CN110165168B - Composite cathode material and preparation method and application thereof - Google Patents
Composite cathode material and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a composite cathode material and a preparation method and application thereof, wherein the composite cathode material comprises a nanocrystalline cathode material, a rock salt defect-rich layer coated on the surface of the nanocrystalline cathode material, and a tubular graphene network structure which is used for in-situ loading of the nanocrystalline cathode material coated with the rock salt defect-rich layer on the surface and is formed by mutually connecting three-dimensional graphene tube covalent bonds; the nanocrystalline anode material has a chemical composition of LiMO2M is at least one of cobalt, manganese, nickel and ruthenium; the composition of the rock salt defect-rich layer is transition metal oxide or/and lithium salt.
Description
Technical Field
The invention relates to a composite cathode material and a preparation method and application thereof, in particular to a novel high-power application composite cathode material based on a rock-salt defect-rich layer-coated layered nanocrystal and a preparation method thereof, and belongs to the field of nanomaterials and the field of electrochemical energy storage devices.
Background
The development and breakthrough of the high-performance new energy storage material with the limited performance of the existing material are key and important supports for researching and developing next-generation high-performance energy storage devices. The electrode material for the lithium ion battery follows a bulk phase energy storage mechanism, high energy storage is realized by relying on the pseudocapacitance de-intercalation reaction of lithium ions in the electrode material crystal, and the high power characteristic of high-speed charge/discharge cannot be realized due to the limit of bulk phase diffusion rate; the future application of traction puts forward the requirement of comprehensive performance generation grade jump considering high energy storage density, high specific power, long service life, high safety and the like to an energy storage device, breaks through the existing research level and cognitive ability from the perspective of structure-activity relation of material structure-performance, develops a new electrode material microstructure and a construction/regulation technology thereof, realizes a novel energy storage/discharge mechanism based on the new structure, and is an important research direction for developing a high-performance new energy storage material breaking through the limit performance of the existing material.
LiMO of traditional lithium battery anode material2The layered material structure has large particle size reaching dozens of microns based on the requirement of electrochemical stability. The stability of the material is ensured, and the problem that the lithium ion conduction cannot be rapidly carried out due to the overlong ion diffusion length under the condition of high-rate charge and discharge cannot be solved. Taking lithium cobaltate as an example, the lithium cobaltate positive electrode material has better high-low temperature performance and rate capability, but the system is only 4.2V, because the current LiCoO2Typically only half of its theoretical capacity is utilized. Such high irreversible capacity is mainly associated with LiCoO2A series of phase changes during lithium intercalation/deintercalation. In a low voltage region, there is an insulator-metal phase transition, and when charged to 4.2V, about 50% of Li ions are extracted and the material undergoes an order-disorder transition from a hexagonal structure to a monoclinic structure, and when charged to 4.5V or more, LiCoO2Undergoes another transition from the O3 phase to the H1-3 or O6 phase. These phase transitions are reversible, but the order-disorder transition substantially reduces Li+And transition to a transition state, mechanical strain and inter/intra particle microcracks, resulting in deeply charged LiCoO2There is a significant capacity fade. Thus, LiCoO is now in phase2The charging voltage is limited to 4.2V. Upgrading LiCoO2The specific energy and specific power can be increased by the charge cut-off voltage of (2), but increasing the charge cut-off voltage gives LiCoO2The safety performance of the device brings hidden danger. To maintain LiCoO2Structural integrity and stable Electrochemical performance, various improved techniques have been developed, among which better results have been achieved by means of doping of metal elements (Mn, Ni, etc.) (Journal of the Electrochemical Society,2000,147(9):3183-s&Interfaces,2016,8(4): 2723-; nanoscale,2014,6(2): 860-; NPG Asia Materials,2014,6(9): e126.), and reacting LiCoO2The charging voltage is increased from 4.2V to 4.35V, the capacity is also increased to 165mAh/g, however, manganese has no electrochemical activity in the charging and discharging processes, and the initial discharge capacity is reduced; despite Ni2+/Ni4+The redox reaction of (2) improves charge-discharge capacity, but Ni2+The close particle radius of (r 0.069nm) and Li + (r 0.076nm) results in cation mixing and poor electrochemical performance. After primary doping, the mixture is charged to 4.4V, and the initial discharge capacity under 0.1C multiplying power is close to 180mAh g-1However, polarization is severe and cycling stability is poor; improved LiCo1-x(Ni0.5Mn0.5)xO2The series of the lithium-nickel mixed-arrangement systems has the advantages that the lithium-nickel mixed-arrangement degree is reduced along with the increase of the cobalt content, and the electrochemical performance can be improved. But unfortunately this is still well below its theoretical capacity (274 mAh/g).
Disclosure of Invention
In view of the above problems, a first object of the present invention is to provide a novel composite cathode material for high power applications, which is low in cost, excellent in electrochemical properties, and capable of mass production. The second purpose is to provide a preparation method of the novel composite cathode material which is low in cost, excellent in electrochemical performance and capable of being produced in a large scale and is oriented to high-power application. The third purpose is to provide the application of the novel composite anode material which is low in cost, excellent in electrochemical performance and capable of being produced in a large scale and faces to high-power application in the field of energy storage devices.
In one aspect, the invention provides a composite cathode material, which comprises a nanocrystalline cathode material, a rock salt defect-rich layer coated on the surface of the nanocrystalline cathode material, and a tubular graphene network structure formed by mutually connecting three-dimensional graphene tube covalent bonds and used for in-situ loading of the nanocrystalline cathode material coated with the rock salt defect-rich layer on the surface;
the nanocrystalline anode material has a chemical composition of LiMO2Laminated positive electrode materialM is at least one of cobalt, manganese, nickel and ruthenium; the composition of the rock salt defect-rich layer is transition metal oxide or/and lithium salt, preferably Li2RuO3、RuO2、Al2O3、IrO2、TiO2And at least one of MgO.
In the disclosure, a rock-salt-rich defect layer is constructed on the surface of a nanocrystalline positive electrode material (preferably, a layered nanocrystalline positive electrode material), namely, the rock-salt-rich defect layer (defect and hole structure) is provided, a core-shell structure is formed first, the rock-salt-rich defect layer is beneficial to the rapid transmission of lithium ions at an interface, and meanwhile, the rock-salt-rich defect layer can also ensure that the nanocrystalline positive electrode material is isolated from electrolyte, so that the stability of an electrode is improved. And moreover, the electrode material is compounded with the three-dimensional graphene tube, so that the electronic conductivity of the electrode material can be further improved, and the close packing structure of the anode material is improved by the tubular graphene network structure formed by the covalent bonds of the three-dimensional graphene tube through interconnection, so that the novel composite electrode material with high specific capacity, high voltage and long service life is finally obtained.
Preferably, the size of the nanocrystalline anode material is 20-200nm, and the inside of the nanocrystalline anode material has a tiny micropore open structure with the size of an atomic cluster below 1 nm.
Preferably, the thickness of the rock salt defect-rich layer is 1-10 nm.
Preferably, the number of graphene layers in the tube wall of the three-dimensional graphene tube is 1-10, the tube diameter is 50-300nm, the tube length is 1-20 μm, and the content of C in the graphene tube is more than 99 wt.%.
Preferably, the tubular graphene network structure accounts for 0.1-10% of the total mass of the composite cathode material.
In another aspect, the present invention further provides a method for preparing the composite cathode material, including:
(1) selecting at least one of transition metal oxide and lithium salt and a nanocrystalline anode material precursor as raw materials, and performing ball milling and mixing to obtain the nanocrystalline anode material coated with a rock salt defect-rich layerThe precursor of the nanocrystalline anode material is Li2CO3And a carbonate salt of M;
(2) loading a precursor of the nanocrystalline anode material rich in the rock salt defect layer in an in-situ manner in a three-dimensional graphene tube structure, and then carrying out roasting treatment at 400-1000 ℃ in a mixed atmosphere containing inert gas and hydrogen to obtain the composite anode material.
In the disclosure, a raw material (at least one of transition metal oxide and lithium salt) of a rock salt defect-rich layer and a nanocrystalline positive electrode material precursor (Li) are selected2CO3And carbonate of M) to obtain a nanocrystalline anode material precursor coated with a rock salt defect-rich layer. And uniformly mixing the graphene oxide powder with the three-dimensional graphene, and then roasting at 400-1000 ℃ in a mixed atmosphere containing inert gas and hydrogen. Firstly, in the roasting process, a rock salt defect-rich layer containing defects and a hole structure is prepared in a hydrogen partial reduction mode, and the rock salt defect-rich layer further inhibits the growth of the nanocrystalline anode material, so that the capacitance characteristic of the composite anode material is improved, and the high-rate electrochemical performance of the composite anode material is improved. Secondly, in the roasting process, the electron conductivity and the close-packed structure of the cathode material are improved by a tubular graphene network structure formed by the covalent bonds among the three-dimensional graphene tubes. Thirdly, in the sintering process, the nanocrystalline anode material is formed and simultaneously loaded in the tubular graphene network structure in situ. In conclusion, the novel composite electrode material with high specific capacity, high voltage and long service life is finally obtained.
Preferably, the ball milling mixing is wet ball milling, and the parameters include: the ball material ratio is (10-35): 1; the solvent is at least one of water, ethanol and acetone, and the mass ratio of the solvent to the raw materials is (0-1): 1; the ball milling speed is 100-10000 r/min, and the ball milling time is 0.5-12 h.
Preferably, the roasting time is 0.5-12 hours.
Preferably, the pressure of the mixed atmosphere is 0.5 to 5 atmospheres.
Preferably, the volume percentage of the inert gas and the hydrogen in the mixed atmosphere is (0.05-0.95): 1, and the inert atmosphere is at least one of argon and nitrogen.
In another aspect, the invention also provides an application of the composite anode material in the preparation of a high-power energy storage device.
Has the advantages that:
the invention discloses a novel composite anode material which is low in cost, excellent in electrochemical performance and capable of being produced in a large scale and faces to high power application and a preparation method thereof, wherein the composite anode material has electrochemical energy storage characteristics such as high specific capacity (more than or equal to 250mAh/g), high voltage (more than or equal to 4.5V), long service life (5 ten thousand cycles @ 80% DOD) and the like. Moreover, the preparation method has simple process, easily controlled process and less equipment investment, and can realize large-scale production. Can be applied to the field of energy storage devices.
Drawings
Fig. 1 is a schematic structural composition diagram of a composite cathode material prepared in the present invention;
fig. 2 shows the electrochemical properties of the lithium cobaltate nanocrystal/graphene tube composite positive electrode material prepared in example 1 and the micron-sized lithium cobaltate positive electrode material prepared in comparative example 1.
Detailed Description
The present invention is further illustrated by the following examples, which are to be understood as merely illustrative and not restrictive.
The invention provides a novel composite anode material with high specific capacity, high voltage, long service life and large-scale production and high power application, which comprises the following components: the structure of the nanocrystalline anode material is shown in fig. 1, and comprises a rock-salt defect-rich layer (the rock-salt defect-rich layer is coated on the surface of the nanocrystalline anode material formed by the nanocrystalline anode material and the rock-salt defect-rich layer) coated on the surface of the nanocrystalline anode material, and a high-conductivity tubular graphene network constructed by three-dimensional graphene tubes and used for loading the composite material in situ. The nanocrystalline anode material in the nanocrystalline anode material with the surface coated with the rock-salt defect-rich layer is a layered nanocrystalline structure with the size of 20-200nm and an extremely-small micropore open structure with the atom cluster size below 1 nm. NanocrystalThe positive electrode material may be LiMO2M is one or more of cobalt, manganese, nickel and ruthenium.
In an alternative embodiment, the main component of the rock-salt defect-rich layer is Li2RuO3、RuO2、Al2O3、IrO2、TiO2And one or more of transition metal oxides such as MgO and lithium salt, which account for 0.0001-1% of the total mass of the composite anode material. The thickness of the rock-salt defect rich layer may be 1-10 nm.
In an alternative embodiment, the three-dimensional graphene tubes are covalently bonded to each other by a highly conductive tubular graphene network. The number of graphene layers in the tube wall of the graphene tube is 1-10, the tube diameter is 50-300nm, the tube length is 1-20 mu m, and the content of C in the graphene tube is more than 99 wt.%.
In one embodiment of the invention, the preparation method of the composite cathode material based on the layered nanocrystal coated by the rock-salt-rich defect layer is simple in process, easy in process control, excellent in electrochemical performance and low in preparation cost, and is suitable for the field of energy storage devices. The following exemplarily illustrates a method for preparing the composite positive electrode material provided by the present invention.
And uniformly mixing a nanocrystalline anode material precursor and one or more of transition metal oxide and lithium salt to obtain the nanocrystalline anode material precursor coated with a rock salt defect-rich layer. Wherein, the mass ratio of the total mass of the transition metal oxide and the lithium salt to the precursor of the nanocrystalline anode material can be 1: (0.0001% -1%). The ball milling is carried out by adopting a wet method, and the ball-material ratio is (10-35): 1; the solvent added during ball milling is one or a mixture of more than two of water, ethanol, acetone and the like, and the mass ratio of the solvent to the mixed material is (0-1): 1; the ball milling speed is 100 plus 10000 r/min, and the ball milling time is 0.5-12 h.
The method comprises the following steps of loading a nanocrystalline positive electrode material precursor coated with a rock salt defect-rich layer on the surface into a three-dimensional graphene tube structure in situ, and controlling the mass ratio of the addition amount of the three-dimensional graphene tube to the composite positive electrode material to be (0.001-0.1): 1.
then, the composite anode material is roasted at high temperature under the mixed atmosphere of inert gas/hydrogen, and the defects are generated by moderate reduction in the roasting process to form the composite anode material. Wherein the inert atmosphere can be argon, nitrogen and the like. The roasting temperature can be 400-1000 ℃. The roasting time can be 0.5-12 h. The volume percentage of the inert gas and the hydrogen in the mixed atmosphere is (0.05-0.95): 1. The pressure of the mixed atmosphere can be 0.5 to 5 atmospheres during the aeration operation.
It should be noted that the nanocrystalline positive electrode material precursor in the present invention is prepared by a sol-gel method, a ball milling method, a coprecipitation method, or the like. The precursor of the nanocrystalline anode material is one or a mixture of lithium carbonate and M hydrochloride.
The present invention will be described in detail by way of examples. It is also to be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the invention, and that certain insubstantial modifications and adaptations of the invention by those skilled in the art may be made in light of the above teachings. The specific process parameters and the like of the following examples are also only one example of suitable ranges, i.e., those skilled in the art can select the appropriate ranges through the description herein, and are not limited to the specific values exemplified below.
Example 1
(1) Mixing Li2CO3(74g) With CoCO3(119g) Ball milling at Li/Co molar ratio of 1, adding small amount of Al2O3(0.18g)、RuO2(0.35g), performing wet ball milling in an ethanol solution, wherein the ball-material ratio is 25:1, the mass ratio of the solvent to the mixed material is 0.5:1, the ball milling rotation speed is 1000 revolutions per minute, and the ball milling time is 5 hours;
(2) and compounding (mixing) the composite positive electrode material with a three-dimensional graphene tube, wherein the proportion of the three-dimensional graphene tube in the composite positive electrode material is 5 wt%, the tube diameter of the graphene tube is 100nm, the tube length is 5 micrometers, the content of C is 99.0 wt%, and the average number of layers of graphene is 5. And (3) sintering the mixture for 10 hours at 600 ℃ under normal pressure in an argon atmosphere to prepare the composite cathode material (the lithium cobaltate nanocrystal/graphene tube composite cathode material). The average size of the nanocrystalline anode material in the obtained composite anode material is 150nm, and the inside of the nanocrystalline anode material has a tiny micropore structure with the atom cluster size of about 1 nm. The thickness of the rock-salt defect-rich layer is about 5nm, and the main components are aluminum oxide and ruthenium oxide. A half cell is prepared based on the obtained composite anode material, and electrochemical performance tests show that: the charging voltage can reach 4.5V, and the specific capacity of 250mAh/g is shown under the condition of 0.5C multiplying power; the battery can still maintain 84% of specific capacity at 6C rate, and shows excellent rate performance (as shown in figure 2). In addition, the battery can realize 5 ten thousand cycles under the condition that the discharge depth is 80%, and the capacity retention rate is more than 70%.
Through contrast discovery, through the size reduction with compound cathode material, promoted cathode material's capacitive characteristic, when improving cathode material's high magnification electrochemical performance, through building rock-salt defective layer on its surface, form the nucleocapsid structure, do benefit to the quick transmission of lithium ion at the interface, the interfacial layer guarantees simultaneously that cathode material keeps apart in with the electrolyte, promotes electrode stability. The composite material is compounded with the three-dimensional graphene tube, so that the electronic conductivity of the electrode material and the close-packed structure of the anode material are improved, and the improvement of high specific capacity, high voltage and long service life of the anode material is facilitated.
Example 2
(1) Mixing Li2CO3(74g)、CoCO3(95.1g) with NiCO3(23.7g) ball-milling in a Li/(Co + Ni) molar ratio of 1, wherein the molar ratio of Co to Ni was 4:1, a small amount of Li was added2RuO3(0.01g)、IrO2(0.02g) and MgO (0.03g) materials are subjected to wet ball milling in an acetone solution, the ball-material ratio is 32:1, the mass ratio of a solvent to a mixed material is 0.7:1, the ball milling rotation speed is 3000 r/min, and the ball milling time is 2 hours;
(2) and compounding the composite anode material with a three-dimensional graphene tube, wherein the proportion of the three-dimensional graphene tube in the composite anode material is 7 wt%, the diameter of the graphene tube is 200nm, the length of the graphene tube is 3 mu m, the content of C is 99.3 wt%, and the average number of graphene layers is 3. Sintering the mixture for 10 hours at 800 ℃ under 1.2 atmospheric pressures in a mixed atmosphere of 5 percent of hydrogen and argon to prepare the composite cathode material. The average size of the nanocrystalline anode material in the obtained composite anode material is 120nm, and an extremely small microporous structure with the internal atomic cluster size of about 1 nm. Wherein the thickness of the rock-salt defect-rich layer is about 3nm, and the main component is Li2RuO3、IrO2And MgO. The electrochemical performance test of the obtained composite anode material assembled half cell shows that: the charging voltage can reach 4.5V; under the condition of 0.5C multiplying power, the specific capacity of 280mAh/g is shown; the battery can still maintain 89% of specific capacity under the 6C multiplying power; the battery can realize 5 ten thousand cycles under the condition that the discharge depth is 80 percent, and the capacity retention rate is more than 75 percent.
Example 3
In example 2, Li2CO3(74g)、CoCO3(71.3g) with NiCO3(47.4g) mixing by a ball milling method according to the molar ratio of Li/(Co + Ni) of 1, wherein the molar ratio of Co to Ni is 3:2, under the condition that other preparation conditions are not changed, the average size of the nanocrystalline anode material in the prepared composite anode material is 55nm, the inside of the composite anode material has an extremely-small microporous structure with the atomic cluster size of about 1nm, the thickness of a rock-salt-rich defect layer is about 1nm, and the main component is Li2RuO3、IrO2And MgO. The obtained composite anode material is assembled into a half cell, and electrochemical performance tests show that: the charging voltage can reach 4.5V, and the specific capacity of 310mAh/g is shown under the condition of 0.5C multiplying power; the battery can still maintain 85% of specific capacity under the 6C multiplying power; the battery can realize 5 ten thousand cycles under the condition that the discharge depth is 80 percent, and the capacity retention rate is more than 80 percent.
Example 4
In example 2, Li2CO3(74g)、CoCO3(71.3g) with NiCO3(47.4g) ball milling mixing at a Li/(Co + Ni) molar ratio of 1, wherein the molar ratio of Co to Ni is 3:2, and TiO is added2(0.01g), under the condition that other preparation conditions are not changed, the average size of the nanocrystalline anode material in the prepared composite anode material is 80nm, the inside of the composite anode material has an atomic cluster scale extremely-small microporous structure of about 1nm, the thickness of the rock-salt-rich defect layer is about 2.2nm, and the main component is TiO2. The obtained composite anode material has electrochemical performance test, the charging voltage can reach 4.5V, and the composite anode material has obvious charge effect under the condition of 0.5C multiplying powerShows a specific capacity of 305 mAh/g; the assembled half-cell battery can still maintain 85% of specific capacity under 6C multiplying power; the battery can realize 5 ten thousand cycles under the condition that the discharge depth is 80 percent, and the capacity retention rate is more than 72 percent.
Comparative example 1
Mixing Li2CO3With CoCO3Mixing by a ball milling method according to the Li/Co molar ratio of 1, and carrying out wet ball milling in an ethanol solution, wherein the ball-material ratio is 25:1, the mass ratio of a solvent to a mixed material is 0.5:1, the ball milling rotating speed is 500 r/min, and the ball milling time is 5 hours. Sintering the mixture for 10 hours at 600 ℃ under the atmosphere of argon and normal pressure to prepare the cathode material with the average size of 6 mu m. Assembling the obtained anode material into a button battery, and an electrochemical performance test shows that: the charging voltage can reach 4.5V, and the specific capacity of 180mAh/g is shown under the condition of 0.5C multiplying power (shown in figure 2); under the condition that the discharge depth is 80%, only 3000 cycles can be realized, and the battery performance is seriously attenuated and even cannot work.
Comparative example 2
The preparation process of the composite cathode material obtained in the comparative example 2 is the same as that of the composite cathode material obtained in the example 1, except that: without addition of Li2RuO3、IrO2And an MgO material. Assembling the obtained composite anode material into a half cell, wherein electrochemical performance tests show that: the charging voltage can reach 4.5V, and the specific capacity of 210mAh/g is shown under the condition of 0.5C multiplying power; the battery can only maintain 72.5% of specific capacity under the 6C multiplying power, 1000 times of circulation can be realized under the condition that the discharge depth of the battery is 80%, the specific capacity of the anode material is seriously attenuated, and even the battery cannot normally work.
Comparative example 3
The preparation process of the composite cathode material obtained in the comparative example 3 is the same as that of the composite cathode material obtained in the example 1, except that: and (3) adding no graphene tube in the step (2), and directly roasting after ball milling and mixing. The obtained composite anode material is tested by electrochemical performance, the charging voltage can reach 4.5V, and the specific capacity of 235mAh/g is displayed under the condition of 0.5C multiplying power; the battery can only maintain 50% of specific capacity under the 6C rate, 5 ten thousand cycles of the battery can be realized under the condition that the discharge depth is 80%, and the capacity retention rate is only 55%.
Comparative example 4
The preparation process of the composite cathode material obtained in the comparative example 4 is the same as that of the composite cathode material obtained in the example 1, except that: adding Al2O3(3.5g)、RuO2(1.8g), the average size of the nanocrystalline positive electrode material in the obtained composite positive electrode material is 80nm, and the inside of the composite positive electrode material has an extremely-small microporous structure with the atomic cluster size of about 1 nm. Wherein the thickness of the rock-salt defect-rich layer is about 12nm, and the main components are aluminum oxide and ruthenium oxide. Electrochemical performance tests show that the composite cathode material comprises the following components: the charging voltage can reach 4.5V, and the specific capacity of 245mAh/g is shown under the condition of 0.5C multiplying power. At 6C rate, only 65% of the specific capacity can be maintained. In addition, the battery can realize 5 ten thousand cycles under the condition that the discharge depth is 80%, and the capacity retention rate is more than 45%.
Claims (11)
1. The composite cathode material is characterized by comprising a nanocrystalline cathode material, a rock salt defect-rich layer coated on the surface of the nanocrystalline cathode material, and a tubular graphene network structure which is used for in-situ loading of the nanocrystalline cathode material coated with the rock salt defect-rich layer on the surface and is formed by connecting three-dimensional graphene tube covalent bonds;
the nanocrystalline anode material has a chemical composition of LiMO2M is at least one of cobalt, manganese, nickel and ruthenium; the composition of the rock salt defect-rich layer is transition metal oxide or/and lithium salt.
2. The composite positive electrode material according to claim 1, wherein the nanocrystalline positive electrode material has a size of 20 to 200nm and has an extremely small microporous open structure with an atomic cluster size of 1nm or less inside.
3. The composite positive electrode material according to claim 1, wherein the thickness of the rock salt defect-rich layer is 1 to 10 nm.
4. The composite cathode material according to claim 1, wherein the number of graphene layers in the tube wall of the three-dimensional graphene tube is 1-10, the tube diameter is 50-300nm, the tube length is 1-20 μm, and the content of C in the graphene tube is more than 99 wt.%.
5. The composite positive electrode material according to claim 1, wherein the tubular graphene network structure accounts for 0.1-10% of the total mass of the composite positive electrode material.
6. The composite positive electrode material according to any one of claims 1 to 5, wherein the composition of the rock-salt defect-rich layer is Li2RuO3、RuO2、Al2O3、IrO2、TiO2And at least one of MgO.
7. A method for preparing a composite positive electrode material according to any one of claims 1 to 6, comprising:
(1) selecting at least one of transition metal oxide and lithium salt and a nanocrystalline anode material precursor as raw materials, and performing ball milling and mixing to obtain the nanocrystalline anode material precursor with the surface coated with a rock salt defect-rich layer, wherein the nanocrystalline anode material precursor is Li2CO3And a carbonate salt of M;
(2) and loading the precursor of the nanocrystalline anode material coated with the rock salt-rich defect layer into the three-dimensional graphene tube structure in situ, and then carrying out roasting treatment at 400-1000 ℃ in a mixed atmosphere containing inert gas and hydrogen to obtain the composite anode material.
8. The method of claim 7, wherein the ball milling mixing is wet ball milling, and the parameters include: the ball material ratio is (10-35): 1; the solvent is at least one of water, ethanol and acetone, and the mass ratio of the solvent to the raw materials is (0-1): 1; the ball milling speed is 100-10000 r/min, and the ball milling time is 0.5-12 hours.
9. The preparation method according to claim 7, wherein the roasting time is 0.5-12 hours.
10. The method according to any one of claims 7 to 9, wherein the pressure of the mixed atmosphere is 0.5 to 5 atmospheres; the volume percentage of the inert gas and the hydrogen in the mixed atmosphere is (0.05-0.95): 1, and the inert atmosphere is at least one of argon and nitrogen.
11. Use of a composite positive electrode material according to any one of claims 1 to 6 for the production of high power energy storage devices.
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