CN112909332A - High-flexibility sulfide composite solid electrolyte and preparation method thereof - Google Patents

High-flexibility sulfide composite solid electrolyte and preparation method thereof Download PDF

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CN112909332A
CN112909332A CN201911228640.7A CN201911228640A CN112909332A CN 112909332 A CN112909332 A CN 112909332A CN 201911228640 A CN201911228640 A CN 201911228640A CN 112909332 A CN112909332 A CN 112909332A
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sulfide
electrolyte
solid electrolyte
composite solid
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姚霞银
徐芳林
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Ningbo Institute of Material Technology and Engineering of CAS
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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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
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    • 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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Abstract

The invention provides a sulfide composite solid electrolyte, a preparation method and an application thereof, wherein the preparation method comprises the following steps: a) dispersing sulfide electrolyte in an organic solvent to obtain sulfide electrolyte suspension; b) and compounding the sulfide electrolyte suspension with a polymer three-dimensional framework, and performing pressurization and densification to obtain the sulfide composite solid electrolyte. Compared with the prior art, the sulfide composite solid electrolyte with high ionic conductivity, controllable thickness and good flexibility is obtained by using the polymer three-dimensional skeleton with the through holes as a carrier and the compounded sulfide electrolyte to form an interconnected electrolyte network structure in the polymer three-dimensional skeleton, so that the defects of high thickness and easiness in cracking of the traditional sulfide solid electrolyte are overcome, the sulfide composite solid electrolyte can be used for soft package battery products, and the preparation method is simple and is easy for industrial production.

Description

High-flexibility sulfide composite solid electrolyte and preparation method thereof
Technical Field
The invention belongs to the field of energy storage, and particularly relates to a high-flexibility sulfide composite solid electrolyte and a preparation method thereof.
Background
The application of the energy storage technology can enable the clean energy with intermittence and strong volatility to become adjustable and controllable, and the energy storage technology occupies an important position in a clean energy power grid. Energy storage technologies mainly include chemical batteries and super capacitors, and among them, lithium ion batteries using organic liquids as electrolytes have been widely used in the production and life of people due to their excellent performance. However, organic electrolytes are prone to leakage and flammable, and present a safety challenge. In recent years, lithium metal batteries are expected to be applied to high-energy density batteries gradually, but the instability of lithium metal and organic electrolyte and the formation of lithium dendrite limit the improvement of the energy density and safety performance of the batteries.
The all-solid-state battery adopts the solid electrolyte without combustibility, has good comprehensive mechanical property, and can inhibit the formation of lithium dendrite, thereby remarkably improving the safety of the battery. In addition, the solid electrolyte has better stability with lithium metal than the organic electrolyte. The solid electrolyte may be mainly classified into an oxide electrolyte, a sulfide electrolyte, and a polymer electrolyte; sulfide electrolytes are considered to be one of the most promising solid electrolytes due to their high ionic conductivity and moderate plasticity.
However, in the application of the sulfide electrolyte to the all-solid-state battery, the following problems still exist: 1) the sulfide electrolyte sheet is thick (0.5-1 mm) and the density of the sulfide electrolyte sheet is 2-3 times that of the organic electrolyte, so that the advantage of high energy density of the battery is difficult to embody; 2) the sulfide electrolyte sheet is brittle and has poor flexibility, is easy to crack under stress and is difficult to apply to a soft package battery product; 3) the preparation method of the sulfide electrolyte sheet is not matched with the existing battery manufacturing technology, and industrial manufacturing is difficult to carry out.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide a high-flexibility sulfide composite solid electrolyte and a preparation method thereof, and the sulfide composite solid electrolyte prepared by the method has a thin thickness, good flexibility and high ionic conductivity.
The invention provides a sulfide composite solid electrolyte which is formed by a polymer three-dimensional framework and a sulfide electrolyte.
Preferably, the thickness of the sulfide composite solid electrolyte is 1-500 mu m, and the room-temperature conductivity is 10-6～10- 1S/cm。
The invention also provides a preparation method of the sulfide composite solid electrolyte, which comprises the following steps:
a) dispersing sulfide electrolyte in an organic solvent to obtain sulfide electrolyte suspension;
b) and compounding the sulfide electrolyte suspension with a polymer three-dimensional framework, and performing pressurization and densification to obtain the sulfide composite solid electrolyte.
Preferably, the sulfide electrolyte is selected from one or more of a sulfide electrolyte represented by formula (I), a sulfide electrolyte represented by formula (II), a modified product of a sulfide electrolyte represented by formula (I), and a modified product of a sulfide electrolyte represented by formula (II);
the preparation method of the sulfide electrolyte modified substance shown in the formula (I) and the formula (II) is preferably selected from one or more of anion and cation substitution, doping or vacancy regulation;
xLiaB·yCcDd·zP2S5formula I;
in the formula I, x is more than or equal to 0 and less than 100, y is more than or equal to 0 and less than 100, z is more than or equal to 0 and less than 100, a is 1 or 2, C is 1 or 2, D is 1, 2 or 5, B is selected from S, Cl, Br or I, C is selected from Li, Si, Ge, P, Sn or Sb, and D is selected from Cl, Br, I, O, S or Se;
xNapEe·yMmNn·zJjQquV formula II;
in formula II, x is more than or equal to 0 and less than 100, y is more than or equal to 0 and less than 100, z is more than or equal to 0 and less than 100, u is more than or equal to 0 and less than 100, P is 1 or 2, E is 0, 1, 2 or 5, M is 1 or 2, N is 0, 1, 2 or 5, J is 1 or 2, Q is 0, 1, 2 or 5, E is selected from S, Cl, I or Br, M is selected from P, Sb, Se, Ge, Si or Sn, N is selected from P, Sb, Se, Si or Sn, J is selected from P, Sb, Se, Ge, Si or Sn, and V is selected from S or P; and at least one of E and V is S;
the organic solvent is selected from one or more of acetonitrile, N-dimethylformamide, tetrahydrofuran, N-methylpyrrolidone, N-methylformamide, anisole, chlorobenzene, o-dichlorobenzene, dimethyl sulfoxide, dichloromethane, trichloromethane, toluene, xylene, N-heptane, N-hexane, cyclohexane, ethyl acetate, ethyl propionate, butyl butyrate, dimethyl carbonate, ethanol, methanol, diethylene glycol dimethyl ether and cyclohexanone;
the solid content in the sulfide electrolyte suspension is 0.005 wt% -70 wt%.
Preferably, the polymer three-dimensional skeleton is made of a polymer by one or more of a breathing pattern method, a self-assembly method, a foaming method, a phase separation method, a reverse phase method, an etching method, a sintering method, a mechanical stretching method, a printing method, an emulsion template method and a 3D printing method; the polymer is selected from one or more of polyarylsulfone series, polyethersulfone series, polymethacrylate series, polyacrylonitrile series, cellulose series, polytetrafluoroethylene series, polyvinylidene fluoride series, polystyrene series, polycarbonate series, polyvinyl chloride series, polyamide series, polyimide series, polyurethane series, ethylene-vinyl acetate copolymer, polyethylene, polypropylene, polybutadiene, polyvinyl alcohol, polydimethylsiloxane and polylactic acid series.
Preferably, the three-dimensional skeleton of the polymer has a through hole structure inside; the thickness of the three-dimensional skeleton of the polymer is 0.5-500 mu m; the average pore diameter is 0.05-100 μm; the mass of the sulfide electrolyte is 5-99.9% of that of the sulfide composite solid electrolyte.
Preferably, the compounding method in step a) is selected from one or more of wet coating, screen printing, spraying, ink-jet printing, high-pressure pouring, dipping and dripping; the pressure densification is performed by one or more of isostatic pressing, rolling and stamping.
Preferably, after the sulfide electrolyte suspension is compounded with the polymer three-dimensional framework, drying is carried out, and then pressurization densification is carried out, so as to obtain the sulfide composite electrolyte; the drying temperature is 20-200 ℃.
Preferably, the sulfide composite solid electrolyte comprises a single layer or a plurality of sulfide electrolyte layers;
preferably, after the sulfide electrolyte suspension is compounded with the polymer three-dimensional framework, drying is carried out to obtain a composite layer; repeatedly preparing a plurality of composite layers, overlapping the composite layers, and performing pressurization densification to obtain the sulfide composite solid electrolyte;
or compounding the sulfide electrolyte suspension with a polymer three-dimensional skeleton, and performing pressure densification to obtain a sulfide composite electrolyte layer, wherein the sulfide composite solid electrolyte comprises a single-layer sulfide composite electrolyte layer;
or repeating the steps a) and b) to prepare a plurality of sulfide composite electrolyte layers together, and superposing the sulfide composite electrolyte layers and compacting under pressure to obtain the sulfide composite solid electrolyte, wherein the sulfide composite solid electrolyte comprises a plurality of sulfide composite electrolyte layers.
The invention also provides an all-solid-state energy storage device which comprises the sulfide composite solid electrolyte.
The invention provides a preparation method of a sulfide composite solid electrolyte, which comprises the following steps: a) dispersing sulfide electrolyte in an organic solvent to obtain sulfide electrolyte suspension; b) and compounding the sulfide electrolyte suspension with a polymer three-dimensional framework, and performing pressurization and densification to obtain the sulfide composite solid electrolyte. Compared with the prior art, the sulfide composite solid electrolyte with high ionic conductivity, controllable thickness and good flexibility is obtained by using the polymer three-dimensional skeleton with the through holes as a carrier and the compounded sulfide electrolyte to form an interconnected electrolyte network structure in the polymer three-dimensional skeleton, so that the defects of high thickness and easiness in cracking of the traditional sulfide solid electrolyte are overcome, the sulfide composite solid electrolyte can be used for soft package battery products, and the preparation method is simple and is easy for industrial production.
Experiments show that the room temperature conductivity of the sulfide composite solid electrolyte prepared by the invention is 10-6～10-1S/cm, elongation at break can reach 105%.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a preparation method of a sulfide composite solid electrolyte, which comprises the following steps: a) dispersing sulfide electrolyte in an organic solvent to obtain sulfide electrolyte suspension; b) and compounding the sulfide electrolyte suspension with a polymer three-dimensional framework, and performing pressurization and densification to obtain the sulfide composite solid electrolyte.
The sources of all raw materials are not particularly limited in the invention, and the raw materials can be either commercially available or self-made.
In the present invention, the sulfide electrolyte is preferably a sulfide solid electrolyte, and more preferably one or more of a sulfide electrolyte represented by formula (I), a sulfide electrolyte represented by formula (II), a modified product of a sulfide electrolyte represented by formula (I), and a modified product of a sulfide electrolyte represented by formula (II);
the preparation method of the sulfide electrolyte modification substance shown in the formulas (I) and (II) is preferably one or more of anion and cation substitution, doping or vacancy regulation.
xLiaB·yCcDd·zP2S5Formula I;
in the formula I, x is more than or equal to 0 and less than 100, y is more than or equal to 0 and less than 100, z is more than or equal to 0 and less than 100, a is 1 or 2, C is 1 or 2, D is 1, 2 or 5, B is selected from S, Cl, Br or I, C is selected from Li, Si, Ge, P, Sn or Sb, and D is selected from Cl, Br, I, O, S or Se;
xNapEe·yMmNn·zJjQquV formula II;
in formula II, x is more than or equal to 0 and less than 100, y is more than or equal to 0 and less than 100, z is more than or equal to 0 and less than 100, u is more than or equal to 0 and less than 100, P is 1 or 2, E is 0, 1, 2 or 5, M is 1 or 2, N is 0, 1, 2 or 5, J is 1 or 2, Q is 0, 1, 2 or 5, E is selected from S, Cl, I or Br, M is selected from P, Sb, Se, Ge, Si or Sn, N is selected from P, Sb, Se, Si or Sn, J is selected from P, Sb, Se, Ge, Si or Sn, and V is selected from S or P; and at least one of E and V is S.
Further preferred is Li3PS4System, Li2P2S6System, Li7PS6System, Li4P2S6System, Li7P3S11System, Li7P2S8X (X ═ Cl, Br, I) system, Li4SiS4System, Li4SnS4System, Li7Ge3PS12System, Li2GeS3System, Li4GeS4System, Li2ZnGeS4System, Li5GaS4System, Li10GeP2S12System, Li6PS5X (X ═ Cl, Br, I) system, Li11Si2PS12System, Li10SiP2S12System, Li11Sn2PS12System, Li10SnP2S12System, Na3PS4System, Na3SbS4System, Na11Sn2PS12System, Na10SnP2S12One or more of a system sulfide solid electrolyte system and a modified product of the above sulfide system; the modifier of the sulfide system is preferably a sulfide electrolyte system substituted by anions and cations, doped or regulated by vacancies, more preferably Li6-xPS5-xCl1+x(x is not less than 0 and not more than 6) system and Li6+xMxSb1-xS5I (M ═ Si, Ge, Sn) (0 ≦ x ≦ 1) system, Li3+3xP1- xZnxS4-xOx(x is not less than 0 and not more than 1) system, Li9.54Si1.74P1.44S11.7Cl0.3、Li3InCl6System, Li11AlP2S12System, Na3PSe4System, Na11Sn2PSe12System with Na3SbS4-xSex(x is more than or equal to 0 and less than or equal to 4) one or more of systems; the sulfide electrolyte in the present invention; most preferably Li10GeP2S12、Li3PS4、Li7P3S11、Li3.25Ge0.25P0.75S4、Li9.54Si1.74P1.44S11.7Cl0.3、Li6PS5Cl、Li6PS5I、Li11Sn2PS12、Li3PS4I、Li6PS5Cl、Li11Si2PS12With Na3PS4One or more of (a).
The organic solvent is preferably one or more of acetonitrile, N-dimethylformamide, tetrahydrofuran, N-methylpyrrolidone, N-methylformamide, anisole, chlorobenzene, o-dichlorobenzene, dimethyl sulfoxide, dichloromethane, trichloromethane, toluene, xylene, N-heptane, N-hexane, cyclohexane, ethyl acetate, ethyl propionate, butyl butyrate, dimethyl carbonate, ethanol, methanol, diethylene glycol dimethyl ether and cyclohexanone.
Dispersing sulfide electrolyte in an organic solvent to obtain sulfide electrolyte suspension; the dispersing method is preferably one or more of mechanical stirring, ultrasonic dispersing, ball milling and roller milling; when the selected sulfide electrolytes contain various types, different sulfide electrolytes can be separately dispersed in an organic solvent to respectively obtain sulfide electrolyte suspension, or different sulfide electrolytes can be mixed and then dispersed in the organic solvent to obtain sulfide electrolyte suspension; the solid content of the obtained sulfide electrolyte suspension is preferably 0.005 wt% to 70 wt%, more preferably 0.005 wt% to 50 wt%, still more preferably 0.005 wt% to 30 wt%, still more preferably 0.005 wt% to 10 wt%, and most preferably 0.05 wt% to 10 wt%; in some embodiments provided herein, the sulfide electrolyte suspension preferably has a solid content of 0.1 wt%, 1 wt%, 2 wt%, 5 wt%, 10 wt%, 3 wt%, 7 wt%, 0.2 wt%, 0.05 wt%, 4.5 wt%, 7.5 wt%, 1.5 wt%, 2.5 wt%, or 0.5 wt%.
Compounding the sulfide electrolyte suspension with a polymer three-dimensional framework; the polymer three-dimensional skeleton preferably has a pore structure communicated with each other inside; thickness of the three-dimensional skeleton of the polymerPreferably 0.5 to 500 μm, more preferably 1 to 300 μm, and further preferably 1 to 277 μm; in some embodiments provided herein, the thickness of the polymeric three-dimensional skeleton is preferably 15 μm, 10 μm, 45 μm, 7 μm, 1 μm, 47 μm, 11 μm, 277 μm, 5 μm, 202 μm, 68 μm, 111 μm, or 21 μm; the aperture of the three-dimensional skeleton of the polymer is preferably 0.05-100 mu m, more preferably 0.5-100 mu m, still more preferably 0.5-80 mu m, and most preferably 0.2-71 mu m; in some embodiments provided herein, the average pore size of the polymeric three-dimensional framework is preferably 5 μm, 15 μm, 0.5 μm, 0.2 μm, 11 μm, 1 μm, 71 μm, 44 μm, 25 μm, 50 μm, 2 μm, or 9 μm; in the present invention, the polymer three-dimensional skeleton is preferably made of one or more of a polymer breathing pattern method, a self-assembly method, a foaming method, a phase separation method, a reverse phase method, an etching method, a sintering method, a mechanical stretching method, a printing method, an emulsion template method, a 3D printing method; the polymer is preferably one or more of polyarylsulfone series, polyethersulfone series, polymethacrylate series, polyacrylonitrile series, cellulose series, polytetrafluoroethylene series, polyvinylidene fluoride series, polystyrene series, polycarbonate series, polyvinyl chloride series, polyamide series, polyimide series, polyurethane series, ethylene-vinyl acetate copolymer, polyethylene, polypropylene, polybutadiene, polyvinyl alcohol, polydimethylsiloxane and polylactic acid series; m of the polymernPreferably 10000-1000000 g/mol, more preferably 20000-800000 g/mol, still more preferably 30000-500000 g/mol, most preferably 30000-400000 g/mol; the mass of the sulfide electrolyte is preferably 5 to 99.9 percent of that of the sulfide composite solid electrolyte, more preferably 15 to 99 percent, even more preferably 30 to 99 percent, even more preferably 40 to 99 percent, even more preferably 50 to 99 percent, even more preferably 70 to 99 percent, and most preferably 80 to 99 percent; in some embodiments provided herein, the mass of the sulfide electrolyte is 96%, 77%, 82%, 80%, 86%, 87%, 90%, 40%, 92%, 99%, 97%, or 75% of the mass of the sulfide composite solid electrolyte; the compounding method is preferably one or more of wet coating, screen printing, spraying, ink-jet printing, high-pressure pouring, dipping and dripping.
After compounding, drying is preferred; the drying is preferably vacuum drying; the drying temperature is preferably 20 ℃ to 200 ℃, more preferably 40 ℃ to 160 ℃, even more preferably 40 ℃ to 120 ℃, and most preferably 60 ℃ to 120 ℃.
After drying, the densification can be directly carried out by pressurization; or repeating the steps to prepare a composite layer obtained after drying, overlapping a plurality of composite layers, and then performing pressurization densification; the pressure densification is performed by one or more of isostatic pressing, rolling and stamping.
After pressurization and densification, a sulfide composite electrolyte layer is obtained and can be directly used as a sulfide composite solid electrolyte; the steps can also be repeated to prepare a plurality of sulfide composite electrolyte layers, the sulfide composite electrolyte layers are superposed and are compacted by pressurization to obtain the sulfide composite solid electrolyte, namely the sulfide composite solid electrolyte can be composed of one sulfide composite electrolyte layer or a plurality of sulfide composite electrolyte layers, and when the sulfide composite solid electrolyte is a plurality of layers, the sulfide composite electrolyte layers can be the same or different; the number of the multiple layers is preferably 2-5, and more preferably 2-3; the pressure densification is the same as that described above and is not described herein again; the thickness of the sulfide composite solid electrolyte is preferably 1-500 μm, more preferably 1-300 μm, still more preferably 1-200 μm, still more preferably 1-100 μm, still more preferably 1-80 μm, and most preferably 2-50 μm; in some embodiments provided herein, the thickness of the sulfide composite solid electrolyte is preferably 22 μm, 12 μm, 51 μm, 10 μm, 2 μm, 56 μm, 15 μm, 292 μm, 11 μm, 24 μm, 257 μm, 25 μm, 16 μm, 427 μm, or 27 μm.
The sulfide composite solid electrolyte with high ionic conductivity, controllable thickness and good flexibility is obtained by using the polymer three-dimensional skeleton with the through holes as a carrier and the composite sulfide electrolyte to form an interconnected electrolyte network structure in the polymer three-dimensional skeleton, so that the defects of high ionic conductivity, easiness in cracking and the like of the traditional sulfide solid electrolyte are overcome, the preparation method is applicable to soft package battery products, and the preparation method is simple and is easy for industrial production.
The invention also provides a sulfide composite solid electrolyte prepared by the method, which is formed by a polymer three-dimensional framework and a sulfide electrolyte; the three-dimensional skeleton of the polymer and the sulfide electrolyte are the same as those described above, and are not described in detail herein.
The room-temperature conductivity of the sulfide composite solid electrolyte is preferably 10-6～10-1S/cm, more preferably 10-5～5×10-2S/cm。
The invention also provides an all-solid-state energy storage device, which comprises the sulfide composite solid electrolyte; the all-solid-state energy storage device comprises an all-solid-state chemical battery and an all-solid-state super capacitor. The electrode of the present invention is not particularly limited, and is a general electrode material for energy storage devices familiar to those skilled in the art, preferably manganese dioxide, LiCoO2、LiNi0.8Co0.15Al0.05O2、LiNi0.6Co0.2Mn0.2O2、LiNi0.5Mn1.5O4、FeS2、Fe1-xS(0≤x≤0.125)、WS2、Co9S8、NiS、Na3V2(PO4)3Graphite, hard carbon, metallic lithium, metallic sodium, carbon nanotubes and other common electrode materials. The assembly method is not particularly limited, and a corresponding assembly method familiar to those skilled in the art can be adopted according to the type of the specific all-solid-state energy storage device.
In order to further illustrate the present invention, the following will describe in detail a high-flexibility sulfide composite solid electrolyte and a method for preparing the same in accordance with the present invention.
The reagents used in the following examples are all commercially available, and the three-dimensional skeletons of the polymers used in the examples of the present invention all have through-holes therein.
Example 1
Preparation of three-dimensional polyurethane skeleton (average pore diameter 5 μ M, thickness 15 μ M, M) by foamingn100000 g/mol); sulfide electrolyte Li10GeP2S12The powder is uniformly dispersed in normal hexane by a mechanical stirring method to obtain Li with the solid content of 0.1 wt%10GeP2S12N-hexane slurry; then, Li is infused by high pressure10GeP2S12Compounding n-hexane into a three-dimensional polyurethane framework; vacuum drying at 60 deg.C, and pressing Li in three-dimensional skeleton of polyurethane by flat plate static pressure10GeP2S12Densification to obtain a 22 μm thick single layer of Li10GeP2S12The composite solid electrolyte sheet, wherein the sulfide electrolyte accounts for 96% of the mass fraction of the composite solid electrolyte sheet.
At room temperature for the prepared Li10GeP2S12Performing electrochemical impedance spectroscopy test on the composite solid electrolyte sheet and performing mechanical property test according to ASTM D882-: lithium ion conductivity 1.02X 10-2S/cm, elongation at break 76%.
Example 2
Preparing polyvinylidene fluoride three-dimensional skeleton (average aperture 5 μ M, thickness 10 μ M, M) by reverse phase methodn400000 g/mol); sulfide electrolyte Li3PS4The powder is evenly dispersed in toluene by a mechanical stirring and ultrasonic dispersion method to obtain Li with the solid content of 1wt percent3PS4Toluene slurry; then, Li is impregnated by3PS4Compounding toluene into a polyvinylidene fluoride three-dimensional framework; vacuum drying at 100 deg.C, and isostatic pressing to obtain Li in polyvinylidene fluoride three-dimensional skeleton3PS4Densification to obtain a 12 μm thick single layer of Li3PS4The composite solid electrolyte sheet, wherein the sulfide electrolyte accounts for 77% of the mass fraction of the composite solid electrolyte sheet.
At room temperature for the prepared Li3PS4Performing electrochemical impedance spectroscopy test on the composite solid electrolyte sheet and performing mechanical property test according to ASTM D882-2009, wherein in the electrochemical impedance spectroscopy test, stainless steel is used as an electrode to obtain the composite solid electrolyte sheetThe results were: lithium ion conductivity 7.1X 10-4S/cm, elongation at break 92%.
Example 3
Preparation of a three-dimensional Polyamide skeleton by etching (average pore size 15 μ M, thickness 45 μ M, M)n30000 g/mol); sulfide electrolyte Li7P3S11The powder is evenly dispersed in ethyl acetate by a ball milling method to obtain Li with the solid content of 2 weight percent7P3S11Ethyl acetate slurry; then, Li is added dropwise7P3S11Compounding ethyl acetate into a polyamide three-dimensional framework; vacuum drying at 110 deg.C, and rolling to obtain Li in polyamide three-dimensional skeleton7P3S11Densification to obtain 51 μm thick single-layer Li7P3S11The composite solid electrolyte sheet, wherein the sulfide electrolyte accounts for 82% of the mass fraction of the composite solid electrolyte sheet.
At room temperature for the prepared Li7P3S11Performing electrochemical impedance spectroscopy test on the composite solid electrolyte sheet and performing mechanical property test according to ASTM D882-2009, wherein in the electrochemical impedance spectroscopy test, stainless steel is used as an electrode, and the obtained result is as follows: lithium ion conductivity 1.5X 10-3S/cm, elongation at break 44%.
Example 4
The polytetrafluoroethylene three-dimensional skeleton (average aperture 5 μ M, thickness 7 μ M, M) is prepared by a sintering methodn100000 g/mol); sulfide electrolyte Li11Si2PS12The powder is uniformly dispersed in anisole by a roller milling method to obtain Li with the solid content of 5 wt%11Si2PS12An anisole slurry; then, Li is impregnated by11Si2PS12Compounding anisole into a polytetrafluoroethylene three-dimensional framework; vacuum drying at 100 deg.C, and stamping to obtain Li in three-dimensional skeleton of polytetrafluoroethylene11Si2PS12Densification to obtain a 10 μm thick single layer of Li11Si2PS12Composite solid electrolyte sheet in which sulfide is electrically chargedThe mass fraction of the electrolyte in the composite solid electrolyte sheet was 80%.
At room temperature for the prepared Li11Si2PS12Performing electrochemical impedance spectroscopy test on the composite solid electrolyte sheet and performing mechanical property test according to ASTM D882-: lithium ion conductivity 1.1X 10-3S/cm, elongation at break 50%.
Example 5
Preparation of polyethylene three-dimensional skeleton (average pore diameter 0.2 μ M, thickness 1 μ M, M) by mechanical stretchingn400000 g/mol); sulfide electrolyte Li3.25Ge0.25P0.75S4The powder is evenly dispersed in tetrahydrofuran by a mechanical stirring and ultrasonic dispersion method to obtain Li with the solid content of 10wt percent3.25Ge0.25P0.75S4Tetrahydrofuran slurry; then, Li is infused by high pressure3.25Ge0.25P0.75S4The tetrahydrofuran is compounded into the three-dimensional framework of the polyethylene; vacuum drying at 40 deg.C, and pressing Li in polyethylene three-dimensional skeleton by flat plate static pressure method3.25Ge0.25P0.75S4Densification to obtain a 2 μm thick single layer of Li3.25Ge0.25P0.75S4The composite solid electrolyte sheet comprises 86% of sulfide electrolyte by mass.
At room temperature for the prepared Li3.25Ge0.25P0.75S4Performing electrochemical impedance spectroscopy test on the composite solid electrolyte sheet and performing mechanical property test according to ASTM D882-: lithium ion conductivity 9.7X 10-4S/cm, elongation at break 105%.
Example 6
Preparation of a three-dimensional skeleton of polyvinyl alcohol by printing (average pore size 11 μ M, thickness 47 μ M, M)n150000 g/mol); sulfide electrolyte Li9.54Si1.74P1.44S11.7Cl0.3The powder was uniformly dispersed in xylene by roll milling to give Li with a solids content of 3 wt%9.54Si1.74P1.44S11.7Cl0.3Xylene slurry; then, Li is added dropwise9.54Si1.74P1.44S11.7Cl0.3Compounding dimethylbenzene into a polyvinyl alcohol three-dimensional framework; vacuum drying at 120 deg.C, and rolling to obtain Li in three-dimensional skeleton of polyvinyl alcohol9.54Si1.74P1.44S11.7Cl0.3Densification to obtain a 56 μm thick single layer of Li9.54Si1.74P1.44S11.7Cl0.3The composite solid electrolyte sheet comprises a sulfide electrolyte, wherein the sulfide electrolyte accounts for 87% of the mass of the composite solid electrolyte sheet.
At room temperature for the prepared Li9.54Si1.74P1.44S11.7Cl0.3Performing electrochemical impedance spectroscopy test on the composite solid electrolyte sheet and performing mechanical property test according to ASTM D882-: lithium ion conductivity 7.4X 10-3S/cm, elongation at break 96%.
Example 7
Preparation of three-dimensional skeleton of polylactic acid by 3D printing method (average pore size 5 μ M, thickness 11 μ M, M)n200000 g/mol); sulfide electrolyte Li6PS5Cl powder is uniformly dispersed in normal hexane by a mechanical stirring method to obtain Li with the solid content of 7 wt%6PS5Cl/n-hexane slurry; then, Li is infused by high pressure6PS5Cl/n-hexane is compounded into the three-dimensional skeleton of the polylactic acid; vacuum drying at 80 deg.C, and pressing Li in three-dimensional skeleton of polylactic acid by flat plate static pressure method6PS5Cl densification to obtain a 15 μm thick single layer Li6PS5And the Cl composite solid electrolyte sheet, wherein the sulfide electrolyte accounts for 90% of the mass fraction of the composite solid electrolyte sheet.
At room temperature for the prepared Li6PS5Cl composite solidPerforming electrochemical impedance spectroscopy test on the electrolyte sheet and performing mechanical property test according to ASTM D882-: lithium ion conductivity 2.4X 10-3S/cm, elongation at break 55%.
Example 8
The three-dimensional polystyrene skeleton (average pore diameter 1 μ M, thickness 11 μ M, M) is prepared by an emulsion template methodn400000 g/mol); sulfide electrolyte Li6PS5I powder is evenly dispersed in acetonitrile by a ball milling method to obtain Li with solid content of 0.2 wt%6PS5I/acetonitrile sizing agent; then, Li is impregnated by6PS5I/acetonitrile is compounded into a polystyrene three-dimensional framework; vacuum drying at 80 deg.C, and rolling to obtain Li in three-dimensional skeleton6PS5I densification to obtain a 15 μm thick single layer Li6PS5The composite solid electrolyte sheet comprises a composite solid electrolyte sheet, wherein the sulfide electrolyte accounts for 80% of the mass of the composite solid electrolyte sheet.
At room temperature for the prepared Li6PS5I, performing electrochemical impedance spectroscopy test on the composite solid electrolyte sheet and performing mechanical property test according to ASTM D882-2009, wherein in the electrochemical impedance spectroscopy test, stainless steel is used as an electrode, and the obtained result is as follows: lithium ion conductivity 1.6X 10-3S/cm, elongation at break 45%.
Example 9
Preparation of a three-dimensional skeleton of polyvinyl chloride by foaming (average pore size 71 μ M, thickness 277 μ M, M)n100000 g/mol); sulfide electrolyte Li11Sn2PS12The powder was uniformly dispersed in cyclohexane by mechanical stirring to give Li with a solid content of 0.05 wt%11Sn2PS12Cyclohexane slurry; then, Li is impregnated by11Sn2PS12Compounding cyclohexane into a polyvinyl chloride three-dimensional framework; vacuum drying at 100 deg.C, and pressing Li in three-dimensional skeleton of polyvinyl chloride by flat plate static pressure11Sn2PS12Densifying to obtain a powder with a thickness of 292 μmSingle layer of Li11Sn2PS12The composite solid electrolyte sheet, wherein the sulfide electrolyte accounts for 40% of the mass fraction of the composite solid electrolyte sheet.
At room temperature for the prepared Li11Sn2PS12Performing electrochemical impedance spectroscopy test on the composite solid electrolyte sheet and performing mechanical property test according to ASTM D882-: lithium ion conductivity 1.1X 10-6S/cm, elongation at break 44%.
Example 10
The polyether sulfone three-dimensional framework (average pore diameter of 2 mu M, thickness of 5 mu M, M) is prepared by a reverse phase methodn50000 g/mol); sulfide electrolyte Li3PS4I the powder was homogeneously dispersed in methylene chloride by roll milling to give Li in a solids content of 4.5% by weight3PS4I/dichloromethane slurry; then, Li is added dropwise3PS4I/dichloromethane is compounded into a polyether sulfone three-dimensional framework; vacuum drying at 80 deg.C, and stamping to obtain Li in polyethersulfone three-dimensional skeleton3PS4I densification to obtain a 11 μm thick single layer Li3PS4The composite solid electrolyte sheet comprises a composite solid electrolyte sheet, wherein the sulfide electrolyte accounts for 92% of the mass of the composite solid electrolyte sheet.
At room temperature for the prepared Li3PS4I, performing electrochemical impedance spectroscopy test on the composite solid electrolyte sheet and performing mechanical property test according to ASTM D882-2009, wherein in the electrochemical impedance spectroscopy test, stainless steel is used as an electrode, and the obtained result is as follows: lithium ion conductivity 1.0X 10-3S/cm, elongation at break 34%.
Example 11
Preparation of a three-dimensional framework of polyarylsulfone by the respiratory Pattern method (average pore size 5 μ M, thickness 15 μ M, M)n40000 g/mol); sulfide electrolyte Li9.54Si1.74P1.44S11.7Cl0.3The powder was uniformly dispersed in xylene by mechanical stirring to give Li with a solid content of 7.5 wt%9.54Si1.74P1.44S11.7Cl0.3Xylene slurry; then, Li is coated by a wet method9.54Si1.74P1.44S11.7Cl0.3Compounding xylene into a three-dimensional skeleton of polyarylsulfone; vacuum drying at 80 deg.C, and pressing Li in three-dimensional skeleton of polyarylsulfone by flat plate static pressure9.54Si1.74P1.44S11.7Cl0.3Densification to obtain a 24 μm thick single layer of Li9.54Si1.74P1.44S11.7Cl0.3The composite solid electrolyte sheet comprises a sulfide electrolyte accounting for 99% of the mass of the composite solid electrolyte sheet.
At room temperature for the prepared Li9.54Si1.74P1.44S11.7Cl0.3Performing electrochemical impedance spectroscopy test on the composite solid electrolyte sheet and performing mechanical property test according to ASTM D882-: lithium ion conductivity 1.2X 10-2S/cm, elongation at break 44%.
Example 12
Preparation of a polystyrene-polyethylene oxide copolymer three-dimensional skeleton (average pore diameter 44 μ M, thickness 202 μ M, M) by a self-Assembly methodn50000 g/mol); sulfide electrolyte Li9.54Si1.74P1.44S11.7Cl0.3With Li7P3S11The powder is respectively and independently dispersed in dimethylbenzene and methylbenzene by an ultrasonic dispersion method to obtain Li with the solid content of 5 wt%9.54Si1.74P1.44S11.7Cl0.3Xylene with 1.5% by weight of Li7P3S11Toluene slurry; li is prepared by screen printing method9.54Si1.74P1.44S11.7Cl0.3Compounding/dimethylbenzene slurry into a polystyrene-polyoxyethylene copolymer three-dimensional framework, wherein the mass fraction of sulfide electrolyte in the composite solid electrolyte sheet is 40%, and then spraying Li7P3S11Compounding the toluene slurry to the sameIn the three-dimensional framework, the sulfide electrolyte accounts for 97 percent of the mass of the composite solid electrolyte sheet. Vacuum drying at 100 deg.C, and isostatic pressing to remove Li in three-dimensional skeleton of polystyrene-polyoxyethylene copolymer9.54Si1.74P1.44S11.7Cl0.3With Li7P3S11The mixture was densified to obtain a 257 μm-thick sulfide-electric composite solid electrolyte sheet.
At room temperature, performing electrochemical impedance spectroscopy test on the prepared sulfide composite solid electrolyte sheet and performing mechanical property test according to ASTM D882-2009, wherein in the electrochemical impedance spectroscopy test, stainless steel is used as an electrode, and the obtained result is as follows: lithium ion conductivity 2.02X 10-3S/cm, elongation at break 74%.
Example 13
Respectively preparing polyvinylidene fluoride three-dimensional frameworks (average aperture is 2 mu M, thickness is 5 mu M, M) by a phase separation methodn400000g/mol) and a polyimide three-dimensional skeleton (average pore diameter 0.5 μ M, thickness 5 μ M, M)n400000 g/mol); sulfide electrolyte Li10GeP2S12With Li3PS4The powder is respectively and independently dispersed in normal hexane and toluene by a ball milling method to obtain Li with the solid content of 2.5wt percent10GeP2S12N-hexane and Li3PS4Toluene slurry; then, Li is printed by ink-jet printing10GeP2S12Compounding n-hexane slurry into a polyvinylidene fluoride three-dimensional framework, wherein sulfide electrolyte Li10GeP2S12Occupying sulfide electrolyte Li10GeP2S1290% of the total mass of the polyvinylidene fluoride three-dimensional skeleton; by high-pressure pouring Li3PS4Compounding the/toluene slurry into a polyimide three-dimensional framework, wherein the sulfide electrolyte Li3PS4Occupying sulfide electrolyte Li3PS490 percent of the total mass of the polyimide three-dimensional skeleton. Vacuum drying at 80 deg.C, then Li10GeP2S12Polyvinylidene fluoride and Li3PS4Polyimide according toLi3PS4/Li10GeP2S12/Li3PS4Sequentially stacking three layers, and rolling to obtain Li in three-dimensional skeleton10GeP2S12With Li3PS4Densifying to obtain the three-layer sulfide composite solid electrolyte sheet with the thickness of 25 mu m.
At room temperature, performing electrochemical impedance spectroscopy test on the prepared three-layer sulfide composite solid electrolyte sheet and performing mechanical property test according to ASTM D882-: lithium ion conductivity 1.04X 10-3S/cm, elongation at break 70%.
Example 14
Preparation of a three-dimensional polycarbonate skeleton (average pore diameter 2 μ M, thickness 7 μ M, M) by foamingn30000 g/mol); sulfide electrolyte Li3.25Ge0.25P0.75S4With Li6PS5Cl powder is mixed and dispersed in chlorobenzene by a mechanical stirring method to obtain Li with the solid content of 2wt percent3.25Ge0.25P0.75S4/Li6PS5Cl/chlorobenzene mixed slurry; subsequently, Li is screen-printed3.25Ge0.25P0.75S4/Li6PS5And compounding the Cl/chlorobenzene mixed slurry into a polycarbonate three-dimensional framework. Vacuum drying at 100 deg.C, and pressing to obtain Li in three-dimensional skeleton of polycarbonate3.25Ge0.25P0.75S4With Li6PS5And the Cl mixture is densified to obtain a single-layer sulfide composite solid electrolyte sheet with the thickness of 16 mu m, wherein the mass fraction of the sulfide electrolyte in the composite solid electrolyte sheet is 87%.
At room temperature, performing electrochemical impedance spectroscopy test on the prepared single-layer sulfide composite solid electrolyte sheet and performing mechanical property test according to ASTM D882-: lithium ion conductivity of 9.2X 10-4S/cm, elongation at break 40%.
Example 15
Preparation of a three-dimensional Polyamide skeleton by etching (average pore size 25 μ M, thickness 68 μ M, M)n30000g/mol), sintering to prepare a polytetrafluoroethylene three-dimensional skeleton (average pore diameter 50 μ M, thickness 111 μ M, M)n100000 g/mol); sulfide electrolyte Li7P3S11With Li11Si2PS12The powder is respectively and independently dispersed in ethyl acetate and anisole by a ball milling method to obtain Li with solid content of 0.5wt percent7P3S11Ethyl acetate and Li11Si2PS12An anisole slurry; spraying Li7P3S11Compounding ethyl acetate slurry to polyamide three-dimensional skeleton, wherein sulfide electrolyte Li7P3S11Occupying sulfide electrolyte Li7P3S1190% of the total mass of the polyamide three-dimensional framework; impregnating Li11Si2PS12Compounding the/anisole slurry into a polytetrafluoroethylene three-dimensional skeleton, wherein a sulfide electrolyte Li11Si2PS12Occupying sulfide electrolyte Li11Si2PS12Vacuum drying at 80 deg.C in 90% of total mass of three-dimensional skeleton, and respectively preparing double-layer Li by superposition method7P3S11Polyamide and Li11Si2PS12A polytetrafluoroethylene electrolyte layer pre-densified by means of isostatic pressing; then the double-layer Li7P3S11Polyamide and Li11Si2PS12Stacking polytetrafluoroethylene electrolyte layers, and rolling to obtain Li in three-dimensional polymer skeleton7P3S11With Li11Si2PS12The thickness was reduced to 427 μm, and a four-layer sulfide composite solid electrolyte sheet was obtained.
At room temperature, performing electrochemical impedance spectroscopy test on the prepared four-layer sulfide composite solid electrolyte sheet and performing mechanical property test according to ASTM D882-An electrode, the results obtained were: lithium ion conductivity 2.2X 10-3S/cm, elongation at break 37%.
Example 16
Preparing polyvinylidene fluoride three-dimensional skeleton (average aperture 2 μ M, thickness 10 μ M, M) by foaming methodn400000g/mol), a polystyrene-polyoxyethylene copolymer three-dimensional skeleton (average pore diameter 0.5 μ M, thickness 5 μ M, M) was prepared by a self-assembly methodn＝50000g/mol)。
Sulfide electrolyte Li6PS5I and Li11Si2PS12The powder was mixed and dispersed in cyclohexane by mechanical stirring to give Li in a solid content of 0.1 wt%6PS5I/Li11Si2PS12Cyclohexane slurry; by wet coating of Li6PS5I/Li11Si2PS12And compounding the cyclohexane slurry into a polystyrene-polyoxyethylene copolymer three-dimensional framework, wherein the mass fraction of the sulfide electrolyte in the composite solid electrolyte sheet is 96%, vacuum drying at 80 ℃, and pre-densifying by a flat-plate static pressure method to obtain a sulfide electrolyte layer I.
Sulfide electrolyte Li7P3S11With Li9.54Si1.74P1.44S11.7Cl0.3The powder is mixed and dispersed in dimethylbenzene by a roll mill method to obtain Li with the solid content of 2 wt%7P3S11/Li9.54Si1.74P1.44S11.7Cl0.3Xylene slurry; li is prepared by screen printing method7P3S11/Li9.54Si1.74P1.44S11.7Cl0.3Compounding the/xylene slurry into a polyvinylidene fluoride three-dimensional framework, wherein the mass fraction of sulfide electrolyte in the composite solid electrolyte sheet is 96%, vacuum drying at 80 ℃, and pre-densifying by a flat-plate static pressure method to obtain a sulfide electrolyte layer II.
And superposing the prepared sulfide electrolyte layers I and II, and densifying the sulfide electrolyte in the three-dimensional polymer skeleton by a rolling method to obtain the double-layer sulfide composite solid electrolyte sheet with the thickness of 27 microns.
At room temperature, performing electrochemical impedance spectroscopy test on the prepared double-layer sulfide composite solid electrolyte sheet and performing mechanical property test according to ASTM D882-: lithium ion conductivity 1.7X 10-3S/cm, elongation at break 70%.
Example 17
Preparation of three-dimensional polyurethane skeleton (average pore diameter 9 μ M, thickness 21 μ M, M) by foamingn100000 g/mol); sulfide electrolyte Na3PS4The powder was uniformly dispersed in n-hexane by mechanical stirring to obtain Na having a solid content of 0.1 wt%3PS4N-hexane slurry; then, Na is infused by high pressure3PS4Compounding n-hexane into a polyurethane three-dimensional framework, wherein the sulfide electrolyte accounts for 75% of the mass of the composite solid electrolyte sheet; vacuum drying at 60 deg.C, and pressing Na in three-dimensional skeleton of polyurethane by flat plate static pressure3PS4Densifying to obtain 25 μm thick single layer of Na3PS4A composite solid electrolyte sheet.
At room temperature on the prepared Na3PS4Performing electrochemical impedance spectroscopy test on the composite solid electrolyte sheet and performing mechanical property test according to ASTM D882-: lithium ion conductivity 7.1X 10-5S/cm, elongation at break 66%.
Example 18
Assembly of all-solid-state chemical battery
And assembling the positive manganese dioxide, the ultrathin and ultra-flexible sulfide composite solid electrolyte sheet prepared in the example 1 and the negative metal lithium into an all-solid-state lithium primary battery. The test results show that: the open-circuit voltage at room temperature of the assembled all-solid-state lithium primary battery was 3.2V.
And assembling the positive electrode lithium cobaltate, the ultrathin and super-flexible sulfide composite solid electrolyte sheet prepared in example 5 and the negative electrode metal lithium into the all-solid-state lithium secondary battery. The test results show that: the assembled all-solid-state lithium secondary battery has good cycle performance, and the capacity retention rate is 87% after 200 cycles at the rate of 0.1C at room temperature.
Mixing positive electrode Li (Ni)0.8Co0.1Mn0.1)O2And the ultrathin and super-flexible sulfide composite solid electrolyte sheet prepared in the step 7 and negative electrode metal lithium are assembled into the all-solid-state lithium secondary battery. The test results show that: the assembled all-solid-state lithium secondary battery has good cycle performance, and the capacity retention rate is 70% after 400 cycles at the rate of 0.1C at room temperature.
And assembling the positive iron disulfide, the ultrathin and super-flexible sulfide composite solid electrolyte sheet prepared in the example 10 and the negative metal lithium into the all-solid-state lithium secondary battery. The test results show that: the assembled all-solid-state lithium secondary battery has good cycle performance, and the capacity retention rate is 81 percent after 300 cycles at the rate of 0.1C at room temperature.
Assembly of all-solid-state supercapacitor
The electrode graphene and the ultrathin and ultra-flexible sulfide composite solid electrolyte sheet prepared in example 15 were assembled into an all-solid-state supercapacitor. The test results show that: the assembled all-solid-state supercapacitor has good cycle performance, and the capacity retention rate is 78% after 700 cycles at room temperature.
Example 19
Assembly of all-solid-state chemical battery
The interface-modified vanadium sodium phosphate positive electrode, the ultrathin and ultra-flexible sulfide composite solid electrolyte sheet prepared in example 17, and the negative electrode metal sodium were assembled into an all-solid-state sodium secondary battery. The test results show that: the assembled all-solid-state sodium secondary battery has good cycle performance, and the capacity retention rate is 86% after 200 cycles at the rate of 0.05 ℃ at 60 ℃.
And the positive iron disulfide, the ultrathin and ultra-flexible sulfide composite solid electrolyte sheet prepared in example 17, and the negative metal sodium were assembled into an all-solid-state sodium secondary battery. The test results show that: the assembled all-solid-state sodium secondary battery has good cycle performance, and the capacity retention rate is 77% after 300 cycles at the rate of 0.1C at room temperature.
Assembly of all-solid-state supercapacitor
And (3) assembling the electrode carbon nano tube and the ultrathin and super-flexible sulfide composite solid electrolyte sheet prepared by the implementation 17 into an all-solid-state supercapacitor. The test results show that: the assembled all-solid-state supercapacitor has good cycle performance, and the capacity retention rate is 76% after 700 cycles at room temperature.

Claims (10)

1. A sulfide composite solid electrolyte is characterized by being formed by a polymer three-dimensional framework and a sulfide electrolyte.
2. The sulfide composite solid electrolyte according to claim 1, wherein the sulfide composite solid electrolyte has a thickness of 1 to 500 μm and a room-temperature conductivity of 10-6～10-1S/cm。
3. A method for preparing a sulfide composite solid electrolyte, comprising:
a) dispersing sulfide electrolyte in an organic solvent to obtain sulfide electrolyte suspension;
b) and compounding the sulfide electrolyte suspension with a polymer three-dimensional framework, and performing pressurization and densification to obtain the sulfide composite solid electrolyte.
4. The production method according to claim 3, characterized in that the sulfide electrolyte is selected from one or more of a sulfide electrolyte represented by formula (I), a sulfide electrolyte represented by formula (II), a modified product of a sulfide electrolyte represented by formula (I), and a modified product of a sulfide electrolyte represented by formula (II);
the preparation method of the sulfide electrolyte modified substance shown in the formula (I) and the formula (II) is preferably selected from one or more of anion and cation substitution, doping or vacancy regulation;
xLiaB·yCcDd·zP2S5formula I;
in the formula I, x is more than or equal to 0 and less than 100, y is more than or equal to 0 and less than 100, z is more than or equal to 0 and less than 100, a is 1 or 2, C is 1 or 2, D is 1, 2 or 5, B is selected from S, Cl, Br or I, C is selected from Li, Si, Ge, P, Sn or Sb, and D is selected from Cl, Br, I, O, S or Se;
xNapEe·yMmNn·zJjQquV formula II;
in formula II, x is more than or equal to 0 and less than 100, y is more than or equal to 0 and less than 100, z is more than or equal to 0 and less than 100, u is more than or equal to 0 and less than 100, P is 1 or 2, E is 0, 1, 2 or 5, M is 1 or 2, N is 0, 1, 2 or 5, J is 1 or 2, Q is 0, 1, 2 or 5, E is selected from S, Cl, I or Br, M is selected from P, Sb, Se, Ge, Si or Sn, N is selected from P, Sb, Se, Si or Sn, J is selected from P, Sb, Se, Ge, Si or Sn, and V is selected from S or P; and at least one of E and V is S;
the organic solvent is selected from one or more of acetonitrile, N-dimethylformamide, tetrahydrofuran, N-methylpyrrolidone, N-methylformamide, anisole, chlorobenzene, o-dichlorobenzene, dimethyl sulfoxide, dichloromethane, trichloromethane, toluene, xylene, N-heptane, N-hexane, cyclohexane, ethyl acetate, ethyl propionate, butyl butyrate, dimethyl carbonate, ethanol, methanol, diethylene glycol dimethyl ether and cyclohexanone;
the solid content in the sulfide electrolyte suspension is 0.005 wt% -70 wt%.
5. The method according to claim 3, wherein the polymer three-dimensional skeleton is made of a polymer by one or more of a breathing pattern method, a self-assembly method, a foaming method, a phase separation method, a phase inversion method, an etching method, a sintering method, a mechanical stretching method, a printing method, an emulsion template method, and a 3D printing method; the polymer is selected from one or more of polyarylsulfone series, polyethersulfone series, polymethacrylate series, polyacrylonitrile series, cellulose series, polytetrafluoroethylene series, polyvinylidene fluoride series, polystyrene series, polycarbonate series, polyvinyl chloride series, polyamide series, polyimide series, polyurethane series, ethylene-vinyl acetate copolymer, polyethylene, polypropylene, polybutadiene, polyvinyl alcohol, polydimethylsiloxane and polylactic acid series.
6. The production method according to claim 3, wherein the inside of the polymer three-dimensional skeleton has an interpenetrating pore structure; the thickness of the three-dimensional skeleton of the polymer is 0.5-500 mu m; the average pore diameter is 0.05-100 μm; the mass of the sulfide electrolyte is 5-99.9% of that of the sulfide composite solid electrolyte.
7. The preparation method according to claim 3, wherein the compounding method in the step b) is selected from one or more of wet coating, screen printing, spraying, ink-jet printing, high-pressure pouring, dipping and dripping; the pressure densification is performed by one or more of isostatic pressing, rolling and stamping.
8. The preparation method according to claim 3, wherein the sulfide electrolyte suspension is dried and then subjected to pressure densification after being compounded with the polymer three-dimensional skeleton to obtain a sulfide composite electrolyte; the drying temperature is 20-200 ℃.
9. The production method according to claim 3, characterized in that the sulfide composite solid electrolyte comprises a single-layer or multi-layer sulfide electrolyte layer;
preferably, the sulfide electrolyte suspension is compounded with a polymer three-dimensional framework and then dried to obtain an electrolyte layer; repeatedly preparing a plurality of electrolyte layers, overlapping the electrolyte layers, and performing pressurization densification to obtain a sulfide composite solid electrolyte;
or compounding the sulfide electrolyte suspension with a polymer three-dimensional skeleton, and performing pressure densification to obtain a sulfide composite electrolyte layer, wherein the sulfide composite solid electrolyte comprises a single-layer sulfide composite electrolyte layer;
or repeating the steps a) and b) to prepare a plurality of sulfide composite electrolyte layers together, and superposing the sulfide composite electrolyte layers and compacting the layers by pressurization to obtain a sulfide composite solid electrolyte; the sulfide composite solid electrolyte includes a multilayer sulfide composite electrolyte layer.
10. An all-solid-state energy storage device comprising the sulfide composite solid electrolyte according to any one of claims 1 to 2 or the sulfide composite solid electrolyte prepared according to any one of claims 3 to 9.
CN201911228640.7A 2019-12-04 2019-12-04 High-flexibility sulfide composite solid electrolyte and preparation method thereof Pending CN112909332A (en)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016139482A (en) * 2015-01-26 2016-08-04 三星電子株式会社Ｓａｍｓｕｎｇ Ｅｌｅｃｔｒｏｎｉｃｓ Ｃｏ．，Ｌｔｄ． Solid electrolyte sheet and all-solid secondary battery
CN107492681A (en) * 2017-08-09 2017-12-19 上海纳晓能源科技有限公司 Solid electrolyte film and preparation method thereof
CN108878965A (en) * 2018-06-11 2018-11-23 成都新柯力化工科技有限公司 A kind of gel polymer electrolyte preparation method based on 3D printing technique
CN110165291A (en) * 2018-02-11 2019-08-23 中国科学院苏州纳米技术与纳米仿生研究所 Solid electrolyte and the preparation method and application thereof
CN110165290A (en) * 2018-02-11 2019-08-23 中国科学院苏州纳米技术与纳米仿生研究所 Solid-state sodium ion electrolyte, preparation method and application
CN110192302A (en) * 2017-05-15 2019-08-30 株式会社Lg化学 The manufacturing method of all-solid-state battery solid electrolyte film and the solid electrolyte film manufactured by the method

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016139482A (en) * 2015-01-26 2016-08-04 三星電子株式会社Ｓａｍｓｕｎｇ Ｅｌｅｃｔｒｏｎｉｃｓ Ｃｏ．，Ｌｔｄ． Solid electrolyte sheet and all-solid secondary battery
CN110192302A (en) * 2017-05-15 2019-08-30 株式会社Lg化学 The manufacturing method of all-solid-state battery solid electrolyte film and the solid electrolyte film manufactured by the method
CN107492681A (en) * 2017-08-09 2017-12-19 上海纳晓能源科技有限公司 Solid electrolyte film and preparation method thereof
CN110165291A (en) * 2018-02-11 2019-08-23 中国科学院苏州纳米技术与纳米仿生研究所 Solid electrolyte and the preparation method and application thereof
CN110165290A (en) * 2018-02-11 2019-08-23 中国科学院苏州纳米技术与纳米仿生研究所 Solid-state sodium ion electrolyte, preparation method and application
CN108878965A (en) * 2018-06-11 2018-11-23 成都新柯力化工科技有限公司 A kind of gel polymer electrolyte preparation method based on 3D printing technique

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