CN116254624A - Porous transition metal-based composite fiber membrane, and in-situ preparation method and application thereof - Google Patents

Porous transition metal-based composite fiber membrane, and in-situ preparation method and application thereof Download PDF

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CN116254624A
CN116254624A CN202310182134.9A CN202310182134A CN116254624A CN 116254624 A CN116254624 A CN 116254624A CN 202310182134 A CN202310182134 A CN 202310182134A CN 116254624 A CN116254624 A CN 116254624A
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transition metal
fiber membrane
based composite
porous transition
porous
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周丹
陈鸿明
刘睿奇
李琰
刘焕明
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University of Science and Technology Beijing USTB
Shunde Innovation School of University of Science and Technology Beijing
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University of Science and Technology Beijing USTB
Shunde Innovation School of University of Science and Technology Beijing
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    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
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Abstract

The invention discloses a porous transition metal-based composite fiber membrane, and an in-situ preparation method and application thereof, and belongs to the field of electrode materials. The invention prepares the carbonizable organic material and the transition metal basic carbonate in a solvent to obtain an electrostatic spinning precursor solution, then performs electrostatic spinning to obtain precursor fibers, and finally performs stabilization and carbonization treatment to obtain the porous transition metal-based composite fiber membrane. The preparation process of the invention is simple, and the in-situ pore-forming around the transition metal oxide can be realized without independently introducing pore-forming agents. When the material is used as an electrode material, the pores formed around the transition metal oxide reserve enough space for ion exchange, so that the volume expansion of the battery in the use process can be effectively avoided, and the battery has high storage capacity and excellent cycle life; meanwhile, the method has the advantages of good conductivity, more active reaction sites, short ion transmission distance, more ion transmission channels and the like.

Description

Porous transition metal-based composite fiber membrane, and in-situ preparation method and application thereof
Technical Field
The invention relates to the field of electrode materials, in particular to a porous transition metal-based composite fiber membrane, and an in-situ preparation method and application thereof.
Background
In recent decades, the development of battery energy storage technology has gained tremendous leap thanks to the advancement of materials. Advanced energy storage batteries represented by lithium ion batteries are widely used in the fields of national economy, military and the like, such as portable electronic equipment, electric automobiles and the like. In addition, in order to meet challenges of lithium resource exhaustion, lithium price rising and the like faced by lithium ion batteries in the future, some novel energy storage battery technologies with similar working principles, such as sodium ion batteries, potassium ion batteries and the like, are also continuously developed and applied.
In order to effectively improve the electrochemical storage performance of the battery and enable the electrochemical storage performance to meet the practical application requirements, the development of advanced electrode materials is an important link. The transition metal-based electrode material has good application prospects in lithium ion batteries, sodium ion batteries and potassium ion batteries by a series of unique physical and chemical characteristics, such as rich reactive sites, relatively high conductivity, stable thermal/mechanical properties, low cost and the like (Journal of Materials Chemistry A,2018,6,2139;Chemical Engineering Journal,2021,413,127508). However, the transition metal-based electrode material often faces problems such as volume expansion during battery cycling, and structural instability of the material is easily induced, thereby resulting in low storage capacity and cycle life of the battery.
To effectively enhance the electrochemical storage performance of transition metal-based electrode materials, various approaches have been adopted (Journal of Materials Chemistry A,2018,6,2139;Chemical Engineering Journal,2021,413,127508). Firstly, the physical size of the material is reduced, and further, the damage to the structural stability caused by volume expansion can be properly reduced. In addition, the transmission path of ions in the battery can be greatly shortened; and secondly, adopting a design thought of space limitation. Typically, the transition metal-based particles are coated or embedded in a relatively rigid matrix material (e.g., a carbonaceous material) whose volume expansion will be limited. In particular, the adoption of the carbonaceous material can also effectively improve the conductivity of the electrode material and greatly improve the ion transmission efficiency of the electrode material. On the basis of the above, the design of porous structures is often used in combination, and the application is very common. On one hand, a proper volume expansion space can be reserved, so that the stability of the structure is ensured; on the other hand, a shortened ion transmission path, rich ion transmission channels and active reaction sites can be realized, so that the storage capacity and the transmission dynamics performance of the electrode material can be effectively improved.
Based on the design thought, people often combine the transition metal-based electrode material with the carbon-based material to prepare the porous composite material. However, in the current preparation research, the porous composite material is often achieved by multi-step reaction, and the porous structure is prepared by a method of independently introducing the pore-forming agent, so that the whole preparation process is relatively complex, and the preparation cost is relatively high. At present, efficient and simple preparation methods and processes still relatively remain to be further developed, so that the capacity, the cycle life and the like of the transition metal-based electrode material still have room for further improvement.
Disclosure of Invention
The invention aims at: aiming at the problems of the prior lithium ion battery, sodium ion battery, lithium ion battery and other ion batteries, the invention provides a porous transition metal-based composite fiber membrane, and an in-situ preparation method and application thereof.
The technical scheme of the invention comprises three aspects of a porous transition metal-based composite fiber membrane, an in-situ preparation method and application thereof, and the specific technical scheme is as follows:
in a first aspect, the present invention provides a method for in situ preparation of a porous transition metal-based composite fiber membrane, comprising the steps of:
s1, taking carbonizable organic materials and transition metal basic carbonate as raw materials, dissolving the raw materials in an organic solvent according to a ratio of 1:0.2-1:2, and stirring to obtain a precursor solution which is uniformly mixed;
s2, transferring the precursor solution obtained in the step S1 into a syringe, and then placing the syringe into an electrostatic spinning machine for electrostatic spinning to obtain precursor fibers;
and S3, stabilizing and carbonizing the precursor fiber obtained in the step S2, so that the porous transition metal oxide/carbon fiber membrane can be obtained in situ.
Further, the carbonizable organic material in S1 is polyacrylonitrile.
Further, the transition metal basic carbonate in S1 is at least one of basic cobalt carbonate, basic nickel carbonate, basic zinc carbonate, basic copper carbonate, and basic iron carbonate.
The organic solvent in S1 is at least one of N, N-Dimethylformamide (DMF), acetone and tetrahydrofuran.
Further, the stirring time in the step S1 is 0.5-240h, and the temperature is 20-80 ℃.
Further, the parameters of the electrostatic spinning in the above step S2 are: spinning voltage: 5-35 kilovolts, spinning distance of 5-30cm, spinning speed: spinning temperature of 0.1-3 ml/hr: 15-40 ℃, spinning humidity: 20-80% relative humidity.
Further, the temperature of the stabilizing treatment in the step S3 is 100-300 ℃, the time is 0.5-5 hours, the temperature rising rate is 0.1-20 ℃/min, and the stabilizing atmosphere is air; the carbonization treatment device is a tube furnace, the carbonization temperature is 500-1200 ℃, the carbonization time is 0.5-20 hours, the carbonization heating rate is 0.1-20 ℃/min, and the carbonization atmosphere is argon or nitrogen.
Further, the in-situ preparation method of the porous transition metal-based composite fiber membrane further comprises the following steps: and (3) carrying out a vulcanization reaction on the porous transition metal oxide/carbon fiber membrane obtained in the step (S3) to obtain the porous transition metal sulfide/carbon fiber membrane in situ.
Further, the in-situ preparation method of the porous transition metal-based composite fiber membrane further comprises the following steps: and (3) carrying out selenizing reaction on the porous transition metal oxide/carbon fiber membrane obtained in the step (S3) to obtain the porous transition metal selenide/carbon fiber membrane in situ.
Further, the in-situ preparation method of the porous transition metal-based composite fiber membrane further comprises the following steps: and (3) carrying out a phosphating reaction on the porous transition metal oxide/carbon fiber film obtained in the step (S3) to obtain the porous transition metal phosphide/carbon fiber film in situ.
In a second aspect, the present invention provides a porous transition metal-based composite fiber membrane, prepared by the above-mentioned in-situ preparation method, wherein the diameter of the fibers in the porous transition metal-based composite fiber membrane is between 50nm and 5 μm, the pore size distribution is between 1 nm and 200 nm, and the specific surface area is between 10 and 200 square meters per gram.
In a third aspect, the present invention provides the use of a porous transition metal based composite fibre membrane which can be used directly as a flexible, self-supporting, binder-free electrode material.
Further, the porous transition metal-based composite fiber membrane may be used for preparing an electrode by a method of grinding, preparing an electrode slurry, and coating a sheet on a current collector.
Compared with the prior art, the invention has the beneficial effects that:
the main mechanism of the technical scheme of the invention is that the transition metal basic carbonate in the precursor is heated and decomposed into transition metal oxide, carbon dioxide and water vapor in the stabilization and carbonization treatment stages, so that uniformly distributed pores are formed around the transition metal oxide, and the transition metal oxide/carbon fiber film with a porous structure is formed in situ, so that a pore-forming agent is not required to be independently used, the preparation method is simple and efficient, and the preparation method can be synthesized in a large scale and has certain advantages in practical production and application. The porous fiber membrane can also be subjected to further processes such as sulfuration, selenization, phosphatization and the like to respectively react in situ to form electrode materials such as a porous transition metal sulfide/carbon fiber membrane, a porous transition metal selenide/carbon fiber membrane, a porous transition metal phosphide/carbon fiber membrane and the like. In addition, the porous transition metal-based composite fiber membrane can be directly used as a flexible, self-supporting and binder-free electrode material when the battery is assembled, and can also be used for preparing an electrode by a method of grinding, preparing electrode slurry and coating a sheet on a current collector. Suitable battery systems for the porous structured composite fibers include lithium ion batteries, sodium ion batteries, potassium ion batteries, and the like. When the material is used as an electrode material, due to the pores formed around the transition metal-based compound, enough space is reserved for ion exchange, and the volume expansion of the battery in the use process can be effectively avoided, so that the battery has high storage capacity and excellent cycle life. Meanwhile, the method has the advantages of good conductivity, more active reaction sites, short ion transmission distance, more ion transmission channels and the like.
Drawings
FIG. 1 is a photograph of a porous cobalt sulfide/carbon fiber membrane prepared in a flat state (a) and in a curved state (b);
FIG. 2 is an SEM image of the porous cobalt sulfide/carbon fiber membrane produced;
FIG. 3 is a graph of the cycling performance of the prepared porous cobalt sulfide/carbon fiber membrane at a current density of 200 milliamp/gram;
fig. 4 is a graph of the cycling performance of the prepared porous cobalt sulfide/carbon fiber membrane at a current density of 1000 milliamp/gram.
Detailed Description
It is noted that relational terms such as "first" and "second", and the like, are used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Moreover, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising one … …" does not exclude the presence of other like elements in a process, method, article, or apparatus that comprises the element.
The features and capabilities of the present invention are described in further detail below in connection with examples.
Example 1
S1, dissolving 0.8g of polyacrylonitrile and 0.8g of basic cobalt carbonate in 8ml of N, N-dimethylformamide solution, stirring to obtain a uniform electrostatic spinning precursor solution, wherein the stirring time is 10 hours, and the temperature is 25 ℃;
s2, transferring the electrostatic spinning precursor solution obtained in the step S1 into a 10mL injector, installing the injector in electrostatic spinning equipment, and carrying out electrostatic spinning, wherein the obtained product is a flexible precursor fiber film, the spinning voltage is 12kV, the spinning distance is 15cm, the spinning speed is 1.2mL/h, the spinning temperature is 25 ℃, and the spinning humidity is 45% relative humidity;
s3, stabilizing and carbonizing the precursor fiber membrane to obtain a porous cobalt oxide/carbon fiber membrane in situ, wherein the stabilizing treatment is to sinter the precursor fiber membrane to 250 ℃ in a muffle furnace at a heating rate of 5 ℃/min, and preserving the heat for 1 hour; sintering atmosphere: air. The carbonization treatment is that sintering is carried out in a tube furnace to 600 ℃ at a heating rate of 5 ℃/min, and the heat is preserved for 2 hours; sintering atmosphere: argon gas.
The diameter of the fiber in the obtained porous cobalt oxide/carbon fiber membrane is concentrated between 200 and 400nm, the pore diameter is distributed between 1 and 100nm, and the specific surface area is about 25 square meters/gram.
Cutting the porous cobalt oxide/carbon fiber film obtained in the step S3 into strips, and mixing the strips with sublimed sulfur powder according to the following ratio of 1:5, respectively placing the materials in an upper air port and a lower air port of a tube furnace, and performing heat treatment at 600 ℃ for 2 hours at a heating rate of 5 ℃/min; and (3) carrying out vulcanization reaction in the presence of argon gas to obtain the porous cobalt sulfide/carbon fiber membrane.
The pictures of the porous cobalt sulfide/carbon fiber film in the flat state and the curved state are shown in (a) and (b) in fig. 1, respectively, and the pictures under a scanning electron microscope are shown in fig. 2.
The obtained porous cobalt sulfide/carbon fiber film is cut into a circular sheet with the diameter of 12mm and is directly used as a flexible, self-supporting and adhesive-free electrode, and the mass of a single electrode sheet is between 2.5 and 3.0 milligrams. Sodium metal is used as a reference electrode/counter electrode, glass fiber is used as a diaphragm, and electrolyte is NaClO of 1 mol/L 4 The solution (the solvent is polycarbonate, and 5% of fluoroethylene carbonate (FEC) by volume fraction is contained). The CR2032 type button sodium ion battery was assembled in an argon-filled glove box. The test voltage ranges from 0.01V to 3.0V, and the test current density is 200 mA/g and 1000 mA/g. The porous cobalt sulfide/carbon nanofiber membrane electrode has good cycle performance, and after 300 times and 1600 times of electrode cycle, the electrode still has discharge capacities of 181.8 milliampere hours/gram and 141.4 milliampere hours/gram.
The performance graphs of the porous cobalt sulfide/carbon fiber membrane at current densities of 200 and 1000 milliamp/gram for 300 and 1600 cycles, respectively, are shown in fig. 3 and 4.
Example 2
S1, dissolving 1.0g of polyacrylonitrile and 0.2g of basic nickel carbonate in 10ml of N, N-dimethylformamide solution to obtain uniform electrostatic spinning precursor solution;
s2, transferring the electrostatic spinning precursor solution obtained in the step S1 into a 20ml injector, installing the injector in electrostatic spinning equipment, and carrying out electrostatic spinning to obtain a flexible precursor fiber film, wherein the spinning voltage is as follows: 15kV, the spinning distance is: 5cm, the spinning rate is: 0.1mL/h, spinning temperature is 15 ℃, spinning humidity: 80% relative humidity;
s3, performing stabilization treatment and carbonization treatment on the precursor fiber membrane to obtain a porous nickel oxide/carbon fiber membrane in situ, wherein the stabilization treatment is to sinter the precursor fiber membrane to 100 ℃ in a muffle furnace at a heating rate of 0.1 ℃/min, and preserving the heat for 20 hours; sintering atmosphere: the air is sintered to 500 ℃ in a tube furnace at a heating rate of 0.1 ℃/min, and the carbonization treatment is carried out for 20 hours; sintering atmosphere: argon gas.
The fiber diameter of the obtained porous nickel oxide/carbon fiber membrane is concentrated between 200 and 400nm, the pore diameter is distributed between 1 and 100nm, and the specific surface area is about 15 square meters/gram.
Cutting the obtained porous nickel oxide/carbon nano film into strips, and mixing the strips with selenium powder according to the following ratio of 1:5, respectively placing the materials in an upper air port and a lower air port of a tube furnace, and performing heat treatment at 600 ℃ for 2 hours at a heating rate of 5 ℃/min; and (3) carrying out selenizing reaction in the presence of argon in the atmosphere to obtain the porous nickel selenide/carbon fiber membrane in situ.
The obtained porous nickel selenide/carbon fiber film is cut into a circular sheet with the diameter of 12mm, and is directly used as a flexible, self-supporting and adhesive-free electrode, and the mass of a single electrode sheet is between 2.5 and 3.0 milligrams. Potassium metal is used as reference electrode/counter electrode, glass fiber diaphragm is adopted, and the electrolyte is KPF of 0.8 mol/L 6 Solution (EC and DEC mixed solution with solvent of 1:1 volume ratio). The CR2032 type button potassium ion battery was assembled in a glove box filled with argon. The test voltage range is 0.01-3.0V and the test current density is 1000 mA/g. The porous nickel oxide/carbon fiber membrane electrode has good cycling stability and still has discharge capacity of more than 100 milliampere hours/gram after 1000 times of cycling.
Example 3
S1, dissolving 0.5g of polyacrylonitrile and 1g of basic copper carbonate in 5ml of N, N-dimethylformamide solution to obtain uniform electrostatic spinning precursor solution;
s2, transferring the electrostatic spinning precursor solution obtained in the step S1 into a 10ml syringe, installing the syringe in electrostatic spinning equipment, and carrying out electrostatic spinning to obtain a flexible fibril film. The spinning voltage is 35kV, the spinning distance is 30cm, the spinning speed is 3mL/h, the spinning temperature is 40 ℃, and the spinning humidity is 20% relative humidity;
s3, stabilizing and carbonizing the precursor fiber membrane to obtain a porous copper oxide/carbon fiber membrane in situ, wherein the stabilizing treatment is to sinter the precursor fiber membrane to 300 ℃ in a muffle furnace at a heating rate of 20 ℃/min, and preserving the heat for 0.1 hour; sintering atmosphere: the air is sintered to 1200 ℃ in a tube furnace at a heating rate of 20 ℃/min, and the temperature is kept for 0.1 hour; sintering atmosphere: argon gas.
The diameter of the fiber in the obtained porous copper oxide/carbon fiber film is concentrated between 200 and 400nm, the pore diameter is distributed between 1 and 100nm, and the specific surface area is about 15 square meters per gram.
The resulting porous copper oxide/carbon fiber film was cut into wafers of 12mm diameter and used directly as a flexible, self-supporting, binder-free electrode with individual electrode plates having a mass of between 2.5 and 3.0 milligrams. Lithium metal is used as a reference electrode/counter electrode, celgard 2400 type diaphragm is adopted, and electrolyte is LiPF with the concentration of 1 mol/liter 6 Solution (EC, DEC, DMC mixed solution with solvent of 1:1:1 volume ratio). The CR2032 type button lithium ion battery was assembled in an argon-filled glove box. The test voltage range is 0.01-3.0V and the test current density is 1000 mA/g. The porous cobalt oxide/carbon nanofiber membrane electrode has good cycling stability and still has a discharge capacity of more than about 120 milliampere hours/gram after 1000 times of cycling.
Comparative example 1
S1, 0.8g of polyacrylonitrile, 0.8g of basic cobalt carbonate and 0.2g of nano SiO 2 Dissolving in 8ml of N, N-dimethylformamide solution, stirring to obtain uniform static electricitySpinning the precursor solution, wherein the stirring time is 1h, and the temperature is 45 ℃;
s2, transferring the electrostatic spinning precursor solution obtained in the step S1 into a 10mL injector, installing the injector in electrostatic spinning equipment, and carrying out electrostatic spinning, wherein the obtained product is a flexible precursor fiber film, the spinning voltage is 15kV, the spinning distance is 15cm, the spinning speed is 1.2mL/h, the spinning temperature is 25 ℃, and the spinning humidity is 45% relative humidity;
s3, stabilizing and carbonizing the precursor fiber membrane to obtain a porous cobalt oxide/carbon fiber membrane in situ, wherein the stabilizing treatment is to sinter the precursor fiber membrane to 250 ℃ in a muffle furnace at a heating rate of 5 ℃/min, and preserving the heat for 1 hour; sintering atmosphere: air. The carbonization treatment is that sintering is carried out in a tube furnace to 500 ℃ at a heating rate of 5 ℃/min, and the heat is preserved for 2 hours; sintering atmosphere: argon gas.
Performing acid etching treatment on the cobalt oxide/carbon fiber film obtained in the step S3 by using an HF solution with the concentration of 40% to remove SiO 2 And finally, washing with deionized water and drying. Cutting the dried porous cobalt oxide/carbon fiber film into strips, and mixing the strips with sublimed sulfur powder according to the following ratio of 1: and 5, respectively placing the materials in an upper air port and a lower air port of a tubular furnace, performing heat treatment at 600 ℃ for 2 hours (the heating rate is 5 ℃/min; the atmosphere is argon), and performing vulcanization reaction to obtain the porous cobalt sulfide/carbon fiber membrane in situ.
The obtained porous cobalt sulfide/carbon fiber film is cut into a circular sheet with the diameter of 12mm and is directly used as a flexible, self-supporting and adhesive-free electrode, and the mass of a single electrode sheet is between 2.5 and 3.0 milligrams. Sodium metal is used as a reference electrode/counter electrode, glass fiber is used as a diaphragm, and electrolyte is NaClO of 1 mol/L 4 The solution (the solvent is polycarbonate, and 5% of fluoroethylene carbonate (FEC) by volume fraction is contained). The CR2032 type button sodium ion battery was assembled in an argon-filled glove box. The test voltage ranges from 0.01V to 3.0V, and the test current density is 200 mA/g and 1000 mA/g. The porous cobalt sulfide/carbon nanofiber membrane electrode had good cycling performance, and after 300 and 1600 cycles of the electrode, respectively, had a discharge capacity of about 120 milliamp hours/gram and about 90 milliamp hours/gram.
From examples 1-3 and comparative example 1, examples 1-3 employed basic carbonate as the pore former to effect in situ pore formation around the transition metal oxide; while comparative example 1 is incorporating nano SiO 2 As a pore former, the pores formed are uniformly distributed throughout the matrix, but not necessarily around the transition metal oxide, and the carbon fiber may undergo significant expansion when used as an electrode material for an ion exchange type battery. Therefore, compared with the prior art, the technical scheme of the invention realizes in-situ pore-forming around the transition metal oxide, can obviously prolong the service life of the ion exchange battery and can also obviously improve the discharge capacity of the battery.
Example 4
S1, dissolving 1.0g of polyacrylonitrile and 1.0g of basic cobalt carbonate in 10ml of N, N-dimethylformamide solution to obtain uniform electrostatic spinning precursor solution;
s2, transferring the electrostatic spinning precursor solution obtained in the step S1 into a 20ml injector, and installing the injector in electrostatic spinning equipment to perform electrostatic spinning, wherein the spinning voltage is as follows: 15kV, the spinning distance is: 15cm, the spinning rate is: 1.2mL/h. The product obtained is a flexible fibril film;
s3, stabilizing and carbonizing the precursor fiber membrane to obtain a porous cobalt oxide/carbon fiber membrane in situ, wherein the stabilizing treatment is to sinter the precursor fiber membrane to 250 ℃ in a muffle furnace at a heating rate of 5 ℃/min, and preserving the temperature for 1 hour, the sintering atmosphere is air, and the carbonizing treatment is to sinter the precursor fiber membrane to 600 ℃ in a tubular furnace at a heating rate of 5 ℃/min, and preserving the temperature for 2 hours, wherein the sintering atmosphere is as follows: argon gas.
Cutting the obtained porous cobalt oxide/carbon nanofiber membrane into strips, and mixing the strips with sodium hypophosphite according to the following ratio of 1:10, respectively placing the materials in an upper air port and a lower air port of a tubular furnace, performing heat treatment at a temperature of 350 ℃ for 2 hours (the heating rate is 3 ℃ per minute; the atmosphere is argon), and performing a phosphating reaction to obtain a porous cobalt phosphide/carbon fiber film in situ; grinding the obtained porous cobalt phosphide/carbon fiber membrane, fully mixing the porous cobalt phosphide/carbon fiber membrane with conductive carbon black and PVDF according to the mass ratio of 8:1:1, and preparing electrode slurry by taking NMP as a solvent. Along with itThen, the electrode paste was coated on a copper foil having a diameter of 12mm, and dried to obtain an electrode sheet. The quality of the active material of the single electrode slice is controlled between 0.8 mg/square centimeter and 1.0 mg/square centimeter. Sodium metal is used as a reference electrode/counter electrode, a glass fiber diaphragm is adopted, and the electrolyte is NaClO of 1 mol/L 4 The solution (the solvent is polycarbonate, and 5% of fluoroethylene carbonate (FEC) by volume fraction is contained). The CR2032 type button sodium ion battery was assembled in an argon-filled glove box. The test voltage range is 0.01-3.0V and the test current density is 1000 mA/g. The porous cobalt phosphide/carbon nanofiber electrode has good cycling stability and still has a discharge capacity of about 300 milliampere hours/gram or more after 1000 times of cycling.
The foregoing examples merely represent specific embodiments of the present application, which are described in more detail and are not to be construed as limiting the scope of the present application. It should be noted that, for those skilled in the art, several variations and modifications can be made without departing from the technical solution of the present application, which fall within the protection scope of the present application.

Claims (10)

1. The in-situ preparation method of the porous transition metal-based composite fiber membrane is characterized by comprising the following steps of:
s1, dissolving a carbonizable organic material and a transition metal basic carbonate serving as raw materials in an organic solvent according to a ratio of 1:0.2-1:2, and stirring to obtain a precursor solution which is uniformly mixed;
s2, transferring the precursor solution obtained in the step S1 into a syringe, and then placing the syringe into an electrostatic spinning machine for electrostatic spinning to obtain precursor fibers;
and S3, stabilizing and carbonizing the precursor fiber obtained in the step S2, so that the porous transition metal oxide/carbon fiber membrane can be obtained in situ.
2. The method for in-situ preparation of a porous transition metal based composite fiber membrane according to claim 1, wherein the carbonizable organic material in S1 is polyacrylonitrile.
3. The method for in situ preparation of a porous transition metal based composite fiber membrane according to claim 1, wherein the transition metal basic carbonate in S1 is at least one of basic cobalt carbonate, basic nickel carbonate, basic zinc carbonate, basic copper carbonate, basic iron carbonate.
4. The method for in-situ preparation of a porous transition metal based composite fiber membrane according to claim 1, wherein the organic solvent in S1 is at least one of N, N-Dimethylformamide (DMF), acetone, and tetrahydrofuran.
5. The method for in situ preparation of a porous transition metal based composite fiber membrane according to any one of claims 1-4, further comprising: and (3) carrying out a vulcanization reaction on the porous transition metal oxide/carbon fiber membrane obtained in the step (S3) to obtain the porous transition metal sulfide/carbon fiber membrane in situ.
6. The method for in situ preparation of a porous transition metal based composite fiber membrane according to any one of claims 1-4, further comprising: and (3) carrying out selenizing reaction on the porous transition metal oxide/carbon fiber membrane obtained in the step (S3) to obtain the porous transition metal selenide/carbon fiber membrane in situ.
7. The method for in situ preparation of a porous transition metal based composite fiber membrane according to any one of claims 1-4, further comprising: and (3) carrying out a phosphating reaction on the porous transition metal oxide/carbon fiber film obtained in the step (S3) to obtain the porous transition metal phosphide/carbon fiber film in situ.
8. A porous transition metal based composite fibre membrane, characterized in that it is produced by the in situ preparation method according to any one of claims 1-7, wherein the fibres in the porous transition metal based composite fibre membrane have a diameter between 50nm and 5 μm, a pore size distribution between 1 nm and 200 nm and a specific surface area between 10 and 200 square meters per gram.
9. Use of a porous transition metal based composite fiber membrane according to claim 8 as a flexible, self-supporting, binder-free electrode material.
10. The use of a porous transition metal based composite fiber membrane according to claim 9, wherein the porous transition metal based composite fiber membrane is used for preparing an electrode by grinding, preparing an electrode slurry, and coating a current collector.
CN202310182134.9A 2023-02-20 2023-02-20 Porous transition metal-based composite fiber membrane, and in-situ preparation method and application thereof Pending CN116254624A (en)

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