The present invention relates generally to thin film energy storage devices, and more particularly to large area energy storage devices with high power and high energy.
Energy storage devices include a wide range of devices such as batteries, thin film batteries (TFBs), capacitors, supercapacitors and ultracapacitors. These energy storage devices are used in a wide variety of applications including micro-power sources (for micro-sensors, smart cards, real time clocks, etc.) and larger power/energy sources (for cell phones, PDAs, laptops, power tools, transportation, heavy industry, power generation and transmission, complementary energy storage for renewable energy generation, etc.).
Despite a great deal of effort within industry and the scientific community, there remains a need to improve the following attributes of energy storage devices: the power delivery ability; the energy storage capacity; the large area scalability; and the manufacturability. Therefore, there is a need for concepts and methods that can significantly reduce the cost of manufacturing and the performance of energy storage devices.
In general, embodiments of this invention provide readily manufacturable, high power, high energy, large area energy storage devices. The approach of the present invention includes, but is not limited to, the use of processes compatible with large area processing tools, such as large area coating systems. The approach of the present invention also includes, but is not limited to, the use of linear processing systems compatible with flexible thin film substrates. The energy storage devices may include batteries, super-capacitors and ultra-capacitors, whose basic structure is comprised of a positive electrode, a solid state electrolyte, and a negative electrode, and may also include negative and/or positive terminal current collectors. Embodiments of the energy storage devices described herein may be comprised of positive electrode materials with high charge capacity and high voltage capability, negative electrode materials with high charge capacity, and electrolytes with high electrochemical stability, high ionic conductivity and very low electrical conductivity.
According to aspects of the invention, a method of manufacturing an energy storage device, where the energy storage device includes a multiplicity of cells integrated on a substrate and the multiplicity of cells are electrically connected in serial, comprises: providing the substrate; depositing layers corresponding to a thin film energy storage device on the substrate, the layers including, in order of deposition, a current collector, a first electrode, an electrolyte and a second electrode; patterning the current collector to form a multiplicity of current collector stripes; patterning the first electrode to form a multiplicity of first electrode stripes, each of the first electrode stripes being on top of a corresponding one of the multiplicity of current collector stripes; and patterning the second electrode to form a multiplicity of second electrode stripes, each of the multiplicity of second electrode stripes corresponding to one of the multiplicity of first electrode stripes; wherein each of the multiplicity of electrically connected cells comprises one of the multiplicity of current collector stripes, the corresponding one of the multiplicity of first electrode stripes, the corresponding one of the multiplicity of second electrode stripes, and a corresponding portion of the layer of the electrolyte. The multiplicity of cells may be configured in a serial chain of cells, and the current collector stripe corresponding to one of the multiplicity of cells is electrically connected to the second electrode stripe corresponding to the cell adjacent to the one of the multiplicity of cells.
According to further aspects of the invention, a second method of manufacturing an energy storage device, where the energy storage device includes a plurality of cells integrated on a substrate and the plurality of cells are electrically connected in serial and in parallel, comprises: providing the substrate; depositing layers corresponding to a thin film energy storage device on the substrate, the layers including, in order of deposition, a current collector, a first electrode, an electrolyte and a second electrode; patterning the current collector to form a multiplicity of current collector stripes; patterning the first electrode to form a plurality of first area electrodes on the multiplicity of current collector stripes, the plurality of first area electrodes being formed in a multiplicity of first area electrode rows, each of the multiplicity of first area electrode rows corresponding to a different one of the multiplicity of current collector stripes; and patterning the second electrode to form a multiplicity of second electrode stripes, each of the multiplicity of second electrode stripes corresponding to a different one of the multiplicity of first electrode stripes; wherein each of the plurality of cells comprises one of the plurality of first area electrodes, and corresponding portions of current collector stripe, second electrode stripe, and electrolyte layer.
According to yet further aspects of the invention, an energy storage device includes a multiplicity of thin film cells formed on a single substrate, the multiplicity of cells being electrically connected in series, each one of the multiplicity of cells comprising: a current collector on the surface of the substrate; a first electrode on the current collector; a second electrode over the first electrode; and an electrolyte layer between the first electrode and the second electrode. A first one of the multiplicity of cells and a second one of the multiplicity of cells are electrically connected in series by the current collector stripe corresponding to the first one of the cells being electrically contacted to the second electrode stripe corresponding to the second one of the cells, and wherein the first one of the cells is adjacent to the second one of the cells on the substrate.
According to further aspects of the invention, a second energy storage device includes a plurality of thin film cells formed on a single substrate, the plurality of cells being electrically connected in a network, the network including both parallel and serial electrical connections between individual cells of the plurality of cells, the plurality of cells comprising: a multiplicity of current collector stripes on the surface of the substrate, the multiplicity of current collector stripes being mutually parallel; a plurality of first cell electrodes on the multiplicity of current collector stripes, the plurality of first cell electrodes corresponding to the plurality of cells; a multiplicity of second electrode stripes over the plurality of first cell electrodes, the multiplicity of second electrode stripes being parallel to the multiplicity of current collector stripes; and an electrolyte layer between the plurality of first cell electrodes and the multiplicity of second electrode stripes. The multiplicity of current collector stripes may provide parallel electrical connection of the plurality of cells. The plurality of cells may comprise rows of cells, and the rows of cells may be electrically connected in series with each other.
These and other aspects and features of the present invention will become apparent to those ordinarily skilled in the art upon review of the following description of specific embodiments of the invention in conjunction with the accompanying figures, wherein:
Embodiments of the present invention will now be described in detail with reference to the drawings, which are provided as illustrative examples of the invention so as to enable those skilled in the art to practice the invention. Notably, the figures and examples below are not meant to limit the scope of the present invention to a single embodiment, but other embodiments are possible by way of interchange of some or all of the described or illustrated elements. Moreover, where certain elements of the present invention can be partially or fully implemented using known components, only those portions of such known components that are necessary for an understanding of the present invention will be described, and detailed descriptions of other portions of such known components will be omitted so as not to obscure the invention. In the present specification, an embodiment showing a singular component should not be considered limiting; rather, the invention is intended to encompass other embodiments including a plurality of the same component, and vice-versa, unless explicitly stated otherwise herein. Moreover, applicants do not intend for any term in the specification or claims to be ascribed an uncommon or special meaning unless explicitly set forth as such. Further, the present invention encompasses present and future known equivalents to the known components referred to herein by way of illustration.
Energy storage devices are described generally herein, and specific examples of TFB devices are provided. However, concepts of the present invention are not limited to TFBs, but are applicable to energy storage devices generally, including batteries, TFBs, capacitors, supercapacitors and ultracapacitors. Furthermore, specific examples of large area TFBs are provided. However, concepts of the present invention are not limited to large area energy storage devices, but are applicable to energy storage devices generally, including micro-power sources (for micro-sensors, smart cards, etc.), larger power/energy sources (for cell phones, PDAs, laptops, power tools, etc.), and large format energy storage devices (meter-scale devices for mounting behind solar panels, for example).
The energy storage devices are formed on substrates. Specific examples of flexible large area substrates, suitable for reel-to-reel processing, are provided. However, concepts of the present invention are not limited to large area substrates, but are applicable to energy storage devices formed on a wide range of substrates, including semiconductor substrates, large area substrates, flexible large area substrates, conducting/metallic and dielectric substrates, etc.
In order to reduce the impact of cell capacity differences, embodiments of the present invention may include a network 20 of battery cells 11 which are electrically connected together both in series and in parallel, as shown schematically in
In some embodiments of the present invention, the layer 108 may include both an anode and a protective coating for the underlying anode layer—the anode would be deposited first, and the protective coating second. For example, if the anode is a reactive metal such as lithium, then a protective coating is required if the structure is to be exposed to air for patterning. The protective coating may include blanket deposition of metals and dielectrics. Examples of potentially suitable metals are Cu, Ti and Al. Suitable dielectric oxides would need to be stable in contact with the anode. Furthermore, the protective coating may also be an anode current collector. The patterning of layer 108, for this embodiment, is the same as described above.
In further embodiments of the present invention, the layer 108 may include both an anode and an anode current collector—the anode would be deposited first, and the anode current collector second. The patterning of layer 108, for this embodiment is the same as described above.
Referring again to
The energy storage devices may be packaged in different formats. For example, energy storage devices on flexible substrates may be rolled into cylinders. Alternatively, energy storage devices may be stacked, and the stacked devices may be electrically connected together, either serially and/or in parallel. Furthermore, energy storage devices may be stacked and then rolled. Dimensions of typical packaged devices may vary from millimeter up to meter scale. The energy storage devices are suitable for a very wide range of applications, including applications requiring one or more of high power, high energy, and high voltage (multiples of single cell voltage). Note that the voltage per cell for a typical thin film battery may be expected to be around 3 to 5 V, and connecting these cells in series may allow much higher voltages to be achieved.
Embodiments of the energy storage devices described herein may be comprised of negative electrode (anode) materials with high charge capacity and high voltage tolerance, positive electrode (cathode) materials with high charge capacity, and electrolytes with high electrochemical stability. The positive electrode materials may include transition metal oxides, phosphates, fluorinated oxides and phosphates, and various mixtures thereof. Examples of metal oxide positive materials are layered materials, such as LiCoO2 and LinNixCOyAlzOm, spinel materials such as LiMn2O4 and Co/Ni substituted Mn oxide, and olivine materials such as LiFePO4. Examples of materials that have high voltage tolerance include LiCoPO4 and LiNiPO4, with open circuit voltages of ˜4.8 and 5.2V, respectively, with respect to a Li metal negative electrode. These materials also present high charge capacities of ˜170 mAh/gm.
High charge capacity negative electrode materials may include Si, Sn, Ge, Al, etc., which will form binary alloys with the ionic charge carrier, Li. The use of such materials offers the potential to eliminate the use of pure Li, which presents significant challenges and complexity in manufacturing. One of the biggest concerns about the alloy negative electrode materials is the potential for stress in the deposited electrode material resulting from large volume changes during charging (MLix-->M+xLi) and discharging (M+xLi-->MLix) cycles. The build-up of stress may be alleviated by using nano-structuring of the deposited layers in grain size, density or porosity, for example, to allow “breathing” of the negative electrode materials during these cycling events.
All of these positive and negative electrode materials may be used in fabricating energy storage devices. Various deposition methods, including standard vacuum deposition methods and non-vacuum deposition methods may be used. For vacuum deposition, PVD and CVD techniques may be used. For doping of the electrode materials, sputter deposition may be used with target materials with the desired composition. Alternatively, the electrode materials may be co-sputtered from several targets to form the correct composition, and, if needed, in a reactive environment. Such methods may be used to add a carbon coating as well. Modulation of the grain structure to achieve nano-structured or porous materials may be achieved by controlling the deposition processes. For example, low temperature deposition may be used to limit the diffusion kinetics and control the grain growth. Various non-vacuum deposition techniques may be used, including ink jet printing, spray coating, spin coating, etc., using appropriate ink, dispersion, and etc., with the desired material composition and grain structure already created prior to deposition.
Electrolytes are desired that have high ionic conductivity, low electrical conductivity and a high and broad electrochemical stability window. There are several candidate materials that may be used in embodiments of the energy storage devices. For vacuum deposited materials, lithium phosphorous oxynitride (LiPON) and variation thereof, lithium containing metal oxides like silicates, tantalates, and etc., and ternary combinations of LiO2, P2O5 and P2S5. Suitable liquid (at room temperature) electrolyte candidates may be ionic liquids and molten salts with solvated Li salts.
Embodiments of the energy storage devices with large form factors may be fabricated using large-area coaters, such as coaters used in the flat panel display, glass coating and thin film solar photovoltaic industries. Large-area coating systems may be beneficial for scaling of production as well as being able to efficiently handle the product's large size and manufacturing worthy throughputs.
Although the present invention has been particularly described with reference to certain embodiments thereof, it should be readily apparent to those of ordinary skill in the art that changes and modifications in the form and details may be made without departing from the spirit and scope of the invention. It is intended that the appended claims encompass such changes and modifications. The following claims define the present invention.