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1.
Angew Chem Int Ed Engl ; 63(17): e202400132, 2024 Apr 22.
Article En | MEDLINE | ID: mdl-38409997

Li-CO2 batteries have received significant attention owing to their advantages of combining greenhouse gas utilization and energy storage. However, the high kinetic barrier between gaseous CO2 and the Li2CO3 product leads to a low operating voltage (<2.5 V) and poor energy efficiency. In addition, the reversibility of Li2CO3 has always been questioned owing to the introduction of more decomposition paths caused by its higher charging plateau. Here, a novel "trinity" Li-CO2 battery system was developed by synergizing CO2, soluble redox mediator (2,2,6,6-tetramethylpiperidoxyl, as TEM RM), and reduced graphene oxide electrode to enable selective conversion of CO2 to Li2C2O4. The designed Li-CO2 battery exhibited an output plateau reaching up to 2.97 V, higher than the equilibrium potential of 2.80 V for Li2CO3, and an ultrahigh round-trip efficiency of 97.1 %. The superior performance of Li-CO2 batteries is attributed to the TEM RM-mediated preferential growth mechanism of Li2C2O4, which enhances the reaction kinetics and rechargeability. Such a unique design enables batteries to cope with sudden CO2-deficient environments, which provides an avenue for the rationally design of CO2 conversion reactions and a feasible guide for next-generation Li-CO2 batteries.

2.
Adv Mater ; 36(23): e2312661, 2024 Jun.
Article En | MEDLINE | ID: mdl-38290062

Solid-state lithium-oxygen (Li-O2) batteries have been widely recognized as one of the candidates for the next-generation of energy storage batteries. However, the development of solid-state Li-O2 batteries has been hindered by the lack of solid-state electrolyte (SSE) with high ionic conductivity at room temperature, high Li+ transference number, and the high stability to air. Herein, the organic molecular porous solid cucurbit[7]uril (CB[7]) with one-dimensional (1D) ion migration channels is developed as the SSE for solid-state Li-O2 batteries. Taking advantage of the 1D ion migration channel for Li+ conduction, CB[7] SSE achieves high ionic conductivity (2.45 × 10-4 S cm-1 at 25 °C). Moreover, the noncovalent interactions facilitated the immobilization of anions, realizing a high Li+ transference number (tLi + = 0.81) and Li+ uniform distribution. The CB[7] SSE also shows a wide electrochemical stability window of 0-4.65 V and high thermal stability and chemical stability, as well as realizes stable Li+ plating/stripping (more than 1000 h at 0.3 mA cm-2). As a result, the CB[7] SSE endows solid-state Li-O2 batteries with superior rate capability and long-term discharge/charge stability (up to 500 h). This design strategy of CB[7] SSE paves the way for stable and efficient solid-state Li-O2 batteries toward practical applications.

3.
J Am Chem Soc ; 146(5): 3373-3382, 2024 Feb 07.
Article En | MEDLINE | ID: mdl-38272666

Reticular chemistry effectively yields porous structures with distinct topological lattices for a broad range of applications. Polyhedral oligomeric silsesquioxane (POSS)-based octatopic building blocks with a rare Oh symmetric configuration and attracting inorganic features have great potential for creating three-dimensional (3D) covalent organic frameworks (COFs) with new topologies. However, the intrinsic flexibility and intensive motion of cubane-type POSS molecules make the construction of 3D regular frameworks challenging. Herein, by fastening three or four POSS cores with per aromatic rigid linker from rational steric directions, we successfully developed serial crystalline 3D COFs with unpresented "the" and scu topologies. Both the experimental and theoretical results proved the formation of target 3D POSS-based COFs. The resultant hybrid networks with designable chemical skeletons and high surface areas maintain the superiorities of both the inorganic and organic components, such as their high compatibility with inorganic salts, abundant periodic electroactive sites, excellent thermal stability, and open multilevel nanochannels. Consequently, the polycubane COFs could serve as outstanding solid electrolytes with a high ionic conductivity of 1.23 × 10-4 S cm-1 and a lithium-ion transference number of 0.86 at room temperature. This work offers a pathway to generate ordered lattices with multiconnected flexible cube motifs and enrich the topologies of 3D COFs for potential applications.

4.
Angew Chem Int Ed Engl ; 63(11): e202319211, 2024 Mar 11.
Article En | MEDLINE | ID: mdl-38198190

Li-N2 batteries have received widespread attention for their potential to integrate N2 fixation, energy storage, and conversion. However, because of the low activity and poor stability of cathode catalysts, the electrochemical performance of Li-N2 batteries is suboptimal, and their electrochemical reversibility has rarely been proven. In this study, a novel bifunctional photo-assisted Li-N2 battery system was established by employing a plasmonic Au nanoparticles (NPs)-modified defective carbon nitride (Au-Nv -C3 N4 ) photocathode. The Au-Nv -C3 N4 exhibits strong light-harvesting, N2 adsorption, and N2 activation abilities, and the photogenerated electrons and hot electrons are remarkably beneficial for accelerating the discharge and charge reaction kinetics. These advantages enable the photo-assisted Li-N2 battery to achieve a low overpotential of 1.32 V, which is the lowest overpotential reported to date, as well as superior rate capability and prolonged cycle stability (≈500 h). Remarkably, a combination of theoretical and experimental results demonstrates the high reversibility of the photo-assisted Li-N2 battery. The proposed novel strategy for developing efficient cathode catalysts and fabricating photo-assisted battery systems breaks through the overpotential bottleneck of Li-N2 batteries, providing important insights into the mechanism underlying N2 fixation and storage.

5.
J Am Chem Soc ; 146(2): 1305-1317, 2024 Jan 17.
Article En | MEDLINE | ID: mdl-38169369

Aprotic lithium-oxygen (Li-O2) batteries are considered to be a promising alternative option to lithium-ion batteries for high gravimetric energy storage devices. However, the sluggish electrochemical kinetics, the passivation, and the structural damage to the cathode caused by the solid discharge products have greatly hindered the practical application of Li-O2 batteries. Herein, the nonsolid-state discharge products of the off-stoichiometric Li1-xO2 in the electrolyte solutions are achieved by iridium (Ir) single-atom-based porous organic polymers (termed as Ir/AP-POP) as a homogeneous, soluble electrocatalyst for Li-O2 batteries. In particular, the numerous atomic active sites act as the main nucleation sites of O2-related discharge reactions, which are favorable to interacting with O2-/LiO2 intermediates in the electrolyte solutions, owing to the highly similar lattice-matching effect between the in situ-formed Ir3Li and LiO2, achieving a nonsolid LiO2 as the final discharge product in the electrolyte solutions for Li-O2 batteries. Consequently, the Li-O2 battery with a soluble Ir/AP-POP electrocatalyst exhibits an ultrahigh discharge capacity of 12.8 mAh, an ultralow overpotential of 0.03 V, and a long cyclic life of 700 h with the carbon cloth cathode. The manipulation of nonsolid discharge products in aprotic Li-O2 batteries breaks the traditional growth mode of Li2O2, bringing Li-O2 batteries closer to being a viable technology.

6.
Angew Chem Int Ed Engl ; 63(5): e202317949, 2024 Jan 25.
Article En | MEDLINE | ID: mdl-38078904

Solid-state lithium (Li) batteries promise both high energy density and safety while existing solid-state electrolytes (SSEs) fail to satisfy the rigorous requirements of battery operations. Herein, novel polyoxometalate SSEs, Li3 PW12 O40 and Li3 PMo12 O40 , are synthesized, which exhibit excellent interfacial compatibility with electrodes and chemical stability, overcoming the limitations of conventional SSEs. A high ionic conductivity of 0.89 mS cm-1 and a low activation energy of 0.23 eV are obtained due to the optimized three-dimensional Li+ migration network of Li3 PW12 O40 . Li3 PW12 O40 exhibits a wide window of electrochemical stability that can both accommodate the Li anode and high-voltage cathodes. As a result, all-solid-state Li metal batteries fabricated with Li/Li3 PW12 O40 /LiNi0.5 Co0.2 Mn0.3 O2 display a stable cycling up to 100 cycles with a cutoff voltage of 4.35 V and an areal capacity of more than 4 mAh cm-2 , as well as a cost-competitive SSEs price of $5.68 kg-1 . Moreover, Li3 PMo12 O40 homologous to Li3 PW12 O40 was obtained via isomorphous substitution, which formed a low-resistance interface with Li3 PW12 O40 . Applications of Li3 PW12 O40 and Li3 PMo12 O40 in Li-air batteries further demonstrate that long cycle life (650 cycles) can be achieved. This strategy provides a facile, low-cost strategy to construct efficient and scalable solid polyoxometalate electrolytes for high-energy solid-state Li metal batteries.

7.
Adv Mater ; 36(15): e2307790, 2024 Apr.
Article En | MEDLINE | ID: mdl-38088221

Applying solar energy into energy storage battery systems is challenging in achieving green and sustainable development, however, the efficient progress of photo-assisted metal-air batteries is restricted by the rapid recombination of photogenerated electrons and holes upon the photocathode. Herein, a 1D-ordered MoS2 nanotube (MoS2-ONT) with confined mass transfer can be used to extend the lifetime of photogenerated carriers, which is capable of overcoming the challenge of rapid recombination of electron and holes. The tubular confined space cannot only promote the orderly separation and migration of charge carriers but also realize the accumulation of charge and the rapid activation of oxygen molecules. The concave surface of MoS2-ONT can improve the carrier separation ability and prolong the carrier lifetime. Meanwhile, the ordered tubular confined space can effectively realize the rapid transfer of charge, ion, and oxygen. Under light irradiation, a fast oxygen reduction reaction kinetics of 70 mW cm-2 for photo-assisted Zn-air battery is achieved, which is the highest value reported for photo-assisted Zn-air batteries. Significantly, the photo-assisted Li-O2 battery based on MoS2-ONT also shows superior rate capability and other exciting battery performance. This work shows the universality of the confined carrier separation strategy in photo-assisted metal-air batteries.

8.
J Colloid Interface Sci ; 656: 146-154, 2024 Feb 15.
Article En | MEDLINE | ID: mdl-37989048

The use of light-assisted cathode is regarded as an effective approach to reduce the overpotential of lithium carbon dioxide (Li - CO2) batteries. However, the inefficient electron-hole separation and the complex discharge-charge reactions hamper the efficiency of CO2 photocatalytic reaction in battery. Herein, a highly reversible force-assisted Li - CO2 battery has been established for the first time by employing a Bi0.5Na0.5TiO3 nanorods piezoelectric cathode. The high-energy electron and holes generated by the piezoelectric cathode with ultrasonic force can effectively enhance the carbon dioxide reduction reaction (CDRR) and carbon dioxide evolution reaction (CDER) kinetics, thereby reducing the overpotentials during the discharge-charge processes. Moreover, the morphology of the discharge product (Li2CO3) can be modified via the dense surface electrons of the piezoelectric cathode, resulting in the promoted decomposition kinetics of Li2CO3 in charging progress. Thus, the force-assisted Li - CO2 battery with the unique piezoelectric cathode can adjust the output and input energy by ultrasonic wave, and provides an ultra-low charging platform of 3.52 V, and exhibits excellent cycle stability (a charging platform of 3.42 V after 100 h cycles). The investigation of the force-assisted process described herein provides significant insights to solve overpotential in the Li - CO2 batteries system.

9.
J Am Chem Soc ; 145(44): 24116-24125, 2023 Nov 08.
Article En | MEDLINE | ID: mdl-37783464

All-solid-state batteries with a high energy density and safety are desirable candidates for next-generation energy storage applications. However, conventional solid electrolytes for all-solid-state batteries encounter limitations such as poor ionic conduction, interfacial compatibility, instability, and high cost. Herein, taking advantage of the ingenious capability of zeolite to incorporate functional guests in its void space, we present an innovative ionic activation strategy based on the "guest wrench" mechanism, by introducing a pair of cation and anion of LiTFSI-based guest species (GS) into the supercage of the LiX zeolite, to fabricate a zeolite membrane (ZM)-based solid electrolyte (GS-ZM) with high Li ionic conduction and interfacial compatibility. The restriction of zeolite frameworks toward the framework-associated Li ions is significantly reduced through the dynamic coordination of Li ions with the "oxygen wrench" of TFSI- at room temperature as shown by experiments and Car-Parrinello molecular dynamics simulations. Consequently, the GS-ZM shows an ∼100% increase in ionic conductivity compared with ZM and an outstanding Li+ transference number of 0.97. Remarkably, leveraging the superior ionic conduction of GS-ZM with the favorable interface structure between GS-ZM and electrodes, the assembled all-solid-state Li-ion and Li-air batteries based on GS-ZM exhibit the best-level electrochemical performance much superior to batteries based on liquid electrolytes: a capacity retention of 99.3% after 800 cycles at 1 C for all-solid-state Li-ion batteries and a cycle life of 909 cycles at 500 mA g-1 for all-solid-state Li-air batteries. The mechanistic discovery of a "guest wrench" in zeolite will significantly enhance the adaptability of zeolite-based electrolytes in a variety of all-solid-state energy storage systems with high performance, high safety, and low cost.

10.
Angew Chem Int Ed Engl ; 62(44): e202311739, 2023 Oct 26.
Article En | MEDLINE | ID: mdl-37723129

Rechargeable lithium-oxygen (Li-O2 ) batteries with high theoretical energy density are considered as promising candidates for portable electronic devices and electric vehicles, whereas their commercial application is hindered due to poor cyclic stability caused by the sluggish kinetics and cathode passivation. Herein, the intrinsic stress originated from the growth and decomposition of the discharge product (lithium peroxide, Li2 O2 ) is employed as a microscopic pressure resource to induce the built-in electric field, further improving the reaction kinetics and interfacial Lithium ion (Li+ ) transport during cycling. Piezopotential caused by the intrinsic stress-strain of solid Li2 O2 is capable of providing the driving force for the separation and transport of carriers, enhancing the Li+ transfer, and thus improving the redox reaction kinetics of Li-O2 batteries. Combined with a variety of in situ characterizations, the catalytic mechanism of barium titanate (BTO), a typical piezoelectric material, was systematically investigated, and the effect of stress-strain transformation on the electrochemical reaction kinetics and Li+ interface transport for the Li-O2 batteries is clearly established. The findings provide deep insight into the surface coupling strategy between intrinsic stress and electric fields to regulate the electrochemical reaction kinetics behavior and enhance the interfacial Li+ transport for battery system.

11.
Angew Chem Int Ed Engl ; 62(37): e202308837, 2023 Sep 11.
Article En | MEDLINE | ID: mdl-37477109

Solid-state electrolytes (SSEs) with high ionic conductivity and superior stability are considered to be a key technology for the safe operation of solid-state lithium batteries. However, current SSEs are incapable of meeting the requirements for practical solid-state lithium batteries. Here we report a general strategy for achieving high-performance SSEs by engineering polymers of intrinsic microporosity (PIMs). Taking advantage of the interconnected ion pathways generated from the ionizable groups, high ionic conductivity (1.06×10-3  S cm-1 at 25 °C) is achieved for the PIMs-based SSEs. The mechanically strong (50.0 MPa) and non-flammable SSEs combine the two superiorities of outstanding Li+ conductivity and electrochemical stability, which can restrain the dendrite growth and prevent Li symmetric batteries from short-circuiting even after more than 2200 h cycling. Benefiting from the rational design of SSEs, PIMs-based SSEs Li-metal batteries can achieve good cycling performance and superior feasibility in a series of withstand abuse tests including bending, cutting, and penetration. Moreover, the PIMs-based SSEs endow high specific capacity (11307 mAh g-1 ) and long-term discharge/charge stability (247 cycles) for solid-state Li-O2 batteries. The PIMs-based SSEs present a powerful strategy for enabling safe operation of high-energy solid-state batteries.

12.
J Am Chem Soc ; 145(10): 5718-5729, 2023 Mar 15.
Article En | MEDLINE | ID: mdl-36880105

The demand for high-energy sustainable rechargeable batteries has motivated the development of lithium-oxygen (Li-O2) batteries. However, the inherent safety issues of liquid electrolytes and the sluggish reaction kinetics of existing cathodes remain fundamental challenges. Herein, we demonstrate a promising photo-assisted solid-state Li-O2 battery based on metal-organic framework-derived mixed ionic/electronic conductors, which simultaneously serve as the solid-state electrolytes (SSEs) and the cathode. The mixed conductors could effectively harvest ultraviolet-visible light to generate numerous photoelectrons and holes, which is favorable to participate in the electrochemical reaction, contributing to greatly improved reaction kinetics. According to the study on conduction behavior, we discover that the mixed conductors as SSEs possess outstanding Li+ conductivity (1.52 × 10-4 S cm-1 at 25 °C) and superior chemical/electrochemical stability (especially toward H2O, O2-, etc.). Application of mixed ionic electronic conductors in photo-assisted solid-state Li-O2 batteries further reveals that a high energy efficiency (94.2%) and a long life (320 cycles) can be achieved with a simultaneous design of SSEs and cathodes. The achievements present the widespread universality in accelerating the development of safe and high-performance solid-state batteries.

13.
ACS Appl Mater Interfaces ; 14(47): 52907-52917, 2022 Nov 30.
Article En | MEDLINE | ID: mdl-36378151

The design of highly efficient electrocatalysts is a promising strategy to improve the electrochemical kinetics of Li-CO2 batteries. However, electrocatalysts usually aim to reduce the energetic barrier for the corresponding electrochemical reactions; little attention has been given to modulating the kinetics that directly determine the local concentration of reaction molecules surrounding catalysts. Herein, we present a systematic study on the role of Li+ reunion on the improvement of reaction kinetics in Li-CO2 batteries with a Cu cone cathode. Specifically, this local, geometry-driven tip effect can enrich the local electron concentration to facilitate Li+ ions diffusion from the bulk electrolyte to the surface of catalyst, leading to boosted catalytic performance. Further studies demonstrate that Cu(II/I) as a solid redox mediator dominates the reversible bulk redox reactions in a Cu cone cathode, which acts as an electron-hole transfer agent and permits the efficient reduction and oxidation of solid Li2CO3, contributing to an accessible theoretical discharge voltage, low charge potential below 3.2 V, impressive rate capability, and a long cycling stability (333 days) for Li-CO2 batteries. The exploitation of the sharp-tip enhancement effect and dynamic creation of catalytic active sites is expected to become routine practice in future mechanistic studies for metal-air batteries.

14.
ACS Nano ; 16(8): 12364-12376, 2022 Aug 23.
Article En | MEDLINE | ID: mdl-35914235

At present, photoassisted Li-air batteries are considered to be an effective approach to overcome the sluggish reaction kinetics of the Li-air batteries. And, the organic liquid electrolyte is generally adopted by the current conventional photoassisted Li-air batteries. However, the superior catalytic activity of photoassisted cathode would in turn fasten the degradation of the organic liquid electrolyte, leading to limited battery cycling life. Herein, we tame the above limitation of the traditional liquid electrolyte system for Li-CO2 batteries by constructing a photoassisted all-solid-state Li-CO2 battery with an integrated bilayer Au@TiO2/Li1.5Al0.5Ge1.5(PO4)3 (LAGP)/LAGP (ATLL) framework, which can essentially improve battery stability. Taking advantage of photoelectric and photothermal effects, the Au@TiO2/LAGP layer enables the acceleration of the slow kinetics of the carbon dioxide reduction reaction and evolution reaction processes. The LAGP layer could resolve the problem of liquid electrolyte decomposition under illumination. The integrated double-layer LAGP framework endows the direct transportation of heat and Li+ in the entire system. The photoassisted all-solid-state Li-CO2 battery achieves an ultralow polarization of 0.25 V with illumination, as well as a high round-trip efficiency of 92.4%. Even at an extremely low temperature of -73 °C, the battery can still deliver a small polarization of 0.6 V by converting solar energy into heat to achieve self-heating. This study is not limited to the Li-air batteries but can also be applied to other battery systems, constituting a significant step toward the practical application of all-solid-state photoassisted Li-air batteries.

15.
Adv Mater ; 34(10): e2107826, 2022 Mar.
Article En | MEDLINE | ID: mdl-35266208

Photoassisted electrochemical reaction is regarded as an effective approach to reduce the overpotential of lithium-oxygen (Li-O2 ) batteries. However, the achievement of both broadband absorption and long term battery cycling stability are still a formidable challenge. Herein, an oxygen vacancy-mediated fast kinetics for a photoassisted Li-O2 system is developed with a silver/bismuth molybdate (Ag/Bi2 MoO6 ) hybrid cathode. The cathode can offer both double advantages for light absorption covering UV to visible region and excellent electrochemical activity for O2 . Upon discharging, the photoexcited electrons from Ag nanoplate based on the localized surface plasmon resonance (LSPR) are injected into the oxygen vacancy in Bi2 MoO6 . The fast oxygen reaction kinetics generate the amorphous Li2 O2 , and the discharge plateau is improved to 3.05 V. Upon charging, the photoexcited holes are capable to decompose amorphous Li2 O2 promptly, yielding a very low charge plateau of 3.25 V. A first cycle round-trip efficiency is 93.8% and retention of 70% over 500 h, which is the longest cycle life ever reported in photoassisted Li-O2 batteries. This work offers a general and reliable strategy for boosting the electrochemical kinetics by tailoring the crystalline of Li2 O2 with wide-band light.

16.
Adv Mater ; 34(2): e2104792, 2022 Jan.
Article En | MEDLINE | ID: mdl-35023599

The photoassisted lithium-oxygen (Li-O2 ) system has emerged as an important direction for future development by effectively reducing the large overpotential in Li-O2 batteries. However, the advancement is greatly hindered by the rapidly recombined photoexcited electrons and holes upon the discharging and charging processes. Herein, a breakthrough is made in overcoming these challenges by developing a new magnetic and optical field multi-assisted Li-O2 battery with 3D porous NiO nanosheets on the Ni foam (NiO/FNi) as a photoelectrode. Under illumination, the photogenerated electrons and holes of the NiO/FNi photoelectrode play a key role in reducing the overpotential during discharging and charging, respectively. By introducing the external magnetic field, the Lorentz force acts oppositely on the photogenerated electrons and holes, thereby suppressing the recombination of charge carriers. The magnetic and optical field multi-assisted Li-O2 battery achieves an ultralow charge potential of 2.73 V, a high energy efficiency of 96.7%, and good cycling stability. This external magnetic and optical field multi-assisted technology paves a new way of developing high-performance Li-O2 batteries and other energy storage systems.

17.
J Am Chem Soc ; 143(35): 14253-14260, 2021 Sep 08.
Article En | MEDLINE | ID: mdl-34459185

Metal halide perovskite quantum dots, with high light-absorption coefficients and tunable electronic properties, have been widely studied as optoelectronic materials, but their applications in photocatalysis are hindered by their insufficient stability because of the oxidation and agglomeration under light, heat, and atmospheric conditions. To address this challenge, herein, we encapsulated CsPbBr3 nanocrystals into a stable iron-based metal-organic framework (MOF) with mesoporous cages (∼5.5 and 4.2 nm) via a sequential deposition route to obtain a perovskite-MOF composite material, CsPbBr3@PCN-333(Fe), in which CsPbBr3 nanocrystals were stabilized from aggregation or leaching by the confinement effect of MOF cages. The monodispersed CsPbBr3 nanocrystals (4-5 nm) within the MOF lattice were directly observed by transmission electron microscopy and corresponding mapping analysis and further confirmed by powder X-ray diffraction, infrared spectroscopy, and N2 adsorption characterizations. Density functional theory calculations further suggested a significant interfacial charge transfer from CsPbBr3 quantum dots to PCN-333(Fe), which is ideal for photocatalysis. The CsPbBr3@PCN-333(Fe) composite exhibited excellent and stable oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) catalytic activities in aprotic systems. Furthermore, CsPbBr3@PCN-333(Fe) composite worked as the synergistic photocathode in the photoassisted Li-O2 battery, where CsPbBr3 and PCN-333(Fe) acted as optical antennas and ORR/OER catalytic sites, respectively. The CsPbBr3@PCN-333(Fe) photocathode showed lower overpotential and better cycling stability compared to CsPbBr3 nanocrystals or PCN-333(Fe), highlighting the synergy between CsPbBr3 and PCN-333(Fe) in the composite.

18.
Small ; 17(26): e2100642, 2021 Jul.
Article En | MEDLINE | ID: mdl-34081392

Directly converting and storing abundant solar energy in next-generation energy storage devices is of central importance to build a sustainable society. Herein, a new prototype of a light-promoted rechargeable and flexible Li-CO2 battery with a TiO2 /carbon cloth (CC) cathode is reported for the direct utilization of solar energy to promote the kinetics of the carbon dioxide reduction reaction and carbon dioxide evolution reaction (CO2 ER). Under illumination, photoelectrons are generated in the conduction band of TiO2 /CC, followed by the enhancing diffusion of electrons and lithium ions during the discharge process. The photoelectrons on the cathode surface can regulate the morphology of the discharge product Li2 CO3 , contributing to boosting the kinetics of the subsequent CO2 ER process. In the reverse charge process, photogenerated holes can favor the decomposition of Li2 CO3 , leading to a negative charge potential of 2.88 V without increased polarization over ≈60 h of cycling. Owing to an ultralow overpotential of 0.06 V between the discharge and charge process, an ultrahigh energy efficiency of 97.9% is attained under illumination. The introduction of a light-promoted flexible Li-CO2 battery can pave the way toward developing the use of solar energy to address the charging overpotential of conventional Li-CO2 batteries.

19.
ACS Appl Mater Interfaces ; 13(22): 26123-26133, 2021 Jun 09.
Article En | MEDLINE | ID: mdl-34056904

Although the lithium-oxygen (Li-O2) battery brings hope for the improvement of high-energy rechargeable batteries, the sluggish oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) kinetics become the major stumbling block. Herein, the incorporation of a plasmonic silver cathode as an advanced strategy to promote ORR and OER kinetics due to strong local surface plasmon resonance (LSPR) is introduced. Chronoamperometry results revealed that the highly energetic electrons and holes excited by LSPR of silver nanostructure facilitated ORR and OER kinetics ascribe to the emission of hot carriers in femtosecond time scale. Furthermore, a relatively rare discharge voltage 3.1 V is obtained, correspondingly, the charge plateau also decline to 3.3 V, the energy efficiency of Li-O2 battery by a 23% increase in comparison with a commercial 5% Pt/C catalyst (discharge and charge plateau of 2.75 and 3.61 V). Additionally, the improvement in the efficient charge transfer manner result in a reversible spherical Li2O2 which further improve the ORR and OER kinetics. The LSPR strategy represents a critical step toward developing fast kinetics and high energy efficiency Li-O2 batteries.

20.
Nat Commun ; 11(1): 2191, 2020 May 04.
Article En | MEDLINE | ID: mdl-32366827

Lithium-oxygen batteries with ultrahigh energy density have received considerable attention as of the future energy storage technologies. The development of effective electrocatalysts and a corresponding working mechanism during cycling are critically important for lithium-oxygen batteries. Here, a single cobalt atom electrocatalyst is synthesized for lithium-oxygen batteries by a polymer encapsulation strategy. The isolated moieties of single atom catalysts can effectively regulate the distribution of active sites to form micrometre-sized flower-like lithium peroxide and promote the decomposition of lithium peroxide by a one-electron pathway. The battery with single cobalt atoms can operate with high round-trip efficiency (86.2%) and long-term stability (218 days), which is superior to a commercial 5 wt% platinum/carbon catalyst. We reveal that the synergy between a single atom and the support endows the catalyst with excellent stability and durability. The promising results provide insights into the design of highly efficient catalysts for lithium-oxygen batteries and greatly expand the scope of future investigation.

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