All-solid-state hydride ion battery and method for manufacturing the same
Patent Information
- Application Number
- JP2026518460
- Authority / Receiving Office
- JP · JP
- Patent Type
- Applications
- Current Assignee / Owner
- Priority Date
- 2023-09-28
- Filing Date
- 2023-12-09
- Publication Date
- 2026-09-30
AI Technical Summary
【0040】 本出願が生み出しうる有益な効果は以下の通りである。
Smart Images
Figure 2026532650000001_ABST
Abstract
Description
[Technical Field]
[0001] This application relates to an all-solid-state hydride ion battery and a method for manufacturing the same, and belongs to the field of clean energy technology. [Background technology]
[0002] Energy plays a crucial role in driving human society and is therefore an indispensable condition for scientific and technological progress and social development. Energy storage technology is of great significance as an important part of how humanity can efficiently utilize energy. Secondary batteries offer advantages such as high efficiency, safety, environmental protection, high energy storage density, and high recyclability, making them the optimal choice for current energy storage devices. Currently, secondary batteries have evolved into various types, including lead-acid batteries, nickel-metal hydride batteries, lithium batteries, as well as redox flow batteries, sodium batteries, and magnesium batteries. Each type of electrochemical energy storage device is limited by the properties of its materials, resulting in different application scenarios. Developing entirely new battery systems can significantly expand the range of applications for electrochemical energy storage.
[0003] When forming compounds, the element hydrogen can very easily lose one electron to become a proton, or gain one electron to become a hydride ion. - Ions are F - , O 2- Similar to the above, it has a larger radius, but contains only one valence electron, resulting in a lower charge density and greater polarization. This differs significantly from proton conduction in materials, where the proton charge density is very high, and in oxides, it often strongly bonds with O, resulting in a high activation energy. Furthermore, the standard redox potential of the hydride ion is -2.3V, which is close to that of the magnesium ion (-2.4V), but its atomic mass is only 1 / 24th that of magnesium, making it promising as an ion conductor material for next-generation high-energy-density, high-potential batteries. -Research into applying high-speed ion conduction to batteries is expected to bring about innovations in electrochemical energy storage technology.
[0004] Several ionic conductors have been reported that could potentially be used as electrolytes in hydride-ion batteries, and they can be broadly classified into two categories. One category is alkaline earth metal-based, including binary hydrides, oxyhydrides, and hydride halides. The other category is rare earth metal-based, mainly oxyhydrides and pure rare earth metal hydrides. However, there are currently no reports of hydride-ion batteries that can withstand repeated charging and discharging cycles. [Overview of the Initiative]
[0005] The all-solid-state hydride-ion battery disclosed in this application can achieve reversible charging and discharging at room temperature. As a completely new electrochemical energy storage device, this invention expands the research framework for electrochemical energy storage and has extremely great applied value.
[0006] The present invention discloses a novel rechargeable hydride ion all-solid-state battery. Specifically, the hydride ion all-solid-state battery includes a positive electrode current collector, a positive electrode active material layer, a hydride ion solid electrolyte, a negative electrode active material layer, and a negative electrode current collector. The negative electrode active material layer contains a metal or a metal hydride with a low hydrogen content, the positive electrode active material layer contains a metal hydride with a high hydrogen content, and the solid electrolyte layer conducts hydride ions.
[0007] According to one aspect of this application, an all-solid-state hydride-ion battery is provided, the all-solid-state hydride-ion battery comprising, in the direction from the positive electrode to the negative electrode, a positive electrode current collector, a positive electrode active material layer, a hydride ion electrolyte layer, a negative electrode active material layer, and a negative electrode current collector in this order. The hydride ion electrolyte layer is a hydride containing rare earth metal elements. The all-solid-state hydride-ion battery is a rechargeable battery.
[0008] Optionally, the all-solid-state hydride ion battery comprises hydride ions (H -The movement of ) enables charging and discharging, and the hydride ion solid electrolyte generates hydride ions (H) inside the battery. - It is used to conduct electricity.
[0009] Optionally, the rare earth metal element includes at least one selected from scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, and lutetium.
[0010] Optionally, the hydride ion electrolyte layer may be selected from rare earth metal hydrides or may contain a portion of rare earth metal hydrides.
[0011] Here, the rare earth metals include at least one selected from scandium (Sc), yttrium (Y), lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), and lutetium (Lu).
[0012] The thickness of the hydride ion electrolyte layer is optionally 0.1 μm to 10 mm.
[0013] Optionally, the thickness of the hydride ion electrolyte layer may be independently selected from any value among 0.1 μm, 0.2 μm, 0.5 μm, 1 μm, 10 μm, 100 μm, 1 mm, 5 mm, and 10 mm, or from a range between any two of these values.
[0014] The thicknesses of the positive electrode active material layer and the negative electrode active material layer are optionally selected independently from 0.2 μm to 1 mm.
[0015] Optionally, the thicknesses of the positive electrode active material layer and the negative electrode active material layer are independently selected from any value among 0.2 μm, 0.5 μm, 1 μm, 10 μm, 100 μm and 1 mm, or a value within a range between any two of these values.
[0016] Optionally, the negative electrode active material layer comprises one type of metal selected from the group consisting of Group IA, Group IIA, Group IIIB, Group IVB and Group VB metals.
[0017] Optionally, the metal in the negative electrode active material layer is a metal of main group elements of Group 1 and Group 2, and a metal of subgroup elements of Group 3, Group 4 and Group 5, and alloys thereof.
[0018] Optionally, the negative electrode active material layer comprises a metal or a hydride with low hydrogen content.
[0019] Optionally, the positive electrode active material layer comprises a hydride with high hydrogen content.
[0020] Optionally, the negative electrode active material layer comprises a metal or a metal hydride with low hydrogen content, and the hydrogen content of the metal hydride with low hydrogen content is 0 to 50% of that in a saturated hydrogenation state.
[0021] Optionally, the positive electrode active material comprises a metal hydride with high hydrogen content, the hydrogen content of the metal hydride with high hydrogen content is 50 to 100% of that in a saturated hydrogenation state, and the relative hydrogen content of the selected low hydrogen content hydride is lower than that of the high hydrogen content metal hydride.
[0022] Optionally, the metals in the metal hydride with low hydrogen content and the metal hydride with high hydrogen content are each independently one selected from the group consisting of Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Pd and Al.
[0023] Optionally, the positive electrode current collector and the negative electrode current collector are independently selected from at least one of gold, silver, copper, palladium, platinum, iron, titanium, cobalt, nickel, and aluminum.
[0024] According to another aspect of this application, a method for manufacturing the above-mentioned all-solid-state hydride-ion battery is provided, wherein the positive electrode active material layer, the hydride-ion electrolyte layer, and the negative electrode active material layer are manufactured by one of the following methods: laminated press molding, integral press molding, or physical vapor deposition, and then assembled to obtain the all-solid-state hydride-ion battery.
[0025] Optionally, the laminated press molding method includes a step of press molding the positive electrode active material layer, the hydride ion electrolyte layer, and the negative electrode active material layer, respectively.
[0026] Preferably, the "laminated press" conditions are such that the solid electrolyte is press-molded individually under 1 to 100 MPa, the positive electrode and negative electrode are press-molded individually, the molded positive electrode, negative electrode and electrolyte are polished, and then the battery is assembled by laminated press.
[0027] The pressure for the press forming is optionally 1 to 100 MPa.
[0028] Optionally, the press forming pressure is independently selected from any value among 1 MPa, 5 MPa, 10 MPa, 20 MPa, 50 MPa, 80 MPa, and 100 MPa, or from a range between any two of these values.
[0029] Optionally, the press forming time is 0.5 to 1 hour.
[0030] Optionally, the press forming time is independently selected from any value among 0.5h, 0.6h, 0.7h, 0.8h, 0.9h, and 1h, or from a range of any two of these values.
[0031] Optionally, the integral press molding method includes integral press molding of the positive electrode active material layer, the hydride ion electrolyte layer, and the negative electrode active material layer.
[0032] Preferably, the "integrated press" involves uniformly feeding all the raw material powders of the components into the press machine in sequence, pressing them under 1 to 100 MPa, and optionally adding a pressure holding time depending on the situation, which is 0.1 to 4 hours, preferably 0.5 to 1 hour.
[0033] Optionally, the pressure for the integral press molding is 1 to 100 MPa.
[0034] Optionally, the pressure for the integral press forming is independently selected from any value among 1 MPa, 5 MPa, 10 MPa, 20 MPa, 50 MPa, 80 MPa, and 100 MPa, or from a range between any two of these values.
[0035] Optionally, the time for the integral press molding is 0.1 to 4 hours.
[0036] Optionally, the time for the integral press forming is independently selected from any value among 0.1h, 0.5h, 1h, 2h, 3h, and 4h, or from a range between any two of these values.
[0037] Optionally, the time for the integral press molding is 0.5 to 1 hour.
[0038] Optionally, the physical deposition method is at least one selected from electron beam deposition, laser deposition, sputtering, and laser pulse deposition.
[0039] According to yet another aspect of this application, an application of the all-solid-state hydride-ion battery in energy storage is provided.
[0040] The beneficial effects that this application may produce are as follows:
[0041] The hydride-ion secondary battery described in this application operates at room temperature and over a wider temperature range, and can undergo multiple charge-discharge cycles. This novel battery is expected to have applications in everyday life and production.
[0042] The novel hydride-ion battery described in this application can achieve charge and discharge, has excellent cycle characteristics, significantly expands the research framework for secondary batteries, and possesses profound applied value. [Brief explanation of the drawing]
[0043] [Figure 1] This is a schematic diagram of the battery structure constructed in Example 1 of this application. [Figure 2] These are the charge and discharge curves of the LaH2 / LaH3-BaH2 / LaH3 battery under different current densities in Example 2 of this application. [Figure 3] This is the reversible repeated charge-discharge curve for 20 or more cycles of a CeH2 / CeH3-SrH2 / CeH3 battery in Example 3 of this application. [Modes for carrying out the invention]
[0044] The present application will be described in detail below by combining examples, but this application is not limited to these examples.
[0045] Unless otherwise specified, all raw materials used in the embodiments of this application were purchased commercially.
[0046] (Example 1: All-solid-state hydride ion battery) As shown in Figure 1, the all-solid-state hydride ion battery includes, in the order of positive electrode current collector, positive electrode active material layer, hydride ion electrolyte layer, negative electrode active material layer, and negative electrode current collector, from the positive electrode to the negative electrode. The hydride ion electrolyte layer is a hydride containing rare earth metal elements. The negative electrode active material layer contains a metal or a hydride with a low hydrogen content, the positive electrode active material layer contains a hydride with a high hydrogen content, and the solid electrolyte layer conducts hydride ions. The all-solid-state hydride ion battery uses hydride ions (H - The movement of ) enables charging and discharging, and the hydride ion solid electrolyte generates hydride ions (H) inside the battery. - It is used to conduct electricity.
[0047] (Example 2 Construction of LaH2 / LaH3-BaH2 / LaH3 Battery) (1) 50 mg of LaH2, 90 mg of LaH3-BaH2 composite electrolyte and 50 mg of LaH3 were each weighed in a glove box, sequentially and uniformly loaded into a mold, and the powders were integrally pressed using a hydraulic press to prepare pellets with a diameter of 10 mm and a thickness of about 1 mm, with a pressing pressure of 100 MPa.
[0048] (2) The obtained pellet was loaded into a stainless steel coin-type battery cell, and nickel foam was used as a current collector on both sides of the pellet to increase the contact area and reduce contact resistance.
[0049] (3) The electrochemical properties of the battery were tested using an electrochemical workstation. A schematic diagram of the battery structure is shown in Figure 1, and charge-discharge curves at different current densities are shown in Figure 2. It can be seen from Figure 2 that the battery can achieve charging and discharging under different current densities, and its capacity can reach 300 mAh g -1 It can be seen that the capacity can reach 300 mAh g
[0050] (Example 3 Construction of CeH2 / CeH3-SrH2 / CeH3 Battery) (1) 50 mg of CeH2, 90 mg of CeH3-SrH2 composite electrolyte and 50 mg of CeH3 were each weighed in a glove box, sequentially and uniformly loaded into a mold, and the powders were integrally pressed using a hydraulic press to prepare pellets with a diameter of 10 mm and a thickness of about 1 mm, with a pressing pressure of 100 MPa.
[0051] (2) The obtained pellet was loaded into a stainless steel coin-type battery cell, and nickel foam was used as a current collector on both sides of the pellet to increase the contact area and reduce contact resistance.
[0052] (3) The electrochemical properties of the battery were tested using an electrochemical workstation. The repeated charge-discharge curve is shown in Figure 3. It can be seen from Figure 3 that this secondary battery can achieve reversible charge and discharge for more than 20 cycles, and has excellent repeated charge-discharge performance.
[0053] (Example 4 PrH 0.1 / LaH x (Construction of a LiAlH4 battery) (1) 1.2 grams of LiAlH4 and 1 gram of electrolyte powder LaH in a glove box x The material was weighed, mixed and polished in a mortar, and used as the positive electrode.
[0054] (2) 1.2 grams of PrH in the glove box 0.1 , 1 gram of electrolyte powder LaH x The material was weighed, mixed and polished in a mortar, and used as the negative electrode.
[0055] (3) The positive electrode powder, negative electrode powder, and electrolyte powder were each pressed under 100 MPa to form pellets, the pressure was maintained for 0.5 hours, and after polishing, they were stacked in order to form a battery.
[0056] (4) The stacked solid batteries were loaded into stainless steel coin-type battery cells, copper foam was used as a current collector, and the electrochemical properties of the batteries were tested using an electrochemical workstation.
[0057] (Example 5 Mg / LaH x (Construction of a MgH2 battery) (1) 0.25 grams of MgH2 and 1 gram of electrolyte powder LaH in a glove box x The material was weighed, mixed and polished in a mortar, and used as the positive electrode.
[0058] (2) 0.25 grams of Mg and 1 gram of electrolyte powder LaH in the glove box x The material was weighed, mixed and polished in a mortar, and used as the negative electrode.
[0059] (3) The positive electrode powder, electrolyte powder, and negative electrode powder were placed in the mold in this order, and each time a powder was added, it was pressed and molded at 50 MPa using a hydraulic press. Finally, the entire battery was pressed under 100 MPa, the pressure was maintained for 0.5 hours, and the stacked pieces formed the battery.
[0060] (4) The stacked solid batteries were loaded into stainless steel coin-type battery cells, copper foam was used as a current collector, and the electrochemical properties of the batteries were tested using an electrochemical workstation.
[0061] (Example 6: Construction of Ti / NdH3-Mg3N2 / TiH2 and study of its properties) (1) 0.4 grams of NdH3-Mg3N2 electrolyte powder was weighed in a glove box, and the powder was pressed using a hydraulic press to produce pellets with a diameter of 10 mm and a thickness of approximately 1 mm at a pressure of 100 MPa.
[0062] (2) Ti was deposited in situ using physical vapor deposition, with a deposition thickness of 1 micron. TiH2 was deposited in situ on the other end of the electrolyte, with a deposition thickness of 1 micron.
[0063] (3) The pellets obtained in step (2) were used as a battery, and aluminum foil was used as a current collector on both sides of the pellets. The characteristics of the battery were tested using an electrochemical workstation.
[0064] (Example 7: Construction of a Li / YH3-BaH2 / CaH2 battery) (1) 5 mg of Li, 90 mg of YH3-BaH2 composite electrolyte, and 20 mg of CaH2 were weighed in a glove box, and then uniformly placed into a mold in that order. The powder was then pressed together using a hydraulic press to produce pellets with a diameter of 10 mm and a thickness of approximately 1 mm at a pressure of 100 MPa.
[0065] (2) The obtained pellets were loaded into a stainless steel coin-type battery cell, and nickel foam was used as a current collector on both sides of the pellets to increase the contact area and reduce contact resistance.
[0066] (3) The electrochemical properties of the battery were tested using an electrochemical workstation.
[0067] (Example 8: Construction of a Ce / SmH2-BaO / NaAlH4 battery) (1) 50 mg of Ce, 90 mg of SmH2-BaO composite electrolyte, and 50 mg of NaAlH4 were weighed in a glove box, and then uniformly placed into a mold in that order. The powder was then pressed together using a hydraulic press to produce pellets with a diameter of 10 mm and a thickness of approximately 1 mm at a pressure of 100 MPa.
[0068] (2) The obtained pellets were loaded into a stainless steel coin-type battery cell, and nickel foam was used as a current collector on both sides of the pellets to increase the contact area and reduce contact resistance.
[0069] (3) The electrochemical properties of the battery were tested using an electrochemical workstation.
[0070] (Example 9: Preparation of Ti / PrH3-MgO / PmH2 and study of its properties) (1) 0.4 grams of PrH3-MgO electrolyte powder was weighed in a glove box, and the powder was pressed using a hydraulic press to produce pellets with a diameter of 10 mm and a thickness of approximately 1 mm at a pressure of 100 MPa.
[0071] (2) Using the sputtering method, PmH2 was deposited onto the electrolyte pellet under a hydrogen atmosphere, with a deposition thickness of 1 micron. Ti was deposited onto the electrolyte under an argon atmosphere, with a deposition thickness of 1 micron.
[0072] (3) The pellets obtained in step 2 were used as a battery, and aluminum foil was used as a current collector on both sides of the pellets. The characteristics of the battery were tested using an electrochemical workstation.
[0073] (Example 10 LaH 2.5 / LaH-NaH / PmH 0.1 Battery construction) (1) Each glove box contains 50 mg of LaH 2.5 90 mg of LaH3-NaH complex electrolyte, and 50 mg of PmH 0.1The powder was weighed, uniformly placed into a mold, and then pressed into a single mass using a hydraulic press to produce pellets with a diameter of 10 mm and a thickness of approximately 1 mm at a pressure of 100 MPa.
[0074] (2) The obtained pellets were loaded into a stainless steel coin-type battery cell, and nickel foam was used as a current collector on both sides of the pellets to increase the contact area and reduce contact resistance.
[0075] (3) The electrochemical properties of the battery were tested using an electrochemical workstation.
[0076] (Example 11 Pd / NdH3-Mg3N2 / PdH 0.6 (The fabrication of and study of its properties) (1) 0.4 grams of NdH3-Mg3N2 electrolyte powder was weighed in a glove box, and the powder was pressed using a hydraulic press to produce pellets with a diameter of 10 mm and a thickness of approximately 1 mm at a pressure of 100 MPa.
[0077] (2) Using a vapor deposition method, Pd was deposited in situ onto the other end of the electrolyte, with a deposition thickness of 0.2 microns. PdH 0.6 The material was deposited on-site, and the deposition thickness was 0.2 microns.
[0078] (3) The pellets obtained in step (2) were used as a battery, and aluminum foil was used as a current collector on both sides of the pellets. The characteristics of the battery were tested using an electrochemical workstation.
[0079] The above descriptions represent only a few embodiments of this application and do not limit this application in any way. While this application discloses preferred embodiments as described above, these are not intended to limit this application, and those skilled in the art can make some changes or modifications using the disclosed technical content without departing from the scope of the technical invention of this application, all of which are equivalent embodiments and all fall within the scope of the technical invention.
Claims
1. All-solid-state hydride ion battery, The material comprises, in the order of positive electrode current collector, positive electrode active material layer, hydride ion electrolyte layer, negative electrode active material layer, and negative electrode current collector, moving from the positive electrode towards the negative electrode. The hydride ion electrolyte layer is a hydride containing rare earth metal elements. The all-solid-state hydride ion battery is characterized in that it is a rechargeable battery.
2. The all-solid-state hydride ion battery according to claim 1, characterized in that the rare earth metal element includes at least one of scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, and lutetium.
3. The thickness of the hydride ion electrolyte layer is 0.1 μm to 10 mm. Preferably, the thickness of the positive electrode active material layer and the negative electrode active material layer is independently selected from 0.2 μm to 1 mm, characterized in that, all solid-state hydride ion battery according to claim 1.
4. The negative electrode active material layer contains one of the metals from Group IA, Group IIA, Group IIIB, Group IVB, and Group VB. Preferably, the negative electrode active material layer contains a metal hydride with a low hydrogen content, and the hydrogen content in the metal hydride with a low hydrogen content is 0 to 50% of the saturated hydrogenation state, as described in claim 1.
5. The positive electrode active material layer contains a metal hydride with a high hydrogen content, and the hydrogen content in the metal hydride with a high hydrogen content is 50-100% of the saturated hydrogenation state. Preferably, the relative hydrogen content of the high-hydrogen-content hydride is higher than that of the low-hydrogen-content metal hydride. Preferably, the metal in the metal hydride with low hydrogen content and the metal hydride with high hydrogen content is independently selected from Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Pd, Al, the all-solid-state hydride ion battery according to claim 1.
6. The all-solid-state hydride ion battery according to claim 1, characterized in that the positive electrode current collector and the negative electrode current collector are independently selected from at least one of gold, silver, copper, palladium, platinum, iron, titanium, cobalt, nickel, and aluminum.
7. A method for producing an all-solid-state hydride ion battery according to any one of claims 1 to 6, A manufacturing method characterized by obtaining the all-solid-state hydride ion battery by fabricating a positive electrode active material layer, a hydride ion electrolyte layer, and a negative electrode active material layer using one of the following methods: laminated press molding, integral press molding, or physical vapor deposition.
8. The aforementioned laminated press molding method includes the step of press molding a positive electrode active material layer, a hydride ion electrolyte layer, and a negative electrode active material layer, respectively. Preferably, the pressure of the press forming is 1 to 100 MPa. Preferably, the manufacturing method according to claim 7, characterized in that the press molding time is 0.5 to 1 hour.
9. The aforementioned integral press molding method includes a step of integrally press molding a positive electrode active material layer, a hydride ion electrolyte layer, and a negative electrode active material layer. Preferably, the pressure of the integral press forming is 1 to 100 MPa. Preferably, the time for the integral press molding is 0.1 to 4 hours. Preferably, the time for the integral press molding is 0.5 to 1 hour. Preferably, the manufacturing method according to claim 7, characterized in that the physical deposition method is at least one selected from electron beam deposition, laser deposition, sputtering, and laser pulse.
10. An application of the all-solid-state hydride-ion battery according to any one of claims 1 to 6 in energy storage.