Anode-free lithium metal batteries are the most promising candidate to outperform lithium metal batteries due to higher energy density and reduced safety hazards with the absence of metallic lithium ...anode during initial cell fabrication. In general, researchers report capacity retention, reversible capacity, or rate capability of the cells to study the electrochemical performance of anode-free lithium metal batteries. However, evaluating the behavior of batteries from limited aspects may easily overlook other information hidden deep inside the meretricious results or even lead to misguided data interpretation. In this work, we present an integrated protocol combining different types of cell configuration to determine various sources of irreversible coulombic efficiency in anode-free lithium metal cells. The decrypted information from the protocol provides an insightful understanding of the behaviors of LMBs and AFLMBs, which promotes their development for practical applications.
Solid‐state lithium–sulfur battery (SSLSB) is attractive due to its potential for providing high energy density. However, the cell chemistry of SSLSB still faces challenges such as sluggish ...electrochemical kinetics and prominent “chemomechanical” failure. Herein, a high‐performance SSLSB is demonstrated by using the thio‐LiSICON/polymer composite electrolyte in combination with sulfurized polyacrylonitrile (S/PAN) cathode. Thio‐LiSICON/polymer composite electrolyte, which processes high ionic conductivity and wettability, is fabricated to enhance the interfacial contact and the performance of lithium metal anodes. S/PAN is utilized due to its unique electrochemical characteristics: electrochemical and structural studies combined with nuclear magnetic resonance spectroscopy and electron paramagnetic resonance characterizations reveal the charge/discharge mechanism of S/PAN, which is the radical‐mediated redox reaction within the sulfur grafted conjugated polymer framework. This characteristic of S/PAN can support alleviating the volume change in the cathode and maintaining fast redox kinetics. The assembled SSLSB full cell exhibits excellent rate performance with 1183 mAh g−1 at 0.2 C and 719 mAh g−1 at 0.5 C, respectively, and can accomplish 50 cycles at 0.1 C with the capacity retention of 588 mAh g−1. The superior performance of the SSLSB cell rationalizes the construction concept and leads to considerations for the innovative design of SSLSB.
A novel configuration of a solid‐state lithium–sulfur battery (SSLSB) is demonstrated by the combination of thio‐LiSICON/polymer composite electrolyte and sulfurized polyacrylonitrile (S/PAN) cathode. The improved interfacial wetting by utilizing the composite electrolyte and the radical‐maintained fast redox kinetics of S/PAN contribute to the high performance of the assembled SSLSB, which leads to the innovative design of SSLSB.
Understanding the mechanism of Li nucleation and growth is essential for providing long cycle life and safe lithium ion batteries or lithium metal batteries. However, no quantitative report on Li ...metal deposition is available, to the best of our knowledge. We propose a model for quantitatively understanding the Li nucleation and growth mechanism associated with the solid–electrolyte interphase (SEI) formation, which we name the Li-SEI model. The current transients at various overpotentials initiate the nucleation and growth of Li metal on bare Cu foil. The Li-SEI model considering a three-dimensional diffusion-controlled instantaneous process (J 3D‑DC) with the simultaneous reduction of electrolyte decomposition (J SEI) due to the SEI fracture is employed for investigating the Li nucleation and growth mechanism. The individual contributions of experimental and theoretical transient states, i.e., the fundamental kinetic values of diffusion coefficient (D), rate of nucleation (N 0), and rate constant of electrolyte decomposition (k SEI), can be determined from the Li-SEI model. Interestingly, J SEI increases with time, indicating that the current contributing from the electrolyte decomposition increases with time due to the SEI fracture upon Li deposition. Meanwhile, the k SEI increases with overpotential, indicating the SEI fracture is more serious at higher overpotential or higher growth rate. The k SEI is smaller in the electrolyte with fluoroethylene carbonate (FEC) additive, indicating that FEC additive can significantly suppress the SEI fracture during Li metal deposition. This proposed model opens a new way to quantitatively understand the Li nucleation and growth mechanism and electrolyte decomposition on various substrates or in different electrolytes.
Zinc metal is considered a promising anode material for aqueous zinc ion batteries. However, it suffers from dendrite growth, corrosion, and low coulombic efficiency (CE) during plating/stripping. ...Herein, a concentrated hybrid (4 m Zn(CF3SO3)2 + 2 m LiClO4) aqueous electrolyte (CHAE) to overcome the challenges facing the Zn anode is reported. The developed electrolyte achieves dendrite‐free Zn plating/stripping and obtains an excellent CE of ≈100%, surpassing the previously reported values. The combination of synchrotron‐based in operando transmission X‐ray microscopy, X‐ray diffraction, and ex situ X‐ray photoelectron spectroscopy analyses indicate that the denser, anion‐derived passivation layer formed using the CHAE facilitates homogeneous current distribution and better prevents freshly deposited Zn from directly contacting the electrolyte than the looser, solvent‐derived layers formed from a dilute hybrid aqueous electrolyte (DHAE). The beneficial effects of the CHAE on the compact, dense, and stable salt‐anion‐derived passivation layer can be attributed to its unique solvation structure, which suppresses the water‐related side reactions and widens the electrochemical potential window. In the hybrid Zn||LiFePO4 configuration, the CHAE‐based cell delivered a stable performance of CE >99% and capacity retention >90% after 285 cycles. In contrast, the DHAE‐based cell exhibits capacity retention of <65% after 170 cycles.
A concentrated hybrid aqueous electrolyte (CHAE) (4 m Zn(CF3SO3)2 + 2 m LiClO4) is developed to address the dendrite formation and low coulombic efficiency upon Zn deposition/stripping. The Zn growth behavior and the formation mechanism of dense anion‐derived passivation layer are unveiled by synchrotron‐based in operando imaging and spectroscopy techniques. The CHAE shows excellent cell performance in Zn||LiFePO4 dual‐ion battery.
Anode‐free lithium‐metal batteries employ in situ lithium‐plated current collectors as negative electrodes to afford optimal mass and volumetric energy densities. The main challenges to such ...batteries include their poor cycling stability and the safety issues of the flammable organic electrolytes. Here, a high‐voltage 4.7 V anode‐free lithium‐metal battery is reported, which uses a Cu foil coated with a layer (≈950 nm) of silicon–polyacrylonitrile (Si‐PAN, 25.5 µg cm−2) as the negative electrode, a high‐voltage cobalt‐free LiNi0.5Mn1.5O4 (LNMO) as the positive electrode and a safe, nonflammable ionic liquid electrolyte composed of 4.5 m lithium bis(fluorosulfonyl)imide (LiFSI) salt in N‐methyl‐N‐propyl pyrrolidiniumbis(fluorosulfonyl)imide (Py13FSI) with 1 wt% lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) as additive. The Si‐PAN coating is found to seed the growth of lithium during charging, and reversibly expand/shrink during lithium plating/stripping over battery cycling. The wide‐voltage‐window electrolyte containing a high concentration of FSI− and TFSI− facilitates the formation of stable solid‐electrolyte interphase, affording a 4.7 V anode‐free Cu@Si‐PAN/LiNi0.5Mn1.5O4 battery with a reversible specific capacity of ≈120 mAh g−1 and high cycling stability (80% capacity retention after 120 cycles). These results represent the first anode‐free Li battery with a high 4.7 V discharge voltage and high safety.
4.7 V Cu@Si‐PAN/LiNi0.5Mn1.5O4 anode‐free Li batteries with a reversible specific capacity of ≈120 mAh g−1 and high capacity retention of 80% after 120 cycles are reported. With the nonflammable F‐rich ionic liquid electrolyte and the seeding Si‐PAN layer (950 nm), an enhanced safety and high‐voltage anode‐free Li battery without dendritic Li growth is demonstrated.
Anode-free batteries (AFBs) are impressive and recent phenomena in the era of energy storage devices due to their high energy density and relative ease of production compared to the traditional ...Lithium metal batteries (LMBs). However, dendrite formation during plating and stripping and low coulombic efficiency (CE) are the main challenges that impede practical implementation of these batteries. Here we report an extremely stable dual-salt electrolyte, 2M LiFSI+1M LiTFSI (2FSI+1TFSI)) in DME/DOL (1:1, v/v), system in comparison to the single salt 3M LiTFSI (3TFSI) in DME/DOL (1:1, v/v), to effectively stabilize AFB composed of LiFePO4 cathode and bare Cu-foil anode for the first time. The electrolyte stabilized anode-free cell with the configuration Cu||LiFePO4 via reductive decomposition of its anions and enabled the cell to be cycled with CE of 98.9% for 100 cycles. This results from the formation of stable, ion conductive and electrically insulating inorganic components rich Solid Electrolyte Interface (SEI) layer on the surface of in-situ deposited Li-metal that blocks the undesirable parasitic reaction between the deposited Li and the electrolyte. Thus, aforesaid SEI mitigates formation of dead lithium and dissolution of the in-situ deposited Li surface during repeated cycling and prolongs cycle life of the battery.
We investigated rechargeable aluminum (Al) batteries composed of an Al negative electrode, a graphite positive electrode, and an ionic liquid (IL) electrolyte at temperatures down to −40 °C. The ...reversible battery discharge capacity at low temperatures could be superior to that at room temperature. In situ/operando electrochemical and synchrotron X-ray diffraction experiments combined with theoretical modeling revealed stable AlCl₄⁻/graphite intercalation up to stage 3 at low temperatures, whereas intercalation was reversible up to stage 4 at room temperature (RT). The higher-degree anion/graphite intercalation at low temperatures affords rechargeable Al battery with higher discharge voltage (up to 2.5 V, a record for Al battery) and energy density. A remarkable cycle life of >20,000 cycles at a rate of 6C (10 minutes charge time) was achievable for Al battery operating at low temperatures, corresponding to a >50-year battery life if charged/discharged once daily.
Room temperature ionic liquids (RTILs) are solvent-free liquids comprised of densely packed cations and anions. The low vapor pressure and low flammability make ILs interesting for electrolytes in ...batteries. In this work, a new class of ionic liquids were formed for rechargeable aluminum/graphite battery electrolytes by mixing 1-methyl-1-propylpyrrolidinium chloride (Py13Cl) with various ratios of aluminum chloride (AlCl
) (AlCl
/Py13Cl molar ratio = 1.4 to 1.7). Fundamental properties of the ionic liquids, including density, viscosity, conductivity, anion concentrations and electrolyte ion percent were investigated and compared with the previously investigated 1-ethyl-3-methylimidazolium chloride (EMIC-AlCl
) ionic liquids. The results showed that the Py13Cl-AlCl
ionic liquid exhibited lower density, higher viscosity and lower conductivity than its EMIC-AlCl
counterpart. We devised a Raman scattering spectroscopy method probing ILs over a Si substrate, and by using the Si Raman scattering peak for normalization, we quantified speciation including AlCl
, Al
Cl
, and larger AlCl
related species with the general formula (AlCl
)
in different IL electrolytes. We found that larger (AlCl
)
species existed only in the Py13Cl-AlCl
system. We propose that the larger cationic size of Py13
(142 Å
)
EMI
(118 Å
) dictated the differences in the chemical and physical properties of the two ionic liquids. Both ionic liquids were used as electrolytes for aluminum-graphite batteries, with the performances of batteries compared. The chloroaluminate anion-graphite charging capacity and cycling stability of the two batteries were similar. The Py13Cl-AlCl
based battery showed a slightly larger overpotential than EMIC-AlCl
, leading to lower energy efficiency resulting from higher viscosity and lower conductivity. The results here provide fundamental insights into ionic liquid electrolyte design for optimal battery performance.
It is essential to decouple the interfacial reactions taking place at the anode and cathode in rechargeable batteries. However, due to the reactive nature of Li, it is challenging to use Li‐metal ...batteries (LMBs) protocol to decouple the interfacial reactions. The by‐products from the anode or cathode become mixed in Li/NMC111 cells, which make decoupling interfacial reactions difficult. Here, reactions at electrodes are successfully decoupled and demystified using a protocol combining anode‐free LMB (AFLMB) with online electrochemical mass spectroscopy. LiPF6 in ethylene carbonate (EC)/diethyl carbonate (DEC) and EC/ethyl methyl carbonate (1:1 v/v%) electrolytes are used to compare interfacial reactions in Li/NMC111 and Cu/NMC111 cells. In Cu/NMC111, the evolution of CO2, CO, and C2H4 gases at the initial stage of first charging is due to interfacial reactions at Cu surface due to solid–electrolyte‐interphase formation. However, the evolution of CO2 and CO gases at high voltage in the entire cycles is associated with chemical and/or electrochemical electrolyte oxidation at the cathode. This work paves a new concept to decouple interfacial reactions at electrodes for developing electrochemically stable electrolytes to improve the performance with the long‐cycling life of AFLMBs and LMBs.
Reductive and oxidative gases evolving at the anode and cathode in Li/NMC111 and Cu/NMC111 are independently studied using a protocol combining EL‐Cell and GC‐MS. Understanding the decoupled interfacial reactions at both electrodes help elucidate the solid–electrolyte‐interphase formation mechanism and develop stable and high‐performance electrolytes.
Lithium dendrite growth dynamics on Cu surface is first visualized through a versatile and facile experimental cell by in operando transmission X-ray microscopy (TXM). Galvanostatic plating and ...stripping cycle(s) are applied on each cell. Upon plating/stripping at ∼1 mA cm–2, mossy lithium is clearly found growing and shrinking on the Cu surface as the application time increases. It is interesting to note that the aspect ratio (height/width) of deposited lithium has increased with charge passed during plating, indicating a faster growing from the base. In addition, the dendritic or mossy lithium has also been observed when various high current densities (25, 12.5, and 6.3 mA cm–2) are applied in different cycles, showing a severe dendritic lithium formation that could be induced by inhomogeneous current distribution. The clear structure of dead lithium is found after the cycling, which also shows a lower efficiency and higher hazard when a higher current density is applied. This work explores TXM as a useful tool for in operando dynamic visualization and quantitative measurement of lithium dendrite, which is difficult to achieve with ex situ measurements and other microscopy techniques. The understanding of the growth mechanism from TXM can be beneficial for the development of safe lithium ion and lithium metal batteries.
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