Disclosure of Invention
The purpose of the invention is: aiming at the defects, the porous ternary composite positive plate and the preparation method and the application thereof are provided.
In order to achieve the purpose, the invention adopts the technical scheme that:
a porous ternary composite positive plate is characterized in that: the porous ternary positive plate comprises the following materials: the material comprises a ternary main material, a conductive agent, a binder, a fast ion conductor, a lithium salt and a pore-forming agent, wherein the mass parts of the materials are respectively as follows: a ternary main material: 80-90 parts of a conductive agent: 1-5 parts of binder: 2-5 parts, fast ion conductor: 2-15 parts, lithium salt: 3-10 parts of pore-forming agent: 2-5 parts.
The ternary main material comprises nickel cobalt lithium manganate (532,622,811), and can be replaced by lithium cobaltate, lithium iron phosphate, lithium-rich manganese base or lithium manganate.
The conductive agent is Surpe-P, acetylene black, KS-6, CNT or graphene.
The binder is polyvinylidene fluoride.
The fast ion conductor is lithium lanthanum zirconium oxygen, lithium lanthanum titanium oxygen or lithium lanthanum zirconium tantalum oxygen.
The lithium salt is LiTFSI, LiClO4,LiBF4,LiPF6Or LiAsF6。
The pore-forming agent is polyvinylpyrrolidone, urea, ammonium carbonate, and low-boiling point alcohol or ketone, wherein the alcohol or ketone is methanol, ethanol, or acetone.
A preparation method of a porous ternary composite positive plate comprises the following steps:
the method comprises the following steps: uniformly mixing a ternary main material, a conductive agent, a binder, a fast ion conductor and lithium salt, and dispersing in an N-methyl pyrrolidone solution;
step two: fully and uniformly stirring by using a vacuum planetary stirrer to obtain anode slurry;
step three: then adding the uniformly dispersed pore-forming agent, and fully and uniformly stirring by using a vacuum planetary stirrer to obtain composite anode slurry;
step four: coating the composite anode slurry on a 12-16 mu m conductive coating aluminum foil by using a coating machine, wherein the coating thickness is 150-plus-material 200 mu m, a grading drying process is adopted, the primary drying temperature is 80-100 ℃, the secondary drying temperature is 110-plus-material 130 ℃, the running speed is 500-plus-material 800mm/min, the rolled pole piece is dried in a vacuum baking box at the temperature of 100-plus-material 110 ℃ for 12-24h, solid electrolyte is coated on the surface of the dried pole piece, and the vacuum pumping treatment is carried out to ensure that the electrolyte fully permeates into the surface of the pole piece to form a composite pole piece;
step five: drying the compounded pole piece in a vacuum drying oven at 80-90 deg.C for 12-24h, and rolling the dried pole piece (the compaction is controlled at 3-3.4 mg/cm)3) And slitting to obtain the composite positive plate.
An application of a porous ternary composite positive plate is provided, the obtained porous ternary composite positive plate, a solid electrolyte and a lithium foil are laminated and assembled to obtain a solid lithium ion battery, the obtained solid lithium ion battery is subjected to charge-discharge cycle test under the conditions of 0.2C charge-discharge and 3.0-4.2V charge-discharge cutoff voltage, the first discharge specific capacity is 135-155mAh/g, and after 300 weeks of cycle, the capacity retention rate is 80-90 percent
Compared with the prior art, the invention achieves the technical effects that: in the invention, the solid electrolyte is poured into the pole piece, so that the compatibility of an electrode/electrolyte interface is improved, the ion transmission capacity in the pole piece is enhanced, and the integral electrochemical performance of the solid battery is improved; the porous ternary composite sheet is applied to the field of solid-state batteries, and has the possibility of large-scale batch production.
Detailed Description
The invention is further described with reference to the following figures and examples:
the first embodiment is as follows:
a porous ternary composite positive plate is characterized in that: the porous ternary positive plate comprises the following materials: the material comprises 532 ternary materials, Surpe-P materials, polyvinylidene fluoride materials, lithium lanthanum zirconium tantalum oxygen materials, LiTFSI materials and acetone, wherein the mass parts of the materials are as follows: ternary 532: 80 parts, Surpe-P: 5 parts of polyvinylidene fluoride: 5 parts of lithium lanthanum zirconium tantalum oxide: 15 parts, LiTFSI: 10 parts, acetone: 5 parts of the raw materials.
A preparation method of a porous ternary composite positive plate comprises the following steps: the method comprises the following steps: uniformly mixing ternary 532, Surpe-P, polyvinylidene fluoride, lithium lanthanum zirconium tantalum oxygen and LiTFSI, and then dispersing the mixture in an N-methylpyrrolidone solution;
step two: fully and uniformly stirring by using a vacuum planetary stirrer to obtain anode slurry;
step three: then adding uniformly dispersed acetone, and fully and uniformly stirring by using a vacuum planetary stirrer to obtain composite anode slurry;
step four: coating the composite positive electrode slurry on a 12-micron conductive coating aluminum foil by using a coating machine, wherein the coating thickness is 150 microns, a graded drying process is adopted, the primary drying temperature is 80 ℃, the secondary drying temperature is 110 ℃, the running speed is 800mm/min, the wound pole piece is dried in a vacuum baking oven at 100 ℃ for 12 hours, solid electrolyte is coated on the surface of the dried pole piece, and the vacuum pumping treatment is carried out to ensure that the electrolyte fully permeates into the surface of the pole piece to form a composite pole piece;
step five: drying the compounded pole piece in a vacuum drying oven at 90 ℃ for 24 hours, and rolling the dried pole piecePressing (compacting is controlled at 3-3.4 mg/cm)3) And slitting to obtain the composite positive plate.
An application of a porous ternary composite positive plate is disclosed, the obtained porous ternary composite positive plate, a solid electrolyte and a lithium foil are laminated and assembled to obtain a solid lithium ion battery, the obtained solid lithium ion battery is subjected to charge-discharge cycle test under the conditions of 0.2C charge-discharge and 3.0-4.2V charge-discharge cutoff voltage, the first discharge specific capacity is 135mAh/g, and after 300 cycles, the capacity retention rate is 80%
Compared with the prior art, the invention achieves the technical effects that: in the invention, the solid electrolyte is poured into the pole piece, so that the compatibility of an electrode/electrolyte interface is improved, the ion transmission capacity in the pole piece is enhanced, and the integral electrochemical performance of the solid battery is improved; the porous ternary composite sheet is applied to the field of solid-state batteries, and has the possibility of large-scale batch production.
Example two:
a porous ternary composite positive plate is characterized in that: the porous ternary positive plate comprises the following materials: ternary 532, acetylene black, polyvinylidene fluoride, lithium lanthanum titanium oxide, LiClO4And polyvinylpyrrolidone, the mass parts of each material are respectively as follows: ternary 532: 85 parts, acetylene black: 2 parts of polyvinylidene fluoride: 3 parts of lithium lanthanum titanium oxide: 7 parts of LiClO4: 4 parts, polyvinylpyrrolidone: 4 parts.
A preparation method of a porous ternary composite positive plate comprises the following steps: the method comprises the following steps: mixing ternary 532, acetylene black, polyvinylidene fluoride, lithium lanthanum titanium oxide and LiClO4Uniformly mixing and dispersing in an N-methyl pyrrolidone solution;
step two: fully and uniformly stirring by using a vacuum planetary stirrer to obtain anode slurry;
step three: then uniformly dispersed polyvinylpyrrolidone is added, and the mixture is fully and uniformly stirred by a vacuum planetary stirrer to obtain composite anode slurry;
step four: coating the composite positive electrode slurry on a 14-micron conductive coating aluminum foil by using a coating machine, wherein the coating thickness is 170 microns, a graded drying process is adopted, the primary drying temperature is 90 ℃, the secondary drying temperature is 120 ℃, the running speed is 800mm/min, the wound pole piece is dried in a vacuum baking oven at 105 ℃ for 18 hours, solid electrolyte is coated on the surface of the dried pole piece, and the vacuum treatment is carried out to ensure that the electrolyte fully permeates into the surface of the pole piece to form a composite pole piece;
step five: drying the compounded pole piece in a vacuum drying oven at 90 ℃ for 24 hours, and rolling the dried pole piece (the compaction is controlled to be 3-3.4 mg/cm)3) And slitting to obtain the composite positive plate.
An application of a porous ternary composite positive plate is disclosed, the obtained porous ternary composite positive plate, a solid electrolyte and a lithium foil are laminated and assembled to obtain a solid lithium ion battery, the obtained solid lithium ion battery is subjected to charge-discharge cycle test under the conditions of 0.2C charge-discharge and 3.0-4.2V charge-discharge cutoff voltage, the first discharge specific capacity is 140mAh/g, and after 300 cycles, the capacity retention rate is 85%
Compared with the prior art, the invention achieves the technical effects that: in the invention, the solid electrolyte is poured into the pole piece, so that the compatibility of an electrode/electrolyte interface is improved, the ion transmission capacity in the pole piece is enhanced, and the integral electrochemical performance of the solid battery is improved; the porous ternary composite sheet is applied to the field of solid-state batteries, and has the possibility of large-scale batch production.
Example three:
a porous ternary composite positive plate is characterized in that: the porous ternary positive plate comprises the following materials: ternary 532, graphene, polyvinylidene fluoride, lithium lanthanum zirconium oxide and LiPF6And ammonium carbonate, wherein the mass parts of the materials are respectively as follows: ternary 532: 90 parts, graphene: 1 part of polyvinylidene fluoride: 2 parts of lithium lanthanum zirconium oxide: 2 parts of LiPF6: 3 parts, ammonium carbonate: and 2 parts.
A preparation method of a porous ternary composite positive plate comprises the following steps: the method comprises the following steps: mixing ternary 532, graphene, polyvinylidene fluoride, lithium lanthanum zirconium oxide and LiPF6Uniformly mixing and dispersing in an N-methyl pyrrolidone solution;
step two: fully and uniformly stirring by using a vacuum planetary stirrer to obtain anode slurry;
step three: then adding uniformly dispersed ammonium carbonate, and fully and uniformly stirring by using a vacuum planetary stirrer to obtain composite anode slurry;
step four: coating the composite positive electrode slurry on a 16-micron conductive coating aluminum foil by using a coating machine, wherein the coating thickness is 200 microns, a graded drying process is adopted, the primary drying temperature is 100 ℃, the secondary drying temperature is 130 ℃, the running speed is 800mm/min, the wound pole piece is dried in a vacuum baking oven at 110 ℃ for 24 hours, solid electrolyte is coated on the surface of the dried pole piece, and the vacuum pumping treatment is carried out to ensure that the electrolyte fully permeates into the surface of the pole piece to form a composite pole piece;
step five: drying the compounded pole piece in a vacuum drying oven at 90 ℃ for 24 hours, and rolling the dried pole piece (the compaction is controlled to be 3-3.4 mg/cm)3) And slitting to obtain the composite positive plate.
An application of a porous ternary composite positive plate is disclosed, the obtained porous ternary composite positive plate, a solid electrolyte and a lithium foil are laminated and assembled to obtain a solid lithium ion battery, the obtained solid lithium ion battery is subjected to charge-discharge cycle test under the conditions of 0.2C charge-discharge and 3.0-4.2V charge-discharge cutoff voltage, the first discharge specific capacity is 155mAh/g, and after 300 cycles, the capacity retention rate is 90 percent
Compared with the prior art, the invention achieves the technical effects that: in the invention, the solid electrolyte is poured into the pole piece, so that the compatibility of an electrode/electrolyte interface is improved, the ion transmission capacity in the pole piece is enhanced, and the integral electrochemical performance of the solid battery is improved; the porous ternary composite sheet is applied to the field of solid-state batteries, and has the possibility of large-scale batch production.
The above embodiments are merely illustrative of the technical ideas and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.