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.

An effective strategy for dendrite free Li metal anodes:Nickel foam decorated with high lattice-matching CoN and CoF_(2) nanosheets for dense deposition

The notorious dendrite and infinite volume change seriously restrict the advancement of lithium metal anodes(LMAs),during the long-term process of stripping/plating.Herein,the nanosheets of metal fluoride(CoF_(2))and metal nitride(CoN)with magnificent lithiophilicity on the nickel(Ni)foam are designed as the“regulator”to uniform the Li plating and build stronger solid electrolyte interface(SEI)layer for dendrite free LMAs.The Ni foam offers abundant space to receive deposited Li metal.The CoN nanosheets can guarantee the fast transfer of electrons,which provides a stable interface of Li^(+)reduction.Moreover,the nanosheet structure with lithiophilicity would accelerate the move of Li+and decrease the nucleation barrier,due to the high lattice-matching of Li and CoN.Meanwhile,the CoF_(2) could increase the content of F(LiF)in the SEI layer,which enhances the strength and avoids the destruction of SEI layer.With the cooperation of CoN and CoF_(2),the composited anode(Li/NF@CNCF)exhibits ultra-long cycle performance(more than 1200 h)and fantastic structure stability at 1 mA·cm^(-2) with 1 mAh·cm^(-2).Based on the LiFePO_(4) and Li/NF@CNCF,the full cells deliver excellent specifical capacity and steady coulombic efficiency.The strategy contributes an effective approach to alleviate the issues of lithium metal anodes in the field of LMAs.

Direct synthesis of tin spheres/nitrogen-doped porous carbon composite by self-formed template method for enhanced lithium storage

To inhibit the agglomeration of tin-based nanomaterials and simplify the complicated synthesis process,a facile and eco-friendly self-formed template method is reported to synthesize tin submicron spheres dispersed in nitrogen-doped porous carbon(Sn/NPC)by pyrolysis of a mixture of disodium stannous citrate and urea.The vital point of this strategy is the formation of Na_(2)CO_(3)templates during pyrolysis.This self-formed Na_(2)CO_(3)acts as porous templates to support the formation of NPC.The obtained NPC provides good electronic conductivity,ample defects,and more active sites.Serving as anode for Li-ion batteries,the Sn/NPC electrode obtains a stable discharge capacity of 674.1 mAh/g after 150 cycles at 0.1 A/g.Especially,a high discharge capacity of 331.2 mAh/g can be achieved after 1100 cycles at 3 A/g.Additionally,a full cell coupled with LiCoO_(2)as cathode yields a discharge capacity of 524.8 mAh/g after 150 cycles at 0.1 A/g.In-situ XRD is implemented to investigate the alloying/dealloying reaction mechanisms.Density functional theory calculation ulteriorly explicates that NPC heightens intrinsic electronic conductivity,and NPC especially pyrrolic-N and pyridinic-N doping facilitates the Li-adsorption ability.Climbing image nudged elastic band method reveals low Li~+diffusion energy barrier in presence of N atoms,which accounts for the terrific electrochemical properties of Sn/NPC electrode.