Littérature scientifique sur le sujet « Post-Li batterie »

Recently, post Li batteries have been intensively researched due to high cost and localization of Li sources, especially for large-scale applications. Concurrently, ceramic electrolytes for post Li batteries also gain much attention to develop all-solid-state post Li batteries. The most intensively researched post Li battery is Na battery because of chemical and electrochemical similarities between Li and Na elements. Many good review papers about Na battery have been published including Na-ion conductive ceramic electrolytes. Contrary, ceramic electrolytes for other post Li batteries like K, Mg, Ca, Zn and Al batteries are hardly summarized. In this review, research on ceramic electrolytes for K, Mg, Ca, Zn and Al batteries is analyzed based on latest papers published since 2019 and suggested future research direction of ceramic electrolytes for post-Li batteries.

Lithium metal batteries are inspiring renewed interest in the battery community because the most advanced designs of Li-ion batteries could be on the verge of reaching their theoretical specific energy density values. Among the investigated alternative technologies for electrochemical storage, the all-solid-state Li battery concept based on the implementation of dry solid polymer electrolytes appears as a mature technology not only to power full electric vehicles but also to provide solutions for stationary storage applications. With an effective marketing started in 2011, BlueSolutions keeps developing further the so-called lithium metal polymer batteries based on this technology. The present study reports the electrochemical performance of such Li metal batteries involving indigo carmine, a cheap and renewable electroactive non-soluble organic salt, at the positive electrode. Our results demonstrate that this active material was able to reversibly insert two Li at an average potential of ≈2.4 V vs. Li+/Li with however, a relatively poor stability upon cycling. Post-mortem analyses revealed the poisoning of the Li electrode by Na upon ion exchange reaction between the Na countercations of indigo carmine and the conducting salt. The use of thinner positive electrodes led to much better capacity retention while enabling the identification of two successive one-electron plateaus.

Over the past few years, the development of lithium (Li)-ion batteries has been extensive. Several production approaches have been adopted to meet the global requirements of Li-ion battery products. In this paper, we propose a scaled-up process for the LiNi0.6Mn0.2Co0.2O2 (NMC622) cathode material for high performance Li-ion batteries. During each synthesis step, the structural and morphological characteristics of the products were comprehensively examined. The performance of the samples was evaluated directly using an 18650 full-cell-type battery. Commercial graphite and LiPF6 electrolyte were used as the anode and electrolyte, respectively. Based on the obtained data, increasing the production scale of NCM622 reduces the overall performance. Nevertheless, a simple post-treatment technique can be used to enhance the overall capacity.

Li metal anodes are the potential solution for high-energy batteries. One of the challenges of applying such a high-energy anode is Li dendrite growth, which results in short-circuit and thermal runaway. Current battery research focuses on developing solid electrolytes to serve as a physical barrier to prevent dendrite growth. However, the Li morphology change during plating and stripping, and the mechanisms of how Li dendrite grows and propagates into a complex composite solid electrolyte are poorly understood. Understanding and controlling Li morphology evolution, dendrite formation, and growth during cycling are crucial to developing dendrite suppression strategies for solid electrolytes and enabling high-energy lithium metal batteries. In this work, Li morphology evolution during initial cycling in a crosslinked PEO-based gel composite electrolyte full cell with NMC 811 cathode is monitored via post-mortem SEM. The results show that severe surface pitting occurs as early as the second stripping cycle. Pit formation and continuous dissolution is the main cause of Li surface roughening and dendrite growth mechanism in the model gel composite electrolyte. Comparing Li dendrite growth mechanisms in liquid, polymer, and solid electrolytes, the observed dendrite growth mechanism resembles that of the liquid electrolyte the most. This study suggests that strategies to improve the electrochemical reversibility of electrodeposited Li reported in liquid electrolytes to control Li morphology and prevent dendrite growth may be transferrable in a gel electrolyte. This work is sponsored by the Laboratory Directed Research and Development Program of Oak Ridge National Laboratory (ORNL), managed by UT-Battelle, LLC for the U.S. Department of Energy under Contract No. DE-AC05-00OR22725. Part of the measurements was performed at the Center for Nanophase Materials Sciences (CNMS), which is sponsored at Oak Ridge National Laboratory by the Scientific User Facilities Division, Office of Basic Energy Sciences.

Development of solid inorganic lithium (Li) ion conducting materials for the use as solid electrolytes is indispensable for the realization of next-generation all-solid-state Li batteries with high safety and reliability. Among various oxide-based solid electrolyte materials, a garnet-type oxide with the formula of Li7La3Zr2O12 (LLZO) has attracted much attention because of its high Li ion conductivity at room temperature, excellent thermal performance, and high stability against Li metal.1,2) However, the formation of a solid-solid interface between LLZO and the Li metal anode is challenging. Poor interfacial connection causes non-uniform Li plating and intergranular penetration of Li dendrite in polycrystalline LLZO when the cell is cycled particularly at high current densities, resulting in internal short-circuit failure.3–5) There is no doubt that the establishment of prevention technology for short-circuit failures is a top priority issue for the development of all-solid-state Li metal batteries.5) On the other hand, from the viewpoint of effective use of material resources, the possibility of reusing LLZO extracted from a solid-state battery after a short-circuit failure occurred is worth considering. In this work, we investigated the reusability of a Ta-doped Li6.55La3Zr1.55Ta0.45O12 (Ta-LLZO) solid electrolyte shorted by Li dendrite growth during electrochemical Li plating/stripping testing for a Li/Ta-LLZO/Li symmetric cell. Ta-LLZO was taken out of a tested cell after the degradation by Li dendrite growth occurred, and then annealed at 700 ºC in air. The annealing temperature was set to suppress possible excess Li loss from Ta-LLZO during post-annealing.6) In the first Li plating/stripping test, the cell was shorted at 0.85 mA cm-2 and the dark gray area with possible Li dendrite growth was confirmed on the surface of Ta-LLZO. This dark gray area turned white but slightly different from the original color of Ta-LLZO by post-annealing. The ionic conductivity of as-synthesized and post-annealed Ta-LLZO was measured and compared. Post-annealed Ta-LLZO retained high room temperature ionic conductivity of 0.82 mS cm-1, which is slightly lower than the conductivity of as-synthesized one (= 0.90 mS cm-1). We also prepared a symmetric cell with the post-annealed Ta-LLZO and Li metal electrodes and the second Li plating/stripping test was carried out. Symmetric cell with post-annealed Ta-LLZO showed stable voltage response. This indicates the possibility of reusing the degraded garnet-type solid electrolyte by Li dendrite growth for an another solid-state Li battery. References 1. R. Murugan, V. Thangadurai, W. Weppner, Angew. Chem., Int. Ed. 46, 7778−7781 (2007). 2. A.J. Samson, K. Hofstetter, S. Bag, V. Thangadurai, Energy Environ. Sci. 12, 2957−2975 (2019). 3. E.J. Cheng, A. Sharafi, J. Sakamoto, Electrochim. Acta 223, 85−91 (2017). 4. R. Inada, S. Yasuda, H. Hosokawa, M. Saito, T. Tojo, Y. Sakurai, Batteries 4, 26 (2018). 5. S. Sarkar, V. Thangadurai, ACS Energy Lett. 7, 1492–1527 (2022). 6. R. Inada, A. Takeda, Y. Yamazaki, S. Miyake. Y. Sakurai, V. Thangadurai, ACS Appl. Energy Mater. 3, 12517–12524 (2020). Figure 1

Lithium sulfur (Li-S) batteries with the high theoretical specific energy of 2600 Wh kg−1 are a promising candidate at the era of the post lithium-ion batteries. In most studies, lithium metal anode is used. To advance the Li-S battery towards practical application, Li-S full cells with low or non-Li metal anode need to be developed. Herein, the latest advances of the Li-S full cells are mainly categorized according to the initial state of the S cathode, i.e., sulfur (S) and lithium sulfide (Li2S). In each part, the challenges and strategies are thoroughly reviewed for the cells with different anodes, such as carbon, silicon, other alloys and metallic Li. The cycling performance comparisons of state-of-the-art Li-S full cells are also included. To achieve the high real energy density for practical applications, the Li-S full cells have to use low excess lithiated graphite, lithiated alloys, or metallic Li as the anodes. Meanwhile, the lean electrolyte is also important to further improve the practical energy density. The review is expected to supply a comprehensive guide to design Li-S full cells.

Imaging techniques are increasingly used to study Li-ion batteries and, in particular, post-Li-ion batteries such as Li–S batteries, Na-ion batteries, Na–air batteries and all-solid-state batteries. Herein, we review recent advances in the field made through the use of these techniques.

Current societal challenges in terms of energy storage have prompted an intensification in the research aiming at unravelling new high energy density battery technologies. These would have the potential of having disruptive effects in the world transition towards a less carbon-dependent energy economy through transport, both by electrification and renewable energy integration. Aside from controversial debates on lithium supply, the development of new sustainable battery chemistries based on abundant elements is appealing, especially for large-scale stationary applications. Interesting alternatives are to use sodium, magnesium or calcium instead of lithium. While for the Na-ion case, fast progresses are expected as a result of chemical similarities with lithium and the cumulated Li-ion battery know-how over the years, for Ca and Mg the situation is radically different. On the one hand, the possibility to use Ca or Mg metal anodes would bring a breakthrough in terms of energy density; on the other, development of suitable electrolytes and cathodes with efficient multivalent ion migration are bottlenecks to overcome. This article is part of a discussion meeting issue ‘Energy materials for a low carbon future’.

This work investigates the electrochemical properties of NMC111 as thin film cathode materials for thin film Li ion batteries. The films were deposited on Si substrate coated with Pt using a radio frequency magnetron sputtering system. The samples were post annealed after deposition and the it’s effect is discussed. Crystalline structures were obtained for samples annealed at 700 oC and O2 atmosphere. The electrochemical properties of all solid state thin film batteries with the crystalline cathode, Lipon electrolyte and Li anode showed good capacity retention. This battery proved to be an effective solution for thin film and microbatteries. Acknowledgement This research was funded under the research grant #51763/ПЦФ-МЦРОАП РК-19 “New materials and devices for defense and aerospace applications” from MDDIAI Republic of Kazakhstan

Thanks to their superior energy and power density, lithium-ion batteries (LIBs) currently dominate the market of power sources for portable devices. The economy of scale and engineering optimizations have driven the cost of LIBs below the 200 $/KWh at the pack level. This catalyzed the market penetration of electric vehicles and made them a viable candidate for stationary energy storage. However, the rapid market expansion of LIBs raised growing concerns about the future sustainability of this technology. In particular, lithium and cobalt supplies are considered vulnerable, primarily because of the geopolitical implications of their high concentration in only a few countries. In the search for the next generation secondary batteries, known as post-lithium ion batteries, candidates that do not use rare metals have been extensively investigated in the last 10 years. Sodium-ion batteries (SIBs) attracted considerable attention thanks to the high abundance of the precursors and wide distribution of sodium on the earth's crust. As a matter of fact, as it will be pointed out during the dissertation, it is not straightforward to allocate the reduction of the price of the alkaline ion precursors to the reduction of the battery price. However, the difficulties in the supply of raw materials for LIBs, such as shortages in lithium carbonates and cobalt ores, could make lithium and cobalt-free systems, such as SIBs, attractive and cost-competitive alternatives. Compared to other, more exotic chemistries including Ca2+, Mg2+ and Al3+ batteries, SIBs are nowadays considered one as the most promising alternative to LIBs. Despite the extensive research, anode materials for SIBs still represent a serious problem for the commercial exploitation of this technology. Accordingly, the doctoral research on SIBs has been focused on anode materials. In particular, the attention was directed towards conversion oxides. Compared to intercalation materials, conversion-based ones have higher capacities but are more challenging to deal with because of the high volume variation during cycling. This challenge was addressed by material's nanostructuring and morphology control which proved to significantly reduce the pulverization of the active material. Different anode candidates have been studied during the doctoral work. Cobalt oxide nanofibers have been here explored as a first prototype for conversion materials in sodium ion batteries. The sodiation-desodiation mechanism is analyzed by means of ex situ XRD which led to a deeper understanding of the conversion reaction in SIBs. A cost-effective and environmentally benign alternative based on iron oxide is then considered. The limits of iron (III) oxide are tackled by combining the advantages of the nanostructuring and the doping with an aliovalent element. Si-doped Fe2O3 nanofibers are synthesized via an easy scalable process based on the electrospinning method. It is found that Si-addition improves the transport properties as well as induces changes in the crystal structure and morphology. In the final section of the thesis, potassium-ion batteries (KIBs) are examined as a promising alternative to sodium ion batteries. KIBs exhibit all the benefits of SIBs, with the additional advantage that graphite, can reversibly accommodate K-ions. On the positive side, Potassium manganese hexacyanoferrate (KMnHCF), has been reported to provide high operating voltages and satisfactory capacity retention. The proposed research activity presents the use of an ionic liquid based electrolyte compatible with the most promising anode and cathode for KIBs. In addition, a high-throughput optimization of the KMnHCF synthesis is reported. The selected candidates are then fully characterized, and their electrochemical properties investigated. The optimized material exhibits the highest ever reported coulombic efficiency for the KMHCF. This find, opens up the possibility of highly efficient, high energy potassium ion batteries.
Thanks to their superior energy and power density, lithium-ion batteries (LIBs) currently dominate the market of power sources for portable devices. The economy of scale and engineering optimizations have driven the cost of LIBs below the 200 $/KWh at the pack level. This catalyzed the market penetration of electric vehicles and made them a viable candidate for stationary energy storage. However, the rapid market expansion of LIBs raised growing concerns about the future sustainability of this technology. In particular, lithium and cobalt supplies are considered vulnerable, primarily because of the geopolitical implications of their high concentration in only a few countries. In the search for the next generation secondary batteries, known as post-lithium ion batteries, candidates that do not use rare metals have been extensively investigated in the last 10 years. Sodium-ion batteries (SIBs) attracted considerable attention thanks to the high abundance of the precursors and wide distribution of sodium on the earth's crust. As a matter of fact, as it will be pointed out during the dissertation, it is not straightforward to allocate the reduction of the price of the alkaline ion precursors to the reduction of the battery price. However, the difficulties in the supply of raw materials for LIBs, such as shortages in lithium carbonates and cobalt ores, could make lithium and cobalt-free systems, such as SIBs, attractive and cost-competitive alternatives. Compared to other, more exotic chemistries including Ca2+, Mg2+ and Al3+ batteries, SIBs are nowadays considered one as the most promising alternative to LIBs. Despite the extensive research, anode materials for SIBs still represent a serious problem for the commercial exploitation of this technology. Accordingly, the doctoral research on SIBs has been focused on anode materials. In particular, the attention was directed towards conversion oxides. Compared to intercalation materials, conversion-based ones have higher capacities but are more challenging to deal with because of the high volume variation during cycling. This challenge was addressed by material's nanostructuring and morphology control which proved to significantly reduce the pulverization of the active material. Different anode candidates have been studied during the doctoral work. Cobalt oxide nanofibers have been here explored as a first prototype for conversion materials in sodium ion batteries. The sodiation-desodiation mechanism is analyzed by means of ex situ XRD which led to a deeper understanding of the conversion reaction in SIBs. A cost-effective and environmentally benign alternative based on iron oxide is then considered. The limits of iron (III) oxide are tackled by combining the advantages of the nanostructuring and the doping with an aliovalent element. Si-doped Fe2O3 nanofibers are synthesized via an easy scalable process based on the electrospinning method. It is found that Si-addition improves the transport properties as well as induces changes in the crystal structure and morphology. In the final section of the thesis, potassium-ion batteries (KIBs) are examined as a promising alternative to sodium ion batteries. KIBs exhibit all the benefits of SIBs, with the additional advantage that graphite, can reversibly accommodate K-ions. On the positive side, Potassium manganese hexacyanoferrate (KMnHCF), has been reported to provide high operating voltages and satisfactory capacity retention. The proposed research activity presents the use of an ionic liquid based electrolyte compatible with the most promising anode and cathode for KIBs. In addition, a high-throughput optimization of the KMnHCF synthesis is reported. The selected candidates are then fully characterized, and their electrochemical properties investigated. The optimized material exhibits the highest ever reported coulombic efficiency for the KMHCF. This find, opens up the possibility of highly efficient, high energy potassium ion batteries.

The global challenge responding to the need of efficient electrical energy storage is answered by rechargeable batteries, which are based on high-rate intercalation reaction of lithium ions into nano- and microstructured porous materials. A class of insetion-type materials is represented by Prussian blue analogues (PBAs), characterized by porous open 3D-frameworks which allow for a facile insertion/ extraction of ions with negligible lattice strain. In the present work we focused on the synthesis and characterization of PBAs in Li-ion and post-Li battery systems, their redox activity, electronic and structural reversibility while cycling. All synthesized materials exhibit good structural stability and negligible lattice strain during (de)insertion of ions and redox processes ascribable to one or more redox species. For instance, copper hexacyanoferrate features two redox sites, copper and iron, contrarily to what reported in the literature, while copper nitroprusside has been demonstrated to possess three redox centres, including the two metals, as well as the non innocent nitrosyl ligand as third site. Electrosynthesized copper hexacyanoferrate results extremely versatile towards a wide selection of ions in aqueous solution, ranging from monovalent to multivalent ions, while titanium hexacyanoferrate may reach a capacity equal to 55 mAh/g in potassium nitrate aqueous solution. This led to the conclusion that a H2O-based system would be feasible for the studied materials, and more in general for this class of compounds. Although they do not feature high specific capacities, they are characterized by good cycling ability and efficiency, as well as ion-versatility which can be favorable to a post-lithium strategy. The investigation of their reaction mechanism has led to the deep understanding of limiting steps, whereby it is possible to tailor new promising materials that could result competitive in the next future.

In recent years, portable applications have experienced an exponential growth and consequently, the demand of batteries has increased accordingly. It is widely known, though, that the performance of batteries decreases with time and use. This loss of performance is easured by the State-of-Health (SoH) of the cells. However, there is no consensus in defining this parameter. Experimental, theoretical or even heuristic approaches can be found in literature and commercial systems, but usually, they only work for particular conditions and they are not linked to the degradation suffered by the cells themselves. The aim of this study is to find a parameter directly related to this degradation. For this purpose, we investigate the irreversible entropy production in Li-ion cells because irreversible entropy is related to energy dissipation and thus, to irrversibilities due to system or energy degradation. In order to evaluate the degradation of the cells and its correspondence to irreversible entropy generation, we studied different Li-ion chemistries (NMC, LFP and LCO). Batteries were cycled at different discharge rates (close to and far from equilibrium) and evaluated at different SoHs. Therefore, capacity fade and impedance rise (the most commonly used techniques in SoH determination) were characterized and related to irreversible entropy generation. In addition, post-mortem analysis was carried out to achieve a deeper knowledge of the causes and effects of degradation. As a result of this study, we introduced a new parameter for system degradation characterization, the Relative-Entropy-Production (REP), defined as the irreversible entropy generation ratio at actual state and the initial state. In particular, we found irreversible entropy production evaluated at low discharge rates was higher as more degraded were the NMC cells. In the case of LFP cells, irreversible entropy production decreased during initial cycles but then increased towards the EoL. This behavior coincided with a capacity increase during initial cycles. In addition, we found a relationship between irreversible entropy generation and the phase transformations taking place during the discharge processes in all the evaluated cells because the materials undergoing phase transformations expand and contract yielding to cracks and other structural. Irreversible entropy production is found to be a promising magnitude to characterize battery aging. Even though much research has still to be carried out, the idea is to define, in the future, a threshold in irreversible entropy production that the cells can stand before considering their EoL is reached.
En els darrers anys, la demanda de bateries ha augmentat considerablement gràcies a la creixent proliferació de dispositius portàtils. Tot i això, és ben sabut que el funcionament de les bateries empitjora amb el temps i l'ús. Aquesta pèrdua de rendiment es mesura amb un paràmetre anomenat State-oh-Health (SoH) encara que, avui dia, no s'ha arribat a un consens per a definir-lo. A la literatura o als mateixos sistemes comercials s'hi poden trobar aproximacions experimentals, teòriques o heurístiques, que generalment funcionen en situacions particulars i que, moltes sovint, no estan directament relacionades amb la degradació que pateixen les cel·les. L'objectiu d'aquest estudi és trobar un paràmetre que estigui directament relacionat amb la degradació patida per les cel·les. Per aquest motiu, ens hem centrat en la producció d'entropia irreversible perquè aquesta està relacionada amb la dissipació d'energia i, per tant, amb les irreversibilitats degudes a la degradació del sistema o de l'energia. Es va treballar amb vàries químiques de bateries d'ions de liti (NMC, LFP i LCO) per tal d’avaluar la degradació patida per aquestes i la correspondència amb la generació d'entropia irreversible. Aquestes cel·les van ser avaluades a taxes baixes i elevades a diferents nivells de SoH. En particular, la disminució de capacitat i l’augment d’impedància, que són les tècniques més utilitzades per a determinar el SoH, van ser determinades i posteriorment relacionades amb la generació d’entropia irreversible. A més a més, l’anàlisi post-mortem de les cel·les ens va permetre obtenir un coneixement major de les causes i els efectes de la degradació. Com a resultat d’aquest estudi, hem introduït un nou paràmetre per a la caracterització de la degradació d’un sistema. Aquest paràmetre l’hem anomenat Relative-Entropy-Production (REP) i l’hem definit com la relació entre la generació d’entropia irreversible en el moment actual i l’estat inicial. En particular, hem trobat que la producció d’entropia irreversible a taxes baixes de descàrrega és més gran com més degradades estan les cel·les de NMC. En canvi, en el cas de les cel·les de LFP, hem trobat que la generació d’entropia irreversible disminueix durant els primers cicles per després augmentar fins al final de la seva vida útil. S’ha vist que aquesta disminució coincideix amb un increment de la capacitat. A més a més, a totes les cel·les amb les que hem treballat, hem trobat una relació entre la producció d’entropia irreversible i les transformacions de fase que tenen lloc als elèctrodes durant la descàrrega. Aquesta relació ha sigut associada al fet de que els materials que pateixen una canvi de fase s’expandeixen i es contrauen el que fa que es produeixin fractures o esquerdes o altres modificacions estructurals. Totes elles produeixen degradació i, per tant, generen entropia irreversible. S’ha trobat que REP i la generació d’entropia irreversible són magnituds prometedores per a caracteritzar l’envelliment de bateries. Encara que queda molta feina per fer, la idea és, en un futur, poder definir un llindar de REP o de generació d’entropia irreversible que les cel·les siguin capaces de suportar abans no es consideri que han assolit el final de les seves vides útils.

博士
國立成功大學
材料科學及工程學系
102
In this study, the cycling tests at different temperatures were carried out for the sputtered Al-Si thin film anode. Both thermal post-treatment and Ag doping can reduce higher resistivity of thin film because of lower crystallization degree. The effects of the two kinds of modification on the microstructure and electrochemical performance were investigated. The thermally post-treated and Ag-doped specimens showed lowered resistivity and different electrochemical properties from others. The transition electron microscope was carried out for the investigation on the mechanism of lithiation-delithiation and the reason of difference among the cycling performance of specimens. The as-deposited Al0.55Si0.35Ag0.1 and thermally post-treated Al0.6Si0.4 (200 ˚C-1 hr) possessed the best performance at RT and 55 ˚C respectively. Their capacity after 30 cycles were 1000 and 1200 mAh/g and both the retention of them is about 99%.

Lithium-ion (Li-ion) rechargeable batteries are used as one of the major energy storage components for implantable medical devices. Reliability of Li-ion batteries used in these devices has been recognized as of high importance from a broad range of stakeholders, including medical device manufacturers, regulatory agencies, patients and physicians. To ensure a Li-ion battery operates reliably, it is important to develop health monitoring techniques that accurately estimate the capacity of the battery throughout its life-time. This paper presents a sparse Bayesian learning method that utilizes the charge voltage and current measurements to estimate the capacity of a Li-ion battery used in an implantable medical device. Relevance Vector Machine (RVM) is employed as a probabilistic kernel regression method to learn the complex dependency of the battery capacity on the characteristic features that are extracted from the charge voltage and current measurements. Owing to the sparsity property of RVM, the proposed method generates a reduced-scale regression model that consumes only a small fraction of the CPU time required by a full-scale model, which makes online capacity estimation computationally efficient. 10 years’ continuous cycling data and post-explant cycling data obtained from Li-ion prismatic cells are used to verify the performance of the proposed method.