High-Energy All-Solid-State Organic–Lithium Batteries Based on Ceramic Electrolytes

Abstract

Recent studies have identified unique properties of organic battery electrode materials such as moderate redox potentials and mechanical softness which are uniquely beneficial for all-solid-state batteries based on ceramic electrolytes. Here, we further explore the promise of organic materials and demonstrate a sulfide electrolytebased organic-lithium battery with a specific energy of 828 Wh kg −1 , rivaling the state-ofthe-art of all-solid-state batteries. Two innovation steps are responsible for the accomplishment. First, the combination of lithium anode and the high-capacity cathode material pyrene-4,5,9,10-tetraone ensures a high theoretical specific energy. Second, the microstructure of the organic cathode is optimized with the introduction of cryomilling, a technique common to processing soft materials but not familiar to electrode fabrication. The cathode material utilization increases to 99.5% as a result, up from the 55−89% previously reported for ceramic electrolyte-based solid-state organic batteries. The improvement highlights the special requirements of solid-state organic electrodes for microstructural engineering while preserving the chemical integrity of components.

Room‐Temperature All‐Solid‐State Lithium–Organic Batteries Based on Sulfide Electrolytes and Organodisulfide Cathodes

“…The lower one (397.9 eV) could be assigned to NLi (or >N − ···Li + ) form, where the electron density on N atoms increased due to partial reduction of PTTCA by LPS. [ 21 ] In the S2p spectrum (Figure S3a, Supporting Information), the relative intensities of CS and PSP increased after ball milling, which might be the clues of the formation of Li 3 TTCA [ 20 ] and P 2 S 7 4−[ 8b,22 ] as the reduction product of PTTCA and the oxidation product of LPS, respectively. The binding energy of N group shifted toward higher value (Δ E b = 400.1 eV − 398.8 eV = 1.3 eV), again verified the Li + ···N coordination because Li + lowered the electron density on N atoms.…”

“…Meanwhile, in the S2p spectra, the proportions of peaks at 161.3 and 162.1 eV (ascribed to the 2p 3/2 peaks of PS···Li/CS···Li and PS/CS forms, respectively) both increased while the peak at 162.9 eV (ascribed to the 2p 3/2 peak of PSP) decreased, agreeing with the formation of thiol‐like Li 3 TTCA and the reduction of interphase constituents between PTTCA and LPS (from P 2 S 7 4− to PS 4 3− ). [ 8b ] The N1s and S2p spectra varied in an inverse way during the subsequent charge process, however, resulting in less N but more PS···Li/CS···Li structures compared to the pristine state. It implied that partial Li 3 TTCA produced in the 1st discharge was unable to revert to PTTCA, possibly due to its poor electronic conductivity [ 30 ] or strong coordination interaction between Li 3 TTCA and LPS.…”

“…Among all kinds of solid electrolytes, sulfide electrolyte is the most appropriate choice to construct room‐temperature ASSLBs because of the highest ionic conductivity (>10 −3 S cm −1 ) and good processability. [ 6 ] In very recent years, a few OEMs including carbonyl‐type COF‐TRO [ 7 ] and PTO, [ 8 ] and azo‐type PBALS [ 9 ] have been tried as cathode for ASSLBs based on sulfide electrolytes. Unfortunately, carbonyl‐type ones cannot release their capacity until at a high temperature like 60 °C, [ 7,8 ] while PBALS can only deliver a low reversible capacity of 128 mAh g −1 at room temperature.…”

“…[ 6 ] In very recent years, a few OEMs including carbonyl‐type COF‐TRO [ 7 ] and PTO, [ 8 ] and azo‐type PBALS [ 9 ] have been tried as cathode for ASSLBs based on sulfide electrolytes. Unfortunately, carbonyl‐type ones cannot release their capacity until at a high temperature like 60 °C, [ 7,8 ] while PBALS can only deliver a low reversible capacity of 128 mAh g −1 at room temperature. [ 9 ] For carbonyl‐type cathode materials that attract most attentions in the field of OEMs, their poor performance at room temperature can be well explained by the hard and soft acids and bases (HSAB) theory.…”

Enhanced electrochemical performance of LiFePO4 of cathode materials for lithium-ion batteries synthesized by surfactant-assisted solvothermal method

“…However, the application of LIB in new energy vehicles has put forward higher requirements for the performance of lithium-ion batteries, which has stimulated a higher wave of research on different electrode materials and cell technologies [3,4]. In recent years, the energy storage field is actively optimizing electrode materials and electrolyte/electrode composite interfaces to improve battery performance [5][6][7][8]. The close combination of solid electrolyte and electrode material and single ion gel polymer electrolyte crosslinked in situ has been reported successively [9,10].…”