CN112768661A - Negative electrode material for lithium ion battery and preparation method thereof - Google Patents
Negative electrode material for lithium ion battery and preparation method thereof Download PDFInfo
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- CN112768661A CN112768661A CN202110099889.3A CN202110099889A CN112768661A CN 112768661 A CN112768661 A CN 112768661A CN 202110099889 A CN202110099889 A CN 202110099889A CN 112768661 A CN112768661 A CN 112768661A
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 69
- 239000007773 negative electrode material Substances 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 69
- 239000002243 precursor Substances 0.000 claims abstract description 45
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000000203 mixture Substances 0.000 claims abstract description 26
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 25
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 23
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000004202 carbamide Substances 0.000 claims abstract description 23
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000001354 calcination Methods 0.000 claims abstract description 17
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 16
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 16
- 239000011261 inert gas Substances 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 15
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 13
- 238000000227 grinding Methods 0.000 claims abstract description 11
- 239000008367 deionised water Substances 0.000 claims abstract description 9
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000010406 cathode material Substances 0.000 claims abstract description 7
- 238000001816 cooling Methods 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 4
- 238000005406 washing Methods 0.000 claims abstract description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- 239000000463 material Substances 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- 238000003837 high-temperature calcination Methods 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 239000001307 helium Substances 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 7
- 238000010438 heat treatment Methods 0.000 description 23
- 239000010439 graphite Substances 0.000 description 19
- 229910002804 graphite Inorganic materials 0.000 description 19
- 229910052681 coesite Inorganic materials 0.000 description 18
- 229910052906 cristobalite Inorganic materials 0.000 description 18
- 229910052682 stishovite Inorganic materials 0.000 description 18
- 229910052905 tridymite Inorganic materials 0.000 description 18
- 230000006872 improvement Effects 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 7
- 229910001220 stainless steel Inorganic materials 0.000 description 7
- 239000010935 stainless steel Substances 0.000 description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 6
- 229910052744 lithium Inorganic materials 0.000 description 6
- 238000005530 etching Methods 0.000 description 5
- XZWYZXLIPXDOLR-UHFFFAOYSA-N metformin Chemical compound CN(C)C(=N)NC(N)=N XZWYZXLIPXDOLR-UHFFFAOYSA-N 0.000 description 5
- 238000012360 testing method Methods 0.000 description 4
- 229910052581 Si3N4 Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 238000003780 insertion Methods 0.000 description 3
- 230000037431 insertion Effects 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 3
- 230000032258 transport Effects 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- AAMATCKFMHVIDO-UHFFFAOYSA-N azane;1h-pyrrole Chemical compound N.C=1C=CNC=1 AAMATCKFMHVIDO-UHFFFAOYSA-N 0.000 description 2
- DLGYNVMUCSTYDQ-UHFFFAOYSA-N azane;pyridine Chemical compound N.C1=CC=NC=C1 DLGYNVMUCSTYDQ-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000006183 anode active material Substances 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000006182 cathode active material Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 230000037427 ion transport Effects 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a negative electrode material for a lithium ion battery and a preparation method thereof, wherein the negative electrode material comprises the following steps: calcining the blend of melamine and urea at a high temperature of 500-600 ℃ to prepare a precursor, wherein the precursor is graphite-phase carbon nitride; fully grinding the prepared precursor, uniformly mixing the precursor with silicon dioxide powder to obtain a mixture, and calcining the mixture at a high temperature of 600-1000 ℃ in an inert gas flow atmosphere to obtain a nitrogen-doped carbon material coated on the surface of silicon dioxide; cooling the obtained calcined product, and then sequentially rinsing the calcined product for multiple times by using an HF solution and deionized water; and drying the obtained washing product under a vacuum condition to obtain the nitrogen-doped hollow carbon spheres, namely the cathode material for the lithium ion battery. Compared with the prior art, the preparation method is simple and feasible, and the prepared cathode material can improve the rate charge and discharge performance of the lithium ion battery and is beneficial to improving the energy density of the lithium ion battery.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a negative electrode material for a lithium ion battery and a preparation method thereof.
Background
Lithium ion batteries have received extensive attention and attention due to their advantages such as high energy density, high operating voltage, good cycle performance, and no memory effect. At present, graphite is mainly used as a negative electrode material of a lithium ion battery, and the lithium ion battery is low in cost, rich in source and stable in electrochemical performance. However, the theoretical gram capacity of graphite is only 372mAh g-1With the advent of the information age, people tend to super fast charge and ultra-high energy density lithium ion batteries, and increasing the gram capacity of the negative electrode of the lithium ion battery is helpful to improve the performance of the lithium ion battery such as rate charge and discharge, energy density and the like. Negative electrode as Li in lithium ion battery+The receptor has a vital function, and the lithium ion battery with the graphite cathode has limited lithium intercalation capacity and obviously low gram capacity, so that the requirements of customers and projects on the performance are difficult to meet.
In view of the above, it is necessary to provide a negative electrode material for a lithium ion battery, which can effectively increase gram capacity and electron ion transport rate while taking dynamic performance into consideration.
Disclosure of Invention
One of the objects of the present invention is: aiming at the defects of the prior art, the preparation method of the negative electrode material for the lithium ion battery is simple and feasible, and the prepared negative electrode material can improve the rate charge and discharge performance of the lithium ion battery and is beneficial to improving the energy density of the lithium ion battery.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a negative electrode material for a lithium ion battery comprises the following steps:
1) calcining the blend of melamine and urea at a high temperature of 500-600 ℃ to prepare a precursor, wherein the precursor is graphite-phase carbon nitride;
2) fully grinding the precursor prepared in the step 1), then uniformly mixing the precursor with silicon dioxide powder to obtain a mixture, and calcining the mixture at a high temperature of 600-1000 ℃ in an inert gas flow atmosphere to obtain a nitrogen-doped carbon material coated on the surface of silicon dioxide;
3) cooling the calcined product obtained in the step 2), and then sequentially rinsing the calcined product for multiple times by using an HF solution and deionized water;
4) and (3) drying the washing product obtained in the step 3) under a vacuum condition to obtain the nitrogen-doped hollow carbon spheres, namely the cathode material for the lithium ion battery.
As an improvement of the preparation method of the negative electrode material for the lithium ion battery, in the step 1), the mass ratio of melamine to urea is 1: (0.8 to 1.2).
As an improvement of the preparation method of the negative electrode material for the lithium ion battery, in the step 1), the temperature is raised to 500-600 ℃ at the temperature rise rate of 4-8 ℃/min, and the material is calcined for 2-7 h.
As an improvement of the preparation method of the negative electrode material for the lithium ion battery, in the step 2), the mass ratio of the precursor to the silicon dioxide powder is 1: (1.5-2.5).
As an improvement of the preparation method of the negative electrode material for the lithium ion battery, in the step 2), the inert gas is at least one of nitrogen, argon and helium.
As an improvement of the preparation method of the negative electrode material for the lithium ion battery, in the step 2), the temperature is raised to 600-1000 ℃ at the heating rate of 2-5 ℃/min, and the high-temperature calcination is carried out for 4-10 h.
As an improvement of the preparation method of the negative electrode material for the lithium ion battery, in the step 3), the concentration of the HF solution is 2-10 mol/L.
As an improvement of the preparation method of the negative electrode material for the lithium ion battery, in the step 3), the number of rinsing times is 3-6.
As an improvement of the preparation method of the negative electrode material for the lithium ion battery, in the step 4), the negative electrode material is vacuum-baked for 6-12 hours at the temperature of 60-100 ℃ under the vacuum condition that the negative pressure value is-0.1 Mpa.
The second purpose of the invention is: the negative electrode material for the lithium ion battery is prepared by the preparation method described in the specification.
Compared with the prior art, the invention has the beneficial effects that:
according to the invention, melamine and urea are blended and subjected to high-temperature calcination to prepare a graphite-phase carbon nitride precursor, a layered nitrogen-doped carbon material is coated on the surface of silicon dioxide powder through high-temperature calcination, and then silicon dioxide serving as a template is etched away by hydrofluoric acid to prepare the nitrogen-doped hollow carbon sphere. On one hand, because the graphite-phase silicon nitride is poor in conductivity, the mixture of the graphite-phase silicon nitride precursor and the silicon dioxide powder is calcined at the temperature of 600-1000 ℃, so that the proportion of nitrogen in the graphite-phase silicon nitride precursor can be changed to improve the conductivity, the relative contents of pyridine nitrogen, pyrrole nitrogen and graphite nitrogen can be changed to improve the lithium storage capacity, and the pyridine nitrogen and the pyrrole nitrogen are more beneficial to the storage of lithium ions. On the other hand, the nitrogen-doped hollow carbon spheres prepared by the method have the characteristics of large specific surface area and strong conductivity, are favorable for improving the electron transport rate, accelerating the insertion and extraction processes of lithium ions and improving the rate charge and discharge performance of the lithium ion battery. In addition, the nitrogen-doped hollow carbon spheres also have high gram capacity, which is beneficial to improving the lithium storage capacity of the cathode and possibly improving the energy density of the lithium ion battery.
Drawings
FIG. 1 is a schematic diagram of the preparation process of the present invention.
Detailed Description
The present invention will be described in further detail with reference to the following detailed description and the accompanying drawings, but the embodiments of the invention are not limited thereto.
1. Preparation method
A first aspect of the present invention provides a method for preparing a negative electrode material for a lithium ion battery, as shown in fig. 1, the method comprising the steps of:
1) calcining the blend of melamine and urea at a high temperature of 500-600 ℃ to prepare a precursor, wherein the precursor is graphite-phase carbon nitride;
2) fully grinding the precursor prepared in the step 1), then uniformly mixing the precursor with silicon dioxide powder to obtain a mixture, and calcining the mixture at a high temperature of 600-1000 ℃ in an inert gas flow atmosphere to obtain a nitrogen-doped carbon material coated on the surface of silicon dioxide;
3) cooling the calcined product obtained in the step 2), and then sequentially rinsing the calcined product for multiple times by using an HF solution and deionized water;
4) and (3) drying the washing product obtained in the step 3) under a vacuum condition to obtain the nitrogen-doped hollow carbon spheres, namely the cathode material for the lithium ion battery.
Preferably, in the step 1), the mass ratio of melamine to urea is 1: (0.8 to 1.2). The melamine and the urea are both substances with higher nitrogen content, and the nitrogen doping effect is more obvious in the carbonization process. This ratio is advantageous for improving the nitrogen doping effect. When one of them is too much or too little, it will result in excessive or incomplete nitrogen doping, resulting in impure graphite phase carbon nitride.
Preferably, in the step 1), the temperature is raised to 500-600 ℃ at the temperature rise rate of 4-8 ℃/min, and the calcination is carried out for 2-7 h. More preferably, the temperature is raised to 540 ℃ at a rate of 5 ℃/min and the mixture is calcined for 4 hours.
Preferably, in the step 2), the mass ratio of the precursor to the silica powder is 1: (1.5-2.5).
Preferably, in the step 2), the inert gas is at least one of nitrogen, argon and helium. More preferably, the inert gas is argon.
Preferably, in the step 2), the temperature is raised to 600-1000 ℃ at the temperature raising rate of 2-5 ℃/min, and the calcination is carried out for 4-10 h. More preferably, the temperature is raised to 600/700/800/900/1000 ℃ at the heating rate of 3 ℃/min, and the high-temperature calcination is carried out for 6 h.
Preferably, in the step 3), the concentration of the HF solution is 2-10 mol/L. More preferably, the concentration of the HF solution is 5 mol/L.
Preferably, in the step 3), the number of rinsing is 3-6.
Preferably, in the step 4), the vacuum baking is carried out for 6-12 hours at the temperature of 60-100 ℃ under the vacuum condition that the negative pressure value is-0.1 Mpa.
2. Negative electrode material for lithium ion battery
The invention provides a negative electrode material for a lithium ion battery, which is prepared by the preparation method.
The cathode material for the lithium ion battery is a nitrogen-doped hollow carbon sphere, has the characteristics of large specific surface area and strong conductivity, is favorable for improving the electron transport rate, accelerating the insertion and extraction process of lithium ions and improving the multiplying power charge and discharge performance of the lithium ion battery. And the nitrogen-doped hollow carbon spheres also have high gram capacity, which is beneficial to improving the lithium storage capacity of the cathode and possibly improving the energy density of the lithium ion battery.
The advantageous effects of the present invention will be described in detail below with reference to examples, comparative examples and performance tests.
Example 1
Preparing a negative electrode material for the lithium ion battery:
1) heating to 540 deg.C at 5 deg.C/min in a muffle furnace, calcining the mixture of melamine and urea at high temperature for 4h to obtain graphite phase carbon nitride (g-C)3N4) Precursor, wherein the mass ratio of melamine to urea is 1: 1;
2) fully grinding the precursor g-C3N4Then subsequently subjecting it toWith silicon dioxide (SiO)2) And fully mixing the powder, wherein the mass ratio of the graphite phase carbon nitride to the silicon dioxide powder is 1: 2, subsequently transferred to a stainless steel crucible with a lid under an inert gas N2Heating to 600 ℃ at a heating rate of 3 ℃/min in the atmosphere, and reacting the g-C at constant temperature3N4And SiO2The mixture is mixed for 6 hours to prepare the nitrogen-doped carbon material which is coated on the surface of the silicon dioxide and is marked as NC @ SiO2；
3) Cooling NC @ SiO2The temperature is reduced to room temperature, and NC @ SiO is firstly rinsed by 5mol/L HF solution2Etching off SiO for 3-6 times2Rinsing the template for 3-6 times by using deionized water, and dissolving to remove residual HF;
4) and baking the NC material precursor in a vacuum oven at 60-100 ℃ for 6-12 h to obtain the nitrogen-doped hollow carbon spheres (NHCS).
Example 2
Preparing a negative electrode material for the lithium ion battery:
1) heating to 540 deg.C at 5 deg.C/min in a muffle furnace, calcining the mixture of melamine and urea at high temperature for 4h to obtain graphite phase carbon nitride (g-C)3N4) Precursor, wherein the mass ratio of melamine to urea is 1: 1;
2) fully grinding the precursor g-C3N4Then mixing it with silicon dioxide (SiO)2) And fully mixing the powder, wherein the mass ratio of the graphite phase carbon nitride to the silicon dioxide powder is 1: 2, subsequently transferred to a stainless steel crucible with a lid under an inert gas N2Heating to 700 ℃ at a heating rate of 3 ℃/min in the atmosphere, and reacting the g-C at constant temperature3N4And SiO2The mixture is mixed for 6 hours to prepare the nitrogen-doped carbon material which is coated on the surface of the silicon dioxide and is marked as NC @ SiO2；
3) Cooling NC @ SiO2The temperature is reduced to room temperature, and NC @ SiO is firstly rinsed by 5mol/L HF solution2Etching off SiO for 3-6 times2Rinsing the template for 3-6 times by using deionized water, and dissolving to remove residual HF;
4) and baking the NC material precursor in a vacuum oven at 60-100 ℃ for 6-12 h to obtain the nitrogen-doped hollow carbon spheres (NHCS).
Example 3
Preparing a negative electrode material for the lithium ion battery:
1) heating to 540 deg.C at 5 deg.C/min in a muffle furnace, calcining the mixture of melamine and urea at high temperature for 4h to obtain graphite phase carbon nitride (g-C)3N4) Precursor, wherein the mass ratio of melamine to urea is 1: 1;
2) fully grinding the precursor g-C3N4Then mixing it with silicon dioxide (SiO)2) And fully mixing the powder, wherein the mass ratio of the graphite phase carbon nitride to the silicon dioxide powder is 1: 2, subsequently transferred to a stainless steel crucible with a lid under an inert gas N2Heating to 800 ℃ at a heating rate of 3 ℃/min in the atmosphere, and reacting the g-C at constant temperature3N4And SiO2The mixture is mixed for 6 hours to prepare the nitrogen-doped carbon material which is coated on the surface of the silicon dioxide and is marked as NC @ SiO2；
3) Cooling NC @ SiO2The temperature is reduced to room temperature, and NC @ SiO is firstly rinsed by 5mol/L HF solution2Etching off SiO for 3-6 times2Rinsing the template for 3-6 times by using deionized water, and dissolving to remove residual HF;
4) and baking the NC material precursor in a vacuum oven at 60-100 ℃ for 6-12 h to obtain the nitrogen-doped hollow carbon spheres (NHCS).
Example 4
Preparing a negative electrode material for the lithium ion battery:
1) heating to 540 deg.C at 5 deg.C/min in a muffle furnace, calcining the mixture of melamine and urea at high temperature for 4h to obtain graphite phase carbon nitride (g-C)3N4) Precursor, wherein the mass ratio of melamine to urea is 1: 1;
2) fully grinding the precursor g-C3N4Then mixing it with silicon dioxide (SiO)2) And fully mixing the powder, wherein the mass ratio of the graphite phase carbon nitride to the silicon dioxide powder is 1: 2, subsequently transferred to a stainless steel crucible with a lid under an inert gas N2Heating to 900 ℃ at a heating rate of 3 ℃/min in the atmosphere, and reacting the g-C at constant temperature3N4And SiO2For 6 hours to obtain the silica surface coatedNitrogen-doped carbon material, denoted NC @ SiO2；
3) Cooling NC @ SiO2The temperature is reduced to room temperature, and NC @ SiO is firstly rinsed by 5mol/L HF solution2Etching off SiO for 3-6 times2Rinsing the template for 3-6 times by using deionized water, and dissolving to remove residual HF;
4) and baking the NC material precursor in a vacuum oven at 60-100 ℃ for 6-12 h to obtain the nitrogen-doped hollow carbon spheres (NHCS).
Example 5
Preparing a negative electrode material for the lithium ion battery:
1) heating to 540 deg.C at 5 deg.C/min in a muffle furnace, calcining the mixture of melamine and urea at high temperature for 4h to obtain graphite phase carbon nitride (g-C)3N4) Precursor, wherein the mass ratio of melamine to urea is 1: 1;
2) fully grinding the precursor g-C3N4Then mixing it with silicon dioxide (SiO)2) And fully mixing the powder, wherein the mass ratio of the graphite phase carbon nitride to the silicon dioxide powder is 1: 2, subsequently transferred to a stainless steel crucible with a lid under an inert gas N2Heating to 1000 ℃ at a heating rate of 3 ℃/min in the atmosphere, and reacting the g-C at constant temperature3N4And SiO2The mixture is mixed for 6 hours to prepare the nitrogen-doped carbon material which is coated on the surface of the silicon dioxide and is marked as NC @ SiO2；
3) Cooling NC @ SiO2The temperature is reduced to room temperature, and NC @ SiO is firstly rinsed by 5mol/L HF solution2Etching off SiO for 3-6 times2Rinsing the template for 3-6 times by using deionized water, and dissolving to remove residual HF;
4) and baking the NC material precursor in a vacuum oven at 60-100 ℃ for 6-12 h to obtain the nitrogen-doped hollow carbon spheres (NHCS).
Comparative example 1
Preparing a negative electrode material for the lithium ion battery:
1) heating to 540 deg.C at 5 deg.C/min in a muffle furnace, calcining the mixture of melamine and urea at high temperature for 4h to obtain graphite phase carbon nitride (g-C)3N4) Precursor, wherein the mass ratio of melamine to urea is 1: 1;
2) fully grinding the precursor g-C3N4Subsequently transferred to a stainless steel crucible with a lid under an inert gas N2Heating to 600 ℃ at a heating rate of 3 ℃/min in the atmosphere, and reacting the g-C at constant temperature3N4The precursor is subjected to 6h, and the nitrogen-doped carbon material precursor is recorded as NC;
3) and cooling the NC to room temperature, and baking the NC material precursor in a vacuum oven at 60-100 ℃ for 6-12 h to obtain the nitrogen-doped carbon material NC.
Comparative example 2
Preparing a negative electrode material for the lithium ion battery:
1) heating to 540 deg.C at 5 deg.C/min in a muffle furnace, calcining the mixture of melamine and urea at high temperature for 4h to obtain graphite phase carbon nitride (g-C)3N4) Precursor, wherein the mass ratio of melamine to urea is 1: 1;
2) fully grinding the precursor g-C3N4Then mixing it with silicon dioxide (SiO)2) And fully mixing the powder, wherein the mass ratio of the graphite phase carbon nitride to the silicon dioxide powder is 1: 2, subsequently transferred to a stainless steel crucible with a lid under an inert gas N2Heating to 600 ℃ at a heating rate of 3 ℃/min in the atmosphere, and reacting the g-C at constant temperature3N4And SiO2The mixture is mixed for 6 hours to prepare the nitrogen-doped carbon material which is coated on the surface of the silicon dioxide and is marked as NC @ SiO2；
3) Cooling NC @ SiO2Cooling to room temperature, and baking NC @ SiO in a vacuum oven at 60-100 DEG C2The precursor of the material is 6-12 h, and the obtained nitrogen-carbon coated SiO is obtained2Surface composite material (NC @ SiO)2)。
Comparative example 3
The conventional graphite is used as a negative electrode material for a lithium ion battery.
Performance testing
The negative electrode materials (examples 1-5 and comparative examples 1-3) are used for preparing the soft package lithium ion battery, and the soft package lithium ion battery comprises a positive plate, a negative plate, an isolating membrane for separating the positive plate from the negative plate, electrolyte and a pack package. The positive plate comprises an aluminum foil and a positive membrane, and the negative plate comprises a copper foil and a negative membrane. In addition, the positive electrode film contains a positive electrode active material, a binder and a conductive agent, and the negative electrode film contains a negative electrode active material, a conductive agent and a binder. The anode active material is lithium cobaltate, and the cathode active material is the cathode material for the lithium ion battery.
The first discharge capacity, the first efficiency, the cycle capacity retention rate and the rate charge and discharge performance of the lithium ion battery anode materials of the examples 1 to 5 and the comparative examples 1 to 3 are tested. The test results are shown in Table 1.
TABLE 1 test results
As can be seen from the test results in table 1, examples 1 to 5 have higher first discharge capacity and first efficiency, higher retention rate of cycle capacity, and better rate charge and discharge performance than comparative examples 1 to 3. The negative electrode material prepared by the preparation method is the nitrogen-doped hollow carbon spheres, has the characteristics of large specific surface area and strong conductivity, is favorable for improving the electron transport rate, accelerating the insertion and extraction processes of lithium ions and improving the rate charge and discharge performance of the lithium ion battery. And the nitrogen-doped hollow carbon spheres also have high gram capacity, which is beneficial to improving the lithium storage capacity of the cathode.
Variations and modifications to the above-described embodiments may also occur to those skilled in the art, which fall within the scope of the invention as disclosed and taught herein. Therefore, the present invention is not limited to the above-mentioned embodiments, and any obvious improvement, replacement or modification made by those skilled in the art based on the present invention is within the protection scope of the present invention. Furthermore, although specific terms are employed herein, they are used in a generic and descriptive sense only and not for purposes of limitation.
Claims (10)
1. A preparation method of a negative electrode material for a lithium ion battery is characterized by comprising the following steps:
1) calcining the blend of melamine and urea at a high temperature of 500-600 ℃ to prepare a precursor, wherein the precursor is graphite-phase carbon nitride;
2) fully grinding the precursor prepared in the step 1), then uniformly mixing the precursor with silicon dioxide powder to obtain a mixture, and calcining the mixture at a high temperature of 600-1000 ℃ in an inert gas flow atmosphere to obtain a nitrogen-doped carbon material coated on the surface of silicon dioxide;
3) cooling the calcined product obtained in the step 2), and then sequentially rinsing the calcined product for multiple times by using an HF solution and deionized water;
4) and (3) drying the washing product obtained in the step 3) under a vacuum condition to obtain the nitrogen-doped hollow carbon spheres, namely the cathode material for the lithium ion battery.
2. The preparation method of the negative electrode material for the lithium ion battery according to claim 1, wherein in the step 1), the mass ratio of melamine to urea is 1: (0.8 to 1.2).
3. The preparation method of the negative electrode material for the lithium ion battery according to claim 1, wherein in the step 1), the temperature is raised to 500-600 ℃ at a temperature rise rate of 4-8 ℃/min and the material is calcined for 2-7 h.
4. The method for preparing the negative electrode material for the lithium ion battery according to claim 1, wherein in the step 2), the mass ratio of the precursor to the silica powder is 1: (1.5-2.5).
5. The method for preparing the negative electrode material for a lithium ion battery according to claim 1, wherein in the step 2), the inert gas is at least one of nitrogen, argon and helium.
6. The preparation method of the negative electrode material for the lithium ion battery according to claim 1, wherein in the step 2), the temperature is raised to 600-1000 ℃ at a temperature rise rate of 2-5 ℃/min and the high-temperature calcination is carried out for 4-10 h.
7. The preparation method of the negative electrode material for the lithium ion battery according to claim 1, wherein in the step 3), the concentration of the HF solution is 2-10 mol/L.
8. The method for preparing the negative electrode material for the lithium ion battery according to claim 1, wherein the number of rinsing in step 3) is 3 to 6.
9. The preparation method of the negative electrode material for the lithium ion battery according to claim 1, wherein in the step 4), the negative electrode material is vacuum-baked at a temperature of 60 to 100 ℃ for 6 to 12 hours under a vacuum condition with a negative pressure value of-0.1 MPa.
10. A negative electrode material for a lithium ion battery, which is characterized by being prepared by the preparation method of any one of claims 1 to 9.
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