includes one or more of graphite, soft carbon, transition metal sulfide, potassium titanate, potassium metal, and potassium alloy.

8. A method for preparing an electrode material coated with an intrinsic dual-conducting heterogeneous layer according to any one of claims 1 to 7, characterized in that: The following steps are involved: Step 1: Disperse the electrode material matrix and the intrinsic dual-conducting isomerized material in a solvent and a dispersant to form a homogeneous slurry with a solid content of 5-60wt%; Step 2: Spray drying and forming, spraying the slurry into the drying chamber through a centrifugal atomizer, controlling the parameters of the centrifugal atomizer to ensure that the mass ratio of the final electrode material matrix to the intrinsic dual-conducting isomer material is 1: (0.005-0.2); Step 3: Post-treatment strengthening: the spray-dried product is heated to 40-400°C at 1-5°C / min under an inert atmosphere, kept warm for 1-3 hours for low-temperature heat treatment, and then chemically cross-linked or surface passivated to obtain an electrode material coated with an intrinsic dual-conducting heterogeneous layer.

9. The preparation method according to claim 8, characterized in that: In step 1, the solvent includes one or more of water, ethanol, N-methylpyrrolidone, and tetrahydrofuran; the dispersant includes one or more of polyvinylpyrrolidone, sodium lauryl sulfate, and polyacrylic acid; in step 2, the centrifugal atomizer speed is 10,000-50,000 rpm, the atomizing disk opening rate is 30%-60%, the atomization pressure is 0.1-0.5 MPa, the feed rate is 5-50 mL / min, and the atomized particle size is 10-100 μm; the drying chamber inlet temperature is set to 80-200°C, and the outlet temperature is set to 40-100°C.

10. A battery device, characterized in that: The battery device includes the electrode material coated with an intrinsic dual-conducting heterogeneous layer according to any one of claims 1 to 7 or the electrode material coated with an intrinsic dual-conducting heterogeneous layer prepared by the preparation method according to claim 8 or 9.

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