From kröhnkite- to alluaudite-type of structure: novel method of synthesis of sodium manganese sulfates with electrochemical properties in alkali-metal ion batteries (original) (raw)
Materials
After more than 30 years of delay compared to lithium-ion batteries, sodium analogs are now emerging in the market. This is a result of the concerns regarding sustainability and production costs of the former, as well as issues related to safety and toxicity. Electrode materials for the new sodium-ion batteries may contain available and sustainable elements such as sodium itself, as well as iron or manganese, while eliminating the common cobalt cathode compounds and copper anode current collectors for lithium-ion batteries. The multiple oxidation states, abundance, and availability of manganese favor its use, as it was shown early on for primary batteries. Regarding structural considerations, an extraordinarily successful group of cathode materials are layered oxides of sodium, and transition metals, with manganese being the major component. However, other technologies point towards Prussian blue analogs, NASICON-related phosphates, and fluorophosphates. The role of manganese in the...
Nature communications, 2014
Potential applications of sodium-ion batteries in grid-scale energy storage, portable electronics and electric vehicles have revitalized research interest in these batteries. However, the performance of sodium-ion electrode materials has not been competitive with that of lithium-ion electrode materials. Here we present sodium manganese hexacyanomanganate (Na2MnII[MnII(CN)6]), an open-framework crystal structure material, as a viable positive electrode for sodium-ion batteries. We demonstrate a high discharge capacity of 209 mAh g(-1) at C/5 (40 mA g(-1)) and excellent capacity retention at high rates in a propylene carbonate electrolyte. We provide chemical and structural evidence for the unprecedented storage of 50% more sodium cations than previously thought possible during electrochemical cycling. These results represent a step forward in the development of sodium-ion batteries.
Lithium ion batteries : active electrode materials based on manganese dioxide
2018
163 Lithium ion batteries: active electrode materials based on manganese dioxide K. Banov, D. Ivanova, L. Fachikov, V. Kotev, T. Stankulov, B. Banov 1,3 1 Institute of Electrochemistry and Energy Systems, IEES, 1, Acad. G. Bonchev str., bl. 10, 1113 Sofia University of Chemical Technology and Metallurgy – UCTM, bul. “Kl. Ohridski” 8, 1756 Sofia 3 European Polytechnical University – EPU, 23, “St. St. Cyril and Methodius” str., 2300 Pernik 4 Institute of Mechanics, IM, 1, Acad. G. Bonchev str., bl. 4, 1113 Sofia
Manganese Sulfate Precursors by Electrolysis Method
2021
The advancement of science and technology in the field of electronics, particularly in the field of energy storage, is increasing the demand for the use of lithium secondary batteries. The use of manganese dioxide (MnO2) as a lithium battery cathode material is focusing the development of lithium batteries on energy storage capacity. Manganese dioxide was chosen as the cathode material for lithium batteries because it has a high storage capacity of about 615 mAh/g compared to other materials such as graphite which has a storage capacity of 372 mAh/g. MnO2 was synthesized by the electrolysis method from manganese sulfate (MnSO4) precursor which was obtained from the Trenggalek manganese ore leaching process. The electrolysis process was carried out for 5 hours using variations in electrolyte temperature of 30, 40, 50, and 60 C as well as variations in a current of 2, 3, 4, and 5 A to determine the effect of electrolyte temperature and current on mass gain, structural polymorphy, and ...
Combustion-synthesized sodium manganese (cobalt) oxides as cathodes for sodium ion batteries
Journal of Solid State Electrochemistry, 2013
We report on the electrochemical properties of layered manganese oxides, with and without cobalt substituents, as cathodes in sodium ion batteries. We fabricated sub-µm sized particles of Na 0.7 MnO 2+z and Na 0.7 Co 0.11 Mn 0.89 O 2+z via combustion synthesis. X-ray diffraction revealed the same layered hexagonal P2-type bronze structure with high crystallinity for both materials. Potentiostatic and galvanostatic charge/discharge cycles in the range 1.5 V…3.8 V vs. Na Na + were performed to identify potential dependent phase transitions, capacity, and capacity retention. After charging to 3.8 V, both materials had an initial discharge capacity of 138 mA h g -1 at a rate of 0.3 C. For the 20 th cycle those values reduced to 75 mA h g -1 and 92 mA h g -1 for Co-free and Co-doped samples, respectively. Our findings indicate that earlier works probably underestimated the potential of (doped) P2-type Na 0.7 MnO 2+z as cathode material for sodium ion batteries in terms of capacity and cycle stability. Apart from doping a simple optimization parameter seems to be the particle size of the active material.
Electronic and Geometric Structures of Rechargeable Lithium Manganese Sulfate Li2Mn(SO4)2 Cathode
ACS Omega, 2019
Here, we report the use of Li 2 Mn(SO 4) 2 as a potential energy storage material and describe its route of synthesis and structural characterization over one electrochemical cycle. Li 2 Mn(SO 4) 2 is synthesized by ball milling of MnSO 4 •H 2 O and Li 2 SO 4 •H 2 O and characterized using a suite of techniques, in particular, ex situ X-ray diffraction, X-ray photoelectron spectroscopy, and X-ray absorption spectroscopy on the Mn and S K-edges to investigate the electronic and local geometry around the absorbing atoms. The prepared Li 2 Mn-(SO 4) 2 electrodes undergo electrochemical cycles to different potential points on the charge−discharge curve and are then extracted from the cells at these points for ex situ structural analysis. Analysis of X-ray absorption spectroscopy (both near and fine structure part of the data) data suggests that there are minimal changes to the oxidation state of Mn and S ions during charge−discharge cycles. However, X-ray photoelectron spectroscopy analysis suggests that there are changes in the oxidation state of Mn, which appears to be different from the conclusion drawn from X-ray absorption spectroscopy. This difference in results during cycling can thus be attributed to electrochemical reactions being dominant at the surface of the Li 2 Mn(SO 4) 2 particles rather than in the bulk.
Alpha manganese dioxide for lithium batteries: A structural and electrochemical study
Materials Research Bulletin, 1992
A highly crystalline ct-MnO 2 phase has been synthesised by acid treatment of LizMnO 3. A neutron-diffraction study has shown that the stoichiometry of this phase is Ao.36Mn0.9102 (or MnO2o0.2A20) where A refers predominantly to H + ions and a very minor concentration of Li + ions. Heat-treatment at 300°C leaves a virtually anhydrous a-MnO 2 product. The absence of any foreign cation such as K ÷, Na ÷ or Rb ÷ within the channels of the structure has raised the possibility of utilizing the a-MnO z framework as a high performance electrode for secondary lithium cells. Preliminary electrochemical data indicate that capacities in excess of 200 mAh/g are achievable from these a-MnO z electrodes in room-temperature lithium cells. Cyclic voltammograms show that lithium is inserted into a-MnO 2 in a two-step process and that this process Js reversible.
2006
New nanostructured manganese oxy-iodides were prepared by redox reaction of sodium permanganate with lithium iodide in aqueous medium at room temperature. Transmission electron microscopy (TEM) showed that they are nanocrystalline with grain size in the 5–10 nm range. TEM and X-ray absorption confirmed the short-range ordered structure of these compounds, which contain octahedrally coordinated manganese atoms. The electrochemical properties were studied as a function of preparation conditions (Li/Mn ratio, carbon incorporation at the synthesis stage and grinding). Best electrochemical results were obtained either on samples with carbon black incorporated directly in the aqueous reaction medium at the synthesis stage, or on samples with carbon mixed after synthesis, submitted to extensive grinding. Typical capacities in the potential window 1.8–3.8 V are 160 and 130 mAh/g at the 40th and 100th cycle, respectively. Step-potential electrochemical spectroscopy and the evolution of X-ray...
All-manganese-based Li-ion batteries with high rate capability and ultralong cycle life
Nano Energy, 2016
High-rate and long-cycle life Li-ion batteries constructed with all-manganese-based electrode materials have been successfully realized. The key to the success is the facile green synthesis of the anode: MnO@C core-shell nanowires with internal void spaces and a uniform carbon coating shell. The unique onedimensional nano-configuration provides reduced solid-state distance for Li-ion/electron transport, enhanced electrical conductivity for charge transfer, and effectively volumetric accommodation for Li-ion insertion/extraction, thus enabling the MnO@C nanostructures to exhibit high-rate Li-ion storage capacity and long cycling stability. When coupled with a nanostructured LiMn 2 O 4 cathode, the all-manganese-based MnO@C∥LiMn 2 O 4 full cell characterizes a high energy density of 397 Wh kg À 1 , high rate capability (215 Wh kg À 1 at a power density of 6.2 kW kg À 1), and an extremely low decay rate of 0.087% per cycle over 1000 cycles. Combining with additional merits of low cost, eco-friendliness, and safe operation, our design will shed light on fabricating high-performance Li-ion batteries from all manganese-based electrode materials.
A High-Rate Manganese Oxide for Rechargeable Lithium Battery Applications
Journal of The Electrochemical Society, 2001
LixMn0 2 made by ion-exchange of glycine-nitrate combustion synthesis-produced orthorhombic Nao. 44 Mn0 2 (GNP-LixMn0 2) has been cycled in lithiurnlliquid electrolyte cell configurations at room temperature and lithium/polymer cell configurations at 85° C over one hundred times without showing capacity fading or phase conversion to spinel. At 2.5 mA/cm 2 in liquid cells (5C rate) or 1 mA/cm 2 (1.5C rate) in polymer cells, 80-95% of the expected capacity is delivered. The remarkable stability is attributable to the unusual double tunnel structure, which cannot easily undergo rearrangement to spinel. The enhanced rate capability of GNP-LixMn0 2 compared to conventionally prepared materials is attributable to the shorter particle length, which allows faster diffusion of lithium ions along the tunnels.
Chemistry of Materials, 2011
We report on the synthesis and characterization of a new metastable polymorph of Li 2 MnSiO 4 adopting the Pn space group, prepared by ion-exchange from Na 2 MnSiO 4. Density-functional theory methods were used to predict the lattice parameters and atom positions of the new polymorph material and those of Na 2 MnSiO 4 and LiNaMnSiO 4 , allowing their identification by X-ray diffraction profiles, as well as the comparison of the measured and calculated cell parameters. The electrochemical activity of this new polymorph as a cathode material for lithium ion batteries was evaluated in coin cells and compared to that of the thermodynamically stable Pmn2 1 polymorph of Li 2 MnSiO 4 , as well as LiNaMnSiO 4 and Na 2 MnSiO 4. Carbon coating, very vital to the electrochemical activity of the material, was added in situ to the material before ion-exchange because the metastable polymorph converts to the stable polymorph above 370°C, as confirmed by differential scanning calorimetry scans. Both Li 2 MnSiO 4 polymorphs display similar charge−discharge curves, except for a marginally lower lithium extraction voltage during the first charge of the Pn structure that may be due to the presence of sodium ion impurities. A discharge capacity of 110 mA h g −1 is initially observed for both Li 2 MnSiO 4 polymorphs and both exhibit similar capacity fades. LiNaMnSiO 4 , however, yields a stable capacity of 45 mA h g −1 , whereas Na 2 MnSiO 4 yields an initial capacity of 20 mAh g −1 , increasing to 60 mAh g −1 with cycling.
Communications in Physics
Orthorhombic Na 0.44 MnO 2 with an S-shape tunnel structure was successfully synthesized by a hydrothermal method. The Na 0.44 MnO 2 material has lattice parameters of a = 9.0842 A, b = 26.2889Å, and c = 2.8245Å. Scanning electron microscope analysis reveals that the morphologies of Na 0.44 MnO 2 consist of Na 0.44 MnO 2 nanowires with diameters of about 30-50 nm and Na 0.44 MnO 2 particles with the size in the range of 200 to 500 nm. The first charge and discharge capacities of Na 0.44 MnO 2 cathode, at 0.1 C between 2.0-4.0 V, are 66.2 mAh g −1 and 62.7 mAh g −1 , respectively. The Na 0.44 MnO 2 has excellent cycle stability with 85.3% of capacity retention over 50 cycles. The coulombic efficiency of Na 0.44 MnO 2 material is approximately 90% after 70 cycles. It is suggested that the structure of Na 0.44 MnO 2 is stable during cycling and Na 0.44 MnO 2 can be a promising cathode material for sodium ion batteries.
Na 2 MnSiO 4 as an attractive high capacity cathode material for sodium-ion battery
Journal of Power Sources, 2017
is prepared via a modified two-step route. It delivered the highest discharge capacity for a polyanion-based compound. Na 2 MnSiO 4 registered impressive sodium storage performance of 210 mAh g À1 at 0.1 C. Electrolyte additive VC forms a metastable passivation film on electrode surface. The amount of VC added greatly influences electrochemical performance of Na 2 MnSiO 4 .
Chemically oxidized manganese dioxides for lithium secondary batteries
Journal of Power Sources
The specific discharge capacity of ␥-MnO 2 was improved with chemical oxidation and vacuum-drying processes. The intergrowth structure and electrochemical performance were studied by X-ray diffraction and electrochemical measurements; the structure-electrochemical property relationships were clarified. Vacuum-dried ␥-MnO 2 showed structural changes with capacity fade as the temperature increased, while the chemically oxidized ␥-MnO 2 showed no structural change without any capacity fading. The latter material showed a first discharge capacity of 275 mAh g −1 , and a reversible capacity of 250 mAh g −1 with two discharge plateaux after second cycle, which is the highest capacity among the ␥-MnO 2 prepared previously.