Secondary battery

Abstract

A secondary battery is provided. The secondary battery includes a solid electrolyte that conducts oxygen ions, a positive electrode configured to contact the solid electrolyte, and a negative electrode configured to contact the solid electrolyte. The positive electrode and the negative electrode include an ion-electron mixed structure for conducting oxygen ions and electrons. In the ion-electron mixed structure, site A corresponds to a first chemical element having a first covalent bond radius, and site B corresponds to a second chemical element having a second covalent bond radius, and ABO 3 structure, and / or Ce is cerium and M is a metal, and CeMO 2 structure is included.

Description

Technical Field

[0001] This disclosure claims the benefit of European Patent Application No. 22382423.6, filed on May 3, 2022.

[0002] This disclosure relates to a secondary battery including a solid electrolyte.

Background Art

[0003] In recent years, secondary batteries (also called rechargeable batteries) have become increasingly important in, for example, energy storage systems for household electrical appliances, the automotive industry, and portable applications. In particular, a secondary battery is an electrochemical cell that generates an electric current. Unlike a primary battery, a secondary battery can be charged and discharged multiple times.

[0004] The most common secondary battery is a lithium-ion rechargeable battery. A lithium-ion rechargeable battery is configured to generate electrical energy by a redox reaction that occurs during intercalation / deintercalation of lithium ions in a positive electrode and a negative electrode. Current lithium-ion rechargeable batteries typically use lithium cobalt oxide (LiCoO 2 ) in the positive electrode, graphite in the negative electrode, a separator, and a liquid electrolyte composed of a lithium salt dissolved in an organic fluid. As a result, lithium-ion rechargeable batteries intensively use important raw materials (e.g., lithium, cobalt) that are harmful to the environment and health. In addition, the liquid electrolyte of a lithium-ion rechargeable battery is flammable and sensitive to safety risks.

[0005] Another type of secondary battery is an all-solid-state lithium battery. An all-solid-state lithium battery uses a solid electrolyte instead of a liquid electrolyte. Even though the solid electrolyte is non-flammable, all-solid-state lithium batteries still use important raw materials (i.e., lithium) that are harmful to the environment and health.

[0006] Similarly, metal-air batteries are known. For example, a lithium-air battery typically includes an electrolyte, a lithium-metal anode, and a cathode in contact with ambient air. As a result, a gas-solid reaction occurs at the cathode. During discharge, lithium ions flow from the anode through the electrolyte and react with oxygen at the cathode to form products such as lithium oxide LiO 2 or lithium peroxide Li 2 O 2 (deposited on the cathode). However, conventional lithium-air batteries have poor cycle performance and still intensively use important raw materials (i.e., lithium) that are harmful to the environment and health.

[0007] International Patent Application Publication No. 2013 / 093044 (A1) describes a metal-air battery that operates at high temperatures, and the battery includes a metal electrode, an air electrode including a mixed electron and oxygen ion conductor, and a solid oxide electrolyte.

[0008] U.S. Patent Application Publication Nos. 2020 / 227779 (A1) and 2005 / 089738 (A1) relate to secondary batteries.

[0009] Furthermore, there are secondary batteries that do not rely on the intercalation / deintercalation of lithium ions in the anode and cathode for generating electrical energy. However, in these secondary batteries, the operating temperature of the secondary battery exceeds 500°C (up to 1000°C). Furthermore, these secondary batteries may use a liquid electrolyte to provide ion conduction. An operating temperature exceeding 500°C is not suitable for, for example, energy storage systems for household appliances, the automotive industry, and portable applications. Under such extreme conditions, the secondary battery elements may be subject to corrosion. Therefore, these secondary batteries may be sensitive to vibration or movement, limiting these secondary batteries to fixed applications.

[0010] Examples of the present disclosure seek to at least partially reduce one or more of the above-described problems. SUMMARY OF THE INVENTION

[0011] In a first aspect, a secondary battery is provided. The secondary battery includes a solid electrolyte that conducts oxygen ions, a positive electrode configured to contact the solid electrolyte, and a negative electrode configured to contact the solid electrolyte. The positive and negative electrodes include an ion-electron mixed structure for conducting oxygen ions and electrons. The mixed ion-electron structure is an ABO 3 structure, where the A site corresponds to a first chemical element having a first covalent radius and the B site corresponds to a second chemical element having a second covalent radius, the ABO 3 structure, and / or a CeMO 2 structure where Ce is cerium and M is a metal, the CeMO 2 structure.

[0012] In this aspect, a secondary battery based on oxygen ion conduction is provided. During discharge or charging, oxygen ions can be exchanged between the positive and negative electrodes. As a result, a lithium-free secondary battery is provided. Thus, the secondary battery can use raw materials (i.e., lithium) that pose less significant environmental and health risks.

[0013] Furthermore, since the secondary battery includes a solid electrolyte for conducting oxygen ions, the safety of the secondary battery can be enhanced. As a result, the solid electrolyte may not decompose and generate gas (e.g., air, O 2 gas, flammable gas).

[0014] Unlike gas-solid reactions that are slow and highly temperature-dependent, oxygen ions can be extracted from the ABO 3 structure and / or the CeMO 2 structure. As a result, oxygen ion conduction can be achieved at low temperatures (i.e., below 400 °C). The extracted oxygen ions can be conducted through the electrolyte into the ABO 3 structure and / or the CeMO 2 structure. Thus, a solid electrode that conducts oxygen ions and the ABO 3 structure and / or the CeMO 2By selecting the structure, an operating temperature of less than 400 °C, particularly from room temperature to 400 °C, and more particularly from 150 °C to 300 °C can be achieved.

[0015] In particular, the ABO 3 structure may include a cubic crystal structure (i.e., space group

[0016]

Number

[0017] An additional ABO 3 structure may be obtained, where the first chemical element (i.e., the A site) and / or the second chemical element (i.e., the B site) may include the configurations of A1 x-1 A2 x and / or B1 y-1 B2 y . As a result, the ABO 3 structure may deviate from the cubic crystal structure because the first chemical element (i.e., the A site) and / or the second chemical element (i.e., the B site) may undergo changes in their oxidation states. Furthermore, depending on the temperature, the ABO 3 structure may include other crystal structures, such as orthorhombic, tetragonal, or trigonal.

[0018] The ABO 3 structure enables the oxygen ions present within the ABO 3 structure to be efficiently extracted or inserted as mobile ions. Therefore, during the charging and / or discharging of a secondary battery at low temperatures (i.e., less than 400 °C), oxygen ions can be conducted within the positive or negative electrode.

[0019] ABO 3 In some examples of the structure, the first covalent bond radius of the first chemical element (i.e., the A site) may be greater than the second covalent bond radius of the second chemical element (i.e., the B site).

[0020] In particular, the A site can be selected from at least one of lanthanum La, calcium Ca, strontium Sr, and barium Ba.

[0021] Furthermore, the B site can be selected from at least one of manganese Mn, chromium Cr, iron Fe, nickel Ni, cobalt Co, and titanium Ti.

[0022] In some examples, ABO 3 The stoichiometry of the structure can be ABO 3-δ (where δ is between -1 and 1).

[0023] In some examples, the plurality of structures can be obtained from an ABO 3 structure (A n+1 B n O 3n+1 , where n = 1, 2, 3). A n+1 B n O 3n+1 The structure may include n ABO 3 structural layers sandwiched between AO rock salt layers. Therefore, the A n+1 B n O 3n+1 structure may be a structure derived from the ABO 3 structure. The A n+1 B n O 3n+1 structure may include the A 2 BO 4 structure (n = 1), and / or the A 3 B 2 O 7 structure (n = 2), and / or the A 4 B 3 O 10 structure (n = 3).

[0024] CeMO 2 Referring to the structure, in some examples, CeMO 2 In the structure, M may be selected from at least one of gadolinium Gd, samarium Sm, lanthanum La, calcium Ca, magnesium Mg, praseodymium Pr, and zirconium Zr.

[0025] Therefore, CeMO 2 The structure may exhibit oxygen vacancies upon introduction of the metal M. As a result, the CeMO 2 structure allows the oxygen ions present in the CeMO 2 structure to be efficiently extracted or inserted as mobile ions at low temperatures (i.e., below 400 °C). The CeMO 2 structure can be had.

[0026] In any case, the ABO 3 structure and the CeMO 2 structure may exhibit ionic conductivity (i.e., oxygen ion conductivity) and electronic conductivity (i.e., conductivity).

[0027] ABO 3 In the structure, the first chemical element (i.e., the A site) and / or the second chemical element (i.e., the B site) does not contain the chemical element: lithium Li.

[0028] Similarly, in the A n+1 B n O 3n+1 structure, the first chemical element (i.e., the A site) and / or the second chemical element (i.e., the B site) does not contain the chemical element: lithium Li.

[0029] Similarly, in the CeMO 2 structure, the metal element M does not contain the chemical element: lithium Li.

[0030] In some examples, the ion-electron mixed structure of the positive electrode and / or the negative electrode may include a thickness of 1 nm to 1 mm, specifically 100 nm to 1 μm.

[0031] In addition, in some examples, the solid electrolyte may be doped ZrO 2 or doped CeO 2 In some of these examples, the doped ZrO 2 and / or the doped CeO 2 may contain a dopant selected from at least one of gadolinium (Gd), samarium (Sm), scandium (Sc), lanthanum (La), calcium (Ca), magnesium (Mg), and yttrium (Y). Thus, the addition of hetero-valent cations to ZrO 2 or CeO 2 can create oxygen vacancies, which can provide a path for oxygen ions to conduct.

[0032] In some examples, the solid electrolyte may have a thickness of 1 nm to 1 mm, specifically 100 nm to 1 μm.

[0033] Furthermore, in some examples, the secondary battery may further include a current collector. In these examples, the current collector may be configured to contact the positive electrode to collect charge from the positive electrode. Alternatively, it may be configured to contact the negative electrode to collect charge from the negative electrode. In particular, the current collector may be a metal.

[0034] In addition, in some examples, the secondary battery may further include an insulating layer such as an electrically insulating layer disposed on at least one of the electrodes. For example, the insulating layer or the electronic insulating layer may be configured to contact at least one of the electrodes.

[0035] In some examples, the insulating layer or the electronic insulating layer may be configured to contact the current collector.

[0036] In both cases, the insulating layer or the electronic insulating layer can avoid oxygen leakage (i.e., there is no oxygen exchange with at least one atmosphere of the electrode on which the insulating layer is disposed), and / or can prevent the flow of current on its surface. As a result, the insulating layer or the electronic insulating layer can prevent self-discharge of the secondary battery (for example, since the insulating layer disposed on at least one of the electrodes isolates at least one of the electrodes from the atmosphere or the outside, there is no oxygen leakage), and / or can prevent the flow of leakage current from the current collector. In some of these examples, the insulating layer or the electronic insulating layer may be made of zirconia ZrO 2 or alumina Al 2 O 3 and may be made from.

[0037] In some examples, the insulating layer or the electronic insulating layer may have a thickness of 1 nm to 1 mm.

[0038] Note that examples including an insulating layer or an electronic insulating layer disposed on at least one of the electrodes may include examples where the insulating layer or the electronic insulating layer is disposed on each electrode. Therefore, both electrodes may be in contact with the insulating layer or the electronic insulating layer.

[0039] The term "oxygen" can be used to refer to any allotrope of oxygen, for example, O 1 , O 2 , O 3 . Therefore, the term "oxygen ion" can be used to refer to any ion of any allotrope of oxygen, for example, O - , O 2- .

[0040] The term "metal" can be used to refer to metals, alkaline earth metals, lanthanides, and transition metals in the periodic table of elements.

[0041] The term "temperature" can be used to refer to the operating temperature of the secondary battery. In addition, room temperature may be used to refer to a temperature of 15°C to 27°C. For example, in the present disclosure, room temperature may be 20°C.

[0042] The term "low temperature" may refer to a temperature below 400 °C, and the term "high temperature" may refer to a temperature above 500 °C.

[0043] The term "structure" may be understood as a spatial pattern along three different directions (i.e., x, y, z) in three-dimensional space, which may be any suitable spatial arrangement, such as, for example, layers, wafers, cubes, cones, cylinders, discs, hexagonal columns, triangular columns, pentagonal columns, tetrahedrons, octahedrons, spheres, and any combination thereof.

[0044] The term "mole percent" may be used to refer to the mole percentage of a first component (e.g., Y 2 ) relative to the total moles of a second component (e.g., ZrO 2 O 3 ).

[0045] In summary, a secondary battery that does not contain lithium and can operate at low temperatures is provided.

Brief Description of the Drawings

[0046] Non-limiting examples of the present disclosure are described below with reference to the accompanying drawings.

Figure 1

Figure 2

Figure 3

Figure 4

Figure 5

Figure 6

Best Mode for Carrying Out the Invention

[0047] In these figures, the same reference numerals are used to indicate corresponding elements.

[0048] FIG. 1 shows a schematic diagram of an example of a secondary battery 100. The secondary battery 100 is an electrochemical cell in which a redox reaction can occur at the electrode 110. Thereby, the secondary battery 100 generates electrical energy by a chemical reaction. The secondary battery 100 includes a positive electrode 112, a negative electrode 114, and a solid electrolyte 120.

[0049] The positive electrode 112 and the negative electrode 114 include an ion-electron mixed structure for conducting oxygen ions and electrons. The ion-electron mixed structure provides ion conductivity for conducting ions and electron conductivity for conducting electrons. In particular, the ion-electron mixed structure has an ABO 3 structure and / or a CeMO 2 structure. Further, the ion-electron mixed structure may include an A n+1 B n O 3n+1 structure.

[0050] ABO 3 In the structure, the A site corresponds to a first chemical element having a first covalent bond radius, and the B site corresponds to a second chemical element having a second covalent bond radius.

[0051] ABO 3 The structure is a cubic crystal structure (i.e., space group

[0052]

Number

[0053] Additional ABO 3 structures may be obtained, where the first chemical element (i.e., the A site) and / or the second chemical element (i.e., the B site) may be A1 x-1 A2 x and / or B1 y-1 B2 y configurations. As a result, the ABO 3 structure may deviate from the cubic crystal structure because the first chemical element (i.e., the A site) and / or the second chemical element (i.e., the B site) can undergo changes in their oxidation states. Furthermore, depending on the temperature, the ABO 3 structure may include other crystal structures, such as orthorhombic, tetragonal, or trigonal.

[0054] In some examples, the first covalent bond radius of the first chemical element (i.e., the A site) may be greater than the second covalent bond radius of the second chemical element (i.e., the B site).

[0055] In particular, in these examples, the first chemical element may be selected from at least one of lanthanum La, calcium Ca, strontium Sr, and barium Ba (see Table 1).

[0056] In addition, in some examples, the second chemical element may be selected from at least one of manganese Mn, chromium Cr, iron Fe, nickel Ni, cobalt Co, and titanium Ti (see Table 1).

[0057] As shown in Table 1, the first chemical element (i.e., the A site) has a first covalent radius that is greater than (or larger than) the second covalent radius of the second chemical element (i.e., the B site). Depending on the molecular shape (e.g., square planar, tetrahedral, octahedral) of the first chemical element and / or the second chemical element, the first chemical element and / or the second chemical element may have different covalent radii. In particular, the first chemical element and / or the second chemical element can have covalent radii depending on the spin state (i.e., high spin or low spin).

[0058] For example, the first covalent radius (i.e., 207 pm) of the lanthanum chemical element (i.e., the A site) is greater than (or larger than) the second covalent radius (i.e., 139 pm) of the chromium chemical element (i.e., the B site). Similarly, the first covalent radius (i.e., 195 pm) of the strontium chemical element (i.e., the A site) is greater than (or larger than) the second covalent radius (i.e., 139 pm) of the chromium chemical element (i.e., the B site).

[0059] Note that the covalent radius parameters listed in Table 1 are parameters that can be retrieved from the paper: Cordero, B. / et al. / Covalent radii revisited,radii revisited. / Dalton Trans / 2832 - 2838(2008)doi:10.1039 / B801115J.

[0060]

Table 1

[0061] In some examples, the stoichiometry of the ABO 3 structure is ABO 3-δ (where δ is between -1 and 1).

[0062] Therefore, the ABO 3 structure may be configured to include oxygen vacancies for conducting oxygen ions, and the ABO 3The structure may be configured to provide electron conduction for conducting electrons. As a result, oxygen ions can be extracted or inserted with respect to the ABO 3 structure. Therefore, oxygen ions can be used as mobile ions. Therefore, oxygen ions can be extracted or inserted into the positive electrode 112 or the negative electrode 114 during charging and / or discharging of the secondary battery 100 at a low temperature, i.e., less than 400 °C, specifically, room temperature to 400 °C, more specifically, 150 °C to 300 °C.

[0063] Further ABO 3 structures can be obtained, where the first chemical element (i.e., the A site) and / or the second chemical element (i.e., the B site) may include the configuration of A1 x-1 A2 x and / or B1 y-1 B2 y As a result, the ABO 3 structure can deviate from the cubic crystal structure because the first chemical element (i.e., the A site) and / or the second chemical element (i.e., the B site) can undergo changes in their oxidation states. Furthermore, depending on the temperature, the ABO 3 structure can include other crystal structures, such as orthorhombic, tetragonal, or trigonal.

[0064] Multiple structures are noted to be obtained from ABO 3 structures (A n+1 B n O 3n+1 , where n = 1, 2, 3). It should be noted that the A n+1 B n O 3n+1 structure can include n ABO 3 structural layers sandwiched between AO rock salt layers. Therefore, the A n+1 B n O 3n+1 structure may be a structure derived from the ABO 3 structure. The A n+1 B n O 3n+1 structure can be an A 2 BO 4 structure (n = 1), and / or an A 3 B2 O 7 Structure (n = 2), and / or A 4 B 3 O 10 It may include Structure (n = 3).

[0065] For example, the positive electrode 112 and / or the negative electrode 114 may include A 2 BO 4 structure. A 2 BO 4 In the BO structure, the A site corresponds to a first chemical element having a first covalent bond radius, and the B site corresponds to a second chemical element having a second covalent bond radius.

[0066] In some examples, the first covalent bond radius of the first chemical element (i.e., the A site) may exceed the second covalent bond radius of the second chemical element (i.e., the B site).

[0067] In particular, in these examples, the first chemical element may be selected from at least one of lanthanum La, calcium Ca, strontium Sr, and barium Ba (see Table 1).

[0068] In some examples, the first chemical element may be further selected from praseodymium Pr and neodymium Nd.

[0069] In addition, in some examples, the second chemical element may be selected from at least one of manganese Mn, chromium Cr, iron Fe, nickel Ni, cobalt Co, and titanium Ti (see Table 1).

[0070] In some examples, the second chemical element may be copper Cu.

[0071] In some examples, A 2 BO 4 The stoichiometry of the structure is A 2 BO 4-δ (where δ is between -1 and 1).

[0072] Therefore, A 2 BO4 The structure may be configured to include oxygen vacancies or oxygen interstitial atoms for conducting oxygen ions, A 2 BO 4 The structure may be configured to provide electronic conduction for conducting electrons. As a result, oxygen ions can be A 2 BO 4 extracted or inserted with respect to the structure. Therefore, oxygen ions can be used as mobile ions. Therefore, oxygen ions can be extracted or inserted with respect to the positive electrode 112 or the negative electrode 114 during charging and / or discharging of the secondary battery 100 at a low temperature, i.e., less than 400°C, specifically, room temperature to 400°C, more specifically, 150°C to 300°C.

[0073] As described above, the positive electrode 112 and / or the negative electrode 114 may include a CeMO 2 structure. In the CeMO 2 structure, Ce is cerium and M is a metal element.

[0074] In some examples, M of the CeMO 2 structure may be selected from at least one of gadolinium Gd, samarium Sm, lanthanum La, calcium Ca, magnesium Mg, praseodymium Pr, and zirconium Zr.

[0075] Therefore, the CeMO 2 structure may be configured to include oxygen vacancies by introducing metal M.

[0076] In some examples, the stoichiometry of the CeMO 2 structure is Ce 1-x M x O 2-δ (where x is between 0 and 1 and δ is between -1 and 1).

[0077] CeMO 2 In the structure, CeMO 2Ce ions in the crystal structure of the structure may be substituted. As a result, deletions may occur in the crystal structure, especially oxygen vacancies. Increasing the substitution of Ce ions with metal ions having a lower valence than the Ce chemical element (for example, Ce 4+ being replaced with La 3+ ) can increase the ionic conductivity of the CeMO 2 structure.

[0078] Therefore, the CeMO 2 structure may thus be configured to include oxygen vacancies for conducting oxygen atoms ions, while the CeMO 2 structure may be configured to provide electronic conduction for conducting electrons. As a result, oxygen ions can be extracted or inserted with respect to the CeMO 2 structure. Therefore, oxygen ions can be used as mobile ions. Therefore, oxygen ions can be extracted or inserted with respect to the positive electrode 112 or the negative electrode 114 during charging and / or discharging of the secondary battery 100 at low temperatures, i.e., less than 400°C, specifically, room temperature to 400°C, more specifically, 150°C to 300°C.

[0079] In some examples, the ion-electron mixed structure of the positive electrode 112 may be a different structure from the ion-electron mixed structure of the negative electrode 114. For example, the positive electrode 112 may be formed from an ABO 3 structure, the negative electrode 114 may be formed from a CeMO 2 structure, or the negative electrode 114 may be formed from an A n+1 B n O 3n+1 structure, particularly an A 2 BO 4 structure (n = 1).

[0080] In some examples, the ion-electron mixed structure of the positive electrode 112 may be the same structure as the ion-electron mixed structure of the negative electrode 114. For example, both the positive electrode 112 and the negative electrode 114 may be formed from an ABO 3 structure, or both may be formed from a CeMO 2 structure. Or both may be An+1 B n O 3n+1 Structure and especially A 2 BO 4 It may be formed from the structure (n = 1).

[0081] In addition, the mixed ion - electron structure of the positive electrode 112 and / or the negative electrode 114 may include a thickness of 1 nm to 1 mm, specifically 100 nm to 1 μm.

[0082] In some examples, the electrode 110 including the positive electrode 112 and the negative electrode 114 can be deposited via conventional synthesis and deposition methods such as physical vapor deposition (PVD), for example, cathodic arc deposition, electron beam physical vapor deposition, close - space sublimation, pulsed laser deposition, etc.; thermal evaporation; electron beam evaporation; sputtering, for example, diode sputtering, RF diode sputtering, triode sputtering, magnetron sputtering, reactive sputtering, or ion beam sputtering; ion - assist deposition; chemical vapor deposition (CVD); sol - gel coating; or atomic layer deposition (ALD), etc.

[0083] Referring to FIG. 1, the positive electrode 112 is configured to contact the solid electrolyte 120. Also, the negative electrode 114 is configured to contact the solid electrolyte 120.

[0084] The solid electrolyte 120 may provide oxygen - ion - conducting ionic conduction (i.e., having an ionic conductivity σ greater than 10 -6 S / m), while the solid electrolyte 120 may be an electronic insulator (i.e., having a conductivity σ less than 10 -4 S / m). In particular, the solid electrolyte 120 that conducts oxygen ions may include doped ZrO 2 or doped CeO 2 and may contain them.

[0085] In some examples, doped ZrO 2 and / or doped CeO 2It may contain a dopant selected from at least one of gadolinium Gd, samarium Sm, scandium Sc, lanthanum La, calcium Ca, magnesium Mg, and yttrium Y.

[0086] ZrO 2 and / or CeO 2 The addition of hetero-valence dopants (i.e., dopants having a valence different from that of zirconium and / or cerium) to ZrO 2 and / or doped CeO 2 can generate oxygen vacancies in the crystal structure. These oxygen vacancies can provide ionic conductivity for conducting oxygen ions.

[0087] The solid electrolyte and the ion and electron mixed structure may be selected to achieve an operating temperature of less than 400 °C, specifically from room temperature to 400 °C, more specifically from 150 °C to 300 °C.

[0088] In some examples, the solid electrolyte 120 can have a thickness of 1 nm to 1 mm, specifically 100 nm to 1 μm.

[0089] In some examples, the solid electrolyte 120 can be deposited via conventional synthesis and deposition methods such as physical vapor deposition (PVD), such as cathodic arc deposition, electron beam physical vapor deposition, proximity space sublimation, pulsed laser deposition; thermal evaporation; electron beam evaporation; sputtering, such as diode sputtering, RF diode sputtering, triode sputtering, magnetron sputtering, reactive sputtering, or ion beam sputtering; ion assist deposition; chemical vapor deposition (CVD); sol-gel coating; or atomic layer deposition (ALD).

[0090] In some examples, the secondary battery 100 may further include a current collector. In particular, the current collector is a conductor (conductivity σ is 10 1It may also be greater than S / m. Further, the current collector may be configured to contact the positive electrode 112 to collect charges (e.g., electrons) from the positive electrode 112, or may be configured to contact the negative electrode 114 to collect charges (e.g., electrons) from the negative electrode 114. Therefore, the current collector can collect charges from at least one of the electrodes 110.

[0091] In these examples, the current collector may be a metal. The metal of the current collector may be selected from at least one of gold Au; nickel Ni; copper Cu; platinum Pt; palladium Pd; or any combination thereof.

[0092] In some of these examples, the metal current collector may further include a first current collector and a second current collector. The first current collector may be configured to contact the positive electrode 112. Therefore, the first current collector may transport charges (e.g., electrons) from the positive electrode 112. The second current collector may be configured to contact the negative electrode 114. Therefore, the second current collector may transport charges (e.g., electrons) from the negative electrode 114.

[0093] In some examples, the current collector may have a thickness of 1 nm to 1 mm, specifically 100 nm to 1 μm.

[0094] In some examples, the current collector can be deposited via conventional synthesis and deposition methods such as physical vapor deposition (PVD), such as cathodic arc deposition, electron beam physical vapor deposition, close sublimation, pulsed laser deposition; thermal evaporation; electron beam evaporation; sputtering, such as diode sputtering, RF diode sputtering, triode sputtering, magnetron sputtering, reactive sputtering, or ion beam sputtering; ion assist deposition; chemical vapor deposition (CVD); sol-gel coating; or atomic layer deposition (ALD).

[0095] In some examples, the secondary battery 100 may further include an insulating layer. The insulating layer is alumina Al 2 O 3and / or zirconia ZrO 2 may be made from. Alumina Al 2 O 3 and zirconia ZrO 2 can be an electrical insulator (i.e., having a conductivity σ of less than 10 -4 S / m).

[0096] In these examples, zirconia ZrO 2 is not doped. Thus, zirconia ZrO 2 may not exhibit ionic conductivity and may not conduct oxygen ions.

[0097] Therefore, an insulating layer made of alumina Al 2 O 3 and / or zirconia ZrO 2 can prevent leakage of oxygen ions from the electrodes 110 (e.g., the positive electrode 112, the negative electrode 114). As a result, self-discharge due to the solid-gas reaction of the secondary battery 100 can be prevented. 2 O 3 and / or zirconia ZrO 2 may not be able to conduct oxygen ions, so it can prevent leakage of oxygen ions from the electrodes 110 (e.g., the positive electrode 112, the negative electrode 114, or the current collector). As a result, self-discharge due to the solid-gas reaction of the secondary battery 100 can be prevented.

[0098] Also, the insulating layer may be disposed on at least one of the electrodes 110 (e.g., the positive electrode 112, the negative electrode 114, or the current collector). Note that the insulating layer may be disposed on any of the positive electrode 112, the negative electrode, or the current collector. In some of these examples, the insulating layer is disposed on the positive electrode 112.

[0099] In some examples, the insulating layer or the electron insulating layer may be disposed on each electrode. Thus, both electrodes (e.g., the positive electrode 112, the negative electrode 114, the current collector) may be in contact with the insulating layer.

[0100] In some examples, the insulating layer may have a thickness of 1 nm to 1 mm.

[0101] In some examples, the insulating layer can be deposited via conventional synthesis and deposition methods such as physical vapor deposition (PVD), such as cathodic arc deposition, electron beam physical vapor deposition, close - space sublimation, pulsed laser deposition; thermal evaporation; electron beam evaporation; sputtering, such as diode sputtering, RF diode sputtering, triode sputtering, magnetron sputtering, reactive sputtering, or ion beam sputtering; ion - assist deposition; chemical vapor deposition (CVD); sol - gel coating; or atomic layer deposition (ALD).

[0102] Figure 2 shows an example of a secondary battery 100. In Figure 2, the secondary battery 100 includes a positive electrode 112, a negative electrode 114, a solid electrolyte 120, a current collector 130, and an insulating layer 140. These elements may be according to any of the embodiments disclosed herein. For example, these elements may correspond to the description with reference to Figure 1.

[0103] In Figure 2, the positive electrode 112 may be configured to contact the solid electrolyte. The negative electrode 114 may be configured to contact the solid electrolyte 120.

[0104] In addition, in Figure 2, the current collector 130 further includes a first current collector 132 configured to contact the positive electrode 112 and a second current collector 134 configured to contact the negative electrode 114. Thereby, the first current collector 132 may collect charges (e.g., electrons) from the positive electrode 112. Similarly, the second current collector 134 may collect charges (e.g., electrons) from the negative electrode 114.

[0105] Furthermore, in Figure 2, the insulating layer 140 is configured to contact the current collector 130.

[0106] In Figure 2, the insulating layer 140 further includes a first insulating layer 142 and a second insulating layer 144. In particular, the first insulating layer 142 is configured to contact the first current collector 132. Also, the second insulating layer 144 is configured to contact the second current collector 134.

[0107] Figure 3 shows the operation of a secondary battery during discharge according to an embodiment of the present disclosure. In Figure 3, the secondary battery 100 includes a positive electrode 112, a negative electrode 114, and a solid electrolyte 120. These elements may be according to any of the embodiments disclosed herein. For example, these elements may correspond to the description with reference to Figure 1.

[0108] As described in the description with reference to FIG. 1 and / or FIG. 2, ABO 3 structure, A n+1 B n O 3n+1 structure, A 2 BO 4 structure, and CeMO 2 structure may include oxygen vacancies. Therefore, ABO 3 structure, A n+1 B n O 3n+1 structure, A 2 BO 4 structure, and CeMO 2 structure may provide ion conduction for conducting oxygen ions. In particular, oxygen ions can be inserted and / or extracted with respect to the electrode 110 (for example, the positive electrode 112, the negative electrode 114).

[0109] Also, ABO 3 structure, A n+1 B n O 3n+1 structure, A 2 BO 4 structure, and CeMO 2 structure may further provide electron conduction for conducting charges.

[0110] In FIG. 3, the positive electrode 112 and the negative electrode 114 are connected via an external circuit 150 (for example, an electrical device and a connector for connecting the electrical device to the secondary battery 100). Therefore, the secondary battery is discharging. As a result, oxygen ions can be extracted from the positive electrode 112. The solid electrolyte 120 configured to contact the positive electrode 112 can conduct the extracted oxygen ions from the positive electrode 112 to the negative electrode 114. Therefore, the extracted oxygen ions can be inserted into the negative electrode 114. In addition, charges (for example, electrons) can be conducted from the negative electrode 114 to the positive electrode 112 via the external circuit 150.

[0111] Oxygen ion conduction is the movement from crystal lattice site to crystal lattice site in the crystal lattice of the ABO 3 structure, or from crystal lattice site to crystal lattice site in the crystal lattice of the A n+1 B n O 3n+1 structure, or from crystal lattice site to crystal lattice site in the crystal lattice of the A 2 BO 4 structure, or from crystal lattice site to crystal lattice site in the crystal lattice of the CeMO 2 structure, and can be the result of thermally activated hopping of oxygen ions.

[0112] By selecting the solid electrolyte 120 for oxygen ion conduction and also the ABO 3 structure and / or the CeMO 2 structure as the electrode 110, an operating temperature of less than 400° C., specifically between room temperature and 400° C., more specifically between 150° C. and 300° C. can be achieved.

[0113] Similarly, by selecting the solid electrolyte 120 for oxygen ion conduction and also the ABO 3 structure and / or the CeMO 2 structure, and / or the A n+1 B n O 3n+1 structure as the electrode 110, an operating temperature of less than 400° C., specifically between room temperature and 400° C., more specifically between 150° C. and 300° C. can be achieved.

[0114] In some examples, the operating temperature of the secondary battery 100 may be from 150°C to 400°C. In particular, when the solid electrolyte 120 can have a thickness exceeding 10 μm, the operating temperature can be between 150°C and 400°C.

[0115] The conduction of oxygen ions and charges (e.g., electrons) can involve redox electrochemical reactions. The redox couple of the electrode 110 can define the voltage of the secondary battery 100.

[0116] During discharge, the negative electrode 114 can be oxidized during the electrochemical reaction. Further, the negative electrode 114 can supply charges (e.g., electrons) to the external circuit 150. Further, the ABO 3 structure and / or the stoichiometry of the CeMO 2 structure may be changed. Similarly, the n+1 A n B 3n+1 O 2 stoichiometry of the structure can be changed. For example, the 4 oxygen stoichiometry of the ABO

[0117] During discharge, the positive electrode 112 can be reduced during the electrochemical reaction. In addition, the external circuit 150 can provide charges (e.g., electrons) to the positive electrode 112. Further, the ABO 3 structure and / or the stoichiometry of the CeMO 2 structure may be changed.

[0118] Conversely, under an external electric field (i.e., when the secondary battery 100 is being charged), oxygen ions can be extracted from the negative electrode 114. The solid electrolyte 120 configured to contact the negative electrode 114 can conduct the extracted oxygen ions from the negative electrode 114 to the positive electrode 112. Therefore, the extracted oxygen ions can be inserted into the positive electrode 112.

[0119] For example, in the case of the ABO 3 structure, the reaction can be as follows.

[0120]

Equation

[0121] In this example, site A contains lanthanum La and strontium Sr.

[0122] In some examples, site B may contain iron Fe. Therefore, electrochemical oxidation and reduction (Fe 3+ / Fe 4+ ) can occur reversibly during the extraction and / or insertion of oxygen ions.

[0123] In these examples, depending on the oxygen stoichiometry of the ABO 3 structure, the redox couples involved in the electrochemical reaction can be the Fe 3+ / Fe 4+ couple and / or the Fe 3+ / Fe 2+ couple.

[0124] FIG. 4 shows a plurality of curves of the secondary battery 100 at temperatures from 373K to 673K as a function of power density, energy density, and electrode thickness according to an example of the present disclosure.

[0125] FIG. 4 represents a plurality of curves of the secondary battery 100 charged at a 5C rate according to temperature. In FIG. 4, the x-axis corresponds to the thickness of the electrode (unit: μm), and the y-axis corresponds to the power density (μW / cm 2 ) and the energy density (mJ / cm 2 ).

[0126] In FIG. 4, the plurality of curves rise from the initial power density (0 μW / cm 2 ) or the initial energy density (0 J / cm 2 ) to the (relative) maximum power density or the (relative) maximum energy density. Thereafter, the plurality of curves decrease from the (relative) maximum power density or the (relative) maximum energy density to the initial power density (0 μW / cm 2 ) or the initial energy density (0 mJ / cm 2 ). Note that it should be noted that the power density value or the energy density value depends on the temperature and the electrode thickness of the secondary battery 100.

[0127] Specifically, in FIG. 4, the secondary battery 100 includes a LaSrCrO 3 (LsCR) positive electrode, a cerium oxide samarium-doped (SDS) solid electrolyte, and a LaSrFeO 3 (LSF) negative electrode. These elements may be according to any of the embodiments disclosed herein. For example, these elements may correspond to the description with reference to FIG. 1. In this example, the cerium oxide samarium-doped (SDS) solid electrolyte includes a thickness of 100 nm.

[0128] In FIG. 4, the curve 400 represents the curve of the secondary battery 100 at a temperature of 373 K (i.e., 100 °C). In particular, the (relative) maximum power density is about 0.035 μW / cm 2 and the (relative) maximum energy density is about 0.02 mJ / cm 2 . At the (relative) maximum power density and / or the (relative) maximum energy density, the electrode thickness is 0.0002 μm.

[0129] In FIG. 4, the curve 402 represents the curve of the secondary battery 100 at a temperature of 423 K (i.e., 150 °C). In particular, the (relative) maximum power density is about 0.3 μW / cm 2 and the (relative) maximum energy density is about 0.2 mJ / cm 2 . At the (relative) maximum power density and / or the (relative) maximum energy density, the electrode thickness is 0.004 μm.

[0130] In FIG. 4, the curve 404 represents the curve of the secondary battery 100 at a temperature of 473 K (i.e., 200 °C). In particular, the (relative) maximum power density is about 2.1 μW / cm 2 and the (relative) maximum energy density is about 1.5 mJ / cm 2 . At the (relative) maximum power density and / or the (relative) maximum energy density, the electrode thickness is 0.03 μm.

[0131] In FIG. 4, curve 406 represents the curve of the secondary battery 100 at a temperature of 523 K (i.e., 250 °C). In particular, the (relative) maximum power density is about 9.1 μW / cm 2 and the (relative) maximum energy density is about 6.9 mJ / cm 2 At the (relative) maximum power density and / or the (relative) maximum energy density, the electrode thickness is 0.14 μm.

[0132] In FIG. 4, curve 408 represents the curve of the secondary battery 100 at a temperature of 573 K (i.e., 300 °C). In particular, the (relative) maximum power density is about 35.1 μW / cm 2 and the (relative) maximum energy density is about 25.1 mJ / cm 2 At the (relative) maximum power density and / or the (relative) maximum energy density, the electrode thickness is 0.51 μm.

[0133] In FIG. 4, curve 410 represents the curve of the secondary battery 100 at a temperature of 623 K (i.e., 350 °C). In particular, the (relative) maximum power density is about 103.4 μW / cm 2 and the (relative) maximum energy density is about 75.1 mJ / cm 2 At the (relative) maximum power density and / or the (relative) maximum energy density, the electrode thickness is 1.5 μm.

[0134] In FIG. 4, curve 412 represents the curve of the secondary battery 100 at a temperature of 673 K (i.e., 400 °C). In particular, the (relative) maximum power density is about 255.7 μW / cm 2 and the (relative) maximum energy density is about 184.8 mJ / cm 2 At the (relative) maximum power density and / or the (relative) maximum energy density, the electrode thickness is 3.75 μm.

[0135] In summary, FIG. 4 shows that the power density value or the energy density value depends on the temperature and the electrode thickness (e.g., the electrode thickness of the positive electrode and / or the electrode thickness of the negative electrode) of the secondary battery 100.

[0136] FIG. 5 shows a plurality of charge curves 500 and a plurality of discharge curves 510 of the secondary battery 100 according to an example of the present disclosure. In FIG. 5, the secondary battery 100 includes a La 0.5 Sr 0.5 Cr 0.2 Mn 0.8 O 3 (LSCrMn) positive electrode, a Y-doped ZrO 2 solid electrolyte, and a La 0.6 Sr 0.4 FeO 3 (LSF) negative electrode. These elements may be according to any of the embodiments disclosed herein. For example, these elements may correspond to the description with reference to FIG. 1. In this embodiment, the Y-doped ZrO 2 solid electrolyte is ZrO 2 O 3 doped with 9.5 mol% of Y 2 . Also, the thickness of the Y-doped ZrO 2 includes 0.5 mm. Also, the thickness of the La 0.5 Sr 0.5 Cr 0.2 Mn 0.8 O 3 (LSCrMn) positive electrode includes 240 nm, and the thickness of the La 0.6 Sr 0.4 FeO 3 (LSF) negative electrode includes 400 nm. The plurality of charge curves 500 and the plurality of discharge curves 510 of the secondary battery 100 provided in this example were measured at 350° C. at an oxygen partial pressure of 0.25 mbar at a 1.5 C rate (i.e., 5 μA in this example).

[0137] In FIG. 5, the plurality of charge curves 500 and the plurality of discharge curves 510 are shown as a function of the cell voltage (V) and as a function of the specific charge (C / cm 3 ).

[0138] In FIG. 5, the x-axis corresponds to the specific charge (C / cm 3 ), and the y-axis corresponds to the cell voltage (V).

[0139] Note that in FIG. 5, the cell voltage is about 0.8V. In addition, the specific charge of the first cycle discharge curve 512 is about 245 C / cm 3 . Further, the specific charge of the discharge curve 514 at the 9th cycle is about 240 C / cm 3 . As a result, there is a difference of about 2% between the specific charge of the 9th cycle discharge curve 514 and the specific charge of the first cycle discharge curve 512. Therefore, a secondary battery 100 with improved cycle characteristics can be obtained.

[0140] Note that similar results can be observed for a plurality of charge curves 500.

[0141] FIG. 6 shows a flowchart of a method for forming the secondary battery 100.

[0142] In block 600, a solid electrolyte according to any of the examples disclosed herein is deposited by conventional synthesis and deposition methods (e.g., thin film deposition methods).

[0143] In block 610, a positive electrode and / or a negative electrode is formed on the solid electrolyte. The positive electrode and / or the negative electrode may be according to any of the examples disclosed herein. The positive electrode and the negative electrode are such that the A site corresponds to a first chemical element having a first covalent bonding radius, and the B site corresponds to a second chemical element having a second covalent bonding radius, and is an ABO 3 structure, and / or a CeMO where Ce is cerium and M is a metal 2 structure.

[0144] In some examples, the method for forming the secondary battery 100 may further include depositing a current collector on the positive electrode and / or the negative electrode.

[0145] In some examples, the method for forming the secondary battery 100 may further include depositing an insulating layer disposed on at least one of the electrodes.

[0146] In these examples, depositing the insulating layer may include depositing the insulating layer on the positive electrode and / or the negative electrode.

[0147] In some of these examples, depositing the insulating layer may include depositing the insulating layer on the current collector.

[0148] For the sake of completeness, various aspects of the present disclosure are described in the following numbered clauses. 1. A secondary battery, a solid electrolyte that conducts oxygen ions, a positive electrode configured to contact the solid electrolyte, a negative electrode configured to contact the solid electrolyte, comprising wherein the positive electrode and the negative electrode include an ion-electron mixed structure for conducting oxygen ions and electrons, the ion-electron mixed structure wherein the A site corresponds to a first chemical element having a first covalent radius, and the B site corresponds to a second chemical element having a second covalent radius, an ABO 3 structure, and / or where Ce is cerium and M is a metal, a CeMO 2 structure, a secondary battery comprising. 2. The secondary battery according to clause 1, wherein the solid electrolyte and the mixed ion-electron structure are selected to achieve an operating temperature of room temperature to 400 °C. 3. The secondary battery according to clause 1 or 2, wherein the first covalent radius of the first chemical element is greater than the second covalent radius of the second chemical element. 4. The secondary battery according to any one of clauses 1 to 3, wherein the first chemical element is selected from at least one of lanthanum La, calcium Ca, strontium Sr, and barium Ba. 5. The secondary battery according to any one of clauses 1 to 4, wherein the second chemical element is selected from at least one of manganese Mn, chromium Cr, iron Fe, nickel Ni, cobalt Co, and titanium Ti. 6. The stoichiometry of the ABO 3 structure is ABO3-δ (where δ is between -1 and 1), the secondary battery according to any one of clauses 1 to 5. 7.CeMO 2 For the M in the structure, at least one selected from gadolinium (Gd), samarium (Sm), lanthanum (La), calcium (Ca), magnesium (Mg), praseodymium (Pr), and zirconium (Zr), the secondary battery according to any one of clauses 1 to 6. 8.CeMO 2 The stoichiometry of the structure is Ce 1-x M x O 2-δ (where x is between 0 and 1 and δ is between -1 and 1), the secondary battery according to any one of clauses 1 to 7. 9. The secondary battery according to any one of clauses 1 to 8, wherein the ion-electron mixed structure of the positive electrode and the ion-electron mixed structure of the negative electrode have the same structure. 10. The secondary battery according to any one of clauses 1 to 8, wherein the mixed ion-electron structure of the positive electrode is different from the mixed ion-electron structure of the negative electrode. 11. The secondary battery according to any one of clauses 1 to 10, wherein the mixed ion-electron structure of the positive electrode and / or the negative electrode has a thickness of 1 nm to 1 mm, specifically 100 nm to 1 μm. 12. The oxygen ion conductive solid electrolyte contains doped ZrO 2 or doped CeO 2 , the secondary battery according to any one of clauses 1 to 11. 13. The doped ZrO 2 and / or the doped CeO 2 contains a dopant selected from at least one of gadolinium (Gd), samarium (Sm), scandium (Sc), lanthanum (La), calcium (Ca), magnesium (Mg), and yttrium (Y), the secondary battery according to clause 11. 14. The secondary battery according to any one of clauses 1 to 10, wherein the solid electrolyte has a thickness of 1 nm to 1 mm, specifically 100 nm to 1 μm. 15. Further comprising a current collector, and the current collector is a positive electrode for collecting charges from the positive electrode, or The secondary battery according to any one of clauses 1 to 12, which is configured to contact a negative electrode for collecting charges from the negative electrode. 16. The current collector comprises a first current collector configured to contact the positive electrode, and a second current collector configured to contact the negative electrode, the secondary battery according to clause 13. 17. The current collector is a metal, the secondary battery according to clause 15 or 16. 18. The metal of the current collector is selected from at least one of gold Au, nickel Ni, copper Cu, platinum Pt, palladium Pd, or any combination thereof, the secondary battery according to clause 17. 19. The current collector has a thickness of 1 nm to 1 mm, specifically 100 nm to 1 μm, the secondary battery according to any one of clauses 15 to 18. 20. The secondary battery according to any one of clauses 1 to 19, further comprising an electron insulating layer disposed on at least one of the electrodes. 21. The electron insulating layer is zirconia dioxide ZrO 2 or alumina Al 2 O 3 and is made therefrom, the secondary battery according to clause 20. 22. When dependent on clauses 15 to 19, the electron insulating layer is configured to contact the current collector, the secondary battery according to clause 20 or 21. 23. The electron insulating layer has a thickness of 1 nm to 1 mm, the secondary battery according to any one of clauses 20 to 22. 24. A method of forming a secondary battery, comprising depositing a solid electrolyte, and forming a positive electrode and a negative electrode on the solid electrolyte, the positive electrode and the negative electrode including an ion-electron mixed structure for conducting oxygen ions and electrons. The ion-electron mixed structure is where the A site corresponds to a first chemical element having a first covalent bonding radius and the B site corresponds to a second chemical element having a second covalent bonding radius, an ABO 3 structure, and / or Ce is cerium and M is a metal, CeMO 2 structure, A method comprising. 25. The method according to clause 24, further comprising depositing a current collector on the positive electrode and / or the negative electrode. 26. Depositing the current collector comprises forming a first current collector on the positive electrode and forming a second current collector on the negative electrode, the method according to clause 25. 27. The method according to any one of clauses 24 to 26, further comprising depositing an electron insulating layer disposed on at least one of the electrodes. 28. Depositing the electron insulating layer comprises depositing an electron insulating layer on the positive electrode and / or the negative electrode, the method according to clause 27. 29. When dependent on clause 25 or 26, depositing the electron insulating layer comprises depositing an electron insulating layer on the current collector, the method according to clause 27. 30. A secondary battery a solid electrolyte that conducts oxygen ions, a positive electrode configured to contact the solid electrolyte, a negative electrode configured to contact the solid electrolyte, the positive electrode and the negative electrode include an ion-electron mixed structure for conducting oxygen ions and electrons, the ion-electron mixed structure where the A site corresponds to a first chemical element having a first covalent bond radius and the B site corresponds to a second chemical element having a second covalent bond radius, ABO 3 structure, and / or A n+1 B n O 3n+1 structure (where n corresponds to 1, 2, or 3), and the A site corresponds to a first chemical element having a first covalent bond radius and the B site corresponds to a second chemical element having a second covalent bond radius, A n+1 Bn O 3n+1 structure, and / or where Ce is cerium and M is a metal, CeMO 2 structure, is included. 31. The secondary battery according to clause 30, wherein the solid electrolyte and the mixed ion electron structure are selected to achieve an operating temperature of room temperature to 400°C. 32. The secondary battery according to clause 30 or 31, wherein the first covalent bond radius of the first chemical element is greater than the second covalent bond radius of the second chemical element. 33. The secondary battery according to any one of clauses 30 to 32, wherein the first chemical element is selected from at least one of lanthanum La, calcium Ca, strontium Sr, and barium Ba. 34. The secondary battery according to any one of clauses 30 to 33, wherein the second chemical element is selected from at least one of manganese Mn, chromium Cr, iron Fe, nickel Ni, cobalt Co, and titanium Ti. 35. n corresponds to 2, and A n+1 B n O 3n+1 structure is A 2 BO 4 for the secondary battery according to any one of clauses 30 to 34. 36. The stoichiometry of the A 2 BO 4 structure is A 2 BO 4-δ (where δ is between -1 and 1) for the secondary battery according to clause 35. 37. The secondary battery according to any one of clauses 20 to 23, wherein the electron insulating layer is disposed on the positive electrode. 38. The secondary battery according to any one of clauses 20 to 23, wherein the electron insulating layer is disposed on the negative electrode. 39. The secondary battery according to any one of clauses 20 to 23, wherein the electron insulating layer is disposed on both electrodes. 40. Further comprising a current collector, the current collector being a positive electrode for collecting charges from the positive electrode, or A secondary battery according to any one of clauses 30 to 36, configured to contact a negative electrode for collecting charge from the negative electrode. 41. The current collector comprises a first current collector configured to contact the positive electrode, and a second current collector configured to contact the negative electrode, the secondary battery according to clause 40. 42. A secondary battery according to any one of clauses 30 to 36, 40, or 41, further comprising an insulating layer disposed on at least one of the electrodes. 43. The secondary battery according to clause 42, wherein the insulating layer is disposed on the positive electrode. 44. The secondary battery according to clause 42, wherein the insulating layer is disposed on the negative electrode. 45. The secondary battery according to clause 42, wherein the insulating layer is disposed on both electrodes. 46. When dependent on clause 40 or 41, the secondary battery according to clause 42, wherein the insulating layer is configured to contact the current collector. 47. The secondary battery according to any one of clauses 40 to 46, wherein the insulating layer is an electron insulating layer.

[0149] Only some examples are disclosed in this specification, but other alternatives, modifications, uses, and / or their equivalents are possible. Further, all possible combinations of the described examples are also covered. Therefore, the scope of the present disclosure should not be limited by specific examples, but should be determined only by fairly reading the following claims. In the claims, if reference signs related to the drawings are described in parentheses, they are only for enhancing the understanding of the claims and should not be construed as limiting the claims.

Claims

1. It is a secondary battery, A solid electrolyte that conducts oxygen ions, A positive electrode configured to contact the solid electrolyte, A negative electrode configured to contact the solid electrolyte, Equipped with, The positive electrode and the negative electrode include an ion-electron mixed structure for conducting oxygen ions and electrons. The aforementioned ionic electronic mixed structure is ABO, where site A corresponds to a first chemical element having a first covalent radius, and site B corresponds to a second chemical element having a second covalent radius. ３ structure, and / or Ce is cerium and M is a metal, so CeMO ２ structure, Includes, The secondary battery is characterized by comprising an insulating layer configured to prevent oxygen leakage, and the insulating layer being placed on the positive electrode.

2. The secondary battery according to claim 1, wherein the first covalent radius of the first chemical element is greater than the second covalent radius of the second chemical element.

3. The secondary battery according to claim 1 or 2, wherein the first chemical element is selected from at least one of lanthanum (La), calcium (Ca), strontium (Sr), and barium (Ba).

4. The secondary battery according to claim 1, wherein the second chemical element is selected from at least one of manganese (Mn), chromium (Cr), iron (Fe), nickel (Ni), cobalt (Co), and titanium (Ti).

5. The aforementioned ABO ３ The stoichiometry of structures is ABO ３－δ The secondary battery according to claim 1, wherein δ is between -1 and 1 in the formula.

6. The aforementioned CeMO ２ The secondary battery according to claim 1, wherein the structure M is selected from at least one of gadolinium Gd, samarium Sm, lanthanum La, calcium Ca, magnesium Mg, praseodymium Pr, and zirconium Zr.

7. The above CeMO ２ The stoichiometry of the structure is Ce １－ｘ M ｘ O ２－δ (where x is between 0 and 1 and δ is between -1 and 1), the secondary battery according to claim 1.

8. The solid electrolyte that conducts oxygen ions is doped ZrO ２ or doped CEO ２ A secondary battery according to claim 1, including the following:

9. The aforementioned doped Zro ２ and / or the doped CeO ２ The secondary battery according to claim 8, wherein the dopant comprises a dopant selected from at least one of gadolinium Gd, samarium Sm, scandium Sc, lanthanum La, calcium Ca, magnesium Mg, and yttrium Y.

10. The secondary battery according to claim 1, wherein the solid electrolyte has a thickness of 1 nm to 1 mm, specifically 100 nm to 1 μm.

11. The current collector is further comprising, The positive electrode for collecting charge from the positive electrode, or The negative electrode for collecting charge from the negative electrode, A secondary battery according to claim 1, configured to be in contact with a device.

12. The aforementioned current collector is A first current collector configured to contact the positive electrode, A second current collector configured to contact the negative electrode, A secondary battery according to claim 11, including the following:

13. The insulating layer is zirconia dioxide ZrO ２ or alumina Al ２ O ３ A secondary battery according to claim 1, manufactured from the above.

14. The secondary battery according to claim 13, wherein, in the case of a dependency of claim 11, the insulating layer is configured to be in contact with the current collector.

15. The secondary battery according to claim 1, wherein the insulating layer has a thickness of 1 nm to 1 mm.

16. The secondary battery according to claim 1, wherein the insulating layer is an electronic insulating layer.

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