Journal of The Electrochemical Society, 158 (12) A1267-A1274 (2011)

0013-4651/2011/158(12)/A1267/8/$28.00 The Electrochemical Society

A1267

Fourier Transform Electrochemical Impedance Spectroscopic Studies on LiFePO4 Nanoparticles of Hollow Sphere Secondary Structures
Geun Gi Min,a Younghoon Ko,b Tae-Hee Kim,b Hyun-Kon Song,b Seung Bin Kim,a and Su-Moon Parkb, ,z
a Department of Chemistry, Pohang University of Science and Technology, Pohang, b Interdisciplinary School of Green Energy, Ulsan National Institute of Science and

Gyeongbuk 790-784, Korea Technology, Ulsan 689-805, Korea

Real-time impedance behaviors of LiFePO4 nanoparticles of two different structures have been investigated as cathode materials for lithium ion batteries using real time Fourier transform electrochemical impedance spectroscopy (FTEIS) techniques during potentiodynamic charging and discharging cycles. The effects of their nanostructures were examined employing hollow sphere secondary structured LiFePO4 particles prepared by sequential precipitations and commercially available non-hollow structured LiFePO4 particles. The battery constructed with the hollow sphere secondary structured LiFePO4 cathode material exhibited improved performances during charging and discharging processes as judged from various impedance parameters compared to those observed for the cell using its non-hollow counterpart. These results appear to have resulted from the enhancement of intrinsic capabilities for electron and charge transport characteristics of LiFePO4 by modifying its secondary structures. The real time impedance measurements were shown to be powerful in studying behaviors of battery electrodes during charging and discharging processes. 2011 The Electrochemical Society. [DOI: 10.1149/2.013112jes] All rights reserved. Manuscript submitted May 27, 2011; revised manuscript received July 26, 2011. Published October 31, 2011.

LiFePO4 is one of attractive cathode materials for lithium ion rechargeable batteries due to its advantages including the low cost, low toxicity, high safety, and structural stability.1, 2 However, its electrochemical reaction kinetics and power performances are limited by its poor electronic and ionic conductivities. Many studies have been conducted to overcome its disadvantages using various synthetic and surface modifying methods.39 As one of the efforts, Lee at el. have recently reported sequential precipitation methods to obtain LiFePO4 nanoparticles having hollow sphere secondary structures.10 The hollow sphere secondary structured LiFePO4 displayed better performances as a cathode material for lithium ion batteries compared to those of commercially available non-hollow LiFePO4 , which was used as a reference for the work. The hollow sphere LiFePO4 showed higher charge and discharge capacities and smaller potential drops than non-hollow LiFePO4 did during its high rate discharges (over 10 C). These results suggest that hollow LiFePO4 may eventually be developed to display higher power and energy densities than non-hollow LiFePO4 when properly engineered. The positive effects exerted by the hollow sphere secondary structures would be due to the reasons such as nano-sized dimensions of primary particles, the enhancement in electrical conductivity by the carbon layer on the primary particles introduced during synthetic procedures, and easy accessibility of Li+ to each LiFePO4 particle caused by hollow sphere structures. Electrochemical impedance spectroscopic techniques have been used for modeling and diagnosing battery systems as a non-destructive method.1114 The techniques offer the means for evaluation of the state of charge (SOC) and the state of health (SOH) of the cells, which are related to the parameters obtained from the AC impedance measurements. However, traditional impedance measurement techniques do not allow real time measurements to be made during another electrochemical experiment as the measurements must be made in the steady state.15 The newly developed Fourier transform electrochemical impedance spectroscopy (FTEIS) offers a powerful tool for the real time determination of impedance parameters in a short period while other electrochemical measurements are being made when properly programmed.16, 17 A full frame EIS measurement is made by applying a small voltage step, which has a period of 1/(the lowest frequency). The FTEIS method combined with a staircase cyclic voltammetric technique may thus be applied to dynamic and transient electrochem Electrochemical Society Active Member.
z

ical impedance measurements1821 on battery systems when properly conducted. In the present study, we conducted real-time impedance measurements using the FTEIS methods for the battery cells constructed using hollow sphere secondary structured LiFePO4 nanoparticles as well as non-hollow structured LiFePO4 nanoparticles as the cathode materials. The impedance data for each LiFePO4 cell during potentiodynamic charging and discharging processes were obtained. Results from the equivalent circuit analysis show that dynamic variations of circuit parameters are observed during charging and discharging processes. The parameters thus obtained help one evaluate electrode kinetic parameters involved in electrochemical reactions, leading to a better understanding of the mechanism for performance improvements of the LiFePO4 nanoparticles as their secondary structures were varied; the results show excellent agreement with the performances reported in the previous study.10 Experimental A coin-type 2016R half cell conguration was used for all electrochemical experiments. Two types of LiFePO4 nanoparticles were used as active materials for the cathode in lithium ion coin cells, i.e., hollow sphere secondary structured LiFePO4 nanoparticles and non-hollow LiFePO4 nanoparticles (200 nm). Hollow sphere nanostructured LiFePO4 was prepared by the sequential precipitation methods in the presence of cetyl-trimethylammonium bromide, which acted as a surfactant and also as a source of carbon, as reported previously.10 The LiFePO4 particles thus obtained had 300 nm secondary particles of a sphere shape with its shell made of primary particles of about 25 nm. The carbon layer of 5 nm was shown to wrap around the primary
Table I. Mass of Pure Active Materials, Thickness, Surface Densities, and Volume Densities for Assembled LiFePO4 Coin Cells. Surface Density, mg/cm2 3.46 5.57 Volume Density, g/cm3 1.12 1.55

Cell Type Hollow Cell Non-hollow Cell

Pure Active Material, g 0.00696 0.0112

Thickness, m 31 36

E-mail: smpark@unist.ac.kr

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A1268
2.5 2.0 1.5 1.0

Journal of The Electrochemical Society, 158 (12) A1267-A1274 (2011)

1.5 Non-Hollow 30 mV/s (100 s) Hollow 30 mV/s (100 s) 1.0

(a)

I (A/g)

0.5 0.0 -0.5 -1.0 -1.5 -2.0 2.0 2.5 3.0 3.5
+

0.5

I (A/g)
0.2 mV/s (21000 s) 0.5 mV/s (8400 s) 1 mV/s (4200 s) 10 mV/s (420 s) 4.0 4.5

0.0

-0.5

-1.0 2.4 2.6 2.8 3.0 3.2 3.4

+

1.5

E (V) vs. Li/Li

3.6

3.8

4.0

(b)

E (V) vs. Li/Li

1.0

0.5

Figure 2. Staircase cyclic voltammograms (SCVs) obtained during FTEIS measurements for coin-type half cells with hollow (broken line) and nonhollow (solid line) structured LiFePO4 nanoparticles. The SCVs were constructed using currents sampled at the end of each step period.

I (A/g)

0.0 0.2 mV/s 0.5 mV/s 1 mV/s 10 mV/s (21000 s) (8400 s) (4200 s) (420 s)

-0.5

-1.0 2.0 2.5 3.0 3.5

+

4.0

4.5

E (V) vs. Li/Li

-2.0 -2.1 -2.2

(c)

-2.3 -2.4 -2.5 -2.6 -2.7 -4.2 -4.0 -3.8 -3.6 -3.4 -3.2 -3.0 -2.8

Anodic Ip Cathodic Ip

in an ethylene carbonate/dimethyl carbonate (EC/DMC, 30:70 vol%) mixed solvent. The detailed parameters for assembling coin cells are listed in Table I. The EG&G model 263A potentiostat/galvanostat was used for cyclic voltammetric experiments of the coin-type half cells. All cells were connected to the instrument as a 2-electrode conguration; the working electrode clip was connected to the cathode of the cell while both the reference and counter electrode clips were connected to the lithium foil anode. The FTEIS measurements were carried out with a homemade fastrise potentiostat, an arbitrary waveform generator (Hewlett Packard, HP 33120A), and a National Instrument NI-5922 high speed data acquisition system operated by a desk top computer using an MS Visual Basic software. The impedance measurements were made by applying a series of ascending and descending potential steps of 20 mV of a period of 666.7 ms in a potential range of 2.5 V to 4.0 V vs. Li/Li+ ; this corresponded to a scan rate of 30 mV/s for a staircase cyclic voltammetric (SCV) experiment. The current was sampled at a rate of 50 k samples/s during all FTEIS measurements. The frequency range was then from 1.5 Hz to 25 kHz for these measurements at every 0.667 s and 20 mV intervals. After the data acquisition, each voltage step and chronoamperometric current obtained thereof were segmented into each step

log |Ip|

log
Figure 1. Cyclic voltammograms recorded at various scan rates in coin-type half cells with cathodes constructed with: (a) hollow sphere secondary structured, (b) non-hollow secondary structured LiFePO4 nanoparticles, and (c) the scan rate dependencies of the CV peak currents for the non-hollow cathode.

Table II. Parameters Obtained from Cyclic Voltammograms Recorded for LiFePO4 Coin Cells. Hollow Cella Scan Rate, mV/s 0.2 0.5 1 10
a

Non-Hollow Cella E0 , Vb Ep , V ipc and ipa , A/g 0.27,0.24 0.40,0.37 0.62,0.53 1.18,0.99 E0 , Vc 3.45 3.44 3.42

Ep , V 0.30 0.35 0.55 1.14

ipc and ipa , A/g 0.26,0.26 0.51,046 0.73,0.58 1.97,1.72

particles. As a result of this modication, not only the inside of the hollows is accessible to the electrolyte but also the conductivity of the cathode material is improved. Details of procedure and related morphological images are described in the original work.10 Commercially available non-hollow nanostructured LiFePO4 was obtained by solid state reactions. The cathode was made up of 80 wt% of the active material, 10 wt% of the Super P carbon black as a conduction enhancer, and 10 wt% of the polyvinylidene uoride (PVDF) binder. A lithium foil was used as an anode. The electrolyte was 1.15 M LiPF6 dissolved

3.46 0.57 3.45 0.90 3.43 1.22 3.50 >1.83

The energy densities were 312 and 256 W h g1 , respectively, for the hollow and the non-hollow cells at a discharge rate of 10 C. b The average E0 value is 3.46 0.03 V for the hollow cell. c The average E0 value is 3.44 0.02 V for the non-hollow cell.

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Journal of The Electrochemical Society, 158 (12) A1267-A1274 (2011)

A1269

Figure 3. (a) Typical 3-dimentional Nyquist plots obtained during the anodic scan of the hollow cell while the voltage was being scanned from 2.5 V to 4.0 V, (b) an impedance spectrum for the hollow cell recorded at 3.9 V, and (c) an equivalent circuit used for data anlaysis. Note that the impedance spectrum shown in (b) was singled out from the spectra shown in (a) (red colored line). The scan directions are indicated by the arrows.

period (666.7 ms). Impedances were then computed from each data packet by taking the rst derivatives of both the potential step and the current obtained thereof, followed by fast Fourier transform (FFT) of the derivative signals with frequencies ranging from 1/ttotal (lower limit frequency, 1.5 Hz) to 1/(2 t) (upper limit frequency, 25 kHz), where t is the sampling interval and ttotal is total sampling period (= n t). All calculations were carried out using a Matlab program (MathWorks, Natick, MA), and the circuit simulation was conducted to t measured impedance data to a proposed equivalent circuit using an EG&Gs ZSimpWin software.

Results and Discussion To compare electrochemical activities of the coin cells whose cathodes are made of hollow sphere secondary structured LiFePO4 (designated as the hollow cell) and non-hollow structured LiFePO4 (nonhollow cell), cyclic voltammetric experiments were rst run between 2.2 V and 4.3 V (vs. Li/Li+ reference electrode) at various scan rates. Cyclic voltammograms (CVs) recorded at scan rates of 0.20, 0.50, 1.0, and 10.0 mV/s are shown in Fig. 1a (hollow cell) and 1b (non-hollow cell). Shown in Fig. 1c is the log(Ip ) vs. log(v) plot for CVs, where ip

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A1270

Journal of The Electrochemical Society, 158 (12) A1267-A1274 (2011)

is the peak current and v is the scan rate. We notice a few points from the CVs shown here. First, the peak separations are generally smaller for the hollow cell than for the non-hollow cell at all scan rates due to more facile electron transfer kinetics of the hollow structured cathode material. Second, the peak heights are similar for the two cells at slow scan rates (0.2 1 mV/s), but it grows signicantly higher at 10 mV/s for the hollow cell than for the non-hollow cell. These show that the electrochemical activity of the cathode in the hollow cell is higher than that in the non-hollow cell, especially at high scan rates. Third, the formal potentials (E0 ) obtained by averaging anodic and cathodic peak potentials are about the same at 3.46 (0.03) and 3.44 (0.02) V, respectively, for hollow and non-hollow structured LiFePO4 cathode materials. This indicates that it is slightly more difcult to oxidize hollow structured LiFePO4 than its non-hollow counterpart but the former undergoes more facile oxidation once the redox reaction gets started. The detailed parameters related to CVs are listed in Table II. Finally, it is seen that slopes of the log(Ip ) vs. log(v) plot are 0.512 and 0.496, respectively, during the anodic and cathodic scans indicating that Ip v1/2 . Thus, the redox reaction of LiFePO4 and the accompanying Li+ transport are diffusion controlled up to the scan rate of at least 10 mV/s. Figure 2 shows staircase cyclic voltammograms (SCVs) obtained during the FTEIS measurements for the hollow (broken line) and nonhollow (solid line) cells recorded between 2.5 V and 4.0 V. The SCVs shown here resemble CVs in Fig. 1 and the currents are signicantly higher for the hollow cell in the entire voltage range. During the anodic scan (from 2.5 V to 4.0 V), the cathode is being charged up, which is accompanied by de-intercalation of lithium ions from the LiFePO4 crystal lattices above 3.45 V vs. Li/Li+ , while the reverse process takes place during the cathodic scan, according to the redox reaction, LiFePO4 Li+ + FePO4 + e . [1]

24 22 20

(a)

RS,

18 16 14 12 10 2.4 2.8 3.2 3.6

+

Charging process Discharging process

4.0

E, V vs. Li/Li
10

(b)
8

RS,

Charging process Discharging process

Due to the relatively high scan rate (30 mV/s), the anodic peak currents were not observed within the potential limit of 4.0 V, but the cathodic peak shows up slightly below 3.1 V due to reduction of FePO4 produced during the anodic scan. These results suggest that the charging process is not completed within the anodic vertex potential due to the sluggish electron and ion transport processes, but reduction of the oxidized species, FePO4 , during the anodic scan is observed during the cathodic scan. Due to the limitation of our equipment, we were not able to slow down scan rates below 30 mV/s. From the SCV-FTEIS experiments, a set of impedance data were obtained during the anodic scan in a frequency range of 1.5 Hz 25 kHz at every 20 mV in a potential range of 2.5 4.0 V. The results are shown in the form of three-dimensional Nyquist plots as a function of different anodic voltages for the hollow cell in Fig. 3a. As the voltage increases, semicircles in Nyquist plots become continuously smaller. A typical impedance spectrum isolated from the set of impedance data shown in Fig. 3a is displayed in Fig. 3b. The semicircle is highly depressed indicating either that there would be two charge transfer steps or that the double layer capacitances must have very large frequency dispersions. We thus used an equivalent circuit shown in Fig. 3c, which is made of two RC semicircles to t the data shown in Fig. 3a and 3b based on Gaberscek et al.s study:22 one for the current collector/electrode contact in the high frequency region and the other for charge transfer across the electrode/electrolyte interface in the low frequency region. Gaberscek et al.22 demonstrated by changing the external pressure on the cell that impedance characteristics of cathode of lithium ion rechargeable batteries are determined by electrical properties of both the current collector/cathode contact as well as the charge transfer across the electrode/electrolyte interface. Here, Rs is the solution resistance, RC the contact resistance, CC the contact capacitance, Cd the double layer capacitance, Rp the polarization resistance, and W the Warburg impedance. Both the measured data ( ) and the tted curve using the equivalent circuit in Fig. 3c are shown in Figure 3b; the ttings were satisfactory as shown by

2.4

2.8

3.2

3.6
+

4.0

E, V vs. Li/Li

Figure 4. Dependence of the solution resistance (Rs ) on scanned potential for the hollow () and the non-hollow ( ) cells during charging (a) and discharging (b) processes.

small 2 values of the order of low 104 throughout the whole voltage region scanned. Many investigators have pointed out that the EIS spectra should be obtained when the system is in an equilibrium or a stationary state.15 One may then debate on whether or not the EIS spectra obtained during the SCV-FTEIS experiment would indeed meet the requirements. Our EIS spectra have been shown to meet the requirements as the time taken for the measurement is shorter than that for the change taking place in system.23 We have demonstrated that EIS spectra obtained for a system, in which fast chemical reactions were known to take place following the electron transfer, at even higher scan rates than the one used in this work (30 mV/s) met the Kramers-Kronig transform criterion as well, which was proposed by Macdonald et al.24 for true impedances. The data analysis using the equivalent circuit shown in Fig. 3c provided related impedance parameters including Rs , RC , CC , Rp , Cd , and W as a function of scanned potential during anodic and cathodic scans. The Rs values thus obtained during charging and discharging processes are shown in Fig. 4. The Rs values did not change much with the average values of 20.2 (0.3) and 20.1 (0.3) , respectively, during charging and discharging cycles for the hollow cell throughout the measured voltage ranges, while they are 6.7 (0.3) and 6.7 (0.2) for the non-hollow cell. Since the Rs values represent the bulk resistances of the electrolyte solution and the cell thickness is small with a large electrode area, these values are reasonable. In the whole

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Journal of The Electrochemical Society, 158 (12) A1267-A1274 (2011)

18 17 16

A1271

(a)

Charging process Discharging process

4.5 4.0 3.5

(b)

Charging process Discharging process

Rc,

Cc, F/cm

15 14 13 12 11 2.4 2.8 3.2 3.6

+

3.0 2.5 2.0 1.5

4.0

2.4

2.8

3.2

3.6
+

4.0

E, V vs. Li/Li

E, V vs. Li/Li

120 110 100

(c)

Charging process Discharging process

2.0

(d)
1.8

Rc,

80 70 60 50 2.4 2.8 3.2 3.6

+

Cc, F/cm

90

1.6
Charging process Discharging process

4.0

1.4 2.4 2.8 3.2 3.6

+

4.0

E, V vs. Li/Li

E, V vs. Li/Li

Figure 5. Contact resistances (Rc s) and capacitances (Cc s) plotted as a function of potential for the hollow [(a) and (b)] and non-hollow [(c) and (d)] cells during charging ( ) and discharging ().

potential range, the Rs values of the cell are larger for the hollow cathode than those for the cell with the non-hollow cathode. The larger values for the hollow cell seem to arise from the interface between the cathode and the electrolyte due to larger amounts of organic compounds surrounding LiFePO4 particles. Figure 5 shows electrical characteristics for current collector/cathode contacts, RC and CC values, obtained during anodic ( ) and cathodic () scans for cells for hollow [(a) and (b)] and non-hollow [(c) and (d)] cathode materials. The contact resistances are signicantly smaller for the hollow cathode material than its non-hollow counterpart. The electrical characteristics of the contacts are shown to vary depending on the state of the electrode. The contact resistances keep decreasing during the charging process and then begin to increase upon potential reversal (Fig. 5a and 5c). For the hollow cell, RC reaches a maximum at around the formal potential and decreases to a minimum. However, it reaches a steady state low value below 3.0 V for the non-hollow cell. At the formal potential where the maximum RC value is observed, the fraction of LiFePO4 and FePO4 is about the same at 0.5. Maximum capacitances are observed at this point as well (Fig. 5b and 5d). The electrical characteristics of the contacts are shown to depend much on the state of the cathode material as will be discussed below. Very similar trends to those described above are noted for the charge transfer processes as shown in Fig. 6. As lithium deposition

and dissolution reactions taking place at the anode during charging and discharging processes are far more kinetically facile than the redox reactions at the cathode, the Rp values obtained in this analysis must be due to the redox reaction of LiFePO4 . In contrast to Rs (Fig. 4), Rp values are much smaller for the hollow cell than those for the non-hollow cell during both potential scans. Thus, the charge transfer is a great deal more facile for the hollow cell than that for the nonhollow cell during both charging and discharging processes, which are consistent with the CVs and SCVs shown in Figs. 1 and 2. During the anodic scan from 2.5 V to 4.0 V (Fig. 6a), Rp decreases rather monotonously at the outset but the rate of decrease becomes faster from about 3.7 V as the overpotential goes well into the Tafel region past the formal potential for redox reactions of LiFePO4 (3.46 and 3.44 V) for both hollow and non-hollow cells. It appears that the rate of electron transfer as well as the mass transfer cannot catch up with the rate of voltage change during the impedance measurements during anodic scans. As pointed out above, we could not slow down the scan speed during our SCV-FTEIS experiments due to the limitations of our instrument. As a result, the SCV peaks do not show up within the anodic potential limit as can be seen in Fig. 2 and this was shown to be true in the impedance measurements as well. Thus Rp is still in the midst of change by the time the potential has reached the anodic limit of 4.0 V. This behavior is readily expected from Fig. 1 as well, in which the anodic peak current was not observed even at 10 mV/s

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A1272

Journal of The Electrochemical Society, 158 (12) A1267-A1274 (2011)

35
20

(a)

Charging process Discharging process

Charging process Discharging process

30 25 20 15 10 5

(b)

Rp,

10

5 2.4 2.8 3.2 3.6

+

Cd, F/cm

15

4.0

2.4

2.8

3.2

3.6
+

4.0

E, V vs. Li/Li
160 140 120

E, V vs. Li/Li
12 11 10
Charging process Discharging process

(c)

Charging process Discharging process

(d)

Cd, F/cm

100

9 8 7 6 5 4

Rp,

80 60 40 20 2.4 2.8 3.2 3.6

+

4.0

2.4

2.8

3.2

3.6
+

4.0

E, V vs. Li/Li

E, V vs. Li/Li

Figure 6. Polarizational resistances (Rc s) and double layer capacitances (Cc s) plotted as a function of potential for the hollow [(a) and (b)] and non-hollow [(c) and (d)] cells during charging ( ) and discharging (). The scan directions are shown by the arrows.

for the non-hollow cell. Finally, it should be pointed out that the charge transfer is a great deal faster for the hollow cell in comparison to the non-hollow cell as evidenced by the polarization resistances, Rp s. During the negative potential scan from 4.0 V to 2.5 V, the potential dependencies of Rp (Fig. 6a and 6c) are signicantly different from those shown during anodic scans. The Rp values show a maximum for both cells at slightly different potentials, 3.50 V for the hollow and 3.45 V for the non-hollow cell. At the potential where the maximum Rp is observed, i.e., formal potential, charge transfer rates for anodic and cathodic processes are the same resulting in a small net current. Thus, oxidation of LiFePO4 would still occur above this potential whose rate decreases as the potential gets negative while reduction of FePO4 would begin at the potential where the Rp value is at its maximum. In other words, the high anodic current at 4.0 V decays as the potential gets negative and reaches a minimum at about 3.5 V (formal potential). At this point, the cathodic current begins to rise and reaches its maximum at about 3.0 V where a minimum Rp is observed (Fig. 6a). At 4.0 V, the charge-transfer resistance for LiFePO4 oxidation is very small, which increases and reaches its maximum of 15.4 at about 3.5 V (Fig. 6a), indicating that rates of charge transfer for both oxidation of LiFePO4 and reduction of FePO4 become signicantly low. Upon further decreasing the potential, Rp reaches its minimum suggesting that the rate of reduction of FePO4 goes through

a maximum. The charge transfer rate during the discharge process reaches the maximum at the potential where a minimum Rp value is observed at about 3.0 V, below which the mass transfer for Li+ controls the overall discharging process (vide infra). As Rct (charge transfer resistance) values represented by maximum Rp values at formal potentials are 15.4 and 129.7 , respectively, for the hollow and non-hollow cells, the electron transfer kinetics are about an order of magnitudes better for the former than the latter. The dependence of Cd at various potential values shown in Fig. 6b and 6d show that the Cd values are about twice for the hollow cell of those of its non-hollow counterpart due perhaps to the difference of its micro-secondary structures. The LiFePO4 nanoparticles of hollow sphere secondary structures must have larger effective surface areas than non-hollow nanoparticles do because of their electrodeelectrolyte interfaces formed inside as well as outside the particles. For the hollow cell (Fig. 6b), the capacitance increases slowly upon anodic scan to 4.0 V, decreases upon scan reversal, and hit the maximum when the charge transfer rate becomes maximum at about 3 V. For the non-hollow cell, the trend is not as clear as for the hollow cell. The double layer capacitances undergo relatively large changes as a function of potential, particularly for the hollow cell, as the pseudo-capacitances due to the Faradaic reactions are coupled with the double layer capacitance.25 However, the contribution of the pseudocapacitance is not as prominent in the case of the non-hollow cell due

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Journal of The Electrochemical Society, 158 (12) A1267-A1274 (2011)

0.06

A1273

(a)
0.05 0.04

Charging process Discharging process

0.03 0.02 0.01 2.4 2.8 3.2 3.6

+

4.0

minimum is reached at about 3.48 V and then increases back to reach a maximum at 3.17 V. The maximum Warburg admittance is thus observed at about the potential where the rate of reduction of FePO4 is maximum when examined with the CVs and SCVs shown in Figs. 1, 2, and 6. In a reversible electrochemical system, the maximum Warburg admittance is observed at the half-wave potential,20, 27 which should be about the same as the formal or standard electrode potential and does not move depending on the scan rate for a reversible electrochemical system. For a reversible electron transfer reaction, the maximum admittance is therefore observed at the same potential regardless the scan direction. In an electrochemically irreversible system as in our present case, however, the peak potential shifts to a more positive or negative potential depending on the scan direction. As a result, we observe peak admittances at quite different potentials depending on anodic or cathodic direction. As the maximum Warburg admittance has the value,20, 27 n 2 F 2 C D 1/2 , [2] 4 RT where C and D are the concentration and diffusion coefcient of either an oxidant or a reductant depending on whether the maximum is observed during an anodic or a cathodic scan, we can conclude that the diffusion coefcient in the hollow cell must be greater than that in the non-hollow cell by about 410 times depending on the potential. One can also see from Fig. 7 that it is slightly easier for Li+ to diffuse out from the crystalline LiFePO4 electrode to the electrolyte solution during its oxidation than the other way around as the Warburg admittances are larger during anodic processes than for cathodic scans. A more important conclusion is that the modication of secondary structures of nanoparticles signicantly affects the Li+ diffusion during charging/discharging processes. Ymax = Conclusions

YW, S*sec

1/2

E, V vs. Li/Li
0.04

(b)
Charging process Discharging process

0.03

YW, S*sec

1/2

0.02

0.01

0.00 2.4 2.8 3.2 3.6

+

4.0

E, V vs. Li/Li

Figure 7. Warburg admittances plotted as a function of scanned potential for the hollow [(a)] and non-hollow [(b)] cells during charging ( ) and discharging ().

to the slow electron transfer kinetics as indicated by a large Rp values (Fig. 6c). Finally, changes in Warburg admittances were also monitored as a function of potential and are shown in Fig. 7 during anodic (a) and cathodic (b) potential scans. The Warburg admittances represent the degree of how facilely lithium ions diffuse in or out of the bulk cathode materials during charging or discharging processes. The diffusion of ions in a solution phase is much faster than that in a solid phase,26 and the Warburg admittance would represent only the bottleneck of two mass transport processes when the two transport paths are connected in series. The Li+ diffusion is induced by the redox chemistry of the Fe3+ /Fe2+ pair in the cathode, and the Warburg admittances shown in Fig. 7 thus represent those due to the Li+ diffusion within the solid matrix. The results show that the Warburg admittance is generally higher for the hollow cell than for the non-hollow one in the whole potential range because the hollow structured nanoparticles are much more available to the electrolyte than the non-hollowed particles as pointed out above. During the anodic potential scan, the Warburg admittance sharply increases above 3.6 V because Li ions begin to diffuse out from solid LiFePO4 during the charging process due to its oxidation to FePO4 causing Li+ to de-intercalate. Again, it is not clear whether a maximum has been reached or not during the anodic scan before the vertex potential due to the fast scan rate. Two noticeable points are observed for the hollow cell during the cathodic scan (Fig. 7a). First, the large admittances observed at 4.0 V undergo a decrease until a

We have demonstrated for the rst time that real-time impedance measurements employing the FTEIS method offer a powerful means for characterizing a battery electrode material during charging and discharging processes by taking LiFePO4 nanoparticles of hollow and non-hollow sphere secondary structures as an example. The lithiumion cell using the hollow sphere secondary structured LiFePO4 as the cathode shows better cell performances as demonstrated by impedance parameters such as smaller polarization resistances (Rp s), higher capacitances (Cd s), and higher mass transport admittances (Y0 s) than the non-hollow structured cathode material. These parameters indicate that the hollow structured LiFePO4 cathode material has a smaller activation barrier for electron transfer and the more efcient ion transport than its non-hollow structured counterpart. The data obtained in real time by monitoring variations of each impedance parameter as a function of potential variation helped elucidate more detailed mechanisms for performance improvements of LiFePO4 nanoparticles in terms of their intrinsic electron and ion transport characteristics when their secondary structures are modied. This study clearly indicates that appropriate modication of secondary structures of nanoparticles can signicantly improve their performances and also that the real time EIS measurements provide much information about an electrochemical reaction, which could otherwise have been difcult to acquire if not impossible. Finally, it should be pointed out that rather poor kinetic parameters for the electrochemical reaction including electron and mass transfer characteristics may lead to rather poor performances for LiFePO4 as a cathode material for high power devices such as in electric vehicular applications. A great deal more fundamental electrochemical databases on other materials are in need for the assessment of their comparative performances for high power devices. Acknowledgment This work was supported by the WCU program (R31-2008-00020012-0) granted to the UNIST. The authors are grateful to Ms.

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A1274

Journal of The Electrochemical Society, 158 (12) A1267-A1274 (2011)

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