CN116002662A - Asphalt-based sodium ion battery negative electrode material and preparation method thereof - Google Patents
Asphalt-based sodium ion battery negative electrode material and preparation method thereof Download PDFInfo
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Abstract
The invention provides an asphalt-based sodium ion battery anode material and a preparation method thereof, belongs to the technical field of energy storage batteries, and can solve the technical problems of lower carbon yield and higher comprehensive cost of the traditional asphalt modification method. The preparation method of the asphalt-based sodium ion battery anode material comprises the following steps: crushing and screening asphalt to obtain crushed asphalt; under the air atmosphere, crushing asphalt for pre-oxidation treatment to obtain oxidized asphalt; after the oxidized asphalt is cooled to room temperature, mixing, heating and coating the cooled oxidized asphalt and unoxidized asphalt according to a certain proportion, and coating the unoxidized asphalt on the exterior of the oxidized asphalt to obtain a coating material; and (3) after the coating material is cooled to room temperature, performing high-temperature carbonization treatment to obtain the asphalt-based sodium ion battery anode material. The asphalt-based sodium ion battery anode material has the characteristics of high carbon yield and low comprehensive cost.
Description
Technical Field
The invention belongs to the technical field of energy storage batteries, and particularly relates to an asphalt-based sodium ion battery anode material and a preparation method thereof.
Background
Sodium ion batteries have the advantages of abundant resources, low cost, environmental friendliness and the like, and are considered to be the most likely alternative to lithium ion batteries as one of ideal power sources for large-scale energy storage application. The performance of sodium ion batteries is mainly determined by the sodium storage anode and cathode materials, which are one of the important components. Among the sodium storage anode materials researched at present, the carbon-based anode not only has a lower sodium intercalation platform, higher capacity and good cycling stability, but also has the advantages of abundant resources, simple preparation and the like, and is the sodium storage anode material with the most application prospect at present. Currently, the precursors used to prepare carbon materials are mainly biomass and resins. The biomass precursor has low carbon yield and the resin precursor has relatively high cost. Therefore, the preparation of carbon materials using both types of precursors is not beneficial to the low cost advantage of sodium ion batteries. As a byproduct of the petroleum industry, pitch is relatively low in price and high in carbon yield, and is an ideal precursor for preparing carbon materials.
However, the electrochemical performance of the sodium ion battery carbon-based negative electrode prepared by directly carbonizing asphalt is poor because asphalt belongs to a soft carbon precursor, melting and ordered rearrangement occur in the high-temperature carbonization process, the graphitization degree is increased, and a highly ordered carbon layer structure is formed. Means for modifying and coating bitumen are often required to improve overall performance. For example, chinese patent CN108878774B discloses that asphalt coating is performed by using natural cotton as a substrate, so that soft and hard composite materials are formed to improve the material performance, but cotton hard carbon with low carbon yield increases the cost; chinese patent CN109148838B discloses a method for asphalt coating using charcoal and bamboo charcoal as substrates, and also has the problem of low carbon production rate by using biomass materials such as charcoal.
It can be seen how to improve the performance and carbon yield of the negative electrode of an asphalt-based sodium ion battery, and to reduce the cost is a key challenge facing the field at present.
Disclosure of Invention
Aiming at the technical problems of lower carbon yield and higher comprehensive cost in the traditional asphalt modification method, the invention provides the asphalt-based sodium ion battery anode material and the preparation method thereof, wherein the asphalt-based sodium ion battery anode material is prepared by taking oxidized asphalt as a coating core and unoxidized asphalt as an outer coating layer, and has the characteristics of high carbon yield and lower cost.
In order to achieve the above purpose, the invention adopts the following technical scheme:
the preparation method of the asphalt-based sodium ion battery anode material comprises the following steps:
crushing raw materials: crushing and screening asphalt to obtain crushed asphalt;
pre-oxidation treatment: under the air atmosphere, pre-oxidizing the crushed asphalt to obtain oxidized asphalt;
and (3) heating and coating treatment: after the oxidized asphalt is cooled to room temperature, mixing, heating and coating the cooled oxidized asphalt and unoxidized asphalt according to a certain proportion, and coating the unoxidized asphalt outside the oxidized asphalt to obtain a coating material;
high-temperature carbonization treatment: and after the coating material is cooled to room temperature, performing high-temperature carbonization treatment to obtain the asphalt-based sodium ion battery anode material.
In one embodiment, the asphalt is selected from any one or a combination of a plurality of petroleum asphalt, coal asphalt and natural asphalt.
In one embodiment, the crushed asphalt has a particle size in the range of 3 to 10 microns in D50.
In one embodiment, the pre-oxidation treatment has an oxidation temperature of 300-500 ℃ and an oxidation time of 3-12 hours.
In one embodiment, the mass ratio of the oxidized asphalt to the unoxidized asphalt is 1 (0.05-0.35).
In one embodiment, the temperature of the mixing, heating and coating treatment of the oxidized asphalt and the unoxidized asphalt is 200-300 ℃ and the time is 0.5-1.5h.
In one embodiment, the high temperature carbonization temperature is 900-1600 ℃ and the carbonization time is 2-8h.
The invention also provides an asphalt-based sodium ion battery anode material which is prepared by the preparation method in any embodiment.
In one embodiment, the coated core of the asphalt-based sodium ion battery anode material is oxidized asphalt, the outer coating layer is unoxidized asphalt, and the thickness of the outer coating layer is 10-50 nanometers.
Compared with the prior art, the invention has the advantages and positive effects that:
1. the invention provides a preparation method of an asphalt-based sodium ion battery anode material, which comprises the steps of pre-oxidizing asphalt to obtain oxidized asphalt, mixing, heating and coating the oxidized asphalt and unoxidized asphalt according to a certain proportion, coating the unoxidized asphalt outside the oxidized asphalt, and finally preparing the asphalt-based sodium ion battery anode material with the oxidized asphalt as a coating core and the unoxidized asphalt as an outer coating layer, wherein the anode material has high yield, the asphalt coated with the core is crosslinked through an oxidation internal structure, the interlayer spacing is increased, the sodium storage is more beneficial, the difficulty that a carbon layer is difficult to embed due to the larger radius of sodium ions is effectively solved, meanwhile, the whole conductivity of the material is improved by coating by adopting conventional asphalt outside, the co-embedding of electrolyte is prevented, the loss of reversible capacity is less, in addition, the asphalt source is wide, the price is low, and the technical problems of low yield and high comprehensive cost existing in the current preparation of the sodium ion battery anode by adopting resin and biomass carbon can be solved;
2. the invention provides a preparation method of a pitch-based sodium ion battery anode material, when pitch is subjected to pre-oxidation treatment, air is used for oxidative crosslinking, pitch is a composite material of hydrocarbon and related nonmetallic derivatives, oxygen functional groups can be introduced in the pre-oxidation process, wide crosslinking formation is promoted, graphitization degree is prevented, a crosslinking agent is not needed, and cost can be further controlled;
3. the invention provides an asphalt-based sodium ion battery anode material which has the characteristics of high carbon yield and low cost.
Drawings
Fig. 1 is an XRD pattern of an asphalt-based sodium ion battery anode material provided by an embodiment of the present invention.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The embodiment of the invention provides a preparation method of an asphalt-based sodium ion battery anode material, which comprises the following steps:
s1, crushing raw materials: crushing and screening asphalt to obtain crushed asphalt;
in the step S1, asphalt is specifically selected from any one or a combination of a plurality of petroleum asphalt, coal asphalt and natural asphalt, and the raw materials are wide in source and low in price, so that the production cost can be effectively controlled; the particle size of the crushed asphalt is 3-10 microns, and can be selected from 3 microns, 4 microns, 5 microns, 6 microns, 7 microns, 8 microns, 9 microns, 10 microns or any value within the limit range. If the particle size range of the crushed asphalt is less than 3-10 microns, the internal crosslinking structure of the peroxidized material is easy to collapse, and the sodium storage structure is damaged; if the particle size exceeds 3-10 microns, insufficient oxidation is caused, oxygen is difficult to introduce into the particle, a cross-linked structure cannot be formed, and the internal structure tends to be orderly and sodium storage is difficult.
S2, pre-oxidation treatment: under the air atmosphere, pre-oxidizing the crushed asphalt to obtain oxidized asphalt;
in the step S2, asphalt is a composite material of hydrocarbon and related nonmetallic derivatives, oxygen functional groups can be introduced in the pre-oxidation process by using air for oxidation crosslinking, so that wide crosslinking formation is promoted, asphalt forms a crosslinked state by air oxidation, the interlayer spacing after carbonization is larger, sodium storage is more facilitated, the graphitization degree can be prevented, a crosslinking agent is not needed, and the cost is further controlled. The oxidation temperature of the pre-oxidation treatment is 300-500 ℃, specifically 300 ℃, 350 ℃, 400 ℃, 450 ℃, 500 ℃ or any value of the above-mentioned limited range falls within the protection scope of the invention, the oxidation time is 3-12h, specifically 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h, 11h, 12h or any value of the above-mentioned limited range falls within the protection scope of the invention.
S3, heating and coating: after the oxidized asphalt is cooled to room temperature, mixing, heating and coating the cooled oxidized asphalt and unoxidized asphalt according to a certain proportion, and coating the unoxidized asphalt outside the oxidized asphalt to obtain a coating material;
in the step S3, mixing, heating and coating the oxidized asphalt and the unoxidized asphalt according to a certain proportion, so that the unoxidized asphalt is coated outside the oxidized asphalt, and a coating material which takes the oxidized asphalt as a coating core and takes the unoxidized asphalt as an outer coating layer is prepared; wherein, the pitch of cladding kernel is through oxidation internal structure cross-linking, and the interlayer spacing increases, is more favorable to storing sodium, effectively solves the difficult point that is difficult to the embedding carbon layer because of sodium ion radius is great, simultaneously, outside adopts conventional pitch to carry out cladding to improve the whole conductivity of material, prevents the co-embedding of electrolyte, less reversible capacity's loss, and in addition, the pitch source is wide, and the low price can solve the technological problem that the present resin of adoption and living beings charcoal preparation sodium ion battery negative pole exists low in productivity, comprehensive cost is high.
Further, the mass ratio of the oxidized asphalt to the unoxidized asphalt is 1 (0.05-0.35), and specifically 1:0.05, 1:0.10, 1:0.15 and 1:0.20, 1:0.25, 1:0.30, 1:0.35 or any number within the above-defined range falls within the scope of the present invention; the temperature of the mixed heating cladding treatment of the oxidized asphalt and the unoxidized asphalt is 200-300 ℃, specifically 200 ℃, 220 ℃, 260 ℃,280 ℃, 300 ℃ or any value of the above-mentioned limited range falls within the protection range of the invention, the time is 0.5-1.5h, specifically 0.5h, 1.0h, 1.5h or any value of the above-mentioned limited range falls within the protection range of the invention.
S4, high-temperature carbonization treatment: and after the coating material is cooled to room temperature, performing high-temperature carbonization treatment to obtain the asphalt-based sodium ion battery anode material.
In the step S4, the high-temperature carbonization treatment is carried out on the coating material, so that the asphalt-based sodium ion battery anode material taking oxidized asphalt as a coating core and unoxidized asphalt as an outer coating layer is finally prepared, the asphalt of the coating core of the anode material is crosslinked through an oxidation internal structure, the interlayer spacing is increased, sodium storage is facilitated, the difficulty that a carbon layer is difficult to embed due to the fact that the radius of sodium ions is large is effectively solved, meanwhile, the overall conductivity of the material is improved by coating through conventional asphalt outside, the co-embedding of electrolyte is prevented, and the loss of reversible capacity is reduced.
Furthermore, the invention also limits the carbonization temperature and carbonization time in the process of preparing the asphalt-based sodium ion battery cathode material, namely, the high-temperature carbonization temperature is 900-1600 ℃, specifically, 900 ℃, 1000 ℃, 1100 ℃, 1200 ℃, 1300 ℃, 1400 ℃, 1500 ℃ and 1600 ℃ or any numerical value in the limiting range falls within the protection range of the invention, the carbonization time is 2-8h, and specifically, 2h, 3h, 4h, 5h, 6h, 7h and 8h or any numerical value in the limiting range falls within the protection range of the invention.
Furthermore, in order to ensure that the performance of the asphalt-based sodium ion battery anode material reaches the expected performance, the thickness of the non-oxidized asphalt coated on the outer layer is definitely limited, namely, the thickness of the non-oxidized asphalt coated on the outer layer is 10-50 nanometers, and particularly, 10 nanometers, 15 nanometers, 20 nanometers, 25 nanometers, 30 nanometers, 35 nanometers, 40 nanometers, 45 nanometers and 50 nanometers can be selected, or any numerical value within the limited range falls within the protection scope of the invention. If the film is too thick, sodium ion transmission is blocked, and capacity exertion is affected; if the electrolyte is too thin, structural defects such as cracks and holes formed in the asphalt oxidation process cannot be repaired, and the internal nuclear structure still can be partially in direct contact with the electrolyte to increase irreversible capacity and reduce performance.
The asphalt-based sodium ion battery anode material provided by the invention is an anode material taking oxidized asphalt as a coating core and unoxidized asphalt as an outer coating layer, and the order of the oxidized asphalt as the coating core and the unoxidized asphalt as the outer coating layer is not changeable, so that the asphalt-based sodium ion battery anode material is characterized in that: the external unoxidized asphalt mainly fills holes of the internal oxidized asphalt, namely, the closed-cell structure sodium storage is prepared, meanwhile, the side reaction that the specific surface area of the material is reduced and is contacted with electrolyte is reduced, the conductivity of the material can be mentioned, once the specific surface area of the oxidized asphalt is changed, the open-cell structure on the surface is contacted with the electrolyte, and a large amount of irreversible capacity loss is caused.
The invention also provides an asphalt-based sodium ion battery anode material, which is prepared by the preparation method in any one of the embodiments.
In a specific embodiment, the coated core of the asphalt-based sodium ion battery anode material is oxidized asphalt, the outer coating layer is unoxidized asphalt, and the thickness of the outer coating layer is 10-50 nanometers.
In order to more clearly and in detail describe the asphalt-based sodium ion battery anode material and the preparation method thereof provided by the embodiment of the invention, the following description will be made with reference to specific embodiments.
Example 1
The embodiment provides a preparation method of an asphalt-based sodium ion battery anode material, which specifically comprises the following steps:
(1) Crushing raw materials: crushing and screening asphalt, and taking 30g of material to obtain unoxidized asphalt with the particle size of 10 microns;
(2) Pre-oxidation treatment: under the air atmosphere, performing 3h pre-oxidation treatment on unoxidized asphalt at 300 ℃ to obtain oxidized asphalt;
(3) And (3) heating and coating treatment: after the oxidized asphalt is cooled to room temperature, heating, mixing and coating the cooled oxidized asphalt and the unoxidized asphalt according to the mass ratio of 1:0.05 for 0.5h, and coating the unoxidized asphalt outside the oxidized asphalt at the heating temperature of 200 ℃ to obtain a coating material;
(4) High-temperature carbonization treatment: and after the coating material is cooled to room temperature, carrying out high-temperature carbonization treatment for 2 hours, and finally preparing the asphalt-based sodium ion battery anode material, wherein the yield is 50%, the D002 is 0.371nm, the coating thickness of unoxidized asphalt is 30nm, the reversible capacity of the half battery is 258.4mAh/g, and the initial efficiency is 73%. The XRD pattern of the asphalt-based sodium ion battery anode material provided in example 1 is shown.
Example 2
The embodiment provides a preparation method of an asphalt-based sodium ion battery anode material, which specifically comprises the following steps:
(1) Crushing raw materials: crushing and screening asphalt, and taking 35g of material to obtain unoxidized asphalt with the particle size of 10 microns;
(2) Pre-oxidation treatment: under the air atmosphere, performing pre-oxidation treatment on unoxidized asphalt at 300 ℃ for 6 hours to obtain oxidized asphalt;
(3) And (3) heating and coating treatment: after the oxidized asphalt is cooled to room temperature, heating, mixing and coating the cooled oxidized asphalt and the unoxidized asphalt according to the mass ratio of 1:0.08 for 0.5h, and coating the unoxidized asphalt outside the oxidized asphalt at the heating temperature of 200 ℃ to obtain a coating material;
(4) High-temperature carbonization treatment: and after the coating material is cooled to room temperature, carrying out high-temperature carbonization treatment for 2 hours, and finally preparing the asphalt-based sodium ion battery anode material, wherein the yield is 54%, the D002 is 0.374nm, the coating thickness of unoxidized asphalt is 35nm, the reversible capacity of the half battery is 261.7mAh/g, and the initial efficiency is 75%.
Example 3
The embodiment provides a preparation method of an asphalt-based sodium ion battery anode material, which specifically comprises the following steps:
(1) Crushing raw materials: crushing and screening asphalt, and taking 35g of material to obtain unoxidized asphalt with the particle size of 8 microns;
(2) Pre-oxidation treatment: under the air atmosphere, performing pre-oxidation treatment on unoxidized asphalt at 300 ℃ for 12 hours to obtain oxidized asphalt;
(3) And (3) heating and coating treatment: after the oxidized asphalt is cooled to room temperature, carrying out heating, mixing and coating treatment on the cooled oxidized asphalt and the unoxidized asphalt according to the mass ratio of 1:0.10, wherein the mixing time is 1h, the heating temperature is 200 ℃, and coating the unoxidized asphalt on the exterior of the oxidized asphalt to obtain a coating material;
(4) High-temperature carbonization treatment: and (3) cooling the coated material to room temperature, and then performing high-temperature carbonization treatment for 2 hours to finally prepare the asphalt-based sodium ion battery anode material, wherein the yield is 52%, the D002 is 0.378nm, the coating thickness of unoxidized asphalt is 45nm, the reversible capacity of the half battery is 261.2mAh/g, and the initial efficiency is 78%.
Example 4
The embodiment provides a preparation method of an asphalt-based sodium ion battery anode material, which specifically comprises the following steps:
(1) Crushing raw materials: crushing and screening asphalt, and taking 45g of material to obtain unoxidized asphalt with the particle size of 5 microns;
(2) Pre-oxidation treatment: under the air atmosphere, performing pre-oxidation treatment on unoxidized asphalt at 450 ℃ for 6 hours to obtain oxidized asphalt;
(3) And (3) heating and coating treatment: after the oxidized asphalt is cooled to room temperature, heating and mixing the cooled oxidized asphalt and the unoxidized asphalt according to the mass ratio of 1:0.08 for 1h at 220 ℃, and coating the unoxidized asphalt on the exterior of the oxidized asphalt to obtain a coating material;
(4) High-temperature carbonization treatment: and after the coating material is cooled to room temperature, carrying out high-temperature carbonization treatment for 2 hours, and finally preparing the asphalt-based sodium ion battery anode material, wherein the yield is 52%, the D002 is 0.395nm, the coating thickness of unoxidized asphalt is 15nm, the reversible capacity of the half battery is 303.5mAh/g, and the initial efficiency is 89%.
Example 5
The embodiment provides a preparation method of an asphalt-based sodium ion battery anode material, which specifically comprises the following steps:
(1) Crushing raw materials: crushing and screening asphalt, and taking 40g of material to obtain unoxidized asphalt with the particle size of 5 microns;
(2) Pre-oxidation treatment: under the air atmosphere, performing pre-oxidation treatment on unoxidized asphalt at 450 ℃ for 9 hours to obtain oxidized asphalt;
(3) And (3) heating and coating treatment: after the oxidized asphalt is cooled to room temperature, heating and mixing the cooled oxidized asphalt and the unoxidized asphalt according to the mass ratio of 1:0.10 for 0.5h at the heating temperature of 200 ℃, and coating the unoxidized asphalt on the exterior of the oxidized asphalt to obtain a coating material;
(4) High-temperature carbonization treatment: and after the coating material is cooled to room temperature, carrying out high-temperature carbonization treatment for 4 hours, and finally preparing the asphalt-based sodium ion battery anode material, wherein the yield is 56%, the D002 is 0.383nm, the coating thickness of unoxidized asphalt is 45nm, the reversible capacity of the half battery is 286.4mAh/g, and the initial efficiency is 87%.
Example 6
The embodiment provides a preparation method of an asphalt-based sodium ion battery anode material, which specifically comprises the following steps:
(1) Crushing raw materials: crushing and screening asphalt, and taking 30g of material to obtain unoxidized asphalt with the particle size of 8 microns;
(2) Pre-oxidation treatment: under the air atmosphere, performing pre-oxidation treatment on unoxidized asphalt at 500 ℃ for 6 hours to obtain oxidized asphalt;
(3) And (3) heating and coating treatment: after the oxidized asphalt is cooled to room temperature, heating and mixing the cooled oxidized asphalt and the unoxidized asphalt according to the mass ratio of 1:0.20 for 0.5h at the heating temperature of 200 ℃, and coating the unoxidized asphalt on the exterior of the oxidized asphalt to obtain a coating material;
(4) High-temperature carbonization treatment: and after the coated material is cooled to room temperature, carrying out high-temperature carbonization treatment for 4 hours, and finally preparing the asphalt-based sodium ion battery anode material, wherein the yield is 55%, the D002 is 0.380nm, the half battery reversible capacity is 278.4mAh/g, the coating thickness of unoxidized asphalt is 40nm, and the initial effect is 82%.
Example 7
The embodiment provides a preparation method of an asphalt-based sodium ion battery anode material, which specifically comprises the following steps:
(1) Crushing raw materials: crushing and screening asphalt, and taking 45g of material to obtain unoxidized asphalt with the particle size of 8 microns;
(2) Pre-oxidation treatment: under the air atmosphere, performing pre-oxidation treatment on unoxidized asphalt at 500 ℃ for 12 hours to obtain oxidized asphalt;
(3) And (3) heating and coating treatment: after the oxidized asphalt is cooled to room temperature, heating and mixing the cooled oxidized asphalt and the unoxidized asphalt according to the mass ratio of 1:0.35 for 0.5h at the heating temperature of 200 ℃, and coating the unoxidized asphalt on the exterior of the oxidized asphalt to obtain a coating material;
(4) High-temperature carbonization treatment: after the coating material is cooled to room temperature, carrying out high-temperature carbonization treatment for 6 hours, and finally preparing the asphalt-based sodium ion battery anode material, wherein the yield is 47%, the D002 is 0.387nm, the coating thickness of unoxidized asphalt is 45nm, the reversible capacity of the half battery is 280.1mAh/g, and the initial efficiency is 85%.
Example 8
The embodiment provides a preparation method of an asphalt-based sodium ion battery anode material, which specifically comprises the following steps:
(1) Crushing raw materials: crushing and screening asphalt, and taking 30g of material to obtain unoxidized asphalt with the particle size of 10 microns;
(2) Pre-oxidation treatment: under the air atmosphere, performing pre-oxidation treatment on unoxidized asphalt at 500 ℃ for 6 hours to obtain oxidized asphalt;
(3) And (3) heating and coating treatment: after the oxidized asphalt is cooled to room temperature, heating and mixing the cooled oxidized asphalt and the unoxidized asphalt according to the mass ratio of 1:0.35 for 0.5h at the heating temperature of 200 ℃, and coating the unoxidized asphalt on the exterior of the oxidized asphalt to obtain a coating material;
(4) High-temperature carbonization treatment: and after the coating material is cooled to room temperature, carrying out high-temperature carbonization treatment for 6 hours, and finally preparing the asphalt-based sodium ion battery anode material, wherein the yield is 45%, the D002 is 0.381nm, the coating thickness of unoxidized asphalt is 50nm, the reversible capacity of the half battery is 269.9mAh/g, and the initial efficiency is 79%.
Comparative example 1
The comparative example provides a preparation method of an asphalt-based sodium ion battery anode material, which comprises the following steps:
and crushing and screening asphalt, taking 30g of material to obtain asphalt with the particle size of 10 microns, and carbonizing the material at 1200 ℃ for 2 hours under the nitrogen atmosphere to finally prepare the asphalt-based sodium ion battery anode material with the yield of 38%, the D002 of 0.344nm and the half-battery reversible capacity of 87.6mAh/g and the initial efficiency of 65%.
Comparative example 2
The comparative example provides a preparation method of an asphalt-based sodium ion battery anode material, which comprises the following steps:
45g of material is taken after asphalt is crushed and sieved, the material is subjected to carbonization treatment for 6 hours at 1400 ℃ under the nitrogen atmosphere, and finally the asphalt-based sodium ion battery anode material is prepared, the yield is 35%, the D002 is 0.341nm, the half-battery reversible capacity is 85.5mAh/g, and the initial efficiency is 62%.
Comparative example 3
The comparative example provides a preparation method of an asphalt-based sodium ion battery anode material, which comprises the following steps:
and crushing and screening asphalt, taking 43g of material, adding the material into 1600 ℃ under nitrogen atmosphere until the particle size of the asphalt is 12 microns, and carbonizing the material for 6 hours to finally prepare the asphalt-based sodium ion battery anode material.
Performance testing
The invention carries out multiple performance tests on the asphalt-based sodium ion battery anode materials prepared in the above examples and comparative examples, such as yield, D002, half-battery reversible capacity, initial efficiency and the like, and the test method and test results are as follows:
the testing method comprises the following steps:
d002 interlayer spacing test: using XRD detection material, calculated according to the formula d002=λ/(2sinθ);
half cell performance test: the prepared hard carbon negative electrode material is used as an electrode, a sodium sheet is used as a counter electrode, and NaPF with the concentration of 1 mol/L is used 6 The battery was assembled in a glove box filled with argon for charge and discharge testing, with the Ethylene Carbonate (EC)/dimethyl carbonate (DEC)/Propylene Carbonate (PC) solution as the electrolyte (molar volume ratio EC/DMC/PC 1:1) and 1% fluoroethylene carbonate (FEC) as the electrolyte additive.
Test results: see table below.
Table 1 results of testing the negative electrode material properties of asphalt-based sodium ion batteries obtained in examples and comparative examples
As a result of analysis, the negative electrode materials prepared in comparative examples 1 to 3 are prepared by carbonizing asphalt oxide at a high temperature, and the negative electrode materials are not ideal in terms of performances such as yield, etc., while the yield of the asphalt-based sodium ion battery negative electrode materials prepared by adopting the preparation process provided in examples 1 to 8 is 52 to 56%, the D002 interlayer distance is 0.371 to 0.395nm, the reversible specific capacity is 258.4 to 303.5mAh/g, and the initial effect is 73 to 89%, and therefore, the negative electrode materials prepared in the invention have the characteristics of high yield and low cost.
XRD pattern analysis
Taking the asphalt-based sodium ion battery anode material prepared in the embodiment 1 as an example, the anode material is subjected to X-ray diffraction analysis to obtain an XRD pattern shown in the figure 1, and the analysis of the figure 1 shows that two broad peaks respectively corresponding to a (002) diffraction peak and a (100) diffraction peak of the material appear near 23 DEG and 43 DEG, wherein the two broad diffraction peaks show that the prepared hard carbon belongs to an amorphous state, and the carbon material with an amorphous structure has good sodium storage capacity and high reversible specific capacity.
Outer coating-unoxidized asphalt thickness screening test
Since the thickness of the outer coating layer-unoxidized asphalt is closely related to each performance of the asphalt-based sodium ion battery anode material of the invention, in order to optimize the most suitable thickness range, the invention also carries out a screening test of the thickness of the outer coating layer-unoxidized asphalt, and a specific test method and test result are as follows:
test grouping and method:
outer coating-unoxidized asphalt thickness: 5nm, 10 nm, 15nm, 25 nm, 30nm, 35nm, 40nm, 45nm, 50nm, 60 nm;
asphalt-based sodium ion battery anode materials of different coating thicknesses were prepared separately with reference to the preparation method as described in example 1, and subjected to electrochemical performance testing.
Test results: see table 2.
TABLE 2 results of thickness screening test of overcoat-unoxidized asphalt
From the above table data, it is understood that the electrochemical performance of the asphalt-based sodium ion battery anode material prepared by the method of reference example 1 is ideal when the thickness of the outer coating layer-unoxidized asphalt is in the range of 10-50 nm, whereas the electrochemical performance of the prepared asphalt-based sodium ion battery anode material cannot be expected when the thickness of the outer coating layer-unoxidized asphalt is below (e.g., 5 nm) or exceeds (e.g., 60 nm), and thus the thickness of the outer coating layer-unoxidized asphalt has an important influence on the electrochemical performance of the asphalt-based sodium ion battery anode material.
Claims (9)
1. The preparation method of the asphalt-based sodium ion battery anode material is characterized by comprising the following steps of:
crushing raw materials: crushing and screening asphalt to obtain crushed asphalt;
pre-oxidation treatment: under the air atmosphere, pre-oxidizing the crushed asphalt to obtain oxidized asphalt;
and (3) heating and coating treatment: after the oxidized asphalt is cooled to room temperature, mixing, heating and coating the cooled oxidized asphalt and unoxidized asphalt according to a certain proportion, and coating the unoxidized asphalt outside the oxidized asphalt to obtain a coating material;
high-temperature carbonization treatment: and after the coating material is cooled to room temperature, performing high-temperature carbonization treatment to obtain the asphalt-based sodium ion battery anode material.
2. The method for preparing an asphalt-based sodium ion battery anode material according to claim 1, wherein the asphalt is selected from any one or a combination of a plurality of petroleum asphalt, coal asphalt and natural asphalt.
3. The method for preparing a negative electrode material for an asphalt-based sodium ion battery according to claim 1, wherein the crushed asphalt has a particle size ranging from 3 to 10 μm in D50.
4. The method for preparing the asphalt-based sodium ion battery anode material according to claim 1, wherein the pre-oxidation treatment has an oxidation temperature of 300-500 ℃ and an oxidation time of 3-12h.
5. The method for preparing the asphalt-based sodium ion battery anode material according to claim 1, wherein the mass ratio of the oxidized asphalt to the unoxidized asphalt is 1 (0.05-0.35).
6. The method for preparing the asphalt-based sodium ion battery anode material according to claim 1, wherein the temperature of the mixed heating cladding treatment of the oxidized asphalt and the unoxidized asphalt is 200-300 ℃ and the time is 0.5-1.5h.
7. The method for preparing a negative electrode material of an asphalt-based sodium ion battery according to claim 1, wherein the high-temperature carbonization temperature is 900-1600 ℃ and the carbonization time is 2-8h.
8. An asphalt-based sodium ion battery anode material, which is prepared by the preparation method according to any one of claims 1-7.
9. The asphalt-based sodium ion battery anode material according to claim 8, wherein the coated inner core of the asphalt-based sodium ion battery anode material is oxidized asphalt, the outer coating layer is unoxidized asphalt, and the thickness of the outer coating layer is 10-50 nanometers.
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