CuS and Cu<sub>2</sub>S as Cathode Materials for Lithium Batteries: A Review

Jiang, Kyle; Chen, Zonghai; Meng, Xiangbo

doi:10.1002/celc.201900066

Cited by 72 publications

(34 citation statements)

References 78 publications

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“…[ 20 ] Note that ICE values also can depend on the exact cycling protocol, [ 26 ] however, results for the studies mentioned here were all obtained with galvanostatic measurements. The voltage profile is similar to the previously reported works of CuS in liquid electrolyte [ 24c,27 ] . The two distinct discharge plateaus appear at 2.1 and 1.7 V suggesting that the electrochemical reaction pathway proceeds in two steps; where, the high voltage (2.1 V) plateau is linked to the formation of Cu 2 S with various stoichiometries (Equation 3) and the low voltage (1.7 V) plateau is associated with the displacement reaction to form copper and Li 2 S (Equation 4).…”

Section: Resultssupporting

confidence: 89%

Macroscopic Displacement Reaction of Copper Sulfide in Lithium Solid‐State Batteries

Santhosha

Nazer

Koerver

et al. 2020

Advanced Energy Materials

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Next to polymer electrolytes, [2] inorganic Li-ion SEs have been developed in recent years. [3] Thiophosphates, garnets, or argyrodites are the most promising inorganic materials classes, each having particular advantages and disadvantages. Despite the considerable improvement in Li + conductivity (some structures exhibit a higher conductivity than liquid electrolytes) the limited electrochemical stability window of SEs often leads to side reactions with low potential negative and high potential positive materials. [4] For this reason, in research studies the lithium negative electrode is often replaced by an In-Li alloy as this alloy provides a more stable interface with many SEs and prevents dendrite formation. [5] The use of Li as negative electrode in SSBs, however, remains an important goal as this is one of the few options to significantly increase the specific energy (Wh kg −1) and energy density (Wh L −1) of the cell. Considering positive electrode materials, the large family of layered oxides is mostly studied as their overall superior behavior is well-known from LIBs. However, also conversion-type materials such as TiS 2 , [6] CoS, [7] FeS 2 , [8] MoS 2 , [9] and NiS [10] are studied due to their much higher specific capacity. An important aspect of SSBs is the preparation of dense cathode composite structures containing SE, active material and, where needed, additives. Close contact between the phases and a suitable 3D structure is required to minimize the Copper sulfide (CuS) is an attractive electrode material for batteries, thanks to its intrinsic mixed conductivity, ductility and high theoretical specific capacity of 560 mAh g −1. Here, CuS is studied as cathode material in lithium solid-state batteries with an areal loading of 8.9 mg cm −2 that theoretically corresponds to 4.9 mAh cm −2. The configuration of the cell is LiLi 3 PS 4 [CuS (70 wt%) + Li 3 PS 4 (30 wt%)]. No conductive additive is used. CuS undergoes a displacement reaction with lithium, leading to macroscopic phase separation between the discharge products Cu and Li 2 S. In particular, Cu forms a network of micrometer-sized, well-crystallized particles that seems to percolate through the electrode. The formed copper is visible to the naked eye. The initial specific discharge capacity at 0.1 C is 498 mAh g(CuS) −1 , i.e., 84% of its theoretical value. The initial Coulomb efficiency (ICE) reaches 95%, which is higher compared to standard carbonate-based liquid electrolytes for the same cell chemistry (≈70%). After 100 cycles, the specific capacity reaches 310 mAh g(CuS) −1. With the current composition, the cell provides 58.2 Wh kg −1 at a power density of 7 W kg −1 , which is superior compared to other transition metal sulfide cathodes.

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Section: Resultssupporting

confidence: 89%

Macroscopic Displacement Reaction of Copper Sulfide in Lithium Solid‐State Batteries

Santhosha

Nazer

Koerver

et al. 2020

Advanced Energy Materials

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“…96 S. However, after the fifth cycle, both charge and discharge show single plateaus at 1.75 and 1.85 V with about 250 mAh g −1 , respectively. This implies that the richer the sulfur content in the composition of Cu x S, the more its electrochemical properties get closer to the behavior of the covellite CuS electrode (Jianga et al, 2019). Cycling performance of both Cu 1 .…”

Section: Resultsmentioning

confidence: 85%

Facile Synthesis of Binder-Free Three-Dimensional CuxS Nanoflowers for Lithium Batteries

et al. 2020

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Copper sulfides (Cu x S) with different stoichiometry are considered as prospective cathode materials for lithium batteries owing to their large energy storage capability. In this work, three-dimensional Cu x S cathodes were synthesized via introducing commercially available copper foam into the solution of dimethyl sulfoxide (DMSO) and sulfur powder. The synthesis procedures were straightforward and ultrafast and did not require additional reagents, high temperature, or long processing time and can be considered as a facile one-step method. Copper sulfide materials with different stoichiometry (x = 1.8, 1.96) were obtained by changing the temperature and the residence time of the copper foam in the DMSO solution. The effects of the temperature and time on phase and morphology of Cu x S were characterized by X-ray diffraction and scanning electron microscopy coupled with energy dispersive X-ray spectroscopy. Electrochemical tests resulted in a stable cyclability of Cu 1. 8 S cathode with 100% Coulombic efficiency and capacity of approximately 250 mAh g −1 .

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“…Unlike the CV curves of the nano‐C–CPO electrode showing well‐maintained CV profiles for several cycles, the CV curve of pristine Cu 2 P 2 O 7 are drastically decayed after initial cycling, which indicates the poor electrochemical performances of pristine Cu 2 P 2 O 7 . In particular, the average operation voltage of the nano‐C–CPO was verified to be ≈2.8 V (vs Li + /Li), which is much higher than that of other conversion‐based electrodes for LIBs, and this result agreed well with the first‐principles calculation. Furthermore, even at 5C, the specific capacity of the nano‐C–CPO was ≈228 mAh g −1 , corresponding to ≈64% of its theoretical capacity.…”

Section: Resultsmentioning

confidence: 97%

Development of Novel Cathode with Large Lithium Storage Mechanism Based on Pyrophosphate‐Based Conversion Reaction for Rechargeable Lithium Batteries

Lee

Park

et al. 2020

Small Methods

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A conversion‐reaction‐based nanosized Cu2P2O7–carbon composite is investigated as a novel cathode material with superior capacity for lithium‐ion batteries. To overcome the sluggish kinetics of the conversion reaction, the nanosized Cu2P2O7–carbon composite is prepared by high‐energy ball‐milling of Cu2P2O7 and conductive carbon to achieve simultaneous nanosizing and carbon mixing. The nanosized Cu2P2O7–carbon composite exhibits a large specific capacity of ≈355 mAh g−1 with an average operation voltage of ≈2.8 V (vs Li+/Li). Moreover, even at 10C (1C = 355 mA g−1), the composite delivers a capacity of ≈215 mAh g−1, corresponding to ≈60% of its theoretical capacity. For 400 cycles at 1C, the nanosized Cu2P2O7–carbon composite exhibits capacity retention of ≈72% compared with the initial capacity as well as high Coulombic efficiency of more than 99%. The reversible conversion reaction mechanism of the nanosized Cu2P2O7–carbon composite under the Li‐cell system is confirmed using various techniques, including operando/ex situ X‐ray diffraction, X‐ray absorption near edge structure spectroscopy, extended X‐ray absorption fine structure spectroscopy, and transmission electron microscopy. It is verified that Cu2P2O7 is converted into Li4P2O7 and metallic Cu0 on discharge and reversibly recovered to Cu2P2O7 on charge.

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CuS and Cu₂S as Cathode Materials for Lithium Batteries: A Review

Cited by 72 publications

References 78 publications

Macroscopic Displacement Reaction of Copper Sulfide in Lithium Solid‐State Batteries

Macroscopic Displacement Reaction of Copper Sulfide in Lithium Solid‐State Batteries

Facile Synthesis of Binder-Free Three-Dimensional CuxS Nanoflowers for Lithium Batteries

Development of Novel Cathode with Large Lithium Storage Mechanism Based on Pyrophosphate‐Based Conversion Reaction for Rechargeable Lithium Batteries

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CuS and Cu2S as Cathode Materials for Lithium Batteries: A Review

Cited by 72 publications

References 78 publications

Macroscopic Displacement Reaction of Copper Sulfide in Lithium Solid‐State Batteries

Macroscopic Displacement Reaction of Copper Sulfide in Lithium Solid‐State Batteries

Facile Synthesis of Binder-Free Three-Dimensional CuxS Nanoflowers for Lithium Batteries

Development of Novel Cathode with Large Lithium Storage Mechanism Based on Pyrophosphate‐Based Conversion Reaction for Rechargeable Lithium Batteries

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CuS and Cu₂S as Cathode Materials for Lithium Batteries: A Review