Primary Batteries Research Articles

Fabrication and Optimization of Primary Batteries Using Ni/Graphene Nanosheet Electrodes

This study aims to investigate the impact of varying the mass ratio of Ni to Graphene Nano Sheets (GNS) and how incorporating GNS affects the performance of a primary battery prototype (Ni/GNS//electrolyte//GNS). The primary battery prototype was developed using both impregnation and alloy methods. Different mass ratios of Ni/GNS to electrolyte to GNS were tested, including ratios of 1:2:1 (A), 2:2:1 (B), 1:2:2 (C), 2:1:2 (D), and 1:1:2 (E). The characterization of GNS, Ni/GNS, and the primary battery prototype involved using X-Ray Diffraction (XRD) and Scanning Electron Microscope-Energy Dispersive X-Ray (SEM-EDX) instruments. A multimeter was employed to measure electrical conductivity, energy density, and power density. A potentiostat/galvanostat was used to measure cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). XRD analysis showed a broad and weak peak at 2θ= 24.32° for GNS, confirming its successful synthesis. Additionally, a peak at 2θ = 43.5° indicated effective deposition of Ni on the GNS surface in Ni/GNS. The SEM-EDX results supported the XRD findings, showing regularly spaced pores and a thin surface layer in GNS. Notably, white spots on the graphene surface in Ni/GNS indicated successful Ni deposition. In terms of electrical conductivity, the highest value was observed in the primary battery prototype for sample D (2:1:2), which measured 1.11 S/cm2. These results were also supported by measurements of energy density and power density in sample D, which achieved the highest values among all samples, with 144,788 Wh/kg and 252,500 W/kg, respectively. Moreover, the CV and EIS measurements remained stable at 0.30 kΩ and 0.88 kΩ, suggesting that GNS could potentially conduct electrons owing to its electrical conductivity.

Bifunctional oxygen electrocatalyst based on Fe, Co, and nitrogen co-doped graphene-coated alumina nanofibers for Zn-air battery air electrode

Aqueous rechargeable zinc-air battery (RZAB) is an emerging environmentally friendly energy storage device for a wide variety of industrial applications such as electric vehicles, consumer electronics, and stationary power plants. For successful commercialization of RZABs, a cost-effective bifunctional catalyst is highly required to catalyze the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) at the air electrode. Dual transition-metal and nitrogen-doped nanocarbon materials have shown good potential as an affordable and scalable bifunctional oxygen electrocatalysts alternative to Pt-group metal-based catalysts for RZAB. To achieve this goal, we have developed electrocatalysts based on Fe, Co, and nitrogen co-doped graphene-augmented inorganic alumina nanofibers (Fe/Co-NGr). The Fe/Co-NGr catalysts demonstrate high oxygen reduction and evolution reaction reversibility (ΔE) of 0.85–0.88 V due to the graphene-covered nanofibrous structure doped with FeCo alloy nanoparticles and containing nitrogen, transition metal (TM) coordinated to nitrogen and TM oxide active sites. The primary zinc-air battery with Fe/Co-NGr air electrode exhibits a high maximum power density of 149 mW cm−2 and a specific capacity of 807 mAh gZn-1. The RZAB assessment has shown a low charge–discharge voltage gap of 0.86 V and high energy utilization efficiency of 58 % up to 90 h of charge–discharge cycling at 5 mA cm−2.

Improvement of the electrochemical properties of Li/CFx primary batteries induced by Nitrogen plasma treatment from silica and carbon fluoride

Improvement of the electrochemical properties of Li/CFx primary batteries induced by Nitrogen plasma treatment from silica and carbon fluoride

Development of novel dilute Mg anode for primary Mg-air battery with great voltage and capacity synergy

Development of novel dilute Mg anode for primary Mg-air battery with great voltage and capacity synergy

A combined computational/experimental study of anode-concerned voltage drop in aqueous primary Mg-air batteries

The voltage drop appearing at Mg anode-electrolyte interface is a critical issue for the battery power and energy density of aqueous primary Mg-air batteries. The respective voltage loss is typically assigned to the deposits layer forming on the anode surface during discharge. In this work, we experimentally and computationally investigate the critical factors affecting the voltage drop at Mg anode towards a deeper understanding of the contribution of deposit and its growth. A two-dimensional (2D) mathematical model is proposed to compute the voltage drop of Mg-0.15Ca wt.% alloy (Mg-0.15Ca) by means of a semi-empirical formulas and experiments-based modification model, considering the effect of discharge current density, the negative difference effect (NDE) and surface deposits layer itself. This model is utilized to simulate the discharge potential of the anode at predefined experimental current densities. The computed voltage drop (half-cell voltage) is in good agreement with the experimental value. The applicability of the mathematical model is successfully validated on the second material (namely high-purity Mg).

Biodegradable Mg-Mo2C MXene Air Batteries for Transient Energy Storage.

Primary batteries are the fundamental power sources in small electronic gadgets and bio/ecoresorbable batteries. They are fabricated from benign and biodegradable materials and are of interest in environmental sensing and implants because of their low toxicity toward the environment and human body during decomposition. However, current bio/ecoresorbable batteries suffer from low operating voltages and output powers because of the occurrence of undesired hydrogen evolution reactions (HERs) at cathodes. Herein, Mo2C MXene was used as a cathode to achieve high operating voltage and areal power. Mo2C provides energy barriers for HERs in alkaline solutions, and such barriers suppress HERs and allow the oxygen reduction reaction to dominate at the cathode. The fabricated battery exhibits an operating voltage and areal power of 1.4 V and 0.92 mW cm-2, respectively. Degradation tests show that the full cell completely degrades within 123 days, leaving only Mo fragments from the electrode and biodegradable encapsulation. This study provides insights into bio/ecoresorbable batteries with high power and operating voltage, which can be used for environmental sensing.

Acetylene/argon mixture plasma to build ultrathin carbon bridge of CFx/C/MnO2 for high-rate lithium primary battery

Acetylene/argon mixture plasma to build ultrathin carbon bridge of CFx/C/MnO2 for high-rate lithium primary battery

Polydopamine-modified MXene/cellulose nanofibers composite film for self-powered humidity sensing and humidity actuating

Humidity sensors are of great significance in the domains of wearable electronic products, environmental and food quality monitoring, and human healthcare. In general, they necessitate an external power source in the form of a battery. Despite considerable efforts, developing self-powered sensing systems without reliance on an external power supply remains a major challenge. Herein, an electrochemical humidity sensor with primary battery structure based on redox reaction was designed, in which polydopamine (PDA)-modified MXene/TEMPO-oxidized cellulose nanofibers/LiCl (PDMM/TOCNFs/LiCl) composite film serves as electrolyte layer. The introduction of TOCNFs confers outstanding structural stability and superior tensile strength upon the composite film. Importantly, the hygroscopic and ionic conductivity properties of the PDMM/TOCNFs/LiCl electrolyte allow the sensor to generate spontaneous voltage over a wide relative humidity (RH) range of 11 – 91%. In addition, the developed sensor exhibits excellent humidity-sensing performances, including high voltage response, fast response/recovery time, and superior humidity-sensing stability. Moreover, mussel-inspired PDA improves the ambient stability of MXene by engineering interfacial interactions, which imparts the hygroscopic PDMM/TOCNFs/LiCl composite film with desirable stability for practical applications. Finally, the potential applications of the sensor and the composite film in human respiration, non-contact sensing, and humidity actuating are demonstrated. This work paves the way for the development of an innovative self-powered humidity sensing system.

Improved lithium-ion battery health prediction with data-based approach

The accurate modeling and forecasting of Battery State of Health (SOH) is crucial for ensuring reliable performance and longevity of lithium-ion batteries. This article introduces a data-driven approach for SOH prediction using Gaussian Process Regression (GPR), selected for its ability to model complex data relationships and capture prediction uncertainty without relying on future load information. Recognizing the effect of reversible capacity recoveries on prediction accuracy, this work employs the ISEA-RWTH 48 Li-ion Cells dataset, deliberately devoid of such recoveries prior to training the GPR model. The GPR model was evaluated and compared with Support Vector Regression (SVR) using the publicly available dataset. First and second End of Life (EOL) scenarios were considered, relevant to primary and secondary battery applications. The results demonstrated the GPR model's superior performance. Particularly, mid-life and late-life predictions displayed better accuracy with GPR, showcasing higher R2 values and lower MAPE values (e.g., mid-life prediction: GPR's average R2 = 0.99, SVR's = 0.9789; GPR's average MAPE = 0.1916, SVR's = 1.3028). Moreover, GPR exhibited the ability to quantify uncertainty in capacity degradation and forecast first and second EOL instances effectively (e.g., mid-life predictions had 1.7 cycle error at 1st EOL and 8.9 cycle error at 2nd EOL). The research also offers valuable insights into the application of machine learning methods for predicting the health degradation of lithium-ion batteries.

Frontiers in Operations: Battery as a Service: Flexible Electric Vehicle Battery Leasing

Problem definition: The electric vehicle (EV) manufacturer NIO adopts a swappable-battery design and a battery-leasing business model known as battery as a service (BaaS). It recently introduced flexible battery leasing, which allows customers to temporarily up-/downgrade their primary leased batteries based on the needs for range. We investigate whether this business model innovation is viable, namely whether introducing flexible battery leasing in BaaS could benefit the manufacturer, the customers, and the environment compared with simple battery leasing. Methodology/results: Adopting a game-theoretical model, we find that introducing flexible battery leasing in BaaS can simultaneously improve the manufacturer profit as well as reduce the total customer cost and the total battery capacity. Such win-win-win outcomes generally occur for large high-capacity battery ranges and moderate high-capacity battery costs—both consistent with the ongoing trend in the EV industry and a model-calibration exercise. We further show that this key finding is robust for correlated regular and peak needs for range and when launching BaaS with flexible battery leasing and that if the manufacturer was to choose a high-capacity battery range for flexible battery leasing, it would choose one such that battery reallocation alone can meet all battery up-/downgrade demand without acquiring additional batteries. Managerial implications: Our findings confirm that flexible battery leasing can be a viable BaaS business model innovation and offer insights into when this may be the case. This insight strengthens the strategic support for EV manufacturers’ potential adoption of the swappable-battery design and the BaaS model, and it may inform their operating policies to implement flexible battery leasing. History: This paper has been accepted in the Manufacturing & Service Operations Management Frontiers in Operations Initiative. Supplemental Material: The online appendix is available at https://doi.org/10.1287/msom.2022.0587 .

Building a Rechargeable Voltaic Battery via Reversible Oxide Anion Insertion in Copper Electrodes.

Voltaic pile, the very first battery built by humanity in 1800, plays a seminal role in battery development history. However, the premature design leads to the inevitable copper ion dissolution issue, which dictates its primary battery nature. To address this issue, solid-state electrolytes, ion exchange membranes, and/or sophisticated electrolytes are widely utilized, leading to high costs and complicated cell configuration. Herein, we build a rechargeable zinc-copper voltaic battery from simple and cheap electrolyte/separator materials, thus eliminating the need to use the above components. Notably, our battery leverages the Zn4SO4(OH)6·xH2O precipitation in ZnSO4 electrolytes, a common side reaction in zinc batteries, to provide a "locally alkaline" environment for copper electrodes. Consequently, oxide (O2-) anion insertion takes place and readily transforms copper to copper(I) oxide (Cu2O) without any copper ion dissolution issue. Therefore, this battery realizes a high capacity of ∼370 mA h g-1 and a long cycling of ∼500 cycles. Our work provides an innovative approach to stabilize anion insertion in metal electrodes for energy storage.

High Energy Density of Ball-Milled Fluorinated Carbon Nanofibers as Cathode in Primary Lithium Batteries.

Sub-fluorinated carbon nanofibers (F-CNFs) can be described as a non-fluorinated core surrounded by a fluorocarbon lattice. The core ensures the electron flux in the cathode during the electrochemical discharge in the primary lithium battery, which allows a high-power density to be reached. The ball-milling in an inert gas (Ar) of these F-CNFs adds a second level of conductive sp2 carbons, i.e., a dual sub-fluorination. The opening of the structure changes, from one initially similar multi-walled carbon nanotube to small lamellar nanoparticles after milling. The power densities are improved by the dual sub-fluorination, with values of 9693 W/kg (3192 W/kg for the starting material). Moreover, the over-potential of low depth of discharge, which is typical of covalent CFx, is suppressed thanks to the ball-milling. The energy density is still high during the ball-milling, i.e., 2011 and 2006 Wh/kg for raw and milled F-CNF, respectively.

Sodium Polymer Electrolytes: A Review

Lithium-based electrolytes are, at least from a thermodynamic standpoint, the most suitable ion-transport materials for energy storage systems. However, lithium-based ionic conductors suffer from safety concerns, and the limited availability of lithium in the Earth’s crust is at the root of the need to consider alternative metal ions. Notably, sodium stands out as the sixth most-prevalent element; therefore, when considering mineral reserves, it as a very attractive candidate as an alternative to the status quo. Even if the specific energy and energy density of sodium are indeed inferior with respect to those of lithium, there is substantial economic appeal in promoting the use of the former metal in stationary energy storage applications. For these reasons, the promise of sodium is likely to extend to other commercial applications, including portable electronics, as well as hybrid and electric vehicles. Widely used organic liquid electrolytes, regardless of their chosen metal cation, are disadvantageous due to leakage, evaporation, and high flammability. Polymer electrolytes are acknowledged as the most effective candidates to overcome these obstacles and facilitate the advancement of next-generation energy storage applications. In this contribution, an in-depth and comprehensive review of sodium polymer electrolytes for primary and secondary batteries is proposed. The overarching goal was to gain insight into successful synthetic strategies and their implications for conduction parameters and conductivity mechanisms. The focus lies on solid, gel, and composite polymer electrolytes. Our hope is that the proposed discussion will be helpful to all operators in the field, whether in tackling fundamental research problems or resolving issues of practical significance.

Electrochemical Impedance Spectroscopy (EIS) and non-linear harmonic analysis (NHA) of Li-SOCl[formula omitted]/SO[formula omitted]Cl[formula omitted] batteries

Electrochemical Impedance Spectroscopy (EIS) is a valuable tool for characterizing primary lithium batteries. Before fitting the spectrum, the so-called Kramers–Kronig(KK) method has to be checked for the reliability and accuracy of the EIS spectrum. The decision to further fit and analyze the spectrum for physical events in the system is made after checking the KK compatibility of the spectrum. In this paper, we propose further confirmation of the reliability and the accuracy of the EIS spectrum by using the Non-linear harmonic analysis (NHA) of the measurement. The study shows that the KK-compatible EIS spectrum shows homogeneous higher harmonics results where one can further verify the spectrum. The phase of the excitation signal and its effects on the NHA are discussed. A measurement method for measuring Li/SOCl2 and SO2Cl2 batteries to obtain the KK-compatible EIS spectrum is introduced.

Integration of galvanic reactions and engineered nanoconfinement in iron-copper nanocomposites for highly-efficient remediation of Cr(VI)-contaminated acidic/alkaline water

To eliminate trace toxic hexavalent chromium (Cr(VI)) from water with different pHs, researchers focused on adsorption, reduction of Cr(VI) to trivalent chromium with followed precipitation while the complex and costly reactivity regulations via adjusting pHs was inevitable. Here we exploit Fe-Cu nanocomposites (CnZVI/Cu) with galvanic reactions and engineered nanoconfinement effect for removing Cr(VI) from acidic/alkaline water directly, consisting of phosphorylated cracked nanoscale zero-valent iron (CnZVI, crack width of 1–2 nm) anode and Cu aggregates cathode. The formed primary battery exhibits strong electrostatic interactions towards ions and outstanding reactivity of reduction and precipitation at acidic/alkaline conditions. The pH inside the cracks at neutral or alkaline conditions is calculated to turn lower for enhancing the dynamics relevant to remediation. Benefiting from those two effects, the removal efficiencies of Cr(VI) through CnZVI/Cu attain more than 99.5 % at pH ≤ 8 and even 96 % at pH of 12 in only 30 min, outperforming the previous works. Its protection on beings (water spinach, zebrafish, and cell) from suffering poisonous Cr(VI), control of adsorbed Cr from migration, and magnetic collectability demonstrate the admirable removal performance, biosafety, and stability, respectively. This work proposes highly-efficient, eco-friendly, convenient, and low-cost technology to scavenge Cr(VI) from acidic/alkaline water.

Ultralight Electrolyte with Protective Encapsulation Solvation Structure Enables Hybrid Sulfur-Based Primary Batteries Exceeding 660 Wh/kg.

An electrochemical couple of lithium and sulfur possesses the highest theoretical energy density (>2600 Wh/kg) at the material level. However, disappointingly, it is out of place in primary batteries due to its low accessible energy density at the cell level (≤500 Wh/kg) and poor storage performance. Herein, a low-density methyl tert-butyl ether was tailored for an ultralight electrolyte (0.837 g/mL) with a protective encapsulation solvation structure which reduced electrolyte weight (23.1%), increased the utilization of capacity (38.1%), and simultaneously forfended self-discharge. Furthermore, active fluorinated graphite partially replaced inactive carbon to construct a hybrid sulfur-based cathode to bring the potential energy density into full play. Our demonstrated pouch cell achieved an incredible energy density of 661 Wh/kg with a negligible self-discharge rate based on the above innovations. Our work is anticipated to provide a new direction to realize the practicality of lithium-sulfur primary batteries.

Magnetostrictive energy conversion ability of Iron Cobalt Vanadium alloy sheet: Experimental and theoretical evaluation

The increasing demand for autonomous devices has made the concept of energy harvesting a significant industrial and academic point of interest. In this domain, an ideal magnetostrictive material for converting mechanical vibrations into electrical energy in a cost-effective way (i.e. competing with the price of primary batteries) remains to be determined. Iron-Cobalt-Vanadium (Permendur, Co49-Fe49-V2) is a promising candidate: it is a soft ferromagnetic material with high magnetization saturation, high magnetostrictive coefficients, low price, and good availability. In this study, the experimental magnetic characterization and simulation of Permendur sheets under tensile stress were performed, and their energy conversion capabilities were assessed. The conversion ability was predicted using thermodynamic Ericsson cycles from reconstructed anhysteretic curves. A maximum of 10.45 mJ cm−3 energy density was obtained under a tensile stress of 480 MPa and a magnetic excitation of 5.5 kA m−1. Then, an additional estimation was proposed to account for the hysteresis losses. For this, major hysteresis loops at different stress levels were considered, yielding an energy density of 3.52 mJ cm−3. Finally, experimental Ericsson cycles were performed to prove the feasibility of the conversion and corroborate the energy level predictions.

Hydrophilic 1T-WS2 Nanosheet Arrays toward Conductive Textiles for High-Efficient and Continuous Hydroelectric Generation and Storage.

Flexible hydroelectric generators (HEGs) are promising self-powered devices that spontaneously derive electrical power from moisture. However, achieving the desired compatibility between a continuous operating voltage and superior current density remains a significant challenge. Herein, a textile-based van der Waals heterostructure is rationally designed between conductive 1T phase tungsten disulfide@carbonized silk (1T-WS2@CSilk) and carbon black@cotton (CB@Cotton) fabrics with an asymmetric distribution of oxygen-containing functional groups, which enhances the proton concentration gradients toward high-performance wearable HEGs. The vertically staggered 1T-WS2 nanosheet arrays on the CSilk fabric provide abundant hydrophilic nanochannels for rapid carrier transport. Furthermore, the moisture-induced primary battery formed between the active aluminum (Al) electrode and the conductive textiles introduces the desired electric field to facilitate charge separation and compensate for the decreased streaming potential. These devices exhibit a power density of 21.6µWcm-2, an open-circuit voltage (Voc) of 0.65V sustained for over 10000s, and a current density of 0.17mAcm-2. This performance makes them capable of supplying power to commercial electronics and human respiratory monitoring. This study presents a promising strategy for the refined design of wearable electronics.

Analysis of world trade data with machine learning to enhance policies of mineral supply chain transparency

The increasing integration of supply chains worldwide and the establishment of resilient material flows emphasize the significance of transparency. As regulations and policies around mineral supply become more stringent, organizations are actively seeking effective tools to assess the transparency of their supply chains. Ensuring supply chain transparency plays a vital role in international trade data since it addresses the issue of inconsistent reporting by two parties involved in a transaction, sometimes referred to as bilateral asymmetries. Nevertheless, bilateral asymmetries might be utilized as a proxy to examine discrepancies in the transparency of supply chains.This paper presents a methodology to evaluate supply chain transparency using bilateral asymmetries as a proxy and provide insights into policy changes. We used a machine learning-based methodology on UN Comtrade data to study asymmetry trends in 116 million trade transactions over 30 years. The analysis demonstrates different levels of asymmetry among commodities and countries, suggesting differences in the transparency of supply chains. We exemplified the implementation of the methodology by analyzing 14 commodities associated with lithium batteries and their primary resources. The findings identify seven commodities that exhibit good (reliable) reporting practices, while two commodities (Cobalt and Lithium Primary Batteries) demonstrate bad (unreliable) reporting patterns. This indicates specific areas that should be examined and improved through policy changes. The paper presents a succinct and practical approach to measuring and strengthening supply chain transparency, giving actionable insights for policymakers and stakeholders for future actions.

Ultra-high-purity Mg-Ge anodes enable a long-lasting, high energy-density Mg-air battery

The primary Mg-air battery shows extraordinary theoretical energy density to satisfy the requirements that traditional rechargeable batteries cannot reach. However, the battery has failed to live to its potential due to its low operating discharge voltage, parasitical anodic hydrogen reaction and irreversible corrosion. To address these issues, we devised a process to generate ultra-high-purity (UHP) Mg-Ge anodes for Mg-air batteries. The Ge addition enhances the anodic reaction activity and suppresses the anodic hydrogen evolution reaction (AHER). Hence, the fabricated UHP Mg-0.5Ge anode exhibited a remarkably high discharge voltage of 1.69 V (0.5 mA cm−2) coupled with a high energy density of 2272 mWh g−1 (20 mA cm−2). These values are higher than all the reported Mg-based anodes in the literature. Furthermore, the minimal impurity content and the development of a Ge-bearing surface layer contribute to the UHP Mg-0.5Ge anodes achieving a 95% intermittent discharge efficiency, which is 3.5 times higher than that of the commonly employed AZ31 anode. The outstanding properties of the fabricated UHP Mg-Ge anode set the stage for advancing the next generation of Mg-air batteries.