CN116477600A - High specific capacity silicon-carbon negative electrode material and preparation method and application thereof - Google Patents
High specific capacity silicon-carbon negative electrode material and preparation method and application thereof Download PDFInfo
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- CN116477600A CN116477600A CN202310257954.XA CN202310257954A CN116477600A CN 116477600 A CN116477600 A CN 116477600A CN 202310257954 A CN202310257954 A CN 202310257954A CN 116477600 A CN116477600 A CN 116477600A
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- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000007773 negative electrode material Substances 0.000 title claims description 26
- 239000005543 nano-size silicon particle Substances 0.000 claims abstract description 45
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000010405 anode material Substances 0.000 claims abstract description 18
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 18
- 239000011248 coating agent Substances 0.000 claims abstract description 15
- 238000000576 coating method Methods 0.000 claims abstract description 15
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 14
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 44
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 35
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 13
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- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
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- 101150058243 Lipf gene Proteins 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
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- IKGXIBQEEMLURG-NVPNHPEKSA-N rutin Chemical compound O[C@@H]1[C@H](O)[C@@H](O)[C@H](C)O[C@H]1OC[C@@H]1[C@@H](O)[C@H](O)[C@@H](O)[C@H](OC=2C(C3=C(O)C=C(O)C=C3OC=2C=2C=C(O)C(O)=CC=2)=O)O1 IKGXIBQEEMLURG-NVPNHPEKSA-N 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/02—Silicon
-
- 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
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/134—Electrodes based on metals, Si or alloys
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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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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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
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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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Abstract
The invention belongs to the field of high-performance lithium ion battery anode materials, and discloses a high-specific-capacity silicon-carbon anode material, and a preparation method and application thereof. The invention adopts the steps of coating an amorphous carbon layer on the surface of nano silicon particles in advance to obtain a core-shell structure silicon-carbon composite material which is coated in a sealing way, and then uniformly dispersing the core-shell structure silicon-carbon composite material in a carbon network matrix to obtain a final material. An electric conduction bridge is formed between the amorphous carbon layer on the surface of the nano silicon particles and the carbon network matrix material, so that the electric conductivity of the nano silicon particles can be effectively improved, the amorphous carbon layer can be used as a protective layer for buffering the volume expansion of the nano silicon particles to maintain the stability of the whole material structure, the electrochemical cycle performance is more excellent, and the amorphous carbon layer has a wide application prospect in a lithium ion battery system.
Description
Technical Field
The invention belongs to the field of high-performance lithium ion battery anode materials, and particularly relates to a high-specific-capacity silicon-carbon anode material, and a preparation method and application thereof.
Background
At present, in order to solve a series of environmental and health problems brought by the traditional fossil energy, energy transformation is urgent. The lithium ion battery is used as a novel power source under energy transformation, and is widely applied to various electronic products and new energy automobiles due to the characteristics of high energy density, safety, environmental protection and the like. The theoretical specific capacity of the graphite material used as the anode material for the earliest commercialized application is only 372mA/g, and the actual development requirement of the future new energy field can not be met. In the research of numerous negative electrode materials of lithium ion batteries, silicon-based negative electrode materials become a current research hot spot due to higher theoretical specific capacity and lower charge/discharge voltage platform. However, silicon-based anode materials still have many limitations in commercial applications, mainly because the intercalation and deintercalation of lithium ions in the battery during the charge and discharge process is accompanied by a large and irreversible volume expansion (about 300%) of the silicon material, and the huge volume expansion tends to cause the destruction of the material structure, so that the electrical contact between the silicon particles and the current collector is lost, thereby causing the rapid attenuation of the circulation capacity. In addition, silicon material, which is a typical semiconductor material, has poor conductivity, resulting in low first cycle efficiency of the material and severe cycle capacity fade.
In view of the above problems, a great deal of research is currently being conducted mainly on structural modification designs and composite materials of silicon-based anode materials. Silicon-carbon composite materials have proven to be an effective method for improving lithium storage performance of silicon-based anodes, where carbon materials play two main roles: firstly, as a buffer matrix for relieving the volume expansion of the silicon material, and secondly, as a conductive medium for improving the overall conductivity of the material, thereby obtaining more excellent electrochemical cycle performance. However, the specific capacity of the existing silicon-carbon composite material is not enough, and further modification is needed to be carried out on the silicon-based negative electrode material so as to obtain the silicon-carbon negative electrode material with high specific capacity.
Disclosure of Invention
In order to overcome the defects and shortcomings of the prior art, the primary purpose of the invention is to provide a preparation method of a high specific capacity silicon-carbon anode material. The invention adopts the steps of coating an amorphous carbon layer on the surface of nano silicon particles in advance to obtain a core-shell structure silicon-carbon composite material which is coated in a sealing way, and then uniformly dispersing the core-shell structure silicon-carbon composite material in a carbon network matrix to obtain a final material. An electric conduction bridge is formed between the amorphous carbon layer on the surface of the nano silicon particles and the carbon network matrix material, so that the electric conductivity of the nano silicon particles can be effectively improved, and the nano silicon particles can be used as a protective layer for buffering the volume expansion of the nano silicon particles to maintain the stability of the whole material structure, and have more excellent electrochemical cycle performance.
The invention also aims to provide the high specific capacity silicon-carbon anode material prepared by the method.
The invention also aims to provide the application of the high-specific-capacity silicon-carbon anode material in a lithium ion battery.
The aim of the invention is achieved by the following scheme:
the preparation method of the high specific capacity silicon-carbon negative electrode material comprises the following steps:
(1) Completely soaking purchased food-grade coconuts (BC, bacterial cellulose) in NaOH solution for heating treatment, filtering and washing to neutrality to obtain BC hydrogel, and drying the BC hydrogel by adopting a freeze-drying technology to obtain white BC aerogel;
(2) Placing the BC aerogel in a tube furnace, and carbonizing in a nitrogen atmosphere to obtain a CBC carbon material;
(3) Acidizing the prepared CBC carbon material;
(4) Coating the surfaces of the nano silicon particles with an organic carbon source, and carbonizing in an inert atmosphere or under nitrogen to obtain a Si/C composite material;
(5) Dispersing the CBC carbon material subjected to the acidification treatment in the step (3) in water, adding the Si/C composite material for liquid phase mixing, and then centrifugally filtering and vacuum drying to prepare the high specific capacity silicon-carbon anode material.
The heating treatment in the step (1) refers to water bath/oil bath treatment at 60-80 ℃ for 2-4 h.
Preferably, the heating treatment in the step (1) is preferably a water bath/oil bath treatment of completely immersing the coconut (15 mm cube) in 2-4 mol/L NaOH solution at 60-80 ℃ for 2-4 hours.
The step (1) of washing to neutrality is preferably washing with water firstly, then soaking with deionized water, and water is changed for a plurality of times until the soaking solution is neutral, wherein the soaking time is preferably 3-7d;
the freeze drying time in the step (1) is 72 hours, and the vacuum degree is 20-50 Pa.
The carbonization treatment in the step (2) is to heat to 300-500 ℃ at a heating rate of 1-3 ℃/min for 2-3 hours, and then heat to 600-800 ℃ at a heating rate of 4-5 ℃/min for 2-4 hours.
The carbonization treatment in the step (2) is preferably followed by grinding and pulverizing the obtained carbonized product and sieving with a 100-mesh sieve to obtain the CBC carbon material.
The acidification treatment in the step (3) refers to the use of HNO with the concentration of 2-4 mol/L 3 And (3) carrying out reflux treatment on the solution for 6-8 hours at 90 ℃, then centrifugally washing to obtain a supernatant which is neutral, collecting a sample, and drying to obtain the acidized CBC carbon material.
In the process of coating the organic carbon source in the step (4), resorcinol and formaldehyde are adopted as coating raw materials.
The step (4) of coating the surfaces of the nano silicon particles with organic carbon sources specifically comprises the following steps: fully dissolving nano silicon and CTAB in water, adding absolute ethyl alcohol, resorcinol, ammonia water and formaldehyde aqueous solution into the solution, uniformly stirring and dissolving, heating at 30-40 ℃ for 4-6 h, finally moving to room temperature and stirring overnight, centrifuging, filtering and washing, drying and collecting a sample, and obtaining the phenolic resin coated silicon composite material. Wherein the dosage ratio of each substance is as follows: resorcinol: formaldehyde=1: 2 (molar ratio), nano silicon: ctab=1: 2-1: 4 (mass ratio), nano silicon (Aladin, 60-100 nm): resorcinol=1: 0.5 to 1:4 (mass ratio).
The carbonization treatment in the step (4) means calcining for 2-4 hours at 600-800 ℃ at a heating rate of 2-4 ℃/min and cooling along with a furnace.
In the liquid phase mixing process in the step (5), the mass ratio of the Si/C composite material to the acidified CBC carbon material is 1:0.5 to 1:4, the liquid phase mixing time is 6-13 h, preferably, ultrasonic dispersion is carried out for 20-30 min, and then magnetic stirring is carried out for 6-12 h.
The vacuum drying in the step (5) refers to drying in a vacuum drying oven at 80-100 ℃ for 12-24 hours.
The high specific capacity silicon-carbon anode material prepared by the method can still effectively maintain the capacity at 1251.7mAh/g after being cycled for 100 circles under the current density of 500 mA/g.
The high specific capacity silicon-carbon anode material has excellent electrochemical performance and wide application prospect in a lithium ion battery system.
Compared with the prior art, the invention has the following advantages:
1) According to the high specific capacity silicon-carbon composite anode material, nano silicon particles are coated with an amorphous carbon layer in advance and then uniformly dispersed in a carbon network matrix, so that the silicon-carbon composite material with a relatively high specific surface area is obtained;
2) According to the invention, the proportion between the nano silicon and the resorcinol is regulated and controlled, the core-shell type silicon-carbon composite material is dispersed in the carbon fiber network matrix material, and a conductive bridge is formed between the amorphous carbon layer on the surface of the silicon particles and the carbon fiber, so that the conductivity of the material is effectively improved, and meanwhile, a strong buffer space is provided for the volume expansion of silicon.
Drawings
Fig. 1 is an XRD pattern of the silicon carbon composites prepared in examples 1 to 4 and the commercialized nano-silicon particles of comparative example 1.
Fig. 2 is a TEM image of the silicon carbon composite material prepared in examples 2 and 4.
FIG. 3 is a thermogravimetric analysis curve of the silicon carbon composites prepared in examples 1 to 4 and the commercial nano-silicon particles of comparative example 1.
Fig. 4 is a raman spectrum of the silicon-carbon composite materials prepared in examples 1 to 4 and the commercialized nano-silicon particles of comparative example 1.
Fig. 5 is an N2 adsorption/desorption isothermal curve and pore size distribution diagram of the silicon carbon composite material prepared in examples 2 and 4 and the commercialized nano-silicon particles of comparative example 1.
FIG. 6 is a graph comparing the cycle performance of the silicon carbon composites prepared in examples 1 to 4 and the commercial nano-silicon particles of comparative example 1 at a current density of 500 mA/g.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but embodiments of the present invention are not limited thereto. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
The reagents used in the examples are commercially available as usual unless otherwise specified.
Example 1
The preparation method of the high specific capacity silicon-carbon negative electrode material comprises the following steps:
1) Coating the nano silicon particles with phenolic resin according to resorcinol: formaldehyde=1: 2 (molar ratio), nano silicon: ctab=1: 2 (mass ratio), nano silicon (Aladin, 60-100 nm): resorcinol=1: 0.5 Firstly, weighing 0.5g SiNPs and 1g CTAB, adding into a beaker filled with 50mL deionized water, and performing ultrasonic dispersion for 20min; to the solution was then added 25mL of absolute ethanol, 0.25g of resorcinol, 0.2mL of aqueous ammonia solution, and 0.35mL of formaldehyde solution (37 wt% formaldehyde solution for Melin), and the solution was dissolved by magnetic stirring and then transferred to a 40℃water bath for 4h water bath. And finally, moving to room temperature and stirring overnight, and then centrifuging, filtering, washing, drying and collecting a sample to obtain the phenolic resin coated silicon composite material.
2) Drying the collected sample under N 2 Under the atmosphereAnd (3) performing high-temperature carbonization treatment, calcining for 3 hours at 700 ℃ at a heating rate of 2 ℃/min, cooling to room temperature, and taking out to obtain the silicon-carbon negative electrode material for the lithium ion battery.
Half cell assembly and performance characterization: the silicon-carbon composite material prepared in example 1 was mixed with a conductive agent acetylene black, a binder PVDF at 8:1:1, slowly adding NMP organic solvent in the grinding process to form uniform electrode slurry, coating the electrode slurry on the surface of a copper foil current collector, and carrying out vacuum drying, punching and tabletting to obtain the negative plate. The prepared negative electrode sheet was placed in a glove box, and a coin cell (CR 2016) was prepared from an active electrode, a separator (PE separator (polyethylene) having a thickness of 25 μm, available from Celgard Co., USA), and an electrolyte (LiPF having a concentration of 1 mol/L) 6 The solute is LiPF 6 The solvent is an EC+DMC+EMC (volume ratio is 1:1:1) system), the metal lithium sheet is used as a counter electrode, and the anode and cathode shells are assembled in a glove box. The assembled battery cycle performance test conditions: the current density is 500mA/g, and the voltage interval is 0.01-3V, and the cycle is 100 circles. The test results are shown in Table 1.
Example 2:
the preparation method of the high specific capacity silicon-carbon negative electrode material comprises the following steps:
1) Coating the nano silicon particles with phenolic resin according to resorcinol: formaldehyde=1: 2 (molar ratio), nano silicon: ctab=1: 2 (mass ratio), nano silicon (Aladin, 60-100 nm): resorcinol=1: 1 (mass ratio), firstly weighing 0.5g SiNPs and 1g CTAB, adding into a beaker filled with 50mL deionized water, and performing ultrasonic dispersion for 20min; then, 25mL of absolute ethyl alcohol, 0.5g of resorcinol, 0.2mL of ammonia water solution and 0.7mL of formaldehyde solution were added to the solution, and the solution was dissolved by magnetic stirring and then transferred to a water bath kettle at 40 ℃ for 4h of water bath. And finally, moving to room temperature and stirring overnight, and then centrifuging, filtering, washing, drying and collecting a sample to obtain the phenolic resin coated silicon composite material.
2) Drying the collected sample under N 2 And (3) carrying out high-temperature carbonization treatment in the atmosphere, calcining for 3 hours at 700 ℃ at a heating rate of 2 ℃/min, cooling to room temperature, and taking out to obtain the silicon-carbon anode material for the lithium ion battery.
The battery assembly and performance characterization conditions were the same as in example 1, except that the negative electrode materials were different, and the test results are shown in table 1.
Example 3:
the preparation method of the high specific capacity silicon-carbon negative electrode material comprises the following steps:
1) Coating the nano silicon particles with phenolic resin according to resorcinol: formaldehyde=1: 2 (molar ratio), nano silicon: ctab=1: 2 (mass ratio), nano silicon (Aladin, 60-100 nm): resorcinol=1: 2 (mass ratio), firstly weighing 0.5g SiNPs and 1g CTAB, adding into a beaker filled with 50mL deionized water, and performing ultrasonic dispersion for 20min; then, 25mL of absolute ethyl alcohol, 1g of resorcinol, 0.2mL of aqueous ammonia solution and 1.4mL of formaldehyde solution were added to the solution, and the solution was magnetically stirred and dissolved, and then transferred to a water bath kettle at 40℃for 4h of water bath. And finally, moving to room temperature and stirring overnight, and then centrifuging, filtering, washing, drying and collecting a sample to obtain the phenolic resin coated silicon composite material.
2) Drying the collected sample under N 2 And (3) carrying out high-temperature carbonization treatment in the atmosphere, calcining for 3 hours at 700 ℃ at a heating rate of 2 ℃/min, cooling to room temperature, and taking out to obtain the silicon-carbon anode material for the lithium ion battery.
The battery assembly and performance characterization conditions were the same as in example 1, except that the negative electrode materials were different, and the test results are shown in table 1.
Example 4:
the preparation method of the high specific capacity silicon-carbon negative electrode material comprises the following steps:
1) Completely soaking coconuts (15 mm cubes) in 4mol/L NaOH solution, treating the coconuts in water bath/oil bath at 80 ℃ for 4 hours, filtering the coconuts, washing the coconuts with deionized water for multiple times, soaking the coconuts in the deionized water for 3 days, and changing water for multiple times until the soaking solution is neutral, thereby obtaining the BC hydrogel. Freeze-drying the obtained BC hydrogel for 72 hours with the vacuum degree of 30Pa to obtain BC aerogel;
2) Carbonizing the BC aerogel, heating to 400 ℃ at a heating rate of 2 ℃/min, preserving heat for 2 hours, and heating to 700 ℃ at a heating rate of 4 ℃/min, preserving heat for 2 hours;
3) Acidizing the prepared CBC material in 3mol/L nitric acid solution, refluxing at 90 ℃ for 6 hours, centrifugally washing for many times until the supernatant is neutral, collecting a sample, and drying to obtain a pretreated CBC carbon material;
4) Coating the nano silicon particles with phenolic resin according to resorcinol: formaldehyde=1: 2 (molar ratio), nano silicon: ctab=1: 2 (mass ratio), nano silicon (Aladin, 60-100 nm): resorcinol=1: 1 (mass ratio), firstly weighing 0.5g SiNPs and 1g CTAB, adding into a beaker filled with 50mL deionized water, and performing ultrasonic dispersion for 20min (ultrasonic power is 360W, ultrasonic frequency is 40 KHz); then, 25mL of absolute ethyl alcohol, 0.5g of resorcinol, 0.2mL of ammonia water solution and 0.7mL of formaldehyde solution were added to the solution, and the solution was dissolved by magnetic stirring and then transferred to a water bath kettle at 40 ℃ for 4h of water bath. Finally, the mixture is moved to room temperature and stirred overnight, and then the mixture is subjected to centrifugation, suction filtration and washing, drying and sample collection, and the collected sample is carbonized in a tube furnace, calcined for 3 hours at 700 ℃ at a heating rate of 2 ℃/min and cooled with the furnace, so that a material coated by an organic carbon source is obtained;
5) The material coated by the organic carbon source and the CBC carbon material obtained in the step (3) are mixed according to the mass ratio of 1:1, carrying out liquid phase mixing, dispersing the pretreated CBC carbon material in a beaker filled with deionized water, adding the Si/C composite material into the beaker, dispersing for 20min by ultrasonic waves (the ultrasonic power is 360W, and the ultrasonic frequency is 40 KHz), magnetically stirring for 8h, centrifuging, filtering, and drying in a vacuum drying oven at 100 ℃ for 24h to obtain a silicon-carbon anode material for the lithium ion battery;
the battery assembly and performance characterization conditions were the same as in example 1, except that the negative electrode materials were different, and the test results are shown in table 1.
Comparative example 1:
the commercial nano silicon particles (Aladin, 60-100 nm) are directly used as the cathode material for half-cell assembly and performance characterization, and the battery assembly mode and performance characterization conditions are the same as those of the embodiment 1, except that the cathode material is different, and the test results are shown in table 1.
Performance test:
fig. 1 is an XRD pattern of the silicon carbon composites prepared in examples 1 to 4 and the commercialized nano-silicon particles of comparative example 1. Wherein (a) is the XRD patterns of examples 1 to 3 and comparative example 1; (b) is the XRD patterns of example 2 and example 4. As is clear from XRD patterns of examples 1 to 4 and comparative example 1, the materials all show three strong peaks of silicon, and no diffraction peak of the carbon material appears, which means that the thin carbon layer formed after pyrolysis and carbonization of the organic matter and the CBC carbon material all belong to an amorphous carbon material, and the amorphous peak is masked by the diffraction peak of silicon with stronger crystallinity;
fig. 2 is a TEM image of the silicon carbon composite material prepared in examples 2 and 4, wherein (a) to (c) are TEM images of example 2; (d) - (f) are TEM images of example 4. From the TEMs of (a) to (c) of example 2, it is clear that: the TEM of examples 4 (d) to (f) showed that the surface carbon layer was coated with a layer having a thickness of about 7 nm: good conductive bridges are formed between the amorphous carbon layer on the surface of the silicon particles and the CBC carbon material, and the material is uniformly distributed on the CBC carbon network matrix;
FIG. 3 shows thermogravimetric analysis curves of examples 1 to 4 and comparative example 1. As can be seen from fig. 3, as the ratio of the amount of nano-silicon to resorcinol increases, the carbon content increases gradually;
fig. 4 is a raman spectrum of the silicon-carbon composite materials prepared in examples 1 to 4 and the commercialized nano-silicon particles of comparative example 1. As can be seen from the figure, as the carbon content increases, I in the composite material D /I G The ratio of (2) is gradually increased, which indicates that the defect degree of the material is large, and the electron conductivity and the rapid diffusion of lithium ions are more favorable to be improved.
FIG. 5 is N of commercial nano-silicon particles of the silicon-carbon composite materials prepared in examples 2 and 4 and comparative example 1 2 Adsorption/desorption isothermal curves and pore size distribution diagrams. As can be seen from the figure, the silicon-carbon negative electrode material prepared in example 4 has a large specific surface area.
The silicon-carbon composite materials prepared in examples 1 to 4 and the commercialized nano-silicon particles of comparative example 1 were subjected to battery assembly and performance tests, and the test results are shown in the following table:
results of cycle performance test of examples 1 to 4 and comparative example 1
FIG. 6 is a graph comparing the cycle performance of the silicon carbon composites prepared in examples 1 to 4 and the commercial nano-silicon particles of comparative example 1 at a current density of 500 mA/g. As can be seen from fig. 6 and table 1, the silicon carbon negative electrode material prepared in example 4 has a higher cycle capacity.
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.
Claims (10)
1. The preparation method of the high specific capacity silicon-carbon anode material is characterized by comprising the following steps of:
(1) Completely soaking coconuts in NaOH solution for heating treatment, filtering and washing to neutrality to obtain BC hydrogel, and drying the BC hydrogel by adopting a freeze drying technology to obtain white BC aerogel;
(2) Placing the BC aerogel in a tube furnace, and carbonizing in a nitrogen atmosphere to obtain a CBC carbon material;
(3) Acidizing the prepared CBC carbon material;
(4) Coating the surfaces of the nano silicon particles with an organic carbon source, and carbonizing in an inert atmosphere or under nitrogen to obtain a Si/C composite material;
(5) Dispersing the CBC carbon material subjected to the acidification treatment in the step (3) in water, adding the Si/C composite material for liquid phase mixing, and then centrifugally filtering and vacuum drying to prepare the high specific capacity silicon-carbon anode material.
2. The method for preparing the high specific capacity silicon-carbon negative electrode material according to claim 1, wherein the method comprises the following steps:
the heating treatment in the step (1) refers to water bath/oil bath treatment at 60-80 ℃ for 2-4 hours;
the concentration of the NaOH solution in the step (1) is 2-4 mol/L.
3. The method for preparing the high specific capacity silicon-carbon negative electrode material according to claim 1, wherein the method comprises the following steps:
the carbonization treatment in the step (2) is to heat to 300-500 ℃ at a heating rate of 1-3 ℃/min for 2-3 hours, and then heat to 600-800 ℃ at a heating rate of 4-5 ℃/min for 2-4 hours.
4. The method for preparing the high specific capacity silicon-carbon negative electrode material according to claim 1, wherein the method comprises the following steps:
the acidification treatment in the step (3) refers to the use of HNO with the concentration of 2-4 mol/L 3 And (3) carrying out reflux treatment on the solution for 6-8 hours at 90 ℃, then centrifugally washing to obtain a supernatant which is neutral, collecting a sample, and drying to obtain the acidized CBC carbon material.
5. The method for preparing the high specific capacity silicon-carbon negative electrode material according to claim 1, wherein the method comprises the following steps:
in the process of coating the organic carbon source in the step (4), resorcinol and formaldehyde are adopted as coating raw materials.
6. The method for preparing the high specific capacity silicon-carbon negative electrode material according to claim 1, wherein the method comprises the following steps:
the step (4) of coating the surfaces of the nano silicon particles with organic carbon sources specifically comprises the following steps: fully dissolving nano silicon and CTAB in water, adding absolute ethyl alcohol, resorcinol, ammonia water and formaldehyde aqueous solution into the solution, uniformly stirring and dissolving, heating at 30-40 ℃ for 4-6 h, finally moving to room temperature and stirring overnight, centrifuging, filtering and washing, drying and collecting a sample to obtain the phenolic resin coated silicon composite material; wherein the dosage ratio of each substance is as follows: the molar ratio of resorcinol to formaldehyde is 1: 2. the mass ratio of the nano silicon to CTAB is 1: 2-1: 4. the mass ratio of the nano silicon to the resorcinol is 1:0.5 to 1:4.
7. the method for preparing the high specific capacity silicon-carbon negative electrode material according to claim 1, wherein the method comprises the following steps:
the carbonization treatment in the step (4) means calcining for 2-4 hours at 600-800 ℃ at a heating rate of 2-4 ℃/min and cooling along with a furnace.
8. The method for preparing the high specific capacity silicon-carbon negative electrode material according to claim 1, wherein the method comprises the following steps:
in the liquid phase mixing process in the step (5), the mass ratio of the Si/C composite material to the acidified CBC carbon material is 1:0.5 to 1:4, the liquid phase mixing time is 6-13 h.
9. A high specific capacity silicon carbon negative electrode material prepared by the method of any one of claims 1-8.
10. The use of the high specific capacity silicon-carbon negative electrode material according to claim 9 in lithium ion batteries.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102709536A (en) * | 2012-06-28 | 2012-10-03 | 东华大学 | Silicon-carbon composite material and preparation method thereof |
| CN103474667A (en) * | 2013-08-16 | 2013-12-25 | 深圳市贝特瑞新能源材料股份有限公司 | Silicon-carbon composite negative electrode material for lithium ion battery and preparation method thereof |
| CN105609711A (en) * | 2014-11-21 | 2016-05-25 | 国家纳米科学中心 | Micro-nano structured silicon-carbon composite microsphere, preparation method and application thereof |
| CN111470486A (en) * | 2020-04-14 | 2020-07-31 | 陕西煤业化工技术研究院有限责任公司 | Three-dimensional silicon-carbon composite negative electrode material, preparation method thereof and application thereof in lithium ion battery |
| CN112510185A (en) * | 2020-11-30 | 2021-03-16 | 南通路远科技信息有限公司 | Silicon-carbon composite negative electrode material and manufacturing method thereof |
| RU2767168C1 (en) * | 2020-12-29 | 2022-03-16 | Федеральное государственное бюджетное учреждение науки Институт проблем химической физики РАН (ИПХФ РАН) | Silicon-carbon material of negative electrode of lithium-ion battery and method of preparation thereof (embodiments) |
| CN114709386A (en) * | 2022-03-24 | 2022-07-05 | 华南理工大学 | Porous silicon-carbon composite material and preparation method and application thereof |
-
2023
- 2023-03-16 CN CN202310257954.XA patent/CN116477600A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102709536A (en) * | 2012-06-28 | 2012-10-03 | 东华大学 | Silicon-carbon composite material and preparation method thereof |
| CN103474667A (en) * | 2013-08-16 | 2013-12-25 | 深圳市贝特瑞新能源材料股份有限公司 | Silicon-carbon composite negative electrode material for lithium ion battery and preparation method thereof |
| CN105609711A (en) * | 2014-11-21 | 2016-05-25 | 国家纳米科学中心 | Micro-nano structured silicon-carbon composite microsphere, preparation method and application thereof |
| CN111470486A (en) * | 2020-04-14 | 2020-07-31 | 陕西煤业化工技术研究院有限责任公司 | Three-dimensional silicon-carbon composite negative electrode material, preparation method thereof and application thereof in lithium ion battery |
| CN112510185A (en) * | 2020-11-30 | 2021-03-16 | 南通路远科技信息有限公司 | Silicon-carbon composite negative electrode material and manufacturing method thereof |
| RU2767168C1 (en) * | 2020-12-29 | 2022-03-16 | Федеральное государственное бюджетное учреждение науки Институт проблем химической физики РАН (ИПХФ РАН) | Silicon-carbon material of negative electrode of lithium-ion battery and method of preparation thereof (embodiments) |
| CN114709386A (en) * | 2022-03-24 | 2022-07-05 | 华南理工大学 | Porous silicon-carbon composite material and preparation method and application thereof |
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