Manganese Batteries Research Articles

A sustainable route: from wasted alkaline manganese batteries to high-performance cathode for aqueous zinc ion batteries

A sustainable route: from wasted alkaline manganese batteries to high-performance cathode for aqueous zinc ion batteries

Predictive pretrained transformer (PPT) for real-time battery health diagnostics

Modeling and forecasting the evolution of battery systems involve complex interactions across physical, chemical, and electrochemical processes, influenced by diverse usage demands and dynamic operational patterns. In this study, we developed a predictive pre-trained Transformer (PPT) model equipped with 1,871,114 parameters that enhance identification of both short-term and long-term patterns in time-series data. This is achieved through the integration of convolutional layers and probabilistic sparse self-attention mechanisms, which collectively enhance prediction accuracy and efficiency in diagnosing battery health. Moreover, the customized hybrid-model fusion supports parallel computing and employs transfer learning, reducing computational costs while enhancing scalability and adaptability. Consequently, this allows for precise real-time health estimations across various battery cycles. We validated this method using a public dataset of 203 commercial lithium iron phosphate (LFP)/graphite batteries charged at rates ranging from 1C to 8C. By using only partial charge data—from an 80 % state of charge to the maximum charging voltage (3.6 V for LFP batteries, 4.2 V for ternary batteries)—and avoiding complex feature engineering, error metrics were achieved below 0.3 % for root mean square error (RMSE), weighted mean absolute percentage error (WMAPE), and mean absolute error (MAE), with an R2 of 98.9 %. The generalization capabilities were further demonstrated across 36 different testing protocols, encompassing 23,480 cycles throughout the entire life cycle, with a total inference time of 9.88 s during the testing phases. Further experiments on 30 nickel cobalt aluminum (NCA) batteries and 36 nickel cobalt manganese (NCM) batteries, across different battery types and operational scenarios, resulted in RMSE, WMAPE, and MAE all below 0.9 %, with R2 values of 94.1 % and 94.4 %, respectively. These findings highlight the potential of our customized deep transfer neural networks to enhance diagnostic accuracy, accelerate training, and improve generalization in real-time applications.

Monoclinic Silver Vanadate (Ag0.33V2O5) as a High-Capacity Stable Cathode Material for Aqueous Manganese Batteries.

Aqueous rechargeable metal batteries have recently garnered considerable attention owing to their low cost, sufficient capacity, and the use of non-flammable water-based electrolytes. Among them, manganese batteries are particularly favored because of their stability, abundance, affordability, and high energy density. Despite their advantages, Mn storage host structures remain underexplored. Therefore, developing innovative host materials is crucial for advancing this field. In this paper, the study reports for the first time, the use of Ag0.33V2O5 as a cathode material in aqueous manganese batteries. The study explains the displacement/intercalation behavior of manganese and silver using electrochemical, structural, and spectroscopic analyses. Additionally, it is shown that cation (Ag+, Mn2+, H+) diffusion pathways can be simulated using diffusion-barrier calculations. Finally, the study demonstrates high-performance manganese batteries that exhibit a remarkable reversible capacity of ≈261.9 mAhg-1 at a current of 0.1 Ag-1 and an excellent cycle retention of 69.1% after 2000 cycles at a current density of 1.5 A/g. The findings of this study contribute to the advancement of aqueous manganese battery technology, offering a promising pathway for developing safer, more cost-effective, and high-performance energy storage systems.

Process and kinetics of ammonium sulfide removal of zinc, nickel and cobalt from manganous sulfate electrolyte

In producing electrolytic manganese and manganese-based lithium batteries, Manganous sulfate solution serves as a crucial intermediate material. During the preparation of manganese sulfate solution by acid leaching, the removal of impurities such as zinc, nickel, and cobalt ions by sulfide precipitation is essential for obtaining high-quality metallic manganese and high-purity manganese sulfate. The results show that when the temperature is 45 °C, the pH is 5.60, the ammonium sulfide dosage is 40 %, the time is 5 min, and the rotation speed is 650 rpm, the sulfidation rates of zinc, nickel and cobalt are 99.07 %, 89.30 %, and 87.70 % respectively. At this time, the loss rate of manganese in the solution after sulfide impurity removal is 11.45 %, and the manganese-impurity ratio is 80.00. Response surface methodology analysis revealed that temperature, pH, and ammonium sulfide concentration significantly affected the manganese loss rate. After process optimization, at a temperature of 32.70 °C, a pH of 5.20, and an ammonium sulfide concentration of 32.73 %, the manganese loss rate decreased to 6.05 %, while the removal rates of Ni, Co, and Zn were 75.35 %, 60.80 %, and 99.51 %, respectively. In the Manganous sulfate electrolyte with or without ammonium sulfate, the sulfide precipitation processes of zinc, nickel and cobalt ion are all first-order reactions, and the reaction order is zinc > nickel > cobalt. More importantly, the density functional theory (DFT) calculation results also confirmed the formation sequence of zinc sulfide > nickel sulfide > cobaltous sulfide, which supported the experimental results well. This study will lay the foundation for process optimization and mechanism elucidation of impurity ions in ammonium sulfate electrolyte precipitated by ammonium sulfate.

State-of-charge estimation for lithium-ion batteries based on modified unscented Kalman filter using improved parameter identification

The full and single hybrid pulse power characterization (HPPC) experiments are conducted on nickel cobalt manganese (NCM) and lithium iron phosphate (LFP) batteries to obtain the accurate relationship between state of charge (SOC) and open circuit voltage (OCV). The pseudo random number generated by the RAND function is used as the initial value of the parameter identification equation for the second-order equivalent circuit model (ECM), and the parameter identification of lithium-ion batteries is achieved through least squares fitting. The unscented Kalman filter (UKF) simulation model is modified by the first order low pass filtering (FOLPF) algorithm to improve the accuracy of SOC estimation of batteries. The results show that the goodness of fit between the real and estimated HPPC pulse voltage values at different SOC values is above 0.99 for both NCM and LFP batteries. Based on the parameter identification results, the maximum error of the HPPC voltage estimated by the second-order ECM is within 0.045 V under both full pulse and single pulse testing conditions while the maximum error of SOC estimation is within 0.025. The UKF model modified by the FOLPF algorithm provides a reference for the accurate SOC estimation of batteries.

A New Design Strategy Enables High Mn‐Utilization Rate in Aqueous Zinc–Manganese Batteries: Constructing Cathodic Local Mn‐Rich Region

AbstractThe deposition–dissolution mechanism with a two‐electron transfer reaction endows aqueous Zn–Mn batteries with a desirable theoretical energy density. However, due to the limited solubility of traditional manganese‐based materials and the competitive Mn shuttle behavior, the practical performance is unsatisfactory. Herein, by synergistically incorporating a novel Mn‐rich Mn4N cathode with a plasma functionalized carbon nanotubes film (PCNT) interlayer, an aqueous Zn–Mn battery with a high Mn‐utilization rate and high energy/power density is successfully developed. Specifically, the Mn4N cathode boasts high manganese content and dissolution activity, thereby offering a copious supply of Mn2+ ions for the battery system. The PCNT interlayer, with abundant micropore structures and functional groups, not only restrains the Mn2+ shuttle by entrapping the dissolved Mn2+ but also offers copious reaction sites, ensuring concentrating Mn2+ on the cathodic side and maximizing their contribution to the electrochemical reaction. Consequently, Mn4N‐PCNT exhibits a low polarization voltage and superior Mn‐utilization rate (64.8%). Without the MnSO4 additive, Mn4N‐PCNT achieves an ultra‐high energy density of 821.9 W h kg−1 and remarkable long‐term cycling stability (90% capacity retention over 9000 cycles). The delightful results demonstrate the practical application potential of Mn4N‐PCNT and open up new avenues for the rational design of advanced Zn–Mn batteries.

Study on the Catalytic Oxidation of Toluene Using CeO2@S-AZMB Prepared from Spent Zn-Mn Batteries

The recycling and utilization of waste alkaline zinc manganese batteries (S-AZMB) has always been a focus of attention in the fields of environment and energy. However, current research mostly focuses on the recycling of purified materials, while neglecting the direct reuse of waste batteries. Here, we propose a new concept of preparing thermal catalysts by combining unpurified S-AZMB with CeO2 by means of ball milling. A series of characterizations and experiments have confirmed that the combination with S-AZMB not only enhances the thermal catalytic activity of CeO2 but also significantly enhances the concentration of surface oxygen vacancies. In the toluene removal experiment, the temperature (T90) at 90% toluene conversions of CeO2@S-AZMB was 180 °C, lower than the 220 °C for CeO2. More noteworthy is that this S-AZMB-based thermal catalyst can maintain a good structure and thermal catalytic stability in cyclic catalysis.

In situ architecting amorphous manganese oxide/MXene heterostructure electrode with fast ion transport and structural stability in aqueous Zn–Mn batteries

An in situ constructed a-MnO2/Ti3C2F heterojunction combines the advantages of 2D layered and amorphous structures, providing abundant ion diffusion channels that facilitate rapid Zn ion diffusion and the reversible formation of ZSH.

PH buffer KH2PO4 boosts zinc ion battery performance via facilitating proton reaction of MnO2 cathode

Zinc-ion batteries (ZIBs) are rapidly emerging as safe, cost-effective, nontoxic, and environmentally friendly energy storage systems. However, mildly acidic electrolytes with depleted protons cannot satisfy the huge demand for proton reactions in MnO2 electrodes and also cause several issues in ZIBs, such as rapidly decaying cycling stability and low reaction kinetics. Herein, we propose a pH-buffering strategy in which KH2PO4 is added to the electrolyte to overcome the problems caused by low proton concentrations. This strategy significantly improves the rate and cycle stability performance of zinc–manganese batteries, delivering a high capacity of 122.5 mAh/g at a high current density of 5 A/g and enabling 9000 cycles at this current density, with a remaining capacity of 70 mAh/g. Ex-situ X-ray diffraction and scanning electron microscopy analyses confirmed the generation/dissolution of Zn3PO4·4H2O and Zn4(OH)6(SO4)·5H2O, byproducts of buffer products and proton reactions. In-situ pH measurements and chemical titration revealed that the pH change during the electrochemical process can be adjusted to a low range of 2.2–2.8, and the phosphate distribution varies with the pH range. Those results reveal that H2PO4− provides protons to the cathode through the chemical balance of HPO42−, HPO42–, and Zn3PO4·4H2O. This study serves as a guide for studying the influences and mechanisms of buffering additives in Zn–MnO2 batteries.

Effect of Na2SiO3 and TEA Electrolyte Additives on the Corrosion Inhibition of Zinc Electrodes and Electrochemical Performance of Rechargeable Alkaline Manganese Batteries

To inhibit hydrogen evolution corrosion, passivation, and zinc dendrite growth during the charging and discharging of the zinc negative electrode of rechargeable alkaline manganese battery containing ultra-fine zinc powders, the effects of the single addition amounts of inorganic corrosion inhibitor Na2SiO3 and organic corrosion inhibitor TEA and their compounding ratio on the corrosion inhibition effect and the charging and discharging performance of alkaline manganese battery were systematically investigated in this paper. SEM and XPS were used to observe the microscopic morphology of the zinc anode, and the inhibition mechanisms of the relevant inhibitors were explored. The results show that, the addition of Na2SiO3 and TEA can synergistically improve the coverage of the protective film, thereby inhibiting hydrogen evolution corrosion, passivation and dendrites of zinc electrodes. Compared to blank electrolyte, when the composite concentration of Na2SiO3 and TEA is 1 g l−1 Na2SiO3+56.25 mg l−1 TEA, the hydrogen evolution corrosion inhibition efficiency can reach 70.56%, the initial specific capacity and the specific capacity after 50 cycles can increase from 160.7 mAh g−1, 58 mAh g−1 to 198.4 mAh g−1, 74 mAh g−1, respectively. This study has great theoretical and engineering value for guiding the design of electrolytes for rechargeable alkaline manganese batteries.

High Areal-Capacity Aqueous Manganese-Based Batteries Enabled by Redox Mediators

Aqueous manganese batteries based on deposition-dissolution of Mn2+/MnO2 reactions have aroused great attention due to their intrinsic low cost, high potential, and high energy.1, 2 However, the incomplete dissolution and exfoliated dead MnO2 would inevitably lead to capacity loss and poor cyclability at high areal capacity application.3, 4 Herein, we apply a redox mediator strategy to dissolve the accumulated MnO2 via a spontaneous chemical reaction between redox mediators iodide and MnO2.5,6 During the discharge process, the iodide (I–) could react with the residual MnO2 and be oxidized to I3 – that could be further reduced back to I– on the electrode, continuing this process until fully dissolved the accumulated MnO2. We will discuss detailed reaction mechanisms verified by ex-situ UV-vis spectroscopy, scanning electron microscopy, and X-ray diffraction. The zinc-manganese (Zn-Mn) battery with iodide mediator showed improved cycling stability at 2.5 mAh cm–2 (400 vs. 100 cycles, static mode) and 15 mAh cm–2 (225 vs. 60 cycles, flow mode). Areal capacity is one of the most important parameters determining system energy for deposition-based batteries.7 The Zn-Mn flow cell could demonstrate a high areal capacity application at 50 mAh cm–2 for 50 cycles. We will discuss how to expand this strategy to other manganese-based batteries and broaden the horizon of aqueous batteries.AcknowledgmentThis work is supported by a grant from the Research Grant Council of the Hong Kong Special Administrative Region, China (project no. C1002-21G).Reference W. Chen, G. Li, A. Pei, Y. Li, L. Liao, H. Wang, J. Wan, Z. Liang, G. Chen, H. Zhang, J. Wang and Y. Cui, Nat. Energy, 2018, 3, 428-435. D. Chao, W. Zhou, C. Ye, Q. Zhang, Y. Chen, L. Gu, K. Davey and S.-Z. Qiao, Angew. Chem. Int. Ed. Engl., 2019, 58, 7823-7828. C. Liu, X. Chi, Q. Han and Y. Liu, Adv. Energy Mater., 2020, 10, 1903589. G. Liang, F. Mo, H. Li, Z. Tang, Z. Liu, D. Wang, Q. Yang, L. Ma and C. Zhi, Adv. Energy Mater., 2019, 9, 1901838. J. Lei, Y. Yao, Z. Wang and Y.-C. Lu, Energy Environ. Sci., 2021, 14, 4418-4426. J. Lei, Y. Yao, Y. Huang and Y.-C. Lu, ACS Energy Letters, 2022, DOI: 10.1021/acsenergylett.2c02524, 429-435. Y. Yao, J. Lei, Y. Shi, F. Ai and Y.-C. Lu, Nat. Energy, 2021, 6 (6), 582–588.

In-situ cation-inserted MnO2 with selective accelerated intercalation of individual H+ or Zn2+ ions in aqueous zinc ion batteries

The recognized energy storage mechanism of neutral aqueous zinc–manganese batteries is the co–insertion/extrusion of H+ and Zn2+ ions. However, modulating the kinetics of a single H+ or Zn2+ ion is scarce, which can provide meaningful insights into the energy storage mechanism of Zn ion batteries. Herein, a distinctive doubly electric field in-situ induced cationic anchoring of two-dimensional layered MnO2 is successfully constructed to modulate the insertion/extrusion of a single H+ or Zn2+ ion. As a result, regulating the intercalation of different metal ions can precisely achieve the accelerated induction for the individual H+ or Zn2+ ions intercalation/deintercalation. Moreover, the introduction of metal ions stabilizes the lattice distortion and alleviates the irreparable structural collapse, leading to an increase in the H+/Zn2+ storage sites, efficiently diminishing the stagnation of the ordered structure and creating the more open channels, which is conducive to facilitating the diffusion of ions. This work delivers some innovative insights into pre-embedding strategies, and also serves as a precious reference for the cathode development of advanced aqueous batteries.

Assessing the feasibility of the Inflation Reduction Act’s EV critical mineral targets

Electric vehicle batteries contain many internationally sourced critical minerals. Seeking a stable mineral supply, the US Inflation Reduction Act sets a market-value-based target for battery critical mineral content. In 2027, for an electric vehicle to be tax-credit eligible, 80% of the market value of critical minerals in its battery must be sourced domestically or from US free-trade partners. We determined that the target may be achievable for fully electric vehicles with nickel cobalt aluminium cathode batteries, but achieving the target with lithium iron phosphate and nickel cobalt manganese batteries would be challenging. We also note that a mass-based target could avoid some of the challenges posed by a market-value target, such as volatile market prices. We further conclude that the approach the Act has taken ignores the environmental effects of mining, non-critical minerals supply, support for recycling and definitions that avoid gamesmanship.

Quasi‐Decoupled Solid–Liquid Hybrid Electrolyte for Highly Reversible Interfacial Reaction in Aqueous Zinc–Manganese Battery

AbstractAqueous zinc–manganese batteries with low cost, reliable safety, and considerable energy density, show promise for grid‐scale storage. Their durable operation is highly dependent on the reversibility and stability of both electrode interfaces, which is limited by the different requirements of the interfaces of manganese‐based cathodes and zinc anodes. Here, a quasi‐decoupled solid–liquid hybrid electrolyte is proposed, which demonstrates good compatibility and high reversibility for both interfaces with different electrolyte environments, showing quasi‐decoupling characteristics. Such a hybrid electrolyte can endow the anode interface with abundant favorable nucleation sites for achieving uniform zinc platting/stripping, as well as limit the presence of free H2O molecules, to suppress side‐reactions. This electrolyte is also adapted to a reversible and stable MnO2/Mn2+ manganese deposition/dissolution reaction at the cathode interface by restricting OH−/H+ ion diffusion, preventing formation of irreversible electrochemically inert MnOOH. As a result, the quasi‐decoupled solid–liquid hybrid electrolyte enables Zn||Zn cycling for more than 500 h, and a specific capacity of a Zn||α‐MnO2 battery up to 348 mAh g−1 at 0.2 A g−1. It also allows 87% capacity retention after 500 cycles at 0.5 A g−1. This work provides a new insight into electrolyte design that focuses on the different requirements of differing electrode interfaces.

Applications and Recycling of Lithium-ion Batteries

With the rise of global warming, people have turned to electricity as a means of reducing greenhouse gas emissions, and Lithium-ion batteries (LIBs) have emerged as a popular energy conservation solution. However, as the use of LIBs increases, the recycling industry is facing significant wastemanagement challenges. The decreasing content of precious metals in LIBs has led to a decline in recycling income. This article explores the application of LIBs in new energy vehicles, and evaluates the challenges faced by the recycling industry and provides suggestions for overcoming them. Currently, lithium iron phosphate, lithium nickel cobalt manganese and lithium nickel cobalt aluminum batteries have been used in new energy vehicle power batteries. The main recycle methods include direct recycling, hydrometallurgy, and pyrometallurgy. The article then suggests that improved recycling lines that use artificial intelligence and renew manufacturing standards may be beneficial solutions. By addressing these challenges, the problems associated with LIB recycling may be transformed into opportunities for the future.

Environmental trade-offs and externalities of electrochemical-based batteries: Quantitative analysis between lithium-ion and vanadium redox flow units

This study aims to increase the scientific knowledge of the environmental impacts and externalities of two promising electrochemical-based techniques for large-scale stationary energy storage: lithium nickel cobalt manganese (NCM) and vanadium redox flow (VRF) batteries. The global warming potential (GWP) and cumulative energy demand (CED) for NCM and VRF batteries are 28 kg CO2eq and 410 MJ and 186 kg CO2eq and 3080 MJ, respectively, for the provision of 1 MWh of electricity. While the trend of the environmental externality results is proportional to the environmental impact results, the environmental costs from GWP and terrestrial ecotoxicity impacts contribute the largest share of the total environmental costs for both batteries. Overall, NCM batteries have favorable environmental performance in terms of their impact values and externalities but still show relatively higher contributions in human toxicity and ozone layer depletion impacts, based on their high resource uses. The VRF batteries, on the other hand, report higher impacts in abiotic depletion, GWP and terrestrial ecotoxicity, mainly due to their great mass of the electrolyte. Our results highlight the importance of substituting the active metals with low-impact metals or carefully considering the origin of key materials while also taking advantage of the properties of the battery to carefully assess possible advancements in battery design. The environmental externality results also provide essential information for the future development of battery industries for stationary applications with energy and environmental benefits.

PVDF−HFP binder for advanced zinc−manganese batteries

In order to optimize and select the appropriate binder to improve the electrochemical performance of aqueous zinc−manganese batteries, the influences of water-soluble binders and oil-based binders on the zinc storage performance of manganese-based cathode materials were systematically investigated. The results show that the water-soluble binders with large numbers of hydroxyl and carboxyl groups are easily soluble in aqueous electrolytes, leading to poor electrochemical performance. Fortunately, the cathodes with polyvinylidene fluoride− hexafluoropropylene (PVDF−HFP) binder display high specific capacity of 264.9 mA·h/g and good capacity retention of 92% after 90 cycles at 100 mA/g. Meanwhile, PVDF−HFP binder with plenty of hydrophobic groups presents excellent ability in inhibiting cracks on the surface of electrode, reducing voltage polarization and charge transfer resistance, as well as maintaining electrode integrity.

Machine-Learning-Assisted Prediction of Maximum Metal Recovery from Spent Zinc–Manganese Batteries

Spent zinc–manganese batteries contain heavy toxic metals that pose a serious threat to the environment. Recovering these metals is vital not only for industrial use but also for saving the environment. Recycling metal from spent batteries is a complex task. In this study, machine-learning-based predictive models are developed for predicting metal recovery from spent zinc–manganese batteries by studying the energy substrates concentration, pH control of bioleaching media, incubating temperature and pulp density. The main objective of this study is to make a detailed comparison among five machine learning models, namely, linear regression, random forest regression, AdaBoost regression, gradient boosting regression and XG boost regression. All the machine learning models are tuned for optimal hyperparameters. The results from each of the machine learning models are compared using several statistical metrics such as R2, mean squared error (MSE), mean absolute error (MAE), maximum error and median error. The XG Boost regression model is observed to be the most effective among the tested algorithms.

Improving stability and reversibility via fluorine doping in aqueous zinc–manganese batteries

Constructing stable and reversible manganese-based cathode is one of the key technologies of aqueous Zn/MnO2 batteries (AZMBs). Herein, a rational strategy of fluorine doping is proposed to improve the reversibility and activity of MnO2. According to the strong bonding induced by high electronegativity of fluorine, the integrity of frameworks can stabilize, and the ion diffusion kinetics is promoted. Meanwhile, the strong ‘pinning effect’ of fluorine effectively retains the electrochemical activity and guides the reversible electrochemical behavior, which plays a critical role in improving both the cycle life and energy efficiency. As expected, a significant specific capacity of 300 mAh/g at 0.6 C and impressive stability over 1,200 cycles at 5 C are achieved without obvious decay. Such high stable Zn/F–MnO2 system may provide novel perspectives for designing high-performance AZMBs.

Towards high-areal-capacity aqueous zinc–manganese batteries: promoting MnO2 dissolution by redox mediators

A mediator strategy is proposed to facilitate MnO2 dissolution and recover ‘lost’ capacity from exfoliated MnO2, which improves the cycling stability at high areal capacity of Zn–Mn2+/MnO2 batteries.