Large-scale Energy Storage Systems Research Articles

Regulation on reacting solvent engineering for scalable synthesis of Na3(VOPO4)2F@carbon nanotubes microsphere cathodes towards high-power and long-lifespan Na-ion batteries

Na3(VOPO4)2F (NVOPF) has emerged as a promising cathode candidate for commercial Na-ion batteries, ascribed to its elevated theoretical energy density and robust structure during the extraction/insertion of two Na+ ions. However, the intrinsic poor electronic conductivity and unscalable materials-preparation technologies make it unexpected to stand out in large-scale energy storage systems. In this study, a spray-drying process technology is implemented to synthesize Na3(VOPO4)2F@carbon nanotubes (NVOPF@CNTs) composite through the reduction of V5+ driven by methanol at room temperature, in which the shortened Na-ion transfer path and the rapid electron mobility are facilitated by the CNTs. The resulting NVOPF@CNTs electrode exhibits exceptional capabilities, including a high discharge capacity (122.1 mA h g−1 at 1 C= 120 mA h g−1), outstanding rate performance (103.1 mA h g−1 at 100 C), and an extended lifespan (71.8 % capacity retention after 6000 cycles at 20 C). Additionally, the Na3(VOPO4)2F//NaTi2(PO4)3 full battery system demonstrates impressive high-power output capabilities (93.3 mA h g−1, 20 C), versatile current switching adaptability, and robust cycling performance (75.3 % of 98.5 mA h g−1 for the initial capacity after 3000 cycles). The study underscores the potential of improving the preparation of vanadium-based phosphate materials to enhance the practical application of Na-ion batteries.

Assessment of carbon dioxide transcritical cycles for electrothermal energy storage with geological storage in salt cavities

Carbon capture, utilisation, and storage (CCUS) technologies are envisaged as critical actors in the energy transition and climate change mitigation framework. Despite the recent advances in CCUS implementation, there is still significant scope for their growth and improvement. On the other hand, developing new large-scale energy storage systems is a key factor for the massive deployment of renewable energy systems. Technologies such as the electrothermal energy storage system based on carbon dioxide transcritical cycles incorporating geological storage (CEEGS) can contribute to both fields. Preliminary studies have shown that the integrated storage system can operate with roundtrip efficiencies exceeding 50%, injecting over 1 million tons of captured carbon dioxide (CO2) annually. It is an early-stage technology with open challenges for successful development, such as an adequate balance between the high- and low-temperature thermal storage reservoirs or the operation definition between the electrothermal system and the carbon dioxide injection and recovery. Underground pressures will oscillate with the charge/discharge process, with operational implications and constraints. Advancing in the concept requires the definition of optimised operation. This work presents a novel analysis of the adaptation of CO2 transcritical cycles to include injection and production processes with the specific scenario of salt cavities. It considers new modifications to adapt the transcritical cycles in closed-mode operation to the conditions required by the salt cavities injection and production processes. Different case studies are evaluated, evaluating the impact of injection and geological storage, production and surface storage, and reinjection into the geological formation. The analyses show roundtrip efficiencies within the range of 49.1–73.0% when the injection, production, and reinjection processes are executed.

Engineering of charge density at the anode/electrolyte interface for long-life Zn anode in aqueous zinc ion battery.

The aqueous zinc ion battery emerges as the promising candidate applied in large-scale energy storage system. However, Zn anode suffers from the issues including Zn dendrite, Hydrogen evolution reaction and corrosion. These challenges are primarily derived from the instability of anode/electrolyte interface, which is associated with the interfacial charge density distribution. In this context, the recent advancements concentrating on the strategies and mechanism to regulate charge density at the Zn anode/electrolyte interface are summarized. Different characterization techniques for charge density distribution have been analysed, which can be applied to assess the interfacial zinc ion transport. Additionally, the charge density regulations at the Zn anode/electrolyte interface are discussed, elucidating their roles in modulating electrostatic interactions, electric field, structure of solvated zinc ion and electric double layer, respectively. Finally, the perspectives and challenges on the further research are provided to establish the stable anode/electrolyte interface by focusing on charge density modifications, which is expected to facilitate the development of aqueous zinc ion battery.

Engineering ternary hydrated eutectic electrolytes to realize rechargeable cathode-free aluminum-ion batteries

Aluminum-ion batteries (AIBs) have been highlighted as a promising candidate for large-scale energy storage due to the abundant reserve, low cost, high specific capacity, and good safety of aluminum. However, the development of AIBs is hindered by the usage of expensive, corrosive, and humidity-sensitive AlCl3-based ionic liquid electrolytes. Herein, we develop a low-cost, non-corrosive, and air-stable ternary hydrate eutectic electrolyte (HEE) composed of aluminum nitrate hydrate, manganese nitrate hydrate, and N,N-dimethylacetamide for cathode-free AIBs. The solvation structure of metal cations and water state in the electrolyte are regulated through the coordination of both water and N,N-dimethylacetamide molecules. The unique structural features of the HEE enables reversible deposition/stripping of AlxMnO2 on the cathodic current collector that are confirmed by various in-situ and ex-situ characterizations, ultimately realizing cathode-free AIBs. The architected cathode-free AIB delivers a discharge specific capacity of 361 mAh g−1 and shows good cycling stability and high air stability. This study provides a valuable insight into the design of rechargeable multi-valent metal ion batteries for advanced large-scale energy storage systems.

Origins of High Air Sensitivity and Treatment Strategies in O3-Type NaMn1/3 Fe1/3Ni1/3O2.

Sodium-ion layered oxides are one of the most highly regarded sodium-ion cathode materials and are expected to be used in electric vehicles and large-scale grid-level energy storage systems. However, highly air-sensitive issues limit sodium-ion layered oxide cathode materials to maximize cost advantages. Industrial and scientific researchers have been developing cost-effective air sensitivity treatment strategies with little success because the impurity formation mechanism is still unclear. Using density functional theory calculations and ab initio molecular dynamics simulations, this work shows that the poor air stability of O3-type NaMn1/3Fe1/3Ni1/3O2 (NMFNO) may be as follows: (1) low percentage of nonreactive (003) surface; (2) strong surface adsorption capacity and high surface reactivity; and (3) instability of the surface sodium ions. Our physical images point out that the high reactivity of the NMFNO surface originates from the increase in electron loss and unpaired electrons (magnetic moments) of the surface oxygen active site as well as the enhanced metal coactivation effect due to the large radius of the sodium ion. We also found that the hydrolysis reaction requires a higher reactivity of the surface oxygen active site, while the carbon hybridization mode transformation in carbonate formation depends mainly on metal activation and does not even require the involvement of surface oxygen active sites. Based on the calculation results and our proposed physical images, we discuss the feasibility of these treatment strategies (including surface morphology modulation, cation/anion substitution, and surface configuration design) for air-sensitive issues.

Thermodynamic and Exergoeconomic Analysis of a Novel Compressed Carbon Dioxide Phase-Change Energy Storage System

As an advanced energy storage technology, the compressed CO2 energy storage system (CCES) has been widely studied for its advantages of high efficiency and low investment cost. However, the current literature has been mainly focused on the TC-CCES and SC-CCES, which operate in high-pressure conditions, increasing investment costs and bringing operation risks. Meanwhile, some studies based on the phase-change CO2 energy storage system also have had the disadvantages of low efficiency and the extra necessity of heat or cooling sources. To overcome the above problems, this paper proposes an innovative compressed CO2 phase-change energy storage system. During the energy charge process, molten salt and water are used to store heat with a smaller temperature difference in heat exchangers, and high-pressure CO2 is reserved in liquid form. During the energy discharge process, throttle expansion is applied to realize the evaporation at room temperature, and CO2 absorbs the reserved heat to improve the power capacity in the turbine and the system energy storage efficiency. The thermodynamic and exergoeconomic studies are performed firstly by using MATLAB. Then, the parametric study based on energy storage efficiency, system unit product cost, and exergy destruction is analyzed. The results show that energy storage efficiency can be improved by lifting liquid CO2 pressure as well as compressor and turbine isentropic efficiencies, and CO2 evaporation pressure has the optimal pressure point. The system unit product cost can be reduced by decreasing liquid CO2 pressure and compressor isentropic efficiency, while CO2 evaporation pressure and turbine isentropic efficiency both have optimal points. Finally, the optimization of two performances is performed by NSGA-II, and they can reach 75.30% and 41.17 $/GJ, respectively. Moreover, the optimal energy storage efficiency is obviously higher than that of other energy storage technologies, indicating the great advantage of the proposed system. This study provides an innovative research method for a new type of large-scale energy storage system.

Suppressing Formation of Zn─Mn─O Phases by In Situ Ti Decoration of MnO2 for Long Lifespan MnO2-Zn Battery.

Mildly-acidic MnO2-Zn batteries are considered as a promising alternative for large-scale energy storage systems for their low toxicity, high safety, and low cost. Though, the degradation of MnO2 with cycling still hinders the further development of the batteries. In this study, it is observed that the decrease in available capacity of MnO2 with charge and discharge is accompanied by a structural transformation with the emergence of Zn─Mn─O phases. An electrodeposition test indicates that the Zn─Mn─O phase is formed from a co-precipitation of Zn and Mn during the charge process. Further, the structural change of MnO2 is suppressed and its cycle stability is improved with the addition of TiOSO4 as a facile electrolyte additive. As a result, under a current of 1200mA g-1, the MnO2 electrode still gives a capacity of 230 mAh g-1 for over 1500 cycles. Capacity retention is 75% after 10000 cycles under a current rate of 4800mA g-1. These findings provide fundamental insights on the degradation mechanism of MnO2 and a new strategy to improve the electrochemical performance of aqueous MnO2-Zn batteries.

The zinc ion concentration dynamically regulated by an ionophore in the outer Helmholtz layer for stable Zn anode

The Zn dendrite limits the practical application of aqueous zinc-ion batteries in the large-scale energy storage systems. To suppress the growth of Zn dendrites, a zinc ionophore of hydroxychloroquine (defined as HCQ) applied in vivo treatment is investigated as the electrolyte additive. HCQ dynamically regulates zinc ion concentration in the outer Helmholtz layer, promoting even Zn plating at the anode/electrolyte interface. This is evidenced by the scanning electron microscopy, which delivers planar Zn plating after cycling. It is further supported by the X-ray diffraction spectroscopy, which reveals the growth of Zn (002) plane. Additionally, the reduced production of H2 during Zn plating/stripping is detected by the in-situ differential electrochemical mass spectrometry (DEMS), which shows the resistance of Zn (002) to hydrogen evolution reaction. The mechanism of dynamic regulation for zinc ion concentration is demonstrated by the in-situ optical microscopy. The hydrated zinc ion can be further plated more rapidly to the uneven location than the case in other regions, which is resulted from the dynamic regulation for zinc ion concentration. Therefore, the uniform Zn plating is formed. A cycling life of 1100 h is exhibited in the Zn||Zn symmetric cell at 1.6 mA cm−2 with the capacity of 1.6 mAh cm−2. The Zn||Cu battery exhibits a cycling life of 200 cycles at 4 mA cm−2 with a capacity of 4 mAh cm−2 and the average Coulombic efficiency is larger than 99 %. The Zn||VO2 battery with HCQ modified electrolyte can operate for 1500 cycles at 4 A g−1 with a capacity retention of 90 %. This strategy in the present work is wished to advance the development of zinc-ion batteries for practical application.

CVD Grown CNTs-Modified Electrodes for Vanadium Redox Flow Batteries.

Vanadium redox flow batteries (VRFBs) are of considerable importance in large-scale energy storage systems due to their high efficiency, long cycle life and easy scalability. In this work, chemical vapor deposition (CVD) grown carbon nanotubes (CNTs)-modified electrodes and Nafion 117 membrane are utilised for formulating a vanadium redox flow battery (VRFB). In a CVD chamber, the growth of CNTs is carried out on an acid-treated graphite felt surface. Cyclic voltammetry of CNT-modified electrode and acid-treated electrode revealed that CNTs presence improve the reaction kinetics of V3+/V2+ and VO2+/VO2+ redox pairs. Battery performance is recorded for analysing, the effect of modified electrodes, varying electrolyte flow rates, varying current densities and effect of removing the current collector plates. CNTs presence enhance the battery performance and offered 96.30% of Coulombic efficiency, 79.33% of voltage efficiency and 76.39% of energy efficiency. In comparison with pristine electrodes, a battery consisting CNTs grown electrodes shows a 14% and 15% increase in voltage efficiency and energy efficiency, respectively. Battery configured without current collector plates performs better as compared to with current collector plates which is possibly due to decrease in battery resistance.

Dendrite suppression enabled longevous sodium metal batteries by sodiophilic Zein/MXene nanofiber modulated polypropylene separator

Sodium metal batteries with low-cost and high-energy density are considered as the most promising candidate for large-scale energy storage systems. However, dendritic growth of sodium metal anode (SMA) severely hampered their viability. Here, we propose the use of polypropylene separators coated by electrospinning nanofibers containing corn protein (Zein) molecules and MXene (V2CTx) sheets on polyacrylonitrile (PAN) skeletons (denoted as PZM) to tackle these issues. The abundant sodiophilic functional groups on Zein and V2CTx as well as the porous network of electrospinning nanofibers can facilitate homogeneous Na metal deposition and achieve dendrite-free SMA. Additionally, the oxygen- and nitrogen-containing functional moieties on the nanofibers benefit the electrolyte up take (395 %), ion-conductivity (1.43 mS cm−1), Na+transference number (0.77) and inorganic-rich SEI. The PZM separator enables Na metal electrodes in symmetric cells to cycle over 3500 h with a stable overpotential of 10 mV at 1 mA cm−2/1 mAh cm−2 and over 1200 h at 5 mA cm−2/10 mAh cm−2. When tested in Na3V2(PO4)3@C||Na full cells, the PZM separator enables a high capacity of 86.2 mAh g−1 over 1000 cycles with an excellent capacity retention of 87.8 %. The proposed biomaterial-based separator modification strategy can spur the development of feasible sodium metal batteries.

Ultralong Cycling and Interfacial Regulation of Bilayer Heterogeneous Composite Solid-State Electrolytes in Lithium Metal Batteries.

Under the background of "carbon neutral", lithium-ion batteries (LIB) have been widely used in portable electronic devices and large-scale energy storage systems, but the current commercial electrolyte is mainly liquid organic compounds, which have serious safety risks. In this paper, a bilayer heterogeneous composite solid-state electrolyte (PLPE) was constructed with the 3D LiX zeolite nanofiber (LiX-NF) layer and in-situ interfacial layer, which greatly extends the life span of lithium metal batteries (LMB). LiX-NF not only offers a continuous fast path for Li+, but also zeolite's Lewis acid-base interaction can immobilize large anions, which significantly improves the electrochemical performance of the electrolyte. In addition, the in-situ interfacial layer at the electrode-electrolyte interface can effectively facilitate the uniform deposition of Li+ and inhibit the growth of lithium dendrites. As a result, the Li/Li battery assembled with PLPE can be stably cycled for more than 2500 h at 0.1 mA cm-2. Meanwhile, the initial discharge capacity of the LiFePO4/PLPE/Li battery can be 162.43 mAh g-1 at 0.5 C, and the capacity retention rate is 82.74% after 500 cycles. These results emphasize that this bilayer heterogeneous composite solid-state electrolyte has distinct properties and shows excellent potential for application in LMB.

Unlocking zinc storage in silver vanadate structures for high-performance aqueous zinc batteries

Zinc-ion batteries (ZIBs) are being increasingly recognized as promising candidates for large-scale energy-storage systems owing to their stability in air, abundance of elemental zinc, low cost, and ease of handling. Although various cathode materials have been explored for ZIBs, silver vanadate stands out for its highly stable structure. However, the presence of silver in silver vanadate may hinder its electrochemical performance, necessitating activation over several cycles. In this study, we introduce an ion-exchange reaction to directly activate silver vanadate. The resulting ion-exchanged zinc vanadate demonstrates superior performance compared with silver vanadate, showcasing stable cycling behavior and high-rate capability. Remarkably, it maintains a capacity retention of 71 % even after 400 cycles. Analysis of the zinc intercalation mechanism reveals a combination of capacitive and diffusion-based processes contributing to energy storage in ZIBs. Post-cycling examinations reveal the presence of dendritic zinc anodes and confirm the stability and safety of the framework, with no silver migration to the anode side. These findings highlight the potential of ZIBs as next-generation energy-storage solutions and underscore the need for continued research in optimizing electrode materials and electrolytes for practical applications.

Biomass derived hard carbon materials for sodium ion battery anodes: Exploring the influence of carbon source on structure and sodium storage performance

Compared to the scarce resources of lithium-ion batteries, sodium ion batteries have gradually become an ideal carrier for large-scale energy storage systems due to their abundant raw material resources. In recent years, hard carbon as an anode material for sodium ion batteries has attracted much attention. Biomass materials have become an ideal hard carbon precursor due to their natural and renewable advantages. This article evaluates the effect of hard carbon derived from three types of biomass waste (peanut shell, coffee grounds, and sugarcane bagasse) on the electrochemical performance of sodium ion batteries through pre carbonization pyrolysis method. The three materials exhibit different structures and surface functional group contents. Compared with coffee grounds and sugarcane bagasse, peanut shell-derived hard carbon has lower structural ordering and smaller specific surface area, and exhibits a higher initial Coulombic efficiency of 53.84 %. The initial reversible capacity of the HC-P electrode is 203.6 mAh/g, and the Coulombic efficiency of the electrode is close to 100 % with a reversible capacity of 127.1 mAh/g and a capacity retention of 81.4 % after cycling 100 at 1C current. The excellent electrochemical properties of HC-P can be attributed to its higher C=O bond content, larger layer spacing and lamellar structure.

In situ constructing a porous organic component-zincophilic Cu clusters layer on zinc anode for high performance aqueous zinc ion batteries

Aqueous zinc ion batteries (AZIBs) with Zn metal anodes stand out as a promising candidate for large-scale energy storage systems, owing to their high safety, low cost, and environmental friendliness. However, the commercialization of AZIBs is plagued by issues such as Zn dendrite growth and side reactions. Herein, an organic component-Cu metal composite layer is constructed on Zn anode (Org-Cu@Zn) by a novel, one-step and in situ spontaneous displacement reaction. The outer porous organic layer with functional groups may serve as migration sites and transport channels for Zn2+ ions, promoting transfer kinetics. The inner zincophilic Cu clusters layer diminishes the interfacial resistance, facilitating Zn2+ ions diffusion and even Zn deposition. Compared to the bare Zn, the unique dual-layer structure exhibits stronger zincophilicity, smaller interface resistance, lower nucleation energy barrier, and stronger anti-corrosion capability, thus effectively suppressing the Zn dendrite growth and side reactions. Remarkably, the Org-Cu@Zn electrode shows an ultra-long lifespan of 3600 h (1800 cycles) with an average Coulombic efficiency of 99.7 %, realizes long cycling stability over 4300 h (1 mA cm−2) and 1350 h (5 mA cm−2), and assures the stable operation of Org-Cu@Zn||ZVO full cells with coin-type configurations.

GRAVITY ENERGY STORAGE TECHNOLOGIES: A Review of the Solid Gravity Energy Storage Applications

The use of renewable energy sources is increasing to reduce the carbon footprint. Renewable energy sources provide limited electricity generation and cannot meet the variable energy demand. Large-scale energy storage systems are needed for sustainability. The applicability of energy storage technology depends on many factors such as energy source, site availability, energy density, storage time, storage capacity, system cost, environmental impact, reliability, durability, and system integration capacity. Solid gravity storage technology is seen as a promising new alternative for large-scale energy storage. There are various types of SGES systems classified according to the application method. In this paper, studies on various SGES methods are reviewed. Studies on the applicability factors of SGES systems and their integration into the electricity grid are evaluated. SGES technology has advantages in terms of geographical compatibility, storage volume, security, and energy conversion efficiency. It has been observed that successful results have been obtained in the theoretical studies. However, there is a need for the development of physical simulations and more comprehensive techno-economic analyses.

Suppressing the Jahn–Teller effect in Mn-based Prussian blue analogues by linear (N[dbnd]O) anions

Manganese-based Prussian blue analogues (PBAs) have been touted as a promising cathode material for sodium-ion batteries (SIBs) due to their low cost, long cycle life and high energy density. However, manganese-based PBAs perform poorly during cycling due to the Jahn-Teller effect. In this study, highly stable manganese nitrosylpentacyanoferrate (Mn[Fe(CN)5NO]) particles were synthesized using a simple hydrothermal method. The presence of nitroso group breaks the symmetry of the crystals to some extent, which is favorable to reduce the Jahn-Teller effect. Through experiments and DFT calculations, we confirm that the presence of linear (NO) anions reduces the lattice volume fluctuations of the samples during charging and discharging, thus contributing to the mitigation of the Jahn-Teller effect. The electrochemical properties of Mn[Fe(CN)5NO] were significantly improved compared to manganese hexacyanoferrate (MnFe[CN]6). Mn[Fe(CN)5NO] exhibited excellent sodium storage performance with an initial discharge capacity as high as 144.5 mAh/g at 20 mA g-1and capacity retention as high as 82.1 % after 400 cycles at 100 mA g−1. This Mn[Fe(CN)5NO] sample provides a promising cathode for sodium-ion batteries in large-scale energy storage systems.

Hydrophobic and zincophilic organic hierarchical nano-membranes with ordered molecular packing for stable zinc metal anodes

Rechargeable aqueous Zn metal batteries hold significant potentials as one of the next-generation energy-storage devices due to their low cost and high safety. However, the uncontrollable dendrite growth and low efficiency in plating/stripping of Zn anodes hinder the commercial application of aqueous Zn-ion batteries (AZIBs). Herein, inspired by hydrophobic lotus, a multifunctional organic hierarchical nano-membrane serving as an artificial protective layer is constructed through the gas-liquid interface method, using self-assembled organic nanosheets (NOS). The organic nano-membrane exhibits ordered molecular packing, accompanied by uniform distribution of zincophilic carbonyl (CO) groups on the Zn metal surface. These groups function as active sites, homogenizing Zn2+ flux and accelerating Zn2+ deposition. Simultaneously, the hydrophobic membrane isolates active water, thereby restraining side reactions, effectively suppressing corrosion and extremely inhibiting dendrite growth. Consequently, NOS@Zn anode exhibits stable cycling over 2400 h and an average coulombic efficiency (CE) of 99.69 % (600 cycles) at 1 mA cm−2. Furthermore, NOS@Zn||CNT-MnO2 full cell presents remarkable capacity retention, approximately 5 times higher than that of Zn||CNT-MnO2 after 3000 cycles at 2 A g−1. This work develops an innovative organic interface modification material paving the way for dendrite-free Zn metal anodes and advancing the practical application of large-scale Zn-based energy storage systems.

Borate modified Co-free LiNi0.5Mn1.5O4 cathode material: A pathway to superior interface and cycling stability in LNMO/graphite full-cells

Cobalt-free LiNi0.5Mn1.5O4 (LNMO) holds great promise as a next-generation cathode material for high-energy and high-power density lithium-ion batteries (LIBs), making it a key contender for large-scale energy storage systems (ESS) and transportation applications. Despite its potential, the commercial utilization of LNMO has been impeded by its rapid capacity deterioration attributed to an unstable LNMO/electrolyte interface caused by the intrinsically high operating voltage of LNMO. Here, we present a pragmatic and scalable strategy to improve the LNMO/electrolyte interface through borate-based surface coating of the LNMO. Optimizing the coating process yielded high-rate capability and stable LNMO/electrolyte interface analyzed by extended float tests. Borate-LNMO materials show superior cycling stability at 25 °C and 45 °C, attributed to a robust cathode electrolyte interphase (CEI) formation. The bare LNMO and 0.25-B2O3-LNMO demostrated a cycling stability of around 41.20 % and 62.50 % respectively after 1000 cycles in LNMO/graphite full-cells. Post-mortem X-ray photoelectron spectroscopy (XPS) analysis revealed fewer side reaction products on borate-LNMO cathodes compared to bare LNMO. Additionally, scanning electron microscopy (SEM) revealed a thicker and denser solid-electrolyte interphase (SEI) on cycled graphite anodes from bare LNMO cells, while a thin and robust SEI was observed on graphite from borate-LNMO cells. Finally, we have conclusively demonstrated that the primary aging mechanism in LNMO/graphite full cells stems from the instability at the LNMO/electrolyte or/and graphite/electrolyte interface, rather than material-related degradation phenomenon. These compelling outcomes underscore the potential of cathode material surface coating in general and especially of borate coating on LNMO as a promising and cost-effective enabler for the use of LNMO in next-generation LIBs.

Effect of geothermal heat transfer on performance of the adiabatic compressed air energy storage systems with the salt cavern gas storage

The temperature and pressure of compressed air influence the output performance of the adiabatic compressed air energy storage system with salt cavern gas storage. However, current studies often overlook the impact of geothermal heat transfer on system performance. In this paper, a mathematical model of the energy storage system with salt cavern gas storage is developed, considering the geothermal heat transfer in wellbore and salt carven. The model is used to illustrate the effects of geothermal heat transfer on the system performance through a sensitivity analysis of some key parameters. The results show that geothermal heat transfer will significantly reduce the gas and energy storage capacity, with a maximum reduction of 15.3 % and 11.1 % at a depth of 2000 m, respectively. Furthermore, this reduction would increase with the depth of the salt cavern. The geothermal energy reduces the round-trip efficiency from 68.7 % to 66.26 % and the energy storage density from 5.18 kWh·m−3 to 4.32 kWh·m−3. For common salt cavern gas storage at a depth of about 600 m ∼ 1200 m, the negative impacts of geothermal heat transfer on round-trip efficiency and energy storage density are less than 2.2 % and 0.5 kWh·m−3, respectively. Sensitivity analysis also demonstrates that the primary factors influencing the system’s performance are the thermal conductivity of the surrounding rock, the volume of the salt cavern, and the length of the wellbores. The secondary factors include the heat transfer coefficient on the inner wall of the salt cavern, the inner pipe radius, and the roughness of the inner pipe. Irrelevant factors include the thermal conductivity of the protective fluid and the thermal conductivity of the cement layer. The proposed comprehensive mathematical model of the system and simulation findings aid in forecasting the performance of storage systems and offer theoretical guidance for the design of large-scale compressed air energy storage systems.

Layer‑by‑layer assembled binder-free hydrated vanadium oxide-acetylene black electrode for flexible aqueous zinc ion battery

Vanadium oxides are potential positive electrode materials for aqueous zinc ion batteries (ZIBs) owing to their advantages of high theoretical capacity, low cost, and so on. Developments of methods for preparing binder-free vanadium oxide electrodes on a large scale and further investigation of their Zn2+ storage mechanisms are essential for expanding their uses in large-scale energy storage systems and wearable electronics. In this work, binder-free electrodes with hydrated vanadium oxide (V2O5·nH2O, denoted as VOH)-acetylene black (AB) on carbon cloth (VOH-AB/CC) are fabricated by a simple and scalable method which combined low-temperature hydrothermal treatment with layer-by-layer drop/spray-coating process. The AB can greatly improve the electrical conductivity of VOH, thereby enhancing the electrochemical performance. The as-prepared electrode with 20 wt% of AB (VOH-AB2/CC) delivers a high capacity of 280 mA h g−1 at 1 A/g and a good rate capability of 205 mA h g−1 at 4 A/g, which is better than many of the reported binder-free vanadium base electrodes. Besides, excellent cycling performance with 89 % retention rate after 3000 cycles at 4 A/g is achieved on the VOH-AB2/CC electrode. Furthermore, a storage mechanism of Zn2+/H+/H2O insertion accompanied by the formation of basic zinc salt precipitate during the discharging process is proposed by the aid of ex-situ XRD and XPS techniques. Additionally, the flexible Quasi-Solid-State ZIB constructed using VOH-AB/CC as positive electrode can work well at different bending states and two ZIBs connected in series can lighten a light-emitting diode even under bending state. This work provides a low-cost, time-saving, environmental-friendly and scalable method to fabricate binder-free hydrated vanadium oxide electrodes for flexible aqueous ZIBs.