The rechargeable secondary Lithium ion (Li-ion) battery is expected to grow to more than $6.3 billion by 2012 from ~$4.6 billion in 2006. With the development of personnel electronics, hybrid and electric vehicles, Li-ion batteries will be more in demand. However, Li-ion batteries are not widely recycled because it is not economically justifiable (in contrast, at present more than 97% Lead-acid batteries are recycled). So far, no commercial methods are available to recycle different chemical Li-ion batteries economically and efficiently. Considering our limited resources, environmental impact, and national security, Li-ion batteries must be recycled. A new methodology with low temperature and high efficiency is proposed in order to recycle Li-ion batteries economically and with industrial viability. The separation and synthesis of cathode materials (most valuable in Li-ion batteries) from recycled components are the main focus of the proposed research. The analytical results showed that the recycling process is practical and has high recovery efficiency, create great commercial value as well.

<p>U&nbsp; ovoj&nbsp; doktorskoj&nbsp; disertaciji&nbsp; ispitivani&nbsp; su&nbsp; elektroliti&nbsp; na&nbsp; bazi binarnih&nbsp; sme&scaron;a&nbsp; imidazolijumovih&nbsp; jonskih&nbsp; tečnosti&nbsp; i&nbsp; laktona&nbsp; koji su&nbsp; pogodni&nbsp; za&nbsp; primenu&nbsp; u&nbsp; litijum-jonskim&nbsp; baterijama.&nbsp; Fizičkohemijska&nbsp; svojstva&nbsp; binarnih&nbsp; sme&scaron;a&nbsp; jonskih&nbsp; tečnosti&nbsp; na&nbsp; bazi imidazolijum katjona i <em>bis </em>(trifluorometilsulfonil)imidnog anjona i laktona ispitana su u celom opsegu molskih udela i na različitim temperaturama.&nbsp; Na&nbsp; osnovu&nbsp; izmerenih&nbsp; gustina,&nbsp; viskoznosti&nbsp; i električne&nbsp; provodljivosti&nbsp; izračunati&nbsp; su&nbsp; različiti&nbsp; fizičko-hemijski parametri i diskutovane&nbsp; interakcije između komponenata sme&scaron;a. Ispitana&nbsp; je&nbsp; termička&nbsp; i&nbsp; elektrohemijska&nbsp; stabilnost&nbsp; odabranih elektrolita.&nbsp; Na&nbsp; osnovu&nbsp; dobijenih&nbsp; rezultata,&nbsp; prvo&nbsp; je&nbsp; odabran odgovarajući&nbsp; lakton&nbsp; koji&nbsp; je&nbsp; kasnije&nbsp; kombinovan&nbsp; sa&nbsp; jonskim<br />tečnostima&nbsp; na&nbsp; bazi&nbsp; imidazola,&nbsp; koje&nbsp; se&nbsp; međusobno&nbsp; razlikuju&nbsp; u dužini&nbsp; bočnog&nbsp; niza&nbsp; katjona.&nbsp; Na&nbsp; osnovu&nbsp; fizičko-hemijskih svojstava&nbsp; na&nbsp; različitim&nbsp; temperaturama&nbsp; i&nbsp; pri&nbsp; različitim&nbsp; sastavima binarnih&nbsp; sme&scaron;a&nbsp; diskutovan&nbsp; je&nbsp; način&nbsp; organizacije&nbsp; njihovih<br />komponenata.&nbsp; U&nbsp; binarne&nbsp; sme&scaron;e&nbsp; koje&nbsp; su&nbsp; se&nbsp; pokazale&nbsp; kao najperspektivnije&nbsp; sa&nbsp; stanovi&scaron;ta&nbsp; električne&nbsp; provodljivosti, viskoznosti,&nbsp; elektrohemijske&nbsp; stabilnosti&nbsp; i&nbsp; (ne)zapaljivosti&nbsp; dodata je litijumova so. Tako dobijeni ternarni sistemi su okarakterisani<br />u zavisnosti od koncentracije litijumove soli. Odabrani elektroliti upotrebljeni su za ispitivanje performansi litijum-jonske ćelije sa elektrodama&nbsp; na&nbsp; bazi&nbsp; anatas&nbsp; TiO₂&nbsp; nanocevi.&nbsp; Cikličnom voltametrijom&nbsp; i&nbsp; galvanostatskim&nbsp; cikliranjem&nbsp; ispitane&nbsp; su<br />performanse ćelije u toku 350 ciklusa punjenja i pražnjenja. Na osnovu&nbsp;&nbsp; ciklovoltametrijskih&nbsp; merenja&nbsp; izračunati&nbsp; su&nbsp; koeficijenti difuzije jona Li^{&nbsp; +}i energija aktivacije za difuziju.&nbsp; Kombinacijom jonskih&nbsp; tečnosti&nbsp; i&nbsp; laktona&nbsp; moguće&nbsp; je&nbsp; dobiti&nbsp; elektrolite&nbsp; smanjene viskoznosti,&nbsp; povećane&nbsp; električne&nbsp; provodljivosti,&nbsp; povećane<br />termičke&nbsp; stabilnosti&nbsp; usled&nbsp; međusobnog&nbsp; stabilizacionog&nbsp; efekta laktona na imidazolijumove jonske tečnosti.</p> / <p>In&nbsp; this&nbsp; doctoral&nbsp; dissertation,&nbsp; binary&nbsp; mixtures&nbsp; based&nbsp; on&nbsp; imidazolium&nbsp; ionic&nbsp; liquids&nbsp; with&nbsp; lactones&nbsp; were&nbsp; tested&nbsp; for&nbsp; use&nbsp; in lithium-ion&nbsp; batteries.&nbsp; The&nbsp; physicochemical&nbsp; properties&nbsp; of&nbsp; binary&nbsp; mixtures&nbsp; of&nbsp; imidazolium&nbsp; based&nbsp; ionic&nbsp; liquids&nbsp; with&nbsp;<em> bis </em>(trifluoromethylsulfonyl)imide&nbsp; anions&nbsp; and&nbsp; lactones&nbsp; were&nbsp; examined&nbsp; throughout&nbsp; the&nbsp; whole&nbsp; composition&nbsp; range&nbsp; and&nbsp; at&nbsp; different temperatures. Based on the measured densities, viscosity&nbsp; and electrical conductivity, various physical chemical parameters&nbsp; and discrete interactions between the components of the mixture are&nbsp; calculated.&nbsp; Thermal&nbsp; and&nbsp; electrochemical&nbsp; stability&nbsp; of&nbsp; selected&nbsp; binary&nbsp; mixtures&nbsp; were&nbsp; examined.&nbsp; Based&nbsp; on&nbsp; obtained&nbsp; results&nbsp; was&nbsp; selected lactone&nbsp; which is later combined with imidazolium based&nbsp; ionic liquid,&nbsp; differing from each other in the length of the cation. Based&nbsp; on&nbsp; the&nbsp; physico-chemical&nbsp; properties&nbsp; at&nbsp; different&nbsp; temperatures and in the different compositions of binary mixtures, the way of organizing their components is discussed. Lithium salt&nbsp; is added to the binary mixtures that have been shown as the most perspective&nbsp; from&nbsp; the&nbsp; standpoint&nbsp; of&nbsp; electrical&nbsp; conductivity, viscosity,&nbsp; electrochemical&nbsp; stability&nbsp; and&nbsp; (non)flammability.&nbsp; The&nbsp; resulting&nbsp; ternary&nbsp; systems&nbsp; are&nbsp; characterized&nbsp; according&nbsp; to&nbsp; the concentration of lithium salt.&nbsp; The selected electrolytes were used to test the performance of the lithium-ion cell with anatase TiO₂ nanotubular&nbsp; electrodes.&nbsp; Cyclic&nbsp; voltammetry&nbsp; and&nbsp; galvanostatic&nbsp; cycling&nbsp; tested&nbsp; the&nbsp; cell&#39;s&nbsp; performance&nbsp; during&nbsp; the&nbsp; 350&nbsp; charge&nbsp; and discharge&nbsp; cycles.&nbsp; Based&nbsp; on&nbsp; cyclic&nbsp; voltammetric&nbsp; measurements, the&nbsp; Li ⁺ ion&nbsp; diffusion&nbsp; coefficients&nbsp; and&nbsp; activation&nbsp; energies&nbsp; for diffusion&nbsp; were&nbsp; calculated.&nbsp; Combination&nbsp; ionic&nbsp; liquid&nbsp; and&nbsp; lactone could&nbsp; be&nbsp; obtained&nbsp; electrolytes&nbsp; with&nbsp; lower&nbsp; viscosity,&nbsp; higher electrical&nbsp; conductivity,&nbsp; improved&nbsp; thermal&nbsp; stability&nbsp; due&nbsp; to stabilization effect of lactone on imidazolium based ionic liquids.</p>

Hunting for improved energy storage devices based on rechargeable Li-ion batteries and other advanced rechargeable batteries is one of the hottest topics in today's society. Both Li- ion batteries and Li-O2 batteries have been studied within the thesis. The research work of this thesis contains two different parts. Part 1. The controlled synthesis of the extreme small sized nanoparticles and their application for Li-ion batteries; Part 2. The study of the O2 reduction mechanism in Li-O2 batteries with aprotic electrolytes. In the first part, two different types of extremely small-sized TiO2 nanoparticles with at lease on dimension less than 3 nm was synthesised via solvothermal/hydrothermal reaction, i.e., anatase nanosheets and TiO2(B). These nanoparticles were obtained without any contamination of long chain organic surfactants. A series of systematic characterisation methods were employed to analyse the size, phase purity, and surface condition. These extremely small-sized nanoparticles exhibit improved capacity, rate performance as anode materials for Li-ion batteries. The shapes of load curves of charge and discharge are significantly modified due to the reduced size of TiO2 nanoparticles. In chapter 3, we will see the variation of the capacity and the load curve shape of the anatase nanosheets according to their thickness and surface conditions. The origin of the excessive capacity is analysed based on the electrochemical data. It has been identified that both pseudocapacitive (interfacial) Li+ storage and the excessive Li+ -storage from the bulk contribute to the increased capacity. In chapter 4, the shape and size of the sub-3 nm TiO2(B) nanoparticles are studied, a method based the PXRD data is established. These nanoparticles demonstrate a reversible capacity of 221 mAh/g at a rate of 600 mA/g and remain 135 mAh/g at 18000 mA/g without significant capacity fading during cycling. In the last part, a systematic study of O2 reduction mechanism for aprotic Li-O2 batteries based on the combination of a series of electrochemical and spectroscopic data is presented. The novel mechanism unifies two previous models for the growth of Li2O2 during discharge, i.e., Li2O2 particle formation in the solution phase and Li2O2 film formation on the electrode surface. The new mechanism provides fundamental conceptions for the improvement of Li2O2 batteries and shed light on the future research of Li2O2 batteries.

Replacing organic liquid electrolytes with nonflammable solid electrolytes can improve safety, offer higher volumetric and gravimetric energy densities, and lower the cost of lithium-ion batteries. However, today’s all-solid-state batteries suffer from low Li-ion conductivity in the electrolyte, slow Li-ion transport across the electrolyte/electrode interface, and slow solid-state Li-ion diffusion within the electrode. Defect chemistry is critical to understanding ionic conductivity and predicting the charge transport through heterogeneous solid interfaces. The goal of this dissertation is to analyze and improve solid state materials for energy storage applications by understanding their defect structure and transport properties. I have investigated defect chemistry of cubic Li7La3Zr2O12 (c-LLZO), one of the most promising candidate solid electrolytes for all-solid-state lithium batteries. By combining conductivity measurements with defect modeling, I constructed a defect diagram of c-LLZO featuring the intrinsic formation of lithium vacancy-hole pairs. The findings provided insights into tailoring single-phase mixed lithium-ion/electron conducting materials for emerging ionic devices, i.e., composite cathodes requiring both fast electronic and ionic paths in solid-state batteries. I suggested that oxygen vacancies could increase the Li-ion conductivity by reducing the amount of electron holes bound with lithium vacancies. Using a simpler but also attractive solid electrolyte Li2ZrO3 (LZO) as an example, I significantly improved Li-ion conductivity by creating extra oxygen vacancies via cation doping. In particular, Fe-doped LZO shows the highest Li-ion conductivity reported for the family of LZO compounds, reaching 3.3 mS/cm at 300 °C. This study brought attentions to the long-neglected oxygen vacancy defects in lithium-ion conductors and revealed their critical role in promoting Li-ion transport. More importantly, it established a novel defect engineering strategy for designing Li-oxide based solid electrolytes for all-solid-state batteries. I surface-modified LiNi0.6Co0.2Mn0.2O2 cathode material with a LZO coating prepared under dry air and oxygen, and systematically investigated the effect of coating atmosphere on their transport properties and electrochemical behaviors. The LZO coating prepared in oxygen is largely amorphous. It not only provided surface protection against the electrolyte corrosion but also enabled faster lithium-ion transport. Additionally, oxygen atmosphere facilitated Zr diffusion from the surface coating to the bulk of LiNi0.6Co0.2Mn0.2O2, which stabilized the crystal structure and enhanced lithium ion diffusion. Consequently, LiNi0.6Co0.2Mn0.2O2 cathodes coated with Li2ZrO3 in oxygen achieved a significant improvement in high-voltage cycling stability and high-rate performance.

Actuellement, les batteries commercialisées fonctionnent avec des électrodes négatives à base de carbone qui présentent une bonne tenue en cyclage mais des capacités massique et volumique limitées et des problèmes de sécurité. Pour améliorer les performances des accumulateurs de nouvelle génération, les métaux purs alliables avec le lithium ont été proposés en raison de leur grande densité d'énergie.<br />L'objectif de cette thèse consiste à élaborer de nouveaux matériaux composites, synthétisés par dispersion ex situ de l'étain dans une matrice inactive (CaSiO3).<br />Les performances du composite de référence sélectionné ‘‘Sn-0,4 CaSiO3'' sont intéressantes : capacité massique réversible de 480 mAh.g-1 et faible polarisation de 140 mV. Cependant, la perte au premier cycle (146 mAh.g-1) est encore trop importante et la tenue en cyclage insuffisante. Pour comprendre les causes de ces deux phénomènes nous avons entrepris l'étude détaillée du mécanisme mis en jeu au cours du premier cycle de restructuration en couplant différentes techniques expérimentales. <br />Les études montrent que le régime influe sur l'étape de restructuration. En régime C/50, la formation d'alliages intermédiaires stables, riches en étain, type LiSn, entraîne une restructuration moins performante que celle réalisée en régime C/10.<br />Nous avons montré que la modification de la matrice de dispersion joue un rôle important sur les paramètres électrochimiques et en particulier sur la perte au premier cycle. Ainsi l'utilisation d'un borosilicate de sodium, plus conducteur, réduit nettement cette perte (90 mAh.g-1).

Ce travail vise à modéliser le vieillissement des batteries lithium-ion soumises à des sollicitations de type véhicule (électrique ou hybride). Cette étude a notamment pour but d'optimiser le dimensionnement des packs batteries pour véhicule et les stratégies de gestion électrique. Une approche originale, de type fatigue mécanique, a été sélectionnée car potentiellement capable de modéliser des sollicitations complexes et variées. Cette approche a été développée pour une batterie lithium-ion spécifique graphite/NCA. Il apparaît qu'un simple cumul de dommage n'est pas entièrement pertinent et que deux contributions au vieillissement sont à l'œuvre : l'une en fonction de la charge échangée et l'autre en fonction du temps. De multiples essais de vieillissement ont été effectués et montrent l'influence très importante de la température, du courant et de l'état de charge sur chacune de ces contributions. Ces essais permettent de mettre en équation l'impact de chacun de ces paramètres sur la vitesse de dégradation. Il en découle un modèle informatique de prévision du vieillissement, capable de prendre en compte les périodes d'arrêt comme de roulage. Les résultats, sur des sollicitations peu à moyennement complexes, donnent une très faible erreur au niveau de la prévision. Des analyses post-mortem ont également été effectuées sur les batteries étudiées afin de comprendre les mécanismes en jeu. Plusieurs analyses (physico-chimiques et électrochimiques, par spectroscopie d'impédance) permettent de relier les principaux mécanismes de vieillissement à chacune des deux contributions : une altération de la structure cristalline du matériau actif d'électrode positive pour la contribution fatigue, la passivation du matériau actif d'électrode négative pour la contribution temporelle. Ces analyses apportent une vision plus complète du vieillissement et justifient les hypothèses effectuées lors de la mise en place du modèle. Elles permettent également d'envisager une généralisation du modèle à d'autres technologies de batteries lithium-ion. D'ailleurs, un essai de généralisation à une autre batterie commerciale a permis de vérifier la fiabilité et de détecter les limites de notre approche.

We have investigated the use of aluminum based amorphous metallic glass as the anode in lithium ion rechargeable batteries. Amorphous metallic glasses have no long-range ordered microstructure; the atoms are less closely packed compared to the crystalline alloys of the same compositions; they usually have higher ionic conductivity than crystalline materials, which make rapid lithium diffusion possible. Many metallic systems have higher theoretical capacity for lithium than graphite/carbon; in addition irreversible capacity loss can be avoided in metallic systems. With careful processing, we are able to obtain nano-crystalline phases dispersed in the amorphous metallic glass matrix. These crystalline regions may form the active centers with which lithium reacts. The surrounding matrix can respond very well to the volume changes as these nano-size regions take up lithium. A comparison study of various kinds of anode materials for lithium rechargeable batteries is carried out. / Singapore-MIT Alliance (SMA)

Current demands on lithium ion battery (LIB) technology include high capacity retention over a life time of many charge and discharge cycles. Maximizing battery longevity is still a major challenge partly due to electrode degradation as a function of repeated cycling. The intercalation of lithium ions into an active material causes the development of stress and strain in active electrode materials which can result in fracture and shifting that can in turn lead to capacity fade and eventual cell failure. The processes leading to active material degradation in cycling LIBs has been studied using a combination of acoustic emission (AE) and in situ X-ray diffraction (XRD) techniques. Safe, low cost custom electrochemical cells were designed and developed for use in battery AE and XRD experiments. These tools were used to monitor the time of material fracture through AE and link these events to lattice strain and phase composition as determined by XRD. Both anode and cathode materials were studied with an emphasis on graphite, silicon, and Li(Mn1.5Ni0.5)O4, and tin. A thermal analogy model for lithiation/delithiation induced fracture of spherical particles capable of predicting when AE should be detected in a cell containing a composite silicon electrode. The results of this work were used to develop an understanding of when and how active materials are degrading as well as to suggest methods of improving their performance and operational longevity.

Within the framework of this thesis, three innovative electrochemical devices have been studied. A part of the work is devoted to an already existing device, laminates which are debonded by the application of a voltage. This type of material can potentially be used in a wide range of applications, including adhesive joints in vehicles to both reduce the total weight and to simplify the disassembly after end-of-life, enabling an inexpensive recycling process. Although already a functioning device, the development and tailoring of this process was slowed by a lack of knowledge concerning the actual electrochemical processes responsible for the debonding. The laminate studied consisted of an epoxy adhesive, mixed with an ionic liquid, bonding two aluminium foils. The results showed that the electrochemical reaction taking place at the releasing anode interface caused a very large increase in potential during galvanostatic polarization. Scanning electron microscopy images showed reaction products growing out from the electrode surface into the adhesive. These reaction products were believed to cause the debonding through swelling of the anodic interface so rupturing the adhesive bond. The other part of the work in this thesis was aimed at innovative lithium ion (Li‑ion) battery concepts. Commercial Li-ion batteries are two-dimensional thin film constructions utilized in most often mechanically rigid products. Two routes were followed in this thesis. In the first, the aim was flexible batteries that could be used in applications such as bendable reading devices. For this purpose, nano-fibrillated cellulose was used as binder material to make flexible battery components. This was achieved through a water-based filtration process, creating flexible and strong papers. These paper-based battery components showed good mechanical properties as well as good rate capabilities during cycling. The drawback using this method was relatively low coulombic efficiencies believed to originate from side-reactions caused by water remnants in the cellulose structure. The second Li-ion battery route comprised an electrochemical process to coat carbon fibers, shown to perform well as negative electrode in Li-ion batteries, from a monomer solution. The resulting polymer coatings were ~500 nm thick and contained lithium ions. This process could be controlled by mainly salt content in the monomer solution and polarization time, yielding thin and apparently pin-hole free coatings. By utilizing the carbon fiber/polymer composite as integrated electrode and electrolyte, a variety of battery designs could possibly be created, such as three-dimensional batteries and structural batteries. / <p>QC 20130403</p>

The exploration of functional materials to store renewable, clean, and efficient energies for electric vehicles (EVs) has become one of the most popular topics in both material chemistry and electrochemistry. Rechargeable lithium batteries and fuel cells are considered as the most promising candidates, but they are both facing some challenges before the practical applications. For example, the low discharge capacity and energy density of the current lithium ion battery cannot provide EVs expected drive range to compete with internal combustion engined vehicles. As for fuel cells, the rapid and safe storage of H2 gas is one of the main obstacles hindering its application. In this thesis, novel mesoporous/nano functional materials that served as cathodes for lithium sulfur battery and lithium ion battery were studied. Ternary lithium transition metal nitrides were also synthesized and examined as potential on-board hydrogen storage materials for EVs. Highly ordered mesoporous carbon (BMC-1) was prepared via the evaporation-induced self-assembly strategy, using soluble phenolic resin and Tetraethoxysilane (TEOS) as precursors and triblock copolymer (ethylene oxide)106(propylene oxide)70(ethylene oxide)106 (F127) as the template. This carbon features a unique bimodal structure (2.0 nm and 5.6 nm), coupled with high specific area (2300 m2/g) and large pore volume (2.0 cm3/g). The BMC-1/S nanocomposites derived from this carbon with different sulfur content exhibit high reversible discharge capacities. For example, the initial capacity of the cathode with 50 wt% of sulfur was 995 mAh/g and remains at 550 mAh/g after 100 cycles at a high current density of 1670 mA/g (1C). The good performance of the BMC-1C/S cathodes is attributed to the bimodal structure of the carbon, and the large number of small mesopores that interconnect the isolated cylindrical pores (large pores). This unique structure facilitates the transfer of polysulfide anions and lithium ions through the large pores. Therefore, high capacity was obtained even at very high current rates. Small mesopores created during the preparation served as containers and confined polysulfide species at the cathode. The cycling stability was further improved by incorporating a small amount of porous silica additive in the cathodes. The main disadvantage of the BMC-1 framework is that it is difficult to incorporate more than 60 wt% sulfur in the BMC-1/S cathodes due to the micron-sized particles of the carbon. Two approaches were employed to solve this problem. First, the pore volume of the BMC-1 was enlarged by using pore expanders. Second, the particle size of BMC-1 was reduced by using a hard template of silica. Both of these two methods had significant influence on improving the performance of the carbon/sulfur cathodes, especially the latter. The obtained spherical BMC-1 nanoparticles (S-BMC) with uniform particle size of 300 nm exhibited one of the highest inner pore volumes for mesoporous carbon nanoparticles of 2.32 cm3/g and also one of the highest surface areas of 2445 m2/g with a bimodal pore size distribution of large and small mesopores of 6 nm and 3.1 nm. As much as 70 wt% sulfur was incorporated into the S-BMC/S nanocomposites. The corresponding electrodes showed a high initial discharge capacity up to 1200 mAh/g and 730 mAh/g after 100 cycles at a high current rate 1C (1675 mA/g). The stability of the cells could be further improved by either removal of the sulfur on the external surface of spherical particles or functionalization of the C/S composites via a simple TEOS induced SiOx coating process. In addition, the F-BMC/S cathodes prepared with mesoporous carbon nanofibers displayed similar performance as the S-BMC/S. These results indicate the importance of particle size control of mesoporous carbons on electrochemical properties of the Li-S cells. By employing the order mesoporous C/SiO2 framework, Li2CoSiO4/C nanocomposites were synthesized via a facile hydrothermal method. The morphology and particle size of the composites could be tailored by simply adjusting the concentrations of the base LiOH. By increasing the ratio of LiOH:SiO2:CoCl2 in the precursors, the particle size decreased at first and then went up. When the molar ratio is equal to 8:1:1, uniform spheres with a mean diameter of 300-400 nm were obtained, among which hollow and core shell structures were observed. The primary reaction mechanism was discussed, where the higher concentration of OH- favored the formation of Li2SiO3 but hindered the subsequent conversion to Li2CoSiO4. According to the elemental maps and TGA of the Li2CoSiO4/C, approximately 2 wt% of nanoscale carbon was distributed on/in the Li2CoSiO4, due to the collapse of the highly ordered porous structure of MCS. These carbons played a significant role in improving the electrochemical performance of the electrode. Without any ball-mill or carbon wiring treatments, the Li2CoSiO4/C-8 exhibited an initial discharge capacity of 162 mAh/g, much higher than that of the sample synthesized with fume silica under similar conditions and a subsequent hand-mixing of Ketjen black. Finally, lithium transition metal nitrides Li7VN4 and Li7MnN4 were prepared by high temperature solid-state reactions. These two compounds were attempted as candidates for hydrogen storage both by density functional theory (DFT) calculations and experiments. The results show that Li7VN4 did not absorb hydrogen under our experimental conditions, and Li7MnN4 was observed to absorb 7 hydrogen atoms through the formation of LiH, Mn4N, and ammonia gas. While these results for Li7VN4 and Li7MnN4 differ in detail, they are in overall qualitative agreement with our theoretical work, which strongly suggests that both compounds are unlikely to form quaternary hydrides.