CN114420910A - 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
- Publication number
- CN114420910A CN114420910A CN202210059421.6A CN202210059421A CN114420910A CN 114420910 A CN114420910 A CN 114420910A CN 202210059421 A CN202210059421 A CN 202210059421A CN 114420910 A CN114420910 A CN 114420910A
- Authority
- CN
- China
- Prior art keywords
- preparation
- core
- nano silicon
- shell structure
- nitrogen
- 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.)
- Granted
Links
- 239000011258 core-shell material Substances 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 47
- 239000002153 silicon-carbon composite material Substances 0.000 title claims abstract description 33
- 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 48
- 239000000463 material Substances 0.000 claims abstract description 42
- 239000003999 initiator Substances 0.000 claims abstract description 25
- 229920000767 polyaniline Polymers 0.000 claims abstract description 25
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000000178 monomer Substances 0.000 claims abstract description 23
- 239000002253 acid Substances 0.000 claims abstract description 18
- 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
- 238000002156 mixing Methods 0.000 claims abstract description 15
- 238000003763 carbonization Methods 0.000 claims abstract description 14
- 239000007788 liquid Substances 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 13
- 239000006185 dispersion Substances 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 7
- 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
- 239000002245 particle Substances 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 peroxydisulfate Chemical compound [O-]S(=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
- 239000003795 chemical substances by application Substances 0.000 abstract description 18
- 238000005530 etching Methods 0.000 abstract description 10
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 5
- 238000012983 electrochemical energy storage Methods 0.000 abstract description 4
- 239000000243 solution Substances 0.000 description 29
- 238000012360 testing method Methods 0.000 description 18
- 239000002131 composite material Substances 0.000 description 14
- 238000011056 performance test Methods 0.000 description 13
- 239000010410 layer Substances 0.000 description 10
- 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
- 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
- 229910052799 carbon Inorganic materials 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
- 239000002612 dispersion medium Substances 0.000 description 4
- 230000006872 improvement Effects 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
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 239000011247 coating layer Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- 238000001132 ultrasonic dispersion Methods 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
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000010406 cathode material Substances 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
- 239000007773 negative electrode material Substances 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
- 238000005096 rolling process Methods 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
- 239000011868 silicon-carbon composite negative electrode material Substances 0.000 description 2
- 238000004088 simulation Methods 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
- 239000013543 active substance 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
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000001351 cycling effect Effects 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
- 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
- 239000011259 mixed solution 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
- 238000001338 self-assembly Methods 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
- 238000001291 vacuum drying Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
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. The preparation method provided by the invention comprises the steps of dispersing aniline monomer and nano silicon powder into acid liquor, mixing with hydrogen peroxide solution and initiator solution for hydrothermal reaction to form polyaniline-coated nano silicon material, and finally performing carbonization treatment to obtain polyaniline-coated nano silicon material with a core-shell structure. The preparation method disclosed by the invention has the advantages that one-step hydrothermal reaction and one-step carbonization are carried out, a plurality of complex and tedious steps are not needed, a template agent or an etching agent is not needed to assist in forming the core shell, the conditions are 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 reagents is avoided; in addition, the preparation method of the invention can also ensure the electrochemical performance of the material, so that the material shows 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 hot spots of current research. The theoretical lithium intercalation capacity of the silicon material at room temperature is 3580mAh/g, which is about ten times of that of the traditional graphite material, and the silicon material is the most potential next-generation lithium ion battery negative electrode material. However, silicon suffers from severe volume expansion, which causes rapid capacity fade, and thus commercialization of silicon anodes still faces many challenges.
The silicon and the carbon material are compounded, which is beneficial to improving the electrochemical performance of the material. The nitrogen doping can improve the conductivity of the carbon material, and the nitrogen-containing polymer can obtain materials with different microstructures by controlling the synthesis conditions, so that the nitrogen-doped carbon-based material is a good raw material for preparing the nitrogen-doped carbon-based material. For example, in the Chinese patent application with the application number of CN201810119502, polyaniline is used as a raw material to prepare the nitrogen-doped silicon-based negative electrode material, so that the structural stability of the material is effectively improved. For example, chinese patent application No. CN201710323485 discloses a method for preparing a nitrogen-doped silicon-carbon composite negative electrode material, which comprises coating a layer of SiO2 on the surface of nano Si by a sol-gel method to obtain Si @ SiO2, then coating Si @ SiO2 with polyacrylamide by inverse suspension polymerization, and etching SiO2 with HF after high-temperature activation to obtain the nitrogen-doped silicon-carbon composite negative electrode material.
However, the conventional preparation method of the nitrogen-doped silicon carbon composite material is carried out in multiple steps, the preparation conditions are harsh, a template agent or an etching agent is required to assist in forming the core shell, and the reagents need to be subjected to post-treatment, so that the preparation cost and complexity are further increased.
Disclosure of Invention
In view of this, the present invention provides 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 the core-shell structure, greatly simplify the process, reduce the preparation cost and ensure 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, a hydrogen peroxide solution and an initiator solution to perform hydrothermal reaction, and performing solid-liquid separation and drying after the reaction is finished to obtain a 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 liquor is 0.2M.
Preferably, the particle size of the nano silicon powder is 50-500 nm.
Preferably, the acid solution is selected from one or more of sulfuric acid solution, phosphoric acid solution and nitric acid solution.
Preferably, the 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 the step a) is 1 to (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 hours.
Preferably, in the step c), the temperature of the carbonization treatment 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.
The preparation method provided by the invention comprises the steps of dispersing aniline monomer and nano silicon powder into acid liquor, mixing with hydrogen peroxide solution and initiator solution for hydrothermal reaction to form polyaniline-coated nano silicon material, and finally performing carbonization treatment to obtain polyaniline-coated nano silicon material with a core-shell structure. The preparation method disclosed by the invention has the advantages that one-step hydrothermal reaction and one-step carbonization are carried out, a plurality of complex and tedious steps are not needed, a template agent or an etching agent is not needed to assist in forming the core shell, the conditions are 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 reagents is avoided; in addition, the preparation method of the invention can also ensure the electrochemical performance of the material, so that the material shows 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: circulating for 10 circles under the current densities of 0.1A/g, 0.2A/g, 0.5A/g and 1A/g in sequence, and then circulating for 10 circles under the current density of 0.1A/g, wherein the corresponding capacities are respectively as follows: capacity at 0.1A/g is above 1066mAh/g → capacity at 0.3A/g is above 894mAh/g → capacity at 0.5A/g is above 834mAh/g → capacity at 1A/g is above 735mAh/g → capacity at 0.1A/g is above 1042 mAh/g. The cycle performance test results were as follows: after 50 cycles of circulation at 0.5A/g, the capacity retention rate still reaches more than 81 percent.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.
FIG. 1 is an SEM image of the N-doped silicon carbon composite material with the core-shell structure obtained in example 1;
FIG. 2 is a high-resolution electron microscope image of the N-doped silicon carbon composite material with the core-shell structure obtained in example 1;
FIG. 3 is an SEM image of the N-doped silicon carbon composite material with the core-shell structure obtained in example 2;
FIG. 4 is an SEM image of the N-doped silicon carbon composite material with the core-shell structure obtained in example 3;
FIG. 5 is an SEM image of the N-doped silicon carbon composite material with the core-shell structure obtained in example 4;
FIG. 6 is a graph showing the effect of the rate capability test on the composite material obtained in example 1;
FIG. 7 is a graph showing the effect of the cycle 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, a hydrogen peroxide solution and an initiator solution to perform hydrothermal reaction, and performing solid-liquid separation and drying after the reaction is finished to obtain a 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.
The preparation method provided by the invention comprises the steps of dispersing aniline monomer and nano silicon powder into acid liquor, mixing with hydrogen peroxide solution and initiator solution for hydrothermal reaction to form polyaniline-coated nano silicon material, and finally performing carbonization treatment to obtain polyaniline-coated nano silicon material with a core-shell structure. The preparation method disclosed by the invention has the advantages that one-step hydrothermal reaction and one-step carbonization are carried out, a plurality of complex and tedious steps are not needed, a template agent or an etching agent is not needed to assist in forming the core shell, the conditions are 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 reagents is avoided; in addition, the preparation method of the invention can also ensure the electrochemical performance of the material, so that the material shows excellent electrochemical energy storage performance and cycle stability.
Concerning step a): and dispersing aniline monomer and nano silicon powder into acid liquor to obtain dispersion liquid.
In the present invention, the aniline is also called aminobenzene, and is a colorless oily liquid. The aniline monomer is not particularly limited in its source 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 invention, the particle size of the nano silicon powder is preferably 50-500 nm, and more preferably 100 nm.
In the invention, the dosage ratio of the aniline monomer to the nano 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 crucial, and the material with high capacity and good cycle performance can be obtained in the above ratio range. In some embodiments of the present invention, the dosage ratio may be specifically 0.5 mL: 0.5g, 3 mL: 0.5g, 5 mL: 0.5g, 10 mL: 0.5g, and more preferably (3-5) mL: 0.5g, within which the capacity and the cycle performance of the material can be further improved.
In the invention, the acid solution is preferably one or more of sulfuric acid solution, phosphoric acid solution and nitric acid solution. The method adopts acid liquor as a dispersion medium, and dopes the generated polyaniline, thereby being beneficial to improving the conductivity of the product and the yield of the product, and the effect can not be achieved if other dispersion media such as organic solvents, water and the like are adopted as the dispersion media. In the present invention, the concentration of the acid solution is preferably 0.2M. In the invention, the amount of the acid solution is not particularly limited, and the acid solution is used as a dispersion medium to sufficiently disperse the aniline monomer and the nano silicon powder, and preferably, the volume ratio of the acid solution to the aniline monomer is (100-200): (0.5-10).
In the invention, the preferred dispersing mode for dispersing the aniline monomer and the nano silicon powder into the acid solution is ultrasonic dispersion. In the present invention, the conditions for the ultrasonic dispersion are preferably: the power is 50-100W, and the time is 15-60 min. Wherein, the power can be 50W, 55W, 60W, 65W, 70W, 75W, 80W, 85W, 90W, 95W and 100W. The time can be 15min, 20min, 25min, 30min, 35min, 40min, 45min, 50min, 55min, 60 min. After the ultrasonic dispersion, the materials are uniformly mixed to obtain a dispersion liquid.
Concerning step b): and mixing the dispersion liquid, the hydrogen peroxide solution and the initiator solution for hydrothermal reaction, and performing 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, and more preferably 0.5mL to 0.5 g.
In the invention, the initiator solution is an aqueous solution of the 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 invention, the mol ratio of the initiator in the initiator solution to the aniline monomer in the step a) is preferably 1: 0.5-3, and specifically can be 1: 0.5, 1: 1, 1: 1.5, 1: 2, 1: 2.5 and 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 method is preferably: under the condition of stirring, firstly adding a hydrogen peroxide solution into the dispersion liquid, stirring and mixing uniformly, then adding an initiator solution, and stirring and mixing uniformly. Wherein the stirring speed is preferably 200-800 rpm, and specifically may be 200rpm, 250rpm, 300rpm, 350rpm, 400rpm, 450rpm, 500rpm, 550rpm, 600rpm, 650rpm, 700rpm, 750rpm, 800 rpm. The time for stirring and mixing after adding the hydrogen peroxide solution is preferably 15-60 min, and specifically may be 15min, 20min, 25min, 30min, 35min, 40min, 45min, 50min, 55min, and 60 min. 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, and 60 min. . And (4) obtaining uniform mixed liquor through the mixing treatment.
In the present invention, after the uniform mixed solution is obtained by the above-mentioned mixing, a hydrothermal reaction is carried out. In the present invention, the temperature of the hydrothermal reaction is preferably 120 to 170 ℃, and specifically 120 ℃, 125 ℃, 130 ℃, 135 ℃, 140 ℃, 145 ℃, 150 ℃, 155 ℃, 160 ℃, 165 ℃ and 170 ℃. In the invention, the time of the hydrothermal reaction is preferably 2-10 h, and specifically can 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 and 10 h. Through the hydrothermal reaction, aniline monomer is polymerized into polyaniline, and the polyaniline is gathered on the surface of the nano silicon to form a coating layer through self-assembly, and in addition, oxygen can overflow from a hydrogen peroxide solution in the heating process, so that a hollow sphere structure is favorably formed, and the polyaniline-coated nano silicon material is formed, wherein a cavity is arranged between a shell layer and a core.
In the present invention, after the hydrothermal reaction, solid-liquid separation is performed. 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 in the present invention, suction filtration is preferable. After the above solid-liquid separation, the obtained solid was dried. In the invention, the drying temperature is preferably 40-80 ℃. And drying to obtain the polyaniline-coated nano silicon material with the core-shell structure.
Concerning 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 for 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, argon, or the like.
In the present invention, the temperature of the carbonization treatment is preferably 400 to 1000 ℃, and specifically may be 400 ℃, 450 ℃, 500 ℃, 550 ℃, 600 ℃, 650 ℃, 700 ℃, 750 ℃, 800 ℃, 850 ℃, 900 ℃, 950 ℃, 1000 ℃. In the invention, the heating rate of the carbonization treatment is preferably 1-10 ℃/min, and specifically can be 1 ℃/min, 2 ℃/min, 3 ℃/min, 4 ℃/min, 5 ℃/min, 6 ℃/min, 7 ℃/min, 8 ℃/min, 9 ℃/min and 10 ℃/min. In the invention, the time for the heat preservation and carbonization treatment after the temperature is raised to the target temperature is preferably 1-6 h, and specifically 1h, 1.5h, 2h, 2.5h, 3h, 3.5h, 4h, 4.5h, 5h, 5.5h and 6 h. And after the carbonization treatment, the polyaniline of the shell layer 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, wherein the core is a Si ball, the surface of the composite material is coated with a carbon layer, and the carbon layer is doped with nitrogen, namely the shell layer is the nitrogen-doped carbon layer, and a cavity is formed between the shell layer and the core nano Si ball, namely the shell layer is not in close contact with the core nano Si ball.
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 formed between the shell and the core nano 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 ball is 50-500 nm, and the wall thickness (namely the shell thickness) is 30-200 nm. The nitrogen content in the composite material is 3at percent to 9at percent.
The invention also provides a lithium ion battery, wherein the cathode 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 cathode material, the conductivity of the material can be improved, and meanwhile, the specific core-shell structure can limit the volume expansion of nano silicon in the charge and discharge processes, so that the improvement of the cycling stability of the material is facilitated.
The preparation method provided by the invention can be realized through one-step hydrothermal reaction and one-step carbonization, does not need a plurality of complex and fussy 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 the operation difficulty, reduces the preparation cost, and avoids post-treatment of the reagents because the template agent or the etching agent is not used; in addition, the preparation method of the invention can also ensure the electrochemical performance of the material, so that the material shows 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: circulating for 10 circles under the current densities of 0.1A/g, 0.2A/g, 0.5A/g and 1A/g in sequence, and then circulating for 10 circles under the current density of 0.1A/g, wherein the corresponding capacities are respectively as follows: capacity at 0.1A/g is above 1066mAh/g → capacity at 0.3A/g is above 894mAh/g → capacity at 0.5A/g is above 834mAh/g → capacity at 1A/g is above 735mAh/g → capacity at 0.1A/g is above 1042 mAh/g. The cycle performance test results were as follows: after 50 cycles of circulation at 0.5A/g, the capacity retention rate still reaches more than 81 percent.
For a further understanding of the invention, reference will now be made to the preferred embodiments of the invention by way of example, and it is to be understood that the description is intended to further illustrate features and advantages of the invention, and not to limit the scope of the claims.
Example 1
1. Preparation of
3mL of aniline and 0.5g of nano silicon (diameter 100nm) powder are dispersed into 160mL of nitric acid solution (concentration is 0.2M), ultrasonically dispersed for 30min under 80W, and uniformly mixed to obtain a dispersion liquid. Under the stirring condition of 500rpm, 0.5mL of hydrogen peroxide solution (with the concentration of 30%) is added into the dispersion liquid, the mixture is stirred and mixed for 30min, finally, ammonium persulfate solution (with the concentration of 0.2M and the molar ratio of aniline to ammonium persulfate of 1: 1) is added, and the mixture is stirred and mixed for 30min to obtain uniform mixed liquid. And then, reacting for 6 hours at 140 ℃ under a hydrothermal condition, and performing suction filtration and drying after the reaction is finished 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 a speed of 2 ℃/min under an inert atmosphere, and preserving heat for 2h 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 performed on the obtained product, as shown in fig. 1 and fig. 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 with a sphere diameter of 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 formed between the nano silicon spheres and the carbon coating layer, the diameter of the nano silicon is about 100nm, and the diameter of the composite spheres is 180 m.
(2) Electrochemical performance test
Mixing and grinding the prepared nitrogen-doped silicon-carbon composite material with the core-shell structure and the conductive carbon black according to the mass ratio of 8: 1 for about 30 min. Polyvinylidene fluoride (PVDF, binder) and N-methyl pyrrolidone (NMP, solvent) were added to the milled material and mixed for about 1 h. Coating the uniformly ground slurry on a copper foil with a smooth and clean surface, and placing the copper foil in a vacuum oven at 80 ℃; taking out the electrode plate after 4 hours, rolling the electrode plate by using a roll machine, putting the electrode plate into a vacuum oven after rolling, performing vacuum drying for 12 hours at 120 ℃, and obtaining the electrode plate with the active substance loading amount of about 1.5mg by using a 12mm circular slicer. Meanwhile, a lithium sheet is taken as a counter electrode, a button type simulation battery is assembled in a glove box, and the electrochemical performance test is carried out after the button type simulation battery is kept stand for 12 hours.
The battery is tested at room temperature in the voltage range of 0.001-3V. The multiplying power test is performed by circulating current density of 0.1A/g, 0.2A/g, 0.5A/g and 1A/g for 10 circles in sequence and then circulating current density of 0.1A/g for 10 circles, and the test results are shown in Table 1. The current density in the charge-discharge cycle test was 0.5A/g, and the test results are shown in Table 2.
Example 2
1. Preparation of
The procedure was as in example 1, except that the aniline monomer was added in an amount of 0.5 mL.
2. Characterization and testing
(1) SEM characterization
Fig. 3 is an SEM image of the nitrogen-doped silicon carbon composite material with the 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 the diameter of the sphere is smaller than that of example 1, mainly because the amount of aniline added is small, and a carbon coating layer with the same thickness cannot be formed on the surface of the nano silicon sphere.
(2) Electrochemical performance test
The procedure was as in example 1, and the test results are shown in tables 1 and 2, respectively.
Example 3
1. Preparation of
The procedure was as in example 1, except that the aniline monomer was added in an amount of 5 mL.
2. Characterization and testing
(1) SEM characterization
Fig. 4 is an SEM image of the nitrogen-doped silicon carbon composite material having the 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, the surface of the sphere is rough, and the spheres grow together.
(2) Electrochemical performance test
The procedure was as in example 1, and the test results are shown in tables 1 and 2, respectively.
Example 4
1. Preparation of
The procedure was as in example 1, except that the aniline monomer was added in an amount of 10 mL.
2. Characterization and testing
(1) SEM characterization
Fig. 5 is an SEM image of the nitrogen-doped silicon carbon composite material with the core-shell structure obtained in example 4, and it can be seen that the obtained composite material has a bulk structure, and the nano silicon spheres are coated in the bulk structure.
(2) Electrochemical performance test
The procedure was as in example 1, and the test results are shown in tables 1 and 2, respectively.
Comparative example 1
Spherical nano-silicon powder with a particle size of 100nm is commercially available. Electrochemical performance tests were performed as in example 1, and the test results are 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 cyclability of the materials obtained in examples 1 to 4 and comparative example 1
The effect of the material of example 1 on the rate capability test and the effect of the cycle performance test are shown in fig. 6 and 7, respectively, fig. 6 is a graph of the effect of the rate capability test on the composite material obtained in example 1, and fig. 7 is a graph of the effect of the cycle performance test on 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 rate capability and the cycle performance of the composite material obtained in the embodiments 1 to 4 of the present invention are both significantly improved, and it is proved that the core-shell structure composite material prepared by the present invention can effectively improve the electrochemical performance of the material. In the embodiments 1 to 4, the electrochemical performance of the composite material obtained in the embodiments 1 and 3 is further remarkably improved when the dosage ratio of the aniline monomer to the nano silicon powder is in the preferable range (3 to 5) mL: 0.5 g.
The foregoing examples are provided to facilitate an understanding of the principles of the invention and their core concepts, 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, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention. The scope of the invention 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 approximate the literal language of the claims, or if they include equivalent structural elements with insubstantial differences from the literal languages of the claims.
Claims (10)
1. A preparation method of a nitrogen-doped silicon-carbon composite material with a core-shell structure is characterized by comprising the following steps:
a) dispersing aniline monomer and nano silicon powder into acid liquor to obtain dispersion liquid;
b) mixing the dispersion liquid, a hydrogen peroxide solution and an initiator solution to perform hydrothermal reaction, and performing solid-liquid separation and drying after the reaction is finished to obtain a 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.
2. The preparation method according to claim 1, wherein in the step a), the 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.
3. The preparation method according to claim 1 or 2, wherein the particle size of the nano silicon powder is 50-500 nm.
4. The method according to claim 1 or 2, wherein the acid solution is one or more selected from sulfuric acid solution, phosphoric acid solution and nitric acid solution.
5. The preparation method according to claim 1, wherein the 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%.
6. The preparation method of claim 1, wherein the molar ratio of the initiator in the initiator solution to the aniline monomer in the step a) is 1: 0.5-3.
7. The preparation method according to claim 1 or 6, wherein 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.
8. The preparation method according to claim 1, wherein in the step b), the temperature of the hydrothermal reaction is 120-170 ℃ and the time is 2-10 h.
9. The preparation method according to claim 1, wherein in the step c), the carbonization treatment temperature is 400-1000 ℃, and the heat preservation time is 1-6 h.
10. The nitrogen-doped silicon carbon composite material with the core-shell structure, which is prepared by the preparation method of any one of claims 1-9.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202210059421.6A CN114420910B (en) | 2022-01-19 | 2022-01-19 | Nitrogen-doped silicon-carbon composite material with core-shell structure and preparation method thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202210059421.6A CN114420910B (en) | 2022-01-19 | 2022-01-19 | Nitrogen-doped silicon-carbon composite material with core-shell structure and preparation method thereof |
Publications (2)
Publication Number | Publication Date |
---|---|
CN114420910A true CN114420910A (en) | 2022-04-29 |
CN114420910B CN114420910B (en) | 2023-12-01 |
Family
ID=81272581
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202210059421.6A Active CN114420910B (en) | 2022-01-19 | 2022-01-19 | Nitrogen-doped silicon-carbon composite material with core-shell structure and preparation method thereof |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN114420910B (en) |
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 |
Also Published As
Publication number | Publication date |
---|---|
CN114420910B (en) | 2023-12-01 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5509458B2 (en) | Negative electrode material and manufacturing method thereof | |
CN113044827B (en) | Nano carbon material composite biomass hard carbon electrode material and preparation method and application thereof | |
CN107634207B (en) | Silicon-inlaid redox graphene/graphite-phase carbon nitride composite material and preparation and application thereof | |
CN107221654B (en) | Three-dimensional porous nest-shaped silicon-carbon composite negative electrode material and preparation method thereof | |
CN113346054B (en) | Preparation method and application of MXene-carbon nanocage-sulfur composite material | |
CN112758911B (en) | Hard carbon material, preparation method and application thereof, and lithium ion battery | |
CN111276677B (en) | Preparation method of carbon nano material/amorphous carbon/silicon monoxide composite material | |
CN111063872A (en) | Silicon-carbon negative electrode material and preparation method thereof | |
CN111244414A (en) | Method for preparing silicon-carbon negative electrode material by magnesiothermic reduction | |
CN113555539A (en) | High-energy-density quick-charging graphite composite negative electrode material, preparation method thereof and lithium ion battery | |
CN111293308B (en) | Negative electrode material, negative electrode, potassium ion battery and preparation method | |
CN107482188B (en) | Hollow core-shell structure composite material and preparation method and application thereof | |
CN106848282B (en) | Negative electrode material for non-aqueous electrolyte secondary battery and preparation method and application thereof | |
CN111564618A (en) | High-capacity lithium ion battery cathode material capable of being industrially produced | |
CN111370688A (en) | Lithium ion battery cathode material and preparation method thereof | |
CN112786869B (en) | Preparation method of ferric oxide/spiral carbon nanofiber composite anode material | |
CN112694080B (en) | Carbon microsphere with embedded conductive network structure, preparation method and energy storage application thereof | |
CN111725492B (en) | Carbon/lithium titanate composite material and preparation method thereof | |
CN113889596A (en) | Preparation method of nitrogen-doped hard carbon-coated artificial graphite composite material | |
CN111710862A (en) | 3D porous Sb/Ti for high-performance potassium ion battery3C2Preparation method of MXene composite material | |
CN108987746B (en) | Three-dimensional porous nano-network structure MoS fixed by ultra-small particles2Composite powder and preparation method and application thereof | |
CN111146423A (en) | Pre-lithiated binary topological structure phosphorus/carbon composite material and preparation method and application thereof | |
CN114420910B (en) | Nitrogen-doped silicon-carbon composite material with core-shell structure and preparation method thereof | |
CN114520328B (en) | Lithium ion battery negative electrode material, preparation method thereof, negative electrode and battery | |
CN112707380B (en) | Hard carbon precursor, soft and hard carbon composite material, and preparation method and application thereof |
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 |