CN115275190A - Self-supporting soft/hard carbon film for negative electrode of sodium ion battery and preparation and application thereof - Google Patents

Self-supporting soft/hard carbon film for negative electrode of sodium ion battery and preparation and application thereof Download PDF

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CN115275190A
CN115275190A CN202211159159.9A CN202211159159A CN115275190A CN 115275190 A CN115275190 A CN 115275190A CN 202211159159 A CN202211159159 A CN 202211159159A CN 115275190 A CN115275190 A CN 115275190A
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hard carbon
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cellulose
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陈成猛
谢莉婧
苏方远
郭晓倩
李晓明
孔庆强
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Guoke Charcoal New Materials (Huzhou) Co.,Ltd.
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Shanxi Institute of Coal Chemistry of CAS
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Abstract

The invention belongs to the technical field of sodium ion batteries, and particularly relates to a self-supporting soft/hard carbon film for a sodium ion battery cathode, and preparation and application thereof. Adding the water/organic compound solution containing the nano-cellulose into a cross-linking agent solution, and performing vacuum impregnation, interface self-assembly, freeze drying and hot pressing treatment to obtain a cross-linked nano-cellulose film; and (3) paving the cross-linked nano cellulose film in an asphalt solution, and performing deposition compounding and hot-pressing carbonization treatment to obtain the self-supporting soft/hard carbon film. The self-supporting soft/hard carbon film obtained by the invention has the advantages of hard carbon and soft carbon, and has higher carbon residue rate; the lithium ion battery anode is directly used for a cathode of a sodium ion battery, and shows high sodium storage capacity, first coulombic efficiency, excellent cycling stability and rate capability.

Description

Self-supporting soft/hard carbon film for negative electrode of sodium ion battery and preparation and application thereof
Technical Field
The invention belongs to the technical field of sodium ion batteries, and particularly relates to a self-supporting soft/hard carbon film for a sodium ion battery cathode, and preparation and application thereof.
Background
The continuous emergence of new-generation intelligent electronic equipment, particularly flexible electronic products, greatly enriches and improves the lives of people. Unlike conventional electronic products, flexible electronic products have many novel features such as flexibility, folding, flexibility, and shape deformation. Therefore, an energy supply system for flexible electronic products, namely a flexible energy storage device, is produced. Among numerous electrochemical energy storage devices, lithium ion batteries are expected to be widely applied to flexible wearable electronic energy storage devices due to high energy density and excellent cycle performance of the lithium ion batteries. However, due to the shortage of lithium resources and the uneven distribution thereof, the cost and reserves of the related raw materials are facing serious problems, greatly hindering the large-scale development of lithium ion batteries. In contrast, although the energy density and the technical maturity of the sodium ion battery are still to be improved, the sodium ion battery becomes a large-scale energy storage technology with great development prospect due to the abundant storage amount and low cost of sodium resources.
The development of electrode materials is the key to the development and application of sodium ion batteries. The negative electrode of current commercial lithium ion batteries is graphite. However, due to thermodynamic limitations, an interlayer compound of sodium and graphite does not exist, so that the graphite used as the negative electrode of the sodium-ion battery causes a large amount of dead sodium to be generated, and a great loss of capacity is caused. In recent years, hard carbon with unique structural advantages of short-range order, larger interlayer spacing, abundant closed pores and the like is obtained, and is considered to be the most practical sodium-ion battery anode material. It is noteworthy that hard carbon, unlike graphite, has a standard structural model, the microstructure and properties of hard carbon depend largely on the properties of the precursor. Hard carbon can be classified into resin base, pitch base and biomass base according to the difference of the precursor. Among them, biomass has been widely used as a precursor of carbon negative electrode materials for alkali metal batteries because of its natural fine structure, reproducibility and low cost. However, in the conventional carbon electrode manufacturing process, the active material, the conductive agent and the current collector are generally bonded into a whole by using the physical effect of the binder. The use of high molecular binders such as polyvinylidene fluoride (PVDF) in large quantities can cause environmental problems due to its toxicity and volatility. Meanwhile, in the slurry preparation process, the existence of the binder can block the internal pores of the active material, and reduce the surface capacity and rate capability of the material. In addition, the electrode material on the metal current collector is also easily peeled off due to the presence of the binder, resulting in a decrease in cycle stability.
Disclosure of Invention
Aiming at the problem that the traditional hard carbon cathode inevitably uses a binder so as to block ion diffusion and electron transfer, the invention aims to provide a high-stability self-supporting soft/hard carbon membrane for a sodium ion battery cathode, and preparation and application thereof. According to the invention, different cross-linking molecules are used for selectively cross-linking active hydroxyl groups on a nano cellulose molecular chain, so that rigid hybrid cross-linking is carried out in the structure of the nano cellulose molecular chain, and controllable preparation of the self-supporting hard carbon film with a super cross-linking framework and rich cross-linking nodes is realized; and further introducing a soft carbon source to realize the construction of a core-shell structure of the soft and hard carbon.
Because no binder is used, the pore structure and the surface functional group of the self-supporting soft/hard carbon membrane can be fully used for storing alkali metal ions, and the structural advantages of the active material are fully exerted to improve the energy storage performance of the active material. Meanwhile, the super-crosslinked self-supporting structure ensures the stability of the electrode structure in the repeated charging and discharging process. The self-supporting soft/hard carbon film obtained by the invention has the advantages of both hard carbon and soft carbon and has higher carbon residue rate; the lithium ion battery anode is directly used for a cathode of a sodium ion battery, and shows high sodium storage capacity, first coulombic efficiency, excellent cycling stability and rate capability.
In order to realize the purpose, the invention is realized by the following technical scheme:
the invention provides a self-supporting soft/hard carbon film for a negative electrode of a sodium ion battery, which is characterized in that: the self-supporting soft/hard carbon film is a hard-soft carbon core-shell structure constructed by rigid hybridization and crosslinking of hard carbon through active hydroxyl groups on a precursor molecular chain of the hard carbon by a crosslinking agent and composite hot-pressing carbonization with a soft carbon precursor, and further forms a film with a super-crosslinking self-supporting three-dimensional network structure, wherein in the hard-soft carbon core-shell structure, core hard carbon is used as a sodium storage matrix, and shell layer soft carbon is used as an electron transport layer.
Preferably, the hard carbon is nano-cellulose, including cellulose nano-fiber, nano-crystal and bacterial cellulose; the soft carbon is high-temperature asphalt, the softening point of the soft carbon is more than or equal to 160 ℃, and the granularity of the soft carbon is less than 20 mu m; the cross-linking agent is at least one of hexamethylenetetramine, melamine, acrylamide, uric acid, urea, p-phenyl diboronic acid, m-phenyl diboronic acid, ammonium dihydrogen phosphate, epichlorohydrin and maleic anhydride.
Preferably, the self-supporting soft/hard carbon film has the aperture of 10 to 500nm, the thickness of 20 to 200 μm, the carbon yield of 20 to 50wt.% and the surface loading of 1 to 30mg/cm 2 The specific surface area is 1 to 200m 2 /g。
The invention also provides a preparation method of the self-supporting soft/hard carbon film, which comprises the following steps:
step 1: adding a water/organic compound solution containing nano-cellulose into a cross-linking agent solution, and performing vacuum impregnation, interface self-assembly and freeze drying to prepare an impregnated nano-cellulose film;
and 2, step: carrying out hot-pressing treatment on the dipped nano-cellulose film to prepare a cross-linked nano-cellulose film;
and 3, step 3: paving the cross-linked nano-cellulose film in an asphalt solution, and performing deposition compounding to prepare a nano-cellulose/asphalt-based composite film;
and 4, step 4: and carrying out hot-pressing carbonization treatment on the nano-cellulose/asphalt-based composite film to obtain the self-supporting soft/hard carbon film.
Preferably, the nanocellulose in step 1 is at least one of cellulose nanofibers, nanocrystals and bacterial cellulose.
Preferably, in the step 1, the crosslinking agent is at least one of hexamethylenetetramine, melamine, acrylamide, uric acid, urea, p-phenyl diboronic acid, m-phenyl diboronic acid, ammonium dihydrogen phosphate, epichlorohydrin and maleic anhydride.
Preferably, the organic solvent in the water/organic compound solution in the step 1 is at least one of isopropanol, absolute ethyl alcohol, propylene glycol, N-methylpyrrolidone, N-dimethylformamide and N, N-dimethylacetamide; the volume percentage of water and the organic solvent in the water/organic compound solution is 1 to 99.
Preferably, the mass ratio of the nanocellulose to the crosslinking agent in the step 1 is 20 to 1 to 5.
Preferably, the temperature of the freeze drying in the step 1 is-20 to-50 ℃ and the time is 4 to 12h.
Preferably, the conditions of the hot pressing treatment in the step 2 are as follows: argon, nitrogen or vacuum atmosphere, the temperature is 150 to 500 ℃, and the time is 0.5 to 15h.
Preferably, the asphalt in the step 3 is high-temperature asphalt, the softening point of the asphalt is more than or equal to 160 ℃, and the granularity of the asphalt is less than 20 mu m; the asphalt solution is prepared from an organic solvent and asphalt according to the mass ratio of 1 to 3, wherein the organic solvent is at least one of carbon disulfide, carbon tetrachloride, toluene, benzene, xylene, n-hexane and petroleum ether.
Preferably, the deposition and compounding in the step 3 adopt spraying, coating, filter pressing or vacuum filtration.
Preferably, the conditions of the hot-pressing carbonization in the step 4 are as follows: when the carbonization temperature is 900 to 1600 ℃, the heating rate is 1 to 10 ℃/min, and the carbonization time is 0.5 to 10h.
The invention also provides the application of the self-supporting soft/hard carbon film as a negative electrode material of the sodium-ion battery.
Compared with the prior art, the invention has the following beneficial effects:
(1) The method selectively crosslinks active hydroxyl on a molecular chain of the nano-cellulose through different crosslinking molecules to perform rigid hybrid crosslinking in the structure of the nano-cellulose, so as to realize controllable preparation of the self-supporting hard carbon film with a super-crosslinked framework and rich crosslinking nodes. The three-dimensional continuous conductive network provided by the carbon nanofibers in the structure is convenient for rapid electron transfer, and simultaneously, the carbon nanofibers serve as a mechanical skeleton connected with each other, so that the stability of the electrode structure in the repeated charging and discharging process is also ensured.
(2) The self-supporting soft/hard carbon film obtained by the invention has the advantages of hard carbon and soft carbon, and has higher carbon residue rate.
(3) The introduction of the chemical cross-linking structure in the hard carbon precursor greatly enhances the disorder degree of the carbonized product, enlarges the interlayer spacing and the closed pore quantity, and is expected to obtain the hard carbon material which has high coulombic efficiency for the first time, excellent rate capability and sodium storage capacity.
(4) The invention introduces soft carbon source to realize the construction of core-shell structure of soft and hard carbon. The soft carbon is used as an electron transport layer, so that the electron transport can be effectively accelerated, and the multiplying power performance of a self-supporting soft/hard carbon film material is improved; the hard carbon is used as a sodium storage matrix, and is beneficial to the desorption of sodium ions. Because no binder is used, the pore structure and the surface functional group of the self-supporting soft/hard carbon membrane can be fully used for storing alkali metal ions, and the structural advantages of the active material are fully exerted to maximally improve the electrochemical performance of the sodium-ion battery.
Drawings
Fig. 1 is a TEM image of a self-supporting soft/hard carbon membrane material prepared in example 1.
Fig. 2 is a graph of rate performance of the self-supporting soft/hard carbon membrane material prepared in example 1.
Fig. 3 is a graph of the cycle performance of the self-supporting soft/hard carbon membrane material prepared in example 1.
Detailed Description
In order that the invention may be more fully understood, reference will now be made to the following more detailed description. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Example 1
A preparation method of a self-supporting soft/hard carbon membrane for a negative electrode of a sodium-ion battery comprises the following steps:
step 1: dissolving 10g of cellulose nanofiber in a 100mL compound solvent system (volume ratio of water to isopropanol =5 = 95), and uniformly stirring; adding 2g of ammonium dihydrogen phosphate into the solution, carrying out vacuum impregnation and interface self-assembly at room temperature, and drying at-20 ℃ for 12h to obtain an impregnated nano cellulose film;
and 2, step: spreading the impregnated nano-cellulose film in a graphite clamp, and carrying out hot-pressing treatment at 150 ℃ for 15h under the argon atmosphere to obtain a cross-linked nano-cellulose film;
and 3, step 3: selecting asphalt with the softening point of 200 ℃ and the granularity of 18 mu m as a soft carbon source, and adding n-hexane into the soft carbon precursor, wherein the mass ratio of n-hexane to asphalt is 1; then, the crosslinked nano-cellulose film is paved in a prepreg asphalt solution, and a nano-cellulose/asphalt-based composite film is prepared through vacuum filtration;
and 4, step 4: and (2) placing the nano-cellulose/asphalt-based composite film into a graphite plate clamp, then placing the graphite plate clamp into a tubular furnace, and carrying out hot-pressing carbonization treatment under the protection of argon, wherein the carbonization temperature is 1600 ℃, the temperature rise rate is 10 ℃/min, and the carbonization time is 0.5h, and finally preparing the self-supporting soft/hard carbon film material.
The self-supporting soft/hard carbon film material prepared in the embodiment has a hypercrosslinked three-dimensional skeleton structure (as shown in fig. 1), the pore diameter is 30nm, the thickness is 40 μm, the carbon yield is 38wt.%, and the area loading is 3mg/cm 2 Specific surface area of 2.1m 2 /g。
The self-supporting soft/hard carbon composite film material prepared by the method is directly used as a working electrode (negative electrode), metal sodium is used as a counter electrode, and 1M NaClO is used 4 (volume ratio of ethylene carbonate to diethyl carbonate is 1) as an electrolyte, and the solution was assembled into a CR2032 button cell in a glove box filled with Ar atmosphere. The electrochemical performance of the battery is tested, and referring to fig. 2 and fig. 3, the test result shows that: the self-supporting soft/hard material prepared in this exampleThe carbon film is used as a negative electrode, when the current density is 20mA/g, the reversible specific capacity can reach 377.8mAh/g, the capacitance can still reach 100% of the initial capacity after 1000 cycles, and the excellent cycle performance is shown.
Example 2
A preparation method of a self-supporting soft/hard carbon film for a negative electrode of a sodium ion battery comprises the following steps:
step 1: dissolving 10g of nanocrystal in 100mL of a compound solvent system (volume ratio of water to propylene glycol =5 = 95), and uniformly stirring; adding 2g of melamine into the solution, carrying out vacuum impregnation and interface self-assembly at room temperature, and drying for 4 hours at the temperature of minus 50 ℃ to obtain an impregnated nano cellulose film;
step 2: spreading the impregnated nano-cellulose film in a graphite clamp, and carrying out hot pressing treatment at 500 ℃ for 0.5h in a nitrogen atmosphere to obtain a crosslinked nano-cellulose film;
and step 3: selecting asphalt with the softening point of 180 ℃ and the granularity of 15 mu m as a soft carbon source, and adding carbon disulfide into the soft carbon precursor, wherein the mass ratio of the carbon disulfide to the asphalt is 3; then the cross-linked nano-cellulose film is paved in a prepreg asphalt solution, and the nano-cellulose/asphalt-based composite film is prepared through vacuum filtration;
and 4, step 4: and (2) placing the nano-cellulose/asphalt-based composite film into a graphite plate clamp, then placing the graphite plate clamp into a tubular furnace, and carrying out hot-pressing carbonization treatment under the protection of argon, wherein the carbonization temperature is 1500 ℃, the temperature rise rate is 5 ℃/min, and the carbonization time is 4h, and finally preparing the self-supporting soft/hard carbon film material.
The self-supporting soft/hard carbon membrane material prepared in this example had a pore size of 20nm, a thickness of 200 μm, a carbon yield of 40wt.%, and an areal loading of 30mg/cm 2 A specific surface area of 78m 2 /g。
The self-supporting soft/hard carbon composite film material prepared by the method is subjected to electrochemical performance test, and the test method is the same as that of the example 1. Tests prove that the self-supporting soft/hard carbon film prepared by the embodiment is used as a negative electrode, the reversible specific capacity can reach 310mAh/g when the current density is 20mA/g, and the electric capacity can still reach 99% of the initial capacity after 1000 cycles.
Example 3
A preparation method of a self-supporting soft/hard carbon membrane for a negative electrode of a sodium-ion battery comprises the following steps:
step 1: dissolving 10g of bacterial cellulose in a 100mL compound solvent system (the volume ratio of water to propylene glycol = 20; adding 2g of hexamethylenetetramine into the solution, carrying out vacuum impregnation and interface self-assembly at room temperature, and drying at-30 ℃ for 3h to obtain an impregnated nano cellulose film;
step 2: paving the impregnated nano-cellulose film in a graphite clamp, and performing hot-pressing treatment at 200 ℃ for 2 hours under the argon atmosphere to prepare a cross-linked nano-cellulose film;
and step 3: selecting asphalt with the softening point of 250 ℃ and the granularity of 18 mu m as a soft carbon source, and adding carbon tetrachloride into the soft carbon precursor, wherein the mass ratio of the carbon tetrachloride to the asphalt is 2; then the cross-linked nano-cellulose film is paved in a prepreg asphalt solution, and a nano-cellulose/asphalt-based composite film is prepared through vacuum filtration;
and 4, step 4: and (2) placing the nano-cellulose/asphalt-based composite film into a graphite plate clamp, then placing the graphite plate clamp into a tubular furnace, and carrying out hot-pressing carbonization treatment under the protection of argon, wherein the carbonization temperature is 1100 ℃, the temperature rise rate is 3 ℃/min, and the carbonization time is 4h, so as to finally prepare the self-supporting soft/hard carbon film material.
The self-supporting soft/hard carbon membrane material prepared in this example had a pore size of 80nm, a thickness of 80 μm, a carbon yield of 35.4wt.%, and an areal loading of 10mg/cm 2 The specific surface area of the coating was 35.4m 2 /g。
The self-supporting soft/hard carbon composite film material prepared by the method is subjected to electrochemical performance test, and the test method is the same as that of the example 1. Tests prove that when the self-supporting soft/hard carbon film prepared by the embodiment is used as a negative electrode, the reversible specific capacity can reach 345.4 mAh/g when the current density is 20mA/g, and the capacitance can still reach 100% of the initial capacity after 1000 cycles.
Example 4
A preparation method of a self-supporting soft/hard carbon membrane for a negative electrode of a sodium-ion battery comprises the following steps:
step 1: dissolving 10g of cellulose nanofiber in a 100mL compound solvent system (the volume ratio of water to isopropanol =10: 90), and uniformly stirring; adding 2g of maleic anhydride into the solution, carrying out vacuum impregnation and interface self-assembly at room temperature, and drying at-30 ℃ for 3h to obtain an impregnated nano-cellulose film;
step 2: spreading the impregnated nano-cellulose film in a graphite clamp, and carrying out hot-pressing treatment at 220 ℃ for 1.5h under the argon atmosphere to obtain a crosslinked nano-cellulose film;
and step 3: selecting asphalt with the softening point of 200 ℃ and the granularity of 15 mu m as a soft carbon source, and adding toluene into the soft carbon precursor, wherein the mass ratio of the toluene to the asphalt is 1; then the cross-linked nano-cellulose film is paved in a prepreg asphalt solution, and the nano-cellulose/asphalt-based composite film is prepared through vacuum filtration;
and 4, step 4: and (2) placing the nano-cellulose/asphalt-based composite film into a graphite plate clamp, then placing the graphite plate clamp into a tubular furnace, and carrying out hot-pressing carbonization treatment under the protection of argon, wherein the carbonization temperature is 1100 ℃, the temperature rise rate is 10 ℃/min, and the carbonization time is 4h, so as to finally prepare the self-supporting soft/hard carbon film material.
The self-supporting soft/hard carbon membrane material prepared in this example had a pore size of 80nm, a thickness of 60 μm, a carbon yield of 30.4wt.%, and an areal loading of 5mg/cm 2 The specific surface area of the coating was 32.4m 2 /g。
The self-supporting soft/hard carbon composite film material prepared by the method is subjected to electrochemical performance test, and the test method is the same as that of the example 1. Tests prove that when the self-supporting soft/hard carbon film prepared by the embodiment is used as a negative electrode, the reversible specific capacity can reach 362.4 mAh/g when the current density is 20mA/g, and the capacitance can still reach 98% of the initial capacity after 1000 cycles.
Example 5
A preparation method of a self-supporting soft/hard carbon membrane for a negative electrode of a sodium-ion battery comprises the following steps:
step 1: dissolving 10g of cellulose nanofiber in a 100mL compound solvent system (the volume ratio of water to isopropanol = 30; adding 3g of acrylamide into the solution, carrying out vacuum impregnation and interface self-assembly at room temperature, and drying for 3 hours at the temperature of-30 ℃ to prepare an impregnated nano cellulose film;
and 2, step: spreading the impregnated nano-cellulose film in a graphite clamp, and carrying out hot-pressing treatment at 200 ℃ for 2h in a vacuum atmosphere to obtain a cross-linked nano-cellulose film;
and 3, step 3: selecting asphalt with the softening point of 250 ℃ and the granularity of 18 mu m as a soft carbon source, and adding benzene into the soft carbon precursor, wherein the mass ratio of benzene to asphalt is 2; then the cross-linked nano-cellulose film is paved in a prepreg asphalt solution, and the nano-cellulose/asphalt-based composite film is prepared through vacuum filtration;
and 4, step 4: and (2) placing the nano-cellulose/asphalt-based composite film into a graphite plate clamp, then placing the graphite plate clamp into a tubular furnace, and carrying out hot-pressing carbonization treatment under the protection of argon, wherein the carbonization temperature is 1300 ℃, the temperature rise rate is 10 ℃/min, and the carbonization time is 3h, and finally preparing the self-supporting soft/hard carbon film material.
The self-supporting soft/hard carbon membrane material prepared in the example has the pore diameter of 50nm, the thickness of 50 μm, the carbon yield of 34.4wt.%, and the area loading of 4mg/cm 2 The specific surface area was 13.4m 2 /g。
The self-supporting soft/hard carbon composite film material prepared by the method is subjected to electrochemical performance test, and the test method is the same as that of the example 1. Tests prove that when the self-supporting soft/hard carbon film prepared by the embodiment is used as a negative electrode, the reversible specific capacity can reach 351.4 mAh/g when the current density is 20mA/g, and the capacitance can still reach 95% of the initial capacity after 1000 cycles.
Example 6
This embodiment is a modification of embodiment 1, and is modified only in that: in the step 1, 20g of cellulose nanofibers are replaced by 10g of cellulose nanofibers, 1g of uric acid is replaced by 2g of ammonium dihydrogen phosphate, and a compound solvent is water/absolute ethyl alcohol (volume ratio = 1.
The self-supporting soft/hard carbon membrane material prepared in the example has the pore diameter of 100nm, the thickness of 110 μm, the carbon yield of 49.8wt.%, and the area loading of 15mg/cm 2 The specific surface area was 152.3m 2 /g。
Example 7
This embodiment is a modification of embodiment 1, and is modified only in that: in the step 1, 1g of urea is replaced by 2g of ammonium dihydrogen phosphate, and a compound solvent is water/N-methyl pyrrolidone (volume ratio = 99; and in the step 3, replacing n-hexane with xylene with the same amount.
The self-supporting soft/hard carbon membrane material prepared in this example had a pore size of 200nm, a thickness of 170 μm, a carbon yield of 45.4wt.%, and an areal loading of 20mg/cm 2 A specific surface area of 200m 2 /g。
Example 8
This embodiment is a modification of embodiment 1, and is modified only in that: in the step 1, ammonium dihydrogen phosphate is replaced by equal amount of urea, and a compound solvent is water/N, N-dimethylformamide (volume ratio = 5; and in the step 3, the n-hexane is replaced by petroleum ether with the same amount.
The self-supporting soft/hard carbon membrane material prepared in the example has a pore diameter of 230nm, a thickness of 120 μm, a carbon yield of 50wt.%, and a surface loading of 8mg/cm 2 A specific surface area of 55m 2 /g。
The self-supporting soft/hard carbon composite film material prepared by the method is subjected to electrochemical performance test, and the test method is the same as that of the example 1. Tests prove that when the self-supporting soft/hard carbon film prepared by the embodiment is used as a negative electrode, the reversible specific capacity can reach 367.4mAh/g when the current density is 20mA/g, and the capacitance can still reach 100% of the initial capacity after 1000 cycles.
Example 9
This embodiment is a modification of embodiment 1, and is modified only in that: in the step 1, ammonium dihydrogen phosphate is replaced by p-phenyl diboronic acid with the same amount; and 4, when the carbonization temperature is 900 ℃, the heating rate is 10 ℃/min, and the carbonization time is 10h.
The self-supporting soft/hard carbon membrane material prepared in this example had a pore size of 350nm, a thickness of 70 μm, a carbon yield of 28.3wt.%, and an areal loading of 12mg/cm 2 The specific surface area is 110m 2 /g。
The self-supporting soft/hard carbon composite film material prepared by the method is subjected to electrochemical performance test, and the test method is the same as that of the example 1. Tests prove that when the self-supporting soft/hard carbon film prepared by the embodiment is used as a negative electrode, the reversible specific capacity can reach 384.3mAh/g when the current density is 20mA/g, and the capacitance can still reach 97% of the initial capacity after 1000 cycles.
Example 10
This embodiment is a modification of embodiment 1, and is modified only in that: in the step 1, ammonium dihydrogen phosphate is replaced by equivalent m-phenyl diboronic acid, and a compound solvent is water/N, N-dimethylacetamide (volume ratio =1 = 99.
The self-supporting soft/hard carbon membrane material prepared in this example had a pore size of 400nm, a thickness of 150 μm, a carbon yield of 25wt.%, and an areal loading of 25mg/cm 2 A specific surface area of 26m 2 /g。
The self-supporting soft/hard carbon composite film material prepared by the method is subjected to electrochemical performance test, and the test method is the same as that of the example 1. Tests prove that when the self-supporting soft/hard carbon film prepared by the embodiment is used as a negative electrode, the reversible specific capacity can reach 365.8mAh/g when the current density is 20mA/g, and the capacitance can still reach 95% of the initial capacity after 1000 cycles.
Example 11
This embodiment is a modification of embodiment 1, and is modified only in that: in the step 1, replacing ammonium dihydrogen phosphate with equal amount of epichlorohydrin; in the step 3, pitch with the softening point of 160 ℃ and the granularity of 15 mu m is selected as a soft carbon source.
The self-supporting soft/hard carbon membrane material prepared in this example had a pore size of 500nm, a thickness of 100 μm, a carbon yield of 30wt.%, and an areal loading of 18mg/cm 2 A specific surface area of 178m 2 /g。
The self-supporting soft/hard carbon composite film material prepared by the method is subjected to electrochemical performance test, and the test method is the same as that of the example 1. Tests prove that when the self-supporting soft/hard carbon film prepared by the embodiment is used as a negative electrode, the reversible specific capacity can reach 374.6mAh/g when the current density is 20mA/g, and the capacitance can still reach 99% of the initial capacity after 1000 cycles.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.

Claims (10)

1. A self-supporting soft/hard carbon membrane for a negative electrode of a sodium ion battery, characterized in that: the self-supporting soft/hard carbon film is a hard-soft carbon core-shell structure constructed by rigid hybridization and crosslinking of hard carbon through active hydroxyl groups on a precursor molecular chain of the hard carbon by a crosslinking agent and composite hot-pressing carbonization with a soft carbon precursor, and further forms a film with a super-crosslinking self-supporting three-dimensional network structure, wherein in the hard-soft carbon core-shell structure, core hard carbon is used as a sodium storage matrix, and shell layer soft carbon is used as an electron transport layer.
2. A self-supporting soft/hard carbon membrane for a negative electrode of a sodium ion battery as defined in claim 1, wherein: the hard carbon is nano-cellulose and comprises cellulose nano-fiber, nano-crystal and bacterial cellulose; the soft carbon is high-temperature asphalt, the softening point of the soft carbon is more than or equal to 160 ℃, and the granularity of the soft carbon is less than 20 mu m; the cross-linking agent is at least one of hexamethylenetetramine, melamine, acrylamide, uric acid, urea, p-phenyl diboronic acid, m-phenyl diboronic acid, ammonium dihydrogen phosphate, epichlorohydrin and maleic anhydride.
3. A self-supporting soft/hard carbon membrane for a negative electrode of a sodium ion battery as defined in claim 2, wherein: the self-supporting soft/hard carbon film has the aperture of 10-500nm, the thickness of 20-200 μm, the carbon yield of 20-50 wt% and the surface loading capacity of 1-30mg/cm 2 The specific surface area is 1 to 200m 2 /g。
4. A preparation method of the self-supporting soft/hard carbon film for the negative electrode of the sodium-ion battery as defined in any one of claims 1 to 3, which is characterized by comprising the following steps: the method comprises the following steps:
step 1: adding water/organic compound solution containing nano-cellulose into a cross-linking agent solution, and performing vacuum impregnation, interface self-assembly and freeze drying to obtain an impregnated nano-cellulose film;
and 2, step: carrying out hot-pressing treatment on the dipped nano-cellulose film to prepare a cross-linked nano-cellulose film;
and step 3: paving the cross-linked nano-cellulose film in an asphalt solution, and performing deposition compounding to prepare a nano-cellulose/asphalt-based composite film;
and 4, step 4: and carrying out hot-pressing carbonization treatment on the nano-cellulose/asphalt-based composite film to obtain the self-supporting soft/hard carbon film.
5. The method for preparing a self-supporting soft/hard carbon membrane for a negative electrode of a sodium-ion battery according to claim 4, wherein the method comprises the following steps: the nano-cellulose in the step 1 is at least one of cellulose nano-fiber, nano-crystal and bacterial cellulose; the cross-linking agent is at least one of hexamethylenetetramine, melamine, acrylamide, uric acid, urea, p-phenylboronic acid, m-phenylboronic acid, ammonium dihydrogen phosphate, epichlorohydrin and maleic anhydride; the organic solvent in the water/organic compound solution is at least one of isopropanol, absolute ethyl alcohol, propylene glycol, N-methyl pyrrolidone, N-dimethylformamide and N, N-dimethylacetamide; the volume percentage of water to an organic solvent in the water/organic compound solution is 1 to 99; the mass ratio of the nano-cellulose to the cross-linking agent is 20 to 1-5.
6. The method for preparing a self-supporting soft/hard carbon membrane for a negative electrode of a sodium-ion battery according to claim 4, wherein the method comprises the following steps: the temperature of freeze drying in the step 1 is-20 to-50 ℃, and the time is 4 to 12h; the conditions of the hot pressing treatment in the step 2 are as follows: argon, nitrogen or vacuum atmosphere, the temperature is 150 to 500 ℃, and the time is 0.5 to 15h.
7. The method for preparing a self-supporting soft/hard carbon film for a negative electrode of a sodium-ion battery according to claim 4, characterized in that: the asphalt in the step 3 is high-temperature asphalt, the softening point of the asphalt is more than or equal to 160 ℃, and the granularity of the asphalt is less than 20 mu m; the asphalt solution is prepared from an organic solvent and asphalt according to the mass ratio of 1 to 3, wherein the organic solvent is at least one of carbon disulfide, carbon tetrachloride, toluene, benzene, xylene, n-hexane and petroleum ether.
8. The method for preparing a self-supporting soft/hard carbon membrane for a negative electrode of a sodium-ion battery according to claim 4, wherein the method comprises the following steps: and the deposition and compounding in the step 3 adopt spraying, coating, filter pressing or vacuum filtration.
9. The method for preparing a self-supporting soft/hard carbon membrane for a negative electrode of a sodium-ion battery according to claim 4, wherein the method comprises the following steps: the conditions of the hot-pressing carbonization in the step 4 are as follows: when the carbonization temperature is 900 to 1600 ℃, the heating rate is 1 to 10 ℃/min, and the carbonization time is 0.5 to 10h.
10. Use of the self-supporting soft/hard carbon film as defined in any one of claims 1 to 3 as a negative electrode material of a sodium ion battery.
CN202211159159.9A 2022-09-22 2022-09-22 Self-supporting soft/hard carbon film for negative electrode of sodium ion battery and preparation and application thereof Active CN115275190B (en)

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