Protein fiber loaded with Ni nanoparticles and preparation method and application thereof
Technical Field
The invention belongs to the field of energy material chemistry, and particularly relates to a Ni nanoparticle-loaded protein fiber and a preparation method and application thereof.
Background
The energy source is a cornerstone for social development. Because the lithium ion battery has the characteristics of high energy density, long service life, good cycling stability, environmental friendliness and the like, the lithium ion battery is widely applied to a plurality of fields in recent years and mainly comprises the following components: the field of traffic power supplies (electric vehicles, electric automobiles, etc.); the field of electric energy storage power sources (water energy, wind energy and the like); mobile communication power supply field (mobile phone, computer, etc.); the field of aerospace military power supplies. In the process of charging and discharging of the lithium ion battery, lithium ions are inserted/removed back and forth between the positive electrode and the negative electrode. The reaction types of lithium ions at the negative electrode are mainly three: the first is the intercalation of lithium ions into the interstitial sites of the negative electrode material to form lithium-intercalation compounds, such as graphite negative electrodes (6C + xLi + xe)-=LixC6) (ii) a The second reaction type is an alloy reaction, such as tin-lithium alloy, and the theoretical specific capacity is 994 mAh/g; the third type of reaction is a conversion reaction, such as a chemical reaction of a transition metal oxide with lithium. Lithium ion batteries with transition metal oxide (NiO) as the negative electrode have received much attention, have prepared many unique structures and exhibit excellent electrochemical properties, such as nanowall structures (Varghese B et al, chem. Mater.2008; 20: 3360-. However, nickel metal does not react with lithium ions and cannot be directly used as a negative energy storage material of a lithium ion battery. The research finds that nickel metal can promote the stability of the solid electrolyte interface and can enhanceStability of electrochemical cycling. The silk serving as a biomass material can be subjected to degumming and low-temperature treatment to prepare carbon fiber with a certain carbonization degree, and can be subjected to de-intercalation reaction with lithium ions. However, since amorphous structure carbon causes structural destruction when reacting with lithium ions, capacity fading is rapid. The nickel layer is coated on the surface of the carbon fiber tube, so that structural instability in an electrochemical process can be stabilized, and the carbon fiber tube is expected to be a low-cost energy storage negative electrode material.
Disclosure of Invention
The invention aims to solve the technical problem of providing a protein fiber loaded with Ni nano-particles, a preparation method and application thereof.
The technical scheme adopted by the invention for solving the technical problems is as follows: a preparation method of protein fiber loaded with Ni nanoparticles specifically comprises the following steps:
1) weighing a certain amount of silkworm cocoon, cutting into pieces, ultrasonically cleaning with anhydrous ethanol, transferring to sodium carbonate Na with a certain concentration2CO3Refluxing in water solution at 100 deg.C for 60min, cooling, filtering to obtain silk fibroin fiber, washing silk fibroin fiber with distilled water for 3 times, and drying at 80 deg.C to obtain dried silk fibroin fiber;
2) soaking the dried silk fibroin fibers in nickel acetate aqueous solution with a certain concentration, stirring and soaking for 24h, then transferring the silk fibroin fibers into dilute ammonia aqueous solution with the mass concentration of 10%, standing for 60min, and then drying in a forced air drying oven at 80 ℃ to obtain the dried nickel hydroxide-loaded silk fibroin fibers;
3) putting the silk fibroin fiber loaded with the nickel hydroxide into a tubular furnace N2Calcining for 2-4 h at 500-800 ℃ in the atmosphere, and naturally cooling to room temperature to obtain the Ni nanoparticle-loaded protein fiber.
The Na is2CO3The concentration of the aqueous solution is 2.0-10 g/L;
the concentration of the nickel acetate aqueous solution is 0.02-0.1 g/mL;
the substances participating in the reaction are all chemically pure.
Furthermore, the invention also provides the protein fiber loaded with the Ni nanoparticles obtained by the preparation method.
Furthermore, the invention also provides the application of the Ni nanoparticle-loaded protein fiber, the protein fiber is used as a lithium ion battery cathode material, the charge and discharge cycle is carried out for 500 times under the current density of 100mA/g, the discharge specific capacity is kept to be 250mAh/g, and the coulombic efficiency is kept to be more than 99.6%.
Compared with the prior art, the Ni nanoparticle-loaded protein fiber prepared by the invention has the following characteristics:
(a) the protein fiber prepared by the invention takes low-price natural silk as a raw material, has simple preparation process and can be produced in batch; (b) the fibroin has reducibility, can reduce divalent nickel into zero-valent nickel in a high-temperature nitrogen atmosphere, can grow in situ and uniformly loads nickel nanoparticles; (c) the Ni nanoparticle-loaded protein fiber prepared by the invention is used as a lithium ion battery cathode material, the battery can keep charge and discharge circulation for 500 times under the current density of 100mA/g, the reversible specific capacity can be kept above 250mAh/g, and the coulombic efficiency is above 99.6%.
Drawings
FIG. 1 is an XRD spectrum of a protein fiber prepared by the present invention;
FIG. 2 is an SEM image of protein fibers prepared by the present invention;
FIG. 3 is a charge-discharge cycle chart of the protein fiber prepared by the present invention.
Detailed Description
The present invention will be described in further detail with reference to examples.
Example 1
Weighing 5g of silkworm cocoon, cutting into pieces, putting into 50mL of absolute ethyl alcohol, and ultrasonically cleaning for 30 min; 2.0g of anhydrous sodium carbonate is dissolved in 1000mL of deionized water, and then the mixture is uniformly stirred to completely dissolve the anhydrous sodium carbonate; transferring the cleaned silkworm cocoons into a sodium carbonate aqueous solution, refluxing in boiling water at 100 ℃ for 60min, cooling and filtering to obtain degummed silk fibroin fibers; washing silk fibroin fiber with distilled water for 3 times, and drying at 80 deg.C to obtain dried productDried silk fibroin fibers; soaking the dried silk fibroin fibers in 0.02g/mL nickel acetate aqueous solution, stirring and soaking for 24h, then transferring the dried silk fibroin fibers into 10% dilute ammonia aqueous solution, standing for 60min, and then drying in a forced air drying oven at 80 ℃ to obtain dried nickel hydroxide-loaded silk fibroin fibers; putting the silk fibroin fiber loaded with the nickel hydroxide into a tubular furnace N2Calcining for 2h at 800 ℃ in the atmosphere, and naturally cooling to room temperature to obtain the Ni nanoparticle-loaded protein fiber. The obtained protein fiber product loaded with Ni nano-particles is subjected to powder X-ray diffraction (XRD) test analysis, and the result shows that the product is a protein fiber material loaded with Ni nano-particles (figure 1); the observation result of a Scanning Electron Microscope (SEM) shows that a large number of nickel particles are uniformly attached to the surface of the protein fiber of the product (figure 2); the obtained protein fiber loaded with Ni nano-particles is used as a lithium ion battery cathode material, and the charge-discharge cycle is carried out for 500 times, the specific discharge capacity is kept to be 250mAh/g, and the coulombic efficiency is kept to be more than 99.6 percent (figure 3).
Example 2
Weighing 5g of silkworm cocoon, cutting into pieces, putting into 50mL of absolute ethyl alcohol, and ultrasonically cleaning for 30 min; dissolving 6.0g of anhydrous sodium carbonate in 1000mL of deionized water, and then uniformly stirring to completely dissolve the anhydrous sodium carbonate; transferring the cleaned silkworm cocoons into a sodium carbonate aqueous solution, refluxing in boiling water at 100 ℃ for 60min, cooling and filtering to obtain degummed silk fibroin fibers; washing silk fibroin fiber with distilled water for 3 times, and drying at 80 deg.C to obtain dried silk fibroin fiber; soaking the dried silk fibroin fibers in 0.1g/mL nickel acetate aqueous solution, stirring and soaking for 24h, then transferring the dried silk fibroin fibers into 10% dilute ammonia aqueous solution, standing for 60min, and then drying in a forced air drying oven at 80 ℃ to obtain dried nickel hydroxide-loaded silk fibroin fibers; putting the silk fibroin fiber loaded with the nickel hydroxide into a tubular furnace N2Calcining for 4h at 500 ℃ in the atmosphere, and naturally cooling to room temperature to obtain the Ni nanoparticle-loaded protein fiber. Carrying out powder X-ray diffraction test on the obtained protein fiber product loaded with the Ni nano particles to analyze the composition structure of the protein fiber product; observation of the product by Scanning Electron Microscopy (SEM)The morphology of (a); and (3) testing the electrochemical performance by taking the obtained protein fiber loaded with the Ni nano particles as a lithium ion battery cathode material.
Example 3
Weighing 5g of silkworm cocoon, cutting into pieces, putting into 50mL of absolute ethyl alcohol, and ultrasonically cleaning for 30 min; dissolving 10g of anhydrous sodium carbonate into 1000mL of deionized water, and then uniformly stirring to completely dissolve the anhydrous sodium carbonate; transferring the cleaned silkworm cocoons into a sodium carbonate aqueous solution, refluxing in boiling water at 100 ℃ for 60min, cooling and filtering to obtain degummed silk fibroin fibers; washing silk fibroin fiber with distilled water for 3 times, and drying at 80 deg.C to obtain dried silk fibroin fiber; soaking the dried silk fibroin fibers in 0.06g/mL nickel acetate aqueous solution, stirring and soaking for 24h, then transferring the dried silk fibroin fibers into 10% dilute ammonia aqueous solution, standing for 60min, and then drying in a forced air drying oven at 80 ℃ to obtain dried nickel hydroxide-loaded silk fibroin fibers; putting the silk fibroin fiber loaded with the nickel hydroxide into a tubular furnace N2Calcining for 3h at 600 ℃ in the atmosphere, and naturally cooling to room temperature to obtain the Ni nanoparticle-loaded protein fiber. Carrying out powder X-ray diffraction test on the obtained protein fiber product loaded with the Ni nano particles to analyze the composition structure of the protein fiber product; observing the appearance of the product by using a Scanning Electron Microscope (SEM); and (3) testing the electrochemical performance by taking the obtained protein fiber loaded with the Ni nano particles as a lithium ion battery cathode material.