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Composite Lithium Metal Structure to Mitigate Pulverization and Enable Long‐Life Batteries
In lithium metal batteries, non‐uniform stripping of lithium results in pit formation, which promotes subsequent non‐uniform, dendritic deposition. This viscous cycle leads to pulverization of lithium which promotes cell shorting or capacity degradation, symptoms further exaggerated by high electrode areal loading and lean electrolytes. Here, to address this challenge, a composite lithium metal anode is engineered that contains uniformly distributed, nanometer‐sized carbon particles. This composite lithium is shown to strip more uniformly since the growth of non‐uniform pits is intercepted by the carbon particles. This mechanism is corroborated by a continuum electrochemical model. Subsequent lithium deposition on carbon particles is also found to be more uniform than on the surface with irregular pits. Notably, the pulverization rate of composite lithium is 26 times slower than that of commercial lithium. Moreover, in a Li‐S battery with sulfurized polyacrylonitrile cathode, the use of the composite anode extends the cycle life by three times when the areal capacity is 8 mAh cm −2 . The approach of using an engineered lithium composite structure to address challenges during both stripping and plating can inform future designs of lithium metal anodes for high areal capacity operations.
Robust Polymer Electrolytes For Flexible Energy Storage (CRADA Final Report)
As part of the Cyclotron Road program, Anthro Energy investigated the formulation, synthesis, and application of advanced supramolecular compounds for lithium-ion batteries. Anthro Energy developed and tested formulations and chemistries to create polymeric materials with improved mechanical strength, safety, and electrochemical performance. These materials were explored for use in next-generation batteries with a variety of form factors. Initially, Anthro Energy tested these materials to create flexible and deformable batteries, which are in high demand for the wearable/flexible electronics industry. In future work, Anthro Energy’s materials may be applied to create rigid structural batteries, or to enable novel chemistries such as silicon anodes or lithium metal anodes. In the process of testing the company’s unique lithium-ion cells, Anthro Energy explored the development and utilization of novel cell components, cell architectures, and testing protocols. These next-generation flexible and structural batteries may eventually enable new categories of electronic devices.
Ultra-efficient polymer binder for silicon anode in high-capacity lithium-ion batteries
As a highly promising anode material for high-capacity lithium-ion batteries (LIBs), the low electronic conductivity and large volume variation of silicon (Si) make the slurry-coating Si based electrode requiring high content of “inert” materials and suffering rapid capacity fading. In this work, a polyimine, synthesized via one-step condensation reaction, has been demonstrated as an ultra-efficient polymer binder that can resolve the above issues. The polyimine binder containing Si electrode delivers superior electrochemical performance: a delithiation specific capacity of 804.4 mAh g –1 with capacity retention of 82.4% after 1000 cycles at the current density of 2 A g –1 . The high efficiency of polyimine binder for Si electrode has also been demonstrated with ultrahigh weight ratio of “active” material to “inert” material (R A/I ). The electrode with 95 wt% of Si (95Si/Polyimine, R A/I = 19) reveals a reversible delithiation capacity of 2114 mAh g –1 (capacity retention ~ 80.4%) over 200 cycles at the current density of 400 mA g –1 . Even at the high current density of 2 A g –1 , a delithiation capacity of 1087.8 mAh g –1 after 500 cycles can be obtained. Molecular simulations and atomic force microscopy (AFM) indentation are utilized to investigate the ultra-efficiency of polyimine binder. With simple manufacturing process and ultra-efficient binder performance, the designed polyimine binder will be definitely meaningful in achieving low-cost and high-capacity LIBs with prolonged cycle life.
Silver-carbon interlayers in anode-free solid-state lithium metal batteries: Current development, interfacial issues, and instability challenges
As an interlayer between the anode and the electrolyte of the all-solid-state lithium metal batteries (ASSLMBs), the silver-carbon (Ag-C) nanocomposite has been reported to significantly increase the energy density and cycle rate of solid-state lithium metal batteries. Ag-C interlayers serve as mixed ionic-electronic conductor that conducts both Li+ ions and electrons and lithium storage capacity. Unfortunately, it was unclear how the Ag-C interlayer regulated lithium plating and stripping. Moreover, the structural and chemical instabilities between the interlayer and the electrolyte, within the interlayer, or beneath the interlayer on lithium substrate are likely to cause cell failure. In this review, we discuss interfacial issues and summarize recent progress in solution strategies for ASSLMBs, with a specific focus on the use of a silver-carbon (Ag-C) nanocomposite interlayer in anode-free setups. Based on the Li transport kinetics among the Ag-C interlayers, the interfacial configurations of Ag-C interlayers are classified as either exterior or internal. Furthermore, the review concludes with a discussion of the perspectives and future prospects, allowing for the improvement of interlayer techniques for solid-state batteries.
Electron Delocalization Enables Sulfone-based Single-solvent Electrolyte for Lithium Metal Batteries
Li-metal batteries (LMB), although providing high energy density, face the grand challenge of identifying good electrolyte solvents for cycling. Common solvents are either only stable against lithium metal anode or only stable against LiNi x MnyCo 1-x-y O 2 (NMC) cathode. There is significant effort trying to increase the cathode stability for ether electrolytes, which are in general stable against lithium metal anode. In comparison, there is much less effort trying to increase the anode stability of electrolytes that are stable against NMC cathode. One example is the sulfone-based electrolyte. It has good cathode stability but is hindered from practical application because of (1) high viscosity and poor wetting capability and (2) poor anode stability. Here, we solve these issues by modifying the sulfone molecules using resonance and electron withdrawing effect. The viscosity is significantly reduced by delocalizing the electrons through introducing additional oxygen on the molecular backbone and applying appropriate fluorination. The resulting molecule 2,2,2-trifluoroethyl mesylate (TFEM) has decreased Lewis basicity and less reactivity toward Li + . In conclusion, the electrolyte based on TFEM as single solvent enables cycling of LMB under harsh conditions of low N/P ratio (21 mg/cm 2 NMC811 and 50 μm Li) with 90 % capacity retention after 160 cycles at C/3 discharge rate.
Electron Delocalization Enables Sulfone-based Single-solvent Electrolyte for Lithium Metal Batteries
Li-metal batteries (LMB), although providing high energy density, face the grand challenge of identifying good electrolyte solvents for cycling. Common solvents are either only stable against lithium metal anode or only stable against LiNi x Mn y Co 1-x-y O 2 (NMC) cathode. There is significant effort trying to increase the cathode stability for ether electrolytes, which are in general stable against lithium metal anode. In comparison, there is much less effort trying to increase the anode stability of electrolytes that are stable against NMC cathode. One example is the sulfone-based electrolyte. It has good cathode stability but is hindered from practical application because of (1) high viscosity and poor wetting capability and (2) poor anode stability. Here, we solve these issues by modifying the sulfone molecules using resonance and electron withdrawing effect. The viscosity is significantly reduced by delocalizing the electrons through introducing additional oxygen on the molecular backbone and applying appropriate fluorination. The resulting molecule 2,2,2-trifluoroethyl mesylate (TFEM) has decreased Lewis basicity and less reactivity toward Li + . The electrolyte based on TFEM as single solvent enables cycling of LMB under harsh conditions of low N/P ratio (21 mg/cm 2 NMC811 and 50 μm Li) with 90 % capacity retention after 160 cycles at C/3 discharge rate.
Interfacial Issues and Modification of Solid Electrolyte Interphase for Li Metal Anode in Liquid and Solid Electrolytes
Abstract The high energy density required for the next generation of lithium batteries will likely be enabled by a shift toward lithium metal anode from the conventional intercalation‐based anode such as graphite. However, several critical challenges for Li metal originate from its highly reactive nature and the hostless reaction of deposition and stripping impede the practical use of Li metal as an anode. The role of the solid electrolyte interphase (SEI) is very important for the Li metal anode where the SEI must protect the dynamically changing surface of the Li metal. Since the SEI‐generating reaction mechanisms for the two different electrolyte systems, liquid and solid, are considerably different, the SEI layers formed between the Li metal and the electrolytes in the two electrolyte systems have substantially different properties, causing different interfacial issues. Inhibition of the interfacial problems requires different strategies to reinforce the SEI layer for each of the electrolyte systems. However, the differences in the two electrolyte systems have not been clearly compared in the prior literature. In this report, the interfacial issues for the two different electrolyte systems are compared and different strategies for SEI modification are provided to overcome the issues.
A single-ion-conducting polymer and high-entropy Li-garnet composite electrolyte with simultaneous enhancement in ion transport and mechanical properties
Enabling the lithium metal anode has been the holy grail for improving the energy density for the next generation advanced batteries. Developing electrolytes that will suppress Li dendrite growth and provide sufficient ionic conductivity remains a major challenge in this field. In this study, we develop a polymer–ceramic composite electrolyte for lithium metal batteries. The polymer matrix is a vinyl ethylene carbonate (VEC) based single-ion-conducting polymer electrolyte. The ceramic filler is a Li 7 La 3 Zr 0.5 Nb 0.5 Ta 0.5 Hf 0.5 O 12 high-entropy Li-garnet (HE Li-garnet) ceramic, which is less prone to surface Li 2 CO 3 formation compared to Al-doped Li garnets. The addition of HE Li-garnet leads to a 7-fold increase in the ionic conductivity (8.6 × 10 −5 S cm −1 at 30 °C) compared to the pure polymer, while maintaining a high Li + transference of 0.73. Proton nuclear magnetic resonance and thermogravimetric analysis results suggest that the addition of HE Li-garnet results in a lower degree of polymerization of VEC, leaving more unpolymerized VEC monomers in the matrix, serving as the governing mechanism for conductivity enhancement. The favorable interactions between HE Li-garnet particles and the polymer matrix lead to a stable and well-mixed composite with 2-fold enhancement of storage modulus at 40 °C. The simultaneous ion transport and mechanical property enhancement significantly improves the composite electrolyte's dendrite resistance and cycle life in Li symmetric cells. This work highlights the positive role HE Li-garnet can play in improving polymer electrolytes to enable lithium metal anodes.
A Review of Nanocarbon-Based Anode Materials for Lithium-Ion Batteries
Renewable and non-renewable energy harvesting and its storage are important components of our everyday economic processes. Lithium-ion batteries (LIBs), with their rechargeable features, high open-circuit voltage, and potential large energy capacities, are one of the ideal alternatives for addressing that endeavor. Despite their widespread use, improving LIBs’ performance, such as increasing energy density demand, stability, and safety, remains a significant problem. The anode is an important component in LIBs and determines battery performance. To achieve high-performance batteries, anode subsystems must have a high capacity for ion intercalation/adsorption, high efficiency during charging and discharging operations, minimal reactivity to the electrolyte, excellent cyclability, and non-toxic operation. Group IV elements (Si, Ge, and Sn), transition-metal oxides, nitrides, sulfides, and transition-metal carbonates have all been tested as LIB anode materials. However, these materials have low rate capability due to weak conductivity, dismal cyclability, and fast capacity fading owing to large volume expansion and severe electrode collapse during the cycle operations. Contrarily, carbon nanostructures (1D, 2D, and 3D) have the potential to be employed as anode materials for LIBs due to their large buffer space and Li-ion conductivity. However, their capacity is limited. Blending these two material types to create a conductive and flexible carbon supporting nanocomposite framework as an anode material for LIBs is regarded as one of the most beneficial techniques for improving stability, conductivity, and capacity. This review begins with a quick overview of LIB operations and performance measurement indexes. It then examines the recently reported synthesis methods of carbon-based nanostructured materials and the effects of their properties on high-performance anode materials for LIBs. These include composites made of 1D, 2D, and 3D nanocarbon structures and much higher Li storage-capacity nanostructured compounds (metals, transitional metal oxides, transition-metal sulfides, and other inorganic materials). The strategies employed to improve anode performance by leveraging the intrinsic features of individual constituents and their structural designs are examined. The review concludes with a summary and an outlook for future advancements in this research field.
Lithium metal pouch cells and methods of making the same
A lithium metal pouch cell having a specific energy ≥300 Wh·kg−1 includes an anode comprising lithium metal and an anode current collector, the anode having an areal capacity N (mAh·cm −2 ); a cathode comprising a cathode material and a cathode current collector, the cathode having an a real capacity P (mAh·cm −2 ), wherein a ratio of N/P is within a range of 0.02 to 5; an electrolyte having an electrolyte mass E and comprising a lithium active salt and a solvent, the lithium metal pouch cell having an electrolyte mass to cell capacity (E/C) ratio within a range of 1 to 6 g·Ah −1 ; a separator positioned between the anode and the cathode; and a packaging material defining a pouch enclosing the anode, cathode, electrolyte, and separator; wherein a protruding tab of the anode current collector and a protruding tab of the cathode current collector are external to the pouch.
Lithium metal pouch cells and methods of making the same
A lithium metal pouch cell having a specific energy ≥300 Wh·kg -1 includes an anode comprising lithium metal and an anode current collector, the anode having an areal capacity N (mAh·cm −2 ); a cathode comprising a cathode material and a cathode current collector, the cathode having an a real capacity P (mAh·cm −2 ), wherein a ratio of N/P is within a range of 0.02 to 5; an electrolyte having an electrolyte mass E and comprising a lithium active salt and a solvent, the lithium metal pouch cell having an electrolyte mass to cell capacity (E/C) ratio within a range of 1 to 6 g·Ah −1 ; a separator positioned between the anode and the cathode; and a packaging material defining a pouch enclosing the anode, cathode, electrolyte, and separator; wherein a protruding tab of the anode current collector and a protruding tab of the cathode current collector are external to the pouch.
High spatial resolution neutron imaging of lithium-ion batteries: Correlating microstructure and lithium transport
Thick electrodes for lithium-ion batteries can increase the overall energy density, but increasing the electrode thickness introduces charge transport limitations. These limitations may be mitigated through proper electrode structuring. Here, high spatial resolution neutron imaging was used to understand the correlation between microstructure and lithium transport in lithium-ion anodes. Batteries with distinct graphite anode microstructures were produced and studied with high spatial resolution in operando neutron radiography to observe the effects of structure on transport. High spatial resolution neutron computed tomography was performed following in operando neutron radiography. X-ray computed tomography and scanning electron microscopy were used to observe the finer scale anode structure to complement neutron imaging. Solvent-free anodes containing a tightly-packed layered structure confined lithium movement close to the separator. This structure limited capacity, but supported better rate capability. Conversely, a more open pore structure in the wet cast anodes yielded higher capacity with reduced rate capability. Together, these results show that lithium distributions can be controlled by the macroscopic structure of the electrodes, the microstructural pore network, and the microscale active areas that support electrochemical reactions. Furthermore, multimodal imaging applying the complementary strengths of neutron and X-ray methods is shown as a tool for advancing battery design.
Lithium Metal as an Anode in Electrochemical Energy Storage
The drastic environmental and economic costs of global warming have driven the necessity to reduce, if not eliminate, a dependency on oil and gas for energy applications. Alternative clean energy reliance has been initiated as a global investment for a more sustainable future. Part of this transitional effort is focused on energy storage via a rechargeable battery. High energy density storage is necessary for utilizing non-dispatchable green energy technologies, as well in the electric transition of our vehicle fleet. Further, understanding methods of extracting, manufacturing, and recycling lithium is necessary to lessen environmental impact. Lithium metal is often considered the “Holy Grail” of battery technology, due to its high theoretical capacity (3,860 mAh/g) and low electrochemical potential (-3.04 V vs. SHE). However, parasitic reactions lead to rapid and dangerous battery failure. Therefore, determining methods of stabilizing lithium metal is paramount for the transition to a greener future.
Improved cycle stability and high-rate capability of LiNbO 3 -coated Li 3 VO 4 as anode material for lithium-ion battery
Lithium vanadate (Li 3 VO 4 ) has garnered considerable attention as an alternative negative electrode material for non-aqueous lithium-ion batteries due to its high capacity, energy efficiency, and stable discharge voltage. Nonetheless, the Li 3 VO 4 material displays a low rate capability, attributed mainly to its poor intrinsic electronic conductivity. Here, in this study, we report the synthesis of lithium niobate LiNbO 3 -coated Li 3 VO 4 (LVO@LNO) using a one-pot sol-gel method. The resulting LVO@LNO demonstrates a high reversible capacity of approximately 530 mAh/g, which is more than double that of free Li 3 VO 4 . To explore the effect of the LNO coating process on the morphological and structural properties, Raman, XRD, operando XRD, XPS, SEM and HTEM analyses were conducted. To explain the enhancement of electronic conductivity in our modified material after a LiNbO 3 coating, we conducted an Ex-Situ electrochemical impedance (EIS) and Density Functional Theory (DFT) computational study. Additionally, we designed a full cell utilizing a 1 wt% LNO-coated LVO anode and NMC-811 cathode. The cell yielded an output voltage of approximately 2.8 V with a high initial specific capacity of 350 mAh/g versus to the anode, at 1C with a capacity retention of 85 % after 100 cycles.
Reactive diffusion of lithium in silicon in anode materials for Li-ion batteries
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Measurement of Three Transport Coefficients and the Thermodynamic Factor in Block Copolymer Electrolytes with Different Morphologies
The design and engineering of composite materials is one strategy to satisfy the materials needs of systems with multiple orthogonal property requirements. In the case of rechargeable batteries with lithium metal anodes, the system requires a separator with fast lithium ion transport and good mechanical strength. In this work, we focus on the system polystyrene-block-poly(ethylene oxide) (SEO) with bis(trifluoromethane)sulfonimide lithium salt (LiTFSI). Ion transport occurs in the salt-containing poly(ethylene oxide)-rich domains. Mechanical rigidity arises due to the glassy nature of polystyrene (PS). If we assume that the salt does not interact with the PS-rich domains, we can describe ion transport in the electrolyte by three transport parameters (ionic conductivity, κ, salt diffusion coefficient, D, and cation transference number, t + 0 ) and a thermodynamic factor, T f . By systematically varying the volume fraction of the conducting phase, Φ c between 0.29 and 1.0, and chain length, N between 80 and 8000, we elucidate the role of morphology on ion transport. We find that κ is the strongest function of morphology, varying by three full orders of magnitude, while D is a weaker function of morphology. To calculate t + 0 and T f , we measure the current fraction, ρ + , and the open circuit potential, U, of concentration cells. We find that ρ + and U follow universal trends as a function of salt concentration, regardless of chain length, morphology, or Φ c , allowing us to calculate t + 0 for any SEO/LiTFSI or PEO/LiTFSI mixture when κ and D are known. Finally, the framework developed in this paper enables predicting the performance of any block copolymer electrolyte in a rechargeable battery.