Chapter 6. Conclusions ············································································
0.5 mA/cm 2
When plotting charge passed before short-circuit with modulus, it is seen that the higher modulus materials can go through more charges before failure, but no linear or log relationship is observed between modulus and Cd (Figure 5-41). However, when the reciprocal of Cd is plotted with modulus, a linear relationship can be observed between
1/Cd and log(modulus) for samples with high moduli (Figure 5-42). By extrapolating the linear relationship, it is observed that with a modulus of about 4.5 MPa, 1/Cd goes to 0 and Cd goes to infinity. Like the result found from galvanostatic polarization data, this value is much smaller than the theoretical modulus required to prevent short-circuit.
0.5 1.0 1.5 2.0 2.5 0 500 1000 1500 2000 2500 3000 3500 Cd (C/cm 2 )
Young's Modulus (MPa)
1 2 3 500 1000 1500 2000 2500 3000 3500 Cd (C/cm 2 )
Young's Modulus (MPa)
Figure 5-41. Total charge passed per cm2 vs. Young’s modulus for POSS-4PEG2k samples under J = 0.5
mA/cm2 with (a) linear scale and (b) log10-scale x-axis.
a
1 2 3 4 5 0.0 5.0x10-4 1.0x10-3 1.5x10-3 2.0x10-3 2.5x10-3 3.0x10-3 3.5x10-3 4.0x10-3 4.5x10-3 1/Cd (cm 2 /C)
Young's Modulus (MPa)
Equation y = a + b*x Weight No Weighting Residual Sum of Squares 1.75383E-8 Pearson's r -0.98244 Adj. R-Square 0.94779 1/Cd Intercept Slope
Figure 5-42. Reciprocal of charge passed to short-circuit vs. Young’s modulus for POSS-4PEG2k under J = 0.5 mA/cm2.
Comparing the results from Figure 5-42 with the work from Ref. [39] and [51] (Figure 5-43), it is seen that the crosslinked network from Ref. [51] or this work do not fall on the Cd vs. modulus relationship proposed in Ref. [39]. This may indicate that crosslinked
polymer electrolyte network may have different correlation from block-copolymers, but this may also mean that there are some other relationships that are important to characterize the property-performance relationship.
Figure 5-43. Reciprocal of total charge passed to short-circuit vs. modulus adapted from [39]. Black dots are data from PEO or PS-b-PEO electrolytes. Yellow dot is data from [51]. Blue dragon is the data from
this work.
From the plot of Cd versus ionic conductivity (Figure 5-44), an inverse relationship
trend is observed, and the linear fit of the data show good fitting but not totally perfect. However, when plotting Cd versus the ratio between modulus and ionic conductivity, the
data show near perfect linear relationships (Figure 5-45). The result gives a relationship of the parameters as:
𝐶𝑑 = 𝑎𝐺𝑛𝜎𝑚+ 𝐶𝑑0
where G is the modulus and σ is the ionic conductivity of the electrolyte, and a, n, m, and 𝐶𝑑0 are the fitting constants. In this case, n ≈ 1, m ≈ -1. The plot also shows that the data from Ref. [51] also follow this relationship.
Figure 5-44. Total charge passed vs. ionic conductivity for POSS-4PEG2k samples under J = 0.5 mA/cm2.
Yellow dot is data from [51].
Figure 5-45. Total charge passed vs. the ratio between Young’s modulus ionic conductivity for POSS- 4PEG2k samples under J = 0.5 mA/cm2. Yellow dot is data from [51].
1.0x10-3 1.5x10-3 2.0x10-3 2.5x10-3 0 500 1000 1500 2000 2500 3000 Cd (C/cm 2 ) Conductivity (S/cm) 0 500 1000 1500 2000 2500 3000 0 500 1000 1500 2000 2500 3000 Cd (C/cm 2 ) Modulus/Conductivity (MPa cm S-1)
Although this result might indicate that materials with very high modulus and low ionic conductivity may have the best performance, when selecting and designing the electrolyte materials, as materials with very high modulus typically have bad contact with electrodes, and low conductivity materials will have low J* that limit the current density that the electrolyte can be used. Therefore, polymer electrolyte materials with Young’s modulus close to 4.5 MPa with good ionic conductivity is desired for lithium-metal polymer battery applications.
Chapter 6. Conclusions
6.1. Summary
The experimental results in this thesis show that:
Addition of PEG250 plasticizer does not change the crosslink network structure of POSS-PEG polymer electrolytes.
The plasticized polymer electrolytes have good thermal, chemical, and electrochemical stabilities.
The electrolytes have good compatibilities with lithium metal and can be used for lithium-metal batteries.
Increase in plasticizer load increases ionic conductivity but decreases in mechanical property.
Total charge passed through the cell before short-circuit increases with modulus and decreases with conductivity of the electrolyte.
Optimal electrolyte material should be soft for good contact, high ionic conductivity for a larger working current density range, and high modulus:conductivity ratio.
6.2. Outlooks
6.2.1. POSS-4PEG6k
One direction for the future work is to study the unplasticized and plasticized POSS-4PEG6k sample which has networks with POSS:PEG ratio of 1:4 using PEG with
molecular weight of 6000 g/mol. Such crosslinking ratio has the most efficient crosslinking density as the end groups of POSS and PEG has the ratio of 1:1. Also, previous work has shown that POSS-4PEG2k has better properties than POSS-2PEG2k [53], so similarly, the properties of POSS-4PEG6k should be more desirable than POSS-2PEG6k.
FTIR spectrum of unplasticized POSS-4PEG6k0 shows very similar characteristic peaks with the unplasticized POSS-2PEG6k0 sample (Figure 6-1). This is expected as the structures as the functional groups on the two samples should be the same.
4000 3500 3000 2500 2000 1500 1000
Transmittance (% T)
Wavenumber (cm^-1) 2PEG6k0
4PEG6k0
Figure 6-1. FTIR spectra of POSS-2PEG6k and POSS-4PEG6k
DSC curves (Figure 6-2) show that POSS-4PEG6k0 has higher Tg, Tm, and crystallinity comparing to POSS-2PEG6k0 (Table 6-1).
-50 0 50
Heat Flow (Endo up)
Temperature (oC) POSS-2PEG6k0
POSS-4PEG6k0
Figure 6-2. DSC curves of POSS-2PEG6k0 and POSS-4PEG6k0.
Table 6-1. Thermal properties of POSS-2PEG6k0 and POSS-4PEG6k0 measured by DSC Tg (˚C) Δcp (J/g-˚C) Tm, onset (˚C) Tm, peak (˚C) ΔH (J/g) %X POSS- 2PEG6k0 -46.95 0.404 14.37 29.41 27.81 13.7% POSS- 4PEG6k0 -38.42 0.314 25.40 38.37 48.39 23.8%
Conductivity data shows that POSS-4PEG6k0 sample has significantly higher ionic conductivity that POSS-4PEG2k0 and POSS-2PEG6k0 at high temperatures (Figure 6-3). As the POSS-4PEG6k0 sample has a melting point of about 38˚C, the sample is crystalline at room temperature, so the conductivity is lower at 30˚C. This may hinder room temperature application of the material, but plasticizing the sample with PEG250 should lower the melting temperature of POSS-4PEG6k similar to the behavior in POSS-2PEG6k shown in Section 4.2, so the plasticized samples may be suitable for room temperature application as they would have even higher conductivity. Also, the galvanostatic polarization experiments of the samples can be used to for further understanding of lithium dendrite growth mechanism in crosslinked and plasticized polymer electrolytes.
2.6 2.7 2.8 2.9 3.0 3.1 3.2 3.3 3.4 1E-4 1E-3 POSS-4PEG2k0 POSS-2PEG6k0 POSS-4PEG6k0 Conductiv ity (S/c m) 1000/T (1/K)
Figure 6-3. Conductivity data of unplasticized crosslinked SPEs.
6.2.2. Mixed plasticizer for SPEs
In the literature [93], it has shown that adding mixed liquid electrolytes can provide different coulombic efficiency and therefore change the performance of the electrolyte in lithium-ion batteries (Figure 6-4). Despite the mechanism of mixed electrolyte in lithium- ion batteries is still not clear, adding a different electrolyte species may improve the performance of the battery significantly, such as 4UA and 5UA samples in Figure 6-4b.
Figure 6-4. (a) 1/(Charge slippage) (Units are cycle/mAh) vs. 1/(1 – CE) (no units) showing that oxidation reactions at the positive electrode account almost exclusively for the departure of coulombic efficiency from the ideal value of 1.00000 and (b) number of cycles to failure at 1.6 Ah (cycling at 1C) vs. 1/(1 – CE).
The solid line is a fit to the results for the non-proprietary additives.[93]
Based on such model, mixed liquid electrolytes as plasticizers in SPE may induce similar improvement of performance. Different electrolytes may also affect the mechanical properties of the SPE differently. Therefore, mixed plasticizers can be researched for crosslinked network SPE.
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