Capacitive energy storage from single pore to porous electrode identified by frequency response analysis

Rate capability,peak power,and energy density are of vital importance for the capacitive energy storage(CES)of electrochemical energy devices.The frequency response analysis(FRA)is regarded as an efficient tool in studying the CES.In the present work,a bi-scale impedance transmission line model(TLM)is firstly developed for a single pore to a porous electrode.Not only the TLM of the single pore is reparameterized but also the particle packing compactness is defined in the bi-scale.Subsequently,the CES properties are identified by FRA,focused on rate capability vs.characteristic frequency,peak power vs.equivalent series resistance,and energy density vs.low frequency limiting capacitance for a single pore to a porous electrode.Based on these relationships,the CES properties are numerically simulated and theoretically predicted for a single pore to a porous electrode in terms of intra-particle pore length,intra-particle pore diameter,inter-particle pore diameter,electrolyte conductivity,interfacial capacitance&exponent factor,electrode thickness,electrode apparent surface area,and particle packing compactness.Finally,the experimental diagnosis of four supercapacitors(SCs)with different electrode thicknesses is conducted for validating the bi-scale TLM and gaining an insight into the CES properties for a porous electrode to a single pore.The calculating results suggest,to some extent,the inter-particle pore plays a more critical role than the intra-particle pore in the CES properties such as the rate capability and the peak power density for a single pore to a porous electrode.Hence,in order to design a better porous electrode,more attention should be given to the inter-particle pore.

Nano-single-crystal-constructed submicron MnCO_(3) hollow spindles enabled by solid precursor transition combined Ostwald ripening in situ on graphene toward exceptional interfacial and capacitive lithium storage

Hollow structuring has been identified as an effective strategy to enhance the cycling stability of electrodes for rechargeable batteries due to the outstanding volume expansion buffering efficiency,which motivates ardent pursuing on the synthetic approaches of hollow materials.Herein,an intriguing route,combining solid precursor transition and Ostwald ripening(SPTOR),is developed to craft nano single-crystal(SC)-constructed MnCO_(3) submicron hollow spindles homogeneously encapsulated in a reduced graphene oxide matrix(MnCO_(3) SMHSs/rGO).It is noteworthy that the H-bonding interaction between Mn_(3)O_(4) nanoparticles(NPs)and oxygen-containing groups on GO promotes uniform anchoring of Mn_(3)O_(4) NPs on GO,mild reductant ascorbic acid triggers the progressive solid-to-solid transition from Mn_(3)O_(4) NPs to MnCO_(3) submicron solid spindles(SMSSs)in situ on GO,and the Ostwald ripening process induces the gradual dissolution of interior polycrystals of MnCO_(3) SMSSs and subsequent recrystallization on surface SCs of MnCO_(3) SMHSs.Remarkably,MnCO_(3) SMHSs/rGO delivers a 500th lithium storage capacity of 2023 mAh g^(-1) at 1000 mAg^(-1),which is 10 times higher than that of MnCO_(3) microspheres/rGO fabricated from a conventional Mn^(2+)salt precursor(202 mAh g^(-1)).The ultrahigh capacity and ultralong lifespan of MnCO_(3) SMHSs/rGO can be primarily attributed to the superior reaction kinetics and reversibility combined with exceptional interfacial and capacitive lithium storage capability,enabled by the fast ion/electron transfer,large specific surface area,and robust electrode pulverization inhibition efficacy.Moreover,fascinating in-depth lithium storage reactions of MnCO_(3) are observed such as the oxidation of Mn^(2+)in MnCO_(3) to Mn^(3+)in charge process after long-term cycles and the further lithiation of Li_(2)CO_(3) in discharge process.As such,the Carbon Energy.SPTOR approach may represent a viable strategy for crafting various hollow functional materials with metastable nanomaterials as precursors.

ZnO-Embedded Expanded Graphite Composite Anodes with Controlled Charge Storage Mechanism Enabling Operation of Lithium-Ion Batteries at Ultra-Low Temperatures

As lithium(Li)-ion batteries expand their applications,operating over a wide temperature range becomes increasingly important.However,the lowtemperature performance of conventional graphite anodes is severely hampered by the poor diffusion kinetics of Li ions(Li^(+)).Here,zinc oxide(ZnO) nanoparticles are incorporated into the expanded graphite to improve Li^(+)diffusion kinetics,resulting in a significant improvement in lowtemperature performance.The ZnO-embedded expanded graphite anodes are investigated with different amounts of ZnO to establish the structurecharge storage mechanism-performance relationship with a focus on lowtemperature applications.Electrochemical analysis reveals that the ZnOembedded expanded graphite anode with nano-sized ZnO maintains a large portion of the diffusion-controlled charge storage mechanism at an ultra-low temperature of-50℃ Due to this significantly enhanced Li^(+)diffusion rate,a full cell with the ZnO-embedded expanded graphite anode and a LiNi_(0.88)Co_(0.09)Al_(0.03)O_(2)cathode delivers high capacities of 176 mAh g^(-1)at20℃ and 86 mAh g^(-1)at-50℃ at a high rate of 1 C.The outstanding low-temperature performance of the composite anode by improving the Li^(+)diffusion kinetics provides important scientific insights into the fundamental design principles of anodes for low-temperature Li-ion battery operation.

Dipolar Glass Polymers for Capacitive Energy Storage at Room Temperatures and Elevated Temperatures

Dielectric polymers are the materials of choice for high energy density film capacitors.The increasing demand for advanced electrical systems requires dielectric polymers to operate efficiently under extreme conditions,especially at elevated temperatures.However,the low permittivity and relatively low operating temperature of dielectric polymers limit the high-temperature capacitive energy storage applications.Fortunately,dipolar glass polymers are demonstrated as the preferred materials to achieve high dielectric constant,low dielectric loss and high energy density at elevated temperatures.In this review,we critically elaborate on the recent progress of dipolar glass polymers based on orientational polarization from molecular engineering.In addition,the general design considerations and various dipole moment entities of dipolar glass polymers are described in detail.High dipolar moment,high dipole density and rotation freedom of dipoles are essential for dipolar glass polymers to gain superior dielectric and energy storage properties.Challenges and future opportunities for dipolar glass polymers towards high-temperature energy storage applications are also provided.

Transformation of Supercapacitive Charge Storage Behaviour in a Multi elemental Spinel CuMn_(2)O_(4) Nanofibers with Alkaline and Neutral Electrolytes

Electrode material has been cited as one of the most important determining factors in classifying an energy storage system’s charge storage mechanism,i.e.,as battery-type or supercapacitive-type.In this paper,we show that along with the electrode material,the electrolyte also plays a role in determining the charge storage behaviour of the system.For the purpose of our research,we chose multi-elemental spinal type CuMn_(2)O_(4) metal oxide nanofibers to prove the hypothesis.The material is synthesized as nanofibers of diameter~120 to 150 nm in large scales by a pilot scale electrospinning set up.It was then tested in three different electrolytes(1 M KOH,1 M Na_(2)SO_(4) and 1 M Li_(2)SO_(4)),two of which are neutral and the third is alkaline(KOH).The cyclic voltammograms and the galvanostatic charge-discharge of the electrode material in a three-electrode sys-tem measurement showed that it exhibit different charge storage mechanism in different electrolyte solutions.For the neutral electrolytes,a capacitive behaviour was observed whereas a battery-type behaviour was seen for the alkaline electrolyte.This leads us to conclude that the charge storage mechanism,along with the active material,also depends on the electrolyte used.