CN113809312B - Nitrogen-doped soft carbon coated silicon-based lithium ion anode material and preparation method and application thereof - Google Patents
Nitrogen-doped soft carbon coated silicon-based lithium ion anode material and preparation method and application thereof Download PDFInfo
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- 239000010703 silicon Substances 0.000 title claims abstract description 65
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 62
- 239000010405 anode material Substances 0.000 title claims abstract description 52
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- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
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Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- 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 relates to a nitrogen-doped soft carbon coated silicon-based lithium ion anode material, and a preparation method and application thereof. Taking a nitrogen-containing gas source or a high-boiling point nitrogen-containing compound as a doping material, and carrying out gas-phase mixing reaction on vapor of the doping material and preheated vapor of a silicon source at 1200-1700 ℃ for 1-24 hours to obtain a nitrogen-doped silicon oxide material; wherein the silicon source vapor is a mixed vapor of silicon vapor and silicon dioxide vapor; the nitrogen-containing gas source is a nitrogen-containing compound which is in a gaseous state at normal temperature, and the high-boiling point nitrogen-containing compound is a nitrogen-containing compound which is in a liquid state or a solid state at normal temperature; cooling the nitrogen doped silicon oxide material to room temperature, discharging, crushing and screening; carrying out flight time secondary ion mass spectrometry analysis test on the crushed and sieved material, and confirming whether the doping uniformity of nitrogen doped in the silicon oxide meets the preset condition; and (3) coating carbon on the material with the doping uniformity meeting the preset condition to obtain the nitrogen-doped silicon-based lithium ion battery anode material.
Description
Technical Field
The invention relates to the technical field of material preparation, in particular to a nitrogen-doped soft carbon coated silicon-based lithium ion anode material, and a preparation method and application thereof.
Background
With the rapid development of new energy automobiles, higher requirements are put on the performance of power batteries in the industry. The positive and negative electrode materials determine key components of the power battery, such as energy density, power density, cycle life, high and low temperature performance and safety performance, and the positive and negative electrode materials are mainly used for freely deintercalating lithium ions so as to realize the charge and discharge functions of the battery. The requirements of the lithium ion battery anode material at least meet the following points: 1. a lower chemical potential; 2. good electrical conductivity; 3. good cycle stability and safety; 4. inexpensive raw materials, and the like.
The negative electrode material is one of the most critical materials in lithium ion battery technology. Currently commercially available graphite anodes have reached their technical bottlenecks due to their low gram capacity. Silicon is one of the most promising lithium ion negative electrode materials to replace it. Silicon-based anode materials with specific capacities up to 4200mAh/g are possessed, and silicon-based anode materials with three-dimensional diffusion channels gradually exhibit the advantage of their high energy density. While silicon-based anode materials can achieve satisfactory energy densities, there are also technical bottlenecks in the materials. The silicon-based anode material has a series of defects such as volume expansion effect, poor conductivity and the like, and limits the practical application thereof.
Nitrogen doping is a relatively common modification. The patent CN110911665A provides a preparation method of a boron and nitrogen doped lithium ion battery cathode material, which comprises the steps of mixing melamine, ammonia borate, tetraethoxysilane, hydrochloric acid, deionized water and ethanol to obtain a colloidal precursor solution, and drying, carbonizing, ball-milling and the like the solution to obtain the boron and nitrogen doped lithium ion battery cathode material. The battery prepared from the obtained anode material has good rate performance and electrochemical performance. But the scheme is also insufficient. Because solid particles are mixed in liquid phase and still undergo mass transfer contact in a solid phase mode after drying, the conditions of uneven reaction and poor particle dispersion still exist, which can influence the consistency of the material obtained by the preparation method and possibly influence the cycle performance of the material.
Disclosure of Invention
The embodiment of the invention provides a nitrogen-doped soft carbon coated silicon-based lithium ion anode material, a preparation method and application thereof, and the anode material of a lithium ion battery, which is obtained through gas phase reaction and is uniformly doped in a bulk phase, has higher cycling stability and better consistency.
In a first aspect, an embodiment of the present invention provides a method for preparing a nitrogen-doped soft carbon coated silicon-based lithium ion anode material, including:
taking a nitrogen-containing gas source or a high-boiling point nitrogen-containing compound as a doping material, and carrying out gas-phase mixing reaction on vapor of the doping material and preheated vapor of a silicon source at 1200-1700 ℃ for 1-24 hours to obtain a nitrogen-doped silicon oxide material; wherein the silicon source vapor is a mixed vapor of silicon vapor and silicon dioxide vapor; the nitrogen-containing gas source is a nitrogen-containing compound which is in a gaseous state at normal temperature, and the high-boiling point nitrogen-containing compound is a nitrogen-containing compound which is in a liquid state or a solid state at normal temperature;
cooling the nitrogen doped silicon oxide material to room temperature, discharging, crushing and screening;
carrying out flight time secondary ion mass spectrometry analysis test on the crushed and sieved material, and confirming whether the doping uniformity of nitrogen doped in the silicon oxide meets the preset condition;
and (3) coating carbon on the material with the doping uniformity meeting the preset condition to obtain the nitrogen-doped silicon-based lithium ion anode material.
Preferably, the nitrogen-containing gas source specifically includes: one or more of nitrogen, ammonia, nitrous oxide or dimethylamine;
the high boiling point nitrogen-containing compound specifically includes: a carboxamide or melamine.
Preferably, the vapour of the doping material is obtained by heating the doping material to a temperature of 25 ℃ to 800 ℃.
Preferably, the silicon vapor and the silicon dioxide vapor in the silicon source vapor are prepared by the following steps of: silica = 1: 1.
Preferably, the mass of nitrogen atoms in the doping material accounts for 100ppm to 100000ppm of the total mass of silicon and silicon dioxide in the silicon source vapor.
Preferably, the preset conditions are specifically: in the time-of-flight secondary ion mass spectrometry analysis and test process, the fluctuation range of the nitrogen atom concentration is within +/-50% in the whole particle sputtering time period.
Preferably, the carbon coating is specifically: placing the materials with the doping uniformity meeting the preset conditions in a rotary furnace, heating to 800-1000 ℃ under a protective atmosphere, introducing an organic gas source for chemical vapor deposition, keeping the temperature for 2-4 hours, and then closing the organic gas source for cooling; wherein, the organic air source specifically includes: one or more of methane, acetylene, propylene or propane.
In a second aspect, an embodiment of the present invention provides a lithium ion battery negative electrode material, which includes the nitrogen doped soft carbon coated silicon-based lithium ion negative electrode material prepared by the preparation method in the first aspect.
In a third aspect, an embodiment of the present invention provides a lithium battery pole piece, where the lithium battery pole piece includes the lithium ion battery negative electrode material described in the second aspect.
In a fourth aspect, an embodiment of the present invention provides a lithium battery, where the lithium battery includes the lithium battery pole piece described in the third aspect.
According to the preparation method of the nitrogen-doped soft carbon coated silicon-based lithium ion anode material, provided by the invention, the nitrogen-containing substance, the silicon vapor and the silicon oxide vapor are subjected to gas phase mixing reaction, so that the reaction substances are fully contacted to obtain the anode material of the lithium ion battery with uniform bulk phase doping, the obtained material has higher cycling stability, and meanwhile, the consistency of the material is better.
Drawings
The technical scheme of the embodiment of the invention is further described in detail through the drawings and the embodiments.
FIG. 1 is a flow chart of a preparation method of a nitrogen-doped soft carbon coated silicon-based lithium ion anode material according to an embodiment of the invention;
fig. 2 is a time-of-flight secondary ion mass spectrum of the nitrogen-doped silicon-based lithium ion battery anode material provided in embodiment 1 of the present invention;
FIG. 3 is a graph of the time-of-flight secondary ion mass spectrum of the uniform nitrogen-doped silicon-based lithium ion battery anode material provided in comparative example 1 of the present invention;
FIG. 4 is a graph of the time-of-flight secondary ion mass spectrum of the negative electrode material of the uniform nitrogen-doped silicon-based lithium ion battery provided in comparative example 2;
fig. 5 is a comparison of time-of-flight secondary ion mass spectra of the uniform nitrogen-doped silicon-based lithium ion battery anode materials provided in example 1 and comparative examples 1-2 of the present invention.
Detailed Description
The invention is further illustrated by the drawings and the specific examples, which are to be understood as being for the purpose of more detailed description only and are not to be construed as limiting the invention in any way, i.e. not intended to limit the scope of the invention.
The preparation method of the nitrogen-doped soft carbon coated silicon-based lithium ion anode material comprises the following steps as shown in fig. 1:
110, taking a nitrogen-containing gas source or a high-boiling point nitrogen-containing compound as a doping material, and carrying out gas-phase mixing reaction on vapor of the doping material and preheated vapor of a silicon source at 1200-1700 ℃ for 1-24 hours to obtain a nitrogen-doped silicon oxide material;
wherein the vapour of the doping material is obtained by heating the doping material to a temperature of 25 ℃ to 800 ℃.
In the doping material, the nitrogen-containing gas source is a nitrogen-containing compound which is in a gaseous state at normal temperature, and can specifically comprise one or more of nitrogen, ammonia, nitrous oxide or dimethylamine; the high boiling point nitrogen-containing compound is a nitrogen-containing compound which is liquid or solid at normal temperature, and may include one or more of a carboxamide or a melamine in particular.
The silicon source vapor is a mixed vapor of silicon vapor and silicon dioxide vapor, preferably silicon in a molar ratio: silica = 1: 1.
The mass of nitrogen atoms in the doped material accounts for 100ppm to 100000ppm of the total mass of silicon and silicon dioxide in the silicon source vapor.
130, performing time-of-flight secondary ion mass spectrometry analysis test on the crushed and sieved material to confirm whether the doping uniformity of nitrogen doped in the silicon oxide meets the preset condition;
the preset conditions of the step are specifically as follows: in the time-of-flight secondary ion mass spectrometry analysis and test process, the fluctuation range of the nitrogen atom concentration is within +/-50% in the whole particle sputtering time period. If this condition is satisfied, it is considered acceptable to perform the next carbon coating step.
And 140, coating carbon on the material with the doping uniformity meeting the preset condition to obtain the nitrogen-doped silicon-based lithium ion anode material.
The carbon coating is specifically as follows: placing the materials with the doping uniformity meeting the preset conditions into a rotary furnace, heating to 800-1000 ℃ under a protective atmosphere, introducing an organic gas source for chemical vapor deposition, keeping the temperature for 2-4 hours, and then closing the organic gas source for cooling;
wherein, organic air source specifically includes: one or more of methane, acetylene, propylene or propane.
According to the preparation method, the nitrogen-containing substance, the silicon vapor and the silicon oxide vapor are subjected to gas-phase mixing reaction, so that the reaction substances are fully contacted to obtain the lithium ion battery anode material with uniform bulk phase doping, the obtained material has higher cycling stability, and meanwhile, the consistency of the material is better.
The nitrogen-doped soft carbon coated silicon-based lithium ion anode material prepared by the preparation method can be used as a lithium ion battery anode material and applied to a lithium battery pole piece and a lithium battery.
In order to better understand the technical scheme provided by the invention, the following specific processes for preparing the lithium battery anode material by applying the method provided by the embodiment of the invention, and the method and the battery characteristics for applying the lithium battery anode material to the lithium battery are respectively described in a plurality of specific examples.
Example 1
1.4kg of silicon powder and 3kg of silicon dioxide are placed in a high-temperature reaction furnace to be heated to steam, 1.6L (2 g in terms of mass) of nitrogen is slowly introduced under the protection of argon, and the mixture is reacted for 3 hours at 1400 ℃ and cooled to room temperature. The output was detected by time-of-flight secondary ion mass spectrometry (TOF-SIMS) after fragmentation. Fig. 2 is a time-of-flight secondary ion mass spectrum of the nitrogen-doped silicon-based lithium ion battery anode material provided in example 1 of the present invention, and is used for comparison with comparative examples.
Placing 2kg of qualified materials into a rotary furnace, heating to 1000 ℃ under the atmosphere of protective argon, and mixing according to the volume ratio of 1:1, introducing argon and an organic mixed gas equal to the argon for chemical vapor deposition, wherein the organic mixed gas is formed by the following components in volume ratio of 1:1, preserving heat for 2 hours, closing an organic air source, and cooling to obtain the uniform nitrogen-doped soft carbon coated silicon-based lithium ion battery anode material, wherein the nitrogen content of the anode material is 0.045%.
The resulting negative electrode material, conductive additive carbon black, binder 1:1, sodium cellulose and styrene-butadiene rubber according to the mass ratio of 95 percent: 2%:3% of the weight was weighed. At room temperature, the mixture is put into a beater for slurry preparation. And uniformly coating the prepared slurry on the copper foil. Drying at 50deg.C in a forced air drying oven for 2 hr, cutting into 8×8mm pole pieces, and vacuum drying at 100deg.C in a vacuum drying oven for 10 hr. And transferring the dried pole piece into a glove box for standby use to assemble a battery.
The simulated cell was assembled in a glove box containing a high purity Ar atmosphere using metallic lithium as the counter electrode, 1 mole LiPF 6 The solution in Ethylene Carbonate (EC)/dimethyl carbonate (DMC) was used as an electrolyte to assemble a battery. The constant current charge and discharge mode test was performed using a charge and discharge meter with a discharge cutoff voltage of 0.005V and a charge cutoff voltage of 1.5V, with the first week of charge and discharge test being performed at C/10 current density and the second week of discharge test being performed at C/10 current density.
Example 2
4.2kg of silicon powder and 9kg of silicon dioxide are placed in a high-temperature reaction furnace to be heated to steam, 23.4L (18 g in terms of mass) of ammonia gas is slowly introduced under the protection of argon gas, and the mixture is reacted for 8 hours at 1200 ℃ and cooled to room temperature. And (5) detecting the qualified products by TOF-SIMS after the discharged materials are crushed. Placing 2kg of qualified materials into a rotary furnace, heating to 850 ℃ under the atmosphere of protective argon, and mixing according to the volume ratio of 1:1, introducing argon and an organic mixed gas equal to the argon for chemical vapor deposition, wherein the organic mixed gas is formed by the following components in volume ratio of 2:3, preserving the temperature of the mixed gas of propylene and methane for 3 hours, closing an organic gas source, and cooling to obtain the uniform nitrogen-doped soft carbon coated silicon-based lithium ion battery anode material, wherein the nitrogen content of the anode material is 0.14%.
The preparation process of the negative electrode tab and the battery assembly and battery testing method were the same as in example 1.
Example 3
2.8kg of silicon powder and 6kg of silicon dioxide are placed in a high-temperature reaction furnace to be heated to steam, 1L (2 g in terms of mass) of nitrous oxide is slowly introduced under the protection of argon, and the mixture is reacted for 5 hours at 1500 ℃ and cooled to room temperature. And (5) detecting the qualified products by TOF-SIMS after the discharged materials are crushed. Placing 2kg of qualified materials into a rotary furnace, heating to 850 ℃ under the atmosphere of protective argon, and mixing according to the volume ratio of 1: and 1, introducing argon and propane equivalent to the argon for chemical vapor deposition, keeping the temperature for 2.5 hours, closing an organic air source, and cooling to obtain the uniform nitrogen-doped soft carbon coated silicon-based lithium ion battery anode material, wherein the nitrogen content of the obtained anode material is 0.014%.
The preparation process of the negative electrode tab and the battery assembly and battery testing method were the same as in example 1.
Example 4
2.8kg of silicon powder and 6kg of silicon dioxide are placed in a high-temperature reaction furnace to be heated to steam, 450g of carbon amide is heated to 400 ℃ to be changed into steam, the steam is mixed with each other, and then the mixture is reacted for 7 hours at 1600 ℃ and cooled to room temperature. And (5) detecting the qualified products by TOF-SIMS after the discharged materials are crushed. Placing 2kg of qualified materials into a rotary furnace, heating to 900 ℃ under the atmosphere of protective argon, and mixing according to the volume ratio of 1:2 introducing argon and acetylene for chemical vapor deposition, keeping the temperature for 3 hours, closing an organic air source, and cooling to obtain the uniform nitrogen-doped soft carbon coated silicon-based lithium ion battery anode material, wherein the nitrogen content of the anode material is 2.4%.
The preparation process of the negative electrode tab and the battery assembly and battery testing method were the same as in example 1.
Example 5
1.4kg of silicon powder and 3kg of silicon dioxide are placed in a high-temperature reaction furnace to be heated to be vapor, 60g of melamine is heated to 320 ℃ to be vapor at the same time, the vapor is mixed with each other to react for 3.5 hours at 1600 ℃, and the mixture is cooled to room temperature. And (5) detecting the qualified products by TOF-SIMS after the discharged materials are crushed. Placing 2kg of qualified materials into a rotary furnace, heating to 1000 ℃ under the atmosphere of protective argon, and mixing according to the volume ratio of 1:1 introducing argon and an organic mixed gas with the same amount as the argon for chemical vapor deposition, wherein the organic mixed gas is formed by the following components in volume ratio of 3:1, preserving heat for 3 hours, closing an organic air source, and cooling to obtain the uniform nitrogen-doped soft carbon coated silicon-based lithium ion battery anode material, wherein the nitrogen content of the anode material is 0.9%.
The preparation process of the negative electrode tab and the battery assembly and battery testing method were the same as in example 1.
Example 6
1.4kg of silicon powder and 3kg of silicon dioxide are placed in a high-temperature reaction furnace to be heated to steam, 30L (30 g in terms of mass) of nitrous oxide is slowly introduced under the protection of argon, and the mixture is reacted for 4 hours at 1400 ℃ and cooled to room temperature. And (5) detecting the qualified products by TOF-SIMS after the discharged materials are crushed. Placing 2kg of qualified materials into a rotary furnace, heating to 1000 ℃ under the atmosphere of protective argon, and mixing according to the volume ratio of 1: and 1, introducing argon and propylene for chemical vapor deposition, keeping the temperature for 2 hours, closing an organic air source, and cooling to obtain the uniform nitrogen-doped soft carbon coated silicon-based lithium ion battery anode material, wherein the nitrogen content of the obtained anode material is 0.43%.
The preparation process of the negative electrode tab and the battery assembly and battery testing method were the same as in example 1.
Example 7
4.2kg of silicon powder and 9kg of silicon dioxide are placed in a high-temperature reaction furnace to be heated to steam, 5L (5 g in terms of mass) of nitrous oxide is slowly introduced under the protection of argon, and the mixture is reacted for 10 hours at 1200 ℃ and cooled to room temperature. And (5) detecting the qualified products by TOF-SIMS after the discharged materials are crushed. Placing 2kg of qualified materials into a rotary furnace, heating to 800 ℃ under the atmosphere of protective argon, and mixing according to the volume ratio of 1:1, introducing argon and an organic mixed gas equal to the argon for chemical vapor deposition, wherein the organic mixed gas is formed by the following components in volume ratio of 3:1, and preserving the heat for 4 hours, closing an organic air source, and cooling to obtain the uniform nitrogen-doped soft carbon coated silicon-based lithium ion battery anode material, wherein the nitrogen content of the anode material is 0.024%.
The preparation process of the negative electrode tab and the battery assembly and battery testing method were the same as in example 1.
Example 8
2.8kg of silicon powder and 6kg of silicon dioxide are placed in a high-temperature reaction furnace to be heated to steam, simultaneously 350g of melamine is heated to 320 ℃ to be changed into steam, the steam is mixed with each other to react for 6.5 hours at 1500 ℃, and the mixture is cooled to room temperature. And (5) detecting the qualified products by TOF-SIMS after the discharged materials are crushed. Placing 2kg of qualified materials into a rotary furnace, heating to 1000 ℃ under the atmosphere of protective argon, and mixing according to the volume ratio of 1:1, introducing argon and an organic mixed gas equal to the argon for chemical vapor deposition, wherein the organic mixed gas is formed by the following components in volume ratio of 2:1, preserving heat for 2 hours, closing an organic air source, and cooling to obtain the uniform nitrogen-doped soft carbon coated silicon-based lithium ion battery anode material, wherein the nitrogen content of the anode material is 2.7%.
The preparation process of the negative electrode tab and the battery assembly and battery testing method were the same as in example 1.
Comparative example 1
This comparative example provides a negative electrode material for a lithium ion battery in comparison with example 1. After 2kg of silicon oxide and 1.9g of carbamide are mechanically mixed, a time-of-flight secondary ion mass spectrometer (TOF-SIMS) test is carried out, and then the mixture is placed in a rotary furnace, and the temperature is raised to 1000 ℃ under the protection of argon, and the volume ratio is 1:1 introducing argon and a mixed gas of propylene and methane with the same amount as the argon for chemical vapor deposition, wherein the volume ratio of the propylene to the methane is 1:1, keeping the temperature for 2 hours, closing an organic air source, and cooling to obtain the negative electrode material of the lithium ion battery for comparison, wherein the nitrogen content of the obtained negative electrode material is 0.045%.
The preparation process of the negative electrode tab and the battery assembly and battery testing method were the same as in example 1.
Comparative example 2
Comparative example 2 provides a negative electrode material for a lithium ion battery in comparison with example 1. Mixing 2kg of silicon oxide and 1.9g of carbamide uniformly by ethanol, and spray drying to obtain the composite silicon oxide material. The composite silicon oxide material is subjected to time-of-flight secondary ion mass spectrometer (TOF-SIMS) detection and then is placed in a rotary furnace to be heated to 1000 ℃ under the protection of argon, and the volume ratio is 1:1, introducing argon and an organic mixed gas equal to the argon for chemical vapor deposition, wherein the organic mixed gas is formed by the following components in volume ratio of 1:1, preserving heat for 2 hours, closing an organic air source, and cooling to obtain the lithium ion battery negative electrode material for comparison, wherein the nitrogen content in the obtained negative electrode material is 0.045%.
The preparation process of the negative electrode tab and the battery assembly and battery testing method were the same as in example 1.
The negative electrode materials of examples 1 to 8 and comparative examples 1 to 2 above were respectively subjected to the initial efficiency, 0.1C reversible capacity, cycle performance at 0.1C magnification, and other index tests, and the results are shown in table 1.
TABLE 1
As can be seen from the data in table 1, in the same case, examples 1 to 8 all adopt bulk phase doping technology to modify silicon-based anode materials by gas phase mixing, and the lithium battery has good performance consistency and high specific charge capacity and cycle performance due to uniform gas phase mass transfer. Comparative examples 1-2 were modified with solid phase coating and liquid phase coating, respectively, and it can be seen from comparative example 1 that although initial effect and specific charge capacity are high, cycle stability after 100 and 500 cycles is poor, which is mainly due to insufficient contact of solid phase reaction, so that nitrogen doping is uneven, and cycle stability is affected. The liquid phase coating is adopted in comparative example 2, so that doping is relatively more uniform than that in comparative example 1, but the improvement of the cycle performance is not obvious because the surface doping technology is adopted only and nitrogen-containing particles are attached to the surface of the silicon oxide.
In addition, fig. 5 is a graph comparing the time-of-flight secondary ion mass spectra of the anode materials of the uniform nitrogen-doped silicon-based lithium ion batteries provided in example 1 and comparative examples 1-2 of the present invention. As can be seen from comparison, when sputtering was started, since example 1 employed vapor phase mixed doping and nitrogen atoms were doped during the preparation of the raw material, the nitrogen atom concentration distribution was uniform in different periods of time during sputtering. Whereas comparative examples 1 and 2 were very non-uniform in nitrogen atom distribution due to the solid and liquid phase doping, respectively. When the sputtering time is more than 250s, the nitrogen atoms are not distributed because the etching is carried out inside, so that the nitrogen atoms are not concentrated, and the vapor phase vapor doping can be doped into the material, and the solid phase doping and the liquid phase doping are only doped on the surface.
According to the preparation method of the nitrogen-doped soft carbon coated silicon-based lithium ion anode material, provided by the invention, the nitrogen-containing substance, the silicon vapor and the silicon oxide vapor are subjected to gas phase mixing reaction, so that the reaction substances are fully contacted to obtain the anode material of the lithium ion battery with uniform bulk phase doping, the obtained material has higher cycling stability, and meanwhile, the consistency of the material is better.
The foregoing description of the embodiments has been provided for the purpose of illustrating the general principles of the invention, and is not meant to limit the scope of the invention, but to limit the invention to the particular embodiments, and any modifications, equivalents, improvements, etc. that fall within the spirit and principles of the invention are intended to be included within the scope of the invention.
Claims (7)
1. The preparation method of the nitrogen-doped soft carbon coated silicon-based lithium ion anode material is characterized by comprising the following steps of:
taking a nitrogen-containing gas source or a high-boiling point nitrogen-containing compound as a doping material, and carrying out gas-phase mixing reaction on vapor of the doping material and preheated vapor of a silicon source at 1200-1700 ℃ for 1-24 hours to obtain a nitrogen-doped silicon oxide material; wherein the silicon source vapor is a mixed vapor of silicon vapor and silicon dioxide vapor; the nitrogen-containing gas source is a nitrogen-containing compound which is in a gaseous state at normal temperature, and the high-boiling point nitrogen-containing compound is a nitrogen-containing compound which is in a liquid state or a solid state at normal temperature; the nitrogen-containing gas source specifically comprises: one or more of nitrogen, ammonia, nitrous oxide or dimethylamine; the high boiling point nitrogen-containing compound specifically includes: a carboxamide or melamine; the vapor of the doping material is obtained by heating the doping material to 25-800 ℃;
cooling the nitrogen doped silicon oxide material to room temperature, discharging, crushing and screening;
carrying out flight time secondary ion mass spectrometry analysis test on the crushed and sieved material, and confirming whether the doping uniformity of nitrogen doped in the silicon oxide meets the preset condition;
coating the materials with doping uniformity meeting preset conditions with carbon to obtain a nitrogen-doped soft carbon coated silicon-based lithium ion anode material;
wherein, the preset conditions are specifically as follows: in the time-of-flight secondary ion mass spectrometry analysis and test process, the fluctuation range of the nitrogen atom concentration is within +/-50% in the whole particle sputtering time period.
2. The method of claim 1, wherein the silicon vapor and the silicon dioxide vapor in the silicon source vapor are in a molar ratio of silicon: silica = 1: 1.
3. The method of claim 1, wherein the mass of nitrogen atoms in the dopant material is 100ppm to 100000ppm based on the total mass of silicon and silicon dioxide in the silicon source vapor.
4. The method according to claim 1, wherein the carbon coating is specifically: placing the materials with the doping uniformity meeting the preset conditions in a rotary furnace, heating to 800-1000 ℃ under a protective atmosphere, introducing an organic gas source for chemical vapor deposition, preserving the heat for 2-4 hours, and then closing the organic gas source for cooling; wherein, the organic air source specifically includes: one or more of methane, acetylene, propylene or propane.
5. The negative electrode material of the lithium ion battery is characterized in that the negative electrode material is the nitrogen-doped soft carbon coated silicon-based lithium ion negative electrode material prepared by the preparation method of any one of claims 1-4.
6. A lithium battery pole piece, characterized in that the lithium battery pole piece comprises the lithium ion battery anode material according to claim 5.
7. A lithium battery comprising the lithium battery pole piece of claim 6.
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