CN114284639B - Inorganic/organic composite separator and method for preparing same - Google Patents

Inorganic/organic composite separator and method for preparing same Download PDF

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CN114284639B
CN114284639B CN202111583875.5A CN202111583875A CN114284639B CN 114284639 B CN114284639 B CN 114284639B CN 202111583875 A CN202111583875 A CN 202111583875A CN 114284639 B CN114284639 B CN 114284639B
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inorganic
precursor
inorganic layer
accounts
solid electrolyte
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CN114284639A (en
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庄志
吴惠康
潘星星
刘倩倩
鲍晋珍
程跃
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Jiangxi Tongrui New Energy Technology Development Co ltd
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Priority to PCT/CN2022/085953 priority patent/WO2023115756A1/en
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/403—Manufacturing processes of separators, membranes or diaphragms
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/446—Composite material consisting of a mixture of organic and inorganic materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
    • H01M50/457—Separators, membranes or diaphragms characterised by the material having a layered structure comprising three or more layers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Composite Materials (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Conductive Materials (AREA)
  • Cell Separators (AREA)

Abstract

The present invention provides an inorganic/organic composite separator comprising: the organic solid electrolyte comprises an organic polymer, wherein the organic polymer is formed by in-situ polymerization reaction in the internal pores of the inorganic layer and on the surface of the inorganic layer.

Description

Inorganic/organic composite separator and method for preparing same
Technical Field
The invention relates to the technical field related to battery diaphragms, in particular to an ion conductor/organic solid electrolyte composite diaphragm and a preparation method thereof.
Background
The diaphragm is a basic component of a lithium battery, and mainly has the function of separating the positive electrode from the negative electrode of the battery, only allowing electrolyte ions to pass through so as to prevent the two electrodes from being in contact and short circuit, and the characteristics of the diaphragm have direct influence on the performance of the battery, for example, the performance of the diaphragm can determine the interface structure, the internal resistance and the like of the battery, and further the performances of the battery such as capacity, cycle life, safety and stability and the like are directly influenced.
The coated separator containing an inorganic oxide such as alumina can effectively improve the thermal stability and electrolyte retention ability of the separator, and thus improve the performance of the lithium battery, but does not contribute substantially to the improvement of the electrical conductivity. In addition, the coating of the separator containing an inorganic solid electrolyte such as Lithium Lanthanum Zirconium Oxide (LLZO) or Lithium Aluminum Titanium Phosphate (LATP) can improve the lithium ion conductivity of the separator, but the inorganic solid electrolyte is difficult to form a densely packed continuous ion conducting network, so that the lithium ion conductivity of the separator is affected, and meanwhile, part of the inorganic solid electrolyte has poor stability to lithium metal, so that a stable interface is difficult to form, and the service life of the battery is further affected.
Disclosure of Invention
In view of the foregoing, the present invention is directed to a composite separator and a method for preparing the same, which uses a membrane containing an inorganic layer as a main body, and performs in-situ polymerization reaction with a surface in an internal pore of the inorganic layer to form an organic polymer as an organic solid electrolyte, so as to solve the problems encountered in the separator at present.
In order to achieve the above purpose, the technical scheme of the invention is realized as follows:
the present invention provides an inorganic/organic composite separator comprising: the organic solid electrolyte comprises an organic polymer, wherein the organic polymer is formed by in-situ polymerization reaction in the internal pores of the inorganic layer and on the surface of the inorganic layer.
Preferably, the internal porosity of the inorganic layer is less than 30%.
Preferably, the inorganic layer comprises one or more of an inorganic solid electrolyte, an inorganic ceramic.
Preferably, the inorganic solid state electrolyte comprises one or a combination of more of an oxide solid state electrolyte and a sulfide solid state electrolyte.
Preferably, the oxide solid electrolyte comprises lithium lanthanum zirconium oxide, lithium aluminum titanium phosphate, and garnet-type oxide Li x Ln 3 M 2 O 12 Wherein Ln is La or Y, M is Zr, nb, sn, sb, te, hf or Ta, and x is from 3 to 7.
Preferably, the sulfide solid state electrolyte comprises a combination of one or more of LGPS, LPS, LPSCl, LSnPS, LSiPS, LGSiPS, LAlPS, LGS, LGZS, LSiS, LSAlS.
Preferably, the inorganic solid electrolyte includes one or more combinations of garnet-type conductive materials, sulfide-type conductive materials, perovskite-type conductive materials, liSiON-type conductive materials, liPON-type conductive materials, and Li 3N-type conductive materials.
Preferably, the inorganic ceramic comprises one or more combinations of aluminum oxide, silicon oxide, metal nitride, metal phosphide, metal sulfide, metal boride.
Preferably, the organic polymer comprises one or more of polyethers, polycarbonates, polyvinylidene fluoride, polyurethanes, polyacrylonitriles, polyimides, polyacrylic acids, and polyacrylic acid metal salts.
Preferably, the organic solid electrolyte further comprises a lithium salt.
Preferably, the organic solid electrolyte further comprises lithium salt and plasticizer.
Preferably, the lithium salt comprises one or more of lithium hexafluorophosphate, lithium dioxaborate, lithium bistrifluoro methanesulfonimide, lithium bistrifluoro sulfimide, lithium perchlorate, lithium difluorooxalato borate, lithium tetrafluoroborate.
Preferably, the plasticizer comprises one or more of ethylene carbonate, propylene carbonate, methyl ethyl carbonate, dimethyl carbonate, diethyl carbonate, fluoroethylene carbonate, bis-fluoroethylene carbonate, vinyl chloride, 1, 3-dioxolane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, tetraethylene glycol dimethyl ether, 1, 3-propane sultone, succinonitrile.
The invention also provides a preparation method of the inorganic/organic composite diaphragm, which comprises the following steps:
providing a base film; forming an inorganic layer on the base film, the inorganic layer having internal pores; filling a precursor in the internal pores of the inorganic layer and distributing the precursor on the surface of the inorganic layer; the precursor is polymerized in situ in the internal pores of the inorganic layer and on the surface of the inorganic layer to form an organic polymer, thereby obtaining an organic solid electrolyte that fills the internal pores of the inorganic layer and is distributed on the surface of the inorganic layer and includes the organic polymer.
Preferably, the in-situ polymerization is performed by standing at room temperature, heating or illumination.
Preferably, the precursor polymer comprises one or more of a cyclic ether compound, a polyethylene glycol diglycidyl ether, and combinations thereof.
Preferably, the inorganic layer comprises one or more of an inorganic solid electrolyte, an inorganic ceramic.
Preferably, the inorganic solid state electrolyte comprises one or a combination of more of an oxide solid state electrolyte and a sulfide solid state electrolyte.
Preferably, the oxide solid electrolyte comprises lithium lanthanum zirconium oxide, lithium aluminum titanium phosphate, and garnet-type oxide Li x Ln 3 M 2 O 12 Wherein Ln is La or Y, M is Zr, nb, sn, sb, te, hf or Ta, and x is from 3 to 7.
Preferably, the sulfide solid state electrolyte comprises a combination of one or more of LGPS, LPS, LPSCl, LSnPS, LSiPS, LGSiPS, LAlPS, LGS, LGZS, LSiS, LSAlS.
Preferably, the inorganic ceramic comprises one or more combinations of aluminum oxide, silicon oxide, metal nitride, metal phosphide, metal sulfide, metal boride.
Preferably, the organic polymer comprises one or more of polyethers, polycarbonates, polyvinylidene fluoride, polyurethanes, polyacrylonitriles, polyimides, polyacrylic acids, and polyacrylic acid metal salts.
The invention has the following beneficial effects:
1) According to the invention, the organic polymer is formed in the internal pores of the inorganic layer through in-situ polymerization reaction, so that the gaps of the inorganic layer can be effectively filled, a continuous lithium ion channel is formed, and the ion conductivity and the stability of the diaphragm are further improved to improve the battery performance.
2) According to the invention, the inorganic layer is formed on one surface of the base film, and the organic polymer is formed on the internal pores and the surface of the inorganic layer through in-situ polymerization reaction, so that the organic polymer forms the protective layer on the surface of the inorganic layer on the surface of the base film, and the interface stability of the separator and the positive electrode or the negative electrode of the battery is further improved, so that the battery performance is improved.
3) According to the invention, the inorganic layers are respectively formed on the two surfaces of the base film, and the organic polymer is formed on the internal pores and the surfaces of the inorganic layers through in-situ polymerization reaction, so that the organic polymer forms the protective layers on the surfaces of the inorganic layers on the two surfaces of the base film, and the interface stability of the separator and the positive electrode and the negative electrode of the battery is further improved, so that the battery performance is improved.
Drawings
FIG. 1 is a schematic structural view of an inorganic/organic composite separator according to an embodiment of the present invention;
FIG. 2 is a schematic structural view of an inorganic/organic composite separator according to another embodiment of the present invention;
FIG. 3 is a flow chart of a method of preparing an inorganic/organic composite separator according to another embodiment of the present invention;
FIG. 4 is a scanning electron micrograph showing a cross-section of the membrane obtained in example 1;
FIG. 5 is a scanning electron micrograph showing a cross-section of the membrane obtained in example 4;
FIG. 6 is a graph of time-voltage and time-current illustrating the voltage and current measured for different times of charge and discharge cycles at normal temperature for a Li-Cu half-cell assembled with the membrane obtained in comparative example 3 as a diaphragm;
FIG. 7 is a graph of time-voltage and time-current illustrating the voltage and current measured for the last 20 charge-discharge cycles at normal temperature for a Li-Cu half-cell assembled with the membrane obtained in comparative example 3 as a diaphragm;
FIG. 8 is a graph showing the relationship between time and voltage and between time and current, and is a graph showing the relationship between time and voltage and between time and current, illustrating the voltage and current measured by different times of charge and discharge cycles at normal temperature for the Li-Cu half-cell assembled with the membrane as a membrane obtained in example 1;
description of the component reference numerals
1 … base film
2 … inorganic layer
3 … organic solid electrolyte
Detailed Description
The following detailed description of the invention refers to the accompanying drawings. It should be understood that the detailed description and specific examples, while indicating and illustrating the invention, are not intended to limit the invention.
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
As shown in fig. 1, one embodiment of the present invention provides an inorganic/organic composite separator comprising: the organic solid electrolyte 3 is formed by in-situ polymerization reaction in the internal pores of the inorganic layer 2 and on the surface of the inorganic layer 2.
Specifically, the base film may be a PE base film or a PP base film according to the material, and may be a wet base film or a dry base film according to the process.
Specifically, the internal porosity of the inorganic layer may be greater than 0% and less than 30%.
Specifically, the inorganic layer may include one or a combination of more of an inorganic solid electrolyte, an inorganic ceramic. For example, the inorganic solid state electrolyte includes one or a combination of more of an oxide solid state electrolyte, a sulfide solid state electrolyte. Also for example, the oxide solid electrolyte includes lithium lanthanum zirconium oxide, lithium aluminum titanium phosphate, garnet-type oxide LixLn 3 M 2 O 12 Wherein Ln is La or Y, M is Zr, nb, sn, sb, te, hf or Ta, x is from 3 to 7, and the sulfide solid state electrolyte comprises LGPS, LPS, LPSCl, LSnPS, LSiPS, LGSiPS,LAlPS, LGS, LGZS, LSiS, LSAlS, a combination of one or more of the foregoing. By way of further example, the inorganic ceramic includes one or more combinations of aluminum oxide, silicon oxide, metal nitride, metal phosphide, metal sulfide, metal boride.
Specifically, the inorganic layer may include one or a combination of more of an inorganic solid electrolyte, an inorganic ceramic. For example, the inorganic solid state electrolyte includes one or more combinations of garnet-type conductive materials, sulfide-type conductive materials, perovskite-type conductive materials, liSiON-type conductive materials, liPON-type conductive materials, and Li 3N-type conductive materials. By way of further example, the inorganic ceramic includes one or more combinations of aluminum oxide, silicon oxide, metal nitride, metal phosphide, metal sulfide, metal boride.
Specifically, the organic polymer may include one or more combinations of polyethers, polycarbonates, polyvinylidene fluoride, polyurethanes, polyacrylonitriles, polyimides, polyacrylic acids, and polyacrylic acid metal salts.
In particular, the organic solid electrolyte may further include a lithium salt in addition to the organic polymer. The addition of lithium salt may increase the number of charge carriers in the solid state electrolyte to increase the conductivity of the battery, examples of which include one or more of lithium hexafluorophosphate, lithium dioxalate borate, lithium bis (trifluoromethanesulfonyl) imide, lithium bis (fluorosulfonyl) imide, lithium perchlorate, lithium difluorooxalato borate, lithium tetrafluoroborate.
In particular, the organic solid electrolyte may further include a lithium salt, a plasticizer, in addition to the organic polymer. As previously described, the addition of lithium salts may increase the number of charge carriers in the solid state electrolyte to increase the conductivity of the battery, examples of which include one or more of lithium hexafluorophosphate, lithium dioxalate borate, lithium bis (trifluoromethanesulfonyl) imide, lithium bis (fluorosulfonyl) imide, lithium difluorooxalato borate, lithium tetrafluoroborate. The addition of the plasticizer may lower the Tg temperature of the organic solid electrolyte (2) to increase the conductivity of the battery, examples of which include one or more of propylene carbonate, ethylene carbonate, dimethyl carbonate, diethyl carbonate, methylethyl carbonate, fluoroethylene carbonate, bisfluoroethylene carbonate, vinyl chloride, 1, 3-dioxolane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, tetraethylene glycol dimethyl ether, 1, 3-propane sultone, succinonitrile.
As shown in fig. 2, another embodiment of the present invention provides an inorganic/organic composite separator substantially similar to the structure shown in fig. 1, except that inorganic layers 2 are formed on both surfaces of a base film 1, an organic solid electrolyte 3 is distributed on one surface of each inorganic layer 2, and an organic polymer is formed on the surface of each inorganic layer 2 by in-situ polymerization. Compared with the structure shown in fig. 1, which only forms an organic/inorganic composite structure on a single surface of the base film and can only contact one of the positive electrode and the negative electrode to improve the interface stability, the structure shown in fig. 2 forms an organic/inorganic composite structure on two surfaces of the base film and can contact the positive electrode and the negative electrode to improve the interface stability and improve the battery performance, but is more beneficial to the performance of the battery.
Referring to fig. 3, another embodiment of the present invention describes a method for preparing the inorganic/organic composite separator, which is described in detail as follows:
first, a base film is provided.
Specifically, the base film can be a PE base film or a PP base film according to materials.
Specifically, the base film may be a wet base film or a dry base film according to the process.
Next, an inorganic layer is formed on the base film, and the inorganic layer has internal pores.
Specifically, an inorganic layer may be formed on one surface of the base film. For example, an inorganic slurry is coated on one surface of the base film, and then dried to form an inorganic layer.
Specifically, an inorganic layer may be formed on each of the two surfaces of the base film. For example, an inorganic slurry is coated on each of the two surfaces of the base film, and then dried to form an inorganic layer.
Specifically, the internal porosity of the inorganic layer may be greater than 0% and less than 30%.
Specifically, the inorganic slurry may further include a solvent and a binder in addition to one or more of an inorganic solid electrolyte and an inorganic ceramic. The addition of the solvent may dissolve and disperse the organic components of the inorganic slurry to uniformly distribute the components of the inorganic slurry over the base film, examples of which include one or more of water, methanol, ethanol, isopropanol, acetonitrile, acetone, DMAc, NMP, THF, DMF, anhydrous hydrazine, toluene, n-heptane, xylene, and anisole. The addition of the binder may stabilize the inorganic layer on the base film, examples of which include one or more combinations of PTFE, FEP copolymers, PFA resins, PCTFF, ECTFE copolymers, ETFE, PVDF, PVF. In addition, in the case where the inorganic slurry includes one of an inorganic solid electrolyte and an inorganic ceramic, the weight ratio between the inorganic solid electrolyte or the inorganic ceramic and the binder may be 3:1 to 25:1, preferably 5:1 to 15:1. furthermore, the solvent may account for 40wt% to 65wt%, the inorganic solid electrolyte or inorganic ceramic may account for 30wt% to 50wt%, and the binder may account for 2wt% to 10wt%, based on the total weight of the inorganic slurry. In the case where the inorganic slurry includes a combination of a plurality of inorganic solid electrolyte and inorganic ceramic, the weight ratio between the inorganic solid electrolyte and the inorganic ceramic as a whole and the binder may be 3:1 to 25:1, preferably 5:1 to 15:1. furthermore, the total weight of the inorganic slurry is taken as a basis, the solvent can account for 40 to 65 weight percent, the whole of the inorganic solid electrolyte and the inorganic ceramic can account for 30 to 50 weight percent, and the binder can account for 2 to 10 weight percent.
Specifically, the inorganic slurry may further include a dispersant, a solvent, and a binder in addition to one or more of an inorganic solid electrolyte and an inorganic ceramic. The addition of the dispersing agent can uniformly distribute the components in the inorganic layer, and examples thereof include one or more of polyvinyl alcohol, polyethylene oxide, polyacrylate and polyvinylpyrrolidone. The addition of the solvent may dissolve and disperse the organic components of the inorganic slurry to uniformly distribute the components of the inorganic slurry over the base film, examples of which include one or more of water, methanol, ethanol, isopropanol, acetonitrile, acetone, DMAc, NMP, THF, DMF, anhydrous hydrazine, toluene, n-heptane, xylene, and anisole. The addition of the binder may stabilize the inorganic layer on the base film, examples of which include one or more combinations of PTFE, FEP copolymers, PFA resins, PCTFF, ECTFE copolymers, ETFE, PVDF, PVF. In addition, in the case where the inorganic slurry includes one of an inorganic solid electrolyte and an inorganic ceramic, the weight ratio between the inorganic solid electrolyte or the inorganic ceramic and the binder may be 3:1 to 25:1, preferably 5:1 to 15:1. furthermore, based on the total weight of the inorganic slurry, the solvent may account for 40wt% to 65wt%, the inorganic solid electrolyte or inorganic ceramic may account for 30wt% to 50wt%, the dispersant may account for 0.05wt% to 0.3wt%, and the binder may account for 2wt% to 10wt%. Further, in the case where the inorganic slurry includes a combination of a plurality of inorganic solid electrolyte and inorganic ceramic, the weight ratio between the inorganic solid electrolyte and the inorganic ceramic as a whole and the binder may be 3:1 to 25:1, preferably 5:1 to 15:1. moreover, based on the total weight of the inorganic slurry, the solvent can account for 40 to 65 weight percent, the whole of the inorganic solid electrolyte and the inorganic ceramic can account for 30 to 50 weight percent, the dispersant can account for 0.05 to 0.3 weight percent, and the binder can account for 2 to 10 weight percent.
Furthermore, a precursor is filled in the internal pores of the inorganic layer and distributed on the surface of the inorganic layer.
Specifically, the precursor may be dropped on the inorganic layer and coated or the inorganic layer may be impregnated with the precursor so that the precursor fills in the internal pores of the inorganic layer and is distributed on the surface of the inorganic layer. For example, a precursor solution may be dropped onto the inorganic layer and coated or the inorganic layer may be immersed in the precursor solution such that the precursor solution fills the internal pores of the inorganic layer and is distributed over the surface of the inorganic layer.
Specifically, the precursor is a unit of an organic polymer, such as a monomer or oligomer, which is formed later, and it is preferable that the precursor has a low viscosity in order to accelerate the efficiency of filling the internal pores of the inorganic layer and distributing the precursor on the surface thereof. For example, the monomer may include a cyclic ether compound; the cyclic ether compound may contain 1 or more oxygen atoms, may contain a single or multiple ring structures, may contain a carbon-carbon double bond, or may contain 1 or more substituents. More for example, the cyclic ether compound may be a substituted or unsubstituted 1, 3-dioxolane or a substituted or unsubstituted 1, 4-dioxane. Also for example, the oligomer may include polyethylene glycol diglycidyl ether.
Specifically, under the condition that the subsequently obtained organic solid electrolyte further comprises lithium salt, the lithium salt and the precursor can be mixed into a precursor solution, and then the precursor solution is dripped into the inorganic layer and coated or the inorganic layer is soaked into the precursor solution, so that the precursor solution is filled in the internal pores of the inorganic layer and distributed on the surface of the inorganic layer. Preferably, the precursor polymer may account for 90wt% to 98wt% and the lithium salt may account for 2wt% to 10wt% based on the total weight of the precursor polymer solution. Preferably, the precursor is an oligomer, such as polyethylene glycol diglycidyl ether. Still more preferably, the precursor is a monomer, such as 1, 3-dioxolane or vinylene carbonate.
Specifically, under the condition that the subsequently obtained organic solid electrolyte further comprises lithium salt and initiator, the lithium salt, the initiator and the precursor can be mixed into a precursor solution, and then the precursor solution is dripped into the inorganic layer and coated or the inorganic layer is soaked into the precursor solution, so that the precursor solution is filled in the internal pores of the inorganic layer and distributed on the surface of the inorganic layer. The initiator may initiate the reaction of the precursor polymer to form the organic polymer. For example, the initiator may include a conventional commercially available thermal initiator, a photoinitiator, or other Lewis acid capable of initiating ring opening polymerization of an epoxy ether. More by way of example, the initiator may include one or more combinations of lithium hexafluorophosphate, lithium tetrafluoroborate, tin difluoride, trifluoroacetic acid, boron trifluoride, aluminum triflate, magnesium triflate, tin triflate, bismuth triflate, azobisisobutyronitrile, azobisisoheptonitrile, dimethyl azobisisobutyrate, benzoyl peroxide, t-butyl benzoyl peroxide, benzophenone, 2-hydroxy-2-methyl-1-phenylketone, 1-hydroxy-cyclohexyl-1-phenylketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholino-1-propanone, benzoin dimethyl ether, ethyl 4- (N, N-dimethylamino) benzoate, isopropylthioxanthone, 4-chlorobenzophenone, methyl o-benzoyl benzoate, 4-methylbenzophenone, 4-phenylbenzophenone, 4-methyldimethanone. Preferably, the precursor polymer may account for 90wt% to 98wt% and the lithium salt may account for 2wt% to 10wt% based on the total weight of the precursor polymer solution. Preferably, the initiator may comprise 0.4wt% to 10wt% based on the total weight of the precursor polymer. Preferably, the precursor is an oligomer, such as polyethylene glycol diglycidyl ether. Still more preferably, the precursor is a monomer, such as 1, 3-dioxolane or vinylene carbonate.
Specifically, under the condition that the subsequently obtained organic solid electrolyte further comprises lithium salt and plasticizer, the lithium salt, the plasticizer and the precursor can be mixed into a precursor solution, and then the precursor solution is dripped into the inorganic layer and coated or the inorganic layer is soaked into the precursor solution, so that the precursor solution is filled in the internal pores of the inorganic layer and distributed on the surface. Preferably, the precursor polymer may account for 45wt% to 53wt%, the lithium salt may account for 2wt% to 10wt%, and the plasticizer may account for 35wt% to 45wt%, based on the total weight of the precursor polymer solution. Preferably, the precursor is a monomer, such as 1, 3-dioxolane or vinylene carbonate. Still more preferably, the precursor is an oligomer, such as polyethylene glycol diglycidyl ether.
Specifically, under the condition that the subsequently obtained organic solid electrolyte further comprises lithium salt, plasticizer and initiator, the lithium salt, plasticizer, initiator and precursor can be mixed into precursor solution, and then the precursor solution is dripped into the inorganic layer and coated or the inorganic layer is soaked into the precursor solution, so that the precursor solution is filled in the internal pores of the inorganic layer and distributed on the surface. The initiator may initiate the reaction of the precursor polymer to form the organic polymer. For example, the initiator may include a conventional commercially available thermal initiator, a photoinitiator, or other Lewis acid capable of initiating ring opening polymerization of an epoxy ether. More by way of example, the initiator may include one or more combinations of lithium hexafluorophosphate, lithium tetrafluoroborate, tin difluoride, trifluoroacetic acid, boron trifluoride, aluminum triflate, magnesium triflate, tin triflate, bismuth triflate, azobisisobutyronitrile, azobisisoheptonitrile, dimethyl azobisisobutyrate, benzoyl peroxide, t-butyl benzoyl peroxide, benzophenone, 2-hydroxy-2-methyl-1-phenylketone, 1-hydroxy-cyclohexyl-1-phenylketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholino-1-propanone, benzoin dimethyl ether, ethyl 4- (N, N-dimethylamino) benzoate, isopropylthioxanthone, 4-chlorobenzophenone, methyl o-benzoyl benzoate, 4-methylbenzophenone, 4-phenylbenzophenone, 4-methyldimethanone. Preferably, the precursor polymer may account for 45wt% to 53wt%, the lithium salt may account for 2wt% to 10wt%, and the plasticizer may account for 35wt% to 45wt%, based on the total weight of the precursor polymer solution. Preferably, the initiator may comprise 0.4wt% to 10wt% based on the total weight of the precursor polymer. Preferably, the precursor is a monomer, such as 1, 3-dioxolane or vinylene carbonate. Still more preferably, the precursor is an oligomer, such as polyethylene glycol diglycidyl ether.
Finally, the precursor is polymerized in situ in the internal pores of the inorganic layer and on the surface of the inorganic layer to form an organic polymer, thereby obtaining an organic solid electrolyte, which is filled in the internal pores of the inorganic layer and distributed on the surface of the inorganic layer and includes the organic polymer.
Specifically, in-situ polymerization may be performed using room temperature standing, heat or light irradiation. In general, the method and conditions for in situ polymerization may be determined depending on the type of the precursor. For example, the heating temperature is 25℃to 80 ℃.
In addition, an embodiment of the present invention provides a solid-state lithium battery, which includes a positive electrode, a negative electrode, and a solid-state electrolyte, wherein the solid-state electrolyte is the solid-state electrolyte composite film.
The main improvement of the provided solid-state lithium battery is that a new solid-state electrolyte is adopted, and the composition of the positive electrode and the negative electrode and the arrangement mode (connection mode) of the positive electrode, the negative electrode and the solid-state electrolyte can be the same as those in the prior art, and the present invention is not repeated herein.
Example 1
Li is selectedOH·H 2 O is used as a lithium source, la (OH) 3 ZrO as a lanthanum source 2 As a zirconium source, al 2 O 3 As an aluminum source. Respectively weighing LiOH H according to stoichiometric ratio (10% -15% of excess lithium source) 2 O、La(OH) 3 、ZrO 2 、Al 2 O 3 . The four raw materials are moved into a zirconia ball milling tank, zirconia balls with the diameter of 10 mm (the weight ratio of the balls to the materials is 10:1) are added, the rotating speed is set to 400rpm/min, and the ball milling is carried out for 10 hours. Transferring the mixed mixture powder into a magnesium oxide crucible, placing the magnesium oxide crucible into a box-type muffle furnace for calcination, wherein the calcination temperature is 950 ℃, and preserving heat for 12 hours. And after natural cooling, obtaining calcined product powder. Ball milling the calcined product powder under the following conditions: the medium is isopropanol, the diameter of zirconia grinding balls is 3 mm (the weight ratio of ball materials is 10:1), the rotating speed is 400rpm/min, the ball milling time is 24 hours, then the powder is dried at 50 ℃ for 6 hours, and the obtained powder is ground by a mortar and sieved to obtain Al-doped LLZO powder (Al-LLZO).
0.3 g of dispersing agent with the solid content of 45% is added into 100 g of deionized water to be fully stirred and dissolved, 96 g of Al-LLZO powder is added, and the mixture is stirred at a high speed, so as to form LLZO dispersion liquid. Then 17 g of binder with 30% solid content is added, stirred uniformly, and finally a small amount of surface wetting agent is added, thus forming the solid electrolyte slurry.
A wet porous base film with the thickness of 9 mu m is selected, LLZO solid electrolyte slurry is coated on one surface of the porous base film, the coating thickness is 3 mu m, and then the film is dried through an oven, so that the film coated with the LLZO layer is obtained.
After 5ml of 1, 3-dioxolane (about 5.3 g) and 5ml of ethylene glycol dimethyl ether (about 4.3325 g) were uniformly mixed, 0.72g of lithium bistrifluoro-methanesulfonimide was added thereto and dissolved with stirring, and then 0.076g of lithium hexafluorophosphate was weighed and rapidly dissolved in the above solution to prepare a polymer electrolyte precursor solution.
And (3) dripping the precursor solution into the membrane coated with the LLZO layer, fully wetting the membrane, penetrating into the internal pores of the LLZO layer, uniformly distributing the membrane on one surface of the LLZO layer, and standing for 24 hours to fully polymerize the precursor solution, thereby obtaining the composite membrane.
Example 2
Al-doped LLZO powder (Al-LLZO) and solid electrolyte slurry preparation procedure were as in example 1.
A wet porous base film with the thickness of 9 mu m is selected, LLZO solid electrolyte slurry is coated on one surface of the porous base film, the coating thickness is 3 mu m, and then the film is dried through an oven, so that the film coated with the LLZO layer is obtained.
After weighing 10g of polyethylene glycol diglycidyl ether, 0.72g of lithium bistrifluoro methanesulfonimide was added, 0.076g of lithium hexafluorophosphate was slowly added, and the mixture was stirred and dissolved to prepare a polymer electrolyte precursor solution.
And (3) dripping the precursor solution into the membrane coated with the LLZO layer to fully wet the membrane, penetrating into the internal pores of the LLZO layer and uniformly distributing the membrane on one surface of the LLZO layer, and standing for 24 hours to enable the precursor solution to perform polymerization reaction, thus obtaining the composite membrane.
Example 3
Al-doped LLZO powder (Al-LLZO) and solid electrolyte slurry preparation procedure were as in example 1.
A wet porous base film with the thickness of 9 mu m is selected, LLZO solid electrolyte slurry is coated on the two side surfaces of the porous base film, the coating thickness is 1.5 mu m respectively, and then the film is dried through an oven, so that the film with the LLZO layers coated on the two sides is obtained.
The prepolymer solution was as in example 1.
And (3) dripping the precursor solution into the membrane coated with the LLZO layers on both sides to fully wet the membrane, penetrating into the internal pores of the LLZO layers and uniformly distributing the membrane on one surface of the LLZO layers, standing the membrane for 24 hours at room temperature, and polymerizing the precursor solution to obtain the composite membrane.
Example 4
Al-doped LLZO powder (Al-LLZO) was prepared as in example 1.
0.3 g of dispersing agent with the solid content of 45% is added into 100 g of deionized water to be fully stirred and dissolved, 56 g of Al-LLZO powder is added, and the mixture is stirred at a high speed, thus forming LLZO dispersion liquid. Then, 10g of binder with 30% of solid content is added, stirred uniformly, and finally a small amount of surface wetting agent is added, thus forming the solid electrolyte slurry.
A wet porous base film with the thickness of 9 mu m is selected, LLZO solid electrolyte slurry is coated on one surface of the porous base film, the coating thickness is 3 mu m, and then the film is dried through an oven, so that the film coated with the LLZO layer is obtained.
The polymer electrolyte precursor solution formulation procedure was as in example 1.
And (3) dripping the precursor solution into the membrane coated with the LLZO layer, fully wetting the membrane, penetrating into the internal pores of the LLZO layer, uniformly distributing the membrane on one surface of the LLZO layer, and standing for 24 hours to fully polymerize the precursor solution, thereby obtaining the composite membrane.
Example 5
Li is mixed with 3 PO 4 、Al 2 O 3 (200-300 mesh) TiO 2 (40 Nm) and (NH) 4 ) 2 HPO 4 Is mixed in stoichiometric proportions (Li 3 PO 4 Excess 20 mol%). Ball milling the mixture, zirconia balls and ethanol in a ball mill for 12 hours, wherein the mass ratio of the zirconia balls to the mixture to the ethanol is 3:1:0.6, the rotation speed of the planetary ball mill is 300rpm/min. The mixed slurry was then heated in an oven at 70 ℃ until the ethanol was completely evaporated. The evaporated powder was fully ground and calcined in a muffle furnace at 900 c for 10 hours at a heating rate of 3 c/min. Grinding the sintered powder, ball milling for 12 hours again according to the proportion, evaporating ethanol at 70 ℃ until the ethanol is completely dried, fully grinding and sieving to obtain LATP powder.
After adding 0.5 g of a dispersant having a solid content of 37% to 100 g of deionized water and sufficiently stirring and dissolving, 85 g of the above-mentioned LATP powder was added and stirred at a high speed to obtain a LATP dispersion. Then, 8.5 g of binder with 45% solid content is added and stirred uniformly, thus forming the solid electrolyte slurry.
A wet porous base film with the thickness of 9 mu m is selected, solid electrolyte slurry is coated on one surface of the porous base film, the coating thickness is 3 mu m, and then the film is dried through an oven, so that the film coated with the LATP layer is obtained.
0.72g of LiTFSI was dissolved in 5ml of vinylene carbonate (VC, about 6.8 g) with stirring, and then 0.033g of Azobisisobutyronitrile (AIBN) was added thereto with stirring to obtain a precursor solution.
And (3) dropwise adding the precursor solution to one surface of the LATP layer, and heating at 60 ℃ for 5 hours to enable the precursor solution to undergo polymerization reaction, thus obtaining the composite diaphragm.
Example 6
LATP powder and solid electrolyte slurry were prepared as in example 5.
A wet porous base film with the thickness of 9 mu m is selected, solid electrolyte slurry is coated on the two side surfaces of the porous base film, the coating thickness is 1.5 mu m respectively, and then the film is dried through an oven, so that the film with the LATP layers coated on the two sides is obtained.
The prepolymer solution was as in example 5.
And (3) dropwise adding the precursor solution to the surface of the double-sided LATP layer, and heating at 60 ℃ for 5 hours to enable the precursor solution to undergo polymerization reaction, thus obtaining the composite membrane.
Example 7
0.11 g of dispersing agent with the solid content of 45% is added into 100 g of deionized water to be fully stirred and dissolved, 80 g of alumina powder is added, and the mixture is stirred at a high speed, thus forming LLZO dispersion liquid. Then, 14.4 g of binder with 42% of solid content is added and stirred uniformly to obtain alumina slurry.
Then, a wet porous base film with a thickness of 9 μm was selected, alumina slurry was applied to one surface of the porous base film to a thickness of 3 μm, and the film was dried by an oven to obtain a film coated with an alumina layer.
The prepolymer solution was formulated as in example 1.
And (3) dropwise adding the precursor solution to one surface of an alumina layer of the membrane, standing at room temperature for 24 hours, and carrying out polymerization reaction on the precursor solution to obtain the composite membrane.
Comparative example 1
Al-doped LLZO powder (Al-LLZO) and solid electrolyte slurry preparation procedure were as in example 1.
A wet porous base film with the thickness of 9 mu m is selected, LLZO solid electrolyte slurry is coated on one surface of the porous base film, the coating thickness is 3 mu m, and then the film is dried through an oven, so that the film coated with the LLZO layer is obtained.
Comparative example 2
LATP powder and solid electrolyte slurry were prepared as in example 5.
A wet porous base film with the thickness of 9 mu m is selected, solid electrolyte slurry is coated on one surface of the porous base film, the coating thickness is 3 mu m, and then the film is dried through an oven, so that the film coated with the LATP layer is obtained.
Comparative example 3
The alumina slurry was prepared as in example 7.
Then, a wet porous base film with a thickness of 9 μm was selected, alumina slurry was applied to one surface of the porous base film to a thickness of 3 μm, and the film was dried by an oven to obtain a film coated with an alumina layer.
Performance characterization analysis
Coating porosity characterization: and (3) intercepting the cross section of the sample, and acquiring the characteristic information of the microstructure of the interface by adopting a scanning electron microscope photographing mode. The inorganic matter ratio of the organic/inorganic coating is estimated by software identification and fitting of the contrast difference of inorganic/organic bright and dark backgrounds in the organic/inorganic coating of the cross section, so that the porosity of the coating is deduced. As shown in fig. 4 and 5, the cross sections of the films of examples 1 and 4 were shown by photographing with a scanning electron microscope, respectively, the inorganic electrolyte layer was formed on the base film except for the base film, and the organic polymer was distributed in the internal pores of the inorganic electrolyte layer and on the inorganic electrolyte layer.
Ion conductivity: assembling a diaphragm sample to be tested into a 2025 button cell, clamping the diaphragm between two stainless steel sheets, and dripping a proper amount of electrolyte (LiPF with the mass molar concentration of 1M) 6 The membrane was fully wetted by dissolution in EC/EMC/dmc=1:1:1 (vol%)) to form an ion-blocking cell. Testing the cross-linked impedance spectrum by adopting an electrochemical workstation, fitting an impedance value according to a spectrogram result, and calculating according to a formula sigma=L/(R×S) to obtain the ionic conductance of the sampleThe rate. Where L is the thickness of the sample, S is the sheet area of the sample, and R is the impedance value.
Stability characterization: the diaphragm characterizes the lithium deposition stability by adopting the cycle short-circuit time of the Li-Cu half battery, so that the diaphragm can regulate and control the lithium deposition and inhibit the lithium dendrite. Specifically, a to-be-measured diaphragm sample is assembled into a button cell, a diaphragm is clamped between a lithium sheet and a copper foil, a single-sided coating diaphragm is coated to face the copper foil, and a proper amount of electrolyte (1M LiTFSI is dissolved in DOL/DME=1:1 (vol%) and 1wt% LiNO) is added dropwise 3 ) The membrane is fully infiltrated. The charge-discharge cycling stability of the LAND battery is tested by adopting a LAND battery charge-discharge instrument, and the constant-current charge-discharge current density is set to be 0.25mA/cm 2 The time was 30 minutes and the charge cut-off voltage was 1V, until the time when the charge voltage was always below 0.05V was noted as the battery lithium dendrite short time t. As shown in fig. 6 (fig. 7 is a close-up view of the end-cycle short circuit of the battery in fig. 6) and 8, which are graphs of the charge-discharge cycle voltage and current at normal temperature for different times of the Li-Cu half-cell with the diaphragm as the diaphragm in comparative example 3 and example 1, respectively, it is known that the Li-Cu half-cell assembled with the diaphragm in example 1 is subjected to the charge-discharge cycle for a long period of time>3400 times) can still provide stable electrical performance, no diaphragm short circuit condition occurs, and the cycling stability is far better than that of comparative example 3<183 times), namely, the separator provided by the invention has excellent dendrite resistance and lithium deposition regulation and control capability and better stability to an electrode, thereby having great potential in improving the long-term cycle performance and the safety of a battery.
The above test results are set forth in table 1 below:
the above description of the common general knowledge will not be described in detail, as will be appreciated by those skilled in the art.
The foregoing description of the embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention. The technical scope of the present invention is not limited to the description, but must be determined according to the scope of claims.

Claims (13)

1. An inorganic/organic composite separator characterized by: comprising the following steps:
a base film;
an inorganic layer; and
An organic solid electrolyte;
the inorganic layer is formed on the base film and has internal pores, the organic solid electrolyte is filled in the internal pores of the inorganic layer and distributed on the surface of the inorganic layer, and the organic solid electrolyte comprises an organic polymer which is formed by in-situ polymerization reaction in the internal pores of the inorganic layer and on the surface of the inorganic layer;
wherein the precursor is a unit of the organic polymer and comprises a cyclic ether compound comprising 1, 3-dioxolane;
wherein the inorganic layer comprises an inorganic solid state electrolyte comprising lithium lanthanum zirconium oxide and an inorganic ceramic comprising aluminum oxide.
2. The inorganic/organic composite separator according to claim 1, wherein:
the base film is a PE base film or a PP base film; and/or
The internal porosity of the inorganic layer is less than 30%.
3. The inorganic/organic composite separator according to claim 1, wherein:
the organic solid electrolyte further comprises a lithium salt; or (b)
The organic solid electrolyte further includes a lithium salt and a plasticizer.
4. An inorganic/organic composite separator according to claim 3, wherein:
the lithium salt comprises one or a combination of a plurality of lithium hexafluorophosphate, lithium dioxalate borate, lithium bistrifluoro methanesulfonimide, lithium bistrifluoro sulfimide, lithium difluorooxalate borate and lithium tetrafluoroborate;
the plasticizer comprises one or more of propylene carbonate, ethylene carbonate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, fluoroethylene carbonate, bisfluoroethylene carbonate, vinyl chloride, 1, 3-dioxolane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, tetraethylene glycol dimethyl ether, 1, 3-propane sultone and succinonitrile.
5. A preparation method of an inorganic/organic composite diaphragm is characterized in that: comprising the following steps:
providing a base film;
forming an inorganic layer on the base film, the inorganic layer having internal pores;
filling a precursor in the internal pores of the inorganic layer and distributing the precursor on the surface of the inorganic layer; and
Polymerizing the precursor in situ in the internal pores of the inorganic layer and on the surface of the inorganic layer to form an organic polymer, thereby obtaining an organic solid electrolyte, which is filled in the internal pores of the inorganic layer and distributed on the surface of the inorganic layer and comprises the organic polymer;
wherein the precursor is a unit of the organic polymer and comprises a cyclic ether compound comprising 1, 3-dioxolane;
wherein the inorganic layer comprises an inorganic solid state electrolyte comprising lithium lanthanum zirconium oxide and an inorganic ceramic comprising aluminum oxide.
6. The method for producing an inorganic/organic composite separator according to claim 5, wherein:
the in-situ polymerization is carried out by standing at room temperature, heating or illumination.
7. The method for producing an inorganic/organic composite separator according to claim 5, wherein:
the step of forming the inorganic layer includes:
and coating inorganic slurry on the base film, and drying to form an inorganic layer.
8. The method for producing an inorganic/organic composite separator according to claim 7, wherein:
the inorganic slurry comprises inorganic solid electrolyte, inorganic ceramic, solvent and binder; or (b)
The inorganic slurry comprises an inorganic solid electrolyte, inorganic ceramics, a dispersing agent, a solvent and a binder.
9. The method for producing an inorganic/organic composite separator according to claim 8, wherein:
the weight ratio between the combination of the inorganic solid electrolyte and the inorganic ceramic and the binder is 3:1 to 25:1.
10. the method for producing an inorganic/organic composite separator according to claim 8, wherein:
under the condition that the inorganic slurry comprises a combination of inorganic solid electrolyte and inorganic ceramic, a solvent and a binder, the solvent accounts for 40-65wt% of the total weight of the inorganic slurry, the combination of the inorganic solid electrolyte and the inorganic ceramic accounts for 30-50wt% of the total weight of the inorganic slurry, and the binder accounts for 2-10wt%;
under the condition that the inorganic slurry comprises a combination of inorganic solid electrolyte and inorganic ceramic, a dispersing agent, a solvent and a binder, the total weight of the inorganic slurry is taken as a basis, the solvent accounts for 40-65wt%, the combination of the inorganic solid electrolyte and the inorganic ceramic accounts for 30-50wt%, the dispersing agent accounts for 0.05-0.3wt%, and the binder accounts for 2-10wt%.
11. The method for producing an inorganic/organic composite separator according to claim 5, wherein:
the step of filling the precursor polymer comprises:
a precursor solution is dripped on the inorganic layer and coated or the inorganic layer is soaked in the precursor solution, so that the precursor solution is filled in the internal pores of the inorganic layer and distributed on the surface of the inorganic layer.
12. The method for producing an inorganic/organic composite separator according to claim 11, wherein:
the precursor solution comprises lithium salt and precursor;
the precursor solution comprises lithium salt, precursor and initiator;
the precursor solution comprises lithium salt, plasticizer and precursor; or (b)
The precursor solution comprises lithium salt, plasticizer, precursor and initiator.
13. The method for producing an inorganic/organic composite separator according to claim 12, wherein:
under the condition that the precursor solution comprises lithium salt and precursor, the precursor accounts for 90-98 wt% based on the total weight of the precursor solution, and the lithium salt accounts for 2-10 wt%;
under the condition that the precursor solution comprises lithium salt, precursor and initiator, the precursor accounts for 90-98 wt% based on the total weight of the precursor solution, the lithium salt accounts for 2-10 wt% based on the total weight of the precursor solution, and the initiator accounts for 0.4-10 wt% based on the total weight of the precursor solution;
under the condition that the precursor solution comprises lithium salt, plasticizer and precursor polymer, the precursor polymer accounts for 45-53 wt%, the lithium salt accounts for 2-10 wt% and the plasticizer accounts for 35-45 wt% based on the total weight of the precursor polymer solution;
under the condition that the precursor solution comprises lithium salt, plasticizer, precursor and initiator, the precursor accounts for 45-53 wt% of the total weight of the precursor solution, the lithium salt accounts for 2-10 wt%, the plasticizer accounts for 35-45 wt%, and the initiator accounts for 0.4-10 wt% of the total weight of the precursor solution.
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