Abstract:
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.

Description:
Notice: More than one reissue application has been filed for the reissue of U.S. Pat. No.  6 , 197 , 450 . The reissue applications are application Ser. Nos.  10 / 382 , 466  and  11 / 866 , 722  and this application, which is a division of application Ser. Nos.  10 / 382 , 466  and  11 / 866 , 722 , for reissue of U.S. Pat. No.  6 , 197 , 450 . 
    
    
     FIELD OF THE INVENTION 
     This invention relates to thin film micro-electrochemical energy storage cells (MEESC), such as microbatteries and double-layer capacitors (DLC). 
     BACKGROUND OF THE INVENTION 
     Advances in electronics have given us pocket calculators, digital watches, heart pacemakers, computers for industry, commerce and scientific research, automatically controlled production processes and a host of other applications. 
     These have become possible largely because we have learned how to build complete circuits, containing millions of electronic devices, on a tiny wafer of silicon no larger than 25-40 mm square and 0.4-0.5 mm thick. Microelectronics is concerned with these miniaturized integrated circuits (ICs), or “chips” as they are called. In a circuit, electrical energy is supplied from, for example, a microbattery or a double-layer capacitor (DLC) and is changed into other forms of energy by appliances in the circuit, which have resistance. 
     Recently, with the tendency of miniaturizing of small-sized electronic devices, there have been developed thin-film microbatteries, which have several advantages over conventional batteries, since battery cell components can be prepared as thin (1-20 μm) sheets built up as layers. Usually, such thin layers of the cathode, electrolyte and anode are deposited using direct-current and radiofrequency magnetron sputtering or thermal evaporation. 
     The area and thickness of the sheets determine battery capacity and there is a need to increase the total electrode area in a given volume. Thin films result in higher current densities and cell efficiencies because the transport of ions is easier and faster through thin-film layers than through thick layers. 
     U.S. Pat. Nos. 5,338,625 and 5,567,210 describe thin-film lithium cells, especially thin-film microbatteries having application as backup or primary integrated power sources for electronic devices and method for making such. The batteries described in these references are assembled from solid state materials, and can be fabricated directly onto a semiconductor chip, the chip package or the chip carrier. These batteries have low energy and power. They have an open circuit voltage at full charge of 3.7-4.5 V and can deliver currents of up to 100 μA/cm 2 . The capacity of a 1 square cm microbattery is about 130 μA/hr. These low values make these batteries useful only for very low power requirements in some microelectronic circuits. 
     A double-layer capacitor (DLC), as opposed to a classic capacitor, is made of an ion conductive layer between two electrodes. In order to make an electric double-layer capacitor smaller and lighter without any change in its capacitance, it is necessary to increase the energy. This may be accomplished, for example, as described in U.S. Pat. No. 5,754,393, by increasing the working voltage by use of an electrolyte having a high decomposition voltage. 
     Advanced etching technologies, such as reactive-ion etching (RIE), electron-cyclotron-resonance (ECR) etching and inductively coupled plasma (ICP) etching have been developed to etch semiconductor devices having extremely small features sizes. By using the ICP technique it is possible to etch small diameter through-cavities such as through-holes with a very high aspect ratio and smooth surfaces in a substrate such as a silicon wafer. 
     The present invention is based on a novel approach, according to which a thin-film micro-electrochemical energy storage cell (MEESC) such as a DLC or a microbattery is created on a macroporous substrate, thus presenting increased capacity and performance. By using the substrate volume, an increase in the total electrode area per volume is accomplished. The cavities within a substrate are formed by deep wet or dry etching of the substrate. For example, holes may be formed by an Inductive Coupling Plasma (ICP) etching using the Bosch process described in U.S. Pat. No. 5,501,893. 
     SUMMARY OF THE INVENTION 
     It is an object of the present invention to provide a micro-electrochemical energy storage cell (MEESC) such as a DLC or a microbattery exhibiting superior performance as compared to such cells known in the art. A more particular object of the invention is to provide a DLC or a microbattery with up to two orders of magnitude increase in capacity. 
     The above objects are achieved by the present invention, wherein a thin-film MEESC is formed on a substrate having etched structures. The use of such a substrate increases the available area for thin film deposition, thus leading to an increase in volume, i.e. capacity of the cell. 
     Thus, the present invention provides a thin-film micro-electrochemical energy storage cell (MEESC) comprising two thin layer electrodes and intermediate to these electrodes, a thin layer of a solid electrolyte consisting of an ionically conducting or electronically non-conducting material such as glass, polymer electrolyte or polycrystalline material, and optionally a fourth thin current collector layer, all these layers being deposited in sequence on a surface of a substrate, wherein the MEESC is characterized in that the substrate is provided with a plurality of cavities with high aspect ratio; said electrodes, solid electrolyte and current collector layers being deposited also throughout the inner surface of said cavities and on both surfaces. 
     In a preferred embodiment the MEESC of the present invention is a thin film microbattery which comprises: 
     a thin layer anode consisting of alkali metal (M), alkali metal alloy, for example alkali metal alloy based on Zn, Al, Mg, or Sn or in the charged state consisting of lithiated carbon or graphite, 
     a thin layer cathode consisting of LiCoO 2 , LiNiO 2 , LiMn 2 O 4 , TiS 2 , V 2 O 5 , V 3 O 8  or lithiated forms of the vanadium oxides, 
     a solid electrolyte intermediate to the anode and cathode layers, which consists of a thin layer of an ionically conducting or electronically non-conducting material such as glass, polymer electrolyte or polycrystalline material, and 
     optionally, a current collector layer; the anode or cathode layer being deposited on a surface of a substrate, the microbattery being characterized in that the substrate is provided with a plurality of cavities with high aspect ratio; said anode, cathode and solid electrolyte layers being deposited also throughout the inner surface of said holes. 
     In cases wherein the microbattery is a lithium ion type, such a battery is fabricated in the discharge state where the cathode is fully lithiated and the alloy, the carbon or the graphite anode is not charged with lithium. 
     According to another preferred embodiment, the MEESC of the present invention is a double-layer capacitor (DLC), which comprises two electrodes made of high surface area carbon powder and intermediate to these electrodes a solid electrolyte layer, preferably a polymer electrolyte. 
    
    
     
       BRIEF DESCRIPTION OF THE DRAWINGS 
       In order to understand the invention and to see how it may be carried out in practice, a preferred embodiment will now be described, by way of non-limiting example only, with reference to the accompanying drawings, in which: 
         FIG. 1  is a schematic diagram of a thin-film microbattery coating a silicon wafer with through-holes. 
         FIG. 2  is a schematic view of a test cell. 
     
    
    
     DETAILED DESCRIPTION OF THE INVENTION 
     Thin-film rechargeable power sources can be applied for computer memory back-up and many other uses, such as autonomous micro electro-mechanical systems (MEMS). Lithium batteries have been brought recently to an extreme stage of miniaturization. Sequential gas phase deposition techniques of anode, electrolyte and cathode layers make it possible to incorporate such lithium batteries on a silicon substrate. In a chemical vapor deposition process gases and/or vapors react to form a solid compound. This reaction usually takes place after adsorption and partial decomposition of the precursors on the substrate surface, though reaction in the gas phase is possible. 
     The thin-film MEESC of the present invention consists of a sandwich of multiple layers, coating the inside of a through-cavity of arbitrary shape, formed in a substrate, for example by means of Inductive Coupled Plasma (ICP) etching when the substrate is made of silicon. Generally, the substrate material is made of a single crystal or amorphous material and is selected from glass, alumina, semiconductor materials for use in microelectronics, or ceramic materials. The substrate material is preferably silicon. 
     The through-cavities etched have very high aspect ratio and smooth surfaces, both features being essential for achieving uniform coating and an increase in the area available for thin-film deposition. The thin-film layers of the electrodes and electrolyte are deposited by either Chemical Vapor Deposition (CVD), casting or plating techniques. In CVD, gases providing the required materials will pass the cavity, undergo a chemical reaction induced by heat, plasma or a combination of the two, and deposit the material uniformly on the inside wall and between the cavities. 
     According to the present invention, for microbattery applications the polymer electrolyte is designed so as to contain at least one material that can be reduced to form an insoluble solid electrolyte interphase (SEI) on the anode surface. Aprotic solvents such as ethylene carbonate (EC), diethylcarbonate (DEC), dimethylcarbonate (DMC), ethyl methyl carbonate (EMC), butyl carbonate, propylene carbonate, vinyl carbonate, dialkylsulfites and any mixtures of these, and metal salts such as LiPF 6 , LiBF 4 , LiAsF 6 , LiCF 3 , and LiN(CF 3 SO 2 ) 2  are considered to be good SEI precursors, as well as other salts such as LiI and LiBr. The polymer electrolyte further contains a polymer, preferably polyethylene oxide, adapted to form a complex with the metal salt and optionally a nanosize ceramic powder to form a composite polymer electrolyte (CPE). 
     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 LiCoO 2 , LiNiO 2 , LiMn 2 O 4 , and lithiated vandium oxides for the lithium ion microbattery, while FeS 2  and TiS 2  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 Al 2 O 3 , SiO 2 , MgO, TiO 2  or mixtures thereof, the cell demonstrates improved charge-discharge performance. 
     For the DLC application additional salts can be used such as amonium and alkyl amonium 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 m 2 /g) carbon. 
       FIG. 1  shows a possible cylindrical geometry implemented in a substrate, for example silicon, of a microbattery. The anode is made, in the charged state, of an alkali metal (M), alkali metal alloy or lithiated carbon. The preferred alkali metal is lithium and the preferred alloys are Al, Mg, Sn and Zn based alloys. The solid electrolyte is made of an ionically conducting glass, preferably Li x PO y N z  where 2&lt;x&lt;3, 2y=3z and 0.18&lt;z&lt;0.43, or Li 2 S-SiS 2  glasses doped with up to 5% LiSO 4  or 30% LiI, or a poly(ethylene oxide) based polymer electrolyte, preferably cross-linked poly(ethylene oxide) with CF 3 SO 3 Li or LiN(CF 3 SO 2 ) 2 . The cathode is made of LiCoO 2 , LiNiO 2 , LiMn 2 O 4 , TiS 2 , V 2 O 5 , V 3 O 13  or the lithiated form of these vanadium oxides. The layers are deposited by CVD, plating, casting or similar known coating techniques, preferably by CVD. Contacts to the anode and cathode are made on either the same side of the wafer using masking, etching, and contact metal deposition, or using both sides of the wafer. 
     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”=b/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. 
     EXAMPLE 1 
     A microbattery, consisting of a carbon anode, composite polymer electrolyte and composite LiCoO 2  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 C 2 H 4  (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 (5×10 6  MW), 0.05 g EC, 0.1 g LiN(CF 3 SO 2 ) 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 LiCoO 2 , 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 5×10 6 ) 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&lt;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 Al 2 O 3  (Buehler), or SiO 2  with an average diameter of about 1.50Å. 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  FIG. 2 , which comprises a hermetically sealed glass container  5 , provided with an outlet  1 , connected to a vacuum pump; the glass cover  3  of the glass container is equipped with a Viton O-ring  4 . On one side of the wafer a contact was made to the carbon anode and on the other side a contact was made to the cathode. The test cell illustrated in  FIG. 2  is connected by wires  7  to tungsten rods  2  which pass through the cover. In the glass container, the battery  6  was cycled between 2.5 and 4.1 V at 0.01 mA and at 25° C. using a Maccor series 2000 battery test system. 
     The cell delivered above 0.4 mAh per cycle for over 20 cycles. The Faradaic efficiency was close to 100%. 
     EXAMPLE 2 
     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 m 2 /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 (5×10 6  MW), 0.05 g EC, 0.1 g LiN(CF 3 SO 2 ) 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. 
     EXAMPLE 3 
     A microbattery, consisting of four thin films: a carbon anode, Al doped Li 2 CO 3  solid electrolyte, LiCoO 2  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 C 2 H 4  (10%) Ar (90%) gas mixture for three minutes over the wafer. A second layer of thin Al doped Li 2 CO 3  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 thin layer of LiCoO 2  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.