Efficient Preconstruction of Three‑Dimensional Graphene Networks for Thermally Conductive Polymer Composites

Electronic devices generate heat during operation and require efficient thermal management to extend the lifetime and prevent performance degradation.Featured by its exceptional thermal conductivity,graphene is an ideal functional filler for fabricating thermally conductive polymer composites to provide efficient thermal management.Extensive studies have been focusing on constructing graphene networks in polymer composites to achieve high thermal conductivities.Compared with conventional composite fabrications by directly mixing graphene with polymers,preconstruction of three-dimensional graphene networks followed by backfilling polymers represents a promising way to produce composites with higher performances,enabling high manufacturing flexibility and controllability.In this review,we first summarize the factors that affect thermal conductivity of graphene composites and strategies for fabricating highly thermally conductive graphene/polymer composites.Subsequently,we give the reasoning behind using preconstructed three-dimensional graphene networks for fabricating thermally conductive polymer composites and highlight their potential applications.Finally,our insight into the existing bottlenecks and opportunities is provided for developing preconstructed porous architectures of graphene and their thermally conductive composites.

Highly Thermally Conductive Polymer/Graphene Composites with Rapid Room‑Temperature Self‑Healing Capacity

Composites that can rapidly self-healing their structure and function at room temperature have broad application prospects.However,in view of the complexity of composite structure and composition,its self-heal is facing challenges.In this article,supramolecular effect is proposed to repair the multistage structure,mechanical and thermal properties of composite materials.A stiff and tough supramolecular frameworks of 2-[[(butylamino)carbonyl]oxy]ethyl ester(PBA)–polydimethylsiloxane(PDMS)were established using a chain extender with double amide bonds in a side chain to extend prepolymers through copolymerization.Then,by introducing the copolymer into a folded graphene film(FGf),a highly thermally conductive composite of PBA–PDMS/FGf with self-healing capacity was fabricated.The ratio of crosslinking and hydrogen bonding was optimized to ensure that PBA–PDMS could completely self-heal at room temperature in 10 min.Additionally,PBA–PDMS/FGf exhibits a high tensile strength of 2.23±0.15 MPa at break and high thermal conductivity of 13±0.2 W m^(−1)K^(−1);of which the self-healing efficiencies were 100%and 98.65%at room temperature for tensile strength and thermal conductivity,respectively.The excellent self-healing performance comes from the efficient supramolecular interaction between polymer molecules,as well as polymer molecule and graphene.This kind of thermal conductive self-healing composite has important application prospects in the heat dissipation field of next generation electronic devices in the future.

Electrochemical Impedance Analysis of Biofunctionalized Conducting Polymer-Modified Graphene-CNTs Nanocomposite for Protein Detection

We report an electrodeposited poly(pyrrole-co-pyrrolepropylic acid) copolymer modified electroactive graphene-carbon nanotubes composite deposited on a glassy carbon electrode to detect the protein antigen(cTnI). The copolymer provides pendant carboxyl groups for the site-specific covalent immobilization of protein antibody, antitroponin I. The hybrid nanocomposite was used as a transducer for biointerfacial impedance sensing for cTnI detection.The results show that the hybrid exhibits a pseudo capacitive behaviour with a maximum phase angle of 49° near 1 Hz,which is due to the inhomogeneous and porous structure of the hybrid composition. The constant phase element of copolymer is 0.61(n = 0.61), whereas, it is 0.88(n = 0.88) for the hybrid composites, indicating a comparatively homogeneous microstructure after biomolecular functionalization. The transducer shows a linear change in charge transfer characteristic(R_(et)) on cTnI immunoreaction for spiked human serum in the concentration range of 1.0 pg mL^(-1)–10.0 ng mL^(-1). The sensitivity of the transducer is 167.8 ± 14.2 Ω cm^2 per decade, and it also exhibits high specificity and good reproducibility.

The roles of polymer-graphene interface and contact resistance among nanosheets in the effective conductivity of nanocomposites

The effective conductivity of graphene-based nanocomposites is suggested by the characteristics of polymer-filler interfacial areas as well as the contact resistance between the neighboring nanosheets.The interfacial properties are expressed by the effective levels of the inverse aspect ratio and the filler volume fraction.Moreover,the resistances of components in the contact regions are used to define the contact resistance,which inversely affects the effective conductivity.The obtained model is utilized to predict the effective conductivity for some examples.The discrepancy of the effective conductivity at various ranks of all factors is clarified.The interfacial conductivity directly controls the effective conductivity,while the filler conductivity plays a dissimilar role in the effective conductivity,due to the incomplete interfacial adhesion.A high operative conductivity is also achieved by small contact distances and high interfacial properties.Additionally,big contact diameters and little tunnel resistivity decrease the contact resistance,thus enhancing the effective conductivity.

Supposition of graphene stacks to estimate the contact resistance and conductivity of nanocomposites

In this study,the effects of stacked nanosheets and the surrounding interphase zone on the resistance of the contact region between nanosheets and the tunneling conductivity of samples are evaluated with developed equations superior to those previously reported.The contact resistance and nanocomposite conductivity are modeled by several influencing factors,including stack properties,interphase depth,tunneling size,and contact diameter.The developed model's accuracy is verified through numerous experimental measurements.To further validate the models and establish correlations between parameters,the effects of all the variables on contact resistance and nanocomposite conductivity are analyzed.Notably,the contact resistance is primarily dependent on the polymer tunnel resistivity,contact area,and tunneling size.The dimensions of the graphene nanosheets significantly influence the conductivity,which ranges from 0 S/m to90 S/m.An increased number of nanosheets in stacks and a larger gap between them enhance the nanocomposite's conductivity.Furthermore,the thicker interphase and smaller tunneling size can lead to higher sample conductivity due to their optimistic effects on the percolation threshold and network efficacy.

Vapor Phase Polymerization Deposition Conducting Polymer Nanocomposites on Porous Dielectric Surface as High Performance Electrode Materials

We report chemical vapor phase polymerization(VPP) deposition of poly(3,4-ethylenedioxythiophene)(PEDOT) and PEDOT/graphene on porous dielectric tantalum pentoxide(Ta_2O_5) surface as cathode films for solid tantalum electrolyte capacitors. The modified oxidant/oxidant-graphene films were first deposited on Ta_2O_5 by dip-coating, and VPP process was subsequently utilized to transfer oxidant/oxidant-graphene into PEDOT/PEDOT-graphene films. The SEM images showed PEDOT/PEDOT-graphene films was successfully constructed on porous Ta_2O_5 surface through VPP deposition, and a solid tantalum electrolyte capacitor with conducting polymer-graphene nano-composites as cathode films was constructed. The high conductivity nature of PEDOT-graphene leads to resistance decrease of cathode films and lower contact resistance between PEDOT/graphene and carbon paste. This nano-composite cathode films based capacitor showed ultralow equivalent series resistance(ESR) ca. 12 m? and exhibited excellent capacitance-frequency performance, which can keep 82% of initial capacitance at 500 KHz. The investigation on leakage current revealed that the device encapsulation process has no influence on capacitor leakage current, indicating the excellent mechanical strength of PEDOT/PEDOT-gaphene films. This high conductivity and mechanical strength of graphene-based polymer films shows promising future for electrode materials such as capacitors, organic solar cells and electrochemical energy storage devices.

Ionic polymer metal composites actuators with enhanced driving performance by incorporating graphene quantum dots

In order to further improve the driving performance of ionic polymer metal composites(IPMCs),Nafion/graphene quantum dots(GQDs)hybrid membranes incorporating GQDs with various contents of 0,0.1 wt.%,0.5 wt.%,1.0 wt.%,2.0 wt.%and 4.0 wt.%were fabricated by solution casting,and then IPMCs were manufactured by electroless plating.The water contents and elastic moduli of the hybrid membranes were tested.The morphology characteristics of the hybrid membranes and the IPMCs were observed,and the current,AC impedance,blocking force and displacement of the IPMCs were measured.The results show that the elastic modulus of the hybrid membranes decreases,the water content increases,and the actuation performance of the IPMCs improves significantly after the addition of GQDs.IPMC with 1.0 wt.%GQDs exhibits the best driving property.Compared with the IPMC without GQDs,the working current,ion conductivity,blocking force,and tip displacement increase by 94.67%,311.11%,53.66%,and 66.07%,respectively.These results lay a solid foundation for the preparation of IPMCs with high performance,and further broaden their applications in biomedical devices and bionic robots.

Thermal conductivity model of filled polymer composites

Theoretical and empirical models for predicting the thermal conductivity of polymer composites were summarized since the 1920s.The effects of particle shape,filler amount,dispersion state of fillers,and interfacial thermal barrier on the thermal conductivity of filled polymer composites were investigated,and the agreement of experimental data with theoretical models in literatures was discussed.Silica with high thermal conductivity was chosen to mix with polyvinyl-acetate （EVA） copolymer to prepare SiO2/EVA co-films.Experimental data of the co-films＇ thermal conductivity were compared with some classical theoretical and empirical models.The results show that Agari＇s model,the mixed model,and the percolation model can predict well the thermal conductivity of SiO2/EVA co-films.

Breaking Through Bottlenecks for Thermally Conductive Polymer Composites:A Perspective for Intrinsic Thermal Conductivity,Interfacial Thermal Resistance and Theoretics

Rapid development of energy,electrical and electronic technologies has put forward higher requirements for the thermal conductivities of polymers and their composites.However,the thermal conductivity coefficient(λ)values of prepared thermally conductive polymer composites are still difficult to achieve expectations,which has become the bottleneck in the fields of thermally conductive polymer composites.Aimed at that,based on the accumulation of the previous research works by related researchers and our research group,this paper proposes three possible directions for breaking through the bottlenecks:(1)preparing and synthesizing intrinsically thermally conductive polymers,(2)reducing the interfacial thermal resistance in thermally conductive polymer composites,and(3)establishing suitable thermal conduction models and studying inner thermal conduction mechanism to guide experimental optimization.Also,the future development trends of the three above-mentioned directions are foreseen,hoping to provide certain basis and guidance for the preparation,researches and development of thermally conductive polymers and their composites.

3D Lamellar-Structured Graphene Aerogels for Thermal Interface Composites with High Through-Plane Thermal Conductivity and Fracture Toughness

Although thermally conductive graphene sheets are efficient in enhancing in-plane thermal conductivities of polymers,the resulting nanocomposites usually exhibit low through-plane thermal conductivities,limiting their application as thermal interface materials.Herein,lamellarstructured polyamic acid salt/graphene oxide(PAAS/GO)hybrid aerogels are constructed by bidirectional freezing of PAAS/GO suspension followed by lyophilization.Subsequently,PAAS monomers are polymerized to polyimide(PI),while GO is converted to thermally reduced graphene oxide(RGO)during thermal annealing at 300℃.Final graphitization at 2800℃ converts PI to graphitized carbon with the inductive effect of RGO,and simultaneously,RGO is thermally reduced and healed to high-quality graphene.Consequently,lamellar-structured graphene aerogels with superior through-plane thermal conduction capacity are fabricated for the first time,and its superior through-plane thermal conduction capacity results from its vertically aligned and closely stacked high-quality graphene lamellae.After vacuum-assisted impregnation with epoxy,the resultant epoxy composite with 2.30 vol% of graphene exhibits an outstanding through-plane thermal conductivity of as high as 20.0 W m^−1 K^−1,100 times of that of epoxy,with a record-high specific thermal conductivity enhancement of 4310%.Furthermore,the lamellar-structured graphene aerogel endows epoxy with a high fracture toughness,~1.71 times of that of epoxy.

Recent progress on thermal conductivity of graphene filled epoxy composites

With the rapid development of the electronic industry, the requirements for packaging materials with high thermal conductivity(TC) are getting higher and higher. Epoxy is widely used as package material for electronic package applications. But it’s intrinsic TC can’t meets the increasing demands. Adding high TC graphene into epoxy matrix is a proper way to reinforce epoxy composites. This review focuses on the filler modification,preparation process and thermal properties of graphene-filled epoxy resin composites. Different ways of covalent and non-covalent modification methods are discussed. The various kinds of graphene coating layer are also summarized. Then we analysis the hybrid filler system in epoxy composite. We hope this review will provide guidance for the development and application of graphene-filled epoxy resin composites.

The Development of Thermal Conductive Polymer Composites for Heat Sink

The thermal and mechanical properties of the polyamide 6/boron nitride and polyphenylene sulfide/graphite composites have been investigated as a function of composition and size of fillers. The addition of highly thermal conductive h-BN and graphite gives rise to large increase （about 2 times） of thermal conductivity of individual polymer. In PPS/graphite system, the higher conductivity value was obtained when smaller graphites were added. Meanwhile, the tensile and flexural strength are reduced upon increasing filler loading.

Wearable and stretchable conductive polymer composites for strain sensors:How to design a superior one?

Wearable and stretchable strain sensors have potential values in the fields of human motion and health monitoring,flexible electronics,and soft robotic skin.The wearable and stretchable strain sensors can be directly attached to human skin,providing visualized detection for human motions and personal healthcare.Conductive polymer composites(CPC)composed of conductive fillers and flexible polymers have the advantages of high stretchability,good flexibility,superior durability,which can be used to prepare flexible strain sensors with large working strain and outstanding sensitivity.This review has put forward a comprehensive summary on the fabrication methods,advanced mechanisms and strain sensing abilities of CPC strain sensors reported in recent years,especially the sensors with superior performance.Finally,the structural design,bionic function,integration technology and further application of CPC strain sensors are prospected.

Adaptive Neuro-Fuzzy Inference System for Prediction of Effective Thermal Conductivity of Polymer-Matrix Composites

In the present study, the adaptive neuro-fuzzy inference system (ANFIS) is developed for the prediction of effective thermal conductivity (ETC) of different fillers filled in polymer matrixes. The ANFIS uses a hybrid learning algorithm. The ANFIS is a class of adaptive networks that is functionally equivalent to fuzzy inference systems (FIS). The ANFIS is based on neuro-fuzzy model, trained with data collected from various sources of literature. ETC is predicted using ANFIS with volume fraction and thermal conductivities of fillers and matrixes as input parameters, respectively. The predicted results by ANFIS are in good agreements with experimental values. The predicted results also show the supremacy of ANFIS in comparison with other earlier developed models.

Flexible piezoresistive pressure sensor based on a graphene-carbon nanotube-polydimethylsiloxane composite

Flexible sensors are used widely in wearable devices, specifically flexible piezoresistive sensors, which are common and easy to manipulate.However, fabricating such sensors is expensive and complex, so proposed here is a simple fabrication approach involving a sensor containing microstructures replicated from a sandpaper template onto which polydimethylsiloxane containing a mixture of graphene and carbon nanotubes is spin coated. The surface morphologies of three versions of the sensor made using different grades of sandpaper are observed, and the corresponding pressure sensitivities and linearity and hysteresis characteristics are assessed and analyzed. The results show that the sensor made using 80-mesh sandpaper has the best sensing performance. Its sensitivity is 0.341 kPa-1in the loading range of 0–1.6 kPa, it responds to small external loading of 100 Pa with a resistance change of 10%, its loading and unloading response times are 0.126 and 0.2 s, respectively,and its hysteresis characteristic is ~7%, indicating that the sensor has high sensitivity, fast response, and good stability. Thus, the presented piezoresistive sensor is promising for practical applications in flexible wearable electronics.

Incorporation of Ionic Conductive Polymers into Sulfide Electrolyte-Based Solid-State Batteries to Enhance Electrochemical Stability and Cycle Life

Sulfide-based inorganic solid electrolytes are promising materials for high-performance safe solid-state batteries.The high ion conductivity,mechanical characteristics,and good processability of sulfide-based inorganic solid electrolytes are desirable properties for realizing high-performance safe solid-state batteries by replacing conventional liquid electrolytes.However,the low chemical and electrochemical stability of sulfide-based inorganic solid electrolytes hinder the commercialization of sulfide-based safe solid-state batteries.Particularly,the instability of sulfide-based inorganic solid electrolytes is intensified in the cathode,comprising various materials.In this study,carbonate-based ionic conductive polymers are introduced to the cathode to protect cathode materials and suppress the reactivity of sulfide electrolytes.Several instruments,including electrochemical spectroscopy,X-ray photoelectron spectroscopy,and scanning electron microscopy,confirm the chemical and electrochemical stability of the polymer electrolytes in contact with sulfide-based inorganic solid electrolytes.Sulfide-based solid-state cells show stable electrochemical performance over 100 cycles when the ionic conductive polymers were applied to the cathode.

A Perspective for Developing Polymer-Based Electromagnetic Interference Shielding Composites

The rapid development of aerospace weapons and equipment,wireless base stations and 5G communication technologies has put forward newer and higher requirements for the comprehensive performances of polymer-based electromagnetic interference(EMI)shielding composites.However,most of currently prepared polymer-based EMI shielding composites are still difficult to combine high performance and multi-functionality.In response to this,based on the research works of relevant researchers as well as our research group,three possible directions to break through the above bottlenecks are proposed,including construction of efficient conductive networks,optimization of multi-interfaces for lightweight and multifunction compatibility design.The future development trends in three directions are prospected,and it is hoped to provide certain theoretical basis and technical guidance for the preparation,research and development of polymer-based EMI shielding composites.

Morphology and conductivity of in-situ PEO-LiClO_4-TiO_2 composite polymer electrolyte

PEO-LiClO4-TiO2 composite polymer electrolyte films were prepared. TiO2 was formed directly in matrix by hydrolysis and condensation reaction of tetrabutyl titanate. The crystallinity, morphology and ionic conductivity of composite polymer electrolyte films were examined by differential scanning calorimetry, scanning electron microscopy, atom force microscopy and alternating current impedance spectroscopy, respectively. The glass transition temperature and the crystallinity of composite polymer electrolytes are decreased compared with those of PEO-LiClO4 polymer electrolyte film. The results show that TiO2 particles are uniformly dispersed in PEO-LiClO4-5%TiO2 composite polymer electrolyte film. The maximal conductivity of 5.5×10、5 Scm at 20 ℃ of PEO-LiClO4-TiO2 film is obtained at 5% mass fraction of TiO2.

Optimized CeO_(2) Nanowires with Rich Surface Oxygen Vacancies Enable Fast Li-Ion Conduction in Composite Polymer Electrolytes

Low-cost and flexible solid polymer electrolytes are promising in all-solid-state Li-metal batteries with high energy density and safety.However,both the low room-temperature ionic conductivities and the small Li^(+)transference number of these electrolytes significantly increase the internal resistance and overpotential of the battery.Here,we introduce Gd-doped CeO_(2) nanowires with large surface area and rich surface oxygen vacancies to the polymer electrolyte to increase the interaction between Gd-doped CeO_(2) nanowires and polymer electrolytes,which promotes the Li-salt dissociation and increases the concentration of mobile Li ions in the composite polymer electrolytes.The optimized composite polymer electrolyte has a high Li-ion conductivity of 5×10^(-4)4 S cm^(-1) at 30℃ and a large Li+transference number of 0.47.Moreover,the composite polymer electrolytes have excellent compatibility with the metallic lithium anode and high-voltage LiNi_(0.8)Mn _(0.1)Co_(0.1)O_(2)(NMC)cathode,providing the stable cycling of all-solid-state batteries at high current densities.