Potassium Dual-Ion Hybrid Batteries with Ultrahigh Rate Performance

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Potassium Dual-Ion Hybrid Battery with Ultrahigh Rate Performance and Excellent Cycling Stability Xuan Ding, Fan Zhang, Bifa Ji, Yi Liu, Jinrui Li, Chun-Sing Lee, and Yongbing Tang ACS Appl. Mater. Interfaces, Just Accepted Manuscript • DOI: 10.1021/acsami.8b15193 • Publication Date (Web): 19 Nov 2018 Downloaded from http://pubs.acs.org on November 20, 2018

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ACS Applied Materials & Interfaces

Potassium Ultrahigh

Dual-Ion

Hybrid

Battery

Rate Performance and

with

Excellent

Cycling Stability Xuan Ding,†, ‡,# Fan Zhang,†,# Bifa Ji,† Yi Liu, † Jinrui Li,† Chun-Sing Lee,*, § and Yongbing Tang*,†

† Functional Thin Films Research Center, Shenzhen Institutes of Advanced Technology, Chinese Academy of Sciences, Shenzhen, 518055, China. ‡ Nano Science and Technology Institute, University of Science and Technology of China, Suzhou, 215123, China § Center of Super-Diamond and Advanced Film (COSDAF), City University of Hong Kong, Hong Kong SAR, 999077, China.

ACS Paragon Plus Environment

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KEYWORDS: dual-ion hybrid battery, potassium-ion electrolyte, hierarchical porous carbon, capacitive anode, graphite cathode

ABSTRACT: Potassium-ion battery (KIB) is regarded as a potential alternative battery technology to conventional lithium-ion battery owing to low potential, natural abundance, and low cost of potassium. However, sluggish reaction kinetic of the much larger K+ ions leads to low rate capability and poor cycling performance of KIBs, restricting KIB’s practical applications. Herein, we propose a novel full battery called potassium dual-ion hybrid battery (KDHB) by employing an absorption-type hierarchical porous carbon as anode material and an anion-intercalation-type expanded graphite as cathode material. Owing to the hybrid mechanism of battery and capacitive reaction, the KDHB exhibits superior rate performance with a high capacity of 82 mAh g-1 even at a high current density of 3 A g-1 with negligible capacity decay. Moreover, the KDHB exhibits excellent cycling performance with 74.2% capacity retention after 2000 cycles at 1 A g-1, which is so far the best performance of the reported KDIBs.

INTRODUCTION Lithium-ion battery (LIB) is one of the most important electrical energy storage devices, owing to its long cycling life and high energy density.1-6 However, with the increasing demand of LIBs for portable electronic devices and electric vehicles, large consumption of lithium is rapidly draining the Earth’s limited lithium reserves. This causes serious concern for the


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sustainable future of LIB and calls for alternatives based on low-cost and naturally abundant cations such as sodium-ion batteries (NIBs),7-13 potassium-ion batteries (KIBs)14-18 and aluminum-ion batteries (AIBs).19-23 Among these battery systems, KIBs are promising candidates owing to the low potential of K/K+ (-2.92 V vs. SHE) comparing to many other systems and its low cost and Earth abundance. While extensive recent efforts have been devoted to developing high performance of KIBs,18, 24-25 its commercial variability is still severely limited by their poor cycling stability and low rate performance, which are both rooted from the much large ionic size of potassium compared to lithium. Meanwhile, another novel battery system called “dual-ion battery” (DIB) has attracted much attention owing to the merits of high working voltage, low cost, and good environmental friendliness.26,27 The working mechanism of DIBs is far different from the conventional LIBs, which typically involve in intercalation/deintercalation of both cations and anions into/from the anode and the cathode respectively during charging/discharging process.28,29 Combining the advantages of DIBs and KIBs, potassium-based dual ion batteries (KDIBs) have been recently designed by several groups. 30-35 Generally, the KDIB consists of graphite as cathode material, intercalation-type graphite or alloy-type Sn as anode material, and KPF6-containing carbonate as electrolyte. During charging process, the PF6- intercalates into the graphite cathode, while the K+ simultaneously reacts with the anode (through either intercalation or alloying process). For instance, recently Lu and co-workers developed a KDIB using graphite as both anode and cathode with 0.8 M KPF6 in carbonate as electrolyte, which delivered a reversible capacity of 53 mAh g-1 after 60 cycles at 0.1 A g-1.32 Simultaneously, Placke et al. also reported a similar dualgraphite KDIB system using K+ containing ionic liquid-based electrolyte, which achieved capacity of 42 mAh g-1 at 0.25 A g-1 with improved cycling stability.31 Nevertheless, neither the


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intercalation-type graphite nor alloy-type Sn anode can enable fast K+ reaction kinetics, which also causes exfoliation of the graphite during intercalation or large volume expansion of Sn during the alloying reaction, thus resulting in unsatisfied rate capability and unstable cycling performance of these KDIBs. To address these issues, we develop a novel potassium dual-ion hybrid battery (KDHB) configuration by employing absorption-type hierarchical porous carbon (named as HPC) as anode material for the first time, while anion-intercalation-type expanded graphite (EG) as cathode material and 1 M KPF6 in carbonate organic solvent as the electrolyte. As we all know, it is important to find a sustainable way to provide power required by our modern social demand.36 We, therefore, choose a biomass material as the precursor for preparing the present HPC with merits of sustainability, environmental-friendliness as well as low cost. Tofu aerogel is employed as the biomass precursor owing to its intrinsic macroporous structure, which is beneficial for homogeneous impregnation of KOH during activation to form hierarchical meso-/micropores as well as high surface area. Besides, the consistent of N in tofu can also contribute to N-doping in the HPC, which is beneficial to improving the electrical conductivity. Benefiting from the high specific surface area and hierarchical porous structure of the HPC anode which can enable fast and large absorption/desorption of K+, the designed HPC-EG KDHB exhibits ultrahigh rate performance up to 3 A g-1 with reversible charge/discharge and negligible capacity decay. Moreover, the KDHB achieves excellent cycling


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performance which delivers a capacity of 63 mAh g-1 after 2000 cycles at 1 A g-1 with 74.2% capacity retention, so far the best performance of the reported KDIBs.30-35

RESULTS AND DISCUSSION

Figure 1. (a) Schematic diagrams showing configuration and mechanism of the designed KDHB battery by using EG as cathode and HPC as anode. (b) An SEM image of HPC-4. (c,d) TEM images of HPC-4 at different magnifications.

The configuration of the novel KDHB battery is schematically shown in Figure 1a. The HPC and expanded graphite (EG) are used as anode and cathode respectively with an electrolyte of 1


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M KPF6 in carbonate solvent mixture (ethylene carbonate: dimethyl carbonate: ethyl methyl carbonate = 4:3:2 v/v/v). Upon charging, the K+ ions move to the HPC anode and are adsorbed in the micro/mesopores of the HPC. At the same time, PF6- anions move to the graphite cathode and intercalate into the graphite layers to form Cx(PF6).26,27, 37 Upon discharging, the K+ ions desorb from the HPC and move back into the electrolyte. Meanwhile, the PF6- anions deintercalate from the graphite layers and move back into the electrolyte. The HPC materials with different specific surface areas were prepared by using biomass as precursor via a combined carbonization and activation method (see Supporting Information), which were named as HPC-1, HPC-2, HPC-3, HPC-4, and HPC-5 according to the KOH/carbide ratio. Figure 1b presents scanning electron microscope (SEM) images of the HPC-4, showing abundant pores. Its microstructure was investigated with transmission electron microscopy (TEM) shown in Figure 1c, d, which show an amorphous and porous structure with curved graphitic walls.


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Figure 2. (a) N2 adsorption-desorption isotherms and (b) pore size distribution of HPC-1, HPC-2, HPC-3, HPC-4, HPC-5 and commercial activated carbon YP50. (c) Galvanostatic chargedischarge curves of HPC-based capacitor at a current density of 0.5 A g-1 over the voltage range of 0-2.7 V. (d) Charge-discharge capacities under different current densities of HPC-4 based symmetric capacitor. N2 adsorption measurements further confirm the porous structure of the HPCs. Figure 2a shows nitrogen adsorption-desorption isotherms of HPC-1, HPC-2, HPC-3, HPC-4, HPC-5, and a commercial active carbon (YP50 from Kuraray). When the weight ratio of KOH is small, HPC1, HPC-2 show type I characteristic adsorption-desorption isotherms, similar to that of YP50, indicating mainly microporous structures. However, HPC-3, HPC-4 and HPC-5 prepared with higher KOH ratio show type IV isotherms with H2 hysteresis loops, revealing mesoporous structures.38,39 Brunauer-Emmett-Teller (BET) specific surface areas of HPC-1, HPC-2, HPC-3, HPC-4, HPC-5, and YP50 were measured to be 1551, 2048, 2675, 3319, 2940, and 1953 m2 g-1 respectively (Figure S1). Pore size distribution curves shown in Figure 1b further confirm the existence of hierarchical micro/mesopores of HPC-3, HPC-4, and HPC-5 with bimodal pore size distribution over 1-2 and 2-5 nm, while HPC-1 and HPC-2 mainly consist of micropores below 2 nm similar to YP50. Moreover, X-ray diffraction (XRD) patterns (Figure S2) of HPC-3, HPC-4, and HPC-5 show much weaker and broader d(002) peaks than those of HPC-1, HPC-2 and YP50, indicating more disturbed structures of HPC-3, HPC-4, and HPC-5 due to the more randomly oriented aromatic carbon sheets in the amorphous carbon materials,40,41 which is in accordance with the surface area result (Figure S1). Raman spectra of the HPC samples (Figure S3) clearly show characteristic peaks at 1340 and 1591 cm-1 representing


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the D band and the G band which is corresponding to the defect and disordered structures and the graphite in-plane vibrations respectively.38,42,43 The ID/IG values of the HPCs are all above 1.0, indicating low degree of graphitization which is consistent with the XRD results. HPC-4 has the highest ID/IG value, indicating its most disordered structure. Besides, all the HPC materials contain around 2.7-3.2 wt% of nitrogen by X-ray energy dispersive (EDX) analysis (Table S1), and the nitrogen is distributed homogeneously in the material (Figure S4), which is originated from the large amount of nitrogen in the biomass precursor. The doping of N in the HPC is beneficial to improving the electrical conductivity (28.6 S m-1 of HPC-4 vs. 11.9 S m-1 of YP50).44-46 The above results indicate that HPC-4 with both the highest surface area and amorphous hierarchical micro/mesoporous structure which are expected to give good capacitive performance. For testing the capacitive properties of the HPC, symmetric supercapacitors based on various HPC electrodes in KPF6-based organic electrolyte were assembled. Figure 2c shows galvanostatic charge-discharge curves over the voltage window of 0-2.7 V at a current density of 0.5 A g-1, indicating typical electronic double layer capacitor (EDLC) capacitive behavior for their nearly straight lines. Based on the charge-discharge curves, the HPC-4 is found to exhibit the highest specific capacitance of 168 F g-1 (corresponding to specific capacity of 63 mAh g-1) among all the HPC materials as expected (Figure S5a,b). Besides, all the cyclic voltammetry (CV) curves of different HPCs show nearly ideal EDLC-type rectangular shapes (Figure S5c), and the curve of HPC-4 shows the largest area, also revealing the highest specific capacitance. Moreover, HPC-4 also shows excellent rate performance with stable capacities of 165, 167.3, 161.9, and 161.8 F g-1 at the current densities of 0.5, 1, 2, and 3 A g-1 respectively (Figure 2d).


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In addition, electrochemical performance of EG/K half cell and HPC-4/K half cell were also investigated (Figure S6, S7). It can be seen from Figure S6 that the discharge capacity of the EG/K half cell is ~ 78, 73, 70, 68, and 66 mAh g-1 at 0.5, 1.0, 1.5, 2.0, and 2.5 A g-1 respectively in 3.0-5.0 V, which also keeps stable at 0.5 A g-1 for over 500 cycles. Meanwhile. the HPC-4 electrode in the HPC-4/K half cell,also shows good rate and cycling performance (Figure S7), with capacity of ~ 83, 79, 64, 60, and 57 mAh g-1 at 0.5, 1.0, 1.5, 2.0, and 2.5 A g-1 respectively in 1.0-3.0 V, which also keeps stable for over 500 cycles at 0.5 A g-1. By employing HPC-4 with excellent capacitive performance as the anode material, and an anion-intercalation-type expanded graphite as cathode material, we prepared a KDHB with 1 M KPF6 in carbonate electrolyte. Figure 3a shows galvanostatic charge-discharge curves of the KDHB at 0.5 A g-1 with no obvious voltage plateaus, which reflects a combination of the intercalation/deintercalation mechanism (Figure S8) and adsorption/desorption mechanism (Figure 2c). According to the CV curves (Figure 3b), the charge curve can be divided into three regions that corresponding to the different stages of PF6- intercalation into graphite which occurred at 2.50-2.79 V (stage I), 2.79-3.20 V (stage II), 3.20-3.80 V (stage III). In the discharge curve, the PF6- deintercalation from graphite result in another three stages of 3.80-3.02 V (stage III’), 3.02-2.47 V (stage II’), 2.47-1.99 V (stage I’). In addition, the KDHB operates over a voltage window of 1.0-3.8 V, enabling a single coin cell to light up one LED in blue color (around 3.0-3.5 V) (inset of Figure 3a).


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Figure 3. (a) Typical galvanostatic charge-discharge curves of the KDHB based on HPC-4 anode at 0.5 A g-1. Inset is a KDHB coin cell which can light up one blue LED. (b) CV curves of the KDHB at a scan rate of 10 mV s-1. (c) Charge-discharge voltage profiles of the KDHB at 0.5 A g-1. (d,e) XRD profiles (d) and Raman spectra (e) of the EG cathode in the KDHB at different charging/discharging states during the initial cycle. (f) SEM images of a HPC-4 anode at the initial state and (g) a corresponding EDX mapping of K element. (h) SEM images of HPC-4 at fully charged state and (i) a corresponding EDX mapping of K element. (j) XPS of K2p spectra of a fresh HPC-4 anode and a fully charged anode.


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Further characterizations on the electrodes were carried out for exploration of the working mechanism of the KDHB. Ex-situ XRD was utilized to investigate the process of the PF6intercalation/deintercalation into/from the EG layers. On the basis of the charge-discharge curves of the KDHB shown in Figure 3c, we chose 10 different charging-discharging voltage states for investigation. In Figure 3d, the initial EG cathode shows a sharp (002) characteristic peak at 26.5° (2θ degree). When charged to 3.0 V, the peak shifts to a lower angle and also splits into two broad peaks. When fully charged to 3.8 V, the new peak at 25° becomes sharper and the original peak at 26.5° becomes weaker, revealing the gradual intercalation of PF6- into the EG layers to form Cx(PF6) compound. During discharging process, the peak at 25° becomes weaker and the intensity of the 002 peak increases, implying the gradual deintercalation of PF6- from the EG layers.28,47,48 When discharged to 1.0 V, the two peaks merge into a broad peak at ~26˚, which is slightly shifted from the initial 002 peak, implying a minor irreversibility of the deintercalation process.27, 33, 49-51 Ex-situ Raman spectra of the EG cathode are shown in Figure 3e. During charging, the G band peak splits into two peaks which are known as the E2g2(i) mode and the E2g2(b) mode. When it is charged to 3.8 V, the E2g2(i) peak and the E2g2(b) peak shift to 1585 and 1605 cm-1 respectively. Meanwhile, the intensity of the D band peak gradually increases, indicating the EG structure is more disordered due to the intercalation of PF6- (Figure S9). During discharging process, the E2g2(i) and E2g2(b) peaks merge into one peak, while the intensity of the D peak gradually decreases. Changes in the Raman spectra matches well with the XRD results, demonstrating the reversibility of the intercalation/deintercalation of PF6-.19, 52 For investigating the HPC anode, energy dispersive X-ray spectroscopy (EDX) mapping was conducted. Figure 3(f-i) show SEM images and K-mapping images of the initial and fully charged HPC anode. The K element signal can be obviously observed at the fully charged state


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(Figure 3i) with a significant increase in K content (from ~0 at% to ~5 at%), indicating adsorption of K+ in the HPC anode. Moreover, X-ray photoelectron spectroscopy (XPS) data (Figure 3j) clearly show the K 2p3/2 and 2p1/2 peaks at 293.1 and 295.9 eV respectively in the fully-charged state, also revealing the K+ adsorption in the HPC anode.

Figure 4. Electrochemical performance of the KDHB based on a HPC-4 anode and 1 M KPF6 in EC/DMC/EMC (4:3:2 v/v/v). a) Charge/discharge curves of the KDHB at various current rates of 0.5, 1.0, 1.5, 2.0, 2.5, 3.0 A g-1. b) Corresponding charge/discharge capacities and Coulombic


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efficiencies of the KDHB at different current rates. c) Long-term cycling performance of the KDHB for 2000 cycles at 1 A g-1. d) Charge/discharge curves of the KDHB at various current rates of 1 A g-1 after 200, 500, 1000, 1500, and 2000 cycles. e) Nyquist plots of the KDHBs at steady state by using a HPC-4 anode and a MCMB anode respectively.

Electrochemical performance of the KDHB is shown in Figure 4. Figure 4a shows chargedischarge curves of the KDHB at current density of 0.5, 1.0, 1.5, 2.0, 2.5, and 3.0 A g-1 respectively, which nearly overlap with each other indicating low electrochemical polarization. Figure 4b shows that the capacities at different current rates are almost the same with 82 mAh g1

(based on the mass of cathode material), demonstrating excellent rate performance of the

KDHB. Moreover, the KDHB exhibits long term cycling performance at 1 A g-1 (Figure 4c). After 2000 cycles, the KDHB keeps a capacity of 63 mAh g-1 with a capacity retention of 74.2% and only 0.013% capacity loss per cycle. In addition, neither the EG cathode (Figure S10a,b) nor the HPC-4 anode (Figure S10c,d) show obvious morphological changes after 2000 cycles, implying good structural stability of the materials. Figure 4d also shows that the charge/discharge curves after 300, 500, 1000, 1500 and 2000 cycles maintain stable with mild capacity loss. To our best knowledge, the present high rate capability and long cycling performance of our KDHB are the best of the reported KDIBs (Table S2).30-35 Electrochemical impedance spectroscopy (EIS) was further conducted, and Figure 4e shows Nyquist plots of the KDHBs using HPC-4 and mesocarbon microbead (MCMB) as anode material respectively at steady state. Each plot consists of one depressed semicircle and a sloping line in the high-andmiddle frequency region and low-frequency region, respectively, which correspond to charge transfer resistance (Rct) and Warburg impedance, respectively.53,54 It can be observed the Rct


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value of the EG-HPC-4 DIB system is far smaller than that of the EG-MCMB DIB system, which indicates faster electrochemical kinetics of the KDHB based on the HPC-4 anode with hierarchical porous structure and large specific surface area due to the physical absorption/desorption mechanism. In addition, we roughly estimated the energy density and power density of the KDHB based on the mass of total electrodes (calculation details is shown in Supporting Information). The KDHB delivers a gravimetric energy density of 117 Wh kg-1 at a power density of 1300 W kg-1, and a volumetric energy density of 70 Wh L-1 at a power density of 778 W L-1. As the KDHB has a combined mechanism of intercalation and absorption, the energy density/power density values are between those of batteries and supercapacitors.55 However, the superior rate performance, long cycling stability as well as low cost of the KDHB make it promising for large energy storage applications.

CONCLUSIONS In summary, we have constructed a low-cost and high-performance KDHB based on absorption-type hierarchical porous carbon anode for the first time. Owing to its hierarchical porous structure and high specific surface area of 3319 m2 g-1, the HPC exhibits fast and stable K+ absorption/desorption kinetics, thus contributing to superior rate capability and long cycling performance of the KDHB. The battery delivers 82 mAh g-1 at high current rate of 3 A g-1 over a voltage window of 1.0-3.8 V with negligible capacity decay, and the capacity also remains at 74.2% with only 0.013% capacity loss per cycle after 2000 cycles at 1 A g-1, which are the best values of reported KDIBs. Therefore, owing to the merits of environmental friendliness, low cost, good safety, and ultrahigh rate performance and excellent cycling stability, this KDHB shows a promising potential as next-generation renewable energy storage devices.


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ASSOCIATED CONTENT

Supporting Information

The Supporting Information is available free of charge on the ACS Publications website at

DOI: Experimental methods, structural and electrochemical data, and supporting tables

(PDF)

AUTHOR INFORMATION

Corresponding Author *E-mail: [email protected] *E-mail: [email protected] Author Contributions # X. Ding and F. Zhang contributed equally to this work.

Notes


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The authors declare no competing financial interest.

ACKNOWLEDGMENTS The authors gratefully acknowledge financial support from the National Natural Science Foundation of China (Grant Nos. 51822210, 51602337 and 51702350), Shenzhen Peacock Plan (KQJSCX20170331161244761 and KQTD2016112915051055), Natural Science Foundation of Guangdong Province (Grant No. 2017A030310482), Shenzhen Science and Technology Planning

Project

JCYJ20170818160918762,

(JSGG20170413153302942, JCYJ20170818153427106,

JCYJ20170307171232348, JCYJ20170818153404696

and

JCYJ20170818153339619), and Scientific Project of Chinese Academy of Sciences (KFJ-STSSCYD-124). REFERENCES

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Potassium Dual-Ion Hybrid Batteries with Ultrahigh Rate Performance

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