Natural poultry manure modified biomass derived hard carbon negative electrode material as well as preparation method and application thereof

Abstract

The invention relates to the technical field of sodium ion battery negative electrode materials, in particular to a natural poultry manure modified biomass derived hard carbon negative electrode material as well as a preparation method and application thereof. The preparation method comprises the following steps: drying, crushing and pre-oxidizing a biomass raw material to obtain a hard carbon precursor; mixing the hard carbon precursor with poultry manure to obtain a modified precursor, and carbonizing the modified precursor to obtain modified pyrolytic hard carbon; and carrying out post-treatment on the modified pyrolytic hard carbon to obtain the natural poultry manure modified biomass derived hard carbon negative electrode material. The natural poultry manure rich in N, P and S elements is used for conducting heteroatom doping on the high-temperature pyrolysis hard carbon, and the prepared biomass derived hard carbon negative electrode material is high in first coulombic efficiency and excellent in rate capability and has great application prospects.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of sodium ion battery negative electrode materials, and particularly relates to a natural poultry manure modified biomass-derived hard carbon negative electrode material and a preparation method and application thereof. BACKGROUND

[0002] The key to developing sodium ion batteries lies in the development of electrode materials with excellent performance, and hard carbon is an ideal commercialized sodium ion battery negative electrode material due to its low voltage platform and high sodium storage capacity. Among numerous hard carbon raw materials, biomass materials have abundant pore structures formed during pyrolysis due to cellulose, hemicellulose and lignin components, and the derived hard carbon has excellent sodium storage capacity, is widely sourced and low in cost, and has been widely studied in recent years. Although most cellulose-based biomass-derived hard carbon currently exhibits high reversible capacity, the initial efficiency can only reach about 85%, and the rate performance is poor, which cannot further broaden its application, and therefore it is urgent to develop a low-cost modification strategy for biomass-derived hard carbon. SUMMARY

[0003] Based on this, the purpose of the present application is to provide a natural poultry manure modified biomass-derived hard carbon negative electrode material and a preparation method and application thereof, which utilizes natural poultry manure rich in N, P and S elements to dope heteroatoms into high-temperature pyrolysis hard carbon, and the prepared biomass-derived hard carbon negative electrode material has high initial coulombic efficiency and excellent rate performance, and has great application prospect.

[0004] To achieve the above-mentioned purpose, the technical scheme adopted by the present application is as follows: The present application first provides a preparation method of a natural poultry manure modified biomass-derived hard carbon negative electrode material, which comprises the following steps: S1. drying, crushing and pre-oxidizing the biomass raw material to obtain a hard carbon precursor; S2. mixing the hard carbon precursor with poultry manure to obtain a modified precursor, and carbonizing the modified precursor to obtain a modified pyrolysis hard carbon; S3. post-treating the modified pyrolysis hard carbon to obtain a natural poultry manure modified biomass-derived hard carbon negative electrode material.

[0005] As a further improvement of the above-mentioned scheme of the present application, in step S1, the biomass raw material is at least one of bamboo powder, peanut shell, coconut shell, sugarcane residue and straw.

[0006] As a further improvement of the above-mentioned scheme of the present application, in step S1, the pre-oxidation treatment is carried out under an air or oxygen atmosphere at 200-400 DEG C for 2-8 h.

[0007] As a further improvement of the above-mentioned scheme of the present application, in step S2, the poultry manure is at least one of chicken manure, pigeon manure and duck manure, and the water content of the poultry manure is 5-10%.

[0008] As a further improvement of the above-mentioned scheme of the present application, in step S2, the mass of the poultry manure in the modified precursor is 2-10% of the mass of the hard carbon precursor.

[0009] As a further improvement of the above-mentioned scheme of the present application, in step S2, the carbonization is carried out under a protective atmosphere, at a heating rate of 2-10℃ / min to 1000-1400℃ and holding for 1-4h.

[0010] As a further improvement of the above-mentioned scheme of the present application, in step S3, the post-treatment comprises acid washing purification, washing and drying in sequence.

[0011] As a further improvement of the above-mentioned scheme of the present application, the acid washing purification is to add the modified pyrolytic hard carbon into an acid solution to obtain a mixed solution, and the mixed solution is stirred for 2-12h; in the mixed solution, the mass fraction of the modified pyrolytic hard carbon is 10-30%, and the acid solution is at least one of dilute hydrochloric acid, dilute sulfuric acid and dilute nitric acid; the washing is washing with deionized water or distilled water for 5-10 times.

[0012] The present application also provides a biomass-derived hard carbon negative material modified by natural poultry manure, which is prepared by the preparation method as described above.

[0013] The present application also provides the application of the biomass-derived hard carbon negative material modified by natural poultry manure prepared by the preparation method as described above in a sodium ion battery.

[0014] Compared with the prior art, the present application has the following beneficial effects: The present application utilizes the natural poultry manure rich in N, P and S elements to dope heteroatoms to high-temperature pyrolytic hard carbon; nitrogen doping can improve electronic conductivity; phosphorus doping can expand the interlayer spacing, which is helpful for sodium ion deintercalation; sulfur doping can introduce abundant active sites and defects on the surface of the hard carbon, promote the storage of more sodium ions through surface adsorption mechanism, and contribute to additional slope capacity. The biomass-derived hard carbon negative material prepared by the present application has a first coulombic efficiency of 89% or more at a current density of 0.05A g -1 , and a reversible capacity of 380 mAh / g or more in the first circle, and still has a discharge capacity of 200 mAh / g at a high current density. -1

[0015] ​The modified hard carbon negative material of the present application has a wide source of raw materials and low price, is a natural product without pollution, has very low cost, and has a simple hard carbon preparation process which is easy to popularize. The modification strategy can effectively control the structure of the hard carbon negative material, improve the initial coulombic efficiency and reversible capacity of the hard carbon negative material, and improve the rate performance of the hard carbon negative material. BRIEF DESCRIPTION OF DRAWINGS

[0016] Figure 1 The first cycle charge-discharge curves of the biomass-derived hard carbon negative materials prepared for Example 1 and Comparative Examples 1-3 at a current density of 0.05 A g -1 The first cycle charge-discharge curves of the biomass-derived hard carbon negative materials prepared for Example 1 and Comparative Examples 1-3 at a current density of 0.05 A g Figure 2 The rate performance comparison chart of the biomass-derived hard carbon negative materials prepared for Example 1 and Comparative Examples 1-3 at different current densities. DETAILED DESCRIPTION

[0017] In order to facilitate the understanding of the present application, the present application will be described more fully below with reference to specific embodiments. However, the present application can be realized in many different forms and is not limited to the embodiments described herein. On the contrary, the purpose of providing these embodiments is to make the disclosure of the present application more thorough and comprehensive.

[0018] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the present application belongs. The terms used in the specification of the present application herein are only for the purpose of describing specific embodiments and are not intended to limit the present application.

[0019] Example 1 The present embodiment proposes a biomass-derived hard carbon negative material modified from natural poultry manure, and the preparation method thereof comprises the following steps: (1) Take 10 g of bamboo powder and dry it in an oven at 80°C for 12 h, and further crush it through a 200-mesh sieve with a pulverizer. Put the sieved fine bamboo powder into a muffle furnace and perform pre-oxidation treatment in air: heat it to 300°C at a heating rate of 5°C / min and keep it at this temperature for 3 h, and then naturally cool it to room temperature to obtain a hard carbon precursor.

[0020] (2) Mix the hard carbon precursor prepared in step (1) with 6 wt% of dry chicken manure (containing 8% of water), and after grinding, transfer it into a tube furnace and introduce nitrogen gas, heat it to 1400°C at a heating rate of 5°C / min and keep it at this temperature for 3 h, and then naturally cool it to room temperature to obtain a modified pyrolytic hard carbon.

[0021] (3) Put the modified pyrolytic hard carbon prepared in step (2) into 60 mL of 1 M dilute hydrochloric acid, stir for 8 h, wash it with distilled water for 5 times until the pH value is 7, and then dry it to obtain a modified hard carbon negative material.

[0022] Example 2 The present example proposes a biomass-derived hard carbon anode material modified by natural poultry manure, and the preparation method thereof comprises the following steps: (1) Take 10 g of peanut shell and dry it in an oven at 80 °C for 12 h, and further crush it through a 200-mesh sieve with a pulverizer; put the sieved fine bamboo powder into a muffle furnace and perform pre-oxidation treatment under air: increase the temperature to 200 °C at a heating rate of 5 °C / min and keep it for 8 h, and naturally cool it to room temperature to obtain a hard carbon precursor.

[0023] (2) Mix the hard carbon precursor prepared in step (1) with 4 wt% of dry pigeon manure (with a water content of 5%), and grind it thoroughly, then transfer it into a tube furnace and introduce nitrogen atmosphere, increase the temperature to 1000 °C at a heating rate of 5 °C / min and keep it for 4 h, and naturally cool it to room temperature to obtain modified pyrolytic hard carbon.

[0024] (3) Add the modified pyrolytic hard carbon prepared in step (2) into 60 mL of 1 M dilute hydrochloric acid, stir for 8 h, wash it with distilled water for 5 times until pH = 7, and then dry it to obtain a modified hard carbon anode material.

[0025] Example 3 The present example proposes a biomass-derived hard carbon anode material modified by natural poultry manure, and the preparation method thereof comprises the following steps: (1) Take 10 g of straw and dry it in an oven at 80 °C for 12 h, and further crush it through a 200-mesh sieve with a pulverizer; put the sieved fine bamboo powder into a muffle furnace and perform pre-oxidation treatment under air: increase the temperature to 400 °C at a heating rate of 5 °C / min and keep it for 2 h, and naturally cool it to room temperature to obtain a hard carbon precursor.

[0026] (2) Mix the hard carbon precursor prepared in step (1) with 8 wt% of dry duck manure (with a water content of 10%), and grind it thoroughly, then transfer it into a tube furnace and introduce nitrogen atmosphere, increase the temperature to 1200 °C at a heating rate of 5 °C / min and keep it for 3 h, and naturally cool it to room temperature to obtain modified pyrolytic hard carbon.

[0027] (3) Add the modified pyrolytic hard carbon prepared in step (2) into 60 mL of 1 M dilute hydrochloric acid, stir for 8 h, wash it with distilled water for 5 times until pH = 7, and then dry it to obtain a modified hard carbon anode material.

[0028] Comparative Example 1 The difference between the present comparative example and Example 1 is that no dry chicken manure is added in step (2) of the present comparative example.

[0029] Comparative Example 2 The difference between this comparative example and Example 1 is that the amount of dried chicken manure added in step (2) of this comparative example is 0.5 wt% of the hard carbon precursor.

[0030] Comparative Example 3 The difference between this comparative example and Example 1 is that the amount of dried chicken manure added in step (2) of this comparative example accounts for 12 wt% of the hard carbon precursor.

[0031] Test case The hard carbon anode materials prepared in Examples 1 and Comparative Examples 1-3 were used to prepare sodium-ion batteries: the hard carbon prepared in Examples 1 and Comparative Examples 1-3, the conductive agent Super P, and sodium carboxymethyl cellulose (CMC) were mixed evenly in ultrapure water at a mass ratio of 9:0.5:0.5, and then coated onto copper foil. After air drying, the mixture was dried at 80 °C for 10 h to obtain the desired anode sheet. In a glove box (O2 and H2O < 0.1 ppm), CR2032 coin cells were assembled using the anode sheets prepared in Examples 1 and Comparative Examples 1-3 as the working electrode, the positive electrode as a sodium metal sheet, and the separator as a glass fiber.

[0032] The electrochemical performance of each prepared sodium-ion battery was tested, and the results are as follows: Figure 1 , Figure 2 As shown.

[0033] Figure 1 Sodium-ion batteries prepared using the hard carbon anode materials of Example 1 and Comparative Examples 1-3 were tested at 0.1 A g. -1 The first charge-discharge curve at current density, from Figure 1 It can be seen that, compared with Comparative Example 1, the first coulombic efficiency and reversible capacity of the modified biomass-derived hard carbon in Example 1 are greatly improved through the synergistic effect of various heteroatoms in poultry manure. However, when the poultry manure modifier is insufficient, the first coulombic efficiency and reversible capacity of the biomass-derived hard carbon in Comparative Example 2 are almost the same as those in Comparative Example 1 without modifier, with almost no improvement. When the poultry manure modifier is excessive, the capacity in Comparative Example 3 decreases significantly because the main components of poultry manure are organic matter, uric acid, and minerals, and excessive addition does not benefit the carbonization of biomass.

[0034] Figure 2 To determine the discharge capacity of sodium-ion batteries prepared using the hard carbon anode materials of Example 1 and Comparative Examples 1-3, from... Figure 2 It can be seen that the rate performance of the modified biomass-derived hard carbon in Example 1 was also improved, at 5 A g -1The discharge capacity of 200 mAh / g at a higher current density is due to the introduction of abundant active sites and defects on the surface, which can promote the storage of more sodium ions through the surface adsorption mechanism, and the expansion of the interlayer spacing facilitates the deintercalation of sodium ions, and the electronic conductivity is also greatly improved; however, when the amount of poultry manure modifier is less in Comparative Example 2, the improvement effect on the electrical properties of the biomass-derived hard carbon negative electrode material is weak, and when the amount of poultry manure modifier is excessive in Comparative Example 3, it has a negative effect on the electrical properties of the biomass-derived hard carbon negative electrode material, because excessive poultry manure will cause the generation of impurities and damage the carbon structure, so the optimal amount of poultry manure modifier is between 2wt%-10wt%.

[0035] The technical features of the above-described embodiments can be combined in any manner. To make the description concise, not all possible combinations of the technical features in the above-described embodiments are described, but as long as the combinations of the technical features do not contradict, they should be considered within the scope of the present disclosure.

[0036] The above-described embodiments only express several implementation manners of the present application, and the description is more specific and detailed, but it should not be understood as a limitation on the scope of the patent. It should be pointed out that for ordinary skilled persons in the art, without departing from the concept of the present application, a number of modifications and improvements can be made, which are all within the protection scope of the present application. Therefore, the protection scope of the patent of the present application should be subject to the appended claims.

Claims

1. A method for preparing a biomass-derived hard carbon anode material modified from natural poultry manure, characterized in that, It includes the following steps: S1. Dry, pulverize and pre-oxidize the biomass raw material to obtain a hard carbon precursor; S2. The hard carbon precursor is mixed with poultry manure to obtain a modified precursor, and the modified precursor is carbonized to obtain modified pyrolytic hard carbon. S3. The modified pyrolytic hard carbon is further processed to obtain a biomass-derived hard carbon anode material modified from natural poultry manure.

2. The method for preparing biomass-derived hard carbon anode material modified from natural poultry manure according to claim 1, characterized in that, In step S1, the biomass raw material is at least one of bamboo powder, peanut shells, coconut shells, sugarcane bagasse, and straw.

3. The method for preparing biomass-derived hard carbon anode material modified from natural poultry manure according to claim 1, characterized in that, In step S1, the pre-oxidation treatment is carried out in an air or oxygen atmosphere at 200-400°C for 2-8 hours.

4. The method for preparing biomass-derived hard carbon anode material modified from natural poultry manure according to claim 1, characterized in that, In step S2, the poultry manure is at least one of chicken manure, pigeon manure, and duck manure, and the water content of the poultry manure is 5-10%.

5. The method for preparing biomass-derived hard carbon anode material modified from natural poultry manure according to claim 1, characterized in that, In step S2, the mass of poultry manure in the modified precursor is 2%-10% of the mass of the hard carbon precursor.

6. The method for preparing biomass-derived hard carbon anode material modified from natural poultry manure according to claim 1, characterized in that, In step S2, the carbonization is carried out under a protective atmosphere, with the temperature increased to 1000-1400℃ at a heating rate of 2-10℃ / min and held for 1-4 hours.

7. The method for preparing biomass-derived hard carbon anode material modified from natural poultry manure according to claim 1, characterized in that, In step S3, the post-processing includes acid washing and purification, washing, and drying in sequence.

8. The method for preparing biomass-derived hard carbon anode material modified from natural poultry manure according to claim 7, characterized in that, The acid washing purification involves adding the modified pyrolytic hard carbon to an acid solution to obtain a mixture, which is then stirred for 2-12 hours. In the mixture, the modified pyrolytic hard carbon accounts for 10%-30% of the mass, and the acid solution is at least one of dilute hydrochloric acid, dilute sulfuric acid, and dilute nitric acid, with a concentration of 0.5-2M. The washing process involves washing 5-10 times with deionized water or distilled water.

9. A biomass-derived hard carbon anode material modified from natural poultry manure, characterized in that, It is prepared by the preparation method described in any one of claims 1-8.

10. The application of a biomass-derived hard carbon anode material modified with natural poultry manure, prepared by any one of claims 1-8, in a sodium-ion battery.

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