CN113629228A - Silicon oxide/phosphide carbonized compound and preparation method and application thereof - Google Patents

Silicon oxide/phosphide carbonized compound and preparation method and application thereof Download PDF

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CN113629228A
CN113629228A CN202110836100.8A CN202110836100A CN113629228A CN 113629228 A CN113629228 A CN 113629228A CN 202110836100 A CN202110836100 A CN 202110836100A CN 113629228 A CN113629228 A CN 113629228A
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phosphide
silicon oxide
composite
carbonized
sio
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CN113629228B (en
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丁旭丽
张宁
赵洪达
谌潇靖
徐嘉豪
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Jiangsu Saier Rubber Co ltd
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Jiangsu University of Science and Technology
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5805—Phosphides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/022—Electrodes made of one single microscopic fiber
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention discloses a silicon oxide/phosphide carbonized compound and a preparation method and application thereof, wherein the chemical formula of the compound is C-SiOx‑MyP, wherein x is more than 0 and less than 2, y is more than 0 and less than 2, M is one of Sn, Fe, Sb and Cu, SiOx:MyThe molar ratio of P is (1-3):1, carbon source and SiOxAnd MyP has a mass ratio of8:1 (10-14); the composite is a fibrous tubular structure. Compared with the prior art, the invention has the following advantages: (1) the silicon oxide/phosphide carbonized composite is of a fiber tubular structure, and a space is reserved for the volume change of silicon oxide in the electrochemical cycle process, so that the stability of a cathode structure is ensured; (2) the negative electrode material prepared from the silicon oxide/phosphide carbonized composite has high coulombic efficiency, high specific capacity, long service life and good conductivity for the first time; (3) the preparation method is beneficial to the construction and batch production of the silicon oxide/phosphide carbonized complex.

Description

Silicon oxide/phosphide carbonized compound and preparation method and application thereof
Technical Field
The invention belongs to the technical field of electrochemical materials, and relates to a negative electrode and a secondary battery containing a novel composite material, in particular to a silicon oxide/phosphide carbonized composite and a preparation method and application thereof.
Background
Most of the negative electrode materials of lithium ion batteries used in the prior art are carbon-based negative electrode materials, including graphite and graphite derivatives. However, the theoretical specific capacity of the cathode material is only 372mAh/g, the requirements of social development can not be met, and the new generation of power ion batteries are required to have the characteristics of high specific energy, long service life, safety and environmental protection. In addition, the preparation process of the carbon negative electrode material is complex, so that the search for a negative electrode material of a lithium ion battery with high specific capacity, low cost and environmental protection is still challenging work. Among various anode materials, silicon-based anode materials have been the focus and focus of research, mainly because the theoretical specific capacity of silicon is up to 4200mAh/g, the storage capacity in the earth crust is abundant (27%), and the working voltage is low (0.3V). However, the practical application and commercialization of silicon-based negative electrode materials are limited by the disadvantages of large volume deformation (about-300%) caused by the intercalation and deintercalation of lithium ions during the charge and discharge processes and poor conductivity due to the semiconductor characteristics. Compared with a pure silicon negative electrode, the silicon oxide (2615mAh/g) generates a smaller volume expansion effect (160%) and a longer cycle life in the charge-discharge process, but the development of the silicon oxide negative electrode material is seriously influenced by low initial coulombic efficiency (ICE: 20-30%) and weak conductivity.
CN111082006A discloses a silica composite negative electrode material and a preparation method thereof, the composite material firstly carries out carbon coating on the silica powder, then carries out surface in-situ growth of nano carbon fibers, and then carries out secondary granulation to obtain the silica composite negative electrode material. This prior art has the following drawbacks: the toxicity is high in the experimental synthesis process, the cost is high, and simultaneously the obtained carbon has high hardness and cannot play a good buffering role in the volume change of the silicon monoxide. In addition, the cycle stability of the composite material is relatively poor, and the first coulombic efficiency is also relatively low.
CN110526251A discloses a preparation method of a silicon dioxide negative electrode material of a lithium ion battery, and the composite material is prepared by the following steps: adding a proper amount of sodium bicarbonate into a mixed solution of water and ethanol, uniformly stirring, sequentially adding weighed hexadecyl trimethyl ammonium bromide (CTAB) and Tetraethoxysilane (TEOS) into the mixed solution, stirring for reaction, and performing suction filtration cleaning, acid washing, suction filtration, calcination and heat preservation to obtain the catalyst. The prior art has the following defects: a large amount of organic solvent is used in the synthesis process, so that the toxicity is high, and the manufacturing steps are complex, so that the manufacturing cost of the material is greatly increased.
Disclosure of Invention
The technical problem to be solved is as follows: aiming at the problems of large volume change, easy structure damage, poor conductivity and the like of silicon-based and alloy negative electrode materials in the prior art in the circulating process, the invention provides a composite material which has stable structure, high first coulombic efficiency, high specific capacity, long service life and good conductivity in the circulating process, namely a silicon oxide/phosphide carbonized compound and a preparation method and application thereof.
The technical scheme is as follows: a silicon oxide/phosphide carbonized composite having the formula C-SiOx-MyP, wherein x is more than 0 and less than 2, y is more than 0 and less than 2, M is one of Sn, Fe, Sb and Cu, SiOx:MyThe molar ratio of P is (1-3):1, carbon source and SiOxAnd MyThe mass ratio of P is 8:1 (10-14); (ii) a The composite is a fibrous tubular structure.
Preferably, the silicon oxide is a powder having a particle size of 20nm to 50 μm.
Preferably, C in the complex is at least one of citric acid, oleic acid, malic acid, glucose, sucrose, sodium oleate, sodium citrate, sodium malate and polyvinylpyrrolidone.
A method of preparing a silicon oxide/phosphide carbide composite as described in any one of the preceding claims, said method comprising the steps of:
s1, dispersing SiO in N, N-dimethylformamide, adding polyvinylpyrrolidone after fully dissolving, and uniformly stirring to obtain a solution A, wherein the mass ratio of SiO to polyvinylpyrrolidone is 1: (6-8);
s2, dissolving triphenylphosphine in N, N dimethylformamide, adding ferric nitrate nonahydrate, copper nitrate, stannic chloride and antimony chloride or one of acetates of Sn, Fe, Sb and Cu after the triphenylphosphine is fully dissolved, wherein the molar ratio of phosphorus elements to metal elements in the triphenylphosphine is 3-6:1, fully and uniformly mixing, adding polyvinylpyrrolidone, mixing and stirring to obtain a uniform and transparent solution B, wherein the mass ratio of the polyvinylpyrrolidone to the phosphide is 1: 2;
s3, pumping the solution A in the S1 into a syringe A, pumping the solution B in the S2 into a syringe B, connecting the syringes A and B by using concentric needles, wherein the syringe A is positioned at the inner diameter of the concentric needle, and the syringe B is positioned at the outer diameter of the concentric needle; fixing the injector on a bayonet of a push injection pump of the electrostatic spinning machine, adjusting the height and distance of the injector, adding a positive voltage of 15-20 KV to the injector A, adding a negative voltage of-3-5 KV to a rotating shaft, adjusting the push injection speed of 0.020-0.075 mm/min, and starting the electrostatic spinning machine to prepare the silicon oxide/phosphide composite material;
and S4, drying the product of S3, and then carbonizing in a tube furnace, introducing argon-hydrogen mixed gas into the tube furnace, heating at a rate of 5 ℃/min, keeping at 200 ℃ for 1 hour, keeping at 550 ℃ for 2 hours, and then naturally cooling to room temperature to obtain the silicon oxide/phosphide carbonized compound.
Preferably, the concentric needle gauge is 16G or 18G.
The use of any of the above silicon oxide/phosphide carbonized composites in the preparation of a secondary battery anode material.
Preferably, the negative electrode material comprises a conductive agent and a binder, and the mass contents are respectively as follows: 50-99.5 wt% of silicon oxide/phosphide carbonized composite, 0.1-40 wt% of conductive agent and 0.1-40 wt% of binder.
Preferably, the conductive agent is at least one of carbon black, acetylene black, natural graphite, carbon nanotubes, graphene and carbon fibers; the binder is at least one of polytetrafluoroethylene, polyvinylidene fluoride, polyurethane, polyacrylic acid, polyamide, polypropylene, polyvinyl ether, polyimide, styrene-butadiene copolymer, sodium carboxymethylcellulose and sodium alginate.
Preferably, the secondary battery comprises a positive electrode, a diaphragm and an electrolyte; wherein the positive electrode is lithium cobaltate, lithium manganate, lithium nickelate, lithium iron phosphate or lithium composite metal oxide; the diaphragm is one of an aramid diaphragm, a non-woven fabric diaphragm, a polyethylene microporous film, a polypropylene-polyethylene double-layer or three-layer composite film and a ceramic coating diaphragm thereof; the electrolyte comprises an electrolyte and a solvent, wherein the electrolyte is LiPF6、LiBF4、LiClO4、LiAsF6、LiCF3SO3、LiN(CF3SO2) At least one of LiBOB, LiCl, LiBr and LiI; the solvent includes at least one of Propylene Carbonate (PC), dimethyl carbonate (DMC), Ethyl Methyl Carbonate (EMC), 1, 2-Dimethoxyethane (DME), Ethylene Carbonate (EC), Butylene Carbonate (BC), diethyl carbonate (DEC), Ethyl Acetate (EA), and ethylene sulfite (GS).
The working principle of the silicon oxide/phosphide carbonized complex and the preparation method thereof is as follows: in the negative electrode material prepared from the silicon oxide/phosphide carbonized composite, phosphide forms a nano-wire structure, and meanwhile, silicon oxide particles are uniformly dispersed in fibers, so that a unique fiber tubular structure is formed. The carbon composite effectively improves the problem of poor conductivity of the carbon composite and the silicon oxide, improves the first coulomb efficiency of the silicon oxide, and simultaneously reserves a space for the volume change of the silicon oxide by the tubular structure, thereby ensuring the stability of the structure. The invention puts two anode materials, namely silicon oxide and phosphide, which are independently researched before, into a composite system for research, fully exerts the advantages of the silicon oxide and the phosphide and overcomes the problems of the silicon oxide and the phosphide. In addition, in the electrostatic spinning method adopted by the invention, the phosphorus source and the carbon source can spontaneously carry out self-assembly reaction in the reaction process to obtain a fibrous composite structure, so that the self-deficiency of phosphide in the process of serving as the lithium battery cathode material is effectively improved, and the problems of poor conductivity, serious volume expansion and the like of the silicon oxide cathode material are complemented.
Has the advantages that: (1) the silicon oxide/phosphide carbonized composite is of a fiber tubular structure, and a space is reserved for the volume change of silicon oxide in the electrochemical cycle process, so that the stability of a cathode structure is ensured; (2) the negative electrode material prepared from the silicon oxide/phosphide carbonized composite has high coulombic efficiency, high specific capacity, long service life and good conductivity for the first time; (3) the preparation method is beneficial to the construction and batch production of the silicon oxide/phosphide carbonized complex.
Drawings
FIG. 1 is a Transmission Electron Microscope (TEM) image of example 1 prepared according to the present invention;
FIG. 2 is an X-ray diffraction (XRD) pattern of example 1 prepared in accordance with the present invention;
FIG. 3 is a charge and discharge curve of example 1 prepared in accordance with the present invention;
FIG. 4 is an electrochemical cycling test curve for example 1 prepared in accordance with the present invention;
FIG. 5 shows an electrochemical impedance spectrum of example 1 prepared according to the present invention (FIG. 5(a)) and an electrochemical impedance spectrum of comparative example 1 (FIG. 5 (b)).
Detailed Description
The following examples further illustrate the present invention but are not to be construed as limiting the invention. Modifications and substitutions to methods, procedures, or conditions of the invention may be made without departing from the spirit and substance of the invention. Unless otherwise specified, the technical means used in the examples are conventional means well known to those skilled in the art.
Example 1
0.8g of polyvinylpyrrolidone was dissolved in 10mL of N, N-dimethylformamide, and after sufficiently stirring and dissolving, 0.1g of silica was added and sufficiently stirring was again carried out to obtain solution A. 1.6g polyvinyl pyridineThe pyrrolidone was dissolved in 20mL of N, N dimethylformamide, and after fully stirred and dissolved, 2.0g of triphenylphosphine and 0.8g of ferric nitrate nonahydrate were added, and fully stirred and dissolved again to obtain a solution B. Carrying out electrostatic spinning on the solution, extracting 5mL of solution A as the inner diameter of electrostatic spinning by using an injector, extracting 10mL of solution B as the outer diameter of the electrostatic spinning by using an injector, connecting the solutions A and B by using a coaxial needle head with the model of 18G, respectively placing the solutions A and B in an injection A of an electrostatic spinning machine, setting the positive voltage of the electrostatic spinning to be 17KV, the negative voltage to be-3 KV, the inner diameter speed to be 0.03mm/min, the outer diameter speed to be 0.06mm/min, setting the temperature to be 50 ℃ and the humidity to be 30%, carrying out electrostatic spinning operation, placing the material in a 50 ℃ oven after the electrostatic spinning is finished, and carrying out drying treatment for 12 h. And after drying, carbonizing the sample, placing the sample in a tubular furnace filled with argon-hydrogen mixed gas (5% hydrogen), controlling the temperature rise rate at 5 ℃/min, keeping the sample at 200 ℃ for 1 hour, keeping the sample at 550 ℃ for 2 hours, and then naturally cooling the sample to room temperature. The solid powder obtained after carbonization is a target product C-SiO-FeP4。
Example 2
0.8g of polyvinylpyrrolidone was dissolved in 10mL of N, N-dimethylformamide, and after sufficiently stirring and dissolving, 0.04g of silica was added and sufficiently stirring was again carried out to obtain solution A. 1.6g of polyvinylpyrrolidone was dissolved in 20mL of N, N-dimethylformamide, and after sufficiently stirring and dissolving, 2.0g of triphenylphosphine and 0.8g of ferric nitrate nonahydrate were added, and sufficiently stirring and dissolving were performed again to obtain solution B. Carrying out electrostatic spinning operation on the solution, extracting 5mL of solution A as the inner diameter of electrostatic spinning by using an injector, extracting 10mL of solution B as the outer diameter of the electrostatic spinning by using an injector, connecting the solutions A and B by using a coaxial needle head with the model of 18G, respectively placing the solutions A and B in a push injection A of an electrostatic spinning machine, and placing the solution B at a bayonet of a push injection B, wherein the positive voltage of the electrostatic spinning is 17KV, the negative voltage is-3 KV, the inner diameter speed is 0.03mm/min, the outer diameter speed is 0.060mm/min, the set temperature is 50 ℃, the humidity is 30%, carrying out the electrostatic spinning operation, and after the electrostatic spinning is finished, placing the material in a 50 ℃ oven, and carrying out drying treatment for 12 hours. Carbonizing the sample after drying, and placing the sample in a mixed gas containing argon and hydrogenIn a (5% hydrogen) tube furnace, the temperature rise rate is controlled at 5 ℃/min, the temperature is kept for 1 hour at the temperature of 200 ℃, and the temperature is naturally reduced to the room temperature after being kept for 2 hours at the temperature of 550 ℃. The solid powder obtained after carbonization is a target product C-SiO-FeP4。
Example 3
0.8g of polyvinylpyrrolidone was dissolved in 10mL of N, N-dimethylformamide, and after sufficiently stirring and dissolving, 1.0g of triphenylphosphine and 0.4g of ferric nitrate nonahydrate were added, and sufficiently stirring and dissolving were performed again to obtain solution A. 1.6g of polyvinylpyrrolidone was dissolved in 20mL of N, N-dimethylformamide, and after sufficiently stirring and dissolving, 0.08g of silica was added and sufficiently stirring was again carried out to obtain solution B. Carrying out electrostatic spinning operation on the solution, extracting 5mL of solution A as the inner diameter of electrostatic spinning by using an injector, extracting 10mL of solution B as the outer diameter of the electrostatic spinning by using an injector, connecting the solutions A and B by using a coaxial needle head with the model of 18G, respectively placing the solutions A and B in a push injection A of an electrostatic spinning machine, and placing the solution B at a bayonet of a push injection B, wherein the positive voltage of the electrostatic spinning is 17KV, the negative voltage is-3 KV, the inner diameter speed is 0.03mm/min, the outer diameter speed is 0.060mm/min, the set temperature is 50 ℃, the humidity is 30%, carrying out the electrostatic spinning operation, and after the electrostatic spinning is finished, placing the material in a 50 ℃ oven, and carrying out drying treatment for 12 hours. And after drying, carbonizing the sample, placing the sample in a tubular furnace filled with argon-hydrogen mixed gas (5% hydrogen), controlling the temperature rise rate at 5 ℃/min, keeping the sample at 200 ℃ for 1 hour, keeping the sample at 550 ℃ for 2 hours, and then naturally cooling the sample to room temperature. The solid powder obtained after carbonization is a target product C-SiO-FeP4。
Comparative example 1
To compare with the phosphide in example 1, we carried out a comparative test. 0.8g of polyvinylpyrrolidone was dissolved in 10mL of N, N-dimethylformamide, and after sufficiently stirring and dissolving, 0.1g of silica was added and sufficiently stirring was again carried out to obtain solution A. Carrying out electrostatic spinning on the solution, extracting 10mL of solution by using an injector to carry out electrostatic spinning, connecting the solution by using a needle head with the model of 18G, placing the solution at an injection A bayonet of an electrostatic spinning machine, setting the positive voltage of the electrostatic spinning to be 17KV, the negative voltage to be-3 KV, the injection speed to be 0.3mm/min, the set temperature to be 50 ℃ and the humidity to be 30%, carrying out electrostatic spinning operation, placing the material in a 50 ℃ oven after the electrostatic spinning is finished, and carrying out drying treatment for 12 hours. And after drying, carbonizing the sample, placing the sample in a tubular furnace filled with argon-hydrogen mixed gas (5% hydrogen), controlling the temperature rise rate at 5 ℃/min, keeping the sample at 200 ℃ for 1 hour, keeping the sample at 550 ℃ for 2 hours, and then naturally cooling the sample to room temperature. The solid powder obtained after carbonization is the target product C-SiO.
Example 1 characterization and analysis of results of the negative electrode material:
the scanning electron micrograph shows that example 1 is a tubular fiber structure. The results are shown in FIG. 1, where the phosphide filament structure is evident, and the silica is uniformly dispersed therein, thereby forming a unique tubular fiber structure.
The material prepared in example 1 was examined by an X-ray diffractometer and we succeeded in obtaining the target product by this synthesis process as seen by X-ray diffraction pattern (XRD).
Uniformly dispersing the negative electrode materials, the conductive agent acetylene black and the binder sodium alginate prepared in the examples 1,2 and 3 and the comparative example 1 in deionized water to form slurry, uniformly coating the slurry on copper foil, putting the copper foil into a baking oven at 50-140 ℃ for drying, cutting the electrode plate coated with the active substance into small wafers, assembling the battery, wherein the test battery adopts a conventional button battery, a lithium foil is used as a counter electrode, and LiPF is used as a test battery6The organic solution (EC: DEC ═ 1: 1) was used as an electrolyte, and the assembly was completed in a glove box.
Electrochemical tests were carried out on a battery composed of the material of example 1, the results of which are shown in fig. 3.
It can be seen from the charge-discharge curves of the cycle test that the first coulombic efficiency of example 1 can reach 58%, which is significantly higher than the first coulombic efficiency of non-composite carbon fibers, silicon oxide and phosphide.
The electrochemical test was performed on the battery composed of the material of example 1 and the material of comparative example 1, and the results thereof are shown in fig. 4 and 5.
It can be seen from the cycling performance test that the sample synthesized in example 1 has a higher specific capacity maintenance rate. This is mainly due to the unique tubular structure, which can provide sufficient volume change space for the active material, and the carbon layer can effectively expand and contract to adapt to the volume change of the silicon oxide during the charge and discharge processes.
As can be seen from the impedance tests of fig. 5(a) and 5(b), the sample of example 1 has a smaller impedance resistance, whereas comparative example 1 exhibits a larger impedance. The electrochemical activity of the composite material is activated due to the appearance of phosphide, and the transport power of lithium ions in the active material is enhanced, so that the interface transport capacity of the active material is improved to a certain extent.
In addition, the electrostatic spinning synthesis method has the advantages of low equipment cost, high fiber yield, suitability for various materials and the like, and the synthesis process is favorable for reducing the cost, promoting industrialization and the like.

Claims (9)

1. Silicon oxide/phosphide carbide composite, characterized in that the chemical formula of the composite is C-SiOx-MyP, wherein x is more than 0 and less than 2, y is more than 0 and less than 2, M is one of Sn, Fe, Sb and Cu, SiOx:MyThe molar ratio of P is (1-3):1, carbon source and SiOxAnd MyThe mass ratio of P is 8:1 (10-14); the composite is a fibrous tubular structure.
2. The silicon oxide/phosphide carbide composite of claim 1, wherein the silicon oxide is a powder having a particle size of 20nm to 50 μm.
3. The silica/phosphide carbonization composite of claim 1, wherein the C in the composite is derived from at least one of citric acid, oleic acid, malic acid, glucose, sucrose, sodium oleate, sodium citrate, sodium malate, and polyvinylpyrrolidone.
4. A method of preparing a silicon oxide/phosphide carbonized composite as set forth in any one of claims 1 to 3, characterized in that the method comprises the steps of:
s1, dispersing SiO in N, N-dimethylformamide, adding polyvinylpyrrolidone after fully dissolving, and uniformly stirring to obtain a solution A, wherein the mass ratio of SiO to polyvinylpyrrolidone is 1: (6-8);
s2, dissolving triphenylphosphine in N, N dimethylformamide, adding ferric nitrate nonahydrate, copper nitrate, stannic chloride and antimony chloride or one of acetates of Sn, Fe, Sb and Cu after the triphenylphosphine is fully dissolved, wherein the molar ratio of phosphorus elements to metal elements in the triphenylphosphine is 3-6:1, fully and uniformly mixing, adding polyvinylpyrrolidone, mixing and stirring to obtain a uniform and transparent solution B, wherein the mass ratio of the polyvinylpyrrolidone to the phosphide is 1: 2;
s3, pumping the solution A in the S1 into a syringe A, pumping the solution B in the S2 into a syringe B, connecting the syringes A and B by using concentric needles, wherein the syringe A is positioned at the inner diameter of the concentric needle, and the syringe B is positioned at the outer diameter of the concentric needle; fixing the injector on a bayonet of a push injection pump of the electrostatic spinning machine, adjusting the height and distance of the injector, adding a positive voltage of 15-20 KV to the injector A, adding a negative voltage of-3-5 KV to a rotating shaft, adjusting the push injection speed of 0.020-0.075 mm/min, and starting the electrostatic spinning machine to prepare the silicon oxide/phosphide composite material;
and S4, drying the product of S3, and then carbonizing in a tube furnace, introducing argon-hydrogen mixed gas into the tube furnace, heating at a rate of 5 ℃/min, keeping at 200 ℃ for 1 hour, keeping at 550 ℃ for 2 hours, and then naturally cooling to room temperature to obtain the silicon oxide/phosphide carbonized compound.
5. The method of claim 4 wherein the concentric needle gauge is 16G or 18G.
6. Use of the silicon oxide/phosphide carbonized composite as set forth in any one of claims 1 to 3 for producing a negative electrode material for a secondary battery.
7. The application of claim 6, wherein the negative electrode material comprises a conductive agent and a binder, and the mass contents are respectively as follows: 50-99.5 wt% of silicon oxide/phosphide carbonized composite, 0.1-40 wt% of conductive agent and 0.1-40 wt% of binder.
8. The use according to claim 7, wherein the conductive agent is at least one of carbon black, acetylene black, natural graphite, carbon nanotubes, graphene, carbon fibers; the binder is at least one of polytetrafluoroethylene, polyvinylidene fluoride, polyurethane, polyacrylic acid, polyamide, polypropylene, polyvinyl ether, polyimide, styrene-butadiene copolymer, sodium carboxymethylcellulose and sodium alginate.
9. The use of claim 6, wherein the secondary battery comprises a positive electrode, a separator, an electrolyte; wherein the positive electrode is lithium cobaltate, lithium manganate, lithium nickelate, lithium iron phosphate or lithium composite metal oxide; the diaphragm is one of an aramid diaphragm, a non-woven fabric diaphragm, a polyethylene microporous film, a polypropylene-polyethylene double-layer or three-layer composite film and a ceramic coating diaphragm thereof; the electrolyte comprises an electrolyte and a solvent, wherein the electrolyte is LiPF6、LiBF4、LiClO4、LiAsF6、LiCF3SO3、LiN(CF3SO2) At least one of LiBOB, LiCl, LiBr and LiI; the solvent comprises at least one of propylene carbonate, dimethyl carbonate, methyl ethyl carbonate, 1, 2-dimethoxyethane, ethylene carbonate, butylene carbonate, diethyl carbonate, ethyl acetate and ethylene sulfite.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114824239A (en) * 2022-02-26 2022-07-29 江苏科技大学 Tin-antimony oxide composite material, preparation method thereof and application thereof in preparation of battery cathode
CN117038851A (en) * 2023-10-10 2023-11-10 江苏正力新能电池技术有限公司 Porous negative electrode and preparation method and application thereof

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20040023106A1 (en) * 2002-08-02 2004-02-05 Benson Martin H. Apparatus and method for fracture absorption layer
CN102516585A (en) * 2011-12-22 2012-06-27 中国科学院青岛生物能源与过程研究所 Biomass cellulose porous composite diaphragm used for lithium ion secondary cell
CN110556534A (en) * 2019-09-10 2019-12-10 太原理工大学 red phosphorus/polyvinylpyrrolidone carbon fiber battery negative electrode material and preparation and application thereof
CN110797521A (en) * 2019-12-05 2020-02-14 江苏科技大学 Silicon-based negative electrode material for lithium ion battery, preparation thereof, negative plate and secondary battery
CN112993253A (en) * 2021-01-15 2021-06-18 北京科技大学 High-performance silicon-based lithium ion battery cathode material and preparation method thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20040023106A1 (en) * 2002-08-02 2004-02-05 Benson Martin H. Apparatus and method for fracture absorption layer
CN102516585A (en) * 2011-12-22 2012-06-27 中国科学院青岛生物能源与过程研究所 Biomass cellulose porous composite diaphragm used for lithium ion secondary cell
CN110556534A (en) * 2019-09-10 2019-12-10 太原理工大学 red phosphorus/polyvinylpyrrolidone carbon fiber battery negative electrode material and preparation and application thereof
CN110797521A (en) * 2019-12-05 2020-02-14 江苏科技大学 Silicon-based negative electrode material for lithium ion battery, preparation thereof, negative plate and secondary battery
CN112993253A (en) * 2021-01-15 2021-06-18 北京科技大学 High-performance silicon-based lithium ion battery cathode material and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
任杰 等: "Ni2P/SiO2 催化剂制备及其乙酸加氢制乙醇催化性能评价", 《化工学报》 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114824239A (en) * 2022-02-26 2022-07-29 江苏科技大学 Tin-antimony oxide composite material, preparation method thereof and application thereof in preparation of battery cathode
CN117038851A (en) * 2023-10-10 2023-11-10 江苏正力新能电池技术有限公司 Porous negative electrode and preparation method and application thereof
CN117038851B (en) * 2023-10-10 2023-12-15 江苏正力新能电池技术有限公司 Porous negative electrode and preparation method and application thereof

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