CN112768646A - Method for preparing antimony-based alloy/nitrogen-doped carbon composite porous material by self-template method, composite porous material and application - Google Patents

Method for preparing antimony-based alloy/nitrogen-doped carbon composite porous material by self-template method, composite porous material and application Download PDF

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CN112768646A
CN112768646A CN202011409759.7A CN202011409759A CN112768646A CN 112768646 A CN112768646 A CN 112768646A CN 202011409759 A CN202011409759 A CN 202011409759A CN 112768646 A CN112768646 A CN 112768646A
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antimony
nitrogen
porous material
composite porous
doped carbon
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杨涛
钟家松
李心悦
毛启楠
朱怡雯
沈飚
李贵显
李敢
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Hangzhou Dianzi University
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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
    • H01M4/36—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
    • 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
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • 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
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • 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 belongs to the technical field of composite materials, and particularly relates to a method for preparing an antimony-based alloy/nitrogen-doped carbon composite porous material by a self-template method, the antimony-based alloy/nitrogen-doped carbon composite porous material and application. The method for preparing the antimony-based alloy/nitrogen-doped carbon composite porous material by the self-template method has the characteristics of cheap and easily-obtained raw materials, simple preparation process, pure phase, environmental protection, high yield and easiness in production, and has good application prospect; when the antimony-based alloy/nitrogen-doped carbon composite porous material is used as a lithium ion battery cathode material, the safety of the battery is improved, and the battery has higher specific capacity and rate capability and longer cycle life.

Description

Method for preparing antimony-based alloy/nitrogen-doped carbon composite porous material by self-template method, composite porous material and application
Technical Field
The invention relates to the technical field of composite materials, in particular to a method for preparing an antimony-based alloy/nitrogen-doped carbon composite porous material by a self-template method, the antimony-based alloy/nitrogen-doped carbon composite porous material and application.
Background
Lithium Ion Batteries (LIBs) have been widely used in our modern life as portable electronic devices due to their long cycle life, high energy density, low self-discharge characteristics, safe operating voltage and no memory effect. However, current LIBs are not sufficient to meet the ever-increasing demands of large-scale applications including electric vehicles, hybrid vehicles, and emerging smart grids. Where energy density and cycle life are the most important features of LIBs that must be upgraded and improved. As a cathode material widely used in lithium ion batteries, the theoretical capacity of graphite is limited (372 mAh.g.)-1) The rate capability is poor and it is difficult to satisfy the urgency of large-scale energy application. New anode materials need to be explored to meet the continuing growth in demand.
The antimony-based alloy material can provide higher theoretical capacity than commercial graphite, and is a promising lithium ion negative electrode material based on a multi-electron alloying reaction mechanism. Furthermore, a suitable operating voltage (about 0.4V) can avoid growth of dendrites and ensure high safety. However, the large volume change caused by the alloying/dealloying reaction during the cycle will cause severe structural collapse, electrode pulverization, and rapid decrease in the capacity of the electrode. It is an effective strategy to build uniform nanoporous composites by alloying Sb with other metals and simultaneously bonding them to the porous carbon matrix. The traditional method of preparing composite materials is simple loading, where antimony or alloys are easily released from the carbon matrix in rapidly repeated cycles, easily leading to rapid capacity drop. In addition, the high surface energy of antimony or alloy nanoparticles can spontaneously cause agglomeration. These have limited the development of antimony-based alloy materials as negative electrode materials for lithium ion batteries to some extent.
Disclosure of Invention
In order to solve the problems, the invention provides a method for preparing an antimony-based alloy/nitrogen-doped carbon composite porous material by a self-template method, the preparation method adopts a dissolved salt template which is spontaneously formed by reaction and is easily dissolved in water as a pore-forming agent, and the method has the characteristics of cheap and easily-obtained raw materials, simple preparation process, easy recovery of the template, environmental protection, no pollution and high yield, and is expected to be applied in a large scale;
the invention provides an antimony-based alloy/nitrogen-doped carbon composite porous material prepared by the method, and the prepared antimony-based alloy/nitrogen-doped carbon composite porous material has strong M-N covalent bonds, enhances the interface ion storage capacity and stability between the antimony-based alloy and a carbon material, and simultaneously prevents the combination and falling of the alloy and carbon and avoids agglomeration;
the invention also provides an antimony-based alloy/nitrogen-doped carbon composite porous material which is used as a lithium ion battery cathode material for application; when the material is applied to the lithium ion battery as a negative electrode material, the material has multiple characteristics of high conductivity, high specific surface area, high volume change inhibition effect, relatively safer working voltage platform and enhanced pseudocapacitance, so that the safety of the lithium ion battery is improved, the cycle stability and the rate capability of the lithium ion battery are also improved, and the assembled lithium ion battery has better electrochemical performance.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a method for preparing an antimony-based alloy/nitrogen-doped carbon composite porous material by a self-template method comprises the following steps:
a) adding metal soluble salt, an antimony source, citrate and a nitrogen source into a solvent, uniformly mixing, and drying to obtain a precursor;
b) carrying out heat treatment on the precursor under a non-oxidizing protective atmosphere to obtain an intermediate product;
c) and washing the intermediate product with water or absolute ethyl alcohol, and drying after washing to obtain the antimony-based alloy/nitrogen-doped carbon composite porous material.
In the step a), the raw materials are simply and continuously stirred to prepare the transparent solution, and then the transparent solution is dried to prepare the precursor. In the step b), synthesizing the composite porous material by means of heat treatment and removing the template in the composite porous material. In the step c), the template agent in the intermediate product is thoroughly removed by washing with water or absolute ethyl alcohol, so as to prepare the antimony-based alloy/nitrogen-doped carbon composite porous material, wherein the mass ratio of the intermediate product to deionized water or ethyl alcohol is in the range of 1:10-300, and the preferred mass ratio of the intermediate product to deionized water or ethyl alcohol is 1: 50. In the invention, the drying equipment can be an oven or a heating table, the temperature range is 60-100 ℃, the temperature is preferably 80 ℃, the heating time is set to be 6-24 hours, and the time is preferably 6 hours; of course, the drying treatment in the present invention is not a critical step of the present invention, as long as the corresponding product obtained is dried, and is not limited to the above-mentioned equipment and temperature.
Preferably, the solvent is one of water, a mixture of ethanol and water, or a mixture of methanol and water.
Wherein, when one of the mixed liquid of ethanol and water or the mixed liquid of methanol and water is adopted, the ratio of the mixed liquid is (1-2) to 1, and the most preferable ratio is 1: 1.
Preferably, the antimony source is antimony trichloride or antimony acetate.
Preferably, the nitrogen source is at least one of urea, melamine or dicyandiamide.
Preferably, the metal soluble salt is one of a ferrous salt, a ferric salt, a cobalt salt, a nickel salt, a copper salt or a zinc salt.
Preferably, the metal soluble salt is one of iron acetate, cobalt acetate, nickel acetate, copper acetate, zinc acetate, ferrous sulfate, cobalt sulfate, nickel sulfate, copper sulfate, zinc sulfate, iron chloride, cobalt chloride, nickel chloride, copper chloride, zinc chloride, iron nitrate, cobalt nitrate, nickel nitrate, copper nitrate, or zinc nitrate.
Preferably, in the step b), the heat treatment temperature is 600-900 ℃, and the treatment time is 2-6 hours; the heating and cooling rate is 2-10 deg.C/min.
Preferably, in step b), the heat treatment temperature is 700 ℃ and the treatment time is 3 hours; the heating and cooling rates are 5 ℃/min.
The antimony-based alloy/nitrogen-doped carbon composite porous material is prepared by the method for preparing the antimony-based alloy/nitrogen-doped carbon composite porous material by the self-template method.
An application of an antimony-based alloy/nitrogen-doped carbon composite porous material, which is applied as a lithium ion battery cathode material.
Therefore, the invention has the following beneficial effects:
(1) the method for preparing the antimony-based alloy/nitrogen-doped carbon composite porous material by the self-template method has the characteristics of cheap and easily-obtained raw materials, simple preparation process, relative environmental protection, high yield and easiness in industrial production. The cheese antimony-based alloy/nitrogen-doped carbon composite porous material prepared by the self-template method is prepared by a simple stirring synergistic low-temperature solid phase method, the raw materials mainly comprise acetate, chloride, citrate, urea, dicyandiamide and the like, the source is wide, the price is low, the template formed by reaction is easily soluble in water, and can be recycled repeatedly.
(2) When the antimony-based alloy/nitrogen-doped carbon composite porous material is used as a lithium ion battery cathode material, in the charging and discharging processes, the volume effect in the repeated circulation process can be reduced due to the synergistic enhancement of the characteristics of the porous structure and the nano structure. Secondly, the unique porous structure having many micropores and mesopores can generate more active sites, enabling close contact with an electrolyte, shortening an ion diffusion path and promoting rapid ion transport, resulting in an increase in rate; at the same time, the three-dimensional carbon framework provides a robust conductive network that facilitates improved electron transport and increased conductivity of the electrode. In addition, the high surface area in the unique structure promotes the existence of pseudocapacitance behavior in the charging/discharging process, and is beneficial to improving the rate capability of the material. Finally, antimony-based materials have higher theoretical capacities and higher operating voltages than commercial graphite. Therefore, when the cheese antimony-based alloy/nitrogen-doped carbon composite porous material prepared by the self-template method is used as the negative electrode material of the lithium ion battery, the safety of the battery is improved, higher specific capacity and rate capability and longer cycle life are achieved in the charging and discharging processes, and the assembled battery is far superior to common commercial graphite in electrochemical performance.
Drawings
FIG. 1 is an XRD pattern of the intermediate product of example 1;
FIG. 2 is an XRD pattern of a nickel-antimony alloy/nitrogen-doped carbon composite porous material (NS @ NPC), a cobalt-antimony alloy/nitrogen-doped carbon composite porous material (CS @ NPC), an iron-antimony alloy/nitrogen-doped carbon composite porous material (FS @ NPC) in examples 1-3;
FIG. 3 is an SEM photograph of a Ni-Sb alloy/N-doped carbon composite porous material (NS @ NPC) in example 1;
FIG. 4 is an SEM photograph of a cobalt antimony alloy/nitrogen doped carbon composite porous material (CS @ NPC) in example 2;
FIG. 5 is an SEM photograph of an Fe-Sb alloy/N-doped carbon composite porous material (FS @ NPC) in example 3;
in FIG. 6, a, b and c are respectively the nitrogen adsorption/desorption curves and the pore size distribution diagrams of the Ni-Sb alloy/N-doped carbon composite porous material (NS @ NPC), the Co-Sb alloy/N-doped carbon composite porous material (CS @ NPC) and the Fe-Sb alloy/N-doped carbon composite porous material (FS @ NPC) in examples 1 to 3;
fig. 7 shows the electrochemical cycling stability and rate capability of the batteries manufactured in examples 1-3 respectively by using the nickel-antimony alloy/nitrogen-doped carbon composite porous material (NS @ NPC), the cobalt-antimony alloy/nitrogen-doped carbon composite porous material (CS @ NPC), and the iron-antimony alloy/nitrogen-doped carbon composite porous material (FS @ NPC) as the negative electrode material of the lithium ion battery.
Detailed Description
The technical solution of the present invention will be further described with reference to the following embodiments.
It is to be understood that the described embodiments are merely a few embodiments of the invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
General examples
A method for preparing an antimony-based alloy/nitrogen-doped carbon composite porous material by a self-template method comprises the following steps:
a) adding metal soluble salt, an antimony source, citrate and a nitrogen source into a solvent, uniformly mixing, and drying to obtain a precursor; the solvent is one of water, mixed liquid of ethanol and water or mixed liquid of methanol and water, wherein when one of the mixed liquid of ethanol and water or the mixed liquid of methanol and water is adopted, the proportion of the mixed liquid is (1-2): 1, most preferably in a ratio of 1: 1; the antimony source is antimony trichloride or antimony acetate, the nitrogen source is at least one of urea, melamine or dicyandiamide, the metal soluble salt is one of ferric acetate, cobalt acetate, nickel acetate, copper acetate, zinc acetate, ferrous sulfate, cobalt sulfate, nickel sulfate, copper sulfate, zinc sulfate, ferric chloride, cobalt chloride, nickel chloride, cupric chloride, zinc chloride, ferric nitrate, cobalt nitrate, nickel nitrate, cupric nitrate or zinc nitrate
b) Carrying out heat treatment on the precursor under a protective atmosphere to obtain an intermediate product; the heat treatment temperature is 600-900 ℃, and the treatment time is 2-6 hours; the heating and cooling rate is 2-10 ℃/min, preferably, the heat treatment temperature is 700 ℃, and the treatment time is 3 hours; the heating and cooling rate is 5 ℃/min;
c) and washing the intermediate product with water or absolute ethyl alcohol, and drying after washing to obtain the antimony-based alloy/nitrogen-doped carbon composite porous material.
The antimony-based alloy/nitrogen-doped carbon composite porous material is prepared by the method for preparing the antimony-based alloy/nitrogen-doped carbon composite porous material by the self-template method.
The application of the antimony-based alloy/nitrogen-doped carbon composite porous material is used as an additive material of a lithium ion battery;
washing the cut copper sheet with dilute hydrochloric acid, washing the copper sheet with deionized water to be neutral, washing the copper sheet with ethanol twice, and air-drying the copper sheet at room temperature; mixing the antimony-based alloy/nitrogen-doped carbon composite porous material, CMC and acetylene black according to the proportion of (8-9): (1-0.5): (1-0.5) is prepared into slurry, the slurry is coated on a washed copper sheet, the copper sheet is dried for 24 hours in a vacuum oven at the temperature of 60-80 ℃, the pole piece is placed in a tablet press, the pole piece is pressed under the pressure of 6-10MPa, and 1M LiPF is used6And 1wt% FEC as additive EC/DEC/EMC (v/v/v =1:1:1) as electrolyte, Celgard 2340 as separator, in an argon glove box (H)2O＜0.01 ppm，O2< 0.01 ppm) was assembled into a battery.
Example 1
26.5 g of nickel acetate, 27 g of antimony trichloride, 150 g of sodium citrate and 30 g of dicyandiamide are dissolved in succession in 1.5 l of distilled water and, after stirring for 2 hours, the clear solution is stirred continuously at 80 ℃ until dry.
The obtained powder is mixed with N2Heating at 700 ℃ for 3 hours under an atmosphere. After cooling to room temperature, the obtained black sample was washed several times with hot water, and then dried in a vacuum oven at 80 ℃ for 12 hours to obtain a nickel-antimony alloy/nitrogen-doped carbon composite porous material (NS @ NPC).
Preparing the obtained nickel-antimony alloy/nitrogen-doped carbon composite porous material (NS @ NPC) with CMC and acetylene black into slurry according to a certain mass ratio (9: 0.5: 0.5), coating the slurry on a washed copper sheet, drying the copper sheet in a vacuum oven at 80 ℃ for 12 hours, putting the sheet in a tablet press, pressing the sheet under 8 MPa, and using 1M LiPF6And 1wt% FEC as additive EC/DEC/EMC (v/v/v =1:1:1) as electrolyte, Celgard 2340 as separator, in an argon glove box (H)2O＜0.01 ppm, O2＜0.01 ppm) was assembled into a battery.
Example 2
26.5 g of cobalt acetate, 27 g of antimony trichloride, 150 g of sodium citrate and 30 g of dicyandiamide are dissolved in succession in 1.5 l of distilled water and, after stirring for 2 hours, the clear solution is stirred continuously at 80 ℃ until dry.
The obtained powder is mixed with N2Heating at 700 ℃ for 3 hours under an atmosphere. After cooling to room temperature, the obtained black sample was washed several times with hot water, and then dried in a vacuum oven at 80 ℃ for 12 hours to obtain a cobalt antimony alloy/nitrogen doped carbon composite porous material (CS @ NPC).
Preparing the obtained cobalt-antimony alloy/nitrogen-doped carbon composite porous material (CS @ NPC) with CMC and acetylene black according to a certain mass ratio (8: 1:1) into slurry, coating the slurry on a washed copper sheet, drying the copper sheet in a vacuum oven at 80 ℃ for 12 hours, putting the sheet in a tablet press, pressing the sheet under 8 MPa, and using 1M LiPF6And 1wt% FEC as additive EC/DEC/EMC (v/v/v =1:1:1) as electrolyte, Celgard 2340 as separator, in an argon glove box (H)2O＜0.01 ppm，O2< 0.01 ppm) was assembled into a battery.
Example 3
26.5 g of ferrous acetate, 27 g of antimony trichloride, 150 g of sodium citrate and 30 g of dicyandiamide are dissolved in succession in 1.5 l of distilled water and, after stirring for 2 hours, the clear solution is stirred continuously at 80 ℃ until dry.
The obtained powder is mixed with N2Heating at 700 ℃ for 3 hours under an atmosphere. After cooling to room temperature, the obtained black sample was washed several times with hot water, and then dried in a vacuum oven at 80 ℃ for 12 hours to obtain an iron-antimony alloy/nitrogen-doped carbon composite porous material (FS @ NPC).
Preparing the obtained iron-antimony alloy/nitrogen-doped carbon composite porous material (FS @ NPC) into slurry by a certain mass ratio (8: 1:1) of CMC and acetylene black respectively, coating the slurry on a washed copper sheet, drying the copper sheet in a vacuum oven at the temperature of 80 ℃ for 12 hours, putting the sheet in a tablet press, pressing the sheet again under the pressure of 8 MPa, and using 1M LiPF6And 1wt% FEC as additive EC/DEC/EMC (v/v/v =1:1:1)Electrolyte, Celgard 2340 as separator, in argon glove box (H)2O＜0.01 ppm, O2< 0.01 ppm) was assembled into a battery.
Example 4
12.9 g of nickel chloride, 22.8 g of antimony trichloride, 100 g of potassium citrate and 50 g of melamine are dissolved in succession in 1.5 l of distilled water and, after stirring for 2 hours, the clear solution is left stirring at 80 ℃ until dry.
The obtained powder is mixed with N2Heating at 800 deg.C for 4 hours under an atmosphere. After cooling to room temperature, the resulting black sample was washed several times with hot water and then dried in a vacuum oven at 60 ℃ for 12 hours.
Preparing the obtained nickel-antimony alloy/nitrogen-doped carbon composite porous material into slurry with CMC and acetylene black according to a certain mass ratio (9: 0.5: 0.5), coating the slurry on a washed copper sheet, drying the copper sheet in a vacuum oven at 80 ℃ for 12 hours, putting the sheet in a tablet press, pressing the sheet again under 8 MPa, and using 1M LiPF6And 1wt% FEC as additive EC/DEC/EMC (v/v/v =1:1:1) as electrolyte, Celgard 2340 as separator, in an argon glove box (H)2O＜0.01 ppm，O2< 0.01 ppm) was assembled into a battery.
Example 5
12.9 g of copper chloride, 22.8 g of antimony trichloride, 100 g of potassium citrate and 50 g of melamine are dissolved in succession in 1.5 l of distilled water and, after stirring for 2 hours, the clear solution is left stirring at 80 ℃ until dry.
The obtained powder is mixed with N2Heating at 800 deg.C for 4 hours under an atmosphere. After cooling to room temperature, the resulting black sample was washed several times with hot water and then dried in a vacuum oven at 60 ℃ for 12 hours.
Preparing the obtained copper antimony alloy/nitrogen-doped carbon composite porous material into slurry with CMC and acetylene black according to a certain mass ratio (9: 0.5: 0.5), coating the slurry on a washed copper sheet, drying the copper sheet in a vacuum oven at 80 ℃ for 12 hours, putting the sheet in a tablet press, pressing the sheet again under 8 MPa, and using 1M LiPF6And 1wt% FEC as additive EC/DEC/EMC (v/v/v =1:1:1) as electrolyte Celgard 2340 as a diaphragm in an argon glove box (H)2O＜0.01 ppm，O2< 0.01 ppm) was assembled into a battery.
Example 6
12.9 g of zinc chloride, 22.8 g of antimony trichloride, 100 g of potassium citrate and 50 g of melamine are dissolved in succession in 1.5 l of distilled water and, after stirring for 2 hours, the clear solution is left stirring at 80 ℃ until dry.
The obtained powder is mixed with N2Heating at 800 deg.C for 4 hours under an atmosphere. After cooling to room temperature, the resulting black sample was washed several times with hot water and then dried in a vacuum oven at 60 ℃ for 12 hours.
Preparing the obtained zinc-antimony alloy/nitrogen-doped carbon composite porous material into slurry with CMC and acetylene black according to a certain mass ratio (9: 0.5: 0.5), coating the slurry on a washed copper sheet, drying the copper sheet in a vacuum oven at 80 ℃ for 12 hours, putting the sheet in a tablet press, pressing the sheet again under 8 MPa, and using 1M LiPF6And 1wt% FEC as additive EC/DEC/EMC (v/v/v =1:1:1) as electrolyte, Celgard 2340 as separator, in an argon glove box (H)2O＜0.01 ppm，O2< 0.01 ppm) was assembled into a battery.
Example 7
18.3 g of cobalt nitrate, 29.9 g of antimony acetate, 150 g of sodium citrate and 50 g of urea are dissolved in succession in 1.5 l of a mixture of distilled water and ethylene glycol and stirred for 2 hours, after which the clear solution is left stirring at 100 ℃ until dry.
The obtained powder is mixed with N2Heating at 800 deg.C for 6 hours under an atmosphere. After cooling to room temperature, the resulting black sample was washed several times with hot water and then dried in a vacuum oven at 80 ℃ for 12 hours.
Preparing the obtained cobalt-antimony alloy/nitrogen-doped carbon composite porous material with CMC and acetylene black according to a certain mass ratio (8: 1:1) into slurry, coating the slurry on a washed copper sheet, drying the copper sheet in a vacuum oven at 80 ℃ for 12 hours, putting the sheet in a tablet press, re-pressing the sheet under 8 MPa, and using 1M LiPF6And 1wt% FEC as additive EC/DEC/EMC (v/v/v =1:1:1) as electrolyte, Celgard 2340 as a diaphragm in an argon glove box (H)2O＜0.01 ppm，O2< 0.01 ppm) was assembled into a battery.
Example 8
18.3 g of zinc nitrate, 29.9 g of antimony acetate, 150 g of sodium citrate and 50 g of urea are dissolved in succession in 1.5 l of a mixture of distilled water and ethylene glycol and stirred for 2 hours, after which the clear solution is left stirring at 100 ℃ until dry.
The obtained powder is mixed with N2Heating at 800 deg.C for 6 hours under an atmosphere. After cooling to room temperature, the resulting black sample was washed several times with hot water and then dried in a vacuum oven at 80 ℃ for 12 hours.
Preparing the obtained zinc-antimony alloy/nitrogen-doped carbon composite porous material with CMC and acetylene black according to a certain mass ratio (8: 1:1) into slurry, coating the slurry on a washed copper sheet, drying the copper sheet in a vacuum oven at 80 ℃ for 12 hours, putting the sheet in a tablet press, re-pressing the sheet under 8 MPa, and using 1M LiPF6And 1wt% FEC as additive EC/DEC/EMC (v/v/v =1:1:1) as electrolyte, Celgard 2340 as separator, in an argon glove box (H)2O＜0.01 ppm，O2< 0.01 ppm) was assembled into a battery.
Example 9
18.3 g of copper nitrate, 29.9 g of antimony acetate, 150 g of sodium citrate and 50 g of urea are dissolved in succession in 1.5 l of a mixture of distilled water and ethylene glycol and stirred for 2 hours, after which the clear solution is left stirring at 100 ℃ until dry.
The obtained powder is mixed with N2Heating at 800 deg.C for 6 hours under an atmosphere. After cooling to room temperature, the resulting black sample was washed several times with hot water and then dried in a vacuum oven at 80 ℃ for 12 hours.
Preparing the obtained copper antimony alloy/nitrogen-doped carbon composite porous material with CMC and acetylene black according to a certain mass ratio (8: 1:1) into slurry, coating the slurry on a washed copper sheet, drying the copper sheet in a vacuum oven at 80 ℃ for 12 hours, putting the sheet in a tablet press, re-pressing the sheet under 8 MPa, and using 1M LiPF6And EC/DEC/EMC (v/v/v =1:1:1) with 1wt% FEC as an additive as an electrolyte,celgard 2340 as septum in argon glove box (H)2O＜0.01 ppm，O2< 0.01 ppm) was assembled into a battery.
And (3) performance testing:
for the batteries assembled and manufactured in the above embodiments 1 to 3, the electrochemical workstation is respectively adopted to test the CV curve and the impedance, and the blue test system is adopted to test the relevant electrochemical performances of the battery, such as the capacity-voltage curve, the cycling stability, the rate capability, the specific capacity, the capacity retention rate and the like. The voltage range is 0.01-3V. The specific capacity and rate capability of the battery under low current density and high current density are superior to the theoretical capacity of graphite, and the battery shows good electrochemical performance.
And (3) testing results:
the intermediate product of example 1 is shown in FIG. 1 to compound the requirements of the present invention; the XRD patterns in fig. 2 show that the finally obtained materials in examples 1-3 are the corresponding antimony-based alloy/nitrogen-doped carbon composite porous materials.
FIGS. 3-5 show typical SEM images of NS @ NPC, CS @ NPC and FS @ NPC composites, respectively, in which NiSb, CoSb and FeSb nanoparticles are all distributed in a Swiss cheese-like porous nitrogen-doped carbon skeleton.
N of NS @ NPC, CS @ NPC and FS @ NPC in FIG. 62The adsorption/desorption isotherms can all be classified as type IV isotherms with H2 hysteresis loops, indicating that they have a mesoporous structure (fig. 6a, 6b and 6 c). All samples exhibited similar adsorption characteristics over a low relative pressure range, indicating the presence of a high density of micropores in the samples. The pore size distribution curves in the inset show pore sizes in the range of 1-40 nm. The specific surface areas of NS @ NPC, CS @ NPC and FS @ NPC are calculated according to the Brunauer-Emmett-Teller method and are respectively as high as 804 m, 940 m and 883 m2·g-1。
FIG. 7a shows the current density at 0.2A g-1Time NS @ NPC, CS @ NPC and FS @ NPC electrodes. At 0.2 A.g-1After the next 200 cycles, NS @ NPC, CS @ NPC and FS @ NPC electrodes can maintain high reversible capacity up to 989, 1486 and 1296 mAh g-1. FIG. 7b shows the rate behavior of NS @ NPC, CS @ NPC and FS @ NPC electrodes at different current densitiesCan be used. At current densities of 0.1, 0.2, 0.5, 1, 2, 5 and 10 A.g-1The average discharge capacity of the NS @ NPC composite material was 1111, 887, 656, 563, 440, 347 and 261 mAh g-1. For CS @ NPC electrodes, at 0.1, 0.2, 0.5, 1, 2, 5 and 10A · g-1Average discharge capacities at current densities of 1214, 1016, 835, 701, 589, 458 and 343 mAh g-1Whereas FS @ NPC electrodes showed 1096, 858, 685, 581, 496, 393, and 296 mAh · g, respectively, at the corresponding current densities-1The rate capability of (2). These cycle and rate properties are superior to existing antimony-based alloys.
It will be understood that modifications and variations can be made by persons skilled in the art in light of the above teachings and all such modifications and variations are intended to be included within the scope of the invention as defined in the appended claims.

Claims (10)

1. A method for preparing an antimony-based alloy/nitrogen-doped carbon composite porous material by a self-template method is characterized by comprising the following steps:
a) adding metal soluble salt, an antimony source, citrate and a nitrogen source into a solvent, uniformly mixing, and drying to obtain a precursor;
b) carrying out heat treatment on the precursor under a protective atmosphere to obtain an intermediate product;
c) and washing the intermediate product with water or absolute ethyl alcohol, and drying after washing to obtain the antimony-based alloy/nitrogen-doped carbon composite porous material.
2. The method for preparing the antimony-based alloy/nitrogen-doped carbon composite porous material by the self-template method according to claim 1, wherein the method comprises the following steps: the solvent is one of water, mixed liquid of ethanol and water or mixed liquid of methanol and water.
3. The method for preparing the antimony-based alloy/nitrogen-doped carbon composite porous material by the self-template method according to claim 1, wherein the method comprises the following steps: the antimony source is antimony trichloride or antimony acetate.
4. The method for preparing the antimony-based alloy/nitrogen-doped carbon composite porous material by the self-template method according to claim 1, wherein the method comprises the following steps: the nitrogen source is at least one of urea, melamine or dicyandiamide.
5. The method for preparing the antimony-based alloy/nitrogen-doped carbon composite porous material by the self-template method according to claim 1, wherein the method comprises the following steps: the metal soluble salt is one of ferrous salt, ferric salt, cobalt salt, nickel salt, copper salt or zinc salt.
6. The method for preparing the antimony-based alloy/nitrogen-doped carbon composite porous material by the self-template method according to claim 1 or 5, wherein the method comprises the following steps: the metal soluble salt is one of iron acetate, cobalt acetate, nickel acetate, copper acetate, zinc acetate, ferrous sulfate, cobalt sulfate, nickel sulfate, copper sulfate, zinc sulfate, ferric chloride, cobalt chloride, nickel chloride, copper chloride, zinc chloride, ferric nitrate, cobalt nitrate, nickel nitrate, copper nitrate or zinc nitrate.
7. The method for preparing the antimony-based alloy/nitrogen-doped carbon composite porous material by the self-template method according to claim 1, wherein the method comprises the following steps: in the step b), the heat treatment temperature is 600-; the heating and cooling rate is 2-10 deg.C/min.
8. The method for preparing the antimony-based alloy/nitrogen-doped carbon composite porous material by the self-template method according to claim 1 or 7, wherein the method comprises the following steps: in the step b), the heat treatment temperature is 700 ℃, and the treatment time is 3 hours; the heating and cooling rates are 5 ℃/min.
9. An antimony-based alloy/nitrogen-doped carbon composite porous material produced by the method of any one of claims 1 to 8.
10. Use of the antimony-based alloy/nitrogen-doped carbon composite porous material according to claim 9 as a negative electrode material of a lithium ion battery.
CN202011409759.7A 2020-12-04 2020-12-04 Method for preparing antimony-based alloy/nitrogen-doped carbon composite porous material by self-template method, composite porous material and application Pending CN112768646A (en)

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