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ITEAM - An international mechanistic approach to modeling glass behavior over geologic time scales - 15527

Vitrification is a common worldwide solution for radioactive waste immobilization. Although the excellent chemical durability of glass has been demonstrated in ancient man-made and natural analogues, the lack of an international consensus on a glass corrosion rate law limits the application of glass in high-level waste repository performance models. The contributions of physical and chemical processes controlling the long-term glass dissolution rate in geologic disposal remain uncertain resulting in this non-consensus. A thorough mechanistic understanding of waste form durability in geologic environments would improve public and regulator confidence. In addition, this understanding could lead to cost savings if it becomes possible to take credit for the true durability of the waste form itself in system evaluations rather than requiring expensive engineered barrier systems. To this end, five nations (US, UK, France, Japan, and Belgium) have joined together to formulate a joint plan for collaborative research into the mechanisms controlling the long-term corrosion of glass. Over the last five years, the coordinated research performed by these countries has produced a new level of understanding about the glass corrosion mechanisms, specifically as they apply to glasses similar in composition to the French R7T7 glass. Some recent results are presented as they relate to several mechanisms that are thought to control glass alteration at long time periods. It is important to understand the effects of each particular mechanism on the overall radionuclide release and the relative importance of each process model to the performance assessment calculation. In addition, a new series of experiments calls out potential sources of error due to the use of irregular shapes (such as crushed glass powder) in dissolution experiments. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Advanced Waste Management Concepts for Uranium and Plutonium Multi-Recycling - 18533

The multiple recycling of plutonium and uranium will play a major role in gradually achieving a fully closed nuclear fuel cycle in the future, once the first Generation IV fast reactors (FR) are deployed in the NPP fleet. To reach this objective, optimizations of current processes and technologies and, in some cases, the development of innovative concepts are required to meet the scientific, technical and economic challenges imposed by the treatment of spent fuels with an increasingly higher Pu content. Based on the significant past experience acquired by France in LWR and FR MOX fuel treatment, the CEA is running R and D studies to develop new efficient processes for Pu recycling and for FR MOX fuel fabrication. More compact and economically competitive processes, ensuring the safety/security of the facilities (particularly as regards criticality and proliferation resistance) have to be developed taking into account that the amounts of plutonium involved will be one order of magnitude higher than in UOX fuels. New concepts of head-end treatment, dissolution, and separation have been proposed. Consequently, effluent and waste management must be adapted to these processes and to the characteristics of fast reactor MOX fuels. New waste treatment processes are suggested: 1) Cladding waste and undissolved metallic particles could be treated simultaneously in a melting process. The molten metal could be decontaminated by a specific slag and the oxides recovered, in particular PuO{sub 2}, would be recycled at the frond-end of the process, 2) Fission Products and Actinides (FPA) containment glass will also be optimized to accommodate significant amounts of iron, nickel and chromium coming from hull corrosion, and / or decontamination slag coming from the metal melting process. 3) New peraluminous-type glass formulations are under development to accept increased amounts of FPA, as well as iron, nickel, and chromium. The first trials to evaluate the melting process have indicated that metallic compounds from the dissolution residues could be easily incorporated into a molten metal at levels of 1, 2 and 3 w%. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Experimental Investigation and Mathematical Modeling of Cold Cap Behavior in High-Level-Waste Glass Melter

The cold cap is a layer of reacting melter feed floating on the surface of molten glass in a glass-melting furnace. The cold cap consists of two distinct portions, of which the upper allows the reaction gases to escape through open pores, whereas the lower portion traps the gases within the continuous glass-forming melt, creating foam. The temperature span over the cold cap is ~1000 K. Data needed to simulate the cold cap mathematically include the kinetics of multiple reactions, reaction enthalpies, heat capacity, density, porosity, and heat conductivity as functions of both the temperature and the rate of heating. These data were produced via crucible experiments. The mathematical model has been completed. It relates the cold cap thickness, the rate of melting, the temperature field, and cold cap structure (foaming, dissolution of quartz particles, and formation and subsequent dissolution of crystalline phases, such as spinel) to the cold cap bottom temperature, the fraction of heat flow to the upper cold cap surface, the melt foaminess, and the chemical and physical nature of melter feed materials. To verify the model, cold caps were produced in a laboratory-scale melter and their structure is currently investigated.

Hrma, Pavel R.↗

Encapsulating Various Sulfur Allotropes within Graphene Nanocages for Long-Lasting Lithium Storage

The encapsulation of sulfur within carbon matrices is widely utilized in the cathode of a rechargeable lithium-sulfur battery, whose energy density largely depends on the design of the carbon structure. Here, an advanced graphene nanocage structure with the capability of hosting both cyclo-S-8 and smaller sulfur molecules (S2-4) is reported. The cage inner cavity is partially filled with S-8 to form a yolk-shell structure that enables free volumetric variation of S-8 during (de)lithiation. In the graphene shell of the cage, S-8 are downsized to S2-4 to activate extra sulfur loading sites within graphene layers. Importantly, the graphene shell exhibits inward volumetric variation upon (de)lithiation of the loaded S2-4, and the overall electrode strain is thus minimized. This prototyped design promises an ultimate solution to maximize sulfur loading in carbon matrices as well as to circumvent the polysulfide dissolution problem and boost the commercialization of lithium-sulfur batteries in the future.

Yuan, Yifei↗

Advanced Characterization Techniques in Promoting Mechanism Understanding for Lithium-Sulfur Batteries

Due to the numerous advantages, such as high specific capacity, etc., lithium-sulfur batteries (Li-S batteries) have attracted much attention as next-generation energy storage systems. To meet future needs for commercial application, Li-S batteries will require both improved cycle life and high energy density. It is of critical importance to understand the fundamental mechanisms in Li-S system to further improve the whole battery performance. Various advanced characterization techniques, over the past few years, have proven their important role in promoting the mechanism understanding for Li-S batteries. Here, we review the recent progress of mechanism understanding, including redox reactions, Li polysulfides dissolution, and etc., in Li-S systems based on the advanced characterization techniques. Special focus is placed on how these advanced characterization techniques are being employed and what characteristic or capability they possess. The necessity of combination of multiple characterization, difference between ex situ and in situ experimental methods, as well as importance of characterization conditions in Li-S batteries are also discussed.

Zhao, Enyue↗

In Situ Construction of Uniform and Robust Cathode–Electrolyte Interphase for Li-Rich Layered Oxides

The high-energy-density Li-rich layered oxides (LLOs) as promising cathodes for Li-ion batteries suffer from the dissolution of transition metals (especially manganese) and severe side reactions in conventional electrolytes, which greatly deteriorate their electrochemical performance. Herein, an in situ “anchoring + pouring” synergistic cathode-electrolyte interphase (CEI) construction is realized by using 1,3,6-hexanetricarbonitrile (HTCN) and tris(trimethylsilyl) phosphate (TMSP) electrolyte additives to alleviate the challenges of an LLO (Li 1.13 Mn 0.517 Ni 0.256 Co 0.097 O 2 ). HTCN with three nitrile groups can tightly anchor transition metals by coordinative interaction to form the CEI framework, and TMSP will electrochemically decompose to reshape the CEI layer. The uniform and robust in situ constructed CEI layer can suppress the transition metal dissolution, shield the cathode against diverse side reactions, and significantly improve the overall electrochemical performance of the cathode with a discharge voltage decay of only 0.5 mV/cycle -1 . Further investigations based on a series of experimental techniques and theoretical calculations have revealed the composition of in situ constructed CEI layers and their distribution, including the enhanced HTCN anchoring effect after lattice densification of LLOs. Finally, this study provides insights into the in situ CEI construction for enhancing the performance of high-energy and high-voltage cathode materials through effective, convenient and economical electrolyte approaches.

25 ENERGY STORAGE↗

Revealing the Roles of CuF 2 /NiF 2 Incorporation in the Electrochemical Performance of FeF 3 Cathodes in Solid‐State Batteries

Mixed metal fluorides have been considered as a promising candidate to lower the voltage hysteresis of conversion-type iron fluoride cathodes, but their cycling stability is limited due to transition metal dissolution and interphase growth in liquid electrolyte batteries. Here, we study the role of incorporating CuF 2 and NiF 2 in the electrochemical performance of FeF 3 cathode in halide-based solid-state batteries to test whether we can transfer the kinetic benefit of low voltage hysteresis to solid-state batteries while using solid electrolyte to eliminate transition metal dissolution and stabilize the interphase. Synchrotron X-ray absorption spectroscopy results indicated the redox reactions are attributed to Cu 0 /Cu + and Fe 0 /Fe 2+ in 25CuF 2 -75FeF 3 and Ni 0 /Ni 2+ and Fe 0 /Fe 3+ in 10NiF 2 -90FeF 3 . While no apparent improvement in electrode kinetics can be observed, the incorporation of CuF 2 and NiF 2 can largely improve the cycling stability of FeF 3 cathodes. In conclusion, the results demonstrate the advantages of using solid-state concept to improve the cycling stability of conversion-type cathodes.

25 ENERGY STORAGE↗

Constructing Highly Durable Fuel Cell Catalysts Through Integrating Graphitic Shell‐Protected Composite Carbon Support with Gaseous Co Deposition‐Driven PtCo Intermetallics

Metal dissolution, nanoparticle agglomeration, and carbon support corrosion cause significant performance degradation of current PtCo catalysts under acidic and oxidative oxygen reduction reaction. Here, in this study, an integrated strategy is presented to design high-performance Pt 3 Co intermetallic catalysts by regulating gaseous Co deposition-driven diffusion into Pt nanoparticles supported on a composite carbon. The composite carbon is derived from ZIF-8/polyaniline, consisting of a high-surface-area (HSC) core and a protective graphitic shell (GS), which is employed to design 40 wt.% Pt/HSC@GS catalyst. The corresponding membrane electrode assemblies (MEAs) can maintain 1.09 A cm −2 at 0.7 V (20. 7% loss) after 10 000 cycles (1.0–1.5 V for carbon stability) and 1.15 A cm −2 (16.1% loss) after 150 000 cycles (0.60–0.95 V for catalyst stability). A ordered Pt 3 Co intermetallic is synthesized via a gaseous Co-deposition process, which yields a homogeneous Co-rich layer onto the Pt nanoparticles on the composite support, thereby facilitating Co diffusion into Pt crystal during subsequent ordering annealing to form the ordered intermetallic structure. This gaseous deposition leads to a thin carbon layer on PtCo nanoparticles, inhibiting particle growth during the annealing and mitigating Co dissolution under dynamic electrochemical conditions. The PtCo catalyst achieves impressive MEA performance and long-term durability (1.45 A cm −2 at 0.7 V after 120 000 cycles) under heavy-duty conditions.

30 DIRECT ENERGY CONVERSION↗

Operando Observations and First-Principles Calculations of Reduced Lithium Insertion in Au-Coated LiMn 2 O 4

The deposition of protective coatings on the spinel LiMn 2 O 4 (LMO) lithium–ion battery cathode is effective in reducing Mn dissolution from the electrode surface. Although protective coatings positively affect LMO cycle life, much remains to be understood regarding the interface formed between these coatings and LMO. Using operando powder X–ray diffraction with Rietveld refinement, it is shown that, in comparison to bare LMO, the lattice parameter of a model Au–coated LMO cathode is significantly reduced upon relithiation. Less charge passes through Au–coated LMO in comparison to bare LMO, suggesting that the reduced lattice parameter is associated with decreased Li + solubility in the Au–coated LMO. Density functional theory calculations show that a more Li + –deficient near–surface is thermodynamically favorable in the presence of the Au coating, which may further stabilize these cathodes through suppressing formation of the Jahn–Teller distorted Li 2 Mn 2 O 4 phase at the surface. Electronic structure and chemical bonding analyses show enhanced hybridization between Au and LMO for delithiated surfaces leading to partial oxidation of Au upon delithiation. Furthermore, this study suggests that, in addition to transition metal dissolution from electrode surfaces, protective coating design must also balance potential energy effects induced by charge transfer at the electrode–coating interface.

25 ENERGY STORAGE↗

Hybrid Additive Manufacturing and Electric Field-Assisted Sintering of High-temperature Heat Exchangers via Sacrificial Channel Molds

A hybrid manufacturing approach, integrating additive manufacturing (AM) with powder methodology via electric field-assisted sintering (EFAS), was developed for the fabrication of high-temperature compact heat exchangers (CHX) from refractory metals. The methodology employed additively manufactured sacrificial channel molds (SCMs) as shapeholders for CHX channels, which were embedded in metal powders using EFAS. Following embedding, the SCMs were chemically dissolved to form the internal channel network. SCMs were fabricated using both digital light processing (DLP) and direct ink writing (DIW) from chemically reactive, calcium-based ceramic feedstocks with varying ratios of Al2O3 reinforcement. The microstructure, phase composition, and dissolution behavior of both as-printed and embedded SCMs were investigated. The shrinkage behavior of the SCMs embedded in refractory metals, as well as the interfacial characteristics between the SCMs and metal matrix, were studied. The results showed that the SCMs containing sufficient chemical reactive ceramics dissolved effectively before and after embedding. The as-printed SCMs retained the phase composition of their feedstocks, but the embedded SCMs containing calcium-based ceramics and Al2O3 exhibited the formation of calcium aluminates due to high temperature exposure during embedding. Most SCMs exhibited a cellular Al2O3 network filled with Ca-rich ceramics. Shrinkage after embedding was strongly dependent on SCM density, with lower density SCMs exhibiting greater shrinkage. A thin SCM-affected zone was observed at the metal matrix surface, characterized by increased porosity compared to the bulk matrix. This effect was attributed to infiltration of the SCM materials into powder particle boundaries under pressure, followed by their removal during dissolution. This study demonstrates the feasibility of manufacturing CHXs from hard-to-process refractory metals for use in harsh environments.

36 - MATERIALS SCIENCE↗

Electrolyzer and Fuel Cell Recycling for a Circular Hydrogen Economy

Abstract Electrolyzers and fuel cells will be crucial for achieving global clean hydrogen and industrial decarbonization goals. However, the nascent clean hydrogen sector faces uncertainties around material supply chains and technology end‐of‐life management. This work aims to guide the transition to a circular hydrogen economy by using process modeling, techno‐economic analysis, and life cycle assessment to evaluate the material cost, energy use, greenhouse gas (GHG) emissions, toxicity, and water use of five potential recycling strategies for proton exchange membrane electrolyzers (PEMWE) and fuel cells (PEMFC). Hydrometallurgy, acid dissolution, and electrochemical dissolution are shown to offer 2–7 times improvement across all assessed metrics relative to the manufacturing of PEMWE and PEMFC from raw materials. Recycling can also lower the raw material demand, material cost, energy use, and GHG emissions associated with PEMWE and PEMFC deployment in the United States in 2050 by 23%, 19%, 21%, and 16%, respectively. This study provides key insights into the costs, benefits, and complexities of recycling strategies for PEMWE and PEMFC, aiding the development of a circular economy that is synergistic with clean hydrogen deployment.

08 HYDROGEN↗

Mn versus Al in Layered Oxide Cathodes in Lithium-Ion Batteries: A Comprehensive Evaluation on Long-Term Cyclability

Nickel-rich layered oxide cathodes with the composition LiNi 1-x-y Co x Mn y O 2 (NCM, (1-x-y) ≥ 0.6) are under intense scrutiny recently to contend with commercial LiNi 0.8 Co 0.15 Al 0.05 O 2 (NCA) for high-energy-density batteries for electric vehicles. However, a comprehensive assessment of their electrochemical durability is currently lacking. Herein, two in-house cathodes, LiNi 0.8 Co 0.15 Al 0.05 O 2 and LiNi 0.7 Co 0.15 Mn 0.15 O 2 , are investigated in a high-voltage graphite full cell over 1500 charge-discharge cycles (≈5–10 year service life in vehicles). Despite a lower nickel content, NCM shows more performance deterioration than NCA. Critical underlying degradation processes, including chemical, structural, and mechanical aspects, are analyzed via an arsenal of characterization techniques. Overall, Mn substitution appears far less effective than Al in suppressing active mass dissolution and irreversible phase transitions of the layered oxide cathodes. The active mass dissolution (and crossover) accelerates capacity decline with sustained parasitic reactions on the graphite anode, while the phase transitions are primarily responsible for cell resistance increase and voltage fade. With Al doping, on the other hand, secondary particle pulverization is the more limiting factor for long-term cyclability compared to Mn. Finally, these results establish a fundamental guideline for designing high-performing Ni-rich NCM cathodes as a compelling alternative to NCA and other compositions for electric vehicle applications.

25 ENERGY STORAGE↗

Stabilized Co-Free Li-Rich Oxide Cathode Particles with An Artificial Surface Prereconstruction

Li-rich metal oxide (LXMO) cathodes have attracted intense interest for rechargeable batteries because of their high capacity above 250 mAh g –1 . However, the side effects of hybrid anion and cation redox (HACR) reactions, such as oxygen release and phase collapse that result from global oxygen migration (GOM), have prohibited the commercialization of LXMO. GOM not only destabilizes the oxygen sublattice in cycling, aggravating the well-known voltage fading, but also intensifies electrolyte decomposition and Mn dissolution, causing severe full-cell performance degradation. In this study, an artificial surface prereconstruction (ASR) for Li 1.2 Mn 0.6 Ni 0.2 O 2 particles with a molten-molybdate leaching is conducted, which creates a crystal-dense anion-redox-free LiMn 1.5 Ni 0.5 O 4 shell that completely encloses the LXMO lattice (ASR-LXMO). Differential electrochemical mass spectroscopy and soft X-ray absorption spectroscopy analyses demonstrate that GOM is shut down in cycling, which not only stabilizes HACR in ASR-LXMO, but also mitigates the electrolyte decomposition and Mn dissolution. ASR-LXMO displays greatly stabilized cycling performance as it retains 237.4 mAh g –1 with an average discharge voltage of 3.30 V after 200 cycles. More crucially, while the pristine LXMO cycling cannot survive 90 cycles in a pouch full-cell matched with a commercial graphite anode and lean (2 g A –1 h –1 ) electrolyte, ASR-LXMO shows high capacity retention of 76% after 125 cycles in full-cell cycling.

25 ENERGY STORAGE↗

A Cobalt– and Manganese–Free High–Nickel Layered Oxide Cathode for Long–Life, Safer Lithium–Ion Batteries

High-nickel LiNi 1–x–y Mn x Co y O 2 and LiNi 1–x–y Co x Al y O 2 cathodes are receiving growing attention due to the burgeoning demands on high-energy-density lithium-ion batteries. The presence of both cobalt and manganese in them, however, triggers multiple issues, including high cost, high toxicity, rapid surface deterioration, and severe transition-metal dissolution. Herein, a Co- and Mn-free ultrahigh-nickel LiNi 0.93 Al 0.05 Ti 0.01 Mg 0.01 O 2 (NATM) cathode that exhibits 82% capacity retention over 800 deep cycles in full cells, outperforming two representative high-Ni cathodes LiNi 0.94 Co 0.06 O 2 (NC, 52%) and LiNi 0.90 Mn 0.05 Co 0.05 O 2 (NMC, 60%) is presented. It is demonstrated that a titanium-enriched surface along with aluminum and magnesium as the stabilizing ions in NATM not only ameliorates unwanted side reactions with the electrolyte and structural disintegrity, but also mitigates transition-metal dissolution and active lithium loss on the graphite anode. As a result, the graphite anode paired with NATM displays an ultrathin (≈8 nm), monolayer anode-electrolyte interphase architecture after extensive cycling. Furthermore, NATM displays considerably enhanced thermal stability with an elevated exothermic temperature (213 °C for NATM vs 180 and 190 °C for NC and NMC, respectively) and remarkably reduced heat release. This work sheds light on rational compositional design to adopt ultrahigh-Ni cathodes in lithium-based batteries with low cost, long service life, and improved thermal stability.

25 ENERGY STORAGE↗

Insights into the Crossover Effects in Cells with High‐Nickel Layered Oxide Cathodes and Silicon/Graphite Composite Anodes

Abstract Silicon anodes are regarded as one of the most promising alternatives to graphite (Gr) anodes due to their ultrahigh capacity, abundance, and low cost. Coupling Si‐based anodes with high‐nickel layered oxide cathodes LiNi x Mn y Co 1− x − y O 2 (NMC, x ≥ 0.8) can enhance the driving range for electric vehicles. Transition‐metal (TM) ion dissolution and deposition has been a long‐known failure mode for Gr‐based lithium‐ion batteries. However, the mechanistic insight associated with TM ion deposition on Si‐based anodes has rarely been reported. Herein, the impact of in situ deposited TM ions on SiO x /Gr composite anodes and the individual influences of Ni, Mn, and Co on the structural and electrochemical stability along with the underlying degradation mechanisms are presented. TM ion dissolution causes a greater deleterious impact on Si than on Gr, with different TM ions exhibiting different influences on anode‐electrolyte interphase formation. Specifically, Ni deposit induces more aggressive salt decomposition; Co deposit has negligible effect on salt decomposition, but significantly accelerates solvent decomposition; and Mn deposit aggravates both salt and solvent decompositions, resulting in worse full cell performance. The extent of degradation decreases in the order Mn 2+ > Ni 2+ > Co 2+ . The systematic comparisons presented can guide further development of high energy systems.

Zhang, Xianhui↗

Increasing the Pressure‐Free Stripping Capacity of the Lithium Metal Anode in Solid‐State‐Batteries by Carbon Nanotubes

Abstract Lithium metal is the key anode material for solid‐state‐batteries as its successful implementation will drastically increase their energy and power densities. However, anode contact loss during stripping leads to dendrites upon plating and subsequent cell failure. Design strategies to mitigate these issues are crucial to enable the use of lithium metal anodes. This paper reports the dissolution kinetics of composite anodes made of lithium metal and carbon nanotubes (CNTs) with a garnet‐type solid electrolyte (SE). In addition to an enhancement of the effective diffusion within the anode, its dissolution is fundamentally changed from being 2D to 3D. By maintaining contact with the SE, the CNTs facilitate lithium transport to the interface, which yields more than 20 mAh cm −2 discharge capacity at 100 µ A cm −2 without the application of external stack pressure ( > 1 MPa). Conclusions drawn from electrochemical data on the anode microstructure are validated using cryo‐focused‐ion‐beam scanning electron microscopy and correlated with the mechanical properties. Micro‐indentation, acoustic analysis, and stress–strain testing show that mechanical properties of the anode, like yield strength and hardness, are adjustable. Overall, it is shown that the mechanical and electrochemical properties of Li–CNT composite electrodes can be tailored to suit the requirements of a practical cell.

Fuchs, Till↗

Strong Lithium Polysulfide Chemisorption on Electroactive Sites of Nitrogen-Doped Carbon Composites For High-Performance Lithium–Sulfur Battery Cathodes

Despite the high theoretical capacity of lithium–sulfur batteries, their practical applications are severely hindered by a fast capacity decay, stemming from the dissolution and diffusion of lithium polysulfides in the electrolyte. A novel functional carbon composite (carbon-nanotube-interpenetrated mesoporous nitrogen-doped carbon spheres, MNCS/CNT), which can strongly adsorb lithium polysulfides, is now reported to act as a sulfur host. The nitrogen functional groups of this composite enable the effective trapping of lithium polysulfides on electroactive sites within the cathode, leading to a much improved electrochemical performance (1200 mAh g -1 after 200 cycles). The enhancement in adsorption can be attributed to the chemical bonding of lithium ions by nitrogen functional groups in the MNCS/CNT framework. Furthermore, the micrometer-sized spherical structure of the material yields a high areal capacity (ca. 6 mAh cm -2 ) with a high sulfur loading of approximately 5 mg cm -2 , which is ideal for practical applications of the lithium–sulfur batteries.

carbon materials↗

Structural evolution of recycled tire rubber in asphalt

ABSTRACT The performance of recycled‐tire‐rubber‐modified asphalt mainly depends on the structure of rubber in the asphalt. The effects of the curing temperature, mixing time, and shearing on the evolution of the chemical structure and morphological structure of crumb rubber in asphalt were investigated. The crosslink density, compositions, and morphological evolution of the residual crumb rubber were characterized. The results show that the structure evolution of tire rubber in asphalt was greatly affected by the curing temperature. At a low curing temperature (180°C), the crosslinking network of the tire rubber was broken down, and this led to the partial dissolution of natural rubber (NR). However, at high curing temperature (240°C), the dissolution of NR, synthetic rubber, carbon black, and inorganic filler was observed. The released carbon black covered with a thin layer of bound rubber dispersed at a microstructured or nanostructured size in the asphalt. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133 , 42954.

Yao, Hongru↗