Dual Insurance Design Achieves Long-Life Cycling of Li-Metal

Jun 28, 2019 - Here, a dual insurance system is reported to avoid short-circuit occurrence and cycling performance decline through a two-step procedur...
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Article Cite This: ACS Appl. Energy Mater. 2019, 2, 5292−5299

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Dual Insurance Design Achieves Long-Life Cycling of Li-Metal Batteries under a Wide Temperature Range Wei Fan,†,‡,§,⊥ Xiuling Zhang,†,‡,§,⊥ and Congju Li*,†,‡ †

School of Energy and Environmental Engineering, University of Science and Technology Beijing, Beijing 100083, China Beijing Key Laboratory of Resource-Oriented Treatment of Industrial Pollutants, Beijing 100083, China § University of Chinese Academy of Sciences, Beijing 100049, P. R. China ‡

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S Supporting Information *

ABSTRACT: Li-metal batteries show great potential in energy storage devices but still suffer a lot from dendrite growth, which restricts its long-time application due to safety and cycling concerns. Here, a dual insurance system is reported to avoid short-circuit occurrence and cycling performance decline through a two-step procedure. An Al2O3/PVDF-HFP layer is sandwiched into the in situ polymerized PMMA coat. The PMMA is so hard that the dendrites are not easy to impale; moreover, the electrospun Al2O3/PVDF-HFP layer could react with plunged lithium dendrites and inhibit the short circuit from occurring. Not only does the obtained composite polymer electrolyte (CPE) ensure desirable ionic conductivity (3.43 × 10−4 S cm−1 at 25 °C), wide electrochemical window, and considerable cycling stability but also dendrite inhibition and cycling stability are improved. The assembled full cell could cycle steadily under a wide temperature range and current density with desirable performance, when compared with abnormal cycling of liquid electrolyte under elevated temperatures. This work combines two methods to ensure the safety of Li-metal batteries, which enlightens a new thought for safe electrolyte design. KEYWORDS: polymer electrolyte, lithiation, dual insurance, electrospinning, wide temperature range

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INTRODUCTION

Traditional solid electrolytes suffer a lot from low ionic conductivity (polymer electrolyte) or fragile properties (inorganic solid electrolyte), which could hardly accommodate the desirable electrochemical performances and volume expansion during charging/discharging processes.26−28 Recently, a lot of methods have been applied to design functional polymer electrolytes and composite electrodes by electronic and ionic design to improve the safety performance of batteries.29−36 Xie et al. discussed a way to control dendrite growth direction, further inhibiting short circuit from occurring.7 Xu et al. investigated the electrolyte additive in enhancing battery performance.20 Lee and Zhang’s groups pay a lot of attention to the Janus membrane to inhibit dendrite growth and performance improvement.37−39 Cui and coworkers explored a sandwich structure to investigate the lithiation reaction.40 Goodenough et al. discussed Al2O3 nanoparticles in enhancing battery performance.41−43 Al2O3 nanoparticles are normally applied as coating materials and further improve anode material performance. Although these methods work on dendrite inhibition and performance improvement to some degree, safety issues still exist during long time cycling. Aiming to effectively inhibit dendrite growth

Flexible electrochemical and energy storage devices which combine safety with high energy density are highly rated in the forthcoming smart energy era.1−3 Lithium-metal batteries have attracted great attention due to their high theoretical energy density and low anode potential.4,5 Although such advantages have made it an appropriate energy storage candidate for use, the safety concerns and performance decline induced by lithium dendrite formation pose severe dangers in practical application.6−9 Conventional liquid electrolyte could hardly inhibit the dendrite formation, mainly because Li metal is thermodynamically unstable in carbonate ester solvent.10,11 The repeated processes of lithium plating and stripping during charging and discharging processes could easily induce volumetric expansion, which would further produce solid electrolyte interphase (SEI) cracks and lithium dendrite growth.12−14 The formed lithium dendrites not only have great hidden dangers such as separator impaling and safety concerns but also cause liquid electrolyte consumption and fresh lithium exposure, which cause undesirable properties during long time cycling.15,16 The electrolyte additive is a feasible way, but it cannot totally inhibit the dendrite growth.17−20 Hence, researchers turn to solid electrolyte or gel electrolyte for help, which contains limited solvent, while it possesses a certain modulus, aiming to successfully restrain the dendrite formation during long-cycle cycling.10,21−25 © 2019 American Chemical Society

Received: May 28, 2019 Accepted: June 28, 2019 Published: June 28, 2019 5292

DOI: 10.1021/acsaem.9b01032 ACS Appl. Energy Mater. 2019, 2, 5292−5299

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ACS Applied Energy Materials

Figure 1. (a) Fabrication process of the CPE membrane. SEM images of (b) cellulose membrane, (c) Al2O3/PVDF-HFP layer, (d) PMMA coat, and (e) cross section of the CPE membrane. (f) EDS of the Al element of the CPE membrane. (g) TGA of the CPE membrane. Material Analysis. The morphologies of CPE and lithium metal foil were observed by a SEM (SU8020) at 5 kV 10 μA. Thermogravimetric analysis (TGA) was tested under a flow of nitrogen at the rate of 10 °C min−1, from room temperature to 500 °C. Energy-dispersive X-ray spectroscopy (EDS) was applied to analyze different elements of CPE by SU 8020. Electrochemical Analysis. The galvanostatic charging−discharging of battery cells was carried out by the commercial battery testing system (LAND CT2001A). The voltage range of charge/discharge was 2.0−4.0 V. AC impedances (from 100 kHz to 0.01 Hz) of the batteries were performed by an electrochemical workstation (CHI660E). The electrochemical stability of CPE was tested by linear sweep voltammetry (LSV) and cyclic voltammetry (CV) performed with an SS|CPE|Li coin cell at a scan rate of 1 mV s−1. The CV test of Al2O3|CPE|Li is at the rate of 0.1 mV S−1. The ionic conductivity of the CPE was calculated by the following equation

and avoid short circuiting further prolong the cycling life of batteries. Herein, a composite polymer electrolyte is designed through a two-step process, which is decorated with an Al2O3/PVDFHFP layer on a conventional cellulose membrane and is coated by in situ polymerized PMMA on both sides. First, dendrites could hardly form in a gel electrolyte system because of limited solvent. Moreover, the PMMA layer is rigid enough that dendrites are difficult to penetrate. Importantly, even though dendrites impale into the outer layer, the Al2O3/PVDF-HFP layer could definitely consume the Li dendrites and avoid further growth. Such a designed complex structure could guarantee the mechanical and electrochemical performances on one hand and could also avoid short circuit and safety concerns on the other hand.

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σ = d /RS

EXPERIMENTAL METHODS

where d is the thickness of CPE; R is the interfacial resistance; and S is the area of electrolyte. For the LFP|Li test, LiFePO4, super-P, and poly(vinylidene fluoride) (PVDF) are dissolved in N-methyl-2-pyrrolidone at the weight ratio of 80:10:10. Then the slurry was cast onto an aluminum foil. The cast film was dried in a vacuum oven at 120 °C for 720 min. The Al2O3 cathode is prepared in the same way. The coin cells are assembled in an Ar-filled glovebox with the concentrations of moisture and oxygen below 0.01 ppm.

Preparation of the Al2O3/PVDF-HFP Layer. Amounts of 2.0 g of polyacrylonitrile (PVDF-HFP) and 1.0 g of Al2O3 particles were dissolved in 15 mL (N,N-dimethylformamide (DMF):acetone = 1:1) of solution, with magnetic stirring for over 12 h to ensure the solution became homogeneous. The equipment used for the electrospinning process is a commercial electrospinning machine (TL-Pro). The operating voltage was 20 kV, and the advanced rate was kept at a rate of 0.6 mL h−1 in the electrospinning process, with electrospinning on the commercial cellulose membrane for 30 min. Preparation of the PMMA Coat. Amounts of 5 mL of MMA (methyl methacrylate) and 0.01 g of AIBN (azodiisobutyronitrile) were added together and heated at 90 °C for about 30 min for prepolymerization until it became viscous. Then, it was poured onto the previously prepared membrane to form a coat of the system. Then, it was heated at 60 °C for 1 h, followed by vacuum drying under 60 °C for 12 h and preparing for use. After that, it was immersed into the LiTFSI/PC solvent as a polymer electrolyte.

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RESULTS AND DISCUSSION As shown in Figure 1a, the CPE membrane is produced through a two-step process. First, a Al2O3/PVDF-HFP layer is electrospun uniformly onto a cellulose membrane. Afterward, prepolymerized PMMA is poured onto the prepared membrane to get in situ polymerized and act as an outer 5293

DOI: 10.1021/acsaem.9b01032 ACS Appl. Energy Mater. 2019, 2, 5292−5299

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ACS Applied Energy Materials

Figure 2. (a) LSV of liquid electrolyte. (b) LSV of CPE. (c) CV of liquid electrolyte and CPE under high voltage range. (d) Li|CPE|Li under 1 mA cm−2 and 1 mAh cm−2. (e) Li|CPE|Li under 0.5 mA cm−2 and 1 mAh cm−2.

flexible enough for bending and twisting (Figures S3 and S4). In order to ensure the application in evaluated temperature, the thermogravimetric analysis (TGA) is applied to test. It could be observed in Figure 1g that there are two weight loss stages in the image, which demonstrate PMMA and cellulose in the system relatively. Additionally, the major weight loss happened up to 350 °C, which guarantees the possibility to be applied in an elevated temperature environment. The PMMA layer in the system evaluates the thermal stability and hardness of the membrane, while the cellulose membrane ensures the flexibility. The combination of flexibility and high modulus is highly rated in the repeated charging/discharging process of the cell. The sandwiched Al2O3/PVDF-HFP layer uniformly covers one side of cellulose, which participates in safety enhancement and extending the cycle life of Li-metal batteries. Electrochemical stability is essentially important in battery cycling in the long run, avoiding the side reactions that occur

coat of the system. The SEM images in Figure 1b−d vividly reveal the morphology of the membrane during various processes. As depicted in Figure 1c, the apparent Al2O3 nanoparticles and PVDF-HFP nanofibers could be seen after the electrospinning process. Then, a homogeneous surface (Figure 1d) is obtained after the in situ polymerization reaction, which further exhibits that the PMMA covers the membrane as a coat of the system. The cross section in Figure 1e and the inset image could also verify the result, showing the membrane is prepared layer by layer. The thickness of cellulose is 90 μm, and after the electrospinning process, the thickness of the Al2O3/PVDF-HFP layer is 25 μm; the thickness of the PMMA layer is 55 μm; and the total thickness of CPE is 170 μm (Figure S1). The Al and other elements mapping in Figure 1f and Figure S2 reveal that the Al2O3/PVDF-HFP layer is sandwiched into the membrane. The fully prepared composite membrane is 5294

DOI: 10.1021/acsaem.9b01032 ACS Appl. Energy Mater. 2019, 2, 5292−5299

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ACS Applied Energy Materials

Figure 3. (a) Voltage profile of the Al2O3 nanoparticle electrodes. (b) CV of the Al2O3|Li cell. (c) The mechanistic explanation of dendrite inhibition and short-circuit avoidance of liquid electrolyte and our designed CPE.

between the interface of electrolyte and electrodes and performance decline. The linear sweep voltammetry (LSV) and cyclic voltammetry (CV) are definitely adopted in order to evaluate the stability of electrolytes with the Li|StSt (stainless steel) cell. As can be vividly observed in Figure 2a,b, compared with liquid electrolyte (LiTFSI dissolved in PC), CPE is quite stable up to 5.1 V, which enables CPE to be applied in wider voltage range and thus in more situations. There are two main reasons corresponding to this question. For one thing, for the electrochemical window, it represents the electrochemical stability of batteries. The reason why CPE is more stable than

liquid electrolyte is because there is less liquid solution and less side reactions that occur during the elevation of voltage. For another, the bonding effects of lithium salt together with polymer improved decomposition voltage a lot and achieved a wider electrochemical window. Additionally, the CV is performed at the range of −0.5 to 4.5 V to illustrate the oxidation and reduction of batteries (Figure 2c). It could be seen that compared with CPE liquid electrolyte reveals its relatively distinct current response and instability under higher voltage. Hence, the LSV and CV both demonstrate that our designed CPE shows wider electrochemical window range and 5295

DOI: 10.1021/acsaem.9b01032 ACS Appl. Energy Mater. 2019, 2, 5292−5299

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Figure 4. SEM characterization of the cycled Li anodes. SEM images of top view (a−c) and cross section (d−f) and for the Li anodes after 20 cycles in LiTFSI/PC liquid electrolyte separately, CPE, and CPE cycled for 50 cycles, respectively.

when it is compared with our designed CPE, two major advantages could be summarized as shown in the right section of Figure 3c (the white region means no liquid electrolyte exists in this system). First, the coated PMMA is so hard that the dendrites could hardly form and impale. Moreover, even if the dendrite is formed and impales the coated PMMA, the plunged dendrites could be lithiatedly reacted by Al2O3 particles, further avoiding the short-circuit occurrence (white region). Thus, not only could the produced CPE greatly reduce the possibility of dendrite formation but also the short circuit of the cell could be effectively avoided, further improving the safety performance and cycling property of the battery in practical applications, and this method enlightens a new way for electrolyte production and safer battery design. In order to investigate the stability of the Li metal anode, SEM is applied to characterize the morphologies of Li metal anode under different cycle numbers and different occasions. It could be vividly seen from Figure 4a that the morphology of the Li metal surface is full of Li dendrites after cycling for 20 cycles by using liquid electrolyte. Additionally, the corrosion of Li metal is so serious that the corrosion layer reaches up to almost 100 μm, which poses an inevitable danger of separator impaling and performance decline (Figure 4d). In contrast, the cell with CPE cycling under the same occasion seems improved a lot. It seems that little dendrite appeared on the Li metal surface (Figure 4b), and the corrosion layer (Figure 4e) is also ignorable. Moreover, the cycles of the cell with CPE are prolonged to 50 cycles as revealed in Figure 4c,f. Bulky rather than sharp dendrites are formed on the Li metal surface, and the corrosion layer seems to be thinner. These endeavors and effects greatly reduce the risk of dendrite formation, and short circuit occurs. To investigate the battery performance of CPE, the LFP| CPE|Li cell is assembled for further investigation. Since desirable ionic conductivies are achieved among various temperatures, the cell is tested under different circumstances to evaluate its properties. As demonstrated in Figure S9, the cell shows satisfied discharge capacity of 134.1, 133.7, 131.2, 119.6, 108.6, and 95.7 mAh g−1 at 0.1, 0.2, 0.5, 1, 2, and 5 C over the voltage range of 2.0−4.0 V under room temperature. Moreover, the LFP|CPE|Li cell is tested at 0.5 C under room

better stability. As a vital parameter of measuring electrolyte, the ionic conductivity in Figure S6 is tested under various temperatures. It could be directly seen that CPE delivers 3.43 × 10−4 S/cm at 30 °C and 8.66 × 10−4 S/cm at 80 °C. With the elevation of temperature, higher activity and lower active energy could be achieved apparently. Similar results could also be verified by Figure S7, which investigates that the impedance of the Li|CPE|Li cell certainly declines with temperature elevation, which also verifies the lower interface impedance and higher activity under elevated temperature. Moreover, the symmetric Li|CPE|Li cell is studied to investigate the stability of CPE through evaluating the overpotential change of the plating and stripping process. It could be vividly seen in Figure 2e that the Li|CPE|Li cell is quite stable, and no voltage increment occurs under 0.5 mA cm−2 and 1 mAh cm−2 for at least 1200 h. Additionally, as shown in Figure 2d, the Li|CPE| Li also keeps steady for 400 h under higher current density (1 mA cm−2 and 1 mAh cm−2), verifying the stability of CPE, and could accommodate various current densities. In this work, we have introduced a dual-insurance system to partly inhibit dendrite growth and short circuiting. An Al2O3/ PVDF-HFP layer is sandwiched into the CPE. Al 2 O 3 nanoparticles are introduced, aiming to react with Li dendrites, while PVDF-HFP nanofibers are applied to make it as a whole. The voltage profile of the Al2O3|Li cell is illustrated in Figure 3a, and it is discharged to a voltage of 0.01 V and shows a discharge capacity of 80 mAh g−1, indicating Al2O3 could react with Li metal under this circumstance. Moreover, the cyclic voltammetry (CV) of the prepared Al2O3|Li cell in Figure 3b indicates a clear reduction peak at the potential of 0.5 V, which could be related to the plateau in the discharge voltage curve in Figure 3a. The obtained results reveal that the Al2O3 electrodes could electrochemically react with Li metal, which further lies a solid foundation for further research. As for the mechanism of dendrite inhibition and short-circuit avoidance, it could be vividly illustrated in Figure 3c. The blue region in the left part of Figure 3c means liquid electrolyte. On the condition that Li metal is electrochemically unstable in liquid electrolyte, dendrites are easily formed during the charging/discharging process. With the growth of dendrites, a conventional separator could easily be impaled and destroyed, further inducing battery performance decline and short circuiting. On the contrary, 5296

DOI: 10.1021/acsaem.9b01032 ACS Appl. Energy Mater. 2019, 2, 5292−5299

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Figure 5. Li-metal battery testing results. (a) The cycle performance of CPE-based LMB under 50 °C under 1 C. (b) The rateability test of CPEbased LMB at 50 °C from 0.1 to 10 C. (c) The charge/discharge profiles of CPE-based LMB at 50 °C from 0.1 to 10 C. (d) The typical charge/ discharge profiles of CPE-based LMB at 50 °C. (e) The typical charge/discharge profiles of CPE-based LMB at 70 °C under 2 C. (f) The cycle performance of CPE-based LMB under 70 °C. (g) The EIS plot of LiFePO4|CPE|Li under different temperature.

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CONCLUSIONS In summary, we have successfully designed a composite polymer electrolyte (CPE) in a two-step way: electrospinning and in situ polymerization. The PMMA coat is hard enough for dendrites to impale, while the electrospun Al2O3/PVDF-HFP layer could electrochemically react with pierced lithium dendrites just in case. The dual insurance design not only extends the cycling life of Li-metal batteries but also excellent electrochemical properties are ensured. The ionic conductivity of prepared CPE achieves 3.43 × 10−4 S cm−1 at 25 °C; the electrochemical window reaches up to 5.1 V; and the symmetric Li|CPE|Li stripping/plating occurs for over 1200 h under 0.5 mA cm−2 without overpotential increment. The desirable electrochemical properties and dendrite growth restraint contribute to LPFP|CPE|Li cycling for 500 cycles under 50 °C with 95.52% capacity retention. Thus, the CPE enlightens a novel and creative way for electrolyte design and battery cycling life extension.

temperature, with 72.5% capacity retention after cycling for 350 cycles (Figure S10). Furthermore, considering that the CPE reveals excellent thermal stability, the LFP|CPE|Li cell is tested under elevated temperature of 50 and 70 °C to illustrate its properties. It is shown in Figure 5b that the LFP|CPE|Li cell delivers discharge capacity of 162.5, 149.8, 139.3, 131, 123.2, 109.5, and 89.7 mAh g−1 at 0.1, 0.2, 0.5, 1, 2, 5, and 10 C under 50 °C, and the charging/discharging profiles are demonstrated in Figure 5c. What’s more, it also reveals excellent long life cycling property as depicted in Figure 5a, which shows 116 mAh g−1 discharge capacity in the first cycle and keeps 95.52% capacity retention after cycling for 500 cycles at 1 C. In contrast, LFP|LiTFSI/PC|Li is quite abnormal and is accompanied by side reactions under higher temperature (Figure S12). The charging/discharging profiles under this occasion of CPE are illustrated in Figure 5d, and the decreased polarization effect with the increase of temperature indicates an enhancement of power. Furthermore, the performance of the LFP|CPE|Li cell under 70 °C is also illustrated to verify the stable property and variation tendency. The LFP|CPE|Li cell reveals a 128.5 mAh g−1 discharge capacity in the first cycle and keeps 84.28% capacity retention after 300 cycles at 2 C (Figure 5e). The specific charging/discharging profiles are supplemented in Figure 5f. Elevated temperatures increase the activity of the cell, which could be manifested by the impedance change (Figure 5g) and decreased polarization effect of the cell charging/discharging profiles.

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ASSOCIATED CONTENT

S Supporting Information *

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acsaem.9b01032. Brief statement in nonsentence format listing the contents of the material (PDF) 5297

DOI: 10.1021/acsaem.9b01032 ACS Appl. Energy Mater. 2019, 2, 5292−5299

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ACS Applied Energy Materials

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AUTHOR INFORMATION

Corresponding Author

*E-mail: [email protected]. ORCID

Congju Li: 0000-0001-6030-7002 Author Contributions ⊥

W.F. and X.Z. contributed equally to this work.

Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS This work is supported by the National Natural Science Foundation of China (NSFC Nos. 51503005 and 21274006), the Programs for Beijing Science and Technology Leading Talent (Grant no. Z161100004916168), the Fundamental Research Funds for the Central Universities (No. 06500100), and the “Ten thousand plan” National High-level personnel of special support program, China.

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DOI: 10.1021/acsaem.9b01032 ACS Appl. Energy Mater. 2019, 2, 5292−5299

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DOI: 10.1021/acsaem.9b01032 ACS Appl. Energy Mater. 2019, 2, 5292−5299