Lignin-based Porous Carbon Research Articles

A molecular-chemistry-manipulation strategy toward functional lignin-based porous carbon nanospheres with tunable-pore structure

Porous carbon nanospheres derived from biomass materials have inspired numerous interests in various areas. Nevertheless, their fabrications mainly depend on template-assisted or chemical activation routes. Here, a molecular-chemistry-manipulation strategy was proposed innovatively by taking advantage of the heterogeneous self-condensation characters of lignin molecules under thermal stimulation, opening a practical and versatile synthetic platform for the construction of lignin-based hierarchical porous carbon nanospheres (LHPCS). We can manipulate the condensed kinetics by tuning the environmental variables and forming designated nanospheres with inhomogeneous molecular chemistry. This intraparticle difference could provide a possibility to tune its refined structure for synthesizing hierarchical porous carbon nanospheres. Such LHPCS behaved the specific surface area of 962 m2 g−1 and pore volume of 0.76 cm3 g−1, as well as regulable pore ratios (15.5–22.9 % of macropore, 12.7–37 % for mesopore and 45–68.9 % for micropore). Besides, the monodisperse spherical morphology with hierarchical interleaved channels affords them excellent performance in optical management and energy storage, including pore-determined photothermal properties, extremely low reflectance of ca. 1.9 %, stable multi-angles specular reflectance, and anti-self-discharge induced by charge rearrangement. Our proposed molecular chemistry strategy provides an alternative pathway for constructing gradient and adjustable pore structures.

Preparation of nitrogen-doped lignin-based porous carbon materials and their application in a supercapacitor

Preparation of nitrogen-doped lignin-based porous carbon materials and their application in a supercapacitor

Preparation of lignin-based porous carbon through thermochemical activation and nitrogen doping for CO2 selective adsorption

Preparing CO2 adsorbents from biomass feedstock has garnered considerable attention due to its potential for fostering sustainable, economic, and eco-friendly development. Introduction of nitrogen-containing functional groups can enhance the affinity for CO2 of biochar but also inevitably affect the pore structure. The challenge lies in ascertaining and regulating the effect of N-doping on the pore structure. In this work, lignin was activated using KOH, and then followed by urea N-doping through pyrolysis or hydrothermal methods. At small dosages of KOH (the mass ratio of KOH/lignin = 0.25), in addition to introducing nitrogen-containing functional groups, urea modification boosted pore volume of <1 nm favorable for CO2 adsorption through etching carbon skeleton, while the small dosage of KOH reduced its inherent corrosive hazards. Correlation analysis showed that the dominant influencing factor for CO2 adsorption at ambient temperature and pressure was the pore volume with pore size of 0.6–0.8 nm, whereas nitrogen content (especially N-5 content) was the main influencing factor at high temperatures (50 °C) and low pressures (0.15 bar). The peak enhancement of the C–N bond under the CO2 adsorption at 50 °C by in situ diffuse reflectance infrared Fourier transform test indicated that the nitrogen-containing functional groups have a chemisorption effect on CO2. The adsorbent PK-0.25-HU exhibited adsorption capacity of 4.46 mmol/g (25 °C, 1 bar), 2.97 mmol/g (50 °C, 1 bar). Dynamic separation coefficient of CO2/N2 reached 93.82 in a gas mixture of CO2/N2 = 15 %/85 %.

Fabrication of N and S co-doped lignin-based porous carbon aerogels loaded with FeCo alloys and their application to oxygen evolution and reduction reactions in Zn-air batteries

Zn-air batteries are a highly promising clean energy sustainable conversion technology, and the design of dual-function electrocatalysts with excellent activity and stability is crucial for their development. In this work, FeCo alloy loaded biomass-based N and S co-doped carbon aerogels (FeCo@NS-LCA) were fabricated from chitosan and lignosulfonate-metal chelates via liquid nitrogen pre-frozen synergistic high-temperature carbonization with application in electrocatalytic reactions. The abundant oxygen-containing functional groups on lignosulfonates have a chelating effect on metal ions, which can avoid the aggregation of metal nanoparticles during carbonation and catalysis, facilitating the construction of a nanoconfinement catalytic system with biomass carbon as the domain-limiting body and FeCo nanoparticles as the active sites. FeCo@NS-LCA exhibited catalytic activity (E1/2 = 0.87 V, JL = 5.7 mA cm−2) comparable to the commercial Pt/C in the oxygen reduction reaction (ORR), excellent resistance to methanol toxicity and stability. Meanwhile, the overpotential of oxygen evolution reaction (OER) was 324 mV, close to that of commercial RuO2 catalysts (351 mV). This study utilizes the coordination action of lignosulfonate to provide a novel and environmentally friendly method for the preparation of confined nano-catalysts and provides a new perspective for the high-value utilization of biomass resources.

Enhanced SO2, NO, and Cr (VI) removal by lignin-derived high N-doped activated carbon through one-pot strategy: Structure development, structure–performance relationship and mechanism insight

The production of high-performance activated carbon (AC) is recognized as an essential strategy for the effective utilization of lignin resources. In this work, the N-doped AC was successfully prepared by blending sodium lignosulfonate (SL) and different ratios of FeCl3 through one-pot strategy. The AC structure evolution and performance were obtained by a series of characterization and tests. The results showed that, during the activation process, FeCl3 first complexed with urea and catalyzed the depolymerization of SL, and the rapid pore development was mainly caused by the template, including formed FeCl2, Na2Fe3Cl8 and Na6FeCl8. The ratio of FeCl3/SL adjusts the AC physicochemical texture. AC-3 processed a super total specific surface area and pore volume, respectively up to 2048 m2/g and 1.47 cm3/g. Meanwhile, AC-2 showed a higher nitrogen content of 11.4 %. The as-prepared AC shows super desulfurization, denitrification and Cr (Ⅵ) removal ability. AC-2 displayed maximum sulfur capacity and NO conversion, up to 199.1 mg/g and 42.4 %. This enhanced performance is primarily attributed to the pore structure induced by FeCl3 activation, which provides a foundation for adsorption and catalytic processes, further augmented by the increased active sites due to nitrogen doping. AC-3 achieved an extremely high Cr (VI) adsorption capacity, up to 386.2 mg/g, which was primarily attributed to the redox effect of N-containing and O-containing groups on Cr (VI), in addition, the effect of physical adsorption including pore structure is not neglectable. This study highlights the significant potential of environmentally friendly lignin-based porous carbon materials for removing contaminants in both gas and liquid phases.

Full utilization of poplar sawdust with chemical-mechanical pretreatment for coproduction of xylooligosaccharides, fermentable sugars and porous carbon materials

In recent decades, one of the major challenges of biorefinery is the full utilization of lignocellulosic components for coproduction of value-added materials. In this context, we proposed an integrated process of acetic acid (AC) pretreatment, Papir Forsknings Institutet (PFI) refining and enzymatic hydrolysis to coproduce xylooligosaccharides, fermentable sugars and lignin-based porous carbon materials. Results showed AC pretreatment (170 ºC, 60 min, 5 w/v % acetic acid and 5% 2-naphthol addition based on dry mass of biomass) resulted in maximum xylooligosaccharids (XOS) yield of 51.08%. The integrated process of AC pretreatment assisted by 2-naphthol-7-sulfonate addition and PFI post-refining led to cellulose hydrolysis yield of 98.20% and lignin-based porous carbon materials with methylene blue adsorption capacity of up to 749.17 mg/g. Moreover, it was found lignin repolymerization inhibitors (i.e. 2-naphthol, 2-naphthol-7-sulfonate) in acid pretreatment helped increase the specific surface area of substrate and decrease surface lignin coverage, which enhanced cellulose accessibility to cellulase enzymes. Moreover, they enhanced lignin detaching during enzymatic hydrolysis, which reduced cellulase aggregation and promoted the ease of cellulose hydrolysis. Results demonstrated an efficient pretreatment strategy to maximize coproduction of xylooligosaccharids, fermentable sugars and lignin materials from lignocellulosic biomass for full utilization.

Lignin-based porous carbon adsorbents for CO2 capture.

A major driver of global climate change is the rising concentration of atmospheric CO2, the mitigation of which requires the development of efficient and sustainable carbon capture technologies. Solid porous adsorbents have emerged as promising alternatives to liquid amine counterparts due to their potential to reduce regeneration costs. Among them, porous carbons stand out for their high surface area, tailorable pore structure, and exceptional thermal and mechanical properties, making them highly robust and efficient in cycling operations. Moreover, porous carbons can be synthesized from readily available organic (waste) streams, reducing costs and promoting circularity. Lignin, a renewable and abundant by-product of the forest products industry and emerging biorefineries, is a complex organic polymer with a high carbon content, making it a suitable precursor for carbon-based adsorbents. This review explores lignin's sources, structure, and thermal properties, as well as traditional and emerging methods for producing lignin-based porous adsorbents. We examine the physicochemical properties, CO2 adsorption mechanisms, and performance of lignin-derived materials. Additionally, the review highlights recent advances in lignin valorization and provides critical insights into optimizing the design of lignin-based adsorbents to enhance CO2 capture efficiency. Finally, it addresses the prospects and challenges in the field, emphasizing the significant role that lignin-derived materials could play in advancing sustainable carbon capture technologies and mitigating climate change.

Effect of hydrothermal pH values on the morphology of special microspheres of lignin-based porous carbon and the mechanism of carbon dioxide adsorption

The study reports the economic and sustainable syntheses of a lignin-based porous carbon (LPC) for CO2 capture application. The pH values of hydrothermal solution affected the polymerization and aromatization of spheroidization, with morphological changes from blocky to microsphere. In addition, the reliable mechanisms of CO2 adsorption were proposed by combining experiments with Gaussian16 simulations based on DFT. The electrostatic attraction of oxygen-containing functional groups and the diffusivity resistance of CO2 in the pores are the key factors for the CO2 adsorption. ​The carboxyl groups have the strongest electrostatic attraction to CO2. LPC-pH 1 has the highest carboxyl group content, possessing a CO2 adsorption capacity of up to 5.10 mmol/g at 0℃, 1 bar. Furthermore, CO2 diffusion resistance became a main factor as the adsorption temperature increases. The innovative combination of quantum chemical calculations and microscopic properties provides a viable pathway for an insight into the future control of lignin-based carbon formation.

Bidirectional pore-creating strategy towards lignin-based heteroatom-doped porous carbon for supercapacitors

Significant pursuits have been committed to manufacturing high-performance lignin carbon-based supercapacitor electrode materials due to their high carbon content, abundant raw resources, and environmentally-friendly. However, the pessimistic accessible porous structure and appetency to the electrolyte of electrode materials are two vital factors for restricting its performance. Here, a bidirectional pore-creating strategy is proposed to construct heteroatom-doped lignin-based porous carbon (HLPC) materials with a high electrochemical active area at supramolecular-level. In this process, activated-mediates with different pore-forming functions are assembled into lignin-based supramolecules by electrostatic forcing, and then hierarchical pore-creation and heteroatom doping are accomplished simultaneously in the pyrolysis process. The obtained carbon materials possess a tunable specific surface area of 543.4–1502.3 m2 g−1 and high heteroatom content of 9.4–16.2 at.%. Benefit from its admirable physicochemical properties, the HPLCs deliver a high ions appetency, ultrahigh capacitance of 380.5 F g−1 at 0.2 A g−1, and extremely long cyclic stability (100% after 10,000 cycles), which is superior 2.5-fold than that of YP-80F at the same mass loading. More promising, symmetrical electrode devices based on HLPCs possess a preeminent energy density of 30.0 Wh kg−1 in aqueous electrolyte. Overall, this protocol provides a new avenue for promoting the advancement of electrode materials in industrial-scale supercapacitors and manufacturing high-value-added products from plentiful bio-waste.

In-situ growth of homogeneous δ-MnO2 within lignin based porous carbon to reassemble uniform mesoporous crosslinked 3D-network structure for supercapacitors

In order to enhance the electrochemical performances of lignin based porous carbon (LPC), a feasible strategy is to incorporate homogeneous δ-MnO2 nanosheets within the LPC substrate via in-situ redox deposition. This work clarified the effects of different LPC supports and KMnO4 solution concentration on in-situ growth of MnO2 and the electrochemical performances of MnO2/LPC composite. The surface topography of δ-MnO2 significantly depends upon the pores feature of LPC. In-situ growth of δ-MnO2 embedded within LPC nanostructure also has a similar type of N2 adsorption-desorption isotherms of nanopores with the original LPC, belong to the type-IV isotherm with a hysteresis loop of H4 type. Moreover, as the KMnO4 solution concentration increases from 1 to 6 mM, the crystal form of δ-MnO2 within LPC maintains, while the electrochemical performances of MnO2/LPC can be improved. Such a uniform 3D-interlinked mesoporous nanostructure of Mn-4/LPC-CO composite electrode exhibits the highest specific capacitance of 198 F g−1 at 1 A g−1, much higher 190% than that of LPC (104 F g−1). Furthermore, the assembled symmetrical supercapacitor by using as-prepared Mn-4/LPC-CO composite exhibits a high energy density of 3.82 Wh kg−1 at the power density of 125 W kg−1 in voltage range of 0–1 V. This study offers a facile and low-cost approach for fabrication of biomass-based functional nanomaterials that can be used in energy storage devices.

Preparation of porous carbon materials from black liquor lignin and its utilization as CO2 adsorbents

Lignin-based porous carbon materials are estimated as promising CO2 capture adsorbents with thanks to their charateristics as abundant distribution, low-cost preparation and high stability. In this work, a series of porous carbon materials were synthesized from the pulping waste (black liquor lignin) through chemical activation and template method. The morphological structure, porosity and surface chemical properties of the obtained porous carbon materials identified by SEM, XRD, Raman, BET and XPS were highly influenced by the synthesis methods. The porous carbon material prepared by KOH activation (C-BLL-KOH) possessed the most disorder carbon structure, along with the largest BET surface area up to 1336.5 m2/g and the highest microporosity accounting for 93.2% of the total pore volume, which is beneficial for capturing CO2. The sulfur-contained functional groups in chemically-activated carbon materials were dominated by oxidized sulfur species and oxygen element was mainly in the form of hydroxyl groups. CO2 adsorption performance of these lignin-based porous carbon materials was carried out at different temperatures (0 °C, 25 °C and 50 °C) to investigate the effect of synthesis method. The most remarkable CO2 capture capacity was achieved for C-BLL-KOH, which was up to 5.20 mmol/g at 0 °C, 3.60 mmol/g at 25 °C and 2.23 mmol/g at 50 °C at a CO2 partial pressure of 100 kPa. This result suggested the KOH activation was an effective route to convert black liquor lignin to porous carbon materials as potential absorbents for CO2 capture.

A porous carbon based on the surface and structural regulation of wasted lignin for long-cycle lithium-ion battery

Lignin, as the second most abundant source in nature, is considered as a good precursor for hard carbon. However, direct carbonization of pure lignin leads to low surface area and porosity. Herein we develop a method to prepare lignin-based porous carbon by a self-template method assisted with surface modification. The oxygen-containing functional groups are introduced to regulate the surface chemistry of lignin. And the metal ions are chosen to coordinate with the oxygen-containing group in the lignin, which can form the carbonates to act as the self template to regulate the pores structure. The aromatic skeleton of lignin can also disperse the metal ions to bring uniform pore-forming sites. The results show that the carbonized lignin modified by chloroacetic acid (CCL) shows mesopores with surface area of 233.4384 m2 g−1. As anode for lithium-ion batteries (LIBs), the CCL shows a specific capacity of 500 mAh g−1 at 50 mA g−1. The capacity retention was 99 % after 1000 cycles at 1000 mA g−1, which are superior to most reported carbon anode. This work proposes a low-cost anode for LIBs and put forward a regulation strategy for bio-mass carbon. Besides, it would reduce the discard of lignin and alleviate the pollution.

Constructing monodisperse blueberry-like lignin-based porous carbon nanospheres for high-performance supercapacitors

Biomass-based porous carbon nanospheres are potential materials for energy storage because of their high specific surface area, environment-friendly, and abundant raw materials. Lignin is the most plentiful aromatic ring polymer in nature, which is the optimal candidate for developing porous carbon nanospheres. However, it is an enormous challenge to develop carbon nanospheres originated from lignin with uniform size, monodisperse and abundant pores. Herein, monodisperse blueberry-like lignin-based porous carbon nanospheres (ACS) are constructed through pre-carbonization and activation methods. The as-prepared ACS presents an adjustable specific surface area range of 557.9–2237.9 m2 g−1 and surface oxygen content of 5.5–8.48 at.%, which endows their excellent electrochemical performance with the capacitance of 254.2 F g−1 at 0.2 A g−1, energy density of 6.3 Wh kg−1, as well as long cycle stability in 6 M KOH electrolyte. In comparison with all-lignin based carbon nanospheres without activation, the capacitance and energy density enhance around 1 time. When the ACS-based electrodes are assembled in 1 M Na2SO4 electrolyte, the voltage window enhances to 2 V, and the energy density is 22.4 Wh kg−1, which elevates about 3.5 times compared with in KOH electrolyte. The relatively higher electrochemical behavior indicates that ACS derived from industrial waste can not only be a promising candidate for the application of energy storage, but also can solve the problem of waste of renewable resources.

Preparation of in-situ nitrogen-doped lignin-based porous carbon and its efficient adsorption of chloramphenicol in water.

Porous carbon is an excellent absorbent for pollutants in water. Here, we report a breakthrough in performance of porous carbon based on lignin prepared using sodium lignosulfonate (SLS), potassium carbonate and melamine as precursor, activator and nitrogen source, respectively. A series of characterization tests confirmed that in-situ nitrogen doping greatly enhanced porous structure, resulting in a specific surface area of 2567.9 m2g-1 and total pore volume of 1.499 cm3g-1, which is nearly twice that of non-nitrogen-doped porous carbon. Moreover, adsorption experiments revealed that at 303K, the saturated adsorption capacity of chloramphenicol was as high as 713.7mgg-1, corresponding to an improvement of 33.7%. Further, the prepared porous carbon exhibited a strong anti-interference against metal ions and humic acid. The adsorption process was confirmed to be an endothermic reaction dominated by physical adsorption, indicating that an increase in temperature is conducive to adsorption. The results of this study show that nitrogen-doped lignin-based porous carbon prepared by in-situ doping is a promising material to significantly alleviate water pollution owing to its low cost, excellent pore structure and good adsorption properties.

Shape-stabilized phase change material with high phase change enthalpy made of PEG compounded with lignin-based carbon

Lignin-based porous carbon (LTC), lignin-based hierarchical porous carbon (LTCA) and lignin-based ordered porous carbon (MC) with different pore structures were prepared by template method and chemical activation method using lignin as raw material. The lignin-based carbon composite phase change materials were prepared by vacuum impregnation with polyethylene glycol (PEG) and porous carbon material. The results showed that LTCA has the largest loading capacity of Phase change Materials, which could load 85% of PEG; MC has the largest phase transition enthalpy value (ΔHm), which is 89.7 J·g−1. When the loading amount is the same as 60%, the thermal conductivity of LTCA/PEG is the largest, which is 0.5167 W/mK, 53.8% higher than that of pure PEG. Under constant heating at 70 °C, the pure cotton fabric and the polyurethane coated fabric reached 60 °C in the 4th and 10th second, The cotton fabric coated with composite phase change material reached 60 °C only at 16 s, and a significant slowdown in the temperature rise rate occurred between 50–60 °C. It showed that the cotton fabric coated with composite phase change material had good phase change temperature regulation performance.

Preparation and characteristic of high surface area lignin-based porous carbon by potassium tartrate activation

In order to study the property of lignin-based porous carbon activated by potassium tartrate, the effects of activator types, activator/lignin mass ratio and activation temperature on the surface morphology, specific surface area and pore size distribution of alkali lignin based porous carbon materials were systematically investigated. Meanwhile, the methyl orange adsorption capacity and adsorption kinetics of the lignin-based porous carbon were also evaluated. The N2 adsorption-desorption experiment results showed that the specific surface area value of lignin-based porous carbon materials activated by potassium tartrate (APC-J), KOH (APC-K), and NaOH (APC-Na) are 947, 1113 and 762 m2/g, respectively. Meanwhile, APC-J has a special microporous structure, while the pore structures of APC-K and APC-Na are mainly mesopores. The best specific surface area of lignin-based porous carbon materials was 1911 m2/g obtaining from APC-J-2-8 sample (mass ratio 2:1, activation temperature 800 °C). The adsorption experiment of methyl orange (MO) showed that the adsorption kinetics of APC-J-2-8 conformed to the quasi-second-order kinetic model, mainly chemical adsorption. The isothermal adsorption process conforms to the Langmuir adsorption isothermal adsorption model, which is a single molecular layer adsorption, and the maximum adsorption amounts are 526.31 mg/g.

Preparation of lignin-based porous carbon as an efficient absorbent for the removal of methylene blue

Lignin is the most abundant renewable aromatic polymer in the world, but its complex structure makes it difficult for efficient utilization. In this study, lignin-based porous carbon (LPC) was prepared through hydrothermal treatment and KOH activation and then used as an adsorbent for the adsorption of methylene blue (MB). The influence of contact time, initial MB concentration, solution pH and adsorption selectivity on adsorption performance was explored. Hierarchical LPC showed a high specific surface area up to 3382.32 m2/g and a large number of active sites. The maximum adsorption capacity of MB was as high as 1119.18 mg/g. The adsorption kinetic was in well agreement with pseudo-second-order model. Langmuir isotherm model fitted well to the adsorption experimental data. The maximum adsorption capacity calculated from Langmuir isotherm model (1119.65 mg/g) approached the experimental result. Moreover, the LPC exhibited the outstanding selective adsorption property to cationic dyes, where the adsorption capacities of malachite green and rhodamine B were 2467.30 mg/g and 1657.82 mg/g, respectively. In addition to electrostatic interaction due to the negatively charged surface of LPC, hydrogen bonding and π-π stacking interactions were responsibility for the adsorption mechanism. On account of low-cost, excellent adsorption properties and favorable reusability, the LPC has the promising potential as a lignin-based absorbent for removing cationic dyes in wastewater treatment.

Specific Surface Area Characteristic Analysis of Porous Carbon Prepared from Lignin-Polyacrylonitrile Copolymer by Activation Conditions

In this study, we investigated the effect of temperature on specific surface area and electrochemical properties when lignin-based porous carbon (LBPC) with potassium hydroxide (KOH) is activated. After preparing LBPCs using lignin-polyacrylonitrile (PAN) copolymer, which was synthesized by graft polymerizing lignin and acrylonitrile as a precursor, activated LBPCs (KA-LBPC-6, 7, 8, 9) were manufactured by activating LBPC with KOH at 600℃, 700℃, 800℃ and 900℃. To identify the surface characteristics of KA-LBPC, observations were made with a scanning electron microscopy (SEM), and the pore characteristics were identified via specific surface area analysis. The electrochemical properties were analyzed using a three-electrode system. The experiment has shown that micropores formed by activation can be observed in SEM images. KA-LBPC-7 had the best pore characteristics among KA-LBPCs, with a specific surface area of 2480.1 m2/g, a micropore volume of 0.64 cm3/g, and a mesopore volume of 0.76 cm3/g. KA-LBPC-7 showed the best electrochemical properties with a specific capacitance of 151.3 F/g at the scan rate of 2 mV/s.

Ni/MnO2 doping pulping lignin-based porous carbon as supercapacitors electrode materials

Lignin extracted from pulping black liquor as carbon source, C4H6O4Ni·4H2O as acatalyst and KMnO4 as dopant, a lignin-based porous carbon material (PC-Ni/MnO2) co-doped with Ni and MnO2 was prepared and used in electrode materials for supercapacitors. During the high-temperature carbonization process, part of amorphous carbon generates a multi-layer graphene structure, causing the PC-Ni/MnO2 to has a high degree of graphitization. Meanwhile, KMnO4 gradually decomposes and reacts with C to produce MnO2. The lignin-based porous carbon material has a higher pseudocapacitance, the specific capacitance of PC-Ni/MnO2 can reach 267.34 F g−1 at a current density of 0.1 A g−1. After 5 000 cycles charge and discharge test, the specific capacitance retention rate kept 83.6% at a current density of 1 A g−1, showing good rate performance and electrochemical stability. A symmetrical supercapacitor prepared by PC-Ni/MnO2 as electrodes, its energy density can reach 28 Wh·kg−1 as the power density of the capacitor is 360 W kg−1. And the supercapacitor also exhibited good cyclic stability with 86.3% retention of initial capacitance after 5000 cycles at 1.0 A g−1. When two such supercapacitors in series, a LED lamp can be light. These induct that the doping of Ni and MnO2 can improve the capacitance characteristics, showing that the biomass porous carbon has great practical application value.

Designing the effective microstructure of lignin-based porous carbon substrate to inhibit the capacity decline for SnO2 anode

As the traditional anode material of lithium-ion batteries, tin dioxide (SnO2) has the characteristics of a high theoretical capacity and stable crystal structure. However, the alloying/de-alloying reaction between tin and lithium ions causes volume expansion and continuously generates an SEI film, which causes the electrode to fall off the current collector and the capacity fade rapidly. Generally, a composite of carbon materials and SnO2 can alleviate the expansion and pulverization phenomena. However, the microstructure of carbon materials is complex and changeable, which makes it difficult to definitively state the influence mechanism of the microstructure on the lithium storage performance of composite materials. Here, three kinds of lignin-based porous carbons (LPCs) with different microstructural characteristics, along with a high graphitization, high specific surface area and hierarchical porosity, are obtained by regulating the process of gas exfoliation and in situ activation. Furthermore, a series of LPC/SnO2 composites are obtained by an ultrasonic dispersion and ball milling method. Electrochemical property results show that the hierarchical porous LPCs are more conducive to the dispersion/coating of SnO2 nanoparticles and that the reversible specific capacity of the electrode material increases from 64 to 620 mA h g−1, effectively mitigating the expansion and pulverization of SnO2 during the lithium storage process.