CN107331854B - Composite electrode material with multi-stage nanostructure and prepared by coating carbon fiber loaded with metal nanoparticles with transition metal oxide - Google Patents

Composite electrode material with multi-stage nanostructure and prepared by coating carbon fiber loaded with metal nanoparticles with transition metal oxide Download PDF

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CN107331854B
CN107331854B CN201710726845.2A CN201710726845A CN107331854B CN 107331854 B CN107331854 B CN 107331854B CN 201710726845 A CN201710726845 A CN 201710726845A CN 107331854 B CN107331854 B CN 107331854B
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王宇
于心如
颜岩
唐海通
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Jilin University
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Abstract

Transition metal nanoparticle and transition metal oxide loaded carbon fiber composite electrode material CNF @ M with multistage nanostructure xO y@M 1Belonging to the technical field of lithium battery preparation. The method comprises the steps of coating polyacrylonitrile fiber (PAN) with sodium alginate, generating a PAN-transition metal alginate precursor through the coordination reaction of the polyacrylonitrile fiber and transition metal ions, and firing under the protection of inert gas by controlling the heating temperature to obtain CNF @ M with a groove structure xO yAnd the composite material is ball-milled with metal powder to obtain the composite electrode material with the multistage nano structure. The invention has the advantages of low preparation cost, large-scale preparation, high specific capacity, good cycling stability, difficult decomposition and the like. For example, the specific capacity can still reach 542.8mAhg after 100 cycles under the condition of charging and discharging of 200mA ‑1. Wherein M represents a transition metal selected from Sn, Fe, Co, Ni, Mn and Zn, x is an integer of 1-3, y is an integer of 1-4, M represents a transition metal selected from the group consisting of Cu, Mo, V 1Fe, Co or Ni.

Description

Composite electrode material with multi-stage nanostructure and prepared by coating carbon fiber loaded with metal nanoparticles with transition metal oxide
Technical Field
The invention belongs to the technical field of lithium battery preparation, and particularly relates to a lithium batteryComposite electrode material (CNF @ M) with multi-stage nanostructure and prepared by coating carbon fiber with transition metal oxide and loading metal nanoparticles xO y@M 1)。
Background
Global warming and depletion of traditional fossil energy sources have become major crisis facing the world today. The direct consequence of these two crisis is environmental pollution, represented by haze. Detailed analytical data indicate that the coal and the motor vehicle tail gas are the main causes of air pollution in Jingjin Ji area. With the increase of the environmental protection attention of the country and the increasing increase of the environmental awareness of the whole people, new energy automobiles represented by electric automobiles become important components for realizing the national energy strategic guarantee and environmental protection. The lithium ion battery has the advantages of small volume, high specific energy, long cycle life, no memory effect, low cost, environmental friendliness and the like, has become a representative of a new-generation green secondary battery, has wide application prospect in the fields of national defense, aerospace, communication, portable electronic products, electric automobiles and the like, and is concerned by people all the time. However, the specific capacity of the positive and negative electrode materials of the current lithium ion batteries is lower (positive electrode lithium iron phosphate: 170 mAhg) -1Negative electrode graphite: 370mAhg -1) And the requirement of high capacity of power batteries required in the fields of electric automobiles and the like cannot be met. The development of a novel electrode material with high specific capacity and good cycling stability is the key for improving the performance of the battery, and is an important research direction in the field of lithium ion batteries at present. The metal oxide nano structure has the characteristics of high specific capacity, environmental friendliness, high safety and the like, and is always the main research direction in the field of lithium ion electrode materials. However, some intrinsic defects of the metal oxide nanostructure (such as poor conductivity, poor cycling stability and high preparation cost) greatly restrict the large-scale industrial production and application of lithium batteries using metal oxides as electrode materials.
The composition and structure of the electrode material have close relationship with the electrochemical performance of the lithium ion battery. The material for quick charge and discharge requires good conductivity, the electrode material requires high cycle stability for long-term application of the battery, and the large-scale industrial production of the battery is requiredThe preparation cost is low. In general, optimizing the material composition and structure can effectively improve the conductivity of the material. The composite electrode material prepared by using the carbon fiber as the core and the multilevel composite structure with the groove structure metal oxide and the sulfide as the shell can effectively improve the conductivity and the cycling stability of the electrode material. The Li research group (acsappl. mater. interfaces.2016,8,30256.) produced by coating SNS and SnO on carbon fibers 2Coating a layer of carbon at 1.0Ag on the outer surface of the substrate -1Has higher specific capacity under the current density. In addition, the composition and structure of the electrode material are closely related to electrochemical performance. In recent years, a great deal of research shows that small-sized nanoparticles, porous structures of materials and multi-component composite one-dimensional nanostructures can effectively improve the specific capacity, the cycling stability and the rate capability of electrode materials. For example, the Qi research group of the university of beijing (j.am.chem.soc.,2011,133,933.) successfully synthesized mesoporous TiO using solvothermal techniques 2Effectively improves the cycling stability and specific capacity of the material. Kim et al (ACS Nano 2016,10,11317.) of Korea advanced technology research institute successfully prepared SnO prepared by silver nanoparticle modified electrospinning technology 2the/NiO nanotube greatly improves the specific capacity of the battery.
The research results fully show that the carbon fiber @ metal oxide @ metal ion has a multistage nano structure and has an attractive prospect in the field of lithium battery research. However, it is rare to efficiently and inexpensively synthesize such a multi-stage composite electrode material having a high specific capacity and a long cycle life.
Disclosure of Invention
The invention aims to provide a composite electrode material CNF @ M with a multistage nanostructure, wherein the composite electrode material CNF @ M is prepared by coating carbon fiber loaded with metal nanoparticles by using transition metal oxide xO y@M 1M represents transition metal and is Sn, Fe, Co, Ni, Mn or Zn, and x and y are integers; when the transition metal ion is divalent (e.g. Ni) 2+、Zn 2+) X is 1, y is 1, and the corresponding metal oxide is NiO and ZnO; when the transition metal ion is trivalent (e.g. Fe) 3+) X is 2, y is 3, and the corresponding metal oxide is Fe 2O 3(ii) a When the transition metal ion is tetravalent(e.g., Sn) 4+、Mn 4+) X is 1, y is 2, and the corresponding metal oxide is SnO 2、MnO 2(ii) a When the transition metal ion is Co, x is 3, y is 4 (belonging to spinel structure), and the corresponding metal oxide is Co 3O 4；M 1Fe, Co or Ni.
The invention takes Polyacrylonitrile (PAN), sodium alginate and transition metal salt as raw materials, and obtains the CNF @ M with the one-dimensional multilevel nano structure after the heating burning under the coordination reaction and the protection of inert gas xO yAnd then ball-milled with metal powder (Fe, Co or Ni).
) Preparing the CNF @ M with the multi-stage nano structure xO y@M 1A composite electrode material. Wherein the sizes of the transition metal oxide and the transition metal nano particles are about 5-10 nanometers; the specific capacity can still reach 500mA hg after being cycled for 100 times -1。
The invention relates to a CNF @ M with a multi-stage nano structure xO y@M 1A composite electrode material prepared by the steps of:
a. adding sodium alginate into deionized water, and uniformly stirring to form a sodium alginate solution;
b. cutting Polyacrylonitrile (PAN) protofilament, dispersing the Polyacrylonitrile (PAN) protofilament in water at 75-90 ℃, stirring for 2-4 hours, performing suction filtration, adding the Polyacrylonitrile (PAN) protofilament into the sodium alginate solution, stirring for 4-8 hours at normal temperature to enable sodium alginate to be coated on the surface of polyacrylonitrile, and centrifuging to obtain polyacrylonitrile fiber coated with sodium alginate;
c. mixing the soluble salt of the transition metal with deionized water, or adding the soluble salt of the transition metal and the transition metal into the deionized water for mixing and stirring to obtain a solution containing + 2-valent transition metal ions;
d. adding polyacrylonitrile fiber coated with sodium alginate into a solution containing transition metal ions, stirring and mixing uniformly, and then carrying out centrifugal washing and drying by using water to obtain a precipitate precursor of the polyacrylonitrile coated with the transition metal alginate;
e. coating the precipitate of polyacrylonitrile with the above transition metal alginateAnnealing the precursor for 2-4 hours at 400-500 ℃ under the protection of inert gas to obtain the one-dimensional multilevel nanostructure CNF @ M xO yA composite electrode material precursor;
f. mixing the above one-dimensional multilevel nano structure CNF @ M xO yThe composite electrode material precursor and metal powder (Fe, Co or Ni) are mixed in a proportion of 4-10: 1 for 10-20 hours to obtain the multi-level nano-structure CNF @ M xO y@M 1A composite electrode material;
specifically, step a is to add 1-5 g of sodium alginate ((C) to 500mL of deionized water 6H 7NaO 6) nN is a positive integer and represents the number average polymerization degree of sodium alginate), and stirring for 5-24 hours at the temperature of 20-40 ℃;
b, shearing the PAN precursor into 5-8 mm; the precursor is twisted together in the stirring process due to the overlong size of the precursor, so that a large amount of alginate precursors which are not coated on the surface of the PAN precursor exist in the product;
step c, adding 10-35 g of transition metal salt into 500mL of deionized water, and stirring for 10-30 minutes; the filtering metal salt is Fe 2+、Co 2+、Ni 2+、Mn 2+Or Zn 2+Soluble salts of transition metals, e.g. ferrous chloride tetrahydrate (FeCl) 2·7H 2O), cobalt sulfate heptahydrate (CoSO) 4·7H 2O), nickel sulfate hexahydrate (NiSO) 4·6H 2O), manganese chloride tetrahydrate (MnCl) 2·4H 2O) and zinc chloride (ZnCl) 2) And the like. Due to Sn 2+Has strong hydrolytic power and can adopt metallic tin to reduce Sn 4+Preparation of Sn 2+The aqueous solution of (a): adding 5-18 g of stannic chloride into 500mL of deionized water, stirring for 10-30 minutes, then adding 1-6 g of metallic tin, stirring for 30-60 minutes, and centrifuging to obtain supernatant, namely the required Sn 2+And (3) solution. Although Sn and Fe are divalent in the precursor, the valence of Sn and Fe is respectively changed into tetravalent and trivalent after heating and burning;
the mixing time in the step d is 3-12 hours; the drying condition is 60-100 ℃, and the drying time is 6-12 hours.
The invention provides a method for synthesizing the multi-level nano-structure CNF @ M with high efficiency, large amount and low cost xO y@M 1A preparation method of the composite electrode material. The size of the transition metal oxide and the transition metal nano particles is between 5 and 10 nanometers, and the composite material has remarkable groove structure characteristics and good electrochemical performance and can be widely applied to the field of lithium batteries.
(1) The prepared nano-structure CNF @ M has a multi-stage nano-structure xO y@M 1The transition metal oxide or the transition metal nano-particles have smaller size (5-10 nanometers), so that the diffusion distance of lithium ions can be effectively shortened, the mobility of the lithium ions is further improved, and the lithium ions are favorably inserted and extracted.
(2) The invention relates to a multistage nano-structure CNF @ M xO y@M 1The groove structure on the surface can effectively reduce the huge volume change of the transition metal oxide or the transition metal nano particles caused by the insertion and the extraction of lithium ions in the charging and discharging processes, thereby maintaining the structural stability of the composite material, further improving the specific capacitance of the battery and prolonging the cycle life.
(3) The invention has a multistage nano-structure CNF @ M xO y@M 1The transition metal oxide and the transition metal nano-particles have obvious synergistic effect, and the reversibility of electrode reaction can be effectively improved. Furthermore, the central graphitized carbon fibers can significantly improve the electrical conductivity of the electrode material.
(4) PAN and sodium alginate ((C) used in the invention 6H 7NaO 6) nAnd n is 50-200) is a high-molecular compound with high yield and low price, and the sodium alginate solution can be recycled. The preparation method provided by the invention has the characteristics of low preparation cost, simple method, easiness in operation, reliable production process, good repeatability, high yield and the like.
Drawings
FIG. 1: example 1A preparation of a catalyst having a multilevel nanostructure CNF @ SnO 2Scanning electron microscope for materialsThe photo shows that the groove structure of the surface can be clearly seen. The grooves have obvious orientation, and the whole surface can be regarded as formed by stacking a plurality of layers with groove structures, which indicates that the groove structures of the surface are derived from the surface layer structures of PAN;
FIG. 2: example 1A preparation of a catalyst having a multilevel nanostructure CNF @ SnO 2High-resolution electron microscope photograph of @ Ni composite electrode material, wherein the part with obvious lattice diffraction is transition metal oxide SnO 2The sizes of the nano particles and the metal nickel nano particles are between 5 and 10 nanometers, and the figure shows that the metal oxide and the metal nickel nano particles are uniformly distributed on the surface of the carbon fiber; the shell layer formed by the transition metal oxide is uniformly coated on the surface of the carbon fiber, and then the metal nano particles are loaded on the surface of the metal oxide shell layer through ball milling. The carbon fiber, the transition metal oxide, and the metal nanoparticles are hierarchically combined together, rather than being uniformly mixed together, thereby forming a multi-stage nanostructure.
FIG. 3: example 1A preparation of a catalyst having a multilevel nanostructure CNF @ SnO 2XRD pattern of @ Ni composite electrode material, which is sufficient to show that the transition metal oxide is pure SnO 2The nano particles have the size not larger than 10 nanometers, and the metal Sn generated in the annealing process can be oxidized into SnO in the ball milling process 2；
FIG. 4: example 1A preparation of a catalyst having a multilevel nanostructure CNF @ SnO 2Raman characterization curve of @ Ni composite electrode material, 1350cm -1The peak indicates amorphous carbon, 1600cm -1The peak represents graphite type carbon, and Raman data shows that the composite structure comprises amorphous carbon and graphite type carbon, and the proportion of the amorphous carbon to the graphite type carbon is 1.46: 1;
FIG. 5: example 1A preparation of a catalyst having a multilevel nanostructure CNF @ SnO 2The thermogravimetric curve of the @ Ni composite electrode material; the sample has obvious weight loss in the temperature range of 400-750 ℃, which shows that about 30 percent of amorphous carbon is burnt;
FIG. 6: example 1A preparation of a catalyst having a multilevel nanostructure CNF @ SnO 2The @ Ni composite electrode material has three electrochemical cycle curves in the range of 0.01-3.0V at 0.2 millivolt per secondThe reduction curve corresponds to SnO 2Two peaks of the oxidation curve respectively correspond to Li xSn and Li 2O, experiments show that the composite material has good specific capacity and charge-discharge cycle performance;
FIG. 7: example 1A preparation of a catalyst having a multilevel nanostructure CNF @ SnO 2The circulation curve of the @ Ni composite electrode material shows that the sample has the capacity of 542.8 milliampere per gram at the current of 200 milliampere, the capacity of 500 milliampere per gram is still obtained after 100 times of circulation, and the coulomb efficiency still reaches 100 percent. This shows that the material has better electrochemical stability;
FIG. 8: example 1A preparation of a catalyst having a multilevel nanostructure CNF @ SnO 2The impedance curve of the @ Ni composite electrode material, in the range of 1 hz to 1 mhz, the sample showed lower ohmic impedance and charge transfer impedance, indicating that the material had lower electrochemical impedance.
Detailed Description
Example 1
CNF @ SnO with multistage nanostructure 2The preparation process of the @ Ni composite electrode material comprises the following specific three steps:
synthesis of PAN-tin alginate:
5 g of sodium alginate was added to 500mL of deionized water, and the mixture was stirred at room temperature for 6 hours to completely dissolve the sodium alginate. Then, 2.5 g of PAN precursor which is cut into 5 mm is put into 500mL of deionized water, stirred for 3 hours at the temperature of 80 ℃, added into the sodium alginate solution after suction filtration, stirred for 12 hours at the room temperature, and then centrifugally washed; 18 grams of tin tetrachloride was added to 500 grams of deionized water and stirred for 30 minutes to completely dissolve. And then 6 g of metallic tin is added into the stannic chloride solution, stirred and reacted for 6 hours at room temperature, and centrifuged to obtain supernatant, namely the required stannic chloride solution. Then, fully mixing the PAN coated with the sodium alginate with a tin dichloride solution for 4 hours to obtain PAN-tin alginate precipitate; after centrifugal washing, the mixture is dried for 20 hours at the temperature of 60 ℃ to obtain the PAN-tin alginate precursor.
2. Having a multilevel of nanometersStructure CNF @ SnO 2Synthesis of composite materials
Putting the PAN-tin alginate precursor prepared in the step 1 into a muffle furnace at 450 ℃, and annealing for 6 hours under the protection of inert gas to convert 1 g of PAN-tin alginate into CNF @ SnO with a multistage nano structure 2The mass of the product of the composite material is 0.75 g.
3.CNF @ SnO with multi-stage nano structure 2Synthesis of @ Ni composite electrode material
1 g of CNF @ SnO prepared in step 2 2Mixing with 0.1 g of metallic nickel powder, and ball milling for 15 hours to obtain CNF @ SnO with a multistage nano structure 2@ Ni composite electrode material, product mass 0.8 grams.
CNF@SnO 2The scanning electron micrograph of the material is shown in FIG. 1, and it can be seen that SnO on the surface of the carbon fiber 2The layer has a distinct trench structure; CNF @ SnO 2High resolution transmission electron micrograph of @ Ni material (FIG. 2) clearly shows all nanoparticles (SnO) at the surface 2And metal Ni) are all between 5 and 10 nanometers in size; CNF @ SnO 2The XRD pattern of the @ Ni material is shown in figure 3, and all diffraction peaks are completely consistent with standard cards (tetragonal SnO2JCPDS 70-4177 and cubic Ni JCPDS No. 70-1849); CNF @ SnO 2The Raman characterization of the @ Ni material is shown in FIG. 4, and carbon in the composite material is in an amorphous state and a graphite state, and the proportion of carbon in the composite material is 1.46: 1; CNF @ SnO 2The thermogravimetric curve of the @ Ni material As shown in FIG. 5, approximately 30% of the amorphous carbon is burned off after heating to 800 deg.C; CNF @ SnO 2The electrochemical cycle curve of the @ Ni material is shown in FIG. 6, and the specific capacity of the composite material after 100 cycles under the charging and discharging conditions of 200mA is 542.8mAhg -1The material has good cycle stability; CNF @ SnO 2The cyclic voltammogram of the @ Ni material is shown in FIG. 7, which indicates that the material forms an SEI layer in the first charge-discharge process; CNF @ SnO 2The impedance curve for the @ Ni material is shown in FIG. 8, indicating that the material has a lower electrochemical impedance.
Example 2
CNF @ Fe with multistage nanostructure 2O 3The preparation process of the @ Ni composite electrode material comprises the following specific three steps:
synthesis of PAN-ferrous alginate:
1 g of sodium alginate was added to 500mL of deionized water, and the mixture was stirred at room temperature for 6 hours to completely dissolve the sodium alginate. Then, 2.5 g of PAN precursor which is cut into 5 mm is put into 500mL of deionized water, stirred for 3 hours at the temperature of 80 ℃, added into the sodium alginate solution after suction filtration, stirred for 12 hours at the room temperature, and then centrifugally washed; 20 grams of ferrous chloride was added to 400mL of deionized water and stirred for 30 minutes to completely dissolve it. Then, fully mixing the sodium alginate-coated PAN protofilament with a ferrous chloride solution for 12 hours to obtain PAN-ferrous alginate precipitate; after centrifugal washing, the PAN-ferrous alginate precursor can be prepared after drying for 10 hours at the temperature of 60 ℃.
2.CNF@Fe 2O 3Synthesis of (2)
Putting the PAN-ferrous alginate precursor prepared in the step 1 into a muffle furnace at 500 ℃, and annealing for 4 hours under the protection of inert gas to convert the PAN-ferrous alginate into CNF @ Fe 2O 3A composite nanostructure.
3.CNF@Fe 2O 3Synthesis of @ Ni
1 g of CNF @ Fe prepared in step 2 2O 3Mixing with 0.1 metal Ni powder, ball milling for 15 hours to obtain the final product with multilevel structure CNF @ Fe 2O 3@ Ni composite nanomaterial. The product obtained in this example has similar structural characteristics to those of example 1.
Example 3
CNF @ Co with multistage nano structure 3O 4The preparation process of the @ Ni composite electrode material comprises the following specific three steps:
synthesis of PAN-cobalt alginate:
5 g of sodium alginate was added to 500mL of deionized water, and the mixture was stirred at room temperature for 6 hours to completely dissolve the sodium alginate. Then, 2.5 g of PAN precursor which is cut into 5 mm is put into 500mL of deionized water, stirred for 3 hours at the temperature of 80 ℃, added into the sodium alginate solution after suction filtration, stirred for 12 hours at the room temperature, and then centrifugally washed; 10 grams of cobalt chloride was added to 400mL of deionized water and stirred for 30 minutes to completely dissolve it. Then fully mixing the sodium alginate-coated PAN protofilament with a ferrous chloride solution for 12 hours to obtain PAN-cobalt alginate precipitate; after centrifugal washing, the mixture is dried for 10 hours at the temperature of 60 ℃ to obtain the PAN-cobalt alginate precursor.
2.CNF@Co 3O 4Synthesis of (2)
Putting the PAN-cobalt alginate precursor prepared in the step 1 into a muffle furnace at 500 ℃, and annealing for 4 hours under the protection of inert gas to convert the PAN-cobalt alginate into CNF @ Co 3O 4A composite nanostructure.
3.CNF@Co 3O 4Synthesis of @ Ni
1 g of CNF @ Co prepared by step 2 3O 4Mixing with 0.1 metal Ni powder, ball milling for 15 hours to obtain the final product with multilevel structure CNF @ Co 3O 4@ Ni composite nanomaterial. The product obtained in this example has similar structural characteristics to those of example 1.
Example 4
CNF @ MnO with multistage nano structure 2The preparation process of the @ Ni composite electrode material comprises the following specific three steps:
synthesis of PAN-manganese alginate:
5 g of sodium alginate was added to 500mL of deionized water, and the mixture was stirred at room temperature for 6 hours to completely dissolve the sodium alginate. Then, 2.5 g of PAN precursor which is cut into 5 mm is put into 500mL of deionized water, stirred for 3 hours at the temperature of 80 ℃, added into the sodium alginate solution after suction filtration, stirred for 12 hours at the room temperature, and then centrifugally washed; 15 grams of manganese chloride was added to 400mL of deionized water and stirred for 30 minutes to completely dissolve it. Then fully mixing the sodium alginate-coated PAN protofilament with a manganese chloride solution for 12 hours to obtain PAN-manganese alginate precipitate; after centrifugal washing, drying for 10 hours at the temperature of 60 ℃ to obtain the PAN-manganese alginate precursor.
2.CNF@MnO 2Synthesis of (2)
Putting the PAN-manganese alginate precursor prepared in the step 1 into a muffle furnace at 450 ℃,under the protection of inert gas, annealing for 4 hours to convert PAN-manganese alginate into CNF @ MnO 2A composite nanostructure.
3.CNF@MnO 2Synthesis of @ Ni
1 g of CNF @ MnO prepared in step 2 2Mixing with 0.1 g of metal Ni powder, and ball-milling for 15 hours to obtain the product with the multilevel structure CNF @ MnO 2@ Ni composite nanomaterial. The product obtained in this example has similar structural characteristics to those of example 1.
Example 5
CNF @ SnO with multistage nanostructure 2The preparation process of the @ Fe composite electrode material comprises the following specific three steps:
synthesis of PAN-tin alginate:
5 g of sodium alginate was added to 500mL of deionized water, and the mixture was stirred at room temperature for 6 hours to completely dissolve the sodium alginate. Then, 2.5 g of PAN precursor which is cut into 5 mm is put into 500mL of deionized water, stirred for 3 hours at the temperature of 80 ℃, added into the sodium alginate solution after suction filtration, stirred for 12 hours at the room temperature, and then centrifugally washed; 18 grams of tin tetrachloride was added to 500 grams of deionized water and stirred for 30 minutes to completely dissolve. And then 6 g of metallic tin is added into the stannic chloride solution, stirred and reacted for 6 hours at room temperature, and centrifuged to obtain supernatant, namely the required stannic chloride solution. Then, fully mixing the PAN coated with the sodium alginate with a tin dichloride solution for 4 hours to obtain PAN-tin alginate precipitate; after centrifugal washing, the mixture is dried for 20 hours at the temperature of 60 ℃ to obtain the PAN-tin alginate precursor.
2.CNF @ SnO with multi-stage nano structure 2Synthesis of composite materials
Putting the PAN-tin alginate precursor prepared in the step 1 into a muffle furnace at 450 ℃, and annealing for 6 hours under the protection of inert gas to convert the tin alginate into CNF @ SnO with a multistage nano structure 2A composite material.
3.CNF @ SnO with multi-stage nano structure 2Synthesis of @ Fe composite electrode material
1CNF @ SnO prepared by step 2 20.25 g of metalMixing and ball-milling iron powder for 15 hours to obtain CNF @ SnO with a multistage nano structure 2@ Fe composite electrode material. The product obtained in this example has similar structural characteristics to those of example 1.
Example 6
The preparation process of the CNF @ ZnO @ Ni composite electrode material with the multistage nano structure comprises the following steps:
synthesis of PAN-Zinc alginate:
5 g of sodium alginate was added to 500mL of deionized water, and the mixture was stirred at room temperature for 6 hours to completely dissolve the sodium alginate. Then, 2.5 g of PAN precursor which is cut into 5 mm is put into 500mL of deionized water, stirred for 3 hours at the temperature of 80 ℃, added into the sodium alginate solution after suction filtration, stirred for 12 hours at the room temperature, and then centrifugally washed; 20 grams of zinc acetate was added to 400mL of deionized water and stirred for 30 minutes to completely dissolve. Then fully mixing the sodium alginate-coated PAN precursor with a zinc acetate solution for 8 hours to obtain PAN-zinc alginate precipitate; after centrifugal washing, the mixture is dried for 10 hours at the temperature of 60 ℃ to obtain the PAN-zinc alginate precursor.
Synthesis of CNF @ ZnO
And (3) placing the PAN-zinc alginate precursor prepared in the step (1) in a muffle furnace at 500 ℃, and annealing for 4 hours under the protection of inert gas to convert the PAN-zinc alginate into a CNF @ ZnO composite nanostructure.
Synthesis of CNF @ ZnO @ Ni
And (3) mixing and ball-milling 1 g of CNF @ ZnO prepared in the step (2) and 0.25 g of metal Ni powder for 15 hours to obtain the CNF @ ZnO @ Ni composite nano material with the multilevel structure. The product obtained in this example has similar structural characteristics to those of example 1.
Example 7
The preparation process of the CNF @ NiO @ Ni composite electrode material with the multistage nano structure comprises the following steps:
synthesis of PAN-nickel alginate:
5 g of sodium alginate was added to 500mL of deionized water, and the mixture was stirred at room temperature for 6 hours to completely dissolve the sodium alginate. Then, 2.5 g of PAN precursor which is cut into 5 mm is put into 500mL of deionized water, stirred for 3 hours at the temperature of 80 ℃, added into the sodium alginate solution after suction filtration, stirred for 12 hours at the room temperature, and then centrifugally washed; 18 grams of nickel chloride was added to 400mL of deionized water and stirred for 20 minutes to completely dissolve it. Then fully mixing the PAN protofilament coated with the sodium alginate with a nickel chloride solution for 12 hours to obtain PAN-nickel alginate precipitate; after centrifugal washing, the mixture is dried for 10 hours at the temperature of 60 ℃ to obtain the PAN-nickel alginate precursor.
Synthesis of CNF @ NiO
And (3) placing the PAN-nickel alginate precursor prepared in the step (1) in a muffle furnace at 450 ℃, and annealing for 4 hours under the protection of inert gas to convert the PAN-nickel alginate into a CNF @ NiO composite nano structure.
Synthesis of CNF @ NiO @ Ni
And (3) mixing and ball-milling 1 g of CNF @ NiO prepared in the step (2) and 0.1 g of metal Ni powder for 15 hours to obtain the CNF @ NiO @ Ni composite nano material with the multilevel structure.
Example 8
CNF @ SnO with multistage nanostructure 2The preparation process of the @ Co composite electrode material comprises the following specific three steps:
synthesis of PAN-tin alginate:
5 g of sodium alginate was added to 500mL of deionized water, and the mixture was stirred at room temperature for 6 hours to completely dissolve the sodium alginate. Then, 2.5 g of PAN precursor which is cut into 5 mm is put into 500mL of deionized water, stirred for 3 hours at the temperature of 80 ℃, added into the sodium alginate solution after suction filtration, stirred for 12 hours at the room temperature, and then centrifugally washed; 18 grams of tin tetrachloride was added to 500 grams of deionized water and stirred for 30 minutes to completely dissolve. And then 6 g of metallic tin is added into the stannic chloride solution, stirred and reacted for 6 hours at room temperature, and centrifuged to obtain supernatant, namely the required stannic chloride solution. Then, fully mixing the PAN coated with the sodium alginate with a tin dichloride solution for 4 hours to obtain PAN-tin alginate precipitate; after centrifugal washing, the mixture is dried for 20 hours at the temperature of 60 ℃ to obtain the PAN-tin alginate precursor.
2.CNF @ SnO with multi-stage nano structure 2Synthesis of composite materials
Putting the PAN-tin alginate precursor prepared in the step 1 into a muffle furnace at 450 ℃, and annealing for 6 hours under the protection of inert gas to convert the tin alginate into CNF @ SnO with a multistage nano structure 2A composite material.
3.CNF @ SnO with multi-stage nano structure 2Synthesis of @ Co composite electrode material
1 gram of CNF @ SnO prepared by step 2 2Mixing with 0.25 g of metallic cobalt powder, and ball-milling for 15 hours to obtain CNF @ SnO with a multistage nano structure 2@ Co composite electrode material. The product obtained in this example has similar structural characteristics to those of example 1.

Claims (7)

1. Transition metal nanoparticle and transition metal oxide loaded carbon fiber composite electrode material CNF @ M with multistage nanostructure xO y@M 1The preparation method comprises the following steps:
a. adding sodium alginate into deionized water, and uniformly stirring to form a sodium alginate solution;
b. cutting down polyacrylonitrile precursor, dispersing the polyacrylonitrile precursor in water at the temperature of 75-90 ℃, stirring for 2-4 hours, then carrying out suction filtration, then adding the polyacrylonitrile precursor into the sodium alginate solution obtained in the step a, stirring for 4-8 hours at normal temperature, coating the sodium alginate on the surface of polyacrylonitrile, and then centrifuging to obtain the polyacrylonitrile fiber coated with the sodium alginate;
c. mixing the soluble salt of the transition metal with deionized water, or adding the soluble salt of the transition metal and the transition metal into the deionized water for mixing and stirring to obtain a solution containing + 2-valent transition metal ions;
d. adding polyacrylonitrile fiber coated with sodium alginate into a solution containing + 2-valent transition metal ions, stirring and mixing uniformly, and then carrying out centrifugal washing and drying on water to obtain a precipitate precursor of the polyacrylonitrile coated with the transition metal alginate;
e. coating the precipitate precursor of polyacrylonitrile with the transition metal alginateAnnealing for 2-4 hours at 400-500 ℃ under the protection of inert gas to obtain the one-dimensional multi-stage nano-structure composite electrode material CNF @ M xO yA precursor;
f. the one-dimensional multi-level nano-structure composite electrode material CNF @ M xO yPrecursor and metal powder M 1The ratio of (1) to (10): 1 for 10-20 hours to obtain the composite electrode material CNF @ M with the multistage nanostructure xO y@M 1；
Wherein M represents a transition metal, Sn, Fe, Co, Ni, Mn or Zn, x is an integer of 1, 2 or 3, y is an integer of 1, 2, 3 or 4, M is a transition metal 1Fe, Co or Ni.
2. The carbon fiber composite electrode material CNF @ M supporting transition metal nanoparticles and transition metal oxides and having a multilevel nanostructure as claimed in claim 1 xO y@M 1The method is characterized in that: step a, adding 1-5 g of sodium alginate into 500mL of deionized water, and stirring for 5-24 hours at 20-40 ℃.
3. The carbon fiber composite electrode material CNF @ M supporting transition metal nanoparticles and transition metal oxides and having a multilevel nanostructure as claimed in claim 1 xO y@M 1The method is characterized in that: and step b, shearing the polyacrylonitrile protofilament into 5-8 mm.
4. The carbon fiber composite electrode material CNF @ M supporting transition metal nanoparticles and transition metal oxides and having a multilevel nanostructure as claimed in claim 1 xO y@M 1The method is characterized in that: step c, adding 10-35 g of transition metal salt into 500mL of deionized water, and stirring for 10-30 minutes to obtain a solution containing + 2-valent transition metal ions; the transition metal salt being Fe 2 +、Co 2+、Ni 2+、Mn 2+Or Zn 2+A +2 valent soluble salt of a transition metal.
5. The carbon fiber composite electrode material CNF @ M supporting transition metal nanoparticles and transition metal oxides and having a multilevel nanostructure according to claim 4 xO y@M 1The method is characterized in that: the transition metal salt is ferrous chloride tetrahydrate, cobalt sulfate heptahydrate, nickel sulfate hexahydrate, manganese chloride tetrahydrate or zinc chloride.
6. The carbon fiber composite electrode material CNF @ M supporting transition metal nanoparticles and transition metal oxides and having a multilevel nanostructure as claimed in claim 1 xO y@M 1The method is characterized in that: step c, adding 5-18 g of stannic chloride into 500mL of deionized water, stirring for 10-30 minutes, then adding 1-6 g of metallic tin, stirring for 30-60 minutes, and centrifuging to obtain supernatant, namely the supernatant containing + 2-valent transition metal ions Sn 2+The solution of (1).
7. The carbon fiber composite electrode material CNF @ M supporting transition metal nanoparticles and transition metal oxides and having a multilevel nanostructure as claimed in claim 1 xO y@M 1The method is characterized in that: the mixing time in the step d is 3-12 hours; the drying condition is 60-100 ℃, and the drying time is 6-12 hours.
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