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Bacterial cellulose nanofiber (BCNF) with high thermal stability produced by an ecofriendly process has emerged as a promising solution to realize safe and sustainable materials in the large-scale battery. However, an understanding of the actual thermal behavior of the BCNF in the full-cell battery has been lacking, and the yield is still limited for commercialization. Here, we report the entire process of BCNF production and battery manufacture. We systematically constructed a strain with the highest yield (31.5%) by increasing metabolic flux and improved safety by introducing a Lewis base to overcome thermochemical degradation in the battery. This report will open ways of exploiting the BCNF as a "single-layer" separator, a good alternative to the existing chemical-derived one, and thus can greatly contribute to solving the environmental and safety issues.
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Chemical databases store information such as molecular formulas, chemical structures, and the physical and chemical properties of compounds. Although the massive databases of organic compounds exist, the search of target materials is constrained by a lack of physical and chemical properties necessary for specific applications. With increasing interest in the development of energy storage systems such as high-voltage rechargeable batteries, it is critical to find new electrolytes efficiently. Here we build a search map to screen organic additives and solvents with novel core and functional groups, and thus establish a database of electrolytes to identify the most promising electrolyte for high-voltage rechargeable batteries. This search map is generated from MAssive Molecular Map BUilder (MAMMBU) by combining a high-throughput quantum chemical simulation with an artificial neural network algorithm. MAMMBU is designed for predicting the oxidation and reduction potentials of organic compounds existing in the massive organic compound database, PubChem. We develop a search map composed of â¼1 000 000 redox potentials and elucidate the quantitative relationship between the redox potentials and functional groups. Finally, we screen a quinoxaline compound for an anode additive and apply it to electrolytes and improve the capacity retention from 64.3% to 80.8% near 200 cycles for a lithium ion battery in experiments.
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Rechargeable magnesium batteries have lately received great attention for large-scale energy storage systems due to their high volumetric capacities, low materials cost, and safe characteristic. However, the bivalency of Mg(2+) ions has made it challenging to find cathode materials operating at high voltages with decent (de)intercalation kinetics. In an effort to overcome this challenge, we adopt an unconventional approach of engaging crystal water in the layered structure of Birnessite MnO2 because the crystal water can effectively screen electrostatic interactions between Mg(2+) ions and the host anions. The crucial role of the crystal water was revealed by directly visualizing its presence and dynamic rearrangement using scanning transmission electron microscopy (STEM). Moreover, the importance of lowering desolvation energy penalty at the cathode-electrolyte interface was elucidated by working with water containing nonaqueous electrolytes. In aqueous electrolytes, the decreased interfacial energy penalty by hydration of Mg(2+) allows Birnessite MnO2 to achieve a large reversible capacity (231.1 mAh g(-1)) at high operating voltage (2.8 V vs Mg/Mg(2+)) with excellent cycle life (62.5% retention after 10000 cycles), unveiling the importance of effective charge shielding in the host and facile Mg(2+) ions transfer through the cathode's interface.
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The phase transition of layered manganese oxides to spinel phases is a well-known phenomenon in rechargeable batteries and is the main origin of the capacity fading in these materials. This spontaneous phase transition is associated with the intrinsic properties of manganese, such as its size, preferred crystal positions, and reaction characteristics, and it is therefore very difficult to avoid. The introduction of crystal water by an electrochemical process enables the inverse phase transition from spinel to a layered Birnessite structure. Scanning transmission electron microscopy can be used to directly visualize the rearrangement of lattice atoms, the simultaneous insertion of crystal water, the formation of a transient structure at the phase boundary, and layer-by-layer progression of the phase transition from the edge. This research indicates that crystal water intercalation can reverse phase transformation with thermodynamically favored directionality.
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We have screened 142 cyclic organic compounds in search of novel functional additives and nonaqueous solvents for use in lithium-ion batteries through the use of ab initio calculations, and have determined redox potentials for all molecules. We have estimated the range of variation in oxidation potentials through heteroatom replacement and structure modification. By analyzing the oxidative properties of these compounds, we have shown that substituted heteroatoms and isomers in cyclic organic molecules can induce large variations of oxidation potentials more than 2.3 V. Calculations of reduction potentials show that the substituted heteroatoms, isomers, and the number of double bonds in cyclic organic molecules can change reduction potentials more than 1.7 V. Additionally, we have identified seventeen and twelve compounds that could serve as additives in eliciting film formation on cathodes and anodes, respectively. We have also identified five compounds that could function in the overcharge protection of over-lithiated layered oxide cathodes. Finally, we have identified five compounds that could serve as electrochemically stable solvents for high-voltage (>6 V vs. Li/Li(+)) applications. These inductive screenings and their analyses and findings extend our empirical knowledge into quantitative estimation in the design of materials.
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To achieve a zero-carbon-emission society, it is essential to increase the use of clean and renewable energy. Yet, renewable energy resources present constraints in terms of geographical locations and limited time intervals for energy generation. Therefore, there is a surging demand for developing high-performance energy storage systems (ESSs) to effectively store the energy during the peak time and use the energy during the trough period. To this end, supercapacitors hold great promise as short-term ESSs for rapid power recovery or frequency regulation to improve the quality and reliability of power supply. In particular, the electrical double layer capacitor (EDLC) which offers long and stable cycle retention, high power densities, and fast charge/discharge characteristics with a moderate operating voltage window, is a suitable candidate. Yet, for implementation of the EDLC in ESSs, further research effort is required in terms of increasing the operating voltage and energy densities while maintaining the long-term cycle stability and power densities which are desirable aspects for ESS operation. Here, we examine the advances in EDLC research to achieve a high operating voltage window along with high energy densities, covering from materials and electrolytes to long-term device perspectives for next-generation supercapacitor-based ESSs.
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Aqueous rechargeable battery has been an intense topic of research recently due to the significant safety issues of conventional Li-ion batteries (LIBs). Amongst the various candidates of aqueous batteries, aqueous zinc ion batteries (AZIBs) hold great promise as a next generation safe energy storage device due to its low cost, abundance in nature, low toxicity, environmental friendliness, low redox potential, and high theoretical capacity. Yet, the promise has not been realized due to their limitations, such as lower capacity compared to traditional LIB, dendrite growth, detrimental degradation of electrode materials structure as ions intercalate/de-intercalate, and gas evolution/corrosion at the electrodes, which remains a significant challenge. To address the challenges, various 2D materials with different physiochemical characteristics have been utilized. This review explores fundamental physiochemical characteristics of widely used 2D materials in AZIBs, including graphene, MoS2, MXenes, 2D metal organic framework, 2D covalent organic framework, and 2D transition metal oxides, and how their characteristics have been utilized or modified to address the challenges in AZIBs. The review also provides insights and perspectives on how 2D materials can help to realize the full potential of AZIBs for next-generation safe and reliable energy storage devices.
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To modify oxide structure and introduce a thin conductive film on Li4Ti5O12, thermal nitridation was adopted for the first time. NH3 decomposes surface Li4Ti5O12 to conductive TiN at high temperature, and surprisingly, it also modifies the surface structure in a way to accommodate the single phase Li insertion and extraction. The electrochemically induced Li4+deltaTi5O12 with a TiN coating layer shows great electrochemical properties at high current densities.
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Improving one property without sacrificing others is challenging for lithium-ion batteries due to the trade-off nature among key parameters. Here we report a chemical vapor deposition process to grow a graphene-silica assembly, called a graphene ball. Its hierarchical three-dimensional structure with the silicon oxide nanoparticle center allows even 1 wt% graphene ball to be uniformly coated onto a nickel-rich layered cathode via scalable Nobilta milling. The graphene-ball coating improves cycle life and fast charging capability by suppressing detrimental side reactions and providing efficient conductive pathways. The graphene ball itself also serves as an anode material with a high specific capacity of 716.2 mAh g-1. A full-cell incorporating graphene balls increases the volumetric energy density by 27.6% compared to a control cell without graphene balls, showing the possibility of achieving 800 Wh L-1 in a commercial cell setting, along with a high cyclability of 78.6% capacity retention after 500 cycles at 5C and 60 °C.
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Lithium-metal-based batteries, owing to the extremely high specific energy, have been attracting intense interests as post-Li-ion batteries. However, their main drawback is that consumption/de-activation of lithium metal can be accelerated when O2 or S used in the cathode crosses over to the metal, reducing the lifetime of the batteries. In use of ceramic solid state electrolyte (SSE) separator, despite the capability of gas blocking, thick and heavy plates (~0.3 mm) are necessitated to compensate its mechanical fragility, which ruin the high specific energy of the batteries. Here, we demonstrate fabrication of a new membrane made of micron-sized SSE particles as Li-ion channels embedded in polymer matrix, which enable both high Li-ion conduction and gas-impermeability. Bimodal surface-modification was used to control the energy of the particle/polymer interface, which consequently allowed channel formation via a simple one-step solution process. The practical cell with the new membrane provides a cell-specific energy of over 500 Wh kg-1, which is the highest values ever reported.
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Tetrathiafulvalene (TTF) is investigated as a conductive film-making additive on an overlithiated layered oxide (OLO) cathode. When the OLO/graphite cell is cycled at high voltage, carbonate-based electrolyte without the additive decomposes continuously to form a thick and highly resistant surface film on the cathode. In contrast, TTF added into the electrolyte becomes oxidized before the electrolyte solvents, creating a thinner film on the cathode surface. This film inhibits further electrolyte decomposition through cycling and stabilizes the interface between the cathode and the electrolyte. The cells containing the OLO cathode with TTF-added electrolyte afforded enhanced capacity retention and rate capability, making TTF a prospective electrolyte additive for higher energy density lithium-ion cells.
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The electrochemical cycling performance of vanadium oxide nanotubes (VOx-NTs) for Mg-ion insertion/extraction was investigated in acetonitrile (AN) and tetramethylsilane (TMS)-ethyl acetate (EA) electrolytes with Mg(ClO4)2 salt. When cycled in TMS-EA solution, the VOx-NT exhibited a higher capacity retention than when cycled in AN solution. The significant degradation of capacity in AN solution resulted from increased charge-transfer resistance caused by the reaction products of the electrolyte during cycling. Mixed TMS-EA solvent systems can increase the cell performance and stability of Mg-electrolytes owing to the higher stability of TMS toward oxidation and the strong Mg-coordination ability of EA. These results indicate that the interfacial stability of the electrolyte during the charging process plays a crucial role in determining the capacity retention of VOx-NT for Mg insertion/extraction.
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We report on the synergetic effects of silicon (Si) and BaTiO3 (BTO) for applications as the anode of Li-ion batteries. The large expansion of Si during lithiation was exploited as an energy source via piezoelectric BTO nanoparticles. Si and BTO nanoparticles were dispersed in a matrix consisting of multiwalled carbon nanotubes (CNTs) using a high-energy ball-milling process. The mechanical stress resulting from the expansion of Si was transferred via the CNT matrix to the BTO, which can be poled, so that a piezoelectric potential is generated. We found that this local piezoelectric potential can improve the electrochemical performance of the Si/CNT/BTO nanocomposite anodes. Experimental measurements and simulation results support the increased mobility of Li-ions due to the local piezoelectric potential.
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Silicon is receiving discernable attention as an active material for next generation lithium-ion battery anodes because of its unparalleled gravimetric capacity. However, the large volume change of silicon over charge-discharge cycles weakens its competitiveness in the volumetric energy density and cycle life. Here we report direct graphene growth over silicon nanoparticles without silicon carbide formation. The graphene layers anchored onto the silicon surface accommodate the volume expansion of silicon via a sliding process between adjacent graphene layers. When paired with a commercial lithium cobalt oxide cathode, the silicon carbide-free graphene coating allows the full cell to reach volumetric energy densities of 972 and 700 Wh l(-1) at first and 200th cycle, respectively, 1.8 and 1.5 times higher than those of current commercial lithium-ion batteries. This observation suggests that two-dimensional layered structure of graphene and its silicon carbide-free integration with silicon can serve as a prototype in advancing silicon anodes to commercially viable technology.
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Lithium metal has shown a lot of promise for use as an anode material in rechargeable batteries owing to its high theoretical capacity. However, it does not meet the cycle life and safety requirements of rechargeable batteries owing to electrolyte decomposition and dendrite formation on the surfaces of the lithium anodes during electrochemical cycling. Here, we propose a novel electrolyte system that is relatively stable against lithium metal and mitigates dendritic growth. Systematic design methods that combined simulations, model-based experiments, and in situ analyses were employed to design the system. The reduction potential of the solvent, the size of the salt anions, and the viscosity of the electrolyte were found to be critical parameters determining the rate of dendritic growth. A lithium metal anode in contact with the designed electrolyte exhibited remarkable cyclability (more than 100 cycles) at a high areal capacity of 12â mAh cm(-2).
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We report a new discovery for enhancing the energy density of manganese oxide (Nax MnO2 ) cathode materials for sodium rechargeable batteries by incorporation of aluminum. The Al incorporation results in NaAl(0.1) Mn(0.9) O2 with a mixture of tunnel and layered crystal structures. NaAl(0.1) Mn(0.9) O2 shows a much higher initial discharge capacity and superior cycling performance compared to pristine Na(0.65) MnO2 . We ascribe this enhancement in performance to the formation of a new orthorhombic layered NaMnO2 phase merged with a small amount of tunnel Na(0.44) MnO2 phase in NaAl(0.1) Mn(0.9) O2 , and to improvements in the surface stability of the NaAl(0.1) Mn(0.9) O2 particles caused by the formation of Al-O bonds on their surfaces. Our findings regarding the phase transformation and structure stabilization induced by incorporation of aluminum, closely related to the structural analogy between orthorhombic Na(0.44) MnO2 and NaAl(0.1) Mn(0.9) O2 , suggest a strategy for achieving sodium rechargeable batteries with high energy density and stability.
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Alumínio/química , Fontes de Energia Elétrica , Compostos de Manganês/química , Óxidos/química , Sódio/química , Cristalografia por Raios X , Eletroquímica , EletrodosRESUMO
Problems related to tremendous volume changes associated with cycling and the low electron conductivity and ion diffusivity of Si represent major obstacles to its use in high-capacity anodes for lithium ion batteries. We have developed a group IVA based nanotube heterostructure array, consisting of a high-capacity Si inner layer and a highly conductive Ge outer layer, to yield both favorable mechanics and kinetics in battery applications. This type of Si/Ge double-layered nanotube array electrode exhibits improved electrochemical performances over the analogous homogeneous Si system, including stable capacity retention (85% after 50 cycles) and doubled capacity at a 3C rate. These results stem from reduced maximum hoop strain in the nanotubes, supported by theoretical mechanics modeling, and lowered activation energy barrier for Li diffusion. This electrode technology creates opportunities in the development of group IVA nanotube heterostructures for next generation lithium ion batteries.
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Cristalização/métodos , Fontes de Energia Elétrica , Eletrodos , Germânio/química , Lítio/química , Nanotubos/química , Nanotubos/ultraestrutura , Silício/química , Desenho de Equipamento , Análise de Falha de Equipamento , Íons , Teste de Materiais , Tamanho da PartículaRESUMO
When the electrode is specifically designed by impregnation with an electronic and ionic mixed-conductor, improvement in the electrochemical properties was observed. The presence of an active redox center may contribute to the enhancement of the surface electronic/ionic transport properties by enhancing electrical connection and isotropic Li(+) ion transport.