CN110690439B - P, N co-doped C/SiO prepared from silicon-containing biomassxGreen method for composite negative electrode material of lithium ion battery - Google Patents
P, N co-doped C/SiO prepared from silicon-containing biomassxGreen method for composite negative electrode material of lithium ion battery Download PDFInfo
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Abstract
The invention discloses a method for preparing P, N codoped C/SiO by using silicon-containing biomassxA green method for preparing the composite negative electrode material of Li-ion battery includes such steps as mixing clean raw material with concentrated H3PO4Uniformly mixing the solution, soaking, drying and carbonizing and activating; washing carbonized biomass with distilled water and diluted KOH solution to obtain P-doped C/SiOxA composite material; doping the obtained P with C/SiOxUniformly mixing the composite material with a nitrogen source, soaking, drying, and carbonizing and activating; then washing with distilled water and dilute nitric acid solution, and drying in vacuum to obtain P, N co-doped C/SiOxA composite cathode material of a lithium ion battery. The material of the invention overcomes the defects of the prior C/SiOxThe lithium ion battery composite negative electrode material has the defects of low coulombic efficiency and high resistance for the first time, realizes the maximum conversion of silicon-containing biomass into high-quality products, and basically realizes zero emission and zero pollution.
Description
Technical Field
The invention belongs to the technical field of lithium ion battery materials, and particularly relates to a method for preparing P, N co-doped C/SiO by using silicon-containing biomassxA green method for a composite cathode material of a lithium ion battery.
Background
The lithium ion battery has the advantages of large energy density, high average output voltage, small self-discharge, no memory effect, wide working temperature range, excellent cycle performance, quick charge and discharge, high charging efficiency, large output power, long service life, no toxic or harmful substances and the like, and is widely applied to the fields of consumer electronics products, military products, aviation products and the like. The common negative electrode material of the lithium ion battery is graphite, the graphite has good conductivity and a layered structure, is very suitable for the intercalation and the deintercalation of lithium ions, shows higher coulombic efficiency and better cycle stability, but has lower maximum theoretical specific capacity, and limits the further improvement of the specific energy of the lithium ion battery.
At present, several methods for preparing nitrogen-doped silicon-carbon negative electrode materials have been successively disclosed, so as to improve the performance of lithium ion batteries, for example: chinese patent publication No. CN104377351B discloses a silicon-carbon-nitrogen composite negative electrode material and a preparation method thereof, chinese patent application publication No. CN108807896A discloses a preparation method of a nitrogen-doped carbon-coated silicon-carbon composite material, and chinese patent application publication No. CN108539140A discloses a preparation method of a nitrogen-doped silicon/carbon core-shell structure negative electrode material for a lithium ion battery, but these preparation methods all use chemical reagents as a carbon source and a silicon source, and use a relatively complicated synthesis process to prepare the negative electrode material for the nitrogen-doped silicon-carbon lithium ion battery.
The siliceous biomass mainly comprises silicon dioxide and organic components (cellulose, lignin and hemicellulose), mainly comes from residues of the production process of grain crops, has large yield, takes rice hulls as an example, the annual yield of rice in China currently exceeds one hundred million and eight thousand tons by statistics, accounts for about one third of the total annual yield of the whole world, and is at the first position in the world, a large amount of rice hulls are generated in the rice processing process, each ton of rice can generate about 200kg of rice hulls, and the rice hulls are small in natural stacking density (about 120 kg/m)3) The method brings great inconvenience to transportation, and on the other hand, most rice processing enterprises do not have a reasonable and effective process to utilize the rice hulls, so that a lot of rice hulls are discarded as agricultural wastes, along with the development of rice processing technology in China, the rice processing enterprises are gradually increased, the scales of the enterprises are also gradually increased, the amount of rice processed in days is gradually increased, at least 20-80 tons of rice hulls have to be processed by factories every day, the rice hulls are accumulated too much in the days, and if wind and rain are encountered, the surrounding environment is polluted to a certain degree. Therefore, the silicon-containing biomass is compounded with the nitrogen-containing substance and carbonized, and the composite material has important significance in being applied to battery negative electrode materials.
Chinese patent application publication No. CN104617275A discloses a method for preparing a silicon-carbon composite from silicon-containing biomass as a raw material, which comprises the following steps: acid boiling silicon-containing biomass to remove inorganic salt ion impurities, cleaning, drying, grinding into powder, carbonizing in inert atmosphere to obtain a composite product of silicon dioxide and carbon, uniformly mixing the carbonized product, magnesium powder and molten salt, and putting the mixture into a tubular furnace to react in inert atmosphere to obtain the porous silicon-carbon composite material with porous silicon nanoparticles uniformly distributed in carbon. The method has the advantages of simple and easy process, rich and cheap raw materials, and because the added molten salt is melted to absorb heat to control the reaction temperature, the obtained silicon-carbon composite well keeps the structure that the silicon dioxide in the original silicon-containing biomass is naturally embedded in the organic matter, and the obtained silicon nanoparticles have uniform particle size distribution and can be applied to the field of lithium ion battery cathode materials. However, the silicon-carbon composite material obtained by the process steps of the patent has poor electrochemical performance, and the process steps of adopting acid, magnesium powder and molten salt pollute the environment, are complicated in steps and have high cost.
Disclosure of Invention
In order to overcome the defects, the invention aims to provide a method for preparing P, N codoped C/SiO by using silicon-containing biomassxThe green method of the lithium ion battery composite negative electrode material is simple to operate, green and environment-friendly, low in cost and very suitable for large-scale production and application.
In order to achieve the purpose, the invention adopts the following technical scheme:
p, N co-doped C/SiO prepared from silicon-containing biomassxThe green method of the composite negative electrode material of the lithium ion battery comprises the following steps:
(1) washing and drying the silicon-containing biomass raw material;
(2) crushing the clean raw materials obtained in the step (1), and screening the crushed raw materials through a 70-120-mesh screen;
(3) mixing the clean raw material obtained in the step (2) with concentrated H3PO4Uniformly mixing the solution, soaking, drying, putting into a tubular furnace with nitrogen as protective gas, and carbonizing and activating;
(4) dissolving the carbonized biomass obtained in the step (3) in distilled water and diluted KOHWashing the solution to remove the activator and the by-product to obtain the P-doped C/SiOxComposite material, x is more than or equal to 0<2, simultaneously collecting the generated waste liquid;
(5) doping the P obtained in the step (4) with C/SiOxUniformly mixing the composite material with a nitrogen source, soaking, drying, putting into a tubular furnace with nitrogen as protective gas, and carbonizing and activating;
(6) washing the carbonized biomass obtained in the step (5) with distilled water and dilute nitric acid solution to remove byproducts, and drying in vacuum to obtain P, N codoped C/SiOxNegative electrode material of lithium ion battery, x is more than or equal to 0<2, simultaneously collecting the generated waste liquid;
(7) and (4) mixing the waste liquid generated in the steps (4) and (6), and neutralizing to obtain the nitrogen, phosphorus and potassium liquid fertilizer.
Preferably, the silicon-containing biomass raw material in the step (1) is one or more of buckwheat hulls, barley hulls, bamboo, straw, reeds, silvergrass and wheat hulls.
Preferably, the raw material in the step (3) is mixed with concentrated H3PO4The mass ratio of the solution is 1: 1-6, and the soaking time is 6-27 h.
Preferably, the carbonization activation temperature in the step (3) is 390-630 ℃, and the carbonization activation time is 0.3-3.0 h.
Preferably, the concentration of the diluted KOH solution in the step (4) is 0.4-1.5 mol/L.
Preferably, the nitrogen source in step (5) is urea, ammonium nitrate, ammonium carbonate or ammonium bicarbonate.
Preferably, the P is doped with C/SiO in the step (5)xThe mass ratio of the composite material to the nitrogen source is 1.5-9: 1, and the soaking time is 6-27 h.
Preferably, the carbonization activation temperature in the step (5) is 420-800 ℃, and the carbonization activation time is 0.4-2.2 h.
Preferably, the concentration of the dilute nitric acid solution in the step (6) is 0.2-2.6 mol/L.
The invention has the following positive beneficial effects:
1. p, N codoping prepared in the present inventionC/SiOxIn the lithium ion battery composite cathode material, the-C-O-PO is connected on the surface of the material and the inner wall of the hole3H2The group can generate-C-O-PO on the surface of the electrode in the first charge-discharge process3Li2The film has SEI film-like effect, and can inhibit electron transfer and accelerate Li+Thereby effectively improving the first coulombic efficiency of the material. P, N, the codoping can also enhance the conductivity, reduce the resistance, improve the cycle performance and the rate capability of the battery, and simultaneously prepare the waste liquid generated in the whole process into the nitrogen, phosphorus and potassium compound liquid fertilizer; thereby realizing the maximum conversion of the silicon-containing biomass into high-quality products, basically realizing zero emission and zero pollution.
2. The invention uses concentrated phosphoric acid as an activating agent, distilled water and a potassium hydroxide solution as a washing agent to neutralize and remove excessive phosphoric acid, uses urea and the like as nitrogen sources, introduces nitrogen atoms into materials, uses a nitric acid solution to wash final products, removes metal ions, and obtains P, N co-doped C/SiOxThe lithium ion battery composite negative electrode material has an obvious pore structure and a larger specific surface area, volume expansion during desorption and intercalation of lithium ions is solved, pulverization is prevented, and an amorphous carbon protective layer with uneven thickness is covered on SiOxOn the surface of the particles, effectively relieving SiOxThe volume of the nano particles expands in the charging and discharging process, the specific capacity can reach 607mA/g under the current density of 1A/g, which is nearly 2 times of that of the cathode of the conventional graphite lithium battery, the coulombic efficiency of the material is close to 100%, and the cycling stability is good.
Drawings
FIG. 1 is a flow chart of a preparation method of the present invention;
FIG. 2 is a cycle performance diagram of the negative electrode material of the lithium ion battery of example 1 at 1.0A/g;
FIG. 3 is an XPS map of a negative electrode material for a lithium battery according to example 1 of the present invention;
FIG. 4 is an SEM image of the negative electrode material of the lithium battery in example 1 of the present invention;
FIG. 5 is a TEM image of a negative electrode material for a lithium battery of example 1 of the present invention;
FIG. 6 is the bookP, N codoped C/SiO prepared in invention example 1xEIS diagram of lithium ion battery composite cathode.
Detailed Description
The invention will be further illustrated with reference to some specific examples.
Example 1
P, N co-doped C/SiO prepared from silicon-containing biomassxThe green method of the composite negative electrode material of the lithium ion battery comprises the following steps:
(1) washing and drying the rice hulls;
(2) crushing the clean rice hulls obtained in the step (1), and screening the crushed rice hulls through a 100-mesh screen;
(3) mixing the clean rice hull obtained in the step (2) with 85% concentrated H3PO4Uniformly mixing the solution according to the mass ratio of 1:4, soaking for 10h, drying, putting into a tubular furnace with nitrogen as protective gas, and carbonizing and activating for 2h at 500 ℃;
(4) washing the carbonized biomass obtained in the step (3) with distilled water and 1.0mol/L diluted KOH solution, removing an activating agent and a byproduct, and obtaining the P-doped C/SiOxComposite material, x is more than or equal to 0<2, simultaneously collecting the generated waste liquid;
(5) doping the P obtained in the step (4) with C/SiOxUniformly mixing the composite material and urea according to a mass ratio of 8:1, soaking for 24 hours, drying, putting into a tubular furnace with nitrogen as protective gas, and carbonizing and activating for 1 hour at 550 ℃;
(6) washing the carbonized biomass obtained in the step (5) with distilled water and 1.0mol/L dilute nitric acid solution to remove byproducts, and drying in vacuum to obtain P, N codoped C/SiOxNegative electrode material of lithium ion battery, x is more than or equal to 0<2, simultaneously collecting the generated waste liquid;
(7) and (4) mixing the waste liquids generated in the steps (4) and (6), and neutralizing to obtain the nitrogen, phosphorus and potassium liquid composite fertilizer.
The following table 1 is a chemical component analysis table of the nitrogen, phosphorus and potassium compound fertilizer prepared in example 1, and realizes the recycling of waste liquid.
Table 1 chemical composition of NPK complex fertilizer prepared in example 1
FIG. 1 is a process flow diagram of the preparation method of the present invention.
FIG. 2 shows P, N codoped C/SiO alloy prepared in example 1xA cycle performance diagram of the lithium ion battery composite negative electrode material; the specific capacity of the traditional graphite lithium battery cathode is only 375mA/g, while the specific capacity of the material prepared by the invention can reach 607mA/g under the current density of 1A/g, which is nearly 2 times of that of the traditional graphite lithium battery cathode, and the coulomb efficiency of the material is close to 100%.
FIG. 3 shows P, N codoped C/SiO alloy prepared in example 1xXPS diagram of composite cathode material of lithium ion battery; the material consists of C, O, Si, P and N elements, and shows that P, N two elements are successfully doped into C/SiOxA composite cathode material of a lithium ion battery.
FIG. 4 shows P, N codoped C/SiO alloy prepared in example 1xThe SEM image of the composite negative electrode material of the lithium ion battery has an obvious pore structure and a large specific surface area, the large number of pores can relieve volume expansion of lithium ions during de-intercalation and intercalation, pulverization is prevented, transmission of the lithium ions can be accelerated, conductivity of the material is improved, the large specific surface area provides more attachment sites for the lithium ions, and specific capacity of the material is increased.
FIG. 5 shows P, N codoped C/SiO alloy prepared in example 1xTEM image of lithium ion battery composite negative electrode material, dark color nano SiOxThe particles were uniformly distributed in the carbon skeleton, and SiO was not observedxAgglomeration of nanoparticles. As can be seen, the amorphous carbon protective layer with non-uniform thickness is covered on SiOxThe surface of the particles can effectively relieve SiO by the structurexThe volume expansion of the nano particles in the charge and discharge process contributes to the good cycle stability of the material, and the pore structure on the material is uniformly distributed in P, N codoped C/SiOxThe lithium ion battery composite cathode material.
FIG. 6 is a drawing showingP, N Co-doping C/SiO prepared in example 1xEIS diagram of lithium ion battery composite cathode, comparing with unmodified material, P, N codoped C/SiOxThe electrode reaction resistance of the lithium ion battery composite electrode is obviously smaller than that of the unmodified C/SiOxA lithium ion battery composite electrode.
Example 2
P, N co-doped C/SiO prepared from silicon-containing biomassxThe green method of the composite negative electrode material of the lithium ion battery comprises the following steps:
(1) washing testa Fagopyri Esculenti, and drying;
(2) crushing the clean buckwheat hulls obtained in the step (1), and screening the crushed buckwheat hulls with a 80-mesh screen;
(3) mixing the clean buckwheat hulls obtained in the step (2) with 85% concentrated H3PO4Uniformly mixing the solution according to the mass ratio of 1:5, soaking for 24h, drying, putting into a tubular furnace with nitrogen as protective gas, and carbonizing and activating for 1.5h at 550 ℃;
(4) washing the carbonized biomass obtained in the step (3) with distilled water and 1.5mol/L diluted KOH solution, removing an activating agent and a byproduct, and obtaining the P-doped C/SiOxComposite material, x is more than or equal to 0<2, simultaneously collecting the generated waste liquid;
(5) doping the P obtained in the step (4) with C/SiOxUniformly mixing the composite material and ammonium nitrate according to the mass ratio of 9:1, soaking for 6 hours, drying, putting into a tubular furnace with nitrogen as protective gas, and carbonizing and activating for 2.2 hours at 500 ℃;
(6) washing the carbonized biomass obtained in the step (5) with distilled water and 1.2mol/L dilute nitric acid solution to remove byproducts, and drying in vacuum to obtain P, N codoped C/SiOxNegative electrode material of lithium ion battery, x is more than or equal to 0<2, simultaneously collecting the generated waste liquid;
(7) and (4) mixing the waste liquids generated in the steps (4) and (6), and neutralizing to obtain the nitrogen, phosphorus and potassium liquid composite fertilizer.
Example 3
P, N co-doped C/SiO prepared from silicon-containing biomassxThe green method of the composite negative electrode material of the lithium ion battery comprisesThe method comprises the following steps:
(1) washing bamboo, and drying;
(2) crushing the clean bamboo obtained in the step (1), and screening the crushed bamboo with a 70-mesh screen;
(3) mixing the clean bamboo obtained in step (2) with 85% concentrated H3PO4Uniformly mixing the solution according to the mass ratio of 1:6, soaking for 6h, drying, putting into a tubular furnace with nitrogen as protective gas, and carbonizing and activating for 1h at 600 ℃;
(4) washing the carbonized biomass obtained in the step (3) with distilled water and 0.6mol/L diluted KOH solution, removing an activating agent and a byproduct, and obtaining the P-doped C/SiOxComposite material, x is more than or equal to 0<2, simultaneously collecting the generated waste liquid;
(5) doping the P obtained in the step (4) with C/SiOxUniformly mixing the composite material and ammonium carbonate according to the mass ratio of 5:1, soaking for 12h, drying, putting into a tubular furnace with nitrogen as protective gas, and carbonizing and activating for 1.5h at 600 ℃;
(6) washing the carbonized biomass obtained in the step (5) with distilled water and 2.0mol/L dilute nitric acid solution to remove byproducts, and drying in vacuum to obtain P, N codoped C/SiOxNegative electrode material of lithium ion battery, x is more than or equal to 0<2, simultaneously collecting the generated waste liquid;
(7) and (4) mixing the waste liquids generated in the steps (4) and (6), and neutralizing to obtain the nitrogen, phosphorus and potassium liquid composite fertilizer.
Example 4
P, N co-doped C/SiO prepared from silicon-containing biomassxThe green method of the composite negative electrode material of the lithium ion battery comprises the following steps:
(1) washing and drying the wheat hulls;
(2) crushing the clean wheat hulls obtained in the step (1), and screening the crushed wheat hulls with a 120-mesh screen;
(3) mixing the clean wheat hulls obtained in the step (2) with 85% concentrated H3PO4Uniformly mixing the solution according to the mass ratio of 1:3, soaking for 27h, drying, putting into a tubular furnace with nitrogen as protective gas, and carbonizing and activating for 3h at 420 ℃;
(4) washing the carbonized biomass obtained in the step (3) with distilled water and 0.4mol/L diluted KOH solution, removing an activating agent and a byproduct, and obtaining the P-doped C/SiOxComposite material, x is more than or equal to 0<2, simultaneously collecting the generated waste liquid;
(5) doping the P obtained in the step (4) with C/SiOxThe mass ratio of the composite material to the ammonium bicarbonate is 1.5: 1, uniformly mixing, soaking for 18h, drying, putting into a tubular furnace with nitrogen as protective gas, and carbonizing and activating for 2h at 700 ℃;
(6) washing the carbonized biomass obtained in the step (5) with distilled water and 0.5mol/L dilute nitric acid solution to remove byproducts, and drying in vacuum to obtain P, N codoped C/SiOxNegative electrode material of lithium ion battery, x is more than or equal to 0<2, simultaneously collecting the generated waste liquid;
(7) and (4) mixing the waste liquids generated in the steps (4) and (6), and neutralizing to obtain the nitrogen, phosphorus and potassium liquid composite fertilizer.
Example 5
P, N co-doped C/SiO prepared from silicon-containing biomassxThe green method of the composite negative electrode material of the lithium ion battery comprises the following steps:
(1) washing and drying the reed;
(2) crushing the clean reed obtained in the step (1), and screening the crushed reed with a 90-mesh screen;
(3) mixing the clean reed obtained in the step (2) with 85% concentrated H3PO4Uniformly mixing the solution according to the mass ratio of 1:1, soaking for 16h, drying, putting into a tubular furnace with nitrogen as protective gas, and carbonizing and activating for 0.3h at 630 ℃;
(4) washing the carbonized biomass obtained in the step (3) with distilled water and 1.0mol/L diluted KOH solution, removing an activating agent and a byproduct, and obtaining the P-doped C/SiOxComposite material, x is more than or equal to 0<2, simultaneously collecting the generated waste liquid;
(5) doping the P obtained in the step (4) with C/SiOxUniformly mixing the composite material and urea according to the mass ratio of 6:1, soaking for 27h, drying, putting into a tubular furnace with nitrogen as protective gas, and carbonizing and activating for 2h at 420 ℃;
(6) washing the carbonized biomass obtained in the step (5) with distilled water and 2.6mol/L dilute nitric acid solution to remove byproducts, and drying in vacuum to obtain P, N codoped C/SiOxNegative electrode material of lithium ion battery, x is more than or equal to 0<2, simultaneously collecting the generated waste liquid;
(7) and (4) mixing the waste liquids generated in the steps (4) and (6), and neutralizing to obtain the nitrogen, phosphorus and potassium liquid composite fertilizer.
Example 6
P, N co-doped C/SiO prepared from silicon-containing biomassxThe green method of the composite negative electrode material of the lithium ion battery comprises the following steps:
(1) washing and drying the straws;
(2) crushing the clean straws obtained in the step (1), and screening the straws by a 100-mesh screen;
(3) mixing the clean straw obtained in the step (2) with 85% concentrated H3PO4Uniformly mixing the solution according to the mass ratio of 1:5, soaking for 15h, drying, putting into a tubular furnace with nitrogen as protective gas, and carbonizing and activating for 2h at 390 ℃;
(4) washing the carbonized biomass obtained in the step (3) with distilled water and 1.2mol/L diluted KOH solution, removing an activating agent and a byproduct, and obtaining the P-doped C/SiOxComposite material, x is more than or equal to 0<2, simultaneously collecting the generated waste liquid;
(5) doping the P obtained in the step (4) with C/SiOxUniformly mixing the composite material and ammonium nitrate according to the mass ratio of 3:1, soaking for 15h, drying, putting into a tubular furnace with nitrogen as protective gas, and carbonizing and activating for 0.4h at 800 ℃;
(6) washing the carbonized biomass obtained in the step (5) with distilled water and 0.2mol/L dilute nitric acid solution to remove byproducts, and drying in vacuum to obtain P, N codoped C/SiOxNegative electrode material of lithium ion battery, x is more than or equal to 0<2, simultaneously collecting the generated waste liquid;
(7) and (4) mixing the waste liquids generated in the steps (4) and (6), and neutralizing to obtain the nitrogen, phosphorus and potassium liquid composite fertilizer.
Finally, the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting, and other modifications or equivalent substitutions made by the technical solutions of the present invention by those of ordinary skill in the art should be covered within the scope of the claims of the present invention as long as they do not depart from the spirit and scope of the technical solutions of the present invention.
Claims (4)
1. P, N co-doped C/SiO prepared from silicon-containing biomassxThe green method for the composite negative electrode material of the lithium ion battery is characterized by comprising the following steps of:
(1) washing and drying the silicon-containing biomass raw material;
(2) crushing the clean raw materials obtained in the step (1), and screening the crushed raw materials through a 70-120-mesh screen;
(3) uniformly mixing the sieved raw material obtained in the step (2) with an activating agent, soaking, drying, and putting into a tubular furnace with nitrogen as protective gas for carbonization and activation;
the activating agent is 85% concentrated H3PO4A solution;
(4) washing the carbonized biomass obtained in the step (3) with distilled water and diluted KOH solution to remove an activating agent and byproducts to obtain the P-doped C/SiOxComposite material, x is more than or equal to 0<2, simultaneously collecting the generated waste liquid;
(5) doping the P obtained in the step (4) with C/SiOxUniformly mixing the composite material with a nitrogen source, soaking, drying, putting into a tubular furnace with nitrogen as protective gas, and carbonizing and activating;
(6) washing the carbonized biomass obtained in the step (5) with distilled water and dilute nitric acid solution to remove byproducts, and drying in vacuum to obtain P, N codoped C/SiOxNegative electrode material of lithium ion battery, x is more than or equal to 0<2, simultaneously collecting the generated waste liquid;
(7) mixing the waste liquid generated in the steps (4) and (6), and neutralizing to obtain a nitrogen, phosphorus and potassium liquid fertilizer;
the mass ratio of the sieved raw materials to the activating agent in the step (3) is 1: 1-6, and the soaking time is 6-27 h;
the nitrogen source in the step (5) is urea, ammonium nitrate, ammonium carbonate or ammonium bicarbonate;
p-doped C/SiO in the step (5)xThe mass ratio of the composite material to the nitrogen source is 1.5-9: 1, and the soaking time is 6-27 h;
the carbonization activation temperature in the step (5) is 420-800 ℃, and the carbonization activation time is 0.4-2.2 h;
the concentration of the dilute KOH solution in the step (4) is 0.4-1.5 mol/L.
2. The method for preparing P, N codoped C/SiO by using silicon-containing biomass according to claim 1xThe green method for the composite cathode material of the lithium ion battery is characterized in that the silicon-containing biomass raw material in the step (1) is one or more of buckwheat hulls, barley hulls, bamboos, straws, reeds, silvergrass and wheat hulls.
3. The method for preparing P, N codoped C/SiO by using silicon-containing biomass according to claim 1xThe green method for the composite negative electrode material of the lithium ion battery is characterized in that the carbonization activation temperature in the step (3) is 390-630 ℃, and the carbonization activation time is 0.3-3.0 h.
4. The method for preparing P, N codoped C/SiO by using silicon-containing biomass according to claim 1xThe green method for the lithium ion battery composite negative electrode material is characterized in that the concentration of the dilute nitric acid solution in the step (6) is 0.2-2.6 mol/L.
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| CN112599733B (en) * | 2020-12-09 | 2022-07-12 | 南昌大学 | Synthesis method of phosphorus-doped Si/SiOx/C negative electrode material |
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| CN107601502A (en) * | 2017-10-19 | 2018-01-19 | 天津工业大学 | The preparation and the application in terms of capacitive property of a kind of nitrogen phosphorus doping porous charcoal |
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