CN112216819A - Large-scale production method of copper-lithium composite electrode - Google Patents
Large-scale production method of copper-lithium composite electrode Download PDFInfo
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- CN112216819A CN112216819A CN201910619192.7A CN201910619192A CN112216819A CN 112216819 A CN112216819 A CN 112216819A CN 201910619192 A CN201910619192 A CN 201910619192A CN 112216819 A CN112216819 A CN 112216819A
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Abstract
The invention discloses a large-scale production method of a copper-lithium composite electrode, which comprises the following steps of (1) taking a copper foil, and pressing an insulating film on the edges of two sides of the rough surface of the copper foil respectively; (2) the copper foil processed in the step (1) bypasses the lower part of a cathode roller of the electrolytic cell, the smooth surface of the copper foil is attached to the lower half part of the cathode roller, the lower half part is immersed in electrolyte of the electrolytic cell, and the anode of the cell is a high-purity lithium ingot; (3) switching on direct current, adjusting current density, and depositing lithium on the rough surface of the exposed copper foil to form a lithium layer to obtain a composite copper lithium foil; (4) drawing the composite copper lithium foil out of the electrolytic cell, and stripping the insulating film laminated in the step (1); (5) cleaning the composite copper lithium foil stripped of the insulating film to remove residual electrolyte, and drying; (6) pressing a cellulose diaphragm on the surface of the lithium layer of the dried composite copper lithium foil; (7) cutting, putting into a box for bagging, filling argon gas for sealing, and obtaining the copper-lithium composite electrode. The invention has high copper-lithium bonding strength and controllable lithium quality, and is suitable for industrial production.
Description
Technical Field
The invention relates to a large-scale production method of a copper-lithium composite electrode, belonging to the technical field of electrochemistry.
Background
The current production methods of the copper-lithium composite electrode comprise the following steps:
1. the invention patent application CN201710890899.2 (publication No. CN107819104A) adopts a spacing type local pressure enhancement method to uniformly adhere a lithium metal foil on the surface of a copper foil to form a lithium-copper composite negative electrode foil. The invention improves the contact between the lithium metal cathode and the copper foil, and avoids the problem of infirm bonding between the lithium metal foil and the copper foil, thereby preventing the power failure of the lithium metal in the working process of the battery. The method has the following defects: according to the method, the lithium sheets are pressed on two sides of the copper foil, so that the bonding force between the lithium metal foil and the copper foil is still poor, the operability is poor, the electrode preparation efficiency is low, and the large-scale production is not facilitated. The thickness of the lithium sheet is difficult to control, and accurate lithium embedding cannot be achieved.
The lithium metal is soft and light in self quality, the compounding between the lithium metal (such as a lithium foil) and a current collector (such as a copper foil) is very difficult to operate technically, the mechanical properties of the two metals are greatly different, and the hardness and yield strength of lithium are far lower than those of other metals, so that when the pressure is too high during mechanical pressing, the surface of the lithium foil is subjected to plastic deformation and extends, the copper foil is not deformed due to high strength, and the compounding between the lithium metal and the current collector is not uniform in deformation at the moment, so that the defects of wrinkles, waves, damages, bubbles, strip distortion, arching and the like are certainly caused, and a smooth composite belt with high surface quality is difficult to obtain; if the pressure is too low, lithium and copper are difficult to obtain good mechanical strength, the composite strength between the lithium metal and the current collector is low, a metal lithium layer and a metal foil of the current collector fall off and peel off in the use process of the battery, the resistance of a lithium metal electrode can be continuously increased, and the overall electrical performance and the cycle performance of the battery are influenced.
2. In the invention patent application CN201811565485.3 (publication No. CN109742323A), a metal transition layer is introduced between a copper foil current collector and a lithium-containing metal foil, and then the lithium foil is pressed, so that the bonding strength between copper and lithium is improved, a smooth composite lithium metal negative electrode with high surface quality is obtained, and the overall conductivity of the pole piece is also improved. The method has the following defects: the transition layer needs to be added, and the production cost of the electrode is increased; the transition layer contains nickel, titanium, iron, hafnium and niobium; the self-discharge performance and safety performance of the battery are affected. The transition layer is added to occupy the effective space in the battery, and the energy density of the battery is inevitably reduced. The method is difficult to realize large-scale production.
3. Invention patent CN201810358135.3 (publication No. 108470879 a): taking the passivated lithium powder and the copper particles according to the mass ratio (0.5-2) of 1, and uniformly mixing the copper particles, the solvent, the binder and the passivated lithium powder to obtain slurry; and coating the slurry on a substrate, drying for 0.5-24 h under the conditions of vacuum and 25-60 ℃, and volatilizing the solvent to obtain the lithium-copper composite metal negative plate. The method reduces the internal contact resistance of copper and lithium, can effectively inhibit the formation of dendritic lithium, prevents the safety problems of short circuit and the like caused in the circulation process of the battery, and greatly improves the safety, stability and service life of the battery. The method has the following defects: although the formation of dendritic lithium can be inhibited, copper particles are contained, the internal pressure of the battery increases after the battery is cycled for a period of time, the copper particles have the risk of puncturing a diaphragm, the internal short circuit of the battery can be caused, and the potential safety hazard is caused. The passivated lithium powder is expensive and the electrode production cost is high.
Disclosure of Invention
The invention aims to solve the technical problem of providing a production method of a copper-lithium composite electrode, and the method is suitable for large scale.
In order to solve the technical problems, the method for producing the copper-lithium composite electrode on a large scale comprises the following steps
(1) Taking a copper foil, and pressing an insulating film on the edges of two sides of the rough surface of the copper foil respectively; the copper foil and the insulating film are dried, and the insulating film is symmetrically arranged on two sides of the rough surface of the copper foil;
(2) the copper foil processed in the step (1) bypasses the lower part of a cathode roller of the electrolytic cell, the polished surface is attached to the lower half part of the cathode roller, the lower half part is immersed in electrolyte of the electrolytic cell, the anode of the cell is a high-purity lithium ingot, the lithium content of the high-purity lithium ingot is more than or equal to 99.9 percent, the high-purity lithium ingot is used as the anode and is connected with the anode of a direct current power supply, and the copper foil is attached to the cathode roller and is connected with the cathode of the power supply;
(3) switching on direct current, adjusting current density, and depositing lithium on the rough surface of the exposed copper foil to form a lithium layer to obtain a composite copper lithium foil;
(4) drawing the composite copper lithium foil out of the electrolytic cell, stripping the insulating film laminated in the step (1), and rolling and recovering the stripped insulating film;
(5) placing the composite copper lithium foil with the insulating film stripped into a cleaning tank, cleaning residual electrolyte with a solvent, and then placing the composite copper lithium foil into an oven filled with argon protection for drying;
(6) mechanically pressing a cellulose diaphragm on the surface of the lithium layer of the dried composite copper lithium foil; the cellulose diaphragm only needs to cover the lithium-plated area, the uncovered area only has copper foil, the pole ear position is formed by cutting, and finally the pole ear position and the pole ear are welded.
(7) And cutting by laser knife die cutting according to the size requirement, putting into a box for bagging, filling argon gas for sealing, and obtaining the copper-lithium composite electrode.
Furthermore, the whole production process is carried out in a drying room, the dew point temperature is less than or equal to minus 50 ℃, and the environmental temperature of the drying room is 15-25 ℃.
Further, the copper foil used in the step (1) is a battery-grade double-sided electrolytic copper foil, a single-sided photo-electrolytic copper foil or a rolled copper foil (all the three are battery-grade copper foils), the thickness is 3-100 mu m, and the roughness of the smooth surface is less than or equal to 0.3 mu m.
Further, the insulating film used in the step (1) comprises a base material and a binder coated on the base material, wherein the base material is polyethylene terephthalate (PET), Polyimide (PI), Polyethylene (PE) or polypropylene (PP), and the binder is acrylic adhesive, silica gel or polyvinylidene fluoride, namely, the insulating film and the copper foil are firstly bonded by the binder and then fixed by mechanical pressing.
Furthermore, the insulating films are symmetrically arranged on two sides of the rough surface of the copper foil, the thickness of the insulating films is 10-200 mu m, and the width of each side of the attached copper foil is 2-100 mm. The function of the insulating film: insulating, wherein no metal lithium plating layer is arranged at the joint, and a tab welding empty foil position is reserved for the prepared electrode; increasing the tensile strength of the copper foil.
Further, the cathode roller used in the step (2) comprises a cylindrical main body, sealing rings are symmetrically arranged on two sides of the main body, the sealing rings are fixed on the cathode roller in a bonding mode, and the sealing rings are made of fluororubber, ethylene propylene diene monomer rubber, silicon rubber, nitrile butadiene rubber or chloroprene rubber. The cathode roller comprises a cylindrical cathode roller main body and a sealing ring, wherein mounting grooves are formed in two sides of the cathode roller main body, a conductive roller surface is arranged in the middle of the cathode roller main body, the surface of each mounting groove is lower than the surface of the conductive roller surface, the sealing ring is arranged in the mounting grooves, the thickness of the sealing ring is 1-100 mm, and the width of the sealing ring is 1-200 mm; the sealing ring is 3-200 μm higher than the surface of the conductive roller. The sealing ring is matched with proper tension to form sealing with the smooth surface of the copper foil, so that electrolyte is prevented from entering the conductive roller surface of the cathode roller, and metal lithium is prevented from being separated out on the smooth surface.
Further, the temperature of the electrolyte is 15-60 ℃, and the electrolyte comprises a solvent and lithium salt, wherein the solvent is one or more than two of ethylene carbonate, propylene carbonate, butylene carbonate, methyl ethyl carbonate, dimethyl carbonate, diethyl carbonate, dipropyl carbonate, methyl propyl carbonate, ethyl propyl carbonate, 1, 4-butyrolactone, methyl propionate, methyl butyrate, ethyl acetate, ethyl propionate and ethyl butyrate; the lithium salt is one or more than two of lithium hexafluorophosphate, lithium difluorophosphate, lithium tetrafluoroborate, lithium hexafluoroarsenate, lithium perchlorate, lithium bis (fluorosulfonyl) imide or lithium bis (trifluoromethanesulfonyl) imide.
Further, the direct current density in the step (3) is 1-150A/dm2Preferably 40 to 120A/dm2。
Further, in the step (5), one or more of ethylene carbonate, propylene carbonate, butylene carbonate, ethyl methyl carbonate, dimethyl carbonate, diethyl carbonate, dipropyl carbonate, methyl propyl carbonate, ethyl propyl carbonate, 1, 4-butyrolactone, methyl propionate, methyl butyrate, ethyl acetate, ethyl propionate and ethyl butyrate are used as a cleaning solvent.
Further, the drying in the step (5) is carried out at the temperature of 30-180 ℃ under the protection of argon, and preferably at the temperature of 60-100 ℃.
The whole process of the invention is continuously carried out by traction.
According to the invention, the lithium layer is deposited on the rough surface of the copper foil by an electrolytic method to produce the copper-lithium composite electrode, and the bonding strength between the lithium metal and the rough surface of the copper foil is ensured by forming a metal bond and a mechanical embedding effect. On the premise of ensuring the electrode performance, the invention does not introduce substances which influence the self-discharge and safety performance of the battery, increase the electrode cost and reduce the energy density of the battery. The thickness tolerance of the lithium sheet produced industrially at present is +/-3 mu m, the weight consistency of the lithium sheet with certain thickness and unit size is difficult to ensure, the accurate capacity of the electrode is influenced, and the lithium layer has controllable weight, smooth surface and high surface quality, improves the consistency of the electrode and is convenient for large-scale production.
Specifically, the method comprises the following steps: 1. the insulating film is pasted on the edge of the copper foil, so that the width of a lithium layer coating is controlled, and the tensile strength of the copper foil can be greatly improved by the insulating film; 2. sealing rings slightly higher than the surface of the cathode roll are symmetrically arranged on two sides of the cathode roll, so that the copper foil and the cathode roll form sealing under certain tension, and the smooth surface of the copper foil is ensured to have no metal lithium plating layer; 3. the manufactured electrode has three layers, the copper foil layer is used as a current collector, a tab is welded at an empty foil position, and meanwhile, the manufactured electrode has better tensile strength and is convenient for continuous production operation; the lithium layer provides a lithium source; because the lithium layer is soft in texture and easy to stretch and deform, and a cutting die is easy to adhere during cutting, the weight of lithium in the electrode is further influenced, and the cellulose diaphragm is pressed on the surface of the lithium layer, so that metal lithium is prevented from adhering to a cutter during cutting of the electrode, the weight of the electrode is ensured, and the production efficiency is improved; in addition, a diaphragm is arranged in the battery, the common material of the diaphragm is PP or PE, the thickness of the diaphragm is usually 10-20 μm, if the fibrous diaphragm is not laminated on a lithium layer, the direct contact of metal lithium and the diaphragm in the battery is avoided (if the metal lithium is directly contacted with the diaphragm, the diaphragm has the risk of being punctured after the battery is pressed), the internal short circuit of the battery is prevented, the safety performance of the battery is improved, and meanwhile, the micropores of the cellulose diaphragm also ensure the functions of absorbing electrolyte and keeping the electrolyte of an electrode, so that the cycle performance of the battery is improved.
Drawings
FIG. 1 is a schematic view of a process for fabricating a copper-lithium composite electrode according to the present invention;
FIG. 2 is a schematic view of the structure of the present invention after the insulating film and the copper foil are combined;
FIG. 3 is a schematic view of the structure of the anode and cathode rollers of the electrolytic cell according to the present invention;
FIG. 4 is a schematic structural diagram of a cathode roll according to the present invention;
FIG. 5 is a schematic structural view of the cathode roll with a sealing ring according to the present invention;
FIG. 6 is a schematic perspective view of FIG. 5;
FIG. 7 is a schematic structural diagram of a copper-lithium composite electrode according to the present invention;
FIG. 8 is a schematic diagram of the lithium plating of the present invention.
In the figure: 1-copper foil; 2-an insulating film; 3-a cathode roll; 301-cathode roll body; 302-mounting a recess; 303-sealing ring; 4-an anode; 5-a metallic lithium layer; 6-fibrous separator.
Detailed Description
The present invention will be described more specifically with reference to examples. The practice of the present invention is not limited to the following examples, and any modification or variation of the present invention is within the scope of the present invention.
Example 1:
in a drying room, the dew point temperature is less than or equal to minus 50 ℃, the ambient temperature of the drying room is 25 ℃, a layer of Polyimide (PI) insulating film which is coated with silica gel and has the thickness of 30 mu m and the width of 40mm is symmetrically pressed on the two side edges of the rough surface of the dry double-sided photoelectrolysis copper foil with the width of 380mm and the thickness of 8 mu m, and the composite insulating film copper foil is prepared, as shown in figure 2. The edge of the insulating film 2 is aligned and pressed with the edge of the copper foil 1, and the width of the insulating film which is not jointed in the middle of the rough surface of the copper foil 1 is 300 mm.
And (3) winding the composite insulating film copper foil below a cathode roller 3 of the electrolytic cell, enabling the smooth surface to be attached to the lower half part of the cathode roller 3, and placing the lower half part of the cathode roller 3 in electrolyte of the electrolytic cell. The cathode roller 3 comprises a cathode roller main body 301 and a sealing ring 303, the cathode roller main body 301 is a titanium rotary drum with the diameter of 2000mm and the width of 400mm (namely the height of a cylinder), mounting grooves 302 are symmetrically arranged on two sides of the titanium rotary drum, and the middle part of the cathode roller main body is a conductive roller surface higher than the mounting grooves 302. Electrodes are arranged around the drum at an interelectrode distance of about 5mm, and a U-shaped anode is disposed below the cathode roller 3. A fluororubber sealing ring with the width of 40mm is arranged in the mounting groove 302, and the surface of the sealing ring 303 is 10 microns higher than the surface of the conductive roller; the surface width of the conductive roller is 320 mm; the smooth surface of the copper foil is centrally attached to the surface of the cathode roller; the edges of the copper foils are symmetrically attached to the sealing ring on the roll surface of the cathode roll, and the sealing ring 303 and the smooth surface of the copper foils form sealing by matching with certain pulling force, so that electrolyte is prevented from entering the surface of the conductive roll, and a lithium plating layer is formed on the smooth surface of the copper foils.
The electrolyte comprises the following components: propylene Carbonate (PC) Ethylene Carbonate (EC), Ethyl Methyl Carbonate (EMC), diethyl carbonate (DEC) were mixed in a mass ratio of PC: EC: EMC: DEC: 20:30:30:20, and the concentration of LiPF6 was 0.8 mol/L. The anode of the electrolytic cell is a lithium ingot with the purity of 99.9 percent, direct current is switched on, and the temperature of the electrolyte is adjusted to be as follows: 40 ℃ and current density: 20A/dm2Lithium is deposited on the surface of the copper foil bonded to the rotary drum. After the completion, the copper foil with the lithium plated on the surface is transferred out, Polyimide (PI) insulating films on two sides of the rough surface are stripped and recovered, meanwhile, the copper-lithium composite foil passes through a cleaning tank, cleaning liquid is pure dimethyl carbonate (DMC), and residual electrolyte is washed away; then, the copper-lithium composite foil is dried and cooled in an oven which is filled with argon for protection and has the temperature of 60 ℃, so that the copper-lithium composite foil with the lithium plating thickness of 20 mu m and the width of 300mm can be continuously manufactured, and then a cellulose diaphragm with the width of 304mm and the thickness of 30 mu m is pressed and covered on the lithium plating surface; the width of the cellulose diaphragm exceeding the lithium layer is 2mm respectively; the copper-lithium composite electrode with the width of 100mm, the length of 148mm, the tab bit width of 50mm and the length of 20mm can be manufactured by 1-4 laser cutting die punching, the copper-lithium composite electrode with the width of 100mm, the length of 148mm and the lithium layer thickness of 20 microns is manufactured, a sheet is put into a box and is put into an aluminum-plastic film bag to be filled with argon gas and sealed, and the manufactured copper-lithium composite electrode is shown in figure 7.
Example 2:
symmetrically pressing a layer of Polyimide (PI) insulating film which is 30 micrometers thick and is 40mm wide and coated with silica gel on the rough surface edge of a dried double-sided photoelectrolysis liquid copper foil which is 380mm wide and 10 micrometers thick at the dew point temperature of less than or equal to minus 50 ℃ in a drying room at the temperature of 20 ℃; the width of the non-bonded insulating film in the middle of the rough surface of the copper foil is 300mm, and the composite insulating film copper foil is prepared.
The smooth surface of the copper foil of the composite insulating film is attached to and bypasses a cathode roller of an electrolytic cell, a cathode roller 3 is arranged in the electrolytic cell, the cathode roller 3 comprises a cathode roller main body 301 and a sealing ring 303, the cathode roller main body 301 is a titanium rotary drum with the diameter of 2000mm and the width of 400mm, mounting grooves 302 are symmetrically arranged on two sides, the middle part is a conductive roller surface, electrodes are arranged at the distance between electrodes of about 5mm around the drum, a U-shaped anode is arranged below the cathode roller in a matched mode, and the lower half part of the cathode roller is immersed in electrolyte of the electrolytic cell. A fluorine rubber sealing ring with the width of 40mm is arranged on the mounting groove 302, and the surface of the sealing ring is 15 microns higher than the surface of the cathode roller conductive roller; the surface width of the conductive roller is 320 mm; the smooth surface of the copper foil is centrally attached to the surface of the cathode roller; the edges of the copper foils are symmetrically attached to the sealing ring 303 of the cathode roller 3, and the sealing ring and the smooth surface of the copper foils form sealing by matching with certain pulling force, so that electrolyte is prevented from entering the surface of the conductive roller, and a lithium plating layer is formed on the smooth surface of the copper foils.
The electrolyte comprises the following components: the mass ratio of Ethylene Carbonate (EC), Ethyl Methyl Carbonate (EMC) and diethyl carbonate (DEC) is EC: EMC: DEC: 40: 20 and the concentration of LiPF6 was 1.2 mol/L. The anode of the electrolytic cell is a lithium ingot with the purity of 99.9 percent, direct current is switched on, and the temperature of the electrolyte is adjusted to be as follows: 50 ℃ and current density: 60A/dm2Separating lithium out of the surface of the rotary drum laminated copper foil, taking out the copper foil with the lithium plated on the surface, stripping and recovering Polyimide (PI) insulating films on two sides of the rough surface, simultaneously enabling the copper-lithium composite foil to pass through a cleaning tank, enabling cleaning solution to be pure Ethyl Methyl Carbonate (EMC), and washing away residual electrolyte; then, the copper-lithium composite foil passes through an oven which is filled with argon for protection and has the temperature of 80 ℃ for drying and cooling, namely, the copper-lithium composite foil with the thickness of 50 mu m and the width of 300mm of a lithium plating layer can be continuously manufactured, and then a cellulose diaphragm with the width of 304mm and the thickness of 30 mu m is pressed and covered on a lithium plating surface; the width of the cellulose diaphragm exceeding the lithium layer is 2mm respectively; and punching by using a 1-out-4 laser cutter die with the main body width of 100mm, the length of 148mm, the tab bit width of 50mm and the length of 20mm to obtain the copper-lithium composite electrode with the width of 100mm and the length of 148mm, wherein a lithium layer with the thickness of 50 mu m is filled in an aluminum-plastic film bag, and the copper-lithium composite electrode is packaged into a box, filled with argon gas and sealed to finish the production of the electrode.
Example 3:
in a drying room, the dew point temperature is less than or equal to minus 50 ℃, under the environment of 15 ℃, the edge of the rough surface of the dry double-sided photoelectrolyte copper foil with the width of 380mm and the thickness of 12 mu m is symmetrically pressed with a layer of Polyimide (PI) insulating film which is 30 mu m, has the width of 40mm and is coated with silica gel; the width of the non-bonded insulating film in the middle of the rough surface of the copper foil is 300mm, and the composite insulating film copper foil is prepared.
The smooth surface of the copper foil of the composite insulating film is attached to and bypasses a cathode roller of an electrolytic cell, a cathode roller 3 is arranged in the electrolytic cell, the cathode roller 3 comprises a cathode roller main body 301 and a sealing ring 303, the cathode roller main body 301 is a titanium rotary drum with the diameter of 2000mm and the width of 400mm (namely the height of a cylinder), mounting grooves 302 are symmetrically arranged on two sides, the middle part is a conductive roller surface, electrodes are arranged at the interelectrode distance of about 5mm around the drum, a U-shaped anode is arranged below the cathode roller in a matched mode, and the lower half part of the cathode roller is immersed in electrolyte of the electrolytic cell. A fluorine rubber sealing ring with the width of 40mm is arranged on the mounting groove 302, and the surface of the sealing ring is 20 micrometers higher than the surface of the cathode roller conductive roller; the surface width of the conductive roller is 320 mm; the smooth surface of the copper foil is centrally attached to the surface of the cathode roller; the edges of the copper foil are symmetrically attached to the sealing ring 303 of the cathode roller 3, and the sealing ring 303 and the smooth surface of the copper foil 1 form sealing by matching with certain pulling force, so that electrolyte is prevented from entering the surface of the conductive roller, and a lithium plating layer is formed on the smooth surface of the copper foil
The electrolyte comprises the following components: the mass ratio of Ethylene Carbonate (EC), Ethyl Methyl Carbonate (EMC) and diethyl carbonate (DEC) is EC: EMC: DEC: 30: 40: 30 and the concentration of LiPF6 was 1.5 mol/L. The anode of the electrolytic cell is a lithium ingot with the purity of 99.9 percent, direct current is switched on, and the temperature of the electrolyte is adjusted to be as follows: 60 ℃, current density: 100A/dm2Precipitating lithium on the surface of a rotary drum laminated copper foil, migrating the copper foil with the lithium plated on the surface, stripping and recovering Polyimide (PI) insulating films on two sides of a rough surface, simultaneously enabling a copper-lithium composite foil to pass through a cleaning tank, wherein the cleaning solution is dimethyl carbonate (DMC), and the mass ratio of Ethyl Methyl Carbonate (EMC) is DMC: washing off residual electrolyte by using a mixed solution with EMC 1: 1; then passing through an oven filled with argon for protection and at the temperature of 100 ℃ for drying and cooling, namely continuously manufacturing the copper-lithium composite foil with the thickness of 100 mu m and the width of 300mm of a lithium plating layer, and then pressing and covering a cellulose diaphragm with the width of 304mm and the thickness of 30 mu m on a lithium plating surface; the width of the cellulose diaphragm exceeding the lithium layer is 2mm respectively; the thickness of the lithium layer with the width of 100mm and the length of 148mm can be obtained by punching with a 1-out-4 laser cutting die with the main body width of 100mm, the length of 148mm, the tab bit width of 50mm and the length of 20mmThe electrode is a 100 mu m copper-lithium composite electrode, and the electrode is produced by putting the collected sheet into a box, putting the box into an aluminum plastic film bag, filling argon gas and sealing.
Claims (10)
1. A large-scale production method of a copper-lithium composite electrode is characterized by comprising the following steps: the method comprises
(1) Taking a copper foil, and pressing an insulating film on the edges of two sides of the rough surface of the copper foil respectively;
(2) the copper foil processed in the step (1) bypasses the lower part of a cathode roller of the electrolytic cell, the smooth surface of the copper foil is attached to the lower half part of the cathode roller, the lower half part is immersed in electrolyte of the electrolytic cell, and the anode of the cell is a high-purity lithium ingot;
(3) switching on direct current, adjusting current density, and depositing lithium on the rough surface of the exposed copper foil to form a lithium layer to obtain a composite copper lithium foil;
(4) drawing the composite copper lithium foil out of the electrolytic cell, and stripping the insulating film laminated in the step (1);
(5) cleaning the composite copper lithium foil stripped of the insulating film to remove residual electrolyte, and drying;
(6) pressing a cellulose diaphragm on the surface of the lithium layer of the dried composite copper lithium foil;
(7) cutting, putting into a box for bagging, filling argon gas for sealing, and obtaining the copper-lithium composite electrode.
2. The mass production method of a copper-lithium composite electrode according to claim 1, characterized in that: the whole production process is carried out in a drying room, the dew point temperature is less than or equal to minus 50 ℃, and the environmental temperature of the drying room is 15-25 ℃.
3. The mass production method of a copper-lithium composite electrode according to claim 1, characterized in that: the copper foil used in the step (1) is a battery-grade double-sided electrolytic copper foil, a single-sided photoelectrolysis copper foil or a rolled copper foil, the thickness is 3-100 mu m, and the roughness of the smooth surface is less than or equal to 0.3 mu m.
4. The mass production method of a copper-lithium composite electrode according to claim 1, characterized in that: the insulating film used in the step (1) comprises a base material and a binder coated on the base material, wherein the base material is polyethylene terephthalate, polyimide, polyethylene or polypropylene, and the binder is acrylic adhesive, silica gel or polyvinylidene fluoride.
5. The mass production method of a copper-lithium composite electrode according to claim 1 or 4, characterized in that: the insulating films are symmetrically arranged on two sides of the rough surface of the copper foil, the thickness of the insulating films is 10-200 mu m, and the width of each side of the attached copper foil is 2-100 mm.
6. The mass production method of a copper-lithium composite electrode according to claim 1, characterized in that: the cathode roller used in the step (2) comprises a cylindrical cathode roller main body, wherein sealing rings are symmetrically arranged on two sides of the cathode roller main body, and the thickness of each sealing ring is 1-100 mm; the width is 1-200 mm; the sealing ring is 3-200 μm higher than the surface of the cathode roller.
7. The mass production method of a copper-lithium composite electrode according to claim 1, characterized in that: the temperature of the electrolyte is 15-60 ℃, and the electrolyte comprises a solvent and lithium salt, wherein the solvent is one or more than two of ethylene carbonate, propylene carbonate, butylene carbonate, ethyl methyl carbonate, dimethyl carbonate, diethyl carbonate, dipropyl carbonate, methyl propyl carbonate, ethyl propyl carbonate, 1, 4-butyrolactone, methyl propionate, methyl butyrate, ethyl acetate, ethyl propionate and ethyl butyrate; the lithium salt is one or more than two of lithium hexafluorophosphate, lithium difluorophosphate, lithium tetrafluoroborate, lithium hexafluoroarsenate, lithium perchlorate, lithium bis (fluorosulfonyl) imide or lithium bis (trifluoromethanesulfonyl) imide.
8. The mass production method of a copper-lithium composite electrode according to claim 1, characterized in that: the direct current density of the step (3) is 1-150A/dm2。
9. The mass production method of a copper-lithium composite electrode according to claim 1, characterized in that: and (5) cleaning by using one or more of ethylene carbonate, propylene carbonate, butylene carbonate, methyl ethyl carbonate, dimethyl carbonate, diethyl carbonate, dipropyl carbonate, methyl propyl carbonate, ethyl propyl carbonate, 1, 4-butyrolactone, methyl propionate, methyl butyrate, ethyl acetate, ethyl propionate and ethyl butyrate as a cleaning solvent.
10. The mass production method of a copper-lithium composite electrode according to claim 1, characterized in that: and (5) drying at the temperature of 30-180 ℃ under the protection of argon.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114346048A (en) * | 2021-12-22 | 2022-04-15 | 长沙矿冶研究院有限责任公司 | Lithium sheet die cutting equipment and lithium sheet die cutting process |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101076914A (en) * | 2004-12-13 | 2007-11-21 | 松下电器产业株式会社 | Laminate including active material layer and solid electrolyte layer, and all solid lithium secondary battery using the same |
| CN101207977A (en) * | 2006-12-20 | 2008-06-25 | 富葵精密组件(深圳)有限公司 | Method for making flexible circuit board with break difference structure |
| US20090117352A1 (en) * | 2005-05-06 | 2009-05-07 | Rolls-Royce Plc | Component fabrication |
| CN104241598A (en) * | 2013-06-18 | 2014-12-24 | 赵军辉 | Composite negative electrode, preparation method of negative electrode and lithium-sulfur secondary battery with negative electrode |
| CN106450489A (en) * | 2016-12-16 | 2017-02-22 | 天津力神电池股份有限公司 | In-situ preparation method of lithium-sulfur battery based on hard carbon anode |
| CN106450488A (en) * | 2016-12-16 | 2017-02-22 | 天津力神电池股份有限公司 | In-situ preparation method of lithium-sulfur battery based on silicon cathode |
| CN106711430A (en) * | 2016-12-27 | 2017-05-24 | 中南大学 | Production method of lithium/carbon fiber or porous carbon paper/copper foil composite negative electrode used for lithium-sulfur battery |
| CN106784600A (en) * | 2016-12-23 | 2017-05-31 | 天津力神电池股份有限公司 | One kind is containing lithium cathode sheet and preparation method thereof |
| CN108346778A (en) * | 2018-02-07 | 2018-07-31 | 清华大学 | A kind of electrochemical method preparing ultra-thin lithium an- ode |
| TWI656682B (en) * | 2018-10-16 | 2019-04-11 | 長春石油化學股份有限公司 | Electrolytic copper foil, electrode comprising the same, and lithium ion battery comprising the same |
-
2019
- 2019-07-10 CN CN201910619192.7A patent/CN112216819B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101076914A (en) * | 2004-12-13 | 2007-11-21 | 松下电器产业株式会社 | Laminate including active material layer and solid electrolyte layer, and all solid lithium secondary battery using the same |
| US20090117352A1 (en) * | 2005-05-06 | 2009-05-07 | Rolls-Royce Plc | Component fabrication |
| CN101207977A (en) * | 2006-12-20 | 2008-06-25 | 富葵精密组件(深圳)有限公司 | Method for making flexible circuit board with break difference structure |
| CN104241598A (en) * | 2013-06-18 | 2014-12-24 | 赵军辉 | Composite negative electrode, preparation method of negative electrode and lithium-sulfur secondary battery with negative electrode |
| CN106450489A (en) * | 2016-12-16 | 2017-02-22 | 天津力神电池股份有限公司 | In-situ preparation method of lithium-sulfur battery based on hard carbon anode |
| CN106450488A (en) * | 2016-12-16 | 2017-02-22 | 天津力神电池股份有限公司 | In-situ preparation method of lithium-sulfur battery based on silicon cathode |
| CN106784600A (en) * | 2016-12-23 | 2017-05-31 | 天津力神电池股份有限公司 | One kind is containing lithium cathode sheet and preparation method thereof |
| CN106711430A (en) * | 2016-12-27 | 2017-05-24 | 中南大学 | Production method of lithium/carbon fiber or porous carbon paper/copper foil composite negative electrode used for lithium-sulfur battery |
| CN108346778A (en) * | 2018-02-07 | 2018-07-31 | 清华大学 | A kind of electrochemical method preparing ultra-thin lithium an- ode |
| TWI656682B (en) * | 2018-10-16 | 2019-04-11 | 長春石油化學股份有限公司 | Electrolytic copper foil, electrode comprising the same, and lithium ion battery comprising the same |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114346048A (en) * | 2021-12-22 | 2022-04-15 | 长沙矿冶研究院有限责任公司 | Lithium sheet die cutting equipment and lithium sheet die cutting process |
| CN114346048B (en) * | 2021-12-22 | 2024-02-20 | 长沙矿冶研究院有限责任公司 | Lithium sheet die cutting equipment and lithium sheet die cutting process |
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|---|---|
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