Nanostructured energy materials for electrochemical energy conversion and storage: A review

Nanostructured materials have received tremendous interest due to their unique mechanical/electrical properties and overall behavior contributed by the complex synergy of bulk and interfacial properties for efficient and effective energy conversion and storage. The booming development of nanotechnology affords emerging but effective tools in designing advanced energy material. We reviewed the significant progress and dominated nanostructured energy materials in electrochemical energy conversion and storage devices, including lithium ion batteries, lithium-sulfur batteries, lithium-oxygen batteries, lithium metal batteries, and supercapacitors. The use of nanostructured electrocatalyst for effective electrocatalysis in oxygen reduction and oxygen evolution reactions for fuel cells and metal-air batteries was also included. The challenges in the undesirable side reactions between electrolytes and electrode due to high electrode/electrolyte contact area, low volumetric energy density of electrode owing to low tap density, and uniform production of complex energy materials in working devices should be overcome to fully demonstrate the advanced energy nanostructures for electrochemical energy conversion and storage. The energy chemistry at the interfaces of nanostructured electrode/electrolyte is highly expected to guide the rational design and full demonstration of energy materials in a working device. (C) 2016 Science Press and Dalian Institute of Chemical Physics, Chinese Academy of Sciences. Published by Elsevier B.V. and Science Press. All rights reserved.

Recent progress on discovery and properties prediction of energy materials:Simple machine learning meets complex quantum chemistry

In nature,the properties of matter are ultimately governed by the electronic structures.Quantum chemistry(QC)at electronic level matches well with a few simple physical assumptions in solving simple problems.To date,machine learning(ML)algorithm has been migrated to this field to simplify calculations and improve fidelity.This review introduces the basic information on universal electron structures of emerging energy materials and ML algorithms involved in the prediction of material properties.Then,the structure-property relationships based on ML algorithm and QC theory are reviewed.Especially,the summary of recently reported applications on classifying crystal structure,modeling electronic structure,optimizing experimental method,and predicting performance is provided.Last,an outlook on ML assisted QC calculation towards identifying emerging energy materials is also presented.

In situ transmission electron microscopy and artificial intelligence enabled data analytics for energy materials

Energy materials are vital to energy conversion and storage devices that make renewable resources viable for electrification technologies. In situ transmission electron microscopy(TEM) is a powerful approach to characterize the dynamic evolution of material structure, morphology, and chemistry at the atomic scale in real time and in operando. In this review, recent advancements of in situ TEM techniques for studying energy materials, including catalysts, batteries, photovoltaics, and thermoelectrics, are systematically discussed and summarized. The topics include a broad range of material transformations that are in situ stimulated by heating, biasing, lighting, electron-beam illuminating, and cryocooling under vacuum, liquid, or gas environments within TEM, as well as the mechanistic understanding of the associated solid-solid, solid-liquid, and solid-gas reactions elucidated by in situ TEM examination and operando measurements. Special focus is also put on the emerging progress of artificial intelligence enabled microscopy data analytics, including machine learning enhanced tools for retrieving useful information from massive TEM imaging, diffraction, and spectroscopy datasets, highlighting its merits and potential for automated in situ TEM experimentation and analysis. Finally, the pressing challenges and future perspectives on in situ TEM study for energy-related materials are discussed.

Vision for energy material design:A roadmap for integrated data-driven modeling

The application scope and future development directions of machine learning models(supervised learning, transfer learning, and unsupervised learning) that have driven energy material design are discussed.

Photon-in/photon-out endstation for studies of energy materials at beamline 02B02 of Shanghai Synchrotron Radiation Facility

A new photon-in/photon-out endstation at beamline 02B02 of the Shanghai Synchrotron Radiation Facility for studying the electronic structure of energy materials has been constructed and fully opened to users.The endstation has the capability to perform soft x-ray absorption spectroscopy in total electron yield and total fluorescence yield modes simultaneously.The photon energy ranges from 40 eV to 2000 eV covering the K-edge of most low Z-elements and the L-edge of 3d transition-metals.The new self-designed channeltron detector allows us to achieve good fluorescence signals at the low photon flux.In addition,we synchronously collect the signals of a standard reference sample and a gold mesh on the upstream to calibrate the photon energy and monitor the beam fluctuation,respectively.In order to cross the pressure gap,in situ gas and liquid cells for soft x-ray absorption spectroscopy are developed to study the samples under realistic working conditions.

Electrochemical characterization of MnO_2 as electrocatalytic energy material for fuel cell electrode

Development of inexpensive non Pt based high electrocatalytic energy materials is the need of the hour for fuel cell electrode to produce clean alternative green energy from synthesized bio alcohol using biomass. MnO 2,electro synthesized at different current density is found to be well performed electrocatalytic material,comparable to Pt,with higher current density,very lowovervoltage for the electrochemical oxidation of methanol. From EIS study,the polarization resistance of the coated MnO 2is found to be much lowand electrical double layer capacitance is high,the effect increases with increase in current density of electro deposition. XRD,EDX and AAS analysis confirm the M nO 2deposition. The morphology of SEM images exhibits an enhanced 3D effective substrate area,for electro oxidation of the fuel. A fewnano structured grains of the deposited M nO 2is also observed at higher current density. The fact supports that a high energetic inexpensive electro catalytic material has been found for fuel cell electrode to synthesis renewable energy from methanol fuel.

Uncover the Aesthetic Simplicity Associated with Mass Transfer in Energy Materials

Aesthetics,referred frequently to as a philosophical term,has played a starring role in forming and evolving a number of aspects of human society,including arts,politics,economics,ethics,etc.Indeed,exploring and investigating the aesthetic phenomena in the scientific field have aroused insightful research findings,which in turn has stimulated research interests in such a science-aesthetics field.In particular,better-evaluated aesthetic aspects of the materials field are expected to be uncovered upon the exceedingly-exposed fundamental breakthroughs in researching the basic structure and functionality of materials.In this report,we glimpse into the aesthetic simplicity of energy materials and comprehend specifically the mass transfer functionalities of key categories of energy materials through an intuitive and bottom-up approach.Our effort aspires to shed new lights on the functionality understanding and manipulation of functional materials in general.

High-entropy oxides as energy materials:from complexity to rational design

High-entropy oxides(HEOs),with their multi-principal-element compositional diversity,have emerged as promising candidates in the realm of energy materials.This review encapsulates the progress in harnessing HEOs for energy conversion and storage applications,encompassing solar cells,electrocatalysis,photocatalysis,lithium-ion batteries,and solid oxide fuel cells.The critical role of theoretical calculations and simulations is underscored,highlighting their contribution to elucidating material stability,deciphering structure-activity relationships,and enabling performance optimization.These computational tools have been instrumental in multi-scale modeling,high-throughput screening,and integrating artificial intelligence for material design.Despite their promise,challenges such as fabrication complexity,cost,and theoretical computational hurdles impede the broad application of HEOs.To address these,this review delineates future research perspectives.These include the innovation of cost-effective synthesis strategies,employment of in situ characterization for micro-chemical insights,exploration of unique physical phenomena to refine performance,and enhancement of computational models for precise structure-performance predictions.This review calls for interdisciplinary synergy,fostering a collaborative approach between materials science,chemistry,physics,and related disciplines.Collectively,these efforts are poised to propel HEOs towards commercial viability in the new energy technologies,heralding innovative solutions to pressing energy and environmental challenges.

A seven-crystal spectrometer for high-energy resolution X-ray spectroscopy at Shanghai Synchrotron Radiation Facility

A Johann-type X-ray spectrometer was successfully developed at the hard X-ray branch(in-vacuum undulator with a 24-mm periodic length)of the energy material beamline(E-line)at the Shanghai Synchrotron Radiation Facility(SSRF).This spectrometer was utilized to implement X-ray emission spectroscopy(XES),high-energy resolution fluorescence-detected X-ray absorption spectroscopy(HERFD-XAS),and resonant inelastic X-ray scattering.Seven spherically bent crystals were positioned on the respective vertical 500-mm-diameter Rowland circles,adopting an area detector to increase the solid angle to 1.75%of 4πsr,facilitating the study of low-concentrate systems under complex reaction conditions.Operated under the atmosphere pressure,the spectrometer covers the energy region from 3.5 to 18 keV,with the Bragg angle ranging from 73°to 86°during vertical scanning.It offers a promised energy resolution of sub-eV(XES)and super-eV(HERFD-XAS).Generally,these comprehensive core-level spectroscopy methods based on hard X-rays at the E-line with an extremely high photon flux can meet the crucial requirements of a green energy strategy.Moreover,they provide substantial support for scientific advances in fundamental research.

In Situ Mineralization of Biomass-Derived Hydrogels Boosts Capacitive Electrochemical Energy Storage in Free-Standing 3D Carbon Aerogels

Here,a novel fabrication method for making free-standing 3D hierarchical porous carbon aerogels from molecularly engineered biomass-derived hydrogels is presented.In situ formed flower-like CaCO_(3)molecularly embedded within the hydrogel network regulated the pore structure during in situ mineralization assisted one-step activation graphitization(iMAG),while the intrinsic structural integrity of the carbon aerogels was maintained.The homogenously distributed minerals simultaneously acted as a hard template,activating agent,and graphitization catalyst.The decomposition of the homogenously distributed CaCO_(3)during iMAG followed by the etching of residual CaO through a mild acid washing endowed a robust carbon aerogel with high porosity and excellent electrochemical performance.At 0.5 mA cm^(-2),the gravimetric capacitance increased from 0.01 F g^(-1)without mineralization to 322 F g^(-1)with iMAG,which exceeds values reported for any other free-standing or powder-based biomass-derived carbon electrodes.An outstanding cycling stability of~104%after 1000 cycles in 1 M HClO4 was demonstrated.The assembled symmetric supercapacitor device delivered a high specific capacitance of 376 F g^(-1)and a high energy density of 26 W h kg^(-1)at a power density of 4000 W kg^(-1),with excellent cycling performance(98.5%retention after 2000 cycles).In combination with the proposed 3D printed mold-assisted solution casting(3DMASC),iMAG allows for the generation of free-standing carbon aerogel architectures with arbitrary shapes.Furthermore,the novel method introduces flexibility in constructing free-standing carbon aerogels from any ionically cross-linkable biopolymer while maintaining the ability to tailor the design,dimensions,and pore size distribution for specific energy storage applications.

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.

Machine learning for advanced energy materials

The screening of advanced materials coupled with the modeling of their quantitative structural-activity relation-ships has recently become one of the hot and trending topics in energy materials due to the diverse challenges,including low success probabilities,high time consumption,and high computational cost associated with the traditional methods of developing energy materials.Following this,new research concepts and technologies to promote the research and development of energy materials become necessary.The latest advancements in ar-tificial intelligence and machine learning have therefore increased the expectation that data-driven materials science would revolutionize scientific discoveries towards providing new paradigms for the development of en-ergy materials.Furthermore,the current advances in data-driven materials engineering also demonstrate that the application of machine learning technology would not only significantly facilitate the design and development of advanced energy materials but also enhance their discovery and deployment.In this article,the importance and necessity of developing new energy materials towards contributing to the global carbon neutrality are presented.A comprehensive introduction to the fundamentals of machine learning is also provided,including open-source databases,feature engineering,machine learning algorithms,and analysis of machine learning model.Afterwards,the latest progress in data-driven materials science and engineering,including alkaline ion battery materials,pho-tovoltaic materials,catalytic materials,and carbon dioxide capture materials,is discussed.Finally,relevant clues to the successful applications of machine learning and the remaining challenges towards the development of advanced energy materials are highlighted.

Liquid metal material genome： Initiation of a new research track towards discovery of advanced energy materials

As the basis of modern industry, the roles materials play are becoming increasingly vital in this day and age. With many superior physical properties over conventional fluids, the low melting point liquid metal material, especially room-temperature liquid metal, is recently found to be uniquely useful in a wide variety of emerging areas from energy, electronics to medical sciences. However, with the coming enormous utilization of such materials, serious issues also arise which urgently need to be addressed. A biggest concern to impede the large scale application of room-temperature liquid metal technologies is that there is currently a strong shortage of the materials and species available to meet the tough requirements such as cost, melting point, electrical and thermal conductivity, etc. Inspired by the Material Genome Initiative as issued in 2011 by the United States of America, a more specific and focused project initiative was proposed in this paper--the liquid metal material genome aimed to discover advanced new functional alloys with low melting point so as to fulfill various increasing needs. The basic schemes and road map for this new research program, which is expected to have a worldwide significance, were outlined. The theoretical strategies and experimental methods in the research and development of liquid metal material genome were introduced. Particularly, the calculation of phase diagram （CALPHAD） approach as a highly effective way for material design was discussed. Further, the first-principles （FP） calculation was suggested to combine with the statistical thermo- dynamics to calculate the thermodynamic functions so as to enrich the CALPHAD database of liquid metals. When the experimental data are too scarce to perform a regular treatment, the combination of FP calculation, cluster variation method （CVM） or molecular dynamics （MD）, and CALPHAD, referred to as the mixed FP-CVM- CALPHAD method can be a promising way to solve the problem. Except for the theoretical strategies, several parallel processing experimental methods were also analyzed, which can help improve the efficiency of finding new liquid metal materials and reducing the cost. The liquid metal material genome proposal as initiated in this paper will accelerate the process of finding and utilization of new functional materials.

A perspective on sustainable energy materials for lithium batteries

Lithium ion battery has achieved great success in portable electronics and even recently electronic vehicles since its commercialization in 1990s.However,lithium-ion batteries are confronted with several issues in terms of the sustainable development such as the high price of raw materials and electronic products,the emerging safety accidents,etc.The recent progresses are herein emphasized on lithium batteries for energy storage to clearly understand the sustainable energy chemistry and emerging energymaterials.The Perspective presents novel lithium-ion batteries developed with the aims of enhancing the electrochemical performance and sustainability of energy storage systems.First,revolutionary material chemistries,including novel low-cobalt cathode,organic electrode,and aqueous electrolyte,are discussed.Then,the characteristics of safety performance are analyzed and strategies to enhance safety are subsequently evaluated.Battery recycling is considered as the key factor for a sustainable society and related technologies are present as well.Finally,conclusion and outlook are drawn to shed lights on the further development of sustainable lithium-ion batteries.

Highlights on inorganic solid state chemistry and energy materials

This review highlights the recent research progress on inorganic solid state energy materials in China,from synthesis and fundamental properties to their applications.It describes the significant contributions of Chinese scholars in the field of inorganic solid state chemistry and energy materials including green catalysts,fuel cells,lithium batteries,solar cells,hydrogen storage materials,thermoelectric materials,luminescent materials and superconductors,and then outlines the ongoing rapid progress of novel inorganic solid state materials and the development of reliable and reproducible preparation methods for inorganic solid state materials in China.Finally,we conclude the paper by considering future developments of inorganic solid state chemistry and energy materials in China.

A Study on Alien Invasive Plants from the Interactive Mechanism between Species Niche and Material/Energy Flow

[Objective]This study was to reveal the essence of mechanism about how the alien invasive plants spread.[Method]Species niche and material/energy flow were used as basic research indicators to analyze the intrinsic mechanism of alien plants invasion.[Result]Most of the invasive plants have not been explicitly defined and their effective control methods not brought forward.[Conclusion]Overrun of alien invasive plants depends on whether the niche of a species could be continuously met at spatial level.Based on this we put forward corresponding control measures,proposed an assumption to establish a cylinder-network model and discussed the definition of alien invasive plants.

Review： Tip-based vibrational spectroscopy for nanoscale analysis of emerging energy materials

Vibrational spectroscopy is one of the key instrumentations that provide non-invasive investigation of structural and chemical composition for both organic and inorganic materials. However, diffraction of light funda- mentally limits the spatial resolution of far-field vibrational spectroscopy to roughly half the wavelength. In this article, we thoroughly review the integration of atomic force microscopy （AFM） with vibrational spectroscopy to enable the nanoscale characterization of emerging energy materials, which has not been possible with far-field optical techniques. The discussed methods utilize the AFM tip as a nanoscopic tool to extract spatially resolved electronic or molecular vibrational resonance spectra of a sample illuminated by a visible or infrared （IR） light source. The absorption of light by electrons or individual functional groups within molecules leads to changes in the sample＇s thermal response, optical scattering, and atomic force interactions, all of which can be readily probed by an AFM tip. For example, photothermal induced resonance （PTIR） spectroscopy methods measure a sample＇s local thermal expansion or temperature rise. Therefore, they use the AFM tip as a thermal detector to directly relate absorbed IR light to the thermal response of a sample. Optical scattering methods based on scanning near-field optical microscopy （SNOM） correlate the spectrum of scattered near-field light with molecular vibrational modes. More recently, photo-induced force microscopy （PiFM） has been developed to measure the change of the optical force gradient due to the light absorption by molecular vibrational resonances using AFM＇s superb sensitivity in detecting tip-sample force interactions. Such recent efforts successfully breech the diffraction limit of light to provide nanoscale spatial resolution of vibrational spectroscopy,which will become a critical technique for characterizing novel energy materials.

MXene-based materials for electrochemical energy storage

Rechargeable batteries and supercapacitors are widely investigated as the most important electrochemical energy storage devices nowadays due to the booming energy demand for electric vehicles and hand-held electronics. The large surface-area-to-volume ratio and internal surface areas endow two-dimensional（2D） materials with high mobility and high energy density; therefore, 2D materials are very promising candidates for Li ion batteries and supercapacitors with comprehensive investigations. In 2011, a new kind of 2D transition metal carbides, nitrides and carbonitrides, MXene, were successfully obtained from MAX phases. Since then about 20 different kinds of MXene have been prepared. Other precursors besides MAX phases and even other methods such as chemical vapor deposition（CVD） were also applied to prepare MXene, opening new doors for the preparation of new MXene. Their 2D nature and good electronic properties ensure the inherent advantages as electrode materials for electrochemical energy storage. In this review, we summarize the recent progress in the development of MXene with emphasis on the applications to electrochemical energy storage. Also, future perspective and challenges of MXene-based materials are briefly discussed regrading electrochemical energy storage.

Preface to Special Topic:Graphene and 2D Materials for Energy Storage

Graphene, a single layer of graphite, has been one of the first real two dimensional （2D） materials isolated in 2004. Thus, graphene is becoming a cutting edge material that opens up new horizons to a whole family of 2D materials beyond the limited current applicability of graphene. The unique advantages of graphene and analogue 2D materials, such as atomic-scale thickness, high specific surface area, mechanically flexible robustness, superior storage capacity, endow them as high-performance electrodes lbr electrochemical energy storage devices. Although it is hard to say whether or not graphene and 2D materials will be implemented in future energy technologies, the recent achievements in this field demonstrate that their roles will be noticeable in the near future.

A Brief Analysis of Energy Conservation Ways by Building Materials for Ecological Architecture

The development of society and economy in China is bringing growth to all industries. In particular, the development of China’s building industry has attracted much attention. Building materials are an important part of and widely used in the building industry. Energy conservation by building materials has become an inevitable way of sustainable development. Centering on the building industry, this paper mainly discusses in detail the energy conservation ways by ecological architecture and building materials.