Positive pole piece applied to flexible solid-state lithium battery and preparation method thereof
Technical Field
The invention relates to the field of new energy lithium batteries, relates to a positive pole piece applied to a flexible solid-state lithium battery, and particularly relates to a preparation method of the positive pole piece applied to the flexible solid-state lithium battery.
Background
In recent years, intelligent terminal equipment is continuously developed, the updating speed is faster and faster, the flexibility of devices and equipment is always a goal commonly pursued by product developers and consumers, and a small technical progress is achieved in the fields of flexible display and flexible wearable equipment in recent years, however, the flexibility of a flexible battery accompanying flexible equipment is not really achieved, and the development of flexible products is greatly limited. Lithium ion secondary batteries are widely used because they have the advantages of being rechargeable, having high energy density, having long life, etc., but flexible lithium ion secondary batteries have not yet been successfully developed. One of the main reasons is that no positive pole piece with good flexibility is prepared at present, and active substances are easy to peel off from a current collector in the bending and twisting processes of the traditional positive pole piece, so that the performance of the battery is rapidly reduced after the battery is bent and twisted, and even a safety problem is caused.
Compared with the traditional liquid lithium ion battery, the solid lithium ion battery is safer and has higher energy density because the solid electrolyte is adopted to replace the electrolyte, and simultaneously has the characteristic of flexibility because the solid electrolyte can be a polymer film with very good flexibility. At present, a solid-state flexible battery is generally prepared by sequentially plating a positive electrode material, an electrolyte material and a negative electrode material on a flexible substrate, and the prepared battery has certain flexibility, but has small capacity and high cost. In order to prepare a high-capacity and low-cost flexible solid-state battery, the preparation of the flexible pole piece is the key.
Disclosure of Invention
The purpose of the invention is: aiming at the defects, the positive pole piece applied to the flexible solid-state lithium battery and the preparation method thereof are provided.
In order to achieve the purpose, the invention adopts the technical scheme that:
a positive pole piece applied to a flexible solid lithium battery is made of the following materials, and comprises: active substance, fast ion conductor, conductive agent, film forming agent, lithium salt and solvent.
The active substance is one of lithium cobaltate, lithium iron phosphate and a ternary cathode material, and the mass percentage of the active substance is 80-95%.
The fast ion conductor is one of inorganic fast ion conductor materials such as lithium lanthanum zirconium oxygen, lithium lanthanum zirconium tantalum oxygen, lithium lanthanum titanium oxygen and aluminum-doped lithium lanthanum titanium oxygen, the particle size of the powder is 0.3-1 micron, and the mass percentage is 1-5%.
The conductive agent is one or a mixture of several of acetylene black, carbon fiber, carbon nano tube and graphene, and the mass percentage of the conductive agent is 1-5%.
The film forming agent is one or a mixture of two of polyoxyethylene, polyvinylidene fluoride and polymethyl methacrylate in a proportion, and the mass percentage is 1-10%.
The lithium salt is one of Li-TFSI, LiClO4, LiPF6, LiBO4 and LiAsF6, and the mass ratio of the lithium salt is 1-8%.
The solvent is N-methyl pyrrolidone solvent, wherein the solvent is a solid material composed of active substances, fast ion conductors, conductive agents and film forming agents, and the proportion of the solid material is 30% -50%.
A preparation method of a positive pole piece applied to a flexible solid-state lithium battery is characterized by comprising the following steps:
step one, slurry preparation: dissolving a film forming agent into a solvent, stirring for dissolving, adding a conductive agent after the film forming agent is dissolved, stirring for dispersing, adding a fast ion conductor, continuously performing dispersion stirring, adding an active substance after uniform dispersion, fully stirring, then adding the obtained slurry into the rest solvent, adjusting the mass ratio of the solid content to be 30-50% and the viscosity to be 10000, and finally adding a lithium salt for stirring;
step two, coating and baking: coating the prepared slurry, selecting a release film as a coating substrate, controlling the humidity dew point to be below-20 ℃ in a coating environment, and then baking to form a film, wherein the baking is divided into four stages of baking at 80 ℃, baking at 110 ℃, baking at 130 ℃ and baking at 80 ℃, and the baking time is 1min, 3min, 5min and 3min respectively;
step three, current collector preparation: separating the dried pole piece from the release film, and plating a current collector layer on one surface of the film material by using an evaporation method on the separated pole piece film, wherein the thickness of the current collector layer is 100 nanometers;
step four, storage: and (4) carrying out vacuum sealing storage on the prepared pole piece for standby.
The release film is one of a PET release film, a surface-treated aluminum foil and a surface-treated copper foil.
The current collector may be one of platinum, gold, and aluminum.
Compared with the prior art, the invention achieves the technical effects that: the pole piece prepared by the method can form a film in a self-supporting mode, has good flexibility, and meanwhile, the lithium salt mixed with the fast ion conductor and the film-forming agent is uniformly dispersed in the pole piece, so that a lithium ion channel can be well provided, and the pole piece has good ion conductivity without electrolyte, so that the pole piece is suitable for being applied to a solid lithium ion battery.
Drawings
Fig. 1 is a charge and discharge curve at 0.1C for making a flexible solid state lithium battery.
Detailed Description
The invention is further described with reference to the following figures and examples:
the first embodiment is as follows:
the invention relates to a positive pole piece applied to a flexible solid-state lithium battery, which is made of the following materials: active substance, fast ion conductor, conductive agent, film forming agent, lithium salt and solvent.
The active substance is lithium iron phosphate, and the mass percentage of the active substance is 80%.
The fast ion conductor is lithium lanthanum zirconium oxygen, the particle size of the powder is 0.3 micron, and the mass ratio is 5%.
The conductive agent is carbon fiber, and the mass percentage of the conductive agent is 5%.
The film forming agent is polyoxyethylene and the mass ratio is 5.
The lithium salt is LiClO4, and the mass ratio is 5.
The solvent is N-methyl pyrrolidone solvent, wherein the solvent comprises 30% of solid materials consisting of lithium iron phosphate, lithium lanthanum zirconium oxide, carbon fibers and polyethylene oxide.
A preparation method of a positive pole piece applied to a flexible solid-state lithium battery is characterized by comprising the following steps: step one, slurry preparation: dissolving polyoxyethylene into an N-methylpyrrolidone solvent, stirring for dissolving, adding carbon fiber after dissolving, stirring for dispersing, adding lithium lanthanum zirconium oxygen, continuously dispersing and stirring, adding an active substance after uniform dispersion, fully stirring, then adding the obtained slurry into the rest N-methylpyrrolidone solvent, adjusting the mass ratio of the solid content to be 30%, adjusting the viscosity to be 10000, and finally adding LiClO4 for stirring;
step two, coating and baking: coating the prepared slurry, selecting a release film as a coating substrate, controlling the humidity dew point to be below-20 ℃ in a coating environment, and then baking to form a film, wherein the baking is divided into four stages of baking at 80 ℃, baking at 110 ℃, baking at 130 ℃ and baking at 80 ℃, and the baking time is 1min, 3min, 5min and 3min respectively;
step three, current collector preparation: separating the dried pole piece from the release film, and plating a current collector layer on one surface of the film material by using an evaporation method on the separated pole piece film, wherein the thickness of the current collector layer is 100 nanometers;
step four, storage: and (4) carrying out vacuum sealing storage on the prepared pole piece for standby.
The release film is a PET release film.
The current collector is platinum.
Example two:
the invention relates to a positive pole piece applied to a flexible solid-state lithium battery, which is made of the following materials: active substance, fast ion conductor, conductive agent, film forming agent, lithium salt and solvent.
The active substance is a ternary cathode material, and the mass percentage of the active substance is 83%.
The fast ion conductor is lithium lanthanum zirconium tantalum oxygen, the particle size of the powder is 0.4 micron, and the mass ratio is 1%.
The conductive agent is a carbon nano tube, and the mass percentage of the conductive agent is 1%.
The film forming agent is polyvinylidene fluoride, and accounts for 10% by mass.
The lithium salt is LiPF6, and the mass percentage of the lithium salt is 5%.
The solvent is N-methyl pyrrolidone solvent, wherein the solvent contains solid materials of active substances, fast ion conductors, conductive agents and film forming agents, and the proportion of the solid materials is 40%.
A preparation method of a positive pole piece applied to a flexible solid-state lithium battery is characterized by comprising the following steps: step one, slurry preparation: dissolving polyvinylidene fluoride into an N-methyl pyrrolidone solvent, stirring for dissolving, adding carbon nano tubes after dissolving, stirring for dispersing, adding lithium lanthanum zirconium tantalum oxygen for continuously dispersing and stirring, adding a ternary cathode material after uniformly dispersing, fully stirring, adding the obtained slurry into the rest N-methyl pyrrolidone solvent, adjusting the mass ratio of the solid content to be 40%, adjusting the viscosity to be 10000, and finally adding LiPF6 for stirring;
step two, coating and baking: coating the prepared slurry, selecting a release film as a coating substrate, controlling the humidity dew point to be below-20 ℃ in a coating environment, and then baking to form a film, wherein the baking is divided into four stages of baking at 80 ℃, baking at 110 ℃, baking at 130 ℃ and baking at 80 ℃, and the baking time is 1min, 3min, 5min and 3min respectively;
step three, current collector preparation: separating the dried pole piece from the release film, and plating a current collector layer on one surface of the film material by using an evaporation method on the separated pole piece film, wherein the thickness of the current collector layer is 100 nanometers;
step four, storage: and (4) carrying out vacuum sealing storage on the prepared pole piece for standby.
The release film is an aluminum foil with a treated surface.
The current collector is gold.
Example three:
the invention relates to a positive pole piece applied to a flexible solid-state lithium battery, which is made of the following materials: active substance, fast ion conductor, conductive agent, film forming agent, lithium salt and solvent.
The active substance is lithium iron phosphate, and the mass ratio of the active substance is 85%.
The fast ion conductor is aluminum-doped lithium lanthanum titanium oxide, the particle size of the powder is 0.6 micron, and the mass ratio is 3%.
The conductive agent is graphene, and the mass ratio of the conductive agent is 3%.
The film forming agent is polymethyl methacrylate, and the mass percentage of the film forming agent is 1%.
The lithium salt is LiBO4, and the mass percentage of the lithium salt is 8%.
The solvent is N-methyl pyrrolidone solvent, wherein the solvent is 45% of solid material composed of active substance, fast ion conductor, conductive agent and film forming agent.
A preparation method of a positive pole piece applied to a flexible solid-state lithium battery is characterized by comprising the following steps: step one, slurry preparation: dissolving polymethyl methacrylate into an N-methyl pyrrolidone solvent, stirring for dissolving, adding graphene after the polymethyl methacrylate is dissolved, stirring and dispersing, adding aluminum-doped lithium lanthanum titanium oxide, continuously stirring for dispersing, adding lithium iron phosphate after uniform dispersion, fully stirring, adding the obtained slurry into the rest of the N-methyl pyrrolidone solvent, adjusting the mass ratio of the solid content to be 45%, adjusting the viscosity to be 10000, and finally adding a lithium salt for stirring;
step two, coating and baking: coating the prepared slurry, selecting a release film as a coating substrate, controlling the humidity dew point to be below-20 ℃ in a coating environment, and then baking to form a film, wherein the baking is divided into four stages of baking at 80 ℃, baking at 110 ℃, baking at 130 ℃ and baking at 80 ℃, and the baking time is 1min, 3min, 5min and 3min respectively;
step three, current collector preparation: separating the dried pole piece from the release film, and plating a current collector layer on one surface of the film material by using an evaporation method on the separated pole piece film, wherein the thickness of the current collector layer is 100 nanometers;
step four, storage: and (4) carrying out vacuum sealing storage on the prepared pole piece for standby.
The release film is a PET release film.
The current collector may be aluminum.
Example four:
the invention relates to a positive pole piece applied to a flexible solid-state lithium battery, which is made of the following materials: active substance, fast ion conductor, conductive agent, film forming agent, lithium salt and solvent.
The active substance is lithium cobaltate, and the mass ratio of the active substance is 90%.
The fast ion conductor is lithium lanthanum titanium oxide, the particle size of the powder is 0.8 micron, and the mass ratio is 2%.
The conductive agent is acetylene black, and the mass percentage of the conductive agent is 2%.
The film forming agent is a mixture of polyvinylidene fluoride and polymethyl methacrylate, and the mass percentage of the film forming agent is 3%.
The lithium salt is Li-TFSI and accounts for 3% of the mass.
The solvent is N-methyl pyrrolidone solvent, wherein the solvent contains 34% of solid material composed of active substance, fast ion conductor, conductive agent and film forming agent.
A preparation method of a positive pole piece applied to a flexible solid-state lithium battery is characterized by comprising the following steps: step one, slurry preparation: dissolving a mixture of polyvinylidene fluoride and polymethyl methacrylate in an N-methyl pyrrolidone solvent, stirring and dissolving, adding acetylene black after the mixture is dissolved, stirring and dispersing, adding lithium lanthanum titanium oxide, continuously dispersing and stirring, adding lithium cobaltate after the mixture is uniformly dispersed, fully stirring, adding the obtained slurry into the rest N-methyl pyrrolidone solvent, adjusting the mass ratio of the solid content to be 34 percent and the viscosity to be 10000, and finally adding a lithium salt for stirring;
step two, coating and baking: coating the prepared slurry, selecting a release film as a coating substrate, controlling the humidity dew point to be below-20 ℃ in a coating environment, and then baking to form a film, wherein the baking is divided into four stages of baking at 80 ℃, baking at 110 ℃, baking at 130 ℃ and baking at 80 ℃, and the baking time is 1min, 3min, 5min and 3min respectively;
step three, current collector preparation: separating the dried pole piece from the release film, and plating a current collector layer on one surface of the film material by using an evaporation method on the separated pole piece film, wherein the thickness of the current collector layer is 100 nanometers;
step four, storage: and (4) carrying out vacuum sealing storage on the prepared pole piece for standby.
The release film is one of a PET release film, a surface-treated aluminum foil and a surface-treated copper foil.
The current collector may be one of platinum, gold, and aluminum.
Example five:
the invention relates to a positive pole piece applied to a flexible solid-state lithium battery, which is made of the following materials: active substance, fast ion conductor, conductive agent, film forming agent, lithium salt and solvent.
The active substance is lithium iron phosphate, and the mass percentage of the active substance is 95%.
The fast ion conductor is lithium lanthanum zirconium oxygen, the particle size of the powder is 1 micron, and the mass ratio is 1%
The conductive agent is a mixture of carbon fibers and carbon nanotubes, and accounts for 1% by mass.
The film forming agent is a mixture of polyethylene oxide and polymethyl methacrylate, and the mass ratio of the film forming agent to the polymethyl methacrylate is 2%.
The lithium salt is LiAsF6, and the mass percentage of the lithium salt is 1%.
The solvent is N-methyl pyrrolidone solvent, wherein the solvent contains 50% of solid materials composed of active substances, fast ion conductors, conductive agents and film forming agents.
A preparation method of a positive pole piece applied to a flexible solid-state lithium battery is characterized by comprising the following steps: step one, slurry preparation: dissolving a mixture of polyethylene oxide and polymethyl methacrylate in an N-methylpyrrolidone solvent, stirring for dissolving, adding a mixture of carbon fibers and carbon nanotubes after the mixture is dissolved, stirring for dispersing, adding lithium lanthanum zirconium oxygen, continuing to disperse and stir, adding lithium iron phosphate after uniform dispersion, fully stirring, adding the obtained slurry into the rest of the N-methylpyrrolidone solvent, adjusting the mass ratio of the solid content to be 50%, adjusting the viscosity to 10000, and finally adding LiAsF6 for stirring;
step two, coating and baking: coating the prepared slurry, selecting a release film as a coating substrate, controlling the humidity dew point to be below-20 ℃ in a coating environment, and then baking to form a film, wherein the baking is divided into four stages of baking at 80 ℃, baking at 110 ℃, baking at 130 ℃ and baking at 80 ℃, and the baking time is 1min, 3min, 5min and 3min respectively;
step three, current collector preparation: separating the dried pole piece from the release film, and plating a current collector layer on one surface of the film material by using an evaporation method on the separated pole piece film, wherein the thickness of the current collector layer is 100 nanometers;
step four, storage: and (4) carrying out vacuum sealing storage on the prepared pole piece for standby.
The release film is a PET release film.
The current collector is platinum.
Example six:
as shown in fig. 1, the prepared flexible positive electrode sheet, solid polymer electrolyte membrane and lithium metal sheet are cut into pieces, then are stacked and assembled, then are packaged by using a flexible packaging material, the packaged battery is tested at a multiplying power of 0.1C to reach a designed capacity, and after 500 times of bending (curvature radius is 4cm), the capacity retention rate is 97%.
Compared with the prior art, the invention achieves the technical effects that: the pole piece prepared by the method can form a film in a self-supporting mode, has good flexibility, and meanwhile, the lithium salt mixed with the fast ion conductor and the film-forming agent is uniformly dispersed in the pole piece, so that a lithium ion channel can be well provided, and the pole piece has good ion conductivity without electrolyte, so that the pole piece is suitable for being applied to a solid lithium ion battery.
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.