Lignin has been explored extensively as a renewable precursor for carbon materials, considering its abundance as a major component of plant cell walls and its sustainability as a byproduct of both lignocellulosic biorefinery and the paper-making industry. Despite the extensive efforts to define the process–property relationship, it remains largely unknown how lignin biosynthesis and its chemistry would impact the resultant carbon fiber properties, for both mechanical and electroconductive performances. Such inadequate understanding fundamentally limits feedstock design and selection to improve carbon fiber properties toward broader commercial applications. Using lignin from a broad range of biomass feedstocks for carbon fiber manufacturing, we have fundamentally explored the structure–function relationship between lignin chemistry and carbon fiber performance. Specifically, lignin extracted from hardwood (sugar maple), softwood (loblolly pine and red cedar), and herbaceous plants (corn stover and switchgrass) was used for carbon fiber manufacturing, considering the very different lignin structures from these feedstocks. Linear regression models were established to define the relationship between carbon fiber mechanical properties and lignin structural characteristics. The results highlighted that the content of β-O-4 linkages correlates significantly with the tensile strength and elastic modulus of lignin carbon fibers, indicating that more linear β-O-4 linkages would promote the carbon fiber mechanical performance. Moreover, electroconductive properties are essential for broader energy device application of lignin-based carbon fibers, yet the mechanisms controlling their electroconductivity are largely unknown. We hereby demonstrated that a higher β-O-4 content also promotes the electroconductivity of lignin carbon fibers. Microstructure analysis further revealed that the crystallite size and content of the pre-graphitic turbostratic carbon structure in lignin-based carbon fibers were enhanced as the β-O-4 linkages increased. The content of β-O-4 linkages has shown a strong correlation with the crystallite content in a linear regression model. This study thus revealed the underlying mechanisms regarding how the lignin structure in planta defines the resultant carbon fiber properties. Moreover, the study also highlighted the correlation between the mechanical and electroconductive properties of lignin-based carbon fibers, both of which were defined by the lignin structure.

Traditional lignocellulosic feedstock research has focused on biomass characteristics essential for improving saccharification efficiency, yet the key biomass features underlying high-quality renewable lignin materials remain unknown. Nevertheless, modern biorefinery cannot achieve sustainability and cost-effectiveness unless the lignin stream can be valorized. We hereby addressed these scientific gaps by investigating biomass characteristics defining lignin-based carbon materials properties. Lignin from eight sorghum samples with diverse characteristics was fabricated into carbon fibers (CFs). Remarkably, only lignin uniformity was found to define CF mechanical performance, highlighting the new structure-property relationship. Contrarily, lignin content and composition did not impact on carbon material properties. Mechanistic study by XRD and Raman spectroscopy revealed that higher lignin uniformity enhanced CF microstructures, in particular, turbostratic carbon content. The study for the first time highlighted lignin uniformity as an important biomass structure determinant for renewable products, which opened up new avenues for feedstock design toward diverse products enabling sustainable and cost-effective bioeconomy.