CN113745663A - Film type sodium ion secondary battery and preparation method thereof - Google Patents
Film type sodium ion secondary battery and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a film type sodium ion secondary battery and a preparation method thereof, wherein the film type sodium ion secondary battery comprises a shell, a positive pole piece and a negative pole piece, wherein the positive pole piece and the negative pole piece are connected through pressing, and are both positioned in the shell; a preparation method of a film type sodium ion secondary battery comprises the steps of selecting raw materials; step two, spray sputtering; step three, drying and rolling; step four, stirring; step five, packaging and forming; according to the invention, the anode material and the cathode material sprayed with turbid liquid are dried, so that solid electrolyte is formed on the surfaces of the anode material and the cathode material, the mode that the existing battery adopts liquid electrolyte is changed, and the safety performance of the battery is improved.
Description
Technical Field
The invention relates to the technical field of batteries, in particular to a film type sodium ion secondary battery and a preparation method thereof.
Background
Lithium ion batteries have been widely used in various fields such as energy storage, electric vehicles, electric tools, mobile digital devices, and the like. With the widespread use of lithium ion batteries, especially the rapid development of the electric automobile market, lithium resources are largely consumed and are about to be exhausted. The current lithium ion battery technology has the problems of high price, poor material stability, poor long-cycle safety performance and the like in the large-scale energy storage stage. Meanwhile, considering the energy consumption of lithium ion battery material manufacturing, battery production and cycle, the lithium ion battery with 1kWh needs to consume about 400kWh of energy and generate about 75kg of carbon dioxide gas (equivalent to the amount of gas discharged by 35L of gasoline combustion), and the main energy consumption is the production of electrode materials. Therefore, the environmental benefits of lithium ion batteries can be gradually developed only after the batteries are cycled hundreds of times (> 400).
The crustal content of lithium element is only 0.0065%, and the global lithium storage of more than 76% is intensively distributed in south America. The lithium resource reserves are little, and the global distribution is uneven, so that the cost of the lithium ion battery is always high. The sodium element of the same main group has a content of about 2.8% in the shell, is 430 times as abundant as lithium resources, and has similar physicochemical properties with lithium. According to the principle of a lithium ion rocking chair type battery, a sodium ion-rich compound can be similar to a lithium ion-rich positive electrode material, can provide sodium ions which can be extracted and inserted and a structure, and is matched with corresponding electrolyte, a diaphragm and a negative electrode to form the room-temperature sodium ion battery. The development of sodium ion batteries provides an important direction for reducing the cost of secondary ion batteries. The sodium ion battery generates battery voltage through different potentials of positive and negative electrodes of the battery, realizes the embedding and emigration of sodium ions between the positive and negative electrodes, and completes charge storage and release.
The thin film battery of the sodium ion battery is not reported at present, so that the design of a thin film type sodium ion secondary battery and a preparation method thereof are necessary.
Disclosure of Invention
The present invention is directed to a thin film type sodium ion secondary battery and a method for manufacturing the same, which solves the above problems of the related art.
In order to achieve the purpose, the invention provides the following technical scheme: a film type sodium ion secondary battery comprises a shell, a positive pole piece and a negative pole piece, wherein the positive pole piece and the negative pole piece are connected through pressing, and the positive pole piece and the negative pole piece are both located inside the shell.
A preparation method of a film type sodium ion secondary battery comprises the steps of selecting raw materials; step two, spray sputtering; step three, drying and rolling; step four, stirring; step five, packaging and forming;
in the first step, firstly, selecting a certain amount of active substances, a conductive agent, a binder, an NMP solvent, a current collector, a sodium salt, a mixed solvent, a PEO polymer and PVDF for later use, wherein the active substances are sodium vanadium phosphate serving as a carbon-coated sodium fast-ion conductor material, the conductive agent is one or a mixture of more of superconducting carbon black, a carbon nano tube and acetylene black, the binder is one or a mixture of more of PVDF, PTFE, polyaniline and polyurethane, and the current collector is an aluminum foil current collector or a nickel foil current collector;
in the second step, 80-95% of active substances, 2-10% of conductive agents and 3-10% of binders are respectively weighed from the standby materials selected in the first step according to mass percentage, then a proper amount of NMP solvent is weighed from the first step, then the weighed active substances, conductive agents and binders are placed in the NMP solvent to be dispersed by a dispersion machine to obtain anode slurry, then the obtained anode slurry is coated on the current collector weighed in the first step in a spray sputtering mode, the sputtering thickness is 20-100 micrometers, then the current collector sputtered with the anode slurry is placed in a drying box to be dried, and then the dried current collector is rolled to obtain the anode material;
in the third step, 80-95% of active substances, 2-10% of conductive agents and 3-10% of binders are respectively weighed from the standby materials selected in the first step according to mass percentage, then a proper amount of NMP solvent is weighed from the first step, then the weighed active substances, conductive agents and binders are placed in the NMP solvent and dispersed by a dispersion machine to obtain anode slurry, then the obtained anode slurry is coated on the current collector weighed in the first step in a spray sputtering mode, the sputtering thickness is 50-150 microns, then the current collector sputtered with the anode slurry is placed in a drying box to be dried, and then the dried current collector is rolled to obtain a cathode material;
wherein in the fourth step, NaClO is mixed with4、NaPF6、NaN(SO2CF3)2、NaSO3CF3And NaBF4Dissolving one or more sodium salts in one or more solvents selected from DMC, EMC, DEC and PC, adding 50-80% PEO polymer and PVDF, and stirring to obtain suspension;
in the fifth step, the turbid liquid prepared and formed in the fourth step is coated on the positive electrode material and the negative electrode material obtained in the second step and the negative electrode material obtained in the third step in a spray sputtering mode, then the positive electrode material and the negative electrode material are respectively dried to obtain a positive electrode piece and a negative electrode piece, then the dried positive electrode piece and the dried negative electrode piece are pressed, and finally the thin film battery can be prepared by using a shell for packaging.
Preferably, in the second step, the dispersing time is 20-30min, the rotating speed of the stirring shaft in the dispersing process is 1500r/min, and the solid content in the anode slurry is 30-70%.
Preferably, in the second step, the drying temperature is divided into three sections, the first section drying temperature is 30-40 ℃, the drying time is 5-10min, the second section drying temperature is 40-60 ℃, the drying time is 20-30min, the third section drying temperature is 90-100 ℃, the drying time is 30-60min, the humidity in the drying oven is kept at 40-60% in the drying process, when the third section drying is completed, the humidity in the drying oven is stopped to be kept, and then the residual moisture on the surface of the current collector is dried by using the residual heat in the drying oven.
Preferably, in the third step, the dispersing time is 25-35min, the rotating speed of the stirring shaft in the dispersing process is 1300r/min, and the solid content in the anode slurry is 30-70%.
Preferably, in the third step, the drying temperature is divided into three sections, the first section drying temperature is 25-35 ℃, the drying time is 3-5min, the second section drying temperature is 35-55 ℃, the drying time is 5-20min, the third section drying temperature is 55-80 ℃, the drying time is 20-30min, the humidity in the drying oven is kept at 40-60% in the drying process, when the third section drying is completed, the humidity in the drying oven is stopped to be kept, and then the residual moisture on the surface of the current collector is dried by using the residual heat in the drying oven.
Preferably, in the fifth step, the shell is made of an aluminum-plastic film, the thickness of the prepared thin film battery is 0.1-0.5mm, and the matching ratio of the positive and negative electrode surface capacities in the thin film battery is 1: 2.
Compared with the prior art, the invention has the beneficial effects that: according to the invention, the positive electrode material and the negative electrode material sprayed and sputtered with turbid liquid are dried, so that solid electrolyte is formed on the surfaces of the positive electrode material and the negative electrode material, the mode that the existing battery adopts liquid electrolyte is changed, and the safety performance of the battery is improved.
Drawings
FIG. 1 is a schematic view of the overall structure of the present invention;
FIG. 2 is a flow chart of a method of the present invention;
FIG. 3 is a diagram showing the charge and discharge of a thin film battery in example 1 of the present invention;
FIG. 4 is a graph showing the cycle performance of the thin film battery in example 1 of the present invention;
in the figure: 1. a housing; 2. a positive electrode plate; 3. and (5) a negative pole piece.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Referring to fig. 1, an embodiment of the present invention: a film type sodium ion secondary battery comprises a shell 1, a positive pole piece 2 and a negative pole piece 3, wherein the positive pole piece 2 and the negative pole piece 3 are connected through pressing, and the positive pole piece 2 and the negative pole piece 3 are both located in the shell 1.
Referring to fig. 2-4, an embodiment of the present invention:
example 1:
a preparation method of a film type sodium ion secondary battery comprises the steps of selecting raw materials; step two, spray sputtering; step three, drying and rolling; step four, stirring; step five, packaging and forming;
in the first step, firstly, selecting a certain amount of active substances, a conductive agent, a binder, an NMP solvent, a current collector, a sodium salt, a mixed solvent, a PEO polymer and PVDF for later use, wherein the active substances are sodium vanadium phosphate serving as a carbon-coated sodium fast-ion conductor material, the conductive agent is one or a mixture of more of superconducting carbon black, a carbon nano tube and acetylene black, the binder is one or a mixture of more of PVDF, PTFE, polyaniline and polyurethane, and the current collector is an aluminum foil current collector or a nickel foil current collector;
in the second step, 80% of active substances, 10% of conductive agents and 10% of binders are respectively weighed from the standby materials selected in the first step according to the mass percentage, then a proper amount of NMP solvent is weighed from the first step, then the weighed active substances, conductive agents and binders are placed in the NMP solvent and dispersed by a dispersion machine to obtain the anode slurry, the dispersion time is 20min, the rotating speed of a stirring shaft in the dispersion process is 1500r/min, the solid content in the anode slurry is 30%, then the obtained anode slurry is coated on the current collector weighed in the first step in a spray sputtering mode, the sputtering thickness is 20 micrometers, then the current collector sputtered with the anode slurry is placed in a drying box for drying treatment, the drying temperature is divided into three sections, the first section drying temperature is 30 ℃, and the drying time is 5min, the second stage drying temperature is 40 ℃, the drying time is 20min, the third stage drying temperature is 90 ℃, the drying time is 30min, the humidity in the drying box is maintained at 40% in the drying process, when the third stage drying is completed, the humidity in the drying box is stopped to be maintained, then the residual moisture on the surface of the current collector is dried by utilizing the waste heat in the drying box, and then the dried current collector is rolled to obtain the anode material;
in the third step, 80% of active substances, 10% of conductive agents and 10% of binders are respectively weighed from the standby materials selected in the first step according to the mass percentage, then a proper amount of NMP solvent is weighed from the first step, then the weighed active substances, conductive agents and binders are placed in the NMP solvent and dispersed by a dispersion machine to obtain anode slurry, the dispersion time is 25min, the rotating speed of a stirring shaft in the dispersion process is 1300r/min, the solid content in the anode slurry is 30%, then the obtained anode slurry is coated on the weighed current collector in the first step in a spray sputtering mode, the sputtering thickness is 50 micrometers, then the current collector sputtered with the anode slurry is placed in a drying box to be dried, the drying temperature is divided into three sections, the first section drying temperature is 25 ℃, and the drying time is 3min, the second stage drying temperature is 35 ℃, the drying time is 5min, the third stage drying temperature is 55 ℃, the drying time is 20min, the humidity in the drying box is maintained at 40% in the drying process, when the third stage drying is completed, the humidity in the drying box is stopped to be maintained, then the residual moisture on the surface of the current collector is dried by utilizing the waste heat in the drying box, and then the dried current collector is rolled to obtain the negative electrode material;
wherein in the fourth step, NaClO is mixed with4、NaPF6、NaN(SO2CF3)2、NaSO3CF3And NaBF4Dissolving one or more sodium salts in one or more solvents selected from DMC, EMC, DEC and PC, adding 50-80% PEO polymer and PVDF, and stirring to obtain suspension;
in the fifth step, the turbid liquid prepared and formed in the fourth step is coated on the turbid liquid obtained in the second step and the turbid liquid obtained in the third step in a spray sputtering modeThe method comprises the following steps of preparing a positive electrode material and a negative electrode material, respectively drying the positive electrode material and the negative electrode material to obtain a positive electrode piece 2 and a negative electrode piece 3, then pressing the dried positive electrode piece 2 and the dried negative electrode piece 3, finally packaging the positive electrode material and the negative electrode material by using a shell 1 to obtain the thin film battery, wherein the shell 1 is made of an aluminum-plastic film, the thickness of the thin film battery prepared at the same time is 0.1mm, the capacity matching ratio of positive and negative electrode surfaces in the thin film battery is 1:2, a charge-discharge diagram of the thin film battery is shown in figure 3, a cycle performance diagram of the thin film battery is shown in figure 4, and the reaction equation of the positive electrode in the thin film battery is Na3V2(PO4)3－2e－→NaV2(PO4)3+2Na, negative reaction equation is Na3V2(PO4)3+Na++e－→Na4V2(PO4)3。
Example 2:
a preparation method of a film type sodium ion secondary battery comprises the steps of selecting raw materials; step two, spray sputtering; step three, drying and rolling; step four, stirring; step five, packaging and forming;
in the first step, firstly, selecting a certain amount of active substances, a conductive agent, a binder, an NMP solvent, a current collector, a sodium salt, a mixed solvent, a PEO polymer and PVDF for later use, wherein the active substances are sodium vanadium phosphate serving as a carbon-coated sodium fast-ion conductor material, the conductive agent is one or a mixture of more of superconducting carbon black, a carbon nano tube and acetylene black, the binder is one or a mixture of more of PVDF, PTFE, polyaniline and polyurethane, and the current collector is an aluminum foil current collector or a nickel foil current collector;
wherein in the second step, 95% of active substance, 2% of conductive agent and 3% of binder are respectively weighed according to the mass percentage from the standby material selected in the first step, then a proper amount of NMP solvent is weighed from the first step, then the weighed active substance, conductive agent and binder are placed in the NMP solvent and dispersed by a dispersion machine to obtain the anode slurry, the dispersion time is 20min, the rotation speed of a stirring shaft in the dispersion process is 1500r/min, the solid content in the anode slurry is 30%, then the obtained anode slurry is coated on the current collector weighed in the first step in a spray sputtering mode, the sputtering thickness is 20 microns, then the current collector sputtered with the anode slurry is placed in a drying box for drying treatment, the drying temperature is divided into three sections, the first section drying temperature is 30 ℃, and the drying time is 5min, the second stage drying temperature is 40 ℃, the drying time is 20min, the third stage drying temperature is 90 ℃, the drying time is 30min, the humidity in the drying box is maintained at 40% in the drying process, when the third stage drying is completed, the humidity in the drying box is stopped to be maintained, then the residual moisture on the surface of the current collector is dried by utilizing the waste heat in the drying box, and then the dried current collector is rolled to obtain the anode material;
in the third step, 95% of active substances, 2% of conductive agents and 3% of binders are respectively weighed from the standby materials selected in the first step according to the mass percentage, then a proper amount of NMP solvent is weighed from the first step, then the weighed active substances, conductive agents and binders are placed in the NMP solvent and dispersed by a dispersion machine to obtain anode slurry, the dispersion time is 25min, the rotating speed of a stirring shaft in the dispersion process is 1300r/min, the solid content in the anode slurry is 30%, then the obtained anode slurry is coated on the weighed current collector in the first step in a spray sputtering mode, the sputtering thickness is 50 micrometers, then the current collector sputtered with the anode slurry is placed in a drying box for drying treatment, the drying temperature is divided into three sections, the first section drying temperature is 25 ℃, and the drying time is 3min, the second stage drying temperature is 35 ℃, the drying time is 5min, the third stage drying temperature is 55 ℃, the drying time is 20min, the humidity in the drying box is maintained at 40% in the drying process, when the third stage drying is completed, the humidity in the drying box is stopped to be maintained, then the residual moisture on the surface of the current collector is dried by utilizing the waste heat in the drying box, and then the dried current collector is rolled to obtain the negative electrode material;
wherein the above stepsIn the fourth step, NaClO is mixed with4、NaPF6、NaN(SO2CF3)2、NaSO3CF3And NaBF4Dissolving one or more sodium salts in one or more solvents selected from DMC, EMC, DEC and PC, adding 50-80% PEO polymer and PVDF, and stirring to obtain suspension;
in the fifth step, the formed turbid liquid prepared in the fourth step is coated on the positive electrode material and the negative electrode material obtained in the second step and the third step respectively in a spray sputtering mode, then the positive electrode material and the negative electrode material are respectively dried to obtain a positive electrode piece 2 and a negative electrode piece 3, then the dried positive electrode piece 2 and the dried negative electrode piece 3 are pressed, finally the thin film battery can be manufactured by using a shell 1 for packaging, the shell 1 is made of an aluminum-plastic film, the thickness of the thin film battery manufactured at the same time is 0.3mm, and the capacity matching ratio of the positive electrode surface and the negative electrode surface in the thin film battery is 1: 2.
Example 3:
a preparation method of a film type sodium ion secondary battery comprises the steps of selecting raw materials; step two, spray sputtering; step three, drying and rolling; step four, stirring; step five, packaging and forming;
in the first step, firstly, selecting a certain amount of active substances, a conductive agent, a binder, an NMP solvent, a current collector, a sodium salt, a mixed solvent, a PEO polymer and PVDF for later use, wherein the active substances are sodium vanadium phosphate serving as a carbon-coated sodium fast-ion conductor material, the conductive agent is one or a mixture of more of superconducting carbon black, a carbon nano tube and acetylene black, the binder is one or a mixture of more of PVDF, PTFE, polyaniline and polyurethane, and the current collector is an aluminum foil current collector or a nickel foil current collector;
in the second step, 90% of active substances, 5% of conductive agents and 5% of binders are respectively weighed from the standby materials selected in the first step according to the mass percentage, then a proper amount of NMP solvent is weighed from the first step, then the weighed active substances, conductive agents and binders are placed in the NMP solvent and dispersed by a dispersion machine to obtain the anode slurry, the dispersion time is 20min, the rotating speed of a stirring shaft in the dispersion process is 1500r/min, the solid content in the anode slurry is 30%, then the obtained anode slurry is coated on the current collector weighed in the first step in a spray sputtering mode, the sputtering thickness is 20 micrometers, then the current collector sputtered with the anode slurry is placed in a drying box for drying treatment, the drying temperature is divided into three sections, the first section drying temperature is 30 ℃, and the drying time is 5min, the second stage drying temperature is 40 ℃, the drying time is 20min, the third stage drying temperature is 90 ℃, the drying time is 30min, the humidity in the drying box is maintained at 40% in the drying process, when the third stage drying is completed, the humidity in the drying box is stopped to be maintained, then the residual moisture on the surface of the current collector is dried by utilizing the waste heat in the drying box, and then the dried current collector is rolled to obtain the anode material;
in the third step, 90% of active substances, 5% of conductive agents and 5% of binders are respectively weighed from the standby materials selected in the first step according to the mass percentage, then a proper amount of NMP solvent is weighed from the first step, then the weighed active substances, conductive agents and binders are placed in the NMP solvent and dispersed by a dispersion machine to obtain anode slurry, the dispersion time is 25min, the rotating speed of a stirring shaft in the dispersion process is 1300r/min, the solid content in the anode slurry is 30%, then the obtained anode slurry is coated on the weighed current collector in the first step in a spray sputtering mode, the sputtering thickness is 50 micrometers, then the current collector sputtered with the anode slurry is placed in a drying box for drying treatment, the drying temperature is divided into three sections, the first section drying temperature is 25 ℃, and the drying time is 3min, the second stage drying temperature is 35 ℃, the drying time is 5min, the third stage drying temperature is 55 ℃, the drying time is 20min, the humidity in the drying box is maintained at 40% in the drying process, when the third stage drying is completed, the humidity in the drying box is stopped to be maintained, then the residual moisture on the surface of the current collector is dried by utilizing the waste heat in the drying box, and then the dried current collector is rolled to obtain the negative electrode material;
wherein in the fourth step, NaClO is mixed with4、NaPF6、NaN(SO2CF3)2、NaSO3CF3And NaBF4Dissolving one or more sodium salts in one or more solvents selected from DMC, EMC, DEC and PC, adding 50-80% PEO polymer and PVDF, and stirring to obtain suspension;
in the fifth step, the formed turbid liquid prepared in the fourth step is coated on the positive electrode material and the negative electrode material obtained in the second step and the third step respectively in a spray sputtering mode, then the positive electrode material and the negative electrode material are respectively dried to obtain a positive electrode piece 2 and a negative electrode piece 3, then the dried positive electrode piece 2 and the dried negative electrode piece 3 are pressed, finally the thin film battery can be manufactured by using a shell 1 for packaging, the shell 1 is made of an aluminum-plastic film, the thickness of the thin film battery manufactured at the same time is 0.5mm, and the capacity matching ratio of the positive electrode surface and the negative electrode surface in the thin film battery is 1: 2.
The thickness of the thin film batteries obtained in the above examples was counted, and the results are shown in the following table
| Thickness of | |
| Example 1 | 0.1mm |
| Example 2 | 0.3mm |
| Example 3 | 0.5mm |
Based on the above, the invention has the beneficial effects that in the process of preparing the thin film battery, the prepared and molded suspension is sprayed and sputtered on the positive electrode material and the negative electrode material, so that the positive electrode material and the negative electrode material are dried, and the solid electrolyte is remained on the surfaces of the positive electrode material and the negative electrode material, thereby changing the mode of using the liquid electrolyte in the existing battery, improving the safety of the thin film battery, and meanwhile, in the process of preparing, the sectional type drying treatment is carried out on the current collector with the residual positive electrode slurry and the negative electrode slurry, so that the drying speed of the current collector is favorably and sufficiently reduced, the falling off of the residual positive electrode slurry and the residual negative electrode slurry sprayed and sputtered on the current collector is avoided, and the yield of the thin film battery is further improved.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.
Claims (7)
1. The utility model provides a film type sodium ion secondary battery, includes casing (1), positive pole piece (2) and negative pole piece (3), its characterized in that: the positive pole piece (2) and the negative pole piece (3) are connected through pressing, and the positive pole piece (2) and the negative pole piece (3) are both located inside the shell (1).
2. A preparation method of a film type sodium ion secondary battery comprises the steps of selecting raw materials; step two, spray sputtering; step three, drying and rolling; step four, stirring; step five, packaging and forming; the method is characterized in that:
in the first step, firstly, selecting a certain amount of active substances, a conductive agent, a binder, an NMP solvent, a current collector, a sodium salt, a mixed solvent, a PEO polymer and PVDF for later use, wherein the active substances are sodium vanadium phosphate serving as a carbon-coated sodium fast-ion conductor material, the conductive agent is one or a mixture of more of superconducting carbon black, a carbon nano tube and acetylene black, the binder is one or a mixture of more of PVDF, PTFE, polyaniline and polyurethane, and the current collector is an aluminum foil current collector or a nickel foil current collector;
in the second step, 80-95% of active substances, 2-10% of conductive agents and 3-10% of binders are respectively weighed from the standby materials selected in the first step according to mass percentage, then a proper amount of NMP solvent is weighed from the first step, then the weighed active substances, conductive agents and binders are placed in the NMP solvent to be dispersed by a dispersion machine to obtain anode slurry, then the obtained anode slurry is coated on the current collector weighed in the first step in a spray sputtering mode, the sputtering thickness is 20-100 micrometers, then the current collector sputtered with the anode slurry is placed in a drying box to be dried, and then the dried current collector is rolled to obtain the anode material;
in the third step, 80-95% of active substances, 2-10% of conductive agents and 3-10% of binders are respectively weighed from the standby materials selected in the first step according to mass percentage, then a proper amount of NMP solvent is weighed from the first step, then the weighed active substances, conductive agents and binders are placed in the NMP solvent and dispersed by a dispersion machine to obtain anode slurry, then the obtained anode slurry is coated on the current collector weighed in the first step in a spray sputtering mode, the sputtering thickness is 50-150 microns, then the current collector sputtered with the anode slurry is placed in a drying box to be dried, and then the dried current collector is rolled to obtain a cathode material;
wherein in the fourth step, NaClO is mixed with4、NaPF6、NaN(SO2CF3)2、NaSO3CF3And NaBF4Dissolving one or more sodium salts in one or more solvents selected from DMC, EMC, DEC and PC, adding 50-80% PEO polymer and PVDF, and stirring to obtain suspension;
in the fifth step, the suspension prepared and molded in the fourth step is coated on the positive electrode material and the negative electrode material obtained in the second step and the third step respectively in a spray sputtering mode, then the positive electrode material and the negative electrode material are dried respectively to obtain a positive electrode piece (2) and a negative electrode piece (3), then the dried positive electrode piece (2) and the dried negative electrode piece (3) are pressed, and finally the thin film battery can be prepared by packaging the positive electrode piece (2) and the negative electrode piece (3) by using a shell (1).
3. The method for manufacturing a film-type sodium ion secondary battery according to claim 2, characterized in that: in the second step, the dispersion time is 20-30min, the rotating speed of the stirring shaft in the dispersion process is 1500r/min, and the solid content in the anode slurry is 30-70%.
4. The method for manufacturing a film-type sodium ion secondary battery according to claim 2, characterized in that: in the second step, the drying temperature is divided into three sections, the first section drying temperature is 30-40 ℃, the drying time is 5-10min, the second section drying temperature is 40-60 ℃, the drying time is 20-30min, the third section drying temperature is 90-100 ℃, the drying time is 30-60min, the humidity in the drying box is kept at 40-60% in the drying process, when the third section drying is completed, the humidity in the drying box is stopped to be kept, and then the residual moisture on the surface of the current collector is dried by utilizing the residual heat in the drying box.
5. The method for manufacturing a film-type sodium ion secondary battery according to claim 2, characterized in that: in the third step, the dispersion time is 25-35min, the rotating speed of the stirring shaft in the dispersion process is 1300r/min, and the solid content in the anode slurry is 30-70%.
6. The method for manufacturing a film-type sodium ion secondary battery according to claim 2, characterized in that: in the third step, the drying temperature is divided into three sections, the first section drying temperature is 25-35 ℃, the drying time is 3-5min, the second section drying temperature is 35-55 ℃, the drying time is 5-20min, the third section drying temperature is 55-80 ℃, the drying time is 20-30min, the humidity in the drying box is kept at 40-60% in the drying process, when the third section drying is completed, the humidity in the drying box is stopped to be kept, and then the residual moisture on the surface of the current collector is dried by utilizing the residual heat in the drying box.
7. The method for manufacturing a film-type sodium ion secondary battery according to claim 2, characterized in that: in the fifth step, the shell (1) is made of an aluminum plastic film, the thickness of the prepared thin film battery is 0.1-0.5mm, and the matching ratio of the positive and negative electrode surface capacities in the thin film battery is 1: 2.
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