Boosting rate performance of layered lithium-rich cathode materials by oxygen vacancy induced surface multicomponent integration

The rapid development of electric vehicles and portable energy storage systems demands improvements in the energy density and cost-effectiveness of lithium-ion batteries,a domain in which Lithium-rich layered cathode(LLO)materials inherently excel.However,these materials face practical challenges,such as low initial Coulombic efficiency,inferior cycle/rate performance,and voltage decline during cycling,which limit practical application.Our study introduces a surface multi-component integration strategy that incorporates oxygen vacancies into the pristine LLO material Li1.2Mn_(0.6)Ni_(0.2)O_(2).This process involves a brief citric acid treatment followed by calcination,aiming to explore rate-dependent degradation behavior.The induced surface oxygen vacancies can reduce surface oxygen partial pressure and diminish the generation of O_(2)and other highly reactive oxygen species on the surface,thereby facilitating the activation of Li ions trapped in tetrahedral sites while overcoming transport barriers.Additionally,the formation of a spinel-like phase with 3D Li+diffusion channels significantly improves Li^(+)diffusion kinetics and stabilizes the surface structure.The optimally modified sample boasts a discharge capacity of 299.5 mA h g^(-1)at a 0.1 C and 251.6 mA h g^(-1)at a 1 C during the initial activation cycle,with an impressive capacity of 222.1 mA h g^(-1)at a 5 C.Most notably,it retained nearly 70%of its capacity after 300 cycles at this elevated rate.This straightforward,effective,and highly viable modification strategy provides a crucial resolution for overcoming challenges associated with LLO materials,making them more suitable for practical application.

A Review:Pre-lithiation Strategies Based on Cathode Sacrificial Lithium Salts for Lithium-Ion Capacitors

Similar to lithium-ion batteries(LIBs),during the first charge/discharge process of lithium-ion capacitors(LICs),lithium-intercalated anodes(e.g.,silicon,graphite,and hard carbon)also exhibit irreversible lithium intercalation behaviors,such as the formation of a solid electrolyte interface(SEI),which will consume Li^(+)in the electrolyte and significantly reduce the electrochemical performance of the system.Therefore,pre-lithiation is an indispensable procedure for LICs.At present,commercial LICs mostly use lithium metal as the lithium source to compensate for the irreversible capacity loss,which has the demerits of operational complexity and danger.However,the pre-lithiation strategy based on cathode sacrificial lithium salts(CSLSs)has been proposed,which has the advantages of low cost,simple operation,environmental protection,and safety.Therefore,there is an urgent need for a timely and comprehensive summary of the application of CSLSs to LICs.In this review,the important roles of pre-lithiation in LICs are detailed,and different pre-lithiation methods are reviewed and compared systematically and comprehensively.After that,we systematically discuss the pre-lithiation strategies based on CSLSs and mainly introduce the lithium extraction mechanism of CSLSs and the influence of intrinsic characteristics and doping amount of CSLSs on LICs performance.In addition,a summary and outlook are conducted,aiming to provide the essential basic knowledge and guidance for developing a new pre-lithiation technology.

Facile construction of a multilayered interface for a durable lithium‐rich cathode

Layered lithium-rich manganese-based oxide(LRMO)has the limitation of inevitable evolution of lattice oxygen release and layered structure transformation.Herein,a multilayer reconstruction strategy is applied to LRMO via facile pyrolysis of potassium Prussian blue.The multilayer interface is visually observed using an atomic-resolution scanning transmission electron microscope and a high-resolution transmission electron microscope.Combined with the electrochemical characterization,the redox of lattice oxygen is suppressed during the initial charging.In situ X-ray diffraction and the high-resolution transmission electron microscope demonstrate that the suppressed evolution of lattice oxygen eliminates the variation in the unit cell parameters during initial(de)lithiation,which further prevents lattice distortion during long cycling.As a result,the initial Coulombic efficiency of the modified LRMO is up to 87.31%,and the rate capacity and long-term cycle stability also improved considerably.In this work,a facile surface reconstruction strategy is used to suppress vigorous anionic redox,which is expected to stimulate material design in high-performance lithium ion batteries.

Electrochemical performance of all-solid lithium ion batteries with a polyaniline film cathode

We have prepared a high-density polyaniline（PANI） paste（50 mg/m L）, with similar physical properties to those of paints or pigments. The synthesis of PANI is confirmed by Fourier transform infrared（FT-IR） spectroscopy. The morphologies of PANI, doped PANI, and doped PANI paste are confirmed by scanning electron microscopy（SEM）. Particles of doped PANI paste are approximately 40–50 nm in diameter, with a uniform and cubic shape. The electrochemical performances of doped PANI paste using both liquid and solid polymer electrolytes have been measured by galvanostatic charge and discharge process. The cell fabricated with doped PANI paste and the solid polymer electrolyte exhibits a discharge capacity of ～87 μAh/cm2（64.0 m Ah/g） at the second cycle and～67 μAh/cm2（50.1 m Ah/g） at the 100 th cycle.

Crosslinked polyacrylonitrile precursor for S@pPAN composite cathode materials for rechargeable lithium batteries

S@pPAN has become promising cathode materials in rechargeable batteries due to its high compressed density,low E/S ratio,no polysulfide dissolution,no self-discharge,and stable cycling.However,it is a big challenge to enhance its sulfur content which determines its practical specific capacity.Herein,we prepare crosslinked PAN as precursor,leading to effective enhancement of sulfur content up to 55 wt%and a reversible specific capacity of 838 mAh g _(composites)^(-1) at 0.2C.Because of the microporous structure and high specific area,crosslinked PAN provides more space to accommodate sulfur molecule and improve the interfacial reaction of S@pPAN as well.This work provides a promising direction to design S@pPAN for lithium sulfur batteries with high energy density.

HIGH TEMPERATURE SUPERCONDUCTOR YBa_2CuaO_(7-x) AS A LITHIUM BATTERY CATHODE

Superconductor YBa_2Cu_3O_(7-x) used as a material for lithium battery was examined in 1NLiClO_4 propylene carbonate/1,2-dimethoxyethane (1:1) solution. YBa_2Cu_3O_(7-x) exhibited 150 mAh/g of discharge capacity at 250 uA/cm^2 discharge current. An ac impedance measurements was carried out, the results have shown that the electrode reaction has low charge-transfer resistance and the chemical diffusion coeffic ient of Li^+ has a value of 10^(-11) cm^2/sec.

THE ELECTROCHEMICAL BEHAVIOUR OF THE NEW VANADIUM BRONZE (Li_3V_5O_(15)) CATHODE IN SECONDARY LITHIUM BATTERY

A new kind of vanadium bronze with rich lithium (Li_5V_5O_(15))was prepared from Li_2CO_3 and V_2O_5 at 680℃ for 24 hrs. The charge and discharge curves of bronze electrode were determined in organic electrolyte. One mole of this material could be incorporated up to 4 mole lithium at 0.2mA/cm^2 and 1.0V cut-off voltage, corresponding capacity about 340Ah/kg. Compared with the cell of Li/Li_(1+x)V_3O_5 the cell of Li/new bronze had higher capacity, smoother discberge curve, but lower plateau voltage (about 1.8V). The cycling behaviour of this material was good. The electrode insertion reaction was controlled by the lithium diffusion process in the bronze. This new bronze could be used for low voltage rechargeable lithium battery.

Critical role of corrosion inhibitors modified by silyl ether functional groups on electrochemical performances of lithium manganese oxides

Lithium manganese oxides(Li Mn2 O4, LMO) have attracted significant attention as important cathode materials for lithium-ion batteries(LIBs), which require fast charging based on their intrinsic electrochemical properties. However, these properties are limited by the rapid fading of cycling retention, particularly at high temperatures, because of the severe Mn corrosion triggered by the chemical reaction with fluoride(F-) species existing in the cell. To alleviate this issue, three types of silyl ether(Si–O)-functionalized task-specific additives are proposed, namely methoxytrimethylsilane, dimethoxydimethylsilane, and trimethoxymethylsilane. Ex-situ NMR analyses demonstrated that the Si-additives selectively scavenged the F-species as Si forms new chemical bonds with F via a nucleophilic substitution reaction due to the high binding affinity of Si with F-, thereby leading to a decrease in the F concentration in the cell. Furthermore, the addition of Si-additives in the electrolyte did not significantly affect the ionic conductivity or electrochemical stability of the electrolyte, indicating that these additives are compatible with conventional electrolytes. In addition, the cells cycled with Si-additives exhibited improved cycling retention at room temperature and 45 °C. Among these candidates, a combination of MTSi and the LMO cathode was found to be the most suitable choice in terms of cycling retention(71.0%), whereas the cell cycled with the standard electrolyte suffered from the fading of cycling retention triggered by Mn dissolution(64.4%). Additional ex-situ analyses of the cycled electrodes using SEM, TEM, EIS, XPS, and ICP-MS demonstrated that the use of Si-additives not only improved the surface stability of the LMO cathode but also that of the graphite anode, as the Si-additives prevent Mn corrosion. This inhibits the formation of cracks on the surface of the LMO cathode, facilitating the formation of a stable solid electrolyte interphase layer on the surface of the graphite anode. Therefore, Si-additives modified by Si–O functional groups can be effectively used to increase the overall electrochemical performance of the LMO cathode material.

One-time sintering process to modify xLi2MnO3(1-x)LiMO2 hollow architecture and studying their enhanced electrochemical performances

To solve the critical problems of lithium rich cathode materials, e.g., structure instability and short cycle life, we have successfully prepared a ZrO2-coated and Zr-doping xLi2MnO3·(1–x)LiMO2 hollow architecture via one-time sintering process. The modified structural materials as lithium-ion cathodes present good structural stability and superior cycle performance in LIBs. The discharge capacity of the ZrO2-coated and Zr-doped hollow pristine is 220 mAh g-1 at the 20th cycle at 0.2 C(discharge capacity loss, 2.7%)and 150 m Ah g-1 at the 100 th cycle at 1 C(discharge capacity loss, 17.7%), respectively. However, hollow pristine electrode only delivers 203 m Ah g-1 at the 20 th cycle at 0.2 C and 124 mAh g-1 at the 100 th cycle at 1 C, respectively, and the corresponding to capacity retention is 92.2% and 72.8%, respectively.Diffusion coefficients of modified hollow pristine electrode are much higher than that of hollow pristine electrode after 100 cycles(approach to 1.4 times). In addition, we simulate the adsorption reaction of HF on the surface of ZrO2-coated layer by the first-principles theory. The calculations prove that the adsorption energy of HF on the surface of ZrO2-coated layer is about-1.699 e V, and the ZrO2-coated layer could protect the hollow spherical xLi2MnO3·(1–x)LiMO2 from erosion by HF. Our results would be applicable for systematic amelioration of high-performance lithium rich material for anode with the respect of practical application.

Enabling Argyrodite Sulfides as Superb Solid-State Electrolyte with Remarkable Interfacial Stability Against Electrodes

While argyrodite sulfides are getting more and more attention as highly promising solid-state electrolytes(SSEs)for solid batteries,they also suffer from the typical sulfide setbacks such as poor electrochemical compatibility with Li anode and high-voltage cathodes and serious sensitivity to humid air,which hinders their practical applications.Herein,we have devised an effective strategy to overcome these challenging shortcomings through modification of chalcogen chemistry under the guidance of theoretical modeling.The resultant Li_(6.25)PS_(4)O_(1.25)Cl_(0.75)delivered excellent electrochemical compatibility with both pure Li anode and high-voltage LiCoO_(2)cathode,without compromising the superb ionic conductivity of the pristine sulfide.Furthermore,the current SSE also exhibited highly improved stability to oxygen and humidity,with further advantage being more insulating to electrons.The remarkably enhanced compatibility with electrodes is attributed to in situ formation of helpful electrolyte–electrode interphases.The formation of in situ anode–electrolyte interphase(AEI)enabled stable Li plating/stripping in the Li|Li_(6.25)PS_(4)O_(1.25)Cl_(0.75)|Li symmetric cells at a high current density up to 1 mA cm^(-2)over 200 h and 2 mA cm^(-2)for another 100 h.The in situ amorphous nano-film cathode–electrolyte interphase(CEI)facilitated protection of the SSE from decomposition at elevated voltage.Consequently,the synergistic effect of AEI and CEI helped the LiCoO_(2)|Li_(6.25)PS_(4)O_(1.25)Cl_(0.75)|Li full-battery cell to achieve markedly better cycling stability than that using the pristine Li_(6)PS_(5)Cl as SSE,at a high area loading of the active cathode material(4 mg cm^(-2))in type-2032 coin cells.This work is to add a desirable SSE in the argyrodite sulfide family,so that high-performance solid battery cells could be fabricated without the usual need of strict control of the ambient atmosphere.

High-voltage LiCoO_(2) cathodes for high-energy-density lithiumion battery

As the earliest commercial cathode material for lithium-ion batteries,lithium cobalt oxide(LiCoO_(2)) shows various advantages,including high theoretical capacity,excellent rate capability,compressed electrode density,etc.Until now,it still plays an important role in the lithium-ion battery market.Due to these advantages,further increasing the charging cutoff voltage of LiCoO_(2)to guarantee higher energy density is an irresistible development trend of LiCoO_(2)cathode materials in the future.However,using high charging cutoff voltage may induce a lot of negative effects,especially the rapid decay of cycle capacity.These are mainly caused by rapid destruction of crystal structure and aggravation of interface side reaction at high voltage during the cycle.Therefore,how to maintain a stable crystal structure of LiCoO_(2)to ensure the excellent long cycle performance at high voltage is a hot research issue in the further application of LiCoO_(2).In this review,we summarized the failure causes and extensive solutions of LiCoO_(2)at high voltage and promoted some new modification strategies.Moreover,the development trend of solving the failure problem of high-voltage LiCoO_(2)in the future such as defect engineering and high-temperature shock technique is also discussed.

Urea combustion synthesis of LiNi_(0.5)Mn_(1.5)O_4 as a cathode material for lithium ion batteries

LiNi0.5Mn1.5O4 was synthesized by combustion synthesis （UCS） using urea as fuel. X-ray diffraction and scanning electron microscope measurements showed that the spinel structure LiNio.sMnl.504 with the space group Fd3m was formed during urea combustion. Both structure and particle size could be adjusted by the amount of urea and the heat treatment temperature used in the UCS. For the LiNi0.5Mn1.5O4 sample prepared with a urea/Li molar ratio of 0.57 and a heat treatment temperature of 900℃, the particle-size distribution fell in a narrow range of 1-2 Dm. Electrochemical tests indicated that this LiNi0.sMnl.504 sample delivered a discharge capacity of 133.6 mAh/g with a capacity retention rate of 99.6% after 20 cycles at 0.5 C.

A novel in situ wrappingapproach leads to long-cycle stable cathode for lithium sulfur (Li-S) batteries

With the support by the National Natural Science Foundation of China,the research group led by Prof.Chen Liwei(陈立桅)at the Suzhou Institute of Nano-Tech and Nano-Bionics(SINANO),Chinese Academy of Sciences in collaboration with Prof.Chen Hongwei(陈宏伟)from Huaqiao University demonstrated a novel in situ wrapping strategy that leads to long-cycle life cathode for Li-S batteries,which was published in Nature Communications(2017,8:479).

Microwave-assisted polyol synthesis of LiMnPO4/C and its use as a cathode material in lithium-ion batteries

We synthesized LiMnPO4/C with an ordered olivine structure by using a microwave-assisted polyol process in 2：15 （v/v） water-diethylene glycol mixed solvents at 130℃ for 30min. We also studied how three surfactants-hexadecyltrimethylammonium bromide, polyvinylpyrrolidone k30 （PVPk30）, and polyvinylpyrrolidone k90 （PVPk90）-affected the structure, morphology, and performance of the prepared samples, characterizing them by using X-ray diffraction, scanning electron microscopy, trans- mission electron microscopy, charge/discharge tests, and electrochemical impedance spectroscopy. All the samples prepared with or without surfactant had orthorhombic structures with the Pnmb space group. Surfactant molecules may have acted as crystal-face inhibitors to adjust the oriented growth, morphol- ogy, and particle size of LiMnPO4. The microwave effects could accelerate the reaction and nucleation rates of LiMnPO4 at a lower reaction temperature. The LiMnPO4/C sample prepared with PVPk30 exhib- ited a flaky structure coated with a carbon layer （-2 nm thick）, and it delivered a discharge capacity of 126 mAh/g with a capacity retention ratio of -99.9% after 50 cycles at 1C. Even at 5C, this sample still had a high discharge capacity of 110 mAh/g, demonstrating good rate performance and cycle performance. The improved performance of LiMnPO4 likely came from its nanoflake structure and the thin carbon layer coating its LiMnPO4 particles. Compared with the conventional polyol method, the microwave-assisted polyol method had a much lower reaction time.

Influence of cerium doping on structure and electrochemical properties of LiNi0.5Mn1.5O4 cathode materials

Pristine LiNi_（0.5）Mn_（1.5）O_4 and cerium doped LiCe_xNi_（0.5–x）Mn_（1.5）O_4（x=0.005, 0.01, 0.02） cathode materials were synthesized by solid-state method. The effect of Ce doping content on structure and electrochemical properties of LiNi_（0.5）Mn_（1.5）O_4 cathode material was systematically investigated. The samples were characterized by X-ray diffraction（XRD）, Fourier transformation infrared spectrometer（FT-IR）, scanning electron microscopy（SEM）, electrochemical impedance spectroscopy（EIS）, cyclic voltammetry（CV） and constant-current charge/discharge tests. The results showed that Ce doping did not change the cubic spinel structure with Fd3m space group, but effectively restrained the formation of Li_xNi_（1–x）O impurity phase. Appropriate Ce doping（x=0.005） could decrease the extent of confusion between lithium ions and transition metal ions, increase the lattice parameter and Ni/Mn disordering degree（Mn^（3＋） content）. The synergic effects of the above factors led to the optimal electrochemical performance of LiCe_（0.005）Ni_（0.495）Mn_（1.5）O_4 sample. The discharge capacity at 10 C rate could reach 115.4 mAh/g, 94.82% of that at 0.2C rate, and the capacity retention rate after 100 cycles at 1C rate could reach 94.51%. However, heavier Ce doping had an adverse effect on the electrochemical properties, which might be due to the lower disordering degree and existence of more CeO_2 secondary phase.

Nd^(3+)-doped Li_3V_2(PO_4)_3 cathode material with high rate capability for Li-ion batteries

A series of Nd^3＋-doped LiNdxV2-x（PO4）3（x = 0.00, 0.02, 0.05, 0.08 or 0.1） composites are synthesized by the rheological phase reaction method. The XRD results indicate that Nd3＋ions have been successfully merged into a lattice structure. Doped samples show good electrochemical performance in high discharge rate and long cycle. In the potential range of 3.0–4.3 V, Li3Nd0.08V1.92（PO4）3exhibits an initial discharge capacity of 115.8 m Ah/g at 0.2 C and retain 80.86% of capacity retention at 2 C in the 51 st cycle.In addition, Li3Nd0.05V1.95（PO4）3holds at 100.4 m Ah/g after 80 cycles at 0.2 C with a capacity retention of92.4%. Finally, the CV test proves that the potential polarization of Li3Nd0.08V1.92（PO4）3decreased compared with the un-doped one.

A nanoporous nitrogen-doped graphene for high performance lithium sulfur batteries

A nanoporous N-doped reduced graphene oxide（p-N-rGO） was prepared through carbothermal reaction between graphene oxide and ammonium-containing oxometalates as sulfur host for Li-S batteries.The p-N-rGO sheets have abundant nanopores with diameters of 10-40 nm and the nitrogen content is 2.65 at%.When used as sulfur cathode,the obtained p-N-rGO/S composite has a high reversible capacity of 1110mAhg^-1 at 1C rate and stable cycling performance with 781.8 mAhg-1 retained after 110 cycles,much better than those of the rGO/S composite.The enhanced electrochemical performance is ascribed to the rational combination of nanopores and N-doping,which provide efficient contact and wetting with the electrolyte,accommodate volume expansion and immobilize polysulfides during cycling.

“Soft” graphene oxide-organopolysulfide nanocomposites for superior pseudocapacitive lithium storage

We report a “soft” graphene oxide-polymeric organosulfide nanocomposite with improved pseudocapacitive performance for high-potential（1–2.8 V vs. Li^0/Li~＋）, high-capacity（278 mAh/g） and stable（500 cycles） lithium storage.

Nanocomposite LiFePO_4·Li_3V_2(PO_4)_3/C synthesized by freeze-drying assisted sol-gel method and its magnetic and electrochemical properties

Nano-sized LiFePO_4·Li_3V_2（PO_4）_3/C was synthesized via a sol-gel route combining with freeze-drying. X-ray diffraction results show that this composite mainly consists of olivine Li Fe PO4 and monoclinic Li3 V2（PO4）3 phases with small amounts of V-doped LiFePO_4 and Fe-doped Li_3V_2（PO_4）_3. The magnetic properties of LiFePO_4·Li_3V_2（PO_4）_3/C are significantly different from LiFePO_4/C. Trace quantities of ferromagnetic impurities and Fe_2P are verified in LiFePO_4/C and LiFePO_4·Li_3V_2（PO_4）_3/C by magnetic tests, respectively. LiFePO_4·Li_3 V_2（PO_4）_3/C possesses relatively better rate capacities and cyclic stabilities, especially at high charge-discharge rates.The initial discharge capacities are 136.4 and 130.0 mA h g^（-1）,and the capacity retentions are more than 98% after 100 cycles at 2C and 5C, respectively, remarkably better than those of LiFePO_4/C. The excellent electrochemical performances are ascribed to the mutual doping of V^（3＋）and Fe^（2＋）, complementary advantages of LiFePO_4 and Li_3V_2（PO_4）_3 phases, the residual high-ordered carbon and Fe_2P with outstanding electric conductivity in the nanocomposite.

Pressure-induced polymerization of butyndioic acid and its Li^＋ salt

Conductive organic polymers with carbonyl groups are considered as potential cathode materials of the Li^＋ battery. Driven by extremely high pressure, 2-butyndioic acid and its Li~＋ salt polymerize at around 4 and 10 GPa, respectively, which demonstrates that pressure-induced polymerization is a robust method for synthesizing substituted polyacetylene-like conductors.