Recent advances in solving Li_(2)CO_(3) problems in garnet-based solid-state battery: A systematic review(2020-2023)

Garnet solid electrolytes are one of the most promising electrolytes for solid-state batteries.However,Li_(2)CO_(3) is a critical issue that hinders the practical application of garnet-based solid-state lithium-ion batteries.There are two sources of Li_(2)CO_(3) contamination.The main one is the aging of garnet electrolytes in the atmosphere.Garnet electrolytes can react with H_(2)O and CO_(2) in the air to form Li_(2)CO_(3),which reduces ion conductivity,increases electrode/garnet electrolyte interface resistance,and deteriorates the electrochemical performance of the battery.Various strategies,such as elemental doping,grain boundary manipulation,and interface engineering,have been suggested to address these issues.The other is the passivation layer(Li_(2)CO_(3),Li_3N,LiOH,Li_(2)O) formed on the surface of the lithium foil after long-term storage,which is ignored by most researchers.To better understand the current strategies and future trends to address the Li_(2)CO_(3) problem,this perspective provides a systematic review of journals published in this field from 2020-2023.

Garnet and Zircon U-Pb Geochronology and Geochemistry Reveal Genesis of the Dafang Au-Pb-Zn-Ag Deposit,Southern Hunan

Garnet is a primary mineral in skarn deposits and plays a significant role in recording copious mineralization and metallogenic information.This study systematically investigates the geochemistry and geochronology of garnet and zircon in the Dafang Au-Pb-Zn-Ag deposit,which represents prominent gold mineralization in southern Hunan,China.Garnet samples with distinct zoning patterns and compositional variations were identified using various analytical techniques,including Backscattered Electron(BSE)imaging,Cathodoluminescence(CL)response,textural characterization,and analysis of rare-earth elements(REE),major contents,and trace element compositions.The garnet was dated U-Pb dating,which yielded a lower intercept age of 161.06±1.93 Ma.This age is older than the underlying granodiorite porphyry,which has a concordia age of 155.13±0.95 Ma determined by zircon U-Pb dating.These results suggest that the gold mineralization may be related to the concealed granite.Two groups of garnet changed from depleted Al garnet to enriched Al garnet,and the rare earth element(REE)patterns of these groups were converted from light REE(LREE)-enriched and heavy REE(HREE)-depleted with positive europium(Eu)anomalies to medium REE(MREE)-enriched from core to rim zoning.The different REE patterns of garnet in various zones may be attributed to changes in the fluid environment and late superposition alteration.The development of distal skarn in the southern Hunan could be a significant indicator for identifying gold mineralization.

Reasonable design a high-entropy garnet-type solid electrolyte for all-solid-state lithium batteries

Traditional garnet solid electrolyte(Li_(7)La_(3)Zr_(2)O_(12))suffers from low room temperature ionic conductivity,poor air stability,high sintering temperature and energy consumption.Considering the development prospects of high-entropy materials with high structural disorder and strong component controllability in the field of electrochemical energy storage,herein,a novel high-entropy garnet-type oxide solid electrolyte,Li_(5.75)Ga_(0.25)La_(3)Zr_(0.5)Ti_(0.5)Sn_(0.5)Nb_(0.5)O_(12)(LGLZTSNO)was constructed by partially replacing the Li and Zr sites in Li_(7)La_(3)Zr_(2)O_(12)with Ga and Ti/Sn/Nb elements,respectively.The experimental and density functional theory(DFT)calculation results show that the high-entropy LGLZTSNO electrolyte has preferable room temperature ion conductivity,air stability,interface contact performance with lithium anode,and the ability to suppress lithium dendrites.Thanks to the improvement of electrolyte performance,the critical current density of Li/Ag@LGLZTSNO/Li symmetric cell was increased from 0.42 to 1.57 mA cm^(−2),and the interface area specific impedance(IASR)was reduced from 765.2 to 42.3Ωcm^(2).Meanwhile,the Li/Ag@LGLZTSNO/LFP full cell also exhibits excellent rate performance and cycling performance(148 mA h g^(−1)at 0.1 C and 124 mA h g^(−1)at 0.5 C,capacity retention up to 84.8%after 100 cycles at 0.1 C),showing the application prospects of high-entropy LGLZTSNO solid electrolyte in high-performance all solid state lithium batteries.

Dual-interlayers constructed by Ti_(3)C_(2)T_(x)/ionic-liquid for enhanced performance of solid garnet batteries

Li(6.4)La_(3)Zr_(1.4)Ta_(0.6)O_(12)(LLZTO) solid garnet-type electrolyte has been widely reported due to its outstanding safety and electrochemical stability.However,the inherent rigidity and brittleness of LLZTO lead to poor contact with anode/cathode and the operation failure of full cells.Herein,the dual-interlayers are constructed as the fast interfacial ion-migration channel by using Ti_(3)C_(2)T_(x)(MXene,Txis-O,-OH,-F) with trace ionic liquid(IL),which promote the intimate contact between LLZTO and anode/cathode and suppress Li-dendrites growth.Notably,IL can wet the cathode to promote intimate interface contact and be decomposed into some inorganic compounds(such as Li3N,LiF,and Li2Sx),resulting in reduced interfacial resistance and fast Li-ion transportation.Consequently,in the prepared Li-symmetric cell,the interfacial resistance on the anode side plunges to 33.1 Ω cm^(-2),and stably maintains over 1000 h without short circuit at 0.05 mA cm^(-2).The full cell of Li|LiFePO4delivers a high initial capacity of 158.52 mA h g^(-1)and outstanding retention of 90.18% after 100 cycles at 60℃ and 0.2 C.Our work provides an efficient strategy to design dual-interlayers between LLZTO and anode/cathode for the interfacial modification to enhance the performance of solid garnet batteries.

LiCoO_(2) sintering aid towards cathode-interface-enhanced garnet electrolytes

Garnet-type Li_7La_(3)Zr_(2)O_(12)(LLZO) has high ionic conductivity and good compatibility with lithium metal.High-temperature processing has been proven an effective method to decrease the interface resistance of cathodeILLZO.However,its application is still hindered by the interlayer co-diffusion with the cathode and high sintering temperature(>1200℃).In this work,a new garnet-type composite solid-state electrolyte(SSE) Li_(6.54)La_(2.96)Ba_(0.04)Zr_(1.5)Nb_(0.5)O_(12)-LiCoO_(2)(LLBZNO-LCO) is firstly proposed to improve the chemical stability and electrochemical properties of garnet with high-temperature processing.Small doses of LCO(3%) can significantly decrease the LCOISSE interface resistance from 121.2 to 10.1 Ω cm~2,while the sintering temperature of garnet-type LLBZNO decreases from 1230 to 1000℃.The all-solid-state battery based on the sintered LLBZNO-LCO SSE exhibits excellent cycling stability.Our approach achieves an enhanced LCOISSE interface and an improved sintering activity of garnet SSE,which provides a new strategy for optimizing the comprehensive performance of garnet SSE.

Magnetic triangular bubble lattices in bismuth-doped yttrium iron garnet

Magnetic bubbles have again become a subject of significant attention following the experimental observation of topologically nontrivial magnetic skyrmions. In recent work, tailoring the shape of the bubbles is considered a key factor for their dynamics in spintronic devices. In addition to the reported circular, elliptical, and square bubbles, here we observe triangular bubble domains in bismuth-doped yttrium iron garnet(Bi-YIG) using Kerr microscopy. The bubble domains evolve from discrete circular to latticed triangular and hexagonal shapes. Further, the orientation of the triangular bubbles in the hexagonal lattices can be flipped by decreasing the magnetic field. The sixfold in-plane magnetic anisotropy of Bi-YIG(111) crystal, which is presumably the mechanism underlying the triangular shape of the bubbles, is measured as1179 erg/cm~3. The study of the morphologies of topologically trivial bubbles in YIG offers insight into nontrivial spin textures, which is appealing for future spintronic applications.

Progress and perspective of interface design in garnet electrolyte-based all-solid-state batteries

Inorganic solid-state electrolytes(SSEs)are nonflammable alternatives to the commercial liquid-phase electrolytes.This enables the use of lithium(Li)metal as an anode,providing high-energy density and improved stability by avoiding unwanted liquid-phase chemical reactions.Among the different types of SSEs,the garnet-type electrolytes witness a rapid development and are considered as one of the top candidates to pair with Li metal due to their high ionic conductivity,thermal,and electrochemical stability.However,the large resistances at the interface between garnet-type electrolytes and cathode/anode are the major bottlenecks for delivering desirable electrochemical performances of all-solid-state batteries(SSBs).The electrolyte/anode interface also suffers from metallic dendrite formation,leading to rapid performance degradation.This is a fundamental material challenge due to the poor contact and wettability between garnet-type electrolytes with electrode materials.Here,we summarize and analyze the recent contributions in mitigating such materials challenges at the interface.Strategies used to address these challenges are divided into different categories with regard to their working principles.On one hand,progress has been made in the anode/garnet interface,such as the successful application of Li-alloy anode and different artificial interlayers,significantly improving interfacial performance.On the other hand,the desired cathode/garnet interface is still hard to reach due to the complex chemical and physical structure at the cathode.The common methods used are nanostructured cathode host and sintering additives for increasing the contact area.On the basis of this information,we present our views on the remaining challenges and future research of electrode/garnet interface.This review not only motivates the need for further understanding of the fundamentals,stability,and modifications of the garnet/electrode interfaces but also provides guidelines for the future design of the interface for SSB.

U-Pb Geochronology and Geochemistry of Stratiform Garnet from the Aqishan Pb-Zn Deposit,Eastern Tianshan,Xinjiang,NW China:Constraints on Genesis of the Deposit

The Aqishan lead-zinc deposit,located in the Jueluotag metallogenic belt of eastern Tianshan,Xinjiang,Northwest China,has a stratiform occurrence in the marine volcanic tuff of the Yamansu Formation.The ore body has a typical double-layer structure,having a stratified,stratoid,lenticular upper part and a veined,stockwork-like lower part.The occurrence of the upper orebody is consistent with that of the volcanic tuff wall rock.The ore minerals are mainly chalcopyrite,pyrite,sphalerite,galena and magnetite,the altered minerals mainly being silicified,such as sericite,chlorite,epidote,garnet.The garnetized skarn,being stratiform and stratoid,is closely related to the upper part of the orebody.Geological observations show that the limestone in the ore-bearing Yamansu Formation is not marbleized and skarnized.Spatially,it is associated with the ferromanganese deposits in the marine volcanic rocks of the Yamansu Formation.These geological features reflect the likelihood that the Aqishan lead-zinc deposit is a hydrothermal exhalation sedimentary deposit.The results from the EPMA show that the garnet is mainly composed of grossular-andradite series,contents being in a range of 34.791-37.8%SiO_(2),32.493-34.274%CaO,8.454-27.275%FeO,0.012-15.293%Al_(2)O_(3),0.351-1.413%MnO,and lower values of 0.013-1.057%TiO_(2).The content of SiO_(2) vs.CaO and FeO vs.Al_(2)O_(3) has a significant positive correlation.The results of ICP-MS analysis for the garnet show that the REE pattern is oblique to right in general.The total amount of rare earth elements is relatively low,ΣREE=71.045-826.52 ppm,which is relatively enriched for LREE and depleted for HREE.LREE/HREE=8.66-4157.75,La_(N)/Yb_(N)=23.51-984.34,with obvious positive Eu and Ce anomalies(δEu=2.27-76.15,δCe=0.94-1.85).This result is similar to the REE characteristics of ore-bearing rhyolite volcanic rocks,showing that the garnet was formed in an oxidizing environment and affected by clear hydrothermal activity.The U-Pb isotopic dating of garnet by fs-LA-HR-ICP-MS gives an age of 316.3±4.4 Ma(MSWD=1.4),which is consistent with the formation time of the Yamansu Formation.According to the study of deposit characteristics and geochemical characteristics,this study concludes that the Aqishan lead-zinc deposit is a hydrothermal exhalation sedimentary deposit,the garnet being caused by hydrothermal exhalative sedimentation.

Densification and lithium ion conductivity of garnet-type Li_(7-x)La_3Zr_(2-x)Ta_xO_(12) (x=0.25) solid electrolytes

The garnet-type Li7La3Zr2O12 ceramic is a promising solid electrolyte for all-solid-state secondary lithium batteries. However, it faces the problem of lithium volatilization during sintering, which may cause low density and deterioration of ionic conductivity. In this work, the effects of sintering temperature and addition on the density as well as the lithium ion conductivity of Li7-xLa3Zr2-xTaxO12 （LLZTO, x=0.25） ceramics prepared by solid state reaction have been studied. It is found that optimization of the sintering temperature leads to a minor increase in the ceramic density, yielding an optimum ionic conductivity of 2.9×10-4 S·cm-1 at 25℃. Introduction of Li 3 PO 4 addition in an appropriate concentration can obviously increase the density, leading to an optimum ionic conductivity of 7.2×10-4 S·cm-1 at 25℃. This value is superior to the conductivity data in most recent reports on the LLZTO ceramics.

Synthesis of Neodymium-Doped Yttrium Aluminum Garnet (Nd∶YAG) Nano-Sized Powders by Low Temperature Combustion

The homogeneously dispersed, less agglomerated (Nd0.01Y0.99)3Al5O12 nano-sized powders were synthesized by the low temperature combustion (LCS), using Nd2O3, Y2O3, Al(NO3)3·9H2O, ammonia water and citric acid as starting materials. This method effectively solves the problems caused by solid-state reaction at high temperature and hard agglomerates brought by the chemical precipitation method. The powders were characterized by TG-DTA, XRD, FT-IR, TEM respectively and the photoluminescence (PL) spectra of (Nd0.01Y0.99)3Al5O12 green and sintered ceramic disks were measured. The results show that the forming temperature of YAG crystal phase is 850 ℃ and YAP crystal phase appearing during the calcinations transforms to pure YAG at 1050 ℃. The particle size of the powders synthesized by the LCS is in a range of 20～50 nm depending on the thermal treatment temperatures. The effectively induced cross section (σin) with the value 4.03×10-19 cm2 of (Nd0.01Y0.99)3Al5O12 ceramics is about 44% higher than that of single crystal.

DIFFUSION MODELLING IN GARNET FROM TSO MORARI ECLOGITE AND IMPLICATIONS FOR EXHUMATION MODELS

The results of recent geothermobarometric and geochronological investigations of scarce eclogites of the NW Himalaya (Tso Morari (Ladakh), India and Kaghan Valley, Pakistan) have caused a major rethink of tectonometamorphic models for India\|Asia collision. Numerous petrologic studies have been undertaken on the age and origin of metamorphism in the Higher Himalayan Crystallines (HHC) and Lesser Himalaya formations (LH) and their relationship to granite magmatism and movements along the Main Central Thrust (MCT) and South Tibetan Detachment Fault (STDF). However, all of these events are essentially Miocene (or younger) in age and can clearly be distinguished from subduction and exhumation processes undergone by the eclogites which are of Eocene age (Tonarini et al. 1993; Spencer & Gebauer; 1996; de Sigoyer et al. 1999) and relate to the very early stages of the collision. Eclogites of eastern Ladakh are mafic lenses found in granitic gneisses (Ordovician intrusive age: Girard & Bussy 1999) and their surrounding late Pre\|Cambrian to early Cambrian sedimentary units in the Tso Morari dome (see Steck et al. 1998). Detailed petrological and geochronological studies (Guillot et al. 1997; de Sigoyer et al. 1997, 1999) have identified an eclogite facies stage (2000±300)MPa, (580±60)℃ followed by isothermal decompression associated with glaucophane growth at around (1100±200)MPa. Dating of different phases by different methods yielded ages around 55Ma for this stage ((55±17) Ma, U\|Pb, Aln; (55±12) Ma, Lu\|Hf, Grt\|Cpx\|Rt; (55±7) Ma, Sm\|Nd, Grt\|Gln\|Rt). A subsequent amphibolite facies overprint at slightly higher temperature (610±70)℃ was dated at 45～48Ma (metabasite: (47±11) Ma, Sm\|Nd, Grt\|Hbl; metapelite: (45±4) Ma, Rb\|Sr, Mu\|Ap\|WR and (48±2) Ma, Ar\|Ar, Phe). By (30±1) Ma (Ar\|Ar, Bt\|Mu) retrogression into the greenschist facies had occurred (de Sigoyer et al. 1999). These data indicate a two stage history with early exhumation being much faster (>4mm/a) than the later evolution (1～2mm/a).

Early Cooling History of Eclogites from the Dabie-Sulu Orogen: Constraints from Diffusion Kinetics of Garnet

For the first time, we apply different geospeedometric models to garnet zoning patterns that were obtained in this study from detailed EMP analyses for garnets from eclogites and granulite in the Dabie-Sulu orogen. Various zonings of cation diffusion were preserved in the garnets, enabling the acquirement of average cooling rates for the high-to ultrahigh-pressure rocks without using geochronological approaches. The coesite-bearing hot eclogites yield fast cooling rates of about 20 to 30℃/Ma subsequent to peak metamorphic temperatures, whereas the cold eclogite gives a relatively slow cooling rate of 8℃/Ma at its initial exhumation. A very slow cooling rate of <0.3℃/Ma is obtained for the granulite at Huangtuling, suggesting that the granulite may not be involved in the continental deep subduction.

Yttrium aluminum garnet (Y_3A_(l5)O_(12)) nanopowders synthesized by the chemical method

The homogeneously dispersed, less agglomerated YAG nanopowders are synthesized by the citrate-gel method followed by low-temperature self-propagating combustion reaction, using Y2O3, Al(NO3)3?9H2O and citric acid as starting materials. This method effectively solves the problems caused by solid-state reaction at high temperature and the hard ag-glomerates brought by the chemical precipitation method. The powders are characterized by TG-DTA, XRD, FT-IR and TEM respectively. The experiments show that the forming temperature of YAG crystal phase is 850°C and the pseudo-YAG crystalline appears during the calcination and transforms to pure YAG at 1050°C. The powders with sizes less than 50 nm are observed by TEM micrography, which is consistent with the result calculated by Scherrer's formula. The powders consist of single grains.

Preparation of Neodymium-Doped Yttrium Aluminum Garnet Transparent Ceramics by Homogeneous Precipitation Method

substitutes tion, high loosely dis Neodymium doped-yttrium aluminum garnet （Nd ： YAG） transparent polycrystalline ceramics already become of single crystals because they are provided with easy fabrication, low cost, large size, highly doped concentraheat conductivity, mass fabrication, multi-layers and multi-filnctions. The Nd：YAG precursor powders with persed , slightly agglomerated, super fine and YAG cubic crystal phase were synthesized at 1100 ℃ by the homogeneous precipitation method, using Nd2O3, Y2O3, Al（NO3）3·9H2O and urea as raw materials, （NH4）2SO4 as electrical stabilizer, TEOS as sintering additive. The Nd：YAG transparent ceramics were prepared after being vacuum sintered at 1700 ℃ for 5 h. The Nd：YAG ceramic materials were characterized by the TG-DTA, XRD, FT-IR, TEM, FEG-ESEM and FT-PL. The results show that the crystallization temperature of YAG is 850 ℃ and the intermediate crystal phase YAP forming during the heat treatment transforms to YAG cubic crystal phase at 1050 ℃. The lasing wavelength of （Nd0.01 Y0.99）3Al5O12 transparent ceramics is 1.065 μm and there exists a slight red-shift compared to the single crystal with the same chemical composition. The optical transmittance is 45 % in the visible light and 58 % in the near infrared light and the optical transmittance descends with the decreasing the wavelength.

Preparation of neodymium-doped yttrium aluminum garnet powders and fibers

Using nitrate precursors, a novel spray-drying assisted citrate gel process for the preparation of neodymium-doped yttrium alumi- num garnet （YAG） phase was developed. Synthesis of single-phase polycrystalline YAG was achieved at temperatures as low as 800 ℃ using the spray-drying methodology whilst conventional approaches currently available require 1000 ℃. Initially, a solution was prepared by mixing aluminum and yttrium nitrates, citric acid, etilenglycol and neodymium oxide. This solution was dried by pulverization （spray dryer） to obtain aggregated precursor powders of the compound. These aggregates were calcined at 800, 850 and 900 ℃ to determine the phase evolution from amorphous to crystalline by X-ray diffraction （XRD）. The morphology of aggregates was characterized by scanning electron microscopy （SEM） and transmission electron microscopy （TEM）. Moreover, through XRD it was determined that the crystallization of YAG phase started at about 800 ℃ without any intermediate phases. The powders were composed of spherical aggregates with an average diameter of 1 um. From these powders, ceramic fibers with additions of 2at.% and 5at.% Nd, were extracted from the melt with diameters ranging from 30 um to 50 um.

Liquid phase epitaxy magnetic garnet films and their applications

Liquid phase epitaxy （LPE） is a mature technology. Early experiments on single magnetic crystal films fabricated by LPE were focused mainly on thick films for microwave and magneto-optical devices. The LPE is an excellent way to make a thick film, low damping magnetic garnet film and high-quality magneto-optical material. Today, the principal challenge in the applied material is to create sub-micrometer devices by using modern photolithography technique. Until now the magnetic garnet films fabricated by LPE still show the best quality even on a nanoscale （about 100 nm）, which was considered to be impossible for LPE method.

Nanostructured yttrium aluminum garnet powders synthesized by co-precipitation method using tetraethylenepentamine

Tetraethylenepentamine(C8H23N5,TEPA) has been used as a novel precipitant to synthesize yttrium aluminum garnet(Y3Al5O12,YAG) precursor from a mixed solution of aluminum and yttrium nitrates via a normal-strike co-precipitation method without controlling the pH value during precipitation process.The original precursor was analyzed by thermogravimetry/differential scanning calorimetry(TG/DSC).The evolution of phase composition and micro-structure of the as-synthesized YAG powders were characterized by X-ray ...

Lithiated Nafion-garnet ceramic composite electrolyte membrane for solid-state lithium metal battery

Single-ion conducting solid polymer electrolytes are expected to play a vital role in the realization of solid-state Li metal batteries.In this work,a lithiated Nafion(Li-Nafion)-garnet ceramic Li6.25La3 Zr2 Al0.25O12(LLZAO)composite solid electrolyte(CSE)membrane with 30μm thickness was prepared for the first time.By employing X-ray photoelectron spectroscopy and transmission electron microscope,the interaction between LLZAO and Li-Nafion was investigated.It is found that the LLZAO interacts with the Li-Nafion to form a space charge layer at the interface between LLZAO and Li-Nafion.The space charge layer reduces the migration barrier of Li-ions and improves the ionic conductivity of the CSE membrane.The CSE membrane containing 10 wt%LLZAO exhibits the highest ionic conductivity of2.26×10-4 S cm-1 at 30℃among the pristine Li-Nafion membrane,the membrane containing 5 wt%,20 wt%,and 30 wt%LLZAO,respectively.It also exhibits a high Li-ion transference number of 0.92,and a broader electrochemical window of 0-+4.8 V vs.Li+/Li than that of 0-+4.0 V vs.Li+/Li for the pristine Li-Nafion membrane.It is observed that the CSE membrane not only inhibits the growth of Li dendrites but also keeps excellent electrochemical stability with the Li electrode.Benefitting from the above merits,the solid-state LiFePO4/Li cell fabricated with the CSE membrane was practically charged and discharged at 30℃.The cell exhibits an initial reversible discharge specific capacity of 160 mAh g-1 with 97%capacity retention after 100 cycles at 0.2 C,and maintains discharge specific capacity of 126 mAh g-1 after500 cycles at 1 C.The CSE membrane prepared with Li-Nafion and LLZAO is proved to be a promising solid electrolyte for advanced solid-state Li metal batteries.

Neodymium-doped Yttrium Aluminum Garnet Transparent Laser Ceramics Prepared by Co-precipitation Method

Transparent polycrystaUine neodymiumdoped yttrium aluminum garnet ceramics （Nd：YAG） with better chemical stability, excellent optical and high temperature mechanical property is becoming a new laser host material. The Nd：YAG precursor powders with loosely dispersed, slightly agglomerated and YAG cubic crystal phase were synthesized at 1100 ℃ by the co-precipitation method combined with the reverse strike,

Diffusion in garnet： a review

With improvements on high-pressure experimental techniques in multi-anvil apparatus and the development of new analytical tools, major progress has been made on diffusion in garnets in the past several decades. The data obtained in the experimental determination of diffusion coefficients in garnets are of fundamental importance for diffusion modeling and timescales of geological and planetary processes. In this review, we have compiled experimental data on self-diffusion(Si, O, cations), trace element diffusion(Li, Y, Ga, Cr, Sr, REEs), and interdiffusion(Ca–Fe/Mg, Si–Al) in garnet in the light of new advances and recent applications. In addition, some empirical relationships among diffusion parameters(pre-exponential factor D_0,activation energy E, ionic radius) are also discussed. We hope that this review can provide a useful data digest and guide to future study of diffusion in garnet.