Powder Anode Research Articles

A 3-D binder-free nanoporous anode for a safe and stable charging of lithium ion batteries

Nb2O5 is considered as a promising safe anode material for lithium ion batteries due to its high operating voltage (>1V) that prevents the formation of the solid electrolyte interface; however, the low intrinsic conductivity and pulverization during long-term charge/discharge process limit its practical use. To address these twin adverse issues, we report on the development of a 3-D nanoporous anode that is binder-free by uniformly depositing in-situ orthorhombic Nb2O5 nanocrystals inside the highly conductive carbon nanotube sponge. The end result is a novel 3-D hybrid anode that delivers a maximum reversible capacity of 230mAhg−1 within a voltage window of 1.0–3.0V versus Li/Li+. At a current density of 1Ag−1 (5C), the hybrid anode exhibits a specific capacity of ∼150mAhg−1 with an 82% retention after 1000 charge/discharge cycles, which represents an improved cycling stability and rate capability compared to conventional powder anodes.

Inorganic–organic layer by layer hybrid membranes for lithium–sulfur batteries

Layer by layer assembly of hybrid inorganic/organic membrane encapsulating the sulfur particle impedes polysulfide dissolution or protecting the lithium metal.

Temperature effects on SEI formation and cyclability of Si nanoflake powder anode in the presence of SEI-forming additives

Silicon nanoflake powder (Si LeafPowder®, Si-LP) used as an anode material for lithium-ion batteries has demonstrated superior cycle performance at 30°C in an ethylene-carbonate-based electrolyte solution because its characteristic thin-film-based structure resists pulverization. However, capacity fading was accelerated at 60°C owing to enhanced decomposition of the electrolyte solution and growth of a solid electrolyte interface (SEI), which leads to loss of the electronic contact between Si-LP particles. The SEI-forming additives vinylene carbonate (VC), fluoroethylene carbonate (FEC), and difluoroethylene carbonate improved the capacity retention and Coulombic efficiency at 30°C. Although VC is the most effective additive at 60°C, the discharge capacity was decreased dramatically at −5°C owing to poor ionic and electronic conductivity of the SEI layer formed from the VC-added electrolyte solution. The added FEC produced better performance in a wide temperature range of −5 to 60°C because the SEI layer formed in the FEC-added electrolyte solution had higher ionic and electronic conductivity than that formed from VC, even at −5°C. To obtain Si anodes with high discharge capacity and long cycle life, an appropriate choice of SEI-forming additive taking into account the operating temperature is important.

Electrochemical Properties of Li Metal Batteries with P(PEGMA)-Coated Lithium Trivanadate Cathode and Li Powder Anode

Electrochemical Properties of Li Metal Batteries with P(PEGMA)-Coated Lithium Trivanadate Cathode and Li Powder Anode

Development of plasma sprayed Ni/YSZ anodes for metal supported solid oxide fuel cells

Solid oxide fuel cells (SOFCs) offer a promising technique for producing electricity by clean energy conversion through an electrochemical reaction of fuel and air. Plasma spraying could be a potential manufacturing route for commercial SOFCs, as it provides a distinct advantage especially in case of metal supported cells (MSCs) by allowing rapid processing at relatively low processing temperatures preventing thus the degradation of the metallic substrate. The objective of this work was to develop nickel/yttria stabilised zirconia (Ni/YSZ) anodes with high porosity and homogeneous phase distribution by atmospheric plasma spraying for MSCs. Various feedstock material approaches were explored in this study, both with single injection as well as separate injection of different feedstock materials , and with and without the use of pore formers to create additional porosity. The advantages and issues with each material route were investigated and discussed. It was shown that agglomerated Ni/YSZ/polyester feedstock material resulted in the best distribution of Ni and YSZ in the anode microstructure with homogeneous porosity. Subsequently, the Ni/YSZ/polyester material route with different amounts and size distributions of polyester was chosen to develop anode symmetrical cells using a commercial zirconia sheet as support for electrochemical testing. The Ni/YSZ/polyester anode powder with 10wt.% standard size polyester exhibited the best electrochemical performance. The results show that plasma spraying of the agglomerated Ni/YSZ/polyester could be a promising route to achieve high performance and rapid production anodes without using the carcinogenic nickel oxide.

All solid-state battery using layered oxide cathode, lithium-carbon composite anode and thio-LISICON electrolyte

The investigation of a lithium-carbon composite (Li–C) anode for application in all-solid-state battery, based on (Li2S)0.75-(P2S5)0.25 glassy thio-LISICON electrolyte (Li2S-P2S5) is herein reported. The Li–C anode material is prepared by a mechanochemical, single step synthesis procedure. The Li–C/electrolyte interface is characterized in terms of cyclic voltammetry, electrochemical impedance spectroscopy and galvanostatic cycling in comparison with lithium metal, in order to evaluate the improvements in terms of resistance and lithium stripping deposition ability. Li–C anode powder is pressed into a pellet together with the Li2S-P2S5 electrolyte and Li2ZrO3-coated, Li[Ni0.8Co0.15Al0.05]O2 cathode powder (NCA-LZO), to form a new type of solid-state battery operating at room temperature. The Li–C/Li2S-P2S5/NCA-LZO battery shows remarkable cycling performance under galvanostatic conditions, particularly if compared to a more conventional configuration employing lithium metal as the anode. In addition, the all solid-state battery is characterized at various current densities, showing satisfactory rate capability. Under long term-cycling condition, performed at low current and prolonged to more than 250days, the cell shows a stability over 100cycles without fading. This is considered a remarkable result suggesting the solid-state cell here studied as suitable candidate for efficient and safe energy storage.

Morphology-controlled hydrothermal synthesis of acanthosphere FeCO3 as an excellent performance anode material for lithium ion batteries

A special acanthosphere shaped FeCO3 anode powder material was synthesized successfully through controlled hydrothermal method. It delivered an initial specific discharge-charge capacity of 2100/1087mAhg−1 at a current density of 100mAg−1, and exhibited a high discharge capacity of 238mAhg−1 even at a current of 10,000mAg−1. Furthermore, its capacity would return to the initial capacity level even if the discharge/charge current got back from 10,000mAg−1 to 100mAg−1. Galvanostatic intermittent titration technique (GITT) method was used to investigate the lithiation mechanism of FeCO3 electrode, and results showed that the lithium ion diffusion was driven by two step reactions, the first transition from FeCO3 to Fe and the second reduction of newly grated LiCO3, respectively. High diffusion coefficients of Li ions also give the reason for the high capacity under large rate charge-discharge condition.

Comparision of Electrochemical Properties of Lithium Sulfur Battery with Lithium Foil Anode and Li Powder Anode

Lithium Sulfur (Li-S) battery has a theoretically high specific capacity of 1675 mAh/g, which one of the most promising energy source for electric vehicles (EVs), hybrid electric vehicles (HEVs). However, Li-S batteries have problems resulting from the polysulfides dissolution into the electrolyte, volumetric extension of sulfur and insulating property of elemental sulfur. These causes make the loss of active materials and the capacity fading phenomenon. Even we address the as-mentioned issues, we necessarily encounter the formation of dendrite on the lithium metal anode. In our research, we use a lithium powder as an anode material to suppress the dendritic issue of lithium metal. The examination was conducted by comparing between the lithium foil and lithium powder. The cyclic voltammetry were tested at the scan rate of 0.1mV/s and 0.5mV/s with voltage range of 1.5V to 3.0V. Cells were tested at the current densities of 0.2 C-rate and 0.5 C-rate with 1.7V to 2.8V.

Accelerated desulphurization of waste lead battery paste in a high-gravity rotating packed bed

Pb-paste as the major composition in waste lead acid battery has an important role in the process of lead recycling. However, low liquid-solid mass transfer rates in conventional reactors have a significant limitation for the industrial application of Pb-paste desulphurization using hydrometallurgical process. In this paper, a cost-effective mass-transfer intensified approach for Pb-paste desulphurization with Na2CO3 solution in a rotating packed bed (RPB) reactor was presented. The effects of various variables on the desulphurization degree of PbSO4 were firstly explored. The results indicated that the increases in rotating speed, Na2CO3 concentration and Na2CO3/PbSO4 molar ratio were beneficial to the process. Temperature and reactant flow rate had obvious effects on the desulphurization degree only at a low reactant concentration. Further, the desulphurization processes of the simulated Pb-pastes were comparatively investigated. It was found that the RPB reactor markedly intensified the process in a very short contact time (about 1s), thereby achieving a continuous desulphurization process. Only one cycle liquid-solid contact could make the desulphurization degrees of PbSO4, anode powder and cathode powder reach 99.7%, 98.9% and 97.2%, respectively. Compared to a stirred tank reactor, the desulphurization time was greatly shortened by at least 2 orders of magnitude.

Preparation of Nickel Oxide-Samarium-Doped Ceria Carbonate Composite Anode Powders by Using High-Energy Ball Milling for Low-Temperature Solid Oxide Fuel Cells

The characteristics of the starting powder in powder preparation method are important for enhancement of cell performance. In this study, the composite anode powders of NiO–samarium-doped ceria carbonates (SDCC) were prepared by using different NiO loadings (50–70 wt.%) via high-energy ball milling. The composite anode powders were ball-milled in ethanol at a milling speed of 550 rpm. The obtained NiO–SDCC composite anode powders were characterized by XRD, FTIR, FESEM, and EDS. Results indicate that the composite anode powders demonstrated good chemical compatibility between NiO and SDCC, given that no new phases were detected in the XRD analysis. FTIR spectra confirmed that the composite anode powders contain carbonates in amorphous state after high-energy ball milling. FESEM investigation revealed well-distributed fine particles and significant reduction of particle size at nanoscale compared with the powder prepared using NiO particles as the starting material. EDS mapping verified the homogeneity of the composite powder with good elemental distribution. Thus, high-energy ball milling is an effective method to prepare NiO–SDCC composite anode powders within a relatively short processing time.

Influence of Calcination on the Properties of Nickel Oxide-Samarium Doped Ceria Carbonate (NiO-SDCC) Composite Anodes

Apart from its composition, the starting powder properties such as particle size potentially affect the triple phase boundary and the electrochemical performance. Calcination process has been identified as one of the factors that influence the particle size of the composite anode powders. This study investigates the correlation between calcination temperature and properties (i.e., chemical, physical, and thermal) of NiO–samarium-doped ceria carbonate (SDCC) composite anodes. NiO–SDCC composite anode powder was prepared with NiO and SDCC through high-energy ball milling. The resultant composite powder was subjected to calcination at various temperatures ranging from 600°C to 800°C. Characterizations of the composite anode were performed through X-ray diffraction (XRD), Fourier transform infrared spectroscopy, energy dispersive spectroscopy, field emission scanning electron microscopy (FESEM), thermogravimetric analysis (TGA), dilatometry, and porosity measurements. The composite anodes exhibited good chemical compatibility during XRD after calcination and sintering. The FTIR result verified the existence of carbonates in all the composite anodes. The increment in calcination temperature from 600°C to 800°C resulted in the growth of nanoscale particles, as evidenced by the FESEM micrographs and crystallite size. Nonetheless, the porosity obtained remained within the acceptable range for a good anodic reaction (20% to 40%). The TGA results showed gradual mass loss in the range of 400°C to 600°C (within the low-temperature solid oxide fuel cell region). The composite anodes calcined at 600°C and 700°C revealed a good thermal expansion coefficient that matches that of the SDCC electrolyte.

The Effect of NiO Content on the Physical Properties of NiO–Samarium Doped Ceria Carbonate Composite Anode Powder for Solid Oxide Fuel Cells

The microstructure, specific surface area, and pore size distribution of nickel oxide–samarium doped ceria carbonate (NiO–SDCC) composite anodes were investigated with respect to wt.% NiO. Four types of composite anode powders were prepared by mechanically mixing NiO with SDCC electrolytes at different wt.% (50:50, 60:40, 70:30 and 80:20). XRD results demonstrated that the crystalline phase structure of NiO and SDCC does not show any phase change, but only exhibits the NiO and SDCC interface within the NiO–SDCC composite anode powder. SEM and BET results show that wt.% NiO considerably influenced the particle connectivity between NiO and SDCC, particle size, specific surface area, and pore size distribution. Specific surface area, and pore size increased whereas particle size decreased with an increase in wt.% NiO. The highest surface area (11.9 m2/g) and the largest pore volume (0.14 cm3/g) were obtained for NiO–SDCC (60:40) composite anode powder. Therefore, the composite anode with large specific surface area displays the highest catalytic activity and the lowest interfacial polarization resistance at the anode/electrolyte interface.

Characterization of spent nickel–metal hydride batteries and a preliminary economic evaluation of the recovery processes

Valuable metal materials can be recovered from spent nickel–metal hydride (NiMH) batteries. However, little attention has been paid to the metal compositions of individual components of NiMH batteries, although this is important for the selection of the appropriate recycling process. In this study, NiMH batteries were manually disassembled to identify the components and to characterize the metals in each of these. A preliminary economic analysis was also conducted to evaluate the recovery of valuable metals from spent NiMH batteries using thermal melting versus simple mechanical separation. The results of this study show that metallic components account for more than 60% of battery weight. The contents of Ni, Fe, Co, and rare earth elements (REEs) (i.e., valuable metals of interest for recovery) in a single battery were 17.9%, 15.4%, 4.41%, and 17.3%, respectively. Most of the Fe was in the battery components of the steel cathode collector, cathode cap, and anode metal grid, while Ni (>90%) and Co (>90%) were mainly in the electrode active materials (anode and cathode metal powders). About 1.88 g of REEs (Ce, La, and Y) could be obtained from one spent NiMH battery. The estimated profits from recovering valuable metals from spent NiMH batteries by using thermal melting and mechanical processes are 2,329 and 2,531 USD/ton, respectively, when including a subsidy of 1,710 USD/ton. The findings of this study are very useful for further research related to technical and economic evaluations of the recovery of valuable metals from spent NiMH batteries. Implications: The spent nickel–metal hydride (NiMH) batteries were manually disassembled and their components were identified. The metals account for more than 60% of battery weight, when Ni, Fe, Co, and rare earth elements (REEs) were 17.9%, 15.4%, 4.41%, and 17.3%, respectively, in a single battery. The estimated profits of recovering valuable metals from NiMH batteries by using thermal melting and mechanical processing are 2,329 and 2,531 USD/ton, respectively, when including a subsidy of 1,710 USD/ton. These findings are very useful to develop or select the recovery methods of valuable metals from spent NiMH batteries.

Anthraquinone‐Based Polymer as Cathode in Rechargeable Magnesium Batteries

Mg batteries are a promising battery technology that could lead to safer and significantly less expensive non-aqueous batteries with energy densities comparable or even better than state-of-the-art Li-ion batteries. Although the first prototype Mg battery using stable Mo6S8 as cathode was introduced over fifteen years ago, major challenges remain to be solved. In particular, the design of high energy cathode materials and the development of non-corrosive electrolytes with high oxidative stability are issues that need to be tackled. Herein, we present a new, general, and robust approach towards achieving stable cycling of Mg batteries. The core of our approach is the use of stable polymer cathode and Mg powder anode coupled with non-nucleophilic electrolytes. Our systems exhibit an excellent rate capability and significant improvement in electrochemical stability.

Characterization of MOy–MxCe1−xO2−δ (M: Co, Ni & Cu) nano powders and anode materials for low and intermediate temperature solid oxide fuel cells

The development of new anode materials is necessary for low and intermediate temperature solid oxide fuel cells (SOFCs) to improve fuel cell lifetime and performance and to decrease operating temperature. In this study, new nanocrystalline anode powder materials with the novel composition: MOy–MxCe1−xO2−δ (M = Ni, Co and Cu) were synthesized by glycine nitrate process (GNP). The crystal structure, morphology, specific surface area (SSA), particle size and distribution of the synthesized powders, and cell performance were investigated using various techniques (e.g., BET, SEM, XRD, TEM). The results demonstrated significant improvement on the powder characteristics to optimize the property of the anode materials. The synthesized nano powders consisted of two main phases with fluorite and rock salt crystal structure. The nano scale particle size and distribution ranged from 5 to 600 nm with a high SSA of 14.95–20.50 m2 g−1, which are quite important characteristics for high performance anode materials such as porosity, density and contact surface area. Electrolyte supported single cells having LSM/GDC/ceria-based anode produced from aforementioned nano powders exhibited high performance of 0.35 W cm−2 at 700 °C under 25 ml/min pure and dry methane (CH4) feeding. Dry hydrogen (99.9%) was used as a starting gas to reduce anode layer side for 30 min.

New Generation High Performance Lithium-Ion Capacitor Laminate Cells

In recent years considerable research has been focused on the development of high energy density EC capacitors. Among all the energy storage systems that have been investigated and developed in the last few years, Lithium-ion Capacitors (LICs) have emerged to be one of the most promising because LICs achieve higher energy density than conventional Electric Double-Layer Capacitors (EDLCs), and better power performance than Li-ion batteries (LIBs) as well being capable of long cycle life which is shown in Fig. 1. LICs contain a pre-lithiated LIB anode electrode and an EDLC cathode electrode. Previously, we have reported a LIC with activated carbon (AC) cathode and hard carbon (HC)/stabilized lithium metal powder (SLMP) anode electrodes with high energy density, high power density and long cycle life1-7. From all the study before, we have achieved a high energy density LIC pouch cell4 with an energy density as high as 30 Wh kg-1 but only with a usable specific power of about 1.0 kW kg-1 and a maximum specific power of 2.0 kW kg-1. Therefore in this paper, we wish to report new generation high performance LIC laminate cells with higher power density and longer cycle life by sacrificing the energy density of the cells. The low temperature performance of the LIC laminate cells is also included in this paper. It can be concluded from the following data figures (from Fig. 2 to Fig. 4) that the specific energy and energy density as high as 20 Wh kg-1 and 38 Wh L-1 have been achieved, respectively. The laminate cells obtained a maximum specific power of 7.8 kW kg-1, respectively. The developed LICs can operate in a temperature as wide as from -40 degree C to +70 degree C. After 50,000 cycles, the LIC laminate cells still have 92% of the initial discharge capacity.

Effect of Pth-Coated Li Powder Anode in Lithium Metal Batteries System

The Li metal anode is one of interested electrode which applied on the post-LIB (Li ion battery) system. However the dendrite growth on the Li surface made hard to commercialized Li metal anode battery. In this reason, we fabricated Li powder by Droplet Emulsion Technique (DET) and coated polythiophene (Pth) on the Li powder by polymerization method.[1] The thiophene monomer and FeCl3 was stirred in CHCl3 solution and polymerized by in situ on the surface of lithium powder.[2] This experiment formatted uniformly PTh layer on the Li powder surface. This Pth layer was helpful to suppressed the lithium dendrite growth when Li ion deposited on the Li powder (charge process). To fabricate the electrode Pth-coated lithium powder was placed on the stainless steel (SUS) mesh (15 Φ) and pressed 20 kg cm-2 regularly. Also the LiV3O8 (LVO) was used as cathode electrode because it is non-lithiated material. The cell was assembled in the coin type cell (CR2032) in Dry room. The morphology of lithium dendrite was observed by the FE-SEM, TEM and the coating layer was investigated by NMR and FT-IR. The conductivity of lithium powder anode and polythiophene-coated lithium powder was also measured by impedance analysis. All the cell were charged and discharged to 25% of the theoretical lithium capacity (965 mAhg-1) at 0.2 0.5, 1, 2 C-rate respectively. The result was analyzed EIS and CV. [1] Shin-Kook Kong, Bok-Ki Kim, Woo-Young Yoon, J. Electrochem. Soc, 159 9) A1551-A1553 (2012) [2] Haipeng Guo, Li Liu, Hong, Hong Shu, Xiukang Yang, Zhenhua Yang, Meng Zhou, Jinli Tan, Zichao Yan, Hai Hu, Xianyou Wang, J. Power Sources, 247 (2014) 117-126

New Generation High Performance Lithium-Ion Capacitor Laminate Cells

In recent years considerable research has been focused on the development of high energy density EC capacitors. Among all the energy storage systems that have been investigated and developed in the last few years, Lithium-ion Capacitors (LICs) have emerged to be one of the most promising because LICs achieve higher energy density than conventional Electric Double-Layer Capacitors (EDLCs), and better power performance than Li-ion batteries (LIBs) as well being capable of long cycle life which is shown in Fig. 1. LICs contain a pre-lithiated LIB anode electrode and an EDLC cathode electrode. Previously, we have reported a LIC with activated carbon (AC) cathode and hard carbon (HC)/stabilized lithium metal powder (SLMP) anode electrodes with high energy density, high power density and long cycle life1-7. From all the study before, we have achieved a high energy density LIC pouch cell4 with an energy density as high as 30 Wh kg-1 but only with a usable specific power of about 1.0 kW kg-1 and a maximum specific power of 2.0 kW kg-1. Therefore in this paper, we wish to report new generation high performance LIC laminate cells with higher power density and longer cycle life by sacrificing the energy density of the cells. The low temperature performance of the LIC laminate cells is also included in this paper. It can be concluded from the following data figures (from Fig. 2 to Fig. 4) that the specific energy and energy density as high as 20 Wh kg-1 and 38 Wh L-1 have been achieved, respectively. The laminate cells obtained a maximum specific power of 7.8 kW kg-1, respectively. The developed LICs can operate in a temperature as wide as from -40 degree C to +70 degree C. After 50,000 cycles, the LIC laminate cells still have 92% of the initial discharge capacity.

Erratum to: “Technology for manufacturing lithium-ion (polymer) batteries using powder anode nanocomposite systems”

The formation of powder anode nanocomposite systems via pyrolysis and mechanochemistry and the technology for manufacturing lithium-ion (polymer) batteries based on anode electrodes were considered.

Electrochemical Performance of Gas-Atomized Si-Alloy Anode for Lithium-Ion Battery

Introduction Si is focused as high capacity active anode material of lithium-ion battery. However, the large volume changes that occur during charge-discharge cycles cause cracking and falling conductivity of electrode. In order to prevent from these problems, various materilas that have structure covering Si surface by some substances such as SiOx have been studied1,2. We have improved conductivity of Si anode material by fabricating the unique microstructure that crystalized alloy-matrix phases around Si phases3.Here, the Si-alloy powder was prepared by gas atomization. One of the important features of gas atomization process is to be able to produce quenched powder in large volume. In this study, we investigated influence of Si composition and paticle size of gas-atomized Si-alloys on electrochemical properties for anode material such as cycle stability, initial clulombic efficiency, swelling of electrode during charge-discharge cycles. Experiment Si-alloy powder (d50 = 18 µm) was prepared by gas atomization. Fine powder (d50 = 2~5 µm) was obtained by planetary ball mill. An electrode was prepared by coating slurry of 80 mass% Si-alloy powder, 5 mass% ketjen black and 15 mass% polyamic-acid on SUS foil. The electrode was tested in a 2032-type coin cell assembled using a lithium foil anode, a separator and electrolyte (1M LiPF6 in EC/DEC (1:1 volume ratio)). The charge-discharge performance was evaluated at 25 degrees C and the current density of 0.2 mA (1st cycle), 0.2C-rate (from 2nd cycle to 50th cycle) in the potential range of 0.002-1.0 V vs. Li/Li+. Results and Discussions Fig.1 shows SEM image of Si-Sn-Fe-Cu alloy powder. The microstructure of the powder is composed of three phases (Si, Si-Fe and Sn-Cu phases). It can be seen that the Si phase is surrounded by Si-Fe and Sn-Cu phases. Fig.2 shows cycle life performance of Si-alloy powder anodes having different particle size. When patricle size is large (d50 = 18 µm), the discharge capacity dropped with increasing cycle number. On the other hand, cycle stability of the fine powder (d50 = 2 µm) was drastically improved. Fig.3 shows the relationship between the initial columbic efficiency and the Si composition of the Si-alloy. The initial coulombic efficiency decreaced by the particle size reduction and improved by increasing of the Si contens in the Si-alloy. It was clarified that the particle size and the Si contents in the Si-alloy powder affected the electrochemical performance.