Approaching Ultimate Synthesis Reaction Rate of Ni-Rich Layered Cathodes for Lithium-Ion Batteries

Nickel-rich layered oxide LiNi_(x)Co_(y)MnzO_(2)(NCM,x+y+z=1)is the most promising cathode material for high-energy lithium-ion batteries.However,conventional synthesis methods are limited by the slow heating rate,sluggish reaction dynamics,high energy consumption,and long reaction time.To overcome these chal-lenges,we first employed a high-temperature shock(HTS)strategy for fast synthesis of the NCM,and the approaching ultimate reaction rate of solid phase transition is deeply investigated for the first time.In the HTS process,ultrafast average reaction rate of phase transition from Ni_(0.6)Co_(0.2)Mn_(0.2)(OH)_(2) to Li-containing oxides is 66.7(%s^(-1)),that is,taking only 1.5 s.An ultrahigh heating rate leads to fast reaction kinetics,which induces the rapid phase transition of NCM cathodes.The HTS-synthesized nickel-rich layered oxides perform good cycling performances(94%for NCM523,94%for NCM622,and 80%for NCM811 after 200 cycles at 4.3 V).These findings might also assist to pave the way for preparing effectively Ni-rich layered oxides for lithium-ion batteries.

A new Ignition-Growth reaction rate model for shock initiation

Accurately predicting reactive flow is a challenge when characterizing an explosive under external shock stimuli as the shock initiation time is on the order of a microsecond.The present study constructs a new Ignition-Growth reaction rate model,which can describe the shock initiation processes of explosives with different initial densities,particle sizes and loading pressures by only one set of model parameters.Compared with the Lee-Tarver reaction rate model,the new Ignition-Growth reaction rate model describes better the shock initiation process of explosives and requires fewer model parameters.Moreover,the shock initiation of a 2,4-Dinitroanisole(DNAN)-based melt-cast explosive RDA-2(DNAN/HMX(octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazoncine)/aluminum)are investigated both experimentally and numerically.A series of shock initiation experiments is performed with manganin piezoresistive pressure gauges and corresponding numerical simulations are carried out with the new Ignition-Growth reaction rate model.The RDA-2 explosive is found to have higher critical initiation pressure and lower shock sensitivity than traditional explosives(such as the Comp.B explosive).The calibrated reaction rate model parameters of RDA-2 could provide numerical basis for its further application.

Direct measurement of the break-out ^(19)F(p,γ)^(20)Ne reaction in the China Jinping underground laboratory(CJPL)

Calcium production and the stellar evolution of first-generation stars remain fascinating mysteries in astrophysics.As one possible nucleosynthesis scenario,break-out from the hot carbon–nitrogen–oxygen(HCNO)cycle was thought to be the source of the calcium observed in these oldest stars.However,according to the stellar modeling,a nearly tenfold increase in the thermonuclear rate ratio of the break-out ^(19)F(p,γ)^(20) Ne reaction with respect to the competing ^(19)F(p,α)^(16) O back-processing reaction is required to reproduce the observed calcium abundance.We performed a direct measurement of this break-out reaction at the China Jinping underground laboratory.The measurement was performed down to the low-energy limit of E_(c.m.)=186 keV in the center-of-mass frame.The key resonance was observed at 225.2 keV for the first time.At a temperature of approximately 0.1 GK,this new resonance enhanced the thermonuclear ^(19)F(p,γ)^(20) Ne rate by up to a factor of≈7.4,compared with the previously recommended NACRE rate.This is of particular interest to the study of the evolution of the first stars and implies a stronger breakdown in their“warm”CNO cycle through the ^(19)F(p,γ)^(20) Ne reaction than previously envisioned.This break-out resulted in the production of the calcium observed in the oldest stars,enhancing our understanding of the evolution of the first stars.

Energy diffusion controlled reaction rate in dissipative Hamiltonian systems

In this paper the energy diffusion controlled reaction rate in dissipative Hamiltonian systems is investigated by using the stochastic averaging method for quasi Hamiltonian systems. The boundary value problem of mean first- passage time （MFPT） of averaged system is formulated and the energy diffusion controlled reaction rate is obtained as the inverse of MFPT. The energy diffusion controlled reaction rate in the classical Kramers bistable potential and in a two-dimensional bistable potential with a heat bath are obtained by using the proposed approach respectively. The obtained results are then compared with those from Monte Carlo simulation of original systems and from the classical Kraraers theory. It is shown that the reaction rate obtained by using the proposed approach agrees well with that from Monte Carlo simulation and is more accurate than the classical Kramers rate.

Reaction rates in blanket assemblies of a fusion-fission hybrid reactor

To validate neutronics calculation for the blanket design of fusion-fission hybrid reactor,experiments for measuring reaction rates inside two simulating assemblies are performed.Two benchmark assemblies were developed for the neutronics experiments.A D-T fusion neutron source is placed at the center of the setup.One of them consists of three layers of depleted uranium shells and two layers of polyethylene shells,and these shells are arranged alternatively.The ^(238)U capture reaction rates are measured using depleted uranium foils and an HPGe gamma spectrometer.The fission reaction rates are measured using a fission chamber coated with depleted uranium.The other assembly consists of depleted uranium and LiH shells.The tritium production rates are measured using the lithium glass scintillation detector which is placed in the LiH region of the assembly.The measured reaction rates are compared with the calculated ones predicted using MCNP code,and C/E values are obtained.

Key Role of Some Specific Occupied Molecular Orbitals of Short Chain n-Alkanes in Their Surface Tension and Reaction Rate Constants with Hydroxyl Radicals: DFT Study

Basing on the DFT calculations we propose the new theoretical model which describes both the surface tension σ of the short chain n-alkanes at their normal boiling points and their reaction rate constants with hydroxyl radicals OH• (at 297 ± 2 K) on the basis of their molecular orbital electronic characteristics. It has been shown that intermolecular dispersion attraction within the surface liquid monolayer of these compounds, as well as their reaction rate constants k with OH• radicals are determined by the energies Eorb of the specific occupied molecular orbitals which are the same in the determination of both the above physico-chemical characteristics of the studied n-alkanes. The received regression equations confirm the theoretically found dependences between the quantities of σ and k and the module |Eorb|. For the compounds under study this fact indicates the key role of their electronic structure particularities in determination of both the physical (surface tension) and the chemical (reaction rate constants) properties.

Determination of the stellar reaction rate for ^(12)C(α, γ)^(16)O: using a new expression with the reaction mechanism

The astrophysical reaction rate of 12C（α,γ）16O plays a key role in massive star evolution. However, this reaction rate and its uncertainties have not been well determined yet, especially at T9=0.2. The existing results even disagree with each other to a certain extent. In this paper, the El, E2 and total （E1＋E2） 12C（α,γ）16O reaction rates are calculated in the temperature range from T9=0.3 to 2 according to all the available cross section data. A new analytic expression of the 12C（α,γ）16O reaction rate is brought forward based on the reaction mechanism. In this expression, each part embodies the underlying physics of the reaction. Unlike previous works, some physical parameters are chosen from experimental results directly, instead of all the parameters obtained from fitting. These parameters in the new expression, with their 3σ fit errors, are obtained from fit to our calculated reaction rate from T9=0.3 to 2. Using the fit results, the analytic expression of 12C（α,γ）16Oreaction rate is extrapolated down to T9=0.05 based on the underlying physics. The 12C（α,γ）16O reaction rate at T9=0.2 is （8.78 ± 1.52） × 10^15 cm3s^-1mol^-1. Some comparisons and discussions about our new 12C（α,γ）16Oreaction rate are presented, and the contributions of the reaction rate correspond to the different part of reaction mechanism are given. The agreements of the reaction rate below T9=2 between our results and previous works indicate that our results are reliable, and they could be included in the astrophysical reaction rate network. Furthermore, we believe our method to investigate the 12C（α,γ）16O reaction rate is reasonable, and this method can also be employed to study the reaction rate of other astrophysical reactions. Finally, a new constraint of the supernovae production factor of some isotopes are illustrated according to our 12C（α,γ）16O reaction rates.

Measurement of absolute reaction rates in Be, Pb and Fe spherical systems

The absolute reaction rates in Be,Pb and Fe have been measured by using the activation foil technique with different reaction energy thresholds.Thicknesses of Be,Pb and Fe spheres were 5.3,19.1 and 31.9cm.respectively,Eight kinds of activation folis were used for Fe,and four kinds each for Be and Pb,The total experimental er5ror was about 5-7%.The measured results were compared to the values calculated with the 1-D ANISN code and the ENDF/B-VI library data.The average ratio of the experimental to the calculational is less than 7% for Be and Pb,about 5-30% for Fe.

Rate Coefficients of Roaming Reaction H+MgH Using Ring Polymer Molecular Dynamics

The ring-polymer molecular dynamics(RPMD)was used to calculate the thermal rate coefficients of the multi-channel roaming reaction H+MgH→Mg+H_(2).Two reaction channels,tight and roaming,are explicitly considered.This is a pioneering attempt of exerting RPMD method to multichannel reactions.With the help of a newly developed optimization-interpolation protocol for preparing the initial structures and adaptive protocol for choosing the force constants,we have successfully obtained the thermal rate coefficients.The results are consistent with those from other theoretical methods,such as variational transition state theory and quantum dynamics.Especially,RPMD results exhibit negative temperature dependence,which is similar to the results from variational transition state theory but different from the ones from ground state quantum dynamics calculations.

Measurement of Reaction Rate of Gelled Acids and Calcite with the Rotating Disk Apparatus

An investigation has been made to study the reaction kinetics of gelled acids with calcite using a rotating disk apparatus. The rheological experiments revealed that all gelled acids behaved as non-Newtonian shear thinning fluids. With the rotating disk apparatus, the reaction kinetics parameters, activation energy, and effective diffusion coefficients were determined. It was found that the reaction of gelled acid with calcite was mass transfer limited at low polymer concentration and moving toward surface reaction limited at higher polymer concentration. And the diffusion rate marginally decreased, with increasing the polymer concentration.

A statistical model for predicting thermal chemical reaction rate

A simple model based on the statistics of individual atoms [Europhys. Lett. 94 40002 （2011）] or molecules [Chin. Phys. Lett. 29 080504 （2012）] was used to predict chemical reaction rates without empirical parameters, and its physical basis was further investigated both theoretically and via MD simulations. The model was successfully applied to some reactions of extensive experimental data, showing that the model is significantly better than the conventional transition state theory. It is worth noting that the prediction of the model on ab initio level is much easier than the transition state theory or unimolecular RRKM theory.

A melt-cast Duan-Zhang-Kim mesoscopic reaction rate model and experiment for shock initiation of melt-cast explosives

A melt-cast Duan-Zhang-Kim(DZK)mesoscopic reaction rate model is developed for the shock initiation of melt-cast explosives based on the pore collapse hot-spot ignition mechanism.A series of shock initiation experiments was performed for the Comp B melt-cast explosive to estimate effects of the loading pressure and the particle size of granular explosive component,and the mesoscopic model is validated against the experimental data.Further numerical simulations indicate that the initial density and formula proportion greatly affect the hot-spot ignition of melt-cast explosives.

Rate Coecients and Kinetic Isotope E ects of Cl+XCl→XCl+Cl(X=H,D,Mu)Reactions from Ring Polymer Molecular Dynamics

The ring-polymer molecular dynamics(RPMD)was used to calculate the thermal rate coefficients and kinetic isotope effects of the heavy-light-heavy abstract reaction Cl+XCl→XCl+Cl(X=H,D,Mu).For the Cl+HCl reaction,the excellent agreement between the RPMD and experimental values provides a strong proof for the accuracy of the RPMD theory.And the RPMD results are also consistent with results from other theoretical methods including improved-canonical-variational-theory and quantum dynamics.The most novel finding is that there is a double peak in Cl+MuCl reaction near the transition state,leaving a free energy well.It comes from the mode softening of the reaction system at the peak of the potential energy surface.Such an explicit free energy well suggests strongly there is an observable resonance.And for the Cl+DCl reaction,the RPMD rate coefficient again gives very accurate results compared with experimental values.The only exception is at the temperature of 312.5 K,results from RPMD and all other theoretical methods are close to each other but slightly lower than the experimental value,which indicates experimental or potential energy surface deficiency.

Mixed Quantum Classical Reaction Rates based on the Phase Space Formulation of the Hierarchical Equations of Motion

In a previous work[J.Chem.Phys.140,174105(2014)],we have shown that a mixed quantum classical(MQC)rate theory can be derived to investigate the quantum tunneling effects in the proton transfer reactions.However,the method is based on the high temperature approximation of the hierarchical equation of motion(HEOM)with the Debye-Drude spectral density,and results in a multistate Zusman type of equation.We now extend this theory to include quantum effects of the bath degrees of freedom.By writing the full HEOM into a multidimensional partial differential equation in phase space,we can define a new reaction coordinate,and the previous method can be generalized to the full quantum regime.The validity of the new method is demonstrated by using numerical examples,including the spin-Boson model,and the double well model for proton transfer reaction.The new method is found to resolve some key problems of the previous theory based on high temperature approximation,including possible numerical instability in long time simulation and wrong rate constant at low temperatures.

Measurement of niobium reaction rate for material surveillance tests in fast reactors

A highly accurate and precise technique for measurement of the 93 Nb(n,n’)93m Nb reaction rate was established for the material surveillance tests,etc.in fast reactors.The self-absorption effect on the measurement of the characteristic X-rays emitted by 93m Nb was decreased by the dissolution and evaporation to dryness of niobium dosimeter.A highly precise count of the number of 93 Nb atoms was obtained by measuring the niobium solution concentration using inductively coupled plasma mass spectrometry.X-rays of 93m Nb were measured accurately by means of comparing the X-ray intensity of irradiated niobium solution with that of the solution in which stable 93 Nb was added.The difference between both intensities indicates the effect of 182 Ta,which is generated from an impurity tantalum,and the intensity of X-rays from 93m Nb was evaluated.Measurement error of the 93 Nb(n,n’)93m Nb reaction rate was reduced to be less than 4%,which was equivalent to the other reaction rate errors of dosimeters used for Joyo dosimetry.In addition,an advanced technique using Resonance Ionization Mass Spectrometry was proposed for the precise measurement of 93m Nb yield,and 93m Nb will be resonance-ionized selectively by discriminating the hyperfine splitting of the atomic energy levels between 93 Nb and 93m Nb at high resolution.

A QUANTITATIVE STUDY ON ENHANCEMENT OF TYPE Ⅱ PHOTOSENSITIZED OXIDATION REACTION RATE BY HEAVY WATER

A method for quantitative evaluating the enhancement of the rate of Type Ⅱ photosensitized oxidation by D_2O was suggested. The effect of substrate concentration on this process was also discussed.

Fusion Reaction Rate Coefficient for Different Beam and Target Scenarios

Fusion power output is proportional not only to the fuel particle number densities participating in reaction but also to the fusion reaction rate coefficient （or reactivity）, which is dependent on reactant velocity distribution functions. They are usuMly assumed to be dual Maxwellian distribution functions with the same temperature for thermal nuclear fusion circumstances. However, if high power neutral beam injection and minority ion species ICRF plasma heating, or multi-pinched plasma beam head-on collision, in a converging region are required and investigated in future large scale fusion reactors, then the fractions of the injected energetic fast ion tail resulting from ionization or charge exchange will be large enough and their contribution to the non-Maxwellian distribution functions is not negligible, hence to the fusion reaction rate coefficient or calculation of fusion power. In such cases, beam-target, and beam-beam reaction enhancement effect contributions should play very important roles. In this paper, several useful formulae to calculate the fusion reaction rate coefticient for different beam and target combination scenarios are derived in detail

Stellar reaction rate of 55Ni（p,γ）56Cu in Type I X-ray bursts

56Cu is close to the waiting-point nucleus 56Ni and lies on the rapid proton capture（rp） process path in Type I X-ray bursts（XRBs）. In this work, we obtained a revised thermonuclear reaction rate of 55Ni（p,γ）56Cu in the temperature region relevant to XRBs. This rate was recalculated based on the recent experimental level structure in 56Cu, the recently measured proton separation energy of Sp = 579.8（7.1） keV, together with shell-model calculation, and the mirror nuclear structure in 56Co. The associated uncertainties in the rates were estimated by a Monte Carlo method. Our revised rate is significantly different from the recent results, which were partially based on experimental results; in addition, we found that a result in a previous work was incorrect. We recommend our revised rate to be incorporated in the future astrophysical network calculations.

Molecular Orbital Nature of Solubility of Shot Chain n-Alkanes in Water and Their Reaction Rate Constants with Nitronium Cations: A DFT Study

The new theoretical models describe both the solubility S of the shot chain n-alkanes in water at 298.15 K, and their reaction rate constants k with nitronium cation NO2+ at 293.15 K on the basis of their molecular orbital characteristics. It is shown that both the quantities S and k are determined by the energies Eorb of the specific virtual (for S) and occupied (for k) molecular orbitals of these n-alkanes. The obtained regression equations confirm the theoretically found dependences of S and k on the absolute value of Eorb. This fact demonstrates that the electronic structure particularities of the studied n-alkanes play a crucial role in both their above-mentioned physicochemical properties.