CN112397715A - Hard carbon material, preparation method thereof and sodium ion battery - Google Patents
Hard carbon material, preparation method thereof and sodium ion battery Download PDFInfo
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Abstract
The invention relates to the technical field of sodium ion batteries, and provides a preparation method of a hard carbon material, which comprises the following steps: firstly, mixing a coal-based material and a hard carbon precursor, and then pressing to obtain hard sheets; the hard carbon precursor is carbohydrate and/or gelatin; and then carbonizing the obtained hard sheet at high temperature to obtain the hard carbon material. According to the invention, the hard carbon precursor is tightly contacted with the coal-based material by means of tabletting, so that the reaction activities of the hard carbon precursor and the coal-based material are greatly improved, the hard carbon precursor and the coal-based material are fully subjected to a crosslinking reaction in the high-temperature carbonization treatment process, the carbonization yield is effectively improved, the defects formed in the carbonization process are reduced, the specific surface area is reduced, and the disorder and the carbon layer spacing of a carbon layer in the carbonization process are increased. The sodium ion battery obtained by using the hard carbon material obtained by the preparation method provided by the invention as a negative electrode material of the sodium ion battery has high sodium storage capacity and first coulombic efficiency.
Description
Technical Field
The invention relates to the technical field of sodium ion battery materials, in particular to a hard carbon material, a preparation method thereof and a sodium ion battery.
Background
The sodium ion battery has the advantages of rich resources, high energy conversion rate and good safety, and is expected to be applied to the next generation of large-scale energy storage devices. The negative electrode material is one of the main problems restricting the development of the sodium ion battery at present. The amorphous carbon material has low graphitization degree, high disorder degree and large carbon layer spacing, and shows extremely high specific capacity when being applied to the cathode of a sodium ion battery, so the amorphous carbon material is widely concerned by researchers.
Amorphous carbon materials can be divided into hard carbon materials and soft carbon materials, wherein the hard carbon materials have low graphitization degree and poor multiplying power performance, the soft carbon materials have high graphitization degree and low sodium storage capacity, and researchers often adopt a soft-hard combination mode to complement the advantages of the hard carbon materials and the soft carbon materials and improve the performance. For example, Li et al in the literature (j.mater.chem.a,2016,4, 96-104) report that soft carbon precursor pitch in combination with hard carbon precursor lignin increases the degree of disorder of the material by inhibiting the graphitization of the pitch by emulsification of the lignin, thereby reducing defects and improving coulombic efficiency. However, the lignin is very expensive, and the sodium storage specific capacity of the best sample is only 254mAh g-1And lacks practical application prospect.
Although the advantages of the soft and hard combination can be skillfully combined, the improvement of the sodium storage capacity by the method is still insufficient. In addition to the hard-soft bonding approach, many researchers have focused on the hard-hard bonding approach. The sodium storage capacity is improved through the interaction between hard carbon precursors, the defects are reduced, and the first-turn coulombic efficiency is improved. For example, Yang et al, by using the interaction between epoxy resin and lignin to form a cross-linked network structure, improve the sodium storage performance (chem. Eng. J, 2018, 341, 280-one 288), and the sodium storage capacity is up to 316mAh g in the battery test-1. However, the method also needs expensive lignin, and the capacity of the lignin material per se is as high as 290mAh g-1Therefore, the method has higher sodium storage performance because of the material; meanwhile, the epoxy resin and the high-purity lignin have relatively high cost, so that the realization of large-scale production is difficult. Zhang et al adopts sucrose and phenolic resin to mix and then carbonize and pyrolyze (ACS appl. Mater. interfaces, 2017,9, 23766-; however, phenolThe cost of the aldehyde resin is also high and the components are uncertain, which is also difficult to adapt to mass production.
Compared with carbon sources such as epoxy resin, lignin, phenolic resin and the like, the coal is used as an organic matter with high carbon content, has various types, rich reserves and low cost, and can be effectively prepared on a large scale. Although the coal material has the advantages, the carbon material pyrolyzed by the coal-based material is adopted as the negative electrode material of the sodium-ion battery, and the sodium storage capacity of the carbon material is 250mAh g-1About, the first-week coulombic efficiency is about 65%, so that the sodium storage capacity still needs to be improved, and the first-circle coulombic efficiency is lower and cannot meet the practical requirement, so that the performance of the coal-based carbon material needs to be improved urgently. In recent years, researchers have modified coal-based materials by adopting a soft carbon coating mode, and in a patent of a method for improving the performance of a coal-based sodium ion battery negative electrode material and application thereof (application number CN202010141998.2), a soft carbon precursor and the coal-based material are mixed and then are heated in an air atmosphere to be fused together, so that the coulombic efficiency and the tap density are improved. However, the carbon material prepared by using coal as a raw material in the scheme has the highest specific sodium storage capacity of only 271.4mAh g-1. Therefore, a method for preparing a carbon material with high sodium storage specific capacity by using inexpensive materials such as coal as raw materials is needed.
Disclosure of Invention
In view of the above, the present invention aims to provide a hard carbon material, a preparation method thereof and a sodium ion battery. The preparation method provided by the invention takes the coal-based material with wide resources, low cost and stable components and the hard carbon precursor as raw materials, and the prepared hard carbon material has high sodium storage capacity when being used as the cathode material of the sodium-ion battery.
In order to achieve the above object, the present invention provides the following technical solutions:
a method of preparing a hard carbon material, comprising the steps of:
(1) mixing the coal-based material and the hard carbon precursor, and pressing to obtain a hard sheet; the hard carbon precursor is carbohydrate and/or gelatin;
(2) and (2) carrying out high-temperature carbonization on the hard sheet obtained in the step (1) to obtain a hard carbon material.
Preferably, the coal-based material in step (1) includes at least one of anthracite, bituminous coal and lignite.
Preferably, the mass ratio of the coal-based material to the hard carbon precursor in the step (1) is 1: 1-10: 1.
Preferably, the pressing pressure in the step (1) is 3-30 Mpa, and the pressing time is 1-12 min.
Preferably, the atmosphere of the high-temperature carbonization treatment in the step (2) is an inert atmosphere.
Preferably, the inert atmosphere comprises at least one of nitrogen, helium, argon, neon and xenon.
Preferably, the highest temperature of the high-temperature carbonization in the step (2) is 600-1500 ℃, and the heat preservation time at the highest temperature is 0.5-5 h.
Preferably, the temperature rise rate of the high-temperature carbonization in the step (2) is 0.5-10 ℃/min.
The invention also provides the hard carbon material prepared by the preparation method.
Preferably, the specific surface area of the hard carbon material is 1-10 m2 g-1(ii) a The (002) crystal face interlayer spacing of the hard carbon material is 0.37-0.39 nm.
The invention also provides a sodium ion battery prepared from the hard carbon material in the technical scheme, and the hard carbon material is used as a negative electrode material of the sodium ion battery.
The invention provides a preparation method of a hard carbon material, which comprises the following steps: firstly, mixing a coal-based material and a hard carbon precursor, and then pressing to obtain hard sheets; the hard carbon precursor is carbohydrate and/or gelatin; and then carbonizing the obtained hard sheet at high temperature to obtain the hard carbon material. According to the invention, a hard carbon precursor and a coal-based material which is wide in resource, low in cost and stable in components are used as carbon sources, the two carbon sources are tightly contacted by a tabletting method, and a stable structure which is mutually crosslinked is formed by high-temperature carbonization treatment; wherein the means for tabletting is a hard carbon precursorThe carbon-based carbon material is in close contact with a coal-based material, so that the reactivity of the carbon-based carbon material and the coal-based material is greatly improved, the carbon-based material and the coal-based material are subjected to a crosslinking reaction fully in a high-temperature carbonization treatment process, the carbonization yield is effectively improved, the defects formed in the carbonization process are reduced, the specific surface area is reduced, and the disorder of a carbon layer and the spacing between carbon layers in the carbonization process are increased. The hard carbon material obtained by the preparation method provided by the invention is used as a negative electrode material of a sodium ion battery, has high sodium storage capacity and first coulombic efficiency, and has the reversible sodium storage capacity up to 350mAh g-1And the coulombic efficiency of the first circle is as high as more than 85 percent, which is far higher than the reversible sodium storage capacity of 271.4mAhg of the sodium-ion battery prepared by the coal-based material disclosed by the prior art-1And a first week coulombic efficiency of 65%.
Drawings
FIG. 1 is a digital photograph of a hard sheet obtained after the completion of the tabletting in the preparation process of example 1;
fig. 2 is a Scanning Electron Microscope (SEM) photograph of the hard carbon material prepared in example 1;
FIG. 3 is a BET isothermal adsorption curve and a pore size distribution curve of the hard carbon material prepared in example 1;
fig. 4 is an X-ray diffraction pattern (XRD) of the hard carbon material prepared in example 1;
FIG. 5 is a charge-discharge curve diagram of a sodium ion battery prepared in application example 1;
fig. 6 is a cycle diagram of a sodium ion battery prepared in application example 1;
fig. 7 is a sodium ion battery charge and discharge curve of the hard carbon material prepared in comparative example 1;
fig. 8 is a cycle graph of a sodium ion battery of the hard carbon material prepared in comparative example 1;
FIG. 9 is a charge-discharge curve chart of a sodium ion battery prepared in application example 2;
FIG. 10 is a graph showing the cycle profile of a sodium-ion battery prepared in application example 2;
FIG. 11 is a charge-discharge curve diagram of a sodium ion battery prepared in application example 3;
fig. 12 is a graph showing the cycle profile of the sodium ion battery prepared in application example 3.
Detailed Description
The invention provides a preparation method of a hard carbon material, which comprises the following steps:
(1) mixing the coal-based material and the hard carbon precursor, and pressing to obtain a hard sheet;
the hard carbon precursor is carbohydrate and/or gelatin;
(2) and (2) carrying out high-temperature carbonization on the hard sheet obtained in the step (1) to obtain a hard carbon material.
According to the invention, the coal-based material and the hard carbon precursor are mixed and then pressed to obtain the hard sheet.
In the present invention, the coal-based material preferably includes at least one of anthracite, bituminous coal and lignite, more preferably bituminous coal and/or lignite. In the present invention, the bituminous coal and/or lignite is cheaper among coal-based materials as a raw material for preparing a hard carbon material.
In the present invention, the hard carbon precursor is a carbohydrate and/or gelatin, preferably at least one of sucrose, glucose and gelatin. In the present invention, the sucrose, glucose and gelatin are used as common raw materials with coal-based materials, which are common and inexpensive in hard carbon materials.
The sources of the coal-based material and the hard carbon precursor are not specially specified in the invention, and the coal-based material and the hard carbon precursor which are well known to those skilled in the art can be adopted.
In the invention, the mass ratio of the coal-based material to the hard carbon precursor is preferably 1: 1-10: 1, and more preferably 2: 1-5: 1. In the invention, the hard carbon material obtained by controlling the mass ratio of the coal-based material to the hard carbon precursor in the range has better electrochemical performance.
In the invention, the particle sizes of the coal-based material and the hard carbon precursor are preferably 0.5-12 μm, and more preferably 1-10 μm. In the invention, the particle sizes of the coal-based material and the hard carbon precursor are controlled within the range, so that the obtained hard carbon material has good electrochemical performance.
The invention preferably mixes the coal-based material and the hard carbon precursor in a ball milling manner. The ball milling mode is not specially specified, and the particle sizes of the coal-based material and the hard carbon precursor are ball milled to the required specification.
In the present invention, the compression is preferably performed in a tablet press die. The invention does not specify the type of tablet press dies, and the coal-based material and the hard carbon precursor are pressed together using tablet press dies well known to those skilled in the art.
In the invention, the pressing pressure is preferably 3-30 Mpa, more preferably 5-20 Mpa; the pressing time is preferably 1-12 min, and more preferably 2-10 min. In the invention, the pressing pressure and the pressing time adopt the values in the range, and the obtained hard carbon material has better electrochemical performance.
After obtaining the hard sheet, the invention carries out high-temperature carbonization on the hard sheet to obtain the hard carbon material.
In the present invention, the atmosphere of the high-temperature carbonization is preferably an inert atmosphere. In the present invention, the inert atmosphere preferably includes at least one of nitrogen, helium, argon, neon, and xenon, and more preferably nitrogen. In the invention, the nitrogen is a common inert atmosphere gas provider, and the hard sheet is subjected to high-temperature carbonization treatment, so that the electrochemical performance of the material can be prevented from being reduced due to the oxidation of the hard sheet by oxygen in the air.
In the present invention, the temperature increase method of the high-temperature carbonization is preferably a temperature programmed method. In the present invention, the temperature is preferably programmed to be raised to an intermediate temperature and then to a maximum temperature. In the invention, the intermediate temperature is preferably 100-600 ℃, and more preferably 200-500 ℃. In the invention, the heat preservation time at the intermediate temperature is preferably 0.4-5 h, and more preferably 0.5-3 h. In the invention, the highest temperature is preferably 600-1500 ℃, and more preferably 800-1400 ℃; the heat preservation time at the highest temperature is preferably 0.5-5 h, and more preferably 2-3 h. In the present invention, the temperature increase rate of the high-temperature carbonization is preferably 0.4 to 10 ℃/min, and more preferably 0.5 to 5 ℃/min. In the present invention, the temperature increase rates of the intermediate temperature and the maximum temperature are both within the above ranges, and the temperature increase rate of the intermediate temperature and the temperature increase rate of the maximum temperature may be the same or different. In the invention, the obtained hard carbon material has good carbonization effect by adopting the temperature rising mode and the temperature rising rate as well as the carbonization temperature and the carbonization time, thereby improving the electrochemical performance of the material and reducing the influence of the temperature rising process on the experimental result.
After the high-temperature carbonization is finished, the product after the high-temperature carbonization is preferably sequentially cooled and washed to obtain the hard carbon material.
In the present invention, the end temperature of the temperature decrease is preferably room temperature.
The invention has no special regulation on the cooling mode, and the natural cooling mode is adopted.
In the present invention, the washing preferably includes acid washing and water washing in this order.
In the present invention, the acid to be pickled is preferably a medium strong acid, and more preferably at least one of hydrochloric acid, sulfuric acid and phosphoric acid. In the invention, the acid can remove some mineral impurities possibly brought in during the carbonization process of the carbon material, and simultaneously, the influence of acid washing on the carbon material is avoided.
In the present invention, the acid washing is preferably performed by washing the product after the high-temperature carbonization in a boiled aqueous acid solution. In the present invention, the concentration of the aqueous acid solution is preferably 2 to 4M, and more preferably 3M. In the invention, the hard carbon material obtained by washing with the acid aqueous solution with the concentration has better electrochemical performance. In the invention, the pickling time is preferably 1-5 h, and more preferably 2-4 h. In the invention, the acid washing is carried out in a boiling way, so that the reaction rate of the acid and impurities contained in the carbon material can be accelerated, and the reaction can be more uniform.
In the present invention, the washing method is preferably washing the product after the high-temperature carbonization in boiled water. In the invention, the time for washing is preferably 1-5 h, and more preferably 2-4 h. In the invention, the water washing can remove acid remained on the surface of the carbon material in the acid washing process, and the water washing can accelerate the water washing speed by adopting the boiling mode.
In the invention, the pH of the washing liquid after washing is preferably 6-7, and more preferably 7. In the present invention, the pH of the solution after washing with water is 7, and the electrochemical performance of the obtained carbon material is good.
The invention also provides the hard carbon material prepared by the preparation method.
In the invention, the specific surface area of the hard carbon material is preferably 1-10 m2 g-1More preferably 9m2 g-1. In the invention, the interlayer spacing of the (002) crystal plane of the hard carbon material is preferably 0.37-0.39 nm, and more preferably 0.382 nm. In the present invention, the carbon yield of the hard carbon material is preferably 47% to 52%, more preferably 49.2%. In the invention, the hard carbon material has the characteristics and has better electrochemical performance.
The invention also provides the hard carbon material in the technical scheme as a negative electrode material of the sodium-ion battery.
The structure of the sodium ion battery is not particularly limited, and the hard carbon material can be used as the negative electrode material of the sodium ion battery by adopting the sodium ion battery structure well known to the technical personnel in the field.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Mixing 14g of lignite and 6g of sucrose (the mass ratio of the coal-based material to the hard carbon precursor is 7:3), putting the mixture into a ball mill, and carrying out ball milling for 4 hours at the revolution of 400r/min (the particle sizes of the lignite and the sucrose are both in the range of 1-10 microns); taking out the powder, pouring the powder into a die of a tablet press, keeping the pressure of 15MPa for 5min to obtain a hard tablet, and taking out the hard tablet, wherein a digital photo of the hard tablet is shown in figure 1; as can be seen from fig. 1, the hard tablets obtained after compression by the falling tablet press are round and have a relatively smooth surface without defects.
Putting the hard sheet into a tube furnace, carrying out high-temperature carbonization in nitrogen atmosphere, raising the temperature to 400 ℃ at the speed of 2 ℃/min, and preserving the temperature for 2 h; then heating to 1200 ℃ at the heating rate of 5 ℃/min, preserving the heat for 2h, and finally naturally cooling to room temperature; and boiling the product in hydrochloric acid with the concentration of 3M for 4h, and then boiling the product with deionized water for 4h and cleaning the product until the pH value is 7 to obtain the final product, namely the hard carbon material.
The obtained hard carbon material was scanned with an electron microscope, and the result is shown in fig. 2; as can be seen from fig. 2, the obtained hard carbon material particles had a particle size of 5 μm and a relatively smooth surface without significant defects.
The obtained hard carbon material was subjected to an isothermal nitrogen adsorption specific surface area test, and the result thereof is shown in fig. 3; the resulting hard carbon material had a specific surface area of 9m calculated by DFT according to FIG. 32The pore diameter distribution is mainly micropore.
The obtained hard carbon material was subjected to X-ray diffraction spectrum test, and the result is shown in fig. 4. According to the calculation of fig. 4, the half-peak width is 8 degrees, the angle corresponding to the (002) peak is 23.75 degrees, and the crystal face spacing is 0.382nm, which indicates that the hard carbon material has low graphitization degree, large graphite layer spacing and sufficient sodium storage sites; and a larger interlayer spacing indicates a higher degree of disorder in the material.
The hard carbon material prepared in example 1 was tested for carbonization yield, high-resolution transmission and raman spectroscopy, and the following results were obtained:
carbonization yield: 49.2 percent; (actual carbonization yield of brown coal was 53.7%, actual carbonization yield of sucrose was 20.8%, and theoretical yield after mixing both in 7-3 was 43.8%)
High resolution transmission characterization results: the graphite crystal lattice stripe disorder degree of the material is higher.
Test results of raman spectroscopy: the ratio of peak areas IG/IDIs 0.55, the disorder degree of the material is higher.
Application example 1
The powder of hard carbon material prepared in example 1 was mixed with sodium carboxymethyl cellulose in a ratio of 95: 5 mass ratio ofAdding appropriate amount of water, grinding to obtain slurry, uniformly coating the slurry on a current collector copper foil, drying, and cutting into (10 × 10) mm2The pole piece of (2). The pole piece is dried for 10 hours at 120 ℃ under the vacuum condition and then transferred to a glove box for standby. The cell was assembled in a glove box under Ar atmosphere, with sodium metal as the counter electrode, NaClO at 1M concentration4And dissolving in Ethylene Carbonate (EC) and diethyl carbonate (DEC) (volume ratio of 1:1) as electrolyte to assemble the CR2025 button cell.
Performance testing
The battery prepared in application example 1 was subjected to a charge and discharge performance test under the following test conditions: the charging and discharging mode is constant current charging and discharging; the current density is 0.03Ag-1(ii) a The discharge cutoff voltage was 0.001V and the charge cutoff voltage was 3V. The test results are shown in fig. 5 and 6.
As can be seen from the charging and discharging curves of FIG. 5, the first week sodium storage specific capacity is as high as 343mAh g-1The first week coulombic efficiency is 83%, and the sodium storage capacity is higher.
As can be seen from the cyclic curve of FIG. 6, the Ag concentration is 0.05Ag-1After 50 cycles, the capacity retention rate of the lithium ion battery reaches 92 percent.
Comparative example 1
The experiment was performed as in example 1, except that the powder was directly pretreated after ball milling without a tablet press process.
Preparing into battery
The powder of hard carbon material prepared in comparative example 1 was mixed with sodium carboxymethyl cellulose in a ratio of 95: 5, adding a proper amount of water, grinding to form slurry, then uniformly coating the slurry on a current collector copper foil, drying, and cutting into (10 multiplied by 10) mm2The pole piece of (2). The pole piece is dried for 10 hours at 120 ℃ under the vacuum condition and then transferred to a glove box for standby. The cell was assembled in a glove box under Ar atmosphere, with sodium metal as the counter electrode, NaClO at 1M concentration4Tests were carried out in CR2025 button cells assembled in solution in Ethylene Carbonate (EC) and diethyl carbonate (DEC) (1: 1 by volume) as electrolytes.
Performance testing
The battery prepared in comparative example 1 was used for the charge and discharge performance test under the following conditions: the charging and discharging mode is constant current charging and discharging; the current density is 0.03Ag-1(ii) a The discharge cutoff voltage was 0.001V and the charge cutoff voltage was 3V. The test results are shown in fig. 7 and 8.
As can be seen from the charge-discharge curve of FIG. 7, the Ag content is 0.03Ag-1The first week sodium storage specific capacity is up to 260mAh g under the current density of-1The first week coulombic efficiency was 75%.
As can be seen from the cyclic curve of FIG. 8, the Ag concentration is 0.05Ag-1The capacity retention rate after 50 cycles at the current density of (3) was 86%.
Example 2
Mixing 5g of bituminous coal and 5g of glucose, and then putting the mixture into a ball mill to perform ball milling for 3 hours at the revolution of 400r/min (the particle sizes of the bituminous coal and the glucose are both in the range of 1-10 mu m); taking out the powder, pouring the powder into a tablet press die, keeping the pressure of 20MPa for 10min to obtain a hard tablet, putting the hard tablet into a tube furnace, carrying out high-temperature carbonization in nitrogen atmosphere, raising the temperature to 500 ℃ at the speed of 3 ℃/min, and keeping the temperature for 0.5 h. Then heating to 800 ℃ at the heating rate of 4 ℃/min, preserving the heat for 2h, and finally naturally cooling to room temperature. And boiling the product in hydrochloric acid with the concentration of 3M for 4h, and then boiling the product with deionized water for 4h and cleaning the product until the pH value is 7 to obtain the final product, namely the hard carbon material. (the mass ratio of the coal-based material to the hard carbon precursor is 1:1)
Application example 2
The powder of hard carbon material prepared in example 2 was mixed with sodium carboxymethyl cellulose in a ratio of 95: 5, adding a proper amount of water, grinding to form slurry, then uniformly coating the slurry on a current collector copper foil, drying, and cutting into (10 multiplied by 10) mm2The pole piece of (2). The pole piece is dried for 10 hours at 120 ℃ under the vacuum condition and then transferred to a glove box for standby. The cell was assembled in a glove box in an Ar atmosphere, with sodium metal as the counter electrode and NaClO at 1M concentration4And dissolving in Ethylene Carbonate (EC) and diethyl carbonate (DEC) (volume ratio of 1:1) as electrolyte to assemble the CR2025 button cell.
Performance testing
The battery prepared in example 2 was usedAnd (3) testing the charge and discharge performance under the following test conditions: the charging and discharging mode is constant current charging and discharging; the current density is 0.03Ag-1(ii) a The discharge cutoff voltage was 0.001V and the charge cutoff voltage was 3V. The test results are shown in fig. 9 and 10.
As can be seen from the charge-discharge curve of FIG. 9, the Ag content is 0.03Ag-1The first week sodium storage specific capacity is up to 312mAh g under the current density of-1The first week coulombic efficiency is 82%, and the sodium storage capacity is higher.
As can be seen from the cycle curve of FIG. 10, the temperature at 0.05Ag-1After 50 cycles, the capacity retention rate of the lithium ion battery reaches 88 percent.
Example 3
Mixing 8g of bituminous coal and 2g of gelatin (the mass ratio of the coal-based material to the hard carbon precursor is 4:1), putting the mixture into a ball mill, and carrying out ball milling for 4 hours at the revolution of 400r/min (the particle sizes of the bituminous coal and the gelatin are both within the range of 1-10 mu m); taking out the powder, pouring the powder into a tablet press die, keeping the pressure of 5MPa for 2min to obtain a hard tablet, putting the hard tablet into a tube furnace, carrying out high-temperature carbonization in nitrogen atmosphere, raising the temperature to 200 ℃ at the speed of 0.5 ℃/min, and keeping the temperature for 3 h. Then heating to 1400 ℃ at the heating rate of 2 ℃/min, preserving the heat for 2h, and finally naturally cooling. And boiling the product in hydrochloric acid with the concentration of 3M for 2h, boiling the product with deionized water for 2h, and washing the product with deionized water until the pH value is 7 to obtain the final product, namely the hard carbon material.
Application example 3
The powder of hard carbon material prepared in example 3 was mixed with sodium carboxymethyl cellulose in a ratio of 95: 5, adding a proper amount of water, grinding to form slurry, then uniformly coating the slurry on a current collector copper foil, drying, and cutting into (10 multiplied by 10) mm2The pole piece of (2). The pole piece is dried for 10 hours at 120 ℃ under the vacuum condition and then transferred to a glove box for standby. The cell was assembled in a glove box under Ar atmosphere, with sodium metal as the counter electrode, NaClO at 1M concentration4And dissolving in Ethylene Carbonate (EC) and diethyl carbonate (DEC) (volume ratio of 1:1) as electrolyte to assemble the CR2025 button cell.
Performance testing
Battery prepared in application example 3And (3) carrying out a charge and discharge performance test under the following test conditions: the charging and discharging mode is constant current charging and discharging; the current density is 0.03Ag-1(ii) a The discharge cutoff voltage was 0.001V and the charge cutoff voltage was 3V. The test results are shown in fig. 11 and 12.
As can be seen from the charge-discharge curve of FIG. 11, the Ag content is 0.03Ag-1The first week sodium storage specific capacity is up to 326mAh g under the current density of-1The first week coulombic efficiency is 81%, and the sodium storage capacity is higher.
As can be seen from the cyclic curve of FIG. 12, the Ag is 0.05Ag-1After 50 cycles, the capacity retention rate reaches 90 percent under the current density of (1).
It can be seen from the above examples and comparative examples that the electrochemical performance of the battery is significantly improved in the test when the hard carbon material prepared by the method provided by the invention is used as the negative electrode material of the battery in the sodium ion battery. In addition, from the aspect of electrochemical performance, the method improves the disorder degree of the material, reduces defects, and obviously improves the reversible specific capacity, the first-turn coulombic efficiency and the cycle retention rate.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A method of preparing a hard carbon material, comprising the steps of:
(1) mixing the coal-based material and the hard carbon precursor, and pressing to obtain a hard sheet;
the hard carbon precursor is carbohydrate and/or gelatin;
(2) and (2) carrying out high-temperature carbonization on the hard sheet obtained in the step (1) to obtain a hard carbon material.
2. The method according to claim 1, wherein the coal-based material in the step (1) includes at least one of anthracite, bituminous coal, and lignite.
3. The preparation method according to claim 1, wherein the mass ratio of the coal-based material to the hard carbon precursor in the step (1) is 1: 1-10: 1.
4. The method according to claim 1, wherein the pressing pressure in step (1) is 3 to 30MPa, and the pressing time is 1 to 12 min.
5. The production method according to claim 1, wherein the atmosphere of the high-temperature carbonization in the step (2) is an inert atmosphere.
6. The method of claim 5, wherein the inert atmosphere comprises at least one of nitrogen, helium, argon, neon, and xenon.
7. The method according to claim 1, wherein the highest temperature of the high-temperature carbonization in the step (2) is 600 to 1500 ℃, and the holding time at the highest temperature is 0.5 to 5 hours.
8. The production method according to claim 1 or 7, wherein the temperature rise rate of the high-temperature carbonization in the step (2) is 0.5 to 10 ℃/min.
9. The hard carbon material prepared by the preparation method of any one of claims 1 to 8, wherein the specific surface area of the hard carbon material is 1 to 10m2 g-1(ii) a The (002) crystal face interlayer spacing of the hard carbon material is 0.37-0.39 nm.
10. A sodium ion battery, characterized in that the hard carbon material according to claim 9 is used as a negative electrode material.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113097557A (en) * | 2021-03-05 | 2021-07-09 | 山东玉皇新能源科技有限公司 | Sodium ion battery and preparation method thereof |
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| WO2024036902A1 (en) * | 2022-08-18 | 2024-02-22 | 广东邦普循环科技有限公司 | Carbonaceous material and preparation method therefor, and sodium-ion battery |
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001052706A (en) * | 1999-08-11 | 2001-02-23 | Konoko Kagi Kofun Yugenkoshi | Carbon material for negative electrode of secondary battery and manufacture of the negative electrode using the carbon material |
| CN104681786A (en) * | 2015-03-04 | 2015-06-03 | 深圳市贝特瑞新能源材料股份有限公司 | Coal-based anode material, preparation method and lithium-ion battery |
| CN105185997A (en) * | 2015-10-27 | 2015-12-23 | 中国科学院物理研究所 | Sodion secondary battery negative electrode material and preparing method and application thereof |
| CN107403915A (en) * | 2017-07-13 | 2017-11-28 | 南京大学 | The manganese-based anode material of sodium-ion battery |
| CN107611435A (en) * | 2017-09-13 | 2018-01-19 | 陕西科技大学 | A kind of method that three-dimensional porous sodium-ion battery carbon material used as anode is prepared based on peanut coat |
| CN107732240A (en) * | 2017-09-05 | 2018-02-23 | 合肥工业大学 | The preparation method of anode material of lithium-ion battery, and negative material prepared therefrom |
| CN108923042A (en) * | 2018-07-24 | 2018-11-30 | 南京大学 | Sodium-ion battery stratiform manganese-based anode material and preparation method thereof |
-
2020
- 2020-10-10 CN CN202011078447.2A patent/CN112397715B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001052706A (en) * | 1999-08-11 | 2001-02-23 | Konoko Kagi Kofun Yugenkoshi | Carbon material for negative electrode of secondary battery and manufacture of the negative electrode using the carbon material |
| CN104681786A (en) * | 2015-03-04 | 2015-06-03 | 深圳市贝特瑞新能源材料股份有限公司 | Coal-based anode material, preparation method and lithium-ion battery |
| CN105185997A (en) * | 2015-10-27 | 2015-12-23 | 中国科学院物理研究所 | Sodion secondary battery negative electrode material and preparing method and application thereof |
| CN107403915A (en) * | 2017-07-13 | 2017-11-28 | 南京大学 | The manganese-based anode material of sodium-ion battery |
| CN107732240A (en) * | 2017-09-05 | 2018-02-23 | 合肥工业大学 | The preparation method of anode material of lithium-ion battery, and negative material prepared therefrom |
| CN107611435A (en) * | 2017-09-13 | 2018-01-19 | 陕西科技大学 | A kind of method that three-dimensional porous sodium-ion battery carbon material used as anode is prepared based on peanut coat |
| CN108923042A (en) * | 2018-07-24 | 2018-11-30 | 南京大学 | Sodium-ion battery stratiform manganese-based anode material and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 金川集团有限公司: "《第十九次金川科技攻关大会 论文集 第1辑》", 31 December 2010 * |
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