Metal composite sheet electrode material and manufacturing method and winding system thereof

Abstract

The invention discloses a metal composite sheet electrode material and a manufacturing method and a winding system thereof, and the method comprises the steps: carrying out the rolling of a linear composite component through a rolling unit into a strip-shaped composite component, and enabling the diameter of the linear composite component to be 1-500 microns; putting the active metal into a heating container in the inert environment unit, and heating until the active metal is molten into a liquid state; the strip-shaped composite component is pulled to enter the liquid active metal through rotation of the winding shaft, so that the liquid active metal dipping the surface of the strip-shaped composite component is solidified to form a coating, and an active metal composite material is obtained; and winding the active metal composite material in a plane perpendicular to a winding shaft through the winding shaft to obtain the metal composite sheet with the winding structure. When the metal composite sheet is applied to an electrode material of a metal battery, the advantage of high capacity of a metal lithium or sodium electrode can be kept, dendritic crystal growth can be inhibited, and metal volume expansion can be controlled.

Description

[0001] This application is a divisional application, the parent application of which is the invention patent application filed on April 16, 2019, with application number "201910302875.X" and invention title "A winding system and its usage method". Technical Field

[0002] This invention belongs to the field of electrochemical materials, specifically relating to a metal composite thin-film electrode material, its fabrication method, and its winding system. Background Technology

[0003] In recent years, with the rapid development of mobile devices, vehicle electrification, grid storage, and big data transmission, the demand for high-energy-density batteries has steadily increased. Among existing energy storage systems, lithium-ion batteries, the most widely used and highest-energy-density battery, are no longer sufficient to meet application demands. Metal battery systems, which use metals with relatively negative electrode potentials such as lithium, sodium, zinc, magnesium, aluminum, mercury, and iron as the negative electrode, are promising. Lithium metal batteries have the highest specific capacity (3860 mAh / g) and the lowest electrochemical potential (-3.04 V), making them a potential next-generation high-energy-density battery system. Furthermore, sodium metal batteries and zinc metal batteries also have very broad application prospects due to their abundant resources.

[0004] However, when lithium, sodium, and zinc are used as electrode materials in battery systems, they all have the same problems: (1) During repeated charging and discharging, dendrites are unevenly deposited at the metal interface. As the dendrites grow, they may puncture the separator, causing a short circuit in the battery and leading to safety issues. (2) Due to the lack of a framework structure in metals, the volume expands infinitely during charging and discharging, causing the solid electrolyte membrane (SEI membrane) on the electrode surface to rupture, which seriously damages the stability of the electrode, resulting in a decrease in coulombic efficiency and a reduction in cycle life.

[0005] To address dendrite growth, existing technologies employ methods such as depositing an oxide passivation layer (Al2O3) on the metal electrode surface or adding functional ion additives to achieve uniform metal deposition and suppress dendrite growth. Other researchers have proposed enhancing the mechanical strength of the separator or using solid-state electrolyte encapsulation to avoid safety issues caused by dendrite puncture. Solutions to the volume expansion problem of metals primarily involve depositing metals onto porous three-dimensional metal meshes or carbon materials to form metal composite electrodes. However, this method reduces the electrode's energy density and is complex to implement. How to suppress dendrite growth in the metal anode while simultaneously addressing the volume expansion issue is a pressing problem for metal battery systems and is of great significance for the future development of electrochemical energy storage. Summary of the Invention

[0006] To overcome the problems of dendrite growth and volume expansion during charging and discharging when lithium, sodium, and zinc are used as electrode materials in metal batteries, which can lead to reduced battery performance and even safety hazards, this invention provides a winding system and its usage method for preparing active metal composite sheets with high capacity, high rate capability, and cycle stability.

[0007] The present invention adopts the following technical solution: A winding system includes an inert environment unit and a winding unit housed within the inert environment unit. The inert environment unit includes a main chamber, an inlet / outlet chamber, and an inert gas storage tank. The winding unit is located within the main chamber. The inert gas storage tank is connected to the main chamber via a pipeline. The main chamber is equipped with a heating container for heating an active metal to a molten state. The winding unit includes a winding shaft, a rotating shaft, and a traction shaft, which are respectively fixed on a winding substrate.

[0008] Furthermore, the inert environment unit also includes a vacuum pump for pumping inert gas, which is connected to the main chamber and the feed / discharge chamber via pipelines.

[0009] Furthermore, the inert environment unit is a sunken space.

[0010] Furthermore, a first door is provided between the main compartment and the inlet / outlet compartment, and a second door is provided on the side of the inlet / outlet compartment opposite to the first door.

[0011] Furthermore, the winding system further includes a cooling unit housed within the main chamber of the inert environment unit for rapidly solidifying the liquid active metal, the cooling unit including a cooling device; the cooling device may be a cooling device or a fan.

[0012] Furthermore, the winding system further includes a pressure roller housed within the main chamber of the inert environment unit for further pressing the active metal composite material before winding it.

[0013] Furthermore, the winding system further includes a surface modification unit housed within the main compartment of the inert environment unit for surface modification of the composite components.

[0014] Furthermore, the surface modification unit is selected from at least one of heating equipment, spraying equipment, vapor deposition equipment, electroplating equipment, sputtering equipment, chemical reaction device, liquid phase chemical deposition or vapor phase chemical deposition device, which deposits a layer of metal, metal oxide or two-dimensional material on the surface of the composite component through modification.

[0015] Furthermore, the composite component is in the form of a strip or a line.

[0016] Furthermore, when the composite component is in the form of a strip, its thickness is 3 micrometers to 50 micrometers and its width is 10 micrometers to 0.5 centimeters.

[0017] Furthermore, when the composite component is linear, its diameter is 1 to 500 micrometers.

[0018] Furthermore, the winding system further includes a rolling unit housed within the main compartment of the inert environment unit for rolling the linear composite components into a strip.

[0019] A method for fabricating an active metal composite sheet using the above-described winding system includes the following steps: 1) Fill the inert environment unit with inert gas, place the wound composite components on the rotating shaft, and then pass them through the traction shaft and fix them on the winding shaft in sequence. 2) Place the active metal into the heating container in the inert environment unit and heat it until the active metal melts into a liquid state; 3) By rotating the winding shaft, the composite component is drawn into the liquid active metal at a speed of 0.1~100 cm / s. The traction and lifting are continued at a speed of 0.1~100 cm / s, so that the composite component leaves the surface of the liquid active metal. After 1~600s, the liquid active metal coated on the surface of the composite component solidifies to form a coating (because the ambient temperature is lower than the melting temperature, the liquid active metal coating on the surface of the composite component solidifies immediately), thus obtaining the active metal composite material. 4) The active metal composite material is wound through a winding shaft in a plane perpendicular to the winding shaft (with the winding shaft as the axis) at a rotation speed of 100~5000 r / min to obtain an active metal composite sheet with a winding structure.

[0020] Furthermore, in step 3), after the composite component leaves the surface of the active metal liquid, a cooling step is also included; the cooling step is to reduce the ambient temperature to 0~40℃ by means of a cooling device; or to remove the heat of the liquid metal on the surface of the composite component by means of a fan.

[0021] Furthermore, the method may also include step 5) between step 3) and step 4): further rolling the obtained active metal composite material through a pressure roller so that the active metal can be more evenly distributed on the surface of the composite component.

[0022] Furthermore, in step 3), before the composite component enters the liquid active metal, step 6) is also included: sending the composite component into the surface modification unit for surface modification.

[0023] Furthermore, the surface modification specifically refers to depositing a layer of metal, metal oxide, or two-dimensional material on the surface of the composite component through heating, spraying, evaporation, electroplating, sputtering, chemical reaction replacement, liquid phase chemical deposition, or gas phase chemical deposition, thereby modifying the deposition of a layer of metal, metal oxide, or two-dimensional material on the surface of the composite component.

[0024] Furthermore, the active metal refers to a metal with electrochemical activity in an electrochemical energy storage system, including zinc, silver, or gold; the metal oxide includes zinc oxide, copper oxide, aluminum oxide, iron oxide, or tin oxide; and the two-dimensional material includes titanium carbide, graphene, MXenes, boron nitride, or black phosphorus.

[0025] Further, in step 1), the inert atmosphere is one or more of nitrogen, argon, or helium, preferably argon; in step 2), the active metal includes lithium, sodium, and zinc.

[0026] Further, in step 2), when the active metal is lithium, the heating temperature range is set between 180℃ and 1320℃, preferably between 180℃ and 600℃; when the active metal is sodium, the heating temperature range is set between 97℃ and 885℃, preferably between 97℃ and 600℃; when the active metal is zinc, the heating temperature range is set between 420℃ and 910℃, preferably between 500℃ and 600℃.

[0027] Furthermore, when the selected composite component is linear, the step of rolling the linear material into a strip by a rolling unit is included before step 2).

[0028] Further, step 3) specifically involves: the composite component is pulled by the rotation of the winding shaft at a speed of 0.1~100 cm / s through a traction shaft into the interior of the heating container (the interior of the liquid active metal), and then pulled away from the heating container at a speed of 0.1~100 cm / s to contact another traction shaft, and then pulled through yet another traction shaft at a speed of 0.1~100 cm / s before being fixed on the winding shaft. The rotation of the winding shaft provides traction and lifting force so that the composite component undergoes heat treatment, cooling treatment, surface treatment, or rolling treatment. During the process of passing through the interior of the liquid active metal, the surface of the strip composite component is coated with liquid active metal material.

[0029] Furthermore, in step 4), depending on the shape of the winding, the shape of the thin sheet perpendicular to the winding axis can be circular, square, rectangular, rhomboid, elliptical, etc.

[0030] Furthermore, the active metal composite sheet includes a wound structure, wherein the wound structure has a cross-section perpendicular to a winding axis, and the cross-section containing the winding axis has an array structure. The array structure includes interconnected composite components and active metals, and the composite components and active metals are arranged alternately on the cross-section. In the array structure, the width of the active metal is between 10 nanometers and 500 micrometers, and the mass percentage of the active metal in the composite sheet is 50% to 99%. The thickness of the active metal sheet is between 10 micrometers and 500 micrometers.

[0031] The beneficial effects of this invention are that the process of preparing metal composite sheets using this system is simple, solves the technical problem of the difficulty in composite processing of lithium, sodium, and zinc metals, is suitable for industrial production, and the composite metal sheets obtained by this method have a high active metal content and an array structure. When applied to the electrode materials of metal batteries, they can maintain the high capacity advantages of lithium, sodium, and zinc metal electrodes, while also suppressing dendrite growth and controlling metal volume expansion, exhibiting excellent high capacity, high rate capability, long lifespan, and safety. It has great application prospects in metal battery systems and can be widely used in mobile phones, power tools, electric vehicles, mobile electronic devices, energy storage systems, and other fields. Attached Figure Description

[0032] Figure 1 This is a schematic diagram of a winding system according to an embodiment of the present invention; Figure 2 This is a schematic diagram of a winding system containing a cooling unit according to an embodiment of the present invention; Figure 3 This is a schematic diagram of a winding system comprising a cooling unit and a pressure roller according to an embodiment of the present invention; Figure 4 This is a schematic diagram of a winding system comprising a cooling unit, a pressure roller, and a surface modification unit according to an embodiment of the present invention. Figure 5 This is a schematic diagram of a winding system comprising a cooling unit, a pressing roller, a surface modification unit, and a rolling unit, according to an embodiment of the present invention. Figure 6 This is a schematic diagram of the winding system containing a roller pressing unit according to an embodiment of the present invention; Figure 7 This is a schematic diagram of the composition of the winding system in a sinking inert gas environment according to an embodiment of the present invention; Figure 8 A schematic diagram (square) of the active metal composite electrode sheet prepared by the winding system of the present invention, perpendicular to the winding axis plane. Figure 9 A schematic diagram (circle) of the active metal composite electrode sheet prepared by the winding system of the present invention, perpendicular to the winding axis plane. Figure 10 A schematic diagram of the cross-sectional array structure of the active metal composite electrode sheet prepared by the winding system of the present invention; The reference numerals in the attached figures are: 1-Strip composite component; 10-Linear composite component; 11-Rolling unit; 12-Active metal; 2-Composite thin film; 3-Wound shaft; 31-Rotation shaft; 4- Heating container; 51~57 - Traction axle 1 ~ 7; 6-Inert environment unit; 61-Main compartment; 62-Inlet / outlet compartment; 63-Vacuum pump; 64-Inert gas storage tank; 65-Second compartment door; 66-First compartment door; 7-Cooling unit; 71-Cooling equipment; 72-Fan; 8-Pressure roller; 9-Surface modification unit. Detailed Implementation

[0033] To further understand the present invention, preferred embodiments of the present invention are described below in conjunction with examples. However, it should be understood that these descriptions are only for further illustrating the features and advantages of the present invention, and not for limiting the scope of the claims of the present invention.

[0034] like Figure 1-7 As shown, a winding system includes an inert environment unit 6 and a winding unit housed within the inert environment unit 6. The inert environment unit 6 includes a main chamber 61, an inlet / outlet chamber 62, and an inert gas storage tank 64. The winding unit is located within the main chamber 61. The inert gas storage tank 64 is connected to the main chamber 61 via a pipeline. The main chamber 61 is equipped with a heating container 4 for heating an active metal 12 to a molten state. The winding unit includes a winding shaft 3, a rotating shaft 31, and traction shafts 51, 52, and 53, which are respectively fixed on a winding base 15.

[0035] In a specific implementation, the inert environment unit may also include a vacuum pump 63 for pumping inert gas, and the vacuum pump 63 is connected to the main chamber 61 and the inlet / outlet chamber 62 respectively through pipelines.

[0036] In practice, the inert environment unit 6 can be a sunken space.

[0037] In specific implementation, a first door 65 may be provided between the main compartment 61 and the inlet / outlet compartment 62, and a second door 66 may be provided on the side of the inlet / outlet compartment opposite to the first door 65.

[0038] In a specific implementation, the winding system further includes a cooling unit 7 housed in the main chamber 62 of the inert environment unit 6 for rapidly solidifying the liquid active metal 12. The cooling unit 7 includes a cooling device 71; the cooling device 7 can be a cooling device or a fan.

[0039] In a specific implementation, the winding system also includes a pressure roller 8 housed in the main chamber 62 of the inert environment unit 6 for further pressing the active metal composite material before winding it.

[0040] In a specific implementation, the winding system further includes a surface modification unit 9 housed in the main compartment 62 of the inert environment unit 6 for surface modification of the composite component; the surface modification unit 9 is selected from at least one of heating equipment, spraying equipment, vapor deposition equipment, electroplating equipment, sputtering equipment, chemical reaction device, liquid phase chemical deposition or vapor phase chemical deposition device, which deposits a layer of metal, metal oxide or two-dimensional material on the surface of the composite component through modification.

[0041] In specific implementation, the composite component is in the form of a strip or a line; when the composite component is in the form of a strip, its thickness is 3 micrometers to 50 micrometers and its width is 10 micrometers to 0.5 centimeters; when the composite component is in the form of a line, its diameter is 1 to 500 micrometers.

[0042] In a specific implementation, the winding system further includes a rolling unit 11, which is housed in the main compartment 62 of the inert environment unit 6 and is used to roll the linear composite components into a strip.

[0043] A method for fabricating an active metal composite sheet 2 using the above-described winding system includes the following steps: 1) Fill the inert environment unit 6 with inert gas, place the wound composite component on the rotating shaft, and then pass it through the traction shaft and fix it on the winding shaft in sequence. 2) Place the active metal into the heating container 4 in the inert environment unit 6, and heat it until the active metal 12 melts into a liquid state (close the first chamber door 66, open the second chamber door 65 to put the active metal 12 into the inlet / outlet chamber 62, turn on the vacuum pump 63 to evacuate the inlet / outlet chamber 62 until the vacuum degree drops to 0, open the inert gas storage tank 64 to fill the inlet / outlet chamber 62 with inert gas, repeat several times, and when the inlet / outlet chamber 62 is full of inert gas, open the first chamber door 66, put the active metal 12 into the main chamber 61, and close the second chamber door 65). 3) By rotating the winding shaft, the composite component is drawn into the liquid active metal at a speed of 0.1~100 cm / s. The traction and lifting are continued at a speed of 0.1~100 cm / s, so that the composite component leaves the surface of the liquid active metal. After 1~600s, the liquid active metal coated on the surface of the composite component solidifies to form a coating (because the ambient temperature is lower than the melting temperature, the liquid active metal coating on the surface of the composite component solidifies immediately), thus obtaining the active metal composite material. 4) The active metal composite material is wound around a winding shaft in a plane perpendicular to the winding shaft (with the winding shaft as the center) at a rotation speed of 100~5000 r / min to obtain an active metal composite sheet 2 with a wound structure. Depending on the winding shape, the shape of the prepared active metal composite sheet 2 perpendicular to the winding shaft in the plane can be circular, square, rectangular, rhomboid, elliptical, etc., see [reference needed]. Figures 8-10 The active metal composite sheet 2 includes a wound structure, the wound structure being a cross-section perpendicular to a winding axis. The cross-section containing the winding axis has an array structure, the array structure including interconnected strip-shaped composite components 1 and active metal 12, with the strip-shaped composite components 1 and active metal 12 arranged alternately on the cross-section. In the array structure, the width w of the active metal 12 is between 10 nanometers and 500 micrometers, and the mass percentage of the active metal 12 in the composite sheet is 50% to 99%. The thickness d of the active metal 12 sheet is between 10 micrometers and 500 micrometers.

[0044] In specific implementation, step 3) includes a cooling step after the composite component leaves the surface of the active metal liquid; the cooling step is to reduce the ambient temperature to 0~40℃ by cooling equipment 71; or to remove the heat of the liquid metal on the surface of the composite component by a fan.

[0045] In specific implementation, the method may also include step 5) between step 3) and step 4): further rolling the obtained active metal composite material through a pressure roller so that the active metal can be more evenly distributed on the surface of the composite component.

[0046] In specific implementation, before the composite component enters the liquid active metal in step 3), step 6) is also included: sending the composite component into the surface modification unit 9 for surface modification.

[0047] In specific implementation, the surface modification specifically refers to depositing a layer of metal, metal oxide, or two-dimensional material on the surface of the composite component through heating, spraying, evaporation, electroplating, sputtering, chemical reaction replacement, liquid phase chemical deposition, or gas phase chemical deposition, thereby modifying the deposition of a layer of metal, metal oxide, or two-dimensional material on the surface of the composite component.

[0048] In specific implementation, the active metal refers to a metal with electrochemical activity in an electrochemical energy storage system, including zinc, silver, or gold; the metal oxide includes zinc oxide, copper oxide, aluminum oxide, iron oxide, or tin oxide; and the two-dimensional material includes titanium carbide, graphene, MXenes, boron nitride, or black phosphorus.

[0049] In specific implementation, in step 1), the inert atmosphere is one or more of nitrogen, argon or helium, preferably argon; in step 2), the active metal includes lithium, sodium and zinc.

[0050] In specific implementation, in step 2), when the active metal is lithium, the heating temperature range is set between 180℃ and 1320℃, preferably between 180℃ and 600℃; when the active metal is sodium, the heating temperature range is set between 97℃ and 885℃, preferably between 97℃ and 600℃; when the active metal is zinc, the heating temperature range is set between 420℃ and 910℃, preferably between 500℃ and 600℃.

[0051] In specific implementation, when the selected composite component is linear, the step of rolling the linear material into a strip by a rolling unit is included before step 2).

[0052] In specific implementation, step 3) is as follows: the composite component is pulled by the rotation of the winding shaft at a speed of 0.1~100 cm / s through a traction shaft into the interior of the heating container 4 (the interior of the liquid active metal), and then pulled away from the heating container at a speed of 0.1~100 cm / s to contact another traction shaft. It continues to be pulled through another traction shaft at a speed of 0.1~100 cm / s and is then fixed on the winding shaft. The rotation of the winding shaft provides traction and lifting force so that the composite component undergoes heat treatment, cooling treatment, surface treatment or rolling treatment. During the process of passing through the interior of the liquid active metal, the surface of the strip composite component is coated with liquid active metal material.

[0053] The present invention will be further described below with reference to embodiments.

[0054] Example 1 like Figure 1As shown, this embodiment provides a winding system, including an inert environment unit 6 and a winding unit housed within the inert environment unit 6. The inert environment unit 6 includes a main chamber 61, an inlet / outlet chamber 62, a vacuum pump 63, and an inert gas storage tank 64. The winding unit is located within the main chamber 61. A first door 66 is provided between the main chamber 61 and the inlet / outlet chamber 62. The inlet / outlet chamber 62 has a second door 65 on the side opposite to the door 66. The vacuum pump 63 is connected to the main chamber 61 and the inlet / outlet chamber 62 via pipelines. The inert gas storage tank 64 is connected to the main chamber 61 via a pipeline. A heating container 4 for heating active metal to a molten state is provided within the main chamber 61. The winding unit includes a winding shaft 3, a rotating shaft 31, and traction shafts 51, 52, and 53, which are respectively fixed on a winding base 15.

[0055] Copper strip is selected as the strip-shaped composite component 1, lithium metal as the active metal 12, and argon as the inert gas. The thickness of the copper strip is 5~30 micrometers and the width is 80~200 micrometers.

[0056] 1) Fill the inert environment unit 6 with inert gas (argon), place the copper strip on the rotating shaft 31, and pull the copper strip through the traction shafts 51, 52, and 53 in sequence before fixing it on the winding shaft 3 (pull the copper strip through the traction shaft 51 into the interior of the heating container 4, then pull it away from the heating container 4 and contact the traction shaft 52, and continue to pull it through the traction shaft 53 before fixing it on the winding shaft 3).

[0057] 2) Place the active lithium metal into the heating container 4 in the inert environment unit 6, and heat it to 300~500℃ until the lithium metal melts into a liquid state.

[0058] 3) The copper strip is slowly drawn into the interior of the liquid lithium metal at a speed of 0.5~2cm / s by the rotation of the winding shaft 3. The copper strip 11 is then pulled and lifted at a speed of 0.5~2cm / s to leave the surface of the liquid lithium metal. After the copper strip 11 leaves the liquid lithium metal in the heating container 4 by pulling and lifting (0.5~2cm / s), the lithium metal coating on the surface of the copper strip solidifies after 1~10s due to the ambient temperature being lower than the melting temperature, thus obtaining a strip-shaped lithium metal / copper composite material.

[0059] 4) The strip-shaped lithium / copper composite material is wound around a winding shaft 3 in a plane perpendicular to the winding shaft at a rotation speed of 2000 r / min to obtain a lithium / copper composite sheet with a wound structure (active metal composite sheet 2). Depending on the winding shape, the shape of the prepared lithium / copper composite sheet perpendicular to the winding shaft can be circular, square, rectangular, rhomboid, elliptical, etc., see [reference needed]. Figures 8-10 .

[0060] Example 2 The difference between this embodiment and Embodiment 1 is that this embodiment further includes a cooling unit 7 housed within the main compartment 61 of the inert environment unit 6. The cooling unit 7 includes a cooling device 71, such as... Figure 2 As shown.

[0061] Copper strip was selected as component 1 of the strip-shaped composite, sodium metal as active metal 12, and argon as an inert gas. The thickness of the copper strip was 5-20 micrometers, and the width was 80-500 micrometers.

[0062] 1) Fill the inert environment unit 6 with inert gas (argon), place the copper strip on the rotating shaft 31, and pull the copper strip through the traction shafts 51, 52, and 53 in sequence to fix it on the winding shaft 3 (pull the copper strip through the traction shaft 51 into the interior of the heating container 4, then pull it away from the heating container 4 and contact the traction shaft 52, and continue to pull it through the traction shaft 53 before fixing it on the winding shaft 3).

[0063] 2) Place the active metallic sodium into the heating container 4 in the inert environment unit 61, and heat it to 300~600℃ until the metallic sodium melts into a liquid state.

[0064] 3) The copper strip is slowly drawn into the liquid sodium metal at a speed of 0.1~2cm / s by the rotation of the winding shaft 3. The copper strip is then pulled and lifted at a speed of 0.1~2cm / s to leave the surface of the liquid sodium metal. After the copper strip leaves the liquid sodium metal in the heating container 4, it enters the cooling unit 7. The cooling device 71 maintains the ambient temperature of the cooling unit 7 at 10~30℃. Since the ambient temperature is lower than the melting temperature, the liquid sodium metal coating on the surface of the copper strip solidifies after 1~10 seconds to form a coating, thus obtaining a strip-shaped sodium metal / copper composite material.

[0065] 4) The strip-shaped sodium / copper composite material is wound around a winding shaft 3 in a plane perpendicular to the winding shaft at a rotation speed of 400 r / min to obtain a sodium / copper composite sheet with a wound structure (active metal composite sheet 2). Depending on the winding shape, the shape of the prepared sodium / copper composite sheet perpendicular to the winding shaft can be circular, square, rectangular, rhomboid, elliptical, etc., see [reference needed]. Figures 8-10 .

[0066] Example 3 The difference between this embodiment and Embodiment 1 is that this embodiment further includes a cooling unit 7 and a pressure roller 8 housed within the main chamber 61 of the inert environment unit 6. The cooling unit 7 includes a cooling device 71, such as... Figure 3 As shown.

[0067] Aluminum strip is selected as component 1 of the strip-shaped composite, zinc is selected as the active metal 12, and argon is selected as the inert gas. The thickness of the aluminum strip is 3~20 micrometers and the width is 80~500 micrometers.

[0068] 1) Fill the inert environment unit 6 with inert gas (argon), place the aluminum strip on the rotating shaft 31, and pull the aluminum strip through the traction shafts 51, 52, 53 and the pressure roller 8 in sequence, and fix it on the winding shaft 3 (pull the aluminum strip through the traction shaft 51 into the interior of the heating container 4, then pull it away from the heating container 4 and contact the traction shaft 52, continue to pull it through the traction shaft 53 and enter the pressure roller 8, and then leave the pressure roller 8 and fix it on the winding shaft 3).

[0069] 2) Place the active metallic zinc into the heating container 4 in the inert environment unit 61, and heat it to 500~700℃ until the metallic zinc melts into a liquid state.

[0070] 3) The aluminum strip is slowly drawn into the liquid zinc at a speed of 0.1~2cm / s by the rotation of the winding shaft 3. The aluminum strip is then pulled and lifted at a speed of 0.1~2cm / s to leave the surface of the liquid zinc. After the aluminum strip leaves the liquid zinc in the heating container 4, it enters the cooling unit 7. The cooling device 71 maintains the ambient temperature of the cooling unit 7 at 10~30℃. Since the ambient temperature is lower than the melting temperature, the liquid zinc on the surface of the aluminum strip is quickly solidified to form a coating after 1~10 seconds, resulting in a strip of zinc / aluminum composite material.

[0071] 4) After the strip of zinc / aluminum composite material is pressed by the pressure roller 8, it is then wound by the winding shaft 3 at a speed of 800 r / min in a plane perpendicular to the winding shaft to obtain a zinc / aluminum composite sheet (active metal composite sheet 2) with a wound structure. Depending on the winding shape, the shape of the zinc / aluminum composite sheet 2 perpendicular to the winding shaft can be circular, square, rectangular, rhomboid, elliptical, etc., see [link to relevant documentation]. Figures 8-10 .

[0072] Example 4 The difference between this embodiment and Embodiment 1 is that this embodiment further includes a cooling unit 7, a pressure roller 8, and a surface modification unit 9 housed within the main chamber 61 of the inert environment unit 6. The cooling unit 7 includes a cooling device 71, and the winding unit further includes traction shafts 54 and 55 respectively fixed to the winding base 15. Figure 4 As shown.

[0073] Carbon fiber tape was selected as component 1 of the tape-shaped composite, sodium metal as active metal 12, and argon as an inert gas. The thickness of the carbon fiber tape was 3-20 micrometers, and the width was 80-500 micrometers.

[0074] 1) Fill the inert environment unit 6 with inert gas (argon), place the carbon fiber strip on the rotating shaft 31, and pull the carbon fiber strip through the traction shafts 54, 55, 51, 52, and 53 in sequence to fix it on the winding shaft 3 (pull the carbon fiber strip through the traction shaft 51 into the interior of the heating container 4, then pull it away from the heating container 4 and contact the traction shaft 52, and continue to pull it through the traction shaft 53 before fixing it on the winding shaft 3).

[0075] 2) Place the active metallic sodium into the heating container 4 in the inert environment unit 61, and heat it to 300~600℃ until the metallic sodium melts into a liquid state.

[0076] 3) The carbon fiber belt is slowly drawn into the interior of the surface modification unit 9 at a speed of 0.1~2cm / s by the rotation of the winding shaft 3, and a layer of metallic zinc (thickness 1~500nm) is sprayed onto the surface of the carbon fiber belt.

[0077] 4) Continue to pull at a rate of 0.1~2cm / s, the carbon fiber strip with surface coating enters the liquid sodium metal in the heating container 4, and then continue to pull and lift slowly at a rate of 0.1~2cm / s to make the carbon fiber strip leave the surface of the liquid sodium metal. Through the action of pulling and lifting, after the carbon fiber strip leaves the liquid sodium metal in the heating container 4, it enters the cooling unit 7 and the cooling fan 72. Due to the effect of the fan blowing away heat, the liquid sodium metal coating on the surface of the carbon fiber strip quickly solidifies after 1~10 seconds to form a coating, thus obtaining a strip-shaped sodium metal / carbon fiber composite material.

[0078] 5) The strip-shaped sodium / carbon fiber composite material is wound around a winding shaft 3 in a plane perpendicular to the winding shaft at a rotation speed of 1000 r / min to obtain a sodium / carbon fiber composite sheet (active metal composite sheet 2) with a wound structure. Depending on the winding shape, the shape of the prepared sodium / carbon fiber composite sheet perpendicular to the winding shaft can be circular, square, rectangular, rhomboid, elliptical, etc., see [reference needed]. Figures 8-10 .

[0079] Example 5 The difference between this embodiment and Embodiment 1 is that this embodiment further includes a cooling unit 7, a pressing roller 8, a surface modification unit 9, and a rolling unit 11 housed within the main chamber 61 of the inert environment unit 6. The cooling unit 7 includes a cooling device 71, and the winding unit further includes traction shafts 54, 55, 56, and 57 respectively fixed to the winding base 15. Figure 5 As shown.

[0080] The composite material used is copper wire as the linear component 10, lithium metal as the active metal 12, and argon as the inert gas. The diameter of the copper wire is 10~500 micrometers.

[0081] 1) Fill the inert environment unit 6 with inert gas (argon), place the copper wire on the rotating shaft 31, and pull the copper wire through the traction shaft 56 at a speed of 0.1~2cm / s to enter the rolling unit 11. Through the rolling action, the copper wire is rolled into a copper strip with a thickness of 3~50 micrometers. 2) Place the active lithium metal into the heating container 4 in the inert environment unit 61 and heat it to 300~500℃ until the lithium metal melts into a liquid state.

[0082] 3) The copper strip after being rolled by the rolling unit 11 is pulled through the traction shaft 57 at a speed of 0.1~2cm / s and then enters the surface modification unit 9 (continued to be pulled through the traction shafts 54 and 55). A layer of metallic zinc or silver (thickness 1~500nm) is deposited on the surface of the copper strip by vapor deposition or spraying.

[0083] 4) The surface-treated copper strip is slowly drawn into the liquid lithium metal at a speed of 0.1~2cm / s by the rotation of the winding shaft 3 (the copper strip is drawn into the heating container 4 through the traction shaft 51, then drawn away from the heating container 4 and contacts the traction shaft 52, and then drawn through the traction shaft 53 and fixed on the winding shaft 3). The copper strip is drawn and lifted at a speed of 0.1~2cm / s, so that it leaves the surface of the liquid lithium metal. Through the action of drawing and lifting, when the copper strip leaves the liquid lithium metal in the heating container 4, it enters the cooling unit 7. The cooling device 71 keeps the ambient temperature of the cooling unit 7 at 10~30℃. Since the ambient temperature is lower than the melting temperature, the liquid lithium metal coated on the surface of the copper strip is quickly solidified to form a coating after 1~10 seconds, thus obtaining a strip-shaped lithium metal / copper composite material.

[0084] 5) After passing through the pressure roller 8, the strip-shaped lithium / copper composite material is wound onto the winding shaft 3 in a plane rotating at 500 r / min perpendicular to the winding shaft to obtain a lithium / copper composite sheet (active metal composite sheet 2) with a wound structure. Depending on the winding shape, the resulting lithium / copper composite sheet can have a circular, square, rectangular, rhomboid, or elliptical shape in the plane perpendicular to the winding shaft, etc. (See below) Figures 8-10 .

[0085] Example 6 The difference between this embodiment and Embodiment 1 is that this embodiment further includes a roller pressing unit 11 housed within the main chamber 61 of the inert environment unit 6, and the winding unit further includes traction shafts 54, 55, 56, and 57 respectively fixed to the winding base 15, as shown below. Figure 6 As shown.

[0086] Copper wire was selected as the linear composite component 10, lithium metal as the active metal 12, and argon as the inert gas. The diameter of the copper wire ranged from 2 to 200 micrometers.

[0087] 1) Fill the inert environment unit 6 with inert gas argon, place the composite copper wire on the rotating shaft 31, and pull the copper wire through the traction shaft 56 at a speed of 0.1~2cm / s into the rolling unit 11. Through the rolling action, the copper wire is rolled into a copper strip with a thickness of 3~50 micrometers.

[0088] 2) Place the active lithium metal into the heating container 4 in the inert environment unit 61 and heat it to 300~500℃ until the sodium metal melts into a liquid state.

[0089] 3) The surface-treated copper strip is slowly drawn into the liquid lithium metal at a speed of 0.1~2 cm / s by the rotation of the winding shaft 3 (the copper strip is drawn into the heating container 4 through the traction shaft 51, then drawn away from the heating container 4 and contacts the traction shaft 52, and then drawn through the traction shaft 53 and fixed on the winding shaft 3). The copper strip is drawn and lifted at a speed of 0.1~2 cm / s, so that it leaves the surface of the liquid lithium metal. Through the action of drawing and lifting, when the copper strip leaves the liquid lithium metal in the heating container 4, the liquid lithium metal on the surface of the copper strip solidifies after 1~10 seconds due to the ambient temperature being lower than the melting temperature, thus forming a coating, and a strip of lithium metal / copper composite material is obtained.

[0090] 4) The strip-shaped lithium / copper composite material is wound around a winding shaft 3 in a plane perpendicular to the winding shaft at a rotation speed of 700 r / min to obtain a lithium / copper composite sheet with a wound structure (active metal composite sheet 2). Depending on the winding shape, the shape of the prepared lithium / copper composite sheet perpendicular to the winding shaft can be circular, square, rectangular, rhomboid, elliptical, etc., see [reference needed]. Figures 8-10 .

[0091] Example 7 The difference between this embodiment and Embodiment 1 is that the inert environment unit 6 in this embodiment is a sunken space (submerged underground), and also includes a cooling unit 7 and a pressure roller 8 housed within the main chamber 61 of the inert environment unit 6. The cooling unit 7 includes a cooling device 71, and this embodiment does not include a vacuum pump 63. Figure 7 As shown.

[0092] Copper strip is selected as the strip-shaped composite component 1, sodium metal as the active metal, and helium as the inert gas. The thickness of the copper strip is 5-20 micrometers, and the width is 80-500 micrometers. In this embodiment, the inert gas is filled into the interior of the sunken space to obtain an inert gas environment, taking advantage of the fact that the mass of the inert gas is greater than that of air.

[0093] 1) Fill the inert environment unit 61 with inert gas (helium), place the copper strip on the rotating shaft 31, and pull the copper strip through the traction shafts 51, 52, 53 and the pressure roller 8 in sequence before fixing it on the winding shaft 3 (the copper strip is pulled through the traction shaft 51 into the interior of the heating container 4, then pulled away from the heating container 4 and contacts the traction shaft 52, and continues to be pulled through the traction shaft 53 and enters the pressure roller 8, and then leaves the pressure roller 8 and is fixed on the winding shaft 3).

[0094] 2) Place the active metallic sodium into the heating container 4 in the inert environment unit 61, and heat it to 300~600℃ until the metallic sodium melts into a liquid state.

[0095] 3) The copper strip is slowly drawn into the liquid sodium metal at a speed of 0.1~2cm / s by the rotation of the winding shaft 3. The copper strip is then pulled and lifted at a speed of 0.1~2cm / s until it leaves the surface of the liquid sodium metal. After the copper strip leaves the liquid sodium metal in the heating container 4, it enters the cooling unit 7. The cooling device 71 keeps the ambient temperature of the cooling unit 7 at 10~30℃. Since the ambient temperature is lower than the melting temperature, the liquid sodium metal coating on the surface of the copper strip solidifies rapidly after 1~10 seconds to form a coating, thus forming a strip-shaped sodium metal / copper composite material.

[0096] 4) The strip-shaped sodium / copper composite material is wound around a winding shaft 3 in a plane perpendicular to the winding shaft at a rotation speed of 500 r / min to obtain a sodium / copper composite sheet (active metal composite sheet 2) with a wound structure. Depending on the winding shape, the shape of the prepared sodium / copper composite sheet perpendicular to the winding shaft can be circular, square, rectangular, rhomboid, elliptical, etc., see [reference needed]. Figures 8-10 .

[0097] The above embodiments are merely exemplary embodiments of the present invention and are not intended to limit the present invention. The scope of protection of the present invention is defined by the claims. Those skilled in the art can make various modifications or equivalent substitutions to the present invention within its spirit and scope of protection, and such modifications or equivalent substitutions should also be considered to fall within the scope of protection of the present invention.

Claims

1. A method for fabricating a metal composite thin-film electrode material, characterized in that, Includes the following steps: The inert environment unit is filled with inert gas, and the linear composite component is rolled into a strip composite component by a rolling unit, wherein the diameter of the linear composite component is 1 to 500 micrometers; preferably, the linear composite component is copper wire. The active metal is placed in a heating container in an inert environment unit and heated until it melts into a liquid state. The active metal is selected from lithium, sodium, or zinc. The strip-shaped composite component is drawn into the liquid active metal at a speed of 0.1 to 100 cm / s by rotating the winding shaft. The strip-shaped composite component is then pulled and lifted at a speed of 0.1 to 100 cm / s to leave the surface of the liquid active metal. After 1 to 600 seconds, the liquid active metal coating on the surface of the strip-shaped composite component solidifies to form a coating, thus obtaining an active metal composite material. The active metal composite material is wound around a winding shaft in a plane perpendicular to the winding shaft at a speed of 100 to 5000 rpm to obtain a metal composite sheet with a winding structure.

2. A method for fabricating a metal composite thin-film electrode material, characterized in that, Includes the following steps: The inert environment unit is filled with inert gas. The wound strip composite component is placed on the rotating shaft and then passed through the traction shaft and fixed on the winding shaft. The strip composite component is selected from copper strip, aluminum strip or carbon fiber strip, and its thickness is 3 to 50 micrometers and its width is 10 micrometers to 0.5 centimeters. The active metal is placed in a heating container in an inert environment unit and heated until it melts into a liquid state. The active metal is selected from lithium, sodium, or zinc. The strip-shaped composite component is drawn into the liquid active metal at a speed of 0.1 to 100 cm / s by rotating the winding shaft. The strip-shaped composite component is then pulled and lifted at a speed of 0.1 to 100 cm / s to leave the surface of the liquid active metal. After 1 to 600 seconds, the liquid active metal coated on the surface of the strip-shaped composite component solidifies to form a coating, thus obtaining a strip-shaped active metal composite material. The strip-shaped active metal composite material is wound through a winding shaft in a plane perpendicular to the winding shaft at a rotation speed of 100 to 5000 rpm to obtain a metal composite sheet with a winding structure.

3. The method as described in claim 1 or 2, characterized in that, Before the strip-shaped composite component enters the liquid active metal, the strip-shaped composite component is fed into a surface modification unit for surface modification, wherein the surface modification includes depositing a two-dimensional material on the surface of the strip-shaped composite component, the two-dimensional material being selected from titanium carbide, graphene, MXenes, boron nitride, or black phosphorus.

4. The method as described in claim 3, characterized in that, The surface modification is achieved through spraying, evaporation, electroplating, sputtering, liquid phase chemical deposition, or vapor phase chemical deposition.

5. The method as described in claim 1 or 2, characterized in that, After the strip-shaped composite component leaves the surface of the active metal liquid, a cooling step is also included; the cooling step is to reduce the ambient temperature to 0-40°C by using a cooling device, or to remove the heat of the liquid metal on the surface of the strip-shaped composite component by using a fan. And / or, the resulting strip of active metal composite material is further rolled using a pressure roller.

6. A metal composite thin-film electrode material, characterized in that, The electrode material has an array structure formed by winding an active metal composite material, wherein the active metal and the composite component are arranged in the same manner in a cross section perpendicular to the winding axis, and the electrode material is prepared by the method of any one of claims 1 to 5.

7. A winding system for producing metal composite sheet electrode materials, characterized in that, The system includes an inert environment unit and a winding unit housed within the inert environment unit. The inert environment unit includes a main chamber, an inlet / outlet chamber, and an inert gas storage tank. The winding unit is located within the main chamber. The inert gas storage tank is connected to the main chamber via a pipeline. The main chamber contains a heating container for heating the active metal to a molten state. The winding unit includes a winding shaft, a rotating shaft, and a traction shaft, all fixed to a winding substrate. The winding system further includes: A rolling unit housed within the main compartment of the inert environment unit is used to roll the linear composite components into a strip; and / or, A surface modification unit is disposed within the main compartment of the inert environment unit, the surface modification unit being configured to deposit a layer of two-dimensional material on the surface of the composite component, the two-dimensional material being selected from titanium carbide, graphene, MXenes, boron nitride, or black phosphorus.

8. The winding system as claimed in claim 7, characterized in that, The surface modification unit is selected from at least one of spraying equipment, vapor deposition equipment, electroplating equipment, sputtering equipment, liquid phase chemical deposition apparatus or vapor phase chemical deposition apparatus.

9. The winding system as claimed in claim 7, characterized in that, It also includes a cooling unit housed within the main compartment of the inert environment unit, the cooling unit comprising cooling equipment or a fan.

10. The winding system as claimed in claim 7, characterized in that, It also includes a pressure roller housed within the main compartment of the inert environment unit for further rolling the active metal composite material before it is wound.

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