Multilevel carbon architecture of subnanoscopic silicon for fast‐charging high‐energy‐density lithium‐ion batteries

Silicon(Si)is widely used as a lithium‐ion‐battery anode owing to its high capacity and abundant crustal reserves.However,large volume change upon cycling and poor conductivity of Si cause rapid capacity decay and poor fast‐charging capability limiting its commercial applications.Here,we propose a multilevel carbon architecture with vertical graphene sheets(VGSs)grown on surfaces of subnanoscopically and homogeneously dispersed Si–C composite nanospheres,which are subsequently embedded into a carbon matrix(C/VGSs@Si–C).Subnanoscopic C in the Si–C nanospheres,VGSs,and carbon matrix form a three‐dimensional conductive and robust network,which significantly improves the conductivity and suppresses the volume expansion of Si,thereby boosting charge transport and improving electrode stability.The VGSs with vast exposed edges considerably increase the contact area with the carbon matrix and supply directional transport channels through the entire material,which boosts charge transport.The carbon matrix encapsulates VGSs@Si–C to decrease the specific surface area and increase tap density,thus yielding high first Coulombic efficiency and electrode compaction density.Consequently,C/VGSs@Si–C delivers excellent Li‐ion storage performances under industrial electrode conditions.In particular,the full cells show high energy densities of 603.5 Wh kg^(−1)and 1685.5 Wh L^(−1)at 0.1 C and maintain 80.7%of the energy density at 3 C.

Particle Size Optimization of Thermochemical Salt Hydrates for High Energy Density Thermal Storage

Thermal energy storage(TES)solutions offer opportunities to reduce energy consumption,greenhouse gas emissions,and cost.Specifically,they can help reduce the peak load and address the intermittency of renewable energy sources by time shifting the load,which are critical toward zero energy buildings.Thermochemical materials(TCMs)as a class of TES undergo a solid-gas reversible chemical reaction with water vapor to store and release energy with high storage capacities(600 kWh m^(-3))and negligible self-discharge that makes them uniquely suited as compact,stand-alone units for daily or seasonal storage.However,TCMs suffer from instabilities at the material(salt particles)and reactor level(packed beds of salt),resulting in poor multi-cycle efficiency and high-levelized cost of storage.In this study,a model is developed to predict the pulverization limit or Rcrit of various salt hydrates during thermal cycling.This is critical as it provides design rules to make mechanically stable TCM composites as well as enables the use of more energy-efficient manufacturing process(solid-state mixing)to make the composites.The model is experimentally validated on multiple TCM salt hydrates with different water content,and effect of Rcrit on hydration and dehydration kinetics is also investigated.

3D printing encouraging desired in-situ polypyrrole seed-polymerization for ultra-high energy density supercapacitors

The tireless pursuit of supercapacitors with high energy density entails the parallel advancement of wellsuited electrode materials and elaborately engineered architectures.Polypyrrole(PPy)emerges as an exceedingly conductive polymer and a prospective pseudocapacitive materials for supercapacitors,yet the inferior cyclic stability and unpredictable polymerization patterns severely impede its real-world applicability.Here,for the first time,an innovative seed-induced in-situ polymerization assisted 3D printing strategy is proposed to fabricate PPy-reduced graphene oxide/poly(vinylidene difluoride-cohexafluoropropylene)(PVDF-HFP)(PPy-rGO/PH)electrodes with controllable polymerization behavior and exceptional areal mass loading.The preferred active sites uniformly pre-planted on the 3D-printed graphene substrates serve as reliable seeds to induce efficient polypyrrole deposition,achieving an impressive mass loading of 185.6 mg cm^(-2)(particularly 79.2 mg cm^(-2)for polypyrrole)and a superior areal capacitance of 25.2 F cm^(-2)at 2 mA cm^(-2)for a 12-layer electrode.In agreement with theses appealing features,an unprecedented areal energy density of 1.47 mW h cm^(-2)for a symmetrical device is registered,a rarely achieved value for other PPy/rGO-based supercapacitors.This work highlights a promising route to preparing high energy density energy storage modules for real-world applications.

Topological Structure-Modulated Collagen Carbon as Two-in-One Energy Storage Configuration toward Ultrahigh Power and Energy Density

Efficient energy storage devices with suitable electrode materials,that integrate high power and high energy,are the crucial requisites of the renewable power source,which have unwrapped new possibilities in the sustainable development of energy and the environment.Herein,a facile collagen microstructure modulation strategy is proposed to construct a nitrogen/oxygen dual-doped hierarchically porous carbon fiber with ultrahigh specific surface area(2788 m^(2)g^(-1))and large pore volume(4.56 cm^(3)g^(-1))via local microfibrous breakage/disassembly of natural structured proteins.Combining operando spectroscopy and density functional theory unveil that the dual-heteroatom doping could effectively regulate the electronic structure of carbon atom framework with enhanced electric conductivity and electronegativity as well as decreased diffusion resistance in favor of rapid pseudocapacitive-dominated Li^(+)-storage(353 mAh g^(-1)at 10 A g^(-1)).Theoretical calculations reveal that the tailored micro-/mesoporous structures favor the rapid charge transfer and ion storage,synergistically realizing high capacity and superior rate performance for NPCF-H cathode(75.0 mAh g^(-1)at 30 A g^(-1)).The assembled device with NPCF-H as both anode and cathode achieves extremely high energy density(200 Wh kg^(-1))with maximum power density(42600 W kg^(-1))and ultralong lifespan(80%capacity retention over 10000 cycles).

"Win-Win"Scenario of High Energy Density and Long Cycling Life in a Novel Na_(3.9)MnCr_(0.9)Zr_(0.1)(PO_(4))_(3)Cathode

The development of high-energy and long-lifespan NASICON-type cathode materials for sodium-ion batteries has always been a research hotspot but a daunting challenge.Although Na_(4)MnCr(PO_(4))_(3)has emerged as one of the most promising high-energy-density cathode materials owing to its three-electron reactions,it still suffers from serious structural distortion upon repetitive charge/discharge processes caused by the Jahn-Teller active Mn^(3+).Herein,the selective substitution of Cr by Zr in Na_(4)MnCr(PO_(4))_(3)was explored to enhance the structural stability,due to the pinning effect of Zr ions and the≈2.9-electron reactions,as-prepared Na_(3.9)MnCr_(0.9)Zr_(0.1)(PO_(4))_(3)/C delivers a high capacity retention of 85.94%over 500 cycles at 5 C and an ultrahigh capacity of 156.4 mAh g^(-1)at 0.1 C,enabling the stable energy output as high as 555.2 Wh kg^(-1).Moreover,during the whole charge/discharge process,a small volume change of only 6.7%was verified by in situ X-ray diffraction,and the reversible reactions of Cr^(3+)/Cr^(4+),Mn^(3+)/Mn^(4+),and Mn^(2+)/Mn^(3+)redox couples were identified via ex situ X-ray photoelectron spectroscopy analyses.Galvanostatic intermittent titration technique tests and density functional theory calculations further demonstrated the fast reaction kinetics of the Na_(3.9)MnCr_(0.9)Zr_(0.1)(PO_(4))_(3)/C electrode.This work offers new opportunities for designing high-energy and high-stability NASICON cathodes by ion doping.

High energy density in ultra-thick and flexible electrodes enabled by designed conductive agent/binder composite

Thick electrodes can increase incorporation of active electrode materials by diminishing the proportion of inactive constituents,improving the overall energy density of batteries.However,thick electrodes fabricated using the conventional slurry casting approach frequently exhibit an exacerbated accumulation of carbon additives and binders on their surfaces,invariably leading to compromised electrochemical properties.In this study,we introduce a designed conductive agent/binder composite synthesized from carbon nanotube and polytetrafluoroethylene.This agent/binder composite facilitates production of dry-process-prepared ultra-thick electrodes endowed with a three-dimensional and uniformly distributed percolative architecture,ensuring superior electronic conductivity and remarkable mechanical resilience.Using this approach,ultra-thick LiCoO_(2)(LCO) electrodes demonstrated superior cycling performance and rate capabilities,registering an impressive loading capacity of up to 101.4 mg/cm^(2),signifying a 242% increase in battery energy density.In another analytical endeavor,time-of-flight secondary ion mass spectroscopy was used to clarify the distribution of cathode electrolyte interphase(CEI) in cycled LCO electrodes.The results provide unprecedented evidence explaining the intricate correlation between CEI generation and carbon distribution,highlighting the intrinsic advantages of the proposed dry-process approach in fine-tu ning the CEI,with excellent cycling performance in batteries equipped with ultra-thick electrodes.

A high-entropy-designed cathode with V^(5+)-V^(2+) multi-redox for high energy density sodium-ion batteries

Na_(3)V_(2)(PO_(4))_(3)(NVP)is gifted with fast Na^(+)conductive NASICON structure.But it still suffers from low electronic conductivity and inadequate energy density.Herein,a high-entropy modification strategy is realized by doping V^(3+)site with Ga^(3+)/Cr^(3+)/Al^(3+)/Fe^(3+)/In^(3+)simultaneously(i.e.Na_(3)V_(2-x)(GaCrAlFeIn)_x(PO_(4))_(3);x=0,0.04,0.06,and 0.08)to stimulate the V^(5+)■V^(2+)reversible multi-electron redox.Such configuration high-entropy can effectively suppress the structural collapse,enhance the redox reversibility in high working voltage(4.0 V),and optimize the electronic induced effect.The in-situ X-ray powder diffraction and in-situ electrochemical impedance spectroscopy tests efficaciously confirm the robust structu ral recovery and far lower polarization throughout an entire charge-discharge cycle during 1.6-4.3 V,respectively.Moreover,the density functional theory calculations clarify the stronger metallicity of high-entropy electrode than the bare that is derived from the more mobile free electrons surrounding the vicinity of Fermi level.By grace of high-entropy design and multi-electron transfer reactions,the optimal Na_(3)V_(1.7)(GaCrAlFeIn)_(0.06)(PO_(4))_(3)can exhibit perfect cycling/rate performances(90.97%@5000 cycles@30 C;112 mA h g^(-1)@10 C and 109 mA h g^(-1)@30 C,2.0-4.3 V).Furthermore,it can supply ultra-high185 mA h g^(-1)capacity with fa ntastic energy density(522 W h kg^(-1))in half-cells(1.4-4.3 V),and competitive capacity(121 mA h g^(-1))as well as energy density(402 W h kg^(-1))in full-cells(1.6-4.1 V),demonstrating enormous application potential for sodium-ion batteries.

A Number Theoretic Analysis of the Enthalpy, Enthalpy Energy Density, Thermodynamic Volume, and the Equation of State of a Modified White Hole, and the Implications to the Quantum Vacuum Spacetime, Matter Creation and the Planck Frequency

In this paper, we analyze the enthalpy, enthalpy energy density, thermodynamic volume, and the equation of state of a modified white hole. We obtain new possible mathematical connections with some sectors of Number Theory, Ramanujan Recurring Numbers, DN Constant and String Theory, that enable us to extract the quantum geometrical properties of these thermodynamic equations and the implication to the quantum vacuum spacetime geometry of our early universe as they act as the constraints to the nature of quantum gravity of the universe.

Boosting Pseudocapacitive Behavior of Supercapattery Electrodes by Incorporating a Schottky Junction for Ultrahigh Energy Density

Pseudo-capacitive negative electrodes remain a major bottleneck in the development of supercapacitor devices with high energy density because the electric double-layer capacitance of the negative electrodes does not match the pseudocapacitance of the corresponding positive electrodes.In the present study,a strategically improved Ni-Co-Mo sulfide is demonstrated to be a promising candidate for high energy density supercapattery devices due to its sustained pseudocapacitive charge storage mechanism.The pseudocapacitive behavior is enhanced when operating under a high current through the addition of a classical Schottky junction next to the electrode-electrolyte interface using atomic layer deposition.The Schottky junction accelerates and decelerates the diffusion of OH-/K+ions during the charging and discharging processes,respectively,to improve the pseudocapacitive behavior.The resulting pseudocapacitive negative electrodes exhibits a specific capacity of 2,114 C g^(-1)at 2 A g^(-1)matches almost that of the positive electrode’s 2,795 C g^(-1)at 3 A g^(-1).As a result,with the equivalent contribution from the positive and negative electrodes,an energy density of 236.1 Wh kg^(-1)is achieved at a power density of 921.9 W kg^(-1)with a total active mass of 15 mg cm-2.This strategy demonstrates the possibility of producing supercapacitors that adapt well to the supercapattery zone of a Ragone plot and that are equal to batteries in terms of energy density,thus,offering a route for further advances in electrochemical energy storage and conversion processes.

Spontaneous local redox reaction to passivate CNTs as lightweight current collector for high energy density lithium ion batteries

Extensive usage of highly conductive carbon materials with large specific surface area(e.g.,carbon nanotubes,CNTs)in lithium ion batteries(LIBs),especially as current collector of anodes,suffers from low initial coulombic efficiency(ICE),large interfacial resistance,and severe embrittlement,as the large specific surface area often results in severe interfacial decomposition of the electrolyte and the formation of thick and fluffy solid electrolyte interphase(SEI)during cycling of LIBs.Herein,we demonstrate that when the CNT-based current collector and Na foil(which are being stacked intimately upon each other)are being placed in Na+-based organic electrolyte,local redox reaction between the Na foil and the electrolyte would occur spontaneously,generating a thin and homogeneous NaF-based passivating layer on the CNTs.More importantly,we found that owing to the weak solvation behaviors of Na+in the organic electrolyte,the resulting passivation layer,which is rich in NaF,is thin and dense;when used as the anode current collector in LIBs,the pre-existing passivating layer can function effectively in isolating the anode from the solvated Li+,thus suppressing the formation of bulky SEI and the destructive intercalation of solvated Li+.The relevant half-cell(graphite as anode)exhibits a high ICE of 92.1%;the relevant pouch cell with thus passivated CNT film as current collectors for both electrodes(LiCoO_(2)as cathode,graphite as anode)displays a high energy density of 255 Wh kg^(-1),spelling an increase of 50%compared with that using the conventional metal current collectors.

The Fluorination of Boron-Doped Graphene for CF_(x) Cathode with Ultrahigh Energy Density

The enhancement of the fluorination degree of carbon fluorides(CF_(x))compounds is the most effective method to improve the energy densities of Li/CF_(x)batteries because the specific capacity of CF_(x)is proportional to the molar ratio of F to C atoms(F/C).In this study,B-doped graphene(BG)is prepared by using boric acid as the doping source and then the prepared BG is utilized as the starting material for the preparation of CF_(x).The B-doping enhances the F/C ratio of CF_(x)without hindering the electrochemical activity of the C–F bond.During the fluorination process,B-containing functional groups are removed from the graphene lattice.This facilitates the formation of a defect-rich graphene matrix,which not only enhances the F/C ratio due to abundant perfluorinated groups at the defective edges but also serves as the active site for extra Li+storage.The prepared CF_(x)exhibits the maximum specific capacity of 1204 mAh g^(−1),which is 39.2%higher than that of CF_(x)obtained directly from graphene oxide(without B-doping).An unprecedented energy density of 2974 Wh kg^(−1)is achieved for the asprepared CF_(x)samples,which is significantly higher than the theoretically calculated energy density of commercially available fluorinated graphite(2180 Wh kg^(−1)).Therefore,this study demonstrates a great potential of B-doping to realize the ultrahigh energy density of CF_(x)cathodes for practical applications.

Fluorinated soft carbon as an ultra-high energy density potassium-ion battery cathode enabled by a ternary phase K_(x)FC

Fluorinated carbons(CFx)have been widely applied as lithium primary batteries due to their ultra-high energy density.It will be a great promise if CFx can be rechargeable.In this study,we rationally tune the C-F bond strength for the alkaline intercalated CFx via importing an electronegative weaker element K instead of Li.It forms a ternary phase K_(x)FC instead of two phases(LiF+C)in lithium-ion batteries.Meanwhile,we choose a large layer distance and more defects CFx,namely fluorinated soft carbon,to accommodate K.Thus,we enable CFx rechargeable as a potassium-ion battery cathode.In detail fluorinated soft carbon CF_(1.01) presents a reversible specific capacity of 339 mA h g^(-1)(797 Wh kg^(-1))in the 2nd cycle and maintains 330 mA h g^(-1)(726 Wh kg^(-1))in the 15th cycle.This study reveals the importance of tuning chemical bond stability using different alkaline ions to endow batteries with rechargeability.This work provides good references for focusing on developing reversible electrode materials from popular primary cell configurations.

Enhanced High-Temperature Energy Storage Performance of All-Organic Composite Dielectric via Constructing Fiber-Re in forced Structure

Optimizing the high-temperature energy storage characteristics of energy storage dielectrics is of great significance for the development of pulsed power devices and power control systems.Selecting a polymer with a higher glass transition temperature(T_(g))as the matrix is one of the effective ways to increase the upper limit of the polymer operating temperature.However,current high-T_(g)polymers have limitations,and it is difficult to meet the demand for high-temperature energy storage dielectrics with only one polymer.For example,polyetherimide has high-energy storage efficiency,but low breakdown strength at high temperatures.Polyimide has high corona resistance,but low high-temperature energy storage efficiency.In this work,combining the advantages of two polymer,a novel high-T_(g)polymer fiber-reinforced microstructure is designed.Polyimide is designed as extremely fine fibers distributed in the composite dielectric,which will facilitate the reduction of high-temperature conductivity loss for polyimide.At the same time,due to the high-temperature resistance and corona resistance of polyimide,the high-temperature breakdown strength of the composite dielectric is enhanced.After the polyimide content with the best high-temperature energy storage characteristics is determined,molecular semiconductors(ITIC)are blended into the polyimide fibers to further improve the high-temperature efficiency.Ultimately,excellent high-temperature energy storage properties are obtained.The 0.25 vol%ITIC-polyimide/polyetherimide composite exhibits high-energy density and high discharge efficiency at 150℃(2.9 J cm^(-3),90%)and 180℃(2.16 J cm^(-3),90%).This work provides a scalable design idea for high-performance all-organic high-temperature energy storage dielectrics.

Thin NASICON Electrolyte to Realize High Energy Density Solid-State Sodium Metal Battery

The solid-state electrolyte in a solid-state battery acts as an electrons'barrier and an ions'bridge between the two electrodes.As solid-state electrolyte does not store the mobile ions,it is necessary to achieve a thin solid-state electrolyte to reduce the internal resistance and enhance the energy density.In this work,a thin NASICON solid-state electrolyte,with a stoichiometry of Na_(3)Zr_(2)Si_(2)PO_(12),is fabricated by the tape-casting method and its thickness can be easily controlled by the gap between substrate and scraper.The areal-specific resistance and the flexural strength increase with the electrolyte thickness.A solid-state sodium metal battery with 86 pm thick Na_(3)Zr_(2)Si_(2)PO_(12)exhibits a reversible specific capacity of 73-78 mAh g^(-1)with a redox potential of 3.4 V at 0.2 C.This work presents the importance of electrolyte thickness to reduce internal resistance and achieve a high energy density for sodium batteries.

Green and sustainably designed intercalation-type anodes for emerging lithium dual-ion batteries with high energy density

Lithium dual-ion batteries(LiDIBs)have attracted significant attention owing to the growing demand for modern anode materials with high energy density.Herein,rust encapsulated in graphite was achieved by utilizing ammonium bicarbonate(ABC)as a template,which resulted in mesoporous Fe3O4embedded in expanded carbon(Fe3O4@G(ABC))via simple ball milling followed by annealing.This self-assembly approach for graphite-encapsulated Fe3O4composites helps enhance the electrochemical performance,such as the cycling stability and superior rate stability(at 3 A/g),with improved conductivity in Li DIBs.Specifically,Fe3O4@G-1:4(ABC)and Fe3O4@G-1:6(ABC)anodes in a half-cell at 0.1 A/g delivered initial capacities of 1390.6 and 824.4 mA h g^(-1),respectively.The optimized anode(Fe3O4@G-1:4(ABC))coupled with the expanded graphite(EG)cathode in Li DIBs provided a substantial initial specific capacity of 260.9 mA h g^(-1)at 1 A/g and a specific capacity regain of 106.3 mA h g^(-1)(at 0.1 A/g)after 250 cycles,with a very high energy density of 387.9 Wh kg^(-1).The strategically designed Fe3O4@G accelerated Li-ion kinetics,alleviated the volume change,and provided an efficient conductive network with excellent mechanical flexibility,resulting in exceptional performance in Li DIBs.Various postmortem analyses of the anode and cathode(XRD,Raman,EDS,and XPS)are presented to explain the intercalation-type electrochemical mechanisms of Li DIBs.This study offers several advantages,including safety,low cost,sustainability,environmental friendliness,and high energy density.

New carbon-nitrogen-oxygen compounds as high energy density materials

Molecular crystals are complex systems exhibiting various crystal structures,and accurately modeling the crystal structures is essential for understanding their physical behaviors under high pressure.Here,we perform an extensive structure search of ternary carbon-nitrogen-oxygen(CNO)compound under high pressure with the CALYPSO method and first principles calculations,and successfully identify three polymeric CNO compounds with Pbam,C2/m and I4m2symmetries under 100 GPa.More interestingly,these structures are also dynamically stable at ambient pressure,and are potential high energy density materials(HEDMs).The energy densities of Pbam,C2/m and I4m2 phases of CNO are about2.30 kJ/g,1.37 kJ/g and 2.70 kJ/g,respectively,with the decompositions of graphitic carbon and molecular carbon dioxide andα-N(molecular N_(2))at ambient pressure.The present results provide in-depth insights into the structural evolution and physical properties of CNO compounds under high pressures,which offer crucial insights for designs and syntheses of novel HEDMs.

Sb-Cu alloy cathode with a novel lithiation mechanism of ternary intermetallic formation: Enabling high energy density and superior rate capability of liquid metal battery

Antimony(Sb) is an attractive cathode for liquid metal batteries(LMBs) because of its high theoretical voltage and low cost.The main obstacles associated with the Sb-based cathodes are unsatisfactory energy density and poor rate-capability.Herein,we propose a novel Sb_(64)Cu_(36)cathode that effectively tackles these issues.The Sb_(64)Cu_(36)(melting point:525℃) cathode presents a novel lithiation mechanism involving sequentially the generation of Li_(2)CuSb,the formation of Li_(3)Sb,and the conversion reaction of Li_(2)CuSb to Li_(3)Sb and Cu.The generated intermetallic compounds show a unique microstructure of the upper floated Li_(2)CuSb layer and the below cross-linked structure with interpenetrated Li_(2)CuSb and Li_(3)Sb phases.Compared with Li_(3)Sb,the lower Li migration energy barrier(0.188 eV) of Li_(2)CuSb significantly facilitates the lithium diffusion across the intermediate compounds and accelerates the reaction kinetics.Consequently,the Li‖Sb_(64)Cu_(36)cell delivers a more excellent electrochemical performance(energy density:353 W h kg^(-1)at 0.4 A cm^(-2);rate capability:0.59 V at 2.0 A cm^(-2)),and a much lower energy storage cost of only 38.45 $ kW h^(-1)than other previously reported Sb-based LMBs.This work provides a novel cathode design concept for the development of high-performance LMBs in applications for large-scale energy storage.

Mechanical behavior of rock under uniaxial tension:Insights from energy storage and dissipation

Many rock engineering projects show that the growth of tensile cracks is often an important cause of engineering disasters,and the mechanical behavior of rocks is essentially the transmission,storage,dissipation and release of energy.To investigate the tensile behavior of rock from the perspective of energy,uniaxial tension tests(UTTs)and uniaxial compression tests(UCTs)were carried out on three typical rocks(granite,sandstone and marble).Different unloading points were set before the peak stress to separate elastic energy and dissipated energy.The input energy density ut,elastic energy density ue,and dissipated energy density ud at each unloading point were calculated by integrating stress-strain curves.The results show that there is a strong linear relationship between the three energy parameters and the square of the unloading stress in UCT,but this linear relationship is weaker in UTT.The ue and ud increase linearly with the increase in ut in UCT and UTT.Based on the phenomenon that ue and ud increase linearly with ut,the applicability of W_(et)^(p) index in UTT was proved and the relative energy storage capacity and absolute energy distribution characteristics of three rocks in UCT and UTT were evaluated.The tensile behavior of marble and sandstone in UTT can be divided into two stages vaguely according to the energy distribution,but granite is not the case.In addition,based on dissipated energy,the damage evolution of three types of rocks in UCT and UTT was discussed.This study provides some new insights for understanding the tensile behavior of rock.

Revealing the correlation between adsorption energy and activation energy to predict the catalytic activity of metal oxides for HMX using DFT

Traditional selection of combustion catalysis is time-consuming and labor-intensive.Theoretical calculation is expected to resolve this problem.The adsorption energy of HMX and O atoms on 13 metal oxides was calculated using DMol3,since HMX and O are key substances in decomposition process.And the relationship between the adsorption energy of HMX,O on metal oxides(TiO_(2),Al_(2)O_(3),PbO,CuO,Fe_(2)O_(3),Co_(3)O_(4),Bi_(2)O_(3),NiO)and experimental T30 values(time required for the decomposition depth of HMX to reach 30%)was depicted as volcano plot.Thus,the T30 values of other metal oxides was predicted based on their adsorption energy on volcano plot and validated by previous experimental data.Further,the adsorption energy of HMX on ZrO_(2)and MnO_(2)was predicted based on the linear relationship between surface energy and adsorption energy,and T30 values were estimated based on volcano plot.The apparent activation energy data of HMX/MgO,HMX/SnO_(2),HMX/ZrO_(2),and HMX/MnO_(2)obtained from DSC experiments are basically consistent with our predicted T30 values,indicating that it is feasible to predict the catalytic activity based on the adsorption calculation,and it is expected that these simple structural properties can predict adsorption energy to reduce the large quantities of computation and experiment cost.

Co-Harvest Phase-Change Enthalpy and Isomerization Energy for High-Energy Heat Output by Controlling Crystallization of Alkyl-Grafted Azobenzene Molecules

Photoisomerization-induced phase change are important for co-harvesting the latent heat and isomerization energy of azobenzene molecules.Chemically optimizing heat output and energy delivery at alternating temperatures are challenging because of the differences in crystallizability and isomerization.This article reports two series of asymmetrically alkyl-grafted azobenzene(Azo-g),with and without a methyl group,that have an optically triggered phase change.Three exothermic modes were designed to utilize crystallization enthalpy(△H_(c))and photothermal(isomerization)energy(△H_(p))at different temperatures determined by the crystallization.Azo-g has high heat output(275-303 J g^(-1))by synchronously releasing△H_(c)and△H_(p)over a wide temperature range(-79℃to 25℃).We fabricated a new distributed energy utilization and delivery system to realize a temperature increase of 6.6℃at a temperature of-8℃.The findings offer insight into selective utilization of latent heat and isomerization energy by molecular optimization of crystallization and isomerization processes.