Chemical Ion Exchange Research Articles

Microbe-assisted phytoremediation for sustainable management of heavy metal in wastewater - A green approach to escalate the remediation of heavy metals.

Water pollution from Heavy metal (HM) contamination poses a critical threat to environmental sustainability and public health. Industrial activities have increased the presence of HMs in wastewater, necessitating effective remediation strategies. Conventional methods like chemical precipitation, ion exchange, adsorption, and membrane filtration are widely used but possess various limitations. These include high costs, environmental impacts, and the potential for generating secondary pollutants, highlighting the need for sustainable alternatives. Phytoremediation, enhanced by microbial interactions, offers an eco-friendly solution to this issue. The unique physiological and biochemical traits of plants, combined with microbial metabolic capabilities, enable efficient uptake and detoxification of HMs. Microbial enzymes play a crucial role in these processes by breaking down complex compounds, enhancing HM bioavailability, and facilitating their conversion into less toxic forms. Synergistic interactions between root-associated microbes and plants further improves metal absorption and stabilization, boosting phytoremediation efficiency. However, challenges remain, including the limited bioavailability of contaminants and plant resilience in highly polluted environments. Recent advancements focus on improving microbial-assisted phytoremediation through mechanisms like bioavailability facilitation, phytoextraction, and phytostabilization. Genetic engineering facilitates the altering of genes that control plant immune responses and growth which improves the ability of plants to interact beneficially with microbes to thrive in HM rich environments while efficiently cleaning contaminated wastewater. This review examines these strategies and highlights future research directions to enhance wastewater remediation using phytoremediation technologies.

Enhanced removal of Cd(II) and As(III) from waters using S-Fe-C composites: Performance and mechanisms

Protecting ecosystems and human health from potentially toxic elements (PTEs) like Cd(II) and As is critical. The results showed that SnZVI particles were uniformly dispersed in biocarbon matrix. The pseudosecond- order kinetics and Langmuir model can better match the adsorption process of Cd(II) and As(III) by SFC., with the maximum removal capacity of 405 mg·g−1 and 349 mg·g−1, respectively. Biochar enhances electron transport and prevents S-nZVI agglomeration. The removal mechanisms of SFC, including chemical precipitation, ion exchange and oxidation, shows great potential for remediation of PTEs pollution in irrigation water.

Sonochemical post-synthesis modification of Y zeolite with iron species

Faujasite is a zeolite that, when in a Y structure, is widely used as a catalyst to produce fuel by fluid catalytic cracking (FCC) and is recently being investigated for applications in sustainable processes. Hence, there is an increased interest in modifying Y zeolites with metals such as Fe to improve and optimize their catalytic properties. Several post-synthesis methods such as chemical vapor deposition, impregnation and ion exchange have been explored for the introduction of Fe. Nevertheless, these currently developed methods can be time-consuming and unable to selectively tune the Fe species. Therefore, this study explores the use of ultrasonic irradiation in a liquid state modification of a Fe-exchanged Y zeolite (FeY) in a buffer solution with different pH values (5 and 9) and oxidation states of Fe ions (ferrous and ferric) for the introduction of Fe species. At the tested ultrasonic modification conditions, the zeolitic structure was preserved with slight Si/Al ratio and pore structure adjustments in correlation with the introduced Fe species (ions, hydroxides and oxides). Setting the sonochemical method as a potential path for the search of reaction conditions for the design and fabrication of Fe-modified zeolitic materials with tuned properties for a wide range of applications.

Comparison of cost and performance between traditional and green processes for producing bimetallic carbide based oxygen reduction electrocatalysts

Chemical (ion exchange resin) and biomass (water hyacinth leaves) as carbon precursors are adopted to prepare two kinds of bimetallic carbide (Fe2MoC)-based catalytic materials. It is found that, compared with the material that use ion-exchange resin as carbon precursor (N–Fe2MoC-RG), the material that use water hyacinth as carbon precursor (N–Fe2MoC-WHG) has more advantages in cost, environment protection, synthesis simplicity, and catalytic activity for oxygen reduction reaction (ORR). Therein, the N–Fe2MoC-WHG as a cathode catalyst displays a half-wave potential of 0.905 V (vs. RHE) for catalyzing ORR in alkaline media, and gets a high peak power density of 1.52 W cm−2 in alkaline electrolyte membrane fuel cell; moreover, the N–Fe2MoC-WHG displays higher power-density retention or growth rate at lower relative humidity, higher back pressure, higher working temperature and higher catalyst loading, compared with the N–Fe2MoC-RG. The N–Fe2MoC-WHG is one of the most active precious metal-free catalysts reported so far, and its stability is very excellent.

Comparative Study of Biosorption and Traditional Methods for Heavy Metal Removal from Industrial Wastewater in Panipat

In this research paper, I have thoroughy described about the topic Comparative Study of Biosorption and Traditional Methods for Heavy Metal Removal from Industrial Wastewater in Panipat.” Industrial wastewater contamination by toxic heavy metals poses a significant environmental threat globally, especially in rapidly industrializing regions like Panipat District in Haryana, India. Panipat, renowned for its extensive textile and chemical industries, generates substantial volumes of wastewater laden with heavy metals such as lead (Pb), cadmium (Cd), and mercury (Hg). Recent studies have revealed that the concentrations of these metals in Panipat's industrial effluents frequently surpass the permissible limits set by environmental regulations. Traditional methods for heavy metal removal, including chemical precipitation and ion exchange, are widely utilized but often entail high operational costs and the generation of secondary pollutants like sludge. Biosorption, an emerging and sustainable technology, offers a promising alternative by utilizing biological materials such as algae, bacteria, and agricultural waste to adsorb heavy metals from wastewater. This study aims to investigate the effectiveness, cost-effectiveness, and environmental impact of biosorption compared to traditional methods in Panipat District. By examining heavy metal removal efficiencies, conducting cost analysis, and assessing environmental implications, this research seeks to provide valuable insights into sustainable wastewater treatment practices.

Efficiently removal the lanthanides using electroreduction diffusion method/high-temperature adsorption technique

The consumption of electricity and the price of molten salt are key factors that limit the pyroprocessing of nuclear fuel. This paper proposes a strategy to reduce costs associated with pyroprocessing of spent fuel by combining electrolytic refining and molecular sieve adsorption for fission product removal and radioactive waste salt recovery. Firstly, we investigated the electrochemical process of ytterbium on a gallium film electrode in LiCl-KCl using various methods, calculating its kinetic parameters at different temperatures. Potentiostatic electrolysis experiments were conducted at 773 K, resulting in the formation of Ga-Yb alloy as the electrodeposited product with a ytterbium removal rate reaching 93.78 %. Then, we studied the adsorption behavior and mechanism of ytterbium through electrorefining combined with molecular sieve adsorption. Experimental results showed that the extraction rate achieved more than 99.99 %, significantly reducing electrolysis costs while increasing target nuclide removal rates. Finally, we investigated the molten salt adsorption mechanism using molecular sieves, identifying chemical ion exchange as the primary mechanism based on recalibration using pseudo-first-order, pseudo-second-order, and Weber-Morris kinetic models. In conclusion, combining electrodeposition and high-temperature adsorption provides an effective approach for recovering and utilizing waste salt in pyroprocessing.

Engineered Biochar for Metal Recycling and Repurposed Applications

Heavy metal pollution is posing significant threats to the environment and human health. Engineered biochar, derived from various biomass sources through thermochemical processes, has emerged as a promising solution for metal pollutant remediation and metal recovery. This review explores the latest advancements in the preparation, characterization, and application of engineered biochar for metal adsorption, recycling, and utilization. It begins by discussing the significance of metal adsorption and providing an overview of biochar properties. The review examines the preparation and characterization techniques, emphasizing feedstock selection, thermochemical conversion methods, and surface modifications. Mechanisms of metal adsorption, such as physical and chemical adsorption, ion exchange, and surface complexation, are critically discussed. Moreover, factors influencing metal adsorption capacity, including biochar properties, metal characteristics, and environmental conditions, are critically analyzed. The efficacy of engineered biochar in adsorbing specific metals, including heavy metals, transition metals, and rare earth elements, is reviewed with recent studies and key findings. Furthermore, the recycling and regeneration of metal-loaded biochar are discussed, focusing on recycling and repurposed application techniques alongside challenges and economic considerations. Finally, future perspectives are provided for the enlightening of future research. This review is unique in addressing the potential of metal-adsorbed biochar as a novel precursor to produce catalytical and electrochemical materials.

Production of hydrochar from the hydrothermal carbonisation of food waste feedstock for use as an adsorbent in removal of heavy metals from water

AbstractIn this research, discarded butternut peels were converted into hydrochar products through hydrothermal carbonisation (HTC), with adjustments made to the temperature (ranging from 180 to 260℃) and residence time (spanning 45–180 min). The findings indicated that both the temperature and time of carbonisation significantly influenced the yield of hydrochar (HC), as well as its physiochemical and structural properties. Higher temperatures and prolonged residence time led to decreased yield, elevated fixed carbon content and an increased fuel ratio. Furthermore, raising the process conditions increased HHV and reduced the oxygen-containing functional groups. The HC yield dropped from 28.75 to 17.58% with increased carbonisation temperature and time. The findings of this study also suggest that modified hydrochar is a promising material for removing heavy metals from wastewater. It is a relatively low-cost and abundant material that can be produced from various biomass feedstocks, including food waste. In addition, it is a sustainable and environmentally friendly option for wastewater treatment. Hydrochar-based systems offer several advantages over traditional methods of heavy metal removal, such as chemical precipitation and ion exchange. The unique physicochemical characteristics of hydrochar, including its porous structure and oxygen-rich functional groups, offer a high surface area and more binding sites for heavy metal ions. By changing the physicochemical properties of hydrochar with chemicals like phosphoric acid, it is possible to increase its adsorption capacity. The Freundlich isotherm was the best fit for the adsorption data for all three metal ions (Pb2+, Cu2+ and Cd2+), indicating that the adsorption process is multilayer and heterogeneous.

Removal of Heavy Metals by Pseudomonas sp. - Model Fitting and Interpretation.

Industrial and urban modernization processes generate significant amounts of heavy metal wastewater, which brings great harm to human production and health. The biotechnology developed in recent years has gained increasing attention in the field of wastewater treatment due to its repeatable regeneration and lack of secondary pollutants. Pseudomonas, being among the several bacterial biosorbents, possesses notable benefits in the removal of heavy metals. These advantages encompass its extensive adsorption capacity, broad adaptability, capacity for biotransformation, potential for genetic engineering transformation, cost-effectiveness, and environmentally sustainable nature. The process of bacterial adsorption is a complex phenomenon involving several physical and chemical processes, including adsorption, ion exchange, and surface and contact phenomena. A comprehensive investigation of parameters is necessary in order to develop a mathematical model that effectively measures metal ion recovery and process performance. The aim of this study was to explore the latest advancements in high-tolerance Pseudomonas isolated from natural environments and evaluate its potential as a biological adsorbent. The study investigated the adsorption process of this bacterium, examining key factors such as strain type, contact time, initial metal concentration, and pH that influenced its effectiveness. By utilizing dynamic mathematical models, the research summarized the biosorption process, including adsorption kinetics, equilibrium, and thermodynamics. The findings indicated that Pseudomonas can effectively purify water contaminated with heavy metals and future research will aim to enhance its adsorption performance and expand its application scope for broader environmental purification purposes.

Application prospects of graphene in environmental science

Nanomaterials and graphene, as cutting-edge materials, have play a crucial role in environmental governance. The introduction of nanomaterials brings new hope to environmental governance. Graphene not only improves the efficiency and cost-effectiveness of water treatment but also drives innovation and development in environmental technologies. This article provides a summary and analysis review starting from the characteristics of nanomaterials and Graphene, comprehensively reviewing Graphenes advantage in environmental technologies and discovered its application in this area. The research summarized the conclusion that Graphenes characteristics make it suitable for addressing environmental issues such as water pollution, its composites can play an important role in water treatment process including water purification, heavy metal adsorption, organic compound adsorption and removal through different preparation and reaction mechanisms. By introducing Nanopore structures and artificially designed stacking structures on graphene membranes, the permeation performance could be modulated and improved. By the way of physical and chemical adsorption, ion exchange, electrochemical and photocatalysis, Graphene and its oxide could be applied to remove heavy metal ion and organic substances from polluted water. The article also introduced the main preparation methods of Graphene and its potential secondary pollution problem. This article provides valuable insights for scientific research and engineering practices in environmental protection and sustainable development.

Enhancing irrigation water quality efficiently with potassium feldspar-derived adsorbent: Heavy metal detoxification and nutrient augmentation

The pollution of Pb2+ and Cd2+ in both irrigation water and soil, coupled with the scarcity of vital mineral nutrition, poses a significant hazard to the security and quality of agricultural products. An economical potassium feldspar-derived adsorbent (PFDA) was synthesized using potassium feldspar as the main raw material through ball milling-thermal activation technology to solve this problem. The synthesis process is cost-effective and the resulting adsorbent demonstrates high efficiency in removing Pb2+ and Cd2+ from water. The removal process is endothermic, spontaneous, and stochastic, and follows the quasi-second-order kinetics, intraparticle diffusion, and Langmuir model. The adsorption and elimination of Pb2+ and Cd2+ is largely dependent on monolayer chemical sorption. The maximum removal capacity of PFDA for Pb2+ and Cd2+ at room temperature is 417 and 56.3 mg·g−1, respectively, which is superior to most mineral-based adsorbents. The desorption of Pb2+/Cd2+ on PFDA is highly challenging at pH≥3, whereas PFDA and Pb2+/Cd2+ are recyclable at pH≤0.5. When Pb2+ and Cd2+ coexisted, Pb2+ was preferentially removed by PFDA. In the case of single adsorption, Pb2+ was mainly adsorbed onto PFDA as Pb2SiO4, PbSiO3·xH2O, Pb3SiO5, PbAl2O4, PbAl2SiO6, PbAl2Si2O8, Pb2SO5, and PbSO4, whereas Cd2+ was primarily adsorbed as CdSiO3, Cd2SiO4, and Cd3Al2Si3O12. After the complex adsorption, the main products were PbSiO3·xH2O, PbAl2Si2O8, Pb2SiO4, Pb4Al2Si2O11, Pb5SiO7, PbSO4, CdSiO3, and Cd3Al2Si3O12. The forms of mineral nutrients in single and complex adsorption were different. The main mechanisms by which PFDA removed Pb2+ and Cd2+ were chemical precipitation, complexation, electrostatic attraction, and ion exchange. In irrigation water, the elimination efficiencies of Pb2+ and Cd2+ by PFDA within 10 min were 96.0 % and 70.3 %, respectively, and the concentrations of K+, Si4+, Ca2+, and Mg2+ increased by 14.0 %, 12.4 %, 55.7 %, and 878 %, respectively, within 60 min. PFDA holds great potential to replace costly methods for treating heavy metal pollution and nutrient deficiency in irrigation water, offering a sustainable, cost-effective solution and paving a new way for the comprehensive utilization of potassium feldspar.

Review of Sulfate Removal in Low Concentration Brine Solutions

Sulfate is a common ion present in natural water bodies at low concentrations and as effluent in different metallurgical processes. The discharge of sulfate in rivers and waterbodies can cause direct and indirect damage to the environment. Regulatory agencies have been increasing the constraints in sulfate content limit for discharge focused on human equity and environmental protection. A common practice is the precipitation of sulfate with lime, but the remaining solution still has ca. 1,500 mg L-1 of sulfate, which is not acceptable for disposal or reuse. This work describes the main routes for sulfate removal such as chemical precipitation, biological degradation, ion exchange, and separation through membranes and discusses the main advantages and issues of each approach. One of the main challenges is to scale up the tests and show the performances at the industrial level. The subject must be the focus of constant study to obtain relevant results so that usual technologies are replaced by more innovative, cheap and efficient methods.

A chromium-incorporated all-inorganic polyoxoniobate framework material: Good chemical stability and selective ion exchange capability

An all-inorganic three-dimensional (3D) polyoxoniobate (PONb) framework, Na6K4[(Nb6O19)CrIII(H2O)2]2·38H2O (1) has been synthesized via the hydrothermal method. The fundamental building unit of [(Nb6O19)CrIII(H2O)2]210− is connected by K+ ions, forming a 3D framework structure with channels along the b-axis. Compound 1 exhibits good thermal stability, and selectively absorbs Co2+ ions while excluding Ni2+ ions from acetonitrile solutions, PXRD analysis confirms that its framework remains intact after adsorption, indicating its potential as an effective ion-exchange material.

Green remediation of mercury-contaminated soil using iron sulfide nanoparticles: Immobilization performance and mechanisms, effects on soil properties, and life cycle assessment

Mercury (Hg) pollution in soil has grown into a severe environmental issue. Effective in situ immobilization techniques are crucially demanded. In this study, we explored the application of carboxymethyl cellulose stabilized iron sulfide nanoparticles (CMC-FeS) for in situ immobilization of Hg in soil. CMC-FeS (a CMC-to-FeS molar ratio of 0.0004) was prepared via the reaction between FeSO4 and Na2S using CMC as a stabilizer. Remedying the Hg-polluted soil using 0.03 % CMC-FeS via batch experiments effectively reduced the acid leachable Hg by 97.5 % upon equilibrium after 71 days. Column elution tests demonstrated that the addition of CMC-FeS decreased the peak Hg concentration by 89.9 % and the total Hg mass eluted by 94.9 % after 523 pore volumes. CMC-FeS immobilized Hg in soil via chemical precipitation, ion exchange, and surface complexation. After the CMC-FeS treatment, Hg was transformed from more available exchangeable, carbonate-bound, and organic material-bound forms into the less available residual fraction, reducing the environmental risk of soil Hg from medium to low. The application of CMC-FeS boosted the soil enzyme activities and enhanced the soil bacterial diversity whereas decreased the production of methylmercury. CMC-FeS also facilitated long-term immobilization of Hg in soil. The acid leachable Hg and relative Hg bioaccessibility was decreased. Lift cycle assessment indicated that the preparation and application of CMC-FeS for in situ Hg remediation in soil met green chemistry principles. The present study confirms that CMC-FeS can be applied as an efficient and “green” amending agent for long-term Hg immobilization in soil/sediment.

Ferric nitrate-induced phase transformation of Bi2O3 with ion exchange property for enhanced chloride removal from high-salinity wastewater

The bismuth oxide (Bi2O3)-based method for removing chloride (Cl−) ions has garnered considerable interest because of its superior selectivity and efficiency in removing Cl−. However, the slow release of Bi3+ poses a challenge to the effectiveness of Bi2O3. In this study, a novel chloride removal agent composed mainly of Fe3+-doped Bi5O7NO3 (BF-x) was synthesized through the phase transformation of Bi2O3 by ferric nitrate. By optimizing the Fe/Bi mass ratio to 3 %: 1 (BF-3), a remarkable Cl− removal efficiency of 86.4 % was achieved, representing a substantial improvement compared to the 31.2 % removal efficiency observed for pure Bi2O3. The investigation of the mechanism and formation energy calculation revealed the inherent instability of Bi5O7NO3 in comparison to that of Bi2O3, which facilitated the release of Bi3+ and enabled the direct formation of BiOCl precipitate through ion exchange of NO3– with Cl−. The synergistic effect of chemical precipitation and ion exchange contributes to the excellent Cl− removal performance of BF-3. The final Cl− removal product, comprised of BiOCl and FeOOH, exhibited significant photocatalytic efficacy in the decomposition of organic contaminants. This study proposes a novel strategy for designing and preparing high-efficiency Cl− removal agents.

Synergistic Removal of Nitrogen and Phosphorus in Constructed Wetlands Enhanced by Sponge Iron

Insufficient denitrification and limited phosphorus uptake hinder nitrogen and phosphorus removal in constructed wetlands (CWs). Sponge iron is a promising material for the removal of phosphorus and nitrogen because of its strong reducing power, high electronegativity, and inexpensive cost. The influence of factors including initial solution pH, dosage, and the Fe/C ratio was investigated. A vertical flow CW with sponge iron (CW-I) was established, and a traditional gravel bed (CW-G) was used as a control group. The kinetic analysis demonstrated that for both nitrogen and phosphorus, pseudo-second-order kinetics were superior. The theoretical adsorption capacities of sponge iron for nitrate (NO3−-N) and phosphate (PO43−-P) were 1294.5 mg/kg and 583.6 mg/kg, respectively. Under different hydraulic retention times (HRT), CW-I had better total nitrogen (TN) and total phosphorus (TP) removal efficiencies (6.08–15.18% and 5.00–20.67%, respectively) than CW-G. The enhancing effect of sponge iron on nitrogen and phosphorus removal was best when HRT was 48 h. The increase in HRT improved not only the nitrogen and phosphorus removal effects of CWs but also the reduction capacity of iron and the phosphorus removal effect. The main mechanisms of synergistic nitrogen and phosphorus removal were chemical reduction, ion exchange, electrostatic adsorption, and precipitation formation.

Research Progress in the Treatment of High-Salinity Wastewater

The generation of high-salinity wastewater is closely associated with various industries, containing a plethora of dissolved salts such as chlorides, sulfates, and carbonates, which pose a significant threat to the environment and human health. Consequently, the treatment of high-salinity wastewater has emerged as a pivotal environmental challenge in contemporary society. This review aims to elucidate the sources and characteristics of high-salinity wastewater, as well as the current status and trends in the field of high-salinity wastewater treatment. First and foremost, we explore the means by which high-salinity wastewater is generated in different industries and the principal salt components it contains. We revisit conventional methods for high-salinity wastewater treatment, including chemical precipitation, ion exchange, evaporation-crystallization, and reverse osmosis, while emphasizing the application of biotechnological approaches. This includes the utilization of salt-tolerant microorganisms, biological adsorption, biodegradation processes, and various types of bioreactors. Advanced oxidation technologies also play a crucial role in high-salinity wastewater treatment. We introduce advanced oxidation techniques such as ozone oxidation, UV-catalyzed oxidation, and high-pressure water oxidation, emphasizing their potential in degrading organic compounds and reducing salt concentration. Furthermore, we discuss hybrid approaches, such as case studies combining biological treatment with advanced oxidation technologies, and the advantages and challenges associated with these integrated techniques. Finally, we provide an outlook on future trends, including research on novel and efficient biodegrading agents, advancements and innovations in advanced oxidation technologies, and the development of intelligent high-salinity wastewater treatment systems. Policy and industry trends will also influence the direction of high-salinity wastewater treatment field development. In summary, high-salinity wastewater treatment represents a complex and pressing environmental challenge. However, through the integration of diverse treatment technologies and ongoing research efforts, it is anticipated that more effective, cost-efficient, and environmentally friendly solutions can be developed to mitigate the impact of high-salinity wastewater on ecosystems and society.

Magnetic biochar enhanced copper immobilization in agricultural lands: Insights from adsorption precipitation and redox

Biochar has exceeded expectations for heavy metal immobilization and has been prepared from widely available sources and inexpensive materials. In this research, coconut shell biochar (CSB), bamboo biochar (BC), magnetic coconut shell charcoal (MCSB), and magnetic bamboo biochar (MBC) were manufactured via co-pyrolysis, and their adsorption properties were tested. The pseudo-secondary (R2 = 0.980–0.985) adsorption kinetic fittings for the four biochas were superior to the pseudo-primary kinetics (R2 = 0.969–0.982). Unmodified biochar adsorption isotherms were more consistent with the Freundlich model, while magnetic biochar fitted Langmuir models better. The maximum adsorption capacity of MCSB for Cu(Ⅱ) reached 371.50 mg g−1. The adsorption mechanisms quantitatively analysis of the biochar indicated that chemical precipitation and ion exchange contributed to the adsorption, in which the magnetic biochar metal-π complexation also enhanced the adsorption. The pot experiment revealed that MCSB (2.0 %DW) significantly enhanced the biomass of lettuce, and facilitated the immobilization of DTPA-Cu (p < 0.05). SEM-EDS, XPS, and FTIR were utilized for morphological characterization and functional group identification, and the increased active adsorption sites (-OH, –COOH, CO, and Fe–O) of MCSB enhanced chemisorption and π-π EDA complexation with Cu(Ⅱ). EEM-PARAFAC and RDA analysis further elucidated that magnetic biochar immobilized copper and reduced biotoxicity (efficiency: 76.12%) by adjusting soil pH, phosphate, and SOM release (negative correlation). The presence of iron oxides (FeOx) promoted in situ adsorption of metallic copper and offered new insights into soil remediation.

Crystal structure and electronic structure calculations of a novel organic triphosphate complex: excellent electrochemical properties with ultra-efficient lithium storage capacity

A new organic–inorganic hybrid molecule, cyclohexyl ammonium dihydride triphosphate, was synthesized at room temperature with slow evaporation, yielding a new triphosphate complex HO10P3·(C6H14N)4·2(H2O) using the chemical ion exchange process.

Structural and Electrochemical Investigation of 3D Tunnel Type Li0.44MnO2 Cathode Material for Secondary Li-Ion Batteries

The design of new cathode materials remains a key goal in the development of (post) Li-ion batteries. In that regard, densely packed structures like Li0.44MnO2 are judicious for study. The presence of Mn as a transition metal makes it more attractive due to its sustainable nature, low cost, elemental abundance, structural diversity/polymorphism, and rich oxidation states (2+ to 7+) offering tunable redox potential [1]. Here, we have investigated Mn-based tunnel-type Li0.44MnO2 oxide for secondary LIBs. i) Li44MnO2 (LMO) was prepared by a soft chemical method using the corresponding sodium manganese oxide (Na0.44MnO2) as a parent compound [2]. The crystal structure of Li0.44MnO2 maintains the parent Na0.44MnO2-type tunnel structure which is analogous to Na4Mn4Ti5O18 having an orthorhombic (s.g. Pbam) crystal system [3]. To understand redox chemistry, this material was studied for both cationic (Mn) and anionic (O) redox reactions using ex-situ X-ray photoelectron spectroscopy. The lithium (de)insertion mechanism of Li0.44MnO2 was explored involving ab initio calculations and in-situ X-ray diffraction experiments. Combined with electrochemical measurements, structural characterizations, and first principles DFT calculations revealed the capacity correlated strongly with both cationic and anionic redox reactions. ii) We have studied the phase transition of Li44MnO2 from a 3D tunnel-type structure to a cubic spinel structure by in-situ X-ray diffraction and Raman spectroscopy. The mechanism of transformation was elucidated by employing transmission electron microscopy. In this case, diffusion-less transformation occurs involving the rearrangement of atoms during heating [4]. An increase in the average redox potential from the pristine orthorhombic phase to the final spinel phase was observed by electrochemical studies. iii) Further to improve the electrochemical performance of Li0.44MnO2, Ti was used as a dopant. The Li0.44[Mn1-xTix]O2 (x=0, 0.11, 0.22, 0.33, 0.44, 0.56) series were obtained with chemical ion exchange from Na precursors. The Na precursors (Na0.44[Mn1-xTix]O2) were prepared via a simple solid-state route. Ti-substituted compositions exhibited similar crystal structures to their parent LMO i.e. orthorhombic framework with Pbam symmetry. A tunnel-type morphology was observed in all cases. The electrochemical performance of Ti-substituted LMO as cathode material for LIBs was studied in a half-cell configuration. The structure and electrochemical properties of Ti-doped LMO, reaching the highest capacity of 128 mAh/g, will be described. Keywords: batteries; cathode; tunnel type manganese oxides; phase transformation; doping