All-solid-state hydride battery and preparation method therefor

Abstract

Disclosed in the present application are an all-solid-state hydride battery and a preparation method therefor. The all-solid-state hydride battery sequentially comprises, from a positive electrode to a negative electrode, a positive electrode current collector, a positive electrode active layer, a hydride electrolyte layer, a negative electrode active layer and a negative electrode current collector, wherein the hydride electrolyte layer is a hydride containing a rare earth metal element; the negative electrode active material layer comprises a metal or a low-hydrogen-content hydrogen-containing compound; the positive electrode active material layer comprises a high-hydrogen-content hydrogen-containing compound; and the solid-state electrolyte layer conducts hydride anions. The present invention, as a new hydride battery, can achieve charging and discharging, has relatively good cycling performance, greatly broadens the research system of a secondary battery, and has a profound application value.

Description

All-solid-state negative hydrogen ion battery and preparation method thereof Technical Field

[0001] [Corrected 22.04.2024 according to Rule 91] The present application relates to an all-solid-state negative hydrogen ion battery and a preparation method thereof, belonging to the field of clean energy technology. Background Art

[0002] [Corrected 22.04.2024 in accordance with Rule 91] Energy has a profound impact on human society, making it a prerequisite for scientific and technological progress and social development. Energy storage technology, as a crucial component of humanity's efficient energy utilization, is of great significance. Secondary batteries, with their advantages of high efficiency, safety, environmental friendliness, high energy storage density, and high recycling rate, have become the preferred energy storage device. Currently, secondary batteries have developed into lead-acid batteries, nickel-metal hydride batteries, lithium batteries, flow batteries, sodium batteries, and magnesium batteries. Due to the limitations of material properties, each type of electrochemical energy storage device has its own application scenarios. The development of new battery systems can greatly expand the application range of electrochemical energy storage.

[0003] [Corrected 22.04.2024 according to Rule 91] When forming a compound, the element hydrogen can either easily lose an electron to become a proton or gain an electron to become a hydrogen ion. - The radius of the ion is larger than that of F - , O 2- It is similar to hydrogen ions, but it only contains one valence charge, so the charge density is small and it is easier to polarize. This is very different from proton conduction in materials. Protons have a high charge density and are often strongly bonded to O in oxides, resulting in a high activation energy. In addition, the standard redox potential of hydrogen ions is -2.3V, close to that of magnesium ions (-2.4V), but its atomic mass is only 1 / 24 of that of magnesium, which makes it a promising ion conductor material for the next generation of high energy density and high potential batteries. - The application of rapid ion conduction in batteries is expected to revolutionize electrochemical energy storage technology.

[0004] [Corrected 22.04.2024 in accordance with Rule 91] Several ionic conductors have been reported as potential electrolytes for hydride batteries. These mainly fall into two categories: alkaline earth metal-based, including binary hydrides, oxyhydrides, and halogenated hydrides; and rare earth metal-based, primarily oxyhydrides and pure rare earth metal hydrides. However, no hydride batteries capable of cyclic charge and discharge have yet been reported.

[0005] [Corrected 22.04.2024 in accordance with Rule 91] Summary of the invention

[0006] [Corrected 22 April 2024 in accordance with Rule 91] The all-solid-state hydrogen-ion battery disclosed in this application can achieve reversible charge and discharge at room temperature. As a novel electrochemical energy storage device, this invention will broaden the research framework of electrochemical energy storage and has great application value.

[0007] [Corrected 22.04.2024 in accordance with Rule 91] The present invention discloses a novel rechargeable and dischargeable hydride ion all-solid-state battery. Specifically, the hydride ion all-solid-state battery comprises 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 comprises a metal or a low-hydrogen metal hydride, the positive electrode active material layer comprises a high-hydrogen metal hydride, and the solid electrolyte layer conducts hydride ions.

[0008] [Corrected 22.04.2024 according to Rule 91] According to one aspect of the present application, an all-solid-state hydrogen-ion battery is provided, wherein the all-solid-state hydrogen-ion battery comprises, from the positive electrode to the negative electrode, a positive electrode current collector, a positive electrode active layer, a hydrogen-ion electrolyte layer, a negative electrode active layer, and a negative electrode current collector;

[0009] [Corrected 22.04.2024 in accordance with Rule 91] The hydride ion electrolyte layer is a hydride containing a rare earth metal element;

[0010] [Corrected 22.04.2024 in accordance with Rule 91] The all-solid-state negative hydrogen ion battery is a rechargeable and dischargeable battery.

[0011] [Corrected 22.04.2024 according to Rule 91] Optionally, the all-solid-state negative hydrogen ion battery is provided by negative hydrogen ions (H - ) migration to achieve charging and discharging, and the hydrogen ion solid electrolyte is used to conduct hydrogen ions (H - ).

[0012] [Corrected 22.04.2024 according to Rule 91] Optionally, 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.

[0013] [Corrected 22.04.2024 according to Rule 91] Optionally, the selected hydride ion electrolyte layer is selected from rare earth metal hydrides or partially comprises rare earth metal hydrides;

[0014] [Corrected 22.04.2024 in accordance with Rule 91] The rare earth metals include at least one of 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).

[0015] [Corrected 22.04.2024 according to Rule 91] Optionally, the thickness of the hydrogen anion electrolyte layer is 0.1um to 10mm.

[0016] [Corrected 22.04.2024 according to Rule 91] Optionally, the thickness of the hydrogen ion electrolyte layer is independently selected from any value among 0.1um, 0.2um, 0.5um, 1um, 10um, 100um, 1mm, 5mm, 10mm or a range between any two of the above.

[0017] [Corrected 22.04.2024 according to Rule 91] Optionally, the thickness of the positive electrode active layer and the negative electrode active layer are independently selected from 0.2um to 1mm.

[0018] [Corrected 22.04.2024 according to Rule 91] Optionally, the thickness of the positive electrode active layer and the negative electrode active layer are independently selected from any value among 0.2um, 0.5um, 1um, 10um, 100um, 1mm or a range between any two of the above.

[0019] [Corrected 22.04.2024 according to Rule 91] Optionally, the negative electrode active layer comprises one of the metals of Groups IA, IIA, IIIB, IVB and VB.

[0020] [Corrected 22.04.2024 according to Rule 91] Optionally, the metal of the negative electrode active layer is a metal of the first and second main groups and the third, fourth and fifth sub-groups and their alloys.

[0021] [Corrected 22.04.2024 according to Rule 91] Optionally, the negative electrode active layer comprises a metal or a hydride containing a low hydrogen content.

[0022] [Corrected 22.04.2024 according to Rule 91] Optionally, the positive electrode active material layer contains a hydride containing a high hydrogen content.

[0023] [Corrected 22.04.2024 according to Rule 91] Optionally, the negative electrode active layer comprises a metal or a metal hydride with a low hydrogen content, and the hydrogen content of the metal hydride with a low hydrogen content is 0 to 50% of the saturated hydrogenated state.

[0024] [Corrected 22.04.2024 according to Rule 91] Optionally, the positive electrode active material includes a metal hydride with a high hydrogen content, the hydrogen content of the metal hydride with a high hydrogen content is 50 to 100% of the saturated hydrogenated state, and the relative hydrogen content of the selected low hydrogen content hydride is lower than that of the high hydrogen content metal hydride.

[0025] [Corrected 22.04.2024 according to Rule 91] Optionally, the metal in the low-hydrogen metal hydride and the high-hydrogen metal hydride is independently selected from one 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.

[0026] [Corrected 22.04.2024 according to Rule 91] 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.

[0027] [Corrected 22.04.2024 according to Rule 91] According to another aspect of the present application, a method for preparing the above-mentioned all-solid-state hydrogen-ion battery is provided, wherein the positive electrode active layer, the hydrogen-ion electrolyte layer and the negative electrode active layer are prepared by a layered pressing molding method, an integrated pressing molding method or a physical deposition method, and assembled to obtain the all-solid-state hydrogen-ion battery.

[0028] [Corrected 22.04.2024 according to Rule 91] Optionally, the layered pressing molding method includes: pressing and molding the positive electrode active layer, the hydrogen anion electrolyte layer and the negative electrode active layer separately.

[0029] [Corrected 22.04.2024 according to Rule 91] Preferably, the “layered pressing” condition is that the solid electrolyte is pressed into shape separately at a pressure of 1 to 100 MPa, and the positive and negative electrodes are pressed into shape separately, and the formed positive and negative electrodes and the electrolyte are polished and then laminated and pressed to form a battery.

[0030] [Corrected 22.04.2024 according to Rule 91] Optionally, the pressure of the pressing is 1 to 100 MPa.

[0031] [Corrected 22.04.2024 according to Rule 91] Optionally, the pressure of the press molding is independently selected from any value among 1MPa, 5MPa, 10MPa, 20MPa, 50MPa, 80MPa, 100MPa or a range between any two of the above.

[0032] [Corrected 22.04.2024 according to Rule 91] Optionally, the pressing time is 0.5 to 1 hour.

[0033] [Corrected 22.04.2024 according to Rule 91] Optionally, the pressing time is independently selected from any value among 0.5h, 0.6h, 0.7h, 0.8h, 0.9h, 1h or a range between any two of the above.

[0034] [Corrected 22.04.2024 according to Rule 91] Optionally, the integrated pressing method includes: pressing and molding the positive electrode active layer, the hydrogen anion electrolyte layer, and the negative electrode active layer as a whole.

[0035] [Corrected 22.04.2024 according to Article 91] Preferably, "one-piece pressing ” The raw material powders of all components are uniformly put into a tablet press in order, compressed at 1-100 MPa, and the pressure maintenance time is optionally increased as appropriate, the time being 0.1-4 hours, preferably 0.5-1 hour.

[0036] [Corrected 22.04.2024 according to Rule 91] Optionally, the pressure of the integral pressing is 1 to 100 MPa.

[0037] [Corrected 22.04.2024 according to Rule 91] Optionally, the pressure of the integral press molding is independently selected from any value among 1MPa, 5MPa, 10MPa, 20MPa, 50MPa, 80MPa, 100MPa or a range between any two of the above.

[0038] [Corrected 22.04.2024 according to Rule 91] Optionally, the time for the integral pressing is 0.1 to 4 hours.

[0039] [Corrected 22.04.2024 according to Rule 91] Optionally, the time for the integral pressing is independently selected from any value among 0.1h, 0.5h, 1h, 2h, 3h, 4h or a range between any two of the above.

[0040] [Corrected 22.04.2024 according to Rule 91] Optionally, the time for the integral pressing is 0.5 to 1 hour.

[0041] [Corrected 22.04.2024 according to Rule 91] Optionally, the physical deposition method is selected from at least one of electron beam evaporation, laser evaporation, sputtering, and laser pulse.

[0042] [Corrected 22.04.2024 according to Rule 91] According to another aspect of the present application, there is provided an application of the above-mentioned all-solid-state hydrogen-ion battery in energy storage.

[0043] [Corrected 22.04.2024 in accordance with Rule 91] The beneficial effects that this application can produce include:

[0044] [Corrected 22.04.2024 according to Rule 91] The hydrogen negative ion secondary battery provided in this application can operate at room temperature and a wide temperature range, and can achieve multiple cycles of charge and discharge. This new battery is expected to be used in actual life and production.

[0045] [Corrected 22.04.2024 according to Rule 91] The new negative hydrogen ion battery provided by this application can realize charging and discharging, has good cycle performance, greatly broadens the research system of secondary batteries, and has far-reaching application value. BRIEF DESCRIPTION OF THE DRAWINGS

[0046] [Corrected 22.04.2024 according to Rule 91] Figure 1 is a schematic diagram of the battery structure constructed in Example 1 of the present application.

[0047] [Corrected 22.04.2024 according to Rule 91] Figure 2 shows the charge and discharge curves of the LaH2 / LaH3-BaH2 / LaH3 battery at different current densities in Example 2 of the present application.

[0048] [Corrected 22.04.2024 according to Rule 91] Figure 3 shows the reversible cycle charge and discharge curves of the CeH2 / CeH3-SrH2 / CeH3 battery in Example 3 of the present application for more than 20 times. DETAILED DESCRIPTION

[0049] [Corrected 22.04.2024 according to Rule 91] The present application is described in detail below with reference to embodiments, but the present application is not limited to these embodiments.

[0050] [Corrected on 22.04.2024 according to Rule 91] Unless otherwise stated, the raw materials in the examples of this application were purchased through commercial channels.

[0051] [Corrected 22.04.2024 according to Rule 91] Example 1 All-solid-state hydrogen negative ion battery

[0052] [Corrected 22.04.2024 according to Rule 91] As shown in FIG1 , the all-solid-state hydrogen-ion battery comprises, from the positive electrode to the negative electrode, a positive electrode active layer, a hydrogen-ion electrolyte layer, a negative electrode active layer, and a negative electrode current collector; the hydrogen-ion electrolyte layer is a hydride containing a rare earth metal element. The negative electrode active material layer contains a metal or a hydride containing a low hydrogen content, the positive electrode active material layer contains a hydride containing a high hydrogen content, and the solid electrolyte layer conducts hydrogen ions. The all-solid-state hydrogen-ion battery conducts hydrogen ions (H - ) migration to achieve charging and discharging, and the hydrogen ion solid electrolyte is used to conduct hydrogen ions (H - ).

[0053] [Corrected 22.04.2024 according to Rule 91] Example 2 Construction of LaH2 / LaH3-BaH2 / LaH3 Battery

[0054] [Corrected 22.04.2024 according to Rule 91] (1) In a glove box, 50 mg of LaH2, 90 mg of LaH3-BaH2 composite electrolyte, and 50 mg of LaH3 were weighed and evenly placed into a mold in that order. The powders were pressed into a sheet with a diameter of 10 mm and a thickness of about 1 mm using a hydraulic press at a pressure of 100 MPa;

[0055] [Corrected 22.04.2024 according to Rule 91] (2) The obtained thin sheet was loaded into a stainless steel battery buckle, and nickel foam was used as current collector on both sides of the thin sheet to increase the contact area and reduce the contact resistance;

[0056] [Corrected 22.04.2024 according to Rule 91] (3) The electrochemical performance of the battery was tested using an electrochemical workstation. The battery structure is shown in Figure 1, and the charge and discharge curves at different current densities are shown in Figure 2. It can be seen from Figure 2 that the battery can be charged and discharged at different current densities, and its capacity is as high as 300 mA hg -1 .

[0057] [Corrected 22.04.2024 according to Rule 91] Example 3 Construction of CeH2 / CeH3-SrH2 / CeH3 Battery

[0058] [Corrected 22.04.2024 according to Rule 91] (1) In a glove box, 50 mg of CeH2, 90 mg of CeH3-SrH2 composite electrolyte, and 50 mg of CeH3 were weighed and evenly placed into a mold in that order. The powders were pressed into a sheet with a diameter of 10 mm and a thickness of about 1 mm using a hydraulic press at a pressure of 100 MPa.

[0059] [Corrected 22.04.2024 according to Rule 91] (2) The obtained thin sheet was loaded into a stainless steel battery buckle, and nickel foam was used as current collector on both sides of the thin sheet to increase the contact area and reduce the contact resistance;

[0060] [Corrected 22.04.2024 according to Rule 91] (3) The electrochemical performance of the battery was tested using an electrochemical workstation. The cyclic charge and discharge curve is shown in FIG3 . FIG3 shows that the secondary battery can achieve reversible charge and discharge for more than 20 times, and has good cyclic charge and discharge performance.

[0061] [Corrected 22.04.2024 according to Rule 91] Example 4 Construction of PrH 0.1 / LaH x / LiAlH4 battery

[0062] [Corrected 22.04.2024 according to Rule 91] (1) Weigh 1.2 g of LiAlH4 and 1 g of electrolyte powder LaH in the glove box. x , mixed and ground in a mortar as the positive electrode;

[0063] [Corrected 22.04.2024 according to Rule 91] (2) Weigh 1.2 g of PrH in the glove box. 0.1 , 1 gram of electrolyte powder LaH x , mixed and ground in a mortar as the negative electrode;

[0064] [Corrected 22.04.2024 according to Rule 91] (3) The positive and negative electrode powders and the electrolyte powders are pressed into thin sheets at 100 MPa, the pressure is maintained for 0.5 h, the sheets are polished, and the sheets are stacked in order to form a battery;

[0065] [Corrected 22.04.2024 according to Rule 91](4) The stacked solid-state batteries were loaded into stainless steel battery buckles, and copper foam was used as the current collector. The electrochemical performance of the batteries was tested using an electrochemical workstation.

[0066] [Corrected 22.04.2024 according to Rule 91] Example 5 Construction of Mg / LaH x / MgH2 battery

[0067] [Corrected 22.04.2024 according to Rule 91] (1) Weigh 0.25 g of MgH2, 1 g of electrolyte powder LaH x , mixed and ground in a mortar to serve as the positive electrode;

[0068] [Corrected 22.04.2024 according to Rule 91] (2) Weigh 0.25 g of Mg, 1 g of electrolyte powder LaH in the glove box. x , mixed and ground in a mortar as the negative electrode;

[0069] [Corrected 22.04.2024 according to Rule 91] (3) Place the positive electrode powder, electrolyte powder, and negative electrode powder into the mold in sequence, and use a hydraulic press to press the powder into shape at 50 MPa each time, and finally press the entire battery at 100 MPa, maintaining the pressure for 0.5 h, to form a stacked battery;

[0070] [Corrected 22.04.2024 according to Rule 91](4) The stacked solid-state batteries were loaded into stainless steel battery buckles, and copper foam was used as the current collector. The electrochemical performance of the batteries was tested using an electrochemical workstation.

[0071] [Corrected 22.04.2024 according to Rule 91] Example 6 Construction of Ti / NdH3-Mg3N2 / TiH2 and study of its properties

[0072] [Corrected 22.04.2024 according to Rule 91] (1) In a glove box, weigh 0.4 g of NdH3-Mg3N2 electrolyte powder and press the powder into a sheet with a diameter of 10 mm and a thickness of about 1 mm using a hydraulic press at a pressure of 100 MPa;

[0073] [Corrected 22.04.2024 according to Rule 91] (2) Using a physical deposition method, in situ deposit Ti to a thickness of 1 μm. In situ deposit TiH2 on the other end of the electrolyte to a thickness of 1 μm;

[0074] [Corrected 22.04.2024 according to Rule 91] (3) The sheet obtained in step (2) was used as a battery, and aluminum foil was used as current collectors on both sides of the sheet. The battery performance was tested using an electrochemical workstation.

[0075] [Corrected 22.04.2024 according to Rule 91] Example 7 Construction of Li / YH3-BaH2 / CaH2 Battery

[0076] [Corrected 22.04.2024 according to Rule 91] (1) In a glove box, 5 mg of Li, 90 mg of YH3-BaH2 composite electrolyte, and 20 mg of CaH2 were weighed and placed evenly in the mold in that order. The powders were pressed into a sheet with a diameter of 10 mm and a thickness of about 1 mm using a hydraulic press at a pressure of 100 MPa.

[0077] [Corrected 22.04.2024 according to Rule 91] (2) The obtained thin sheet was loaded into a stainless steel battery buckle, and nickel foam was used as current collector on both sides of the thin sheet to increase the contact area and reduce the contact resistance;

[0078] [Corrected 22.04.2024 according to Rule 91] (3) The electrochemical performance of the battery was tested using an electrochemical workstation.

[0079] [Corrected 22.04.2024 according to Rule 91] Example 8 Construction of Ce / SmH2-BaO / NaAlH4 Battery

[0080] [Corrected 22.04.2024 according to Rule 91] (1) In a glove box, 50 mg of Ce, 90 mg of SmH2-BaO composite electrolyte, and 50 mg of NaAlH4 were weighed and placed evenly in the mold in that order. The powders were pressed into a sheet with a diameter of 10 mm and a thickness of about 1 mm using a hydraulic press at a pressure of 100 MPa.

[0081] [Corrected 22.04.2024 according to Rule 91] (2) The obtained thin sheet was loaded into a stainless steel battery buckle, and nickel foam was used as current collector on both sides of the thin sheet to increase the contact area and reduce the contact resistance;

[0082] [Corrected 22.04.2024 according to Rule 91] (3) The electrochemical performance of the battery was tested using an electrochemical workstation.

[0083] [Corrected 22.04.2024 according to Rule 91] Example 9 Preparation of Ti / PrH3-MgO / PmH2 and Study of Its Properties

[0084] [Corrected 22.04.2024 according to Rule 91] (1) 0.4 g of PrH3-MgO electrolyte powder was weighed in a glove box and pressed into a sheet with a diameter of 10 mm and a thickness of about 1 mm using a hydraulic press at a pressure of 100 MPa;

[0085] [Corrected 22.04.2024 according to Rule 91] (2) Using a sputtering method, in a hydrogen atmosphere, PmH2 was deposited on the above-mentioned electrolyte sheet to a thickness of 1 μm. In an argon atmosphere, Ti was deposited on the electrolyte to a thickness of 1 μm;

[0086] [Corrected 22.04.2024 according to Rule 91] (3) The sheet obtained in step 2 was used as a battery, and aluminum foil was used as current collectors on both sides of the sheet. The battery performance was tested using an electrochemical workstation.

[0087] [Corrected 22.04.2024 according to Rule 91] Example 10 Construction of LaH 2.5 / LaH-NaH / PmH 0.1 Battery

[0088] [Corrected 22.04.2024 according to Rule 91] (1) Weigh 50 mg of LaH 2.5 , 90 mg LaH3-NaH composite electrolyte, and 50 mg PmH 0.1, put them into the mold evenly in order, and use a hydraulic press to press the powder into a thin sheet with a diameter of 10mm and a thickness of about 1mm at a pressure of 100MPa;

[0089] [Corrected 22.04.2024 according to Rule 91] (2) The obtained thin sheet was loaded into a stainless steel battery buckle, and nickel foam was used as current collector on both sides of the thin sheet to increase the contact area and reduce the contact resistance;

[0090] [Corrected 22.04.2024 according to Rule 91] (3) The electrochemical performance of the battery was tested using an electrochemical workstation.

[0091] [Corrected 22.04.2024 according to Rule 91] Example 11 Preparation of Pd / NdH3-Mg3N2 / PdH 0.6 And study its performance

[0092] [Corrected 22.04.2024 according to Rule 91] (1) In a glove box, weigh 0.4 g of NdH3-Mg3N2 electrolyte powder and press the powder into a sheet with a diameter of 10 mm and a thickness of about 1 mm using a hydraulic press at a pressure of 100 MPa;

[0093] [Corrected 22.04.2024 according to Rule 91] (2) Pd was in situ deposited on the other end of the electrolyte using the evaporation method with a deposition thickness of 0.2 μm. 0.6 , the deposition thickness is 0.2 μm;

[0094] [Corrected 22.04.2024 according to Rule 91] (3) The sheet obtained in step (2) was used as a battery, and aluminum foil was used as current collectors on both sides of the sheet. The battery performance was tested using an electrochemical workstation.

[0095] [Corrected on 22.04.2024 according to Rule 91] The above are only a few embodiments of the present application and do not limit the present application in any form. Although the present application is disclosed as above with preferred embodiments, it is not intended to limit the present application. Any technician familiar with this profession, without departing from the scope of the technical solution of the present application, makes slight changes or modifications using the technical content disclosed above, which are equivalent to equivalent implementation cases and fall within the scope of the technical solution.

Claims

1. [Corrected 22.04.2024 in accordance with Rule 91] An all-solid-state negative hydrogen ion battery, characterized in that: The all-solid-state hydrogen-ion battery comprises, from the positive electrode to the negative electrode, a positive electrode current collector, a positive electrode active layer, a hydrogen-ion electrolyte layer, a negative electrode active layer and a negative electrode current collector; The hydrogen anion electrolyte layer is a hydride containing a rare earth metal element; The all-solid-state negative hydrogen ion battery is a rechargeable and dischargeable battery.

2. [Corrected 22.04.2024 in accordance with Rule 91] The all-solid-state hydrogen-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. [Corrected 22.04.2024 in accordance with Rule 91] The all-solid-state hydrogen-ion battery according to claim 1, characterized in that: The thickness of the hydrogen anion electrolyte layer is 0.1um to 10mm; Preferably, the thickness of the positive electrode active layer and the negative electrode active layer are independently selected from 0.2 um to 1 mm.

4. [Corrected 22.04.2024 in accordance with Rule 91] The all-solid-state negative hydrogen ion battery according to claim 1, characterized in that: The negative electrode active layer comprises one of group IA, IIA, IIIB, IVB, and VB metals; Preferably, the negative electrode active layer comprises a metal hydride with a low hydrogen content, and the hydrogen content of the metal hydride with a low hydrogen content is 0 to 50% of the saturated hydrogenation state.

5. [Corrected 22.04.2024 in accordance with Rule 91] The all-solid-state negative hydrogen ion battery according to claim 1, characterized in that: The positive electrode active layer contains a metal hydride with a high hydrogen content, wherein the hydrogen content of the metal hydride with a high hydrogen content is 50 to 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 metals in the metal hydride with low hydrogen content and the metal hydride with high hydrogen content are independently selected from one 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.

6. [Corrected 22.04.2024 in accordance with Rule 91] The all-solid-state hydrogen-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. [Corrected 22.04.2024 in accordance with Rule 91] A method for preparing an all-solid-state negative hydrogen ion battery according to any one of claims 1 to 6, characterized in that: The positive electrode active layer, the hydrogen anion electrolyte layer and the negative electrode active layer are prepared by a layered pressing method, an integrated pressing method or a physical deposition method, and assembled to obtain the all-solid-state hydrogen anion battery.

8. [Corrected 22.04.2024 in accordance with Rule 91] The method according to claim 7, characterized in that The layered pressing method comprises: pressing and forming the positive electrode active layer, the hydrogen anion electrolyte layer and the negative electrode active layer respectively; Preferably, the pressure of the compression molding is 1 to 100 MPa; Preferably, the compression molding time is 0.5 to 1 hour.

9. [Corrected 22.04.2024 in accordance with Rule 91] The method according to claim 7, characterized in that The integrated pressing method comprises: pressing and molding the positive electrode active layer, the hydrogen anion electrolyte layer, and the negative electrode active layer as a whole; Preferably, the integral pressing pressure is 1 to 100 MPa; Preferably, the integral pressing time is 0.1 to 4 hours; Preferably, the integral pressing time is 0.5 to 1 hour; Preferably, the physical deposition method is selected from at least one of electron beam evaporation, laser evaporation, sputtering, and laser pulse.

10. [Corrected 22.04.2024 in accordance with Rule 91] Use of the all-solid-state negative hydrogen ion battery as claimed in any one of claims 1 to 6 in energy storage.

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