Thin film magnesium battery magnesium-aluminum-manganese oxide positive electrode target material, preparation method and thin film magnesium battery

Abstract

The present application relates to thin film magnesium battery magnesium aluminate manganese positive target material, preparation method and thin film magnesium battery, belong to magnesium battery technical field. Including: magnesium salt powder is mixed with manganese trioxide and aluminum oxide powder to obtain mixed powder; the mixed powder is put into a ball mill tank and mixed with zirconium oxide balls, then a dispersing agent is added and the mixing and ball milling are continued; then a binder is added to the ball mill tank and the ball milling is continued; the synthesized powder after ball milling is sieved through a 500 mesh sieve, the sieved synthesized powder is weighed, poured into a vibrating mold, pressed, and a molded blank is formed; the blank is put into a cold isostatic pressing machine, pressed and pressure maintained, and a magnesium aluminate manganese positive target material blank after cold isostatic pressing is obtained; the magnesium aluminate manganese positive target material blank is put into an atmosphere sintering furnace or a vacuum sintering furnace, and after multi-stage heat preservation and multi-stage cooling, the furnace is naturally cooled to room temperature, and a thin film magnesium battery magnesium aluminate manganese positive target material is obtained. The composition of the thin film magnesium battery magnesium aluminate manganese positive target material of the present application is uniform, and thin film deposition is facilitated.

Description

Technical Field

[0001] This invention relates to the field of magnesium battery technology, and in particular to a magnesium aluminum manganate cathode target for thin-film magnesium batteries, its preparation method, and the thin-film magnesium battery itself. Background Technology

[0002] Currently, theoretical research on all-solid-state thin-film magnesium batteries has begun. All-solid-state thin-film magnesium batteries utilize solid-state materials for all cell units, including the positive and negative electrodes and the electrolyte. Their structure is simpler than traditional magnesium-ion batteries. The solid electrolyte not only conducts magnesium ions but also acts as a separator, possessing advantages such as high mechanical strength, absence of liquid components, lack of flammable and volatile components, and good temperature resistance. However, research on all-solid-state thin-film magnesium batteries remains theoretical; no technology has yet been developed to provide the actual fabrication techniques and finished products that demonstrate the composition and functional structure of all-solid-state thin-film magnesium batteries. Summary of the Invention

[0003] In view of the above, the present invention aims to provide a magnesium aluminum manganate cathode target, a preparation method, and a thin-film magnesium battery. The present invention can provide a magnesium aluminum manganate cathode target for all-solid-state thin-film magnesium batteries.

[0004] The objective of this invention is mainly achieved through the following technical solutions:

[0005] On one hand, the present invention provides a method for preparing a magnesium aluminum manganate cathode target for thin-film magnesium batteries, comprising:

[0006] Step 1: Mix magnesium salt powder with manganese tetroxide and aluminum oxide powder to obtain a mixed powder, and control the mass ratio of magnesium salt, manganese tetroxide and aluminum oxide to be 1.1~1.5:0.8~1:0.04~0.15;

[0007] Step 2: Place the above mixed powder into a ball mill jar and mix it with zirconia balls, then add a dispersant and continue mixing and ball milling;

[0008] Step 3: Then add binder into the ball mill jar and continue ball milling;

[0009] Step 4: After ball milling, the synthetic powder is passed through a 500-mesh sieve. The sieved synthetic powder is poured into a vibrating mold and pressed to form a molded blank.

[0010] Step 5: Place the billet into a cold isostatic press, apply pressure and hold pressure to obtain the cold isostatically pressed magnesium aluminum manganate cathode target billet.

[0011] Step 6: Place the aluminum magnesium manganate cathode target blank into an atmosphere sintering furnace or a vacuum sintering furnace, and after multi-stage heat preservation and multi-stage cooling, allow it to cool naturally to room temperature in the furnace to obtain the aluminum magnesium manganate cathode target for thin-film magnesium batteries.

[0012] Furthermore, step 6, the step of using an atmosphere sintering furnace, includes:

[0013] S601. Place the aluminum magnesium manganate cathode target blank into an atmosphere sintering furnace, continuously introduce N2+Ar mixed gas, raise the temperature from room temperature to 190-210℃, and hold for 3-4 hours.

[0014] S602, heat up again to 540-560℃, and continuously purge N2+Ar mixed gas, and keep at this temperature for 5-7 hours;

[0015] S603, heat up again to 740-760℃, and continuously purge N2+Ar mixed gas, and keep at this temperature for 7-9 hours;

[0016] S604, heat up again to 940-960℃, and continuously purge N2+Ar mixed gas, and keep at this temperature for 9-11 hours;

[0017] S605, heat up again to 1130~1160℃, and continuously pass N2+Ar mixed gas through, and keep at this temperature for 5~7h;

[0018] S606, slowly cool to 490-510℃ in the furnace, and hold for 3-5 hours;

[0019] S607, and then naturally cooled to room temperature in the furnace to obtain the magnesium aluminum manganate cathode target for thin-film magnesium batteries.

[0020] Furthermore, step 6, which involves using a vacuum sintering furnace, includes:

[0021] S601. Place the aluminum magnesium manganate cathode target blank into a vacuum sintering furnace, maintaining a vacuum level of 10. -3 Below Pa, the temperature is raised from room temperature to 190–210℃ and held for 3–4 hours;

[0022] S602, raise the temperature again to 540-560℃ and keep it warm for 5-7 hours;

[0023] S603, heat again to 740-760℃, and keep warm for 7-9 hours;

[0024] S604, heat again to 940-960℃, and hold for 9-11 hours;

[0025] S605, heat up again to 1130~1160℃, and keep warm for 5~7 hours;

[0026] S606, slowly cool to 490-510℃ in the furnace, and hold for 3-5 hours;

[0027] S607, and then naturally cooled to room temperature in the furnace to obtain the magnesium aluminum manganate cathode target for thin-film magnesium batteries.

[0028] Furthermore, in step 4, the pressure is controlled at 1450-1550 tons.

[0029] Furthermore, in step 1, the magnesium salt includes one or more of magnesium oxide, magnesium carbonate, magnesium nitrate, and magnesium hydroxide.

[0030] Furthermore, in step 2, the mass ratio of dispersant to mixed powder is controlled to be 1.4 to 1.8:100.

[0031] Furthermore, in step 2, the ball milling process includes:

[0032] S201. Ball milling in a milling jar at an initial speed of 110-150 rpm for 3-5 hours;

[0033] S202. Grind the balls in a milling jar at a speed of 310-330 rpm for more than 13 hours.

[0034] Furthermore, in step 3, the mass ratio of the binder to the mixed powder is controlled to be 0.8 to 1.1:100.

[0035] Furthermore, in step 5, the pressure is controlled to be increased to 300-350 MPa and maintained for 40-60 minutes.

[0036] The present invention also provides a thin-film magnesium aluminum manganese oxide positive electrode target for a magnesium battery, which is prepared by the above-described preparation method.

[0037] The present invention also provides an all-solid-state thin-film magnesium battery, wherein the positive electrode of the all-solid-state thin-film magnesium battery is prepared using the above-mentioned aluminum magnesium manganate positive electrode target for thin-film magnesium batteries.

[0038] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0039] 1) The preparation method of this invention first mixes magnesium salt powder with manganese tetroxide and alumina powder to obtain a mixed powder. Then, the mixed powder is mixed with zirconia balls, followed by the addition of a dispersant and further mixing and ball milling. A binder is then added, and ball milling continues. The ball-milled synthetic powder is sieved (e.g., 500 mesh), poured into a vibrating mold, and pressed to form a molded blank. The blank is placed in a cold isostatic press and pressed and held to obtain a cold isostatically pressed magnesium aluminum manganate cathode target blank. Finally, the magnesium aluminum manganate cathode target blank is placed in an atmosphere sintering furnace or a vacuum sintering furnace for multi-stage heat preservation and cooling, followed by natural cooling to room temperature to obtain a thin-film magnesium battery magnesium aluminum manganate cathode target. This invention's preparation method ensures the successful preparation of a thin-film magnesium battery magnesium aluminum manganate cathode target by precisely controlling the proportions of raw materials, the order of addition of each raw material, the ball milling process parameters, the sintering steps, and the process parameters of each step.

[0040] 2) The aluminum magnesium manganate cathode target of the thin film magnesium battery of the present invention has a uniform composition, no segregation, good grain size consistency, controllable grain deviation, no single phase and defect components, no cracks in the target material, which facilitates thin film deposition.

[0041] 3) The positive electrode layer of the all-solid-state thin-film magnesium battery of the present invention is prepared using the magnesium aluminum manganese oxide positive electrode target of the present invention. The all-solid-state thin-film magnesium battery of the present invention has high safety and extremely high capacity and capacity retention. In addition, the all-solid-state thin-film magnesium battery of the present invention also has excellent interfacial bonding and coordination, with very low interfacial internal resistance. It can easily realize the direct series connection of multiple single cells, the direct parallel connection of multiple single cells, and the series and parallel combination of multiple single cells, which conveniently achieves the goal of increasing the output voltage of the battery, increasing the single cell capacity of the battery pack, or achieving a perfect combination of voltage boosting and capacity expansion.

[0042] In this invention, the above-described technical solutions can be combined with each other to achieve more preferred combinations. Other features and advantages of this invention will be set forth in the following description, and some advantages may become apparent from the description or be learned by practicing the invention. The objectives and other advantages of this invention can be realized and obtained from what is particularly pointed out in the description. Attached Figure Description

[0043] The accompanying drawings are for illustrative purposes only and are not intended to limit the scope of the invention.

[0044] Figure 1 This is a schematic diagram of the positive electrode target of Embodiment 1 of the present invention;

[0045] Figure 2 This is a schematic diagram of the positive electrode target material according to Embodiment 2 of the present invention;

[0046] Figure 3 This is a schematic diagram of the positive electrode target of Embodiment 3 of the present invention;

[0047] Figure 4 This is a schematic diagram of the positive electrode target of Comparative Example 2 of the present invention. Detailed Implementation

[0048] The preferred embodiments of the present invention are described in detail below, which are mainly used to explain the principles of the present invention and are not intended to limit the scope of the present invention.

[0049] This invention provides a method for preparing a magnesium aluminum manganate cathode target for thin-film magnesium batteries, comprising:

[0050] Step 1: Mix magnesium salt powder with manganese tetroxide and aluminum oxide powder to obtain a mixed powder;

[0051] Step 2: Place the above mixed powder into a ball mill jar and mix it with zirconia balls, then add a dispersant and continue mixing and ball milling;

[0052] Step 3: Then add binder into the ball mill jar and continue ball milling;

[0053] Step 4: After ball milling, the synthetic powder is passed through a 500-mesh sieve. The sieved synthetic powder is weighed and then poured into a vibrating mold. Pressure is applied to form a molded blank.

[0054] Step 5: Place the billet into a cold isostatic press, apply pressure and hold pressure to obtain the cold isostatically pressed magnesium aluminum manganate cathode target billet.

[0055] Step 6: Place the aluminum magnesium manganate cathode target blank into an atmosphere sintering furnace or a vacuum sintering furnace, and after multi-stage heat preservation and multi-stage cooling, allow it to cool naturally to room temperature in the furnace to obtain the aluminum magnesium manganate cathode target for thin-film magnesium batteries.

[0056] Specifically, in step 1 above, the magnesium salt may include one or more of magnesium oxide, magnesium carbonate, magnesium nitrate, and magnesium hydroxide.

[0057] Specifically, in step 1 above, the mass ratio of magnesium salt, manganese tetroxide and aluminum oxide is controlled to be 1.1-1.5: 0.8-1: 0.04-0.15.

[0058] Specifically, in step 2 above, to ensure uniform mixing of the powders and to control the particle size of the powders by adjusting the size of the zirconia balls, thus ensuring uniformity in grain size and crystal structure of the sintered magnesium aluminum manganate product, and to guarantee that the powders are broken down and in close contact, reducing the chemical kinetic barrier during synthesis, the particle size of the zirconia balls is controlled to be 0.5 mm to 1.5 mm. When the zirconia ball particle size is outside this range, the mixed powder has a large particle size deviation, resulting in uneven mixing, the presence of many elemental substances, and the inability to sputter the sintered target material.

[0059] Specifically, in step 2 above, the grinding jar is a hard ceramic jar or a stainless steel jar lined with hard ceramic.

[0060] Specifically, in step 2 above, the total volume of the zirconia balls is controlled to be no more than 1 / 3 of the volume of the ball mill jar, and the total volume of the mixed powder is 1 / 5 to 2 / 5 of the volume of the ball mill jar. Preferably, the total volume of the mixed powder is 1 / 3 of the volume of the ball mill jar.

[0061] Specifically, in step 2 above, considering that too much dispersant would be wasteful, while too little dispersant would cause the powder to agglomerate and fail to mix and contact sufficiently, which would be detrimental to synthesis and sintering, the mass ratio of dispersant to mixed powder is controlled at 1.4–1.8:100.

[0062] Specifically, in step 2 above, the dispersant may include isopropanol and isotetracycline. Preferably, the mass ratio of isopropanol to isotetracycline is 1-3:4-6.

[0063] Specifically, in step 2 above, the ball milling process includes:

[0064] S201. Ball milling in the mill jar at an initial speed of 110-150 rpm for 3-5 hours;

[0065] S202. Grind the balls in a milling jar at a speed of 310-330 rpm for more than 13 hours.

[0066] Specifically, in step 2 above, the ball milling process first uses a lower rotation speed and then a higher rotation speed. This ensures that the powder is mixed evenly, facilitating subsequent synthesis reactions. Without using the appropriate ball milling parameters, the mixture will be uneven, containing many elemental substances, and the sintered target material will not be able to be sputtered.

[0067] Specifically, in step 3 above, polyvinyl butyral can be used as the binder. Too much binder will be wasteful, while too little binder will prevent the uniformly mixed raw material powder from fully contacting and rapidly participating in the chemical reaction during sintering. Therefore, the mass ratio of binder to mixed powder should be controlled at 0.8–1.1:100.

[0068] Specifically, in step 3 above, in order to ensure that the powder is mixed evenly, the ball mill speed is controlled at 175-190 rpm and the ball milling time is 8-10 h.

[0069] Specifically, in step 4 above, to ensure the uniformity of grain size and crystal phase structure of the sintered magnesium aluminum manganate product, the synthetic powder is controlled to pass through a 500-mesh sieve. If this parameter is not within the range, the powder particle size will be dispersed, resulting in large voids in the target compact, preventing complete ceramization after sintering and hindering sputtering deposition.

[0070] Specifically, in step 4 above, considering that excessive pressure would place high demands on the equipment, while insufficient pressure would be ineffective, the pressure is controlled at 1450–1550 tons to form the molded blank.

[0071] Specifically, in step 5 above, considering that excessive pressure during the cold isostatic pressing process places high demands on the equipment, while insufficient pressure renders it ineffective, the pressure is controlled to be increased to 300–350 MPa and held for 40–60 minutes.

[0072] Specifically, step 6 above, which involves using an atmosphere sintering furnace, includes:

[0073] S601. Place the aluminum magnesium manganate cathode target blank into an atmosphere sintering furnace, continuously introduce N2+Ar mixed gas, raise the temperature from room temperature to 190-210℃, and hold for 3-4 hours; wherein, the volume ratio of N2 to Ar is 6.5-7.5:3.

[0074] S602, raise the temperature again to 540-560℃, and continuously purge the N2+Ar mixed gas for 5-7 hours; wherein the volume ratio of N2 to Ar is 6-7:4.

[0075] S603, heat up again to 740-760℃, and continuously purge the N2+Ar mixed gas for 7-9 hours; wherein the volume ratio of N2 to Ar is 6-7:4.

[0076] S604, heat again to 940-960℃, and continuously purge N2+Ar mixed gas for 9-11 hours; wherein the volume ratio of N2 to Ar is 6-7:4.

[0077] S605, heat again to 1130~1160℃, and continuously purge N2+Ar mixed gas for 5~7h; wherein, the volume ratio of N2 to Ar is 6~7:4;

[0078] S606, slowly cool to 490-510℃ in the furnace, and hold for 3-5 hours;

[0079] S607, and then naturally cooled to room temperature in the furnace to obtain the magnesium aluminum manganate cathode target for thin-film magnesium batteries.

[0080] Specifically, in S606 and S607 above, in order to ensure the uniformity of the microstructure of the obtained aluminum magnesium manganate cathode target, it is necessary to first slowly cool it to 490-510℃ in the furnace and hold it for 3-5 hours; then cool it naturally to room temperature in the furnace.

[0081] Specifically, step 6 above, which involves using a vacuum sintering furnace, includes:

[0082] S601. Place the aluminum magnesium manganate cathode target blank into a vacuum sintering furnace, maintaining a vacuum level of 10. -3 Below Pa, the temperature is raised from room temperature to 190–210℃ and held for 3–4 hours;

[0083] S602, raise the temperature again to 540-560℃ and keep it warm for 5-7 hours;

[0084] S603, heat again to 740-760℃, and keep warm for 7-9 hours;

[0085] S604, heat again to 940-960℃, and hold for 9-11 hours;

[0086] S605, heat up again to 1130~1160℃, and keep warm for 5~7 hours;

[0087] S606, slowly cool to 490-510℃ in the furnace, and hold for 3-5 hours;

[0088] S607, and then naturally cooled to room temperature in the furnace to obtain the magnesium aluminum manganate cathode target for thin-film magnesium batteries.

[0089] Specifically, in S602 to S605 above, the vacuum level is always maintained at 10. -3 Below pa.

[0090] Specifically, in S606 and S607 above, in order to ensure the uniformity of the microstructure of the obtained aluminum magnesium manganate cathode target, it is necessary to first slowly cool it to 490-510℃ in the furnace and hold it for 3-5 hours; then cool it naturally to room temperature in the furnace.

[0091] Specifically, in step 6 above, the parameters such as temperature, atmosphere, and holding time for each of the multiple heating stages are all taken into account the chemical reaction kinetics requirements of sintering. These parameters are controlled to ensure the uniformity of composition and the required grain structure of the synthesized magnesium aluminum manganate during the sintering process. Sintering outside this temperature range will result in incomplete ceramization of the target material, leading to over-sintering, under-sintering, porosity, and deformation, rendering the target material unusable.

[0092] Specifically, in step 6 above, the resulting thin-film magnesium aluminum manganese oxide cathode target has a uniform composition, no segregation, good grain size consistency, controllable grain deviation, no single-phase or defect components, and no cracks within the target, facilitating thin-film deposition. The grain size of the thin-film magnesium aluminum manganese oxide cathode target is between 340 nm and 410 nm, the flatness of the target after sintering is approximately 0.13–0.17 mm, and the relative density of the sintered target is approximately 93%–96.5%.

[0093] The present invention also provides a thin-film magnesium aluminum manganese magnesium cathode target material for magnesium batteries, which is prepared by the above method.

[0094] The present invention also provides an all-solid-state thin-film magnesium battery, wherein the positive electrode of the all-solid-state thin-film magnesium battery is prepared using the above-mentioned aluminum magnesium manganate positive electrode target for thin-film magnesium batteries.

[0095] Specifically, the aforementioned all-solid-state thin-film magnesium battery includes a positive electrode layer, an electrolyte layer, and a negative electrode layer. The positive electrode layer is prepared using the aforementioned magnesium aluminum manganate positive electrode target for thin-film magnesium batteries.

[0096] Specifically, the preparation method of the above-mentioned all-solid-state thin-film magnesium battery includes:

[0097] Step 1: Deposit a thin film of magnesium anode on the surface of copper foil;

[0098] Step 2: Next, a solid electrolyte film is deposited on the negative electrode magnesium film;

[0099] Step 3: Deposit a positive electrode film on the solid electrolyte film using the above-mentioned magnesium aluminum manganate positive electrode target for thin film magnesium batteries;

[0100] Step 4: After formation, an all-solid-state thin-film magnesium battery is obtained.

[0101] Specifically, the all-solid-state thin-film magnesium battery of the present invention, in addition to high safety, also has high capacity and capacity retention. For example, with a capacity of 17970 mAh or higher (e.g., 17970–52736 mAh), the capacity remains essentially unchanged after more than 10,000 cycles. Furthermore, the all-solid-state thin-film magnesium battery of the present invention also has excellent interfacial bonding and compatibility, with very low interfacial resistance, for example, less than 0.01 ohms / cm. 2 It can very easily realize the direct series connection of multiple single cells, the direct parallel connection of multiple single cells, and the series and parallel combination of multiple single cells, which can conveniently increase the output voltage of the battery, increase the single cell capacity of the battery pack, or achieve a perfect combination of voltage boosting and capacity expansion.

[0102] The preparation method and application of the magnesium aluminum manganate cathode target for thin-film magnesium batteries of the present invention will be further described below with reference to specific embodiments. Unless otherwise specified, all raw materials used are commercially available.

[0103] Example 1

[0104] This embodiment provides a method for preparing a magnesium aluminum manganate cathode target for thin-film magnesium batteries, including:

[0105] Step 1: Mix magnesium salt powder with manganese tetroxide and aluminum oxide powder to obtain a mixed powder; the magnesium salt used is magnesium oxide, and the mass ratio of magnesium oxide, manganese tetroxide and aluminum oxide is 1.2:0.8:0.05;

[0106] Step 2: Place the above mixed powder into a ball mill jar and mix it with zirconia balls with a particle size of 0.5 mm to 1.5 mm. Then add a dispersant and continue mixing and ball milling. The ball mill jar is a hard ceramic jar. The total volume of the zirconia balls occupies 1 / 3 of the volume of the ball mill jar, and the total volume of the mixed powder occupies 1 / 3 of the volume of the ball mill jar. The mass ratio of dispersant to mixed powder is 1.5:100.

[0107] Specifically, in step 2, the ball milling process includes:

[0108] S201, the ball mill jar is used to ball mill at an initial speed of 120 rpm for 4.5 hours;

[0109] S202, ball milling in a milling jar at a speed of 320 rpm for 13 hours;

[0110] Step 3: Then add binder into the ball mill jar and ball mill at 185 rpm for 9 hours; the mass ratio of binder to mixed powder is 0.9:100.

[0111] Step 4: After ball milling, the synthetic powder is passed through a 500-mesh sieve. The sieved synthetic powder is weighed and then poured into a vibrating mold. It is then pressed with 1500 tons to form a molded blank.

[0112] Step 5: Place the billet into a cold isostatic press, pressurize it to 330 MPa, hold the pressure for 50 minutes, and obtain the cold isostatically pressed magnesium aluminum manganate cathode target billet.

[0113] Step 6: Place the aluminum magnesium manganate cathode target blank into an atmosphere sintering furnace for multi-stage heat preservation and multi-stage cooling, and then let it cool naturally to room temperature with the furnace to obtain the aluminum magnesium manganate cathode target for thin film magnesium battery.

[0114] Step 6 includes:

[0115] S601. Place the aluminum magnesium manganate cathode target blank into an atmosphere sintering furnace and continuously introduce a N2+Ar (ratio 7:3) mixed gas. Raise the temperature from room temperature to 200℃ and hold for 3.5 hours.

[0116] S602, raise the temperature to 550℃ again, and keep it at that temperature for 6 hours while continuously introducing a N2+Ar (ratio 6:4) mixed gas;

[0117] S603, raise the temperature again to 750℃, and continuously introduce a N2+Ar (ratio 6:4) mixed gas, and keep it at this temperature for 8 hours;

[0118] S604, raise the temperature again to 950℃, and continuously introduce a N2+Ar (ratio 6:4) mixed gas, and keep it at this temperature for 10 hours;

[0119] S605, raise the temperature to 1150℃ again, and continuously introduce a N2+Ar (ratio 6:4) mixed gas, and keep it at this temperature for 6 hours;

[0120] S606, slowly cool to 500℃ in the furnace and hold for 4 hours;

[0121] S607, and then naturally cooled to room temperature in the furnace to obtain the magnesium aluminum manganate cathode target for thin-film magnesium batteries.

[0122] The thin-film magnesium battery aluminum manganate magnesium cathode target obtained in this embodiment is as follows: Figure 1As shown, the positive electrode target has a uniform composition, no segregation, good grain size consistency, controllable grain deviation, no single phase or defect components, and no cracks within the target, facilitating thin film deposition. Specifically, in this embodiment, the grain size of the magnesium aluminum manganese oxide positive electrode target for the thin-film magnesium battery is between 340 nm and 390 nm, the flatness of the target after sintering is approximately 0.17 mm, and the relative density of the sintered target is 96.3%.

[0123] Example 2

[0124] This embodiment provides a method for preparing a magnesium aluminum manganate cathode target for thin-film magnesium batteries, including:

[0125] Step 1: Mix magnesium salt powder with manganese tetroxide and aluminum oxide powder to obtain a mixed powder; the magnesium salt used is magnesium oxide, and the mass ratio of magnesium oxide, manganese tetroxide and aluminum oxide is 1.3:0.8:0.06;

[0126] Step 2: Place the above mixed powder into a ball mill jar and mix it with zirconia balls with a particle size of 0.5 mm to 1.5 mm. Then add a dispersant and continue mixing and ball milling. The ball mill jar is a hard ceramic jar. The total volume of the zirconia balls occupies 1 / 3 of the volume of the ball mill jar, and the total volume of the mixed powder occupies 1 / 3 of the volume of the ball mill jar. The mass ratio of dispersant to mixed powder is 1.6:100.

[0127] Specifically, in step 2, the ball milling process includes:

[0128] S201. The ball mill jar is used to ball mill at an initial speed of 140 rpm for 3 hours.

[0129] S202, ball milling in a milling jar at a speed of 320 rpm for 13 hours;

[0130] Step 3: Then add binder into the ball mill jar and ball mill at 185 rpm for 9 hours; the mass ratio of binder to mixed powder is 1:100.

[0131] Step 4: After ball milling, the synthetic powder is passed through a 500-mesh sieve. The sieved synthetic powder is weighed and then poured into a vibrating mold. It is then pressed with 1550 tons to form a molded blank.

[0132] Step 5: Place the billet into a cold isostatic press, pressurize it to 310 MPa, hold the pressure for 60 minutes, and obtain the cold isostatically pressed magnesium aluminum manganate cathode target billet.

[0133] Step 6: Place the aluminum magnesium manganate cathode target blank into an atmosphere sintering furnace for multi-stage heat preservation and multi-stage cooling, and then let it cool naturally to room temperature with the furnace to obtain the aluminum magnesium manganate cathode target for thin film magnesium battery.

[0134] Step 6 includes:

[0135] S601. Place the aluminum magnesium manganate cathode target blank into an atmosphere sintering furnace and continuously introduce a N2+Ar (ratio 6.5:3) mixed gas. Raise the temperature from room temperature to 210℃ and hold for 3 hours.

[0136] S602, raise the temperature again to 560℃, and continuously purge the mixture of N2+Ar (ratio 6.5:4) for 6 hours;

[0137] S603, heat up to 745℃ again, and continuously purify with a N2+Ar (ratio 6.5:4) mixed gas for 9 hours;

[0138] S604, raise the temperature again to 940℃, and continuously purify with a N2+Ar (ratio 6.5:4) mixed gas for 11 hours;

[0139] S605, raise the temperature again to 1150℃, and continuously introduce a N2+Ar (ratio 6.5:4) mixed gas, and keep it at this temperature for 5.5 hours;

[0140] S606, slowly cooled to 495℃ in the furnace, and held at that temperature for 4.5 hours;

[0141] S607, and then naturally cooled to room temperature in the furnace to obtain the magnesium aluminum manganate cathode target for thin-film magnesium batteries.

[0142] The thin-film magnesium battery aluminum manganate magnesium cathode target obtained in this embodiment is as follows: Figure 2 As shown, the positive electrode target has a uniform composition, no segregation, good grain size consistency, controllable grain deviation, no single phase or defect components, and no cracks within the target, facilitating thin film deposition. Specifically, in this embodiment, the grain size of the magnesium aluminum manganese oxide positive electrode target for the thin-film magnesium battery is between 345nm and 395nm, the flatness of the target after sintering is approximately 0.16mm, and the relative density of the sintered target is 96%.

[0143] Example 3

[0144] This embodiment provides a method for preparing a magnesium aluminum manganate cathode target for a thin-film magnesium battery. Steps 1-5 are the same as in Example 1 and will not be repeated here. The method also includes:

[0145] Step 6: Place the aluminum magnesium manganate cathode target blank into a vacuum sintering furnace, perform multi-stage heat preservation and multi-stage cooling, and then allow it to cool naturally to room temperature in the furnace to obtain the aluminum magnesium manganate cathode target for thin-film magnesium batteries.

[0146] Step 6 includes:

[0147] S601. Place the aluminum magnesium manganate cathode target blank into a vacuum sintering furnace, maintaining a vacuum level of 10. -3 Below Pa, the temperature is increased from room temperature to 200℃ and held for 3.5 hours;

[0148] S602, raise the temperature again to 550℃ and keep it warm for 6 hours;

[0149] S603, heat up to 750℃ again and keep warm for 8 hours;

[0150] S604, heat up to 950℃ again and keep warm for 10 hours;

[0151] S605, heat up to 1150℃ again and keep warm for 6 hours;

[0152] S606, slowly cool to 500℃ in the furnace and hold for 4 hours;

[0153] S607, and then naturally cooled to room temperature in the furnace to obtain the magnesium aluminum manganate cathode target for thin-film magnesium batteries.

[0154] Specifically, in S602 to S605 above, the vacuum level is always maintained at 10. -3 Below pa.

[0155] The thin-film magnesium battery aluminum manganate magnesium cathode target obtained in this embodiment is as follows: Figure 3 As shown, the positive electrode target has a uniform composition, no segregation, good grain size consistency, controllable grain deviation, no single phase or defect components, and no cracks within the target, facilitating thin film deposition. Specifically, in this embodiment, the grain size of the magnesium aluminum manganese oxide positive electrode target for the thin-film magnesium battery is between 345nm and 390nm, the flatness of the target after sintering is approximately 0.165mm, and the relative density of the sintered target is 96.5%.

[0156] Example 4

[0157] This embodiment provides an all-solid-state thin-film magnesium battery. The fabrication method of this embodiment for depositing a single-cell all-solid-state thin-film magnesium battery includes:

[0158] Step 1: Deposit a negative electrode magnesium film on a 1 square meter copper foil surface. The thickness of the negative electrode magnesium film is 4.5 μm.

[0159] Step 2: Next, a solid electrolyte film is deposited on the negative electrode magnesium film, with a thickness of 1.5 μm;

[0160] Step 3: Deposit a positive electrode film on the solid electrolyte film using the magnesium aluminum manganate positive electrode target of Example 1 above; the thickness of the positive electrode film is 15 μm;

[0161] Step 4: After formation, an all-solid-state thin-film magnesium battery is obtained.

[0162] The interfacial resistance of the all-solid-state thin-film magnesium battery in this embodiment is less than 0.01 ohms / cm. 2 With a capacity of 17970 mAh, the capacity remains essentially unchanged after more than 10,000 cycles.

[0163] Example 5

[0164] This embodiment provides an all-solid-state thin-film magnesium battery. The fabrication method for this embodiment involves depositing two series-connected all-solid-state thin-film magnesium batteries.

[0165] The magnesium anode film thickness of each thin-film magnesium battery was 5.5 μm, deposited on a 1 square meter copper foil surface. The solid electrolyte film thickness of each subsequent battery was 2.0 μm. Using the magnesium aluminum manganese oxide cathode target from Example 2, the cathode film thickness of the resulting thin-film magnesium battery was 18.5 μm. After formation, the battery achieved a capacity of 22164 mA h; the capacity remained essentially unchanged after more than 10000 cycles; and the interfacial resistance was less than 0.01 ohms / cm. 2 .

[0166] Example 6

[0167] This embodiment provides an all-solid-state thin-film magnesium battery. The method for depositing two parallel all-solid-state thin-film magnesium batteries includes:

[0168] The negative electrode magnesium film thickness of each battery cell deposited on a 1 square meter copper foil surface is 6.5 μm. The subsequent solid electrolyte film thickness of each battery cell is 2.5 μm. Using the magnesium aluminum manganese oxide positive electrode target from Example 3, the positive electrode film thickness of the resulting magnesium battery is 22 μm. After formation, the battery exhibits a capacity of 52736 mA h; the capacity remains essentially unchanged after more than 10000 cycles; and the interfacial resistance is less than 0.01 ohms / cm. 2 .

[0169] Comparative Example 1

[0170] This comparative example provides a method for preparing a magnesium aluminum manganate cathode target for thin-film magnesium batteries, as detailed below:

[0171] Step 1: Mix magnesium salt powder with manganese tetroxide and aluminum oxide powder to obtain a mixed powder; the magnesium salt used is magnesium oxide, and the mass ratio of magnesium oxide, manganese tetroxide and aluminum oxide is 1.1:0.8:0.05;

[0172] Step 2: Place the above mixed powder into a ball mill jar and mix it with zirconia balls with a particle size of 0.5 mm to 1.3 mm. Then add a dispersant and continue mixing. Ball mill at 150 rpm for 3 hours. The ball mill jar is a hard ceramic jar. The total volume of the zirconia balls occupies 2 / 5 of the volume of the ball mill jar, and the total volume of the mixed powder occupies 1 / 3 of the volume of the ball mill jar. The mass ratio of dispersant to mixed powder is 1.3:100.

[0173] Step 3: Then add binder into the ball mill jar and ball mill at 145 rpm for 5 hours; the mass ratio of binder to mixed powder is 0.5:100.

[0174] Step 4: After ball milling, the synthetic powder is passed through a 500-mesh sieve. The sieved synthetic powder is weighed and then poured into a vibrating mold. It is then pressed with 800 tons to form a molded blank.

[0175] Step 5: Place the billet into a cold isostatic press, pressurize it to 100 MPa, and hold the pressure for 40 minutes. However, a suitable aluminum magnesium manganate cathode target billet cannot be obtained.

[0176] The process parameters in this comparative example are unsuitable, and it is impossible to obtain the magnesium aluminum manganate cathode target for thin-film magnesium batteries.

[0177] Comparative Example 2

[0178] This comparative example provides a method for preparing a magnesium aluminum manganate cathode target for thin-film magnesium batteries, as detailed below:

[0179] In step 2 of this comparative example, the particle size of the zirconia spheres is 1.8–2.5 mm; S601 is omitted, and the remaining steps are the same as those in Example 1.

[0180] The positive electrode target of this comparative example is as follows: Figure 4 As shown, the target material has large grain deviations, uneven mixing, and contains many elemental substances, making it impossible to sputter the sintered target material.

[0181] Comparative Example 3

[0182] This comparative example provides a method for preparing a magnesium aluminum manganate cathode target for thin-film magnesium batteries, as detailed below:

[0183] In step 2 of this comparative example, the ball milling process is directly carried out at 300-350 rpm for more than 12 hours; S602 is omitted, and the remaining steps are the same as those in Example 1.

[0184] In this comparative example, the powder was not mixed evenly and contained many elemental substances, so the sintered target material could not be sputtered.

[0185] Comparative Example 4

[0186] This comparative example provides a method for preparing a magnesium aluminum manganate cathode target for thin-film magnesium batteries, as detailed below:

[0187] In step 4 of this comparative example, the synthetic powder is controlled to pass through a 300-mesh sieve; the remaining steps are the same as those in Example 1.

[0188] The target blank in this comparative example has large voids, and cannot be completely ceramicized after sintering, thus making sputtering deposition impossible.

[0189] Comparative Example 5

[0190] This comparative example provides a method for preparing a magnesium aluminum manganate cathode target for thin-film magnesium batteries, as detailed below:

[0191] In step 6 of this comparative example, steps S603-S607 are performed directly; the remaining steps are the same as those in Example 1.

[0192] The target material in this comparative example cannot be fully ceramicized and is therefore unusable.

[0193] The above description is only a preferred embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any changes or substitutions that can be easily conceived by those skilled in the art within the scope of the technology disclosed in the present invention should be included within the scope of protection of the present invention.

Claims

1. A method for preparing a magnesium aluminum manganate cathode target for a thin-film magnesium battery, characterized in that, include: Step 1: Mix magnesium salt powder with manganese tetroxide and aluminum oxide powder to obtain a mixed powder, wherein the mass ratio of magnesium salt, manganese tetroxide and aluminum oxide is 1.1~1.5:0.8~1:0.04~0.15; Step 2: Place the above mixed powder into a ball mill jar and mix it with zirconia balls. Then add a dispersant and continue mixing and ball milling. Control the particle size of the zirconia balls to be 0.5 mm to 1.5 mm. Step 3: Then add binder into the ball mill jar and continue ball milling; Step 4: After ball milling, the synthetic powder is passed through a 500-mesh sieve. The sieved synthetic powder is poured into a vibrating mold and pressed to form a molded blank. Step 5: Place the billet into a cold isostatic press, apply pressure and hold pressure to obtain the cold isostatically pressed magnesium aluminum manganate cathode target billet. Step 6: Place the aluminum magnesium manganate cathode target blank into an atmosphere sintering furnace or a vacuum sintering furnace, and after multi-stage heat preservation and multi-stage cooling, allow it to cool naturally to room temperature in the furnace to obtain the aluminum magnesium manganate cathode target for thin-film magnesium batteries. In step 2, the ball milling process includes: S201, ball milling in the mill jar at an initial speed of 110-150 rpm for 3-5 hours; S202, ball milling in a milling jar at a speed of 310~330 rpm for more than 13 hours; In step 4, the pressure is controlled to be 1450~1550 tons; In step 5, the pressure is controlled to be increased to 300~350MPa and held for 40~60min; Step 6, the step of using an atmosphere sintering furnace, includes: S601. Place the aluminum magnesium manganate cathode target blank into an atmosphere sintering furnace, continuously introduce N2+Ar mixed gas, raise the temperature from room temperature to 190~210℃, and hold for 3~4 hours. S602, raise the temperature again to 540~560℃, and continuously introduce N2+Ar mixed gas, and keep it at this temperature for 5~7 hours; S603, heat up again to 740~760℃, and continuously purge N2+Ar mixed gas, and keep at this temperature for 7~9 hours; S604, heat up again to 940~960℃, and continuously purge N2+Ar mixed gas, and keep at this temperature for 9~11 hours; S605, heat up again to 1130~1160℃, and continuously purge N2+Ar mixed gas, and keep at this temperature for 5~7 hours; S606, slowly cool to 490~510℃ in the furnace, and hold for 3~5 hours; S607, and then naturally cooled to room temperature in the furnace to obtain the magnesium aluminum manganate cathode target for thin-film magnesium batteries; Step 6, the step of using a vacuum sintering furnace, includes: S601. Place the aluminum magnesium manganate cathode target blank into a vacuum sintering furnace, maintaining a vacuum level of 10. -3 Below Pa, the temperature is raised from room temperature to 190~210℃ and held for 3~4 hours; S602, raise the temperature again to 540~560℃, and keep it at that temperature for 5~7 hours; S603, heat again to 740~760℃, and keep warm for 7~9 hours; S604, heat again to 940~960℃, and keep warm for 9~11 hours; S605, heat up again to 1130~1160℃, and keep warm for 5~7 hours; S606, slowly cool to 490~510℃ in the furnace, and hold for 3~5 hours; S607, and then naturally cooled to room temperature in the furnace to obtain the magnesium aluminum manganate cathode target for thin-film magnesium batteries.

2. The preparation method according to claim 1, characterized in that, In step 6, the step of using an atmosphere sintering furnace, S601, the aluminum magnesium manganate cathode target blank is placed in the atmosphere sintering furnace, and N2+Ar mixed gas is continuously introduced, the temperature is raised from room temperature to 200~210℃, and held for 3~4 hours.

3. The preparation method according to claim 1, characterized in that, In step 6, the step of using a vacuum sintering furnace involves, in step S601, placing the aluminum magnesium manganate cathode target blank into the vacuum sintering furnace and maintaining a vacuum degree of 10. -3 Below Pa, the temperature is raised from room temperature to 200~210℃ and kept at that temperature for 3~4 hours.

4. The preparation method according to claim 1, characterized in that, In step 4, the pressure is controlled to be 1500~1550 tons.

5. The preparation method according to claim 1, characterized in that, In step 2, the mass ratio of dispersant to mixed powder is controlled to be 1.4~1.8:

100.

6. The preparation method according to claim 1, characterized in that, In step 2, S201 and the ball milling jar are ball-milled at an initial speed of 120-150 rpm for 3-5 hours.

7. The preparation method according to claim 1, characterized in that, In step 3, the mass ratio of binder to mixed powder is controlled to be 0.8~1.1:

100.

8. The preparation method according to claim 1, characterized in that, In step 5, the pressure is controlled to be increased to 310~350MPa and held for 40~60min.

9. A thin-film magnesium aluminum manganese oxide positive electrode target for magnesium batteries, characterized in that, The thin-film magnesium battery aluminum manganese magnesium cathode target is prepared by the preparation method described in any one of claims 1-8.

10. A fully solid-state thin-film magnesium battery, characterized in that, The positive electrode of the all-solid-state thin-film magnesium battery is prepared using the magnesium aluminum manganate positive electrode target of the thin-film magnesium battery as described in claim 9.

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