Solid energy harvester of transition metal oxide

Abstract

To provide an energy harvester device that uses solid-state electrolytes to generate on-demand energy from a surrounding environment for a variety of applications, and a method for manufacturing the same.SOLUTION: In a solid-state energy harvester, oxygen carries negative charges (electrons) and enters a cathode 7A3, and nestles into a crystal structure and defects of a cathode material 3101 (e.g., Co3O4) to make an excess of electrons. The excess of electrons freely moves to a separator layer 7A2, and is attracted by lower electronegativity of WO2.9 and facilitated by CeO2 "electrolyte" 3102. A transition metal suboxide (e.g.,Ti4O7) in an anode 7A1 has greater electronegativity than Co3O43101 of a cathode 7A3, so that electrons are released by the oxygen reacting with hydroxyl ions and form, in an anode body 3103, water vapor which is released into an environment. In addition, the solid-state energy harvester may produce power in the presence of water vapor and oxygen by two current collectors 7B1, 7B2 and a load 3104.SELECTED DRAWING: Figure 31

Description

Technical Field

[0001] All references cited herein, including but not limited to patents and patent applications, are hereby incorporated by reference in their entirety.

[0002] (Cross - Reference to Related Applications) This application claims the benefit of U.S. Provisional Patent Application No. 62 / 641,779, filed on Mar. 12, 2018, which is hereby incorporated by reference in its entirety.

Background Art

[0003] An energy harvester is a device that collects energy from the environment without storing energy. For example, see U.S. Pat. No. 8,115,683, U.S. Pat. No. 10,147,863, U.S. Pat. No. 10,142,125, and U.S. Pat. No. 10,141,492. For example, energy harvesters can collect energy from various sources (e.g., solar power, thermal energy, wind energy, salinity gradients, kinetic energy, piezoelectric, pyroelectric, thermoelectric, and RF capture devices such as ore radios). There are very high - energy generators such as wind and solar, as well as very low - energy ones such as piezoelectric harvesters and RF harvesters. However, these energy harvesters do not store energy but take in energy from the surroundings. sources (e.g., solar power, thermal energy, wind energy, salinity gradients, kinetic energy, piezoelectric, pyroelectric, thermoelectric, and RF capture devices such as ore radios). There are also very high - energy generators such as wind and solar, as well as very low - energy ones such as piezoelectric harvesters and RF harvesters. However, these energy harvesters do not store energy but take in energy from the surroundings.

[0004] In recent years, efforts have been made to manufacture batteries that move charge using only electrons rather than ions. (Sigler, D., “All - Electron Ba ​​​​​​​​​"Battery - Stanford Strikes Again," CAFE Foundation (3 / 28 / 2015) (cafe.foundation / blog / electron - battery - stanford - strikes)) However, these devices store energy rather than incorporating it. Foundation (3 / 28 / 2015) (cafe.foundation / bl og / electron - battery - stanford - strikes)) However, these devices store energy rather than incorporating it. However, these devices store energy rather than incorporating it.

[0005] What is needed is an energy harvester device that uses a solid electrolyte to generate ambient energy from the surrounding environment for various applications. What is needed is an energy harvester device that uses a solid electrolyte to generate ambient energy from the surrounding environment for various applications. SUMMARY OF THE INVENTION

[0006] Aspects described herein provide a solid energy harvester, a solid energy harvesting system, and related methods using various oxides of transition metals that, in certain aspects, allow for non - integer valence states in the mass of their crystal structures. Aspects described herein do not use a liquid electrolyte and use electrons to move charge. Aspects described herein provide a solid energy harvester, a solid energy harvesting system, and related methods using various oxides of transition metals that, in certain aspects, allow for non - integer valence states in the mass of their crystal structures. Aspects described herein do not use a liquid electrolyte and use electrons to move charge. Aspects described herein provide a solid energy harvester, a solid energy harvesting system, and related methods using various oxides of transition metals that, in certain aspects, allow for non - integer valence states in the mass of their crystal structures. Aspects described herein do not use a liquid electrolyte and use electrons to move charge. Aspects described herein do not use a liquid electrolyte and use electrons to move charge.

[0007] Exemplary oxides used in the described aspects shift their polarity in response to gaseous oxygen and gaseous water vapor present in the environment. In one aspect, the power generated by the energy harvester is continuous as long as two components (e.g., gaseous oxygen and gaseous water vapor) are present. Without being bound to a particular theory, water vapor is thought to play an important role including self - ionization of its molecules into hydroxyl ions and protons. This can expand the exchange potential of cerium sub - oxide, enabling subsequent redox reactions. Exemplary oxides used in the described aspects shift their polarity in response to gaseous oxygen and gaseous water vapor present in the environment. In one aspect, the power generated by the energy harvester is continuous as long as two components (e.g., gaseous oxygen and gaseous water vapor) are present. Without being bound to a particular theory, water vapor is thought to play an important role including self - ionization of its molecules into hydroxyl ions and protons. This can expand the exchange potential of cerium sub - oxide, enabling subsequent redox reactions. Exemplary oxides used in the described aspects shift their polarity in response to gaseous oxygen and gaseous water vapor present in the environment. In one aspect, the power generated by the energy harvester is continuous as long as two components (e.g., gaseous oxygen and gaseous water vapor) are present. Without being bound to a particular theory, water vapor is thought to play an important role including self - ionization of its molecules into hydroxyl ions and protons. This can expand the exchange potential of cerium sub - oxide, enabling subsequent redox reactions. Exemplary oxides used in the described aspects shift their polarity in response to gaseous oxygen and gaseous water vapor present in the environment. In one aspect, the power generated by the energy harvester is continuous as long as two components (e.g., gaseous oxygen and gaseous water vapor) are present. Without being bound to a particular theory, water vapor is thought to play an important role including self - ionization of its molecules into hydroxyl ions and protons. This can expand the exchange potential of cerium sub - oxide, enabling subsequent redox reactions. Exemplary oxides used in the described aspects shift their polarity in response to gaseous oxygen and gaseous water vapor present in the environment. In one aspect, the power generated by the energy harvester is continuous as long as two components (e.g., gaseous oxygen and gaseous water vapor) are present. Without being bound to a particular theory, water vapor is thought to play an important role including self - ionization of its molecules into hydroxyl ions and protons. This can expand the exchange potential of cerium sub - oxide, enabling subsequent redox reactions. Exemplary oxides used in the described aspects shift their polarity in response to gaseous oxygen and gaseous water vapor present in the environment. In one aspect, the power generated by the energy harvester is continuous as long as two components (e.g., gaseous oxygen and gaseous water vapor) are present. Without being bound to a particular theory, water vapor is thought to play an important role including self - ionization of its molecules into hydroxyl ions and protons. This can expand the exchange potential of cerium sub - oxide, enabling subsequent redox reactions. This can expand the exchange potential of cerium sub - oxide, enabling subsequent redox reactions.

[0008] The embodiments described herein can also be used as a battery or a capacitor.

[0009] In certain embodiments, the transition metal oxides described herein can be "suboxides" of tungsten, titanium, and cobalt. Each average valence is less than the stable integer value of the oxide of that element, and thus is called a "suboxide". In this embodiment, the valence is the average value over the entire crystalline quantity. This imbalance provides each compound with a different electronegativity for each compound. The active cathode material Co3O4 has a lower electronegativity than the anode material Ti4O7 and is thus "electropositive" with respect to the anode. In one embodiment, the solid electrolyte (SSE) comprises CeO2, and tungsten suboxide WO moves the charge. 2.9

[0010] Without being bound by a particular theory, it is believed that oxygen enters the cathode, carrying its two negative charges ( electrons) and being incorporated into the crystal structure. The defects in Co3O4 create excess electrons, which slip onto the CeO2 crystal together with the loosely bound oxygen atoms and carry two electrons. These electrons move freely throughout the cell and are attracted to the low electronegativity of WO 2.9 and are facilitated by the CeO2 "electrolyte". The anode Ti4O7 collects the excess electrons and can release them into the external circuit to generate energy.

[0011] The embodiments described herein include a solid electrolyte (SSE) comprising a mixture of a first transition metal suboxide and a lanthanide oxide or lanthanum dioxide, a first layer comprising a second transition metal suboxide and the SSE, and a second layer comprising a third transition metal suboxide and the SSE. , where the first transition metal oxide and the second transition metal oxide are different from each other, providing a solid energy harvester.

[0012] In one aspect, a solid energy harvester is provided having a first layer comprising a first transition metal oxide, a second layer comprising a second transition metal oxide, and a third layer comprising a third transition metal oxide. In this aspect, the second layer is disposed between the first layer and the third layer, and the first transition metal oxide, the second transition metal oxide, and the third transition metal oxide are different from each other. In another aspect, the first layer functions as an anode and the second layer functions as a cathode having no intermediate layer of solid electrolyte. In a further aspect, each of all the layers further comprises cerium dioxide. In yet another aspect, all the layers of the first layer further comprise tungsten oxide. In a further aspect, each of all the layers further comprises a binder. The binder can be a polymer binder such as, for example, poly(vinyl alcohol) (PVA), carboxymethyl cellulose (CMC), or polytetrafluoroethylene (PTFE). In another aspect, the binder is unsintered PTFE. harvester. In this aspect, the second layer is disposed between the first layer and the third layer, and the first transition metal oxide, the second transition metal oxide, and the third transition metal oxide are different from each other. In another aspect, the first layer functions as an anode and the second layer functions as a cathode having no intermediate layer of solid electrolyte. In a further aspect, each of all the layers further comprises cerium dioxide. In yet another aspect, all the layers of the first layer further comprise tungsten oxide. In a further aspect, each of all the layers further comprises a binder. The binder can be a polymer binder such as, for example, poly(vinyl alcohol) (PVA), carboxymethyl cellulose (CMC), or polytetrafluoroethylene (PTFE). In another aspect, the binder is unsintered PTFE. In this aspect, the second layer is disposed between the first layer and the third layer, and the first transition metal oxide, the second transition metal oxide, and the third transition metal oxide are different from each other. In another aspect, the first layer functions as an anode and the second layer functions as a cathode having no intermediate layer of solid electrolyte. In a further aspect, each of all the layers further comprises cerium dioxide. In yet another aspect, all the layers of the first layer further comprise tungsten oxide. In a further aspect, each of all the layers further comprises a binder. The binder can be a polymer binder such as, for example, poly(vinyl alcohol) (PVA), carboxymethyl cellulose (CMC), or polytetrafluoroethylene (PTFE). In another aspect, the binder is unsintered PTFE. In another aspect, the first layer functions as an anode and the second layer functions as a cathode having no intermediate layer of solid electrolyte. In a further aspect, each of all the layers further comprises cerium dioxide. In yet another aspect, all the layers of the first layer further comprise tungsten oxide. In a further aspect, each of all the layers further comprises a binder. The binder can be a polymer binder such as, for example, poly(vinyl alcohol) (PVA), carboxymethyl cellulose (CMC), or polytetrafluoroethylene (PTFE). In another aspect, the binder is unsintered PTFE. In a further aspect, each of all the layers further comprises cerium dioxide. In yet another aspect, all the layers of the first layer further comprise tungsten oxide. In a further aspect, each of all the layers further comprises a binder. The binder can be a polymer binder such as, for example, poly(vinyl alcohol) (PVA), carboxymethyl cellulose (CMC), or polytetrafluoroethylene (PTFE). In another aspect, the binder is unsintered PTFE. In yet another aspect, all the layers of the first layer further comprise tungsten oxide. In a further aspect, each of all the layers further comprises a binder. The binder can be a polymer binder such as, for example, poly(vinyl alcohol) (PVA), carboxymethyl cellulose (CMC), or polytetrafluoroethylene (PTFE). In another aspect, the binder is unsintered PTFE. In a further aspect, each of all the layers further comprises a binder. The binder can be a polymer binder such as, for example, poly(vinyl alcohol) (PVA), carboxymethyl cellulose (CMC), or polytetrafluoroethylene (PTFE). In another aspect, the binder is unsintered PTFE. In a further aspect, each of all the layers further comprises a binder. The binder can be a polymer binder such as, for example, poly(vinyl alcohol) (PVA), carboxymethyl cellulose (CMC), or polytetrafluoroethylene (PTFE). In another aspect, the binder is unsintered PTFE. The binder can be a polymer binder such as, for example, poly(vinyl alcohol) (PVA), carboxymethyl cellulose (CMC), or polytetrafluoroethylene (PTFE). In another aspect, the binder is unsintered PTFE. In another aspect, the binder is unsintered PTFE.

[0013] In another aspect, the anode electrode and the cathode electrode also contain carbon. In this aspect, both carbon black and powdered graphite improve performance (such as power density). In another aspect, the SSE remains unchanged. In this aspect, the separated charges are present at both ends of the high-resistance SSE layer. In this aspect, both carbon black and powdered graphite improve performance (such as power density). In another aspect, the SSE remains unchanged. In this aspect, the separated charges are present at both ends of the high-resistance SSE layer. In another aspect, the SSE remains unchanged. In this aspect, the separated charges are present at both ends of the high-resistance SSE layer. In this aspect, the separated charges are present at both ends of the high-resistance SSE layer. BRIEF DESCRIPTION OF THE DRAWINGS

[0014]

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DETAILED DESCRIPTION OF THE INVENTION

[0015] The methods, compositions, and devices disclosed below can be described generally and specifically. It should be noted that if the description is specific to an aspect, that aspect should in no way limit the scope of the apparatus or method. The features and properties of this disclosure will become more apparent from the detailed description set forth below when interpreted in conjunction with the accompanying drawings.

[0016] ​​Aspects disclosed herein include a solid state electrolyte (SSE) comprising a mixture of a first transition metal oxide and a lanthanide oxide or lanthanum dioxide, a first layer comprising a second transition metal oxide and the SSE, and a second layer comprising a third transition metal oxide and the SSE, and provide a solid energy harvester. In this aspect, the first transition metal oxide and the second transition metal oxide are different from each other. A solid energy harvester is provided that includes a first layer comprising a first transition metal oxide and a solid state electrolyte (SSE), a second layer comprising a mixture of a second transition metal oxide and a lanthanide oxide or lanthanum dioxide, where the mixture forms the SSE, and a third layer comprising a third transition metal oxide and the SSE, where the first transition metal oxide and the third transition metal oxide are different from each other. The term "oxide" indicates that the average valence is less than the stable integral value of the element. This value is, for example, the average over the entire crystalline mass. This valence imbalance results in different electronegativities for each compound. For example, a cathode material (e.g., Co3O4) has a lower electronegativity than an anode material (e.g., Ti4O7) and is thus "electropositive" with respect to the anode. The term "transition metal" refers to an element whose atoms have a partially filled d subshell or can give rise to cations with an incomplete d subshell. (IUPAC, Compendium of Chemical Terminology, 2nd ed. ("Gold The aspects disclosed herein provide a solid energy harvester that includes a first layer comprising a first transition metal oxide and a solid state electrolyte (SSE), a second layer comprising a mixture of a second transition metal oxide and a lanthanide oxide or lanthanum dioxide, where the mixture forms the SSE, and a third layer comprising a third transition metal oxide and the SSE, where the first transition metal oxide and the third transition metal oxide are different from each other.

[0017] The aspects disclosed herein provide a solid energy harvester that includes a first layer comprising a first transition metal oxide and a solid state electrolyte (SSE), a second layer comprising a mixture of a second transition metal oxide and a lanthanide oxide or lanthanum dioxide, where the mixture forms the SSE, and a third layer comprising a third transition metal oxide and the SSE, where the first transition metal oxide and the third transition metal oxide are different from each other. The term "oxide" indicates that the average valence is less than the stable integral value of the element. This value is, for example, the average over the entire crystalline mass. This valence imbalance results in different electronegativities for each compound. For example, a cathode material (e.g., Co3O4) has a lower electronegativity than an anode material (e.g., Ti4O7) and is thus "electropositive" with respect to the anode. The term "transition metal" refers to an element whose atoms have a partially filled d subshell or can give rise to cations with an incomplete d subshell. (IUPAC, Compendium of Chemical Terminology, 2nd ed. ("Gold The aspects disclosed herein provide a solid energy harvester that includes a first layer comprising a first transition metal oxide and a solid state electrolyte (SSE), a second layer comprising a mixture of a second transition metal oxide and a lanthanide oxide or lanthanum dioxide, where the mixture forms the SSE, and a third layer comprising a third transition metal oxide and the SSE, where the first transition metal oxide and the third transition metal oxide are different from each other. The term "oxide" indicates that the average valence is less than the stable integral value of the element. This value is, for example, the average over the entire crystalline mass. This valence imbalance results in different electronegativities for each compound. For example, a cathode material (e.g., Co3O4) has a lower electronegativity than an anode material (e.g., Ti4O7) and is thus "electropositive" with respect to the anode.

[0018] The term "oxide" indicates that the average valence is less than the stable integral value of the element. This value is, for example, the average over the entire crystalline mass. This valence imbalance results in different electronegativities for each compound. For example, a cathode material (e.g., Co3O4) has a lower electronegativity than an anode material (e.g., Ti4O7) and is thus "electropositive" with respect to the anode. The term "transition metal" refers to an element whose atoms have a partially filled d subshell or can give rise to cations with an incomplete d subshell. (IUPAC, Compendium of Chemical Terminology, 2nd ed. ("Gold The aspects disclosed herein provide a solid energy harvester that includes a first layer comprising a first transition metal oxide and a solid state electrolyte (SSE), a second layer comprising a mixture of a second transition metal oxide and a lanthanide oxide or lanthanum dioxide, where the mixture forms the SSE, and a third layer comprising a third transition metal oxide and the SSE, where the first transition metal oxide and the third transition metal oxide are different from each other. The term "oxide" indicates that the average valence is less than the stable integral value of the element. This value is, for example, the average over the entire crystalline mass. This valence imbalance results in different electronegativities for each compound. For example, a cathode material (e.g., Co3O4) has a lower electronegativity than an anode material (e.g., Ti4O7) and is thus "electropositive" with respect to the anode. The term "transition metal" refers to an element whose atoms have a partially filled d subshell or can give rise to cations with an incomplete d subshell. (IUPAC, Compendium of Chemical Terminology, 2nd ed. ("Gold

[0019] The term "transition metal" refers to an element whose atoms have a partially filled d subshell or can give rise to cations with an incomplete d subshell. (IUPAC, Compendium of Chemical Terminology, 2nd ed. ("Gold The term "oxide" indicates that the average valence is less than the stable integral value of the element. This value is, for example, the average over the entire crystalline mass. This valence imbalance results in different electronegativities for each compound. For example, a cathode material (e.g., Co3O4) has a lower electronegativity than an anode material (e.g., Ti4O7) and is thus "electropositive" with respect to the anode. endium of Chemical Terminology, 2nd ed. ("Gold Book")(1997), (2006 -); Groups 3 to 12 of the periodic table). "Transition "Metal oxide" refers to an oxide of a transition metal. The term "oxide" refers to an oxide containing a smaller amount of oxygen compared to an oxide. For example, the average valence of the oxide is smaller than the stable integer value of the oxide of that element, and the value is averaged over the entire crystalline mass. In one aspect, the first transition metal oxide is tungsten suboxide, cobalt suboxide, Co 3O4, Na

[0020] 1.0 Mo 1.5 WO 6.0 , Na 0.9 Mo6O 17 , Na 1.0 Ti1 .5 WO 4.5 , Na 1.2 Ti 0.34 WO4, Ti4O7, Ti5O9, K 1.28 Ti8O 16 , K 1.04 Ti8O 16 , K 0.48 Ti8O 16 , Na4WO3, Na 0.90 WO 1.81 , Na 0.82 WO 1.81 , Na 0.74 WO 1.81 , K 0. 9WO3, WO 2.72 , WO 2.82 , WO 2.9 , Na2WO4, Na 8.2 WO, Na2O2WO3, Na 1.2 Ti 0.34 WO4, Na 1.2 Cu 0.31 WO 7.2 , Na 1.2 Mo 0.31 WO 5.2 , and selected from the group consisting of Na2O4WO3 .

[0021] In another aspect, the second transition metal oxide is tungsten suboxide, cobalt suboxide, C o3O4, Na 1.0 Mo 1.5 WO 6.0 , Na 0.9 Mo6O 17 , Na 1.0 Ti 1.5 WO 4.5 , Na 1.2 Ti 0.34 WO4, Ti4O7, Ti5O9, K 1.2 8Ti8O 16 , K 1.04 Ti8O 16 , K 0.48 Ti8O 16 , Na4WO3, N a 0.90 WO 1.81 , Na 0.82 WO 1.81 , Na 0.74 WO 1.81 , K0 .9 WO3, WO 2.72 , WO 2.82 , WO 2.9 , Na2WO4, Na 8.2 WO , Na2O2WO3, Na 1.2 Ti 0.34 WO4, Na 1.2 Cu 0.31 WO 7. 2, Na 1.2 Mo 0.31 WO 5.2 and selected from the group consisting of Na2O4WO3. .

[0022] In a further aspect, the third transition metal oxide is tungsten suboxide, cobalt suboxide , Co3O4, Na 1.0 Mo 1.5 WO 6.0 , Na 0.9 Mo6O 17 , Na 1.0 Ti 1.5 WO 4.5 , Na 1.2 Ti 0.34 WO4, Ti4O7, Ti5O9, K1 .28 Ti8O 16 , K 1.04 Ti8O 16 , K 0.48 Ti8O 16 , Na4WO3 , Na 0.90 WO 1.81 , Na 0.82 WO 1.81 , Na 0.74 WO 1.81 , K 0.9 WO3, WO 2.72 , WO 2.82 , WO 2.9 , Na2WO4, Na 8.2 WO, Na2O2WO3, Na 1.2 Ti 0.34 WO4, Na 1.2 Cu 0.31 WO 7.2 Na 1.2 Mo 0.31 WO 5.2 Selected from the group consisting of and Na2O4WO3 is.

[0023] In yet another aspect, the transition metal oxide (i.e., the first transition metal oxide, the second transition metal oxide, or the third transition metal oxide) is selected from the group consisting of boron, iron, copper, and nickel is.

[0024] In another aspect, the first transition metal oxide is an alkali metal oxide. The term "alkali metal" refers to the Group 1 metals from the IUPAC (International Union of Pure and Applied Chemistry) periodic table of the elements (e.g., lithium (Li), sodium (Na), potassium (K), rubidium (R bium), cesium (Cs)) b), cesium (Cs), and francium (Fr)). In one aspect, the alkali metal oxide is selected from the group consisting of rubidium and cesium.

[0025] In another aspect, the lanthanide oxide is cerium dioxide, lanthanum oxide or lanthanum dioxide, praseodymium oxide or praseodymium dioxide, neodymium oxide or neodymium dioxide, promethium oxide or promethium dioxide, samarium oxide or samarium dioxide, europium oxide or europium dioxide, gadolinium oxide or gadolinium dioxide, terbium oxide or terbium dioxide, dysprosium oxide or dysprosium dioxide, holmium oxide or holmium dioxide, erbium oxide or erbium dioxide, thulium oxide or thulium dioxide, ytterbium oxide or ytterbium dioxide, and lutetium oxide or lutetium dioxide.

[0026] In a further aspect, the first transition metal oxide is Ti4O7. In yet another aspect, the second transition metal oxide is WO 2.9 . In another aspect, the third transition metal oxide is Co3O4.

[0027] In a further aspect, the first and second layers substantially comprise noble metals. The term "noble metal" refers to metal elements that are resistant to corrosion and oxidation (e.g., ruthenium (Ru), rhodium (Rh), palladium (Pd), silver (Ag), osmium (Os), iridium (Ir), platinum (Pt), gold (Au), mercury (Hg), [2][3][4] rhenium (Re )[5] and copper (Cu)). In yet another aspect, the first and second layers are noble includes.

[0028] A solid harvester having a first layer, a second layer, and a third layer may each further comprise a binder ( Examples: un-sintered Teflon (PTFE), FEP, paraffin, and epoxy). The term "binder" refers to molecules that hold the active ingredient particles together (like insects in a spider web).

[0029] In a further aspect, the anode and cathode may also comprise carbon (e.g., carbon black such as Cabot Vulcan XC72R (also simply called "V72") or powdered graphite such as Alfa Aesar graphite mills "Nano 307" powder). In this aspect, the cathode and / or anode loading may carry about 0.5% to about 5% carbon. In another aspect, since the SSE separator layer does not contain carbon, charge separation is enhanced across its higher impedance compared to the anode and cathode.

[0030] A further aspect provides a solid energy harvester where the first layer is the anode and the third layer is the cathode. In this aspect, the second layer may be the SSE separator. In this aspect, the anode may contain between about 0.01% and about 14% water. The cathode may comprise between about 0.01% and about 4% water. In another aspect, the anode contains about 7% water and the cathode contains about 2% water. In yet another aspect, the SSE contains about 2% water.

[0031] The term "anode" refers to the electrode that releases electrons and becomes the negative terminal of the energy harvester. The term "cathode" refers to the electrode that consumes electrons and becomes the positive terminal of the energy harvester. Refers to an electrode. The term "charge" refers to the movement of electrons as electrons for ionizing, radicalizing, or energizing an energy harvester into a "charged" state.

[0032] In yet another aspect, the first transition metal oxide, the second transition metal oxide, and the third transition metal oxide each have a stoichiometric composition Mx-y, where M is a transition metal, x is the basic valence of transition metal M, y is a deviation from 1, when M is titanium, x is 4 and y is at least 0.5, when M is cobalt, x is 3 and y is at least 0.3, when M is tungsten, x is 5 and y is at least 0.2.

[0033] In another aspect, the first layer of the solid energy harvester is electrically connected to the first current collector, and the second layer is electrically connected to the second current collector. The term "current collector" refers to a conductive material that collects electrons from the reaction layer and passes them to another layer or an external circuit. The first and second current collectors may comprise a metal selected from the group consisting of gold, nickel, copper, brass, bronze, and carbon.

[0034] The first current collector and the second current collector may comprise a porous material. In another aspect, the porous material comprises pores in excess of about 50%. The pores may have a diameter of from about 10 μm to about 40 μm.

[0035] In yet another aspect, the first current collector and the second current collector each comprise a foam metal. The foam metal may be a porous material (e.g., a material having pores in excess of 50%), and the pores may have a diameter of from about 10 μm to about 40 μm.

[0036] The first current collector and the second current collector may each include a perforated metal. The term "perforated metal" refers to a conductive layer that makes the layer porous but still provides high conductivity to electrons, containing many small pores. When the active material is compressed within the pores, electrons or ions can also freely pass through the layer similarly.

[0037] In a further aspect, the first current collector and the second current collector may each include a porous conductive material (e.g., carbon). The carbon porous material may have pores exceeding about 50%, and the pores may have a diameter of about 10 μm to about 40 μm.

[0038] A further aspect provides a solid energy harvester system having a first energy harvester and a second energy harvester as described herein. In this aspect, the first layer of the first energy harvester is electrically connected to the third layer of the second energy harvester. In this aspect, each of the first layers of the first and second energy harvesters may include titanium oxide, each of the third layers of the first and second energy harvesters may include cobalt oxide, and the second layer may include cerium dioxide and tungsten oxide. aspect, the first layer of the first energy harvester is electrically connected to the third layer of the second energy harvester. In this aspect, each of the first layers of the first and second energy harvesters may include titanium oxide, each of the third layers of the first and second energy harvesters may include cobalt oxide, and the second layer may include cerium dioxide and tungsten oxide. aspect, the first layer of the first and second energy harvesters may each include titanium oxide, the third layer of the first and second energy harvesters may each include cobalt oxide, and the second layer may include cerium dioxide and tungsten oxide. aspect, the first layer of the first and second energy harvesters may each include titanium oxide, the third layer of the first and second energy harvesters may each include cobalt oxide, and the second layer may include cerium dioxide and tungsten oxide. aspect, the first layer of the first and second energy harvesters may each include titanium oxide, the third layer of the first and second energy harvesters may each include cobalt oxide, and the second layer may include cerium dioxide and tungsten oxide. aspect, the first layer of the first and second energy harvesters may each include titanium oxide, the third layer of the first and second energy harvesters may each include cobalt oxide, and the second layer may include cerium dioxide and tungsten oxide.

[0039] In another aspect, the first layer of the first energy harvester and the third layer of the second energy harvester may each be operably attached to a current collector. In another aspect, the first layer of the first energy harvester and the third layer of the second energy harvester may each be operably attached to a current collector.

[0040] A further aspect is a first layer comprising a first transition metal oxide, tungsten oxide, and cerium dioxide, a second layer comprising cerium dioxide and tungsten oxide, and a third layer comprising cobalt oxide. A third layer comprising a second transition metal oxide, tungsten oxide, and cerium oxide is provided for a solid energy harvester. In this aspect, the first transition metal oxide is different from the second transition metal oxide, and the metal oxides are bonded together using a binder wherein the first layer further comprises titanium oxide, the second layer further comprises cobalt oxide, and the energy harvester generates an electric current in the presence of oxygen and water vapor.

[0041] A further aspect provides a solid energy harvester in which carbon is added to the first and third layers to increase conductivity while leaving the second layer unchanged, thus enabling charge separation across its separator layer of relatively low conductivity.

[0042] In another aspect, a first layer is formed by grinding a first mixture comprising a first transition metal oxide, a lanthanide, a solid electrolyte, and a binder, a second layer is formed by grinding a second mixture comprising a lanthanide and a solid electrolyte with a binder, a third layer is formed by grinding a third mixture comprising a second transition metal oxide, a solid electrolyte, and a binder, and the first layer is connected to the second layer and the second layer is connected to the third layer, to provide a method of manufacturing a solid energy harvester. In this aspect, the first layer is an anode, the second layer is an SSE separator, the third layer is a cathode, and the first transition metal oxide is different from the second transition metal oxide.

[0043] The first transition metal oxide and the second transition metal oxide are tungsten oxide, cobalt oxide, Co3O4, Na respectively​1.0 Mo 1.5 WO 6.0 , Na 0.9 Mo6 O 17 , Na 1.0 Ti 1.5 WO 4.5 , Na 1.2 Ti 0.34 WO4, Ti4O7 , Ti5O9, K 1.28 Ti8O 16 , K 1.04 Ti8O 16 , K 0.48 Ti8O 16 , Na4WO3, Na 0.90 WO 1.81 , Na 0.82 WO 1.81 , Na 0. 74 WO 1.81 , K 0.9 WO3, WO 2.72 , WO 2.82 , WO 2.9 , Na2 WO4, Na 8.2 WO, Na2O2WO3, Na 1.2 Ti 0.34 WO4, Na 1. 2Cu 0.31 WO 7.2 , Na 1.2 Mo 0.31 WO 5.2 , and Na2O4WO It may be independently selected from the group consisting of 3.

[0044] The first mixture, the second mixture, and the third mixture can be ground with a high-shear, high-intensity blender. In another aspect, the first layer, the second layer, and the third layer are not separated by a physical separator.

[0045] In a further aspect, the first transition metal oxide and the second transition metal oxide are each , selected from the group consisting of titanium, cobalt, tungsten, or cesium. The first transition metal oxide may comprise titanium suboxide.

[0046] In yet another aspect, water may be added to the first mixture, the second mixture, and the third mixture before grinding. In a further aspect, the first mixture has about 10% or less water, and the second and third mixtures have 5% or less water. In one aspect, the first mixture and the second mixture each have a water content of less than about 10 weight percent or less than about 25 weight percent. In yet another aspect, each of the first layer, the second layer, and the third layer has a water content of less than about 5 weight percent.

[0047] In another aspect, the second transition metal oxide comprises cobalt suboxide. In a further aspect, each of the first layer, the second layer, and the third layer comprises a solid electrolyte comprising tungsten suboxide and cerium dioxide.

[0048] In yet another aspect, each of the first binder, the second binder, and the third binder is , selected from the group consisting of un-sintered polytetrafluoroethylene (PTFE), FEP, paraffin, and epoxy .

[0049] In a further aspect, each of the first binder, the third binder, and the third binder is less than about 50 volume percent of each of the first layer, the second layer, and the third layer.

[0050] In another aspect, a method of manufacturing a solid energy harvester is the first mixture, the second mixture and the third mixture, or the first mixture and the second mixture and the third mixture of Further include compressing the combination with a roller mill to generate back extrusion. Including.

[0051] In a further aspect, the anode comprises a mixture of about 17% (w / w) CeO2, 33% (w / w) WO 2.9 , 50% (w / w) Ti4O7, and 40 volume percent powdered PTFE .

[0052] In one aspect, the cathode comprises a mixture of about 17% (w / w) CeO2, 33% (w / w) WO2 .9 , 50% (w / w) Co3O4, and 40 volume percent powdered PTFE .

[0053] In yet another aspect, the anode comprises a mixture of about 17% (w / w) CeO2, 33% (w / w) of WO 2.9 , 50% (w / w) Ti4O7, and 40 volume percent powdered PTF E, the solid electrolyte (SSE) comprises a mixture of about 67% (w / w) WO 2.9 , 33% (w / w) CeO2, and 40 volume percent powdered PTFE, and the cathode comprises a mixture of about 17% (w / w) CeO2, 33% (w / w) WO 2.9 , 50% (w / w) Co3O4, and 40 volume percent powdered PTFE.

[0054] In another aspect, each of the first layer, the second layer, and the third layer contains Teflon particles, each of the first binder and the second binder comprises powder, and each of the first layer and the second layer is produced by using a roller mill to force the powder through the rollers of the mill and extrude the Teflon particles into fibrils.

[0055] In one aspect, the solid-state energy harvester comprises a non-conductive, essentially gas impermeable housing. The non-conductive, substantially gas impermeable housing includes a gas inlet and and a gas outlet on an opposite side of the housing. The coating is selected from the group consisting of sodium polyacrylate and polycarbonate. The term non-conductive refers to a material that does not conduct electrons. The term "impermeable" refers to the ability of the cell to allow the passage of most gases in any environment while it is functioning. This refers to materials that are not gas-permeable (gas leakage is less than 1%).

[0056] A further embodiment is an anode comprising a first transition metal suboxide and a second transition metal suboxide. A solid electrolyte (SSE) having a mixture of lanthanide and lanthanide oxide or lanthanide dioxide is and a cathode including a third transition metal suboxide. -Provide a harvester.

[0057] In another embodiment, a first transition metal suboxide, a second transition metal suboxide, and a third transition metal suboxide are The genus suboxides are distinct from each other.

[0058] In one embodiment, the anode and cathode are made of carbon (e.g., black carbon or graphite). The amount of carbon in the anode may be from about 2% to about 6%. In an embodiment, the amount of carbon in the anode is 3%.

[0059] In a further embodiment, the separator further comprises Ti4O7.

[0060] In yet another aspect, the solid-state energy harvester includes an energy storage unit (e.g., Can be used as a battery, capacitor, or at least a second energy storage unit Can be connected to a knit or an array of energy storage units.

[0061] A further aspect provides a first layer comprising a first transition metal suboxide and a solid state electrolyte (SSE), a second layer comprising a second transition metal suboxide, and a SSE, wherein the first layer and the second layer are different from each other, and provide a two-layer solid energy harvester. wherein the first transition metal suboxide and the second transition metal suboxide are different from each other, and provide a two-layer solid energy harvester. wherein the first transition metal suboxide and the second transition metal suboxide are different from each other, and provide a two-layer solid energy harvester. Provide.

[0062] In another aspect, the first layer of the solid energy harvester is separated from the second layer by a layer of a conductive metal (e.g., gold). The term "conductive metal" refers to a metal that allows current to flow with low resistance in one or multiple directions. The conductive metal can be an expander metal (e.g., nickel, gold, titanium, brass, copper, etc.). In another aspect, the first layer of the solid energy harvester is separated from the second layer by a layer of a conductive metal (e.g., gold). The term "conductive metal" refers to a metal that allows current to flow with low resistance in one or multiple directions. The conductive metal can be an expander metal (e.g., nickel, gold, titanium, brass, copper, etc.). In another aspect, the first layer of the solid energy harvester is separated from the second layer by a layer of a conductive metal (e.g., gold). The term "conductive metal" refers to a metal that allows current to flow with low resistance in one or multiple directions. The conductive metal can be an expander metal (e.g., nickel, gold, titanium, brass, copper, etc.). In another aspect, the first layer of the solid energy harvester is separated from the second layer by a layer of a conductive metal (e.g., gold). The term "conductive metal" refers to a metal that allows current to flow with low resistance in one or multiple directions. The conductive metal can be an expander metal (e.g., nickel, gold, titanium, brass, copper, etc.).

[0063] Yet another aspect provides a method of manufacturing a two-layer solid energy harvester by pulverizing a first mixture comprising a first transition metal suboxide, a lanthanide, a solid electrolyte comprising the first transition metal suboxide, and a binder to form a first layer, pulverizing a second mixture comprising a second transition metal suboxide, a solid electrolyte, and a binder to form a third layer, and connecting the first layer to the second layer, wherein the first layer is an anode, the second layer is a cathode, and the first transition metal suboxide and the second transition metal suboxide are different from each other. wherein the first layer is an anode, the second layer is a cathode, and the first transition metal suboxide and the second transition metal suboxide are different from each other. wherein the first layer is an anode, the second layer is a cathode, and the first transition metal suboxide and the second transition metal suboxide are different from each other. wherein the first layer is an anode, the second layer is a cathode, and the first transition metal suboxide and the second transition metal suboxide are different from each other. wherein the first layer is an anode, the second layer is a cathode, and the first transition metal suboxide and the second transition metal suboxide are different from each other.

[0064] (Transition metal oxides and defect theory) The general theory described herein applies to exemplary active components within an energy harvester, such as Ti4O7, WO 2.9 , Co3O4 and CeO2. Elements of non-stoichiometric metal oxyanides called Magnéli phases exhibit a low bandgap and resistivity and the highest conductivity. These phases have high oxygen vacancies, and electron connectivity increases with increasing oxygen vacancies . Electrons from the d orbitals are split into two different energy parts called the t2g and eg orbitals. The electron conduction pathway can be switched back and forth by the drift of charged oxygen vacancies . The conductivity of the conduction band can arise from either of these oxygen vacancies and / or metal-induced defects. The low stoichiometric composition is suggested to arise from either oxygen vacancies or interstitial metals, as represented by the following two redox reactions in Kroger-Vink notation respectively . [Number] and [Number]

[0065] For example, Zhang et al. “The rol e of single oxygen or metal induced defe ct and correlated multiple defects in th e formation of conducting filaments”, De partment of Precision Instrument, Centre ​​​for Brain Inspired Computing Research, Please refer to Tsinghua University, Beijing, China, which is hereby incorporated by reference in its entirety.

[0066] These equations can be used to individually describe charge transfer reactions, for example, as follows: as follows: O x o +h→O0

[0067] Here, O x o represents an oxygen ion located at an oxygen lattice site with a neutral charge, h represents a hole, and O0 represents a singlet oxygen atom with a single charge. Also, Ce x ce +e - →Ce ’ ce’

[0068] Here, Ce x ce represents a cerium ion at a cerium lattice site with a neutral charge, Ce ’ ce’ represents an interstitial cerium anion with a single negative charge.

[0069] This is an exemplary explanation of how a cerium ion at a cerium lattice site with a neutral charge can receive an electron and become a charged cerium ion at that lattice site, and how the charge can move in the solid electrolyte described herein. This is an exemplary illustration of how a cerium ion at a cerium lattice site with a neutral charge can receive an electron

[0070] For example, "Solid state aspects of oxidation catalysis" by Gellings et al., which is hereby incorporated by reference in its entirety, describes similar processes. l., Laboratory for Inorganic Materials S cience, University of Twente, PO Box 217 , NL-7500 AE Enschede, The Netherlands, (2000), please also refer to.

[0071] In the case of proton defects in oxides, an example of the purification reaction between water molecules and oxygen vacancies is as follows There is.

Number

[0072] In this reaction, two substantially positive hydroxy groups are formed at the normal oxygen positions. The formation of proton defects by reaction with hydrogen is shown below. The reaction with holes is as follows. The additional defect reaction in which proton defects are formed by reaction with hydrogen is shown below. The reaction with holes is as follows. There is.

Number

Number

[0073] Also, as shown in the following equation, Gellings et al. have proposed that at low temperatures, the dissolution of water in the Li / MgO catalyst occurs by reaction with oxygen or oxygen vacancies. There is.

Number

[0074] The conductivity at low temperature (e.g., 673 K) is induced by OH O ions as the main charge carriers. This indicates the importance of water in the charge transport in both the Ti4O7 anode and the CeO2 solid "electrolyte".

[0075] As shown in the following equations, CeO2 can store and transport oxygen and is theorized to decompose water to release hydrogen in its reduced state (the entire analysis model of the oxidation and reduction of CeO2 by B . Bulfin, et al., School of Physics,Trin . Bulfin, et al., School of Physics, Trinity College Dublin, College Green, Dublin 2, Ireland, J. Phys. Chem. C,2013,117(4 6), pp 24129-24137, DOI:10.1021 / jp406578 z, Publication Date (Web): October 16, 2 013, is referred to for the analysis model of the oxidation and reduction of CeO2). CeO2→CeO 2-δ +δ / 2O2 and CeO 2-δ +δH2O→CeO2+δH2

[0076] Bulfin et al. explain the relationship between cerium dioxide and its sub-oxide state and the resulting activities of these molecules, mainly related to the production of synthetic fuels and catalytic converters. The relationship described by Bulfin et al. uses the Arrhenius equation, which is almost It shows that the rate constant of almost all chemical reactions increases by the negative power of the reciprocal of the absolute temperature. According to Bulfin et al., the effect has been shown at temperatures above 500 °C. However, many of the graphs by Bulf in et al. show that some activities occur at ambient temperature.

[0077] In one aspect, the energy harvester described herein is WO 2.9 , CeO2, Co 3O4, Ti4O7 and un-sintered PTFE powder, and has five components. Table 1 below shows the composition of an exemplary aspect, and except for the PTFE binder shown in volume percent, the ratios are in weight percent. Components 1 and 2 in Table 1 are the components of the solid-state electrolyte (SSE), component 3 is the active component of the anode, and component 4 is the active component of the cathode. P TFE is a binder. The three electrodes shown in Table 1 include a titanium-containing anode, a separator, and a cobalt-containing cathode. The moisture value was measured and the ratios were determined from the results of several factor experiments shown in Table 1 below. The "separator" layer can be omitted from the design, resulting in a two-electrode design which can be achieved.

Table 1

[0078] In one aspect, cerium dioxide (CeO2) and tungsten suboxide are used as the solid-state electrolyte . In this aspect, tungsten suboxide is WO 2.9 . In this aspect , the components are present in a ratio of 2 parts of WO 2.9 to 1 part of CeO2.

[0079] Cerium dioxide is a large molecule (MW = 172) having oxygen atoms in the outer part of the crystal structure .12). Since the oxygen atoms are loosely attached, they can easily move from one molecule to the next. Figure 1 shows cerium atoms 101 and oxygen atoms 102. Without being bound by a particular theory, the difference in atomic size between cerium atoms 101 and oxygen atoms 102 is considered to enable the oxygen atoms to move relatively freely and catalyze redox reactions. Figure 1 shows how an exemplary oxygen atom is loosely bound to a large lanthanide cerium.

[0080] In another aspect, the energy harvester contains a low percentage of water. Neutral water has a molar concentration of H and OH ions of 1x10 used in the above equation, as shown below. -7 + - ions and is shown as follows. H2O → H + + OH - 2H2O → 2H2 + O2

[0081] As described in Zhang's literature, CeO2 can catalyze the reaction. Without wishing to be bound by a particular theory, the following two mechanisms may be involved.

[0082] (Mechanism 1) The use of CeO2 as a catalyst with mobile oxygen atoms is described in the article "Structural, redox and catalytic chemistry of ceria based materials", by G. Ranga Rao et al., Bulletin of Catalysis, which is incorporated herein by reference in its entirety. x and catalytic chemistry of ceria based materials”, by G. Ranga Rao et al., Bul Bulletin of the Catalysis Society of India (2003) 122-134. CeO2 as a catalyst exerts a catalytic effect on the conversion of methane gas to CO2 and water among other pollutant scrubbing catalysts and is used for this purpose.

[0083] The following equations (where 201 = Ce4+, 202 = O2-, 203 = vacancy, 204 = Ce3 + as shown in Figure 2) represent the steps of the process. Here, V = vacancy. H2 + Ce +4 4O -2 4 <- Step 1 -> Equation 3 Ce +4 4O -2 4H2 <- Step 2 -> Equation 4 Ce +4 2Ce +3 2O -2 3H + V + OH - <- Step 3 -> Equation 5 Ce +4 2Ce +3 2O -2 3V + H2O <- Step 4 -> Equation 6 Ce +4 2Ce +3 2O -2 3V Equation 7 Overall reaction equation H2 + Ce +4 4O -2 4 → Ce +4 2Ce +3 2O -2 3V Equation 8

[0084] (Mechanism 2) Cerium dioxide (CeO2) is well known for its oxygen mobility. CeO2 undergoes a rapid redox cycle as follows, for example. 2CeO2 → Ce2O3 + 1 / 2O2 Equation 9 Ce +4 → Ce +3 Eo = 1.61 ​​Cerium dioxide stores / releases O2 by the redox couple Ce +4 / Ce +3 and thus functions as an oxygen buffer. This is a reversible reaction and serves as an oxygen storage material. The reaction moves in the opposite direction under anoxic conditions (e.g., under argon). This promotes other electrode reactions with Ti4O7 and Co3O4 as will be described below. Although not wishing to be bound by a particular theory, the actual mechanism may be some combination of the two pathways described above, combined with the "defect theory" above.

[0085] (Interaction between dissolved oxygen and water) In another aspect, the energy harvester preferably contains a small amount of water within the electrode, which

[0086] triggers a response to the presence of oxygen or, conversely, to the removal of oxygen by flooding with argon (0% oxygen). Oxygen does not ionize when dissolved in water but is held between water molecules as shown in FIG. 3. Here, rectangle 301 highlights the water molecules (oxygen is 102, hydrogen is 302), and it does not represent an element itself. Oxygen molecules 303 become closely related to the retention of dioxygen molecules and thus to the transport of those molecules hither and thither. In conventional energy harvesters this could be regarded as an "electrolyte", but in current energy harvesters, since the electrodes can be separated by nickel expanded metal charge transport occurs within the electrodes rather than between them. Combining this understanding of the paragraphs dealing with defects in the crystal structure of the suboxide, one aspect of charge transport is the free flow of charge by a relatively small amount of water. (oxygen is 102, hydrogen is 302), and it does not represent an element itself. Oxygen molecules 303 become closely related to the retention of dioxygen molecules and thus to the transport of those molecules hither and thither. In conventional energy harvesters this could be regarded as an "electrolyte", but in current energy harvesters, since the electrodes can be separated by nickel expanded metal charge transport occurs within the electrodes rather than between them. Combining this understanding of the paragraphs dealing with defects in the crystal structure of the suboxide, one aspect of charge transport is the free flow of charge by a relatively small amount of water. In conventional energy harvesters this could be regarded as an "electrolyte", but in current energy harvesters, since the electrodes can be separated by nickel expanded metal charge transport occurs within the electrodes rather than between them. Combining this understanding of the paragraphs dealing with defects in the crystal structure of the suboxide, one aspect of charge transport is the free flow of charge by a relatively small amount of water.

[0087] ​​​In certain embodiments, the anode may contain from 0.01% to 15% water. In other embodiments, the anode may contain from 0.1% to 10%, from 1% to 8%, or from 2% to 5% water. In certain embodiments, the second layer may contain water between 0.01% and 8%. In other embodiments, the second layer may contain from 0.1% to 5%, from 1% to 4%, or from 2% to 3% water. In certain embodiments the cathode may contain water between 0.01% and 5%. In other embodiments, the cathode may contain from 0.1% to 10%, from 1% to 8%, or from 2% to 5% water.

[0088] In one embodiment, the WO 2.9 and CeO2 separator is positioned between the anode and the cathode and likely enables charge transfer on oxygen atoms. This intermediate layer contains, in one example, cerium dioxide mixed with tungsten suboxide (WO ), in a uniform weight. Tungsten can have many oxidation states, but +6 and +4 are the most stable. WO 9 gives tungsten a valence of +5.8, which is the average across the entire crystal. WO 2.9 is available from global-tungsten.com . Tungsten can have many oxidation states, but +6 and +4 are the most stable. WO 2. 9 gives tungsten a valence of +5.8, which is the average across the entire crystal. WO 2.9 is available from global-tungsten.com .

[0089] Figure 4 shows the crystal structure of WO 2.9 and the effect of dehydration on charge transport. The octahedra shown at 401 are tungsten orbital fields, the large black dots 301 represent water molecules, the small black dots 102 represent singlet oxygen in the crystal, and the small light dots 302 represent hydrogen atoms. While not wishing to be bound by any particular theory, the water molecules shown in Figure 4 are thought to enable more movement of the WO 3 crystal components. WO 3 x(WO 3-x also exists in the case shown (), but part of the charge carrying oxygen is missing from the crystal clusters. Figure 4 shows the effect on the crystal structure when the crystal is dehydrated from "a" having sufficient water molecules 301 to "b" mildly dehydrated, and finally to "c" completely dehydrated. In one aspect, the energy harvester is made in the dehydrated "c" state and can then spontaneously hydrate from "b" to "a" in situ. even when shown as The following reaction scheme is illustrative. Reduction ("V" = "vacancy") 2(W -O-W

[0090] 2(W +6 -O-W +6 ) + 4e - + O2 → Equation 10 2(W +5 -V-W +5 )2(O) + 4e - → Equation 11 2(W +5 -O-W +5 ) + 4e - Equation 12 Total: 2(W +6 -O-W +6 ) + O2 → 2(W +5 -O-W +5 ) + 2e - Oxidation 2(W +5 -O-W +5 ) + O2 → Equation 13 2(W +6 -O-W +6 ) + (O) + 2e - → Equation 14 2W +5 + O2 → Equation 15 (W +6 -O-W +6 ) + (O) + 2e - Equation 16 W +6 → W +4 (W +6 → W +5 (unknown)) Eo ~ ± 0.91 volts E o Source: http: / / hyperphysics.phy-astr.gsu.e du / hbase / Chemical / electrode.html Total: 2 (W +5 -O-W +5 ) + O2 → 2 (W +6 -O-W +6 ) + 2 (O) + 2e - Equation 17 Total of the separation reaction 2 (W +6 -O-W +6 ) + O2 < -H2O-> 2 (W +5 -O-W +5 ) + 2e - Equation 18 And 2 (W +5 -O-W +5 ) + O2 < -H2O-> 2 (W +6 -O-W +6 ) + 2 (O) + 2e - Equation 19 And 2Ce2O3 + 2O -2 < -H2O-> 4CeO2 + 4e - Equation 20

[0091] In one aspect, oxygen enters the separator and both singlet oxygen and electrons are discharged and move to the anode In this aspect, singlet oxygen reacts with cerium oxide to move more electrons Water can play a catalytic role in these events

[0092] In one aspect, the active component of the cathode is cobalt (II, III) suboxide (Co3O4 ) is. Figure 5 shows Co +2 as sphere #2 (501), Co +3 as sphere #3 (502) and shows the crystal structure of Co3O4 where oxygen atoms are bright-colored spheres #1 (202) ​ Cobalt has two oxidation states, +2 and +3, both of which are present in this crystal. The oxygen atoms are loosely bound to the large cobalt atoms and are more electronegative than those in the Ti4O7 anode. The mixing of CeO2 and Co3O4 enables the dispersion of oxygen atoms that carry charges, and the valence of cobalt decreases from +2 and +3 in Co3O4 to +2 in CoO, and oxygen atoms are released into the oxygen pool related to CeO2. Due to the above reaction, as shown in the following route equation, depending on the direction of the oxygen concentration, the reversible oxidation-reduction of CeO2-Co3O4 microcrystals releases or absorbs oxygen. O2 + 4e

[0093] → 2O Equation 19 2Co3O4 → 6CoO + O2 Equation 20 - → 2O -2 Equation 19 2Co3O4 → 6CoO + O2 Equation 20 The sum of these two equations (cations are reduced at the cathode via Co +2.67 ←→ Co +2 ): 2Co3O4 + 4e → 6CoO + O - → 6CoO + O -2 Equation 21 The above Equation 9: 2CeO2 → Ce2O3 + 1 / 2O2 Equation 9 The sum of Equation 21 and Equation 9: Co3O4 + 4e - + 2CeO2 → 3CoO + O -2 + Ce2O3 + 1 / 2O2 Equation 22 Focusing only on the cations: Co +2.67 + Ce +4 → Co +2 + Ce +3 + 1.76e - E o ~1.715

[0094] The above description shows that in the embodiments described in this specification, oxygen atoms receive charges from one cation This is an example of a free-flowing method for conveying one thing to another.

[0095] In one embodiment, the active component of the anode is Ti4O7 (Ti n O 2n-1 Also represented as ) where n is 4 to 10. Ti n O 2n-1 The non-magneli phase It is one of the stoichiometric titanium oxides, and has a low band gap and low resistivity. The highest electrical conductivity has been reported for O7. The atomic structure of this molecule is shown in Figure 6, where In each Ti4O7 molecule, titanium atoms are arranged in the order of 601-604, i.e., "Ti1" to "Ti4 " and oxygen is shown as "O" atom 102. In the case of Ti4O7, titanium The valence state is +3.5, which means that the crystal As electrons flow through the separator, the Ti4O7 molecules transport them to the magnetrons. It is passed through the anode conduction band in the Neri phase and then through the anode current collector electrode.

[0096] The equation can be summarized as follows: H2O→H + +OH - formula 23 4Ti2O3+2OH - +2O -2 →2Ti4O7+H2O+2e - formula 24 Equation 9 above (expressed in anodic form): Ce2O3+1 / 2O2→2CeO2 formula 9 The sum of Equation 12 and Equation 9: 4Ti2O3+2OH - +O -2 +2Ce2O3+O2→2Ti4O7+H2O+4Ce O2+2e - formula 24 Looking at only the cations: Ti +3 +Ce+4 →Ti +3.5 +Ce +3 E o ~1.085 Complete flow of the energy harvester: Cathode: Co3O4 + 2e - + 4CeO2 → 3CoO + 2Ce2O3 + O2 + 1 / 2O 2 Anode: 4Ti2O3 + 2OH - + O -2 + 2Ce2O3 + O2 → 2Ti4O7 + H 2O + 4CeO2 + 2e - Overall reaction equation: Co3O4 + 4CeO2 + 4Ti2O3 + 2OH - + 2H + + 1 / 2O2 + 2 Ce2O3 → 3CoO + 2Ce2O3 + 2Ti4O7 + 2H2O + 4CeO2 In this way, oxygen and water (dissociating) enter the cathode, and the final acceptor of oxygen is water vapor that generates hydroxy ions.

[0097] Table 2 below shows the relevant potentials, which are similar to the potentials observed in the OCV experiment as shown in Figure 10.

Table 2

[0098] (Supplier of the materials used) Ti4O7, Ti-Dynamics, Magnéli phase titanium suboxide - N82, www. Ti-dynamics.com.

[0099] WO 2.9 , “Blue tungsten oxide” http: / / globaltungste n.com #P005016

[0100] Co3O4 Cobalt(II,III) oxide, www.fishersci.c ​​om # AAA1612130

[0101] CeO2 Cerium(IV) oxide, www.fishersci.com #AC 199125000,

[0102] Teflon 30 dispersion "DISP30" www.fishersci.com #501 090482 or www.chemours.com.

[0103] PTFE 7CX: www.chemours.com

[0104] Daikin F104 un sintered Teflon powder

[0105] Cabot Vulcan XC72R (GP-3875) Carbon V72

[0106] Asbury Graphite Mills "Nano 307"

[0107] Crossbond Expanded Metal 4Ni 5-060 P&L x 4: Dexmet Dexmet Corporation, Wallingford, Connecticut, Burns Industrial Rd S22 、06492 (www.dexmet.com)

[0108] Nickel 10 mil shims stock, (www.mcmaster.com) #9707 K79

[0109] 3 / 4 inch silver bezel: (www.riogrande.com) #950272

[0110] 24kt gold cyanide plating solution: (www.riogrande.com)#335 082

[0111] 24kt Gold Plate for Anode: (www.riogrande.com) #608030

[0112] Rolling Mill Manufactured by Durston (www.durston.co.uk, #DRM F13 0R)

Example

[0113] (Example 1: Pellet Electrode) The pellet electrode is made as follows.

[0114] When the weight of the powder is measured, the anode is 17% CeO2, 33% WO x , 50% T i4O7, the solid separator is 33.3% CeO2 and 66.7% WO x , and the cathode is 17% CeO2, 33% WO x , 50% Co3O4, and the binder is 4 0 volume% of Teflon 7c.

[0115] Mix the powder in a high-strength blender. Prepare a 3 / 4-inch compression cylinder and lubricate the cylinder with a small amount of Polymist F-5AEx with Ocean Mont sintered Teflon powder. Place a 3 / 4-inch cross-bond expanded metal disk ( Dexmet, 4Ni 5-00 P&Lx4) at the bottom of the compression cylinder. Pour the mixed powder into the cylinder. Add another 3 / 4-inch cross-bond expanded metal disk on top of the powder. Place a stainless steel cover plate on top of the cylinder. Compress to 5000 pounds ( 11,318 psi) and hold for several seconds. Remove from the cylinder and measure and record the weight and thickness.

[0116] Since the density of all components is known, use the weight and volume to obtain the resulting pellet Calculate the porosity of the pellets. Select the pressure that provides good binding and good porosity of the powder . In this example, it was found that 5000 pounds is a typical pressure.

[0117] Next, place the pellets in a humidity chamber with 100% relative humidity for 4 days to bring the internal moisture content to approximately 5% for the anode, approximately 3.5% for the separator, and approximately 0.6% for the cathode.

[0118] Figure 7A shows the physical arrangement of an energy harvester with three electrodes, having an anode 7A4 housed between the layers within a gold bezel held by an anode pellet 7A1, a separator pellet 7A2, a cathode pellet 7A3, a nickel cross-bond expanded metal 7A6, and an epoxy adhesive 7A5. Each pellet also has nickel expanded metal 7A6 on each surface.

[0119] The separator pellet 7A2 is often omitted from the design, resulting in a two-electrode design.

[0120] (Example 2: Rolled Electrodes) Embodiments of the rolled electrodes are created as follows.

[0121] When measuring the weight of the powder, the anode is 17% CeO2, 33% WO x , 50% T i4O7, the solid separator is 33.3% CeO2 and 66.7% WO x , and the cathode is 17% CeO2, 33% WO , 50% Co3O4, and the binder x is 40% by volume of Teflon 7c. Mix in a high-strength blender.

[0122] Adjust the gap of the precision rolling mill with a diameter of 60 mm made by Durston (www.durston.co.uk, #DRM F130R) to 0.178 mm (0.007 inches). The rollers must be highly parallel. With the rollers horizontal, pour powder into the roller nip. Slowly rotate the rollers towards the nip to draw the powder into the nip and create a self - standing sheet under the rollers. Remove the sheet and place it on a clean piece of paper. Use an arch punch, for example, a punch with a diameter of 3 / 4 inch (19 mm) from McMaster - Carr #3427A19 to cut disks from each sheet. In one aspect, the cathode is 1 inch in diameter, the separator is 7 / 8 inch in diameter, and the anode is 3 / 4 inch in diameter to ensure no short - circuit of the cross - electrodes. In a more refined manufacturing situation, the diameters can be the same.

[0123] Lay the cathode sheet on a current collector (such as gold or gold - plated nickel or other metals, etc.). The in - electrode current collector may or may not be used on this first sheet. When using an in - electrode current collector, 10 - mil nickel shim stock, flattened nickel expanded metal can be used, or it can be used without a spacer (sheets in direct contact). Following the protocol used for the current collector, next place the separator sheet, and then place the anode sheet. Place a current collector on top of the anode.

[0124] The resulting energy harvester is incorporated into a test device using, for example, a compressive force of 40 psi.

[0125] Figure 7B shows the physical arrangement of a three - electrode thin - rolled energy harvester. In this example does not use a metal spacer. In Figure 7B, an anode layer 7A1, an anode current collector 7 B1, and an anode layer 7A1, a separator layer 7A2, sandwiched between the cathode current collector 7B2 and a cathode layer 7A3 are present. None of these energy harvesters in these examples contain an insulating separator, like almost all liquid electrolyte energy harvesters.

[0126] The separator layer 7A2 is often omitted from the design, resulting in a two-electrode design.

[0127] (Example 2B: Rolled Electrode) To solve the sticking problem on the above rollers, another embodiment of the rolled electrode was created as follows

[0128] When weighing the powder, the anode is 17% CeO2, 33% WO x , 50% T i4O7, the solid separator is 33.3% CeO2 and 66.7% WO x and the cathode is 17% CeO2, 33% WO x , 50% Co3O4, and the binder is 40 vol% Teflon 7c. Mix with a high-strength blender.

[0129] Use a precision rolling mill with a diameter of 60 mm (801 in Figure 8) manufactured by Durston (www.durston.co.uk, #DRM F130R) placed in the vertical position (801). 1 / 16 inch (1.58 mm) sintered Teflon sheet (McMaster-Carr #8545K 13) or a sheet with a width of about 100 mm (about 4 inches) and a length of about 150 mm (about 6 inches) thicker and cut two sheets 802. Set the gap of the roller mill to the Teflon sheet Adjust so that it becomes the thickness doubled plus 0.007 inches (0.178 mm). Alternatively, instead of under a constant gap, the roller can compress with air pressure. Thus, the thickness of the powder entering the mill can vary more than when using a constant gap. A pair of 4-inch pancake cylinders (Mead Fluid Dynamics SS-400X1.125-FB) under 50 psi giving 1257 pounds weight can be used. About 25 psi (630 pounds force) can be used to produce a strong sheet while maintaining porosity in a useful range (e.g., 0% to about 50% porosity). Pour the well-mixed powder onto a single sheet 803, correct the thickness and width between the stainless steel rods, and place the second sheet on top. Rotate the roller slowly towards the nip, draw the Teflon sheet and the powder into the nip, and create a self-standing sheet between the Teflon sheets.

[0130] The Teflon sheet 802 can be replaced, for example, with a Teflon-coated metal sheet of the same size cut from a cookie sheet. Use a safety razor or other sharp instrument to remove the electrode sheet 804 and place it on a clean piece of paper. Use an arch punch, for example a punch with a diameter of 3 / 4 inch (19 mm) (such as McMaster Carr's #3427A19), to cut discs from each sheet. Lay the cathode sheet on a current collector (such as gold-plated brass or nickel). If necessary, a current collector can be used for this first sheet. 10-mil nickel shim stock, flattened nickel expanded metal can be used, or used without a spacer (sheets in direct contact). ​​​​​It is possible. Next, the separator sheet is placed according to the protocol used for the current collector, and then the anode sheet is placed. A current collector is placed on the anode. Here, a nickel or brass shim stock with a gold plating was used. The resulting energy harvester is incorporated into a test device using, for example, a compressive force of 40 psi.

[0131] In another embodiment, the cathode is 1 inch in diameter, the separator is 7 / 8 inch in diameter , and the anode is 3 / 4 inch in diameter. In this embodiment, short circuits between the electrodes are reduced or eliminated. In another embodiment, the diameters can be the same.

[0132] The separator layer can be omitted with the anode and cathode simply placed in direct contact with each other. In another embodiment, the anode and cathode have a concentration gradient of materials, for example, near the interface between the electrodes to create a higher impedance.

[0133] In some embodiments where carbon (graphite or carbon black) is added to the anode and cathode electrodes, no additive is added to the SSE layer located between the anode and cathode. Charge separation in this embodiment is achieved by using a higher impedance of the SSE layer. In a further embodiment, the load cannot be lower than the total output impedance of the completed unit.

[0134] In the construction of many energy harvesters, the cell is placed within a plastic sealed container. Exemplary plastic sealed containers have been made from polyacrylate and polycarbonate, but can be composed of any non-conductive plastic material. The ones used When using polycarbonate, the adhesive is "airplane glue", and when using polyacrylate it is methyl ethyl ketone (MEK). In one aspect, the functional cells are surrounded by a space with gas inlets and outlets to enhance the control of gaseous reactants and make the resulting cells more robust. When using a sealed container, the gas is pumped across the electrodes at a rate of 5 - 300 ml / min, depending on the test conducted at an exemplary rate of 50 ml / min per cell .

[0135] (Example 3: Test) The test apparatus holds the energy harvester at 125 pounds weight on an anode and a cathode current collector where nickel 200 plated with gold or brass is on a cast acrylic support . The tests were conducted using a Solartron S1287 electrochemical interface and a Solartron S1250 frequency response analyzer, although many other test apparatuses would function similarly. The pellet was tested as an individual and as an energy harvester between gold electrodes. The entire apparatus was placed inside a plastic bag for gas environment experiments. Typically, the tests can be run in air (2 0% O2), 100% O2, and argon (0% oxygen). When testing the assembled energy harvester, the cathode can be used as the working electrode and the working reference. The anode is the counter electrode and the reference electrode. In this example, a negative current is expected during a short circuit or a potentiostatic discharge of the energy harvester.

[0136] When the energy harvester cell is incorporated into an airtight sealed container, the gas is sent to the cell through a port at one end of the sealed container and the gas is released from the exhaust portal. Typically , The tests were conducted in air (20% O2), 100% O2, and argon (0% oxygen). .

[0137] The tests included the following combinations. - Open circuit voltage (OCV) for 1 minute. - AC impedance spectroscopy from 1 MHz to 1 mHz with 10 data points per decade. method. - The units are normalized to the physical conditions by measuring the thickness of the compressed electrode or pellet and knowing the surface area. - Polarization curve from OCV to zero volts. - From this, the exchange potential (E o ), limiting current density, and power density are obtained. - Cyclic voltammogram from OCV to +1.0 volts, -1.0 volts, 5 cycles at 50 mV / second. - The data obtained from this are as follows. - R functional is the maximum current at +1 volt and the minimum current at -1.0 volts taken, and using Ohm's law (R functional = dV / di), it is calculated by calculating the gradient between these two points as the resistance. - Hysteresis at 0 volts: When electrons are consumed and released during cycling, as in the case of an electrochemical or capacitive system, the current spreads in the current as it rises compared to when it falls in the direction of the potential. Essentially, in contrast to simply passing through the system, electrons are consumed or released (as they pass through the resistance). The greater this hysteresis, the more suitable the crystal is for energy storage or release. The current density that spreads in the positive and negative directions is hysteresis and can be measured as the voltage at zero current.

[0138] (Example 4) CeO2 is used in the same proportion in all three 2.9 electrodes of the Ti4O7 anode, WO separator, and Co3O4 cathode. CeO2 is mixed with 10% Teflon 7c by DuPont. Each pellet contains 2 grams of active material and (of Dexmet) pure nickel expanded metal on both sides. The pellets are manufactured as described above and held at 10 0% relative humidity for 4 days to obtain a moisture content of 3.7% in the anode, 1.6% in the separator, and 0.5% in the cathode pellets. To assemble the energy harvester, the

[0139] periphery of the anode pellet is adhered to a silver bezel plated with gold while holding it under 40 PSI compression for 5 minutes with an epoxy resin to ensure good contact with the gold. The separator is sealed around its periphery with an epoxy resin, which ensures that all oxygen must be transported through the separator from the cathode. Next, the energy harvester with this pellet design

[0140] After each of the above short - circuits, the energy harvester was left standing in oxygen for 1 hour. Figure 10 shows the recovery of the energy harvester. The energy harvester recovered stably after a complete short - circuit (even after 25 hours of continuous short - circuit).

[0141] Next, the energy harvester was left standing in various atmospheres. Figure 11 shows the results of this experiment where the energy har vester was started in air (20% oxygen). After about 5 minutes, the atmosphere was changed to pure oxygen and the current density increased from about 30 mV to about 70 mV. Next, after about 20 minutes, the atmosphere was changed to pure argon (0% oxygen) and the potential dropped to zero and then below it. Next, after about 4 hours, the atmosphere was returned to ambient air (20% oxygen) and the potential returned to about 45 m V. This shows a strong influence of the external gas on the performance of this energy harvester.

[0142] Next, complete short - circuits were performed with various gases. Figure 12 shows the current densities obtained in three gas environments as a bar graph. Since the current is the cathode current, it has negative values. Therefore, as shown in Figure 12, it is necessary to multiply by - 1. The strong influence due to the presence of air in the atmosphere is seen in the first bar, then oxygen (second bar), and finally argon (0% oxygen) (third bar).

[0143] Figure 13 shows the voltammogram of the energy harvester 28716.4 (October 14, 2016, cell #4 ). This shows that the current density is 170 uA / cm and the exchange potential is approximately 100 mV after leaving the energy harvester standing in air for 48 hours 2 . ​​​​​is. The voltammogram also shows 5 nW / cm at 0.066 volts 2 is shown. This data is not impedance compensated.

[0144] Figure 14 shows that the AC impedance of this energy harvester is acceptably low Both the compression of the pellets and the cross-bond expanded metal current distribution of the nickel are helpful for impedance problems. Figure 15 is the Nyquist plot of this energy harvester, showing a large charge transfer resistance (R ) of 18.8 kΩ. ct )

[0145] (Example 6: Elimination of water as a liquid electrolyte) Functionality is improved by water absorption. To test whether water is a liquid electrolyte, five expanded metal disks 1601, a separator pellet 7A2, anode 7A1, and five more expanded metal disks 1601 and cathode pellet 7A3 are shown. A five-layer dry nickel expanded metal inserted between the electrodes in FIG. 16 is used to construct an energy harvester. The power supply for the electrodes was the above well-tested energy harvester . Next, under pressure, the anode and separator were re-epoxy sealed 7A5 from external contact with any air, and the cathode pellet 7A3 was left exposed to the air. The energy harvester was reassembled and tested. In this example, electrons and gas, rather than ions, can pass between the electrodes. The pellets were fabricated according to Example 1 above.

[0146] Figure 17 shows two voltammograms of these energy harvesters 30616.1 (November 2, 2016, cell #1). The upper line shows the electrodes placed close to each other​​ in a state where the lower line shows the performance of five expandable metal disks separating each electrode Even when there is no possibility of ion movement between the electrodes, the energy harvester operates, demonstrating that such ion movement is unnecessary and that charge actually passes through via electrons and perhaps also over charged gas molecules but not as ions.

[0147] Figures 18A and 18B are graphs of a series of short - circuit discharges and OCV natural recharges all conducted in air (20% oxygen). The combination of discharges is shown in Figure 18A. Here, the top line is the energy harvester with the electrodes in close contact, and the lower set of lines shows the performance of five layers of expandable metal placed between the electrodes. The operating performance clearly continues without ion transport but with electrons and perhaps only charged gas. Figure 18B is for the same combination but for the voltage recovery after a one - hour discharge. Again, the top line is the energy harvester with the electrodes in contact with each other, and the lower combination is several recharges with electrodes physically separated from each other. Again, the performance is clear without ion transport of charge. This energy harvester moves charge only via electrons.

[0148] Figure 18B is for the same combination but for the voltage recovery after a one - hour discharge. In this case too, the top line is the energy harvester with the electrodes in contact with each other, and the lower combination is several recharges with electrodes physically separated from each other. In this case too, the performance is clear without ion transport of charge. This energy harvester moves charge only via electrons. These experiments, which separate the electrodes and allow electrons and gas to pass freely, show that charge is passing between the electrodes using only electrons or charged gas. Oxygen ionization occurs within each individual electrode (using water vapor as a reagent), and as electrons move from each cathode towards the anode, it has oxygen passing as a gas.

[0149] (using water vapor as a reagent) and has oxygen passing as a gas as electrons move from each cathode towards the anode.

[0150] ​​​​​​​​​​ The improvement in performance when the electrodes are assembled in close proximity to each other is a physical advantage, not an electrochemical one.

[0151] Without being bound by a particular theory, the water present in the energy harvester is thought to act as a reagent within the individual electrodes rather than as an electrolyte

[0152] (Example 7) Figure 19 shows a three-layer thin film energy harvester prepared as described in Examples 2A and 2B above, using a rolling mill as described in Figure 8 (Run number: 36416). A gold-plated 10-mil brass shim stock diameter 1-inch disk 7B1 and 7B2 was used, placed between pairs of gold-plated current collectors 7B1 and 7B2 sheets, with each thin layer anode 7A1, separator 7A2, and cathode 7A3 disposed therebetween.

[0153] Figure 20 shows the voltammogram of a discrete electrode energy harvester having the curve of the three-layer thin rolled electrode energy harvester described in Figure 19, where the electrodes are simply compressed on top of each other without a spacer. The top line had a brass spacer plated with gold between the electrodes. The bottom line was made without a spacer, but the electrodes were compressed together. It showed a lower voltage, but the current density was 10 times higher. Both energy harvesters were run, but the resulting parameters were different. The performance did not degrade even when liquids, ions, and gases were completely blocked, indicating that this energy harvester moves charge using only electrons.

[0154] ​Figure 21 shows the long - term OCV of this thin - electrode energy harvester with a solid spacer between the electrodes of cell 36516 (December 31, 2016). This energy harvester was first exposed to oxygen when the OCV reached 0.12 volts, and then it dropped slightly, but still maintained the voltage. For about 700 minutes, it was given more oxygen and the performance was improved again. Note that the environmental "chamber" is just a plastic bag with a cable tie closing the top. This is by no means an airtight seal. Therefore atmospheric gas diffuses over time. At about 825 minutes, argon was filled into the bag and a sharp drop in performance was observed. At about 875 minutes, oxygen was re - introduced into the "chamber" and the performance recovered again. These results show that the energy harvester functions whether the electrodes are sandwiched together or separated by a nickel - impermeable layer . This indicates that the active ingredient can be rolled or coated onto the metal foil to increase the surface area . (Example 8) Figure 22 shows a cross - section of a three - layer energy harvester manufactured using the Teflon rolling method described in Example 2B above. In this case, each electrode has a different diameter, with the bottom layer being a cathode 7A3 with a diameter of 1 inch (25.4 mm), a separator 7A2 of 7 / 8 inch (22.2 mm), and an anode 7A1 of 3 / 4 inch (19 mm). The paper insulator is made so that the current collector does not short - circuit the anode and the separator 2201 to the current - collector disks 7B1 and 7B2. This prevents accidental short - circuits from occurring between the anode and the cathode or the energy harvester from short - circuiting directly.

[0155] (Example 8) Figure 22 shows a cross - section of a three - layer energy harvester manufactured using the Teflon rolling method described in Example 2B above. In this case, each electrode has a different diameter, with the bottom layer being a cathode 7A3 with a diameter of 1 inch (25.4 mm), a separator 7A2 of 7 / 8 inch (22.2 mm), and an anode 7A1 of 3 / 4 inch (19 mm). The paper insulator is made so that the current collector does not short - circuit the anode and the separator 2201 to the current - collector disks 7B1 and 7B2. This prevents accidental short - circuits from occurring between the anode and the cathode or the energy harvester from short - circuiting directly. The energy har has a bottom - layer cathode 7A3 with a diameter of 1 inch (25.4 mm), a separator 7A2 of 7 / 8 inch (22.2 mm), and an anode 7A1 of 3 / 4 inch (19 mm). The paper insulator is designed to prevent the current collector from short - circuiting the anode and the separator 2201 to the current - collector disks 7B1 and 7B2, thus preventing accidental short - circuits between the anode and the cathode and direct short - circuits of the energy harvester. The energy har vester The energy harvester has undergone various tests and demonstrated the best performance among all previous tests. .

[0156] Short - circuit test: Figure 23 shows the current density of three 24 - hour complete short - circuit tests of cell 24417 (September 1, 2017). The current density is much higher than that of previous tests using thin electrodes that gradually become smaller to prevent accidental short - circuits between the electrodes. Some conditions such as gas exchange can be observed in these lines. Considering the lowest line which was the first discharge. The energy harvester was dried after manufacture. Near 90% of the test, it was exposed to 100% relative humidity (RH) and the performance was significantly improved. The next line above that shows that the same energy harvester continued in air and 100% RH until pure oxygen was introduced at 20% of the test. At about 25%, pure argon was introduced to remove all oxygen from the test chamber. At 85%, air was introduced (20% oxygen). The top line shows that after standing in 100% RH air, oxygen was introduced at the end of the 24 - hour test and the output of the current density increased significantly. The effect of oxygen in the atmosphere is clear in the open - circuit voltage which results in the highest value given by oxygen. The current density between the electrodes is much higher than that of previous tests using thin electrodes that gradually become smaller to prevent accidental short - circuits between the electrodes. Some conditions such as gas exchange can be observed in these lines. Considering the lowest line which was the first discharge. The energy harvester was dried after manufacture. Near 90% of the test, it was exposed to 100% relative humidity (RH) and the performance was significantly improved. The next line above that shows that the same energy harvester continued in air and 100% RH until pure oxygen was introduced at 20% of the test. At about 25%, pure argon was introduced to remove all oxygen from the test chamber. At 85%, air was introduced (20% oxygen). The top line shows that after standing in 100% RH air, oxygen was introduced at the end of the 24 - hour test and the output of the current density increased significantly. The effect of oxygen in the atmosphere is clear in the open - circuit voltage which results in the highest value given by oxygen. The energy harvester was dried after manufacture. Near 90% of the test, it was exposed to 100% relative humidity (RH) and the performance was significantly improved. The next line above that shows that the same energy harvester continued in air and 100% RH until pure oxygen was introduced at 20% of the test. At about 25%, pure argon was introduced to remove all oxygen from the test chamber. At 85%, air was introduced (20% oxygen). The top line shows that after standing in 100% RH air, oxygen was introduced at the end of the 24 - hour test and the output of the current density increased significantly. The effect of oxygen in the atmosphere is clear in the open - circuit voltage which results in the highest value given by oxygen. The effect of oxygen in the atmosphere is clear in the open - circuit voltage which results in the highest value given by oxygen.

[0157] OCV recovery test: Figure 24 shows the OCV after each long - term discharge in Figure 23. The bottom line shows the OCV recovery in argon (with little oxygen). Note that the test chamber was not completely sealed from oxygen contamination from the air. The middle line is in air and the top line is 100% oxygen. Again, clearly, the atmospheric gas plays a major role in the performance. The bottom line shows the OCV recovery in argon (with little oxygen). Note that the test chamber was not completely sealed from oxygen contamination from the air. The middle line is in air and the top line is 100% oxygen. Again, clearly, the atmospheric gas plays a major role in the performance. The middle line is in air and the top line is 100% oxygen. Again, clearly, the atmospheric gas plays a major role in the performance.

[0158] Figure 25 summarizes the OCV between tests from the graph shown in Figure 24. The light gray bars indicate the rate of increase (i.e., the initial slope of recovery), and the dark bars indicate the voltage reached after 30 seconds.

[0159] The energy harvester was tested with varying rest times, mostly in 24-hour full short-circuit discharge cycles. Figure 26 plots the full short-circuit discharges of the lifespan of this energy harvester (Run number 24417) in the order of testing. Most of the bars represent the current density at the end of the 24-hour test in 100% RH air. The two light gray bars #4 and #5 were discharged for 1 hour each in sulfur. The fifth bar from the end (#20) is a 12-day discharge in 100% RH air. The fourth bar from the end (#21) was a series of environmental gas changes. The longest discharge is shown by the last bar (#24), which shows the current density after a 5-day discharge. This increased the current output over time. The energy harvester appears to self-charge during discharge. The total discharge of this energy harvester during this series of tests over 560 hours (23 days) outputs 1.5 coulombs.

[0160] The last bar of this test was repeatedly interrupted to obtain impedance values. Figure 27 shows this long-term discharge over several days of discharge with changes in the atmospheric gas composition. To measure the impedance number, the discharge was interrupted several times for several minutes (described later in Figure 29). In this long-term test, there was a period of gas testing starting from a dry state and continuing with a 100% RH air environment for about 24 hours. After 12 days, a series of gas tests as described in Figure 27 were performed. Subsequently, at approximately 290 hours (12 days), the chamber was filled with argon to replace oxygen.

[0161] Figure 28 shows exemplary results where the first portion had air and then oxygen at approximately 294.5 hours (12.25 days) with an increase in output. Subsequently, the oxygen was replaced with argon at approximately 294 hours. Thereafter, air was introduced until approximately 300 hours when argon was introduced 30 minutes later. Subsequently, argon was applied several times to stably diffuse the atmosphere into the test chamber. Again, the importance of oxygen is shown in this energy harvester.

[0162] Regarding Figure 27, the chamber was refilled with 100% Rh air and operated for an additional 6 days. Not only was it fully recovered, but the current density after the test also increased. This cell operated for nearly 20 days without degradation, and the current density was improved during the course of the test.

[0163] Figure 29 shows the 65 kHz AC impedance as a function of current density when the energy harvester is humidified from a dry state to a water-saturated state. A semi-logarithmic relationship (R value of 99%) exists, indicating a first-order relationship. Without intending to be bound by a particular theory, this appears to show that the ingress of water caused a change in impedance with an increase in current density. In this example, the AC impedance decreases and the current density increases. 2

[0164] (Example 10) The three-layer energy harvester is the Teflon rolling described in Example 2B above: rolled electrodes ​​​​​​​​​​​​​It was produced using the machine method. In this example, Teflon (PTFE) was added as an aqueous suspension called Teflon 30. These particles are very small compared to the aforementioned T7c powder.

[0165] The recipe for this 12-gram mixture is as follows.

Table 3

[0166] In this embodiment, 40 volume percent of Teflon was added to each electrode as was used for Teflon 7C.

[0167] The procedure was as follows. (1) Weigh the active powder as usual without using Teflon 7C. (2) Place the powder in a 100 cc beaker and add 50 cc of distilled water. (3) Insert a stir bar and whirl it into a deep vortex without aspirating air. (4) Add Teflon emulsion T30 in droplets. (5) Stir for about 30 minutes. (6) Prepare a Buchner funnel and filter the slurry under high vacuum. (7) Place the filter paper with the filter cake on a glass dish. (8) Put it in a drying oven at 120°C until dry (about 6 hours for this 12-gram recipe). (9) Or place it in a desiccator at room temperature until dry (about 24 hours). (10) After adding a small amount of water to the recipe, scrape the dry cake from the paper and grind it with a high-shear blender. (11) Use a rolling mill to form the electrode.

[0168] The resulting electrode is more robust than the dry method and somewhat easily formed an energy harvester.

[0169] Figure 30 shows the first voltammograms after building several energy harvesters. The limiting currents obtained are shown. The first bar shows the new Teflon 7C binder used before humidification. The first bar shows the limiting current (LC) of the new energy harvester. The second bar shows the L C. The third was produced using liquid emulsion T30 binder, which is resistant to evaporation. Thus, the initial performance of the energy harvester to remove water is shown.

[0170] Although the present invention does not wish to be bound by a particular theory, FIG. The diagram shows the charge flow of an exemplary energy harvester. Oxygen has two negative charges. It is believed that oxygen enters the cathode 7A3 carrying a charge (electrons). O1 (e.g., Co3O4) crystal structures and defects, and their loosely bound acids Create an excess electron that slides onto the CeO2 crystal with the elementary atom, and carry two electrons with it. These electrons are free to move to the separator layer 7A2 and form WO 2.9 Low electronegativity The transition of anode 7A1 is promoted by the CeO2 “electrolyte” 3102. Transition metal suboxides (e.g., Ti4O7) are more effective than Co3O43101 in cathode 7A3. It has a large electronegativity. These electrons are given up by oxygen reacting with hydroxyl ions. The anode body 3103 is then released to form water vapor that is released into the environment. 1 accumulates excess electrons that create a potential across the load 3104 and transfers the electrons to the cathode current collector Switch back to 7B2.

[0171] Layer 7A2 is optionally not included.

[0172] (Example 11) Low impedance, three - electrode design:

[0173] In this aspect, the cell uses a high - impedance portion to separate charges. For example, the anode and cathode maintain high impedance while reducing the impedance of the electrodes in a layer of SSE (Figure 32) positioned between the electrodes as a solid separator, and may include carbon (e.g., black or graphite). In another aspect, Ti4O7 is added to the SSE to increase the DC resistance. In this aspect, the power density can be increased by about 10 times. .

[0174] In the exemplary aspect of Figure 32, "A" is the anode, composed of an active compound with added carbon, "Sep" is the SSE, and "C" is the cathode with added carbon. In another aspect, the carbon loading can be about 5%. In another aspect, Ti4O7 or other impedance - increasing components can be added to the SSE separator layer to increase its resistance. Carbon is tested in the form of carbon black using Cabot Vulcan XC72R (also simply called "V72") and "Nano307" powdered graphite from Asbury Graphite Mills alternately. A loading of less than 5% is optimal, but even 0.5% is beneficial. Also, a mixture of the two types of carbon was tested.

[0175] For a better understanding of the impedance characteristics of the exemplary cell, the DC resistance of the components was measured. Table 4 shows the DC resistance of the cell components. Components 1 - 4 are chemical raw materials, components 5 - 6 are carbon - free and carbon - containing anodes, 7 is the SSE, and 8 and 9 are carbon - free and carbon - containing cathodes. Items 5 - 9 all contain 40 volume percent of un - sintered Teflon powder. ​​​​​​​​​​​

Table 4

[0176] Figure 33 shows that an exemplary three - layer design produces a discharge rate 12.5 times higher than that of 34818 cells (December 14, 2018). This was the best test prior to when the electrodes did not contain carbon. This cell had a two - electrode design. .5 times higher than that of 34818 cells (December 14, 2018). This was the best test prior to when the electrodes did not contain carbon. This cell had a two - electrode design. than previously, and was the best test. This cell had a two - electrode design.

[0177] Figure 34 shows the complete short - circuit discharge of cells with carbon in the electrodes and without carbon with an eight - fold increase in current density. Figure 34 shows the complete short - circuit discharge of cells with carbon in the electrodes and without carbon with an eight - fold increase in current density.

[0178] As shown in Figure 35, the constant - potential discharge of the cell starts with air containing moisture (20% oxygen), then becomes oxygen with 100% moisture in 4.5 hours. In 6 hours, the gas is changed to argon containing moisture (0% oxygen), and returns to air containing moisture in 12 hours. In this mode, the oxygen content appears to affect the output. Without being bound by a particular theory, the fact that the argon atmosphere does not reach zero suggests that water vapor is electrolyzed to generate its own oxygen in situ. next becomes oxygen with 100% moisture in 4.5 hours. In 6 hours, the gas is changed to argon containing moisture (0% oxygen), and returns to air containing moisture in 12 hours. In this mode, the oxygen content appears to affect the output. Without being bound by a particular theory, the fact that the argon atmosphere does not reach zero suggests that water vapor is electrolyzed to generate its own oxygen in situ. next becomes oxygen with 100% moisture in 4.5 hours. In 6 hours, the gas is changed to argon containing moisture (0% oxygen), and returns to air containing moisture in 12 hours. In this mode, the oxygen content appears to affect the output. Without being bound by a particular theory, the fact that the argon atmosphere does not reach zero suggests that water vapor is electrolyzed to generate its own oxygen in situ. next becomes oxygen with 100% moisture in 4.5 hours. In 6 hours, the gas is changed to argon containing moisture (0% oxygen), and returns to air containing moisture in 12 hours. In this mode, the oxygen content appears to affect the output. Without being bound by a particular theory, the fact that the argon atmosphere does not reach zero suggests that water vapor is electrolyzed to generate its own oxygen in situ. next becomes oxygen with 100% moisture in 4.5 hours. In 6 hours, the gas is changed to argon containing moisture (0% oxygen), and returns to air containing moisture in 12 hours. In this mode, the oxygen content appears to affect the output. Without being bound by a particular theory, the fact that the argon atmosphere does not reach zero suggests that water vapor is electrolyzed to generate its own oxygen in situ. next becomes oxygen with 100% moisture in 4.5 hours. In 6 hours, the gas is changed to argon containing moisture (0% oxygen), and returns to air containing moisture in 12 hours. In this mode, the oxygen content appears to affect the output. Without being bound by a particular theory, the fact that the argon atmosphere does not reach zero suggests that water vapor is electrolyzed to generate its own oxygen in situ.

[0179] Figure 36 shows the power curves of three design examples. The bottom curve is for a two - electrode design and does not contain carbon. The upper two curves are for three - electrode designs. One has 3% nanographite to separate charge across a relatively high impedance, and the other has an anode and cathode with 3% Vulcan 72 carbon black added and has an SSE layer between the two. Figure 36 shows the power curves of three design examples. The bottom curve is for a two - electrode design and does not contain carbon. The upper two curves are for three - electrode designs. One has 3% nanographite to separate charge across a relatively high impedance, and the other has an anode and cathode with 3% Vulcan 72 carbon black added and has an SSE layer between the two. Figure 36 shows the power curves of three design examples. The bottom curve is for a two - electrode design and does not contain carbon. The upper two curves are for three - electrode designs. One has 3% nanographite to separate charge across a relatively high impedance, and the other has an anode and cathode with 3% Vulcan 72 carbon black added and has an SSE layer between the two. Figure 36 shows the power curves of three design examples. The bottom curve is for a two - electrode design and does not contain carbon. The upper two curves are for three - electrode designs. One has 3% nanographite to separate charge across a relatively high impedance, and the other has an anode and cathode with 3% Vulcan 72 carbon black added and has an SSE layer between the two. Figure 36 shows the power curves of three design examples. The bottom curve is for a two - electrode design and does not contain carbon. The upper two curves are for three - electrode designs. One has 3% nanographite to separate charge across a relatively high impedance, and the other has an anode and cathode with 3% Vulcan 72 carbon black added and has an SSE layer between the two.

[0180] Next, carbon black was used for the anode and cathode at the same loading level as graphite in the previous run. After "activation" (24 hours of short circuit, then 6 hours of OCV), this cell with carbon black had a slightly higher power density than graphite, but graphite achieved a slightly higher exchange potential. In another aspect, carbon black and graphite can be mixed in the electrodes. In one aspect, carbon can be added to the anode and cathode at about 2% to about 6%. In another aspect, the amount of carbon added to the anode and cathode can be about 4%. When the binder is liquid-based, these electrodes can be manufactured using a coating method and then removed. The coating energy harvester was developed using a 25% dilution of a latex medium (lot 03717). Each electrode was a rolled material, then reground and fibrillated into fine Teflon fibrils. Next, the resulting mixture was mixed 50 / 50 with a 25% solution of a latex binder to obtain a thick paint-like material. The paint-like material was coated on a 1-mil nickel sheet pre-coated with a thin coat of 50% diluted Timrex LB1016 graphite conductive paint. Each electrode was dried between applications. The final thickness was 12 mils (0.012 inches or 0.3 mm). Next, disks were punched out using a 3 / 4-inch arch punch. The resulting energy harvester demonstrated feasibility but resulted in lower current density values compared to the rolling or pellet methods.

[0181]

[0182] (Example 12)

[0183] ​​​​​​​​​​​​​​Assembly mode and method: In one aspect, this energy harvester is assembled as follows can be. (a) A solid anode current collector that needs to be a material that does not react with the active ingredient. This can be nickel , gold, gold-plated metal or carbon, and should cover most or all of the anode surface. should cover. (b) An anode composed of a mixture of a solid electrolyte and a transition metal oxide. The physical form of this layer is compressed using a porous binder and held together. Also, it may be applied as a paint using a liquid binder that dries after application. (c) A layer called a "separator" consisting only of a solid electrolyte and a binder. It may be the same thickness as the anode and the cathode, may be thinner than the anode and the cathode , or may not all be present together. (d) A cathode composed of a solid electrolyte and a transition metal oxide with a lower electronegativity than the oxide used in the anode. (e) A cathode current collector that should be a material that does not react with the active ingredient. This can be nickel , gold, gold-plated metal or carbon, and should cover most or all of the cathode surface. should cover. This layer is preferably porous, such as foamed metal, porous metal of porous carbon .

[0184] Binder: The powders described here are not sintered and are bonded using a binder . Therefore, they are "green" (unsintered). Binders that can function in this energy harvester include fibrillated polytetrafluoroethylene (PTFE), latex, egg white, hydrogen gel, or other organic or inorganic binders with low conductivity may be included. . The material is porous and has a very high internal impedance that is higher than the active ingredient of the present invention. It is necessary to have. The binder can be started with a solvent that becomes a high-impedance, highly porous binder when dried. It can be started.

[0185] Additional uses: This energy harvester can be used in low-power applications where there is a constant supply of air. Preferably, this air is moving, such as in the flow from a ventilation fan or on a moving vehicle. In the case of a digital clock, the energy harvester case needs to be porous enough to be in contact with the air. Examples include, but are not limited to, the following list. (a) Gas sensors based on sensitivity to the gas composition in the atmosphere, (b) Low-power devices such as electronic clocks and low-power LEDs, (c) Places where there is a constant air movement, such as in the flow of a moving vehicle, a cooling fan or a ventilation fan, on the blades of a windmill, or on the wings of an aircraft. (d) Coating the anode part on a solid surface and then coating a subsequent layer to form a porous current collector that provides a large surface area and high current output in many applications. (e) On the wings of an aircraft, etc. (f) Coating the anode part on a solid surface and then coating a subsequent layer to form a porous current collector that provides a large surface area and high current output in many applications. Unless otherwise specified, the potential (Eo) reported here is from the following source: en.wikipedia.org / wiki / Standard_ele

[0186] ctro_potential_(data_page). Unless otherwise specified, the potential (Eo) reported here is from the following source: en.wikipedia.org / wiki / Standard_ele ctro_potential_(data_page).

[0187] The term "energy harvester" as used herein is not limited to a sealed body equipped with electrodes in a mechanical manner, but can be open to the environment on one or more sides of the device. The term "solid energy harvester" can be interpreted as a "solid energy source". It can be obtained. It can be obtained.

[0188] This device can function as an energy storage unit such as a battery or a capacitor. It is possible.

[0189] The definitions of the Kroger-Vink notation used here can be found in many information sources, including more academic sites such as Wikipedia (https: / / en.wikipedia.org / wiki / Kroger-Vink_notation) and (https: / / www.tf.uni-kiel.de / matwis / amat / def_en / kap_2 / backbone / r2_4_2.htm). ps: / / en.wikipedia.org / wiki / Kroger-Vink_no tation) and (https: / / www.tf.uni-kiel.de / matw is / amat / def_en / kap_2 / backbone / r2_4_2.htm including more academic sites such as Wikipedia (https: / / en.wikipedia.org / wiki / Kroger-Vink_notation) and (https: / / www.tf.uni-kiel.de / matwis / amat / def_en / kap_2 / backbone / r2_4_2.htm).

[0190] The references cited in this disclosure are hereby incorporated by reference in their entirety.

[0191] Although the present invention has been disclosed with reference to specific embodiments, numerous modifications, alterations, and changes can be made to the described embodiments without departing from the scope and scope of the invention as defined in the appended claims. Accordingly, the present invention is not intended to be limited to the described embodiments, but rather is intended to have all ranges defined by the language of the following claims and their equivalents. As defined in the appended claims, without departing from the scope and scope of the invention, numerous modifications, alterations, and changes can be made to the described embodiments. Therefore, the present invention is not limited to the described embodiments, but rather is intended to have all ranges defined by the language of the following claims and their equivalents. Rather, the present invention is not limited to the described embodiments, but is intended to have all ranges defined by the language of the following claims and their equivalents. It is intended to have all ranges defined by the language of the following claims and their equivalents.

Claims

1. A solid energy harvester, comprising: a first layer, which is an anode and comprises a solid electrolyte (SSE) having a first transition metal oxide and cerium dioxide; a second layer, which is a cathode and comprises an SSE having a second transition metal oxide and cerium dioxide, wherein the first transition metal oxide and the second transition metal oxide are different from each other, the solid energy harvester.

2. The first transition metal oxide or the second transition metal oxide is tungsten monoxide, cobalt monoxide, Na １．０ Mo １．５ WO ６．０ ,Na ０．９ Mo ６ O １７ ,Na １．０ Ti １．５ WO ４．５ ,Na １．２ Ti ０．３４ WO ４ ,Ti ４ O ７ ,Ti ５ O ９ ,K １．２８ Ti ８ O １６ ,K １．０４ Ti ８ O １６ ,K ０．４８ Ti ８ O １６ ,Na ４ WO ３ ,Na ０．９０ WO １．８１ ,Na ０．８２ WO １．８１ ,Na ０．７４ WO １．８１ ,K ０．９ WO ３ ,WO ２．７２ ,WO ２．８２ ,WO ２．９ ,Na ２ WO ４ ,Na ８．２ WO,Na ２ O ２ WO ３ ,Na １．２ Ti ０．３４ WO ４ ,Na １．２ Cu ０．３１ WO ７．２ ,Na １．２ Mo ０．３１ WO ５．２ ,and Na ２ O ４ WO ３ The solid energy harvester according to claim 1, selected from the group consisting of

3. The first transition metal oxide is Ti ４ O ７ The solid energy harvester according to claim 1, wherein the first transition metal oxide is TiO ７ .

4. The second transition metal oxide is Co ３ O ４ The solid energy harvester according to claim 1, wherein the second transition metal oxide is CoO

5. The solid energy harvester according to claim 1, wherein each of the first layer and the second layer substantially does not contain a noble metal.

6. The solid energy harvester according to claim 1, wherein the first layer and the second layer each further comprise a binder.

7. The solid energy harvester according to claim 6, wherein the binder is selected from the group consisting of unsintered Teflon (PTFE), FEP, paraffin, and epoxy.

8. The solid energy harvester according to claim 1, wherein the anode contains about 0.01% to about 14% water.

9. The first transition metal oxide and the second transition metal oxide each have a stoichiometric composition M ｘ－ｙ O ｚ where M is a transition metal, x is the basic valence of the transition metal M, y is a deviation from 1, when M is titanium, x is 4 and y is at least 0.5, when M is cobalt, x is 3 and y is at least 0.3, when M is tungsten, x is 5 and y is at least 0.2, z is an integer, the solid energy harvester according to claim 1.

10. The solid energy harvester according to claim 1, wherein the first layer is electrically connected to a first current collector, and the second layer is electrically connected to a second current collector.

11. The solid energy harvester according to claim 10, wherein the first and second current collectors comprise a metal selected from the group consisting of gold, nickel, copper, brass, bronze, porous carbon, and carbon.

12. The solid energy harvester according to claim 10, wherein at least one of the first current collector and the second current collector comprises a porous material.

13. The solid energy harvester according to claim 1, wherein the first layer and the second layer are in contact with each other.

14. The solid energy harvester according to claim 13, wherein no oxide is included on the surface where the first layer and the second layer are in contact with each other.

15. a first layer comprising a first transition metal oxide; A solid energy harvester comprising a second layer containing a second transition metal oxide, wherein the first transition metal oxide and the second transition metal oxide are different from each other, the first layer and the second layer are bonded using a binder, the first layer further comprises titanium oxide, the second layer further comprises cobalt oxide, the solid energy harvester generates an electric current in the presence of oxygen and water vapor, A solid energy harvester, wherein each of the first layer and the second layer further comprises cerium dioxide.

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