Abstract
A polymorphic lithium-silicon compounds for use in pure silicon anode of lithium-ion battery and use thereof are provided. The pure silicon anode includes nucleuses which have one or more structures of Li.sub.4.1Si_Cmcm, Li.sub.13Si.sub.4_Pbam, Li.sub.2Si_C12m1, and LiSi_I41/AZ. It was generally believed Li.sub.4.1Si_Cmcm to be a high-temperature stable phase, not presenting at room temperature or in the pure silicon anode of lithium-ion battery, but this present invention proves that Li.sub.4.1Si_Cmcm can exist in the disclosed material. After lithiation process, the pure silicon anode can have a structure of one or more of Li.sub.4.1Si_Cmcm, Li.sub.13Si.sub.4_Pbam, Li.sub.2Si_C12m1, and LiSi_I41/AZ, with extremely improved capacity. The present disclosure may increase the electrical capacity of the pure silicon anode in actual use and solve the problem of the existing pure silicon anode that the volume expansion after repeated lithiation and delithiation leads to electrode damage and battery failure.
Claims
1. A polymorphic lithium-silicon compound for a pure silicon anode of a lithium-ion battery, characterized in that the polymorphic lithium-silicon compound has an X-ray powder diffraction pattern substantially the same as that shown in FIG. 5 and an X-ray absorption spectrum substantially the same as that shown in FIG. 6A.
2. A pure silicon anode of a lithium-ion battery, comprising a first polymorphic lithium-silicon compound, wherein the first polymorphic lithium-silicon compound comprises a Li4.1 Si_Cmcm having X-ray diffraction peaks at 2θ positions of 15.75±0.1 degree, 20.72±0.1 degree, 24.11±0.1 degree, 26.05±0.1 degree, 27.15±0.1 degree, 39.52±0.1 degree, 41.36±0.1 degree and 43.16±0.1 degree under a Cu target Kα X-ray radiation.
3. The pure silicon anode claim 2, wherein an X-ray absorption peak appears at 1847±2 eV in the X-ray absorption spectrum.
4. A pure silicon anode for lithium-ion batteries, comprising one or more nucleus, wherein the nucleus comprises the first polymorphic lithium-silicon compound of claim 2.
5. The pure silicon anode for lithium-ion batteries of claim 4, wherein the nucleus has a size between 1 nm and 5,000,000 nm.
6. A method to prepare a pure silicon anode of lithium-ion batteries, the method comprising: plating a protective layer on the surface of a pure silicon powder except tiny sites to produce one or more exposed surface; and performing a lithiation reaction to induce a flux of lithium ions having a lithium ion concentration higher than 4 atomic percent per unit area in contact with the exposed surface; wherein a lithiation rate of the lithiation reaction or a delithiation rate of the delithiation reaction is controlled between 0.5 C and 30 C.
7. The pure silicon anode for lithium-ion batteries of claim 4, wherein the pure silicon anode for lithium-ion batteries is composed of hollow, multilayer, porous, nanowire, nanopillar or nanoparticle morphology, which has a shell thickness, a film thickness, a mold wall thickness and a line width between 1 nm and 100 nm.
8. The pure silicon anode of claim 2, further comprising a second polymorphic lithium-silicon compound selected from one or more groups consisting of a Li.sub.13Si.sub.4_Pbam, a Li.sub.2Si_C12/m1, and a LiSi_I41AZ, wherein: the Li.sub.13Si.sub.4_Pbam having X-ray diffraction peaks at 2θ positions of 12.33±0.1 degree, 20.72±0.1 degree, and 22.6±0.1 degree under the Cu target Kα X-ray radiation; the Li.sub.2Si_C12/m1 having X-ray diffraction peaks at 2θ positions of 14.05±0.1 degree and 23.61±0.1 degree under the Cu target Kα X-ray radiation; and the LiSi_I41AZ having X-ray diffraction peaks 2θ positions of 18.77±0.1 degree and 19.28±0.1 degree under the Cu target Kα X-ray radiation.
9. The method of claim 6, further comprising placing and compacting the pure silicon powder in a groove of a substrate prior to performing the lithiation reaction.
10. The method of claim 9, wherein the substrate comprises copper.
11. The method of claim 9, wherein the substrate and the pure silicon powder are covered by a screen.
12. The method of claim 6, further comprising performing the delithiation reaction after performing the lithiation reaction, wherein an electrolyte of EC/DEC+FEC is used in performing the lithiation reaction and the delithiation reaction.
13. A method for preparing a pure silicon anode for lithium-ion batteries, the method comprising: forming a protective layer on a surface of a pure silicon powder and allowing one or more sites on the surface to have the protective layer with uneven thickness; and performing a pre-lithiation reaction that induces a flux of lithium ions having a lithium ion concentration higher than 4 atomic percent per unit area at the one or more sites.
14. The method of claim 13, wherein forming the protective layer comprises allowing the one or more sites on the surface to be exposed from the protective layer.
15. The method of claim 13, wherein after performing the pre-lithiation reaction, the pure silicon anode being transformed to an amorphous structure comprising one or more short-range-ordering structures.
16. The method of claim 15, wherein performing the pre-lithiation reaction comprises controlling a first voltage and a lithiation rate of a lithiation reaction to be in a range of from about 0.5 C to about 30 C.
17. The method of claim 16, wherein a duration of the lithiation reaction is controlled to limit the lithiation reaction at the surface of the pure silicon powder.
18. The method of claim 16, wherein the pre-lithiation reaction further comprises performing a delithiation reaction with a second voltage having an opposite polarity to the first voltage.
19. The method of claim 16, further comprising performing a nucleation process that expands the short-range-ordering structures in the pure silicon powder.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
[0017] FIG. 1A illustrates a schematic diagram of a manufacturing method for implanting the nucleus of one or more of Li.sub.4.1Si_Cmcm, Li.sub.13Si.sub.4_Pbam, Li.sub.2Si_C12m1, and LiSi_I41/AZ into the pure silicon anode, according to an embodiment of the present disclosure.
[0018] FIG. 1B illustrates a schematic diagram of the pure silicon anode powder containing the nucleus, according to an embodiment of the present disclosure.
[0019] FIG. 2 illustrates an X-ray absorption spectrum of the silicon-based powder after the nucleus is implanted, according to an embodiment of the present disclosure.
[0020] FIG. 3 illustrates a schematic diagram of the structural changes of the pure silicon anode after lithiation, according to an embodiment of the present disclosure.
[0021] FIG. 4A illustrates structural diagrams of Li.sub.4.1Si_Cmcm, according to an embodiment of the present disclosure.
[0022] FIG. 4B illustrates structural diagrams of a commonly formed lithium-silicon compound Li.sub.15Si.sub.4_I-43d, according to a comparative embodiment of the present disclosure.
[0023] FIG. 5 illustrates X-ray diffraction patterns of Li.sub.4.1Si_Cmcm, Li.sub.13Si.sub.4_Pbam, Li.sub.2Si_C12m1, and LiSi_I41/AZ, according to an embodiment of the present disclosure.
[0024] FIGS. 6A and 6B illustrate X-ray absorption spectra of the specifically designed silicon anode as well as the simulated X-ray absorption spectra from theoretical calculations of Li.sub.4.1Si_Cmcm, Li.sub.13Si.sub.4_Pbam, Li.sub.2Si_C12m1, and LiSi_I41/AZ, according to an embodiment of the present disclosure.
[0025] FIGS. 7A and 7B illustrate X-ray absorption spectra of Li.sub.4.1Si_Cmcm, Li.sub.13Si.sub.4_Pbam, Li.sub.2Si_C12m1, and LiSi_I41/AZ as well as the simulated X-ray absorption spectra from theoretical calculations of Li.sub.17Si.sub.4_F-43m, Li.sub.15Si.sub.4_I-43d, Li.sub.12Si.sub.7_Pnma, and Li.sub.5Si.sub.2_R-3m, according to an embodiment of the present disclosure.
[0026] FIG. 8 illustrates a diagram of an electrical capacity test of the pure silicon anode for lithium-ion batteries made by the crystal of the present invention, according to an embodiment of the present disclosure.
[0027] FIG. 9 illustrates a schematic diagram of a lithium-ion battery having the anode of the present invention, according to an embodiment of the present disclosure.
[0028] FIG. 10A illustrates a schematic diagram of a nucleus used in the pure silicon anode with a hollow structure, according to an embodiment of the present disclosure.
[0029] FIG. 10B illustrates a result of observing the pure silicon anode powder with a hollow structure using a transmission electron microscope, according to an embodiment of the present disclosure.
[0030] Among the figures, 100 is pure silicon anode powder with nucleus species; 102 is nucleus species; 104 is silica powder; 200 is lithium-ion battery; 202 is anode; 204 is cathode; and 206 is separation membrane.
DETAILED DESCRIPTION
[0031] In order to have a further understanding of the present invention, the following embodiments are exemplified.
[0032] Pre-lithiation is an electrochemical reaction in which lithiation and delithiation reactions are performed on the silicon anode. After the lithiation and delithiation reactions, the silicon anode will transform to an amorphous structure, leaving behind a nano-scale nucleus. In the present invention, before performing the lithiation reaction, a special protective layer is fabricated on the powder surface and a specific site is left for the lithiation reaction (uneven powder coating). The lithium flux (Li.sup.+ ion flux) at the specific site is therefore relatively high, resulting in the formation nucleus with short-range-ordering structures of Li.sub.4.1Si_Cmcm, Li.sub.13Si.sub.4_Pbam, Li.sub.2Si_C12m1, or LiSi_I41/AZ, which is different from the Li.sub.15Si.sub.4_I-43d ordering structure of traditional electrodes.
[0033] Please refer to FIGS. 1A and 1B. In the present invention, a protective layer is disposed on the surface of the (silicon) powder and tiny sites are left uncovered to expose the surface of the powder. Next, the powders are compacted and placed in a groove of a copper substrate, which is then covered by a screen to prevent the powder from shedding. Next, an electrochemical method is used to carry out lithiation and delithiation reactions, in which the electrolyte is EC/DEC+FEC including LiPF.sub.6. Because the lithiation reaction will only occur at the sites that are not covered by the protective layer, a relatively high lithium flux (having a lithium ion concentration of greater than 4 atomic percent per unit area) may be generated at these sites by properly controlling the voltage and lithiation rate (between 0.5 C and 30 C). The period of lithiation reaction under high lithium flux is controlled so that the lithiation reaction occurs only on the surface without diffusion into the powder. Therefore, the lithiation is controlled by the surface reaction instead of the diffusion reaction. After the lithiation reaction, a reverse bias is applied to carry out the delithiation reaction. Consequently, powders containing the special nucleuses can be obtained. FIG. 2 shows X-ray absorption spectra of silicon that has not undergone the lithiation and delithiation reactions and silicon that has been embedded by the nucleus after the reaction.
[0034] Please refer to FIG. 3. When the pure silicon anode material powder has the nucleus as described in the present invention, during the lithiation process, the theory of nucleation can be utilized to make the entire powder form one or more structures of Li.sub.4.1Si_Cmcm, Li.sub.13Si.sub.4_Pbam, Li.sub.2Si_C12m1, and LiSi_I41/AZ.
[0035] The present invention uses X-ray diffraction spectroscopy and X-ray absorption spectroscopy to identify the specially designed pure silicon anodes of the present invention. After the lithiation reaction, one or more lithium-silicon compounds of Li.sub.4.1Si_Cmcm, Li.sub.13Si.sub.4_Pbam, Li.sub.2Si_C12m1, and LiSi_I41/AZ are formed. FIGS. 4A and 4B show differences between the final phase Li.sub.4.1Si_Cmcm and the commonly formed phase Li.sub.15Si.sub.4_I-43d.
[0036] FIG. 5 shows an X-ray diffraction spectrum that was obtained by synchrotron radiation X-ray with a wavelength of 0.6888 angstrom and energy resolution of 10.sup.−4 (ΔE/E, where E is the X-ray energy), wherein a two-dimensional detector was used to collect diffraction signals. For facilitating comparison, diffraction patterns with the X-ray wavelength of 0.6888 angstrom were converted into patterns with a wavelength of 1.5406 angstrom (a wavelength of X-ray emitted from a Cu target). Peaks in FIG. 5 indicate the existence of compounds Li.sub.4.1 Si_Cmcm, Li.sub.13Si.sub.4_Pbam, Li.sub.2Si_C12m1, and LiSi_I41/AZ in the specially designed silicon anode of the present invention.
[0037] X-ray absorption spectroscopy was performed using synchrotron radiation X-rays. When the X-ray energy was scanned from 1770 eV to 2130 eV, the Lytel detector was used to collect fluorescent signals that emitted from the sample. The incident X-ray energy and the fluorescent intensity were recorded to obtain the X-ray absorption spectrum of the Si K-edge. Please refer to FIGS. 6A and 6B. Because the X-ray absorption spectrum was composed of charge transfer between electronic states and multiple scattering between incident x-ray and scattering x-ray by atoms, such spectrum may reflect valence of the atoms, surrounding environment of the atoms and symmetry of atomic structure. To further identify X-ray absorption spectra, FDMNES was also used to simulate X-ray absorption spectra based on the theory of X-ray absorption and X-ray multiple scattering. The simulated X-ray absorption spectrum of silicon identical to the experimental one can ensure the reliability of simulations.
[0038] Referring to FIGS. 6A and 6B, the absorption spectrum obtained in the experiment has a clear absorption peak at 1847 eV. Compared to simulated spectra, it is found that the position of the absorption peak of 1847 eV is equivalent to the positions of the absorption peak of the four compounds Li.sub.4.1Si_Cmcm, Li.sub.13Si.sub.4_Pbam, Li.sub.2Si_C12m1, and LiSi_I41/AZ, indicating existence of one or more of these four compounds, and also indicating that these four compounds have same atomic surroundings, atomic symmetry relationship or electronic structure. By aligning the X-ray absorption spectra with the X-ray diffraction pattern, it is confirmed that the pure silicon anode of the present invention has one or more compounds among Li.sub.4.1Si_Cmcm, Li.sub.13Si.sub.4_Pbam, Li.sub.2Si_C12m1, and LiSi_I41/AZ.
[0039] In contrast, the simulation spectra of the four compounds Li.sub.17Si.sub.4_F-43m, Li.sub.15Si.sub.4_I-43d, Li.sub.12Si.sub.7_Pnma, and Li.sub.5Si.sub.2_R-3m (as shown in FIG. 7B), especially the Li.sub.15Si.sub.4_I-43d simulation spectrum formed after the lithiation of the ordinary pure silicon anode, show that the strongest absorption peak of these four compounds locating at about 1838 eV, which is significantly different from the absorption peak of the experimental spectrum. This indicates that the pure silicon anode of the present invention has none of the four compounds of Li.sub.17Si.sub.4_F-43m, Li.sub.15Si.sub.4_I-43d, Li.sub.12Si.sub.7_Pnma, and Li.sub.5Si.sub.2_R-3m. This also shows that the above four compounds have significantly different atomic surrounding environments, atomic symmetry relationships or electronic structures, compared to the four compounds of Li.sub.4.1Si_Cmcm, Li.sub.13Si.sub.4_Pbam, Li.sub.2Si_C12m1, and LiSi_I41/AZ formed after lithiation of the pure silicon anode of the present invention.
[0040] Please refer to FIG. 2. Using X-ray absorption spectroscopy for identification, an existence of a nucleus can be clearly found. A structure of the nucleus is one or more of Li.sub.4.1Si_Cmcm, Li.sub.13Si.sub.4_Pbam, Li.sub.2Si_C12m1, and LiSi_I41/AZ. The nucleus has the same atomically surrounding environment, atomic structure symmetry or electronic structure as the above four compounds.
[0041] Please refer to FIGS. 2 and 3. When the powder of pure silicon anode has the nucleus described in the present invention, the nucleation theory can be utilized to cause the entire powder to form one or more compounds of Li.sub.4.1Si_Cmcm, Li.sub.13Si.sub.4_Pbam, Li.sub.2_Si_C12m1, and LiSi_I41/AZ during the lithiation process. The nucleus has the same atomically surrounding environment, atomic structure symmetry, or electronic structure as the above four structures.
[0042] With reference to FIG. 8, when the pure silicon anode forms one or more compounds of Li.sub.4.1Si_Cmcm, Li.sub.13Si.sub.4_Pbam, Li.sub.2Si_C12m1, and LiSi_I41/AZ, because of the final phase of Li.sub.4.1Si_Cmcm, the capacity of pure silicon anodes can be greatly increased. When the special pure silicon anode of the present invention is used to assemble the pole pieces and form a half-cell (the electrolyte being EC+DEC+10% FEC) and a lithiation and delithiation test (lithiation/delithiation rate of 0.1 C) is performed, it is found that after 250 cycles of lithiation and delithiation, the pure silicon anode of the present invention can still maintain a capacity of about 2,500 mAh/g. Compared with the traditional graphite electrode, the electrical capacity of the pure silicon anode of the present invention is increased by more than 6 times. Compared with the ordinary pure silicon anode with lithium-silicon compound Li.sub.15Si.sub.4_I-43d after lithiation, the capacity is significantly improved.
[0043] Please refer to FIG. 9, which is a schematic diagram showing the lithium-ion battery prepared in accordance with the present invention. The lithium-ion battery 200 includes an anode 202, a cathode 204, and an isolation film 206 between the anode 202 and the cathode 204.
[0044] Please refer to FIGS. 10A and 10B. According to the present invention, the method for producing a special nucleus can also be used on silicon anodes with various appearances (such as hollow powder).
[0045] The above are only the preferred embodiments of the present invention and are not used to limit the scope of implementation of the present invention, which means that all simple and equivalent changes and modifications made in accordance with the content of the claimed scope and the detailed description of the patent application of the present invention fall within the scope of the invention patent.
