Suppressed Internal Intrinsic Stress Engineering in High-Performance Ni-Rich Cathode Via Multi layered In Situ Coating Structure

LiNi_(x)Co_(y)Al_(z)O_(2)(NCA)cathode materials are drawing widespread attention,but the huge gap between the ideal and present cyclic stability still hinders their further commercial application,especially for the Ni-rich LiNi_(x)Co_(y)Al_(z)O_(2)(x>0.8,x+y+z=1)cathode material,which is owing to the structural degradation and particles'intrinsic fracture.To tackle the problems,Li_(0.5)La_(2)Al_(0.5)O_(4)in situ coated and Mn compensating doped multilayer LiNi_(0.82)Co_(0.14)Al_(0.04)O_(2)was prepared.XRD refinement indicates that La-Mn co-modifying could realize appropriate Li/Ni disorder degree.Calculated results and in situ XRD patterns reveal that the LLAO coating layer could effectively restrain crack in secondary particles benefited from the suppressed internal strain.AFM further improves as NCA-LM2 has superior mechanical property.The SEM,TEM,XPS tests indicate that the cycled cathode with LLAO-Mn modification displays a more complete morphology and less side reaction with electrolyte.DEMS was used to further investigate cathode-electrolyte interface which was reflected by gas evolution.NCA-LM2 releases less CO_(2)than NCA-P indexing on a more stable surface.The modified material presents outstanding capacity retention of 96.2%after 100 cycles in the voltage range of 3.0-4.4 V at 1C,13%higher than that of the pristine and 80.8%at 1 C after 300 cycles.This excellent electrochemical performance could be attributed to the fact that the high chemically stable coating layer of Li_(0.5)La_(2)Al_(0.5)O_(4)(LLAO)could enhance the interface and the Mn doping layer could suppress the influence of the lattice mismatch and distortion.We believe that it can be a useful strategy for the modification of Ni-rich cathode material and other advanced functional material.

Tuning Li/Ni mixing by reactive coating to boost the stability of cobalt-free Ni-rich cathode

Cobalt-free cathode materials are attractive for their high capacity and low cost,yet they still encounter issues with structural and surface instability.AlPO_(4),in particular,has garnered attention as an effective stabilizer for bulk and surface.However,the impact of interfacial reactions and elemental interdiffusion between AlPO_(4) and LiNi_(0.95)Mn_(0.05)O_(2) upon sintering on the bulk and surface remains elusive.In this study,we demonstrate that during the heat treatment process,AlPO_(4) decomposes,resulting in Al doping into the bulk of the cathode through elemental interdiffusion.Simultaneously,PO_(4)^(3-)reacts with the surface Li of material to form a Li_3PO_(4) coating,inducing lithium deficiency,thereby increasing Li/Ni mixing.The suitable Li/Ni mixing,previously overlooked in AlPO_(4) modification,plays a pivotal role in stabilizing the bulk and surface,exceeding the synergy of Al doping and Li_3PO_(4) coating.The presence of Ni^(2+)ions in the lithium layers contributes to the stabilization of the delithiated structure via a structural pillar effect.Moreover,suitable Li/Ni mixing can stabilize the lattice oxygen and electrode-electrolyte interface by increasing oxygen removal energy and reducing the overlap between the Ni^(3+/4+)e_g and O^(2-)2p orbitals.These findings offer new perspectives for the design of stable cobalt-free cathode materials.

Achieving a superior Na storage performance of Fe-based Prussian blue cathode by coating perylene tetracarboxylic dianhydride amine

Fe-based Prussian blue(Fe-PB)cathode material shows great application potential in sodium(Na)-ion batteries due to its high theoretical capacity,long cycle life,low cost,and simple preparation process.However,the crystalline water and vacancies of Fe-PB lattice,the low electrical conductivity,and the dissolution of metal ions lead to limited capacity and poor cycling stability.In this work,a perylene tetracarboxylic dianhydride amine(PTCDA)coating layer is successfully fabricated on the surface of Fe-PB by a liquid-phase method.The aminated PTCDA(PTCA)coating not only increases the specific surface area and electronic conductivity but also effectively reduces the crystalline water and vacancies,which avoids the erosion of Fe-PB by electrolyte.Consequently,the PTCA layer reduces the charge transfer resistance,enhances the Na-ion diffusion coefficient,and improves the structure stability.The PTCA-coated Fe-PB exhibits superior Na storage performance with a first discharge capacity of 145.2 mAh g^(−1) at 100 mA g^(−1).Long cycling tests exhibit minimal capacity decay of 0.027%per cycle over 1000 cycles at 1 A g^(−1).Therefore,this PTCA coating strategy has shown promising competence in enhancing the electrochemical performance of Fe-PB,which can potentially serve as a universal electrode coating strategy for Na-ion batteries.

Effect of 10% Si addition on cathodic arc evaporated TiAlSiN coatings

The effect of 10% Si （mole fraction） addition on TiAlSiN coatings was studied. Ti0.5Al0.5N, Ti0.5Al0.4Si0.1N and Ti0.55Al0.35Si0.1N coatings were deposited on WC？Co substrates by cathodic arc evaporation. The microstructure and mechanical properties were characterized by X-ray diffraction （XRD）, X-ray photoelectron spectroscopy （XPS）, scanning electron microscopy （SEM）, nano-indentation measurement and scratch test. The mechanisms of how Si affects the properties and failure modes of TiAlSiN coatings were also discussed. The results show that the addition of 10% Si results in the formation of nc-（Ti,Al,Si）N/a-Si3N4 nano-composite structure. The hardness and toughness of TiAlSiN coatings increase, whereas the coating adhesion strength decreases. Compared with Ti0.55Al0.35Si0.1N coating, Ti0.5Al0.4Si0.1N coating has higher hardness but lower toughness. The dominant failure mode of TiAlN coating is wedging spallation due to low toughness and strong interfacial adhesion. The dominant failure mode of TiAlSiN coatings is buckling spallation due to improved toughness and weakened interfacial adhesion.

Homogenous coating of Li^(+)conductive Li_(5)AlO_(4)on single-crystalline nonstoichiometric Li_(1.04)Ni_(0.92)Al_(0.04)O_(2)for rechargeable lithium-ion batteries

Cobalt-free,nickel-rich LiNi_(1-x)Al_(x)O_(2)(x≤0.1)is an attractive cathode material because of high energy density and low cost but suffers from severe structural degradation and poor rate performance.In this study,we propose a molten salt-assisted synthesis in combination with a Li-refeeding induced aluminum segregation strategy to prepare Li_(5)AlO_(4)-coated single-crystalline slightly Li-rich Li_(1.04)Ni_(0.92)Al_(0.04)O_(2).The symbiotic formation of Li_(5)AlO_(4)from reaction between molten lithium hydroxide and doped aluminum in the bulk ensures a high lattice matching between the Ni-rich oxide and the homogenous conductive Li_(5)AlO_(4)that permits high Li^(+)conductivity.Benefiting from mitigated undesirable side reactions and phase evolution,the Li_(5)AlO_(4)-coated single-crystalline Li_(1.04)Ni_(0.92)Al_(0.04)O_(2)delivers a high specific capacity of220.2 mA h g^(-1)at 0.1 C and considerable rate capability(182.5 mA h g^(-1)at 10 C).Besides,superior capacity retention of 90.8%is obtained at 1/3 C after 100 cycles in a 498.1 mA h pouch full cell.Furthermore,the particulate morphology of Li_(1.04)Ni_(0.92)Al_(0.04)O_(2)remains intact after cycling at a cutoff voltage of 4.3 V,whereas slightly Li-deficient Li_(0.98)Ni_(0.97)Al_(0.05)O_(2)features intragranular cracks and irreversible lattice distortion.The results highlight the value of molten salt-assisted synthesis and Li-refeeding induced elemental segregation strategy to upgrade Ni-based layered oxide cathode materials for advanced Li-ion batteries.

Research and development of 3PP coating steel pipes

The industrial application of an exterior three-layer anticorrosive polypropylene coating system(3PP)on large-diameter(larger than Φ600 mm)steel pipes was developed using an experimental process simulation study and the optimization of raw materials inspection,steel pipe surface pretreatments,and water cooling control on a coating application process.The coating properties meet ISO standard 21809 on buried or submerged 3PP pipelines used in the petroleum and natural gas industries.Differential scanning calorimetry and X-ray diffraction were used to analyze the crystallinities and grain sizes of polypropylene(PP)top coats with different cooling rates.Increasing the melt cooling rate reduces the crystallinity and grain size of the PP top coat and enhances its strength and toughness.

Two-Dimensional Graphitic Carbon-Nitride(g-C_(3)N_(4))-Coated LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2) Cathodes for High-Energy-Density and Long-Life Lithium Batteries

High-capacity nickel-rich layered oxides are promising cathode materials for high-energy-density lithium batteries.However,the poor structural stability and severe side reactions at the electrode/electrolyte interface result in unsatisfactory cycle performance.Herein,the thin layer of two-dimensional(2D)graphitic carbon-nitride(g-C_(3)N_(4))is uniformly coated on the LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)(denoted as NCM811@CN)using a facile chemical vaporization-assisted synthesis method.As an ideal protective layer,the g-C_(3)N_(4)layer effectively avoids direct contact between the NCM811 cathode and the electrolyte,preventing harmful side reactions and inhibiting secondary crystal cracking.Moreover,the unique nanopore structure and abundant nitrogen vacancy edges in g-C_(3)N_(4)facilitate the adsorption and diffusion of lithium ions,which enhances the lithium deintercalation/intercalation kinetics of the NCM811 cathode.As a result,the NCM811@CN-3wt%cathode exhibits 161.3 mAh g^(−1)and capacity retention of 84.6%at 0.5 C and 55°C after 400 cycles and 95.7 mAh g^(−1)at 10 C,which is greatly superior to the uncoated NCM811(i.e.129.3 mAh g^(−1)and capacity retention of 67.4%at 0.5 C and 55°C after 220 cycles and 28.8 mAh g^(−1)at 10 C).The improved cycle performance of the NCM811@CN-3wt%cathode is also applicable to solid–liquid-hybrid cells composed of PVDF:LLZTO electrolyte membranes,which show 163.8 mAh g^(−1)and the capacity retention of 88.1%at 0.1 C and 30°C after 200 cycles and 95.3 mAh g^(−1)at 1 C.

CATHODIC PROCESS AND WEAR RESISTANCE OF ELECTRO-DEPOSITED RE-Ni-W-P-SiC COMPOSITE COATING

Cathodic deposition current density of the composite coatings increases when SiC par-ticles and rare earth (RE) were added in the bath, which is profitable for Ni- W-P alloy to deposit in the cathod, forming Ni-W-P-SiC and RE-Ni-W-P-SiC composite coatings. On the contrary, the addition of PTFE in the bath decreases cathodic deposition current density of the coatings. The current density increases a little when the amount of RE is 7-9g/l; however, the current density increases greatly when the amount of RE is increased to 11-13g/l. Bui ij the amount of RE is raised further, the current density decreases. Hardness and wear resistance of RE-Ni-W-P-SiC composite coating have been studied, and the results show that the hardness and wear resistance of RE-Ni-W-P-SiC composite coating increase with increasing heat treatment tempera-ture, which reach peak values at 400℃; while the hardness and wear resistance of the coating decrease with the rise of heat treated temperature continuously.

Cathodic micro-arc electro-deposition of ZrO_2 coatings in an aqueous solution containing colloidal particles

By a novel technique-cathodic micro-arc electro-deposition (CMED), ZrO_2coatings were deposited on an FeCrAl alloy. Experimental results show that the necessary conditionsfor obtaining ZrO_2 coatings are to apply a pulse peak voltage over a critical value and addmoderate amounts of ZrO_2 colloidal particles and Zr(NO_3)_4 in the aqueous solution. Theas-deposited coatings are porous because hydrogen, water, and other vapors are generated andreleased from the coatings to the solution during the spark reaction. The coatings containmonoclinic and tetragonal crystalline ZrO_2 with certain degree of amorphous structure. Theprocessing parameters and mechanism of CMED were discussed.

The Effect of Annealing under Non-vacuum on the Optical Properties of TiAlN Non-vacuum Solar Selective Absorbing Coating Prepared by Cathodic Arc Evaporation

TiAIN solar selective absorbing coatings which were deposited on 304L stainless steel using cathodic arc evaporation method were annealed under non-vacuum at different temperatures with different times. The optical properties （absorptance and emittance） of the coatings were measured by a spectrophotometer. It was found that, after being annealed for 2 hours at different temperatures, the absorptance of the coatings reached the highest value of 0.92 at 700 ℃ while the emittance got the lowest value of 0.38 at 800 ℃. When the coatings were annealed at 600 ℃ for 24 hours, the optical properties changed to 0.92/0.44 （absorptance/ emittance）. By measuring the structure, morphology, elements and surface roughness of the coatings, it was found that both the elemental composition and the surface roughness of the coatings changed as a result of annealing, and these changes caused the change of the optical properties of the coatings.

An electrochemical method for evaluating the resistance to cathodic disbondment of anti-corrosion coatings on buried pipelines

Methods for evaluating the resistance to cathodic disbondment （RCD） of anti-corrosion coatings on buried pipelines were reviewed. It is obvious that these traditional cathodic disbondment tests （CDT） have some disadvantages and the evaluated results are only simple figures and always rely on the subjective experience of the operator. A new electrochemical method for evaluating the RCD of coatings, that is, the potentiostatic evaluation method （PEM）, was developed and studied. During potentiostatic anodic polarization testing, the changes of stable polarization current of specimens before and after cathodic disbonding （CD） were measured, and the degree of cathodic disbondment of the coating was quantitatively evaluated, among which the equivalent cathodic disbonded distance AD was suggested as a parameter for evaluating the RCD. A series of testing parameters of the PEM were determined in these experiments.

Friction and Wear Performances of Cathodic Arc Ion Plated TiAlSiN Coating under Oil Lubricated Condition

TiAlSiN coating was deposited on H13 hot work mould steel using cathodic arc ion plating（CAIP）. The surface-interface morphologies and phases of the obtained coating were analyzed using field emission scanning electron microscopy（FESEM） and X-ray diffraction（XRD）, respectively, and the morphologies, distributions of chemical elements and profiles of worn tracks were also researched using scanning electron microscopy（SEM）, energy disperse spectroscopy（EDS）, and optical microscope（OM）, respectively. The friction-wear performances of TiAlSiN coating under oil lubricated and dry fiction conditions were investigated, and the wear mechanisms of TiAlSiN coating were discussed. The experimental results show that the coating is primarily composed of（Ti, Al）N, AlTiN, and TiN hard phases, Si_3N_4 exists between the（Ti, Al）N crystal grains, increasing the coating microhardness to 3200 HV. The TiAlSiN coating has excellent performances of reducing friction and wear resistance, the average coefficient of friction（COF） of TiAlSiN coating under oil lubricated condition is only 0.05, lowered than the average COF of 0.211 under dry friction condition, the wear rate decreases by about 81.2% compared with that under dry friction condition. The wear mechanism of TiAlSiN coating under oil lubricated and dry friction conditions is composed of abrasive wear, fatigue wear, and abrasive wear, respectively. The internal friction of oil lubrication is a main factor of decreasing fatigue wear.

Cathodic phosphate coating containing nano zinc particles on magnesium alloy

A technology for preparation of a cathodic phosphate coating mainly containing nano metallic zinc particles and phosphate compounds on magnesium alloy was developed.The influence of cathodic current density on the microstructure of the cathodic phosphate coating was investigated.The results show that the crystals of the coating are finer and the microstructures of the outer surface of the coatings are zigzag at the cathodic density of 0.2-0.5 A/dm^2.The content of nano metallic zinc particles in the coating decreases with the increase of the thickness of the coatings and tends to be zero when the coating thickness is 4.14μm.The cathodic phosphate coating was applied to be a transition coating for improving the adhesion between the paints and the magnesium alloys. The formation mechanism of the cathodic phosphate coating was investigated as well.

Structure and Performance of TiC-containing Diamond-like Carbon Nanocomposite Coatings Deposited by Rectangular Cathodic Arc Ion-plating

TiC-containing diamond-like carbon （TiC-DLC） nanocomposite coatings were deposited by a rectangular cathodic arc ion-plating system using C2H2 as reacting gas. Raman spectroscopy and transmission electron microscopy analysis show that with increasing flow rate of C2H2, the structure of nanocomposite coatings changes from TiC nanograin-containing to graphite nanograin-containing DLC. The harness measurements show that the hardness decreases from 28 GPa to 18 GPa with increasing C2H2 flow rate. The scratch test show that a high critical load （〉40 N） was obtained and exhibited a good adhesion between the coating and the substrate. Wear experiment shows that the friction coefficient of TiC-DLC nanocomposite coatings decreases with increasing C2H2. A low friction coefficient of 0.07 was obtained at 480 sccm C2H2.

Evaluation of Cathodic Arc Deposited Thick CrAlSiN Coatings by Erosion Test

CrAlSiN with thickness up to 16 μm was deposited on tungsten carbide via multi-deposition process by cathode arc deposition technique. Scratch and water-sand jet impingement erosion tests were carried out to evaluate the adhesion by determining the worn surface of the coatings. Results showed that the failure mode of the adhesion can be concluded that the weak bond of each CrAlSiN layer as compared to the strong bond between the coating and substrate. The average surface roughness of the coatings before the erosion test was about the same level. After the erosion test of 30 minutes, the eroded CrAlSiN coatings exhibited improved average surface roughness as compared to the original CrAlSiN coatings. Further increasing the erosion up to 60 minutes, the wear and minor peeling of the CrAlSiN coating between each layer was observed. A further research to improve the bond strength between each layer was needed.

Effect of silane and zirconia on the thermal property of cathodic electrophoretic coating on AZ31 magnesium alloy

Magnesium alloys,the lightest structural metal,are used in the field of aeronautics and astronautics more and more,however they are still limited for the poor corrosion resistant and high temperature property.In order to satisfy the need of long time store and short time operation at elevated temperature,coating with excellent corrosion resistance and thermal resistance was prepared on the surface of Mg alloy AZ31B.The cathodic electrophoretic deposition was applied for the preparation of coating.The bonding of organic electrophoretic deposition coating with substrate was improved using silane pretreatment.Nano-ZrO_(2) powder treated by silane was added into electrophoretic deposition solution.The corrosion resistance property of electrophoretic coating was evaluated using Machu test,and thermal characteristic using the thermal shock experiment and DTA respectively.The morphology of the coating was examined by SEM.It is found that both the corrosion resistant and thermal shock resistant properties can be improved by modifying the Mg specimen with APS silane,while adding nano-ZrO_(2)powder treated by GPS silane to the coating has the optimal effect.And the results also show that the main reason of the coating damage after thermal shock at 400°C or 500°C is mainly for the thermal stress.

Recent progress of surface coating on cathode materials for high-performance lithium-ion batteries

Lithium-ion batteries (LIB) have received substantial attention in the last 10 years,as they offer great promise as power sources that can lead to the electric vehicle (EV) revolution in the next 5 years.Since the cathode serves as a key component in LIB,its properties significantly affect the performance of the whole system.Recently,the cathode surface modification based on coating technique has been widely employed to enhance the electrochemical performances by improving the material conductivity,stabilising the physical structure of materials,as well as preventing the reactions between the electrode and electrolyte.In this work,we reviewed the present of a number of promising cathode materials for Li-ion batteries.After that,we summarized the very recent research progress focusing on the surface coating strategies,mainly including the coating materials,the coating technologies,as well as the corresponding working mechanisms for cathodes.At last,the challenges faced and future guidelines for optimizing cathode materials are discussed.In this study,we propose that the structure of cathode is a crucial factor during the selection of coating materials and technologies.

Structure and Properties of Ti-Si-N Coatings Synthesized by Combining Cathode Arc and Middle-frequency Magnetron Sputtering

Ti-Si-N composite coatings were synthesized on a novel combining cathode and middle-frequency magnetron sputtering system, designed on an industrial scale. Ti was produced from the arc target and Si from magnetron target during deposition. The influences of negative bias voltage and Si content on the hardness and microstructure of the coatings were investigated. The composite coatings prepared under optimized conditions were characterized to be nc-TiN/a-Si3N4 structure with grain sizes of TiN ranging from 8-15 nm and exhibited a high hardness of 40 GPa. The enhancement of the hardness is suggested to be caused by the nanograin-amorphous structure effects.

Stabilized cobalt-free lithium-rich cathode materials with an artificial lithium fluoride coating

Iron-substituted cobalt-free lithium-rich manganese-based materials,with advantages of high specific capacity,high safety,and low cost,have been considered as the potential cathodes for lithium ion batteries.However,challenges,such as poor cycle stability and fast voltage fade during cycling under high potential,hinder these materials from commercialization.Here,we developed a method to directly coat LiF on the particle surface of Li_(1.2)Ni_(0.15)Fe_(0.1)Mn_(0.55O2).A uniform and flat film was successfully formed with a thickness about 3 nm,which can effect-ively protect the cathode material from irreversible phase transition during the deintercalation of Li^(+).After surface coating with 0.5wt%LiF,the cycling stability of Li_(1.2)Ni_(0.15)Fe_(0.1)Mn_(0.55O2) cycled at high potential was significantly improved and the voltage fade was largely suppressed.

ZnS coating of cathode facilitates lean‐electrolyte Li‐S batteries

Tremendous effort has been devoted to lithium‐sulfur batteries,where flooded electrolytes have been employed ubiquitously.The use of lean electrolytes albeit indispensable for practical applications often causes low capacity and fast capacity fading of the sulfur cathode;thus,the electrolyte/sulfur active mass ratios below 5μL/mg have been rarely reported.Herein,we demonstrate that ZnS coating transforms sulfur cathode materials electrolyte‐philic,which tremendously promotes the performance in lean electrolytes.The ZnS‐coated Li2S@graphene cathode delivers an initial discharge capacity of 944mAh/g at an E/S ratio of 2μL/mg at the active mass loading of 5.0 mg Li2S/cm^2,corresponding to an impressive specific energy of 500Wh/kg based on the mass of cathode,electrolyte,and the assumed minimal mass of lithium metal anode.Density functional theory calculations reveal strong binding between ZnS crystals and electrolyte solvent molecules,explaining the better wetting properties.We also demonstrate the reversible cycling of a hybrid cathode of ZnS‐coated Li2S@graphene mixed with VS2 as an additive at an E/AM(active mass)ratio of 1.1μL/mg,equivalent to the specific energy of 432 Wh/kg on the basis of the mass of electrodes and electrolyte.