CN115714200B - Method for preparing solid-state battery by selective solidification - Google Patents
Method for preparing solid-state battery by selective solidification Download PDFInfo
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Abstract
A method for preparing solid-state battery by selective solidification, which uses oxide solid electrolyte, organic electrolyte, small amount of additive, cross-linking agent and other materials to realize the preparation process of high-performance solid-state battery by simple post-battery heat treatment. Different from the main stream in-situ curing method, the invention realizes different polymerization reactions in the battery by utilizing one-step high-temperature curing, and solves the interface problems of the anode, electrolyte and cathode in the solid-state battery in a targeted way; the precursor with self-adaption/self-healing characteristics is adopted for polymerization on the positive electrode side, so that the problem of poor solid-solid fixation of active particles caused by volume expansion in the charge and discharge process is solved; the high-conductivity annular organic micromolecules are adopted at the electrolyte side, and are subjected to ring-opening polymerization by utilizing the oxide solid electrolyte, so that the high-conductivity polymer is formed, the ion conductivity of the electrolyte is improved, and the overall rate performance of the battery is improved.
Description
Technical Field
The invention belongs to the technical field of all-solid-state batteries, relates to an assembly, post-treatment and preparation process of a solid-state battery, and in particular relates to a preparation method of the solid-state battery, which utilizes a selective curing strategy to respectively realize a high-voltage electrode and a high-conductivity electrolyte.
Background
Secondary lithium ion batteries have been used in various fields including battery automobiles, portable electronic devices, etc. because of their advantages of high specific capacity, high voltage, wide temperature range, high coulombic efficiency, high cycle performance, and no memory effect. Secondary lithium ion batteries are considered to be one of the most potential electrochemical energy storage technologies. However, the current commercial lithium ion battery uses organic electrolyte, and the characteristics of flammability, volatility and the like cause the safety of the battery to be insufficient.
Solid state lithium batteries use solid state electrolytes as the ion conducting medium with intrinsic safety that is not flammable. At present, the composite solid electrolyte has been widely concerned because of the advantages of flexibility, low cost, easy industrialization and the like. The composite solid electrolyte is formed by compositing polymer electrolyte and inorganic solid electrolyte (oxide solid electrolyte and sulfide solid electrolyte), and has higher ionic conductivity and mechanical strength compared with pure polymer-based electrolyte, so that the composite solid electrolyte has higher application potential. However, the ionic conductivity of the composite solid electrolyte still cannot meet the use standard of commercial batteries, and in addition, volume shrinkage/expansion occurs in the inside of the positive electrode of the solid battery due to charge and discharge of the active material, so that the solid fixation between the active particles and the solid electrolyte fails during the charge and discharge process, and finally the battery fails.
Disclosure of Invention
Aiming at the problems of solid-solid contact failure and low electrolyte conductivity in the positive electrode, a selective curing strategy is adopted, a self-adaptive/self-healing type in-situ cured polymer electrolyte is used in the positive electrode layer, the electrolyte is used as an ion path, and the electrolyte expands and contracts along with expansion and contraction of active particles in the charge and discharge process of the battery to form a self-adaptive interface so as to relieve contact failure; and in-situ polymerization is adopted to realize thermal polymerization after the battery is assembled by the two in-situ polymerization, and selective curing is realized by different curing mechanisms, so that the solid-state battery with long service life and high specific energy is finally obtained.
The invention aims at realizing the following technical scheme:
a method for preparing solid-state battery by selective solidification, as shown in figure 1, the positive electrode side of the battery comprises active substance, conductive carbon and self-healing electrolyte, the electrolyte side comprises oxide solid electrolyte and high ionic conductivity organic electrolyte, the battery is prepared by a double-layer coating method, firstly, the prepared composite positive electrode slurry is coated on a current collector, after drying, the oxide solid electrolyte slurry is coated on the positive electrode to form a positive electrode-electrolyte frame structure, then the organic electrolyte is filled (the positive electrode-electrolyte has a porous structure, the organic liquid electrolyte can infiltrate into the electrode and the electrolyte), lithium metal is attached, after the battery is assembled, the organic electrolyte is polymerized into electrolytes with different functions in a positive electrode layer and an electrolyte layer respectively, namely, the solid-state battery with high performance is obtained by selective solidification. The self-adaptive electrode active material can expand and shrink in volume in the charge and discharge process, and the self-healing electrolyte is different from the traditional electrolyte, and can expand and shrink along with the expansion and shrinkage of the active particles, so that the interface contact failure between the solid electrolyte and the solid active particles is relieved, and the self-adaptive effect is achieved.
Further, the oxide solid electrolyte is one of garnet structure, olivine structure or NASICON type, specifically Li 0.34 La 0.567 TiO 3 (LLTO)、Li 7 La 3 Zr 2 O 12 (LLZO)、Li 6.4 La 3 Zr 1.4 Ta 0.6 O 12 (LLZTO)、Li 2.88 PO 3.73 N 0.14 (LiPON)、Li 1.3 Al 0.3 Ti 1.7 (PO4) 3 (LATP)、Li 1.5 Al 0.5 Ge 1.5 P 3 O 12 One or more of them.
Further, the method comprises the following steps:
step one: composite positive electrode slurry and pole piece preparation
(1) According to 80-95:5-10:5-10:1-5 mass ratio, namely weighing the positive electrode active substance, the binder, the conductive agent and the self-healing electrolyte initiator, adding a solvent for dissolution, wherein the mass of the solvent is 1-2 times of the total mass of the positive electrode active substance, the binder, the conductive agent and the initiator, adding the raw materials into a glass bottle with a magnetic stirrer, stirring and dissolving for 12-24 hours, and the rotating speed is 300-800r/min;
(2) Coating the uniformly stirred positive electrode slurry on an aluminum foil by using an adjustable scraper, and putting the aluminum foil into a vacuum oven to be dried for 8-24 hours at 80-150 ℃ to obtain a dried positive electrode plate with a self-healing initiator inside; the initiator has the function that after the organic liquid electrolyte prepared later is poured into the electrode, part of components are polymerized and solidified into a self-adaptive polymer under the condition of the initiator; when the material receives extrusion deformation, deformation occurs, and when stress disappears, the material restores the original shape, wherein in the positive electrode, the positive electrode active material expands to generate stress on the electrolyte, so that the electrolyte is extruded and deformed, when lithium ions are separated out, the positive electrode active material contracts again, and the electrolyte has a self-healing function and also restores the original shape, so that the state of being tightly attached to active particles in the charging and discharging process is achieved, namely the self-adaption is achieved.
Step two: electrolyte slurry and preparation of electrolyte layer
(1) According to 80-95:1-5, weighing oxide solid electrolyte, a binder and a solvent, wherein the mass ratio of the total mass of the oxide solid electrolyte and the binder to the solvent is 1: 1-5, adding the raw materials into a glass bottle with a magnetic stirrer, stirring and dissolving for 12-24 hours at the rotating speed of 300-800r/min to obtain uniform electrolyte slurry;
(2) And (3) coating the electrolyte slurry on the positive electrode sheet obtained in the first step by using a doctor blade, as shown in (2) in fig. 1, adjusting the doctor blade to a proper height, continuously putting the positive electrode sheet into a vacuum oven, drying at 80-150 ℃ for 8-24 hours to obtain a dried composite sheet which is formed by sequentially forming aluminum foil, a positive electrode layer and an electrolyte layer from bottom to top, then punching the point composite sheet into a small wafer with the diameter of 14mm by using an MSK-T10 slicer, putting the obtained round electrode sheet into a tablet press, adjusting the working temperature of the tablet press to 35-60 ℃, applying pressure to the round electrode sheet, and increasing the density to a value between 2MPa and 30 MPa. The time of applying the pressure is 5-20 minutes, and finally the compact composite sheet is obtained. The oxide solid electrolyte is an initiator of the high-conductivity electrolyte, and the high-valence metal element and the lithium hydroxide/lithium carbonate on the surface of the oxide solid electrolyte can enable another part of solvent in the organic electrolyte to be solidified and polymerized at high temperature to form a high-conductivity substance.
Step three: electrolyte preparation and heat treatment after battery assembly
(1) The cyclic organic solvent, lithium salt and self-healing electrolyte precursor are mixed according to the proportion of 70-80: 5-15: mixing 1-5 mass ratio, stirring the solution at 25-60 ℃ for 5-12 hours until the solution is uniform, and obtaining organic electrolyte solution;
(2) Placing the aluminum foil-positive electrode layer-electrolyte layer composite sheet obtained in the second step into the positive electrode shell of the button cell (2025), pouring the organic electrolyte solution (50-100 microliters) into the composite sheet, adding a lithium metal negative electrode, sequentially stacking a steel sheet and a shrapnel negative electrode shell, and pressing into a cell as shown in fig. 4;
(3) The cells were then placed in an oven and treated at 80-150 ℃ for 10-24 hours to give selectively cured solid state cells. At high temperature, the organic solvent in the organic electrolyte solution is at the electrolyte side surrounded by LiOH/LiCO on the surface of the oxide solid electrolyte particles 3 And high-valence metal ions (La, ti, ta, ge, etc.) to generate ring-opening polymerization reaction to generate ion conductors with high conductivity, namely high-conductivity organic liquid electrolyte, which is favorable for rapid charge and discharge of the battery and inhibits the formation of negative lithium dendrites; and the self-adaptive electrolyte precursor in the electrolyte in the positive electrode side is polymerized into the self-adaptive electrolyte under the action of the initiator, so that the volume expansion of active substances is relieved, and the capacity and the cycle life of the battery are improved.
Further, in the first step (1), the positive electrode active material is one of lithium iron phosphate, lithium cobalt oxide, ternary nickel cobalt lithium manganate, spinel lithium manganate and sodium ion positive electrode material; the binder is one or more of polyvinyl alcohol (PVA), polyvinylidene fluoride (PVDF), polyethylene glycol, polymethyl methacrylate (PMMA) and Polytetrafluoroethylene (PTFE) which are compounded; the conductive agent is one of acetylene black, 350G, carbon fiber (VGCF), carbon Nanotubes (CNTs), ketjen black EC300J, ketjenblackEC JD, carbon ECP600 JD; the initiator is Azoisobutyronitrile (AIBN), lithium hexafluorophosphate (LiPF) 6 ) One or more of dimethyl Azodiisobutyrate (AIBME) and benzoyl peroxide; the solvent is acetonitrile, N-methylpyrroleOne or more of alkanone, ethanol, propanol, isopropanol and acetone.
Further, in the second step (1), the binder is one or more of polyvinyl alcohol (PVA), polyvinylidene fluoride (PVDF), polyethylene glycol, polymethyl methacrylate (PMMA), and Polytetrafluoroethylene (PTFE); the solvent is one or more of acetonitrile, N-methyl pyrrolidone, ethanol, propanol, isopropanol and acetone.
Further, in the step three (1), the cyclic organic solvent is one of a ternary-ring, a quaternary-ring, a five-membered-ring, a six-membered-ring alkane, alkene, ester or benzene organic matter, and specifically may be one or more of Ethylene Carbonate (EC), dioxolane (DOL), fluoroethylene carbonate (FEC), tetrahydrofuran (THF) and N-methylpyrrolidone (NMP), and the lithium salt is lithium perchlorate (LiClO) 4 ) Lithium hexafluorophosphate (LiPF) 6 ) Lithium bis (trifluoromethanesulfonyl) imide (LiTFSI), lithium hexafluoroarsenate (LiAsF) 6 ) Lithium tetrafluoroborate (LiBF) 4 ) The self-healing electrolyte precursor is one or a combination of a plurality of nitrile ethyl acrylate (CA), polyethylene oxide (PEO), polyvinyl alcohol (PVA), polyvinylidene fluoride (PVDF), polyethylene glycol, polymethyl methacrylate (PMMA), polyethylene glycol diacrylate (PEGDA), polyvinyl carbonate (PPC), pentaerythritol tetraacrylate (PETEA) and gamma-methacryloxypropyl trimethoxysilane.
A solid state battery prepared by the above method.
Compared with the prior art, the invention has the following advantages:
1. the selective curing strategy adopted by the invention is different from the main stream in-situ curing method, and the invention realizes different polymerization reactions in the battery by utilizing one-step high-temperature curing, thereby pertinently solving the interface problem of the anode, electrolyte and cathode in the solid-state battery;
2. the precursor with self-adaption/self-healing characteristics is adopted for polymerization on the positive electrode side, so that the problem of poor solid-solid fixation of active particles caused by volume expansion in the charge and discharge process is solved;
3. the high-conductivity annular organic micromolecules are adopted at the electrolyte side, and are subjected to ring-opening polymerization by utilizing oxide solid electrolyte, so that a high-conductivity polymer is formed, the ion conduction capacity of the electrolyte is improved, and the overall rate performance of the battery is improved;
4. the invention realizes the assembly of the electrode-electrolyte in the solid-state battery by combining a double-layer coating method with a pouring method, is different from the traditional composite solid-state electrolyte, has uniform dispersion and higher proportion of the oxide solid electrolyte, can improve the conductivity, simultaneously realizes the uniform deposition of lithium metal and reduces the generation of dendrites;
5. the invention adopts high proportion oxide solid electrolyte, has intrinsic safety, greatly improves the safety of the battery, and in addition, compared with the traditional in-situ curing technology, the battery assembled by the invention realizes high reversible capacity and long cycle life of the solid battery.
Drawings
FIG. 1 is a schematic diagram of a selectively cured battery preparation flow;
FIG. 2 is an optical photograph of a composite sheet;
FIG. 3 is a Scanning Electron Microscope (SEM) picture of a compact;
FIG. 4 is a block diagram of an assembled 2025 button cell;
FIG. 5 is an electrochemical impedance spectrum of a high ionic conductivity electrolyte of the present invention;
fig. 6 is a cycle performance diagram of an all-solid battery of the present invention;
fig. 7 is a graph showing the impedance contrast before and after cycling of an all-solid battery according to the present invention;
FIG. 8 is a graph of impedance contrast before and after cycling of a prior art assembled battery;
fig. 9 is a charge-discharge graph of the all-solid battery of the present invention;
fig. 10 is a charge-discharge graph of the assembled all-solid battery of example 2;
fig. 11 is a charge-discharge graph of the assembled all-solid battery of example 3.
Detailed Description
The following description of the present invention refers to the accompanying drawings and examples, but is not limited to the same, and modifications and equivalents of the present invention can be made without departing from the spirit and scope of the present invention.
The invention realizes the preparation of the high-performance solid-state battery by using the materials such as the oxide solid-state electrolyte, the organic electrolyte, a small amount of additives, the cross-linking agent and the like through simple post-heat treatment of assembled batteries. Different polymerization reactions inside the battery are realized by regulating and controlling the internal components of the positive electrode and the electrolyte and utilizing a one-step high-temperature curing method, so that the interface problem of the positive electrode, the electrolyte and the negative electrode inside the solid-state battery is solved in a targeted manner; the positive electrode side adopts a precursor with self-adaption/self-healing characteristics for polymerization; the electrolyte side adopts high-conductivity annular organic micromolecules, and the high-conductivity annular organic micromolecules are subjected to ring-opening polymerization by utilizing oxide solid electrolyte to form a high-conductivity polymer; the assembly of the electrode-electrolyte in the solid-state battery is achieved by a double-layer coating method in combination with a casting method.
Example 1:
the preparation steps of the solid-state battery respectively realizing the high-voltage electrode and the high-conductivity electrolyte by utilizing the selective curing strategy are as follows:
step one: composite positive electrode slurry and pole piece preparation
(1) Weighing ternary nickel cobalt lithium manganate, binder polyvinylidene fluoride (PVDF), conductive Carbon Nanotubes (CNTs) and self-healing electrolyte initiator lithium hexafluorophosphate (LiPF) 6 Hereinafter referred to as initiator) in a mass ratio of 84:5:5:1, adding N-methyl pyrrolidone, wherein the mass of the N-methyl pyrrolidone is 1.5 times of the total mass of active substances, a binder, a conductive agent and an initiator, adding the raw materials into a glass bottle with a magnetic stirrer, stirring and dissolving for 18 hours, and the rotating speed is 600r/min;
(2) Coating the uniformly stirred positive electrode slurry on an aluminum foil by using an adjustable scraper, and putting the aluminum foil into a vacuum oven for drying at 120 ℃ for 8 hours to obtain a dry positive electrode plate with a self-healing initiator inside;
step two: electrolyte slurry and preparation of electrolyte layer
(1) Weighing oxide solid electricityElectrolyte Li 1.3 Al 0.3 Ti 1.7 (PO 4 ) 3 (LATP) binder polyvinylidene fluoride (PVDF) with a mass ratio of 95:5, adding a solvent N-methyl pyrrolidone, wherein the mass ratio of the total mass of the oxide solid electrolyte and the binder to the solvent is 1:1.5; adding the raw materials into a glass bottle with a magnetic stirrer, stirring and dissolving for 24 hours at the rotating speed of 600r/min to obtain uniform electrolyte slurry;
(2) And (3) coating the electrolyte slurry on the positive electrode sheet obtained in the first step by using a doctor blade, as shown in (2) in fig. 1, adjusting the doctor blade to a proper height, continuously putting the positive electrode sheet into a vacuum oven, drying at 120 ℃ for 8 hours to obtain an aluminum foil-positive electrode layer-electrolyte layer composite sheet, then punching the composite sheet into a small wafer with the diameter of 14mm for later use, placing the obtained positive electrode sheet and the obtained optical photograph of the composite sheet into a tablet press, and adjusting the working temperature of the tablet press to 35-60 ℃ and the pressure to 20MPa. The time for applying the pressure was 15 minutes, and a compact composite sheet was finally obtained.
Step three: electrolyte preparation and heat treatment after battery assembly
(1) The organic solvent, namely cyclic organic small molecule Ethylene Carbonate (EC) and lithium salt lithium bis (trifluoromethanesulfonyl) imide (LiTFSI), and self-healing/self-adapting electrolyte precursor (combination of pentaerythritol tetraacrylate and gamma-methacryloxypropyl trimethoxysilane, the ratio is 1:1, and the precursor is named as precursor) are mixed according to the ratio of 80:15:5, mixing the materials in a mass ratio, and stirring the solution at 30 ℃ for 12 hours until the materials are uniform to obtain an organic electrolyte solution;
(2) Putting the composite sheet in the second step into the positive electrode shell of the button cell (2025), pouring the organic electrolyte (60 microliters) into the composite sheet, adding a lithium metal negative electrode, sequentially stacking a steel sheet and a shrapnel negative electrode shell, and pressing to form the cell, wherein the structure of the cell is shown in figure 4;
(3) Then the battery is put into an oven and treated for 18 hours at 100 ℃ to obtain a selectively solidified solid-state battery, as shown in an SEM (SEM) picture of a composite positive electrode (comprising electrode particles and electrolyte) in fig. 3, the electrolyte still keeps good contact with the electrode particles after circulation, indicating high compatibility and adaptability of the self-healing electrolyte with the active particles; as shown in fig. 5, the electrolyte layer was applied separately, cured in the same way, and assembled into a block cell, the conductivity obtained from the impedance was 0.174mS/cm, indicating its higher ionic conductivity; the cycle performance is shown in fig. 6, and compared with the existing in-situ curing technology, the capacity retention rate is greatly improved from 30.88% to 87.68%, and the cycle life of the battery is prolonged by the method. In addition, the discharge capacity is improved from 75mAh/g to 140mAh/g, which shows that the method improves the rate capability of the battery. As shown in fig. 7 and 8, compared with the existing in-situ curing technology, the impedance change of the battery after circulation is smaller, after circulation, the conventional in-situ curing battery has larger interface impedance which is 341 Ω, and the selective curing strategy provided by the invention adopts self-healing electrolyte for the positive electrode, and the interface impedance after circulation is only 104 Ω, which indicates that the method of the invention obviously relieves the problem of poor solid-solid contact of active particles caused by volume expansion in the charge and discharge process; as shown in fig. 9, the battery assembled by the method has high reversible capacity of 138mAh/g and charge-discharge efficiency of more than 96%.
Example 2:
step one: composite positive electrode slurry and pole piece preparation
(1) Weighing ternary nickel cobalt lithium manganate, binder polyvinylidene fluoride (PVDF), conductive Carbon Nanotubes (CNTs) and self-healing electrolyte initiator lithium hexafluorophosphate (LiPF) 6 Hereinafter referred to as initiator) in a mass ratio of 90:3:3:1, adding N-methyl pyrrolidone, wherein the mass of the N-methyl pyrrolidone is 1.5 times of the total mass of active substances, a binder, a conductive agent and an initiator, adding the raw materials into a glass bottle with a magnetic stirrer, stirring and dissolving for 18 hours, and the rotating speed is 600r/min;
(2) Coating the uniformly stirred positive electrode slurry on an aluminum foil by using an adjustable scraper, and putting the aluminum foil into a vacuum oven for drying at 120 ℃ for 8 hours to obtain a dry positive electrode plate with a self-healing initiator inside;
step two: electrolyte slurry and preparation of electrolyte layer
(1) Weighing oxide solid electrolyte Li 1.5 Al 0.5 Ge 1.5 P 3 O 12 The binder polyvinylidene fluoride (PVDF) has a mass ratio of 95:5, adding a solvent N-methyl pyrrolidone, wherein the mass ratio of the total mass of the oxide solid electrolyte and the binder to the solvent is 1:1.5; adding the raw materials into a glass bottle with a magnetic stirrer, stirring and dissolving for 24 hours at the rotating speed of 500r/min to obtain uniform electrolyte slurry;
(2) And (3) coating the electrolyte slurry on the positive electrode sheet obtained in the first step by using a doctor blade, as shown in (2) in fig. 1, adjusting the doctor blade to a proper height, continuously putting the positive electrode sheet into a vacuum oven, drying at 80 ℃ for 18 hours to obtain an aluminum foil-positive electrode layer-electrolyte layer composite sheet, then punching the composite sheet into a small wafer with the diameter of 14mm for later use, placing the obtained positive electrode sheet and the obtained optical photograph of the composite sheet into a tablet press, and adjusting the working temperature of the tablet press to 35-60 ℃ and the pressure to 20MPa. The time for applying the pressure was 15 minutes, and a compact composite sheet was finally obtained.
Step three: electrolyte preparation and heat treatment after battery assembly
(1) The organic solvent, namely cyclic organic small molecule Ethylene Carbonate (EC) and lithium salt lithium bis (trifluoromethanesulfonyl) imide (LiTFSI), and self-healing/self-adapting electrolyte precursor (combination of pentaerythritol tetraacrylate and gamma-methacryloxypropyl trimethoxysilane, the ratio is 1:1, and the precursor is named as precursor) are mixed according to the ratio of 80:15:5, mixing the materials in a mass ratio, and stirring the solution at 30 ℃ for 12 hours until the materials are uniform to obtain an organic electrolyte solution;
(2) Putting the composite sheet in the second step into a positive electrode shell of the button cell (2025), pouring the organic electrolyte (60 microliters) into the composite sheet, adding a lithium metal negative electrode, sequentially stacking a steel sheet and a shrapnel negative electrode shell, and pressing to form the cell;
(3) The cells were then placed in an oven and treated at 100 ℃ for 18 hours to give selectively cured solid state cells. As shown in fig. 10, the battery assembled by the method has a high discharge capacity, and the charge-discharge efficiency is also greater than 96%.
Example 3:
step one: composite positive electrode slurry and pole piece preparation
(1) Weighing ternary nickel cobalt lithium manganate, polytetrafluoroethylene (PTFE) as binder, carbon Nanotubes (CNTs) as conductive agent and lithium hexafluorophosphate (LiPF) as self-healing electrolyte initiator 6 Hereinafter referred to as initiator) in a mass ratio of 84:5:5:1, adding acetone, wherein the mass of the acetone is 2 times of the total mass of active substances, adhesive, conductive agent and initiator, adding the raw materials into a glass bottle with a magnetic stirrer, stirring and dissolving for 10 hours, and rotating at 1500r/min;
(2) Coating the uniformly stirred positive electrode slurry on an aluminum foil by using an adjustable scraper, and putting the aluminum foil into a vacuum oven for drying at 120 ℃ for 8 hours to obtain a dry positive electrode plate with a self-healing initiator inside;
step two: electrolyte slurry and preparation of electrolyte layer
(1) Weighing oxide solid electrolyte Li 1.3 Al 0.3 Ti 1.7 (PO 4 ) 3 (LATP) a binder Polytetrafluoroethylene (PTFE) with a mass ratio of 90:10, adding a solvent acetone, wherein the mass ratio of the total mass of the oxide solid electrolyte and the binder to the solvent is 1:1.5; adding the raw materials into a glass bottle with a magnetic stirrer, stirring and dissolving for 24 hours at the rotating speed of 600r/min to obtain uniform electrolyte slurry;
(2) And (3) coating the electrolyte slurry on the positive electrode sheet obtained in the first step by using a doctor blade, as shown in (2) in fig. 1, adjusting the doctor blade to a proper height, continuously putting the positive electrode sheet into a vacuum oven, drying at 120 ℃ for 8 hours to obtain an aluminum foil-positive electrode layer-electrolyte layer composite sheet, then punching the composite sheet into a small wafer with the diameter of 14mm for later use, placing the obtained positive electrode sheet and the obtained optical photograph of the composite sheet into a tablet press, and adjusting the working temperature of the tablet press to 35-60 ℃ and the pressure to 20MPa. The time for applying the pressure was 15 minutes, and a compact composite sheet was finally obtained.
Step three: electrolyte preparation and heat treatment after battery assembly
(1) The organic solvent, namely cyclic organic small molecule Ethylene Carbonate (EC) and lithium salt lithium bis (trifluoromethanesulfonyl) imide (LiTFSI), and self-healing/self-adapting electrolyte precursor (combination of pentaerythritol tetraacrylate and gamma-methacryloxypropyl trimethoxysilane, the ratio is 1:1, and the precursor is named as precursor) are mixed according to the ratio of 80:15:5, mixing the materials in a mass ratio, and stirring the solution at 30 ℃ for 12 hours until the materials are uniform to obtain an organic electrolyte solution;
(2) Putting the composite sheet in the second step into a positive electrode shell of the button cell (2025), pouring the organic electrolyte (60 microliters) into the composite sheet, adding a lithium metal negative electrode, sequentially stacking a steel sheet and a shrapnel negative electrode shell, and pressing to form the cell;
(3) The battery was then placed in an oven and treated at 80 ℃ for 24 hours to give a selectively cured solid state battery, as shown in fig. 11, the battery assembled by this method had a high discharge capacity, and the charge-discharge efficiency was also greater than 96%.
Claims (6)
1. A method of preparing a solid state battery by selective curing, characterized by: the positive electrode side of the battery comprises self-healing electrolyte, the electrolyte side comprises oxide solid electrolyte and organic electrolyte, the battery is prepared by a double-layer coating method, firstly, the prepared composite positive electrode slurry is coated on a current collector, after drying, the oxide solid electrolyte slurry is coated on the positive electrode to form a positive electrode-electrolyte frame structure, then, the organic electrolyte is filled, lithium metal is attached, and after the battery is assembled, the solid battery is obtained through heat treatment;
the method comprises the following steps:
step one: composite positive electrode slurry and pole piece preparation
(1) According to 80-95:5-10:5-10:1-5 mass ratio of positive electrode active material, binder, conductive agent and self-healing electrolyte initiator, adding solvent to dissolve, wherein the mass is 1-2 times of the total mass of the positive electrode active material, binder, conductive agent and initiator, and magnetically stirring and dissolving the raw materials;
(2) Coating the anode slurry which is uniformly stirred on an aluminum foil, and drying for 8-24 hours at 80-150 ℃ to obtain an anode plate;
step two: electrolyte slurry and preparation of electrolyte layer
(1) According to 80-95:1-5, weighing oxide solid electrolyte, a binder and a solvent, wherein the mass ratio of the total mass of the oxide solid electrolyte and the binder to the solvent is 1: 1-5, magnetically stirring and dissolving the raw materials to obtain electrolyte slurry;
(2) Coating the electrolyte slurry on the positive electrode plate obtained in the step one, and drying at 80-150 ℃ for 8-24 hours;
step three: electrolyte preparation and heat treatment after battery assembly
(1) The cyclic organic solvent, lithium salt and self-healing electrolyte precursor are mixed according to the proportion of 70-80: 5-15: mixing 1-5 mass ratio, stirring the solution at 25-60 ℃ for 5-12 hours until the solution is uniform, and obtaining organic electrolyte solution; the self-healing electrolyte precursor is one or a combination of a plurality of nitrile ethyl acrylate, polyethylene oxide, polyvinyl alcohol, polyvinylidene fluoride, polyethylene glycol, polymethyl methacrylate, polyethylene glycol (glycol) diacrylate, polyethylene carbonate, pentaerythritol tetraacrylate and gamma-methacryloxypropyl trimethoxysilane;
(2) Putting the aluminum foil-anode layer-electrolyte layer composite sheet obtained in the second step into an anode shell, pouring the organic electrolyte solution into the composite sheet, adding a lithium metal anode, sequentially stacking a steel sheet and an elastic sheet anode shell, and pressing to obtain a battery;
(3) The cells were then placed in an oven and treated at 80-150 ℃ for 10-24 hours to give selectively cured solid state cells.
2. A method for producing a solid-state battery by selective solidification according to claim 1, wherein: the oxide solid electrolyte is one of garnet structure, olivine structure or NASICON type.
3. A method of preparing a solid state battery by selective curing according to claim 1, wherein: in the first step (1), the positive electrode active material is one of lithium iron phosphate, lithium cobalt oxide, ternary nickel cobalt lithium manganate, spinel lithium manganate and sodium ion positive electrode material; the binder is one or more of polyvinyl alcohol, polyvinylidene fluoride, polyethylene glycol, polymethyl methacrylate and polytetrafluoroethylene; the conductive agent is one of acetylene black, 350G, carbon fiber, carbon nanotube and ketjen black; the initiator is one or more of azoisobutyronitrile, lithium hexafluorophosphate, dimethyl azodiisobutyrate and benzoyl peroxide; the solvent is one or more of acetonitrile, N-methyl pyrrolidone, ethanol, propanol, isopropanol and acetone.
4. A method of preparing a solid state battery by selective curing according to claim 1, wherein: in the second step (1), the binder is one or more of polyvinyl alcohol, polyvinylidene fluoride, polyethylene glycol, polymethyl methacrylate and polytetrafluoroethylene; the solvent is one or more of acetonitrile, N-methyl pyrrolidone, ethanol, propanol, isopropanol and acetone.
5. A method of preparing a solid state battery by selective curing according to claim 1, wherein: in the third step (1), the cyclic organic solvent is one of ternary-ring, quaternary-ring, five-membered-ring, six-membered-ring alkane, alkene, ester or benzene organic matters, and the lithium salt is one of lithium perchlorate, lithium hexafluorophosphate, lithium bistrifluoromethane sulfonyl imide, lithium hexafluoroarsenate and lithium tetrafluoroborate.
6. A solid-state battery prepared by the method of any one of claims 1 to 5.
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