CN111554926B - Preparation method of wheat straw/carbon nanotube for long-cycle nitrogen-doped lithium battery negative electrode material - Google Patents

Preparation method of wheat straw/carbon nanotube for long-cycle nitrogen-doped lithium battery negative electrode material Download PDF

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CN111554926B
CN111554926B CN202010410277.7A CN202010410277A CN111554926B CN 111554926 B CN111554926 B CN 111554926B CN 202010410277 A CN202010410277 A CN 202010410277A CN 111554926 B CN111554926 B CN 111554926B
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黄剑锋
钟辛子
曹丽云
欧阳海波
甘雨
邵宇飞
马闯
石泓彬
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Shaanxi University of Science and Technology
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Abstract

A method for preparing wheat straw/carbon nano tube for a long-cycle nitrogen-doped lithium battery negative electrode material adopts the wheat straw as a reaction raw material, and effectively relieves the serious pollution pressure caused by hundreds of billions of tons of wheat straw burned every year in China. Aiming at the advantages of hollow porous structure and larger specific area of the wheat straw, the invention adopts mixed alkali to carry out structural activation treatment on the precursor, improves the interface combination and fully opens the pore structure of the material; the structure of the precursor is recombined by adopting the phosphoric acid mixed solution, a stable three-dimensional structure with constant internal and external pressure is constructed, the collapse phenomenon possibly occurring in the hollow porous structure of the wheat straw in the heat treatment process is effectively prevented, the blocking phenomenon possibly existing in the internal movement process of lithium ions is reduced, and the comprehensive electrochemical performance of the material is improved. The prepared sulfur-doped lithium battery cathode material has excellent performance and ultra-long electric cycle life, and the electronic bearing capacity of the sulfur-doped lithium battery cathode material is greatly improved.

Description

Preparation method of wheat straw/carbon nanotube for long-cycle nitrogen-doped lithium battery negative electrode material
Technical Field
The invention belongs to the field of preparation of lithium ion battery cathode materials, and particularly relates to a preparation method of wheat straw/carbon nano tube for a long-cycle nitrogen-doped lithium battery cathode material.
Background
Lithium ion batteries are one of the current representatives of emerging energy storage technologies, and have been in a state of commercialization and industrialization. According to statistics, in 2019, the number of produced tablets in the lithium ion market all over the world is up to 121.8 hundred million, and the tablets are only used as a quebracho in the aspects of production quantity and application dimension, so that the biscuit becomes the fragrant pastry in the investment market. Lithium ion batteries are widely used because of their advantages of long cycle life, high operating voltage, no memory effect, small self-discharge, wide operating temperature range, etc. The lithium ion battery concept is provided to realize long time of industrialized production and mature technical development, but the cathode material still has the defects of low stability, low capacity and the like, thereby seriously influencing the large-scale popularization and use of the lithium ion battery and being an urgent key problem at present. Therefore, scientific and systematic research on the lithium battery cathode material is carried out, the innovation of the technology is realized early, the energy density and the safety of the battery are improved, and the lithium battery cathode material is the necessary route for the health development of the lithium battery, namely, Patil A, Patil V, Choi J W, et al.solid electrolytes for rechargeable lithium battery batteries, a review [ J ]. Journal of Nanoscience and Nanotechnology,2017,17(1): 29-71.
Wheat straw material is a biomass material which has great interest, and becomes a hot spot of scientific research in recent years. In the wheat straw material, the wheat straw accounts for about 54-44% of the whole weight, the utilization rate is high, the wheat straw material has a rich porous hollow structure, the outer skin has a honeycomb-shaped characteristic, the main components comprise pectin, cellulose, hemicellulose, lignin and the like, the yield is high, and the wheat straw material is a precursor prepared from excellent biological carbon.
At present, biomass materials are carbonized mainly by means of thermal decomposition. The pyrolysis reaction refers to pyrolysis reaction of biomass in an air-free environment, and the temperature, the carbonization time, the concentration of an activator, and the like are important factors to be controlled in the reaction. Selvamini V and the like adopt fresh garlic skins as raw materials and are carbonized for 2h at 850 ℃, and the specific capacity of the obtained lithium ion battery negative electrode material is 145mAh/g [ Selvamini V, Ravikumar R, Suryanayan V, et al. The carbonaceous material is put in an inert gas atmosphere and is pyrolyzed at high temperature by a vacuum tube furnace, wherein the carbonization temperature is below 1500 ℃ so as to prevent the internal structure of the biomass material from being damaged and the performance of the material from being reduced.
Disclosure of Invention
The invention aims to provide the preparation method of the wheat straw/carbon nano tube for the long-cycle nitrogen-doped lithium battery cathode material, which has the advantages of simple process operation, low reaction temperature, short production period, environment-friendly raw materials, large reserves and great popularization potential.
In order to achieve the purpose, the invention adopts the following technical scheme:
1) washing the surface of the wheat straw by using a mixed acid solution to remove impurities on the surface of the wheat straw, shearing the wheat straw into strip-shaped solid A, and freeze-drying the solid A to obtain strip-shaped solid B;
2) soaking 5-20 g of strip-shaped solid B in an acetone mixed solution, then dropwise adding a mixed alkali solution into the solution to adjust the pH of the solution to 9-10, carrying out ultrasonic treatment, filtering out a surface clear solution, and washing a product with a mixed acid solution to obtain a reaction precursor C;
3) soaking 5-10 g of reaction precursor C in 20-300 ml of sodium iodate mixed solution, dropwise adding phosphoric acid mixed solution to adjust the pH value of the solution to 5-6, then adding 5-20 g of carbon nanotubes with the diameter of 20-100 nm into the solution, and carrying out homogeneous treatment on the solution at 100-200 ℃ for 1-4 h to obtain a reaction product D;
4) washing the reaction product D with a mixed acid solution, then washing with an ethanol solution, filtering the solution, and drying the product to obtain a powdery solid E;
5) uniformly mixing the powdery solid E and 5-30 g of ammonium vanadate in a porcelain boat, and then placing the porcelain boat in a tubular furnace in the atmosphere of argon gas to be sintered and carbonized at 1000-1500 ℃ to obtain a carbonized product F;
6) and washing the carbonized product F with deionized water and an ethanol solution, and drying the product after the solution is filtered, thereby obtaining the long-circulation nitrogen-doped lithium battery cathode material with a developed pore structure.
The mixed acid solution in the step 1, 2 and 4) comprises, by mass, 40-60% of acetic acid, 30-50% of deionized water, 8-10% of sodium phosphate and 2-22% of sodium tripolyphosphate.
The method comprises the following steps of 1) cutting wheat straws into long-strip-shaped solid A with the diameter of 3-5 mm and the length of 2-6 cm, and then carrying out freeze drying treatment for 2h at-15 to-5 ℃ to obtain long-strip-shaped solid B.
The acetone mixed solution in the step 2) comprises, by mass, 40-60% of acetone, 30-50% of deionized water and 10-30% of sodium carbonate.
The mixed alkali solution in the step 2) comprises 40-60% of potassium hydroxide, 30-55% of deionized water and 5-30% of xylene by mass, and the ultrasonic treatment time is 10-40 min.
The sodium iodate mixed solution in the step 3) comprises 50-70% of sodium iodate, 20-40% of deionized water and 10-30% of xylene by mass.
The phosphoric acid mixed solution in the step 3) comprises 20-50% of phosphoric acid, 10-40% of sodium tripolyphosphate and 40-70% of deionized water in percentage by mass.
The concentration of the ethanol solution in the step 4 and the step 6) is 10-40 g/L.
And the drying temperature in the steps 4 and 6) is 50-80 ℃.
Compared with the prior art, the invention has the following beneficial technical effects:
the invention adopts the wheat straws as reaction raw materials, the wheat straws belong to biomass raw materials, the yield is large and easy to obtain, the environment is friendly, the cost of the raw materials is greatly reduced, waste is turned into wealth, and the serious pollution pressure caused by hundreds of billions of tons of wheat straws burned every year in China is effectively relieved. Aiming at the advantages of hollow porous structure and larger specific area of the wheat straw, the invention adopts mixed alkali to carry out structural activation treatment on the precursor, improves the interface combination and fully opens the pore structure of the material; the structure of the precursor is recombined by adopting the mixed acid, a stable three-dimensional structure with constant internal and external pressure is constructed, the collapse phenomenon possibly occurring in the hollow porous structure of the wheat straw in the heat treatment process is effectively prevented, the blocking phenomenon possibly existing in the internal movement process of lithium ions is reduced, and the comprehensive electrochemical performance of the material is improved. The prepared long-cycle nitrogen-doped lithium battery cathode material has excellent performance and ultra-long electric cycle life, greatly improves the electronic bearing capacity, and has great development potential and use value in the energy field.
The invention also has the following beneficial effects:
firstly, adjusting and repairing the structure of the wheat straw washed by weak acid by using low-cost mixed solution such as acetone, sodium carbonate and the like, eliminating possible weak acid ions and hydroxyl groups on the surface of the wheat straw, adjusting the wettability of the inner structure and the outer structure of the wheat straw, weakening the pressure difference between the inside and the outside of the pipe, and preventing the collapse of a three-dimensional structure;
the method has the advantages that (II) the mixed solution of sodium iodate, xylene and the like is adopted to repair the tubular structure of the wheat straw, so that the three-dimensional structure inside the wheat straw is looser, the introduction of negative ion groups accelerates the process of homogeneous reaction, reduces the temperature of the homogeneous reaction, greatly reduces the production cost and avoids further damage to the structure in the high-temperature homogeneous reaction process;
thirdly, ammonia gas is provided to introduce a nitrogen source into the biomass material in a mode of decomposing ammonium vanadate at high temperature, the decomposition temperature of the ammonium vanadate is close to the optimal activation temperature of the biomass carbon material, the efficient introduction of the nitrogen source is ensured, and the production cost and the preparation period are greatly reduced;
and (IV) the specific surface area of the wheat straw material is large, and efficient surface chemical reaction can be realized by introducing the nitrogen source in a gas flowing mode, so that the efficiency is improved. The nitrogen element is introduced into the three-dimensional structure of the wheat straw, so that more lithium ion doping active sites can be provided, the transmission and transportation of lithium ions in the negative electrode are guaranteed, and the service life, the energy storage potential and the comprehensive electrochemical performance of the material are improved.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) photograph of a long-cycle nitrogen-doped lithium battery cathode material prepared in example 1 of the present invention;
FIG. 2 is a first three-cycle charge and discharge diagram of the long-cycle nitrogen-doped lithium battery anode material prepared in example 2 of the present invention;
FIG. 3 shows that the negative electrode materials of the long-cycle nitrogen-doped lithium battery prepared in example 3 of the present invention are respectively 0.1Ag-1、0.2Ag-1、0.4Ag-1、1.0Ag-1、0.1Ag-1Current density of (2) and charge and discharge cycle performance diagram of 55 cycles.
Detailed Description
The present invention will be described in further detail with reference to preferred embodiments thereof.
Example 1:
1) mixing 40% of acetic acid, 30% of deionized water, 8% of sodium phosphate and 22% of sodium tripolyphosphate according to mass percentage to prepare a mixed acid solution;
2) washing the surface of wheat straw by using a mixed acid solution to remove impurities on the surface, then shearing the wheat straw into a strip-shaped solid A with the diameter of 3-5 mm and the length of 2-6 cm, and then carrying out freeze drying treatment for 2h at-12 ℃ to obtain a strip-shaped solid B;
3) soaking 10g of strip-shaped solid B in an acetone mixed solution, then dropwise adding a mixed alkali solution into the solution to adjust the pH value of the solution to 10, carrying out ultrasonic treatment for 40min, filtering out a surface clear solution, and then washing a product with the mixed acid solution to obtain a reaction precursor C;
the acetone mixed solution comprises 40% of acetone, 30% of deionized water and 30% of sodium carbonate by mass percent;
the mixed alkali solution comprises 40% of potassium hydroxide, 55% of deionized water and 5% of xylene by mass percent;
4) soaking 7g of the reaction precursor C in 100ml of sodium iodate mixed solution, dropwise adding phosphoric acid mixed solution to adjust the pH value of the solution to 5.5, then adding 12g of carbon nanotubes with the diameter of 20-100 nm into the solution, and carrying out homogeneous phase treatment on the solution at 180 ℃ for 2 hours to obtain a reaction product D;
the sodium iodate mixed solution comprises 50% of sodium iodate, 20% of deionized water and 30% of xylene by mass percent;
the phosphoric acid mixed solution comprises 30% of phosphoric acid, 20% of sodium tripolyphosphate and 50% of deionized water by mass percentage;
5) washing the reaction product D with a mixed acid solution, then washing with an ethanol solution with the concentration of 40g/L, filtering the solution, and drying the product at 80 ℃ to obtain a powdery solid E;
6) uniformly mixing the powdery solid E and 15g of ammonium vanadate in a porcelain boat, and then putting the porcelain boat in a tube furnace to sinter and carbonize at 1100 ℃ in the atmosphere of argon gas to obtain a carbonized product F;
7) and washing the carbonized product F with deionized water and an ethanol solution with the concentration of 20g/L, and drying the product at 70 ℃ after the solution is filtered, thereby obtaining the long-circulation nitrogen-doped lithium battery cathode material with a developed pore structure.
As can be seen from fig. 1, the long-cycle nitrogen-doped lithium battery negative electrode material prepared in example 1 is a fluffy three-dimensional network structure, and has a developed pore structure.
Example 2:
1) mixing 40% of acetic acid, 50% of deionized water, 8% of sodium phosphate and 2% of sodium tripolyphosphate according to mass percentage to prepare a mixed acid solution;
2) washing the surface of wheat straw by using a mixed acid solution to remove impurities on the surface, then shearing the wheat straw into a strip-shaped solid A with the diameter of 3-5 mm and the length of 2-6 cm, and then carrying out freeze drying treatment for 2h at-15 ℃ to obtain a strip-shaped solid B;
3) soaking 8g of strip-shaped solid B in an acetone mixed solution, then dropwise adding a mixed alkali solution into the solution to adjust the pH value of the solution to 9, carrying out ultrasonic treatment for 10min, filtering out a surface clear solution, and then washing a product with a mixed acid solution to obtain a reaction precursor C;
the acetone mixed solution comprises 40% of acetone, 50% of deionized water and 10% of sodium carbonate by mass percent;
the mixed alkali solution comprises 50% of potassium hydroxide, 45% of deionized water and 5% of xylene by mass percent;
4) soaking 8g of reaction precursor C in 200ml of sodium iodate mixed solution, dropwise adding phosphoric acid mixed solution to adjust the pH value of the solution to be 5, then adding 8g of carbon nanotubes with the diameter of 20-100 nm into the solution, and carrying out homogeneous phase treatment on the solution at 100 ℃ for 4 hours to obtain a reaction product D;
the sodium iodate mixed solution comprises 60% of sodium iodate, 25% of deionized water and 15% of xylene by mass percent;
the phosphoric acid mixed solution comprises 20% of phosphoric acid, 10% of sodium tripolyphosphate and 70% of deionized water by mass percentage;
5) washing the reaction product D with a mixed acid solution, then washing with an ethanol solution with the concentration of 10g/L, filtering the solution, and drying the product at 50 ℃ to obtain a powdery solid E;
6) uniformly mixing the powdery solid E and 5g of ammonium vanadate in a porcelain boat, and then putting the porcelain boat in a tubular furnace to sinter and carbonize at 1000 ℃ in an argon atmosphere to obtain a carbonized product F;
7) and washing the carbonized product F with deionized water and an ethanol solution with the concentration of 10g/L, and drying the product at 50 ℃ after the solution is filtered, thereby obtaining the long-circulation nitrogen-doped lithium battery cathode material with a developed pore structure.
As can be seen from fig. 2, the first cycle of the sample has excellent charge and discharge performance, and the capacity stability is good in the first three cycles of the charge and discharge processes, which indicates that the sample has a stable structure and good electrochemical performance.
Example 3: 1) mixing 41% of acetic acid, 35% of deionized water, 9% of sodium phosphate and 15% of sodium tripolyphosphate according to mass percentage to prepare a mixed acid solution;
2) washing the surface of wheat straw by using a mixed acid solution to remove impurities on the surface, then shearing the wheat straw into a strip-shaped solid A with the diameter of 3-5 mm and the length of 2-6 cm, and then carrying out freeze drying treatment for 2h at-5 ℃ to obtain a strip-shaped solid B;
3) soaking 20g of strip-shaped solid B in an acetone mixed solution, then dropwise adding a mixed alkali solution into the solution to adjust the pH of the solution to 9, carrying out ultrasonic treatment for 25min, then filtering out a surface clear solution, and washing a product with a mixed acid solution to obtain a reaction precursor C;
the acetone mixed solution comprises 45% of acetone, 40% of deionized water and 15% of sodium carbonate by mass percent;
the mixed alkali solution comprises 40% of potassium hydroxide, 30% of deionized water and 30% of xylene by mass percent;
4) soaking 9g of reaction precursor C in 260ml of sodium iodate mixed solution, dropwise adding phosphoric acid mixed solution to adjust the pH value of the solution to be 5, then adding 20g of carbon nanotubes with the diameter of 20-100 nm into the solution, and carrying out homogeneous phase treatment on the solution at 120 ℃ for 3.5 hours to obtain a reaction product D;
the sodium iodate mixed solution comprises 50% of sodium iodate, 40% of deionized water and 10% of xylene by mass percent;
the phosphoric acid mixed solution comprises 40% of phosphoric acid, 15% of sodium tripolyphosphate and 45% of deionized water by mass percentage;
5) washing the reaction product D with a mixed acid solution, then washing with an ethanol solution with the concentration of 25g/L, and drying the product at 60 ℃ after the solution is filtered to obtain a powdery solid E;
6) uniformly mixing the powdery solid E and 25g of ammonium vanadate in a porcelain boat, and then putting the porcelain boat in a tubular furnace to be sintered and carbonized at 1500 ℃ in the atmosphere of argon gas to obtain a carbonized product F;
7) and washing the carbonized product F with deionized water and an ethanol solution with the concentration of 30g/L, and drying the product at 55 ℃ after the solution is filtered, thereby obtaining the long-circulation nitrogen-doped lithium battery cathode material with a developed pore structure.
As can be seen from fig. 3, in the process of charging and discharging, the sample in example 3 can clearly see that it has a smaller voltage difference through the change of the voltage platform, and has better long cycle performance and charge storage capacity.
Example 4:
1) mixing 60% of acetic acid, 30% of deionized water, 8% of sodium phosphate and 2% of sodium tripolyphosphate according to mass percentage to prepare a mixed acid solution;
2) washing the surface of wheat straw by using a mixed acid solution to remove impurities on the surface, then shearing the wheat straw into a strip-shaped solid A with the diameter of 3-5 mm and the length of 2-6 cm, and then carrying out freeze drying treatment for 2h at-10 ℃ to obtain a strip-shaped solid B;
3) soaking 12g of strip-shaped solid B in an acetone mixed solution, then dropwise adding a mixed alkali solution into the solution to adjust the pH value of the solution to 10, carrying out ultrasonic treatment for 20min, filtering out a surface clear solution, and then washing a product with a mixed acid solution to obtain a reaction precursor C;
the acetone mixed solution comprises 50% of acetone, 35% of deionized water and 15% of sodium carbonate by mass percent;
the mixed alkali solution comprises 40% of potassium hydroxide, 50% of deionized water and 10% of xylene by mass percent;
4) soaking 10g of reaction precursor C in 300ml of sodium iodate mixed solution, dropwise adding phosphoric acid mixed solution to adjust the pH value of the solution to be 6, then adding 5g of carbon nano tube with the diameter of 20-100 nm into the solution, and carrying out homogeneous phase treatment on the solution at 150 ℃ for 2.5h to obtain a reaction product D;
the sodium iodate mixed solution comprises 70% of sodium iodate, 20% of deionized water and 10% of xylene by mass percent;
the phosphoric acid mixed solution comprises 50% of phosphoric acid, 10% of sodium tripolyphosphate and 40% of deionized water by mass percentage;
5) washing the reaction product D with a mixed acid solution, then washing with an ethanol solution with the concentration of 20g/L, and drying the product at 70 ℃ after the solution is filtered to obtain a powdery solid E;
6) uniformly mixing the powdery solid E and 10g of ammonium vanadate in a porcelain boat, and then putting the porcelain boat in a tube furnace to sinter and carbonize at 1200 ℃ in the atmosphere of argon gas to obtain a carbonized product F;
7) and washing the carbonized product F with deionized water and an ethanol solution with the concentration of 40g/L, and drying the product at 80 ℃ after the solution is filtered, thereby obtaining the long-circulation nitrogen-doped lithium battery cathode material with a developed pore structure.
Example 5:
1) mixing 45% of acetic acid, 40% of deionized water, 8% of sodium phosphate and 27% of sodium tripolyphosphate according to mass percentage to prepare a mixed acid solution;
2) washing the surface of wheat straw by using a mixed acid solution to remove impurities on the surface, then shearing the wheat straw into a strip-shaped solid A with the diameter of 3-5 mm and the length of 2-6 cm, and then carrying out freeze drying treatment for 2h at-14 ℃ to obtain a strip-shaped solid B;
3) soaking 15g of strip-shaped solid B in an acetone mixed solution, then dropwise adding a mixed alkali solution into the solution to adjust the pH of the solution to 9.5, carrying out ultrasonic treatment for 35min, then filtering out a surface clear solution, and washing a product with a mixed acid solution to obtain a reaction precursor C;
the acetone mixed solution comprises 55% of acetone, 32% of deionized water and 13% of sodium carbonate by mass percent;
the mixed alkali solution comprises 45% of potassium hydroxide, 35% of deionized water and 20% of xylene by mass percent;
4) soaking 6g of reaction precursor C in 150ml of sodium iodate mixed solution, dropwise adding phosphoric acid mixed solution to adjust the pH value of the solution to be 6, then adding 15g of carbon nano tube with the diameter of 20-100 nm into the solution, and carrying out homogeneous phase treatment on the solution at 200 ℃ for 1h to obtain a reaction product D;
the sodium iodate mixed solution comprises 55% of sodium iodate, 30% of deionized water and 15% of xylene by mass percent;
the phosphoric acid mixed solution comprises 22% of phosphoric acid, 18% of sodium tripolyphosphate and 60% of deionized water in percentage by mass;
5) washing the reaction product D with a mixed acid solution, then washing with an ethanol solution with the concentration of 35g/L, and drying the product at 65 ℃ after the solution is filtered to obtain a powdery solid E;
6) uniformly mixing the powdery solid E and 30g of ammonium vanadate in a porcelain boat, and then putting the porcelain boat in a tube furnace to sinter and carbonize at 1300 ℃ in the atmosphere of argon gas to obtain a carbonized product F;
7) and washing the carbonized product F with deionized water and 35g/L ethanol solution, filtering the solution, and drying the product at 65 ℃ to obtain the long-circulation nitrogen-doped lithium battery cathode material with a developed pore structure.
Example 6:
1) mixing 50% of acetic acid, 32% of deionized water, 10% of sodium phosphate and 8% of sodium tripolyphosphate according to mass percentage to prepare a mixed acid solution;
2) washing the surface of wheat straw by using a mixed acid solution to remove impurities on the surface, then shearing the wheat straw into a strip-shaped solid A with the diameter of 3-5 mm and the length of 2-6 cm, and then carrying out freeze drying treatment for 2h at-8 ℃ to obtain a strip-shaped solid B;
3) soaking 5g of strip-shaped solid B in an acetone mixed solution, then dropwise adding a mixed alkali solution into the solution to adjust the pH of the solution to 9.5, carrying out ultrasonic treatment for 30min, filtering out a surface clear solution, and washing a product with a mixed acid solution to obtain a reaction precursor C;
the acetone mixed solution comprises 60% of acetone, 30% of deionized water and 10% of sodium carbonate by mass percent;
the mixed alkali solution comprises 60% of potassium hydroxide, 35% of deionized water and 5% of xylene by mass percent;
4) soaking 5g of the reaction precursor C in 20ml of sodium iodate mixed solution, dropwise adding phosphoric acid mixed solution to adjust the pH value of the solution to be 6, then adding 10g of carbon nanotubes with the diameter of 20-100 nm into the solution, and carrying out homogeneous phase treatment on the solution at 130 ℃ for 3 hours to obtain a reaction product D;
the sodium iodate mixed solution comprises 50% of sodium iodate, 30% of deionized water and 20% of xylene by mass percent;
the phosphoric acid mixed solution comprises 20% of phosphoric acid, 40% of sodium tripolyphosphate and 40% of deionized water by mass percentage;
5) washing the reaction product D with a mixed acid solution, then washing with an ethanol solution with the concentration of 30g/L, and drying the product at 55 ℃ after the solution is filtered to obtain a powdery solid E;
6) uniformly mixing the powdery solid E and 20g of ammonium vanadate in a porcelain boat, and then putting the porcelain boat in a tubular furnace to sinter and carbonize at 1400 ℃ in the atmosphere of argon gas to obtain a carbonized product F;
7) and washing the carbonized product F with deionized water and an ethanol solution with the concentration of 25g/L, and drying the product at 60 ℃ after the solution is filtered, thereby obtaining the long-circulation nitrogen-doped lithium battery cathode material with a developed pore structure.

Claims (4)

1. A preparation method of wheat straw/carbon nano tube for a long-cycle nitrogen-doped lithium battery negative electrode material is characterized by comprising the following steps:
1) washing the surface of the wheat straw by using a mixed acid solution to remove impurities on the surface of the wheat straw, shearing the wheat straw into strip-shaped solid A, and freeze-drying the solid A to obtain strip-shaped solid B;
2) soaking 5-20 g of strip-shaped solid B in an acetone mixture, then dropwise adding a mixed alkali solution into the acetone mixture to adjust the pH of the solution to 9-10, carrying out ultrasonic treatment, filtering out a surface clear solution, and washing a product with a mixed acid solution to obtain a reaction precursor C;
the acetone mixture consists of 40-60% of acetone, 30-50% of deionized water and 10-30% of sodium carbonate in percentage by mass;
the mixed alkali solution consists of 40-60% of potassium hydroxide, 30-55% of deionized water and 5-30% of dimethylbenzene by mass percent, and the ultrasonic treatment time is 10-40 min;
3) soaking 5-10 g of reaction precursor C in 20-300 ml of sodium iodate mixed solution, dropwise adding phosphoric acid mixed solution to adjust the pH value of the solution to 5-6, then adding 5-20 g of carbon nanotubes with the diameter of 20-100 nm into the solution, and carrying out homogeneous treatment on the solution at 100-200 ℃ for 1-4 h to obtain a reaction product D;
the sodium iodate mixed solution consists of 50-70% of sodium iodate, 20-40% of deionized water and 10-30% of xylene by mass percentage;
the phosphoric acid mixed solution consists of 20-50% of phosphoric acid, 10-40% of sodium tripolyphosphate and 40-70% of deionized water in percentage by mass;
4) washing the reaction product D with a mixed acid solution, then washing with an ethanol solution, filtering the solution, and drying the product to obtain a powdery solid E;
5) uniformly mixing the powdery solid E and 5-30 g of ammonium vanadate in a porcelain boat, and then placing the porcelain boat in a tubular furnace in the atmosphere of argon gas to be sintered and carbonized at 1000-1500 ℃ to obtain a carbonized product F;
6) washing the carbonized product F with deionized water and an ethanol solution, and drying the product after the solution is filtered to obtain the long-circulation nitrogen-doped lithium battery cathode material with a developed pore structure;
the mixed acid solution in the step 1, 2 and 4) is composed of, by mass, 40-60% of acetic acid, 30-50% of deionized water, 8-10% of sodium phosphate and 2-22% of sodium tripolyphosphate.
2. The method for preparing the wheat straw/carbon nanotube for the long-cycle nitrogen-doped lithium battery negative electrode material according to claim 1, which is characterized in that: the method comprises the following steps of 1) cutting wheat straws into long-strip-shaped solid A with the diameter of 3-5 mm and the length of 2-6 cm, and then carrying out freeze drying treatment for 2h at-15 to-5 ℃ to obtain long-strip-shaped solid B.
3. The method for preparing the wheat straw/carbon nanotube for the long-cycle nitrogen-doped lithium battery negative electrode material according to claim 1, which is characterized in that: the concentration of the ethanol solution in the step 4 and the step 6) is 10-40 g/L.
4. The method for preparing the wheat straw/carbon nanotube for the long-cycle nitrogen-doped lithium battery negative electrode material according to claim 1, which is characterized in that: and the drying temperature in the steps 4 and 6) is 50-80 ℃.
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