Failure mechanism of bulk silicon anode electrodes for lithium-ion batteries

Silicon has been investigated extensively as a promising anode material for rechargeable lithium-ion bat- teries. Understanding the failure mechanism of silicon-based anode electrodes for lithium-ion batteries is essential to solve the problem of low coulombic efficiency and capacity fading on cycling and also to further commercialize this very new energetic material in cells. To reach this goal, the structure changes of bulk silicon particles and electrode after cycling were studied using ex-situ scanning electron microscopy （SEM） and X-ray diffraction （XRD） techniques. The SEM images indicated that the microstructural changes of the bulk silicon particles during cycling led to a layer rupture of the electrode and then the breakdown of the conductive network and the failure of the electrode. The result contributes to the basic understanding of the failure mechanism of a bulk sil- icon anode electrode for lithium-ion batteries.

Effect of modified elastomeric binders on the electrochemical properties of silicon anodes for lithium-ion batteries

Silicon has been investigated intensively as a promising anode material for rechargeable lithium-ion batteries. The choice of a binder is very important to solve the problem of the large capacity fade observed along cycling. The effect of modified elastomeric binders on the electrochemical performance of crystalline nano-silicon powders was studied. Compared with the conventional binder （polyvinylidene fluoride （PVDF））, Si electrodes using the elastomeric styrene butadiene rubber （SBR） and sodium carboxymethyl cellulose （SCMC） com- bined binder show an improved cycling performance. The reversible capacity of the Si electrode with the SCMC/SBR binder is as high as 2221 mA.h/g for 30 cycles in a voltage window between 0.005 and 2 V. The structure changes from SEM images of the silicon electrodes with different binders were used to explore the property improvement.

A high-performance lithium anode based on N-doped composite graphene

Lithium(Li)metal is the most promising electrode for next-gene ration rechargeable batteries.In order to push the commercialization of the lithium metal batteries,a kind of nitrogen(N)-doped composite graphene(NCG)adopted as the Li plating host was prepared to regulate Li metal nucleation and suppress dendrite growth.Furthermore,a new kind of sandwich-type composite lithium metal(STCL)electrode was developed to improve its application.The STCL electrode can be used as convenient as a piece of Li foil but no dendrite growth.In a symmetric battery,the STCL electrode cycled for more than 4500 h with the overpotential of less than 40 mV.And due to the creative design,the STCL promises the Li-S battery with a prolonged cycling lifespan.

Interface stabilization of 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether to high-voltage Li-rich Mn-based layered cathode materials

Non-aqueous electrolyte solvents play a pivotal role in improving the cycling performance of high-voltage Li-rich Mn-based layered cathode materials. In this study, a fluoroether (1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether, TFEPE) was added to 1.2 mol·L^(-1)LiPF_(6)EC/EMC/DEC at different concentrations to synthesize a series of electrolytes for enhancing the cycling performance of highvoltage Li_(1.18)Mn_(0.50)Ni_(0.26)Co_(0.06)O_(2)(LMNC).

Electrochemical properties of high-loading sulfur–carbon materials prepared by in situ generation method

A high sulfur content sulfur–carbon composite was synthesized via in situ generation method in aqueous solution.When the sulfur loading is up to 90%,the electrode still exhibits good cycling performance with a reversible capacity of about 623 mAh·g^(-1)after 100 cycles.To further commercialize the Li–S battery,understanding the capacity degradation mechanism is very essential,especially with a high sulfur loading electrode.To achieve this goal,the electrochemical performance of the high sulfur loading electrode was studied,and the structure change of the electrode after cycling was also examined by ex situ scanning electron microscopy(SEM)and other techniques.The result shows that the Li_(2)S_(2)and Li_(2)S inhomogeneous precipitation contributes to the majority capacity fading of the high sulfur loading Li–S cells.

A scalable synthesis of silicon nanoparticles as high-performance anode material for lithium-ion batteries

In this work, a scalable and cost-effective method including mechanical milling, centrifugation and spray drying was developed to fabricate Si nanoparticles.The synthesized Si nanoparticles show an average size of 62 nm and exhibit a narrow particle size distribution. The influence of particle sizes on electrochemical performance of Si-based electrode was investigated, and it is found that as the particle size decreases in the studied range, the Si particles show a lower specific capacity and a higher irreversible capacity loss(ICL). Furthermore, an oxide layer with thickness of ～3 nm was detected on the surface of the as-received Si nanoparticles, and this layer can be effectively removed by hydrofluoric acid(HF) etching,resulting in much improved electrochemical performance over the as-received samples.

FePO4-coated Li[Li0.2Ni0.13Co0.13Mn0.54]O2 with improved cycling performance as cathode material for Li-ion batteries

Li[Li0.2Ni0.13Coo.13Mn0.54]O2 cathode materials were synthesized by carbonate-based co-precipitation method, and then, its surface was coated by thin layers of FePO4. The prepared samples were characterized by X-ray diffraction （XRD）, field emission scanning electron micro- scope （FESEM）, energy-dispersive spectroscopy （EDS）, and transmission electron microscopy （TEM）. The XRD and TEM results suggest that both the pristine and the coated materials have a hexagonal layered structure, and the FePO4 coating layer does not make any major change in the crystal structure. The FePO4-coated sample exhibits both improved initial discharge capacity and columbic efficiency compared to the pristine one. More significantly, the FePO4 coating layer has a much positive influence on the cycling perfor- mance. The FePO4-coated sample exhibits capacity reten- tion of 82 % after 100 cycles at 0.5℃ between 2.0 and 4.8 V, while only 28 % for the pristine one at the same charge-discharge condition. The electrochemical impe- dance spectroscopy （EIS） results indicate that this improved cycling performance could be ascribed to the presence of FePO4 on the surface of Li[Li0.2Ni0.13Co0.13Mno.54102 par- ticle, which helps to protect the cathode from chemical attacks by HF and thus suppresses the large increase in charge transfer resistance.

Thermal behavior analysis of a pouch type Li[Ni0.7Co0.15Mn0.15]O2-based lithium-ion battery

Since lithium-ion battery with high energy density is the key component for next-generation electrical vehicles, a full understanding of its thermal behaviors at different discharge rates is quite important for the design and thermal management of lithium-ion batteries （LIBs） pack/module. In this work, a 25 Ah pouch type Li[Ni0.7 Co0.15Mn0.15]O2/graphite LIBs with specific energy of 200 Wh.kg-1 were designed to investigate their thermal behaviors, including temperature distribution, heat generation rate, heat capacity and heat transfer coefficient with environment. Results show that the temperature increment of the charged pouch batteries strongly depends on the discharge rate and depth of discharge. The heat generation rate is mainly influenced by the irreversible heat effect, while the reversible heat is important at all discharge rates and contributes much to the middle evolution of the tem- perature during discharge, especially at low rate. Subse- quently, a prediction model with lumped parameters was used to estimate the temperature evolution at different discharge rates of LIBs. The predicted results match well with the experimental results at all discharge rates. Therefore, the thermal model is suitable to predict the average temperature for the large-scale batteries under normal operating conditions.

Crystallinity dependence of electrochemical properties for LiFePO_4

LiFePOa composites were prepared by solid state reactions at different temperatures and time. The crystalline structure and morphology of the composites were analyzed by X-ray diffraction （XRD） and scanning electron microscopy （SEM）, while X-ray absorption spectroscopy （XAS） was employed to characterize the crystallinity. Experimental results show that the electrochemical properties do not monotonously get better with the decrease of particle size and the traditional long reaction time is needless. Moreover, XAS is an effective technique to discover the change in crystallinity.

Improvement of cycle behavior of Si/Sn anode composite supported by stable Si–O–C skeleton

A Si/Sn/SiOC/graphite(SSSG) composite with high efficiency and long-term cycling stability was synthesized by a cost-effective and scalable method, including the processes of mechanical milling and pyrolysis. The composite was characterized by X-ray diffraction(XRD),scanning electron microscope(SEM) and energy dispersive X-ray spectrometry(EDX). The electrochemical properties were investigated until the 25th cycle. As a result, the SSSG composite anode exhibits excellent long-term cycling stability and capacity. Such SSSG composite anode shows excellent cycling stability with a specific capacity of 568.2 mAh·g^(-1) and ~80% capacity retention over 25 cycles at 0.3C rate. The reasons for good electrochemical characteristics are considered that the SiOC net with favorable chemical stability acts as a skeleton to support and segregate Si/Sn nanostructures, and the graphitic mixing in the composite is used as conductive material to enhance the electrical conductivity in this composite. The results suggest that the design of this new structure has the potential to provide a way for the other functional composite materials.

Electrochemical preparation of silicon nanowires from porous Ni/SiO2 blocks in molten CaCl2

Silicon nanowires(SiNWs)with diameter distributions ranging from 80 to 350 nm were prepared by electrochemical reduction of Ni/SiO2 in molten CaCl2.The effect of the content of nickel additives on the morphology of produced silicon was investigated.Large quantities of SiNWs are obtained by the electrochemical reduction of Ni/SiO2 blocks with SiO2 to Ni molar ratio of 20 and 10.Nickel additives repress the growth of irregular branches and promote longitudinal growth of SiNWs.Wire morphologies and surfaces are influenced by the electrolysis temperature.SiNWs become thicker with the increase of the electrolysis temperature.The optimum temperature to prepare single crystal SiNWs with high aspect ratio and extraordinary surface quality seems to be 1173 K.The amorphous layer of the silicon nanowire is thinner compared to the SiNWs obtained from the pure SiO2 pellets.The produced SiNWs show a photoluminescence emission peak at about 758 nm at room temperature.This work demonstrates the potentiality for the electrochemical reduction process to obtain large quantities of SiNWs with high quality.

Lithium-ion cell inconsistency analysis based on three-parameter Weibull probability model

The inconsistency of lithium-ion cells degrades battery performance,lifetime and even safety.The complexity of the cell reaction mechanism causes an irregular asymmetrical distribution of various cell parameters,such as capacity and internal resistance,among others.In this study,the Newman electrochemical model was used to simulate the 1 C discharge curves of 100 LiMn2 O4 pouch cells with parameter variations typically produced in manufacturing processes,and the three-parameter Weibull probability model was used to analyze the dispersion and symmetry of the resulting discharge voltage distributions.The results showed that the dispersion of the voltage distribution was related to the rate of decrease in the discharge voltage,and the symmetry was related to the change in the rate of voltage decrease.The effect of the cells’capacity dominated the voltage distribution thermodynamically during discharge,and the phase transformation process significantly skewed the voltage distribution.The effects of the ohmic drop and polarization voltage on the voltage distribution were primarily kinetic.The presence of current returned the right-skewed voltage distribution caused by phase transformation to a more symmetrical distribution.Thus,the Weibull parameters elucidated the electrochemical behavior during the discharge process,and this method can guide the prediction and control of cell inconsistency,as well as detection and control strategies for cell management systems.

Phase formation and crystallization of LiMn_(x)Fe_(1-x)PO_(4)-C olivine material with different Mn^(2+)contents fabricated at lower calcination temperatures

LiMn_(x)Fe_(1-x)PO_(4)-C cathode materials for lithium ion batteries were synthesized via solid-state method using Li_(2)CO_(3),MnCO_(3),NH_(4)H_(2)PO_(4),FePO_(4) and sucrose as starting raw materials,followed by high-temperature reduction-annealing.A series of calcination experiments at different temperatures reveal that Mn^(2+)-containing materials exhibit a lower temperature for olivine phase formation,for example LiMn_(0.5)Fe_(0.5)PO_(4) olivine phase forms at 275℃,while manganese-free crystalline LiFePO_(4) generally forms at the required temperature of 350℃.Increasing Mn^(2+) content is found to enhance crystallization degree of LiMn_(x)Fe_(1-x)PO_(4) material prepared at lower calcination temperatures.X-ray photoelectron spectroscopy(XPS)results confirm that Mn valence state(+2)remains unchanged up to~250℃ when calcined in ambient atmosphere.The above-mentioned beneficial effect of manganese on phase formation and crystallization of olivine can be well attributed to the stable nature of Mn^(2+)and its strong propensity to form olivine phases.