A review on electrode and electrolyte for lithium ion batteries under low temperature

Under low temperature (LT) conditions (−80 °C∼0 °C), lithium-ion batteries (LIBs) may experience the formation of an extensive solid electrolyte interface (SEI), which can cause a series of detrimental effects such as Li⁺ deposition and irregular dendritic filament growth on the electrolyte surface. These issues ultimately lead to the degradation of the LT performance of LIBs. As a result, new electrode/electrolyte materials are necessary to address these challenges and enable the proper functioning of LIBs at LT. Given that most electrochemical reactions in lithium-ion batteries occur at the electrode/electrolyte interface, finding solutions to mitigate the negative impact caused by SEI is crucial to improve the LT performance of LIBs. In this article, we analyze and summarize the recent studies on electrode and electrolyte materials for low temperature lithium-ion batteries (LIBs). These materials include both metallic materials like tin, manganese, and cobalt, as well as non-metallic materials such as graphite and graphene. Modified materials, such as those with nano or alloying characteristics, generally exhibit better properties than raw materials. For instance, Sn nanowire-Si nanoparticles (SiNPs−In-SnNWs) and tin dioxide carbon nanotubes (SnO₂@CNT) have faster Li⁺ transport rates and higher reversible capacity at LT. However, it′s important to note that when operating under LT, the electrolyte may solidify, leading to difficulty in Li⁺ transmission. The compatibility between the electrolyte and electrode can affect the formation of the solid electrolyte interphase (SEI) and the stability of the electrode/electrolyte system. Therefore, a good electrode/electrolyte system is crucial for successful operation of LIBs at LT.     

Chemomechanically Stable Small Single-crystal Mo-doped LiNi0.6Co0.2Mn0.2O2 Cathodes for Practical 4.5 V-class Pouch-type Li-ion Batteries

High voltage can cost-effectively boost energy density of Ni-rich cathodes based Li-ion batteries (LIBs), but compromises their mechanical, electrochemical and thermal-driven stability. Herein, a collaborative strategy (i.e., small single-crystal design and hetero-atom doping) is devised to construct a chemomechanically reliable small single-crystal Mo-doped LiNi_0.6Co_0.2Mn_0.2O₂ (SS-MN6) operating stably under high voltage (≥4.5 V vs. Li/Li⁺). The substantially reduced particle size combined with Mo⁶⁺ doping absorbs accumulated localized stress to eradicate cracks formation, subdues the surface side reactions and lattice oxygen missing meanwhile, and improves thermal tolerance at highly delithiated state. Consequently, the SS-MN6 based pouch cells are endowed with striking deep cycling stability and wide-temperature-tolerance capability. The contribution here provides a promising way to construct advanced cathodes with superb chemomechanical stability for next-generation LIBs.     

One-Step Calcination Synthesis of Bulk-Doped Surface-Modified Ni-Rich Cathodes with Superlattice for Long-Cycling Li-Ion Batteries

Nickel-rich (Ni≥90 %) layered cathodes are critical materials for achieving higher-energy-density and lower-cost next-generation Li-ion batteries (LIBs). However, their bulk and interface structural instabilities significantly impair their electrochemical performance, thus hindering their widespread adoption in commercial LIBs. Exploiting Ti and Mo diffusion chemistry, we report one-step calcination to synthesize bulk-to-surface modified LiNi_0.9Co_0.09Mo_0.01O₂ (NCMo90) featuring a 5 nm Li₂TiO₃ coating on the surface, a Mo-rich Li⁺/Ni²⁺ superlattice at the sub-surface, and Ti-doping in the bulk. Such a multi-functional structure effectively maintains its structural integrity upon cycling. As a result, such NCMo90 exhibits a high initial capacity of 221 mAh g⁻¹ at 0.1 C, excellent rate performance (184 mAh g⁻¹ at 5 C), and high capacity retention of 94.0 % after 500 cycles. This work opens a new avenue to developing industry-applicable Ni-rich cathodes for next-generation LIBs.     

A Simple Prelithiation Strategy To Build a High‐Rate and Long‐Life Lithium‐Ion Battery with Improved Low‐Temperature Performance

Lithium‐ion batteries (LIBs) are being used to power the commercial electric vehicles (EVs). However, the charge/discharge rate and life of current LIBs still cannot satisfy the further development of EVs. Furthermore, the poor low‐temperature performance of LIBs limits their application in cold climates and high altitude areas. Herein, a simple prelithiation method is developed to fabricate a new LIB. In this strategy, a Li₃V₂(PO₄)₃ cathode and a pristine hard carbon anode are used to form a primary cell, and the initial Li⁺ extraction from Li₃V₂(PO₄)₃ is used to prelithiate the hard carbon. Then, the self‐formed Li₂V₂(PO₄)₃ cathode and prelithiated hard carbon anode are used to form a 4 V LIB. The LIB exhibits a maximum energy density of 208.3 Wh kg⁻¹, a maximum power density of 8291 W kg⁻¹ and a long life of 2000 cycles. When operated at −40 °C, the LIB can keep 67 % capacity of room temperature, which is much better than conventional LIBs.     

Pseudocapacitive Lithium Storage of Cauliflower-Like CoFe2O4 for Low-Temperature Battery Operation

Binary transition-metal oxides (BTMOs) with hierarchical micro–nano-structures have attracted great interest as potential anode materials for lithium-ion batteries (LIBs). Herein, we report the fabrication of hierarchical cauliflower-like CoFe₂O₄ (cl-CoFe₂O₄) via a facile room-temperature co-precipitation method followed by post-synthetic annealing. The obtained cauliflower structure is constructed by the assembly of microrods, which themselves are composed of small nanoparticles. Such hierarchical micro–nano-structure can promote fast ion transport and stable electrode–electrolyte interfaces. As a result, the cl-CoFe₂O₄ can deliver a high specific capacity (1019.9 mAh g⁻¹ at 0.1 A g⁻¹), excellent rate capability (626.0 mAh g⁻¹ at 5 A g⁻¹), and good cyclability (675.4 mAh g⁻¹ at 4 A g⁻¹ for over 400 cycles) as an anode material for LIBs. Even at low temperatures of 0 °C and −25 °C, the cl-CoFe₂O₄ anode can deliver high capacities of 907.5 and 664.5 mAh g⁻¹ at 100 mA g⁻¹, respectively, indicating its wide operating temperature. More importantly, the full-cell assembled with a commercial LiFePO₄ cathode exhibits a high rate performance (214.2 mAh g⁻¹ at 5000 mA g⁻¹) and an impressive cycling performance (612.7 mAh g⁻¹ over 140 cycles at 300 mA g⁻¹) in the voltage range of 0.5–3.6 V. Kinetic analysis reveals that the electrochemical performance of cl-CoFe₂O₄ is dominated by pseudocapacitive behavior, leading to fast Li⁺ insertion/extraction and good cycling life.     

Benign Recycling of Spent Batteries towards All-Solid-State Lithium Batteries

Lithium-ion batteries (LIBs) are one of the most significant energy storage devices applied in power supply facilities. However, a huge number of spent LIBs would bring harmful resource waste and environmental hazards. In this study, a benign hydrometallurgical method using phytic acid as precipitant is proposed to recover useful metallic Mn ions from spent LiMn₂O₄ batteries. Besides Mn-based cathodes, this recovery process is also applicable for other commercial batteries. More importantly, for the first time, the as-obtained manganous complex is employed as a nanofiller in a polyethylene oxide matrix to largely improve Li⁺ conductivity and transference number. As a result, when applied in all-solid-state lithium batteries, high capacity and outstanding cyclic stability are achieved with capacity retention of 86.4 % after 60 cycles at 0.1 C. The recovery of spent lithium batteries not only has benefits for the environment and resources, but also shows great potential application in all-solid-state lithium batteries, which opens up a costless and efficient circulation pathway for clean and reliable energy storage systems.     

Mitigating Swelling of the Solid Electrolyte Interphase using an Inorganic Anion Switch for Low-temperature Lithium-ion Batteries

In overcoming the Li⁺ desolvation barrier for low-temperature battery operation, a weakly-solvated electrolyte based on carboxylate solvent has shown promises. In case of an organic-anion-enriched primary solvation sheath (PSS), we found that the electrolyte tends to form a highly swollen, unstable solid electrolyte interphase (SEI) that shows a high permeability to the electrolyte components, accounting for quickly declined electrochemical performance of graphite-based anode. Here we proposed a facile strategy to tune the swelling property of SEI by introducing an inorganic anion switch into the PSS, via LiDFP co-solute method. By forming a low-swelling, Li₃PO₄-rich SEI, the electrolyte-consuming parasitic reactions and solvent co-intercalation at graphite-electrolyte interface are suppressed, which contributes to efficient Li⁺ transport, reversible Li⁺ (de)intercalation and stable structural evolution of graphite anode in high-energy Li-ion batteries at a low temperature of −20 °C.     

Back Cover: Low-Cost,High-Strength Cellulose-based Quasi-Solid Polymer Electrolyte for Solid-State Lithium-Metal Batteries (Angew. Chem. Int. Ed. 25/2023)

Solid-state lithium-metal batteries are considered as the next generation of high-energy-density batteries. However, their solid electrolytes suffer from low ionic conductivity, poor interface performance, and high production costs, restricting their commercial application. Herein, a low-cost cellulose acetate-based quasi-solid composite polymer electrolyte (C-CLA QPE) was developed with a high Li⁺ transference number ( ) of 0.85 and excellent interface stability. The prepared LiFePO₄ (LFP)|C-CLA QPE|Li batteries exhibited excellent cycle performance with a capacity retention of 97.7 % after 1200 cycles at 1 C and 25 °C. The experimental results and Density Function Theory (DFT) simulation revealed that the partially esterified side groups in the CLA matrix contribute to the migration of Li⁺ and enhance electrochemical stability. This work provides a promising strategy for fabricating cost-effective, stable polymer electrolytes for solid-state lithium batteries.     

Enhanced Li+ migration in solid polymer electrolyte driven by anion-containing polymer-chains

Li-ion batteries with solid polymer electrolytes (SPEs) are safer than conventional liquid electrolytes due to the absence of highly flammable liquid electrolytes. However, their performance is limited by the poor Li⁺ transport in SPEs at room temperature. Anion-containing polymer-chains incorporated SPEs (ASPEs) are therefore developed to enhance Li⁺ diffusion kinetics. Herein, we propose a novel and feasible strategy to incorporate the anion-containing polymer-chains, such as lithiated perfluorinated sulfonic acid (PFSA), into polyvinylidene fluoride (PVDF) polymer-based SPEs. The immobile anion groups from the PFSA-chains impede the migration of mobile anion groups dissociated from the Li salt. The transference number is thus raised from ∼0.3 to 0.52 with the introduction of anion-containing polymer-chains into SPEs. The electrostatic repulsion among anion-containing chains also reduces the close chain stacking and brings 159% increase in the ionic conductivity to 0.83 × 10⁻³ S/cm at 30 °C in contrast with the pure PVDF-based SPE. In addition, LiFeO₄/Li batteries with ASPEs exhibit 55% capacity boost at 0.5 C in contrast to the capacity of batteries with pure-PVDF SPEs, and also offer more than 1000 charge/discharge cycles. Our research findings potentially offer a facile strategy to design thermal stable SPEs with superior Li⁺ transport behaviors towards developing high-performance SPEs-based batteries.     

Boosting Fe Cationic Vacancies with Graphdiyne to Enhance Exceptional Pseudocapacitive Lithium Intercalation

Modulating the electronic structure of electrode materials at atomic level is the key to controlling electrodes with outstanding rate capability. On the basis of modulating the iron cationic vacancies (IV) and electronic structure of materials, we proposed the method of preparing graphdiyne/ferroferric oxide heterostructure (IV-GDY-FO) as anode materials. The goal is to motivate lithium-ion batteries (LIBs) toward ultra-high capacity, superior cyclic stability, and excellent rate performance. The graphdiyne is used as carriers to disperse Fe₃O₄ uniformly without agglomeration and induce high valence of Fe with reducing the energy in the system. The presence of Fe vacancy could regulate the charge distribution around vacancies and adjacent atoms, leading to facilitate electronic transportation, enlarge the lithium-ion diffusion, and decrease Li⁺ diffusion barriers, and thus displaying significant pseudocapacitive process and advantageous lithium-ion storage. The optimized electrode IV-GDY-FO reveals a capacity of 2084.1 mAh g⁻¹ at 0.1 C, superior cycle stability and rate performance with a high specific capacity of 1057.4 mAh g⁻¹ even at 10 C.     

A Designed Durable Electrolyte for High-Voltage Lithium-Ion Batteries and Mechanism Analysis

Rechargeable lithium-ion batteries (LIBs) dominate the energy market, from electronic devices to electric vehicles, but pursuing greater energy density remains challenging owing to the limited electrode capacity. Although increasing the cut-off voltage of LIBs (>4.4 V vs. Li/Li⁺) can enhance the energy density, the aggravated electrolyte decomposition always leads to a severe capacity fading and/or expiry of the battery. Herein, a new durable electrolyte is reported for high-voltage LIBs. The designed electrolyte is composed of mixed linear alkyl carbonate solvent with certain cyclic carbonate additives, in which use of the ethylene carbonate (EC) co-solvent was successfully avoided to suppress the electrolyte decomposition. As a result, an extremely high cycling stability, rate capability, and high-temperature storage performance were demonstrated in the case of a graphite|LiNi_0.6Co_0.2Mn_0.2O₂ (NCM622) battery at 4.45 V when this electrolyte was used. The good compatibility of the electrolyte with the graphite anode and the mitigated structural degradation of the NCM622 cathode are responsible for the high performance at high potentials above 4.4 V. This work presents a promising application of high-voltage electrolytes for pursuing high energy LIBs and provides a straightforward guide to study the electrodes/electrolyte interface for higher stability.     

Armor-like Inorganic-rich Cathode Electrolyte Interphase Enabled by the Pentafluorophenylboronic Acid Additive for High-voltage Li||NCM622 Batteries

Lithium metal batteries (LMBs) comprising Li metal anode and high-voltage nickel-rich cathode could potentially realize high capacity and power density. However, suitable electrolytes to tolerate the oxidation on the cathode at high cut-off voltage are urgently needed. Herein, we present an armor-like inorganic-rich cathode electrolyte interphase (CEI) strategy for exploring oxidation-resistant electrolytes for sustaining 4.8 V Li||LiNi_0.6Co_0.2Mn_0.2O₂ (NCM622) batteries with pentafluorophenylboronic acid (PFPBA) as the additive. In such CEI, the armored lithium borate surrounded by CEI up-layer represses the dissolution of inner CEI moieties and also improves the Li⁺ conductivity of CEI while abundant LiF is distributed over whole CEI to enhance the mechanical stability and Li⁺ conductivity compared with polymer moieties. With such robust Li⁺ conductive CEI, the Li||NCM622 battery delivered excellent stability at 4.6 V cut-off voltage with 91.2 % capacity retention after 400 cycles. The excellent cycling performance was also obtained even at 4.8 V cut-off voltage.     

Enhanced Surface Interactions Enable Fast Li+ Conduction in Oxide/Polymer Composite Electrolyte

Li⁺‐conducting oxides are considered better ceramic fillers than Li⁺‐insulating oxides for improving Li⁺ conductivity in composite polymer electrolytes owing to their ability to conduct Li⁺ through the ceramic oxide as well as across the oxide/polymer interface. Here we use two Li⁺‐insulating oxides (fluorite Gd_0.1Ce_0.9O_1.95 and perovskite La_0.8Sr_0.2Ga_0.8Mg_0.2O_2.55) with a high concentration of oxygen vacancies to demonstrate two oxide/poly(ethylene oxide) (PEO)‐based polymer composite electrolytes, each with a Li⁺ conductivity above 10^?4 S cm^?1 at 30 °C. Li solid‐state NMR results show an increase in Li⁺ ions (>10 %) occupying the more mobile A2 environment in the composite electrolytes. This increase in A2‐site occupancy originates from the strong interaction between the O^2? of Li‐salt anion and the surface oxygen vacancies of each oxide and contributes to the more facile Li⁺ transport. All‐solid‐state Li‐metal cells with these composite electrolytes demonstrate a small interfacial resistance with good cycling performance at 35 °C.     

Promoting Surface Electric Conductivity for High-Rate LiCoO2

The cathode materials work as the host framework for both Li⁺ diffusion and electron transport in Li-ion batteries. The Li⁺ diffusion property is always the research focus, while the electron transport property is less studied. Herein, we propose a unique strategy to elevate the rate performance through promoting the surface electric conductivity. Specifically, a disordered rock-salt phase was coherently constructed at the surface of LiCoO₂, promoting the surface electric conductivity by over one magnitude. It increased the effective voltage (V_eff) imposed in the bulk, thus driving more Li⁺ extraction/insertion and making LiCoO₂ exhibit superior rate capability (154 mAh g⁻¹ at 10 C), and excellent cycling performance (93 % after 1000 cycles at 10 C). The universality of this strategy was confirmed by another surface design and a simulation. Our findings provide a new angle for developing high-rate cathode materials by tuning the surface electron transport property.     

Low Temperature Synthesis and Characterization of Li1.2-y NayV3O8(0≤y≤1.2) from V2O5 Gel

Without overnight heating and stirring,Li1.2V3O8 and its analogs Li1.2-y NayV3O8(0≤y≤1.2) were successfully synthesized by adding mixed solution of LiOH and NaVO3 to V2O5 gel and dehydrating the prepared gel in 150-350℃.The simplicity awards this synthesis process superiority over other low temperature synthesis routes when mass production is concerned.TG-DTA,XRD and TEM experiments were carried out for physical characterization.By galvanostatic charge-discharge and cyclic voltammetry tests,these products showed better electrochemical performance than high temperature products as cathode active materials in secondary lithium batteries.After treatment of Li1.2V3O8 at 250℃,it exhibited a capacity of 350mAh/g when cycled at current rate of about 60 mA/g over the voltage range of 3.8-1.7V vs,Li^ /Li.The influence of partial substitution of Li by Na was also extensively studied.     

Boosting Li-ion storage in Li2MnO3 by unequal-valent Ti4+-substitution and interlayer Li vacancies building

Lithium rich layered oxide (LRLO) has been considered as one of the promising cathodes for lithium-ion batteries (LIBs). The high voltage and large capacity of LRLO depend on Li₂MnO₃ phase. To ameliorate the electrochemical performance of Li₂MnO₃, also written as Li(Li_1/3Mn_2/3)O₂, we propose a strategy to substitute Mn⁴⁺ and Li⁺ in Mn/Li transition metal layer with Ti⁴⁺, which can stabilize the structure of Li₂MnO₃ by inhibiting the excessive oxidation of O^2? above 4.5 V. More significantly, the unequal-valent substitution brings about the emergence of interlayer Li vacancies, which can promote the Li-ion diffusion based on the enlarged interlayer and increase the capacity by activating the Mn^3+/4+ redox. We designed Li_0.7[Li_1/3Mn_2/3]_0.7Ti_0.3O₂ with high interlayer Li vacancies, which presents a high capacity (290 mAh/g at 10 mA/g) and stable cycling performance (84% over 60 cycles at 50 mA/g). We predict that this strategy will be helpful to further improve the electrochemical performance of LRLOs.     

Supramolecular Polymer Ion Conductor with Weakened Li Ion Solvation Enables Room Temperature All-Solid-State Lithium Metal Batteries

Improved durability, enhanced interfacial stability, and room temperature applicability are desirable properties for all-solid-state lithium metal batteries (ASSLMBs), yet these desired properties are rarely achieved simultaneously. Here, in this work, it is noticed that the huge resistance at Li metal/electrolyte interface dominantly impeded the normal cycling of ASSLMBs especially at around room temperature (<30 °C). Accordingly, a supramolecular polymer ion conductor (SPC) with “weak solvation” of Li⁺ was prepared. Benefiting from the halogen-bonding interaction between the electron-deficient iodine atom (on 1,4-diiodotetrafluorobenzene) and electron-rich oxygen atoms (on ethylene oxide), the O-Li⁺ coordination was significantly weakened. Therefore, the SPC achieves rapid Li⁺ transport with high Li⁺ transference number, and importantly, derives a unique Li₂O-rich SEI with low interfacial resistance on lithium metal surface, therefore enabling stable cycling of ASSLMBs even down to 10 °C. This work is a new exploration of halogen-bonding chemistry in solid polymer electrolyte and highlights the importance of “weak solvation” of Li⁺ in the solid-state electrolyte for room temperature ASSLMBs.     

An Adjustable‐Porosity Plastic Crystal Electrolyte Enables High‐Performance All‐Solid‐State Lithium‐Oxygen Batteries

The limited triple‐phase boundaries (TPBs) in solid‐state cathodes (SSCs) and high resistance imposed by solid electrolytes (SEs) make the achievement of high‐performance all‐solid‐state lithium‐oxygen (ASS Li‐O₂) batteries a challenge. Herein, an adjustable‐porosity plastic crystal electrolyte (PCE) has been fabricated by employing a thermally induced phase separation (TIPS) technique to overcome the above tricky issues. The SSC produced through the in‐situ introduction of the porous PCE on the surface of the active material, facilitates the simultaneous transfer of Li⁺/e^?, as well as ensures fast flow of O₂, forming continuous and abundant TPBs. The high Li⁺ conductivity, softness, and adhesion of the dense PCE significantly reduce the battery resistance to 115 Ω. As a result, the ASS Li‐O₂ battery based on this adjustable‐porosity PCE exhibits superior performances with high specific capacity (5963 mAh g^?1), good rate capability, and stable cycling life up to 130 cycles at 32 °C. This novel design and exciting results could open a new avenue for ASS Li‐O₂ batteries.     

Electrochemical lithium and sodium insertion studies in 3D metal oxy-phosphate framework MoWO3(PO4)2 for battery applications

A new type of three-dimensional (3D) oxy-phosphate materials are explored for the application of Li and Na batteries. The molybdenum tungsten oxy phosphate, MoWO₃(PO₄)₂, was synthesized by solid-state method and evaluated for Li/Na insertion/de-insertion electrode material for the first time. The cell at charged state (vs. Li⁺/Li) showed a discharge capacity of 786 mAh g⁻¹ within the voltage window of 0.3 V with amorphization of crystalline MoWO₃(PO₄)₂ as observed from ex-situ powder XRD analysis. The structural integrity was revealed in this material, even with nearly more than 5 Li⁺ ions into the lattice, leading to the discharge capacity of 250 mAh g⁻¹. The reversible charge/discharge behavior with insertion/de-insertion of 2.4 Li⁺ ions in the voltage range of 1.65 − 3.5 V resulted in 110 and 95 mAh g⁻¹ at C/10 and C/5 rates, respectively. On the other hand, poor cycling performance was noticed for Na ion insertion and desertion, with a discharge capacity of 250 mAh/g within the voltage range of 0.3 − 3.5 V (vs. Na⁺/Na).

     

Polymer/colloid dual-phase electrolyte membrane for rechargeable lithium batteries

In this work, a polymer/ceramic phase-separation porous membrane is first prepared from polyvinyl alcohol–polyacrylonitrile water emulsion mixed with fumed nano-SiO₂ particles by the phase inversion method. This porous membrane is then wetted by a non-aqueous Li–salt liquid electrolyte to form the polymer/colloid dual-phase electrolyte membrane. Compared to the liquid electrolyte in conventional polyolefin separator, the obtained electrolyte membrane has superior properties in high ionic conductivity (1.9 mS?cm^?1 at 30 °C), high Li⁺ transference number (0.41), high electrochemical stability (extended up to 5.0 V versus Li⁺/Li on stainless steel electrode), and good interfacial stability with lithium metal. The test cell of Li/LiCoO₂ with the electrolyte membrane as separator also shows high-rate capability and excellent cycle performance. The polymer/colloid dual-phase electrolyte membrane shows promise for application in rechargeable lithium batteries.