Flexible Ion-Conducting Composite Membranes for Lithium Batteries (original) (raw)
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Flexible Light-Weight Lithium-Ion-Conducting Inorganic–Organic Composite Electrolyte Membrane
ACS energy letters, 2017
A fast Li + ion-conducting membrane is the key component behind a successful performance of an aqueous or hybrid Li-air battery. Currently available ceramic ionic conductors are hardly scalable, difficult to seal, brittle and electrochemically unstable against the commonly used catholytes. In this work, an easily scalable high performance hybrid inorganic-organic membrane is realized that consists of NASICON-type Li 1+x Al x Ge 2-x (PO 4) 3 (LAGP) as the fast ion conducting ceramic filler within a high stability polymer blend. The as-prepared hybrid
Electrochimica Acta, 2019
The use of lithium metal as the anode for Lithium Metal Batteries (LMB) requires having solid or quasi-solid electrolytes able to block dendrites formation during cell cycling. Here we reported on a hybrid electrolyte membrane based on nanostructured yttria-stabilized-zirconia, sintered by means of High Pressure-Field Assisted Sintering Technique (HP-FAST) in order to retain proper nanoporosity, and activated with a standard LiPF 6-EC-DMC solution. By a thorough physico-chemical and functional characterization, we demonstrated that the liquid is effectively nano-confined in the ceramic membrane, and the resulting quasi-solid electrolyte is non-flammable. A remarkable conductivity value of 0.91 mS cm-1 was observed at room temperature, with activation energy of 0.2 eV, and cation transference number, t + =0.55, substantially higher than that of the pure liquid electrolyte. The hybrid electrolyte showed electrochemical stability up to 5.5 V vs. Li + /Li, and excellent resistance to dendrite formation for more than 350 cycles in a Li/electrolyte/Li symmetrical cell. A full cell Li/electrolyte/LiMn 2 O 4 showed more than 90 mAh g-1 at 2C for more
Protection of Lithium Anode by a Highly Porous PVDF Membrane for High-Performance Li–S Battery
ACS Applied Energy Materials, 2020
The Li-S battery is considered as the next-generation energy storage solution largely because of its high energy density. However, the lithium metal anode has suffered from the "shuttle effect" of soluble polysulfide species and the formation of dendrites that cause quick performance decay and safety issues. Here, a polyvinylidene fluoride (PVDF) membrane that contains a hierarchical porous structure was introduced as a protection layer to insulate the lithium anode from polysulfide shuttling and dendrite formation. The PVDF protected Li-S battery showed a capacity of around 850 mAh g-1 and Coulombic efficiency of 98% over 200 cycles at 0.5 C. Both performances are significantly improved from the normal Li-S batteries. The PVDF membrane is stable, easy to coat, and scalable, which offers a convenient, affordable, yet effective strategy for achieving commercialization of high energy density and safe Li-S batteries.
Lithium conducting solid electrolyte Li1+xAlxGe2−x(PO4)3 membrane for aqueous lithium air battery
Solid State Ionics, 2014
We report the preparation and characterization of hybrid inorganic-organic membranes based on NASICON-type Li 1 + x Al x Ge 2 − x (PO 4) 3 (LAGP) as the fast ion conducting ceramic and fast ionic polymeric solid electrolyte PEO: PVDF:LiBF 4 for possible application as Li anode protecting membrane in lithium air batteries. The resulting membranes showed enhanced conductivity of 10 −4 S cm −1 in combination with improved mechanical flexibility when compared to the ceramic along with higher stability in aqueous solutions in comparison with pure polymer.
Solid-state batteries: Unlocking lithium's potential with ceramic solid electrolytes
Recent progress indicates that ceramic materials may soon supplant liquid electrolytes in batteries, offering improved energy capacity and safety. W idespread adoption of electric vehicles (EV) will require dramatic changes to the energy storage market. Total worldwide lithium-ion (Li-ion) battery production was 221 GWh in 2018, while EV demand alone is projected to grow to more than 1,700 GWh by 2030. 1 As economies of scale have been met in Li-ion battery production, price at the pack level has fallen and is expected to break $100/kWh within the next few years. Li-ion batteries are expected to address near-term energy storage needs, with advances in cell chemistry providing steady improvement in cell capacity. Yet Li-ion batteries will eventually approach the practical limits of their energy storage capacity , and the volatile flammable liquid electrolyte in Li-ion cells requires thermal management systems that add cost, mass, and complexity to EV battery packs. Recent progress demonstrates that Li-ion conducting solid electrolytes have fundamental properties to supplant current Li-ion liquid electrolytes. Moreover, using solid electrolytes enables all-solid-state batteries, a new class of lithium batteries that are expected to reach storage capacities well beyond that of today's Li-ion batteries. The promise of a safer high-capacity battery has attracted enormous attention from fundamental research through start-up companies, with significant investment from venture capitalists and automakers. The Li-ion battery The 1970s marked development of the first Li-ion cathode intercalation materials. Cells with a metallic lithium anode were commercialized in the 1980s, but it was soon discovered Solid-state batteries: Unlocking lithium's potential with ceramic solid electrolytes that lithium deposits in dendritic structures upon battery cycling. These dendrites eventually grow through the separa-tor, connecting the anode and cathode and causing a dangerous short circuit of the cell. The solution was to replace the lithium anode with a graphite Li-ion host material, thereby producing the modern Li-ion battery. First introduced by Sony in 1991, the graphite anode is paired with a LiCoO 2 cathode and flooded with a liquid organic electrolyte with dissolved lithium salt. The dissolved lithium provides Li-ion transport within the cell. A thin and porous polymer separator prevents physical contact between the anode and cathode while allowing ionic transport between electrodes. This basic cell structure remains unchanged today, albeit with numerous energy-boosting innovations, including silicon anode additions, electrolyte additives to increase cycle life, and high nickel-content cathodes. These innovations have led to an average of 8% annualized energy density improvement in Li-ion batteries. 2 Despite this progress, the volumetric energy density of Li-ion batteries can only reach a practical limit of about 900 Wh/L at the cell level. For Li-ion batteries, active cathode and anode powders are mixed with binder and cast on a current collector using doctor blade, reverse comma, or slot die coating. These electrodes are slit into desired dimensions, interleaved with a separator, and either wound-as is the case of an 18650 (18 mm diameter; 65 mm length) cylindrical cell-or stacked or folded to produce a prismatic pouch cell. Figure 1 shows 18650 cylindrical wound cells and 10-Ah pouch cells. For EV applications, cells are arranged into modules, which are placed into a battery pack. For example, a Tesla Model 3 contains more than 4,000 individual cylindrical cells, producing about 80 kWh of storage. Other manufacturers , such as GM, use pouch-type cells, with 288 cells producing 60 kWh of storage in the Chevy Bolt. Li-ion battery packs contain significant battery management systems to keep cells within a safe operating range. Heat generated within the pack must be removed by cooling systems to protect both the performance and lifetime of Li-ion cells. Credit: Evan Dougherty/University of Michigan Engineering Communications and Marketing Induction coils heat a die for rapid densification of Li-ion conducting Li 7 La 3 Zr 2 O 12 ceramic solid electrolyte.
“Pore/bead” membrane for rechargeable lithium ion batteries
Journal of Applied Polymer Science, 2013
A special ''pore/bead'' membrane was prepared with a mesoporous inorganic filler (MCM-41) and a P(VDF-HFP) binder. The special ''pore/bead'' structure of the MCM-41 filler not only enhanced the puncture strength of the membrane but also improved its ionic conductivity. The puncture strength of the dried ''pore/bead'' membrane (MCM-41 : P(VDF-HFP) ¼ 1 : 1.5) was 18 N, and showed a slight decrease (16 N) after the membrane was wetted by liquid electrolyte. Additionally, the composite membrane showed excellent thermal dimensional stability. The composite membrane could be activated by adding 1M LiClO 4 -EC/DMC (1 : 1 by volume). The activated membrane displayed a high ionic conductivity about 3.4 Â 10 À3 S cm À1 at room temperature. Its electrochemical stability window was up to 5.3 V vs. Li/Li þ , indicating that it was very suitable for lithium-ion battery application. The battery assembled using the composite electrolyte also showed reasonably good high-rate performance. The approach of preparing a ''pore/ bead'' membrane provides a new avenue for improving both the conductivity and the mechanical strength of polymer electrolytes for lithium batteries.
High-performance electrolyte membranes for plastic lithium batteries
Journal of power sources, 1997
The synthesis, properties, and application of new types of lithium-ion conducting polymeric membranes are reporte,l and discussed. These ionic membranes are dimensionally stable, have a very high ionic conductivity, an acceptable lithium-ion transferenl:e number and a wide electrochemical stability window. Due to these favourable properties, these membranes are suitable for the fabricaticln of advanced-design, high-performance batteries and power source devices.
Langmuir, 2017
Aqueous lithium−air batteries have very high theoretical energy densities, which potentially makes this technology very interesting for energy storage in electric mobility application. However, the aqueous electrolyte requires the use of watertight layer to protect the lithium metal typically a thick NASICON glass-ceramic layer, which adds ohmic resistance and penalizes performance. This paper deals with the replacement of this ceramic electrolyte by a hybrid organic−inorganic membrane. This new membrane combines an ionically conducting inorganic phase for Li-ion transport (Li 1.3 Al 0.3 Ti 1.7 (PO 4) 3 (LATP) and a poly(vinylidene fluoride−co−hexafluoropropylene (PVDF−HFP) polymer for water-tightness and mechanical properties. The Li−ion transport through the membrane is ensured by an interconnected 3−D network of crystalline LATP fibers obtained by coupling an electrospinning process with the sol-gel synthesis followed by a thermal treatment. After an impregnation step with PVDF−HFP, hybrid membranes with different volumetric fractions of PVDF−HFP have been synthesized. These membranes are watertight and have Li−ion conductivities ranging from 10-5 to 10 −4 mS/cm. The conductivity depends on the PVDF−HFP volume fraction and the fibers' alignment in the membrane thickness, which in turn can be tuned by adjusting the water content in the electrospinning chamber during the process. The alignment of fibers parallel to the membrane surface conduces to poor conductivity values while a disordered fibers mat lead to interesting conductivity values (1 x 10-4 mS/cm) at ambient temperature.
Advanced, lithium batteries based on high-performance composite polymer electrolytes
Progress in lithium battery technology may be achieved by passing from a conventional liquid electrolyte structure to a solid-state, polymer configuration. In this prospect, great R&D effort has been devoted to the development of suitable lithium conducting polymer electrolytes. The most promising results have been obtained with systems based on blends between poly(ethylene oxide) and lithium salts. In this work we show that the transport and interfacial properties of these electrolytes may be greatly enhanced by the dispersion of a ceramic filler having an unique surface state condition. The results, in addition to their practical reflection in the lithium polymer electrolyte battery technology, also provide a valid support to the model which ascribes the enhancement of the transport properties of ceramic-added composites to the specific Lewis acid-base interactions between the ceramic surface states and both the lithium salt anion and the PEO-chains.
Journal of …, 1998
The densi®cation of a ceramic electrolyte for rechargeable lithium ion batteries by using different compaction methods is described. The ceramic electrolyte for lithium ions, BPO 4-Li 2 O, is compacted using either static or dynamic compaction methods. A difference in peak width in the X-ray diffraction spectra and a difference in lithium ion conductivity is observed. The dynamically compacted BPO 4-Li 2 O shows an increase of up to three orders of magnitude in total ionic conductivity as compared with statically compacted samples. The total lithium ion conductivity is up to 2.10 À4 S/cm at room temperature, which can compete with polymer electrolytes.