TWI463677B - Integrated electrochemical and solar cell - Google Patents

Description

Integrated electrochemical solar cell

The present invention relates generally to solar cells and thin film batteries, and more particularly to improved designs of integrated electrochemical solar cells and methods of producing the same.

In the past few decades, the field of thin film batteries, especially lithium batteries, has seen significant development. In addition, the recent increase in the price of traditional energy products has focused on alternative energy sources. In particular, photovoltaic solar cells have been significantly improved and their cost has been reduced. At the same time, the price of petrochemical fuel has risen to reflect the point that solar power will be comparable to network power in 2010. Today's second-generation solar cells based on deposition (in other literature or electroplating) on amorphous and microcrystalline thin films on bulk glass pedestals are the most promising in recent years to provide cost savings at network power. electric power.

Photovoltaic cell devices are limited in that they are only capable of providing electrical power when illuminated. This requires a device that must be operated at other times in order to have an alternative power source. In the case of portable electronic devices, automobiles, etc., it is not convenient to turn on the main power outlet. The simplest type of standby power is an electrochemical battery or a battery. Electrochemical cells offer an excellent combination of energy capacity, power density and energy savings. Some batteries are designed to be recharged several times - the so-called secondary battery. Thin film lithium batteries currently provide optimum performance in terms of energy density, power density, and cycle life. Similar to second generation solar cells Yes, it is also made using thin film deposition techniques.

Many individuals have been experimenting with conventional techniques to provide solutions and improvements in the design and production of photovoltaic cell/thin cell combinations. For example, U.S. Patent No. 4,481,265, the entire disclosure of which is incorporated herein by reference. This patent discloses an insulating base having a photovoltaic cell on one side and a battery on the other side, but the inventors have also illustrated how the two devices can be combined on the same surface. The specification of the device describes a battery using a liquid electrolyte, but the patent application scope includes a battery containing an inorganic thin film electrolyte. In 1984, state-of-the-art solid-state batteries provided extremely low performance in liquid electrolyte batteries. It leaves the reader with a judgment on how to make all the solid state devices and what materials to use. The entire manufacturing process described is complex and rough.

U.S. Patent No. 4,740,431 to Little, which is incorporated herein by reference, discloses a more specific and practical method for making integrated solar cells and batteries. The inventors disclose a process whereby a technique developed by the semiconductor industry is used to deposit and pattern a film to deposit solar cells and cells entirely on a susceptor. At the same time, lithium sulfide-based glass appears to be the most forward-looking solid electrolyte for all solid-state batteries.

However, in 1994, Bates et al. described a preferred solid electrolyte based on lithium phosphine oxide (LiPON) and approved in U.S. Patent No. 5,338,625. In addition to exposing the new thin-film solid electrolyte materials, the authors have announced a thin-film battery, which they call a thin-film microbattery, and deposit it using a thin film deposition method. After this important discovery, Many inventors have been allowed to seek patents to improve thin film microbatteries from all aspects.

The thin film microbatteries disclosed by Bates et al. have at least two major drawbacks (and the same as those described by Little), which stems from the fact that all of the cells are made from a film deposited on a non-electrochemically active susceptor. . First, since the electrode is very thin, the disclosed thin film battery has a very low capacity per unit area. Furthermore, since expensive vacuum deposition equipment is required, the manufacturing cost is very high compared to a battery fabricated from a bulk material.

In U.S. Patent No. 5,445,906 (issued 1995), Hobson and Snyder propose an innovative approach to solving the problem of poor capacity, whereby a film is deposited on a large area of resilient susceptor by a hoisting sputtering apparatus. The susceptor is then wound into a solid spiral, thereby achieving a large capacity per unit volume. However, the use of a winch sputtering apparatus further increases the manufacturing cost, and a firmly wound spiral battery is not easily integrated with a large-plane thin film solar cell.

A "method and apparatus for an integrated battery-capacitor device" has been disclosed by Jenson in the United States Patent No. US 2004/0185310, which attempts to provide a solution for an integrated battery device. Jenson's reference teaches depositing a cell over a conductive pedestal layer that is an individual structural component that is separate from the cell. Although all of the arrangements described involve the use of pedestals that are separate and different from the structural components of the battery, Jenson also discloses the integration of the proposed battery and photovoltaic cells.

Therefore, although Jenson's reference relates to both thin film and photovoltaic cells, it does not include the invention contained here: a self-supporting The thin film battery of the cathode or anode layer can be manufactured more easily and more economically than the battery presented by the prior art. In one embodiment of the present invention, since the battery has a significant capacity increase per unit area compared to the conventional thin film battery, the self-supporting layer is significantly thicker (at 50 times the level) than the previously described results. . In addition, the additional portion of the integrated solar cell of the present invention provides an exact solution to the emerging design issues of thin film batteries while providing space, weight, and even speed improvements and ease of manufacture.

The invention discloses an integrated electrochemical solar cell. The integrated battery contains an electrochemical cell and a solar cell. The electrochemical cell comprises a cathode current collector, a self supporting ceramic cathode layer, an anode layer, an anode current collector, and a solid electrolyte layer having a solid electrolyte layer disposed between the cathode layer and the anode layer. Solar cells are a known type of conventional technology and are electrically connected to the self-supporting electrochemical cells of the present invention.

The invention also discloses a method of making an integrated electrochemical solar cell. A preferred embodiment of the disclosed method provides an electrochemical cell formation process comprising the steps of forming an unsupported cathode current collector layer on a ceramic self-supporting cathode layer and forming a solid state on a ceramic self-supporting cathode layer An electrolyte layer, an anode layer formed on the electrolyte layer, an anode current collector layer on the anode layer, and an encapsulation layer deposited on the anode current collector layer. Embodiments of the present invention further include a solar cell forming process comprising the steps of depositing a photovoltaic material on a supporting glass layer, And an integrating step comprising connecting the photovoltaic material to the unsupported cathode current collector layer.

The more specific and important features of the present invention are set forth in the <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; Further features of the invention that form the subject matter of the claims of the invention will be described hereinafter. It will be appreciated by those skilled in the art that the disclosed concept and specific embodiments can be readily utilized as a basis for modification or design of other architectures that achieve the same objectives as the present invention. Those skilled in the art should also understand that the meaning of such equivalent constructions does not violate the spirit and scope of the invention as set forth in the appended claims.

Typically, thin film electrochemical cells (such as thin film lithium cells) are fabricated by depositing layers of various materials onto a base layer or susceptor. Figure 1 illustrates a typical design of a thin film battery 1 of the prior art type. In the prior art, the susceptor 2 can be fabricated from various materials such as metal foil, glass or thin plastic film. The susceptor 2 is then typically placed in a device such as physical vapor deposition (PVD), plasma assisted chemical vapor deposition (PECVD), or chemical vapor deposition (CVD) equipment or similar deposition equipment. The cathode current collector 3 is first deposited on the susceptor 2. Further, a cathode circuit connecting body 4 is fabricated. After the cathode current collector 3 is deposited, the cathode layer 5 is deposited. In the case of lithium thin film batteries, lithium cobaltate (LiCoO ₂ ) is still a preferred cathode material, although it is possible to utilize other materials such as LiMn ₂ O ₄ , LiFePO ₄ , or other materials known to those skilled in the art. The cathode material is typically deposited on the cathode current collector 3 using, for example, sputtering techniques. Although effective, the sputtering technique has physical limitations on the maximum thickness of the layer that can be deposited. Typically, the sputtered layer does not exceed 10 microns (10 μm) thick.

Once the cathode layer 5 is deposited on the susceptor 2, an electrolyte layer 6 is deposited on the cathode layer 5. In the conventional technique shown in FIG. 1, in the case of a lithium thin film battery, the material of the electrolyte is lithium phosphorus oxynitride (LiPON). Typically, in a lithium thin film battery, the electrolyte layer will be on a one micron (1 μm) thick level. Next, the anode layer 7 is deposited on top of the electrolyte layer 6, and then the anode current collector 8 is formed, and the anode circuit connecting body 9 is fabricated. In order to complete the production of a conventional lithium thin film battery, an encapsulation layer 10 is applied over the battery 1 to avoid the introduction of moisture. In the example shown in FIG. 1, the anode layer 7 may be lithium metal or a lithium alloy. As shown in Figure 1, the design and fabrication process of an electrochemical cell of the prior art is complex and encompasses a structural component and a plurality of deposition steps. Therefore, a need exists for a simplified design and method of fabricating an electrochemical cell. Further, there is a need for a simplified design and method for manufacturing an integrated electrochemical solar cell in order to increase the storage capacity per unit cost of the electrochemical cell and to balance the current storage potential of the electrochemical cell with the advancement of solar cell technology.

2 shows an embodiment of a self-supporting electrochemical cell 20 of the type contemplated by the present invention. Although the description herein refers to a lithium battery, the present invention contemplates the use of various materials other than lithium and lithium related electrochemical cells. In contrast to prior art electrochemical cells, the present invention provides a self-supporting cathode layer upon which the remaining electrochemical cell architecture is fabricated. Therefore, the present invention Eliminate the need for individual pedestal layers, thereby saving space and manufacturing costs.

In an embodiment of the invention, a self-supporting cathode layer 23 is first formed from a suitable ceramic cathode material and its additive is selected depending on the desired electrical properties. In embodiments of the present invention, LiCoO _{2 is} used as the cathode material, although it is understood by those skilled in the art that any suitable cathode material can be utilized without departing from the spirit and purpose of the present invention. Examples of suitable cathode materials include metal oxides, metal oxides containing lithium, metal phosphates, metal phosphates containing lithium, metal sulfides, metal sulfides containing lithium, metal sulfur oxides, metal sulfur containing lithium An oxide, a selenide, a mixture of metal oxides (for example, V ₂ O ₅ -TeO ₂ ), and the like.

In another embodiment of the invention, such as lithium niobate (taken from the Li ₂ O-SiO ₂ pseudo-component), lithium phosphate (taken from the Li ₂ O-P ₂ O ₅ pseudo-binary composition) Lithium zirconate (taken from the binary component of Li ₂ O-ZrO ₂ ) and an ionic conductive glass, or an additional electrolyte material of an electrically conductive material such as graphite, can be attached to the cathode material during processing In order to enhance the ion and electronic conductive properties and the overall performance of the self-supporting ceramic cathode layer 23. These additives have the benefit of allowing the self-supporting electrochemical cell 20 to more fully utilize the full thickness of the cathode material to facilitate the charge-discharge cycle.

In a preferred embodiment of the invention, the self supporting ceramic cathode layer 23 is formed to a thickness of between about 0.5 and 1.0 mm. Within the field of the invention, the thickness of the ceramic cathode layer 23 of less than 0.5 mm or greater than 1.0 mm can likewise be used without departing from the spirit or purpose of the invention.

After the self-supporting cathode layer 23 is fabricated, the cathode current collector 21 can be applied to the main surface of one of the self-supporting cathode layers 23. Typically through Sputtering techniques are used to implement the cathode current collector 21, although other deposition techniques well known in the art are also suitable. The cathode current collector 21 can be fabricated from nickel or any other material suitable for transferring current from the battery cathode to an external circuit, such as gold, aluminum, and the like.

After the deposition of the cathode current collector 21, the cathode current connection body 22 can be fabricated. The cathode current connector 22 can be a wiring, circuit, or other connection means for connecting the cathode current collector 21 to an external circuit. On the opposite major surface of the self-supporting cathode layer 23, an electrolyte layer 24 is deposited.

In a preferred embodiment, the electrolyte layer 24 can be deposited by sputtering techniques; however, it is also contemplated to be able to use, for example, chemical vapor deposition (CVD), plasma assisted chemical vapor deposition (PECVD), atomic layer deposition (ALD). Other deposition techniques such as pulsed laser deposition (PLD), plasma spray, and the like. In a preferred embodiment, LiPON is used as the material for the electrolyte, but other suitable electrolyte materials well known to those skilled in the art can also be used, such as LiPONB, Li _3.6 Si _0.6 P _0.4 O ₄ , Li _6.1 V _0.61. Si _0.39 O _5.36 , LiBO ₂ , LiBP, Li ₂ SO ₄ -LiO-B ₂ O ₃ , Li ₂ S-SiS ₂ -P ₂ S ₅ , or LiI-Li ₂ S-P ₂ S ₅ -P ₂ O ₅ and many more. The electrolyte layer 24 is used to allow ions between the self-supporting ceramic cathode layer 23 and the anode layer 25 to pass freely when the cathode layer 23 and the anode layer 25 are connected through an external circuit.

After the electrolyte layer 24 is formed, the anode layer 25 is deposited on the electrolyte layer 24. In a preferred embodiment of the invention, the anode layer 25 is formed of lithium metal. Alternatively, such as lithium carbon alloy, lithium tin alloy, lithium niobium alloy, lithium niobium alloy, lithium magnesium alloy, lithium indium alloy, lithium gallium alloy, Li _x V ₂ O ₅ , V ₂ O ₅ , Cu, SiSn _0.87 O _1.20 N _1.72 and other suitable materials for SnO can be used for the construction of the anode. An anode current collector 26 is formed over the anode layer 25 to connect the anode layer 25 to an external circuit through the anode circuit connector 27. Finally, in some embodiments of the invention, an encapsulation layer 28 is deposited over the electrochemical cell 20 to tightly seal the electrochemical cell 20 from moisture ingress. Thus, the self-supporting electrochemical cell 20 of the present invention is constructed without the use of individual, supported pedestal materials as taught by the prior art.

In another embodiment of the invention, a self-supporting anode is used to form the electrochemical cell, again ignoring the need for a support pedestal as taught by the prior art. FIG. 3 illustrates an electrochemical cell 30 that uses a self supporting anode layer 33. In the embodiment utilizing the self-supporting anode layer 33, the anode material is preferably made of a metal such as lithium, sodium, copper, silver or an alloy thereof with other metals. The anode current collector 31 and the anode circuit connector 32 are formed over one of the main surfaces of the self-supporting anode layer 33. On the opposite major surface, a solid electrolyte layer 34 is formed. The material selected for the solid electrolyte layer 34 will depend on the material used for the self-supporting anode layer 33; however, such an electrolyte material should be selected to ensure that the ions are self-supporting when the anode layer 33 and the cathode layer 35 are connected through an external circuit. The flow of the anode layer 33 to the cathode layer 35. The cathode layer 35 is formed on the solid electrolyte layer 34 and should be composed of a material that will effect an embedding reaction of the battery active ions (i.e., lithium, sodium, copper or silver ions, respectively). A cathode current collector 36 is then formed over the cathode layer 35 prior to the cathode circuit connection to connect the cathode current collector to an external circuit. Finally, in some embodiments of the invention, an encapsulation layer 38 is used to prevent moisture from being introduced into the electrochemical cell 30. The encapsulation layer 38 can be applied by one or more of a variety of different packaging materials to make. For example, in the preferred embodiment, tantalum nitride can be used as the package material. Assuming that the inherent characteristics of tantalum nitride are readily visible to those skilled in the art, a second material, such as tantalum oxide, is often applied over the tantalum nitride to ensure that the encapsulation layer 38 tightly seals the cell 30. Other examples of materials that can be used as part of the encapsulation layer 38 include yttrium oxynitride, parylene, polymer or metal.

Another embodiment of the present invention contemplates integrating the self-supporting electrochemical cells and solar cells described to provide an integrated electrochemical solar cell.

Figure 4 illustrates an integrated electrochemical solar cell 40 contemplated by the present invention. The term "solar cell" as used herein includes any of the known devices used for the purpose of converting solar radiation into electricity. An illustration of a solar cell that can be used in accordance with a preferred embodiment of the present invention can be found in U.S. Patent Nos. 6,309,906 and 4,740,431. In the application of the preferred embodiment, solar cell 42 is first formed over a glass substrate 41 as is well known in the art. The glass base 41 serves to protect the solar cell 42 from damage and even increase the support strength of the fragile solar cell 42. Thereafter, an insulating layer 43 can be formed over the solar cell 42 to isolate the solar cell 42 from the current collector 21. Some examples of insulating layer materials are tantalum nitride, hafnium oxynitride, aluminum oxide, and hafnium oxide. Further, a cathode circuit connector 22 can be provided to connect the cathode current collector 21 to an external circuit. Typically, the insulating layer 43 is relatively thin and unsupported. In the preferred embodiment, the insulating layer 43 is bonded to the cathode current collector 21 by the application of the joint 44. Joint 44 The bonding technique such as semiconductor bonding technique, copper diffusion bonding, copper-tin-copper diffusion bonding or the like is employed, and can be implemented in one or more layers, or an application step, thereby achieving the desired insulating layer 43. Linked to the junction of the cathode current collector 21. For example, in one embodiment, the bond 44 can comprise a deposition of a thin copper layer on the insulating layer 43 prior to the thin layer of tin. Copper can then be used to serve as the cathode current collector 21. When the copper cathode current collector 21 is deposited in close contact with the tin layer of the joint 44 and heated, a copper-tin-copper diffusion bonding process occurs, which results in a solid state between the insulating layer 43 and the cathode current collector 21 through the bonding 44. Engage. In one embodiment, after the cathode current collector 21 and the cathode circuit connector 22 are fabricated, the self-supporting electrochemical cell as outlined in FIG. 2 can be fabricated into a solar cell using fabrication techniques such as those suitable for the selected material. Above. In other embodiments, the solar cell 42 is combined with the glass 41 to produce the self-supporting electrochemical cell shown in FIG. The cathode current collector 21 of the completed self-supporting electrochemical cell 20 is then joined to the insulating layer 43 through a bond 44 as previously outlined. In another embodiment, the solar cell 42 is bonded to the cathode current collector 21 with an adhesive that acts as the insulating layer 43 and the bond 44.

Due to the self-supporting nature of the ceramic cathode layer 23, the integrated electrochemical solar cell 40 of the present invention can be effectively fabricated into a complete package by joining the components fabricated at different times and locations.

A method of fabricating the integrated electrochemical solar cell 40 will now be described with reference to Figs. The method illustrated in Figure 5 points to the formation of the self-supporting electrochemical cell described herein and includes the preparation and fabrication of a self-supporting A ceramic cathode is supported (step 101). In certain embodiments, step 101 includes attaching an electrolyte and/or a conductive material to the cathode material during the preparation period. In other embodiments, the cathode material is mixed with the selected electrolyte and/or conductive material and then subjected to various treatments such as thermal pressure forming to ensure a dense cathode structure. An unsupported cathode current collector is applied to a major surface of the self-supporting ceramic cathode material and a cathode circuit connector is prepared (step 103).

In a preferred embodiment, after the cathode current collector and the cathode circuit connector are prepared and fabricated, during step 105, an electrolyte layer is deposited over the self-supporting cathode anti-main surface. In a preferred embodiment, other deposition techniques such as radio frequency sputtering, molecular beam deposition, atomic layer deposition, pulsed laser deposition, chemical vapor deposition, plasma assisted chemical vapor deposition, or ion beam assisted deposition can be utilized. The electrolyte layer of step 105 is still deposited by sputtering techniques. In the case of selecting a lithium-containing cathode material, the method further includes depositing a lithium protective layer through the sputtering technique of step 107, thereby protecting the electrolyte-lithium interface. Additional anode material is added at step 109 if needed and/or desired, for example, a clean lithium metal foil can be pressed into contact with the protective lithium layer deposited in step 107. The fabrication of the anode current collector and the anode connector occurs in step 111. Finally, to protect the electrochemical cell, an encapsulation layer can be deposited over the cell at step 113.

Turning now to Figure 6, a method of forming an integrated electrochemical solar cell of the present invention is illustrated using copper-tin-copper diffusion bonding to bond solar cells to electrochemical cells. In step 201, providing a solar power Pool unit. The solar cell unit is a combination of a glass susceptor and a solar cell known in the art. In step 203, an insulating layer is deposited over the solar cell material to insulate the solar cell material from the cathode current collector. At step 205, a layer of copper is deposited over the insulating layer. Next, in step 207, a layer of tin is deposited over the copper layer. As described in Little, U.S. Patent No. 4,740,431, an additional step (not shown) can be used to pattern the insulating, copper, and tin layers in such a manner that a plurality of solar cells are connected in series or in parallel to change the electrochemical cell. The way of charging the voltage. At step 209, a ceramic self supporting cathode layer is prepared. In certain embodiments, step 209 includes attaching an electrolyte and/or a conductive material to the cathode material during the preparation period. In other embodiments, the cathode material is mixed with the selected electrolyte and/or conductive material and then subjected to various treatments such as thermal pressure forming to ensure a dense cathode structure. An unsupported cathode current collector is applied to a major surface of the self-supporting ceramic cathode material, and a cathode circuit connector is prepared in step 211. At step 213, a layer of copper is deposited over the cathode current collector. At step 215, the copper layer deposited on the cathode current collector is bonded to the tin layer deposited in step 207 by a copper-tin-copper diffusion technique known in the art. After step 215, an electrochemical cell as indicated previously beginning with step 105 of FIG. 5 is established.

A method of making an integrated solar and electrochemical cell using a self-supporting anode is illustrated in FIG. At step 301, a solar cell known in the art is provided. This solar cell typically comprises a glass base and a layer of photovoltaic material. At step 303, an insulating layer is deposited on the The photovoltaic material on the side of the solar cell. At step 305 prior to the deposition of the tin layer in step 307, a layer of copper is deposited over the insulating layer. As described by Little in U.S. Patent No. 4,740,431, in an optional step 308, certain techniques can be used to draw patterns of insulating, copper, and tin layers in such a manner that a plurality of solar cells are connected in series or in parallel to change the electrification. Learn the way the battery is charged. At step 309, a self supporting anode layer is provided. In a preferred embodiment, the self-supporting anode of the present invention is selected from lithium, sodium, copper, silver, or alloys thereof with other materials. At step 311, an anode current collector and an anode circuit connector are fabricated over one of the two major surfaces of the self-supporting anode. At step 313, a layer of copper is deposited over the anode current collector. At step 315, the tin layer deposited in step 307 and the copper layer deposited in step 313 are bonded using a copper-tin-copper diffusion bonding technique. In the case where copper is selected to serve as the anode current collector material, step 313 may be omitted. Next, at step 318, an electrolyte layer is deposited over the major surface of the anode layer, which surface is opposite the anode current collector. At step 319, the cathode material is prepared and attached to the electrolyte layer. In certain embodiments, step 319 includes attaching an electrolyte and/or a conductive material to the cathode material during the preparation period. In other embodiments, the cathode material is mixed with the selected electrolyte and/or conductive material and then subjected to various treatments such as thermal pressure forming to ensure a dense cathode structure. Next, in step 321, a cathode current collector and a cathode circuit connector are prepared and fabricated. Finally, at step 323, at least the electrochemical cell portion of the device is sealed to prevent moisture from entering the unit.

Figure 8 illustrates another embodiment of the present invention. In step 401, a Self-supporting cathode layer. In certain embodiments, this includes attaching an electrolyte and/or a conductive material to the cathode material during the preparation period. In other embodiments, the cathode material is mixed with the selected electrolyte and/or conductive material and then subjected to various treatments such as thermal pressure forming to ensure a dense cathode structure. Next, in step 403, a cathode current collector and a cathode circuit connector are prepared and fabricated over a major surface of the cathode layer. On the opposite surface of the self-supporting cathode layer, a solid electrolyte layer is deposited at step 405. Next, in step 407, a tin layer of an electrochemically active metal of the battery is deposited over the electrolyte layer. In other embodiments, an alloy of electrochemically active metals of other materials may be allowed to be deposited. Next, in step 409, according to steps 301-315, a solar cell/self-supporting anode layer is fabricated. Thereafter, step 407 is placed on the metal tin layer deposited on the self-supporting cathode-electrolyte layer to closely contact the exposed surface of the self-supporting anode, and heat and pressure are applied in step 411, thereby the cathode-electrolyte layer and the solar cell/ The anode layers are fused together. This treatment is extremely helpful if the two mating surfaces are clean and smooth. Finally, at step 413, at least the electrochemical cell portion of the device is sealed to prevent moisture from entering the unit.

Figure 9 illustrates another method of making an integrated solar and electrochemical cell of the present invention. In this embodiment, it is assumed that the production of the solar cell is difficult to manufacture, and the manufacturing step is effective, especially when a low melting point material such as lithium or sodium is used as the anode. . This embodiment has a thin film solar cell that is directly fabricated on a self-supporting ceramic cathode, eliminating the glass on which the thin film solar cell is deposited. The need for a pedestal, and thereby saving the additional advantage of cost and weight. At step 501, a self supporting ceramic cathode is prepared. In certain embodiments, step 501 includes attaching an electrolyte and/or a conductive material to the cathode material during the preparation period. In other embodiments, the cathode material is mixed with the selected electrolyte and/or conductive material and then subjected to various treatments such as thermal pressure forming to ensure a dense cathode structure. At step 503, a cathode current collector is deposited with the cathode circuit connector and fabricated over one of the two major surfaces of the self supporting ceramic cathode. At step 505, an insulator is deposited over the cathode current collector layer. If necessary, in step 506, as described in Little, U.S. Patent No. 4,740,431, the use of etching or metal lift-off techniques to pattern the insulating and metal layers can be used to connect the majority in series or in parallel. The way a solar cell changes the voltage that charges an electrochemical cell. In step 507, a photovoltaic cell is produced on the insulator layer by the technique disclosed in U.S. Patent No. 6,309,906. At step 509, an electrolyte layer is deposited on the second major surface of the self supporting ceramic cathode. At step 510, a metal protective layer can be deposited to protect the exposed surface of the electrolyte and to ensure good interfacial contact between the electrolyte and the anode. The metal protective layer selected in step 510 may be an electrochemically active metal (eg, lithium, sodium, copper or silver), an alloy of an electrochemically active metal with other metals, or an alloy known to form an electrochemically active metal having a battery. Metal. In step 511, the anode layer is fabricated and attached to the cell, for example by fusing the anode to the protective metal layer deposited on the electrolyte in step 510. At step 513, an anode current collector and an anode circuit connector are fabricated and deposited over the anode layer. Finally, at step 515 An encapsulation layer is deposited.

It is to be understood that the above description is intended to be illustrative rather than limiting. Although various features and advantages of the embodiments of the invention are disclosed herein, it will be apparent to those skilled in the <RTIgt; The scope of the present invention should be determined by reference to the scope of the claims and the scope of the equivalents of the claims. The invention has been described above.

1‧‧‧Study technology type thin film battery

2‧‧‧Base

3‧‧‧Cathodic current collector

4‧‧‧Cathode circuit connector

5‧‧‧ cathode layer

6‧‧‧ electrolyte layer

7‧‧‧anode layer

8‧‧‧Anode current collector

9‧‧‧Anode circuit connector

10‧‧‧Encapsulation layer

20‧‧‧ Self-supporting electrochemical cell of the invention

21‧‧‧ Cathode Current Collector

22‧‧‧Cathode circuit connector

23‧‧‧ Self-supporting cathode layer

24‧‧‧ electrolyte layer

25‧‧‧ anode layer

26‧‧‧Anode current collector

27‧‧‧Anode current connector

28‧‧‧Encapsulation layer

30‧‧‧Electrochemical battery

31‧‧‧Anode current collector

32‧‧‧Anode circuit connector

33‧‧‧ Self-supporting anode layer

34‧‧‧Solid electrolyte layer

35‧‧‧ cathode layer

36‧‧‧Cathodic current collector

37‧‧‧ Cathode circuit connector

38‧‧‧Encapsulation layer

40‧‧‧Integrated electrochemical solar cells

41‧‧‧ glass base

42‧‧‧ solar cells

43‧‧‧Insulation

44‧‧‧Join

1 is a cross-sectional view of a typical thin film electrochemical cell known from the prior art; FIG. 2 is a cross-sectional view of the self-supporting electrochemical cell of the present invention; and FIG. 3 is an electrochemical cell using the self-supporting anode of the present invention. Figure 4 is a cross-sectional view of an integrated electrochemical solar cell of the present invention; Figure 5 is a flow chart showing one embodiment of a fabrication process in accordance with the present invention; and Figure 6 is an embodiment of a fabrication process in accordance with the present invention. 7 is a flow chart of one embodiment of a production processing program according to the present invention; and FIG. 8 is a flow chart of an embodiment of a production processing program according to the present invention; 9 is a flow chart of one embodiment of a production process described in accordance with the present invention.

Throughout the drawings, like reference characters refer to like elements.

21‧‧‧ Cathode Current Collector

23‧‧‧ cathode

24‧‧‧ Electrolytes

25‧‧‧Anode

26‧‧‧Anode current collector

27‧‧‧Cathode circuit connector

28‧‧‧Package

40‧‧‧Integrated electrochemical solar cells

41‧‧‧ glass base

42‧‧‧ solar cells

43‧‧‧Insulation

44‧‧‧Join

Claims (50)

An integrated electrochemical solar cell comprising: an electrochemical cell comprising: a self-supporting ceramic cathode layer having a bottom surface and an upper surface, the self-supporting ceramic cathode layer having a thickness of 0.5 to 1.0 mm The supporting ceramic cathode layer has no pedestal layer; an unsupported cathode current collector disposed on the bottom surface of the self-supporting ceramic cathode layer; an insulator disposed on the unsupported cathode current collector; and a solid electrolyte layer configured Above the upper surface of the self-supporting ceramic cathode layer; an anode layer disposed on the electrolyte layer; and an anode current collector disposed on the anode layer; a solar cell electrically connected to An electrochemical cell produced on the insulating layer; and an encapsulation layer disposed over the integrated electrochemical solar cell. The integrated electrochemical solar cell of claim 1, wherein the anode layer further comprises a lithium alloy. The integrated electrochemical solar cell of claim 2, wherein the lithium alloy is lithium alloyed with a material of a group consisting of C, Sn, Si, Ge, Al, Mg, In, and Ga. The integrated electrochemical solar cell of claim 1, wherein the anode layer comprises lithium metal. An integrated electrochemical solar cell according to claim 1, wherein the self-supporting ceramic cathode layer is made of a lithium-containing metal oxide. The integrated electrochemical solar cell of claim 1, wherein the self-supporting ceramic cathode layer is made of a metal oxide. An integrated electrochemical solar cell according to claim 1, wherein the self-supporting ceramic cathode layer is made of a metal sulfide. The integrated electrochemical solar cell of claim 1, wherein the self-supporting ceramic cathode layer is made of lithium containing a metal sulfide. The integrated electrochemical solar cell of claim 1, wherein the self-supporting ceramic cathode layer is made of metal oxysulfide. The integrated electrochemical solar cell of claim 1, wherein the self-supporting ceramic cathode layer is made of lithium containing metal oxysulfide. The integrated electrochemical solar cell of claim 1, wherein the self-supporting ceramic cathode layer is made of selenide. An integrated electrochemical solar cell according to claim 1, wherein the self-supporting ceramic cathode layer is made of a metal phosphate. An integrated electrochemical solar cell according to claim 1, wherein the self-supporting ceramic cathode layer is made of lithium containing a metal phosphate. The integrated electrochemical solar cell of claim 1, wherein the self-supporting ceramic cathode layer is made of a mixture of one or more of a metal oxide, a phosphate or a sulfide. The integrated electrochemical solar cell of claim 1, wherein the self-supporting ceramic cathode layer comprises a mixture of a cathode material and an electrolyte. The integrated electrochemical solar cell of claim 1, wherein the self-supporting ceramic cathode layer further comprises a conductive material. Such as the integrated electrochemical solar power of claim 1 m, wherein the electrolyte layer is lithium phosphorus oxynitride. An integrated electrochemical solar cell according to claim 1, wherein the electrolyte layer is selected from the group consisting of Li _3.4 V _0.6 Si _0.4 O ₄ and Li _6.1 V _0.61 Si _0.39 O _5.36 . The integrated electrochemical solar cell of claim 1, wherein the electrolyte layer is selected from the group consisting of LiBO ₂ , LiBP, and Li ₂ SO ₄ -Li ₂ OB ₂ O ₃ . The integrated electrochemical solar cell of claim 1, wherein the electrolyte layer is composed of Li ₂ S-SiS ₂ -P ₂ S ₅ and LiI-Li ₂ SP ₂ S ₅ -P ₂ O ₅ Group selected. An integrated electrochemical solar cell according to claim 10, wherein the anode layer comprises lithium metal. An integrated electrochemical solar cell according to claim 15 wherein the anode layer comprises a lithium alloy. The integrated electrochemical solar cell of claim 15, wherein the anode layer comprises a group selected from the group consisting of Li _x V ₂ O ₅ , V ₂ O ₅ , Cu, SiSn _0.87 O _1.20 N _1.72, and SnO. Material. A method of fabricating an integrated electrochemical solar cell, the method comprising: an electrochemical cell formation process comprising: fabricating an unsupported cathode current collector on a ceramic self-supporting cathode layer, the ceramic self-supporting cathode having no basis a seat layer; forming an insulating layer on the ceramic self-supporting cathode layer; forming a solid electrolyte layer on the ceramic self-supporting cathode layer; forming an anode layer on the electrolyte layer; and forming an anode on the anode layer Current collection a solar cell forming process comprising the steps of: depositing a photovoltaic material on the insulating layer after the step of forming the insulating layer and before the step of forming the solid electrolyte layer; an electrical connection step is: After the step of fabricating an anode current collector layer on the anode layer, electrically connecting the solar cell to the electrochemical cell; and a package forming process, comprising the steps of: applying at least one encapsulating material to the integrated electrification Learn solar cells. The method of claim 24, wherein the electrochemical cell formation process further comprises a densification step comprising forming the cathode layer using at least one high temperature preparation technique. The method of claim 25, wherein the densifying step comprises hot press forming. The method of claim 25, wherein the electrochemical cell forming process further comprises the step of mixing the electrolyte material with the material used to form the ceramic self-supporting cathode layer prior to the densifying step. The method of claim 27, wherein the electrochemical cell forming process further comprises the step of mixing a conductive material with the material used to form the ceramic self-supporting cathode layer and the electrolyte material prior to the densifying step. The method of claim 28, wherein the electrochemical cell formation process further comprises the step of depositing a metal layer over the solid electrolyte layer. The method of claim 24, wherein the step of forming the solid electrolyte layer on the ceramic self-supporting cathode layer further comprises depositing a solid electrolyte material on the ceramic self-supporting cathode layer by a sputtering technique. The method of claim 24, wherein the step of forming the solid electrolyte layer on the ceramic self-supporting cathode layer further comprises depositing a solid electrolyte material on the ceramic self-supporting cathode layer by radio frequency sputtering. The method of claim 24, wherein the step of forming the solid electrolyte layer on the ceramic self-supporting cathode layer further comprises depositing a solid electrolyte material on the ceramic self-supporting cathode layer by molecular beam deposition. The method of claim 24, wherein the step of forming the solid electrolyte layer on the ceramic self-supporting cathode layer further comprises depositing a solid electrolyte material on the ceramic self-supporting cathode layer by atomic layer deposition. The method of claim 24, wherein the step of forming the solid electrolyte layer on the ceramic self-supporting cathode layer further comprises depositing a solid electrolyte material on the ceramic self-supporting cathode layer by pulsed laser deposition. The method of claim 24, wherein the step of forming the solid electrolyte layer on the ceramic self-supporting cathode layer further comprises depositing a solid electrolyte material on the ceramic self-supporting cathode layer by chemical vapor deposition. The method of claim 24, wherein the step of forming the solid electrolyte layer on the ceramic self-supporting cathode layer further comprises depositing a solid electrolyte material on the ceramic self-supporting cathode layer by plasma assisted chemical vapor deposition. on. The method of claim 24, wherein the step of forming the solid electrolyte layer on the ceramic self-supporting cathode layer further comprises depositing a solid electrolyte material on the ceramic self-supporting cathode layer by ion beam assisted deposition. The method of claim 25, wherein the electrochemical cell forming process further comprises the step of depositing a first sealing layer over the electrochemical cell. The method of claim 38, wherein the material for the first sealing layer is tantalum nitride. The method of claim 38, wherein the material for the first sealing layer is yttrium oxynitride. The method of claim 38, wherein the material for the first sealing layer is parylene. The method of claim 38, wherein the material for the first sealing layer is a polymer. The method of claim 38, wherein the electrochemical cell forming process further comprises the step of depositing a second sealing layer on the electrochemical cell. The method of claim 43, wherein the material used for the first sealing layer is tantalum nitride, and the material used for the second sealing layer is oxygen. Phlegm. The method of claim 43, wherein the material used for the first sealing layer is yttrium oxynitride, and the material used for the second sealing layer is metal. The method of claim 43, wherein the material used for the first sealing layer is tantalum nitride, and the material used for the second sealing layer is metal. The method of claim 43, wherein the material used for the first sealing layer is tantalum nitride, and the material used for the second sealing layer is a polymer. The method of claim 43, wherein the material used for the first sealing layer is yttrium oxynitride, and the material used for the second sealing layer is a polymer. An integrated electrochemical solar cell comprising: an electrochemical cell comprising: a self-supporting ceramic cathode layer having a bottom surface and an upper surface, the self-supporting ceramic cathode layer having a thickness of 0.5 to 1.0 mm Thickness, the self-supporting ceramic cathode layer has no pedestal layer, the self-supporting ceramic cathode layer comprises LiCoO ₂ , a mixture of an electrolyte material and a conductive material; and an unsupported cathode current collector disposed at the bottom layer of the self-supporting ceramic cathode layer Above the surface; an insulator disposed on the unsupported cathode current collector; an electrolyte layer disposed on the upper surface of the self-supporting ceramic cathode layer, the electrolyte layer comprising lithium phosphorus oxynitride; an anode a layer disposed on the electrolyte layer, the anode layer comprising a lithium alloy; and an anode current collector disposed on the anode layer; and a solar cell electrically connected to the electrification generated on the insulator Learning a battery; and an encapsulation layer disposed on the integrated electrochemical solar cell. An integrated electrochemical solar cell comprising: an electrochemical cell comprising: a self-supporting ceramic cathode layer having a bottom surface and an upper surface, the self-supporting ceramic cathode layer having a thickness of 0.5 to 1.0 mm Thickness, the self-supporting ceramic cathode layer has no pedestal layer, the self-supporting ceramic cathode layer comprises LiCoO ₂ , a mixture of an electrolyte material and a conductive material; and an unsupported cathode current collector disposed at the bottom layer of the self-supporting ceramic cathode layer Above the surface; an insulator disposed on the unsupported cathode current collector; an electrolyte layer disposed on the upper surface of the self-supporting ceramic cathode layer, the electrolyte layer comprising lithium phosphorus oxynitride; an anode a layer disposed over the electrolyte layer, the anode layer comprising lithium metal; and an anode current collector disposed over the anode layer; and a solar cell electrically coupled to the electrification generated on the insulator Learning a battery; and an encapsulation layer disposed on the integrated electrochemical solar cell.