Daniel Buchholz

Extraordinary Performance of Carbon-Coated Anatase TiO2 as Sodium-Ion Anode.

The synthesis of in situ polymer‐functionalized anatase TiO2 particles using an anchoring block copolymer with hydroxamate as coordinating species is reported, which yields nanoparticles (≈11 nm) in multigram scale. Thermal annealing converts the polymer brushes into a uniform and homogeneous carbon coating as proven by high resolution transmission electron microscopy and Raman spectroscopy. The strong impact of particle size as well as carbon coating on the electrochemical performance of anatase TiO2 is demonstrated. Downsizing the particles leads to higher reversible uptake/release of sodium cations per formula unit TiO2 (e.g., 0.72 eq. Na+ (11 nm) vs only 0.56 eq. Na+ (40 nm)) while the carbon coating improves rate performance. The combination of small particle size and homogeneous carbon coating allows for the excellent electrochemical performance of anatase TiO2 at high (134 mAh g−1 at 10 C (3.35 A g−1)) and low (≈227 mAh g−1 at 0.1 C) current rates, high cycling stability (full capacity retention between 2nd and 300th cycle at 1 C) and improved coulombic efficiency (≈99.8%).

Water sensitivity of layered P2/P3-NaxNi0.22Co0.11Mn0.66O2 cathode material

Sodium-based layered oxides undergo several structural changes upon the (de-)sodiation process and reveal a strong tendency towards water intercalation at lower sodium contents. However, valuable information about their handling during the investigation are still rare. Herein, we report an investigation of the water sensitivity of layered NaxNi0.22Co0.11Mn0.66O2 with mixed P2/P3 structure via X-ray diffraction. At lower sodium contents, i.e. below x ≈ 0.33 or above 3.6 V vs. Na/Na+, a strong tendency for the uptake of water is observed, supported by the appearance of new diffraction peaks confirming a dramatically increased interlayer distance. However, at high sodium content (x > 0.33) the material can be processed in open air without major changes.

Layered Na‐Ion Cathodes with Outstanding Performance Resulting from the Synergetic Effect of Mixed P‐ and O‐Type Phases

Herein, the synthesis of new quaternary layered Na‐based oxides of the type NaxMnyNizFe0.1Mg0.1O2 (0.67≤ x ≤ 1.0; 0.5≤ y ≤ 0.7; 0.1≤ z ≤ 0.3) is described. The synthesis can be tuned to obtain P2‐ and O3‐type as well as mixed P‐/O‐type phases as demonstrated by structural, morphological, and electrochemical properties characterization. Although all materials show good electrochemical performance, the simultaneous presence of the P‐ and O‐type phases is found to have a synergetic effect resulting in outstanding performance of the mixed phase material as a sodium‐ion cathode. The mixed P3/P2/O3‐type material, having an average elemental composition of Na0.76Mn0.5Ni0.3Fe0.1Mg0.1O2, overcomes the specific drawbacks associated with the P2‐ and O3‐type materials, allowing the outstanding electrochemical performance. In detail, the mixed phase material is able to deliver specific discharge capacities of up to 155 mAh g−1 (18 mA g−1) in the potential range of 2.0–4.3 V. In the narrower potential range of 2.5–4.3 V the material exhibits high average discharge potential (3.4 V versus Na/Na+), exceptional average coulombic efficiencies (>99.9%), and extraordinary capacity retention (90.2% after 601 cycles). The unexplored class of P‐/O‐type mixed phases introduces new perspectives for the development of layered positive electrode materials and powerful Na‐ion batteries.

Life cycle assessment of sodium-ion batteries

Sodium-ion batteries are emerging as potential alternatives to lithium-ion batteries. This study presents a prospective life cycle assessment for the production of a sodium-ion battery with a layered transition metal oxide as a positive electrode material and hard carbon as a negative electrode material on the battery component level. The complete and transparent inventory data are disclosed, which can easily be used as a basis for future environmental assessments. Na-ion batteries are found to be promising under environmental aspects, showing, per kWh of storage capacity, environmental impacts at the lower end of the range published for current Li-ion batteries. Still significant improvement potential is given, especially by reducing the environmental impacts associated with the hard carbon production for the anode and by reducing the nickel content in the cathode active material. For the hard carbons, the use of organic waste can be considered to be promising in this regard. Nevertheless, when looking at the energy storage capacity over lifetime, achieving a high cycle life and good charge–discharge efficiency is fundamental. This represents the main challenge especially when competing with LFP–LTO type Li-Ion batteries, which already show extraordinarily long lifetimes.

P-type NaxNi0.22Co0.11Mn0.66O2 materials: linking synthesis with structure and electrochemical performance

P-type layered oxides are promising cathode materials for sodium-ion batteries and a wide variety of compounds have been investigated so far. Nevertheless, detailed studies on how to link synthesis temperature, structure and electrochemistry are still rare. Herein, we present a study on P-type NaxNi0.22Co0.11Mn0.66O2 materials, investigating the influence of synthesis temperature on their structure and electrochemical performance. The change of annealing temperature leads to various materials of different morphologies and either P3-type (700 °C), P3/P2-type (750 °C) or P2-type (800–900 °C) structure. Galvanostatic cycling of P3-type materials revealed high initial capacities but also a high capacity fade per cycle leading to a poor long-term cycling performance. In contrast, pure P2-type NaxNi0.22Co0.11Mn0.66O2, synthesized at 800 °C, exhibits lower initial capacities but a stable cycling performance, underlined by a good rate capability, high coulombic efficiencies and high average discharge capacity (117 mA h g−1) and discharge voltage (3.30 V vs. Na/Na+) for 200 cycles.

Pectin, Hemicellulose, or Lignin? Impact of the Biowaste Source on the Performance of Hard Carbons for Sodium-Ion Batteries

Hard carbons are currently the most widely used negative electrode materials in Na-ion batteries. This is due to their promising electrochemical performance with capacities of 200-300 mAh g-1 and stable long-term cycling. However, an abundant and cheap carbon source is necessary in order to comply with the low-cost philosophy of Na-ion technology. Many biological or waste materials have been used to synthesize hard carbons but the impact of the precursors on the final properties of the anode material is not fully understood. In this study the impact of the biomass source on the structural and electrochemical properties of hard carbons is unraveled by using different, representative types of biomass as examples. The systematic structural and electrochemical investigation of hard carbons derived from different sources-namely corncobs, peanut shells, and waste apples, which are representative of hemicellulose-, lignin- and pectin-rich biomass, respectively-enables understanding and interlinking of the structural and electrochemical properties.

The use of protic ionic liquids with cathodes for sodium-ion batteries

Herein, we report for the first time the use of a protic ionic liquid as a component of a new Na-ion battery electrolyte. The protic ionic liquid has been tested in combination with two different types of sodium-ion cathode materials, polyanionic Na3V2(PO4)3 and layered Na0.67Mn0.89Mg0.11O2, in order to reveal its impact on the electrode material electrochemical performance. The results evidence that this novel electrolyte performs very well in combination with a polyanionic electrode material, while it shows poor performance with a layered oxide material.

Aqueous Processing of Na0.44MnO2 Cathode Material for the Development of Greener Na-Ion Batteries

The implementation of aqueous electrode processing of cathode materials is a key for the development of greener Na-ion batteries. Herein, the development and optimization of the aqueous electrode processing for the ecofriendly Na0.44MnO2 (NMO) cathode material, employing carboxymethyl cellulose (CMC) as binder, are reported for the first time. The characterization of such an electrode reveals that the performances are strongly affected by the employed electrolyte solution, especially, the sodium salt and the use of electrolytes additives. In particular, the best results are obtained using the 1 M solution of NaPF6 in EC/DEC (ethylene carbonate/diethyl carbonate) 3:7 (v/v) + 2 wt % FEC (fluoroethylene carbonate). With this electrolyte, the outstanding capacity of 99.7 mA h g-1 is delivered by the CMC-NMO cathode after 800 cycles at a 1C charge/discharge rate. On the basis of this excellent long-term performance, a full sodium cell, composed of a CMC-based NMO cathode and hard carbon from biowaste (corn cob), has been assembled and tested. The cell delivers excellent performances in terms of specific capacity, capacity retention, and long-term cycling stability. After 75 cycles at a C/5 rate, the capacity of the NMO in the full-cell approaches 109 mA h g-1 with a Coulombic efficiency of 99.9%.

Research Update: Hard carbon with closed pores from pectin-free apple pomace waste for Na-ion batteries

Herein, we report a hard carbon derived from industrial bio-waste, i.e., pectin-free apple pomace. The structural, morphological, and electrochemical properties of the hard carbon are reported. The impact of the bio-waste on the closed porosity is discussed, providing valuable insights into the sodium storage mechanism in hard carbons. Most importantly, the hard carbon delivers good electrochemical performance, high specific capacities of 285 mAh g−1, and a very good capacity retention of 96% after 230 cycles at 0.1 C.

Impact of the Acid Treatment on Lignocellulosic Biomass Hard Carbon for Sodium-Ion Battery Anodes

The investigation of phosphoric acid treatment on the performance of hard carbon from a typical lignocellulosic biomass waste (peanut shell) is herein reported. A strong correlation is discovered between the treatment time and the structural properties and electrochemical performance in sodium-ion batteries. Indeed, a prolonged acid treatment enables the use of lower temperatures, that is, lower energy consumption, for the carbonization step as well as improved high-rate performance (122 mAh g-1 at 10 C).