Polymer-Derived Silicon Oxycarbide Ceramics as Promising Next-Generation Sustainable Thermoelectrics

Kousaalya, Adhimoolam Bakthavachalam; Zeng, Xiaoyu; Karakaya, Mehmet; Tritt, Terry M.; Pilla, Srikanth; Rao, Apparao M.

doi:10.1021/acsami.7b17394

Cited by 29 publications

(8 citation statements)

References 30 publications

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“…PDCs are well-known to exhibit a wide range of conductivity (σ) from the insulating to the conducting regime depending on the material composition, free carbon content, and processing method. [4,61] σ of PDCs pyrolyzed at temperatures below 1300 °C is poor, usually being below 10 −5 S cm −1 at room temperature. [14,20,21,[62][63][64][65][66][67][68][69][70][71][72][73][74] Poor σ limits the functional applications of PDCs.…”

Section: Abnormal Electrical Behaviors In Pdc-sicnmentioning

confidence: 99%

Abnormal Graphitization Behavior in Near‐Surface/Interface Region of Polymer‐Derived Ceramics

Lin

Pan

et al. 2022

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A free carbon phase has been proven to be beneficial for many structural and functional properties of PDCs, such as electrical conductivity, [8][9][10][11][12][13][14] electromagnetic properties, [15][16][17] electrochemical properties, [18,19] piezoelectricity, [20,21] corrosion resistance, [22] and oxidation resistance. [23] In high-temperature sensing applications, the concentration and morphology of free carbon strongly affect the electrical properties of devices and the selectivity/sensitivity of sensors. [4] In energy applications, PDCs are considered promising for electrical energy storage in devices ranging from cell phones to electric cars. [24] The electrical conductivity or free carbon morphology of PDC-based anode materials for lithium ion batteries plays an important role in achieving high reversible capacity, good rate performance, and reliable cycle stability. [25] In electromagnetic wave absorbing and shielding applications, an increase in the free carbon concentration of PDCs leads to an increase in the dielectric loss and, in turn, improves the total shielding effectiveness in terms of both absorption and reflection shielding effectiveness. [26] Therefore, the microstructural evolution of carbon and the properties resulting from the same are of great interest in this research area.This leads to the fundamental and common question of how to effectively regulate the structural evolution of carbon to further enhance the performance of PDCs. The polymer-toceramic transformation process of most PDCs mainly includes the synthesis of a preceramic precursor, shaping, cross-linking, and pyrolysis. [2,27] Amorphous PDCs undergo a devitrification process to form an amorphous multiphase system through a redistribution reaction of chemical bonds under hightemperature conditions. [2,27] The separated free carbon phase undergoes a graphitization process that plays an important role in the microstructural evolution of PDCs. [4] Many studies have claimed that the amount of free carbon within PDCs strongly depends on the thermal stability of the hydrocarbon linkages rather than on the percentage of the total carbon content of the polymer; therefore, a large number of new precursor solutions (e.g., polysiloxane or polysilazane, carbon-rich or carbonpoor polymers) and optimized heat-treatment parameters (e.g., temperature, atmosphere, and holding time) have been designed and explored to improve the graphitization level of The in situ free carbon generated in polymer-derived ceramics (PDCs) plays a crucial role in their unique microstructure and resultant properties. This study advances a new phenomenon of graphitization of PDCs. Specifically, whether in micro-/nanoscale films or millimeter-scale bulks, the surface/interface radically changes the fate of carbon and the evolution of PDC nanodomains, promotes the graphitization of carbon, and evolves a free carbon enriched layer in the near-surface/interface region. Affected by the enrichment behavior of free carbon in the near-surface/interface region, PDCs exhibit h...

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Section: Abnormal Electrical Behaviors In Pdc-sicnmentioning

confidence: 99%

Abnormal Graphitization Behavior in Near‐Surface/Interface Region of Polymer‐Derived Ceramics

Lin

Pan

et al. 2022

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“…The integration of polymer-derived ceramics (PDCs) in anode materials for lithium-ion batteries is an attractive prospect that has been the focus of numerous studies since the early work on lithiation of PDCs, reported in 1994 . PDCs, which are generally carbide and oxycarbide materials formed by the pyrolysis of silicon-based preceramic polymers, − are of growing interest toward diverse applications including electrochemical energy storage, − microbial bioelectrochemical systems, microelectromechanical systems, electromagnetic shielding, and thermoelectrics . The development of PDCs is motivated by their remarkable chemical stability and the versatile routes with which they can be processed. , Coupled with tunable properties of electrical conductivity, permittivity, and thermal conductivity, PDCs offer utilitarian pathways toward effective energy materials. ,, …”

Section: Introductionmentioning

confidence: 99%

Polymer-Derived SiOC Integrated with a Graphene Aerogel As a Highly Stable Li-Ion Battery Anode

Shao

Hanaor

Wang

et al. 2020

ACS Appl. Mater. Interfaces

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Amorphous polymer-derived silicon oxycarbide (SiOC) is an attractive candidate for Li-ion battery anodes, as an alternative to graphite, which is limited to a theoretical capacity of 372 mAh/g. However, SiOC tends to exhibit poor transport properties and cycling performance as the result of sparsely distributed carbon clusters and inefficient active sites. To overcome these limitations, we designed and fabricated a layered graphene/SiOC heterostructure by solvent assisted infiltration of a polymeric precursor into a modified 3D graphene aerogel skeleton. The use of a high-melting-point solvent facilitated the precursor's freeze-drying, which following pyrolysis yielded SiOC as a layer supported on the surface of nitrogen doped reduced graphene oxide aerogels. The fabrication method employed here modifies the composition and microstructure of the SiOC phase. Among the studied materials, highest levels of performance were obtained for a sample of moderate SiOC content, in which the graphene network constituted 19.8wt% of the system. In these materials a stable reversible charge capacity of 751 mAh/g was achieved at low charge rates. At high charge rates of 1480 mA/g the capacity retention was ~95% (352 mAh/g) after 1000 consecutive cycles. At all rates, Colombic efficiencies >99% were maintained following the first cycle. Performance across all indicators was majorly improved in the graphene aerogel/SiOC nanocomposites, compared with unsupported SiOC. Performance was attributed to mechanisms across multiple lengthscales. The presence of oxygen rich SiO4−xCx tetrahedra units and a continuous free-carbon network within the SiOC provide sites for reversible lithiation, while high ionic and electronic transport is provided by the layered graphene/SiOC heterostructure.

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“…In this work, polymer-derived ceramics (PDCs) technology was used to develop SiOC ceramic materials through a pure liquid system. Combined with 3D printing technology, the limitations of hot-pressing and other formulation methods on material [42] SiOC 1450-1650 hotpressed -1.30-1.80 [43] SiOC 1100-1200 PECS 2.22 0.82 [44] SiOC 1000 3D printing shapes have been overcome. After optimizing the resin formulation, which has a better fluidity when there was no solvent and it was suitable for 3D printing.…”

Section: Discussionmentioning

confidence: 99%

3D Printing of Complex‐type SiOC Ceramics Derived From Liquid Photosensitive Resin

et al. 2019

ChemistrySelect

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SiOC ceramics have been successfully synthesized using photosensitive resin as a liquid precursor through digital light processing 3D printing technology and pyrolysis. Liquid photosensitive resin has excellent fluidity (processable viscosity 0.068 Pa⋅s) which is beneficial for 3D printing. The liquid resin formulation was designed without solvent and filler. After researching the ratio of raw materials and temperature conditions, SiOC ceramic materials with complex structures can be produced without cracks. SiOC ceramics were characterized by SEM, XRD, Raman spectrometry and FT‐IR. The as‐prepared SiOC ceramic has excellent hardness (1.85 GPa) and high thermal conductivity (1.431 W/mK).

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Polymer-Derived Silicon Oxycarbide Ceramics as Promising Next-Generation Sustainable Thermoelectrics

Cited by 29 publications

References 30 publications

Abnormal Graphitization Behavior in Near‐Surface/Interface Region of Polymer‐Derived Ceramics

Abnormal Graphitization Behavior in Near‐Surface/Interface Region of Polymer‐Derived Ceramics

Polymer-Derived SiOC Integrated with a Graphene Aerogel As a Highly Stable Li-Ion Battery Anode

3D Printing of Complex‐type SiOC Ceramics Derived From Liquid Photosensitive Resin

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