Understanding the Mechanism for Capacity Decay of V6O13-Based

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Cite This: ACS Appl. Mater. Interfaces 2018, 10, 29667−29674

Understanding the Mechanism for Capacity Decay of V6O13-Based Lithium-Metal Polymer Batteries Xiaoyue Shi,†,§,∥ Jian Du,†,§,∥ Timothy G. J. Jones,‡ Xilong Wang,† and Han-Pu Liang*,† †

QingDao Institute of Bioenergy and Bioprocess Technology, Chinese Academy of Sciences, QingDao 266101, China Schlumberger Cambridge Research, High Cross, Madingley Road, Cambridge CB3 0EL, U.K. § University of Chinese Academy of Sciences, Beijing 100049, China ‡

ACS Appl. Mater. Interfaces 2018.10:29667-29674. Downloaded from pubs.acs.org by KAOHSIUNG MEDICAL UNIV on 09/05/18. For personal use only.

S Supporting Information *

ABSTRACT: Capacity decay has been a well-known phenomenon in battery technology. V6O13 has been proved to be one of promising cathode materials for the lithium-metal polymer battery owing to high electrochemical capacity and electronic conductivity. However, these V6O13based cathodes suffer from characteristic capacity decline under operating conditions, and it is also difficult to achieve the theoretical capacities of V6O13. Herein, we report, for the first time, the thermal instability between the components in the cathode composites using various analytical methods, such as in situ thermal gravimetric analysis: infrared spectroscopy, scanning electron microscopy, and X-ray diffraction techniques. This thermal instability is believed to be a chemical reaction between the binding material (polyalkylene glycols) and V6O13, which enables an improved understanding of the decay in the capacity of V6O13-based cathodes and initial capacities that are significantly below the theoretical value. The identification of the reaction between cathode and binding materials may trigger the further investigation of capacity decay of other cathode materials, paving the way to the design and development of high-capacity batteries. KEYWORDS: lithium-metal polymer battery, V6O13, thermal gravimetric analysis-infrared spectroscopy, capacity decay, thermal instability g−1.25 However, the reported capacity of V6O13 cathode materials listed in Table S1,22−39 with an average measured value of approximately 320 mAh g−1, is still a major challenge since it is significantly smaller than the theoretical value. V6O13 has been reported as cathode material for Li-metal polymer batteries by West et al.40 These batteries consist of a lithium foil anode, a polymer electrolyte, and a vanadium oxide (V6O13) cathode, which have shown the capability for large battery applications and being deployed at elevated temperatures for oil and gas well logging and drilling.27,41 However, V6O13-based lithium-metal polymer batteries suffer from characteristic capacity decay during cycling at elevated temperatures.25,27,40 For example, it has been reported in our previous study that the initial discharge capacity of the V6O13 cathode could achieve a value of 351 mAh g−1, but suffered from an approximate 40% decay in this capacity upon cycling at the temperature of 125 °C.27 It is therefore of considerable importance to study the reasons for the low initial capacity of V6O13 cathodes and the subsequent marked decay in capacity.

1. INTRODUCTION Interest in lithium-metal polymer batteries has grown dramatically in recent years driven by the increasing demand for power sources for portable electronic devices and electric vehicles.1−4 This type of battery shows a greater potential to meet the growing need for high energy densities due to the inherent limitations of state-of-the-art lithium-ion battery.1,5,6 The use of polymer electrolytes could minimize the safety concerns that exist with lithium-ion batteries, such as suppression of dendrite growth,7−11 which have plagued this type of battery for years. Lithium-metal polymer batteries, which use lithium-metal anodes, offer a theoretical capacity of 3860 mAh g−1.9,12,13 However, the achieved capacity is subject to the restricted capacity of the cathode materials in the cell system.14−17 Vanadium oxides have been widely investigated as cathode materials due to their low cost, ease of synthesis, and high theoretical capacities.17−21 The vanadium oxide V6O13 is less toxic than V2O5, has long been known to exhibit a high capacity and its use in cathodes continues to attract attention.22−39 Theoretically, V6O13 can electrochemically incorporate up to eight lithium ions in each formula unit with all of the vanadium ions being reduced to an oxidation state of +3, which would enable the capacity to reach 417 mAh © 2018 American Chemical Society

Received: June 26, 2018 Accepted: August 9, 2018 Published: August 9, 2018 29667

DOI: 10.1021/acsami.8b10629 ACS Appl. Mater. Interfaces 2018, 10, 29667−29674

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ACS Applied Materials & Interfaces

Figure 1. Typical (a) scanning electron microscopy (SEM) image, (b) energy dispersive X-ray spectroscopy (EDS) spectrum, and (c) element overlay image of V6O13-based cathode composites.

cathode composite. The energy-dispersive X-ray spectroscopy (EDS) spectrum shown in Figure 1b confirms the presence of the elements of C, O, S, F, and V, which are derived from V6O13, carbon, lithium imide, and the polymer binder. Figure 1c is an element overlay image of the area shown in Figure 1a collected through an EDS mapping technique. The SEM image, EDS spectrum, and element mapping image give a reasonably accurate description of the structure of the cathode and the distribution of elements within it. The V6O13-based cathode composites were removed from the current collectors and further evaluated by an in situ TGAIR technique. In the present experiments, cathode composites were heated to target temperatures of 125, 150, and 180 °C and held at these temperatures for 30 min. TGA profiles run at the target temperatures are shown in Figure S1, in which the weight losses are 0.37, 1.06, and 2.68%. It is evident from the TGA profiles in Figure S1 that the weight loss of the V6O13based cathode composites increases with temperature. To understand what happens to the cathode composites at elevated temperatures based on weight losses alone, the online infrared spectrometer in the TGA-IR technique was used to identify the components in the exhaust gas from the TGA process. The three-dimensional (3D) image of the in situ IR spectra of exhaust gas from a V6O13-based cathode composite is shown in Figure 2a for a target temperature of 180 °C and a hold time of 30 min. The image clearly shows the evolution of the components as function of time and whose absorption bands can be assigned to C−H stretching, the symmetric and asymmetric stretching modes of OCO in CO2, the O−H

The decay in the capacitance of batteries with cathodes based on V6O13 after charging/discharging cycles has been well known for many years, and several mechanisms have been proposed. West et al. attributed the decay in capacity to the loss of contact between particles in the electrode, particularly at high lithium contents,40 whereas Macklin et al. proposed that the loss of capacity of V6O13 was due to a crystalline transition on cycling.25 An early study by Hua proposed that the loss of capacity was due to the irreversible intercalation of lithium ions into V6O13 during the initial stages of charge/ discharge cycling;42 over a range of charge/discharge rates, the residual lithium content was determined to be four ions per V6O13, i.e., 50% of the theoretical capacity. Barker et al. proposed that the decline in capacity over extended cell cycling was due to the loss of electrical contact between particles in composite cathodes and not structural changes in V6O13.43 In the present article, various analytical techniques have been deployed to characterize V6O13-based cathode composites. A reaction within V6O13-based cathode composites is identified with both thermogravimetric analysis-infrared spectroscopy (TGA-IR) and X-ray diffraction (XRD) techniques, which may provide a new explanation for the well-known capacity decline of such cathodes.

2. RESULTS AND DISCUSSION Cathode composites were fabricated by mixing jet-milled V6O13 fine particles with carbon powder, lithium imide, and polymer binder to form a paste that was coated onto nickel foil current collectors. Figure 1a shows a typical scanning electron microscopy (SEM) image of the surface of V6O13-based 29668


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The spectra also show the presence of carbonyl (CO) stretching bands at approximately 1793 and 1758 cm−1. There are small peaks at 2970, 2864, and 1127 cm−1 in the individual spectrum of the exhaust gas at 150 °C (red), whereas these bands are pronounced from the individual spectrum at 180 °C (green). The absorptions bands at 2968, 2862, 1455, 1369, 1258, 1131, and 884 cm−1 correspond to the spectrum of the cyclic ether 1,4-dioxane. It should be noted that the spectrum at 180 °C is identified as 1,4-dioxane by the Nicolet library of spectra. The comparison of TGA-IR spectrum of gas phase from V6O13-based cathode composites (red) and 1,4-dioxane (blue) is shown in Figure S2. The presence of dioxane in the thermal breakdown products of poly(ethylene oxide) has been reported by Voorhees et al.44 for the pyrolysis of the polymer under nitrogen gas at 450 °C and by Finocchio et al.45 for the pyrolysis of polymer− montmorillonite clay composites over the temperature range 275−425 °C. Voorhees et al. also reported the release of oxalic acid from poly(ethylene oxide) pyrolysed under nitrogen at 450 °C.44 The carbonyl bands at 1793 and 1758 cm−1 may be explained by the possible presence of diethyl oxalate. The typical low- and high-magnification SEM images of cathode composites before and after cycling are shown in Figure 3. It should be noted that the scale bars in Figure 3a,c correspond to 10 μm, and the scale bars in Figure 3b,d correspond to 5 μm. Upon close observation, it is evident from the SEM images in Figure 3c,d, in comparison with those in Figure 3a,b, show the presence of the voids in the cathode composites after 40 cycles at 125 °C. In combination with the TGA profiles in Figure S1 and the TGA-IR spectra in Figure 2, it appears that these voids may be caused by the release of lowmolecular-weight compounds from the cathode composites. The most likely explanation is that a reaction occurs between the components in the V6O13-based cathode composites at a temperature of approximately 150 °C that results in the partial decomposition of the polymer binder and the release of lowmolecular-weight (volatile) polymer fragments.

Figure 2. (a) In situ three-dimensional (3D) image of IR spectra at 180 °C and (b) comparison of individual spectra of the TGA exhaust gas from V6O13-based cathode composites heated at target temperatures of 125, 150, and 180 °C.

stretching and H−O−H bending modes of water vapor, and a C−O stretching mode. The values of absorbance of these characteristic bands were approximately constant after the target temperature of 180 °C was attained. Figure 2b shows individual spectra of the exhaust gas from the TGA analysis of V6O13-based cathode composites heated at target temperatures of 125, 150, and 180 °C. The absorption bands in the range of 3500−3960 and 1300−2000 cm−1 shown in Figure 2b can be assigned to water vapor, and the bands between 2300 and 2400 cm−1 are attributed to carbon dioxide.

Figure 3. (a) Low- and (b) high-magnification SEM images of cathode, (c) low- and (d) high-magnification SEM images of cathode after 40 cycles. 29669


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ACS Applied Materials & Interfaces One control experiment was carried out, in which a piece of cathode composite was annealed at 150 °C for 90 h in a tube furnace under an argon atmosphere, with the aim of understanding the changes in crystal structure of cathode composites subjected to high temperatures. The red curve in Figure 4 is the XRD pattern of the cathode composites after

Figure 5. (a) In situ three-dimensional (3D) image of IR spectra at 180 °C of the TGA exhaust gases of mixture of V6O13 and polymer binder and (b) a comparison of the in situ individual spectra of TGA exhaust gas from a mixture of V6O13 and polymer binder and a cathode composite.

Figure 4. Comparison of the X-ray diffraction (XRD) patterns of a V6O13-based cathode composite, a V6O13-based cathode composite annealed at 150 °C for 90 h under argon and commercial V2O3.

the annealing process. It is observed that {001} crystal plane of V6O13 becomes more pronounced and is shifted after the annealing process, in comparison with the blue curve of pristine cathode composites in Figure 4. In addition, it is interesting to note that additional weak shoulder peaks at 2θ of 24 and 33° are present in the XRD pattern. Among the XRD patterns of commercial V2O3, V2O4, V2O5, and V6O13 studied in our previous report,27 the peak at 2θ of 24° is only present in the XRD pattern of V2O3 shown in Figure 4. The XRD patterns were carefully compared and it appears there is an obvious overlapped peak at 2θ of 24° and three weak peaks at 33, 41.5, and 54° indicated by the dotted lines. The presence of these overlapping peaks may be assigned to different crystal planes of V2O3, which suggests the reduction of V6O13 to V2O3 at a temperature of 150 °C. To understand the reaction in V6O13-based cathode composites in more detail, the TGA-IR technique was used to determine the thermal stability of the four individual components. The thermal gravimetric analysis (TGA) profiles of carbon powder, V6O13, polymer binder, and lithium imide are shown in Figure S3. The TGA profiles of above components show their weight losses to be 0.15, 0.44, 0.22, and 0.27%, respectively, over the temperature range of 200− 500 °C. The highest weight loss was obtained for V6O13, which is well understood and can be attributed to water vapor and ammonia, as discussed in our previous report.27 The TGA profiles confirm that no obvious weight changes are observed from individual components at 200 °C and therefore that the individual components of the cathode composites are thermally stable at this temperature. In addition, the in situ IR technique has not detected any organic components in the exhaust gas from the TGA experiments of these samples at 180 °C. The TGA-IR technique was deployed to understand the thermal stability of a mixture of V6O13 and polymer binder (polyalkylene glycols). Figure 5a shows the 3D image of the IR spectra of the exhaust gas from a mixture of V6O13 and polymer binder when heated to a target temperature of 180 °C

and held for 30 min, whereas Figure 5b compares the individual spectra of the TGA exhaust gas from the mixture of V6O13 and polymer binder and cathode composites. The 3D images in Figures 2a and 5a show very similar evolution of absorption bands, which are dominated by the presence of 1,4dioxane. The individual spectra in Figure 5b are almost identical, indicating that the TGA exhaust gases from the cathode composite and the mixture of V6O13 and polymer binder are almost identical. It is therefore concluded that the anomalous reaction in the cathode composite is due to the reaction between V6O13 and the polymer binder, which has not, to the best of our knowledge, been reported previously for V6O13-based Li-metal polymer batteries. Several further control experiments with the TGA-IR technique were conducted to understand the initiation temperature of the reaction between V6O13 and the polymer binder. A mixture of V6O13 and polymer binder was heated to various target temperatures of 135, 140, and 150 °C and held for 30 min. Weight losses of 0.59, 1.28, and 2.23% were obtained from the TGA profiles in Figure S4, where a significant increase in weight loss is observed as the temperature is increased above 140 °C. The 3D image of IR spectra of the TGA exhaust gas from mixtures of V6O13 and polymer binder at 150 °C is shown in Figure 6a, which confirms the presence of dioxane, CO2, and water vapor. Figure 6b compares the individual spectra of the TGA exhaust gas from mixtures of V6O13 and polymer binder at target temperature of 135, 140, and 150 °C, and it is reasonable to conclude that the reaction between V6O13 and the polymer binder is initiated at a temperature of 140 °C. Further control experiments were carried out to analyze a mixture of V6O13 and the carbon (Ketjenblack EC300J) with the TGA-IR technique. Figure 7a,b shows the TGA profile and 3D image of the IR spectra of TGA exhaust gas from a mixture of V6O13 and carbon, respectively. The TGA profile in Figure 7a shows that the weight loss of a mixture of V6O13 and carbon 29670


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bands at 2363 and 2332 cm−1 confirm the presence of a large amount of CO2, indicated by an arrow in Figure 7b. The presence of CO2 suggests that V6O13 could also react with the carbon used in the cathode composites, although it is possible that CO2 may originate from the surrounding atmosphere or the oxidation and/or decomposition of residual organic material in the TGA furnace. To ensure the CO2 was due to the reaction between V6O13 and carbon, an additional control experiment was undertaken, namely, the replacement of Ketjenblack EC300J carbon with carbon−13C. The TGA profile of a mixture of V6O13 and carbon−13C shown in Figure 7c exhibits a weight loss of 5.28%, which is also larger than that of V6O13 (3.4%).27 In addition, the 3D image of the IR spectra of the TGA exhaust gas from the mixture of V6O13 and carbon−13C shows the presence of a pronounced absorption band, which is indicated by an arrow in Figure 7d. The individual IR spectrum (blue) in Figure 7e shows that the absorption bands are at 2298 and 2266 cm−1 and are assigned to 13CO2, which are different from those of 12CO2 from the individual IR spectrum (red) in Figure 7e. This control experiment shows the presence of a large amount of 13CO2 from the mixture of V6O13 and carbon−13C, which excludes other possible sources of CO2 and confirms the reaction carbon−13C with V6O13. The TGA profiles of both carbon and carbon−13C show negligible weight

Figure 6. (a) In situ three-dimensional (3D) image of IR spectra of the TGA exhaust gases of mixture of V6O13 and polymer binder at 150 °C and (b) comparison of individual spectra of mixtures of V6O13 and polymer binder at target temperature of 135, 140, and 150 °C.

is 5.3%, which is 1.88% higher than that of V6O13 (3.42%), as reported previously.27 In addition, the pronounced absorption

Figure 7. TGA profile and 3D image of IR spectra of TGA exhaust gas from a mixture of V6O13 and Ketjenblack EC300J carbon (a, b) and from a mixture of V6O13 and carbon−13C (c, d), and (e) comparison of individual IR spectra of TGA exhaust gases from the above mixtures. 29671


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Figure 8. (a) Comparison of the TGA profiles of the mixture of V6O13 and polymer binder with the mixture of LiFePO4 and polymer binder at 180 °C for 30 min. (b) Cycle performance of lithium-metal polymer batteries fabricated with LiFePO4-based cathode at 125 °C.

composites above a temperature of approximately 220 °C. The results of this study indicate that there is likely to be a redox reaction between the polymer binder and V6O13 when the battery is used at elevated temperatures or generates temperature hot spots during charging and discharging. The reduction of V6O13 and the oxidation of polymer binder appear to create voids in cathode composites, which may be able to account for capacities invariably below the theoretical value and the capacity decay of V6O13 cathodes.

loss over the temperature range 25−500 °C, and it is therefore reasonable to conclude that V6O13 reacts with carbon over this temperature range. Figure 7d shows that 13CO2 is first detected at a time of around 11 min, which corresponds to a temperature of approximately 220 °C for the initiation of the reduction of V6O13 by carbon−13C. Figure 8a compares the TGA profile of the mixture of V6O13 and polymer binder with that of the mixture of LiFePO4 and polymer binder when heated to a target temperature of 180 °C and held for 30 min. It is evident that the weight loss of 0.31% for the mixture of LiFePO4 and polymer binder is negligible in comparison with that of 12.4% for the mixture of V6O13 and polymer binder, which suggests that LiFePO4 should not react with polymer binder at the temperature of 180 °C as V6O13. Figure 8b shows the cycling performance of the lithium-metal polymer batteries fabricated with LiFePO4 instead of V6O13 tested at 125 °C. The initial discharge capacity of the LiFePO4 cathode is about 145 mAh g−1. Upon cycling, the capacity almost maintains a steady state during the 23 cycles, and the reversible capacity of 137 mAh g−1 could be reserved. The capacity decay of LiFePO4 cathode is around 5.5%, which indicates big contrast with about 40% capacity decay in the case of V6O13 cathode of its initial capacity in the very beginning cycles in our previous report.27 Therefore, it seems that the 40% capacity decay of V6O13 cathode in our previous report could be attributed to the thermal instability of V6O13 cathode.

4. EXPERIMENTAL SECTION 4.1. Chemicals. V6O13 samples were purchased from Stratcor Inc. and jet-milled prior to use. The carbon additive was Ketjenblack EC300J and was supplied by AkzoNobel. The lithium salt of bis(trifluoromethane)sulfonimide, commonly referred to as lithium imide, and carbon−13C were obtained from Sigma-Aldrich, whereas the polymer binder was supplied by Nippon Shokubai Co., Ltd, Japan. The compositions of polymer binders are classified as trade secrets and are not known in detail, although they are described as polyalkylene glycols. All of these materials were dried and stored under vacuum. Cathode composites were fabricated by coating a slurry of V6O13, carbon conductivity additive, polymer binder, and lithium imide onto nickel foil in a dry room with a dew point temperature of −40 °C or lower. LiFePO4 was obtained from Phostech, and LiFePO4-based cathode composites were prepared with the similar process and formulation to V6O13-based cathode. 4.2. Characterization Methods. Scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDS) were carried out on an FEI XL30 FEG environmental scanning electron microscope (ESEM) equipped with an energy dispersive X-ray analyzer (Phoenix). The operating voltage of the SEM was in the range 10−20 kV. Thermal gravimetric analysis (TGA) was conducted on a thermal gravimetric analyzer (TA instrument, Q5000IR) to investigate the weight changes of samples as a function of temperature under an inert gas atmosphere. Helium purge gas (BIP, Air Products) was introduced at a flow rate of 10 mL min−1 in all experiments, and restek triple filters were used to remove residual oxygen and moisture. An on-line infrared spectrometer (NICOLET 380, Thermo Scientific) was used to analyze simultaneously the exhaust gas from the TGA furnace in the in situ thermal gravimetric analysis (TGA): infrared spectroscopy (IR) technique. The transmission line, which connected the TGA to the glass flow cell inside the spectrometer, was kept at a temperature of 150 °C to prevent vapor condensation. Powder X-ray diffraction (XRD) patterns were collected using a Bruker D8-Advance X-ray diffractometer with Cu Kα radiation (0.1542 nm) at an operating voltage of 40 kV (scan speed 2 and increment 0.02). A tube

3. CONCLUSIONS In summary, we have demonstrated the thermal instability of the V6O13-based cathode composite for use in the lithiummetal polymer rechargeable battery by the logical characterization with extensive techniques. The analysis of the cathode composites and its individual components using the TGA-IR technique shows the evolution of dioxane and possibly diethyl oxalate at a temperature of approximately 150 °C. In addition, the XRD patterns of cathode composites annealed at 150 °C indicate a change in composition, which is attributed to the formation of V2O3 by the reduction of V6O13. Control experiments using the TGA-IR technique indicate that the reaction in the cathode composites is due to a reaction between polymer binder and V6O13, and this reaction occurs at approximately 140 °C. Further control experiments show that V6O13 can also react with carbon additives in cathode 29672


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furnace (Carbolite, MTF12/38/250) was used to heat the V6O13based cathode composites under an inert gas atmosphere.

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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/acsami.8b10629. Experimental section; capacity of V6O13 in lithium batteries; TGA-IR of V6O13-based cathode composites heated at various target temperatures; comparison of TGA-IR spectrum of gas phase from V6O13-based cathode composites and 1,4-dioxane; TGA profiles of carbon (Ketjenblack EC300J), V6O13, polymer binder and Li imide [LiN(CF3SO2)2]; TGA profiles of mixtures of V6O13 and polymer binder carried out at various target temperatures (PDF)

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AUTHOR INFORMATION

Corresponding Author

*E-mail: [email protected]. ORCID

Han-Pu Liang: 0000-0002-5476-6197 Author Contributions ∥

X.S. and J.D. contributed equally.

Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS H.-P.L. is thankful for support from the “Hundred Talent Program” of Chinese Academy of Sciences (RENZI[2015] 70HAO, Y5100619AM) and for the kind help from Andrew W. Meredith, Nathan S. Lawrence, Christine R. Jarvis, and Wenlin Zhang.

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REFERENCES

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Understanding the Mechanism for Capacity Decay of V6O13-Based

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