CN115881965A - Lignin-based graphene negative electrode material with high cycle performance - Google Patents
Lignin-based graphene negative electrode material with high cycle performance Download PDFInfo
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Abstract
The invention relates to a high-cycle-performance lignin-based graphene negative electrode material, which belongs to the technical field of lithium ion batteries and comprises the following raw materials in parts by weight: 100-150 parts of aminated graphene microchip, 8-12 parts of modified silicon dioxide-lignin nanospheres, 1-3 parts of dispersing agent, 0.5-2 parts of hydrogen evolution inhibitor and 300-500 parts of deionized water. The multi-layer graphene is modified by adopting the organic high molecular polymer containing amino to form the aminated graphene microchip, so that the flux and the retention rate of the aminated graphene microchip are improved, the transport capacity of lithium ions can be effectively improved, the deposition of lithium dendrites caused by slow transmission of lithium in a negative electrode material is inhibited, and the cycle performance of metal lithium is improved; the modified silicon dioxide-lignin nanospheres reduce the strain force of the electrode in the cyclic charge and discharge process, inhibit the cracking and pulverization of silicon, have more stable performance and improve the cycle performance of the lithium ion battery by modifying the lignin.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a lignin-based graphene negative electrode material with high cycle performance.
Background
In recent years, with the rapid development of new energy industries, the development and application of lithium batteries are receiving general attention. The negative electrode material of the lithium battery is a carrier of lithium ions and electrons in the charging process of the battery, plays a role in storing and releasing energy, is one of important raw materials of the lithium battery, and has important influence on the performance of the lithium battery.
When the metal lithium cathode is applied, the charge-discharge cycle efficiency of the battery is reduced and the interface impedance is increased along with the reaction of the metal lithium and electrolyte in the cycle process; lithium dendrites can cause the problems of reduced safety, electrode active material loss and the like, and severely restrict the application of a metal lithium cathode, so that the defects of low coulomb efficiency, short cycle life, poor safety performance and the like of a lithium ion battery occur.
Disclosure of Invention
In order to solve the technical problems mentioned in the background art, the invention provides a lignin-based graphene negative electrode material with high cycle performance.
The purpose of the invention can be realized by the following technical scheme:
a high-cycle-performance lignin-based graphene negative electrode material comprises the following raw materials in parts by weight: 100-150 parts of aminated graphene microchip, 8-12 parts of modified silicon dioxide-lignin nanospheres, 1-3 parts of dispersing agent, 0.5-2 parts of hydrogen evolution inhibitor and 300-500 parts of deionized water.
Further, the dispersing agent is methanol or ethanol, and the hydrogen evolution inhibitor is barium stearate.
Further, the aminated graphene microchip is prepared by the following steps:
step A1: mixing graphene and an amino-containing organic polymer aqueous solution to obtain a mixed solution;
step A2: and (3) carrying out ultrasonic treatment on the mixed solution for 1-2h, carrying out suction filtration and deposition, and then standing and drying to obtain the aminated graphene microchip.
Further, the amino-containing organic polymer is ethylenediamine or chitosan.
Further, the interlayer spacing of the aminated graphene microchip is 0.3-0.4nm, and the specific surface area is 200-300m 2 /g。
Further, the modified silica-lignin nanosphere is prepared by the following steps:
step B1: dissolving lignin and silicon dioxide in water together, and fully stirring at room temperature to obtain a mixed solution;
and step B2: keeping the temperature of the mixed solution to carry out hydrothermal reaction to obtain a hydrothermal product;
and step B3: after cooling, carrying out solid-liquid separation treatment on the hydrothermal product to obtain a solid-phase product, and drying the solid-phase product for later use;
and step B4: and (3) calcining the dried solid-phase product at high temperature under the protection of inert gas to obtain the modified silicon dioxide-lignin nanospheres.
Further, the temperature preservation range in the step B2 is 80-95 ℃.
Further, the inert gas in the step B4 is nitrogen or argon.
Further, the particle size of the modified silicon dioxide-lignin nanosphere is 10-20 μm.
Further, the high-cycle-performance lignin-based graphene negative electrode material is prepared by the following steps:
uniformly mixing the aminated graphene nanoplatelets, the modified silicon dioxide-lignin nanospheres, the dispersing agent, the hydrogen evolution inhibitor and the deionized water to obtain a mixture; and filtering and drying the prepared mixture, then placing the mixture in a sintering furnace, raising the temperature at a heating rate of 5-10 ℃/min, roasting at a constant temperature of 500-600 ℃ for 8-10h, raising the temperature at a heating rate of 10-20 ℃/min, roasting at a constant temperature of 800-1000 ℃ for 5-6h, and then cooling to room temperature at a cooling rate of 5-10 ℃/min to obtain the high-cycle-performance lignin-based graphene negative electrode material.
The invention has the beneficial effects that:
according to the invention, the amino-containing organic high molecular polymer is adopted to modify the multi-layer graphene to form the aminated graphene microchip, so that the flux and the retention rate of the aminated graphene microchip are improved, the transport capacity of lithium ions can be effectively improved, the deposition of lithium dendrites caused by slow transmission of lithium in a negative electrode material is inhibited, and the cycle performance of metal lithium is improved;
according to the invention, lignin is modified, the modified silicon dioxide-lignin nanospheres are highly dispersed and have regular shapes, the hollow structure and the silicon carbon layer reduce the strain force caused by volume change of the electrode in the cyclic charge-discharge process, the cracking and pulverization of silicon are inhibited, the shell is the carbon layer, the conductivity can be effectively improved, and the performance is more stable, so that the specific capacity and the cycle performance of the lithium ion battery are improved.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Preparing an ammoniated graphene microchip:
step A1: mixing graphene and an ethylene diamine aqueous solution to obtain a mixed solution;
step A2: carrying out ultrasonic treatment on the mixed solution for 2h, carrying out suction filtration and deposition, then standing and drying to obtain the aminated graphene nanoplatelets, wherein the interlayer spacing of the aminated graphene nanoplatelets is 0.4nm, and the specific surface area is 300m 2 /g。
Example 2
Preparing modified silicon dioxide-lignin nanospheres:
step B1: dissolving lignin and silicon dioxide in water together, and fully stirring at room temperature to obtain a mixed solution;
and step B2: carrying out heat preservation on the mixed solution at the temperature of 95 ℃ to carry out hydrothermal reaction to obtain a hydrothermal product;
and step B3: after cooling, carrying out solid-liquid separation treatment on the hydrothermal product to obtain a solid-phase product, and drying the solid-phase product for later use;
and step B4: and (3) calcining the dried solid-phase product at high temperature under the protection of argon to obtain the modified silicon dioxide-lignin nanospheres, wherein the particle size of the modified silicon dioxide-lignin nanospheres is 10 microns.
Example 3
Preparing modified silicon dioxide-lignin nanospheres:
step B1: dissolving lignin and silicon dioxide in water together, and fully stirring at room temperature to obtain a mixed solution;
and step B2: carrying out heat preservation on the mixed solution at the temperature of 80 ℃ to carry out hydrothermal reaction to obtain a hydrothermal product;
and step B3: after cooling, carrying out solid-liquid separation treatment on the hydrothermal product to obtain a solid-phase product, and drying the solid-phase product for later use;
and step B4: and (3) calcining the dried solid-phase product at high temperature under the protection of argon gas to obtain the modified silicon dioxide-lignin nanospheres, wherein the particle size of the modified silicon dioxide-lignin nanospheres is 20 microns.
Example 4
A preparation method of a lignin-based graphene negative electrode material with high cycle performance comprises the following steps:
uniformly mixing 100g of aminated graphene microchip, 8g of modified silicon dioxide-lignin nanospheres, 1g of methanol, 0.5g of barium stearate and 300g of deionized water to obtain a mixture; and filtering and drying the prepared mixture, then placing the mixture in a sintering furnace, raising the temperature at a heating rate of 5 ℃/min, roasting at the constant temperature of 500 ℃ for 8 hours, raising the temperature at a heating rate of 10 ℃/min, roasting at the constant temperature of 800 ℃ for 5 hours, and then cooling to room temperature at a cooling rate of 5 ℃/min to obtain the high-cycle-performance lignin-based graphene negative electrode material.
Example 5
A preparation method of a lignin-based graphene negative electrode material with high cycle performance comprises the following steps:
uniformly mixing 130g of aminated graphene microchip, 8g of modified silicon dioxide-lignin nanospheres, 3g of methanol, 2g of barium stearate and 500g of deionized water to obtain a mixture; and filtering and drying the prepared mixture, then placing the mixture into a sintering furnace, heating the mixture at a heating rate of 5 ℃/min, roasting the mixture at the constant temperature of 500 ℃ for 8 hours, heating the mixture at a heating rate of 10 ℃/min, roasting the mixture at the constant temperature of 800 ℃ for 5 hours, and cooling the mixture to the room temperature at a cooling rate of 5 ℃/min to obtain the high-cycle-performance lignin-based graphene negative electrode material.
Example 6
A preparation method of a lignin-based graphene negative electrode material with high cycle performance comprises the following steps:
uniformly mixing 150g of aminated graphene microchip, 8g of modified silicon dioxide-lignin nanospheres, 1g of methanol, 0.5g of barium stearate and 300g of deionized water to obtain a mixture; and filtering and drying the prepared mixture, then placing the mixture in a sintering furnace, raising the temperature at a heating rate of 5 ℃/min, roasting at the constant temperature of 500 ℃ for 8 hours, raising the temperature at a heating rate of 10 ℃/min, roasting at the constant temperature of 800 ℃ for 5 hours, and then cooling to room temperature at a cooling rate of 5 ℃/min to obtain the high-cycle-performance lignin-based graphene negative electrode material.
Example 7
A preparation method of a lignin-based graphene anode material with high cycle performance comprises the following steps:
uniformly mixing 100g of aminated graphene microchip, 10g of modified silicon dioxide-lignin nanospheres, 1g of methanol, 0.5g of barium stearate and 300g of deionized water to obtain a mixture; and filtering and drying the prepared mixture, then placing the mixture in a sintering furnace, raising the temperature at a heating rate of 5 ℃/min, roasting at the constant temperature of 500 ℃ for 8 hours, raising the temperature at a heating rate of 10 ℃/min, roasting at the constant temperature of 800 ℃ for 5 hours, and then cooling to room temperature at a cooling rate of 5 ℃/min to obtain the high-cycle-performance lignin-based graphene negative electrode material.
Example 8
A preparation method of a lignin-based graphene anode material with high cycle performance comprises the following steps:
uniformly mixing 100g of aminated graphene microchip, 12g of modified silicon dioxide-lignin nanospheres, 1g of methanol, 0.5g of barium stearate and 300g of deionized water to obtain a mixture; and filtering and drying the prepared mixture, then placing the mixture in a sintering furnace, raising the temperature at a heating rate of 5 ℃/min, roasting at the constant temperature of 500 ℃ for 8 hours, raising the temperature at a heating rate of 10 ℃/min, roasting at the constant temperature of 800 ℃ for 5 hours, and then cooling to room temperature at a cooling rate of 5 ℃/min to obtain the high-cycle-performance lignin-based graphene negative electrode material.
Example 9
A preparation method of a lignin-based graphene anode material with high cycle performance comprises the following steps:
uniformly mixing 100g of aminated graphene microchip, 8g of modified silicon dioxide-lignin nanospheres, 1g of methanol, 0.5g of barium stearate and 300g of deionized water to obtain a mixture; and filtering and drying the prepared mixture, then placing the mixture in a sintering furnace, raising the temperature at a heating rate of 8 ℃/min, roasting at 550 ℃ for 9 hours at constant temperature, raising the temperature at a heating rate of 15 ℃/min, roasting at 900 ℃ for 5.5 hours at constant temperature, and then cooling to room temperature at a cooling rate of 8 ℃/min to obtain the high-cycle-performance lignin-based graphene negative electrode material.
Example 10
A preparation method of a lignin-based graphene negative electrode material with high cycle performance comprises the following steps:
uniformly mixing 100g of aminated graphene microchip, 8g of modified silicon dioxide-lignin nanospheres, 1g of methanol, 0.5g of barium stearate and 300g of deionized water to obtain a mixture; and filtering and drying the prepared mixture, then placing the mixture in a sintering furnace, raising the temperature at a heating rate of 10 ℃/min, roasting at 600 ℃ for 10h at constant temperature, raising the temperature at a heating rate of 20 ℃/min, roasting at 1000 ℃ for 6h, and then cooling to room temperature at a cooling rate of 10 ℃/min to obtain the high-cycle-performance lignin-based graphene negative electrode material.
Comparative example 1
The aminated graphene nanoplatelets of example 4 were replaced with regular graphene, and the remaining raw materials and preparation process remained unchanged.
Comparative example 2
The modified silica-lignin nanospheres of example 4 were replaced with ordinary lignin, and the remaining raw materials and preparation process remained unchanged.
Comparative example 3
The aminated graphene nanoplatelets in example 4 were replaced with ordinary graphene, the modified silica-lignin nanospheres were replaced with ordinary lignin, and the remaining raw materials and preparation process remained unchanged.
The samples prepared in examples 4 to 10 and comparative examples 1 to 3 were subjected to cycle performance testing:
the samples of example 4 to example 10 and comparative example 1 to comparative example 3 were used as a negative electrode material, lithium iron phosphate as a positive electrode, lithium hexafluorophosphate/ethylene carbonate as an electrolyte, and a PP/PE/PP three-layer composite separator to prepare a 1Ah pouch battery, which was cycled 100 times using a voltage range of 0.3c,3.8 to 2.0V, to test the discharge capacity retention ratio of the battery, and the test results are shown in table 1 below:
TABLE 1
| Sample(s) | Discharge capacity retention (%) |
| Example sample 4 | 95 |
| Example sample 5 | 97 |
| Example sample 6 | 96 |
| Example sample 7 | 98 |
| EXAMPLE sample 8 | 94 |
| Example sample 9 | 96 |
| EXAMPLE 10 sample | 95 |
| Comparative example sample 1 | 82 |
| Comparative example sample 2 | 86 |
| Comparative example sample 3 | 77 |
As can be seen from table 1, the retention rate of the battery discharge capacity of the sample in example 7 is significantly higher than that of the samples in other examples and comparative examples, and the battery cycle performance is optimal.
In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing is illustrative and explanatory only and is not intended to be exhaustive or to limit the invention to the precise embodiments described, and various modifications, additions, and substitutions may be made by those skilled in the art without departing from the scope of the invention or exceeding the scope of the claims.
Claims (10)
1. The high-cycle-performance lignin-based graphene negative electrode material is characterized by comprising the following raw materials in parts by weight: 100-150 parts of aminated graphene microchip, 8-12 parts of modified silicon dioxide-lignin nanospheres, 1-3 parts of dispersing agent, 0.5-2 parts of hydrogen evolution inhibitor and 300-500 parts of deionized water.
2. The high-cycle-performance lignin-based graphene anode material as claimed in claim 1, wherein the dispersant is methanol or ethanol, and the hydrogen evolution inhibitor is barium stearate.
3. The high-cycle-performance lignin-based graphene anode material as claimed in claim 1, wherein the aminated graphene microchip is prepared by the following steps:
step A1: mixing graphene and an amino-containing organic polymer aqueous solution to obtain a mixed solution;
step A2: and (3) carrying out ultrasonic treatment on the mixed solution for 1-2h, carrying out suction filtration and deposition, and then standing and drying to obtain the aminated graphene microchip.
4. The high cycle performance lignin-based graphene anode material according to claim 3, wherein the amino-containing organic polymer is ethylenediamine or chitosan.
5. The high-cycle-performance lignin-based graphene anode material as claimed in claim 3, wherein the interlayer spacing of the aminated graphene microchip is 0.3-0.4nm, and the specific surface area is 200-300m 2 /g。
6. The high-cycle-performance lignin-based graphene negative electrode material as claimed in claim 1, wherein the modified silica-lignin nanospheres are prepared by the following steps:
step B1: dissolving lignin and silicon dioxide in water together, and fully stirring at room temperature to obtain a mixed solution;
and step B2: keeping the temperature of the mixed solution to carry out hydrothermal reaction to obtain a hydrothermal product;
and step B3: after cooling, carrying out solid-liquid separation treatment on the hydrothermal product to obtain a solid-phase product, and drying the solid-phase product for later use;
and step B4: and (3) calcining the dried solid-phase product at high temperature under the protection of inert gas to obtain the modified silicon dioxide-lignin nanospheres.
7. The high-cycle-performance lignin-based graphene negative electrode material according to claim 6, wherein the temperature preservation range in step B2 is 80-95 ℃.
8. The high cycle performance lignin-based graphene anode material according to claim 6, wherein the inert gas in step B4 is nitrogen or argon.
9. The high-cycle-performance lignin-based graphene anode material as claimed in claim 6, wherein the particle size of the modified silica-lignin nanosphere is 10-20 μm.
10. The high-cycle-performance lignin-based graphene anode material according to any one of claims 1 to 9, wherein the high-cycle-performance lignin-based graphene anode material is prepared by the following steps:
uniformly mixing the aminated graphene nanoplatelets, the modified silicon dioxide-lignin nanospheres, the dispersing agent, the hydrogen evolution inhibitor and the deionized water to obtain a mixture; and filtering and drying the prepared mixture, then placing the mixture in a sintering furnace, raising the temperature at a heating rate of 5-10 ℃/min, roasting at a constant temperature of 500-600 ℃ for 8-10h, raising the temperature at a heating rate of 10-20 ℃/min, roasting at a constant temperature of 800-1000 ℃ for 5-6h, and then cooling to room temperature at a cooling rate of 5-10 ℃/min to obtain the high-cycle-performance lignin-based graphene negative electrode material.
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| CN117000045A (en) * | 2023-06-01 | 2023-11-07 | 贵州省材料产业技术研究院 | Loose nanofiltration membrane for removing heavy metals and preparation method thereof |
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| CN117000045A (en) * | 2023-06-01 | 2023-11-07 | 贵州省材料产业技术研究院 | Loose nanofiltration membrane for removing heavy metals and preparation method thereof |
| CN117000045B (en) * | 2023-06-01 | 2024-02-20 | 贵州省材料产业技术研究院 | Loose nanofiltration membrane for removing heavy metals and preparation method thereof |
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