CN114373913A - Core-shell structure composite particle and preparation method and application thereof - Google Patents
Core-shell structure composite particle and preparation method and application thereof Download PDFInfo
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- 239000011246 composite particle Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000000843 powder Substances 0.000 claims abstract description 62
- 239000002245 particle Substances 0.000 claims abstract description 43
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 34
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- 240000003183 Manihot esculenta Species 0.000 claims abstract description 28
- 235000016735 Manihot esculenta subsp esculenta Nutrition 0.000 claims abstract description 28
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000005011 phenolic resin Substances 0.000 claims abstract description 22
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- 229910003481 amorphous carbon Inorganic materials 0.000 claims abstract description 19
- 239000007773 negative electrode material Substances 0.000 claims abstract description 18
- 238000010438 heat treatment Methods 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 14
- 229920001187 thermosetting polymer Polymers 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
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- 230000008569 process Effects 0.000 claims description 4
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 2
- 238000010298 pulverizing process Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000010406 cathode material Substances 0.000 abstract description 6
- 239000003792 electrolyte Substances 0.000 abstract description 5
- 230000009467 reduction Effects 0.000 abstract description 2
- 238000007086 side reaction Methods 0.000 abstract description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 31
- 229910052710 silicon Inorganic materials 0.000 description 18
- 239000010703 silicon Substances 0.000 description 18
- 230000014759 maintenance of location Effects 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
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- 238000006243 chemical reaction Methods 0.000 description 2
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- 238000013461 design Methods 0.000 description 2
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- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- KVBYPTUGEKVEIJ-UHFFFAOYSA-N benzene-1,3-diol;formaldehyde Chemical compound O=C.OC1=CC=CC(O)=C1 KVBYPTUGEKVEIJ-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
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- 238000002474 experimental method Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 238000006138 lithiation reaction Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
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- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000013341 scale-up Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 239000011856 silicon-based particle Substances 0.000 description 1
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- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
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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
- H01M4/366—Composites as layered products
-
- 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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
-
- 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
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Composite Materials (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a core-shell structure composite particle, a preparation method and application thereof, wherein the preparation method comprises the following steps: (1) fully homogenizing the negative electrode material powder, the cassava powder and water, and then carrying out spray drying to obtain powder/cassava powder mixed particles; wherein the mass ratio of the negative electrode material powder to the cassava powder is 1 (2-5); (2) mixing the powder/cassava powder mixed particles with thermosetting phenolic resin, performing low-temperature heat treatment, and carbonizing to obtain powder/porous carbon/amorphous carbon particles; wherein the mass ratio of the powder/cassava powder mixed particles to the thermosetting phenolic resin is 1 (0.55-0.7). The core-shell structure composite particle outer-layer carbon ensures structural strength, and avoids outer-layer collapse caused by charring and shrinking of cassava powder; the outer layer is compact and uniform, so that the energy density reduction caused by side reaction between the electrolyte and the outer layer is reduced; the internal porous structure effectively relieves the volume expansion problem of the cathode material, and has good application prospect.
Description
Technical Field
The invention relates to a core-shell structure composite particle and a preparation method and application thereof.
Background
Silicon (Si) is used as an efficient and environment-friendly rechargeable battery cathode material, and the theoretical capacity of the silicon (Si) is 3600mAhg-1) Is obviously higher than that of a commercial graphite anode material (350--1). However, the silicon-based negative electrode greatly expands in volume during lithiation and simultaneously has high reactivity with an organic electrolyte, resulting in rapid capacity fade. In addition, Si has low conductivity, which also limits its practical applications. For silicon-based cathodes, a rational structural design is an effective solution to most of the problems faced by silicon-based cathodes. Therefore, various structural design methods such as a core-shell structure, a yolk-shell structure, a hollow structure and the like are developed to adapt to the volume change of the silicon-based material. Among them, one effective strategy is to encapsulate silicon particles in carbon spheres having voids to form a core-shell structure. The composite structure has the advantages that a buffer space exists between the outer carbon layer and the inner cathode particles, the volume expansion of the silicon cathode is accommodated, meanwhile, the outer carbon particles can avoid the direct contact of the silicon cathode and electrolyte, and the problem of poor conductivity of the silicon cathode is solved.
The effectiveness of the core-shell structure with Si/C having internal voids has been demonstrated in a number of reports. To prepare such core-shell structures, the prior art generally employs a sol-gel process to hydrolyze SiO2Coating Si-based anode, coating with sucrose, glucose, polydopamine and resorcinol formaldehyde resin as carbon source for carbonization coating, and selectively etching SiO with hydrofluoric acid (HF)2A sacrificial layer. However, this preparation method is complicated and expensive in process, is not easy to scale up, and is environmentally friendly in removing HF used for the sacrificial layer, requiring special precautions in handling. Meanwhile, the gaps cause fewer contact sites between the inner cathode particles and the outer carbon layer, and lithium ion transmission and electron transfer are limited。
Disclosure of Invention
The invention aims to solve the technical problems that the preparation method of the Si/C core-shell structure is complex and HF used for removing a sacrificial layer is not environment-friendly in the prior art, so that the core-shell structure composite particle and the preparation method and application thereof are provided.
The invention solves the technical problems through the following technical scheme.
The invention provides a preparation method of core-shell structure composite particles, which comprises the following steps:
(1) fully homogenizing the negative electrode material powder, the cassava powder and water, and then carrying out spray drying to obtain powder/cassava powder mixed particles; wherein the mass ratio of the negative electrode material powder to the cassava powder is 1 (2-5);
(2) mixing the powder/cassava powder mixed particles with thermosetting phenolic resin, performing low-temperature heat treatment, and carbonizing to obtain powder/porous carbon/amorphous carbon particles; wherein the mass ratio of the powder/cassava powder mixed particles to the thermosetting phenolic resin is 1 (0.55-0.7).
In the step (1), the negative electrode material powder is the negative electrode material powder which is conventional in the field and can be Si powder, Sn powder and SiO powderxPowder, Fe2O3Powder, Ge powder, Sb powder or SnS2And (3) pulverizing.
The D50 particle size of the negative electrode material powder can be 100nm-2 μm, preferably 200nm-1 μm.
In the step (1), the mass ratio of the negative electrode material powder, the cassava powder and the water is preferably 1 (2-5) to (8-20), for example 1:3:10 or 1:5: 18.
In step (1), the spray drying is conventional in the art.
In the step (2), the thermosetting phenolic resin is a thermosetting phenolic resin which is conventional in the field. Those skilled in the art will appreciate that the thermosetting phenolic resin is a stable, heat resistant, flame retardant, electrically insulating resin, such as phenolic resin 2123.
In the step (2), the mass ratio of the powder/cassava flour mixed particles to the thermosetting phenolic resin is preferably 1 (0.6-0.7), for example 1: 0.65.
In step (2), the mixing is carried out according to conventional mixing in the art, and may generally be mechanical mixing.
In the step (2), the mechanical mixing device may be a gravity-free mixer, a horizontal ribbon blender or a conical mixer, preferably a horizontal ribbon blender.
In step (2), the time for mechanical mixing may be 0.5 to 3 hours, preferably 2 to 3 hours, for example 2.5 hours.
In step (2), the low-temperature heat treatment is a conventional low-temperature heat treatment operation in the art. The low-temperature heat treatment equipment can be a heating reaction kettle with a stirring device.
In the step (2), the atmosphere of the low-temperature heat treatment is generally a nitrogen atmosphere.
In the step (2), the temperature of the low-temperature heat treatment may be 500-600 ℃, for example, 550 ℃.
In step (2), the time of the low-temperature heat treatment may be 4 to 8 hours, preferably 6 to 8 hours, for example 7 hours.
In step (2), the carbonization is conventional in the art and is generally carried out in a high temperature carbonization apparatus. The composite particles are generally carbonized in a graphite crucible.
Wherein, the carbonization equipment can be a roller kiln.
In the step (2), the atmosphere of the carbonization is generally a nitrogen atmosphere.
In the step (2), the carbonization temperature may be 1500 ℃ at 1000-.
In the step (2), the carbonization time can be 5-10h, preferably 6-8h, for example 7 h.
The invention also provides the core-shell structure composite particle prepared by the preparation method of the core-shell structure composite particle.
The invention also provides a carbon cathode material which adopts the core-shell structure composite particles.
On the basis of the common knowledge in the field, the above preferred conditions can be combined randomly to obtain the preferred embodiments of the invention.
The reagents and starting materials used in the present invention are commercially available.
The positive progress effects of the invention are as follows:
the invention provides a preparation method of core-shell structure composite particles which are free of corrosion, simple and capable of being prepared in large scale, the prepared core-shell structure composite particles adjust the size of internal gaps of the composite particles, provide space for volume expansion of negative electrode powder, increase contact points with an outer carbon layer, facilitate transmission and electron transfer of lithium ions, and the outer carbon layer ensures structural strength, so that outer collapse caused by charring shrinkage of cassava powder is avoided; the outer layer is compact and uniform, so that the energy density reduction caused by side reaction between the electrolyte and the outer layer is reduced; the internal porous structure effectively relieves the volume expansion problem of the cathode material, and has good application prospect.
Drawings
FIG. 1 is an XRD pattern of the silicon powder/porous carbon/amorphous carbon particles obtained in example 1.
FIG. 2 is an SEM image of the complete morphology of the silicon powder/porous carbon/amorphous carbon particles prepared in example 1.
FIG. 3 is an SEM image of damaged particles of silicon powder/porous carbon/amorphous carbon particles obtained in example 1.
FIG. 4 is a graph showing the capacity retention of the silicon powder/porous carbon/amorphous carbon particles obtained in example 1.
Detailed Description
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention. The experimental methods without specifying specific conditions in the following examples were selected according to the conventional methods and conditions, or according to the commercial instructions.
Example 1
(1) Preparing silicon/cassava flour particles: fully homogenizing silicon powder, cassava powder and water in a stirring tank according to the mass ratio of 1:2:8 to obtain mixed slurry, placing the mixed slurry in a spray dryer, and performing spray drying to obtain uniform silicon/cassava powder particles.
(2) Preparation of silicon/porous carbon/phenolic resin particles: mixing the silicon/cassava powder particles and thermosetting phenolic resin (model BR-2123) for 2 hours in a spiral ribbon mixer according to the mass ratio of 1:0.6 to obtain a mixture. And then placing the mixture in a reaction kettle, heating to 550 ℃ at the speed of 5 ℃/min under the atmosphere of nitrogen, and then preserving heat for 6h to obtain the silicon/porous carbon/phenolic resin particles.
(3) Preparing silicon/porous carbon/amorphous carbon particles: putting the powder/porous carbon/phenolic resin into a graphite crucible, then sending the graphite crucible into a roller kiln, preserving heat at 1200 ℃ for 6h under nitrogen atmosphere for carbonization, and completely carbonizing the outer layer phenolic resin into amorphous carbon to obtain silicon/porous carbon/amorphous carbon particles.
The product prepared in example 1 was characterized and fig. 1 is an XRD spectrum of silicon/porous carbon/amorphous carbon particles, which shows that the product is composed of two components, silicon and amorphous carbon.
FIG. 2 is an SEM image of the complete morphology of silicon powder/porous carbon/amorphous carbon particles; fig. 3 is an SEM image of broken particles of silicon powder/porous carbon/amorphous carbon particles. As can be seen from FIG. 2, the particles are regular spherical, the surfaces of the particles are rough and continuous, and the surfaces of the particles are not collapsed, so that the carbonized thermosetting phenolic resin has compact outer layers and better mechanical stress, and the direct contact between the electrolyte and the internal cathode powder is avoided. As is apparent from the broken particles in fig. 3, voids exist inside the core-shell structured particles.
FIG. 4 is a graph of the capacity retention of silicon/porous carbon/amorphous carbon particles. After 200 cycles, the capacity retention rate is 73.5%.
Examples 2 to 7
Examples 2 to 7 the same procedures as in example 1 were repeated except for the points shown in Table 1; finally, a series of cathode material powder/porous carbon/amorphous carbon cathode materials with regular structures and porous interiors are obtained.
The button cell used for testing the electrochemical performance is prepared by respectively uniformly mixing the negative electrode material of the cell prepared in the embodiment 1-7 with a conductive agent and Styrene Butadiene Rubber (SBR) according to a ratio of 85:12:3, coating the mixture on copper foil, drying in vacuum to be used as a negative electrode, taking lithium metal as a counter electrode, using a mixed solution of 1M LiPF6 Ethylene Carbonate (EC) and dimethyl carbonate (DMC) according to a mass ratio of 1:1 as an electrolyte, and assembling a diaphragm into a button cell by using a PE/PP/PE composite membrane. The test conditions were that charging and discharging were carried out at a current density of 0.1C and the charging voltage was limited to 0.005-2V.
TABLE 1
The cycle capacity retention rate of the anode material prepared by the method is greatly improved as can be seen from the cycle capacity retention rate of 200 times obtained by the test in the table.
Comparative example 1
The steps are similar to those of example 1, except that silicon powder, tapioca flour and water are mixed according to the mass ratio of 1:1:3 and then spray-dried, and the silicon powder/porous carbon/amorphous carbon negative electrode material cannot be obtained under the conditions.
Comparative example 2
The procedure is similar to that of example 1, except that silicon powder/tapioca flour particles and phenolic resin are mixed according to the mass ratio of 1:0.2, and under the condition, a silicon powder/porous carbon/amorphous carbon negative electrode material with a compact and complete outer layer cannot be obtained.
Comparative example 3
The procedure is similar to example 1, except that the silicon powder/tapioca flour particles are mixed with phenolic resin according to the mass ratio of 1:0.3, and under the condition, the compact and complete silicon powder/porous carbon/amorphous carbon negative electrode material with the outer layer cannot be obtained.
The upper and lower limit values, the interval and the value of each process parameter (such as heating temperature and time) listed in the invention can realize the invention, and various raw material powders (such as Sn and SiO)x) The present invention can be implemented, and the examples are not intended to be illustrative.
Claims (10)
1. A preparation method of core-shell structure composite particles is characterized by comprising the following steps:
(1) fully homogenizing the negative electrode material powder, the cassava powder and water, and then carrying out spray drying to obtain powder/cassava powder mixed particles; the mass ratio of the negative electrode material powder to the cassava powder is 1 (2-5);
(2) mixing the powder/cassava powder mixed particles with thermosetting phenolic resin, performing low-temperature heat treatment, and carbonizing to obtain powder/porous carbon/amorphous carbon particles; the mass ratio of the powder/cassava powder mixed particles to the thermosetting phenolic resin is 1 (0.55-0.7).
2. The preparation method of the core-shell structure composite particles according to claim 1, wherein the negative electrode material powder is Si powder, Sn powder or SiO powderxPowder, Fe2O3Powder, Ge powder, Sb powder or SnS2Pulverizing;
wherein the D50 particle size of the negative electrode material powder is 100nm-2 μm, preferably 200nm-1 μm.
3. The method for preparing the core-shell structure composite particles according to claim 1, wherein the mass ratio of the negative electrode material powder, the cassava powder and the water is preferably 1 (2-5) to (8-20), such as 1:3:10 or 1:5: 18.
4. The method for preparing core-shell structure composite particles according to claim 1, wherein the mass ratio of the powder/tapioca flour mixed particles to the thermosetting phenolic resin is preferably 1 (0.6-0.7), such as 1: 0.65; and/or the thermosetting phenolic resin is phenolic resin 2123.
5. The method for preparing core-shell structure composite particles according to claim 1, wherein the atmosphere of the low-temperature heat treatment is a nitrogen atmosphere;
and/or the temperature of the low-temperature heat treatment is 500-600 ℃, such as 550 ℃;
and/or the time of the low-temperature heat treatment is 4 to 8 hours, preferably 6 to 8 hours, for example 7 hours.
6. The method for producing core-shell structured composite particles according to claim 1, wherein the mixing is mechanical mixing;
wherein, the mechanical mixing device is a gravity-free mixer, a horizontal spiral-ribbon mixer or a conical mixer, preferably a horizontal spiral-ribbon mixer.
7. Process for the preparation of core-shell structured composite particles according to claim 6, wherein the time of mechanical mixing is 0.5 to 3h, preferably 2 to 3h, such as 2.5 h.
8. The method for preparing core-shell structure composite particles according to claim 1, wherein the carbonization atmosphere is a nitrogen atmosphere;
and/or the temperature of the carbonization is 1000-1500 ℃, preferably 1200-1350 ℃, for example 1300 ℃;
and/or the carbonization time may be 5-10h, preferably 6-8h, for example 7 h.
9. Core-shell structured composite particles, characterized in that they are obtainable by a process for the preparation of core-shell structured composite particles according to any one of claims 1 to 8.
10. A carbon negative electrode material comprising the core-shell structure composite particle according to claim 9.
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| CN102244240A (en) * | 2011-06-15 | 2011-11-16 | 中南大学 | Lithium ion battery composite anode material and preparation method thereof |
| CN103633295A (en) * | 2012-08-23 | 2014-03-12 | 上海杉杉科技有限公司 | Silicon-carbon composite material, lithium ion battery, and preparation method and application of silicon-carbon composite material |
| CN105720258A (en) * | 2014-12-03 | 2016-06-29 | 上海杉杉科技有限公司 | Lithium ion battery negative electrode material and preparation method and application thereof, and lithium ion battery |
| CN110467173A (en) * | 2019-07-31 | 2019-11-19 | 桑德新能源技术开发有限公司 | Amorphous carbon material and preparation method thereof, negative electrode material, lithium ion battery |
| CN113548668A (en) * | 2021-06-22 | 2021-10-26 | 武汉工程大学 | Pomegranate structure microsphere and preparation method and application thereof |
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