Sustainable application of biomass by-products: Corn straw-derived porous carbon nanospheres using as anode materials for lithium ion batteries

doi:10.1016/j.matchemphys.2020.122644

Materials Chemistry and Physics

Volume 243, 1 March 2020, 122644

https://doi.org/10.1016/j.matchemphys.2020.122644 Get rights and content

Highlights

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Porous carbon materials are prepared by using corn straw as raw materials.
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The biomass-derived carbon was nanosphere-shaped and used as anode for lithium-ion batteries.
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This biomass-derived anode possesses excellent electrochemical performance.

Abstract

We propose a green and sustainable development method to convert corn straw into porous carbon nanospheres for lithium ion battery electrode materials. Biomass porous carbon nanospheres were synthesized by high-temperature carbonization and activation using corn straw. Through the comparison of different activator, it is found that the carbon nanospheres activated by CaCl₂ can not only retain the spherical structure, but also obtain rich porous, thereby enabling excellent electrochemical performance (546 mA h g⁻¹ at the end of 100 cycles at 0.2C). The porous carbon nanospheres from low-cost and non-pollution corn straw cellulose are ideal candidate for the negative electrode material of lithium ion batteries.

Introduction

With the growing consumption of mobile telephones, tablets, televisions, digital cameras, electric bicycles, the LIBs industry has developed by leaps and bounds [1,2]. LIBs play an increasingly significant role in the development of social life [3]. In recent years, many countries have strongly supported the development of new energy vehicles. The research of electric vehicles (EVs) and hybrid electric vehicles (HEVs) has led to the development of power batteries, thus promoting the study of electrode materials for LIBs [4]. The rapid development of new energy technology leads to higher requirements for environmental protection and property of electrode materials [5,6]. Many types of carbon materials have been studied as negative anodes for LIBs. However, as the price of petroleum coke, needle coke and other negative raw materials has increased sharply, it has become a trend to seek low-cost, non-pollution carbon materials. Among many kinds of materials, biomass, as an environmental protection and renewable material, has been drawing an increasing attention [7]. Corn straw as an abundance agricultural by-product, is considered to be one of the most promising substitutes to LIBs anode material. In order to make full use of resources, we used corn straw as precursor to prepare negative carbon materials for LIBs.

Detailed investigations indicate that porous carbon materials with high specific surface area make a significant contribution to the performance of negative electrode material of LIBs [8,9]. Porous carbon nanospheres (PCS) has been widely concerned due to its high specific surface area, rich pore structure, high thermal stability, good chemical stability, high electrical conductivity, low density, etc [[10], [11], [12], [13]]. PCS can shorten the distance between lithium ions and electrons, increase diffusion rate and enhance diffusion kinetics [14].

There are many methods for preparing PCS, such as physical activation, chemical activation, catalytic activation, and microwave activation. Owing to the advantages of low activation temperature and short reaction time, chemical activation is widely used for preparing PCS. In the process of activation, new pore structure can be formed by adding activator to improve the specific surface area of the material. The commonly used chemical activators include alkali (KOH, NaOH) [[15], [16], [17]], acid (H₃PO₄) [18], metallic salts (MgCl_2, CaCl_2, ZnCl₂, CuCl₂) [[18], [19], [20], [21], [22]], alkali metal carbonate (K₂CO₃, Na₂CO₃) [23]. Ru. H et al. synthesized bean-dreg-derived carbon treated by KOH, which demonstrated great electrochemical performance (801 mAh g⁻¹ at 0.1C) [24]. Xi. Y et al. reported that lignin-based carbon activated by K₂CO₃ at 900 °C exhibited good electrical properties (494 mAh g⁻¹at a current density of 200 mA g⁻¹) [25].

In this paper, we utilized corn straw as raw material to prepare PCS activated by CaCl₂, ZnCl₂ and CuCl₂, respectively. We investigate the effect of CaCl₂, ZnCl₂ and CuCl₂ as activator on the structure and electrochemical properties of LIBs. As a result, CaCl₂ can form porous and retain the overall topography of the precursor to a greater extent. Carbon nanospheres activated by CaCl₂ deliver excellent rate performance and cycling performance. This method provides the basis for the reuse of biomass by-products.

Section snippets

Material preparation

The corn straw used in the experiment was provided by a farm in Changchun, Jilin Province, China. Corn stalks was washed, and then crushed into powder after drying. Corn straw powder was added to 4% H₂SO₄ at a solid-liquid ratio of 1:10, and stirred at 90 °C for 3 h, and then reacted with 50 g L⁻¹ NaOH at a solid-liquid ratio of 1:15. Separating solids from liquids, the solid was transferred to stainless steel autoclave with water treated at 200 °C for 72 h at a solid-liquid ratio of 1:15 to

Results and discussion

The structure of carbon material has changed greatly from corn straw to PCS. Fig. 1 shows the schematic illustration of the PCS preparation. The preparation process of PCS consists of two steps. In the first step, carbon nanospheres with uniform size and distribution were synthesized from corn straw as raw material by acid-alkali treatment and hydrothermal carbonization. In the second step, carbon nanospheres are activated to make porous by activators to obtain PCS.

The XRD patterns of

Conclusions

A kind of biomass porous carbon nanospheres was successfully prepared by high-temperature carbonization and activation with corn straw cellulose as precursor. The morphology and electrical properties of the activated carbon nanospheres were compared by the application of three activators. Due to the action of the CaCl₂ treatment in the process of chemical activation, the porous carbon nanospheres have rich porous and a larger specific surface area. Porous carbon nanospheres activated by CaCl₂

Declaration of competing interest

The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.

Acknowledgment

This work was financially supported by the Key Scientific and Technological Project of Jilin Province (20180201074GX, 20190201110JC, 20190302037GX); the China Postdoctoral Science Foundation (2017M611321); the Project of Education Department of Jilin Province (JJKH20180130KJ); Open Project of State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, College of Chemistry, Jilin University (2019-8); Project of Jilin Province Development and Reform Commission (2019C046-2).

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Sustainable application of biomass by-products: Corn straw-derived porous carbon nanospheres using as anode materials for lithium ion batteries

Highlights

Abstract

Introduction

Section snippets

Material preparation

Results and discussion

Conclusions

Declaration of competing interest

Acknowledgment

Waste Manag.

Mater. Lett.

Mater. Chem. Phys.

Microporous Mesoporous Mater.

Appl. Surf. Sci.

Chem. Phys. Lett.

International Journal of Electrochemical Science

Electrochim. Acta

Electrochim. Acta

Ind. Crops Prod.

Electrochim. Acta

Appl. Catal. B Environ.

Electrochim. Acta

J. Power Sources

Chem. Phys.

Mater. Lett.

J. Alloy. Comp.

J. Anal. Appl. Pyrolysis

Diam. Relat. Mater.

Hierarchical porous yolk-shell carbon nanosphere for high-performance lithium-sulfur batteries

Part. Part. Syst. Charact.