Thin-film micro-electrochemical energy storage cells (MEESC) such as microbatteries and double-layer capacitors (DLC) are provided. The MEESC comprises two thin layer electrodes, an intermediate thin layer of a solid electrolyte and optionally, a fourth thin current collector layer; said layers being deposited in sequence on a surface of a substrate. The MEESC is characterized in that the substrate is provided with a plurality of through cavities of arbitrary shape, with high aspect ratio. By using the substrate volume, an increase in the total electrode area per volume is accomplished.
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0. 15. A thin-film micro-electrochemical energy storage cell (MEESC) in the form of a microbattery, said microbattery comprising:
a substrate having two surfaces and a plurality of through cavities of arbitrary shape, said cavities having an aspect ratio greater than 1 and a diameter from about 15 μm to about 150 μm;
a thin layer anode;
a thin layer cathode; and
a solid electrolyte intermediate said anode and cathode layers;
wherein at least one of said anode and said cathode is deposited on both surfaces of said substrate; and
wherein said anode layer, said cathode layer, and said solid electrolyte intermediate said anode and cathode layers, are deposited throughout the inner surface of said cavities.
0. 1. A thin-film micro-electrochemical energy storage cell (MEESC) in the form of a microbattery, said microbattery comprising:
a substrate having two surfaces,
a thin layer anode consisting of alkali metal (M), alkali metal alloy or in the charged state consisting of lithiated carbon or graphite,
a thin layer cathode consisting of LiCoO2, LiNiO2, LiMn2O4, TiS2, V2O5, V3O8 or lithiated forms of the vanadium oxides,
a solid electrolyte intermediate to said anode and cathode layers, consisting of a tin layer of an ionically conducting or electronically non-conducting material selected from glass, poly(ethylene oxide) based polymer electrolyte or polycrystalline material, and
optionally, a fourth current collector layer;
said anode or cathode layer being deposited in sequence on both surfaces of said substrate, said microbattery being characterized in that the substrate is provided with a plurality of through cavities of arbitrary shape, with an aspect ratio greater than 1, the diameter of said cavities being from about 15μ to about 150μ; said anode, cathode, solid electrolyte layers and optional current collector layer being also deposited throughout the inner surface of said cavities.
0. 2. The microbattery of
0. 3. The microbattery of
0. 4. The microbattery of
0. 5. The microbattery of
0. 6. A lithium ion type microbattery according to
0. 7. The microbattery of
0. 8. The microbattery of
0. 9. The microbattery of
0. 10. The microbattery of
0. 11. The microbattery of
0. 12. The microbattery of
0. 13. A thin-film micro-electrochemical energy storage cell (MEESC) in the form of a microbattery of
a substrate having two surfaces,
a thin layer anode consisting of alkali metal (M), alkali metal alloy or in the charged state consisting of lithiated carbon or graphite,
a thin layer cathode consisting of LiCoO2, LiNiO2, LiMn2O4, TiS2, V2O5V3O8 or lithiated forms of the vanadium oxides,
a solid electrolyte intermediate to said anode and cathode layers, said solid electrolyte comprising a thin layer of Li2CO3 doped with Al, and
optionally, a current collector layer;
said anode or cathode layer being deposited in sequence on both surfaces of said substrate, said microbattery being characterized in that the substrate is provided with a plurality of through cavities of arbitrary shape, with an aspect ratio greater than 1, the diameter of said cavities being from about 15 μm to about 150 μm;
said anode, cathode, solid electrolyte layers and optional current collector layer being also deposited throughout the inner surface of said cavities.
0. 14. A self-powered semiconductor component comprising a microbattery according to
0. 16. The MEESC of
0. 17. The MEESC of
0. 18. The MEESC of
0. 19. The MEESC of
0. 20. The MEESC of
0. 21. The MEESC of
0. 22. The MEESC of
0. 23. The MEESC of
0. 24. The MEESC of
0. 25. The MEESC of
0. 26. The MEESC of
0. 27. The MEESC of
0. 28. The MEESC of
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While lithium metal foil is typically used for the negative electrode, the negative electrode is not specifically restricted as long as it comprises an electrically conductive film that provides alkali metal in a form effective for the electrode reaction. The preferred microbattery used in the present invention is a lithium ion type battery fabricated in the discharge state wherein the anode is made of Al, Sn, Zn, Mg based alloys, carbon or graphite. Lithium-ion cells made according to the present invention are air stable in the discharged state and are charged only after the assembly of the cell, thus being more favorable in terms of ease of production.
Similarly, the active substance of the positive electrode is not specifically restricted as long as it is of a type in which the metal ions, e.g. lithium ions are intercalated or inserted during discharge and taken out during charge of the battery. Inorganic compounds are typically employed, for example LiCoO2, LiNiO2, LiMn2O4, and lithiated vandium oxides for the lithium ion microbattery, while FeS2 and TiS2 can be used for the lithium metal anode microbattery. Fine powders of these compounds are cast together with the polymer electrolyte. In addition, it was found that where a composite polymer electrolyte and/or a cathode contain up to 15% (V/V) of inorganic nanosize powder such as Al2O3, SiO2, MgO, TiO2 or mixtures thereof, the cell demonstrates improved charge-discharge performance.
For the DLC application additional salts can be used such as ammonium and alkyl ammonium salts. The DLC is made in a similar way as the microbattery: the electrodes are made in a same manner as the cathode layer in microbatteries, but the cathode powder is replaced by a high surface area (over 50 m2/g) carbon.
By etching the substrate with macroporous cavities of various shapes, the microbattery of the present invention has an increased area available for thin film deposition by up to 100 fold. Since the capacity of a battery is directly proportional to its volume, for the same thin-film thickness (typically a few microns for each layer of anode, electrode and cathode and up to a total of about 70 μm), means an increase in volume of up to about two orders of magnitude, i.e. capacity, to about 10,000 microAmp hour per 1 square cm.
For a circular cavity with diameter d in a wafer of thickness h (“aspect ratio”=h/d), the ratio k of surface area after etching to the original, “planar” state is 2 h/d. For a square cavity with side a in the same wafer, k=2 h/a. Thus, for a typical wafer with a thickness of 400 μm (e.g. h=400) and d or a=15 μm, the increase in area is: k=53, while for d=10 μm, k=80.
The invention will be further described in more detail with the aid of the following non-limiting examples.
A microbattery, consisting of a carbon anode, composite polymer electrolyte and composite LiCoO2 cathode was fabricated in the discharged state on a perforated 400 micron thick silicon wafer which contains 100 micron in diameter through holes. A thin carbon film was deposited by CVD at 850 Celsius by passing a C2H4 (10%) Ar (90%) gas mixture for four minutes over the wafer.
A second layer of a composite polymer electrolyte (CPE) was deposited (inside an Ar filled glove box) over the carbon layer by a short vacuum dipping at 50-65 Celsius in acetonitrile (30 ml) suspension consisting of 0.6 g PEO (5×106 MW), 0.05 g EC, 0.1 g LiN(CF3SO2)2 (imide) and 0.03 g alumina. After drying, a second layer of CPE was deposited in the same way to get the desired CPE thickness. A thin cathode layer was deposited (inside the glove box) over the CPE layer by a short vacuum dipping in cyclopentanone (10 ml) suspension consisting of 2 g of ball milled LiCoO2, 0.05 g alumina, 0.2 g PVDF copolymer (ELF 2800) and 0.4 g sub-micron graphite powder. As an option for improving cathode utilization and power capability, a forth PVDF-graphite layer is deposited on the cathode.
Poly(ethylene oxide)(P(EO)) was purchased from Aldrich, (average molecular weight 5×106) and was vacuum dried at 45° to 50° C. for about 24 hours. The imide (Aldrich) was vacuum dried at 200° C. for about 4 hours. All subsequent handling of these materials took place under an argon atmosphere in a VAC glove box with an water content<10 ppm. A polymer electrolyte slurry was prepared by dispersing known quantities of P(EO), imide, and ethylene carbonate (EC) in analytical grade acetonitrile together with the required amount of an inorganic filler, such as Al2O3 (Buehler), or SiO2 with an average diameter of about 150Å. To ensure the formation of a homogeneous suspension, an ultrasonic bath or high-speed homogenizer was used. The suspension was stirred for about 24 hours before the composite cathode was cast. The solvent was allowed to evaporate slowly and then the wafers were vacuum dried at 120° C. for at least 5 hours. The electrochemical characteristics of the microbattery has been examined in the experimental cell showed in
The cell delivered above 0.4 mAh per cycle for over 20 cycles. The Faradaic efficiency was close to 100%.
A DLC, consisting of two carbon electrodes, and composite polymer electrolyte was fabricated on a perforated 400 micron thick silicon wafer which contains 100 micron in diameter through holes in a similar way as described in Example 1. A thin high surface area carbon powder (500 m2/g) (made by 1000 Celsius pyrolysis of cotton) layer was deposited (inside the glove box) on the perforated wafer by a short vacuum dipping in cyclopentanone (10 ml) suspension consisting of 1 g of ball milled carbon, 0.05 g carbon black and 0.1 g PVDF copolymer (ELF 2800). A second layer of a composite polymer electrolyte (CPE) was deposited (inside Ar filled glove box) over the carbon layer by a short vacuum dipping at 50-65 Celsius in an acetonitrile (30 ml) suspension consisting of 0.6 g PEO (5×106 MW), 0.05 g EC, 0.1 g LiN(CF3SO2)2 (imide) and 0.03 g alumina. After drying, another layer of CPE was deposited in the same way to get the desired CPE thickness. A third high surface area carbon layer was deposited in the same way as the first one.
By using the procedure described in Example 1 above, the DLC was cycled at 0.01 mA between 1.2 and 2.5 V for over 1000 cycles of 10 seconds each.
A microbattery, consisting of four thin films: a carbon anode, Al doped Li2CO3 solid electrolyte, LiCoO2 cathode and carbon current collector was fabricated in the discharged state on a perforated 400 micron thick silicon wafer which contains 60 micron in diameter through holes. A thin carbon film was CVD deposited at 850 Celsius by passing a C2H4 (10%) Ar (90%) gas mixture for three minutes over the wafer. A second layer of thin Al doped Li2CO3 solid electrolyte was deposited at 475 Celsius on the first one by CVD following the procedure described in P. Fragnaul et al. J. Power Sources 54, 362 1995. A third film layer of LiCoO2 cathode was deposited at 500 Celsius on the second one following the procedure described in P. Fragnaul et al. J. Power Sources 54, 362 1995. A fourth thin carbon current collector layer was deposited at 800 Celsius on the third one in the same way as the first one.
This cell was cycled (as described in example 1) at 0.01 mA and at room temperature between 2.5 and 4.1 V for more than 10 stable cycles.
Nathan, Menachem, Peled, Emanuel, Haronian, Dan
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