CN114420910B - Nitrogen-doped silicon-carbon composite material with core-shell structure and preparation method thereof - Google Patents
Nitrogen-doped silicon-carbon composite material with core-shell structure and preparation method thereof Download PDFInfo
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- 239000011258 core-shell material Substances 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 44
- 239000002153 silicon-carbon composite material Substances 0.000 title claims abstract description 27
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims abstract description 56
- 239000005543 nano-size silicon particle Substances 0.000 claims abstract description 47
- 239000000463 material Substances 0.000 claims abstract description 41
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000003999 initiator Substances 0.000 claims abstract description 25
- 229920000767 polyaniline Polymers 0.000 claims abstract description 25
- 239000000178 monomer Substances 0.000 claims abstract description 23
- 239000002253 acid Substances 0.000 claims abstract description 21
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 18
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000003763 carbonization Methods 0.000 claims abstract description 14
- 239000007788 liquid Substances 0.000 claims description 27
- 239000006185 dispersion Substances 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 8
- 230000001681 protective effect Effects 0.000 claims description 7
- 238000000926 separation method Methods 0.000 claims description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 238000010000 carbonizing Methods 0.000 claims description 4
- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical compound [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 3
- 238000004321 preservation Methods 0.000 claims description 3
- NGWKGSCSHDHHAJ-YPFQVHCOSA-N Liquoric acid Chemical compound C1C[C@H](O)C(C)(C)C2CC[C@@]3(C)[C@]4(C)C[C@H]5O[C@@H]([C@](C6)(C)C(O)=O)C[C@@]5(C)[C@@H]6C4=CC(=O)C3[C@]21C NGWKGSCSHDHHAJ-YPFQVHCOSA-N 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 abstract description 23
- 238000005530 etching Methods 0.000 abstract description 9
- 238000012983 electrochemical energy storage Methods 0.000 abstract description 4
- 239000002131 composite material Substances 0.000 description 20
- 238000012360 testing method Methods 0.000 description 19
- 239000000243 solution Substances 0.000 description 18
- 238000011056 performance test Methods 0.000 description 12
- 229910052799 carbon Inorganic materials 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000012512 characterization method Methods 0.000 description 8
- 238000001878 scanning electron micrograph Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 239000010410 layer Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 239000003575 carbonaceous material Substances 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 229910052681 coesite Inorganic materials 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229910052906 cristobalite Inorganic materials 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 229910052682 stishovite Inorganic materials 0.000 description 4
- 229910052905 tridymite Inorganic materials 0.000 description 4
- 238000001132 ultrasonic dispersion Methods 0.000 description 4
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 3
- 239000010405 anode material Substances 0.000 description 3
- 239000011247 coating layer Substances 0.000 description 3
- 239000002612 dispersion medium Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000002210 silicon-based material Substances 0.000 description 2
- 239000011870 silicon-carbon composite anode material Substances 0.000 description 2
- 239000012798 spherical particle Substances 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 1
- JHWIEAWILPSRMU-UHFFFAOYSA-N 2-methyl-3-pyrimidin-4-ylpropanoic acid Chemical compound OC(=O)C(C)CC1=CC=NC=N1 JHWIEAWILPSRMU-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 239000006181 electrochemical material Substances 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 239000007770 graphite material Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 239000011863 silicon-based powder Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
Abstract
The invention provides a nitrogen-doped silicon-carbon composite material with a core-shell structure and a preparation method thereof. According to the preparation method provided by the invention, firstly, aniline monomers and nano silicon powder are dispersed into acid liquor, then, the acid liquor is mixed with hydrogen peroxide solution and initiator solution for hydrothermal reaction to form polyaniline-coated nano silicon material, and finally, carbonization treatment is carried out to obtain the polyaniline-coated nano silicon material with a core-shell structure. The preparation method is characterized in that the preparation method is realized by one-step hydrothermal reaction and one-step carbonization, a plurality of complex and complicated steps are not needed, a template agent or an etching agent is not needed to assist in forming the core-shell, the condition is mild, the preparation process and the operation difficulty are greatly simplified, the preparation cost is reduced, and the template agent or the etching agent is not used, so that the post-treatment of the agents is avoided; in addition, the preparation method can ensure the electrochemical performance of the material, so that the material has excellent electrochemical energy storage performance and cycle stability.
Description
Technical Field
The invention relates to the field of electrochemical materials, in particular to a nitrogen-doped silicon-carbon composite material with a core-shell structure and a preparation method thereof.
Background
Lithium ion batteries have been widely used in various fields as an energy storage material, and with the continuous improvement of the performance requirements of lithium ion batteries, high-capacity electrode materials have become a hot spot in current research. The theoretical lithium intercalation capacity of the silicon material at room temperature is 3580mAh/g, which is ten times that of the traditional graphite material, and the silicon material is the anode material of the lithium ion battery of the next generation with the highest potential. However, silicon has serious volume expansion, which causes rapid capacity decay, so commercialization of silicon anodes still faces many challenges.
And silicon and a carbon material are compounded, so that the electrochemical performance of the material is improved. The conductivity of the carbon material can be improved by nitrogen doping, and the nitrogen-containing polymer can obtain materials with different microstructures by controlling synthesis conditions, so that the nitrogen-doped carbon-based material is a good raw material for preparing the nitrogen-doped carbon-based material. According to the Chinese patent application with the application number of CN201810119502, polyaniline is adopted as a raw material to prepare the nitrogen-doped silicon-based anode material, so that the structural stability of the material is effectively improved. The preparation method of the nitrogen-doped silicon-carbon composite anode material is disclosed in Chinese patent application No. CN201710323485, wherein a layer of SiO2 is coated on the surface of nano Si by a sol-gel method to obtain Si@SiO2, then the Si@SiO2 is coated by polyacrylamide by reverse suspension polymerization, and the SiO2 is etched by HF after high-temperature activation to obtain the nitrogen-doped silicon-carbon composite anode material.
However, the preparation methods of the common nitrogen-doped silicon-carbon composite materials are all carried out in multiple steps, the preparation conditions are harsh, a template agent or an etching agent is needed to assist in forming the core-shell, and the agents need to be subjected to post-treatment, so that the preparation cost and the complexity are further increased.
Disclosure of Invention
In view of the above, the present invention aims to provide a nitrogen-doped silicon-carbon composite material with a core-shell structure and a preparation method thereof. The preparation method provided by the invention can obtain the nitrogen-doped silicon-carbon composite material with a core-shell structure, can greatly simplify the process, reduces the preparation cost and ensures the electrochemical performance of the material.
The invention provides a preparation method of a nitrogen-doped silicon-carbon composite material with a core-shell structure, which comprises the following steps:
a) Dispersing aniline monomer and nano silicon powder into acid liquor to obtain dispersion liquid;
b) Mixing the dispersion liquid, the hydrogen peroxide solution and the initiator solution for hydrothermal reaction, and carrying out solid-liquid separation and drying after the reaction is finished to obtain the polyaniline-coated nano silicon material;
c) And carbonizing the polyaniline-coated nano silicon material in a protective atmosphere to obtain the nitrogen-doped silicon-carbon composite material with the core-shell structure.
Preferably, in the step a), the dosage ratio of the aniline monomer to the nano silicon powder is (0.5-10) mL to (0.1-10) g;
the concentration of the acid solution is 0.2M.
Preferably, the granularity of the nano silicon powder is 50-500 nm.
Preferably, the acid liquid is selected from one or more of sulfuric acid liquid, phosphoric acid liquid and nitric acid liquid.
Preferably, the dosage ratio of the hydrogen peroxide solution in the step b) to the nano silicon powder in the step a) is (0.5-10) mL to (0.1-10) g;
the mass percentage concentration of the hydrogen peroxide solution is 30%.
Preferably, the molar ratio of the initiator in the initiator solution to the aniline monomer in step a) is 1: (0.5-3).
Preferably, the initiator in the initiator solution is selected from one or more of persulfate, dichromate and ferric trichloride;
the concentration of the initiator solution is 0.15-0.60M.
Preferably, in the step b), the temperature of the hydrothermal reaction is 120-170 ℃ and the time is 2-10 h.
Preferably, in the step c), the carbonization treatment temperature is 400-1000 ℃ and the heat preservation time is 1-6 h.
The invention also provides the nitrogen-doped silicon-carbon composite material with the core-shell structure, which is prepared by the preparation method in the technical scheme.
According to the preparation method provided by the invention, firstly, aniline monomers and nano silicon powder are dispersed into acid liquor, then, the acid liquor is mixed with hydrogen peroxide solution and initiator solution for hydrothermal reaction to form polyaniline-coated nano silicon material, and finally, carbonization treatment is carried out to obtain the polyaniline-coated nano silicon material with a core-shell structure. The preparation method is characterized in that the preparation method is realized by one-step hydrothermal reaction and one-step carbonization, a plurality of complex and complicated steps are not needed, a template agent or an etching agent is not needed to assist in forming the core-shell, the condition is mild, the preparation process and the operation difficulty are greatly simplified, the preparation cost is reduced, and the template agent or the etching agent is not used, so that the post-treatment of the agents is avoided; in addition, the preparation method can ensure the electrochemical performance of the material, so that the material has excellent electrochemical energy storage performance and cycle stability.
The test result shows that the rate performance test result of the polyaniline-coated nano-silicon material with the core-shell structure prepared by the invention is as follows: the cycle is carried out for 10 circles under the current density of 0.1A/g, 0.2A/g, 0.5A/g and 1A/g in sequence, and the cycle returns to the current density of 0.1A/g for 10 circles, and the corresponding capacities are respectively as follows: the capacity is higher than 1066mAh/g at 0.1A/g, higher than 894mAh/g at 0.3A/g, higher than 834mAh/g at 0.5A/g, higher than 735mAh/g at 1A/g, and higher than 1042mAh/g at 0.1A/g. The cycle performance test results were as follows: after 50 cycles at 0.5A/g, the capacity retention rate still reaches more than 81%.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required to be used in the embodiments or the description of the prior art will be briefly described below, and it is obvious that the drawings in the following description are only embodiments of the present invention, and that other drawings can be obtained according to the provided drawings without inventive effort for a person skilled in the art.
FIG. 1 is an SEM image of a nitrogen-doped silica-carbon composite having a core-shell structure obtained in example 1;
FIG. 2 is a high resolution electron microscope image of the nitrogen-doped silica-carbon composite material with core-shell structure obtained in example 1;
FIG. 3 is an SEM image of a nitrogen-doped silica-carbon composite having a core-shell structure obtained in example 2;
FIG. 4 is an SEM image of a nitrogen-doped silica-carbon composite having a core-shell structure obtained in example 3;
FIG. 5 is an SEM image of a nitrogen-doped silica-carbon composite having a core-shell structure obtained in example 4;
FIG. 6 is a graph showing the effect of the composite material obtained in example 1 on the rate performance test;
FIG. 7 is a graph showing the effect of the cyclic performance test on the composite material obtained in example 1.
Detailed Description
The invention provides a preparation method of a nitrogen-doped silicon-carbon composite material with a core-shell structure, which comprises the following steps:
a) Dispersing aniline monomer and nano silicon powder into acid liquor to obtain dispersion liquid;
b) Mixing the dispersion liquid, the hydrogen peroxide solution and the initiator solution for hydrothermal reaction, and carrying out solid-liquid separation and drying after the reaction is finished to obtain the polyaniline-coated nano silicon material;
c) And carbonizing the polyaniline-coated nano silicon material in a protective atmosphere to obtain the nitrogen-doped silicon-carbon composite material with the core-shell structure.
According to the preparation method provided by the invention, firstly, aniline monomers and nano silicon powder are dispersed into acid liquor, then, the acid liquor is mixed with hydrogen peroxide solution and initiator solution for hydrothermal reaction to form polyaniline-coated nano silicon material, and finally, carbonization treatment is carried out to obtain the polyaniline-coated nano silicon material with a core-shell structure. The preparation method is characterized in that the preparation method is realized by one-step hydrothermal reaction and one-step carbonization, a plurality of complex and complicated steps are not needed, a template agent or an etching agent is not needed to assist in forming the core-shell, the condition is mild, the preparation process and the operation difficulty are greatly simplified, the preparation cost is reduced, and the template agent or the etching agent is not used, so that the post-treatment of the agents is avoided; in addition, the preparation method can ensure the electrochemical performance of the material, so that the material has excellent electrochemical energy storage performance and cycle stability.
Regarding step a): dispersing aniline monomer and nano silicon powder into acid liquor to obtain dispersion liquid.
In the present invention, the aniline is also known as aminobenzene, and is colorless oily liquid. The source of the aniline monomer is not particularly limited in the present invention, and may be commercially available or prepared according to a conventional preparation method well known to those skilled in the art.
In the present invention, the particle diameter of the nano silicon powder is preferably 50 to 500nm, more preferably 100nm.
In the invention, the dosage ratio of the aniline monomer to the nanometer silicon powder is preferably (0.5-10) mL to (0.1-10) g; in the invention, the dosage ratio of the aniline monomer to the nano silicon powder is critical, and the material with high capacity and good cycle performance can be obtained under the proportion range. In some embodiments of the invention, the dosage ratio may be specifically 0.5 mL:0.5 g, 3 mL:0.5 g, 5 mL:0.5 g, 10 mL:0.5 g, more preferably (3-5) mL:0.5 g, within which the capacity and cycle performance of the material can be further improved.
In the invention, the acid liquid is preferably one or more of sulfuric acid liquid, phosphoric acid liquid and nitric acid liquid. The invention adopts acid liquor as dispersion medium, and simultaneously dopes the generated polyaniline, which is beneficial to improving the conductivity of the product and improving the yield of the product, and if other dispersion mediums such as organic solvent, water and the like are adopted as dispersion medium, the effect can not be achieved. In the present invention, the concentration of the acid solution is preferably 0.2M. In the invention, the dosage of the acid liquor is not particularly limited, the acid liquor is used as a dispersion medium to fully disperse the aniline monomer and the nano silicon powder, and the volume ratio of the acid liquor to the aniline monomer is preferably (100-200) to (0.5-10).
In the invention, the dispersion mode of dispersing the aniline monomer and the nano silicon powder into the acid liquid is preferably ultrasonic dispersion. In the present invention, the conditions for ultrasonic dispersion are preferably: the power is 50-100W, and the time is 15-60 min. The power may be specifically 50W, 55W, 60W, 65W, 70W, 75W, 80W, 85W, 90W, 95W, 100W. The time can be 15min, 20min, 25min, 30min, 35min, 40min, 45min, 50min, 55min, 60min. After the ultrasonic dispersion, the materials are uniformly mixed to obtain dispersion liquid.
Regarding step b): and mixing the dispersion liquid, the hydrogen peroxide solution and the initiator solution for hydrothermal reaction, and carrying out solid-liquid separation and drying after the reaction is finished to obtain the polyaniline-coated nano silicon material.
In the present invention, the concentration of the hydrogen peroxide solution is preferably 30% by mass. In the invention, the dosage ratio of the hydrogen peroxide solution to the nano silicon powder in the step a) is preferably (0.5-10) mL to (0.1-10) g, more preferably 0.5mL to 0.5g.
In the invention, the initiator solution is an aqueous solution of an initiator. Wherein the initiator is preferably one or more of persulfate, dichromate and ferric trichloride; wherein the persulfate is preferably one or more of ammonium persulfate, sodium persulfate and potassium persulfate. The dichromate is preferably one or more of sodium dichromate and potassium dichromate. In the present invention, the molar ratio of the initiator in the initiator solution to the aniline monomer in step a) is preferably 1: (0.5-3), and may be specifically 1:0.5, 1:1, 1:1.5, 1:2, 1:2.5, 1:3. In the present invention, the concentration of the initiator solution is preferably 0.15 to 0.60M, and specifically may be 0.15M, 0.20M, 0.25M, 0.30M, 0.35M, 0.40M, 0.45M, 0.50M, 0.55M, 0.60M.
In the present invention, the mixing mode is preferably as follows: under the stirring condition, firstly adding hydrogen peroxide solution into the dispersion liquid, stirring and mixing uniformly, then adding initiator solution, stirring and mixing uniformly. The stirring speed is preferably 200 to 800rpm, and may specifically be 200rpm, 250rpm, 300rpm, 350rpm, 400rpm, 450rpm, 500rpm, 550rpm, 600rpm, 650rpm, 700rpm, 750rpm, or 800rpm. The time for stirring and mixing after adding the hydrogen peroxide solution is preferably 15-60 min, and specifically can be 15min, 20min, 25min, 30min, 35min, 40min, 45min, 50min, 55min, 60min. The time for stirring and mixing after adding the initiator solution is preferably 15-60 min, and specifically can be 15min, 20min, 25min, 30min, 35min, 40min, 45min, 50min, 55min, 60min. . And (3) carrying out the mixing treatment to obtain uniform mixed solution.
In the invention, after the uniform mixed solution is obtained by the mixing, the hydrothermal reaction is carried out. In the present invention, the temperature of the hydrothermal reaction is preferably 120 to 170 ℃, specifically 120 ℃, 125 ℃, 130 ℃, 135 ℃, 140 ℃, 145 ℃, 150 ℃, 155 ℃, 160 ℃, 165 ℃, 170 ℃. In the invention, the time of the hydrothermal reaction is preferably 2-10 h, and specifically may be 2h, 2.5h, 3h, 3.5h, 4h, 4.5h, 5h, 5.5h, 6h, 6.5h, 7h, 7.5h, 8h, 8.5h, 9h, 9.5h, 10h. Through the hydrothermal reaction, aniline monomers are polymerized into polyaniline, the polyaniline is gathered on the surface of the nano silicon to form a coating layer by self-assembly, and in addition, hydrogen peroxide solution overflows oxygen in the heating process, so that a hollow sphere structure is formed, and a cavity is formed between the shell layer and the core of the polyaniline-coated nano silicon material.
In the present invention, the solid-liquid separation is performed after the hydrothermal reaction. In the present invention, the solid-liquid separation method is not particularly limited, and may be a conventional method well known to those skilled in the art, and suction filtration is preferred in the present invention. After the above solid-liquid separation, the obtained solid was dried. In the present invention, the drying temperature is preferably 40 to 80 ℃. And drying to obtain the polyaniline-coated nano silicon material with the core-shell structure.
Regarding step c): and carbonizing the polyaniline-coated nano silicon material in a protective atmosphere to obtain the nitrogen-doped silicon-carbon composite material with the core-shell structure.
In the present invention, the kind of the protective gas providing the protective atmosphere is not particularly limited, and may be a conventional protective gas known to those skilled in the art, such as nitrogen, helium, or argon.
In the present invention, the carbonization treatment is preferably carried out at a temperature of 400 to 1000 ℃, specifically 400 ℃, 450 ℃, 500 ℃, 550 ℃, 600 ℃, 650 ℃, 700 ℃, 750 ℃, 800 ℃, 850 ℃, 900 ℃, 950 ℃ and 1000 ℃. In the invention, the heating rate of the carbonization treatment is preferably 1-10 ℃ per minute, and specifically can be 1 ℃ per minute, 2 ℃ per minute, 3 ℃ per minute, 4 ℃ per minute, 5 ℃ per minute, 6 ℃ per minute, 7 ℃ per minute, 8 ℃ per minute, 9 ℃ per minute, and 10 ℃ per minute. In the invention, the time for the carbonization treatment by heat preservation after the temperature is raised to the above target temperature is preferably 1 to 6 hours, and specifically can be 1 hour, 1.5 hours, 2 hours, 2.5 hours, 3 hours, 3.5 hours, 4 hours, 4.5 hours, 5 hours, 5.5 hours and 6 hours. After the carbonization treatment, shell polyaniline is carbonized to form a nitrogen-doped carbon material, so that the nitrogen-doped silicon-carbon composite material with a core-shell structure is formed, in the composite material, a core is a Si sphere, a carbon layer is coated on the surface of the composite material, nitrogen is doped in the carbon layer, namely, the shell is a nitrogen-doped carbon layer, a cavity is formed between the shell and the core nano Si sphere, namely, the shell and the core nano Si sphere are not in close contact.
The invention also provides the nitrogen-doped silicon-carbon composite material with the core-shell structure, which is prepared by the preparation method in the technical scheme.
In the prepared nitrogen-doped silicon-carbon composite material with the core-shell structure, the core is a Si sphere, the shell is a nitrogen-doped carbon layer, a cavity is arranged between the shell and the core nanometer Si sphere, and the whole is spherical particles with the core-shell structure. The particle size of the spherical particles is 80-800 nm, the particle size of the core nano Si spheres is 50-500 nm, and the wall thickness (namely the thickness of the shell layer) is 30-200 nm. The nitrogen content in the composite material is 3at% -9 at%.
The invention also provides a lithium ion battery, wherein the negative electrode material is the nitrogen-doped silicon-carbon composite material with the core-shell structure in the technical scheme. The nitrogen-doped silicon-carbon composite material with the core-shell structure provided by the invention is used as a lithium ion battery anode material, can improve the conductivity of the material, and meanwhile, the specific core-shell structure can limit the volume expansion of nano silicon in the charge and discharge process, so that the material circulation stability is improved.
The preparation method provided by the invention can be used for carrying out one-step hydrothermal reaction and one-step carbonization, does not need a plurality of complex and complicated steps, does not need a template agent or an etching agent to assist in forming the core-shell, has mild conditions, greatly simplifies the preparation process and operation difficulty, reduces the preparation cost, and avoids the post-treatment of the agents because the template agent or the etching agent is not used; in addition, the preparation method can ensure the electrochemical performance of the material, so that the material has excellent electrochemical energy storage performance and cycle stability.
The test result shows that the rate performance test result of the polyaniline-coated nano-silicon material with the core-shell structure prepared by the invention is as follows: the cycle is carried out for 10 circles under the current density of 0.1A/g, 0.2A/g, 0.5A/g and 1A/g in sequence, and the cycle returns to the current density of 0.1A/g for 10 circles, and the corresponding capacities are respectively as follows: the capacity is higher than 1066mAh/g at 0.1A/g, higher than 894mAh/g at 0.3A/g, higher than 834mAh/g at 0.5A/g, higher than 735mAh/g at 1A/g, and higher than 1042mAh/g at 0.1A/g. The cycle performance test results were as follows: after 50 cycles at 0.5A/g, the capacity retention rate still reaches more than 81%.
For a further understanding of the present invention, preferred embodiments of the invention are described below in conjunction with the examples, but it should be understood that these descriptions are merely intended to illustrate further features and advantages of the invention, and are not limiting of the claims of the invention.
Example 1
1. Preparation
3mL of aniline and 0.5g of nano silicon (diameter 100 nm) powder were dispersed in 160mL of nitric acid solution (concentration 0.2M), and the mixture was subjected to ultrasonic dispersion at 80W for 30min, and the mixture was uniformly mixed to obtain a dispersion. Under the stirring condition of 500rpm, 0.5mL of hydrogen peroxide solution (30% concentration) is added into the dispersion, stirred and mixed for 30min, and finally ammonium persulfate solution (0.2M concentration, molar ratio of aniline to ammonium persulfate 1:1) is added into the dispersion, and stirred and mixed for 30min to obtain a uniform mixed solution. Then, reacting for 6 hours under the hydrothermal condition of 140 ℃, and after the reaction is finished, carrying out suction filtration and drying to obtain the polyaniline-coated nano-silicon material with the core-shell structure. And (3) putting the polyaniline-coated nano silicon material into a carbonization furnace, heating to 800 ℃ at 2 ℃/min under an inert atmosphere, and preserving heat for 2 hours to obtain the nitrogen-doped silicon-carbon composite material with the core-shell structure.
2. Characterization and testing
(1) SEM characterization
Scanning electron microscope observation and high-resolution electron microscope observation are carried out on the obtained product, as shown in fig. 1 and 2, respectively, fig. 1 is an SEM image of the nitrogen-doped silicon-carbon composite material with the core-shell structure obtained in example 1, and fig. 2 is a high-resolution electron microscope image of the nitrogen-doped silicon-carbon composite material with the core-shell structure obtained in example 1. As can be seen from fig. 1, the resulting composite material has a good spherical structure, the diameter of the spheres is about 180nm, and only a few spheres are agglomerated. As can be seen from the high-resolution electron microscope image in FIG. 2, a cavity structure is arranged between the nano silicon ball and the carbon coating layer, the diameter of the nano silicon is about 100nm, and the diameter of the composite ball is 180m.
(2) Electrochemical performance test
And mixing and grinding the prepared nitrogen-doped silicon carbon composite material with the core-shell structure and the conductive carbon black for about 30min according to the mass ratio of 8:1. The milled material was added with polyvinylidene fluoride (PVDF, binder) and N-methylpyrrolidone (NMP, solvent) and milled for about 1h. Coating the uniformly ground slurry on a copper foil with smooth and clean surface, and placing the copper foil in a vacuum oven at 80 ℃; and taking out after 4 hours, rolling by using a pair roller, putting the rolled electrode slices into a vacuum oven, drying at 120 ℃ for 12 hours in vacuum, and obtaining the electrode slices with the active material loading of about 1.5mg by using a 12mm circular slicer. Meanwhile, a lithium sheet is used as a counter electrode, a button type simulated battery is assembled in a glove box, and electrochemical performance test is carried out after standing for 12 h.
The cells were tested at room temperature in the voltage range of 0.001-3V. The multiplying power test is carried out by circulating the current density of 0.1A/g, 0.2A/g, 0.5A/g and 1A/g for 10 circles in sequence, and then circulating the current density of 0.1A/g for 10 circles, and the test result is shown in Table 1. The current density was 0.5A/g in the charge-discharge cycle test, and the test results are shown in Table 2.
Example 2
1. Preparation
The procedure is as in example 1, except that the aniline monomer is added in an amount of 0.5mL.
2. Characterization and testing
(1) SEM characterization
Fig. 3 is an SEM image of the nitrogen-doped silicon-carbon composite material with a core-shell structure obtained in example 2, and it can be seen that the obtained composite material has a good spherical structure, the diameter of the sphere is 110-130nm, and compared with example 1, the diameter of the sphere is smaller, mainly because the addition amount of aniline is small, and the carbon coating layer with the same thickness cannot be generated on the surface of the nano silicon sphere.
(2) Electrochemical performance test
The test results are shown in tables 1 and 2, respectively, following example 1.
Example 3
1. Preparation
The procedure is as in example 1, except that the aniline monomer is added in an amount of 5mL.
2. Characterization and testing
(1) SEM characterization
Fig. 4 is an SEM image of the nitrogen-doped silicon-carbon composite material having a core-shell structure obtained in example 3, and it can be seen that the obtained composite material has a spherical structure, the diameter of the sphere is 200nm, and the surface of the sphere is rough and grows together.
(2) Electrochemical performance test
The test results are shown in tables 1 and 2, respectively, following example 1.
Example 4
1. Preparation
The procedure is as in example 1, except that the aniline monomer is added in an amount of 10mL.
2. Characterization and testing
(1) SEM characterization
Fig. 5 is an SEM image of the nitrogen-doped silicon-carbon composite material with core-shell structure obtained in example 4, and it can be seen that the obtained composite material has a bulk structure in which the nano silicon spheres are coated.
(2) Electrochemical performance test
The test results are shown in tables 1 and 2, respectively, following example 1.
Comparative example 1
Spherical nano silicon powder with the grain diameter of 100nm is sold in the market. Electrochemical performance tests were performed as in example 1, with the test results shown in tables 1 and 2, respectively.
Table 1 rate properties of the materials obtained in examples 1 to 4 and comparative example 1
TABLE 2 cycle properties of the materials obtained in examples 1 to 4 and comparative example 1
The effect of testing the rate performance and the effect of testing the cycle performance of the material of example 1 are shown in fig. 6 and 7, respectively, fig. 6 is a graph of the effect of testing the rate performance of the composite material obtained in example 1, and fig. 7 is a graph of the effect of testing the cycle performance of the composite material obtained in example 1.
As can be seen from the test results in tables 1 and 2, compared with comparative example 1, the multiplying power performance and the cycle performance of the composite materials obtained in examples 1 to 4 are both obviously improved, and the electrochemical performance of the composite material with the core-shell structure prepared by the invention can be effectively improved. In examples 1 to 4, the electrochemical properties of the composite materials obtained in examples 1 and 3, in which the dosage ratio of the aniline monomer to the nano silicon powder is in the preferred range (3 to 5) mL: 0.5g, are further significantly improved.
The principles and embodiments of the present invention have been described herein with reference to specific examples, the description of which is intended only to aid in understanding the method of the invention and its core concept, including the best mode, and also to enable any person skilled in the art to practice the invention, including making and using any devices or systems and performing any incorporated methods. It should be noted that it will be apparent to those skilled in the art that various modifications and adaptations of the invention can be made without departing from the principles of the invention and these modifications and adaptations are intended to be within the scope of the invention as defined in the following claims. The scope of the patent protection is defined by the claims and may include other embodiments that occur to those skilled in the art. Such other embodiments are intended to be within the scope of the claims if they have structural elements that do not differ from the literal language of the claims, or if they include equivalent structural elements with insubstantial differences from the literal language of the claims.
Claims (5)
1. The preparation method of the nitrogen-doped silicon-carbon composite material with the core-shell structure is characterized by comprising the following steps of:
a) Dispersing aniline monomer and nano silicon powder into acid liquor to obtain dispersion liquid;
the dosage ratio of the aniline monomer to the nano silicon powder is (0.5-10) mL to (0.1-10) g;
the concentration of the acid liquor is 0.2M;
the acid liquor is selected from one or more of sulfuric acid liquor, phosphoric acid liquor and nitric acid liquor;
b) Mixing the dispersion liquid, the hydrogen peroxide solution and the initiator solution for hydrothermal reaction, and carrying out solid-liquid separation and drying after the reaction is finished to obtain the polyaniline-coated nano silicon material;
the dosage ratio of the hydrogen peroxide solution in the step b) to the nano silicon powder in the step a) is (0.5-10) mL to (0.1-10) g;
the mass percentage concentration of the hydrogen peroxide solution is 30%;
the concentration of the initiator solution is 0.15-0.60M;
the temperature of the hydrothermal reaction is 120-170 ℃ and the time is 2-10 h;
c) And carbonizing the polyaniline-coated nano silicon material in a protective atmosphere to obtain the nitrogen-doped silicon-carbon composite material with the core-shell structure.
2. The preparation method of claim 1, wherein the granularity of the nano silicon powder is 50-500 nm.
3. The method according to claim 1, wherein the molar ratio of the initiator in the initiator solution to the aniline monomer in step a) is 1:0.5-3.
4. A method of preparing as claimed in claim 1 or 3, wherein the initiator in the initiator solution is selected from one or more of persulphate, dichromate and ferric trichloride.
5. The method according to claim 1, wherein in the step c), the carbonization treatment is performed at a temperature of 400-1000 ℃ for a heat preservation time of 1-6 hours.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012033317A (en) * | 2010-07-29 | 2012-02-16 | Shin Etsu Chem Co Ltd | Cathode material for nonaqueous electrolytic secondary battery and method of manufacturing the same, and lithium ion secondary battery |
| CN107302082A (en) * | 2016-04-15 | 2017-10-27 | 华为技术有限公司 | Silicium cathode material and preparation method thereof, cathode pole piece and lithium ion battery |
| CN108987686A (en) * | 2018-06-20 | 2018-12-11 | 深圳市比克动力电池有限公司 | Polyaniline-coated silicon based composite material and preparation method thereof |
| CN110707288A (en) * | 2018-07-10 | 2020-01-17 | 北京理工大学 | Silicon-based negative electrode active material and preparation method and application thereof |
| CN110752352A (en) * | 2018-07-09 | 2020-02-04 | 湖南师范大学 | Preparation method for carbon-coated silicon negative electrode material synthesized by aid of boron-nitrogen-doped polymer |
| CN113023734A (en) * | 2021-03-03 | 2021-06-25 | 昆山宝创新能源科技有限公司 | Porous nitrogen-doped silicon-based negative electrode material and preparation method thereof, negative electrode plate and lithium ion battery |
| CN113193195A (en) * | 2021-04-25 | 2021-07-30 | 湖北工业大学 | Nitrogen-doped carbon-coated nano silicon composite material with adjustable nitrogen content and preparation method thereof |
| CN113611858A (en) * | 2021-06-24 | 2021-11-05 | 中南大学 | Battery negative electrode active material and preparation method thereof |
-
2022
- 2022-01-19 CN CN202210059421.6A patent/CN114420910B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012033317A (en) * | 2010-07-29 | 2012-02-16 | Shin Etsu Chem Co Ltd | Cathode material for nonaqueous electrolytic secondary battery and method of manufacturing the same, and lithium ion secondary battery |
| CN107302082A (en) * | 2016-04-15 | 2017-10-27 | 华为技术有限公司 | Silicium cathode material and preparation method thereof, cathode pole piece and lithium ion battery |
| CN108987686A (en) * | 2018-06-20 | 2018-12-11 | 深圳市比克动力电池有限公司 | Polyaniline-coated silicon based composite material and preparation method thereof |
| CN110752352A (en) * | 2018-07-09 | 2020-02-04 | 湖南师范大学 | Preparation method for carbon-coated silicon negative electrode material synthesized by aid of boron-nitrogen-doped polymer |
| CN110707288A (en) * | 2018-07-10 | 2020-01-17 | 北京理工大学 | Silicon-based negative electrode active material and preparation method and application thereof |
| CN113023734A (en) * | 2021-03-03 | 2021-06-25 | 昆山宝创新能源科技有限公司 | Porous nitrogen-doped silicon-based negative electrode material and preparation method thereof, negative electrode plate and lithium ion battery |
| CN113193195A (en) * | 2021-04-25 | 2021-07-30 | 湖北工业大学 | Nitrogen-doped carbon-coated nano silicon composite material with adjustable nitrogen content and preparation method thereof |
| CN113611858A (en) * | 2021-06-24 | 2021-11-05 | 中南大学 | Battery negative electrode active material and preparation method thereof |
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