Fibrous hollow hard carbon material capable of being used for sodium-ion battery negative electrode and preparation method thereof

A sodium-ion battery, fibrous technology, used in nanotechnology for materials and surface science, battery electrodes, carbon preparation/purification, etc., can solve problems such as increasing preparation costs and failing to achieve optimal kinetic performance, etc. Achieve the effect of improving resource utilization, good structural stability and long cycle life

Active Publication Date: 2018-11-23
SHANGHAI UNIV
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0005] For example, the artificial synthesis of hollow nanowire hard carbon (Nano Lett. 2012, 12, 3783−3787), because the hollow tubular structure can maintain 60% capacity at 0.2C rate at 2C rate, but this method is based on raw materials Added additional preparation costs
In terms of cost, the current practice is to use low-cost and easily available biomass as raw materials, such as nut shells (Nano Energy 39 (2017) 489–498), but these biomass materials do not have special morphology after carbonization, and thus Under the rate test of 0.1C~2C, the capacity of 2C is less than 1 / 6 of 0.1C, which cannot achieve the effect of optimizing dynamic performance

Method used

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  • Fibrous hollow hard carbon material capable of being used for sodium-ion battery negative electrode and preparation method thereof
  • Fibrous hollow hard carbon material capable of being used for sodium-ion battery negative electrode and preparation method thereof
  • Fibrous hollow hard carbon material capable of being used for sodium-ion battery negative electrode and preparation method thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0047] A kind of preparation method of fibrous hollow hard carbon material, the flow process of its preparation method is as follows figure 1 As shown, it specifically includes the following steps:

[0048] Step 1) Pretreatment of raw materials, take out the fibrous part of the biomass, wash it, dry it and put it in a graphite crucible, and keep it warm at 600°C for 2 hours under a protective atmosphere at a heating rate of 5°C / min for pre-carbonization Post-grinding to prevent fibrous hard carbon materials from hardening after direct pyrolysis at high temperature, resulting in difficulty in refinement, to obtain a precursor. The biomass is kapok fiber, poplar catkin fiber, catkin fiber, sycamore catkin, ramie or jute;

[0049] Step 2) High temperature pyrolysis, the precursor obtained in step 1 is placed in a graphite crucible, at a heating rate of 5°C / min, under a protective atmosphere, after high temperature pyrolysis for 2 hours, cooled naturally, taken out and ground to o...

Embodiment 2

[0051] This embodiment provides a method for performing an electrochemical test on the prepared fibrous hollow hard carbon material. The electrochemical test process is to make pole pieces for sodium-ion battery anode materials and assemble them into button-type batteries to test their electrochemical performance. Hard carbon material and sodium carboxymethyl cellulose binder solution are mixed uniformly at a ratio of 95:5 to obtain slurry, coated on aluminum foil, placed in a vacuum oven at 100°C for 2 hours, dried and cut into Φ10mm size , to get the required negative electrode sheet, the active material loading is 2mg / cm 2 about. The electrolyte system uses 1mol / L sodium perchlorate electrolyte, the solvent is ethylene carbonate and divinyl carbonate mixed at a volume ratio of 1:1 and 1mol / L sodium perchlorate electrolyte, the solvent is ethylene carbonate, carbonic acid Divinyl ester and fluoroethylene carbonate (FEC) were mixed at a volume ratio of 47.5:47.5:5 and assem...

Embodiment 3

[0053] A kind of preparation method of fibrous hollow hard carbon material, the steps not specified in the concrete steps are identical with the method preparation material in the embodiment 1, difference is: the raw material of described step 1 is jute fiber; Described step 2 The temperature of pyrolysis is 1200° C.; the atmosphere in the steps 1 and 2 is argon.

[0054] The fibrous hollow hard carbon material prepared in Example 3 is tested by X-ray diffraction (XRD), and the results are as follows: figure 2 As shown, two severely broadened diffraction peaks of the amorphous carbon curve can be obtained from the figure, and the graphite interlayer spacing is 0.3697 nm, which is beneficial to the storage of sodium ions.

[0055] The fibrous hollow hard carbon material prepared in Example 3 is tested by Raman spectroscopy, and the results are as follows: image 3 As shown, the integrated intensity ratio of the two peaks I D / I G It is 1.6337, indicating that the material s...

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Abstract

The invention discloses a fibrous hollow hard carbon material. The amorphous fibrous hollow hard carbon material with the d002 value within the range of 0.36-0.42 nm and the ID/IG within the range of1.5-2.0 is prepared by taking a fibrous biomass material as a raw material through a direct pyrolysis method. A preparation method thereof comprises the following steps of 1) carrying out pretreatmenton the raw material; and 2) carrying out high-temperature pyrolysis. According to the fibrous hollow hard carbon material, as a negative electrode active material in a sodium-ion secondary battery, the specific capacity of the fibrous hollow hard carbon material is 150-350 mAh/g, the fibrous hollow hard carbon material under 2 C can keep the capacity of 60% or above at 0.1C, and the capacity retention ratio can be kept within the range of 90-100% after 100 weeks of circulation. The fibrous hollow hard carbon material and the preparation method thereof have the advantages that 1, through a stable micron-scale fiber structure, the cycle life is prolonged; 2, a natural tubular hollow structure is utilized, so that the wettability of an electrolyte is improved, the ion transmission distance is shortened, and the dynamics performance of the battery is improved; and 3, the preparation method is simple, and the processing cost for preparing the special morphology is lowered. The fibrous hollow hard carbon material is a very potential negative electrode material of the sodium-ion battery and can be applied to the fields of intelligent power grids, secondary clean energy power generation and other large-scale energy storage systems or power batteries.

Description

technical field [0001] The invention relates to an energy storage battery negative electrode material, in particular to a fibrous hollow hard carbon material which can be used for a sodium ion battery negative electrode and a preparation method thereof. Background technique [0002] In recent years, with the rapid development of human society and the increasing diversification of people's needs, the unrestrained use of fossil energy has led to serious energy shortages and the aggravation of the greenhouse effect. The development of new clean energy has become an urgent problem to be solved. At present, secondary lithium-ion batteries have become the mainstream in the consumer electronics market, power battery market and other fields, and the technology is becoming more and more mature. However, with the large-scale commercial use, the shortage of lithium mines has become the key to hindering its application in large-scale energy storage. Na-ion batteries have similar elect...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C01B32/05C01B32/205B82Y30/00B82Y40/00H01M4/587H01M10/054
CPCH01M4/587H01M10/054B82Y30/00B82Y40/00C01B32/05C01B32/205Y02E60/10
Inventor 俞卓尔邵豫龙刘畅吕迎春郭炳焜
Owner SHANGHAI UNIV
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