Dual modification of LiNi_(0.83)Co_(0.11)Mn_(0.06)O_(2) cathode materials by K^(+) doping and Li_(3)PO_(4) coating for lithium ions batteries

Li_(3)PO_(4)@Li_(0.99)K_(0.01)Ni_(0.83)Co_(0.11)Mn_(O.06)O_(2)(NCM-KP) cathode powders are synthesized via K^(+)doping in calcination processes and H_3PO_4 coating in sol-gel processes.K^(+) precisely enters into the lattice to widen the(003) plane to 0.4746 nm with a lower cationic disordered degree of 1.87%.Moreover,the surface residual lithium salts are treated by H_3PO_4 to generate a uniform Li_(3)PO_(4) coating layer of approximately 11.41 nm,which completely covers on the surface of secondary spherical particles to improve the interfacial stability.At 25℃,the NCM-KP electrode delivers a discharge specific capacity of 148.9 mAh·g^(-1) with a remarkable capacity retention ratio of 84.1% after 200 cycles at 1.0C and retains a high reversible specific capacity of 154.4 mAh·g^(-1) at 5.0C.Even at 1.0C and 60℃,it can maintain a reversible discharge specific capacity of 114.6 mAh·g^(-1) with 0.21% of capacity decay per cycle after 200 cycles,which is significantly lower than 0.40% for the pristine NCM powders.Importantly,the charge transfer resistance of 238.89 Ω for the NCM-KP electrode is significantly lower than 947.41 Ω for the pristine NCM one by restricting the interfacial side reactions.Therefore,combining K+doping and Li_(3)PO_(4) coating is an effective strategy to enable the significant improvement of the electrochemical property of high-nickel cathode materials,which may be mainly attributed to the widened diffusion pathway and the formed Li_(3)PO_(4) protective layer,thus promoting Li~+diffusion rate and preventing the erosion of HF.

Effects of synthesis conditions on layered Li[Ni_(1/3)Co_(1/3)Mn_(1/3)]O_2 positive-electrode via hydroxide co-precipitation method for lithium-ion batteries

Layered Li[Ni1/3Co1/3Mn1/3]O2 was synthesized with complex metal hydroxide precursors that were prepared by a co-precipitation method.The influence of coordination between ammonia and transition-metal cations on the structural and electrochemical properties of the Li[Ni1/3Co1/3Mn1/3]O2 materials was studied.It is found that when the molar ratio of ammonia to total transition-metal cations is 2.7：1,uniform particle size distribution of the complex metal hydroxide is observed via scanning electron microscopy.The average particle size of Li[Ni1/3Co1/3Mn1/3]O2 materials was measured to be about 500 nm,and the tap-density was measured to be approximately 2.37 g/cm3,which is comparable with that of commercialized LiCoO2.XRD analysis indicates that the presently synthesized Li[Ni1/3Co1/3Mn1/3]O2 has a hexagonal layered-structure.The initial discharge capacity of the Li[Ni1/3Co1/3Mn1/3]O2 positive-electrode material is determined to be 181.5 mA·h/g using a Li/Li[Ni1/3Co1/3Mn1/3]O2 cell operated at 0.1C in the voltage range of 2.8-4.5 V.The discharge capacity at the 50th cycle at 0.5C is 170.6 mA·h/g.

Effects of Al,F dual substitutions on the structure and electrochemical properties of lithium manganese oxide

Spinel LiMn2O4 and F, Al-doped spinel LiAl0.05Mn1.95O3.58F0.02 have been synthesized by a soft chemistry method using adipic acid as the chelating agent. The synthesized spine/materials were characterized by differential thermal analysis （DTA） and thermogravimetery （TG）, X-ray diffraction （XRD）, scanning electron microscopy （SEM）, cyclic voltammetry （CV）, and chargedischarge testing. The results indicate that all the samples have high phase purity, and fluorine is important in controlling the morphology; the doped aluminum enhances the stability of spinel LiMn2O4. The charge-discharge tests indicate that LiAl0.05Mn1.95O4 has high capacity retention, which is 92.60% of the initial after 50 cycles. It is found that the novel compound LiAl0.05Mn1.95O3.98F0.02 with smaller particles can offer much higher capacity, whose initial discharge capacity is 126.5 mAh·g^-1. The cyclic voltammetric experiments disclose the enhanced reversibility of the F, Al^3＋-modified spinel as compared with the undoped spinel.

PNb_(9)O_(25) nanofiber as a high-voltage anode material for advanced lithium ions batteries

If the operating voltage of anode materials is below 1.0 V versus Lit/Li,the side reaction between electrolyte and anode materials will occur extensively.Thus,high-voltage anode materials have aroused interest recently.In this work,we report the preparation of PNb9O25 nanofiber via a facile electrospinning method.The PNb9O25 nanofiber shows the high rate performance and excellent cycling performance when it is used as anode in lithium ions batteries.For instance,the PNb9O25 nanofiber can deliver a capacity of 233,212.1,193.8,and 181.4 mA h g^(-1) at 0.2,1,3,and 6C,respectively.After 1000 cycles,it can reach at 134.3 mA h g^(-1) with capacity retention of 70.9%.Meanwhile,the ex situ X-ray photoelectron spectroscopy technique has been adopted to investigate the evolution in valence state of each element for PNb9O25 nanofiber.In addition,the PNb9O25 nanofiber is chosen as the anode material in lithium ion full cell in this work,demonstrating the potential for practical application.

Phase Equilibria of the Aqueous Systems Containing Lithium and Carbonate Ions

1 Introduction Alkaline lakes are widely distributed in the area of the Qinghai-Tibet Plateau.Most of the salt lakes are famous for their high concentration of lithium,potassium,magnesium,boron(Ma,2000).In recent years,as a new energy material,lithium and its compounds are widely used in the new area,such as aerospace industry,nuclear

Design of multifunctional polymeric binders in silicon anodes for lithium‐ion batteries

Silicon(Si)is a promising anode material for lithium‐ion batteries(LIBs)owing to its tremendously high theoretical storage capacity(4200 mAh g−1),which has the potential to elevate the energy of LIBs.However,Si anodes exhibit severe volume change during lithiation/delithiation processes,resulting in anode pulverization and delamination with detrimental growth of solid electrolyte interface layers.As a result,the cycling stability of Si anodes is insufficient for commercialization in LIBs.Polymeric binders can play critical roles in Si anodes by affecting their cycling stability,although they occupy a small portion of the electrodes.This review introduces crucial factors influencing polymeric binders'properties and the electrochemical performance of Si anodes.In particular,we emphasize the structure–property relationships of binders in the context of molecular design strategy,functional groups,types of interactions,and functionalities of binders.Furthermore,binders with additional functionalities,such as electrical conductivity and self‐healability,are extensively discussed,with an emphasis on the binder design principle.

Multilevel carbon architecture of subnanoscopic silicon for fast‐charging high‐energy‐density lithium‐ion batteries

Silicon(Si)is widely used as a lithium‐ion‐battery anode owing to its high capacity and abundant crustal reserves.However,large volume change upon cycling and poor conductivity of Si cause rapid capacity decay and poor fast‐charging capability limiting its commercial applications.Here,we propose a multilevel carbon architecture with vertical graphene sheets(VGSs)grown on surfaces of subnanoscopically and homogeneously dispersed Si–C composite nanospheres,which are subsequently embedded into a carbon matrix(C/VGSs@Si–C).Subnanoscopic C in the Si–C nanospheres,VGSs,and carbon matrix form a three‐dimensional conductive and robust network,which significantly improves the conductivity and suppresses the volume expansion of Si,thereby boosting charge transport and improving electrode stability.The VGSs with vast exposed edges considerably increase the contact area with the carbon matrix and supply directional transport channels through the entire material,which boosts charge transport.The carbon matrix encapsulates VGSs@Si–C to decrease the specific surface area and increase tap density,thus yielding high first Coulombic efficiency and electrode compaction density.Consequently,C/VGSs@Si–C delivers excellent Li‐ion storage performances under industrial electrode conditions.In particular,the full cells show high energy densities of 603.5 Wh kg^(−1)and 1685.5 Wh L^(−1)at 0.1 C and maintain 80.7%of the energy density at 3 C.

Conductivity and applications of Li-biphenyl-1,2-dimethoxyethane solution for lithium ion batteries

The total conductivity of Li-biphenyl-1,2-dimethoxyethane solution（Li_xBp（DME）_（9.65）, Bp = biphenyl, DME = 1,2-dimethoxyethane, x = 0.25, 0.50, 1.00, 1.50, 2.00） is measured by impedance spectroscopy at a temperature range from 0℃ to 40℃. The Li_（1.50）Bp（DME）_（9.65） has the highest total conductivity 10.7 m S/cm. The conductivity obeys Arrhenius law with the activation energy（E_（a（x=0.50））= 0.014 eV, E_（a（x=1.00））= 0.046 eV）. The ionic conductivity and electronic conductivity of Li_xBp（DME）_（9.65） solutions are investigated at 20℃ using the isothermal transient ionic current（ITIC） technique with an ion-blocking stainless steal electrode. The ionic conductivity and electronic conductivity of Li_（1.00）Bp（DME）_（9.65） are measured as 4.5 mS/cm and 6.6 mS/cm, respectively. The Li_（1.00）Bp（DME）_（9.65） solution is tested as an anode material of half liquid lithium ion battery due to the coexistence of electronic conductivity and ionic conductivity. The lithium iron phosphate（LFP） and Li_（1.5）Al_（0.5）Ti_（1.5）（PO_4）_3（LATP） are chosen to be the counter electrode and electrolyte, respectively. The assembled cell is cycled in the voltage range of 2.2 V-3.75 V at a current density of 50 mA/g. The potential of Li_（1.00）Bp（DME）_（9.65） solution is about 0.3 V vs. Li~＋/Li, which indicates the solution has a strong reducibility. The Li_（1.00）Bp（DME）_（9.65） solution is also used to prelithiate the anode material with low first efficiency, such as hard carbon, soft carbon and silicon.

Vanadium Nitride Nanoparticles as Anode Material for Lithium Ion Hybrid Capacitor Applications

A high production efficiency synthesis method was used to produce a stacked vanadium nitride nanoparticle structure with an inexpensive raw material as an anode material and high surface area polystyrene was used the cathode material for lithium ion hybrid capacitors. The Li-HCs cell displayed an excellent specific capacitance of 64.2 F·g^-1 at a current density of 0.25 A·g^-1 and a wide potential window of 0.01 to 3.5 V. Furthermore, the device exhibited a high energy density of 109.3 W·h·kg^-1 at a power density of 512.3 W·kg^-1 and retained an energy density of 69.2 W·h·kg^-1 at a high power density of 3 498.9 W· kg^-1 at 2 A·g^-1. Due to the short synthesis time and simple raw materials, this method is suitable for industrial production.

Solid–liquid Phase Equilibria in the Aqueous Ternary System Containing Lithium,Potassium,and Sulfate ions at 288.15 K

1 Introduction Salt lakes are widely distributed in the western of China,especially in the area of Qinghai-Xizang(Tibet)Plateau.A series of salt lakes in the Qaidam Basin,located in Qinghai Province,China,is famous for their abundance of lithium,potassium and boron resources(Zheng et al,1988;Deng et al,2012).It is well known that the

Suppress oxygen evolution of lithium-rich manganese-based cathode materials via an integrated strategy

Improving the reversibility of anionic redox and inhibiting irreversible oxygen evolution are the main challenges in the application of high reversible capacity Li-rich Mn-based cathode materials.A facile synchronous lithiation strategy combining the advantages of yttrium doping and LiYO_(2) surface coating is proposed.Yttrium doping effectively suppresses the oxygen evolution during the delithiation process by increasing the energy barrier of oxygen evolution reaction through strong Y–O bond energy.LiYO_(2) nanocoating has the function of structural constraint and protection,that protecting the lattice oxygen exposed to the surface,thus avoiding irreversible oxidation.As an Li^(+) conductor,LiYO_(2) nano-coating can provide a fast Li^(+) transfer channel,which enables the sample to have excellent rate performance.The synergistic effect of Y doping and nano-LiYO_(2) coating integration suppresses the oxygen release from the surface,accelerates the diffusion of Li^(+)from electrolyte to electrode and decreases the interfacial side reactions,enabling the lithium ion batteries to obtain good electrochemical performance.The lithium-ion full cell employing the Y-1 sample(cathode)and commercial graphite(anode)exhibit an excellent specific energy density of 442.9 Wh kg^(-1) at a current density of 0.1C,with very stable safety performance,which can be used in a wide temperature range(60 to-15℃)stable operation.This result illustrates a new integration strategy for advanced cathode materials to achieve high specific energy density.

Enhanced axonal regeneration and functional recovery of the injured sciatic nerve in a rat model by lithium-loaded electrospun nanofibrous scaffolds

Increasing evidence indicates that engineered nerve grafts have great potential for the regeneration of peripheral nerve injuries(PNIs).While most studies have focused only on the topographical features of the grafts,we have considered both the biophysical and biochemical manipulations in our applied nanoscaffold.To achieve this,we fabricated an electrospun nanofibrous scaffold(ENS)containing polylactide nanofibers loaded with lithium(Li)ions,a Wnt/β-catenin signaling activator.In addition,we seeded human adipose-derived mesenchymal stem cells(hADMSCs)onto this engineered scaffold to examine if their differentiation toward Schwann-like cells was induced.We further examined the efficacy of the scaffolds for nerve regeneration in vivo via grafting in a PNI rat model.Our results showed that Li-loaded ENSs gradually released Li within 11 d,at concentrations ranging from 0.02 to(3.64±0.10)mmol/L,and upregulated the expression of Wnt/β-catenin target genes(cyclinD1 and c-Myc)as well as those of Schwann cell markers(growth-associated protein 43(GAP43),S100 calcium binding protein B(S100B),glial fibrillary acidic protein(GFAP),and SRY-box transcription factor 10(SOX10))in differentiated hADMSCs.In the PNI rat model,implantation of Li-loaded ENSs with/without cells improved behavioral features such as sensory and motor functions as well as the electrophysiological characteristics of the injured nerve.This improved function was further validated by histological analysis of sciatic nerves grafted with Li-loaded ENSs,which showed no fibrous connective tissue but enhanced organized myelinated axons.The potential of Li-loaded ENSs in promoting Schwann cell differentiation of hADMSCs and axonal regeneration of injured sciatic nerves suggests their potential for application in peripheral nerve tissue engineering.

Rational design of continuous and short-range lithium ion pathways based on polydopamine-anchored metal-organic frameworks for all-solid-state electrolytes

The immerging three dimensional(3D) metal-organic framework(MOF)-reinforced composite solid-state electrolytes have attracted great interest because of the enhanced ionic conductivity and mechanical properties. However, the defective spatial arrangement of MOFs restricted by fabrication methodology leads to insufficient lithium ion transport in electrolytes. Herein, a 3D interconnected MOF framework tailored for all-solid-state electrolytes is rationally designed by a universal polydopamine(PDA)-engineered "double-sided tape" strategy. The PDA serves as a double-sided tape, firmly adhering on the special single-layer Nylon grid as well as offering uniform nucleation sites to anchor the metal nodes to ensure continuous growth of well-ordered MOFs. Benefiting from the Lewis acid feature of MOFs and its cage effect toward TFSI^(-), a fast and homogeneous lithium ion transport can be achieved through the internal channels within neighboring MOFs and the continuous MOFs/polymer interfaces both along the short-range circumferential boundary of Nylon fiber. The resultant composite electrolytes exhibit high lithium ion conductivity and prominent mechanical properties, rendering excellent cyclic stability whether used in coin or pouch cells. This work demonstrates a widely applicable "double-sided tape"strategy for controllable spatial arrangement of MOF nanoparticles on optional substrates, which provides a scalable approach to rationally construct desired lithium ion pathways within composite electrolytes.

Accelerating lithium ion transport via increasing the entropy of the electrolyte for stable lithium metal batteries

Promoting inorganic-rich solid-electrolyte interphase (SEI) formation by constructing anion-rich solvated structures is a promising strategy for improving the long-term cycling of lithium-metal batteries.However,the increase of anions within the solvated structure inevitably reduces the coordination of Li^(+) with the solvent,which leads to a low lithium diffusion coefficient and a decreased lithium conductivity.Here,high entropy electrolyte is achieved by increasing the molecular diversity in electrolyte.Multiple anions (TFSI^(-),FSI^(-),NO_(3)^(-) and PF_(6)^(-)) presented in entropy electrolyte individually coordinate with Li^(+),creating a diverse and anion-rich solvation structure.The large variety of solvation structures leads to a diversified Li^(+) diffusion barriers in the electrolyte,which results in the increase of channels available for Li^(+) diffusion.Thus,three-dimensional diffusion with high Li^(+) diffusion coefficient occurs in HE electrolytes.Furthermore,the anion-rich solvation structures promote the formation of the inorganic-rich SEI.As a result,over 2000 h of reversible Li plating/stripping with a low overpotential less than 27 mV is achieved in Li||Li cell using electrolyte modified by high-entropy strategy.Besides,the Li||LFP full cell with a negative capacity/positive capacity (N/P) ratio of 4.52 exhibits remarkably enhanced cycling stability,retaining 83.6% of its initial capacity after 150 cycles.This strategy offers a novel approach for accelerating Li^(+) transport kinetics and constructing stable SEI in lithium metal batteries.

Smart materials for safe lithium-ion batteries against thermal runaway

In recent years,the new energy storage system,such as lithium ion batteries(LIBs),has attracted much attention.In order to meet the demand of industrial progress for longer cycle life,higher energy density and cost efficiency,a quantity of research has been conducted on the commercial application of LIBs.However,it is difficult to achieve satisfying safety and cycling performance simultaneously.There may be thermal runaway(TR),external impact,overcharge and overdischarge in the process of battery abuse,which makes the safety problem of LIBs more prominent.In this review,we summarize recent progress in the smart safety materials design towards the goal of preventing TR of LIBs reversibly from different abuse conditions.Benefiting from smart responsive materials and novel structural design,the safety of LIBs can be improved a lot.We expect to provide a comprehensive reference for the development of smart and safe lithium-based battery materials.

Nitrogen⁃doped 3D graphene⁃carbon nanotube network for efficient lithium storage

A 3D nitrogen⁃doped graphene/multi⁃walled carbon nanotube(CS⁃GO⁃NCNT)crosslinked network mate⁃rial was successfully synthesized utilizing chitosan and melamine as carbon and nitrogen sources,concomitant with the incorporation of multi⁃wall carbon nanotubes and employing freeze drying technology.The material amalgamates the merits of 1D/2D hybrid carbon materials,wherein 1D carbon nanotubes confer robustness and expedited elec⁃tron transport pathways,while 2D graphene sheets facilitate rapid ion migration.Furthermore,the introduction of nitrogen heteroatoms serves to furnish additional active sites for lithium storage.When served as an anode material for lithium⁃ion batteries,the CS⁃GO⁃NCNT electrode delivered a reversible capacity surpassing 500 mAh·g^(-1),mark⁃edly outperforming commercial graphite anodes.Even after 300 cycles at a high current density of 1 A·g^(-1),it remained a reversible capacity of up to 268 mAh·g^(-1).

Lignin‐derived carbon with pyridine N‐B doping and a nanosandwich structure for high and stable lithium storage

Biomass‐derived carbon is a promising electrode material in energy storage devices.However,how to improve its low capacity and stability,and slow diffusion kinetics during lithium storage remains a challenge.In this research,we propose a“self‐assembly‐template”method to prepare B,N codoped porous carbon(BN‐C)with a nanosandwich structure and abundant pyridinic N‐B species.The nanosandwich structure can increase powder density and cycle stability by constructing a stable solid electrolyte interphase film,shortening the Li^(+) diffusion pathway,and accommodating volume expansion during repeated charging/discharging.The abundant pyridinic N‐B species can simultaneously promote the adsorption/desorption of Li^(+)/PF_(6)^(−) and reduce the diffusion barrier.The BN‐C electrode showed a high lithium‐ion storage capacity of above 1140 mAh g^(−1) at 0.05 A g^(−1) and superior stability(96.5% retained after 2000 cycles).Moreover,owing to the synergistic effect of the nanosandwich structure and pyridinic N‐B species,the assembled symmetrical BN‐C//BN‐C full cell shows a high energy density of 234.7Wh kg^(−1),high power density of 39.38 kW kg−1,and excellent cycling stability,superior to most of the other cells reported in the literature.As the density functional theory simulation demonstrated,pyridinic N‐B shows enhanced adsorption activity for Li^(+) and PF_(6)^(−),which promotes an increase in the capacity of the anode and cathode,respectively.Meanwhile,the relatively lower diffusion barrier of pyridinic N‐B promotes Li^(+) migration,resulting in good rate performance.Therefore,this study provides a new approach for the synergistic modulation of a nanostructure and an active site simultaneously to fabricate the carbon electrode material in energy storage devices.

Insights on advanced g‐C_(3)N_(4)in energy storage:Applications,challenges,and future

Graphitic carbon nitride(g‐C_(3)N_(4))is a highly recognized two‐dimensional semiconductor material known for its exceptional chemical and physical stability,environmental friendliness,and pollution‐free advantages.These remarkable properties have sparked extensive research in the field of energy storage.This review paper presents the latest advances in the utilization of g‐C_(3)N_(4)in various energy storage technologies,including lithium‐ion batteries,lithium‐sulfur batteries,sodium‐ion batteries,potassium‐ion batteries,and supercapacitors.One of the key strengths of g‐C_(3)N_(4)lies in its simple preparation process along with the ease of optimizing its material structure.It possesses abundant amino and Lewis basic groups,as well as a high density of nitrogen,enabling efficient charge transfer and electrolyte solution penetration.Moreover,the graphite‐like layered structure and the presence of largeπbonds in g‐C_(3)N_(4)contribute to its versatility in preparing multifunctional materials with different dimensions,element and group doping,and conjugated systems.These characteristics open up possibilities for expanding its application in energy storage devices.This article comprehensively reviews the research progress on g‐C_(3)N_(4)in energy storage and highlights its potential for future applications in this field.By exploring the advantages and unique features of g‐C_(3)N_(4),this paper provides valuable insights into harnessing the full potential of this material for energy storage applications.

Recovery of valuable metals from spent lithium ion batteries by smelting reduction process based on FeO-SiO_2-Al_2O_3 slag system

NA novel smelting reduction process based on FeO-SiO2-Al2O3 slag system for spent lithium ion batteries with Al cans was developed, while using copper slag as the only slag former. The feasibility of the process and the mechanism of copper loss in slag were investigated. 98.83% Co, 98.39% Ni and 93.57% Cu were recovered under the optimum conditions of slag former/battery mass ratio of 4.0：1, smelting temperature of 1723 K, and smelting mass ratio of time of 30 min. The FeO-SiO2-Al2O3 slag system for the smelting process is appropriate under the conditions of m（FeO）：m（SiO2）=0.58：1？1.03：1, and 17.19%？21.52% Al2O3 content. The obtained alloy was mainly composed of Fe-Co-Cu-Ni solid solution including small amounts of matte. The obtained slag mainly consisted of fayalite and hercynite. Meanwhile, the mechanism of copper loss is the mechanical entrainment from strip-like fayalite particles in the main form of copper sulfide and metallic copper.

Preparation of uniform flower-like CuO and flower-like CuO/graphene composite and their application in lithium ion batteries

Flower-like CuO and flower-like CuO/graphene composite were prepared successfully by hydrothermal method. They were characterized by X-ray diffraction, scanning electron microscopy, nitrogen adsorption, temperature-programmed reduction, and thermogravimetric analysis. It is found that the flower-like CuO microspheres, which are composed of CuO nanosheets, possess an average diameter of 4.2 μm and a Brunauer–Emmett–Teller surface area of 12.6 m2/g. Compared with the flower-like CuO, the obtained flower-like CuO/graphene composite shows an enhanced electrochemical performance with a higher capacity of 603 mA-h/g at 0.1 C rate and 382 mA-h/g at 1 C rate, and exhibits a better cycle stability with a high capacity retention of 95.5 % after 50 cycles even though at 1 C rate.