Mg/Fe site-specific dual-doping to boost the performance of cobalt-free nickle-rich layered oxide cathode for high-energy lithium-ion batteries

Layer-type LiNi0.9Mn0.1O2is promising to be the primary cathode material for lithium-ion batteries(LIBs)due to its excellent electrochemical performance.Unfortunately,the cathode with high nickel content suffers from severely detrimental structural transformation that causes rapid capacity attenuation.Herein,site-specific dual-doping with Fe and Mg ions is proposed to enhance the structural stability of LiNi0.9Mn0.1O2.The Fe3+dopants are inserted into transition metal sites(3b)and can favorably provide additional redox potential to compensate for charge and enhance the reversibility of anionic redox.The Mg ions are doped into the Li sites(3a)and serve as O_(2)^(-)-Mg^(2+)-O_(2)^(-)pillar to reinforce the electrostatic cohesion between the two adjacent transition-metal layers,which further suppress the cracking and the generation of harmful phase transitions,ultimately improving the cyclability.The theoretical calculations,including Bader charge and crystal orbital Hamilton populations(COHP)analyses,confirm that the doped Fe and Mg can form stable bonds with oxygen and the electrostatic repulsion of O_(2)^(-)-O_(2)^(-)can be effectively suppressed,which effectively mitigates oxygen anion loss at the high delithiation state.This dual-site doping strategy offers new avenues for understanding and regulating the crystalline oxygen redox and demonstrates significant potential for designing high-performance cobalt-free nickel-rich cathodes.

A universal multifunctional dual cation doping strategy towards stabilized ultra-high nickel cobalt-free lithium layered oxide cathode

Ultra-high nickel cobalt-free lithium layered oxides are promising cathode material for lithium-ion batteries(LIBs)because of their relatively high capacity and low cost.Nevertheless,the high nickel content would induce bulk structure degradation and interfacial environment deterioration,and the absence of Co element reduces the lithium diffusion kinetics,severely limiting the performance liberation of this kind of cathodes.Herein,a multifunctional Ti/Zr dual cation co-doping strategy has been employed to improve the lithium storage performance of LiNi_(0.9)Mn_(0.1)O_(2)(NM91)cathode.On the one hand,the Ti/Zr co-doping weakens the Li^(+)/Ni^(2+)mixing through magnetic interactions due to the inexistence of unpaired electrons for Ti^(4+)and Zr^(4+),increasing the lithium diffusion rate and suppressing the harmful coexistence of H1 and H2 phases.On the other hand,they enhance the lattice oxygen stability because of the strong Ti-O and Zr-O bonds,inhibiting the undesired H3 phase transition and lattice oxygen loss,improving the bulk structure and cathode-electrolyte interface stability.As a result,the Ti/Zr co-doped NM91(NMTZ)exhibits a 91.2%capacity retention rate after 100 cycles,while that of NM91 is only82.9%.Also,the NMTZ displays better rate performance than NM91 with output capacities of 115 and93 mA h g^(-1)at a high current density of 5 C,respectively.Moreover,the designed NMTZ could enable the full battery to deliver an energy density up to 263 W h kg^(-1),making the ultra-high nickel cobaltfree lithium layered oxide cathode closer to practical applications.

Penetrative and migratory behavior of alkali metal in different binder based TiB_2-C composite cathodes

In electrolyte melts containing K at low temperature, the penetrative and migratory path of alkali metals （K and Na） in pitch, furan, phenolic aldehyde and epoxy based TiB2-C composite cathodes during the electrolysis process were studied by EDS and self-made modified Rapoport apparatus. The electrolysis expansion rates, the diffusion coefficients of the alkali metals and the corrosion rates of the composite cathode were also calculated and discussed. The results show that no matter what kind of binder is used, alkali metals have the same penetrative path in composite cathodes：firstly in pore, then in binder and finally in carbonaceous aggregates. K and Na penetrate into both binder and carbonaceous aggregates, which leads to the expansion of composite cathodes, and K has stronger penetration ability than Na. Electrolysis expansion rate of resin based composite cathode is smaller than that of pitch based composite cathodes, and so do the diffusion coefficient and corrosion rate. Resin based composite cathode has better resistance ability to the penetration of alkali metals than pith based composite cathode, and phenolic aldehyde based composite cathode exhibits the strongest resistance ability. The penetration rate, the diffusion coefficient of alkali metals in phenolic aldehyde based TiB2-C composite cathode and the corresponding corrosion rate are 4.72 mm/h, 2.24×10^-5 cm^2/s and 2.31 mm/a, respectively.

Stabilizing High-Nickel Cathodes via Interfacial Hydrogen Bonding Effects Using a Hydrofluoric Acid-Scavenging Separator

Nickel-rich layered Li transition metal oxides are the most promising cathode materials for high-energydensity Li-ion batteries.However,they exhibit rapid capacity degradation induced by transition metal dissolution and structural reconstruction,which are associated with hydrofluoric acid(HF)generation from lithium hexafluorophosphate decomposition.The potential for thermal runaway during the working process poses another challenge.Separators are promising components to alleviate the aforementioned obstacles.Herein,an ultrathin double-layered separator with a 10 lm polyimide(PI)basement and a 2 lm polyvinylidene difluoride(PVDF)coating layer is designed and fabricated by combining a nonsolvent induced phase inversion process and coating method.The PI skeleton provides good stability against potential thermal shrinkage,and the strong PI-PVDF bonding endows the composite separator with robust structural integrity;these characteristics jointly contribute to the extraordinary mechanical tolerance of the separator at elevated temperatures.Additionally,unique HF-scavenging effects are achieved with the formation of-CO…H-F hydrogen bonds for the abundant HF coordination sites provided by the imide ring;hence,the layered Ni-rich cathodes are protected from HF attack,which ultimately reduces transition metal dissolution and facilitates long-term cyclability of the Ni-rich cathodes.Li||NCM811 batteries(where“NCM”indicates LiNi_(x)Co_(y)Mn_(1-x-y)O_(2))with the proposed composite separator exhibit a 90.6%capacity retention after 400 cycles at room temperature and remain sustainable at 60℃with a 91.4%capacity retention after 200 cycles.By adopting a new perspective on separators,this study presents a feasible and promising strategy for suppressing capacity degradation and enabling the safe operation of Ni-rich cathode materials.

Viability of all-solid-state lithium metal battery coupled with oxide solid-state electrolyte and high-capacity cathode

Owing to the utilization of lithium metal as anode with the ultrahigh theoretical capacity density of 3860 mA h g^(-1)and oxide-based ceramic solid-state electrolytes(SE),e.g.,garnet-type Li7La_(3)Zr_(2)O_(12)(LLZO),all-state-state lithium metal batteries(ASLMBs)have been widely accepted as the promising alternatives for providing the satisfactory energy density and safety.However,its applications are still challenged by plenty of technical and scientific issues.In this contribution,the co-sintering temperature at 500℃is proved as a compromise method to fabricate the composite cathode with structural integrity and declined capacity fading of LiNi_(0.5)Co_(0.2)Mn_(0.3)O_(2)(NCM).On the other hand,it tends to form weaker grain boundary(GB)inside polycrystalline LLZO at inadequate sintering temperature for LLZO,which can induce the intergranular failure of SE during the growth of Li filament inside the unavoidable defect on the interface of SE.Therefore,increasing the strength of GB,refining the grain to 0.4μm,and precluding the interfacial defect are suggested to postpone the electro-chemo-mechanical failure of SE with weak GB.Moreover,the advanced sintering techniques to lower the co-sintering temperature for both NCM-LLZO composite cathode and LLZO SE can be posted out to realize the viability of state-of-the-art ASLMBs with higher energy density as well as the guaranteed safety.

Vapor-grown carbon fibers enhanced sulfur-multi walled carbon nanotubes composite cathode for lithium/sulfur batteries

Vapor-grown carbon fibers （VGCFs） were introduced as conductive additives for sulfur-multiwalled carbon nanotubes （S-MWCNTs） composite cathode of lithium-sulfur batteries. The performance of S-MWCNTs composite cathodes with carbon black and VGCFs as sole conductive additives was investigated using scanning electron microscopy （SEM）, galvanostatic charge-discharge tests and electrochemical impedance spectroscopy （EIS）. The results show that the S-MWCNTs composite cathode with VGCFs displays a network-like morphology and exhibits higher activity and better cycle durability compared with the composite cathode with carbon black, delivering an initial discharge capacity of 1254 mA＆#183;h/g and a capacity of 716 mA＆#183;h/g after 40 cycles at 335 mA/g. The interconnected VGCFs can provide a stable conductive network, suppress the aggregation of cathode materials and residual lithium sulfide and maintain the porosity of cathode, and therefore the electrochemical performance of S-MWCNTs composite cathode is enhanced.

Electrochemical performance of sulfur composite cathode materials for rechargeable lithium batteries

The structure and characteristic of carbon materials have a direct influence on the electrochemical performance of sulfur-carbon composite electrode materials for lithium-sulfur battery. In this paper, sulfur composite has been synthesized by heating a mixture of elemental sulfur and activated carbon, which is characterized as high specific surface area and microporous structure. The composite, contained 70% sulfur, as cathode in a lithium cell based on organic liquid electrolyte was tested at room temperature. It showed two reduction peaks at 2.05 V and 2.35 V, one oxidation peak at 2.4 V during cyclic voltammogram test. The initial discharge specific capacity was 1180.8 mAh g-1 and the utilization of electrochemically active sulfur was about 70.6% assuming a complete reaction to the product of Li2S. The specific capacity still kept as high as 720.4 mAh g^-1 after 60 cycles retaining 61% of the initial discharge capacity.

Hydrothermal synthesis of spindle-like Li_2FeSiO_4-C composite as cathode materials for lithium-ion batteries

In this paper,we report on the preparation of Li2FeSiO4,sintered Li2FeSiO4,and Li2FeSiO4-C composite with spindle-like morphologies and their application as cathode materials of lithium-ion batteries.Spindle-like Li2FeSi04 was synthesized by a facile hydrothermal method with（NH4）2Fe（SO4）2 as the iron source.The spindle-like Li2FeSiO4 was sintered at 600 ℃ for 6 h in Ar atmosphere.Li2FeSiO4-C composite was obtained by the hydrothermal treatment of spindle-like Li2FeSiO4 in glucose solution at 190 ℃ for 3 h.Electrochemical measurements show that after carbon coating,the electrode performances such as discharge capacity and high-rate capability are greatly enhanced.In particular.Li2FeSiO4-C with carbon content of 7.21 wt%delivers the discharge capacities of 160.9 mAh·g-1 at room temperature and 213 mAh·g-1 at45℃（0.1 C）,revealing the potential application in lithium-ion batteries.

Fabrication and performance of La(0.8)Sr(0.2)MnO3/YSZ graded composite cathodes for SOFC

The performance of multi-layer （1 -x）La0.8Sr0.2MnO3/xYSZ graded composite cathodes was studied as electrode materials for intermediate solid oxide fuel cells （SOFC）. The thermal expansion coefficient, electrical conductivity, and electrochemical performance of multi-layer composite cathodes were investigated. The thermal expansion coefficient and electrical conductivity decreased with the increase in YSZ content. The （1 -x）Lao.sSr0.EMnO3/xYSZ composite cathode greatly increased the length of the active triple phase boundary line （TPBL） among electrode, electrolyte, and gas phase, leading to a decrease in polarization resistance and an increase in polarization current density. The polarization current density of the triple-layer graded composite cathode （0.77 A/cm2） was the highest and that of the monolayer cathode （0.13 A/cm2） was the lowest. The polarization resistance （Rp） of the triple-layer graded composite cathode was only 0.182 Ω·cm2 and that of the monolayer composite cathode was 0.323 Ω·cm2. The power density of the triple-layer graded composite cathode was the highest and that of the monolayer composite cathode was the lowest. The triple-layer graded composite cathode had superior performance.

Interface engineering for composite cathodes in sulfide-based all-solid-state lithium batteries

All-solid-state lithium battery(ASLB)based on sulfide-based electrolyte is considered to be a candidate for the next-generation high-energy storage system.Despite the high ionic conductivity of sulfide solid electrolyte,the poor interfacial stability(mechanically and chemically)between active materials and sulfide solid electrolytes in composite cathodes leads to inferior electrochemical performances,which impedes the practical application of sulfide electrolytes.In the past years,various of strategies have been carried out to achieve an interface with low impedance in the composite cathodes.Herein,a review of recent progress of composite cathodes for all-solid-state sulfide-based lithium batteries is summarized,including the interfacial issues,design strategies,fabrication methods,and characterization techniques.Finally,the main challenges and perspectives of composite cathodes for high-performance all-solidstate batteries are highlighted for future development.

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.

Effect of TiB_2 content on resistance to sodium penetration of TiB_2/C cathode composites for aluminium electrolysis

TiB2/C cathode composites with various contents of TiB2 were prepared and their characterizations were observed and compared. The expansion of samples due to sodium and bath penetration was tested with a modified laboratory Rapoport apparatus and the appearances of the cut sections of specimens after electrolysis were studied. The results show that the mass of TiB2/C cathode composites with mass fraction of TiB2 less than 70% appreciably increases, but that of the composites with mass fraction of TiB2 more than 70% decreases slightly after being baked. The resistance to sodium and bath penetration of TiB2/C cathode composites increases with the increase of TiB2 content, especially in the composites with high TiB2 content. TiB2/C cathode composites have high resistance to the penetration of sodium and bath as well as good wettability by molten aluminum, and keep integrality and have little change of appearance after electrolysis, which indicates that TiB2/C cathode composites can be used as inert wettable cathode for aluminum electrolysis.

Facile synthesis and performance of polypyrrole-coated sulfur nanocomposite as cathode materials for lithium/sulfur batteries

In situ chemical oxidation polymerization of pyrrole on the surface of sulfur particles was carried out to synthesize a sulfur/polypyrrole （SIPPy） nanocomposite with core-shell structure. The composite was characterized by elemental analysis, X-ray diffraction, scanning/transmission electron microscopy, and electrochemical measurements. XRD and FTIR results showed that sulfur well dispersed in the core-shell structure and PPy structure was successfully obtained via in situ oxidative polymerization of pyrrole on the surface of sulfur particles. TEM observation revealed that PPy was formed and fixed to the surface of sulfur nanoparticle after polymerization, developing a well-defined core-shell structure and the thickness of PPy coating layer was in the range of 20-30 nm. In the composite, PPy worked as a conducting matrix as well as a coating agent, which confined the active materials within the electrode. Consequently, the as prepared SIPPy composite cathode exhibited good cycling and rate performances for rechargeable lithium/sulfur batteries. The resulting cell containing SIPPy composite cathode yields a discharge capacity of 1039 mAh·g^-1 at the initial cycle and retains 59% of this value over 50 cycles at 0.1 C rate. At 1 C rate, the SIPPy composite showed good cycle stability, and the discharge capacity was 475 mAh·g^-1 after 50 cycles.

Enhancing interfacial stability in solid-state lithium batteries with polymer/garnet solid electrolyte and composite cathode framework

The solid-state lithium battery is considered as an ideal next-generation energy storage device owing to its high safety,high energy density and low cost.However,the poor ionic conductivity of solid electrolyte and low interfacial stability has hindered the application of solid-state lithium battery.Here,a flexible polymer/garnet solid electrolyte is prepared with poly(ethylene oxide),poly(vinylidene fluoride),Li6.75La3 Zr1.75Ta0.25O12,lithium bis(trifluoromethanesulfonyl)imide and oxalate,which exhibits an ionic conductivity of 2.0 ×10^(-4) S cm^(-1) at 55℃,improved mechanical property,wide electrochemical window(4.8 V vs.Li/Li+),enhanced thermal stabilities.Tiny acidic OX was introduced to inhibit the alkalinity reactions between Li6.75La3 Zr1.75Ta0.25O12 and poly(vinylidene fluoride).In order to improve the interfacial stability between cathode and electrolyte,an Al2 O3@LiNi0.5Co0.2Mn0.3O2 based composite cathode framework is also fabricated with poly(ethylene oxide) polymer and lithium salt as additives.The solid-state lithium battery assembled with polymer/garnet solid electrolyte and composite cathode framework demonstrates a high initial discharge capacity of 150.6 mAh g^(-1) and good capacity retention of 86.7% after 80 cycles at 0.2 C and 55℃,which provides a promising choice for achieving the stable electrode/electrolyte interfacial contact in solid-state lithium batteries.

Effect of baking processes on properties of TiB_2/C composite cathode material

Pitch and TiB2/C green composite cathode material were respectively analyzed with simultaneous DSC-TGA, and effects of three baking processes of TiB2/C composite cathode material, i.e. K25, K5 and M5, on properties of TiB2/C composite cathode material were investigated. The results show that thermogravimetrie behavior of pitch and TiB2/C green composite cathode is similar, and appears the largest mass loss rate in the temperature range from 200 to 600 ℃. The bulk density variation of sample K5 before and after baking is the largest （11.9%）, that of sample K25 is the second, and that of sample M5 is the smallest （6.7%）. The crushing strength of sample M5 is the biggest （51.2 MPa）, that of sample K2.5 is the next, and that of sample K5 is the smallest （32.8 MPa）. But, the orders of the electrical resistivity and electrolysis expansion of samples are just opposite with the order of crushing strength. The heating rate has a great impact on the microstructure of sample. The faster the heating rate is, the bigger the pore size and porosity of sample are. Compared with the heating rate between 200 and 600℃ of samples K25 and K5, that of sample M5 is slower and suitable for baking process of TiB2/C composite cathode material.

Structure and Tribological Property of TiBN Nanocomposite Multilayer Synthesized by Ti-BN Composite Cathode Plasma Immersion Ion Implantation and Deposition

A Ti-BN complex cathode is made from Ti and h-BN powders by the powder metallurgy technology, and TiBN coating is obtained by plasma immersion ion implantation and deposition with this Ti-BN composite cathode. The TiBN coating shows a self-forming multilayered nanocomposite structure while with relative uniform elemental distributions. High resolution transmission electron microscopy images reveal that the multilayered structure is derived from different grain sizes in the nanocomposite. Due to the existence of h-BN phase, the friction coefficient of the coating is about 0.25.

Electrochemical performance of La_(1-x)Sr_xCuO_(3-δ)-Sm_(0.15)Ce_(0.85)O_(1.925) composite cathodes in IT-SOFCs

The cathode material La1-xSrxCuO3-δ(x=0.15, 0.2, 0.3, 0.4) was synthesized by a sol-gel method. X-ray diffraction reveals that a single phase of perovskite is formed. The investigation of the electrical properties suggests that La0.7Sr0.3CuO3-δ has the highest electrical conductivity. La0.7Sr0.3CuO3-δ powder was mixed with different amount SDC (Sm0.15Ce0.85O1.925) powder (5wt.%-30wt.%) as composite cathodes. Electrochemical properties of the composite cathodes were researched further. Investigation suggests that the addition of appropriate amount SDC to La0.7Sr0.3CuO3-δ can improve the electrochemical properties and obtain better cathodic performance. Using La0.7Sr0.3CuO3-δ-SDC composite materials as a cathode based on SDC electrolyte, higher current density and power density at intermediate temperatures can be obtained.

Ti_2Ni HYDRIDE COMPOSITE AS HYDROGEN CATHODE FORALKALINE WATER ELECTROLYSIS

A new cathode with Ti2 Ni alloys and Ni/Mo electrocatalyst has been developed for alkaline water electrolysis. The characterization for hydrogen evolution reaction (HER)is carried out in a 30 wt% potassium hydroxide (KOH) solution. The cathode shows a low hydrogen overpotential(η=60 mV at 70℃ in 30 wt% KOH) and ezcellent stability under conditions of continuous electrolysis and intermittent electrolysis with power interruption .

Electrochemical properties of La_(0.8)Sr_(0.2)FeO_(3-δ) based composite cathode for intermediate temperature SOFC

La0.8Sr0.2FeO3-δ is a new kind of cathode material for intermediate SOFC, but its electrochemical activity is relative poor for the lanthanum gallate based solid oxide fuel cell. In this paper, a novel composite cathode of La0.8Sr0.2FeO3-δ/La0.9Sr0.1Ga0.8Mg0.2O3-δ was prepared on the LSGM electrolyte substrate by screen-printing method. The results of cathodic polarization measurements show that the overpotential decreases significantly when the composite cathode is used instead of the La0.8Sr0.2FeO3-δ single layer cathode. The cathodic overpotential of the composite La0.8Sr0.2FeO3-δ/La0.9Sr0.1Ga0.8Mg0.2O3-δ cathode is 150 mV at the current density of 0.2 A·cm-2 at 800 ℃, while the cathodic overpotential of the La0.8Sr0.2FeO3-δ single layer cathode is higher than 260 mV at the same condition. The electrochemical impedance spectroscopy was employed to investigate the polarization resistance of the cathode. The polarization resistance of the composite cathode is 1.20 Ω·cm2 in open circuit condition, while the value of the single La0.8Sr0.2FeO3-δ cathode is 1.235 Ω·cm2.

Composite Cathode Bi_(1.14)Sr_(0.43)O_(2.14)-Ag for Intermediate-temperature Solid Oxide Fuel Cells

Composites consisting of strontium stabilized bismuth oxide （Bi1.14Sr0.43O2.14, SSB） and silver were investigated as cathodes for intermediate-temperature solid oxide fuel cells with doped ceria electrolyte. There were no chemical reactions between the two components. The microstructure of the interfaces between composite cathodes and Ce0.8Sm0.2O1.9 （SDC） electrolytes was examined by scanning electron microscopy （SEM）. Impedance spectroscopy measurements show that the performance of cathode fired at 700 ℃ is the best. When the content of Ag2O is 70 wt%, polarization resistance values for the SSB-Ag cathodes are as low as 0.2 Ωcm^2 at 700℃ and 0.29 Ωcm^2 at 650℃. These results are much smaller than some of other reported composite cathodes on doped ceria electrolyte and indicate that SSB-Ag composite is a potential cathode material for intermediate temperature SOFCs.