Hard carbon negative electrode material of sodium-ion battery based on shell biomass and preparation method of hard carbon negative electrode material

A sodium-ion battery and biomass material technology, applied in the direction of active material electrodes, battery electrodes, carbon preparation/purification, etc., can solve the problem that graphite cannot be used as a negative electrode material of biomass carbon, and the large-scale application production is difficult, and the preparation process is cumbersome and other problems, to achieve the effect of wide and abundant raw material sources, improved reversible capacity, and simple and easy process

Active Publication Date: 2021-11-19
FUDAN UNIV
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Problems solved by technology

[0002] Lithium-ion batteries have a mature industrial scale, but sodium-ion batteries are still in the initial stage of research and development, and have not yet been used in large-scale industrialization
The anode materials prepared by the same process will show completely different results when applied to lithium-ion batteries and sodium-ion batteries respectively. For example, carbon-based materials typically represented by graphite can be used as anode materials for lithium-ion batteries. It has achieved relatively good performance, but when it is applied to the negative electrode material of sodium ion battery, it cannot form a stable intercalation compound at all, so that graphite cannot be used as the negative electrode material of sodium ion battery
[0003] In the prior art, there are carbon anode materials for sodium ion batteries prepared from biological wastes (such as corn cobs, pumpkin vines, straws, etc.) as raw materials. Biomass washing and drying - calcining and crushing - treatment liquid treatment and drying - again sieving and calcining to obtain carbon anode materials suitable for sodium ion batteries, but the preparation process is cumbersome and the preparation time is long, which leads to high production costs and high difficulty in industrialization
In the prior art, wood chips are used as raw materials to cross-link wood chips with ethers, and then high-temperature carbonization is performed again to obtain negative electrode materials for sodium-ion batteries. The preparation process is too cumbersome, and the first Coulombic efficiency is low (less than 85%) , low economic benefits of industrialization
To sum up, the existing negative electrode materials for sodium ion batteries have the disadvantages of complex preparation process, high production cost, and low initial Coulombic efficiency, which makes it difficult to realize large-scale application and production of biomass carbon negative electrode materials in industry

Method used

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  • Hard carbon negative electrode material of sodium-ion battery based on shell biomass and preparation method of hard carbon negative electrode material
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  • Hard carbon negative electrode material of sodium-ion battery based on shell biomass and preparation method of hard carbon negative electrode material

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preparation example Construction

[0039] Such as figure 1 Shown, a kind of preparation method of the sodium-ion battery hard carbon negative electrode material based on husk biomass of the present invention comprises the following steps:

[0040] S1. Using fruit shell biomass materials as biomass raw materials, immerse the biomass raw materials in hydrochloric acid alcohol solution (a mixed solution of dilute hydrochloric acid and ethanol) and sulfuric acid solution in sequence and stir to remove the ash in the biomass raw materials and extract with ethanol The substance is used to oxidize and modify the easily oxidized functional groups in the biomass raw materials to obtain a suspension;

[0041] S2, dispersing the suspension obtained in step S1 in water, filtering and drying to obtain a precursor;

[0042] S3, heating the precursor obtained in step S2 to 450-550°C under the protection of an inert gas for pre-carbonization treatment, and ball milling after cooling to obtain pre-carbon powder;

[0043] S4, ...

Embodiment 1

[0067] The preparation method of the hard carbon negative electrode material for the sodium ion battery based on the husk biomass of the present embodiment, the specific steps are:

[0068] (1) The dried camellia oleifera shell was crushed into powder by a pulverizer, and 10 g of camellia oleifera shell powder was weighed as a biomass raw material, immersed in 60 mL of a mixed solution of 0.5 mol / L dilute hydrochloric acid and 30% ethanol, at room temperature Stir at low temperature for 6 h to remove the ash and ethanol extract in the biomass raw material; filter and add to 60 mL of sulfuric acid with a molar concentration of 6 mol / L, stir at room temperature for 6 h, carry out oxidation modification, and wait for the reaction to complete After that, a brown suspension was obtained;

[0069] (2) The obtained brown suspension was ultrasonically dispersed in water for 30 min, filtered and dried to obtain the precursor, and then put into a tube furnace with argon gas for pre-pyro...

Embodiment 2

[0077] The preparation method of the hard carbon negative electrode material for the sodium ion battery based on the husk biomass of the present embodiment, the specific steps are:

[0078] (1) Weigh 10 g of camellia oleifera shell powder as biomass raw material, immerse in 60 mL of a mixed solution of 0.5 mol / L dilute hydrochloric acid and 30% ethanol, stir at room temperature for 6 h, and remove the ash in the biomass raw material and ethanol extract; filtered, added to 60 mL of sulfuric acid with a molar concentration of 6 mol / L, stirred at room temperature for 6 h, and oxidized and modified. After the reaction was completed, a brown suspension was obtained;

[0079] (2) The obtained brown suspension was ultrasonically dispersed in water for 30 min, filtered and dried to obtain the precursor, and then put into a tube furnace with argon gas for pre-pyrolysis and carbonization, and the temperature was raised to 500 °C at 10 °C / min and kept for 2 h, cooled to room temperature ...

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Abstract

The invention belongs to the technical field of sodium-ion batteries, and particularly relates to a hard carbon negative electrode material of a sodium-ion battery based on shell biomass and a preparation method of the hard carbon negative electrode material. The preparation method comprises the steps of by taking a shell biomass material as a biomass raw material, sequentially immersing the biomass raw material into a hydrochloric acid alcohol solution and a sulfuric acid solution, and stirring to obtain a suspension; dispersing the suspension in water, filtering and drying to obtain a precursor; heating the precursor under the protection of inert gas, carrying out pre-carbonization treatment, cooling, and carrying out ball milling to obtain pre-carbon powder; and heating the pre-carbon powder under the protection of inert gas, carrying out high-temperature carbonization treatment, and cooling to obtain the biomass hard carbon negative electrode material for the sodium-ion battery. The technical process is simple, and the prepared hard carbon negative electrode material for the sodium-ion battery is high in first coulombic efficiency and reversible specific capacity.

Description

technical field [0001] The invention belongs to the technical field of sodium ion batteries, and in particular relates to a negative electrode material of a sodium ion battery and a preparation method thereof. Background technique [0002] Lithium-ion batteries have a mature industrial scale, but sodium-ion batteries are still in the initial research and development stage, and have not yet been used in large-scale industrialization. The anode materials prepared by the same process will show completely different results when applied to lithium-ion batteries and sodium-ion batteries respectively. For example, carbon-based materials typically represented by graphite can be used as anode materials for lithium-ion batteries. It has achieved relatively good performance, but when it is applied to the negative electrode material of sodium ion battery, it cannot form a stable intercalation compound at all, so that graphite cannot be used as the negative electrode material of sodium i...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C01B32/05H01M4/587H01M10/054
CPCC01B32/05H01M4/587H01M10/054H01M2004/027Y02E60/10
Inventor 夏永姚张翔
Owner FUDAN UNIV
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