Conventional Carbonate Research Articles

Review on polymer electrolytes for lithium‐sulfurized polyacrylonitrile batteries

AbstractLithium‐sulfur (Li‐S) batteries are deemed as the next generation of energy storage devices due to high theoretical specific capacity (1675 mAh g−1) and energy density (2600 Wh kg−1). However, the commercial application has always been constrained by lithium polysulfide (LiPSs) shuttling effects and still has a long way to go. Sulfurized polyacrylonitrile (SPAN) is a promising alternative candidate to replace traditional sulfur cathode and is conducive to eliminating LiPSs by realizing “solid‐solid” direct conversion in conventional carbonate electrolytes. However, an over 25% irreversible capacity loss is exhibited inevitably in the first discharge process, the inherent structure of SPAN and the related reaction mechanism remain unclear. In this review, the structure characteristics and electrochemical behaviors of SPAN are summarized for better interpreting current knowledge and favoring the design of high performance materials. In the past few decades, many problems in traditional Li‐S batteries have been solved by improving electrolytes. Polymer electrolytes (PEs) have been widely used due to structural designability, multi‐functionality, exceptional chemical stability, and excellent processability. Surprisingly, the relevant researches on PEs compatible with SPAN remains limited currently. Therefore, the recent modification strategies of gel polymer electrolytes and solid polymer electrolytes in Li‐SPAN batteries are introduced in terms of Li+ transfer and interface engineering, the design principles are concluded, the specific challenges encountered by polymer‐based electrolytes are summarized and the instructive directions for future research on PEs are demonstrated, facilitating the commercialization of Li‐SPAN batteries.

FACIES PARTITIONING AT REGIONAL AND FIELD SCALES IN THE BARREMIAN KHARAIB‐2 CARBONATES, UAE

Carbonates in the Lower Cretaceous (Barremian to early Aptian) Kharaib Formation are reservoir rocks at giant oil fields in the UAE and Qatar. The Barremian Kharaib‐2 member (K60), the focus of this study, is in general composed of a regionally continuous succession of high‐energy, shallow‐water limestones bounded above and below by “dense” low‐energy mud‐rich strata. Despite several decades of research, conventional carbonate facies classification schemes and resulting facies groupings for the Kharaib‐2 member have failed to show a statistically acceptable correlation with core‐ and log‐derived petrophysical data. Moreover, sedimentary bodies potentially responsible for dynamic reservoir heterogeneities have not clearly been identified. This paper proposes a standardized facies classification scheme for the Kharaib‐2 carbonates based on vertical facies proportion curves (VPCs) and variogram analyses of core data to construct stratigraphic correlations at both field and regional scales. Data came from 295 cored wells penetrating the Kharaib‐2 member at ten fields in the on‐ and offshore UAE. Thin, dense intervals separating reservoir units were adopted as fourth‐order transgressive units and were used for stratigraphic correlation. Field‐scale probability maps were used to identify sedimentary bodies such as shallow‐water rudistid shoals.Regional stratigraphic correlations of the Kharaib‐2 member carbonates based on the VPCs identified variations in depositional environments, especially for the lower part of the reservoir unit; depositional facies at fields in the SE of the UAE were interpreted to be more distal compared to those at offshore fields to the NW. At a field scale, the VPCs failed to identify significant lateral variations in the carbonates. However, variogram analyses of cored wells showed spatial concentrations of specific facies in the inner ramp domain which could be correlated with high‐energy depositional bodies such as shoals dominated by rudist debris. The bodies were sinusoidal in plan view with lengths of up to 8 km and widths of ca. 1 km. Although similar‐shaped bodies with these dimensions have been reported from other carbonate depositional systems, they have not previously been reported in the Kharaib Formation. At a regional (inter‐field) scale, the stratigraphic correlation of standardized sedimentary facies remains problematic; however, mapping of facies associations and their relative proportions relative to their environments of deposition demonstrated new patterns for the stratigraphic architecture of the Kharaib‐2 member in the UAE.

Sand improvement by microbial-induced carbonate precipitation with casein micelles

This study explores the incorporation of casein micelles to improve the conventional microbial-induced carbonate precipitation technique used for soil improvement. With a single application of the proposed biocementing agent containing casein micelles, a mixed slurry of natural sand solidified to self-sustaining strength within 48 h at 37°C was obtained. The stress–strain curves of the biocemented specimens obtained from a consolidated drained triaxial compression test exhibited sharp peaks at less than 1% strain. Under effective confining pressures of 30, 50 and 100 kPa, the peak deviatoric stress registered 415, 479 and 536 kPa, respectively – representing 1·8–4·1 times the maximum strength of the original sand. Vaterite calcium carbonate crystals formed by the biocementing agent ensured bridging between sand particles, resulting in the improved cohesion. The cohesion-derived residual strength tended to increase at the critical state in biocemented sand under the lowest confining stress. The localised shear band formed by the crystals may control the movement of sand particles, resulting in a change in volumetric strain behaviour. The formation of casein micelles induced the nucleation and growth of spherical crystals, acting as a casein-mediated vaterite. This formation likely contributed to the improved cohesion of sand observed in this study.

Glycerol Carbonate and Solketal Carbonate as Circular Economy Bricks for Supercapacitors and Potassium Batteries.

Considering the worldwide market of batteries and supercapacitors, the (partial or total) replacement of conventional fossil-derived carbonates with bio-based ones in electrolyte formulations would allow the production of safer and more sustainable devices. In this work, embracing the 7th principle of green chemistry, glycerol derivatives (namely glycerol carbonate and solketal carbonate) are tested as solvents and additives for electrolyte formulations. Glycerol carbonate is innovatively employed as promising electrolyte solvent for electric double-layer capacitors with excellent performances. On the other hand, a solketal carbonate-laden liquid electrolyte is investigated for potassium-based batteries, showing a rather stable electrochemical behaviour and performance close to those of commercial oil-derived alternatives.

Investigation of Piezoelectric Properties in Ca-Doped PbBa(Zr,Ti)O3 (PBZT) Ceramics.

The perovskite-structured materials Pb0.75Ba0.251-xCax(Zr0.7Ti0.3)O3 for x = 1 and 2 at.% were synthesized using the conventional mixed-oxide method and carbonates. Microstructural analysis, performed using a scanning electron microscope, revealed rounded grains with relatively inhomogeneous sizes and distinct grain boundaries. X-ray diffraction confirmed that the materials exhibit a rhombohedral structure with an R3c space group at room temperature. Piezoelectric resonance measurements were conducted to determine the piezoelectric and elastic properties of the samples. The results indicated that a small amount of calcium doping significantly enhanced the piezoelectric coefficient d31. The calcium-doped ceramics exhibited higher electrical permittivity across the entire temperature range compared to the pure material, as well as a significant value of remanent polarization. These findings indicate that the performance parameters of the base material have been significantly improved, making these ceramics promising candidates for various applications.

Cyclic Ether-Based Electrolyte with a Weak Solvation Structure for Advanced Potassium Metal Batteries.

Potassium metal batteries (PMBs) are promising candidates for large-scale energy storage. Conventional carbonate electrolytes exhibit unsatisfactory thermodynamic stability against potassium (K) metal anode. Linear ether is widely adopted because of its compatibility with K metal, but the poor oxidation stability restricts the application with high-voltage cathodes. Herein, a weakly solvating cyclic ether is proposed as a solvent to stabilize the K-electrolyte interface and build a robust solid-electrolyte interphase (SEI). This weakly solvating electrolyte (WSE) possesses an anion-dominated solvation structure, which facilitates the anion decomposition for constructing an inorganic-rich SEI. The superior mechanical properties of the SEI, as examined by atomic force microscopy, prevent the SEI from fracture. Consequently, this WSE achieves highly reversible plating/stripping behavior of K metal for 1300h with a high average Coulombic efficiency of 99.20%. Stable full cells are also demonstrated with a high-voltage cathode at harsh conditions. This work complements the design of WSEs for advanced PMBs by cyclic ether solvents.

Synthesis of a green functional carbon dioxide‐based polycarbonate using bio‐based monomers

AbstractA PPC‐dodecyl glucoside (PPC‐APG) polymer was synthesized by the terpolymerization of carbon dioxide (CO2), propylene oxide (PO), and the bio‐based monomer APG for the first time. The thermal stability and mechanical properties of PPC‐APG were significantly improved compared with those of conventional polypropylene carbonate (PPC), and its glass transition temperature (Tg) was increased by 14°C compared with that of PPC. The 5% heat loss temperature (Td,−5%) and total heat loss temperature (Td,max) of PPC‐APG were increased by 89.1 and 92.1°C, respectively, compared with those of PPC. The tensile strength of PPC‐APG was increased to 25.6 MPa, its elongation at break was decreased to 125.1%, and its thermal elongation and permanent deformation were reduced to 97.2% and 62.9%, respectively, which improved the processability of the material. In addition, the introduction of bio‐based monomers also rendered PPC‐APG functional, and its surface tension reached a maximum of 61.3 mN/m at a concentration of 0.05 g/mL, with a good degradability. The higher surface tension and enhanced degradability of PPC‐APG indicate its potential for application as a plastic printing substrate.

Advanced Ether‐Based Electrolytes for Lithium‐ion Batteries

AbstractLithium‐ion batteries (LIBs) have emerged as vital elements of energy storage systems permeating every facet of modern living, particularly in portable electronic devices and electric vehicles. However, with the sustained economic and social development, new‐generation LIBs with high energy density, wide operating temperature range, fast charge, and high safety are eagerly expected, while conventional ethylene carbonate (EC)‐based carbonate electrolytes fail to satisfy corresponding requirements. Comparatively, ether‐based electrolyte systems with fascinating properties have recently been revived in LIBs fields, and many advanced LIBs with exciting performances under ether‐based electrolytes have been developed. This review provides an extensive overview of the latest breakthroughs concerning ether‐based electrolytes applied in LIBs with intercalation cathodes. To systematically outline the progression of ether‐based electrolytes, this review is categorized from the perspective of anodes as follows: i) graphite anode‐based LIBs; ii) silicon anode‐based LIBs; iii) lithium metal anode‐based LIBs.

Interphase engineering by tunable redox of (p-d) π-bond additive toward extended lifespan of sodium-ion batteries

The durability of the cathode and anode interphases is critical for long-term stable cycling of sodium-ion batteries, however, difficult to achieve precise modulation in conventional carbonate-based electrolytes. Herein, from the perspective of functional additives, the sulfur-containing interphase engineering is introduced by the cyclic sulfate esters with tunable redox mechanism, which are oriented to alter specific decomposition and film-forming pathways on the surface of the cathode and anode, compensating for the deficiencies of the fluorinated interphases, such as improving the inhomogeneous and fragile characteristics, while enhancing the ion transport efficiency. As a result, the cells based on hard carbon (HC) and high voltage Na3V2(PO4)2O2F (NVPF) demonstrate excellent cycling stability (1000 and 8000 cycles with more than 80 % and 83 % capacity retention, respectively). Moreover, the assembled HC//NVPF full cell also achieves a cycle life of more than 2500 cycles with a capacity retention of 91%, which is far superior to that of conventional carbonate electrolytes. Furthermore, the high-voltage oxide cathode also demonstrates extended cycling stability (80 % capacity retention after 300 cycles). In short, the proposed sulfur-based additive strategy enables to effectively improve the problems encountered in carbonate-based electrolytes, providing certain reference and application value.

Revisiting porous foam Cu host based Li metal anode: The roles of lithiophilicity and hierarchical structure of three-dimensional framework

Lithium (Li) metal anode (LMA) is one of the most promising anodes for high energy density batteries. However, its practical application is impeded by notorious dendrite growth and huge volume expansion. Although the three-dimensional (3D) host can enhance the cycling stability of LMA, further improvements are still necessary to address the key factors limiting Li plating/stripping behavior. Herein, porous copper (Cu) foam (CF) is thermally infiltrated with molten Li-rich Li-zinc (Li-Zn) binary alloy (CFLZ) with variable Li/Zn atomic ratio. In this process, the LiZn intermetallic compound phase self-assembles into a network of mixed electron/ion conductors that are distributed within the metallic Li phase matrix and this network acts as a sublevel skeleton architecture in the pores of CF, providing a more efficient and structured framework for the material. The as-prepared CFLZ composite anodes are systematically investigated to emphasize the roles of the tunable lithiophilicity and hierarchical structure of the frameworks. Meanwhile, a thin layer of Cu-Zn alloy with strong lithiophilicity covers the CF scaffold itself. The CFLZ with high Zn content facilitates uniform Li nucleation and deposition, thereby effectively suppressing Li dendrite growth and volume fluctuation. Consequently, the hierarchical and lithiophilic framework shows low Li nucleation overpotential and highly stable Coulombic efficiency (CE) for 200 cycles in conventional carbonate based electrolyte. The full cell coupled with LiFePO4 (LFP) cathode demonstrates high cycle stability and rate performance. This work provides valuable insights into the design of advanced dendrite-free 3D LMA toward practical application.

Valorization of food processing waste: Utilization of pistachio shell as a renewable papermaking filler for paperboard

Valorization of non-edible parts of food is an important method of reducing food processing waste. This study presents a potential application of nutshell wastes as a renewable and organic papermaking filler in paperboard packaging. Five pistachio shells particle (PSP) samples with different particle size distributions were prepared and their performance as a papermaking filler was examined relative to a conventional ground calcium carbonate (GCC) mineral filler. PSP fillers dispersed well in aqueous suspensions and showed better retention in handsheets compared to that of GCC, due to the improved retention by the larger particle sizes of PSPs. When PSP fillers had smaller particles than the pore sizes in the paper fiber network and their particle size distribution were narrow, they showed comparable mechanical properties in handsheets compared to that of GCC. Future research is suggested for successful applications of this organic and renewable filler in papermaking.

CO2 microbubbling system for lithium carbonate precipitation

Lithium carbonate (Li2CO3) is becoming increasingly valuable with the growth of the lithium-ion battery industry. For effective Li2CO3 production, the efficient supply of the carbonate source to the solution is crucial. Conventionally, sodium carbonate has been used as the carbonate source; however, the importance of CO2 utilization has been recently recognized. Conventional CO2-based carbonate sourcing exhibits limited efficiency. In this study, we propose a CO2 microbubbling system based on a rotating nozzle for Li2CO3 precipitation. The CO2 micro-bubbling system demonstrated a 1.6 to 1.9 times greater precipitation reaction rate than that of the conventional CO2 bubbling system. This rate enhancement could be attributed to the increased gas-liquid contact surface and greater residence time due to the generation of CO2 microbubbles. Additionally, the Li2CO3 reaction terminated when the pH of the solution dropped below 9.4–9.7 approximately. The re-dissolution of precipitated Li2CO3 occurred below this pH range as bicarbonate ions became the dominant species over carbonate ions. This study successfully demonstrated that CO2 microbubbling technology could be an excellent alternative for carbonate sourcing systems in the Li2CO3 production industry.

The high-fluorinated bi-molecular combination enables high-energy lithium batteries under challenging environment

The drawbacks of temperature sensitivity, high voltage intolerance, and flammability of lithium batteries are gradually brought to light in conventional carbonate electrolytes. To solve these problems, a localized high concentration electrolyte (LHCE) employing highly fluorinated ethyl trifluoroacetate (TFAE) and 2,2,3,3-tetrafluoro-1-(1,1,2,2-tetrafluoroethoxy) propane (TFEP) is designed. When applied in high-energy lithium batteries, the discharge specific capacity of Li||NMC811 battery can maintain 143.6 mAh/g after 500 cycles at 4.6 V and 1C, and the capacity retention of Li||LNMO battery retains as high as 89.99 % after 500 cycles at 5 V. In addition, this LHCE also possesses the ability to operate the battery under challenging conditions including low temperature, fast charge, safety risks, etc. The LHCE based on TFAE and TFEP has unique solvated structures to generate a moderate LiF-rich interfacial layer, ensuring the fast Li+ migration. This work will provide strong guidance for future electrolyte industrial design of high-energy lithium battery.

In Situ Ions Induced Formation of KxF-Rich SEI Layers toward Ultrastable Life of Potassium-Ion Batteries.

Engineering F-rich solid electrolyte interphase (SEI) layers is regarded as an effective strategy to enable the long-term cycling stability of potassium-ion batteries (KIBs). However, in the conventional KPF6 carbonate electrolytes, it is challenging to form F-containing SEI layers due to the inability of KPF6 to decompose into KxF. Herein, AlCl3 is employed as a novel additive to change the chemical environment of the KPF6 carbonate electrolyte. First, due to the large charge-to-radius ratio of Al3+, the Al-containing groups in the electrolyte can easily capture F from PF6 - and accelerate the formation of KxF in SEI layer. In addition, AlCl3 also reacts with trace H2O or solvents in the electrolytes to form Al2O3, which can further act as a HF scavenger. Upon incorporating AlCl3 into conventional KPF6 carbonate electrolyte, the hard carbon (HC) anode exhibits an ultra-long lifespan of 10000 cycles with a high coulombic efficiency of ≈100%. When coupled with perylene-3,4,9,10-tetracarboxylic dianhydride (PTCDA), the full cell exhibits a high capacity retention of 81% after 360 cycles-significantly outperforming cells using conventional electrolytes. This research paves new avenues for advancing electrolyte engineering towards developing durable batteries tailored for large-scale energy storage applications.

Long-life potassium metal batteries enabled by anion-derived solid electrolyte interphase using concentrated ionic liquid electrolytes

Potassium metal batteries (PMBs) show great potential as next-generation energy storage systems yet face challenges such as the dendritic growth of the potassium anode, leading to issues with cycle life and safety. This study reports a potassium salt-concentrated ionic liquid electrolyte (PCIL) consisting of potassium bis(fluorosulfonyl)imide (KFSI) and 1-methyl-1-propyl pyrrolidinium bis(fluorosulfonyl)imide (Pyr13FSI) to achieve long-life and, safe PMBs. PCIL presents several advantages including outstanding oxidation stability (≈5.2 V), decent ionic conductivity (4.0 mS cm−1 at 25 °C), and negligible flammability. Moreover, PCIL promotes the development of anion-derived solid-electrolyte interphase (SEI) with high inorganic content. This not only hinders the growth of potassium dendrites but also facilitates facile interfacial charge transfer kinetics. Benefiting from these advantages, PMBs (K||KVPO4F) employing PCIL exhibit remarkable cycle performances at both ambient and elevated temperatures (capacity retention after 300 cycles: 74.8% at 25 °C and 82.9% at 45 °C), surpassing the performance of conventional carbonate (1 M KPF6 EC/PC) and dilute potassium ionic liquid electrolyte (PIL). This work demonstrates the tangible capability of PCIL in realizing practical PMBs.

A step closer to sustainable CO2 conversion: Limonene carbonate production driven by ionic liquids

This work aims to advance the biocarbonate concept by developing the first process to produce limonene carbonate based on ionic liquids (ILs). Conventional petroleum-derived cyclic carbonates are recognized products partially composed of CO2 with the main drawback of the high energy consumption that imposes epoxide production. In contrast, natural epoxidable compounds, such as terpenes, stand out in the literature as a more sustainable open research line to enable CO2 conversion processes with better sustainable indicators. Limonene, an abundant natural compound, is identified as a key terpene in the aforementioned discussion. Ammonium-based ILs are experimentally selected and optimized, after covering massive anion and cation substituent tuning, achieving high selectivity and competitive yields to limonene carbonate. The reaction-extraction platform concept, which recovers the catalyst by liquid-liquid extraction, is envisioned and developed using a rational experimental-computational approach. The work concludes with a novel process to effectively produce limonene carbonate by using an IL catalyst and water as an extracting solvent. Ultimately, taking advance of the process simulation, a CO2 emissions assessment was conducted. Using renewable raw materials enhances the sustainability of CO2 conversion to cyclic carbonate, reducing global warming impact compared to fossil-based epoxides. However, limonene extraction and epoxidation have a tangible impact on the overall result of CO2 balance, turning efforts outside battery limits of the CO2 conversion process in the search of a limonene carbonate production line with negative neat CO2 emissions that may change the paradigm in the fixation of CO2 through cycloaddition reactions.

Non‐Fluorinated Ethers to Mitigate Electrode Surface Reactivity in High‐Voltage NCM811‐Li Batteries

AbstractLithium (Li) metal batteries (LMBs) with nickel (Ni)‐rich layered oxide cathodes exhibit twice the energy density of conventional Li‐ion batteries. However, their lifespan is limited by severe side reactions caused by high electrode reactivity. Fluorinated solvent‐based electrolytes can address this challenge, but they pose environmental and biological hazards. This work reports on the molecular engineering of fluorine (F)‐free ethers to mitigate electrode surface reactivity in high‐voltage Ni‐rich LMBs. By merely extending the alkyl chains of traditional ethers, we effectively reduce the catalytic reactivity of the cathode towards the electrolyte at high voltages, which suppresses the oxidation decomposition of the electrolyte, microstructural defects and rock‐salt phase formation in the cathode, and gas release issues. The high‐voltage Ni‐rich NCM811‐Li battery delivers capacity retention of 80 % after 250 cycles with a high Coulombic efficiency of 99.85 %, even superior to that in carbonate electrolytes. Additionally, this strategy facilitates passivation of the Li anode by forming a robust solid‐electrolyte interphase, boosting the Li reversibility to 99.11 % with a cycling life of 350 cycles, which outperforms conventional F‐free ether electrolytes. Consequently, the lifespan of practical LMBs has been prolonged by over 100 % and 500 % compared to those in conventional carbonate‐ and ether‐based electrolytes, respectively.

Non-Fluorinated Ethers to Mitigate Electrode Surface Reactivity in High-Voltage NCM811-Li Batteries.

Lithium (Li) metal batteries (LMBs) with nickel (Ni)-rich layered oxide cathodes exhibit twice the energy density of conventional Li-ion batteries. However, their lifespan is limited by severe side reactions caused by high electrode reactivity. Fluorinated solvent-based electrolytes can address this challenge, but they pose environmental and biological hazards. This work reports on the molecular engineering of fluorine (F)-free ethers to mitigate electrode surface reactivity in high-voltage Ni-rich LMBs. By merely extending the alkyl chains of traditional ethers, we effectively reduce the catalytic reactivity of the cathode towards the electrolyte at high voltages, which suppresses the oxidation decomposition of the electrolyte, microstructural defects and rock-salt phase formation in the cathode, and gas release issues. The high-voltage Ni-rich NCM811-Li battery delivers capacity retention of 80 % after 250 cycles with a high Coulombic efficiency of 99.85 %, even superior to that in carbonate electrolytes. Additionally, this strategy facilitates passivation of the Li anode by forming a robust solid-electrolyte interphase, boosting the Li reversibility to 99.11 % with a cycling life of 350 cycles, which outperforms conventional F-free ether electrolytes. Consequently, the lifespan of practical LMBs has been prolonged by over 100 % and 500 % compared to those in conventional carbonate- and ether-based electrolytes, respectively.

Enhanced Electrochemical Performance of Disordered Rocksalt Cathodes in a Localized High‐Concentration Electrolyte

Enhanced Electrochemical Performance of Disordered Rocksalt Cathodes in a Localized High‐Concentration Electrolyte

Stabilizing high temperature operation and calendar life of LiNi0.5Mn1.5O4

Severe capacity degradation at high operating voltages and poor interphase stability at elevated temperature have thus far precluded the practical application of LiNi0.5Mn1.5O4 (LNMO) as a cathode material for lithium-ion batteries. Addressing these challenges through a combination of experimental and theoretical methods in this work, we demonstrate how a fluorinated carbonate electrolyte enables both high-voltage and high temperature operation by mitigating the traditional interfacial reactions observed in electrolytes with conventional carbonate solvents. Computational studies confirm the exceptional oxidation stability of fluorinated carbonate electrolyte which reduces deprotonation at high voltage. The mitigated deprotonation will then minimize the formation of HF acid which corrodes the LNMO surface and leads to phase transformation and poor interphases. With fluorinated carbonate electrolyte at elevated temperature, it was found on LNMO’s subsurface a reduced amount of Mn3O4 phase which can block Li+ transfer and result in drastic cell failure. Leveraging this approach, LNMO/graphite full cells with a high loading of 3.0 mAh/cm2 achieve excellent cycling stability, retaining ∼84 % of their initial capacity at room temperature (25 °C) after 200 cycles and ∼68 % after 100 cycles at 55 °C. This advanced electrolyte also shows promise for improving calendar life, retaining >30 % more capacity than the carbonate baseline after high temperature storage. These results indicate that electrolytes based on fluorinated carbonates are a promising strategy for overcoming the remaining challenges toward practical commercial application of LNMO.