New insights into the pre-lithiation kinetics of single-crystalline Ni-rich cathodes for long-life Li-ion batteries

Developing single-crystalline Ni-rich cathodes is an effective strategy to improve the safety and cycle life of Li-ion batteries(LIBs).However,the easy-to-loss of Li and O in high-temperature lithiation results in unsatisfactory ordered layered structure and stoichiometry.Herein,we demonstrate the synthesis of highly-ordered and fully-stoichiometric single-crystalline LiNi_(0.83)Co_(0.12)Mn_(0.05)O_(2)(SC-NCM83)cathodes by the regulation of pre-lithiation kinetics.The well-balanced pre-lithiation kinetics have been proved to greatly improve the proportion of layered phase in the intermediate by inhibiting the formation of metastable spinel phase,which promoted the rapid transformation of the intermediate into highly-ordered layered SC-NCM83 in the subsequent lithiation process.After coating a layer of Li_(2)O–B_(2)O_(3),the resultant cathodes deliver superior cycling stability with 90.9%capacity retention at 1C after 300 cycles in pouch-type full batteries.The enhancement mechanism has also been clarified.These findings exhibit fundamental insights into the pre-lithiation kinetics process for guiding the synthesis of high-quality singlecrystalline Ni-rich cathodes.

Nitrogen-doped carbon stabilized Li Fe0.5Mn0.5PO4/rGO cathode materials for high-power Li-ion batteries

Exploring high ion/electron conductive olivine-type transition metal phosphates is of vital significance to broaden their applicability in rapid-charging devices.Herein,we report an interface engineered Li Fe0.5Mn0.5PO4/rGO@C cathode material by the synergistic effects of r GO and polydopamine-derived N-doped carbon.The well-distributed Li Fe0.5Mn0.5PO4nanoparticles are tightly anchored on r GO nanosheet benefited by the coating of N-doped carbon layer.The design of such an architecture can effectively suppress the agglomeration of nanoparticles with a shortened Li+transfer path.Meantime,the high-speed conducting network has been constructed by r GO and N-doped carbon,which exhibits the face-to-face contact with Li Fe0.5Mn0.5PO4nanoparticles,guaranteeing the rapid electron transfer.These profits endow the Li Fe0.5Mn0.5PO4/rGO@C hybrids with a fast charge-discharge ability,e.g.a high reversible capacity of 105 m Ah·g^-1at 10 C,much higher than that of the Li Fe0.5Mn0.5PO4@C nanoparticles(46 mA·h·g^-1).Furthermore,a 90.8%capacity retention can be obtained even after cycling 500 times at 2 C.This work gives a new avenue to fabricate transition metal phosphate with superior electrochemical performance for high-power Li-ion batteries.

Surface-engineering of layered LiNi_(0.815)Co_(0.15)Al_(0.035)O_2 cathode material for high-energy and stable Li-ion batteries

Surface engineering is an effective strategy to restrain the generation of rocksalt NiO phase on surface of layered LiNi0.815Co0.15Al0.035O2（NCA） primary nanoparticles, a representative Ni-rich layered oxides cathode materials. Herein, we demonstrate the kilogram-scale synthesis of few-layer reduced graphene oxide（rGO） conformably coated NCA primary nanoparticles cathode materials by a mechanical wet ball-milling strategy. The lightening rGO coating layer effectively avoids the direct contact of electrolyte and NCA with rapid electrons transfer. As a result, the as-obtained NCA@rGO hybrids with only 1.0 wt% rGO content can deliver a high specific capacity（196 mAh g-1 at 0.2 C） and fast charge/discharge capability（127 mAh g-1 at 5 C）, which is much higher than the corresponding NCA nanoparticles（95 mAh g-1 at 5 C）. Even after100 cycles at 1 C, 91.7% of initial reversible capacity is still maintained. Furthermore, a prismatic pouch cell（240 mAh） is also successfully assembled with the commercial graphite anode.

Interface-strengthened CoP nanosheet array with Co2P nanoparticles as efficient electrocatalysts for overall water splitting

Highly active and durable bifunctional electrocatalysts for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) play a pivotal role in overall water splitting. Herein, we demonstrate the construction of interface-strengthened CoP nanosheet array with Co2P nanoparticles as such an electrocatalyst through a facile hydrothermal reaction and the subsequent phosphorization process. The twodimensional (2D) nanosheets with thickness of^55 nm expose a great number of active sites. The surface chemical state indicates that the strongly coupled CoP/Co2P electrocatalysts can adsorb or generate more targeted intermediates (e.g. OH- or OOH*) for both HER/OER. As a result, the CoP/Co2P electrocatalysts exhibit small overpotentials of 68 and 256 mV to drive 10 mA cm^-2 for HER and OER, respectively, outperforming most of the recently reported Co-based electrocatalysts. Furthermore, an alkaline electrolyzer assembled by using CoP/Co2P as both cathode and anode can achieve a current density of 10 mA cm^-2 at a low voltage of 1.57 V and work continuously for over 58 h. This work provides a feasible structural design for transition metal phosphides electrocatalysts with efficient and stable overall water splitting.

Confining ultrahigh oxygen vacancy SnO_(2) nanocrystals into nitrogen-doped carbon for enhanced Li-ion storage kinetics and reversibility

Oxygen vacancies (V_(o)) engineering has been deemed to an effective tactic for enhancing Li-ion storage kinetics and reversibility of SnO_(2)-based anode materials.Herein,we demonstrated the confinement of ultrahigh V_(o)SnO_(2) nanocrystals into N-doped carbon frameworks to boost their high-rate and cycle life.Density functional theory (DFT) calculations reveal that abundant V_(o) in SnO_(2) facilitates the adsorption to Li-ion with remarkably increased carrier concentration.The 6.0 nm-sized SnO_(2) particles and the embedded design effectively stabilize the structural integrity during de-/lithiation.Meantime,the as-formed large hetero-interface also expedites the electron transfer.These merits guarantee its high-rate performance and superior cycling stability.Consequently,this sample exhibits a high capacity of 1368.9m Ah g^(-1)at 0.1 A g^(-1),and can still maintain 488.5 mAh g^(-1)at 10 A g^(-1)and a long life over 400 cycles at 5 A g^(-1)with 96.6%capacity retention,which is among the best report for Sn-contained anode materials.This work sheds light on ultrahigh Vo and structural design in conversion-type oxides for highperformance lithium-ion batteries (LIBs).

Confining MoS_(2) nanocrystals in MOF-derived carbon for high performance lithium and potassium storage

Developing an efficient synthesis protocol to simultaneously control 2D nanomaterials’size and dispersion is the pivot to optimize their electrochemical performance.Herein,we report the synthesis of uniform MoS_(2) nanocrystals well-anchored into the void space of porous carbon(donated as MoS_(2)3C hybrids)by a simple confined reaction in metal–organic framework(MOF)during carbonization process.The strong confinement effect refrain MoS2 growth and aggregation,generating abundant active centers and edges,which contribute fast lithium/potassium reaction kinetics.In addition to the hybridization with the derived carbon,the MoS_(2)3C hybrids exhibit rapid Liþtransfer rate(~109 cm^(2) s 1)and greatly improved electronic conductivity.Consequently,the MoS23C hybrids show ultrafast rate performances and satisfactory cycling stabilities as anode materials for both lithium and potassium ion batteries.This work demonstrates a universal tactic to achieve high dispersive 2D nanomaterials with tailorable particle size.

Tungsten and phosphate polyanion co-doping of Ni-ultrahigh cathodes greatly enhancing crystal structure and interface stability

The Ni-ultrahigh cathode material is one of the best choices for further increasing energy-density of lithium-ion batteries(LIBs),but they generally suffer from the poor structure stability and rapid capacity fade.Herein,the tungsten and phosphate polyanion co-doped LiNi_(0.9)Co_(0.1)O_(2)cathode materials are successfully fabricated in terms of Li(Ni_(0.9)Co_(0.7))_(1-x)W_(x)O_(2-4y)(PO_(4))_(y) by the precursor modification and subsequent annealing.The higher bonding energy of W—O(672 kJ·mol^(-1))can extremely stabilize the lattice oxygen of Ni-rich oxides compared with Ni—O(391.6 kJ·mol^(-1))and Co—O(368 kJ·mol^(-1)).Meanwhile,the stronger bonding of Ni—(PO_(4)^(3-))vs.Ni—O could fix Ni cations in the transition metal layer,and hence suppressing the Li/Ni disorder during the charge/discharge process.Therefore,the optimized Li(Ni_(0.9)Co_(0.1))_(0.99)W_(0.01)O_(1.96)(PO_4)_(0.01)delivers a remarkably extended cycling life with 95.1%retention of its initial capacity of 207.4 mA·h·g^(-1)at 0.2 C after 200 cycles.Meantime,the heteroatoms doping does not sacrifice the specific capacity even at different rates.

Atomic Interface Catalytically Synthesizing SnP/CoP Hetero-Nanocrystals within Dual-Carbon Hybrids for Ultrafast Lithium-Ion Batteries

Tin phosphides are attractive anode materials for ultrafast lithium-ion batteries(LIBs)because of their ultrahigh Li-ion diffusion capability and large theoretical-specific capacity.However,difficulties in synthesis and large size enabling electrochemical irreversibility impede their applications.Herein,an in situ catalytic phosphorization strategy is developed to synthesize SnP/CoP hetero-nanocrystals within reduced graphene oxide(rGO)-coated carbon frameworks,in which the SnP relative formation energy is significantly decreased according to density functional theory(DFT)calculations.The optimized hybrids exhibit ultrafast charge/discharge capability(260 mA·h·g^(-1)at 50 A·g^(-1))without capacity fading(645 mA·h·g^(-1)at 2 A·g^(-1))through 1500 cycles.The lithiation/delithiation mechanism is disclosed,showing that the 4.0 nm sized SnP/CoP nanocrystals possess a very high reversibility and that the previously formed metallic Co of CoP at a relatively high potential accelerates the subsequent reaction kinetics of SnP,hence endowing them with ultrafast charge/discharge capability,which is further verified by the relative dynamic current density distributions according to the finite element analysis.

Scalable solid-phase synthesis of defect-rich graphene for oxygen reduction electrocatalysis

Defect-engineered carbon materials have been emerged as promising electrocatalysts for oxygen reduction reaction(ORR)in metal-air batteries.Developing a facile strategy for the preparation of highly active nanocarbon electrocatalysts remains challenging.Herein,a low-cost and simple route is developed to synthesize defective graphene by pyrolyzing the mixture of glucose and carbon nitride.Molecular dynamics simulations reveal that the graphene formation is ascribed to two-dimensional layered feature of carbon nitride,and high compatibility of carbon nitride/glucose systems.Structural measurements suggest that the graphene possesses rich edge and topological defects.The graphene catalyst exhibits higher power density than commercial Pt/C catalyst in a primary Zn-air battery.Combining experimental results and theoretical thermodynamic analysis,it is identified that graphitic nitrogen-modified topological defects at carbon framework edges are responsible for the decent ORR performance.The strategy presented in this work can be can be scaled up readily to fabricate defective carbon materials.

Superhydrophobic and mechanically robust polysiloxane composite coatings containing modified silica nanoparticles and PS-grafted halloysite nanotubes

Excellent mechanical properties are the prerequisite for the application of superhydrophobic polymer coatings.However,significantly improving the mechanical properties without affecting other properties such as hydrophobicity is a huge challenge.In this study,a superhydrophobic coating with excellent mechanical properties was prepared by spraying a mixture of polysiloxane resins based on three siloxane monomers,hexadecyltrimethoxysilane(HDTMS) modified nano-SiO_(2)particles(SiO_(2)-HDTMS) and polystyrene-grafted halloysite nanotubes(HNTs-PS).SiO_(2)-HDTMS dispersed homogeneously in polysiloxane coatings and the water contact angle of corresponding coating exceeding 150°,achieving superhydrophobicity.The SiO_(2)-HDTMS/HNTs-PS/polysiloxane composite coatings showed excellent abrasion resistance with the water coating contact angle remaining above 150°after 90 abrasion cycles,indicating that HNTs-PS can significantly improve the mechanical properties of the coating without affecting the hydrophobic properties of the coating.The achieved coating also exhibited excellent antifouling and acid and alkali corrosion resistance.This work provides a convenient and ecologically friendly method to prepare superhydrophobic polysiloxane composite coating with excellent mechanical properties,which is promising in the application of anti-fouling,anti-corrosion,and oil-water separation etc.

Synthesis of silica powder with high pore volume by skeleton reinforcement

In this paper,a method composed of gelation of basic skeleton(first step)and skeleton reinforcement process(second step)was introduced to synthesize silica powder with high pore volume through the reaction between water glass and sulfuric acid.No organic solvents were involved in the entire preparation process and the final product was collected by spray drying.The effect of concentration of base solution,gelation point p H value and skeleton reinforcement time on the BET specific surface area and pore volume of the prepared silica powder were investigated intensively.The results show that,a basic skeleton with good dispersibility and high porosity was obtained when the concentration of base solution was 0.1 mol·L^(-1) and the gelation p H value reached 6.5.Then the basic skeleton grew into a more uniform porous structure after 30 min skeleton reinforcement.Under these optimum conditions,silica powder prepared by skeleton reinforcement method had a BET specific surface area of 358.0 m^(2)·g^(-1),and its pore volume reached 2.18 cm^(3)·g^(-1),which was much higher than that of prepared by skeleton-free method(1.62 cm^(3)·g^(-1))and by direct gelation method(0.31 cm^(3)·g^(-1)).

Retinal layer segmentation using gradient feature calculation in OCT

Retinal diseases pose significant challenges to global healthcare systems,necessitating accurate and efficient diagnostic methods.Optical Coherence Tomography(OCT)has emerged as a valuable tool for diagnosing and monitoring retinal conditions due to its noncontact and noninvasive nature.This paper presents a novel retinal layering method based on OCT images,aimed at enhancing the accuracy of retinal lesion diagnosis.The method utilizes gradient analysis to effectively identify and segment retinal layers.By selecting a column of pixels as a segmentation line and utilizing gradient information from adjacent pixels,the method initiates and proceeds with the layering process.This approach addresses potential issues arising from partial layer overlapping,minimizing deviations in layer segmentation.Experimental results demonstrate the efficacy of the proposed method in accurately segmenting eight retinal boundaries,with an average absolute position deviation of 1.75 pixels.By providing accurate segmentation of retinal layers,this approach contributes to the early detection and management of ocular conditions,ultimately improving patient outcomes and reducing the global burden of vision-related ailments.

Redirecting dynamic structural evolution of nickel-contained RuO_(2) catalyst during electrochemical oxygen evolution reaction

Electrochemical oxygen evolution reaction (OER) is a main efficiency bottleneck of water electrolysis.Commercial ruthenium oxide (RuO_(2)) catalyst displays remarkable activities but poor stability for OER.The instability stems from lattice oxygen oxidation,resulting in the oxidation of Ru^(4+) to soluble Ru^(4+)(x>4) species.Herein,we redirect dynamic structural evolution of Ru-based catalysts through introducing oxidized nickel (Ni) components.By virtue of comprehensive structural characterizations,such as high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM),X-ray photoelectron spectroscopy (XPS),operando Raman and so forth,it is demonstrated that when the atomic content of Ni exceeds that of ruthenium (Ru),the Ni components can efficiently inhibit the Ru^(4+) oxidation and structural collapse.Density functional theory (DFT) calculations suggest that the introduction of Ni component hinders the formation of oxygen vacancies,and makes lattice oxygen mediated mechanism turn to adsorbate evolution mechanism,which eventually improves the stability.The optimized nickel-contained RuO_(2) catalyst delivers an effective reactivity with an overpotential of less than 215 m V to attain 10 m A cm^(-2) and remarkable stability with only 5 mV increment after 5000 potential cycles.This work provides insights into the origin of dynamic structural evolution of transition-metalmodified RuO_(2) electrocatalysts.

Patterned catalyst layer boosts the performance of proton exchange membrane fuel cells by optimizing water management

Mass transport is crucial to the performance of proton exchange membrane fuel cells,especially at high current densities.Generally,the oxygen and the generated water share same transmission medium but move towards opposite direction,which leads to serious mass transfer problems.Herein,a series of patterned catalyst layer were prepared with a simple one-step impressing method using nylon sieves as templates.With grooves 100μm in width and 8μm in depth on the surface of cathode catalyst layer,the maximum power density of fuel cell increases by 10%without any additional durability loss while maintaining a similar electrochemical surface area.The concentration contours calculated by finite element analysis reveal that the grooves built on the surface of catalyst layer serve to accumulate the water nearby while oxygen tends to transfer through relatively convex region,which results from capillary pressure difference caused by the pore structure difference between the two regions.The separation of oxidant gas and generated water avoids mass confliction thus boosts mass transport efficiency.

Flame retardant synergy between interfacial and bulk carbonation in glass fiber reinforced polypropylene

Glass fiber reinforced polypropylene(GF-PP)composites have high flammability on account of wick effect which leads to accelerated flow of the polymer melt along the glass fibers(GF)surface to the flame zone.In this study,dipentaerythritol(DPER),a charring agent,was adsorbed on the GF surface through the hydrogen bond between silane coupling agent and DPER.DPER has a synergistic effect with the intumescent flame retardants(IFR)added in the composites,which can induce interfacial carbonization on the surface of GF,thus transforming the intrinsic smooth GF surface into roughness one.In this way,the negative effect of the wick effect in flame retardancy is weakened.Moreover,the char residues remained on the surface of GF can bring an improved adhesion between GF and char residues formed in the resin so that a more stable barrier char layer is formed.The PP composites with 20 wt%modified glass fiber(M-GF)and 30 wt%IFR can achieve the UL-94 V-0,and its limiting oxygen index(LOI)value increased from 16.5%to 29.5%.Simultaneously,the heat release rate(HRR),total heat release(THR)and total smoke release(TSR)decreased significantly,and the peak of heat release rate(PHRR)reduced60.6%compared with GF-PP.

Analyzing of mixing performance determination factors for the structure of radial multiple jets-in-crossflow

The radial multiple jets-in-crossflow mixing structure(RMJCMS) is extensively used in industrial manufacture. In this research, the effects of thickness of injection ring on mixing performance and factors influencing the mixing performance of RMJCMS were discussed based on the results of computational fluid dynamics. The simulation results showed that the dimensionless mixing distance, with the increase of the thickness of injection ring, drops from 1.1 to 0.18 first and then increases to 0.27 while the uniformity of flux monotonously improves, manifesting that the consistency of flux is not the single element determining the mixing performance. Analyzing the simulation results, a conclusion was drawn that the consistency of flux, penetration mode and interaction among injection flows which can be altered by adjusting the thickness of injection ring, determine the mixing performance of RMJCMS jointly. That is to say, in RMJCMS an injection ring with a suitable thickness can realize the function of injection and rectification simultaneously, which not only improves the mixing performance but also reduces the complexity of RMJCMS as well.

Numerical simulation of flow field and residence time of nanoparticles in a 1000-ton industrial multi-jet combustion reactor

In this work,by establishing a three-dimensional physical model of a 1000-ton industrial multi-jet combustion reactor,a hexahedral structured grid was used to discretize the model.Combined with realizable k–εmodel,eddy-dissipation-concept,discrete-ordinate radiation model,hydrogen 19-step detailed reaction mechanism,air age user-defined-function,velocity field,temperature field,concentration field and gas arrival time in the reactor were numerically simulated.The Euler–Lagrange method combined with the discrete-phase-model was used to reveal the flow characteristics of particles in the reactor,and based on this,the effects of the reactor aspect ratios,central jet gas velocity and particle size on the flow field characteristics and particle back-mixing degree in the reactor were investigated.The results show that with the decrease of aspect ratio in the combustion reactors,the velocity and temperature attenuation in the reactor are intensified,the vortex phenomenon is aggravated,and the residence time distribution of nanoparticles is more dispersed.With the increase in the central jet gas velocities in reactors,the vortex lengthens along the axis,the turbulence intensity increases,and the residence time of particles decreases.The back-mixing degree and residence time of particles in the reactor also decrease with the increase in particle size.The simulation results can provide reference for the structural regulation of nanoparticles and the structural design of combustion reactor in the process of gas combustion synthesis.

Integrated Ni-P-S nanosheets array as superior electrocatalysts for hydrogen generation

Searching for efficient and robust non-noble electrocatalysts for hydrogen generation is extremely desirable for future green energy systems.Here, we present the synthesis of integrated Ni-P-S nanosheets array including Ni_2P and NiS on nickel foam by a simple simultaneous phosphorization and sulfurization strategy. The resultant sample with optimal composition exhibits superior electrocatalytic performance for hydrogen evolution reaction(HER) in a wide pH range. In alkaline media, it can generate current densities of 10, 20 and 100 mA cm^(-2) at low overpotentials of only-101.9,-142.0 and-207.8 mV with robust durability. It still exhibits high electrocatalytic activities even in acid or neutral media. Such superior electrocatalytic performances can be mainly attributed to the synergistic enhancement of the hybrid Ni-P-S nanosheets array with integration microstructure. The kind of catalyst gives a new insight on achieving efficient and robust hydrogen generation.

Regulated adsorption-diffusion and enhanced charge transfer in expanded graphite cohered with N,B bridge-doping carbon patches to boost K-ion storage

The great challenges are remained in constructing graphite-based anode with well built-in structures to accelerate kinetics and enhance stability in the advanced K-ion batteries(KIBs).Here,we firstly report the design of expanded graphite cohered by N,B bridge-doping carbon patches(NBEG)for efficient K-ion adsorption/diffusion and long-term durability.It is the B co-doping that plays a crucial role in maximizing doping-site utilization of N atoms,balancing the adsorption-diffusion kinetics,and promoting the charge transfer between NBEG and K ions.Especially,the robust lamellar structure,suitable interlayer distance,and rich active sites of the designed NBEG favor the rapid ion/electron transfer pathways and high K-ion storage capacity.Consequently,even at a low N,B doping concentration(4.36 at%,2.07 at%),NBEG anode shows prominent electrochemical performance for KIBs,surpassing most of the advanced carbon-based anodes.Kinetic studies,density functional theory simulations,and in-situ Raman spectroscopy are further performed to reveal the K-ion storage mechanism and confirm the critical actions of co-doping B.This work offers the new methods for graphite-electrode design and the deeper insights into their energy storage mechanisms in KIBs.

Bipolar ionomer electrolytes with desirable self-discharge suppression for supercapacitors

Supercapacitors based on electric double layers are prone to serious self-discharge due to electrolyte ion desorption and the resulting energy loss severely limits the application range of supercapacitors.Rational design of polymer electrolyte systems to address this problem shows considerable generality and high feasibility.Herein,we reported a quasi-solid-state bipolar ionomer electrolyte prepared by an in-situ layer-by-layer ultraviolet-curing method,which has an integrated Janus structure with an intermediate binding layer.Based on the synergistic effect of confining impurity ions by ionizable groups and electrostatic repulsion to stabilize the electric double layers and superimposing synergies on both sides,the assembled device not only possesses ideal supercapacitor characteristics,but also exhibits an ultrahigh voltage retention of 71% after being left to stand for 100 h after being fully charged.Furthermore,through the quasi-in-situ energy dispersive X-ray spectroscopy linear scanning,the characteristics of ion diffusion in this ionomer electrolyte are revealed,suggesting its correlation with self-discharge behavior.