CN113314705A - In-situ oxidation growth flower-shaped structure TiO2Preparation method of/MXene/hard carbon sodium ion battery negative electrode material - Google Patents
In-situ oxidation growth flower-shaped structure TiO2Preparation method of/MXene/hard carbon sodium ion battery negative electrode material Download PDFInfo
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- 229910021385 hard carbon Inorganic materials 0.000 title claims abstract description 67
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 31
- 239000007773 negative electrode material Substances 0.000 title claims abstract description 19
- 238000000034 method Methods 0.000 title claims abstract description 18
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 17
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 17
- 230000003647 oxidation Effects 0.000 title claims abstract description 16
- GWBWGPRZOYDADH-UHFFFAOYSA-N [C].[Na] Chemical compound [C].[Na] GWBWGPRZOYDADH-UHFFFAOYSA-N 0.000 title claims abstract description 12
- 235000002017 Zea mays subsp mays Nutrition 0.000 claims abstract description 53
- 241000482268 Zea mays subsp. mays Species 0.000 claims abstract description 53
- 238000000498 ball milling Methods 0.000 claims abstract description 34
- 239000002131 composite material Substances 0.000 claims abstract description 24
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims abstract description 19
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000010438 heat treatment Methods 0.000 claims abstract description 18
- 239000012298 atmosphere Substances 0.000 claims abstract description 15
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000002360 preparation method Methods 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 7
- 238000000227 grinding Methods 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 238000007873 sieving Methods 0.000 claims abstract description 6
- 230000008569 process Effects 0.000 claims description 10
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 5
- 239000012300 argon atmosphere Substances 0.000 claims description 5
- 239000011324 bead Substances 0.000 claims description 5
- 239000003575 carbonaceous material Substances 0.000 claims description 5
- 238000003763 carbonization Methods 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 230000006641 stabilisation Effects 0.000 claims description 5
- 238000011105 stabilization Methods 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 239000010406 cathode material Substances 0.000 claims 1
- 239000012299 nitrogen atmosphere Substances 0.000 claims 1
- 239000002073 nanorod Substances 0.000 abstract description 8
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 7
- 229910052708 sodium Inorganic materials 0.000 abstract description 7
- 239000011734 sodium Substances 0.000 abstract description 7
- 238000003860 storage Methods 0.000 abstract description 4
- 230000009471 action Effects 0.000 abstract description 2
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- 229910001416 lithium ion Inorganic materials 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
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- 239000010431 corundum Substances 0.000 description 3
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- 229910052744 lithium Inorganic materials 0.000 description 3
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention belongs to the technical field of sodium ion batteries, and particularly relates to in-situ oxidation growth of flower-shaped TiO2A preparation method of a negative electrode material of a/MXene/hard carbon sodium ion battery. The method comprises the following steps: (1) heating the popcorn to 230-280 ℃ in the air atmosphere for pre-oxidation treatment; (2) placing the preoxidized popcorn into an atmosphere furnace, and carbonizing at 800-1400 ℃ for 2-3 h to obtain popcorn hard carbon; (3) grinding and sieving the popcorn hard carbon to obtain hard carbon powder with the grain diameter of less than 48 mu m; (4) and mixing the sieved hard carbon powder with a plurality of layers of MXene, and carrying out ball milling by using water as a solvent in an air environment. Generated by collision of ball-milling beadsUnder the action of huge energy, the multiple layers of MXene are peeled off and simultaneously react with air to generate TiO through in-situ oxidation2Nanorods to form flower-like structures of TiO2the/MXene/hard carbon composite material is a sodium ion battery negative electrode material. The invention forms a unique flower-shaped structure through ball milling regulation and control, and increases the sodium storage performance of the material. The composite material is used as the cathode of the room-temperature sodium ion battery, can effectively improve the specific capacity of the battery, and enhances the cycle performance. Meanwhile, the method is simple and easy to operate, has no pollution to the environment, and is suitable for popularization and application.
Description
The invention belongs to the technical field of sodium ion batteries, and particularly relates to in-situ oxidation growth of flower-shaped TiO2A preparation method of a negative electrode material of a/MXene/hard carbon sodium ion battery.
Background
With the exhaustion of non-renewable energy sources such as fossil fuels and the increasing severity of environmental pollution, energy and environmental problems have become significant. Currently, the main energy storage device in the field of secondary batteries is a lithium ion battery. However, due to the increasing demand for electronic devices and electric vehicles, the uneven distribution and increasing price of lithium limit further applications of lithium. In this case, large-scale energy storage using a sodium substitution mechanism with higher abundance is one of the main approaches to solve the problems of environment, resources, and energy. Although lithium ion batteries and sodium ion batteries have similarities in electrochemical mechanisms, the search for suitable electrode materials, particularly negative electrode materials, remains challenging due to the differences in the chemical properties of lithium and sodium.
Carbon is one of the most attractive anode materials due to its abundant reserves, unique structure and electronic properties. Graphite negative electrodes, which are commonly used in lithium ion batteries, show very poor electrochemical performance in sodium ion batteries, because Na+Radius ratio Li+Large radius of Na+It is difficult to efficiently de-intercalate in the graphite material. In contrast, hard carbon does not graphitize completely at high temperature, and the internal structure has larger free space, so that it is the preferred material for the negative electrode of the sodium-ion battery. However, for pure hard carbon, how to improve the capacity and the first coulombic efficiency has been a non-negligible problem.
In this context, this bookThe invention takes popcorn hard carbon and multilayer MXene as raw materials, and constructs TiO with a unique flower-shaped structure in the air atmosphere by a wet ball milling method2a/MXene/hard carbon composite. Due to the excellent conductivity of MXene, the MXene can provide a certain capacity and also can replace a conductive agent in a traditional electrode material, so that the conductivity is improved without adding a conductive material in the process of preparing the electrode. In the ball milling process, multiple layers of MXene are stripped under the action of shearing force, and simultaneously are influenced by huge energy generated by collision of ball milling beads to react with air, and TiO grows in situ through oxidation between the layers2And (4) nanorods. In-situ oxidatively grown TiO2The nanorod can effectively prevent the MXene lamella from being re-stacked, and meanwhile, the lamella structure of the MXene can also prevent TiO2Aggregation of nanorods. This structure can provide more active sites and ion transmission channels, thereby further improving the capacity of the material.
The invention takes rice with low cost and rich raw materials as a precursor, and prepares the popcorn with a fluffy and porous structure by a traditional desk type hand-operated popcorn machine. Firstly, the multilayer MXene and the popcorn hard carbon are regulated and controlled by a ball milling method, and the MXene is stripped and oxidized in the ball milling process, thereby forming unique TiO2The structure of/MXene flower. On flower-like TiO2Under the synergistic effect of/MXene and popcorn hard carbon, the specific capacity and rate capability of the sodium-ion battery are greatly improved. The test proves that the MXene/popcorn hard carbon composite material with the flower-like structure has high reversible sodium electric specific capacity. The invention aims to regulate and control multilayer MXene by ball milling to form flower-shaped TiO with multiple active sites and ion channels2/MXene in flower-like TiO2The storage performance of the sodium-ion battery is improved under the synergistic effect of/MXene and hard carbon.
Disclosure of Invention
To achieve these objects and other advantages in accordance with the purpose of the invention, an in situ oxidation grown flower-like structure TiO is provided2The preparation method of the/MXene/hard carbon sodium ion battery negative electrode material comprises the following steps:
firstly, carrying out thermal stabilization treatment on popcorn by a proper process under normal pressure to obtain preoxidized popcorn;
step two, carrying out high-temperature carbonization on the preoxidized popcorn in an atmosphere furnace, and obtaining a popcorn hard carbon material after natural cooling;
grinding and sieving the popcorn hard carbon to obtain popcorn hard carbon powder with the grain diameter of less than 48 mu m;
step four, mixing the sieved hard carbon powder with multiple layers of MXene, and performing ball milling in an air environment by using water as a solvent to obtain TiO with a flower-like structure2the/MXene/hard carbon composite material is a sodium ion battery negative electrode material.
Preferably, in the first step, pre-oxidation is carried out in an air atmosphere, the temperature is increased to 230-280 ℃ at the speed of 3-10 ℃/min, and the temperature is kept for 6-9 h; carbonizing in an argon atmosphere, heating to 800-1000 ℃ at the speed of 1-5 ℃/min, and preserving heat for 2-5 h; continuously heating to 1200-1400 ℃ at a speed of 1-3 ℃/min on the basis of 1000 ℃, and preserving heat for 2-5 h.
Preferably, in the third step, the filtered sieve is 300-500 meshes.
Preferably, in the fourth step, a planetary ball mill is adopted to mix the hard carbon particles with MXene, the ball milling is carried out in the air atmosphere, the ball milling rotating speed is 300-600 rpm, the ball milling time is 7-16 h, the ratio of the MXene to the popcorn hard carbon is 1: 2-4, the ratio of the MXene/popcorn hard carbon composite material to the ball milling beads is 1: 10-20, and the ratio of the MXene/popcorn hard carbon composite material to the water is 1: 10-15.
The invention at least comprises the following beneficial effects:
1. the popcorn made of rice is used as the precursor of the biomass hard carbon, and the biomass hard carbon has the characteristics of low cost, greenness and safety, and in addition, the material also has a fluffy thin-walled porous structure which can still be stored after high-temperature carbonization.
2. The MXene used in the material is multi-layer MXene which is not commonly used in the aspect of electrochemistry, and compared with single-layer MXene, the MXene has the characteristics of easiness in preparation, high yield and the like. Due to the huge energy generated by the collision of the high-speed shearing force of the ball milling and the ball milling beads, the multiple layers of MXene are stripped in the ball milling process.
3. The method is used for ball milling under the condition of air, and the stripped multilayer MXene reacts with the air to be oxidized in situ to generate TiO under the influence of huge energy generated by ball milling bead collision2And (4) nanorods. TiO 22The stable 1D/2D heterojunction structure can be formed on the surfaces of the nano rods and the sheet layer MXene. The structure can avoid two-dimensional (2D) MXene from being re-accumulated so as to increase the specific surface area of the MXene, and simultaneously, the ordered arrangement of the layer MXene also prevents one-dimensional (1D) TiO2Aggregation of nanorods. The reversible specific capacity of the composite material prepared by the invention as a negative electrode of a sodium ion battery is up to 600mAh/g, and the composite material has good electrochemical performance; the multiplying power performance is good, and the specific capacity is stabilized at 300mAh/g after 60-cycle circulation at different current densities; when the current density returns to 100mA/g, the specific capacity can still be kept at 600mAh/g, which is 100-300 mAh/g higher than that of the negative electrode without flower-shaped structure
4. The preparation method has the characteristics of simple and easy operation, strong repeatability, low cost and no pollution to the environment, and can increase the active sites and the specific surface area of the material and improve the sodium storage capacity.
5. Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention.
Drawings
Fig. 1 (a), (b) and (c) are Scanning Electron Microscope (SEM) images of MXene/hard carbon composite material prepared in example 1 of the present invention at different scales;
FIG. 2 is an X-ray diffraction (XRD) pattern of an MXene/popcorn hard carbon composite prepared in example 1;
FIG. 3 is a graph of electrochemical performance of example 1;
FIG. 4 is an SEM image of an MXene/hard carbon composite material prepared by ball milling and regulating in an argon atmosphere according to comparative example 1 of the invention;
Detailed Description
The present invention will be described in further detail with reference to specific examples. It should be understood that the specific examples are included merely for purposes of explanation and description and are not intended to limit the scope of the invention. Any modification and variation of the present invention can be made without departing from the object and scope of the present invention.
Examples 1-3, comparative example 1 protocol was as follows:
| scheme(s) | Ball milling gas atmosphere | Carbonization temperature (. degree.C.) | Ball milling time (h) | Ball material ratio | Rotational speed (rpm) |
| Example 1 | Air (a) | 800 | 12 | 10∶1 | 600 |
| Example 2 | Air (a) | 1000 | 16 | 20∶1 | 500 |
| Example 3 | Air (a) | 1200 | 10 | 20∶1 | 600 |
| Comparative example 1 | |
800 | 12 | 10∶1 | 600 |
Example 1:
in-situ oxidation growth flower-shaped structure TiO2The preparation method of the negative electrode material of the/MXene/hard carbon sodium ion battery comprises the following steps:
step one, heating the popcorn to 230 ℃ at the normal pressure at the heating rate of 3 ℃/min, preserving the heat for 6 hours, and carrying out thermal stabilization treatment to obtain pre-oxidized popcorn;
step two, putting the corundum boat filled with the preoxidized popcorn into a tube furnace, heating the tube furnace to 800 ℃ at a heating rate of 3 ℃/min in the atmosphere of inert gas, preserving heat for 2 hours, and naturally cooling to obtain the popcorn hard carbon material;
grinding the popcorn hard carbon into powder, and sieving the powder by using a 400-mesh sieve to obtain the popcorn hard carbon small particles with uniform particle size;
step four, mixing the sieved popcorn hard carbon and MXene in an air environment by taking water as a solvent, and then performing ball milling to obtain TiO with a flower-shaped structure2the/MXene/hard carbon composite material is a sodium ion battery negative electrode material. FIG. 1 is a scanning electron microscope image of a composite material obtained in example 1 by ball milling MXene and popcorn hard carbon in an air atmosphere, wherein multiple MXene layers are peeled off and TiO is generated in situ between the layers2Nanorods, thereby forming a unique flower-like structure.FIG. 2 shows TiO prepared in example 12XRD pattern of/MXene/hard carbon composite; where the abscissa is angle and the ordinate is relative intensity. It can be seen from FIG. 2 that TiO is present during the reaction2Characteristic peak of (D), indicating TiO2And the characteristic peaks of HC and MXene do not disappear, which indicates that HC and MXene still exist. FIG. 3 shows TiO prepared in example 12the/MXene/hard carbon composite material is used as the cathode multiplying power performance of the sodium ion battery, and the reversible specific capacity of the composite nano material prepared by the invention as the cathode of the sodium ion battery is up to 600mAh/g, so that the composite nano material has high sodium storage capacity. After 60 cycles of different current densities, the specific capacity is stabilized at 300mAh/g, and when the current density returns to 100mA/g, the specific capacity can still be maintained at 600 mAh/g. The method proves that the negative electrode material of the sodium-ion battery with better electrochemical performance is successfully obtained after ball milling regulation. Fig. 4 is an SEM image of the composite material obtained by ball-milling the sieved hard carbon and the multi-layer MXene in the comparative example 1 in an argon atmosphere using water as a solvent, and it can be seen that the flower-like structure is not formed in the argon atmosphere.
Example 2:
in-situ oxidation growth flower-shaped structure TiO2The preparation method of the negative electrode material of the/MXene/hard carbon sodium ion battery comprises the following steps:
step one, heating the popcorn to 250 ℃ at the speed of 5 ℃/min under normal pressure, preserving heat for 7 hours, and carrying out thermal stabilization treatment to obtain preoxidized popcorn;
step two, putting the corundum boat filled with the preoxidized popcorn into a tube furnace, heating the tube furnace to 1000 ℃ at the heating rate of 5 ℃/min in the atmosphere of inert gas, preserving heat for 4 hours, and naturally cooling to obtain the popcorn hard carbon material;
grinding the popcorn hard carbon into powder, and sieving the powder by using a 300-mesh sieve to obtain the popcorn hard carbon small particles with uniform particle size;
step four, mixing the sieved popcorn hard carbon and MXene in an air environment by taking water as a solvent, and then performing ball milling to obtain TiO with a flower-shaped structure2Per MXene/hard carbon composite, i.e. sodium ionA battery negative electrode material.
Example 3:
in-situ oxidation growth flower-shaped structure TiO2The preparation method of the negative electrode material of the/MXene/hard carbon sodium ion battery comprises the following steps:
step one, heating the popcorn to 240 ℃ at the speed of 6 ℃/min under normal pressure, preserving heat for 8 hours, and carrying out thermal stabilization treatment to obtain preoxidized popcorn;
step two, putting the corundum boat filled with the preoxidized popcorn into a tube furnace, heating the tube furnace to 1000 ℃ at the heating rate of 5 ℃/min in the atmosphere of inert gas, then heating to 1200 ℃ at the heating rate of 3 ℃/min, and preserving heat for 3 hours to obtain the popcorn hard carbon material after natural cooling;
grinding the popcorn hard carbon into powder, and sieving the powder by using a 500-mesh sieve to obtain the popcorn hard carbon small particles with uniform particle size;
step four, mixing the sieved popcorn hard carbon and MXene by using water as a solvent in an air environment, and then carrying out ball milling to obtain TiO with a flower-shaped structure2the/MXene/hard carbon composite material is a sodium ion battery negative electrode material.
Comparative example 1:
replacing the gas atmosphere in the ball milling treatment process with argon from air;
the rest parameters are completely the same as those in the example 2, and the technological process is also completely the same.
Claims (4)
1. In-situ oxidation growth flower-shaped structure TiO2The preparation method of the negative electrode material of the/MXene/hard carbon sodium ion battery is characterized by comprising the following steps:
firstly, carrying out thermal stabilization treatment on the popcorn by a proper process under normal pressure to obtain pre-oxidized popcorn;
step two, carrying out high-temperature carbonization on the preoxidized popcorn in an atmosphere furnace, and obtaining a popcorn hard carbon material after natural cooling;
grinding and sieving the popcorn hard carbon to obtain popcorn hard carbon powder with the grain diameter of less than 48 mu m;
step four, mixing the sieved hard carbon powder with multiple layers of MXene, and performing ball milling in an air environment by using water as a solvent to obtain TiO with a flower-like structure2the/MXene/hard carbon composite material is a sodium ion battery negative electrode material.
2. The in-situ oxidation grown flower-like structure TiO of claim 12The preparation method of the/MXene/hard carbon sodium ion battery negative electrode material is characterized in that in the first step, pre-oxidation is carried out in an air atmosphere, and the temperature rise process is as follows: heating to 200-280 ℃ at a speed of 1-10 ℃/min, and preserving heat for 5-10 h.
3. The in-situ oxidation grown flower-like structure TiO of claim 12The preparation method of the/MXene/hard carbon sodium ion battery negative electrode material is characterized in that the carbonization process comprises the following steps: heating to 800-1000 ℃ at a speed of 1-5 ℃/min in an argon or nitrogen atmosphere, and preserving heat for 2-5 h; and continuously heating to 1200-1400 ℃ at the speed of 1-3 ℃/min on the basis of 1000 ℃, and preserving heat for 2-5 hours to obtain the popcorn hard carbon.
4. The in-situ oxidation grown flower-like structure TiO of claim 12The preparation method of the/MXene/hard carbon sodium ion battery cathode material is characterized in that in the fourth step, ball milling is carried out in an air atmosphere, the ball milling rotating speed is 300-600 rpm, the ball milling time is 7-16 h, the ratio of MXene to popcorn hard carbon is 1: 2-4, the ratio of MXene/popcorn hard carbon composite material to ball milling beads is 1: 10-20, and the ratio of MXene/popcorn hard carbon composite material to water is 1: 10-15.
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|---|---|---|---|---|
| CN115020680A (en) * | 2022-07-15 | 2022-09-06 | 山东大学 | MXene-coated hard carbon negative electrode material of sodium ion battery |
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