High-Defect-Density Graphite for Superior-Performance Aluminum-Ion Batteries with Ultra-Fast Charging and Stable Long Life

Abstract

Rechargeable aluminum-ion batteries (AIBs) are a new generation of low-cost and large-scale electrical energy storage systems. However, AIBs suffer from a lack of reliable cathode materials with insufficient intercalation sites, poor ion-conducting channels, and poor diffusion dynamics of large chloroaluminate anions (AlCl4− and Al2Cl7−). To address these issues, surface-modified graphitic carbon materials [i.e., acid-treated expanded graphite (AEG) and base-etched graphite (BEG)] are developed as novel cathode materials for ultra-fast chargeable AIBs. AEG has more turbostratically ordered structure covered with abundant micro- to nano-sized pores on the surface structure and expanded interlayer distance (d002 = 0.3371 nm) realized by surface treatment of pristine graphite with acidic media, which can be accelerated the diffusion dynamics and efficient AlCl4− ions (de)-intercalation kinetics. The AIB system employing AEG exhibits a specific capacity of 88.6 mAh g−1 (4 A g−1) and ~ 80 mAh g−1 at an ultra-high current rate of 10 A g−1 (~ 99.1% over 10,000 cycles). BEG treated with KOH solution possesses the turbostratically disordered structure with high density of defective sites and largely expanded d-spacing (d002 = 0.3384 nm) for attracting and uptaking more AlCl4− ions with relatively shorter penetration depth. Impressively, the AIB system based on the BEG cathode delivers a high specific capacity of 110 mAh g−1 (4 A g−1) and ~ 91 mAh g−1 (~ 99.9% over 10,000 cycles at 10 A g−1). Moreover, the BEG cell has high energy and power densities of 247 Wh kg−1 and 44.5 kW kg−1. This performance is one of the best among the AIB graphitic carbon materials reported for chloroaluminate anions storage performance. This finding provides great significance for the further development of rechargeable AIBs with high energy, high power density, and exceptionally long life.

Hollow Porous N and Co Dual-Doped Silicon@Carbon Nanocube Derived by ZnCo-Bimetallic Metal–Organic Framework toward Advanced Lithium-Ion Battery Anodes

“…A b -value of 0.5 indicates a diffusion-controlled process, whereas a b -value of 1 represents ideal surface-controlled capacitive behavior. The value of b can be obtained from the slope of the linear relationship between log­( i ) and log­( v ) plots according to the following equation Figure b shows the relationship between log­( i ) and log­( v ), where the linear slope represents the value of b . It can be seen that in the cathodic reaction ( b = 0.722), the charge storage process is a hybrid mechanism, which is simultaneously controlled by both diffusion and capacitive surface reactions, whereas in the anodic reaction ( b = 0.987), the surface-controlled capacitive process has the dominant characteristics, , suggesting that the charge–discharge process in the p-CoNC@Si80 electrode has predominantly surface-controlled capacitive behavior.…”

“…The value of b can be obtained from the slope of the linear relationship between log­( i ) and log­( v ) plots according to the following equation Figure b shows the relationship between log­( i ) and log­( v ), where the linear slope represents the value of b . It can be seen that in the cathodic reaction ( b = 0.722), the charge storage process is a hybrid mechanism, which is simultaneously controlled by both diffusion and capacitive surface reactions, whereas in the anodic reaction ( b = 0.987), the surface-controlled capacitive process has the dominant characteristics, , suggesting that the charge–discharge process in the p-CoNC@Si80 electrode has predominantly surface-controlled capacitive behavior. In addition, the charge contribution ratio of the surface-capacitive and diffusion controls can be calculated by dividing the response of the current at a specific potential by the following two-part equation where i (V) is the current response at a fixed potential V, v is the scan rate, k 1 v is capacitive control, and k 2 v 1/2 is diffusion control.…”

Design Strategies of High‐Performance Positive Materials for Nonaqueous Rechargeable Aluminum Batteries: From Crystal Control to Battery Configuration

“…− anions mainly occurs in carbonaceous materials, including graphite, graphene, metal organic framework (MOF) derivatives, and covalent organic framework (COF). [18][19][20][21][22][23][24][25] The reversible intercalation/deintercalation process of Al 3+ cations usually refers to some oxides, sulfides and selenides. [26][27][28][29][30][31] In recently reported research, AlCl 2…”

“…The reversible intercalation/deintercalation process of AlCl 4 − anions mainly occurs in carbonaceous materials, including graphite, graphene, metal organic framework (MOF) derivatives, and covalent organic framework (COF). [ 18–25 ] The reversible intercalation/deintercalation process of Al 3+ cations usually refers to some oxides, sulfides and selenides. [ 26–31 ] In recently reported research, AlCl 2 + cations can reversibly intercalate/deintercalate into/from organic materials, including phenanthrenequinone triangle (PQ‐Δ), poly(hexaazatrinaphthalene) (PHATN), polyimide, 2,3,5,6‐tetraphthalimido‐ p ‐benzoquinone (TPBQ).…”

Ultrahigh Energy Density and Long-Life Cyclic Stability of Surface-Treated Aluminum-Ion Supercapacitors

“…Therefore, it is necessary to develop high-performance HSCs with ultrastable cyclability that also have a simple metal electrode such as aluminum. Moreover, aluminum has a rich abundance and high energy density resulting from the three-electron redox process (i.e., the intercalation mechanism of the trivalent Al 3+ ion) caused by the oxidation of aluminum ions. − In this regard, many studies have investigated aluminum-ion batteries (AIBs) and supercapacitors using various alloy anodes based on aluminum anode modification in various electrolytes (nonaqueous and aqueous electrolytes). − For example, Wang et al demonstrated lamella-nanostructured eutectic zinc–aluminum alloys as reversible and dendrite-free anodes for aqueous zinc-ion batteries. The aqueous Zn 88 Al 12 /K x MnO 2 batteries were constructed with a eutectic Zn 88 Al 12 alloy sheet as the anode and K x MnO 2 as the cathode, achieving a specific capacity as high as ∼294 mA h g –1 and delivering a high energy density of 230 W h kg –1 while retaining 100% capacity after 200 h (5000 cycles) .…”