In this study, the porous zircon-silicon-carbon (ZSC) matrix was made as anode material to solve severe volume expansion and poor conductivity problem during cycling. The overall logic of making ZSC composite was constructed step by step.
Firstly, studying critical factors for making porous zirconia structure is necessary and on the basis of such experimental results, a porous ZS could be procurable. Besides, a novel idea of calcining gel in vacuum environment was realized and presented interesting results that it can retain more pore volume than under normal calcinations atmosphere, for instance, 3% H2/N2. Secondly, to solve the electronic insulation property, two different carbon coating method were adopted and each for different purpose. Pitch coating has indeed reduce the 1st cycle irreversibility by fulfilling pore volume which can sufficiently reduce surface area. Soaking gel in fructose solution showed better coverage of Si and more homogeneous carbon distribution which indeed improve the poor conductivity of silicon, especially for 100 nm Si.
Another important property of ZSC matrix should be its high tap density, which is around 4 to 5 times larger than nano Si. (ZSC: 0.4-0.5 g/cm3,40 nm Si : 0.08 g/cm3).
Under the same conditions, like solid-to-solvent ratio of slurry, binder property, compression ratio, the higher tap density means larger electrode density. From Table 5.3 and 5.4, the electrode density of ZSC powder increases from 0.8 to 1.3-1.5 g/cm3( increase more than 50%). Combination of better capacity retention and higher electrode density, ZSC powder gives much better volume-based capacity after 50th cycling. Finally, the space for improvement should be to find a better way to well disperse silicon particle in ZSC matrix which can definitely improve the cyclic performance.
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Appendix A
Figure A.1 The ZrO2 gels with different concentration of precursor dried to certain state. (ZrO2 (0.01M) just cracked and others were not far from cracking)
Figure A.2 The collected ZrO2/Si gel from filtration process.
Figure A.3 (left) The viscous gel property of ZrO2(0.01M)-Dry 23hr (right) The crack image of ZrO2(0.01M)-Dry 23hr.
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Figure A.4 The drying process illustration (a) after adding water to induce sol-gel transition and keep static for 30 min (b) drying after 14 hr (c) residual gel (d) decant the solution in (c) to smaller batch.
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Figure A.5 40 nm Si and 100 nm Si disperse in 2-propanol. The solution color also reflects their different color in appearance.
Figure A.6 (Left) Z(0.1), Z(0.01)S(40), and Z(0.01) gel from left to right. (Right) the huge difference of left volume when crack just formed of Z(0.1) and Z(0.01) gel samples.
144
Appendix B
10 20 30 40 50 60 70 80
700qC
500qC
300qC
In tens ity (a.u.)
2
4ZrO2-c ZrO2(0.01M)-Vacuum
Figure B.1 XRD patterns of ZrO2(0.01M) gel calcined at different temperature for 15 min under vacuum condition.
145
1200 1300 1400 1500 1600 1700 1800
33.9%
1200 1300 1400 1500 1600 1700 1800
(b)
1200 1300 1400 1500 1600 1700 1800
(c)
Figure B.2 Raman spectra showing the bonding structure of the C-coatings of (a) ZSC(F13%)V500, (b) ZSC(F13%)V900, and (c) ZSC(P15%)HN900.