Li+-Desolvation Dictating Lithium-Ion Battery Low-Temperature Performances

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Article
Li+-Desolvation Dictating Lithium-Ion Battery Low-Temperature Performances
Qiuyan Li, Dongping Lu, Jianming Zheng, Shuhong Jiao, Langli
Luo, Chongmin Wang, Kang Xu, Ji-Guang Zhang, and Wu Xu
ACS Appl. Mater. Interfaces, Just Accepted Manuscript • DOI: 10.1021/acsami.7b13887 • Publication Date (Web): 17 Nov 2017
Downloaded from http://pubs.acs.org on November 20, 2017
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Page 1 of 21 ACS Applied Materials & Interfaces
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4 Li+-Desolvation Dictating Lithium-Ion Battery Low-Temperature
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7 Performances
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12 Qiuyan Li,a Dongping Lu,a Jianming Zheng,a Shuhong Jiao,a Langli Luo,b Chong-Min Wang,b
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Kang Xu,c Ji-Guang Zhang,a Wu Xua,*
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17 Energy and Environmental Directorate, Pacific Northwest National Laboratory, 902 Battelle
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19 Boulevard, Richland, WA 99354, USA
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21 b
22 Environmental and Molecular Sciences Laboratory, Pacific Northwest National Laboratory,
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24 3335 Innovation Boulevard, Richland, WA 99354, USA
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26 c
Electrochemistry Branch, U.S. Army Research Laboratory, 2800 Powder Mill Road, Adelphi,
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29 MD 20783, USA
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33 KEYWORDS: low temperature; desolvation; ion transfer; electrolyte; lithium ion battery;
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36 cesium cation
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ABSTRACT: Lithium (Li) ion battery (LIB) has penetrated almost every aspects of human life,
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43 from portable electronics, vehicles to grids, and its operation stability in extreme environments
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45 becomes increasingly important. Among these, sub-zero temperature presents a kinetic challenge
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48 to the electrochemical reactions required to deliver the stored energy. In this work, we attempted
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50 to identify the rate-determining process for Li+ migration under such low temperatures, so that an
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52 optimum electrolyte formulation could be designed to maximize the energy output. Substantial
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55 increase in available capacities from graphite||LiNi0.80Co0.15Al0.05O2 chemistry down to -40°C is
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57 achieved by reducing the solvent molecule that more tightly binds to Li+ and thus constitutes
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high desolvation energy barrier. The fundamental understanding is applicable universally to a
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6 wide spectrum of electrochemical devices that have to operate in similar environments.
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11 TOC graphic
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INTRODUCTION
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33 A low-temperature capable lithium (Li) ion battery (LIB) would attract interests for applications
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35 in sub-zero environments such as polar areas on the Earth or outer space.1-3 It has been well
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38 known that the electrolyte plays an important role in controlling the mass transport across the
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40 cell, which includes not only Li+ conduction through the bulk electrolyte, but also its migration
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42 through the solid-electrolyte-interphase (SEI). In particular, the electrolyte formulation dictates
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45 the solvation structure of Li+, which consequently influence not only the SEI formation and
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47 composition but also the energy barrier associated with the desolvation of Li+ at
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electrolyte/electrode interface.4 The resistances and kinetic barrier to Li+ would increase as
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52 temperature goes down, and numerous studies have been seeking the reduction of these
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54 resistances so as to improve the low-temperature capability of LIBs. Successful strategies
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include employing low freezing point solvents like ethyl methyl carbonate (EMC), propylene
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carbonate (PC) and diethyl carbonate (DEC),5-7 and co-solvents like 2,2,2-Trifluoroethyl N-
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6 caproate (TFENH) and carboxylate esters,8-9 utilization of various lithium salts combinations
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8 such as lithium oxalyldifluoroborate (LiODFB)/ lithium tetrafluoroborate (LiBF4),10 lithium
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bis(oxalato)borate (LiBOB)/ LiBF4;11-13 and the other additional additives like lithium-modified
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13 silica nanosalt.14-15 While improvement was achieved, the fundamental mechanism beneath the
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15 origin of the reduced resistances remains unclear, and controversies often arise. It has been noted
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18 early on that bulk ion conductivity of electrolyte may not be the limiting factor determining the
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20 low-temperature performance of an LIB,7, 12, 16 instead Li+ migration across SEI might be the
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22 most sluggish step.4, 17-18
Xu et al.19-20 and Abe et al.21 independently proposed that Li+ ion
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25 transfer barrier through the interface of electrolyte/electrode is overwhelmed by the Li+
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27 desolvation process before intercalating into graphite interlayers. Taking the specific LIB
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chemistry graphite||LiNi0.8Co0.15Al0.05O2 (NCA) as an example, both an electron and a Li+ leave
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32 NCA cathode simultaneously during the charging process and reach to graphite through
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34 electrolyte and external circuit, respectively. Compared with the agile electron transfer via
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37 external circuit, the diffusion journey of Li+ from the cathode to the anode is more complicated.
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39 At the NCA sides, the Li+ will be extracted out from cathode lattice, moves across interphase of
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41 cathode (sometimes named Cathode-Electrolyte-Interphase, CEI), and then enters bulk
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44 electrolyte and gets solvated with solvents or anions. The solvated Li+, now even clumsier,
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46 diffuses through the bulk electrolyte and gets desolvated before it can enter the graphite SEI,
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48 followed by Li+ intercalation into graphitic structure. The reverse process happens during
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51 discharge.22-24 Xu et al proposed that Li+ desolvation is the most sluggish process among those
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53 multiple steps, however understanding of the processes under low temperatures is still unclear,
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which is related extensively to battery’s low temperature performance. A dedicated study to
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6 identify the key component for low temperature Li+ transport is still absent.
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8 The present work aims to fill the above knowledge gap. By leveraging interactive design
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of experiments and applying EIS measurement on symmetric cells including NCA||NCA,
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13 graphite||graphite, lithiated spinel titanate (LTO)||LTO with various electrolytes, the Li+ transport
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15 behavior at temperatures lower than -20°C is examined, with the purpose of distinguishing the
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18 rate-determining step. The results enabled the formulation of low temperature electrolytes that
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20 can efficiently support LIBs to deliver 68% of their nominal capacities down to -40°C.
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25 EXPERIMENTAL SECTION
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27 Materials
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LiNi0.80Co0.15Al0.05O2 (NCA, 1.50 mAh cm−2) and graphite (MAG-10, 1.53 mAh cm−2)
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32 electrodes were obtained from the Cell Analysis, Modeling and Prototyping (CAMP) Facility at
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34 Argonne National Laboratory (ANL) and used as cathode and anode, respectively in coin cells.
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37 Celgard 2500 was used as separator. Li4Ti5O12 (LTO) electrodes were used for symmetric cell
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39 assembly. The electrolyte components such as lithium salt (LiPF6) and solvents (EC, PC, and
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41 EMC) were purchased from BASF and used as received. Cesium hexafluorophosphate (CsPF6,
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44 ≥99.0%) was purchased from SynQuest Laboratories (Alachua, FL) and dried at 65 °C for 4 days
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46 under vacuum prior to use. Preparation of electrolytes and coin cell assembly/disassembly were
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48 conducted in an argon-filled glovebox, where both oxygen and moisture levels were below 1
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51 ppm. The electrolyte formulations are listed in Table 1.
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53 Electrochemical Measurements and Characterization
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The electrochemical performances of graphite||NCA coin cells filled with 100 µL electrolytes
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6 were evaluated in 2325-type coin cells (National Research Council Canada) on Land battery
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8 testers (Wuhan, China). All coin cells were initially subject to two formation cycles at rate of
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0.05C at room temperature in the voltage range of 2.5 to 4.3 V (1C corresponds to a current
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13 density of 1.5 mA cm−2). For temperature tests, the cells were, unless specified otherwise,
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15 charged at a constant rate of 0.2C and a constant voltage charge to 0.1C at room temperature and
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18 then discharged at 0.2C under various temperatures, where all cells were kept under each
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20 temperature for at least 3 hours for thermal equilibrating. The temperatures were controlled by a
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22 Tenney JR environmental chamber. For specific comparison tests, the NCA and graphite
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25 electrodes were harvested from the full cells with various electrolytes after two formation cycles
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27 in the argon-filled glovebox, soaked in EMC solvent for 30 min, rinsed 3 times with fresh EMC
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to remove the residual electrolytes, dried, and then interactively reassembled back into fresh
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32 graphite||NCA coin cells with different electrolytes. For impedance measurements, the NCA and
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34 graphite electrodes retrieved from the full cells after formation cycles as well as the fresh LTO
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37 (without experiencing formation process) were assembled into symmetric cells (i.e. NCA||NCA,
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39 graphite||graphite and LTO||LTO) with various electrolytes, followed by electrochemical
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41 impedance spectroscopy (EIS) measurements under different temperatures. A Solartron 1255B
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44 frequency response analyzer coupled with a Solartron 1287 electrochemical workstation were
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46 employed to measure EIS with a 10 mV perturbation in the frequency range from 106 to 10−3 Hz.
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48 Galvanostatic charge-discharge tests under different temperatures were performed in a Tenney JR
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51 environmental chamber. The ionic conductivities of the electrolytes were measured with
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53 BioLogic MCS 10 Fully Integrated Multichannel Conductivity Spectroscopy. High-resolution
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transmission electron microscope (TEM) was carried out to observe the SEI on graphite particles
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6 on an FEI Tian 80-300 microscope at 300kV.
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10 RESULTS AND DISCUSSION
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Discharge capacities at different temperatures
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15 Cesium cation (Cs+) was identified to enable PC-rich electrolytes (up to 20% by weight) for
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17 stable cycling of graphite electrode by directing EC molecules for surface reduction and forming
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20 an EC-rich SEI.25-26 This “disproportionation” between bulk and interphasial contents of
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22 electrolytes was made possible by the passively “preferential” solvation of Cs+ by EC and the
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24 higher reduction potentials of Cs+-(EC)m solvates as compared with the Li+-(PC)n solvates. The
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27 high PC content in these electrolytes diluted the effect of high melting point EC, and provided an
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29 alternative path to high performance low temperature electrolytes. Figure 1 compares the effect
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31 of CsPF6 on discharge capacity at various temperatures for the graphite||NCA full cells with two
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34 PC contents (20% and 10%) in the solvent mixtures of EC-PC-EMC. With 20% PC (Figure 1a),
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36 the electrolyte with CsPF6 additive (E5) dramatically improves the discharge capacity when
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compared with the electrolyte without CsPF6 additive (E6). The reversible capacity at -40°C is
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41 increased from 9% to 52% of the room temperature capacity with the use of CsPF6. However,
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43 using electrolyte with 10% PC , no obvious difference can be observed in discharge capacities in
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46 the temperature range from 25°C to -40°C, no matter CsPF6 is used or not (Figure 1b). With
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48 presence of CsPF6 additive, a much thinner SEI is formed (see the later section for the TEM
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morphologies of graphite electrodes),25 but it seems this more compact SEI cast little influence
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53 on the delivered capacity. This discrepancy counters the well-accepted belief that Li+-transport
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It is found in our previous research that EC/EMC ratio of the electrolyte plays a critical
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6 role for cell’s low temperature performance (shown in Figure S1).27 However, for fundamental
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8 understanding, there are still several questions need to answer: (1) how does bulk electrolyte
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formulation correlate to the low-temperature discharge capacity? (2) how does SEI composition
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13 affect the low-temperature properties? and (3) what is the determining factor of low-temperature
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15 performance in full cells? Aiming to answer these questions, the Li+ migration process during
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18 discharging at -40°C was studied.
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22 Predominant factor during low-temperature discharge
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25 It has been well established that the energy barrier or resistance determines how fast and how
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27 much Li+ can be extracted out or intercalated back into electrodes.20, 22 A complete pathway of
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29 Li+ transfer during discharge process can be broken down into the following steps (as shown in
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32 Figure 2) in a graphite||NCA full cell. All these steps will possibly affect the discharge capacity at
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34 low temperatures.
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36 1) Li+ extraction from LixC6 anode;
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39 2) Li+ diffusion in the graphite interlayer;
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41 3) Li+ across the solid-solid interface between the graphite electrode and the graphite SEI
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4) Li+ diffusion through the SEI layer of graphite;
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46 5) Li+ solvation in electrolyte;
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48 6) Li+ migration in electrolyte towards NCA cathode surface;
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51 7) Li+ desolvation from electrolyte at the SEI layer on NCA;
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53 8) Li+ diffusion through the CEI layer on NCA;
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55 9) Li+ across the solid-solid interface between the NCA CEI and the NCA electrode
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58 10) Li+ diffusion in the interlayer of NCA;
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11) Li+ reaches appropriate site of the NCA lattice.
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6 At low-temperature which step constitutes the limiting factor to discharge is the subject
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8 of interest. In this work, the same cathode and anode materials were applied for full cells with
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various electrolytes, which indicates that at the selected temperature the diffusion of Li+ in the
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13 interlayer of the electrode materials (Steps 2 and 10) should be considered to be the same, thus
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15 they should be excluded. As reported previously,7, 12 the ionic conductivity of the electrolyte does
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18 not constitute the limiting factor either, which also confirms our results, because electrolyte E2 at
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20 -30°C has a higher ionic conductivity value (shown in Figure S2) compared with the ionic
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22 conductivity of electrolyte E9 at -40°C, while the discharge capacity of the full cells with E2 at -
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25 30°C is lower than that of cells with E9 at -40°C (showed in Figure S3), which cannot well
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27 explain their correlation between capacity and ionic conductivity. Therefore, it is reasonable to
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exclude Step 6 as well.
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32 Li+ charge transfer on the interface of electrolyte/electrode is directly related to the
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34 electrolyte itself and the corresponding SEI formed at the surfaces of NCA and graphite
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37 spontaneously become the focus of analyzing the mechanism of discharge process at low
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39 temperatures. To observe the effect of the CEI and SEI on the cathode/electrolyte and
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41 anode/electrolyte interface in the low-temperature discharge capacity, we selected the cells with
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44 electrolytes E1, E2 and E9 as the experimental subjects with two extreme conditions, where both
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46 E1 and E2 exhibited the worst discharge capacities at -40°C while E9 showed the highest
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48 discharge capacity at -40°C according to our previous report.27 We disassembled cells and
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51 harvested NCA and graphite electrodes after two formation cycles with E1 and E9, which bear
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53 completely formed SEIs on their surfaces with each electrolyte, and subsequently, interactively
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reassembled them back into new full cells by exchanging electrolytes. All these new cells can
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operate normally at room temperature. At low temperatures, however, their different behaviors
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6 reveal the key factor that dictates the low temperature performance. The new graphite||NCA cells
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8 with E9, with exchanged NCA electrode, or graphite electrode, or both harvested from the cells
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containing E1, maintained decent low temperature performances at -40°C (Figure S4). On the
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13 contrary, the new graphite||NCA cells containing E1, no matter the NCA or graphite electrode or
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15 both were recovered from the cells containing E9, did not deliver any capacity at -40°C.
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18 Considering that E1 is frozen at -40°C resulting in large interface resistance between the frozen
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20 E1 and the surface of electrode,27 we repeated the above interactive experiments using E2 and E9
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22 (Figure 3), with the same results obtained. In order to eliminate the interference factor of re-
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25 charge process at room temperature prior to discharging at -40°C, we also directly switched the
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27 100% SOC graphite electrodes from the fully-charged cells with E9 and E1, followed by
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discharging the reassembled cells at -40°C (Figure S5). All discharge capacities at -40°C are
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32 summarized in Figure 4 demonstrating beyond any doubt that the low-temperature performance
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34 is correlated to the bulk electrolyte rather to the SEI formed, and Li+ is free to migrate through
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37 the intrinsic SEI on either cathode or anode at -40°C, despite their formation history. TEM
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39 (Figure 5a-d) also reveal that the morphology and thickness of the SEIs shows no obvious
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41 difference despite different electrolyte formulations. On the contrary, similar discharge capacity
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44 at -40°C is obtained regardless of the apparently different SEIs (Figures 5e and f versus g and h).
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46 Therefore, the above results remove Steps 3, 4 and 8, 9 as limiting factors of low-temperature
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48 kinetics. In other words, the properties of the bulk electrolyte itself dictate the low-temperature
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51 performance.
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53 The overall cell resistance consists of bulk electrolyte (Rb), SEI (RSEI), and charge
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transfer (Rct),22 among which Rct is considered as the most significant factor affecting the low-
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temperature performance of the batteries,17-18 and Xu et al suggested that the desolvation
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6 resistance of Li+ before it enters into the interlayer of materials (Rdesolvation) is a main section of
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8 Rct.20 Having excluded the Li+ migration across SEI and its solid-solid diffusion as the limiting
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factors that affects the low temperature performance, the stripping of a solvated Li+ (step 7)
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13 becomes the only possible main energy-consuming step at low temperature.
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15 Given its moderate intercalation potential (1.50 V vs Li), LTO is an ideal candidate to
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18 further eliminate the complication of Li+ migration due to its nearly interphase-free surface,
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20 whose semicircle of EIS should reasonably represent the resistance of pure Li+ desolvation.20
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22 The symmetric cells with configurations of graphite||graphite, cathode||cathode, and LTO||LTO,
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25 respectively, were assembled and the temperature dependence of their cell impedances was
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27 compared. Among these, the impedance semicircles at high and medium frequency ranges of the
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symmetric NCA||NCA and graphite||graphite cells respectively reflect the sum of all interphasial
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32 components:
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34 Rcathode/cathode = Rct + RSEI of cathode + Rdesolvation + Rb
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37 and Ranode/anode = Rct+ RSEI of anode + Rdesolvation + Rb,
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39 While for LTO||LTO, given the absence of SEI, the cell impedance should be represented
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41 by:
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44 RLTO/LTO = Rct + Rdesolvation + Rb
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46 Given the same Rb and Rdesolvation, each cell should possess rather distinct Rct and RSEI
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48 values. However, despite these different components, similar impedance spectra with almost
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51 identical resistances were obtained for all three symmetric cells at -40°C (Figure 6a). The only
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53 one possible explanation to the EIS spectra shown in Figure 6a is that the resistance from Li+
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desolvation is the predominant factor that overwhelms contributions from all other components.
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By changing electrolytes in LTO||LTO symmetric cells, obvious difference in impedance
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6 spectra arose at -40°C (Figure 6b), where the semicircle (Rdesolvation) gradually becomes larger
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8 with increasing EC/EMC ratio, but the initial interception (Rb) sees no significant change except
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E1. This is because E1 freezes at -40°C, where the bulk electrolyte resistance increases sharply.
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13 Apparently, the different resistance behavior induced by bulk electrolyte composition change can
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15 be attributed to the change of Li+ solvation structure, which is then reflected in the change of
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18 energy barrier for Li+ desolvation. Not surprisingly, this desolvation effect becomes especially
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20 pronounced at -40°C, and starts to dictate the entire Li+ migration process during the discharge of
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22 the Li-ion cell. The temperature-dependence of cell impedances were plotted in Figure 6c for E2
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25 and E9, which demonstrates that the resistance from Li+ desolvation (Rdesolvcation) in E2 increases
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27 at much faster pace than that of E9 below -20°C, due to the higher EC-content in the former and
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the increasing difficulty to strip off the EC molecules from Li+ at low temperatures.
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32 Although Li+ desolvation has been identified as the limiting step for Li+ migration at low
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34 temperatures, it should be pointed out that this step may be determined or at least affected by
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37 factors other than electrolyte compositions; the particle size of electrode (active reaction site,
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39 interface condition) or the driving force from interior of cell may also contribute to the Li+
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41 desolvation process, which need to be further investigated.
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46 Cycling stability at -20°C
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48 To further verify the desolvation effect of various electrolytes on low-temperature performances,
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51 the above electrolyte compositions were further tested under more rigorously conditions, where
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53 graphite||NCA full cells with these electrolytes were both charged and discharged at -20°C
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(Figure 7a). The obvious improvements, no matter in initial discharge capacity or cycling
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stability, were achieved with the electrolyte compositions that contain reduced ratio of EC/EMC.
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6 When the EC content is 10%, the cells with E5 and E9 deliver the initial discharge capacity of
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8 139 and 142 mAh g-1, respectively, which were maintained at 97.7% and 97.5% after 100 cycles,
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respectively, with cycling efficiency of 99.96% and 99.99% (shown in Figure S6). The charge
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13 and discharge profiles of E5 at -20°C (Figure 7b) indicates the low cycle efficiency in the 1st
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15 cycle, but the capacity stabilizes after the 2nd cycle and the electrochemical system also remains
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18 stable after the Li-dendrite is gradually consumed or reacted by electrolyte. It should be noted
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20 that the first discharge capacity delivered after first charging at -20°C is a little lower than that
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22 after charging at room temperature, which is caused by a little Li-plating at first charging process
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25 at -20°C, even E1 shows higher capacity due to the reversible plating Li, shown in Figure 7d;
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27 however, the irreversible capacity becomes larger after 100 cycles that indicates more Li-plating
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occurred due to the increase of resistance during charge process with increasing the ratio of
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32 EC/EMC. When the cells were fully charged to 4.3 V after 100 cycles (shown in Figure 7c), the
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34 high polarization and the low capacity are attributed to the high ratio of EC/EMC at -20°C. We
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37 also found the different states of charge (SOC) of graphite anodes when the cells were opened
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39 (shown in Figure 7e), rather than plenty of Li-dendrite on the surface of graphite. Comparing E5
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41 and E6 as well as E9 and E10 shown in Figure S7, when the EC content is reduced to 10% by
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44 weight in the total solvent, the cells exhibit good cycling stability despite of the electrolytes with
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46 or without CsPF6 additive.
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48 For those different properties of graphite||NCA full cells with various electrolytes at -
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51 20°C, we elaborate the following three aspects for the understanding about Li-ion battery
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53 performances at low-temperatures. 1) For reversible discharge capacity delivery, Li plating
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occurs during charging process at low temperature and gets consumed during cycling process
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resulting in the irreversible capacity loss, while the discharge capacity is mainly determined by
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6 the Li+ desolvation resistance especially for low ratio of EC/EMC; 2) For cycling stability, the
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8 low resistance is responsible for less irreversible Li loss during charge processes. After the
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deposited Li is consumed, the cathode and anode will be operated at non-full charge/discharge
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13 state, which is helpful for cycling at low temperatures; 3) For efficiency, the high efficiency of
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15 cells with E5 and E9 during cycling indicates the electrochemical system is stable and energy
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18 barrier of charging and discharging approaches equilibrium, which further suggests that the
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20 dominant resistance and energy-consuming step of Li+ migration during charge and discharge
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22 processes should be similar at low temperature.
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27 CONCLUSION
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In this work, using combined techniques of analysis and cell-components switching, we
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32 successfully identified that Li+ desolvation process is the major kinetic barrier to Li+ transport at
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34 low temperatures rather than Li+ migration through SEI or diffusion in solid electrodes. The
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37 study confirms the earlier hypothesis that the stripping of solvent sheath of Li+ is the most energy
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39 consuming step for Li+ to enter electrode interior, and this energy barrier becomes ever more
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41 pronounced as temperature decreases below -20 °C. This fundamental understanding sheds light
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44 on a series of complicated interfacial processes that could universally happen in a variety of
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46 electrochemical devices. The efforts led to the development of a number of low temperature
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48 electrolyte formulations that can support cell reactions down to -40°C.
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53 ASSOCIATED CONTENT
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Supporting Information
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The Supporting Information includes the following items.
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6 (1) Comparison of discharge capacity of various electrolytes at different temperatures
7 (2) Ionic conductivities of E2 and E9
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9 (3) Discharge curves
10 (4) Efficiency
11 (5) Cycling stability at -20°C
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14 This material is available free of charge via the Internet at http://pubs.acs.org.
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18 AUTHOR INFORMATION
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20
21 Corresponding Author
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23 * W. Xu. E-mail: wu.xu@pnnl.gov
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28 Notes
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30 The authors declare no competing financial interests.
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35 ACKNOWLEDGMENTS
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37 This work was supported by the Laboratory Directed Research and Development (LDRD)
38
39 Project under Technology Investment Program (TIP) at PNNL as well as the Assistant Secretary
40 for Energy Efficiency and Renewable Energy, Office of Vehicle Technologies of the U.S.
41 Department of Energy (DOE) under Contract No. DE-AC02-05CH11231, Subcontract No.
42
43 6951379 under the Batteries for Advanced Battery Materials Research (BMR). The authors
44 thank Mr. Bryant Polzin of ANL for supplying NCA and graphite electrodes that were produced
45
at the U.S. DOE’s CAMP Facility, ANL. The CAMP Facility is fully supported by the DOE
46
47 Vehicle Technologies Program (VTP) within the core funding of the Applied Battery Research
48 (ABR) for Transportation Program. The TEM characterizations were conducted in the William
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50 R. Wiley Environmental Molecular Sciences Laboratory (EMSL) a national scientific user
51 facility located at PNNL, which is sponsored by DOE’s Office of Biological and Environmental
52 Research. PNNL is operated by Battelle for the Department of Energy under Contract DE-AC05-
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54 76RLO1830.
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60 14
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Table 1. Electrolyte formulations used in this work
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5
6 Electrolyte code Formulation
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8 E1 1.0 M LiPF6 in EC-PC-EMC (5:2:3 by weight) with 0.05M CsPF6
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E2 1.0 M LiPF6 in EC-PC-EMC (4:2:4 by weight) with 0.05M CsPF6
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E6 1.0 M LiPF6 in EC-PC-EMC (1:2:7 by weight)
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25 E10 1.0 M LiPF6 in EC-PC-EMC (1:1:8 by weight)
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19 Figure 1. Discharge profiles of graphite||NCA full cells at different temperatures (a) with E5 and
20 E6 and (b) with E9 and E10.
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29
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31 1) Li+ extraction from LixC6 anode
32 2) Li+ diffusion in the graphite interlayer
33 3) Li+ across the solid-solid interface between the graphite
34 electrode and the graphite SEI
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4) Li+ diffusion through the SEI layer of graphite
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37 5) Li+ solvation in electrolyte
38 6) Li+ migration in electrolyte towards NCA cathode surface
39 7) Li+ desolvation from electrolyte at the SEI layer on NCA
40 8) Li+ diffusion through the CEI layer on NCA
41 9) Li+ across the solid-solid interface between the NCA CEI
42 and the NCA electrode
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10) Li+ diffusion in the interlayer of NCA
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45 11) Li+ reaches appropriate site of the NCA lattice
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47
48 Figure 2. Schematic description of Li+ migration during discharging process
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29 Figure 3. Discharge profiles of new graphite||NCA full cells: (a) E2A+E9C+E2, (b)
30 E9A+E2C+E2, (c) E9A+E9C+E2, (d) E9A+E2C+E9, (e) E2A+E9C+E9, (f) E2A+E2C+E9,
31 where A and C denote anode and cathode, respectively, and E2 and E9 are the electrolytes. E2A
32
33 and E2C are the graphite anode and the NCA cathode from the cell with E2 after two formation
34 cycles, and E9A and E9C are the graphite anode and the NCA cathode from the cell with E9 after
35 two formation cycles. Cells were charged at 0.2C rate to 4.3 V and then at 4.3 V to 0.1C at room
36 temperature.
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29 Figure 4. Summary of discharge capacity at -40°C for the graphite||NCA cells with electrodes
30 that were removed from original full cells with E1, E2, and E9 electrolytes after 2 formation
31 cycles (at the fully discharged state), and then interactively reassembled back into new full cells.
32 EnA and EnC denote the graphite anode and the NCA cathode, respectively retrieved from the
33
34
full cell with the electrolyte En, where n = 1, 2 and 9. 100%SOC means the anode and thee
35 cathode were disassembled from the fully-charged full cells with the related electrolyte. Cells
36 were charged at 0.2C rate to 4.3 V and then at 4.3 V to 0.1C at room temperature.
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23 Figure 5. TEM images of graphite electrodes from full cells with (a) E1, (b) E3, (c) E5, and (d)
24 E9; (e) E5, (f) E6, (g) E9 and (h) E10 after two formation cycles.
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49 Figure 6. Comparison of EIS results for symmetric cells of (a) LTO||LTO, NCA||NCA, and
50 graphite||graphite with E9 at -40°C; (b) LTO||LTO with various electrolytes at -40°C; (c)
51 LTO||LTO with E2 and E9 at various temperatures. Both insets in (b) and (c) show an enlarged
52 part in the high frequency regions.
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42 Figure 7. (a) Cycling performance and efficiency of full cells with various electrolytes; (b)
43
charge and discharge profiles of E5 at -20°C and selected cycles; (c) charge profiles at 101st
44
45 cycle; (d) summary of discharge capacity of graphite||NCA cells with various electrolytes at -
46 20°C but at different charging condition; (e) Optical images of graphite anodes at the end of
47 charged state after 100 cycles in (i) E1; (ii) E2; (iii) E3; (iv) E4; (v) E5; (vi) E9. Test protocol:
48 charge at 0.2C rate to 4.3 V and at 4.3 V to 0.1C, and then discharge at 0.2C to 2.5 V after 2
49 formation cycles; Efficiency is equal to the discharge capacity of previous cycle is divided by the
50
51
charge capacity of next cycle.
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60 20
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REFERENCES
4
5
1. Smart, M. C.; Ratnakumar, B. V.; Whitcanack, L. D.; Chin, K. B.; Surampudi, S.; Croft, H.; Tice, D.; Staniewicz, R., Improved low-
6 temperature performance of lithium-ion cells with quaternary carbonate-based electrolytes. Journal of Power Sources 2003, 119, 349-358.
7 2. Plichta, E. J.; Hendrickson, M.; Thompson, R.; Au, G.; Behl, W. K.; Smart, M. C.; Ratnakumar, B. V.; Surampudi, S., Development of low
8 temperature Li-ion electrolytes for NASA and DoD applications. Journal of Power Sources 2001, 94 (2), 160-162.
9 3. Smart, M. C.; Whitacre, J. F.; Ratnakumar, B. V.; Amine, K., Electrochemical performance and kinetics of
10 Li1+x(Co1/3Ni1/3Mn1/3)1−xO2 cathodes and graphite anodes in low-temperature electrolytes. Journal of Power Sources 2007, 168 (2), 501-
508.
11 4. Li, J.; Yuan, C. F.; Guo, Z. H.; Zhang, Z. A.; Lai, Y. Q.; Liu, J., Limiting factors for low-temperature performance of electrolytes in
12 LiFePO4/Li and graphite/Li half cells. Electrochimica Acta 2012, 59, 69-74.
13 5. Plichta, E. J.; Behl, W. K., A low-temperature electrolyte for lithium and lithium-ion batteries. Journal of Power Sources 2000, 88 (2),
14 192-196.
15 6. Xiao, L. F.; Cao, Y. L.; Ai, X. P.; Yang, H. X., Optimization of EC-based multi-solvent electrolytes for low temperature applications of
lithium-ion batteries. Electrochimica Acta 2004, 49 (27), 4857-4863.
16 7. Zhang, S. S.; Xu, K.; Jow, T. R., A new approach toward improved low temperature performance of Li-ion battery. Electrochemistry
17 Communications 2002, 4 (11), 928-932.
18 8. Lu, W.; Xie, K.; Chen, Z.; Xiong, S.; Pan, Y.; Zheng, C., A new co-solvent for wide temperature lithium ion battery electrolytes: 2,2,2-
19 Trifluoroethyl n-caproate. Journal of Power Sources 2015, 274, 676-684.
20 9. Smart, M. C.; Ratnakumar, B. V.; Chin, K. B.; Whitcanack, L. D., Lithium-Ion Electrolytes Containing Ester Cosolvents for Improved Low
Temperature Performance. Journal of The Electrochemical Society 2010, 157 (12), A1361-A1374.
21
10. Li, S.; Li, X.; Liu, J.; Shang, Z.; Cui, X., A low-temperature electrolyte for lithium-ion batteries. Ionics 2015, 21 (4), 901-907.
22 11. Li, S.; Zhao, Y.; Shi, X.; Li, B.; Xu, X.; Zhao, W.; Cui, X., Effect of sulfolane on the performance of lithium bis(oxalato)borate-based
23 electrolytes for advanced lithium ion batteries. Electrochimica Acta 2012, 65, 221-227.
24 12. Zhang, S.; Xu, K.; Jow, T., Low-temperature performance of Li-ion cells with a LiBF4-based electrolyte. Journal of Solid State
25 Electrochemistry 2003, 7 (3), 147-151.
13. Jow, T. R.; Ding, M. S.; Xu, K.; Zhang, S. S.; Allen, J. L.; Amine, K.; Henriksen, G. L., Nonaqueous electrolytes for wide-temperature-
26
range operation of Li-ion cells. Journal of Power Sources 2003, 119–121, 343-348.
27 14. Won, J. H.; Lee, H. S.; Hamenu, L.; Latifatu, M.; Lee, Y. M.; Kim, K. M.; Oh, J.; Cho, W. I.; Ko, J. M., Improvement of low-temperature
28 performance by adopting polydimethylsiloxane-g-polyacrylate and lithium-modified silica nanosalt as electrolyte additives in lithium-ion
29 batteries. Journal of Industrial and Engineering Chemistry 2016, 37, 325-329.
30 15. Hamenu, L.; Lee, H. S.; Latifatu, M.; Kim, K. M.; Park, J.; Baek, Y. G.; Ko, J. M.; Kaner, R. B., Lithium-silica nanosalt as a low-
temperature electrolyte additive for lithium-ion batteries. Current Applied Physics 2016, 16 (6), 611-617.
31
16. Fan, J., On the discharge capability and its limiting factors of commercial 18650 Li-ion cell at low temperatures. Journal of Power
32 Sources 2003, 117 (1–2), 170-178.
33 17. Zhang, S. S.; Xu, K.; Jow, T. R., Low temperature performance of graphite electrode in Li-ion cells. Electrochimica Acta 2002, 48 (3),
34 241-246.
35 18. Zhang, S. S.; Xu, K.; Jow, T. R., The low temperature performance of Li-ion batteries. Journal of Power Sources 2003, 115 (1), 137-140.
36 19. Xu, K.; von Wald Cresce, A., Li+-solvation/desolvation dictates interphasial processes on graphitic anode in Li ion cells. Journal of
Materials Research 2012, 27 (18), 2327-2341.
37 20. Xu, K.; von Cresce, A.; Lee, U., Differentiating Contributions to “Ion Transfer” Barrier from Interphasial Resistance and Li+
38 Desolvation at Electrolyte/Graphite Interface. Langmuir 2010, 26 (13), 11538-11543.
39 21. Abe, T.; Fukuda, H.; Iriyama, Y.; Ogumi, Z., Solvated Li-Ion Transfer at Interface Between Graphite and Electrolyte. Journal of The
40 Electrochemical Society 2004, 151 (8), A1120-A1123.
41 22. Jow, T. R.; Marx, M. B.; Allen, J. L., Distinguishing Li+ Charge Transfer Kinetics at NCA/Electrolyte and Graphite/Electrolyte Interfaces,
and NCA/Electrolyte and LFP/Electrolyte Interfaces in Li-Ion Cells. Journal of The Electrochemical Society 2012, 159 (5), A604-A612.
42 23. Jow, R.; Zhang, S. S.; Xu, K.; Allen, J., Electrolytes for Low Temperature Operations of Li-Ion Batteries. ECS Transactions 2007, 3 (27),
43 51-58.
44 24. Jow, T. R.; Allen, J.; Marx, M.; Nechev, K.; Deveney, B.; Rickman, S., Electrolytes, SEI and Charge-Discharge Kinetics in Li-ion Batteries.
45 Meeting Abstracts 2009, MA2009-02 (8), 504.
46 25. Xiang, H.; Mei, D.; Yan, P.; Bhattacharya, P.; Burton, S. D.; von Wald Cresce, A.; Cao, R.; Engelhard, M. H.; Bowden, M. E.; Zhu, Z.;
Polzin, B. J.; Wang, C.-M.; Xu, K.; Zhang, J.-G.; Xu, W., The Role of Cesium Cation in Controlling Interphasial Chemistry on Graphite Anode in
47 Propylene Carbonate-Rich Electrolytes. ACS applied materials & interfaces 2015, 7 (37), 20687-20695.
48 26. Zheng, J.; Yan, P.; Cao, R.; Xiang, H.; Engelhard, M. H.; Polzin, B. J.; Wang, C.; Zhang, J.-G.; Xu, W., Effects of Propylene Carbonate
49 Content in CsPF6-Containing Electrolytes on the Enhanced Performances of Graphite Electrode for Lithium-Ion Batteries. ACS applied materials
50 & interfaces 2016, 8 (8), 5715-5722.
51 27. Li, Q.; Jiao, S.; Luo, L.; Ding, M. S.; Zheng, J.; Cartmell, S. S.; Wang, C.-M.; Xu, K.; Zhang, J.-G.; Xu, W., Wide-Temperature Electrolytes
for Lithium-Ion Batteries. ACS applied materials & interfaces 2017, 9 (22), 18826-18835.
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