Low‐Temperature Charge/Discharge of Rechargeable Battery Realized by Intercalation Pseudocapacitive Behavior

Abstract

Conventional intercalation compounds for lithium‐ion batteries (LIBs) suffer from rapid capacity fading and are even unable to charge–discharge with temperature decline, owing to the sluggish kinetics and solvation/desolvation process. In this work, a high‐performance rechargeable battery at ultralow temperature is developed by employing a nanosized Ni‐based Prussian blue (NiHCF) cathode. The battery delivers a high capacity retention of 89% (low temperature of −50 °C) and 82% (ultralow temperature of −70 °C) compared with that at +25 °C. Various characterizations and electrochemical investigations, including operando Fourier transform infrared spectra, in situ X‐ray diffraction, cyclic voltammetry response, and galvanostatic intermittent titration technique are carried out to detect the structural stability and electrochemical behavior at different temperatures. It turns out that the pseudocapacitive behavior drives the desolvation process at the interface, while fast diffusion in the bulk electrode accelerates the movement of Li + from the interface to the bulk materials. The unique synergistic features of intercalation pseudocapacitance at the electrolyte/electrode interface and high diffusion coefficient in the bulk electrode enables the NiHCF cathode with excellent low temperature performance. These findings offer a new direction for the design of LIBs operated at low temperature.

Prussian Blue Cathode with Intercalation Pseudocapacitive Behavior for Low‐Temperature Batteries

“…Co as example. Guided with the aforementioned analysis, we demonstrated the feasibility of such structural features at low temperature with NiFe-PBA cathode, turning out to exhibit high diffusion coefficient of 10 À10 cm 2 s À1 at the temperature of À70 C. [10] The order of magnitude is comparable with those of conventional intercalation compounds, which helped realize excellent performance at low temperature. However, the capacity of 72 mAh g À1 was not high enough due to the one-electron redox center (Fe 2þ /Fe 3þ ) in the lattice.…”

“…[3][4][5][6][7][8][9] Ions' movement became kinetically slow with the decline of temperature, which even hindered the electrochemical process at low temperature. [10] It is therefore needed to explore feasible materials with high diffusion coefficient so as to improve the ions' movement in the bulk electrodes, especially at low temperature. Prussian blue and its analogues (PBAs, Na x M[Fe(CN) 6 ] y • □ 1-y •zH 2 O, M represents transition metal cations such as Ni, Cu, Fe, Mn, Co, etc.)…”

“…are known as a large family of hexacyanoferrates with open framework structure. [10] A general cubic lattice of PBA locates M 2þ coordinated to N atoms (MN 6 octahedra) of CN ligands and Fe 2þ to C atoms (FeC 6 octahedra), forming a rigid 3D framework. [11,12] The large ionic channels and interstices in the lattice allow reversible insertion reactions for large cations, including Na þ , K þ , Zn 2þ , and so on.…”

A durable P2-type layered oxide cathode with superior low-temperature performance for sodium-ion batteries

“…The specific capacities and rate performance can severely deteriorate when the ambient temperature falls to subzero or lower temperature [7,[9][10][11][12][13][14][15][16][17]. LT limitations can be attributed to the reduced conductivity of electrolytes, high barrier for Na + desolvation within the electrode/electrolyte inter-face, and sluggish Na transport kinetics in solid active materials [18][19][20][21][22]. Electrodes with the crystal structure of Na-super-ionic conductors, such as Prussian blue/carbon nanotube composites [23], Na 3 V 2 (PO 4 ) 3 /C [24], Na 3 V 2 (PO 4 )O 2 F [25], and Na 4 Fe 3 (PO 4 ) 2 (P 2 O 7 )/C [26], are preferred for LT applications.…”

A High‐Rate and Long‐Life Rechargeable Battery Operated at −75 oC

“…[23,24] The unique surface-controlled intercalation behavior might be beneficial to circumvent the challenge of sluggish Li + de-solvation and diffusion processes from the electrolyte to the bulk electrode, offering as a candidate substitution of conventional intercalation compounds at low temperature. [25] Researchers discovered the Li + intercalation pseudocapacitive mechanism in orthorhombic phase Nb 2 O 5 , [26][27][28] which delivers fast insertion kinetics through a pseudocapacitive reaction of Li + on the surface of the electrode in nonaqueous electrolytes accompanied by an intercalation reaction. [29,30] In view of such characterizations, Nb 2 O 5 material could be highly suitable for charge storage at low temperature, which has never been investigated up to now.…”