Lithium deposition behavior in hard carbon hosts:Optical microscopy and scanning electron microscopy study

Lithium(Li)metal is an ideal anode for the next generation high-energy-density batteries.However,it suffers from dendrite growth,side reactions,and infinite relative volume change.Effective strategies are using porous carbons or surface modification carbons to guide Li deposition into their pores.While the Li deposition behavior is still ambiguous.Here,we systematically determine their deposition behavior in various surface-modified carbons and in different electrolytes via optical microscopy and scanning electron microscopy study.It is found that Li will not spontaneously deposit into the carbon pores,which is significantly dependent on the carbon surface,current density,areal capacity,and electrolyte.Thus,a“lithiophilic”modified commercial hard carbon with Ag is developed as a stable“host”and efficient surface protection derived from the localized high-concentration electrolyte exhibits a pretty low volume change(5.3%)during cycling at a current density of 2 mA·cm^(−2)and an areal capacity of 2 mAh·cm^(−2).This strategy addresses the volume change and dendrite problems by rationally designed host and electrolyte,providing a broad perspective for realizing Li-metal anode.

Synergy of in-situ heterogeneous interphases tailored lithium deposition

The implementation of a robust artificial solid electrolyte interphase(ASEI)to replace the unstable natural SEI can regulate lithium deposition behaviors and avoid the safety hazards caused by dendrites permeation in lithium metal batteries.Despite of devoted efforts in tailoring components of ASEI,the intrinsic mechanism of interfacial synergy within the heterogeneous interphases has not been well elucidated yet.Herein,we show that the lithium plating/striping behaviors can be substantially enhanced(over 900 h with an overpotential of less than 20 mV at 1 mA·cm^(−2)in Li|Li symmetric cells and 146 cycles in anode-free cells)by regulating the heterogeneous interphases.This favorable ASEI composed of LiF and Li_(3)N components can be in-situ generated during cycling by large-scale fabricated fluorinated boron nitride coatings.Further,the synergy of each heterogeneous component within ASEI was explored theoretically and experimentally.Li_(3)N has high adsorption energy and low ion diffusion barrier,which facilitates the transport of lithium ions and avoids its local accumulation to evolve into dendrites.Both the substrate and LiF are interfacially stable with high electron tunneling barriers,preventing the electrolyte decomposition and parasitic reactions.Finally,the high stiffness of the boron nitride also ensures lithium dendrites are suppressed once they grow,providing a stable environment for long-term cycling of lithium metal batteries.

Classification and mineralization of global lithium deposits and lithium extraction technologies for exogenetic lithium deposits

A reasonable classification of deposits holds great significance for identifying prospecting targets and deploying exploration. The world ’s keen demand for lithium resources has expedited the discovery of numerous novel lithium resources. Given the presence of varied classification criteria for lithium resources presently, this study further ascertained and classified the lithium resources according to their occurrence modes, obtaining 10 types and 5 subtypes of lithium deposits(resources) based on endogenetic and exogenetic factors. As indicated by surveys of Cenozoic exogenetic lithium deposits in China and abroad,the formation and distribution of the deposits are primarily determined by plate collision zones, their primary material sources are linked to the anatectic magmas in the deep oceanic crust, and they were formed primarily during the Miocene and Late Paleogene. The researchers ascertained that these deposits,especially those of the salt lake, geothermal, and volcanic deposit types, are formed by unique slightly acidic magmas, tend to migrate and accumulate toward low-lying areas, and display supernormal enrichment. However, the material sources of lithium deposits(resources) of the Neopaleozoic clay subtype and the deep brine type are yet to be further identified. Given the various types and complex origins of lithium deposits(resources), which were formed due to the interactions of multiple spheres, it is recommended that the mineralization of exogenetic lithium deposits(resources) be investigated by integrating tectono-geochemistry, paleoatmospheric circulation, and salinology. So far, industrialized lithium extraction is primarily achieved in lithium deposits of the salt lake, clay, and hard rock types. The lithium extraction employs different processes, with lithium extraction from salt lake-type lithium deposits proving the most energy-saving and cost-effective.

Genesis of the Jiajika superlarge lithium deposit,Sichuan,China:constraints from He–Ar–H–O isotopes

The Jiajika granitic-and pegmatite-type lithium deposit,which is in the Songpan-Garze Orogenic Belt in western Sichuan Province,China,is the largest in Asia.Previous studies have examined the geochemistry and mineralogy of pegmatites and their parental source rocks to determine the genesis of the deposit.However,the evolution of magmatic-hydrothermal fluids has received limited attention.We analyzed He–Ar–H–O isotopes to decipher the ore-fluid nature and identify the contribution of fluids to mineralization in the late stage of crystallization differentiation.In the Jiajika ore field,two-mica granites,pegmatites(including common pegmatites and spodumene pegmatites),metasandstones,and schists are the dominant rock types exposed.Common pegmatites derived from early differentiation of the two-mica granitic magmas before they evolved into spodumene pegmatites during the late stage of the magmatic evolution.Common pegmatites have~3He/~4He ratios that vary from 0.18 to 4.68 Ra(mean1.62 Ra),and their~(40)Ar/~(36)Ar ratios range from 426.70 to 1408.06(mean 761.81);spodumene pegmatites have~3He/~4He ratios that vary from 0.18 to 2.66 Ra(mean 0.87Ra)and their~(40)Ar/~(36)Ar ratios range from 402.13 to 1907.34(mean 801.65).These data indicate that the hydrothermal fluids were shown a mixture of crust-and mantle-derived materials,and the proportion of crustderived materials in spodumene pegmatites increases significantly in the late stage of the magmatic evolution.Theδ~(18)OH_(2)O–VSMOWvalues of common pegmatites range from 6.2‰to 10.9‰,with a mean value of 8.6‰,andδDV–SMOWvalues vary from-110‰to-72‰,with a mean o f-85‰.Theδ~(18)OH_(2)O–VSMOWvalues of spodumene pegmatites range from 5.3‰to 13.2‰,with a mean of 9.1‰,andδDV–SMOWvalues vary from-115‰to-77‰,with a mean of-91‰.These data suggest that the ore-forming fluids came from primary magmatic water gradually mixing with more meteoric water in the late stage of the magmatic evolution.Based on the He–Ar–H–O and other existing data,we propose that the oreforming metals are mainly derived from the upper continental crust with a minor contribution from the mantle,and the fluid exsolution and addition of meteoric water during the formation of pegmatite contributed to the formation of the Jiajika superlarge lithium deposit.

Freestanding polypyrrole nanotube/reduced graphene oxide hybrid film as flexible scaffold for dendrite-free lithium metal anodes

Lithium metal anode is the most potential anode material for the next generation high-energy rechargeable batteries owing to its highest specific capacity and lowest redox potential.Unfortunately,the uneven deposition of Li during plating/stripping and the formation of uncontrolled Li dendrites,which might cause poor battery performance and serious safety problems,are demonstrating to be a huge challenge for its practical application.Here,we show that a flexible and free-standing film hybriding with polypyrrole(PPy) nanotubes and reduced graphene oxide(rGO) can significantly regulate the Li nucleation and deposition,and further prohibit the formation of Li dendrites,owing to the large specific surface area,rich of nitrogen functional groups and porous structures.Finally,the high Coulombic efficiency and stable Li plating/stripping cycling performance with 98% for 230 cycles at 0.5 mA cm^(-2) and more than 900 hours stable lifespan are achieved.No Li dendrites form even at a Li deposition capacity as high as4.0 mA h cm^(-2).Besides,the designed PPy/rGO hybrid anode scaffold can also drive a superior battery performance in the lithium-metal full cell applications.

An ultra-fast charging strategy for lithium-ion battery at low temperature without lithium plating

Conventional charging methods for lithium-ion battery(LIB)are challenged with vital problems at low temperatures:risk of lithium(Li)plating and low charging speed.This study proposes a fast-charging strategy without Li plating to achieve high-rate charging at low temperatures with bidirectional chargers.The strategy combines the pulsed-heating method and the optimal charging method via precise control of the battery states.A thermo-electric coupled model is developed based on the pseudo-twodimensional(P2D)electrochemical model to derive charging performances.Two current maps of pulsed heating and charging are generated to realize real-time control.Therefore,our proposed strategy achieves a 3 C equivalent rate at 0℃ and 1.5 C at-10℃ without Li plating,which is 10–30 times faster than the traditional methods.The entropy method is employed to balance the charging speed and the energy efficiency,and the charging performance is further enhanced.For practical application,the power limitation of the charger is considered,and a 2.4 C equivalent rate is achieved at 0℃ with a 250 kW maximum power output.This novel strategy significantly expands LIB usage boundary,and increases charging speed and battery safety.

Insights into the nitride-regulated processes at the electrolyte/electrode interface in quasi-solid-state lithium metal batteries

Gel polymer electrolytes(GPEs)are one of the promising candidates for high-energy-density quasi-solid-state lithium metal batteries(QSSLMBs),for their high ionic conductivity and excellent interfacial compatibility.The comprehension of dynamic evolution and structure-reactivity correlation at the GPE/Li interface becomes significant.Here,in situ electrochemical atomic force microscopy(EC-AFM)provides insights into the LiNO_(3)-regulated micromechanism of the Li plating/stripping processes upon cycles in GPE-based LMBs at nanoscale.The additive LiNO_(3)induces the formation of amorphous nitride SEI film and facilitates Li^(+) ion diffusion.It stabilizes a compatible interface and regulates the Li nucleation/growth at steady kinetics.The deposited Li is in the shape of chunks and tightly compact.The Li dissolution shows favorable reversibility,which guarantees the cycling performance of LMBs.In situ AFM monitoring provides a deep understanding into the dynamic evolution of Li deposition/dissolution and the interphasial properties of tunable SEI film,regulating the rational design of electrolyte and optimizing interfacial establishment for GPE-based QSSLMBs.

Layered Ag-graphene films synthesized by Gamma ray irradiation for stable lithium metal ano des in carb on ate-based electrolytes

Lithium metal batteries are considered as high energy density battery systems with very promising prospects and have bee n widely studied.However,The uncon trollable plating/strippi ng behavior,infinite volume change and den drites formation of lithium metal anode restrict the applicati on.The unc on trolled n ucleati on of lithium caused by the non uniform multi-physical field distributions,can lead to the undesirable lithium deposition.Herein,a graphene composite uniformly loaded with Ag nano-particles(Ag NPs)is prepared through a facile Gamma ray irradiation method and assembled into self-supported film with layered structure(Ag-rGO film).Whe n such film is used as a lithium metal an ode host,the uncontrolled deposition is converted into a highly nucleation-induced process.On one hand,the Ag NPs distributed between the in terlayers of graphe ne can preferentially induce lithium nu cleati on and en able uniform deposition morphology of lithium between interlayers.On the other hand,the stable layered graphene structure can accommodate volume change,stabilize the interface between anode and electrolyte and inhibit dendrites formation.Therefore,the layered Ag-rGO film as anode host can reach a high Coulombic efficiency over 93.3% for 200 cycle(786 h)at a current density of 1 mA cm^(-2) for 2 mAh cm^(-2) in carbonate-based electrolyte.This work proposes a facile Gamma ray irradiation method to prepare metal/3D-skeleton structure as lithium anode host and demonstrates the potential to regulate the lithium metal deposition behaviors via manipulating the distribution of lithiophilic metal(e.g.Ag)in 3D frameworks.This may offer a practicable thinking for the subsequent design of the lithium metal anode.

The Metallogenetic Regularities of Lithium Deposits in China

Lithium resources support the development of high-technology industries. China has abundant lithium resources which are mainly distributed in Tibet, Qinghai, Sichuan and Jiangxi. Salt lakes in China have significant lithium reserves, but lithium is mainly produced from hard rock lithium deposits because the extraction from salt lakes requires further improvements. The hard rock lithium deposits mainly occur in granitic pegmatite in the Altay region of Xinjiang and the Jiajika deposit in western Sichuan Province; they mainly formed in the Mesozoic and occurred in a relatively stable stage during orogenic processes. On the basis of the information from 151 lithium deposits or spots, 14 lithium metallogenic series were identified, and granitic pegmatite, granite, and sedimentary types were considered to be the main prediction types of lithium resources. Twelve lithium mineralization belts were divided and a series of maps showing the lithium metallogenetic regularity in China were drawn. We conclude that the hard rock and brine type of lithium resources possibly have a similar lithium source related to magmatism. The mctallogenic features of the lithium in China were related with the distinct history of tectonic-magmatic activity in China. This study benefits the assessment of, and prospecting for, lithium resources in China.

Fluid Characteristics and Evolution of the Zhawulong Granitic Pegmatite Lithium Deposit in the Ganzi-Songpan Region, Southwestern China

The Zhawulong granitic pegmatite lithium deposit is located in the Ganzi-Songpan orogenic belt.Fluid inclusions in spodumene and coexisting quartz were studied to understand the cooling path and evolution of fluid within albite–spodumene pegmatite.There are three distinguishable types of fluid inclusions:crystal-rich,CO2–NaCl–H2 O,and NaCl–H2 O.At more than 500°C and 350~480 MPa,crystal-rich fluid inclusions were captured during the pegmatitic magma-hydrothermal transition stage,characterized by a dense hydrous alkali borosilicate fluid with a carbonate component.Between 412°C and 278°C,CO2–Na Cl–H2 Ofluid inclusions developed in spodumene(I)and quartz(II)with a low salinity(3.3–11.9 wt%NaCl equivalent)and a high volatile content,which represent the boundary between the transition stage and the hydrothermal stage.The subsequentNaCl–H2 Ofluid inclusions from the hydrothermal stage,between 189°C and 302°C,have a low salinity(1.1–13.9 wt%NaCl equivalent).The various types of fluid inclusions reveal the P–T conditions of pegmatite formation,which marks the transition process from magmatic to hydrothermal.The oreforming fluids from the Zhawulong deposit have many of the same characteristics as those from the Jiajika lithium deposit.The ore-forming fluid provided not only materials for crystallization of rare metal minerals,such as spodumene and beryl,but also the ideal conditions forthe growth of ore minerals.Therefore,this area has favorable conditions for lithium enrichment and excellent prospecting potential.

Research and exploration progress on lithium deposits in China

Since 2012,some advances have been made through the resource investigation,metallogenesis research,and comprehensive utilizing of lithium deposits in China.Firstly,the progress of lithium exploration has been made in Sichuan,Xinjiang,Qinghai and Jiangxi provinces(autonomous region).Li deposits are not only found within the pegmatite rocks but also within the granitic rocks and sedimentary rocks.Secondly,the methods of geological survey,geochemical and geophysical exploration,remote sensing technology and even drilling technology have been improved,which can be delineating orebodies quickly.Thirdly,the mechanisms of Li mineralization were summarized by analyzing the relationship between the Li contents and kinds of geological phenomena.Based on practice,a new understanding of"multi-cycle,deep circulation,integration of internal and external"metallogenic mechanism or"MDIE"metallogenic mechanism for short has been put forwarded further in this paper,and the"five levels+basement"exploration model has been successfully expanded to guide the prospecting work both in the Jiajika and Keeryin pegmatite ore fields in western Sichuan Province.Besides,new progress has been made in the aspect of amblygonite deposits of granite-type and hydrothermal type in the Mufushan-Jiuling ore district,which points out a new direction for prospecting new types of lithium deposits in China.

Geological characteristics,metallogenic regularity,and research progress of lithium deposits in China

China is rich in abundant lithium resources characterized by considerable reserves and a concentrated distribution of metallogenic zones or belts,with proven reserves of 4046.8×10^(3) t(calculated based on Li_(2)O)by 2021.China is also a big consumer of lithium.By 2019,China’s lithium consumption in the battery sector alone had reached 99×10^(3) t,with an average annual growth rate of nearly 26%.China has become the world’s largest importer of lithium resources,showing a severely unbalanced relationship between supply and demand for lithium resources.Therefore,there is an urgent need for the prospecting,exploitation,and study of lithium resources in China.This study collected,organized,and summarized the data on the major lithium deposits in China,analyzed and compared the spatial-temporal distribution patterns,geological characteristics,and metallogenic regularity of these lithium deposits,and summarized the prospecting and research achievements over the last decade.The major lithium deposits in China are distributed in provinces and regions such as Qinghai,Jiangxi,Sichuan,Tibet,and Xinjiang.These deposits are mostly small in scale.According to different genetic types,this study divided lithium deposits into granitic pegmatite type,granite type,saline lake brine type,underground brine type,and sedimentary type,as well as new types including hot spring type and magmatic-hydrothermal type,and summarized the characteristics and key metallogenic factors of these different types of deposits.Sixteen metallogenic prospect areas of lithium deposits were delineated according to the deposit types and the distribution patterns of metallogenic belts.The paper introduced the research progress in major metallogenic models and lithium extraction techniques made over the past decade.Based on the comprehensive analysis of the prospecting potential of lithium deposits,the authors concluded that the future prospecting of lithium resources in China should focus on lithium metallogenic belts,the deep and peripheral areas of currently determined large-scale pegmatite-type lithium deposits,geophysical-geochemical anomalous areas with mineralization clues,and areas with developed large-scale low-grade associated granite-type and sedimentary lithium resources.The study aims to serve as a guide for the future prospecting of lithium deposits in China.

A strongly interactive adatom/substrate interface for dendrite-free and high-rate Li metal anodes

Lithium (Li) metal is considered as one of the most promising anode materials to build next-generation high-energy–density batteries. Nonetheless, dendritic Li deposition has dramatically hindered the practical applications of Li metal batteries (LMBs). Uniformizing Li deposition is a prerequisite to achieve safe and practical LMBs. Herein, an underpotential deposition (UPD) process is first proposed to alter the kinetic and uniformity of Li deposition morphology. Based on the strong interaction between the Li adatoms and manganese (Mn) based substrate, a competition between the UPD and bulk Li deposition is observed, on which the predominance of the UPD scenario tends to uniformize Li nucleation and deposition by the surface coverage of Li monolayers at potentials that are more positive than the Nernst potential of Li metal. Inspired by this process, an advanced hybrid Mn-graphene oxide structure is developed for Li protection, not only enabling dendrite-free Li anodes for high-capacity and -current density cycling, but also improving the interfacial kinetic of Li metal anodes at subzero temperatures, showing potential applicability in low temperature conditions.

Single Zn atoms anchored on hollow carbon nanofiber network for dendrite-free lithium metal anode of flexible Li–S full cell

The attractive energy density of lithium-sulfur(Li-S)batteries makes them desirable energy storage systems;however,the slow reaction kinetics and formation of lithium dendrites prevent them from reaching full potential.To address this issue,hierarchical porous carbon nanofibers network containing Zn single atoms(ZnSA@HPCNF)is synthesized by electrospinning and carbonization.This structure serves as the main anode body,providing excellent chemical anchoring and lipophilicity.The uniform distribution of Zn single atoms and N4coordination supports uniform deposition and continuous plating/stripping of lithium.The results show that the Li|Li/ZnSA@HPCNF symmetrical battery presents stable and low overpotential during 700-and 900-h iterative plating/stripping process at1 and 5 mA·cm^(-2),respectively.Furthermore,the S/CNT||Li/ZnSA@HPCNF full cell shows good flexibility,reversible capacity and cycling stability.This work provides a lithium host strategy based on single-atom dispersed hierarchical porous carbon network,enabling the design of rational lithium metal anodes for use in flexible Li-S full cells.

Engineering the surface of LiCoO2 electrodes using atomic layer deposition for stable high-voltage lithium ion batteries

Developing advanced technologies to stabilize positive electrodes of lithium ion batteries under high-voltage operation is becoming increasingly important,owing to the potential to achieve substantially enhanced energy density for applications such as portable electronics and electrical vehicles.Here,we deposited chemically inert and ionically conductive LiAlO2 interfacial layers on LiCoO2 electrodes using the atomic layer deposition technique.During prolonged cycling at high-voltage,the LiAlO2 coating not only prevented interfacial reactions between the LiCoO2 electrode and electrolyte,as confirmed by electrochemical impedance spectroscopy and Raman characterizations,but also allowed lithium ions to freely diffuse into LiCoO2 without sacrificing the power density.As a result,a capacity value close to 200 mA＆#183;h＆#183;g-1 was achieved for the LiCoO2 electrodes with commercial level loading densities,cycled at the cut-off potential of 4.6 V vs.Li＋/Li for 50 stable cycles;this represents a 40% capacity gain,compared with the values obtained for commercial samples cycled at the cut-off potential of 4.2 V vs.Li＋/Li.

In-situ nanoscale insights into the evolution of solid electrolyte interphase shells:revealing interfacial degradation in lithium metal batteries

The solid electrolyte interphase(SEI)has caught considerable attention as a pivotal factor affecting lithium(Li)metal battery performances.However,the understanding of the interfacial evolution and properties of the on-site formed SEI shells on Li deposits during cycling is still at a preliminary stage.Here,we provide a straightforward visualized evidence of SEI shells’evolution during Li deposition/stripping to reveal anode degradation via in-situ atomic force microscopy(AFM).Nucleation and growth of quasi-spherical Li particles are observed on a Cu substrate,followed by Li stripping and collapse of SEI shells.In the subsequent cycling,new Li deposits tend to nucleate at pristine sites with fresh SEI shells forming on Li.The previously collapsed SEI shells accumulate to increase interface impedance,eventually leading to capacity degradation.Revealing the electrochemical processes and interfacial degradation at the nanoscale will enrich fundamental comprehension and further guide improvement strategies of Li metal anodes.

A New Type of Li Deposit:Hydrothermal Crypto-Explosive Breccia Pipe Type

Lithium is one of the important strategic energy metals,which is in short supply in China.There are three major types of lithium deposits:brine and salt lake type,highly differentiated granite or pegmatite type,and carbonate-clay type.In recent years,some new types of lithium deposits have also begun to receive great attention and subject recent research.There are many crypto-explosive breccia pipe type deposits in the world,including copper,gold,lead,zinc,tungsten and tin deposits,but little is known about this type of lithium deposit.This paper introduces the latest research results of the Weilasituo Sn-Li-Rb polymetallic deposit in Inner Mongolia(NE China),which occurs in the middlesouthern section of the Great Xing’an Range metallogenic belt.A remarkable feature of this deposit is the coexistence of various mineralization types,including granite type Rb and Sn-Zn,hydrothermal crypto-explosive breccia pipe type Li-Rb,quartz vein type Sn-Zn and sulfide vein type Pb-Zn-Ag mineralization.Among them,hydrothermal crypto-explosive breccia pipe type Li-Rb deposit is currently very rare at home and abroad,which is likely a new type of rare metal deposit that worthy of our attention.This paper systematically summarizes the geology,alteration and mineralization,geochemistry,isotopes and geochronology of the Weilasituo deposit,and establishes a new petrogenic and metallogenic model.