CN114068869B - Core-shell structure silicon @ silicon oxide/carbon anode material and preparation method and application thereof - Google Patents
Core-shell structure silicon @ silicon oxide/carbon anode material and preparation method and application thereof Download PDFInfo
- Publication number
- CN114068869B CN114068869B CN202111392573.XA CN202111392573A CN114068869B CN 114068869 B CN114068869 B CN 114068869B CN 202111392573 A CN202111392573 A CN 202111392573A CN 114068869 B CN114068869 B CN 114068869B
- Authority
- CN
- China
- Prior art keywords
- silicon
- core
- silicon oxide
- shell structure
- carbon
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 229910052814 silicon oxide Inorganic materials 0.000 title claims abstract description 46
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 32
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 32
- 239000011258 core-shell material Substances 0.000 title claims abstract description 25
- 239000010405 anode material Substances 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229920000642 polymer Polymers 0.000 claims abstract description 15
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000002243 precursor Substances 0.000 claims abstract description 13
- 238000000197 pyrolysis Methods 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- ZNZYKNKBJPZETN-WELNAUFTSA-N Dialdehyde 11678 Chemical compound N1C2=CC=CC=C2C2=C1[C@H](C[C@H](/C(=C/O)C(=O)OC)[C@@H](C=C)C=O)NCC2 ZNZYKNKBJPZETN-WELNAUFTSA-N 0.000 claims abstract description 11
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 6
- 239000002904 solvent Substances 0.000 claims abstract description 4
- 238000005882 aldol condensation reaction Methods 0.000 claims abstract description 3
- 239000011261 inert gas Substances 0.000 claims abstract description 3
- 239000002994 raw material Substances 0.000 claims abstract description 3
- 239000011863 silicon-based powder Substances 0.000 claims abstract description 3
- 239000010703 silicon Substances 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 19
- 239000000243 solution Substances 0.000 claims description 16
- 239000005543 nano-size silicon particle Substances 0.000 claims description 14
- 239000007773 negative electrode material Substances 0.000 claims description 12
- 239000006185 dispersion Substances 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 7
- 238000004108 freeze drying Methods 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical compound O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 0.000 claims description 7
- 239000012300 argon atmosphere Substances 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 claims description 4
- ZWLUXSQADUDCSB-UHFFFAOYSA-N phthalaldehyde Chemical compound O=CC1=CC=CC=C1C=O ZWLUXSQADUDCSB-UHFFFAOYSA-N 0.000 claims description 4
- ALXPZLQBSUZCHN-UHFFFAOYSA-N 4-phenylcyclohexa-2,4-diene-1,1-dicarbaldehyde Chemical compound C1=CC(C=O)(C=O)CC=C1C1=CC=CC=C1 ALXPZLQBSUZCHN-UHFFFAOYSA-N 0.000 claims description 3
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 229940015043 glyoxal Drugs 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 229940054441 o-phthalaldehyde Drugs 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 9
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 239000002210 silicon-based material Substances 0.000 abstract description 3
- 230000002708 enhancing effect Effects 0.000 abstract 1
- 238000011031 large-scale manufacturing process Methods 0.000 abstract 1
- 230000001351 cycling effect Effects 0.000 description 10
- 230000014759 maintenance of location Effects 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 239000011247 coating layer Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- HSJKGGMUJITCBW-UHFFFAOYSA-N 3-hydroxybutanal Chemical compound CC(O)CC=O HSJKGGMUJITCBW-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- 238000009831 deintercalation Methods 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- 230000002687 intercalation Effects 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- 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 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- -1 lithium hexafluorophosphate Chemical compound 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 239000011115 styrene butadiene Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical class CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Composite Materials (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Silicon Compounds (AREA)
Abstract
The invention discloses a core-shell structure silicon @ silicon oxide/carbon anode material, a preparation method and application thereof, which are characterized in that gamma-aminopropyl triethoxysilane, dialdehyde molecules and nanometer silicon powder are used as raw materials, pure water is used as a solvent, a polymer precursor is prepared through aldol condensation reaction, and then a target product is obtained through pyrolysis under the condition of inert gas. The preparation method disclosed by the invention has the advantages of simple process, small influence on environment, low cost and suitability for large-scale production, and the structure of the obtained material can effectively relieve the problems of large volume expansion rate and poor conductivity of the silicon-based material, thereby being beneficial to enhancing the cycle stability of the lithium ion battery.
Description
Technical Field
The invention belongs to the technical field of new energy, and particularly relates to a core-shell structure silicon@silicon oxide/carbon anode material and a preparation method and application thereof.
Background
As the demand for lithium ion batteries is increasing in emerging markets for portable electronic products and electric vehicles, the development of lithium ion batteries having higher energy densities is becoming more urgent. Silicon is widely recognized as one of the most promising negative electrode materials. Each silicon atom can be combined with four lithium ions to a capacity about ten times that of a graphite anode. In addition, silicon is the second most abundant element in the crust, is environmentally friendly and has a low delithiation potential (0.4 v vs. Li/li+), and is therefore a very potential negative electrode material. However, silicon has a volume change exceeding 300% during lithium intercalation and deintercalation, thereby causing serious particle pulverization and formation of a very unstable Solid Electrolyte Interface (SEI), which may cause problems of rapid capacity fading, limited cycle life, and the like.
Silicon oxide is considered as the most potential silicon-based negative electrode material because it loses a theoretical specific capacity and the volume change of lithium intercalation/deintercalation is reduced as compared with a pure silicon material. The electron conductivity of pure silicon and silicon oxide is not ideal, and it is generally necessary to coat a carbon layer to improve the conductivity and slow down the breaking of the SEI film caused by volume expansion, and the theoretical specific capacity of the carbon coating layer is very low, which reduces the specific capacity of the material itself. By introducing the silicon oxide with high specific capacity and low volume expansion into the carbon layer, the silicon oxide doped with carbon is used as a coating layer of pure silicon material to form an ideal choice.
Disclosure of Invention
The invention provides a preparation method of a silicon @ silicon oxide/carbon anode material with a core-shell structure, which aims to improve the stability of the silicon-based anode material in the cycling process of a lithium ion battery and prolong the service life of the battery.
The invention adopts the following technical scheme to solve the technical problems:
the invention firstly discloses a preparation method of a core-shell structure silicon@silicon oxide/carbon negative electrode material, which takes gamma-aminopropyl triethoxysilane, dialdehyde molecules and nanometer silicon powder as raw materials and pure water as a solvent, and polymer precursors are prepared through aldol ammonia condensation reaction, and then the core-shell structure silicon@silicon oxide/carbon negative electrode material is obtained through pyrolysis under the condition of inert gas, and is marked as Si@SiOx/C. The method specifically comprises the following steps:
step 1, adding dialdehyde molecules into pure water, and uniformly stirring to obtain a solution A;
step 2, adding nano silicon powder into an aqueous solution of sodium dodecyl sulfate, and uniformly stirring to obtain a dispersion liquid B;
step 3, adding the dispersion liquid B into the solution A, uniformly stirring, slowly dropwise adding gamma-aminopropyl triethoxysilane into the solution, and reacting under the stirring condition to obtain a polymer precursor;
and 4, freeze-drying the polymer precursor, and then performing high-temperature pyrolysis in an argon atmosphere to obtain Si@SiOx/C.
Further, the dialdehyde molecule comprises at least one of glyoxal, glutaraldehyde, terephthalaldehyde, phthalaldehyde, and 4, 4-biphenyldicarboxaldehyde.
Further, the molar ratio of the gamma-aminopropyl triethoxysilane to the dialdehyde molecule to the nano silicon powder is 2:1:0.1 to 0.2.
Further, in the step 2, the mass ratio of the nano silicon powder to the sodium dodecyl sulfate is 1:0.5 to 1.
Further, in the step 1, the stirring is performed at a speed of 400r/min for 30 minutes at 80 ℃.
Further, in the step 3, the stirring speed of the reaction is 300-500 r/min, the reaction temperature is 80 ℃, and the reaction time is 30-60 minutes.
Further, in the step 4, the freeze-drying temperature is-50 ℃ and the time is 24 hours, the high-temperature pyrolysis temperature is 600-1000 ℃, the heating rate is 5-20 ℃/min, and the pyrolysis time is 2-4 hours.
The Si@SiOx/C obtained by the preparation method has a core-shell structure, nano silicon particles are wrapped in a carbon-doped silicon oxide spherical shell, and the material can be used in a lithium ion battery cathode.
Compared with the prior art, the invention has the beneficial effects that:
1. the core-shell structure silicon@silicon oxide/carbon anode material provided by the invention takes dialdehyde molecules as a cross-linking agent, nano silicon particles are wrapped in polymer spherical shells containing organic silicon and carbon through hydrolysis condensation reaction of gamma-aminopropyl triethoxysilane, and the polymer spherical shells containing the organic silicon and the carbon are converted into carbon-doped silicon oxide spherical shells through high-temperature pyrolysis under an argon atmosphere. The nano silicon@silicon oxide/carbon with the core-shell structure provides enough buffer for volume expansion, and the carbon doped in the shell can effectively improve the electronic conductivity of the material, thereby being beneficial to improving the cycle stability of a lithium ion battery and prolonging the service life of the battery, and the mass specific capacity of the nano silicon@silicon oxide/carbon is better than that of commercial graphite.
2. The preparation method of the silicon@silicon oxide/carbon anode material provided by the invention has the advantages of simple process, environment friendliness and low cost, and is suitable for mass production.
Drawings
FIG. 1 is a schematic representation of the reaction of gamma-aminopropyl triethoxysilane (APTES) with Terephthalaldehyde (TA), phthalaldehyde (OPA) and 4, 4-Biphenyldicarboxaldehyde (BD), each dialdehyde molecule being linked to two gamma-aminopropyl triethoxysilanes by aldol condensation.
FIG. 2 is a high resolution transmission electron microscope image of a core-shell structured silicon @ silicon oxide/carbon anode material of example 1 of the present invention;
FIG. 3 shows a core-shell structure silicon @ silicon oxide/carbon anode material of example 1 of the present invention at 0.1Ag -1 Cycling performance plot at current density;
FIG. 4 is a graph showing the rate performance of the core-shell structure Si@silica/carbon negative electrode material according to example 1 of the present invention;
FIG. 5 shows a core-shell structure silicon @ silicon oxide/carbon anode material of example 2 of the present invention at 0.1Ag -1 Cycling performance plot at current density;
FIG. 6 shows a core-shell structure silicon @ silicon oxide/carbon anode material of example 3 of the present invention at 0.1Ag -1 Cycling performance plot at current density;
FIG. 7 shows the core-shell structure silicon @ silicon oxide/carbon negative electrode material of examples 1, 2, and 3 of the present invention at 0.1Ag -1 Comparison of cycle performance at current density.
Detailed Description
The technical scheme of the present invention is described in detail below by specific examples, which are implemented on the premise of the technical scheme of the present invention, and detailed implementation and specific operation processes are given, but the protection scope of the present invention is not limited to the following examples.
Example 1
The present example prepares Si@SiOx/C as follows:
step 1, 0.67g (5 mmol) of terephthalaldehyde was added to 200mL of pure water, and stirred at a rate of 400r/min at 80℃for 30 minutes to obtain a solution A.
Step 2, dissolving 0.028g (1 mmol) of nano silicon powder with the particle size of 30nm and 0.028g of sodium dodecyl sulfate in 100mL of pure water, stirring for 30min, and then performing ultrasonic treatment for 30min to obtain dispersion B.
And 3, adding the dispersion liquid B into the solution A, uniformly stirring, and slowly dropwise adding 2.34mL (10 mmol) of gamma-aminopropyl triethoxysilane into the solution A, and reacting for 60min at 80 ℃ under the stirring condition of 400r/min to obtain a polymer precursor.
And 4, freeze-drying the polymer precursor for 24 hours at the temperature of 50 ℃ below zero, and then performing high-temperature pyrolysis for 2 hours at the temperature of 900 ℃ under argon atmosphere (the heating rate is 10 ℃/min), thereby obtaining the core-shell structure silicon@silicon oxide/carbon negative electrode material Si@SiOx/C.
FIG. 2 is a transmission electron microscope image of the Si@SiOx/C material obtained in this example, demonstrating the generation of a core-shell structure.
The Si@SiOx/C material obtained in the embodiment is mixed with superconducting carboqin black, sodium carboxymethyl cellulose and styrene-butadiene latex according to the proportion of 70:20:6:4, adding a proper amount of pure water, mixing uniformly, preparing slurry, coating the slurry on the copper foil, wherein the thickness of the coating layer is 150 mu m, and vacuum drying for 6 hours at 80 ℃ to obtain the electrode slice.
The prepared electrode plate is cut into a circular plate with the diameter of 12mm, a metal lithium plate is used as a counter electrode, a Celgard2400 circular plate with the diameter of 16mm is used as a diaphragm, 1mol/L lithium hexafluorophosphate solution is used as electrolyte (wherein the solvent is a mixed solution obtained by mixing methyl ethyl carbonate and ethylene carbonate according to the volume ratio of 1:1 and then adding 10wt% fluoroethylene carbonate), and the mixture is assembled into the button cell in a glove box. The NEWARE-CT-4008T battery test system and the CHI660E electrochemical workstation were used to test the performance of the button cell at 0.01-3V charge-discharge voltage.
FIG. 3 shows the button cell of the present embodiment at 0.1Ag -1 The cycling performance diagram under the current density can still reach 512mAhg-1 after cycling for 100 circles, the capacity retention rate is 64.9%, the initial coulombic efficiency is 53.2%, and the average coulombic efficiency is 98.20%. The cycle performance of the cathode is far superior to that of a pure silicon cathode.
FIG. 4 is a graph showing the rate performance of the button cell of the present example, at 0.1Ag -1 、0.3Ag -1 、0.5Ag -1 、1Ag -1 、3Ag -1 、5Ag -1 After the multiplying power performance test is carried out under different current densities, the capacity is 0.1A g -1 Can recover to about 450mAhg at current density -1 The material is proved to have excellent cycle stability and rate capability.
Example 2
The present example prepares Si@SiOx/C as follows:
step 1, 0.67g (5 mmol) of terephthalaldehyde was added to 200mL of pure water, and stirred at a rate of 400r/min at 80℃for 30 minutes to obtain a solution A.
Step 2, 0.014g (0.5 mmol) of nano silicon powder with the particle size of 30nm and 0.014g of sodium dodecyl sulfate are dissolved in 100mL of pure water, stirred for 30min, and then sonicated for 30min to obtain dispersion B.
And 3, adding the dispersion liquid B into the solution A, uniformly stirring, and slowly dropwise adding 2.34mL (10 mmol) of gamma-aminopropyl triethoxysilane into the solution A, and reacting for 60min at 80 ℃ under the stirring condition of 400r/min to obtain a polymer precursor.
And 4, freeze-drying the polymer precursor for 24 hours at the temperature of 50 ℃ below zero, and then performing high-temperature pyrolysis for 2 hours at the temperature of 900 ℃ under argon atmosphere (the heating rate is 10 ℃/min), thereby obtaining the core-shell structure silicon@silicon oxide/carbon negative electrode material Si@SiOx/C.
The Si@SiOx/C material obtained in this example was assembled into a button cell in the same manner as in example 1, and the button cell was tested for various properties at 0.01-3V charge-discharge voltage using a NEWARE-CT-4008T cell test system and a CHI660E electrochemical workstation.
FIG. 5 shows the button cell of the present embodiment at 0.1Ag -1 The cycling performance diagram under the current density can still reach 478mAhg < -1 > after cycling for 100 circles, the capacity retention rate is 76.6%, the initial coulombic efficiency is 51.5%, and the average coulombic efficiency is 98.65%.
Example 3
The present example prepares Si@SiOx/C as follows:
step 1, 0.67g (5 mmol) of terephthalaldehyde was added to 200mL of pure water, and stirred at a rate of 400r/min at 80℃for 30 minutes to obtain a solution A.
Step 2, 0.028g (1 mmol) of nano silicon powder with the particle size of 30nm and 0.014g of sodium dodecyl sulfate are dissolved in 100mL of pure water, stirred for 30min, and then sonicated for 30min to obtain dispersion B.
And 3, adding the dispersion liquid B into the solution A, uniformly stirring, and slowly dropwise adding 2.34mL (10 mmol) of gamma-aminopropyl triethoxysilane into the solution A, and reacting for 60min at 80 ℃ under the stirring condition of 400r/min to obtain a polymer precursor.
And 4, freeze-drying the polymer precursor for 24 hours at the temperature of 50 ℃ below zero, and then performing high-temperature pyrolysis for 2 hours at the temperature of 900 ℃ under argon atmosphere (the heating rate is 10 ℃/min), thereby obtaining the core-shell structure silicon@silicon oxide/carbon negative electrode material Si@SiOx/C.
The Si@SiOx/C material obtained in this example was assembled into a button cell in the same manner as in example 1, and the button cell was tested for various properties at 0.01-3V charge-discharge voltage using a NEWARE-CT-4008T cell test system and a CHI660E electrochemical workstation.
FIG. 6 shows the button cell of the present embodiment at 0.1Ag -1 The cycling performance diagram under the current density can still reach 474mAhg-1 after cycling for 100 circles, the capacity retention rate is 65.2%, the initial coulombic efficiency is 52.7%, and the average coulombic efficiency is 98.28%.
FIG. 7 shows the 0.1Ag for the button cell of examples 1, 2, and 3 -1 The cycle performance at current density is compared to the graph, with the highest capacity for example 1 of the three examples and the highest capacity retention after 100 cycles for example 2.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, and alternatives falling within the spirit and principles of the invention.
Claims (8)
1. A preparation method of a core-shell structure silicon@silicon oxide/carbon anode material is characterized by comprising the following steps of: taking gamma-aminopropyl triethoxysilane, dialdehyde molecules and nano silicon powder as raw materials and pure water as a solvent, firstly preparing a polymer precursor through aldol condensation reaction, and then performing pyrolysis under the condition of inert gas to obtain a core-shell structure silicon@silicon oxide/carbon anode material, which is marked as Si@SiOx/C; the core-shell structure silicon@silicon oxide/carbon negative electrode material is prepared by wrapping nano silicon particles inside a carbon-doped silicon oxide spherical shell; the preparation method comprises the following steps:
step 1, adding dialdehyde molecules into pure water, and uniformly stirring to obtain a solution A; the dialdehyde molecule comprises at least one of glyoxal, glutaraldehyde, terephthalaldehyde, o-phthalaldehyde and 4, 4-biphenyldicarboxaldehyde;
step 2, adding nano silicon powder into an aqueous solution of sodium dodecyl sulfate, and uniformly stirring to obtain a dispersion liquid B;
step 3, adding the dispersion liquid B into the solution A, uniformly stirring, slowly dropwise adding gamma-aminopropyl triethoxysilane into the solution, and reacting under the stirring condition to obtain a polymer precursor;
and 4, freeze-drying the polymer precursor, and then performing high-temperature pyrolysis in an argon atmosphere to obtain Si@SiOx/C.
2. The method of manufacturing according to claim 1, characterized in that: the molar ratio of the gamma-aminopropyl triethoxysilane to the dialdehyde to the nanometer silicon powder is 2:1:0.1 to 0.2.
3. The method of manufacturing according to claim 1, characterized in that: in the step 2, the mass ratio of the nano silicon powder to the sodium dodecyl sulfate is 1:0.1 to 1.
4. The method of manufacturing according to claim 1, characterized in that: in step 1, the stirring is performed at a speed of 400r/min for 30 minutes at 80 ℃.
5. The method of manufacturing according to claim 1, characterized in that: in the step 3, the stirring speed of the reaction is 300-500 r/min, the reaction temperature is 80 ℃, and the reaction time is 30-60 minutes.
6. The method of manufacturing according to claim 1, characterized in that: in the step 4, the freeze drying temperature is-50 ℃ and the time is 24 hours, the high-temperature pyrolysis temperature is 600-1000 ℃, the heating rate is 5-20 ℃/min, and the pyrolysis time is 2-4 hours.
7. A core-shell structured silicon @ silicon oxide/carbon anode material prepared by the method of any one of claims 1 to 6.
8. Use of the core-shell structured silicon @ silicon oxide/carbon negative electrode material of claim 7 in a negative electrode of a lithium ion battery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111392573.XA CN114068869B (en) | 2021-11-23 | 2021-11-23 | Core-shell structure silicon @ silicon oxide/carbon anode material and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111392573.XA CN114068869B (en) | 2021-11-23 | 2021-11-23 | Core-shell structure silicon @ silicon oxide/carbon anode material and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114068869A CN114068869A (en) | 2022-02-18 |
| CN114068869B true CN114068869B (en) | 2023-08-29 |
Family
ID=80279302
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111392573.XA Active CN114068869B (en) | 2021-11-23 | 2021-11-23 | Core-shell structure silicon @ silicon oxide/carbon anode material and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114068869B (en) |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2331602A1 (en) * | 1992-11-30 | 1994-05-31 | Canon Kabushiki Kaisha | Method of manufacturing a positive electrode active material of a secondary battery |
| WO2013106782A2 (en) * | 2012-01-11 | 2013-07-18 | Energ2 Technologies, Inc. | Hard carbon materials |
| CN107611406A (en) * | 2017-09-21 | 2018-01-19 | 中南大学 | A kind of preparation method of silicon/graphene/carbon composite negative pole material |
| CN107623116A (en) * | 2017-09-22 | 2018-01-23 | 苏州海旭新材料科技有限公司 | A kind of composite cathode material of lithium ion battery and preparation method thereof |
| CN108183199A (en) * | 2017-11-23 | 2018-06-19 | 合肥国轩高科动力能源有限公司 | Modified silicon-based negative electrode material of lithium ion battery and preparation method thereof |
| CN108807872A (en) * | 2018-04-25 | 2018-11-13 | 福建翔丰华新能源材料有限公司 | A kind of preparation method of the silicon-carbon cathode material of the small spherical structure of caged |
| CN111312996A (en) * | 2018-12-12 | 2020-06-19 | 上海杉杉科技有限公司 | Silicon-carbon composite material, lithium ion battery, preparation method and application |
| CN112310386A (en) * | 2020-11-02 | 2021-02-02 | 哈尔滨工业大学 | Silicon oxide/carbon lithium ion battery cathode material with hollow structure and preparation method and application thereof |
| CN112366301A (en) * | 2020-11-11 | 2021-02-12 | 宁夏博尔特科技有限公司 | Silicon/silicon oxide/carbon composite negative electrode material for lithium ion battery and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11476513B2 (en) * | 2016-11-28 | 2022-10-18 | Amogreentech Co., Ltd. | Heat dissipating elastic body composition and heat dissipating elastic body realized therefrom |
-
2021
- 2021-11-23 CN CN202111392573.XA patent/CN114068869B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2331602A1 (en) * | 1992-11-30 | 1994-05-31 | Canon Kabushiki Kaisha | Method of manufacturing a positive electrode active material of a secondary battery |
| WO2013106782A2 (en) * | 2012-01-11 | 2013-07-18 | Energ2 Technologies, Inc. | Hard carbon materials |
| CN107611406A (en) * | 2017-09-21 | 2018-01-19 | 中南大学 | A kind of preparation method of silicon/graphene/carbon composite negative pole material |
| CN107623116A (en) * | 2017-09-22 | 2018-01-23 | 苏州海旭新材料科技有限公司 | A kind of composite cathode material of lithium ion battery and preparation method thereof |
| CN108183199A (en) * | 2017-11-23 | 2018-06-19 | 合肥国轩高科动力能源有限公司 | Modified silicon-based negative electrode material of lithium ion battery and preparation method thereof |
| CN108807872A (en) * | 2018-04-25 | 2018-11-13 | 福建翔丰华新能源材料有限公司 | A kind of preparation method of the silicon-carbon cathode material of the small spherical structure of caged |
| CN111312996A (en) * | 2018-12-12 | 2020-06-19 | 上海杉杉科技有限公司 | Silicon-carbon composite material, lithium ion battery, preparation method and application |
| CN112310386A (en) * | 2020-11-02 | 2021-02-02 | 哈尔滨工业大学 | Silicon oxide/carbon lithium ion battery cathode material with hollow structure and preparation method and application thereof |
| CN112366301A (en) * | 2020-11-11 | 2021-02-12 | 宁夏博尔特科技有限公司 | Silicon/silicon oxide/carbon composite negative electrode material for lithium ion battery and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| Core-shell structured SiOx@C with controllable mesopores as anode for lithium-ion batteries;Ting Wang，et al.;《Material letters》;第161卷;全文 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114068869A (en) | 2022-02-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106848264A (en) | A kind of porous silicon oxide lithium ion battery negative material and preparation method thereof | |
| CN108493421B (en) | Preparation method of tin-silicon-based graphene ball cathode material for lithium ion battery | |
| WO2021120155A1 (en) | Nano-tin-silicon composite negative electrode material, and preparation method therefor and use thereof | |
| CN111009647B (en) | Lithium borosilicate alloy cathode active material of lithium secondary battery, cathode, preparation and application thereof | |
| CN108172775A (en) | Phosphorus-doped silicon-carbon negative electrode material for lithium ion battery and preparation method thereof | |
| CN111313000B (en) | Lithium-sulfur battery positive electrode material and preparation method and application thereof | |
| CN107464938B (en) | Molybdenum carbide/carbon composite material with core-shell structure, preparation method thereof and application thereof in lithium air battery | |
| CN115101741B (en) | Nitrogen-doped graphene-coated silicon-carbon composite material and preparation method and application thereof | |
| CN112652758B (en) | Silicon oxide/carbon microsphere composite negative electrode material for lithium ion battery and preparation method thereof | |
| CN108682813A (en) | A kind of preparation method and application of Si-C composite material | |
| CN113363473B (en) | Preparation method of high-first-efficiency SiO graphite composite negative electrode material | |
| CN112110448A (en) | Nitrogen-doped carbon and nano-silicon composite anode material and preparation method thereof | |
| CN111960422A (en) | Preparation method and application of two-dimensional silicon nanomaterial | |
| CN111370656B (en) | Silicon-carbon composite material and preparation method and application thereof | |
| CN111313012A (en) | Multiwalled carbon nanotube graphite lithium ion battery negative electrode material and preparation method thereof | |
| CN108091866B (en) | Preparation method of silicon-carbon negative electrode material for lithium ion battery | |
| CN113871605A (en) | Pre-lithiated silicon-based negative electrode material and preparation method and application thereof | |
| CN111584855B (en) | Preparation method of silicon monoxide @ resin carbon/CVD carbon composite negative electrode material | |
| CN110854359B (en) | Silicon/carbon composite material and preparation method thereof | |
| CN114068869B (en) | Core-shell structure silicon @ silicon oxide/carbon anode material and preparation method and application thereof | |
| CN114242962B (en) | Lithium orthosilicate and carbon coated nano-silicon composite material and preparation method and application thereof | |
| CN113130879B (en) | Preparation method of high-adsorption catalytic performance cathode material of lithium-sulfur battery | |
| CN112421002B (en) | High-capacity silicon-carbon material and preparation method thereof | |
| CN111261866B (en) | Preparation method of ZnO/C nano composite microsphere material with capsule structure | |
| CN114122371A (en) | Preparation method of porous silicon-carbon negative electrode material of lithium ion battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |