CN115911303A - Preparation method and application of high-rate silicon-based hard carbon material - Google Patents
Preparation method and application of high-rate silicon-based hard carbon material Download PDFInfo
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- 229910021385 hard carbon Inorganic materials 0.000 title claims abstract description 58
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 31
- 239000010703 silicon Substances 0.000 title claims abstract description 31
- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000010453 quartz Substances 0.000 claims abstract description 23
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- 238000000034 method Methods 0.000 claims abstract description 21
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- 239000011261 inert gas Substances 0.000 claims abstract description 17
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000007773 negative electrode material Substances 0.000 claims abstract description 16
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- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
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- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 4
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
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- 239000005977 Ethylene Substances 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
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- 238000004321 preservation Methods 0.000 claims description 2
- 239000001294 propane Substances 0.000 claims description 2
- MWWATHDPGQKSAR-UHFFFAOYSA-N propyne Chemical compound CC#C MWWATHDPGQKSAR-UHFFFAOYSA-N 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 22
- 239000004005 microsphere Substances 0.000 abstract description 9
- 239000002245 particle Substances 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 4
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- 238000005265 energy consumption Methods 0.000 abstract description 3
- 239000000377 silicon dioxide Substances 0.000 abstract description 3
- 239000000463 material Substances 0.000 description 9
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 6
- 239000002174 Styrene-butadiene Substances 0.000 description 6
- 239000001768 carboxy methyl cellulose Substances 0.000 description 6
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- -1 oxysulfide selenides Chemical class 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 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 description 3
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 3
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- 238000002441 X-ray diffraction Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
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- 229910001220 stainless steel Inorganic materials 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
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Images
Classifications
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- 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
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- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention belongs to the technical field of negative electrode materials, and discloses a preparation method of a high-rate silicon-based hard carbon material, which comprises the following steps of S1: placing fumed silica particles into a vertical quartz tube reactor; s2: introducing inert gas from the top of the quartz tube reactor, then heating the reactor to the carbonization temperature, introducing mixed gas of organic gas and inert gas to carry out chemical vapor deposition after the carbonization temperature is reached, and preserving heat; s3: after S2 is finished, introducing inert gas into the quartz tube reactor again until the reactor is naturally cooled to room temperature to obtain the silicon-based hard carbon composite material; the invention utilizes the chemical vapor deposition method and takes the silicon dioxide of the vapor phase method as the template to prepare the silicon-based hard carbon composite material, the flow for preparing the hard carbon composite material is short, the process is simple, the energy consumption is low, and the specific surface area of the obtained hard carbon microsphere is small. Solves the problems of large specific surface area, poor rate capability, low reversible specific capacity and low first effect of the sodium ion negative electrode material prepared by hard carbon in the prior art.
Description
Technical Field
The invention relates to the technical field of negative electrode materials, in particular to a preparation method and application of a high-rate silicon-based hard carbon material.
Background
The lithium ion battery has the advantages of high working voltage, high energy density, long cycle life, low self-discharge rate, environmental protection and the like, and is widely applied to the fields of notebook computers, mobile phones, digital products, electric automobiles, aerospace and the like. With the large-scale application of portable electronic devices, electric vehicles, and the like, the demand is increasing. However, the high cost and limited storage capacity become obstacles for limiting the further development of lithium ion batteries, and there is a need to develop an energy storage battery system with low cost and excellent performance, in which sodium ion batteries are considered as an ideal alternative due to abundant storage capacity, uniform and wide distribution of sodium element, and similar working mechanism as lithium ion batteries. The existing sodium-storage negative electrode materials comprise traditional carbon-based materials, metal alloys, metal oxysulfide selenides and organic negative electrode materials. However, in the discharging/charging process, the volume expansion/contraction of the negative electrode material is large, which causes poor cycle stability and influences practical application, and the preparation process has high cost and complex synthesis process. Therefore, the development of a sodium ion negative electrode material with high stability and low cost is still urgent.
Among numerous carbon-based negative electrode materials, hard carbon has the advantages of wide source, simple preparation process, good cycle stability and the like, and is considered as the most promising carbon-based negative electrode material. Hard carbon refers to a class of carbon-based materials that are difficult to graphitize completely at high temperature, and is of great interest due to large interlayer space and disordered structure, and such materials are usually formed by disordered stacking of a plurality of graphite microcrystals and have interlayer spacing convenient for sodium ion intercalation and deintercalation. And the hard carbon also has graphite domains and nano holes with random orientation and short-range order and amorphous regions, so that sufficient sites are provided for the storage of sodium ions.
Chemical Vapor Deposition (CVD) is a process in which a vapor of a gaseous or liquid reactant containing the element to be deposited and other gases required for the reaction are introduced into a reaction chamber and a chemical reaction occurs to deposit the desired solid film material on the surface of a heated solid substrate. Therefore, the inorganic composite material prepared by the CVD technology has the following characteristics: the deposition temperature is low, the components of the deposition material are easy to control, the film layer is uniform, and the composition, the appearance, the size, the thickness and the like of the deposition material are controlled by selecting proper process conditions such as precursor concentration, flow rate, reaction temperature, deposition time and the like; the obtained inorganic composite material has excellent step coverage, good repeatability and continuous process. Therefore, the CVD technology is utilized to prepare the hard carbon composite material, and the process of gas phase doping or cladding deposition can be accurately controlled by controlling the parameters of the precursor such as concentration, reaction time and the like, so that the hard carbon composite material meeting the requirements can be obtained.
Disclosure of Invention
The invention aims to provide a preparation method of a high-rate silicon-based hard carbon material, which is characterized in that a chemical vapor deposition method is utilized, silicon dioxide in a vapor phase method is used as a template to prepare the silicon-based hard carbon composite material, the preparation process of the hard carbon composite material is short, the process is simple, the energy consumption is low, and the specific surface area of the obtained hard carbon microspheres is small. Solves the problems of large specific surface area, poor rate capability, low reversible specific capacity and low first effect of the sodium ion negative electrode material prepared by hard carbon in the prior art.
In order to achieve the above purpose, the invention provides the following technical scheme:
a preparation method of a high-magnification silicon-based hard carbon material comprises the following steps:
s1: putting the silica particles obtained by the vapor phase method into a vertical quartz tube reactor;
s2: introducing inert gas from the top of the quartz tube reactor, then heating the reactor to the carbonization temperature, introducing mixed gas of organic gas and inert gas after the carbonization temperature is reached, performing chemical vapor deposition, and preserving heat;
s3: and (3) after the step (S2) is finished, introducing inert gas into the quartz tube reactor again until the reactor is naturally cooled to room temperature, and thus obtaining the required silicon-based hard carbon composite material.
Furthermore, in S2 and S3, the introduced inert gas is one or any two of nitrogen, argon and hydrogen, and the introduction rate of the inert gas is 1-1000 mL/min.
In S2, the organic gas is at least one of methane, ethane, propane, ethylene, acetylene, propyne, benzene, toluene, carbon monoxide and cyclohexane, and the mass ratio of the organic gas to the inert gas is 1:1-10.
Further, in S2, a mixed gas of an organic gas and an inert gas is introduced into the quartz tube reactor under normal pressure.
Further, in S2, in the process of heating to the carbonization temperature, the heating rate before 800 ℃ is 1-30 ℃/min, the heating rate after 800 ℃ is 1-5 ℃/min, the carbonization temperature is 800-1600 ℃, and the heat preservation time is 0.5-8 h.
The silicon-based hard carbon composite material prepared by the preparation method of the high-rate silicon-based hard carbon material is applied to a lithium ion battery negative electrode material or a sodium ion battery negative electrode material.
The beneficial effects of the technical scheme are that:
the silicon-based hard carbon composite material is prepared by using a chemical vapor deposition method and taking vapor-phase-method silicon dioxide as a template, the process for preparing the hard carbon material is short, the process is simple, the energy consumption is low, and the specific surface area of the obtained hard carbon microspheres is small; the hard carbon material is also applied to the cathode materials of sodium ion batteries and lithium ion batteries, and experimental tests show that: when the hard carbon material is used as a sodium ion battery cathode material, the reversible specific capacity (350 is more than or equal to mAh/g), the first coulombic efficiency (more than or equal to 85%) and the rate capability (5C is more than or equal to 300 mAh/g) are high; when the material is a lithium ion battery cathode material, the discharge specific capacity can reach 473mAh/g. The problems of large specific surface area, poor rate capability, low reversible specific capacity and low first effect of the existing sodium ion negative electrode material are effectively solved.
Drawings
FIG. 1 is a schematic structural diagram of a method for preparing a high-rate silicon-based hard carbon material according to the present invention;
FIG. 2 is a scanning electron micrograph of hard carbon microspheres obtained in example 1;
FIG. 3 is an X-ray diffraction pattern of the hard carbon microspheres obtained in example 1;
FIG. 4 is a charge-discharge cycle chart of the sodium ion battery in example 1;
fig. 5 is a graph of the rate cycle of the sodium ion battery in example 2.
Detailed Description
The invention is described in further detail below with reference to the following figures and embodiments:
example 1
A preparation method of a high-magnification silicon-based hard carbon material comprises the following steps:
s1, 200mg of fumed silica particles are placed in a vertical quartz tube reactor, wherein the inner diameter of the quartz tube is 27mm, and the length of the quartz tube is 80cm;
s2, introducing nitrogen into the reactor from the top of the quartz tube at the speed of 300mL/min, heating the reactor to 800 ℃ at the speed of 10 ℃/min, heating to 1450 ℃ at the speed of 2 ℃/min, introducing a mixed gas of methane and nitrogen with the mass ratio of 3:7 into the reactor at the speed of 150mL/min for chemical vapor deposition, and preserving heat for 5 hours;
and S3, after the step S2 is finished, introducing nitrogen into the reactor at the rate of 300mL/min until the reactor is naturally cooled to the room temperature, and thus obtaining the silicon-based hard carbon composite material.
As shown in fig. 1, the method is used for preparing a silicon-based hard carbon composite material;
as shown in fig. 2, which is a scanning electron micrograph of the hard carbon microspheres of the silicon-based hard carbon composite material obtained in this example, it was confirmed that the morphology of the material is irregular block shape, and the particle size is about 2 to 15 μm;
as shown in fig. 3, for the X-ray diffraction pattern of the hard carbon microsphere of the silicon-based hard carbon composite material obtained in this example, two diffraction peaks with relatively wide widths exist near 22 ° and 43 °, which correspond to the (002) and (100) crystal planes of the hard carbon material, and it can be seen from the figure that the half-peak width of the diffraction peak (002) is relatively large, and the angle is relatively small, which indicates that the disorder degree of the material is relatively high and the interlayer spacing is relatively large.
The hard carbon composite material obtained in the embodiment is applied to the negative electrode of a sodium ion battery:
weighing 95wt.% of the hard carbon composite material prepared in the embodiment, adding 2.5wt.% of sodium carboxymethylcellulose (CMC) as a binder, 1.5wt.% of SBR (styrene butadiene latex) as a conductive agent and 150wt.% of water as a solvent, fully grinding to obtain uniform black paste slurry, coating the slurry on a copper foil current collector as a negative plate, assembling a button cell by taking a metal sodium plate as a comparison electrode, adopting an electrolyte as a 1M organic electrolyte (sodium salt is sodium hexafluorophosphate, the solvent is a mixed solution of Ethylene Carbonate (EC) and dimethyl carbonate (DMC) in a mass ratio of 1:1), using glass fiber as a diaphragm, assembling the button cell by taking CR2032 type stainless steel as a cell shell, activating the button cell by charging and discharging circulation for three circles at a current density of 30mA/g, and testing the circulation performance at a current density of 300 mA/g.
As shown in fig. 4, the first-turn charging specific capacity of the hard carbon negative electrode material obtained in this embodiment at a current density of 30mA/g is 365.5mAh/g; after 300 cycles, the specific capacity of 340mAh/g can be still maintained, and the capacity retention rate is 96%.
Example 2
A preparation method and application of a high-magnification silicon-based hard carbon material comprise the following steps:
s1, 100mg of fumed silica particles are placed in a vertical quartz tube reactor, wherein the inner diameter of the quartz tube is 27mm, and the length of the quartz tube is 80cm;
s2, introducing nitrogen into the reactor from the top of the quartz tube at a rate of 250mL/min, heating the reactor to 1000 ℃ at a rate of 50 ℃/min, heating the reactor to 1350 ℃ at a rate of 1 ℃/min, introducing a mixed gas of acetylene and nitrogen into the reactor at a rate of 200mL/min at the moment, wherein the mixed gas of acetylene and nitrogen has a mass ratio of 1:8, performing chemical vapor deposition, and preserving heat for 6 hours;
and S3, after the step S2 is finished, introducing nitrogen into the reactor at the rate of 250mL/min until the reactor is naturally cooled to room temperature, thus obtaining the silicon-based hard carbon composite material.
The hard carbon composite material obtained in the embodiment is applied to the negative electrode of a sodium ion battery:
weighing 95wt.% of the hard carbon microsphere material prepared in the embodiment, adding 2.5wt.% of sodium carboxymethylcellulose (CMC) as a binder, 1.5wt.% of SBR (styrene butadiene latex) as a conductive agent and 150wt.% of water as a solvent, fully grinding to obtain uniform black paste slurry, coating the slurry on a copper foil current collector as a negative plate, assembling a button cell by taking a metal sodium plate as a contrast electrode, and adopting an electrolyte which is 1M organic electrolyte (sodium salt is sodium hexafluorophosphate, the solvent is a mixed solution of Ethylene Carbonate (EC) and dimethyl carbonate (DMC) in a volume ratio of 1:1), glass fiber is a diaphragm, and CR2032 type stainless steel is used as a cell shell to assemble the sodium ion cell.
As shown in FIG. 5, the test cycle of the rate test was conducted for the Na-ion battery at current densities of 30mA/g,60mA/g,150mA/g,300mA/g,600mA/g, and 1500 mA/g. The results show that the capacities of the sodium ion battery under the current densities of 30mA/g,60mA/g,150mA/g,300mA/g,600mA/g and 1500mA/g are 366mAh/g,360mAh/g,354mAh/g,351mAh/g,342mAh/g and 315mAh/g respectively.
Example 3
A preparation method and application of a high-magnification silicon-based hard carbon material comprise the following steps:
s1, putting 1000mg of fumed silica particles into a vertical quartz tube reactor, wherein the inner diameter of the quartz tube is 50mm, and the length of the quartz tube is 150cm;
s2, introducing nitrogen into the reactor from the top of the quartz tube at a speed of 500mL/min, heating the reactor to 9000 ℃ at a speed of 50 ℃/min, heating to 1150 ℃ at a speed of 2 ℃/min, introducing mixed gas of ethane and nitrogen with a mass ratio of 1;
and S3, after the step S2 is finished, introducing nitrogen into the reactor at the speed of 500mL/min until the reactor is naturally cooled to room temperature, thus obtaining the silicon-based hard carbon composite material.
The hard carbon composite material obtained in the embodiment is applied to the negative electrode of a sodium ion battery:
weighing 95wt.% of the hard carbon microsphere material prepared in the embodiment, adding 2.5wt.% of sodium carboxymethylcellulose (CMC) as a binder, 1.5wt.% of SBR (styrene butadiene latex) as a conductive agent, 150wt.% of water as a solvent, fully grinding to obtain uniform black paste slurry, coating the slurry on a copper foil current collector as a negative plate, assembling a button cell by taking a metal lithium plate as a contrast electrode, and assembling a lithium ion battery button cell by taking a 1M organic electrolyte (lithium salt is lithium hexafluorophosphate, solvent is Ethylene Carbonate (EC) with a volume ratio of 1.
The rate performance of the battery is tested under different current densities of 1000mA/g, 2000mA/g, 3000mA/g and the like. The test result shows that the lithium ion battery cathode prepared by the embodiment has good electrochemical performance: under the current density of 150mA/g, the coulombic efficiency of the first circle is 84.2%, and the charge capacity of the first circle is 472mAh/g; under the discharge densities of 1000mA/g, 2000mA/g and 3000mA/g, the charging specific capacities of 420mAh/g, 395mAh/g and 362mAh/g can be respectively maintained.
The above description is only an example of the present invention, and the common general knowledge of the technical solutions or characteristics known in the solutions is not described herein too much. It should be noted that, for those skilled in the art, without departing from the technical solution of the present invention, several variations and modifications can be made, which should also be regarded as the protection scope of the present invention, and these will not affect the effect of the implementation of the present invention and the practicability of the patent. The scope of the claims of the present application shall be determined by the contents of the claims, and the description of the embodiments and the like in the specification shall be used to explain the contents of the claims.
Claims (6)
1. A preparation method of a high-magnification silicon-based hard carbon material is characterized by comprising the following steps: the method comprises the following steps:
s1: putting the silica particles obtained by the vapor phase method into a vertical quartz tube reactor;
s2: introducing inert gas from the top of the quartz tube reactor, then heating the reactor to the carbonization temperature, introducing mixed gas of organic gas and inert gas after the carbonization temperature is reached, performing chemical vapor deposition, and preserving heat;
s3: and (3) after the step (S2) is finished, introducing inert gas into the quartz tube reactor again until the reactor is naturally cooled to room temperature, and obtaining the required silicon-based hard carbon composite material.
2. The preparation method of the high-rate silicon-based hard carbon material according to claim 1, characterized in that: in S2 and S3, the introduced inert gas is one or any two of nitrogen, argon and hydrogen, and the introduction rate of the inert gas is 1-1000 mL/min.
3. The preparation method of the high-rate silicon-based hard carbon material according to claim 1, characterized in that: in S2, the introduced organic gas is at least one of methane, ethane, propane, ethylene, acetylene, propyne, benzene, toluene, carbon monoxide and cyclohexane, and the mass ratio of the organic gas to the inert gas is 1:1-10.
4. The preparation method of the high-rate silicon-based hard carbon material according to claim 1, characterized in that: in S2, mixed gas of organic gas and inert gas is introduced into the quartz tube reactor under the normal pressure state.
5. The preparation method of the high-rate silicon-based hard carbon material according to claim 1, characterized by comprising the following steps: in S2, in the process of heating to the carbonization temperature, the heating rate before 800 ℃ is 1-30 ℃/min, the heating rate after 800 ℃ is 1-5 ℃/min, the carbonization temperature is 800-1600 ℃, and the heat preservation time is 0.5-8 h.
6. The application of the silicon-based hard carbon composite material prepared by the preparation method of the high-rate silicon-based hard carbon material according to any one of claims 1 to 5 in the negative electrode material of a lithium ion battery or the negative electrode material of a sodium ion battery.
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