Academic literature on the topic 'Multi-valent batteries, electrolyte, rechargeable battery'

Abstract The rapid development of portable smart devices and electric vehicles is placing greater demands on the energy density and safety of rechargeable secondary batteries. Lithium-ion batteries using the Solid State Electrolyte (SSE) are considered to be the most promising direction to achieve these goals. Among the latest electrolyte developments, chloride solid electrolytes have attracted much attention due to their physicochemical properties such as high ionic conductivity, ease of deformation and oxidative stability. In this paper, a one-dimensional model of a solid-state Li3HoCl6 battery is proposed based on COSMOL Multiphysics multi-physics field simulation software, and the charge-discharge curves and lithium-ion concentration variation curves at different discharge rates are obtained. The results show that the battery has a stable potential and relatively high-capacity density at low C rates (1.8C~14.4C). Therefore, it has application values at low currents and space for improvement at high currents.

Rechargeable aqueous zinc-ion batteries (ZIBs) have attracted much attention recently due to the high abundance, low cost, high theoretical capacity up to 820 mAh g-1 with multi-valent charge carrier, and compatibility with aqueous electrolyte of the zinc anode.[1] Especially, the introduction of neutral or mild acidic electrolyte greatly improves the reversibility of zinc anode compared to conventional alkaline ZIBs.[2] Among all the cathode candidates, MnO2 is most attractive due to its relatively high energy density, low toxicity and low cost.[3] However, MnO2 electrode suffers from capacity fading during cycling mainly due to Mn dissolution and structural change. The addition of Mn2+ into the mild acidic electrolyte is a common method to suppress Mn dissolution.[4] Other strategies like structural design and surface coatings are also developed to suppress Mn dissolution.[5, 6] Though the cycle performance still cannot meet the demand of application, as the irreversible formation of inactive ZnMn2O4 during cycles still requires to be tackled. Here, we proposed Bi2O3 as a facile electrode additive in the electrode to suppress ZnMn2O4 formation and improve the cyclability of commercial electrolytic manganese dioxide (EMD). XRD, in-situ pH measurements and ICP tests suggest that inactive ZnMn2O4 is formed upon cycling due to the interaction between MnO2 and zincate ions in the electrolyte from localized increase in pH, and Bi2O3 dissolves into the electrolyte in the presence of zincate ions and forms a complex with the zincate ions to suppress the reaction pathway. A high capacity of 269 mAh g-1 is maintained at 100 mA g-1 after 50 cycles with a capacity retention of 91.5% when EMD with 10 wt% of Bi2O3 is tested in ZnSO4 electrolyte without Mn2+ additive. Combining both Bi2O3 electrode additive and Mn2+ electrolyte additive, EMD can maintain a stable capacity of 190 mAh g-1 for 1000 cycles at 1000 mA g-1 (about 3.3C). More characterizations are underway to further understand the role of Bi2O3 and the results will be shown during the meeting. Reference: [1] B. Tang, L. Shan, S. Liang, J. Zhou, Issues and opportunities facing aqueous zinc-ion batteries, Energy & Environmental Science, 12 (2019) 3288-3304. [2] J. Hao, X. Li, X. Zeng, D. Li, J. Mao, Z. Guo, Deeply understanding the Zn anode behaviour and corresponding improvement strategies in different aqueous Zn-based batteries, Energy & Environmental Science, 13 (2020) 3917-3949. [3] N. Zhang, X. Chen, M. Yu, Z. Niu, F. Cheng, J. Chen, Materials chemistry for rechargeable zinc-ion batteries, Chemical Society Reviews, 49 (2020) 4203-4219. [4] H. Pan, Y. Shao, P. Yan, Y. Cheng, K.S. Han, Z. Nie, C. Wang, J. Yang, X. Li, P. Bhattacharya, Reversible aqueous zinc/manganese oxide energy storage from conversion reactions, Nature Energy, 1 (2016) 1-7. [5] J. Huang, Z. Wang, M. Hou, X. Dong, Y. Liu, Y. Wang, Y. Xia, Polyaniline-intercalated manganese dioxide nanolayers as a high-performance cathode material for an aqueous zinc-ion battery, Nature communications, 9 (2018) 1-8. [6] B. Wu, G. Zhang, M. Yan, T. Xiong, P. He, L. He, X. Xu, L. Mai, Graphene scroll‐coated α‐MnO2 nanowires as high‐performance cathode materials for aqueous Zn‐ion battery, Small, 14 (2018) 1703850. Figure 1

Free-standing films based on MnO2@multi-walled carbon nanotubes (MWCNTs)@Polypyrrole (PPy) have been fabricated for aqueous zinc-ion batteries. A simple hydrothermal method was adopted to synthesize ß-MnO2 nanowires. PPy coated the ß-MnO2 nanowires@MWCNTs composite by an in-situ polymerization process. Free-standing films of ß-MnO2@MWCNTs@PPy composite were prepared by a convenient vacuum-assisted filtration. A zinc-ion battery is fabricated with a zinc foil anode and a ß-MnO2@MWCNTs@PPy composite cathode. The Zn//ß-MnO2@ MWCNTs@PPy system in ZnSO4@MnSO4 aqueous electrolyte exhibits high electrochemical performances, such as an initial capacity of 258.5 mAh g-1 at 0.2 A g-1, and about 74.6% retention after 100 cycles with near 100% Coulombic efficiency. The strategy of conductive polymer coating makes the technology of rechargeable zinc-ion batteries (ZIBs) very promising and provides opportunities of organic-inorganic composite materials for energy storage applications.

Zinc-air battery technology is gaining recognition as a promising energy storage device to be used in portable electronics and electric vehicles. Despite possessing high theoretical energy density, environmental and operational safety, and easy accessibility of zinc reservoirs, the successful commercialization of zinc-air batteries suffers due to the poor oxygen electrocatalysis kinetics at the air cathode. The kinetically inept oxygen reduction and oxygen evolution reactions at the cathode lead to a large overpotential barrier and poor charge-discharge cyclic performance of the rechargeable zinc-air battery. This work demonstrates designing a multi-principal metal bifunctional electrocatalyst that is directly deposited on conductive, porous, and flexible substrates to eliminate the necessity of polymeric binders. The flexible bifunctional oxygen electrocatalyst used for the cathode of solid-state ZAB is assembled with gel polymer electrolyte and zinc anode giving excellent charge-discharge cyclic stability and constant discharge voltage (close to 1.65 V). These multi-principal metal electrocatalysts constituting quasi-equimolar concentration, provide numerous combinations of surface functionality, multiple adsorption sites, and electronic environments thus enabling better optimization of the catalytic performance.

In the current study, we prepared a LixLa3Zr2O12 ((Al, Ta) LLZO) powder doped with 0.2 mol of Al and Ta using the sol-gel method and subsequently used it to fabricate solid electrolyte pellets. In pellets with lithium content of 6.2 and 6.82 mol, a cubic phase and a lithium-deficient pyrochlore mixed-phase were respectively observed. However, when the lithium content was 8.06 mol, a lithium-excess phase was also observed. Meanwhile, at 7.44 mol lithium, the (Al, Ta) LLZO ceramic pellets showed a pure cubic garnet phase with no secondary phase. When lithium was added excessively, a non-granular morphology was observed at the (Al, Ta) LLZO fracture surface in which the grains were tightly bonded by the liquid phase formed during sintering. Nyquist plots of the pellets showed that the effect of grain boundaries was eliminated and the pellets exhibited a high lithium ion conductivity of 4.26 × 10−4 S/cm. Using spin coating and multi-step heat treatment, we deposited LiCoO2 (LCO) thin films on (Al, Ta) LLZO pellets to form cathodes. There was no significant interdiffusion between the LCO cathode and (Al, Ta) LLZO solid electrolyte and morphological analysis indicted that a thin interfacial layer (~10 nm) was formed between the LCO and the electrolyte. Finally, we demonstrated an all-solid-state rechargeable battery in the form of a coin cell comprising of an LCO cathode, Li metal anode, and (Al, Ta) LLZO solid electrolyte, which could yield a discharge capacity of ~100 mAh/g.

A lithium–selenium (Li–Se) battery is considered as a promising next-generation energy storage system due to its ultrahigh volumetric energy density. However, the capacity attenuation due to the dissolution and shuttle effect of polyselenides is urgent to be addressed. Herein, 1,4-benzenedithiol (1,4-BDT) and benzeneselenol (PhSeH) are proposed as redox mediator additives in the electrolyte. They both change the multi-step reaction of Se and accelerate the redox kinetics, thus suppressing the shuttle effect of polyselenides and improving the cycling stability and rate performance. The Li–Se cell with 1,4-BDT exhibits steady 450 cycles at 1 C with capacity decay only 0.058% per cycle. Differently, the Li–Se cell with PhSeH features fast kinetics, which shows 91.4% capacity retention after 450 cycles at a high rate of 5 C. Due to the difference of molecular structures between 1,4-BDT and PhSeH, the cyclic oligomers formed in the Li–Se cell with 1,4-BDT diminish the solubility of polyselenides enhancing the cycling stability, while the chain-like diphenyl selenides generated in the Li–Se cell with PhSeH promote kinetics performance through a single-phase reaction. This work provides an effective redox regulation strategy that will stimulate interest in exploration of organic mediators for rechargeable batteries.

Recently, needs to rechargeable batteries have been diversified into various kinds due to expansion of their application range. Not only future high-performance batteries exceeding Li-ion batteries (LiBs), but also new concept ones, which are composed solely of common elements and have performance comparable to current LiBs, have become one of the important recent research targets in this area. Focusing rich abundance and very-high theoretical capacity (2980 mAh g-1, 8046 mAh cm-3) of aluminum (Al) metal, we have created new concept rechargeable batteries with the following anode reaction in chloroaluminate ionic liquids (ILs):1,2 4[Al2Cl7]- + 3e- ⇌ Al + 7[AlCl4]- Many research groups have also reported similar Al metal anode batteries.3 Herein, some sulfur (S) composite cathodes that enable the use of S(IV)/S electrode reaction are designed to greatly enhance the capacity of Al metal anode battery. The preparation and purification processes for 60.0-40.0 mol% AlCl3–[C2mim]Cl and 61.0-26.0-13.0 mol% AlCl3–NaCl–KCl IL electrolytes were identical with those described in our previous articles.1,2 Three types of cathode active materials, S-coated multi-walled carbon nanotube (S-MWCNT), sulfurized polyethylene glycol (SPEG),4 and sulfurized polyacrylonitrile (SPAN),5 were employed. All the S composite electrodes were prepared by pressing the mixtures of 50 wt% S-based cathode active materials, 45 wt% conductive additive (MWCNT), and 5 wt% polytetrafluoroethylene onto Mo plate current collectors. Al metal plate was employed as the anode active material. Electrochemical experiments were carried out with a commonly used three-electrode cell or a two-electrode sealed cell in an Ar gas-filled glove box with O2 and H2O < 1 ppm. Figure 1 shows multiple cyclic voltammograms recorded at a S-MWCNT composite electrode in a three-electrode cell with 60.0-40.0 mol% AlCl3–[C2mim]Cl at 298 K. When the potential scan was initiated from the rest potential to the negative direction, a pair of reduction and oxidation waves appeared with large over potential. These waves gradually varied with an increase in the number of cycles. Considering the article reported by Gao et al.,6 the redox waves observed in Fig. 1a can be regarded to be the following electrochemical reaction (S/S2-): 3S + 8[Al2Cl7]- + 6e- ⇌ Al2S3 + 14[AlCl4]- As for the positive scan from the rest potential (Fig. 1b), several oxidation and reduction waves were observed. Overpotential obviously diminished compared to that for the S/S2-. Similar electrode behavior for S in a Lewis acidic 63-37 mol% AlCl3–NaCl molten salt is reported by Marassi, et al.7 Given that the electrochemical reaction process is the same, the number of electrons involved in the reaction is estimated to be 4. Then, the electrochemical reaction (S(IV)/S) is: [SCl3]+ + 3[Al2Cl7]- + 4e- ⇌ S + 6[AlCl4]- If we can apply this S(IV)/S reaction to the Al metal anode-S cathode rechargeable battery, S cathode capacity becomes double and higher working voltage is expected relative to conventional S/S2- one. Unfortunately, the redox waves for the reaction decrease sharply with increase in the cycle number. The waves almost disappeared at the 5th cycle. Analogous results were also obtained in the 61.0-26.0-13.0 mol% AlCl3–NaCl–KCl. We concluded that the electrode reaction for S(IV)/S on the S-MWCNT composite cathode is not suitable for battery application. However, the use of S-combined active materials, SPEG and SPAN, substantially improved the electrode reaction in the 61.0-26.0-13.0 mol% AlCl3–NaCl–KCl IL at 393 K. Thus, we carried out the charge-discharge test for the Al | SPEG and Al | SPAN batteries with the inorganic IL electrolyte using both S/S2- and S(IV)/S electrode reactions. If SPEG was used, the discharge capacity was ca. 1050 mAh (g-S)-1 at 50th cycle. When using only S/S2- reaction, such high capacity was not attained.2 The S(IV)/S electrode reaction should be directly involved in the capacity increase. Interestingly, the use of SPAN made further improvement possible. One of the typical results is shown in Fig. 2. At the first cycle, the discharge capacity reached ca. 4700 mAh (g-S)-1 and showed ca. 2600 mAh (g-S)-1 even after 50th cycle. These results suggest that the S-combined active material, i.e., SPEG and SPAN, composite electrodes can work as the high-capacity cathodes for Al metal anode rechargeable battery. This research was supported by JST-MIRAI program (JPMJMI17E9). SPAN was provided by ADEKA corporation. References Tsuda, et al., J. Electrochem. Soc., 161, A908 (2014). Tsuda, et al., Chem. Commun., 58, 1518 (2022). Ru, et al., J. Mater. Chem. A, 7, 14391 (2019). Kojima, et al., ECS Trans., 75, 201 (2017). S. Ahmed, et al., Adv. Sci., 8, 2101123 (2021). Gao, et al., Angew. Chem. Int. Ed., 55, 9898 (2016). Marassi, et al., J. Electrochem. Soc., 126, 231 (1979). Figure 1

Developing low-cost, sustainable, and all-climate energy storage devices as alternatives to Li-ion batteries (LIBs) is critical for the global application of electric vehicles, grid-scale electrical energy storages. Among various emerging battery systems beyond LIBs, rechargeable aluminum organic batteries (RAOBs) stand out because of the high theoretical capacity, low cost, abundance, high sustainability, and high safety of Al and organic resources. However, the large ion size of Al complex ions, such as AlCl4 -, AlCl2 + and AlCl2+, or the strong Coulombic interaction between Al3+ ions and active materials, as well as the high diffusion energy barrier of Al3+ ion, lead to poor cyclic stability and sluggish reaction kinetics. Moreover, the reaction mechanism, interphase structure, and the impact of multi-functional groups in redox-active organic materials to the electrochemical performance of RAOBs remains elusive. To address these challenges, we designed and synthesized a redox-active polymer bearing carbonyl and azo groups as the cathode to achieve high-performance and wide-temperature-range RAOBs. The polymeric cathode exhibits a high reversible specific capacity, superior cyclic stability, fast charging capability, and a wide operation temperature range (-40oC to 100oC). X-ray photoelectron spectroscopy (XPS), pair distribution function (PDF) analysis, and soft X-ray absorption near edge structure (XANES) were employed to gain fundamental insight into the carbonyl and azo chemistries in RAOBs, as well as the cathode electrolyte interphase (CEI) structure. We demonstrated a step-by-step alumination/de-alumination reaction for carbonyl and azo groups in the polymer cathode and unravel a Al2O3- and AlN-rich CEI, which is critical for the impressive performance of RAOBs.

Hexacyanoferrates and related cyanometallates exhibit model electron transfer properties that are of importance to many electrochemical and related applications. In particular homo- and heterometallic cyanide bridged networks and derived materials have proven to exhibit very rich and diverse electrochemical properties. Their redox properties can be tuned by adjusting stoichiometry and oxidation state of the constituent metal centers, incorporation of interstitial ions, or preparation methods. Polynuclear cyanometallates are promising open-framework systems for low-cost electrochemical energy storage applications. Both soluble and insoluble analogues of Prussian blue have been explored as cathode materials with lithium, sodium, potassium, magnesium, calcium, and even zinc intercalated ionic carriers. Electrochromic devices are another promising area for employing the unique properties of cyanometallates. Prussian blue itself exhibits electrocatalytic properties toward hydrogen peroxide, and it has been used for biosensing and amperometric detection of glucose, L-cysteine, and glutamate. Also removal of radioactive cesium ions from contaminated water has been successfully achieved with Prussian blue and its metal substituted analogues. It is well-established that the choice of redox-active charge-storage material has a significant impact on the performance of a redox flow battery. The concentration of redox centers and their reaction kinetics have an influence on the available current densities and, thus, the power of the device. Remembering the requirement of good solubility of redox species, the semi-solid slurry approach (provided that the dispersion is homogeneous) represents another effective way to improve the volumetric capacity of the redox electrolyte (i.e. of the electrolyte with dissolved redox couples). An interesting approach to improve current densities involves application of circulating suspensions of electroactive materials. Prussian blue and its metal (Fe, Co, Ni, etc.) substituted analogues, which are electroactive mixed-valence inorganic systems, exhibit very rich and diverse electrochemistry. Their electrochemical properties that can be tuned through the variation of the material composition. Special attention will be paid to the formation of stable colloidal suspensions of truly mixed-valence fast-conducting Berlin Green, iron(III) hexacyanoferrate(III,II), together with multi-layered clay-like nickel(II) hexacyanoferrate(III) structures characterized by fast potassium counter-cation motion. It can be hypothesized that the proposed system could serve as the catholyte redox suspension containing large population of mixed-valence redox centers and capable of fast charge propagation and, consequently, yielding fairly large current densities. The materials can also be explored for sorption of large concentrations of Zn2+ ions and for the improvement of the Zn2+/Zn chemistry. While the application of Zn2+/Zn as the anode active system is well established in redox flow batteries, we are going to address and minimize limitations that include the efficiency of zinc deposition and the hydrogen evolution reaction taking place at the potentials where Zn is electrodeposited. The increase of current density could be achieved not only by reducing the viscosity of the electrolyte, thus accelerating charge-carrier transport, but also – by referencing to our experience with mixed-valent nickel hexacyanoferrate system as charge relay for dye-sensitized solar cells – through improvement of the dynamics of charge propagation by improving mobility of charge compensating counter-ions.

AbstractAqueous rechargeable zinc‐ion batteries (ARZBs) are impeded by the mutual problems of unstable cathode, electrolyte parasitic reactions, and dendritic growth of zinc (Zn) anode. Herein, a triple‐functional strategy by introducing the tetramethylene sulfone (TMS) to form a hydrated eutectic electrolyte is reported to ameliorate these issues. The activity of H2O is inhibited by reconstructing hydrogen bonds due to the strong interaction between TMS and H2O. Meanwhile, the preferentially adsorbed TMS on the Zn surface increases the thickness of double electric layer (EDL) structure, which provides a shielding buffer layer to suppress dendrite growth. Interestingly, TMS modulates the primary solvation shell of Zn2+ ultimately to achieve a novel solvent co‐intercalation ((Zn‐TMS)2+) mechanism, and the intercalated TMS works as a “pillar” that provides more zincophilic sites and stabilizes the structure of cathode (NH4V4O10, (NVO)). Consequently, the Zn||NVO battery exhibits a remarkably high specific capacity of 515.6 mAh g−1 at a low current density of 0.2 A g−1 for over 40 days. This multi‐functional electrolytes and solvent co‐intercalation mechanism will significantly propel the practical development of aqueous batteries.

The present study describes the results on inorganic and organic materials for energy storage and sensors. It contains eight chapters including introduction, experimental and summary sections. The first chapter gives a brief overview of energy storage systems, progress and challenges associated with them along with a few possible solutions to tackle them. The second chapter explains all the experimental details like chemicals used, syntheses procedures, instruments used, and various processes and procedures used in this work. The third chapter demonstrates the ion storage performance of copper phosphosulfide. As an anode for Li-ion battery, it delivers a high capacity and high cycling stability. The pre activated electrode delivers very high stable capacity. The capacity offered by the phosphosulfide is higher than that of the corresponding phosphide and sulfide that indicates the importance of the presence of both P and S in the structure. The mechanism as investigated by in situ Raman spectroscopy and other ex situ techniques suggest a conversion reaction and formation of a thick SEI like film on the electrode surface. As prepared material shows good performance for Mg-ion battery with moderate rate capability. A further improvement in the capacity and importantly the rate performance is achieved by utilizing a multiwall carbon nanotube composite. The composite electrode further delivers high cycling stability at high current rates. Moderate performance is observed for Al-ion battery which may be due to its high charge to size ratio that makes the insertion / extraction process rather slow. The fourth chapter utilizes organic carbonyl compounds as electrodes for mono- and multi-valent metal ion batteries. A layer type, slight off planar polymer is synthesized from benzoquinone and pyrrole and explored as a universal cathode for Li, Mg, Zn and Al-ion batteries. Thousands of stable cycles are observed for all these systems even at very high current rates and show excellent rate performance. For Li-ion battery, the cell performance is studied at high rates of 10 A g-1 which takes only 22 s to charge and discharge. For Mg-ion battery, an alternate alloy anode (AZ31) is explored, and 5000 cycles are observed even at a high current rate of 2 A g-1 . Similarly, for Zn-ion battery, along with good rate performance, a long-term stability of 20000 cycles is achieved at 2 A g-1 . More importantly, even for a more difficult Al-ion system, thousands of stable cycles are obtained at high rates of 0.5 and 1 A g-1 with 100% capacity retention. A surface controlled pseudocapacitive contribution to the overall capacity is responsible for such high performance in all the cases. The off planar geometry is expected to facilitate ion diffusion process thereby resulting in high rate and high performance. Ex situ infrared and X-ray photoelectron spectroscopy measurements show functional group transformation during the ion storage process. Further, an organic dye, vat orange 11 consisting of three conjugated anthraquinone units is studied for Mg- and Zn-ion batteries. It shows better performance than that of a single anthraquinone unit highlighting the benefit of conjugation. Different carbon additives and electrolytes are investigated further to achieve high performance for Mg-ion battery. A capacity fading is observed for Zn-ion battery due to high solubility of the dye in the electrolyte. The fifth chapter explores a few non-nucleophilic electrolytes for Mg-ion batteries with wide electrochemical stability window. It is observed that Mg(HMDS)2 and AlCl3 in a mixture of glymes with ionic liquid additive shows high deposition/ dissolution efficiency with low overpotentials and excellent oxidation stability on a few common substrates. Further, the electrolyte speciation study is carried out with the help of Raman and 27Al NMR spectroscopy. A non-aqueous Li-O2 battery is studied using tin phosphosulfide (SnPS3) as air cathode in the sixth chapter. High cycling performance and low charge-discharge overpotential is observed for the rGO composite as compared to the pristine material. High electronic conductivity and high surface area of rGO is believed to enhance the performance and Li2O2 is obtained as the discharge product. The seventh chapter investigates the gas sensing applications and photodetection activity of Cu3PS4. It is very sensitive towards NH3 gas compared to other analyte gases and can detect as low as 17 ppb with a high response of 160 % for 10 ppm NH3. It shows a fast response and excellent reversibility under ambient conditions. Good sensing properties for NO2 gas has been observed. Preliminary photodetector studies reveal that the phosphosulfide can be used for UV-vis photodetection. The last chapter summarizes the thesis work and gives some future directions to improve the performance further and design new systems. At the end, two appendixes are given where an ionic liquid, 1-ethyl-3-vinylimidazoilum bis(fluorosulfonyl)imide (EVImFSI) containing lithium bis(trifluorosulfonyl)imide (LiTFSI) is used as a wide potential window (~5 V) electrolyte for Li-ion battery and nickel phosphosulfide (NiPS3) is used as electrocatalyst for electrochemical nitrogen reduction to ammonia (NH3).