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The present invention relates to a lithium-ion battery, and particularly relates to a transparent or translucent lithium-ion battery, and methods for fabricating said transparent or translucent lithium-ion battery.
Transparent electronics is a key technology for the new generation of electronic and optoelectronic devices. Transparent devices have widely been applied to different applications like optical circuits, touch screens, displays, and solar cells. Furthermore, the market also provides an incentive for electronic companies to launch various transparent devices, such as transparent mobile and transparent display.
Nevertheless, the battery, considered as a major component in electronic devices, has not been adequately demonstrated as a transparent device since many components of the battery such as anode and cathode materials are generally black in color. Hence fully integrated and transparent devices are hardly to be realized because the battery occupies relatively large area and volume in these devices.
One of the conventional methods for fabricating transparent devices is to reduce the thickness of active materials to substantially less than their optical absorption length. Nevertheless, such method is not adequate for batteries, since active battery materials, mostly, do not have an absorption length long enough in the full voltage window. For example, LiCoO2 and graphite, widely used as the cathode material and anode material in Li-ion batteries, are good light absorbers even with a thickness less than 1 μm. In addition, with such thickness, the battery fails to provide a sufficient amount of energy for storage. Thus, a contradiction appears between the transparency of the battery and the amount of energy stored.
To solve the abovementioned problem, another conventional method is to arrange the electrode materials in a pattern, which occupies merely an areal fraction so that light can transmit freely through the empty space. US2013/0022868 discloses a transparent electrochemical energy storage device, which comprises a pair of electrodes and an electrolyte disposed between the electrodes. Each of the electrodes includes a substrate and a set of electrode materials that are arranged across the substrate in a pattern with a feature dimension no greater than 200 μm and occupy an areal fraction in the range of 5% to 70%. Nevertheless, the transparency and capacity of such energy storage device is low because of poor alignment and packaging.
Consequently, there is an unmet need for a transparent Li-ion battery providing high transparency and adequate energy storage capacity, and being easily manufactured.
Accordingly, a first aspect of the presently claimed invention is to provide a transparent or translucent lithium-ion battery, having high transparency and energy storage capacity.
In accordance with an embodiment of the presently claimed invention, a transparent or translucent lithium-ion battery comprises a pair of electrodes including an anode and a cathode, and an electrolyte. The electrolyte is positioned between the anode and the cathode. The anode comprises a first electrode material holder with first inner structures, a first current collector, and an anode material. The first current collector, comprising a first conductive film, is formed along the walls of the first inner structures of the first electrode material holder. The anode material is deposited on the first current collector, and filled within the first inner structures of the first electrode material holder. The cathode comprises a second electrode material holder with second inner structures, a second current collector and a cathode material. The second current collector, comprising a second conductive film, is also formed along the walls of the second inner structures of the second electrode material holder. The cathode material is deposited on the second current collector, and filled within the second inner structures of the second electrode material holder. The first and second electrode material holders are transparent or translucent, thereby leaving the areas of the electrode materials holders without the inner structures for light transmission that makes the lithium-ion battery be transparent or translucent. Preferably, the first electrode material holder with the first inner structures and/or the second electrode material holder with the second inner structures is an anodized aluminum oxide (AAO) film with channels, or a patterned glass/quartz slice with concave parts.
A second aspect of the presently claimed invention is to provide an electrode for a transparent or translucent lithium-ion battery.
The electrode of the presently claimed invention comprises an electrode material holder with inner structures, a conductive film formed along the walls of the inner structures of the electrode material holder, and an electrode material deposited on the conductive film, and filled within the inner structures of the electrode material holder.
In accordance with an embodiment of the presently claimed invention, the electrode of the present invention comprises an AAO film with channels, a conductive film formed along the walls of the channels of the AAO film, and an electrode material deposited on the conductive film, and filled within the channels of the AAO film.
In accordance with another embodiment of the presently claimed invention, the electrode of the present invention comprises a patterned glass/quartz slice with concave parts, a conductive film formed along the walls of the concave parts of the glass/quartz slice, and an electrode material deposited on the conductive film, and filled within the concave parts.
The electrode of the present invention is an anode when the electrode material is an anode material. The electrode of the present invention is a cathode when the electrode material is a cathode material.
A third aspect of the presently claimed invention is to provide methods for fabricating the transparent or translucent lithium-ion battery of the present invention.
The present invention provides a transparent or translucent lithium-ion battery with high transparency and energy storage capacity. Both of the transparency and energy storage capacity are adjustable in a convenient way. In addition, the lithium-ion battery of the present invention is easily assembled and manufactured in a time efficient way.
Embodiments of the present invention are described in more detail hereinafter with reference to the drawings, in which:
In the following description, transparent/translucent Li-ion batteries, and the corresponding fabrication methods are set forth as preferred examples. It will be apparent to those skilled in the art that modifications, including additions and/or substitutions, may be made without departing from the scope and spirit of the invention. Specific details may be omitted so as not to obscure the invention; however, the disclosure is written to enable one skilled in the art to practice the teachings herein without undue experimentation.
As used herein, a lithium-ion (Li-ion) battery is defined as a transparent Li-ion battery or a translucent Li-ion battery.
The anode 101 comprises an electrode material holder 106a with inner structures, a current collector 107a, and an anode material 108. The current collector 107a, comprising nano-sized conductive films, is formed along the walls of the inner structures of the electrode material holder 106a. The anode material 108 is deposited on the current collector 107a, and filled within the inner structures of the electrode material holder 106a.
Similarly, the cathode 102 comprises an electrode material holder 106b with inner structures, a current collector 107b and a cathode material 109. The current collector 107b, comprising nano-sized conductive films, is also formed along the walls of the inner structures of the electrode material holder 106b. The cathode material 109 is deposited on the current collector 107b, and filled within the inner structures of the electrode material holder 106b.
According to an embodiment of the presently claimed invention, the electrode material holder with the inner structures is a patterned glass or quartz slice with concave parts. The patterns of the patterned glass/quartz slice can include a single shape or multiple shapes, providing concave and convex parts of the electrode material holder, which can be changed according to the requirements of transparency and capacitance of the transparent/translucent Li-ion battery. Each of the concave parts has a depth for holding the electrode material as a trench. The current collector is formed along the wall of the concave parts of the patterned glass/quartz slice, and the electrode material is deposited on the current collector, and filled within the concave parts. No matter which pattern/patterns used, the patterned glass/quartz slice also comprises the concave and convex parts. The concave parts of the patterns can have a diameter close to the infinity to form linear trenches.
Preferably, the patterns are symmetrical with a single shape or multiple shapes. As the thickness of the patterned glass/quartz slice increases, more electrode materials can be filled in to the electrode material holder to increase the energy storage capacity. Nevertheless, it increases also the cost and thickness of the battery. Thus, the preferable thickness of the patterned glass/quartz slice is in the range of 1 to 5 mm, and the preferable depth of the concave parts is in the range of 70 to 120 μm, depending on the etching method for glass or quartz.
The boundary 702 comprises different shapes and sizes, and provides the design for the outside electrode 703. In addition, the boundary 702 blocks the outside materials, such as the sealing glue, to affect the inner materials, such as the electrolyte and electrode materials, and makes the patterns be an integrated full cell, which can be modified according to various designs and requirements.
According to an embodiment of the presently claimed invention, the electrode material holder is an anodized aluminum oxide (AAO) film with self-aligned micro/nano-channels. The current collector is formed along the inners wall of the self-aligned micro/nano-channels. The electrode material is deposited on the current collector, and filled within the self-aligned micro/nano-channels.
In step 903, a voltage is applied to the Al substrate for anodization. Direct current is preferably used for anodization. Different voltages are used for different anodization solutions. The voltage is a key factor to influence the expected diameter and density of the self-aligned channels that can be in the range of several volts to several hundred volts. Temperature is another important factor for anodization, which affects not only the expected diameter and density of the channels, but also the uniformity of the channels. Additionally, the length of the channels and the thickness of the AAO film are determined by the anodizing time. According to an embodiment of the presently claimed invention, 0.3M sulfuric acid, voltage of 12 to 18V, and temperature of 12 to 15° C. are used as for anodization.
In step 904, the anodized Al substrate is cleaned and dried. In step 905, the remaining Al substrate is removed by an acid. Preferably, acidic copper sulfate solution is used.
If more uniformly well aligned AAO channels are required, the firstly-made AAO layer on the Al substrate is removed using an acid solution, such as phosphoric acid and chromic acid under the heating of about 60° C. Then, a second AAO layer is further made under the same conditions as those of preparing the first AAO layer.
In addition, a pre-patterned mask as shown in
Additionally, a transparent thin film such as a thin quartz sheet or a piece of polyethylene terephthalate (PET) can be used to attach on to the AAO film for protection. The transparent thin film can be soft or hard.
After step 903, the anodized Al (AAO/Al) substrate may not be transparent due to the presence of the remaining Al substrate.
However, after removing the remaining Al substrate from the AAO/Al substrate in step 905, a transparent AAO film with self-aligned nano/micro-sized channels is obtained.
Preferably, the thickness of the AAO film is in the range of 1 to 100 μm for having balance between the energy storage and transparency, and the diameter of the channels of the AAO film is in the range of 3 to 200 nm. Accordingly, the present invention is not limited to the AAO film. Other anodized metal oxide films are also applicable as the electrode material holders. For example, an anodized titanium oxide film can be used.
After the formation of the electrode material holder, nano-sized conductive films, being the current collector, are formed along the walls of the inner structures of the electrode material holder. The nano-sized conductive film can comprise nano-sized metals, nano-sized carbon material, transparent metal oxide, or transparent conductive polymer. The nano-sized metals can be platinum (Pt) or gold (Au). The nano-sized carbon material can be carbon nanotubes (CNTs) or graphene. The transparent metal oxide can be indium (III) oxide (In2O3). The transparent conductive polymer can be poly(3,4-alkylenedioxythiophene) (PEDOT), or poly(3,4-ethylenedioxythiophene): poly(styrenesulfonic acid) (PEDOT:PSS). Preferably, the thickness of the nano-sized conductive film is below 50 nm.
The nano-sized metals or the transparent metal oxide can be deposited on the electrode material holder by sputtering or thermal evaporation.
The CNTs or graphene can be fabricated by chemical vapor deposition (CVD). Preferably, the cross-linked CNTs with thin wall are used to achieve better transparency.
The water solution of the transparent conductive polymers of PEDOT or PEDOT:PSS can be filled in to the patterns of the glass/quartz slice (including both convex and concave areas of the pattern), or channels of AAO by brushing. Nano-sized metal particles such as Au and Pt, can be added into PEDOT to enhance the conductivity.
According to an embodiment of the presently claimed invention, the cross-linked CNTs are formed on the walls of the channels of an AAO film as the current collector. Reactants such as organic materials or polymers containing carbon are decomposed with or without catalysts during the heating of the AAO film. The decomposition temperature is about 400-600° C., according to the requirement for conductivity and crystallization of the CNTs. At first, the reactants are sealed in a tube furnace. Inert gases, such as nitrogen or argon, are introduced into the furnace. After a period of time, the furnace is heated to the decomposition temperature. The decomposition temperature is then kept for half an hour to one hour. During cooling down the furnace, an inert gas is kept flowing into the furnace. After the temperature of the furnace drops down to the room temperature, the AAO film coated with the cross-linked CNTs is taken out.
Preferably, a transitional metal layer, such as Ag, is coated on the electrode material holder before coating the conductive material. The transitional metal layer covers only the convex parts of the patterned glass/quartz slice, or the top surface of AAO, because of different surface tension for the convex and concave fields of the pattern, or the top surface and surface of channel wall. In addition, this transitional metal layer can help to remove the excess anode or cathode material together with the conductive material by a glue or tape in a more convenient way.
After the formation of the current collector, a slurry of anode or cathode materials is filled into the patterns of glass/quartz slice (including both convex and concave areas of the patterns), or the channels of AAO film, until that there are enough anode or cathode materials. Then, the anode or cathode materials are dried by heating. Excess anode or cathode materials together with the conductive material on convex areas of patterned glass/quartz slice, or on the top surface of AAO film are removed by a glue or tape, leaving the convex areas, or the area of the AAO film without channels for light transmission.
The slurry of the anode material comprises graphite, carbon black, 1-methyl-2-prrolidone and/or poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP). The slurry of the cathode material comprises Li-contained materials, such as lithium manganese dioxide (LiMn2O4), lithium cobalt oxide (LiCoO2) and lithium iron phosphate (LiFePO4), carbon black, PVDF-HFP and 1-methyl-2-prrolidone.
A slim metal sheet is stuck to the location of the outside electrodes on the patterns, and the anode or cathode of the transparent/translucent Li-ion battery is then formed.
A separator is fabricated and further located between the anode and the cathode. The separator is a gel material, such as poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP). Apart from PVDF-HFP, polyethyleneoxide (PEO), polyacrylonitrile (PAN) or polymethylmethacrylate (PMMA) can also be used as the gel material.
According to an embodiment of the presently claimed invention, PVDF-HFP is prepared as follows. Sylgard 184 silicone elastomer base, Sylgard 184 silicone elastomer curing agent, ethyl acetate and toluene are mixed by stirring or ultrasonicating to form the precursor solution, which is then added into a container. The precursors are dried in an oven to get the solid PVDF-HFP, which is translucent and curved as shown in
According to an embodiment of the presently claimed invention, a full cell of the transparent Li-ion battery is packaged as follows. At first, a semi-dried separator is cut to a suitable size, and is sandwiched between a patterned anode and cathode. The anode and cathode are aligned by a positioning mark in the pattern. The anode, separator and cathode are fixed by clips or any other fixer that can be completed by naked eyes or under a microscope. Transparent UV glue is injected around the anode and/or cathode. Most of the boundary area around the patterned fields is filled with the UV glue. The UV glue is then cured using UV light.
The full cell is further packaged in a glove box. An electrolyte solution is introduced into the separator from the boundary without sealing by the UV glue. The electrolyte solution can be a solution of lithium hexafluorophosphate (LiPF6), lithium hexafluoroarsenate (LiAsF6), lithium tetrafluoroborate (LiBF4), lithium trifluoromethanesulfonate (LiCF3SO3), Lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), or lithium perchlorate (LiClO4) in a solvent of DEC, DMC/EC, DEC/EC, or poly(vinylidene fluoride-hexafluoropropylene). The UV glue is injected again to the remaining boundary of the whole battery, which is not sealed by the UV glue in the previous steps. The UV glue is cured with UV light. Finally, a transparent/translucent Li-ion battery is obtained.
In order to increase the capacity of the whole battery, similar full cells packaged as mentioned above can be stacked up. Owing to the clear positioning mark and boundary, this step is not difficult to be achieved.
The foregoing description of the present invention has been provided for the purposes of illustration and description. It is not intended to be exhaustive or to limit the invention to the precise forms disclosed. Many modifications and variations will be apparent to the practitioner skilled in the art.
The embodiments were chosen and described in order to best explain the principles of the invention and its practical application, thereby enabling others skilled in the art to understand the invention for various embodiments and with various modifications that are suited to the particular use contemplated. It is intended that the scope of the invention be defined by the following claims and their equivalence.
Pursuant to 35 U.S.C. §119(e), this is a non-provisional patent application which claims benefit from U.S. provisional patent application Ser. No. 61/851,408 filed Mar. 7, 2013, and the disclosure of which is incorporated herein by reference.
Number | Date | Country | |
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61851408 | Mar 2013 | US |