Microwave Processed, Onion-like Carbon and Fluoropolymer Passivated Lithium Metal Electrode for Enhanced Li Stripping/Plating Performance
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Poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) has broad applications across various metal-ion battery systems, such as a binder for electrodes, a supporting matrix for electrolytes, and a separator material. Due to its excellent mechanical properties, PVDF-HFP has become an excellent candidate for fabricating gel and solid-state electrolytes in sodium-based batteries. However, in this study, we noticed notable side reactions occurring at the interface of PVDF-HFP membranes and Na metal. These reactions not only alter chemical compositions but also further affect the surface morphology and adhesive properties of membranes. Similar phenomena are observed in other polyfluoroalkyl-based membranes (PVDF and PTFE). Therefore, we systematically studied the reaction mechanisms between the Na metal and these polymers. The influence of different functional groups (−F, −CF 3 , −H) and their arrangement on the reaction extent has also been discussed. Finally, we concluded with the key factors driving these side reactions and provided new perspectives for designing polymers tailored for sodium-based batteries.
We employ a molecular theory of dynamic polymer networks to describe the viscoplastic response of rubbery FK-800, a thermoplastic copolymer of chlorotrifluoroethylene and vinylidene fluoride, over a broad range of thermal histories. The kinetics of crystallization at different annealing temperatures was modeled using a modified Avrami equation, whose parameters were found to evolve through simple relationships over the full temperature range of the rubbery state. By fitting experimental compression data, we discovered predictable trends for the physical parameters in our mechanical model over its full range of crystallinities (up to ≈20%) and provided insights based on molecular-level physics to justify them. Using this, an end-to-end model was developed to predict the yielding and post-yield behavior of rubbery FK-800 for arbitrary thermal histories. The model successfully predicted the highly nonlinear evolution of characteristic mechanical signatures (stiffness, yield point, post-yield drop) throughout the crystallization process. A statistical analysis of variance test was employed to determine that the measured variations in the mechanical behavior of rubbery FK-800 are primarily dictated by its fractional crystallinity, regardless of its exact thermal history.
A method for generating antireflective coatings for polymeric substrates using a deposition process and/or a dissolving process can provide a coating onto the outer surface of the substrate. Some embodiments can include a GLAD generated fluoropolymer coating or a co-evaporated fluoropolymer coating on a substrate that may achieve ultralow refractive index as well as improved adhesion and durability properties on polymeric substrates. In some embodiments, the deposition process is performed such that a fluoropolymer can be evaporated to form chain fragments of the fluoropolymer. The chain fragments diffused into the substrate can subsequently re-polymerize, interlocking with the polymer chains of the substrate. In some embodiments, the co-evaporation process can form a nanoporous polymer chain scaffold of the fluoropolymer, from which a sacrificial material can be dissolved out. The formed coating can be a multilayer or continuously-graded antireflective coating that has strong adhesion with the substrate.
A method for generating antireflective coatings for polymeric substrates using a deposition process and/or a dissolving process can provide a coating onto the outer surface of the substrate. Some embodiments can include a GLAD generated fluoropolymer coating or a co-evaporated fluoropolymer coating on a substrate that may achieve ultralow refractive index as well as improved adhesion and durability properties on polymeric substrates. In some embodiments, the deposition process is performed such that a fluoropolymer can be evaporated to form chain fragments of the fluoropolymer. The chain fragments diffused into the substrate can subsequently re-polymerize, interlocking with the polymer chains of the substrate. In some embodiments, the co-evaporation process can form a nanoporous polymer chain scaffold of the fluoropolymer, from which a sacrificial material can be dissolved out. The formed coating can be a multilayer or continuously-graded antireflective coating that has strong adhesion with the substrate.
A lithium-containing electrode with a protective coating and lithium-containing electrochemical cells including the same are provided herein. The protective coating has a first layer including a first fluoropolymeric matrix and Li—F compounds and a second layer including a second fluoropolymeric matrix. Methods of preparing the protective coating on the lithium-containing electrode by applying a first fluoropolymer and/or a first fluoropolymer precursor and a second fluoropolymer and/or a second fluoropolymer precursor are also provided herein.
A variety of polymeric backsheet materials can be found in fielded photovoltaic (PV) modules, mostly based on fluoropolymer and polyethylene terephthalate (PET) materials. Cost reduction and sustainability considerations drive the recent development of alternative backsheet materials and designs [1]. In some fielded PV installations, polymeric materials are susceptible to environmental degradation in the form of backsheet cracking. To prevent backsheet degradation that can result in a module failure, thorough laboratory reliability testing is needed. In this report we studied the durability of seven commercial and experimental PV backsheets through accelerated stress testing using seven photolytic, hygrometric, and custom tests with the goal to understand if novel fluoropolymer-free backsheets are sufficiently environmentally durable to be commercialized. We divided the mechanisms observed during aging into two categories: core degradation and surface degradation. Although core degradation due to hydrolysis was observed in all commercial PET-, and polyamide (PA)-based backsheets aged with 85 degrees C/85% relative humidity, this test is unlikely to be field relevant. Photo-oxidative reactions on the exposed surface during UV weathering affected all seven backsheets regardless of the outer layer polymer material and additives. This degradation was limited to the outermost micrometers of the surface, except for backsheets containing PA-12, which resulted in surface cracking. A custom test combining UV with water spray caused the most severe backsheet degradation, including surface erosion and loss of insulating properties in polyolefin (PO)- and PA-based backsheets. This highlights the importance of combined accelerated stress testing to screen for complex backsheet degradation mechanisms. We also showed that, with material and design optimization, coextruded experimental PO-based backsheets have the potential to be a durable alternative to commercial PET- and fluoropolymer-based PV backsheets.
Recent interest within the photovoltaic (PV) module industry is largely directed toward enhanced lifetimes in the field, balanced with improved recyclability. Traditionally, fluoropolymer-based backsheets have been used, however, are difficult to recycle. Emerging polyolefin (PO)-based backsheets are more recyclable and can be formulated to be robust. Properties of different fluoropolymer- and non-fluoropolymer-based backsheet coupons and in encapsulated silicon mini modules that have been fielded in Albuquerque, NM and Cocoa, FL are reported here. Seven backsheets were examined: two novel PO's, TPT, APO, PPE, AAA, and KPf. Methods of examination include module electrical performance (I - V flash test), surface morphology (optical microscope and gloss), polymer chemical structure (FTIR), EL imaging, mechanical tensile testing, DC breakdown voltage, DSC (phase transitions), and optical performance (reflectance spectra).
The mechanical properties of fluorinated thermoplastics (i.e., tensile strength and elongation) can vary with changes in injection molding processing parameters. Four fluoropolymers are examined: poly(vinylidene fluoride) (PVDF) and random poly(vinylidene fluoride-co-chlorotrifluoroethylene) (PVDF-CTFE) with three CTFE concentrations. Dog bones were manufactured with various cylinder dwell times and mold cooling times to assess the manufacturing sensitivity to the tensile response. Dwell and cooling times increasingly impact mechanical performance as CTFE concentration increases. Specimens exhibit higher tensile strength as a function of injection order. The first injected specimen exhibits the lowest tensile strength and highest elongation in all copolymers. This trend becomes more pronounced among fluoropolymers with higher CTFE concentration and lower weight-averaged molecular weight. Parallel plate rheology was used to obtain the zero-shear viscosity as a function of material type, process, and injection order. We found that in the copolymers, the first injected sample exhibited a lower zero-shear viscosity than the next, which indicates a lower molecular weight in the first injected specimen. This phenomenon was not presented for the PVDF homopolymer. Copolymer mechanical uncertainties are hypothesized to result from the shorter molecular weight chains extruding out of the specimens' sides as a flash due to higher mobility with CTFE segments.
Delamination between layers in photovoltaic (PV) backsheets is often reported in the literature, causing voids that can collect moisture, diminish module backside heat dissipation, and reduce the backsheet’s effectiveness as a physical barrier. While backsheets with weathering-resistant fluoropolymer outer layers have traditionally been used in modules, more recent backsheets using non-fluoropolymer outer layers, such as polyethylene terephthalate (PET), have been developed. These backsheets have shown signs of premature degradation, and their adhesion degradation, in particular, has not been widely studied. In the present work, the single cantilever beam (SCB) adhesion test was used to quantify the adhesion energy in two commercially available PET-based backsheets. To study the effect of minor changes in formulation, the backsheets were obtained from same manufacturer and product line but during different years. To study the effect of environmental variables on adhesion degradation, the backsheets were subjected to artificial weathering at controlled temperature, humidity, and ultraviolet (UV) radiation in an indoor weathering chamber, and the adhesion energy was quantified at several intervals of exposure time. Layering structure, composition, and adhesion failure mode were compared between the backsheets, using Raman and infrared spectroscopy and thermogravimetric analysis. The results show a large difference in initial (unexposed) adhesion energy between the backsheets, despite very similar structures and compositions. Following exposure, adhesion energy dropped significantly, primarily due to thermo-hydrolytic degradation of the polyurethane (PU)-based adhesive layers. Significant UV-induced adhesion degradation of the PET outer layer surface was also observed. The study represents an important step in understanding adhesion degradation in PET-based backsheets, suggesting ways in which adhesion integrity – and, correspondingly, module service life – can be improved.
Photovoltaic (PV) backsheets provide critical moisture, mechanical, and electrical insulation to the backside of PV modules, but their continued functionality depends upon their ability to remain well adhered over years of harsh environmental exposure. A study of adhesive strength was conducted on several PV backsheet types exposed to indoor accelerated weathering. Two adhesion tests – the wedge test and single cantilever beam test – were used to measure adhesion energy in four backsheets: two with fluoropolymer-based outer (airside) layers – polyvinyl fluoride (PVF), polyvinylidene fluoride (PVDF) – and two with non-fluoropolymer-based outer layers–polyamide (PA) and polyethylene terephthalate (PET). The effects of changes in temperature, ultraviolet (UV) irradiance, relative humidity, and a periodic water spray were studied. The PET-, PVF- and PVDF-based backsheets all showed instances of debonding in an adhesive layer, which is commonly reported. Furthermore, for the PA-, PET-, and PVDF-based backsheets, adhesion energy dropped fairly rapidly with exposure, reaching very low levels by 4000 h. The PVF-based backsheet was relatively robust to weathering. Pull-off of an outer chalking layer in the PA- and PET-based backsheets suggested a sensitivity to UV. Adhesion in these two backsheets was also highly sensitive to changes in moisture level. Changes in UV irradiance and temperature did not show a statistically significant effect on adhesion loss for the exposure levels used. The present work is part of a two-part adhesion study on both field-weathered and indoor-exposed backsheets, and forms a basis for understanding adhesion degradation across a variety of backsheet types and degradation factors.
As the photovoltaic (PV) industry is rapidly expanding around the world, there has been an increasing interest in extending the lifespan of PV modules. Concern has also emerged regarding the recyclability of modules and their component materials, including fluoropolymer-based backsheets. Laminated polyethylene-terephthalate (PET) core backsheets have traditionally been used in the PV industry, but new, coextruded polyolefin (PO) backsheets show promise as an improved alternative. In this work, minimodule and coupon samples of seven different backsheets (made of layers including contemporary PET and fluoropolymers, novel PO, and polyamide materials) were run through hygrometric- or UV photolytic-accelerated aging to identify and better understand each material's degradation modes and the backsheets' field reliability. In addition to the artificial aging, the natural weathering methods used in this article are described. The comprehensive set of chemical, mechanical, and structural characterizations at intermittent read points in this article is presented, including: visual appearance and color; gloss; mechanical tensile testing; I-V performance; electroluminescence (EL) imaging; dielectric breakdown; Fourier-transform infrared-chemical structure; X-ray-polymer structure; and differential scanning calorimetry-crystalline content. After 4000 h of aging, a strong correlation occurs between initial physical characteristics (mechanical tensile test) and operating performance (EL and I-V characteristics).
There are many photovoltaic (PV) applications where lighter weight and/or bendable PV power would be beneficial. This includes the curved surfaces of buildings, buildings with weight limitations, boats, automobiles, or other portable applications. In many of these cases, the bending will be only a single occurrence at installation or the amount of bending, even if repeated, is not dramatic. This allows for crystalline silicon modules to be used. For flexible applications, the dominant material for the frontsheet is polyethylene tetrafluoroethylene (PETFE). As a fluoropolymer it resists soiling, is UV stable, and PETFE is a more mechanically durable fluoropolymer. However, in the interests of keeping costs down, less expensive alternative polymers are desirable. In this study, highly accelerated ultraviolet light and heat stresses are applied to candidate materials and the degradation kinetics are determined to provide information to evaluate their suitability for use in a PV application.
The presence and potential leaching of PFAS (Per- and Polyfluoroalkyl Substances) from solar panels are increasingly mentioned in news articles, raising public concerns. Such concerns may slow the adoption of photovoltaic (PV) technology, despite its central role in the renewable energy sector. The limited transparency from manufacturers about fluorinated materials used in PV modules, along with the scarcity of publicly available testing data, contributes to uncertainty and speculation. This perspective aims to clarify the current state of PFAS presence in solar PV. Although certain fluoropolymers are used in PV manufacturing, the scientific consensus on their toxicity indicates they should not be classified as PFAS. Portraying fluoropolymers as toxic PFAS unnecessarily amplifies concerns and unfairly undermines the perceived environmental sustainability of PV technology.
The mechanical properties of fluorinated thermoplastics (i.e., tensile strength and elongation) can vary with changes in injection molding processing parameters. Four fluoropolymers are examined: poly(vinylidene fluoride) (PVDF) and random poly(vinylidene fluoride-co-chlorotrifluoroethylene) (PVDF-CTFE) with three CTFE concentrations. Dog bones were manufactured with various cylinder dwell times and mold cooling times to assess the manufacturing sensitivity to the tensile response. Dwell and cooling times increasingly impact mechanical performance as CTFE concentration increases. Specimens exhibit higher tensile strength as a function of injection order. The first injected specimen exhibits the lowest tensile strength and highest elongation in all copolymers. This trend becomes more pronounced among fluoropolymers with higher CTFE concentration and lower weight-averaged molecular weight. Parallel plate rheology was used to obtain the zero-shear viscosity as a function of material type, process, and injection order. We found that in the copolymers, the first injected sample exhibited a lower zero-shear viscosity than the next, which indicates a lower molecular weight in the first injected specimen. This phenomenon was not present for the PVDF homopolymer. Copolymer mechanical uncertainties are hypothesized to result from the shorter molecular weight chains extruding out of the specimens’ sides as a flash due to higher mobility with CTFE segments.
As the photovoltaic (PV) industry is rapidly expanding around the world, there has been an increasing interest in extending the lifespan of PV modules. Concern has also emerged regarding the recyclability of modules and their component materials, including fluoropolymer-based backsheets. Laminated polyethylene-terephthalate (PET) core backsheets have traditionally been used in the PV industry, but new, co-extruded polyolefin (PO) backsheets show promise as an improved alternative. Mini-module and coupon samples of seven different backsheets (made of layers including contemporary PET and fluoropolymers, novel PO, and polyamide (PA) materials) were run through hygrometric- or UV photolytic-accelerated aging to identify and better understand each material's degradation modes and the backsheets' field reliability. In addition to the artificial aging, the natural weathering methods used in this study are described. The comprehensive set of chemical, mechanical, and structural characterizations at intermittent read points in this study is presented, including: visual appearance and color; gloss; mechanical tensile testing; I-V performance; electroluminescence (EL) imaging; dielectric breakdown; FTIR-chemical structure; X-ray-polymer structure (WAXS); and DSC-crystalline content. After 4000 h of accelerated aging or 2y of outdoor aging, a strong correlation occurs between initial physical characteristics (mechanical tensile test) and operating performance (EL and I-V characteristics).
The present disclosure relates to a composition that includes a fluoropolymer, a polymerized ionic liquid block copolymer (PILBC), and a catalyst, where the fluoropolymer is configured to affect ionic mobility, and the PILBC is configured to affect a property of the catalyst. In some embodiments of the present disclosure, the property may include at least one of oxygen transport and/or an active site functionality of the catalyst.
This disclosure provides systems, methods, and apparatus related to lithium metal oxyfluorides. In one aspect, a method for manufacturing a lithium metal oxyfluoride having a general formula Li 1+x (MM′) z O 2-y F y , with 0.6 ≤ z ≤ 0.95, 0 < y ≤ 0.67, and 0.0 5 ≤ x ≤ 0.4, the lithium metal oxyfluoride having a cation-disordered rocksalt structure, includes: providing at least one lithium-based precursor; providing at least one redox-active transition metal-based precursor; providing at least one redox-inactive transition metal-based precursor; providing at least one fluorine-based precursor comprising a fluoropolymer; and mixing the at least one lithium-based precursor, the at least one redox-active transition metal-based precursor, the at least redox-inactive transition metal-based precursor, and the at least one fluorine-based precursor comprising a fluoropolymer to form a mixture.