CN-118479454-B - Asphalt-based carbon anode material, two-step pre-oxidation synthesis preparation method and application thereof

CN118479454BCN 118479454 BCN118479454 BCN 118479454BCN-118479454-B

Abstract

The invention provides an asphalt-based carbon anode material, a two-step pre-oxidation synthesis preparation method and application thereof, wherein the two-step pre-oxidation synthesis preparation method of the asphalt-based carbon anode material comprises the steps of uniformly grinding and mixing an asphalt precursor and an initiator to obtain a mixed precursor; carrying out heat treatment on the mixed precursor in an oxidizing atmosphere, cooling to obtain a pre-oxidized precursor I, mixing the pre-oxidized precursor I with an oxidant liquid phase for secondary oxidation to obtain a pre-oxidized precursor II, calcining the pre-oxidized precursor II in an inert gas atmosphere, cooling, grinding, washing and drying to obtain the asphalt-based carbon anode material. The asphalt-based carbon anode material comprises the product prepared by the method. According to the method provided by the invention, through two-step pre-oxidation, oxygen functional groups are introduced into the asphalt precursor to crosslink with asphalt molecules, so that rearrangement of a carbon layer is hindered, graphitization degree after carbonization is reduced, sodium storage capacity is improved, surface capacitance contribution is enhanced, and multiplying power capacity is improved.

Inventors

YANG JIANLONG
ZHANG CHAO
DUAN QIONG
WANG MINGSHAN
LI XING
YANG LIN

Assignees

四川华体照明科技股份有限公司

Dates

Publication Date: 20260508
Application Date: 20240527

Claims (7)

1. The two-step pre-oxidation synthesis preparation method of the asphalt-based carbon anode material is characterized by comprising the following steps of: Uniformly grinding and mixing an asphalt precursor and an initiator to obtain a mixed precursor, wherein the initiator comprises one or more of boric acid, boric oxide, tetraphenylboric acid and sodium tetraphenylborate; carrying out heat treatment on the mixed precursor in an oxidizing atmosphere, and cooling to obtain a pre-oxidized precursor I, wherein the heat treatment comprises the steps of heating to 250-450 ℃ at a heating rate of 2-5 ℃ per minute, and preserving heat for 2-5 hours; Mixing the pre-oxidized precursor I with an oxidant liquid phase for secondary oxidation to obtain a pre-oxidized precursor II, wherein the oxidant is hydrogen peroxide, and the mixed secondary oxidation comprises stirring for 3-5 h under the condition of water bath at 60-90 ℃, and evaporating to obtain a pre-oxidized asphalt precursor II; Calcining the pre-oxidized precursor II in an inert gas atmosphere, cooling, grinding, washing and drying to obtain the asphalt-based carbon anode material, wherein the calcining comprises the steps of heating to 700-1400 ℃ at a heating rate of 3-10 ℃ per minute, and preserving heat for 2-4 hours.
2. The method for preparing a two-step pre-oxidized anode material for asphalt-based carbon according to claim 1, wherein the pitch-based precursor comprises one or more of coal tar pitch, petroleum pitch, natural pitch and mesophase pitch.
3. The preparation method of the asphalt-based carbon anode material according to claim 1, which is characterized in that the asphalt precursor and the initiator are uniformly ground and mixed according to the mass ratio of 1:0.5-5.
4. The preparation method of the asphalt-based carbon anode material by two-step pre-oxidation synthesis is characterized in that the liquid phase comprises deionized water, and the pre-oxidation precursor I and the oxidant are mixed in a liquid phase according to a molar ratio of 1:0.5-3.
5. The preparation method of the asphalt-based carbon cathode material according to claim 1, wherein the washing comprises dispersing the ground product in deionized water, stirring, filtering, washing until the washing liquid is neutral, stirring for 25-35 min, and performing ultrasonic treatment for 5-15 min.
6. The pitch-based carbon negative electrode material is characterized in that the pitch-based carbon negative electrode material is prepared by the two-step pre-oxidation synthesis preparation method of the pitch-based carbon negative electrode material according to any one of claims 1-5.
7. Use of the pitch-based carbon anode material of claim 6 in a sodium ion battery anode material.

Description

Asphalt-based carbon anode material, two-step pre-oxidation synthesis preparation method and application thereof Technical Field The invention relates to the technical field of sodium ion battery anode materials, in particular to an asphalt-based carbon anode material, a two-step pre-oxidation synthesis preparation method and application thereof. Background The progressive consumption of traditional energy and the associated environmental issues drive the development of technology, turning to clean energy sources such as solar, wind and geothermal. However, due to the intermittent nature of these energy sources, the energy storage demand is significantly increased, the use of lithium resources is rapidly increased, and besides the uneven geographical distribution, the concern of rapid exhaustion of lithium resources is also caused, and finally the price of lithium raw materials is increased, which hinders the commercial production of lithium ion batteries. The sodium ion battery has the advantages of abundant resources, low price, long service life, good safety performance and the like, can be used as a supplement of the lithium ion battery, relieves the shortage of lithium resources to a certain extent, ensures national energy safety and social sustainable development, and is considered as an energy storage device for the next generation and can be developed on a large scale by virtue of the advantages. However, commercial applications of sodium ion batteries still lack low cost anode materials, and achieving high performance and low cost sodium ion batteries remains a significant challenge. Therefore, there is a need to find or develop more suitable electrodes that meet the requirements of high energy density and high cycling stability in the most cost effective manner. Pitch is a typical soft carbon precursor and has the advantages of wide availability and low cost. Is expected to be produced in large scale and put into industrial application. However, pitch-derived soft carbon has a relatively ordered microstructure and a structure with a small interlayer distance, resulting in poor electrochemical sodium storage performance and limited Na + storage capacity. Therefore, the asphalt-based carbon anode material, the two-step pre-oxidation synthesis preparation method and the application thereof have important significance. Disclosure of Invention The present invention aims to address at least one of the above-mentioned deficiencies of the prior art. For example, one of the purposes of the invention is to provide a two-step pre-oxidation synthesis preparation method of an asphalt-based carbon anode material with low cost and simple process. For another example, another object of the present invention is to provide a pitch-based carbon anode material with good Na + storage capacity, which meets the requirements of high energy density and high cycle stability. In order to achieve the aim, the invention provides a two-step pre-oxidation synthesis preparation method of a pitch-based carbon anode material, which comprises the steps of uniformly grinding and mixing a pitch precursor and an initiator to obtain a mixed precursor, carrying out heat treatment on the mixed precursor under an oxidizing atmosphere, cooling to obtain a pre-oxidation precursor I, mixing the pre-oxidation precursor I with an oxidant liquid phase for secondary oxidation to obtain a pre-oxidation precursor II, calcining the pre-oxidation precursor II under an inert gas atmosphere, cooling, grinding, washing and drying to obtain the pitch-based carbon anode material. According to one or more exemplary embodiments of an aspect of the present invention, the initiator may include one or more of boric acid, boron oxide, tetraphenylboric acid, sodium tetraphenylborate, phosphoric acid, phosphorus pentoxide, and phosphorus trioxide. According to one or more exemplary embodiments of an aspect of the present invention, the pitch-based precursor may include one or more of coal tar pitch, petroleum pitch, natural pitch, and mesophase pitch. According to one or more exemplary embodiments of an aspect of the present invention, the pitch precursor and the initiator may be uniformly ground and mixed in a mass ratio of 1:0.5-5. According to one or more exemplary embodiments of an aspect of the present invention, the heat treatment may include heating to 250-450 ℃ at a heating rate of 2-5 ℃ per minute and maintaining for 2-5 hours, and the calcination may include heating to 700-1400 ℃ at a heating rate of 3-10 ℃ per minute and maintaining for 2-4 hours. According to one or more exemplary embodiments of an aspect of the present invention, the oxidizing agent may include one or more of hydrogen peroxide, ferric nitrate, sodium nitrate, potassium nitrate, zinc nitrate, and potassium permanganate, the liquid phase may include deionized water, and the pre-oxidation precursor I and the oxidizing agent may be mixed in a ratio of 1:0.5 to 3 by mole. According to on