CN115842217A - Ion-electron-coated mixed conductor diaphragm and preparation method and application thereof - Google Patents
Ion-electron-coated mixed conductor diaphragm and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a coated ion-electron mixed conductor diaphragm and a preparation method and application thereof, wherein the coated ion-electron mixed conductor diaphragm comprises the following components: the lithium ion battery comprises a base film, a solid electrolyte coating which is coated on one side or two sides of the base film and conducts lithium ions, and a mixed coating which is coated on the outer surface of the solid electrolyte coating; the solid electrolyte coating includes: the solid electrolyte, a first dispersing agent, a first binder, a first wetting agent and a first auxiliary agent; the hybrid coating comprises: colloidal particles and a conductive agent; the colloidal particles comprise: one or more of polyvinylidene fluoride PVDF, polyvinylidene fluoride-hexafluoropropylene copolymer PVDF-HFP and polymethyl methacrylate PMMA; the conductive agent includes: one or more of carbon black, carbon nanotube, acetylene black, ketjen black, super P; the ionic and electronic mixed conductor coated diaphragm is applied to a lithium battery, so that the long cycle performance and the safety of the lithium battery can be improved.
Description
Technical Field
The invention relates to the technical field of lithium battery materials, in particular to a diaphragm coated with an ion-electron mixed conductor and a preparation method and application thereof.
Background
Lithium ion batteries are now widely used in various aspects of human daily life, such as electric vehicles, 3C digital, mass storage, small tools, medical devices, aerospace, and the like. However, the problem of thermal safety of lithium ion batteries still is one of the pain problems encountered in human consumption. The carbonate electrolyte used in the traditional commercial lithium ion battery has the problems of flammability, explosiveness and the like, and is very easy to ignite and explode under the use conditions of high temperature, collision, extrusion and the like. In order to improve this problem, researchers have developed solid electrolyte coated separators that utilize the formation reaction of the solid electrolyte during cycling to improve the thermal safety of the battery. However, the small-sized high specific energy battery applied to the 3C digital and other markets is usually coated with a glue layer on the outer side of the ceramic coating, and the safety problems such as internal short circuit and the like caused by thermal shrinkage deformation of the diaphragm are better solved through a hot pressing formation process. However, such a structure design may cause the formation process of the solid electrolyte coating to be unable to be smoothly performed due to the isolation of the glue layer of the non-conducting molecules.
In order to solve the technical problem, a conductive agent is urgently needed to be added into a glue layer on the basis of the original design, and a diaphragm coated with an ion-electron mixed conductor is designed to promote the formation reaction of a solid electrolyte coating, so that the technical advantage that the solid electrolyte coating improves the thermal safety of the battery is fully exerted, the ion conduction impedance in the lithium battery is reduced, the actual specific capacity of the battery under the low-temperature condition is improved, and the long cycle performance and the safety of the battery are greatly improved.
Disclosure of Invention
The invention embodiment provides a coated ion-electron mixed conductor diaphragm and a preparation method and application thereof, wherein a solid electrolyte coating is coated on the surface of at least one side of a base film, and a mixed coating with colloidal particles and a conductive agent is coated on the surface of at least one side of the solid electrolyte coating to obtain the coated ion-electron mixed conductor diaphragm; in addition, the ionic electron coated mixed conductor diaphragm prepared by the invention can also utilize a hot pressing formation process to bond colloidal particles in a glue layer and a positive electrode and a negative electrode together to form an integrated structure, so that the contact with the electrode plates is improved, the resistance is reduced, the thermal safety is improved, the internal impedance of the lithium battery is reduced, and the capacity retention rate in the long-cycle process is improved.
In a first aspect, embodiments of the present invention provide an ion-electron coated mixed conductor membrane, comprising: the lithium ion battery comprises a base film, a solid electrolyte coating and a mixed coating, wherein the solid electrolyte coating is coated on one side or two sides of the base film and conducts lithium ions;
the solid electrolyte coating includes: the solid electrolyte, a first dispersing agent, a first binder, a first wetting agent and a first auxiliary agent; the solid electrolyte includes: li 1+x Al x Ti 2-x (PO 4 ) 3 、Li 1+y Al y Ge 2-y (PO 4 ) 3 、Li 3z La 2/3-z TiO 3 、Li 7-q La 3 Zr 2-q Ta q O 12 X is more than or equal to 0 and less than or equal to 0.5, y is more than or equal to 0 and less than or equal to 0.5, z is more than 0 and less than 2/3, q is more than 0 and less than 2; the particle size of the solid electrolyte is 200nm-1 μm;
the hybrid coating includes: colloidal particles and a conductive agent; the colloidal particles comprise: one or more of polyvinylidene fluoride PVDF, polyvinylidene fluoride-hexafluoropropylene copolymer PVDF-HFP and polymethyl methacrylate PMMA; the conductive agent includes: one or more of carbon black, carbon nanotube, acetylene black, ketjen black, super P.
Preferably, the base film includes: one or more of polyolefin membrane, non-woven fabric membrane, fiber membrane and aramid fiber membrane; the thickness of the basement membrane is 5-15 μm;
the thickness of the solid electrolyte coating is 1-3 μm;
the thickness of the mixed coating is 0.5-1.5 μm.
Preferably, the first dispersant comprises: one or more of polyvinylpyrrolidone, sodium polyacrylate, polyacrylic acid ammonium salt copolymer, polyethylene glycol, polyvinyl alcohol, sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, polymethacrylate, triethylhexyl phosphoric acid, sodium tripolyphosphate, sodium hexametaphosphate or sodium pyrophosphate;
the first binder includes: one or more of polymethyl styrene-butadiene rubber, styrene-acrylic emulsion, polyurethane, polyvinylidene fluoride, carboxymethyl cellulose, polyvinyl alcohol, polytetrafluoroethylene, polyvinyl acetate, methacrylic acid, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, ethacrylic acid and ethyl acrylate;
the first wetting agent comprises: one or more of sodium hexametaphosphate, polyvinylpyrrolidone, polydimethylsiloxane, polyether siloxane, polyoxyethylene ether, polyoxyethylene alkylamine, polyoxyethylene alkylphenol ether, polyoxyethylene fatty alcohol ether, polyoxyethylene octylphenol ether, sodium dodecyl benzene sulfonate, sodium dodecyl sulfate and sodium lauryl sulfate;
the first auxiliary agent comprises: one or more of polyglycol ether, emulsified silicone oil, sodium carboxymethylcellulose, sodium alginate, polydimethylsiloxane, polyacrylamide, polyoxypropylene glycerol ether, polyoxyethylene amide or sodium perfluorooctanoate;
the mass ratio of the solid electrolyte, the first dispersing agent, the first binder, the first wetting agent and the first auxiliary agent is 100: [0.1-2.5]: [2-20]: [3-15]: [0.25-2.5].
Preferably, the hybrid coating further comprises: the second dispersing agent, the second binder, the second wetting agent and the second auxiliary agent;
the second dispersant comprises: one or more of polyvinylpyrrolidone, sodium polyacrylate, polyacrylic acid ammonium salt copolymer, polyethylene glycol, polyvinyl alcohol, sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, polymethacrylate, triethylhexyl phosphoric acid, sodium tripolyphosphate, sodium hexametaphosphate or sodium pyrophosphate;
the second binder includes: one or more of polymethyl styrene-butadiene rubber, styrene-acrylic emulsion, polyurethane, polyvinylidene fluoride, carboxymethyl cellulose, polyvinyl alcohol, polytetrafluoroethylene, polyvinyl acetate, methacrylic acid, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, ethacrylic acid and ethyl acrylate;
the second wetting agent comprises: one or more of sodium hexametaphosphate, polyvinylpyrrolidone, polydimethylsiloxane, polyether siloxane, polyoxyethylene ether, polyoxyethylene alkylamine, polyoxyethylene alkylphenol ether, polyoxyethylene fatty alcohol ether, octylphenol polyoxyethylene ether, sodium dodecyl benzene sulfonate, sodium dodecyl sulfate and sodium lauryl sulfate;
the second auxiliary agent comprises: one or more of polyglycol ether, emulsified silicone oil, sodium carboxymethyl cellulose, sodium alginate, polydimethylsiloxane, polyacrylamide, polyoxypropylene glycerol ether, polyoxyethylene amide or sodium perfluorocaprylate;
the mass ratio of the colloidal particles, the conductive agent, the second dispersing agent, the second bonding agent, the second wetting agent and the second auxiliary agent is [60-95]: [5-40]: [3-15]: [15-60]: [0.3-1]: [6-65].
In a second aspect, an embodiment of the present invention provides a method for preparing the ion-electron mixed conductor coated membrane described in the first aspect, where the method for preparing the ion-electron mixed conductor coated membrane includes:
step S1, preparing solid electrolyte coating slurry, which specifically comprises the following steps: adding a first dispersing agent into a first solvent, uniformly dispersing at a high speed, then adding a solid electrolyte, continuously uniformly dispersing, sanding to obtain slurry of the solid electrolyte with the particle size of 200nm-1 mu m, adding a first wetting agent, a first binder and a first auxiliary agent into the slurry, and uniformly dispersing at a high speed to obtain solid electrolyte coating slurry;
step S2, coating a solid electrolyte coating on the surface of at least one side of the base film: uniformly coating the solid electrolyte coating slurry on the surface of at least one side of the base film by adopting a micro gravure roller coating method, placing the base film in a drying oven for primary drying, forming a solid electrolyte coating on one side or two sides of the base film after drying, and rolling for later use;
step S3, preparing mixed coating slurry, which specifically comprises the following steps: dispersing and uniformly mixing the colloidal particles, the conductive agent, the second dispersing agent, the second adhesive, the second wetting agent, the second auxiliary agent and the second solvent at a high speed according to the mass ratio to obtain mixed coating slurry;
and S4, uniformly coating the mixed coating slurry on the surface of at least one side of the outer side of the solid electrolyte coating in the step S2 by adopting a micro gravure roll coating method or a spraying method, placing the solid electrolyte coating in a baking oven for secondary baking, and drying to obtain the ion-electron coated mixed conductor diaphragm.
Preferably, the solid electrolyte comprises: li 1+x Al x Ti 2-x (PO 4 ) 3 、Li 1+y Al y Ge 2-y (PO 4 ) 3 、Li 3z La 2/3- z TiO 3 、Li 7-q La 3 Zr 2-q Ta q O 12 Wherein x is more than or equal to 0 and less than or equal to 0.5, y is more than or equal to 0 and less than or equal to 0.5, z is more than 0 and less than 2/3, and q is more than 0 and less than 2;
the first dispersant includes: one or more of polyvinylpyrrolidone, sodium polyacrylate, polyethylene glycol, sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, polymethacrylate, sodium hexametaphosphate, polyacrylic ammonium salt copolymer and polyvinyl alcohol;
the first binder includes: one or more of polymethyl styrene-butadiene rubber, styrene-acrylic emulsion, polyurethane, polyvinylidene fluoride, carboxymethyl cellulose, polyvinyl alcohol, polytetrafluoroethylene, polyvinyl acetate, methacrylic acid, ethacrylic acid, polyvinylidene fluoride-hexafluoropropylene copolymer, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate and ethyl acrylate;
the first wetting agent comprises: one or more of polydimethylsiloxane, polyether modified siloxane, polyoxyethylene ether, sodium hexametaphosphate, polyoxyethylene alkylamine, polyoxyethylene alkylphenol ether, polyoxyethylene fatty alcohol ether, polyvinylpyrrolidone, octylphenol polyoxyethylene ether, polyether siloxane, sodium dodecyl benzene sulfonate, sodium dodecyl sulfate and sodium lauryl sulfate;
the first auxiliary agent comprises: one or more of polyglycol ether, sodium carboxymethylcellulose, sodium alginate, polyacrylamide, polyoxyethylene amide, titanate coupling agent and sodium perfluorooctanoate;
the mass ratio of the solid electrolyte, the first dispersing agent, the first binder, the first wetting agent and the first auxiliary agent is 100: [0.1-2.5]: [2-20]: [3-15]: [0.25-2.5];
the first solvent includes: one or more of deionized water, N-methyl pyrrolidone, alcohol, isopropanol and cyclohexane;
the solid content in the solid electrolyte coating slurry is 20-70%.
Preferably, the colloidal particles comprise: one or more of polyvinylidene fluoride PVDF, polyvinylidene fluoride-hexafluoropropylene copolymer PVDF-HFP and polymethyl methacrylate PMMA;
the conductive agent includes: one or more of carbon black, carbon nanotube, acetylene black, ketjen black, and Super P
The second dispersant comprises: one or more of polyvinylpyrrolidone, sodium polyacrylate, polyacrylic acid ammonium salt copolymer, polyethylene glycol, polyvinyl alcohol, sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, polymethacrylate, triethylhexyl phosphoric acid, sodium tripolyphosphate, sodium hexametaphosphate or sodium pyrophosphate;
the second binder includes: one or more of polymethyl styrene-butadiene rubber, styrene-acrylic emulsion, polyurethane, polyvinylidene fluoride, carboxymethyl cellulose, polyvinyl alcohol, polytetrafluoroethylene, polyvinyl acetate, methacrylic acid, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, ethacrylic acid and ethyl acrylate;
the second wetting agent comprises: one or more of sodium hexametaphosphate, polyvinylpyrrolidone, polydimethylsiloxane, polyether siloxane, polyoxyethylene ether, polyoxyethylene alkylamine, polyoxyethylene alkylphenol ether, polyoxyethylene fatty alcohol ether, polyoxyethylene octylphenol ether, sodium dodecyl benzene sulfonate, sodium dodecyl sulfate and sodium lauryl sulfate;
the second auxiliary agent comprises: one or more of polyglycol ether, emulsified silicone oil, sodium carboxymethylcellulose, sodium alginate, polydimethylsiloxane, polyacrylamide, polyoxypropylene glycerol ether, polyoxyethylene amide or sodium perfluorooctanoate;
the mass ratio of the colloidal particles, the conductive agent, the second dispersing agent, the second bonding agent, the second wetting agent and the second auxiliary agent is [60-95]: [5-40]: [3-15]: [15-60]: [0.3-1]: [6-65];
the second solvent includes: one or more of deionized water, N-methyl pyrrolidone, alcohol, isopropanol and cyclohexane;
the solid content in the mixed coating slurry is 10-65%.
Preferably, the base film includes: one or more of polyolefin membrane, non-woven fabric membrane, fiber membrane and aramid fiber membrane; the thickness of the basement membrane is 5-15 μm; the thickness of the solid electrolyte coating is 1-3 μm; the thickness of the mixed coating is 0.5-1.5 μm;
the conditions of the first baking and the second baking are as follows: blowing and drying at 70-100 deg.c for 0.5-4 hr.
In a third aspect, embodiments of the present invention provide a lithium battery comprising the separator coated with an ionic-electronic mixed conductor according to the first aspect.
Preferably, the lithium battery includes: any one of a liquid lithium ion battery, a semi-solid lithium battery, an all-solid lithium battery, a lithium sulfur battery, or a lithium air battery.
The invention embodiment provides a coated ion-electron mixed conductor diaphragm and a preparation method and application thereof, wherein a solid electrolyte coating is coated on the surface of at least one side of a base film, and a mixed coating with colloidal particles and a conductive agent is coated on the surface of at least one side of the solid electrolyte coating to obtain the coated ion-electron mixed conductor diaphragm; in addition, the ionic electron coated mixed conductor diaphragm prepared by the invention can also utilize a hot pressing formation process to bond colloidal particles in a glue layer and a positive electrode and a negative electrode together to form an integrated structure, so that the contact with the electrode plates is improved, the resistance is reduced, the thermal safety is improved, the internal impedance of the lithium battery is reduced, and the capacity retention rate in the long-cycle process is improved.
The preparation method of the ion-electron coated mixed conductor diaphragm provided by the embodiment of the invention is simple and mature in process, and can be compatible with the existing production process of lithium batteries.
Drawings
The technical solutions of the embodiments of the present invention are further described in detail with reference to the accompanying drawings and embodiments.
FIG. 1 is a flow chart of a method for preparing a coated ionic-electronic mixed conductor membrane provided by an embodiment of the invention;
FIG. 2 is a schematic cross-sectional view of a coated ion-electron mixed conductor separator according to an embodiment of the present invention;
fig. 3 is a schematic cross-sectional view of another coated ion-electron mixed conductor separator according to an embodiment of the present invention.
Fig. 4 is a comparative picture of the morphology of the assembled battery of example 1 and comparative example 1 according to the present invention, which is disassembled.
Detailed Description
The invention is described in further detail below with reference to the figures and specific examples, but it should be understood that these examples are for the purpose of illustration only and are not to be construed as limiting the invention in any way, i.e., not as limiting the scope of the invention.
The embodiment of the invention provides an ion-electron-coated mixed conductor diaphragm, which comprises the following components in parts by weight: the lithium ion battery comprises a base film, a solid electrolyte coating which is coated on one side or two sides of the base film and conducts lithium ions, and a mixed coating which is coated on the outer surface of the solid electrolyte coating; the thickness of the solid electrolyte coating is 1-3 μm; the thickness of the mixed coating is 0.5-1.5 μm.
The base film includes: one or more of polyolefin membrane, non-woven fabric membrane, fiber membrane and aramid fiber membrane; the thickness of the base film is 5 μm to 15 μm.
The solid electrolyte coating includes: the solid electrolyte, a first dispersing agent, a first binder, a first wetting agent and a first auxiliary agent; the mass ratio of the solid electrolyte, the first dispersing agent, the first binder, the first wetting agent and the first auxiliary agent is 100: [0.1-2.5]: [2-20]: [3-15]: [0.25-2.5].
Wherein the solid electrolyte comprises: li 1+x Al x Ti 2-x (PO 4 ) 3 、Li 1+y Al y Ge 2-y (PO 4 ) 3 、Li 3z La 2/3-z TiO 3 、Li 7-q La 3 Zr 2-q Ta q O 12 Wherein x is more than or equal to 0 and less than or equal to 0.5, y is more than or equal to 0 and less than or equal to 0.5, z is more than 0 and less than 2/3, and q is more than 0 and less than 2; the particle size of the solid electrolyte is 200nm-1 μm;
the first dispersant comprises: one or more of polyvinylpyrrolidone, sodium polyacrylate, polyacrylic acid ammonium salt copolymer, polyethylene glycol, polyvinyl alcohol, sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, polymethacrylate, triethylhexyl phosphoric acid, sodium tripolyphosphate, sodium hexametaphosphate or sodium pyrophosphate;
the first binder includes: one or more of polymethyl styrene-butadiene rubber, styrene-acrylic emulsion, polyurethane, polyvinylidene fluoride, carboxymethyl cellulose, polyvinyl alcohol, polytetrafluoroethylene, polyvinyl acetate, methacrylic acid, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, ethacrylic acid and ethyl acrylate;
the first wetting agent comprises: one or more of sodium hexametaphosphate, polyvinylpyrrolidone, polydimethylsiloxane, polyether siloxane, polyoxyethylene ether, polyoxyethylene alkylamine, polyoxyethylene alkylphenol ether, polyoxyethylene fatty alcohol ether, polyoxyethylene octylphenol ether, sodium dodecyl benzene sulfonate, sodium dodecyl sulfate and sodium lauryl sulfate;
the first auxiliary agent comprises: one or more of polyglycol ether, emulsified silicone oil, sodium carboxymethyl cellulose, sodium alginate, polydimethylsiloxane, polyacrylamide, polyoxypropylene glycerol ether, polyoxyethylene amide or sodium perfluorocaprylate.
The hybrid coating comprises: colloidal particles and a conductive agent; specifically, the colloidal particles include: one or more of polyvinylidene fluoride PVDF, polyvinylidene fluoride-hexafluoropropylene copolymer PVDF-HFP and polymethyl methacrylate PMMA; the conductive agent includes: one or more of carbon black, carbon nanotube, acetylene black, ketjen black, super P.
The hybrid coating further comprises: the second dispersing agent, the second binder, the second wetting agent and the second auxiliary agent; the mass ratio of the colloidal particles, the conductive agent, the second dispersing agent, the second bonding agent, the second wetting agent and the second auxiliary agent is [60-95]: [5-40]: [3-15]: [15-60]: [0.3-1]: [6-65].
The second dispersant comprises: one or more of polyvinylpyrrolidone, sodium polyacrylate, polyacrylic acid ammonium salt copolymer, polyethylene glycol, polyvinyl alcohol, sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, polymethacrylate, triethylhexyl phosphoric acid, sodium tripolyphosphate, sodium hexametaphosphate or sodium pyrophosphate;
the second binder includes: one or more of polymethyl styrene-butadiene rubber, styrene-acrylic emulsion, polyurethane, polyvinylidene fluoride, carboxymethyl cellulose, polyvinyl alcohol, polytetrafluoroethylene, polyvinyl acetate, methacrylic acid, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, ethacrylic acid and ethyl acrylate;
the second wetting agent includes: one or more of sodium hexametaphosphate, polyvinylpyrrolidone, polydimethylsiloxane, polyether siloxane, polyoxyethylene ether, polyoxyethylene alkylamine, polyoxyethylene alkylphenol ether, polyoxyethylene fatty alcohol ether, polyoxyethylene octylphenol ether, sodium dodecyl benzene sulfonate, sodium dodecyl sulfate and sodium lauryl sulfate;
the second auxiliary agent comprises: one or more of polyglycol ether, emulsified silicone oil, sodium carboxymethyl cellulose, sodium alginate, polydimethylsiloxane, polyacrylamide, polyoxypropylene glycerol ether, polyoxyethylene amide or sodium perfluorocaprylate.
As shown in fig. 1, it can be seen that two sides of the base film are respectively coated with the solid electrolyte coating, and the surface of the solid electrolyte coating is coated with the mixed coating.
The schematic cross-sectional structure of the coated ion-electron mixed conductor separator provided by the embodiment of the invention is shown in fig. 2, and it can be seen that a single side of the base film is coated with the solid electrolyte coating, and the mixed coating is coated on the surface of the solid electrolyte coating.
The embodiment of the invention provides a preparation method of the ion-electron coated mixed conductor diaphragm, and as shown in fig. 3, the preparation method comprises the following steps:
step S1, preparing solid electrolyte coating slurry, which specifically comprises the following steps: adding a first dispersing agent into a first solvent, uniformly dispersing at a high speed, then adding a solid electrolyte, continuously uniformly dispersing, sanding to obtain slurry of the solid electrolyte with the particle size of 200nm-1 mu m, adding a first wetting agent, a first binder and a first auxiliary agent into the slurry, and uniformly dispersing at a high speed to obtain solid electrolyte coating slurry;
wherein the solid electrolyte comprises: li 1+x Al x Ti 2-x (PO 4 ) 3 、Li 1+y Al y Ge 2-y (PO 4 ) 3 、Li 3z La 2/3-z TiO 3 、Li 7-q La 3 Zr 2-q Ta q O 12 Wherein x is more than or equal to 0 and less than or equal to 0.5, y is more than or equal to 0 and less than or equal to 0.5, z is more than 0 and less than 2/3, and q is more than 0 and less than 2;
the first dispersant comprises: one or more of polyvinylpyrrolidone, sodium polyacrylate, polyacrylic acid ammonium salt copolymer, polyethylene glycol, polyvinyl alcohol, sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, polymethacrylate, triethylhexyl phosphoric acid, sodium tripolyphosphate, sodium hexametaphosphate or sodium pyrophosphate;
the first adhesive includes: one or more of polymethyl styrene-butadiene rubber, styrene-acrylic emulsion, polyurethane, polyvinylidene fluoride, carboxymethyl cellulose, polyvinyl alcohol, polytetrafluoroethylene, polyvinyl acetate, methacrylic acid, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, ethacrylic acid and ethyl acrylate;
the first wetting agent comprises: one or more of sodium hexametaphosphate, polyvinylpyrrolidone, polydimethylsiloxane, polyether siloxane, polyoxyethylene ether, polyoxyethylene alkylamine, polyoxyethylene alkylphenol ether, polyoxyethylene fatty alcohol ether, polyoxyethylene octylphenol ether, sodium dodecyl benzene sulfonate, sodium dodecyl sulfate and sodium lauryl sulfate;
the first auxiliary agent comprises: one or more of polyglycol ether, emulsified silicone oil, sodium carboxymethyl cellulose, sodium alginate, polydimethylsiloxane, polyacrylamide, polyoxypropylene glycerol ether, polyoxyethylene amide or sodium perfluorocaprylate;
the mass ratio of the solid electrolyte, the first dispersing agent, the first binder, the first wetting agent and the first auxiliary agent is 100: [0.1-2.5]: [2-20]: [3-15]: [0.25-2.5];
the first solvent includes: one or more of deionized water, N-methyl pyrrolidone, alcohol, isopropanol and cyclohexane;
the solid content in the solid electrolyte coating slurry is 20-70%.
Step S2, coating a solid electrolyte coating on the surface of at least one side of the base film: uniformly coating the solid electrolyte coating slurry on the surface of at least one side of the base film by adopting a micro gravure roller coating method, placing the base film in a drying oven for primary drying, forming a solid electrolyte coating on one side or two sides of the base film after drying, and rolling for later use;
wherein, the base film includes: one or more of polyolefin membrane, non-woven fabric membrane, fiber membrane and aramid fiber membrane; the thickness of the basement membrane is 5-15 μm; the thickness of the solid electrolyte coating is 1-3 μm;
the first baking conditions were: blowing and drying at 70-100 deg.c for 0.5-4 hr.
Step S3, preparing mixed coating slurry, which specifically comprises the following steps: dispersing and uniformly mixing the colloidal particles, the conductive agent, the second dispersing agent, the second adhesive, the second wetting agent, the second auxiliary agent and the second solvent at a high speed according to the mass ratio to obtain mixed coating slurry;
wherein, the micelle includes: one or more of polyvinylidene fluoride PVDF, polyvinylidene fluoride-hexafluoropropylene copolymer PVDF-HFP and polymethyl methacrylate PMMA;
the conductive agent includes: one or more of carbon black, carbon nanotube, acetylene black, ketjen black, and Super P
The second dispersant comprises: one or more of polyvinylpyrrolidone, sodium polyacrylate, polyacrylic acid ammonium salt copolymer, polyethylene glycol, polyvinyl alcohol, sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, polymethacrylate, triethylhexyl phosphoric acid, sodium tripolyphosphate, sodium hexametaphosphate or sodium pyrophosphate;
the second adhesive includes: one or more of polymethyl styrene-butadiene rubber, styrene-acrylic emulsion, polyurethane, polyvinylidene fluoride, carboxymethyl cellulose, polyvinyl alcohol, polytetrafluoroethylene, polyvinyl acetate, methacrylic acid, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, ethacrylic acid and ethyl acrylate;
the second wetting agent includes: one or more of sodium hexametaphosphate, polyvinylpyrrolidone, polydimethylsiloxane, polyether siloxane, polyoxyethylene ether, polyoxyethylene alkylamine, polyoxyethylene alkylphenol ether, polyoxyethylene fatty alcohol ether, polyoxyethylene octylphenol ether, sodium dodecyl benzene sulfonate, sodium dodecyl sulfate and sodium lauryl sulfate;
the second auxiliary agent comprises: one or more of polyglycol ether, emulsified silicone oil, sodium carboxymethylcellulose, sodium alginate, polydimethylsiloxane, polyacrylamide, polyoxypropylene glycerol ether, polyoxyethylene amide or sodium perfluorooctanoate;
the mass ratio of the colloidal particles, the conductive agent, the second dispersing agent, the second bonding agent, the second wetting agent and the second auxiliary agent is [60-95]: [5-40]: [3-15]: [15-60]: [0.3-1]: [6-65];
the second solvent includes: one or more of deionized water, N-methyl pyrrolidone, alcohol, isopropanol and cyclohexane;
the solid content in the mixed coating slurry is 10-65%.
Step S4, uniformly coating the mixed coating slurry on the surface of at least one side of the outer side of the solid electrolyte coating in the step S2 by adopting a micro gravure roller coating method or a spraying method, placing the solid electrolyte coating in a drying oven for secondary baking, and drying to obtain the ion-electron coated mixed conductor diaphragm;
wherein the thickness of the mixed coating is 0.5-1.5 μm; the conditions of the second baking are as follows: blowing and drying at 70-100 deg.c.
The ion-electron-coated mixed conductor diaphragm prepared by the embodiment of the invention can be applied to a lithium battery, and the lithium battery comprises: any one of a liquid lithium ion battery, a semi-solid lithium battery, an all-solid lithium battery, a lithium sulfur battery, or a lithium air battery.
In order to better understand the technical scheme provided by the invention, the following specific examples respectively illustrate the preparation method and the characteristics of the coated ion-electron mixed conductor diaphragm.
Example 1
The embodiment provides a preparation process and a performance test of a coated ion-electron mixed conductor diaphragm, which comprises the following specific steps:
step S1, mixing the following components in a mass ratio of 100:1.2:10:15:0.25 weighing of solid electrolyte Li 1.5 Al 0.5 Ti 1.5 (PO 4 ) 3 First, aDispersing agent sodium polyacrylate, first binder methacrylic acid, first wetting agent polyoxyethylene ether and first auxiliary agent carboxymethylcellulose sodium, adding the first dispersing agent sodium polyacrylate into deionized water, uniformly dispersing at high speed, and then adding solid electrolyte Li 1.5 Al 0.5 Ti 1.5 (PO 4 ) 3 And continuously dispersing uniformly, sanding to obtain slurry of the solid electrolyte with the particle size of 300nm, adding a first binder methacrylic acid, a first wetting agent polyoxyethylene ether and a first auxiliary agent sodium carboxymethyl cellulose into the slurry, and dispersing uniformly at a high speed to obtain solid electrolyte coating slurry with the solid content of 35%.
And S2, uniformly coating the solid electrolyte coating slurry on the surfaces of two sides of a polyolefin film base film with the thickness of 5 microns by adopting a micro gravure roll coating method, placing the polyolefin film base film in an oven for forced air drying for 0.5 hour at the temperature of 100 ℃, forming a single-layer solid electrolyte coating with the thickness of 1 micron on two sides of the polyolefin film base film after drying, and rolling for later use.
Step S3, mixing the following components in a mass ratio of 60:40:3:60:0.5:6, weighing colloidal particle polyvinylidene fluoride, conductive agent carbon black, second dispersing agent sodium pyrophosphate, second binder ethyl acrylate, second wetting agent octylphenol polyoxyethylene ether and second auxiliary agent emulsified silicone oil, adding into second solvent deionized water, dispersing at a high speed, and uniformly mixing to obtain mixed coating slurry with the solid content of 20%.
And S4, uniformly coating the mixed coating slurry on the surfaces of the two sides of the solid electrolyte coating in the step S2 by adopting a spraying method, placing the solid electrolyte coating in an oven for drying for 0.5 hour by blowing at 100 ℃, and drying to obtain the ion-electron coated mixed conductor diaphragm, wherein the thickness of the single-layer mixed coating is 0.5 mu m.
The coated ion-electron mixed conductor separator prepared in this example was used to assemble a button cell by conventional methods: the button cell is assembled by adopting ternary nickel cobalt lithium manganate as a positive active material to prepare a positive electrode and adopting a metal lithium sheet as an active material as a negative electrode.
And (3) testing: the button cell is subjected to a cycle test with a charge cut-off voltage of 2.5V and a discharge cut-off voltage of 4.3V, a low-temperature specific capacity is obtained by the test at 0 ℃, the cycle retention rates of 100 weeks and 300 weeks of cycle are tested at 25 ℃ and normal temperature, and the test data are detailed in Table 1.
Example 2
The embodiment provides a preparation process and a performance test of a coated ion-electron mixed conductor diaphragm, which comprises the following specific steps:
step S1, mixing the following components in a mass ratio of 100:0.1:2:10:2.5 weighing of solid electrolyte Li 1.3 Al 0.3 Ge 1.7 (PO 4 ) 3 Adding polyvinylpyrrolidone into solvent N-methyl pyrrolidone, dispersing uniformly at high speed, and adding solid electrolyte Li 1.3 Al 0.3 Ge 1.7 (PO 4 ) 3 And continuously dispersing uniformly, sanding to obtain slurry of the solid electrolyte with the particle size of 700nm, adding polyvinylidene fluoride, polyether siloxane and polyglycol ether into the slurry, and dispersing uniformly at a high speed to obtain solid electrolyte coating slurry with the solid content of 40%.
And S2, uniformly coating the solid electrolyte coating slurry on the surface of one side of a polyolefin film base film with the thickness of 7 microns by adopting a micro gravure roll coating method, placing the polyolefin film base film in a drying oven for drying for 1 hour by blowing at 70 ℃, forming a solid electrolyte coating with the thickness of 2 microns on one side of the polyolefin film base film after drying, and rolling for later use.
Step S3, weighing colloidal particle polyvinylidene fluoride, a conductive agent SuperP, a second dispersant sodium tripolyphosphate, a second binder polyvinyl acetate, a second wetting agent sodium dodecyl sulfate and a second auxiliary agent polyoxypropylene glycerol ether according to a mass ratio of 80.
And S4, uniformly coating the mixed coating slurry on the surface of one side of the solid electrolyte coating in the step S2 by adopting a spraying method, placing the solid electrolyte coating in a drying oven for drying for 1 hour by blowing at 100 ℃, and drying to obtain the ion-electron-coated mixed conductor diaphragm, wherein the thickness of the single-layer mixed coating is 1 micrometer.
The coated ion-electron mixed conductor separator prepared in this example was used to assemble a button cell by conventional methods: and (3) preparing a positive electrode by adopting ternary nickel cobalt lithium manganate as a positive electrode active substance, and assembling a button cell by adopting a metal lithium sheet as an active substance as a negative electrode.
And (3) testing: the button cell is subjected to a cycle test with a charge cut-off voltage of 2.5V and a discharge cut-off voltage of 4.3V, a low-temperature specific capacity is obtained by the test at 0 ℃, the cycle retention rates of 100 weeks and 300 weeks of cycle are tested at 25 ℃ and normal temperature, and the test data are detailed in Table 1.
Example 3
The embodiment provides a preparation process and a performance test of a coated ion-electron mixed conductor diaphragm, which comprises the following specific steps:
step S1, mixing the following components in a mass ratio of 100:0.1:2:10:2.5 weighing of solid electrolyte Li 0.5 La 0.5 TiO 3 Adding polyvinyl alcohol into isopropanol as solvent, dispersing uniformly at high speed, and adding solid electrolyte Li 0.5 La 0.5 TiO 3 And continuously dispersing uniformly, sanding to obtain solid electrolyte slurry with the particle size of 1 mu m, adding propyl methacrylate, sodium lauryl sulfate and polyoxyethylene amide into the slurry, and dispersing uniformly at a high speed to obtain solid electrolyte coating slurry with the solid content of 40%.
And S2, uniformly coating the solid electrolyte coating slurry on the surface of one side of a fiber diaphragm base film with the thickness of 15 microns by adopting a micro gravure roll coating method, placing the fiber diaphragm base film in a drying oven for drying by blowing at 85 ℃ for 1 hour, forming a single-layer solid electrolyte coating with the thickness of 3 microns on one side of the fiber diaphragm base film after drying, and rolling for later use.
Step 3, weighing the colloidal particle polyvinylidene fluoride-hexafluoropropylene copolymer, the conductive agent Ketjen black, the second dispersant sodium hexametaphosphate, the second binder carboxymethyl cellulose, the second wetting agent sodium dodecyl benzene sulfonate and the second auxiliary agent polyacrylamide according to the mass ratio of 90.
And S4, uniformly coating the mixed coating slurry on the surface of one side of the solid electrolyte coating in the step S2 by adopting a micro gravure roll coating method, placing the solid electrolyte coating in a drying oven for drying for 1 hour by blowing at 80 ℃, and drying to obtain the ion-electron coated mixed conductor diaphragm, wherein the thickness of the single-layer mixed coating is 1.5 mu m.
The coated ion-electron mixed conductor separator prepared in this example was used to assemble a button cell by conventional methods: the button cell is assembled by adopting ternary nickel cobalt lithium manganate as a positive active material to prepare a positive electrode and adopting a metal lithium sheet as an active material as a negative electrode.
And (3) testing: the button cell is subjected to a cycle test with a charge cut-off voltage of 2.5V and a discharge cut-off voltage of 4.3V, a low-temperature specific capacity is obtained by the test at 0 ℃, the cycle retention rates of 100 weeks and 300 weeks of cycle are tested at 25 ℃ and normal temperature, and the test data are detailed in Table 1.
Example 4
The embodiment provides a preparation process and a performance test of a coated ion-electron mixed conductor diaphragm, which comprises the following specific steps:
step S1, mixing the following components in a mass ratio of 100:2.5:20:5:1.5 weighing of solid electrolyte Li 6.8 La 3 Zr 1.8 Ta 0.2 O 12 Adding triethyl hexyl phosphoric acid serving as a first dispersing agent into cyclohexane, uniformly dispersing at a high speed, and then adding Li serving as a solid electrolyte 6.8 La 3 Zr 1.8 Ta 0.2 O 12 And continuously dispersing uniformly, sanding to obtain slurry of the solid electrolyte with the particle size of 700nm, adding a first binder styrene-acrylic emulsion, a first wetting agent polyoxyethylene alkylphenol ether and a first auxiliary agent sodium alginate into the slurry, and dispersing uniformly at a high speed to obtain solid electrolyte coating slurry with the solid content of 45%.
And S2, uniformly coating the solid electrolyte coating slurry on the surfaces of two sides of a non-woven fabric diaphragm base film with the thickness of 9 microns by adopting a micro gravure roll coating method, placing the non-woven fabric diaphragm base film in an oven for blowing and drying for 0.5 hour at the temperature of 90 ℃, forming single-layer solid electrolyte coatings with the thickness of 2 microns on two sides of the non-woven fabric diaphragm base film after drying, and rolling for later use.
Step 3, weighing the colloidal particle polyvinylidene fluoride, the conductive agent carbon black, the second dispersant sodium pyrophosphate, the second binder ethyl acrylate, the second wetting agent octylphenol polyoxyethylene ether, the second auxiliary polydimethylsiloxane and the silicone emulsion according to the mass ratio of 95.5.
And S4, uniformly coating the mixed coating slurry on the surfaces of the two sides of the solid electrolyte coating in the step S2 by adopting a spraying method, placing the solid electrolyte coating in an oven for drying for 0.5 hour by blowing at 100 ℃, and drying to obtain the ion-electron coated mixed conductor diaphragm, wherein the thickness of the single-layer mixed coating is 1 micron.
The coated ion-electron mixed conductor separator prepared in this example was used to assemble a button cell by conventional methods: the button cell is assembled by adopting ternary nickel cobalt lithium manganate as a positive active material to prepare a positive electrode and adopting a metal lithium sheet as an active material as a negative electrode.
And (3) testing: the button cell is subjected to a cycle test with a charge cut-off voltage of 2.5V and a discharge cut-off voltage of 4.3V, a low-temperature specific capacity is obtained by the test at 0 ℃, the cycle retention rates of 100 weeks and 300 weeks of cycle are tested at 25 ℃ and normal temperature, and the test data are detailed in Table 1.
To better illustrate the effects of the examples of the present invention, comparative example 1 was compared with example 1 above.
Comparative example 1
The comparative example provides a preparation process and a test of a double-sided gluing solid electrolyte coating diaphragm, the preparation process of the solid electrolyte coating is the same as the step S1 and the step S2 of the example 1, the preparation method of the glue layer is the same as the step S3 and the step S4 of the example 1, and compared with the example 1, no conductive agent carbon black is added into the glue layer of the diaphragm of the comparative example; the thickness of the basement membrane is 5 mu m, the single-layer thickness of the solid electrolyte coating is 1 mu m, and the single-layer thickness of the glue layer is 0.5 mu m.
The double-sided gummed solid electrolyte coating diaphragm prepared by the comparative example was assembled into a button cell by a conventional method: the button cell is assembled by adopting ternary nickel cobalt lithium manganate as a positive active material to prepare a positive electrode and adopting a metal lithium sheet as an active material as a negative electrode.
And (3) testing: the button cell is subjected to a cycle test with a charge cut-off voltage of 2.5V and a discharge cut-off voltage of 4.3V, a low-temperature specific capacity is obtained by the test at 0 ℃, the cycle retention rates of 100 weeks and 300 weeks of cycle are tested at 25 ℃ and normal temperature, and the test data are detailed in Table 1.
Table 1 summarizes the test data for the membranes of examples 1-4 and comparative example 1.
As can be seen from comparison of test data in table 1, the battery assembled by the ion-electron-coated mixed conductor diaphragm provided in embodiments 1 to 4 of the present invention has a higher actual positive electrode capacity in a low-temperature working environment (0 ℃), which is higher by about 30mAh/g than that in comparison example 1, which indicates that the ion-electron-coated mixed conductor diaphragm provided in the embodiments of the present invention is beneficial to increasing energy density of the battery at an extremely low temperature, and alleviates a serious user mileage anxiety problem in winter when the lithium battery is applied to an electric vehicle. In addition, after the ion-electron mixed conductor coated diaphragm is used at normal temperature, the battery capacity retention rate of the lithium battery is obviously improved, and the cycle performance of the battery is optimized.
After the battery is disassembled, the shape difference of the surface of the negative electrode side of the metal lithium is compared with the shape difference of the ionic-electronic mixed conductor coated diaphragm in the embodiment 1, as shown in fig. 4, the diaphragm coated with the solid electrolyte on the double surfaces in the comparative example 1 is not discolored, and the battery diaphragm in the embodiment 1 is changed into uniform black on the negative electrode side of the metal lithium, because the black passivation film is generated by the formation reaction after the solid electrolyte in the mixed coating of the battery diaphragm in the embodiment 1 is contacted with the negative electrode of the metal lithium, so that the diaphragm is black; the black passivation film formed in the embodiment 1 has the characteristic of conducting lithium ions, so that the ion transmission impedance of the battery can be reduced, particularly the internal resistance of the battery at low temperature is reduced, and the specific capacity at low temperature and the cycle performance of the battery at normal temperature are improved.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are merely exemplary embodiments of the present invention, and are not intended to limit the scope of the present invention, and any modifications, equivalent substitutions, improvements and the like made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (10)
1. A coated ionic-electronic mixed conductor membrane, comprising: the lithium ion battery comprises a base film, a solid electrolyte coating which is coated on one side or two sides of the base film and conducts lithium ions, and a mixed coating which is coated on the outer surface of the solid electrolyte coating;
the solid electrolyte coating includes: the adhesive comprises a solid electrolyte, a first dispersing agent, a first bonding agent, a first wetting agent and a first auxiliary agent; the solid electrolyte includes: li 1+x Al x Ti 2-x (PO 4 ) 3 、Li 1+y Al y Ge 2-y (PO 4 ) 3 、Li 3z La 2/3-z TiO 3 、Li 7- q La 3 Zr 2-q Ta q O 12 Wherein x is more than or equal to 0 and less than or equal to 0.5, y is more than or equal to 0 and less than or equal to 0.5, z is more than 0 and less than 2/3, and q is more than 0 and less than 2; the particle size of the solid electrolyte is 200nm-1 mu m;
the hybrid coating includes: colloidal particles and a conductive agent; the colloidal particles comprise: one or more of polyvinylidene fluoride PVDF, polyvinylidene fluoride-hexafluoropropylene copolymer PVDF-HFP and polymethyl methacrylate PMMA; the conductive agent includes: one or more of carbon black, carbon nanotube, acetylene black, ketjen black, super P.
2. The coated ionic-electronic mixed conductor separator according to claim 1, wherein the base film comprises: one or more of polyolefin membrane, non-woven fabric membrane, fiber membrane and aramid fiber membrane; the thickness of the basement membrane is 5-15 μm;
the thickness of the solid electrolyte coating is 1-3 μm;
the thickness of the mixed coating is 0.5-1.5 μm.
3. The coated ionic-electronic mixed conductor membrane of claim 1, wherein the first dispersant comprises: one or more of polyvinylpyrrolidone, sodium polyacrylate, polyacrylic acid ammonium salt copolymer, polyethylene glycol, polyvinyl alcohol, sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, polymethacrylate, triethylhexyl phosphoric acid, sodium tripolyphosphate, sodium hexametaphosphate or sodium pyrophosphate;
the first binder includes: one or more of polymethyl styrene-butadiene rubber, styrene-acrylic emulsion, polyurethane, polyvinylidene fluoride, carboxymethyl cellulose, polyvinyl alcohol, polytetrafluoroethylene, polyvinyl acetate, methacrylic acid, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, ethacrylic acid and ethyl acrylate;
the first wetting agent comprises: one or more of sodium hexametaphosphate, polyvinylpyrrolidone, polydimethylsiloxane, polyether siloxane, polyoxyethylene ether, polyoxyethylene alkylamine, polyoxyethylene alkylphenol ether, polyoxyethylene fatty alcohol ether, polyoxyethylene octylphenol ether, sodium dodecyl benzene sulfonate, sodium dodecyl sulfate and sodium lauryl sulfate;
the first auxiliary agent comprises: one or more of polyglycol ether, emulsified silicone oil, sodium carboxymethyl cellulose, sodium alginate, polydimethylsiloxane, polyacrylamide, polyoxypropylene glycerol ether, polyoxyethylene amide or sodium perfluorocaprylate;
the mass ratio of the solid electrolyte, the first dispersing agent, the first binder, the first wetting agent and the first auxiliary agent is 100: [0.1-2.5]: [2-20]: [3-15]: [0.25-2.5].
4. The coated ionic-electronic mixed conductor membrane of claim 1, wherein the mixed coating further comprises: the second dispersing agent, the second binder, the second wetting agent and the second auxiliary agent;
the second dispersant comprises: one or more of polyvinylpyrrolidone, sodium polyacrylate, polyacrylic acid ammonium salt copolymer, polyethylene glycol, polyvinyl alcohol, sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, polymethacrylate, triethylhexyl phosphoric acid, sodium tripolyphosphate, sodium hexametaphosphate or sodium pyrophosphate;
the second binder includes: one or more of polymethyl styrene-butadiene rubber, styrene-acrylic emulsion, polyurethane, polyvinylidene fluoride, carboxymethyl cellulose, polyvinyl alcohol, polytetrafluoroethylene, polyvinyl acetate, methacrylic acid, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, ethacrylic acid and ethyl acrylate;
the second wetting agent comprises: one or more of sodium hexametaphosphate, polyvinylpyrrolidone, polydimethylsiloxane, polyether siloxane, polyoxyethylene ether, polyoxyethylene alkylamine, polyoxyethylene alkylphenol ether, polyoxyethylene fatty alcohol ether, polyoxyethylene octylphenol ether, sodium dodecyl benzene sulfonate, sodium dodecyl sulfate and sodium lauryl sulfate;
the second auxiliary agent comprises: one or more of polyglycol ether, emulsified silicone oil, sodium carboxymethylcellulose, sodium alginate, polydimethylsiloxane, polyacrylamide, polyoxypropylene glycerol ether, polyoxyethylene amide or sodium perfluorooctanoate;
the mass ratio of the colloidal particles, the conductive agent, the second dispersing agent, the second bonding agent, the second wetting agent and the second auxiliary agent is [60-95]: [5-40]: [3-15]: [15-60]: [0.3-1]: [6-65].
5. A method of preparing a coated ionic-electronic mixed conductor membrane according to any one of claims 1 to 4, comprising:
step S1, preparing solid electrolyte coating slurry, which specifically comprises the following steps: adding a first dispersing agent into a first solvent, uniformly dispersing at a high speed, then adding a solid electrolyte, continuously uniformly dispersing, sanding to obtain slurry of the solid electrolyte with the particle size of 200nm-1 mu m, adding a first wetting agent, a first binder and a first auxiliary agent into the slurry, and uniformly dispersing at a high speed to obtain solid electrolyte coating slurry;
step S2, coating a solid electrolyte coating on the surface of at least one side of the base film: uniformly coating the solid electrolyte coating slurry on the surface of at least one side of the base film by adopting a micro gravure roller coating method, placing the base film in a drying oven for primary drying, forming a solid electrolyte coating on one side or two sides of the base film after drying, and rolling for later use;
step S3, preparing mixed coating slurry, which specifically comprises the following steps: dispersing and uniformly mixing the colloidal particles, the conductive agent, the second dispersing agent, the second adhesive, the second wetting agent, the second auxiliary agent and the second solvent at a high speed according to the mass ratio to obtain mixed coating slurry;
and S4, uniformly coating the mixed coating slurry on the surface of at least one side of the outer side of the solid electrolyte coating in the step S2 by adopting a micro gravure roll coating method or a spraying method, placing the solid electrolyte coating in a baking oven for secondary baking, and drying to obtain the ion-electron coated mixed conductor diaphragm.
6. The production method according to claim 5, wherein the solid electrolyte comprises: li 1+x Al x Ti 2-x (PO 4 ) 3 、Li 1+y Al y Ge 2-y (PO 4 ) 3 、Li 3z La 2/3-z TiO 3 、Li 7-q La 3 Zr 2-q Ta q O 12 Wherein x is more than or equal to 0 and less than or equal to 0.5, y is more than or equal to 0 and less than or equal to 0.5, z is more than 0 and less than 2/3, and q is more than 0 and less than 2;
the first dispersant includes: one or more of polyvinylpyrrolidone, sodium polyacrylate, polyacrylic acid ammonium salt copolymer, polyethylene glycol, polyvinyl alcohol, sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, polymethacrylate, triethylhexyl phosphoric acid, sodium tripolyphosphate, sodium hexametaphosphate or sodium pyrophosphate;
the first binder includes: one or more of polymethyl styrene-butadiene rubber, styrene-acrylic emulsion, polyurethane, polyvinylidene fluoride, carboxymethyl cellulose, polyvinyl alcohol, polytetrafluoroethylene, polyvinyl acetate, methacrylic acid, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, ethacrylic acid and ethyl acrylate;
the first wetting agent comprises: one or more of sodium hexametaphosphate, polyvinylpyrrolidone, polydimethylsiloxane, polyether siloxane, polyoxyethylene ether, polyoxyethylene alkylamine, polyoxyethylene alkylphenol ether, polyoxyethylene fatty alcohol ether, polyoxyethylene octylphenol ether, sodium dodecyl benzene sulfonate, sodium dodecyl sulfate and sodium lauryl sulfate;
the first auxiliary agent comprises: one or more of polyglycol ether, emulsified silicone oil, sodium carboxymethylcellulose, sodium alginate, polydimethylsiloxane, polyacrylamide, polyoxypropylene glycerol ether, polyoxyethylene amide or sodium perfluorooctanoate;
the mass ratio of the solid electrolyte, the first dispersing agent, the first binder, the first wetting agent and the first auxiliary agent is 100: [0.1-2.5]: [2-20]: [3-15]: [0.25-2.5];
the first solvent includes: one or more of deionized water, N-methyl pyrrolidone, alcohol, isopropanol and cyclohexane;
the solid content in the solid electrolyte coating slurry is 20-70%.
7. The method for preparing according to claim 5, wherein the colloidal particles comprise: one or more of polyvinylidene fluoride PVDF, polyvinylidene fluoride-hexafluoropropylene copolymer PVDF-HFP and polymethyl methacrylate PMMA;
the conductive agent includes: one or more of carbon black, carbon nanotube, acetylene black, ketjen black, super P
The second dispersant comprises: one or more of polyvinylpyrrolidone, sodium polyacrylate, polyacrylic acid ammonium salt copolymer, polyethylene glycol, polyvinyl alcohol, sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, polymethacrylate, triethylhexyl phosphoric acid, sodium tripolyphosphate, sodium hexametaphosphate or sodium pyrophosphate;
the second binder includes: one or more of polymethyl styrene-butadiene rubber, styrene-acrylic emulsion, polyurethane, polyvinylidene fluoride, carboxymethyl cellulose, polyvinyl alcohol, polytetrafluoroethylene, polyvinyl acetate, methacrylic acid, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, ethacrylic acid and ethyl acrylate;
the second wetting agent comprises: one or more of sodium hexametaphosphate, polyvinylpyrrolidone, polydimethylsiloxane, polyether siloxane, polyoxyethylene ether, polyoxyethylene alkylamine, polyoxyethylene alkylphenol ether, polyoxyethylene fatty alcohol ether, polyoxyethylene octylphenol ether, sodium dodecyl benzene sulfonate, sodium dodecyl sulfate and sodium lauryl sulfate;
the second auxiliary agent comprises: one or more of polyglycol ether, emulsified silicone oil, sodium carboxymethylcellulose, sodium alginate, polydimethylsiloxane, polyacrylamide, polyoxypropylene glycerol ether, polyoxyethylene amide or sodium perfluorooctanoate;
the mass ratio of the colloidal particles, the conductive agent, the second dispersing agent, the second bonding agent, the second wetting agent and the second auxiliary agent is [60-95]: [5-40]: [3-15]: [15-60]: [0.3-1]: [6-65];
the second solvent includes: one or more of deionized water, N-methyl pyrrolidone, alcohol, isopropanol and cyclohexane; the solid content in the mixed coating slurry is 10-65%.
8. The production method according to claim 5, wherein the base film comprises: one or more of polyolefin membrane, non-woven fabric membrane, fiber membrane and aramid fiber membrane; the thickness of the basement membrane is 5-15 μm; the thickness of the solid electrolyte coating is 1-3 μm; the thickness of the mixed coating is 0.5-1.5 μm;
the conditions of the first baking and the second baking are as follows: blowing and drying at 70-100 deg.c for 0.5-4 hr.
9. A lithium battery comprising the coated ionic-electronic mixed conductor separator of any of claims 1-4.
10. The lithium battery of claim 9, wherein the lithium battery comprises: any one of a liquid lithium ion battery, a semi-solid lithium battery, an all-solid lithium battery, a lithium sulfur battery or a lithium air battery.
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| CN116606574A (en) * | 2023-05-22 | 2023-08-18 | 山东锌派新能源科技有限公司 | Coating material for improving ion transfer-diffusion effect on battery interface, preparation method and application thereof |
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| CN116606574A (en) * | 2023-05-22 | 2023-08-18 | 山东锌派新能源科技有限公司 | Coating material for improving ion transfer-diffusion effect on battery interface, preparation method and application thereof |
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