CN110459803A - Composite electrolyte membrane and its preparation method and application - Google Patents
Composite electrolyte membrane and its preparation method and application Download PDFInfo
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- CN110459803A CN110459803A CN201910770278.XA CN201910770278A CN110459803A CN 110459803 A CN110459803 A CN 110459803A CN 201910770278 A CN201910770278 A CN 201910770278A CN 110459803 A CN110459803 A CN 110459803A
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
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- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
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- 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
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- H01M2200/00—Safety devices for primary or secondary batteries
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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Abstract
The invention discloses a kind of composite electrolyte membrane and its preparation method and application, which includes: porous membrane substrate, and hot melt macromolecule filler particles are filled in the porous membrane substrate；Organic and inorganic electrolyte filled layer, the organic and inorganic electrolyte filled layer is located in at least part on the porous membrane substrate surface, the organic and inorganic electrolyte filled layer includes organic-inorganic electrolyte, and at least part organic and inorganic electrolyte is filled in the porous membrane substrate；Polymer dielectric buffer layer, the polymer dielectric buffer layer are located at least part of the organic and inorganic electrolyte filled layer and are covered in the porous membrane substrate as the face contacted with electrode.The composite electrolyte membrane has many advantages, such as that security performance height, mechanical strength, room-temperature conductivity are high and good with positive and negative electrode interface compatibility.
Description
Technical field
The invention belongs to solid electrolyte technical fields, specifically, the present invention relates to composite electrolyte membrane and its preparations
Methods and applications.
Background technique
Full solid state polymer electrolyte and fast-ionic conductor composite electrolyte can effectively solve conventional liquid electrolyte
Disadvantage improves the security performance of lithium ion battery.There is good compatibility, excellent between high ionic conductivity and electrode
Mechanical performance, wide electrochemical window etc. are the characteristics that Utopian solid polymer electrolyte should have, but common at present
Full solid state polymer electrolyte be difficult to be provided simultaneously with the above characteristic.Such as traditional PEO system lithium ion battery solid electrolyte
The Shortcomings in terms of conductivity at room temperature and mechanical strength improve the conductivity at room temperature of PEO system solid electrolyte
A kind of method be introduce carbonyldioxy solid electrolyte.But the method for introducing carbonyldioxy solid electrolyte is generally copolymerized or mixes
It closing, copolymerization method is easy to change molecule chain flexibility, the locomitivity of strand is reduced to weaken ionic conductivity, and mixing method
There are consistency problems, are easily reduced the mechanical strength and energy density of electrolyte.Based on this, porous membrane support is used in industry
The mode of surface coated electrolyte glue-line has carried out a large amount of experimental study, it is this can be very by the dielectric film of porous carrier
Improvement electrolyte film strength well, flexibility etc., but since the thickness of porous carrier is generally thicker, and hole is mostly non-
Clear opening, aperture are larger, and control is bad to be easy to cause micro-short circuit, and surface coating technique not can guarantee electrolyte and fill out completely
It fills, will appear hollow phenomenon in actual application, cause ionic conduction that can not carry out, battery impedance increases, and can not carry out
It works normally.
Therefore, existing solid electrolyte membrane is further improved.
Summary of the invention
The present invention is directed to solve at least some of the technical problems in related technologies.For this purpose, of the invention
One purpose is to propose a kind of composite electrolyte membrane and its preparation method and application.The composite electrolyte membrane has security performance
The advantages that height, mechanical strength, room-temperature conductivity are high and good with positive and negative electrode interface compatibility.
In one aspect of the invention, the invention proposes a kind of composite electrolyte membranes, according to an embodiment of the invention, should
Composite electrolyte membrane includes:
Porous membrane substrate, the porous membrane substrate is interior to be filled with hot melt macromolecule filler particles；
Organic and inorganic electrolyte filled layer, the organic and inorganic electrolyte filled layer are located at the porous membrane substrate surface
At least part on, the organic and inorganic electrolyte filled layer includes organic-inorganic electrolyte, and at least part institute
Organic and inorganic electrolyte is stated to be filled in the porous membrane substrate；
Polymer dielectric buffer layer, the polymer dielectric buffer layer are located at the organic and inorganic electrolyte filling
It is covered in the porous membrane substrate at least part of layer and as the face contacted with electrode.
Composite electrolyte membrane according to an embodiment of the present invention fills hot melt macromolecule filler particles in porous membrane substrate,
Aperture and the porosity of porous membrane substrate are advantageously reduced, while when the heating temperature of composite electrolyte membrane reaches hot melt high score
When the fusing point of sub- filler particles, hot melt macromolecule filler particles melt and penetrate into the organic and inorganic electrolyte for being coated on and closing on
Particle surface, to achieve the effect that cut off conductive path, is reduced since hot melt macromolecule filler particles have insulation performance
Thermal runaway risk improves battery heat and abuses security performance；Further, organic and inorganic electrolyte filled layer can make compound electric
Solving plasma membrane has high-compactness, and the mechanical strength and ionic conductivity of composite electrolyte membrane can be effectively ensured；It is outermost poly-
Polymer electrolyte buffer layer can be effectively improved the compatibility of electrode and electrolyte interface in solid state lithium battery, eliminate space charge
Effect layer.The composite electrolyte membrane has security performance height, mechanical strength, room-temperature conductivity high and and positive and negative electrode as a result,
The advantages that interface compatibility is good.
In addition, composite electrolyte membrane according to the above embodiment of the present invention can also have the following additional technical features:
In some embodiments of the invention, the porous membrane substrate is selected from polyolefin, polyimides, poly- terephthaldehyde
In sour second diester, polybutylene terephthalate, cellulose, polyamide, poly(p-phenylene terephthalamide) and spandex at least
One of.It can further improve the comprehensive performance of composite electrolyte membrane as a result,.
In some embodiments of the invention, the porous membrane substrate with a thickness of 4-150 μm, porosity 80-95%,
Average pore size is 5-20 μm.It can further improve the comprehensive performance of composite electrolyte membrane as a result,.
In some embodiments of the invention, the polymer dielectric buffer layer with a thickness of 0.5-50 μm.As a result, may be used
Further increase the comprehensive performance of composite electrolyte membrane.
In some embodiments of the invention, the hot melt macromolecule filler particles are selected from polystyrene, polychlorostyrene second
Alkene, polyacrylate, vinylacetate, polyethylene, polypropylene, polyacrylate copolymer, vinyl acetate co-polymer, poly- third
At least one of alkene copolymer.It can further improve the comprehensive performance of composite electrolyte membrane as a result,.
In some embodiments of the invention, the fusing point of the hot melt macromolecule filler particles is 100-135 DEG C, average
Partial size is 0.2-2 μm.It can further improve the comprehensive performance of composite electrolyte membrane as a result,.
In another aspect of the invention, the invention proposes a kind of method for preparing above-mentioned composite electrolyte membrane, according to
The embodiment of the present invention, this method comprises:
(1) hot melt macromolecule filler particles are mixed with binder, the first solvent, is filled out to obtain hot melt macromolecule
Fill slurry；
(2) hot melt macromolecule filling slurry dip-coating is filled in porous membrane substrate, obtains composite substrate after drying；
(3) inorganic ceramic electrolyte, first polymer electrolyte, the first lithium salts and the second solvent are mixed, to obtain
Organic and inorganic electrolyte slurry；
(4) the organic and inorganic electrolyte slurry is filled in such a way that pressurization repeatedly is poured, dried repeatedly described
Composite substrate obtains modified composite electrolyte membrane after hot pressing；
(5) second polymer electrolyte, the second lithium salts and third solvent are mixed, and mixed slurry is coated on institute
Two surfaces up and down for stating modified composite electrolyte membrane, obtain composite electrolyte membrane after drying.
The method according to an embodiment of the present invention for preparing composite electrolyte membrane fills hot melt macromolecule in porous membrane substrate
Filler particles advantageously reduce aperture and the porosity of porous membrane substrate, while when the heating temperature of composite electrolyte membrane reaches
When the fusing point of hot melt macromolecule filler particles, hot melt macromolecule filler particles melt and penetrate into be coated on close on it is organic-
Inorganic electrolyte particle surface, since hot melt macromolecule filler particles have insulation performance, to reach cutting conductive path
Effect, reduce thermal runaway risk, improve battery heat abuse security performance；Further, organic and inorganic electrolyte filled layer energy
So that composite electrolyte membrane has high-compactness, the mechanical strength and ionic conductivity of composite electrolyte membrane can be effectively ensured；
Outermost polymer dielectric buffer layer can be effectively improved the compatibility of electrode and electrolyte interface in solid state lithium battery, disappear
Except space charge effect layer.The composite electrolyte membrane has security performance height, mechanical strength, room-temperature conductivity high as a result,
And with positive and negative electrode interface compatibility it is good the advantages that.
In addition, composite electrolyte membrane according to the above embodiment of the present invention can also have the following additional technical features:
In some embodiments of the invention, first solvent in step (1), described second in step (3) molten
The third solvent in agent and step (5) is separately selected from N-Methyl pyrrolidone, dimethylformamide, acetonitrile, second
At least one of acetoacetic ester and deionized water.It can further improve the comprehensive performance of composite electrolyte membrane as a result,.
In some embodiments of the invention, in step (1), the solid content of the hot melt macromolecule filling slurry is
10-50wt%, viscosity 100-2000mPa.s.It can further improve the comprehensive performance of composite electrolyte membrane as a result,.
In some embodiments of the invention, in step (2), the time of immersion is 1-5min, drying temperature 60-
80℃.It can further improve the comprehensive performance of composite electrolyte membrane as a result,.
In some embodiments of the invention, in step (3), the inorganic ceramic electrolyte is selected from titanium phosphate aluminium
At least one of lithium, phosphoric acid germanium aluminium lithium, lithium lanthanum zirconium oxygen, Li-La-Ti oxygen, lithium lanthanum zirconium tantalum oxygen and lithium lanthanum zirconium alumina.It as a result, can be into
The comprehensive performance of one step raising composite electrolyte membrane.
In some embodiments of the invention, the institute in the first polymer electrolyte and step (5) in step (3)
Stating second polymer electrolyte is selected from polyether-based polymers, polyamine quasi polymer, polysulfide ether polymer, polyacrylate
At least one of polymer and polyacrylonitrile quasi polymer.It can further improve the comprehensive performance of composite electrolyte membrane as a result,.
In some embodiments of the invention, second lithium in first lithium salts and step (5) in step (3)
Salt is selected from least one of lithium hexafluoro phosphate, double trifluoromethanesulfonimide lithiums, LiBF4 and dioxalic acid lithium borate.
It can further improve the comprehensive performance of composite electrolyte membrane as a result,.
In some embodiments of the invention, in step (3), the inorganic ceramic electrolyte and the first polymer
Electrolyte, first lithium salts mass ratio be 5-50:10-85:5-40.It can further improve composite electrolyte membrane as a result,
Comprehensive performance.
In some embodiments of the invention, in step (4), the temperature of the drying is 60-80 DEG C, time 6-
12h, vacuum degree are not more than -0.8MPa.It can further improve the comprehensive performance of composite electrolyte membrane as a result,.
In some embodiments of the invention, in step (4), the temperature of the hot pressing is 60-80 DEG C, pressure 0.1-
0.8MPa.It can further improve the comprehensive performance of composite electrolyte membrane as a result,.
In some embodiments of the invention, in step (4), the consistency of the modified composite electrolyte membrane is 90-
99%.It can further improve the comprehensive performance of composite electrolyte membrane as a result,.
In some embodiments of the invention, in step (5), the second polymer electrolyte and second lithium salts
Mass ratio be 50-85:15-50wt%.It can further improve the comprehensive performance of composite electrolyte membrane as a result,.
In some embodiments of the invention, in step (5), the temperature of the drying is 60-70 DEG C, time 10-
16h.It can further improve the comprehensive performance of composite electrolyte membrane as a result,.
In an additional aspect of the present invention, the invention proposes a kind of solid state batteries, according to an embodiment of the invention, described
Solid state battery is had above-mentioned composite electrolyte membrane or is prepared using the above-mentioned method for preparing composite electrolyte membrane described multiple
Close dielectric film.Solid state battery according to an embodiment of the present invention, because the battery has above-mentioned composite electrolyte membrane, the combined electrolysis
Hot melt macromolecule filler particles are filled in porous membrane substrate in plasma membrane, advantageously reduce aperture and the hole of porous membrane substrate
Rate, while when the heating temperature of composite electrolyte membrane reaches the fusing point of hot melt macromolecule filler particles, hot melt macromolecule
Filler particles melt and penetrate into the organic and inorganic electrolyte granular surface for being coated on and closing on, due to the filling of hot melt macromolecule
Grain has insulation performance, to achieve the effect that cut off conductive path, reduces thermal runaway risk, improves battery heat and abuses safety
Energy；Further, organic and inorganic electrolyte filled layer can make composite electrolyte membrane have high-compactness, can be effectively ensured
The mechanical strength and ionic conductivity of composite electrolyte membrane；Outermost polymer dielectric buffer layer can be effectively improved solid-state
The compatibility of electrode and electrolyte interface in lithium battery eliminates space charge effect layer.The composite electrolyte membrane has peace as a result,
The advantages that full performance height, mechanical strength, high and good with positive and negative electrode interface compatibility room-temperature conductivity, significantly improve electricity
The performance in pond.
Additional aspect and advantage of the invention will be set forth in part in the description, and will partially become from the following description
Obviously, or practice through the invention is recognized.
Detailed description of the invention
Above-mentioned and/or additional aspect of the invention and advantage will become from the description of the embodiment in conjunction with the following figures
Obviously and it is readily appreciated that, in which:
Fig. 1 is the structural schematic diagram of composite electrolyte membrane according to an embodiment of the invention；
Fig. 2 is the method flow schematic diagram according to an embodiment of the invention for preparing composite electrolyte membrane.
Specific embodiment
The embodiment of the present invention is described below in detail, examples of the embodiments are shown in the accompanying drawings, wherein from beginning to end
Same or similar label indicates same or similar element or element with the same or similar functions.Below with reference to attached
The embodiment of figure description is exemplary, it is intended to is used to explain the present invention, and is not considered as limiting the invention.
In the description of the present invention, it is to be understood that, term " center ", " longitudinal direction ", " transverse direction ", " length ", " width ",
" thickness ", "upper", "lower", "front", "rear", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outside", " up time
The orientation or positional relationship of the instructions such as needle ", " counterclockwise ", " axial direction ", " radial direction ", " circumferential direction " be orientation based on the figure or
Positional relationship is merely for convenience of description of the present invention and simplification of the description, rather than the device or element of indication or suggestion meaning must
There must be specific orientation, be constructed and operated in a specific orientation, therefore be not considered as limiting the invention.
In addition, term " first ", " second " are used for descriptive purposes only and cannot be understood as indicating or suggesting relative importance
Or implicitly indicate the quantity of indicated technical characteristic.Define " first " as a result, the feature of " second " can be expressed or
Implicitly include at least one this feature.In the description of the present invention, the meaning of " plurality " is at least two, such as two, three
It is a etc., unless otherwise specifically defined.
In one aspect of the invention, the invention proposes a kind of composite electrolyte membranes, according to an embodiment of the invention, ginseng
Fig. 1 is examined, which includes: porous membrane substrate 100, organic and inorganic electrolyte filled layer 200 and polymer dielectric
Buffer layer 300.According to an embodiment of the invention, hot melt macromolecule filler particles 110 are filled in porous membrane substrate 100, heat
Fusibleness macromolecule filler particles 110 are filled in the macrovoid of porous membrane substrate 100, advantageously reduce porous membrane substrate 100
Aperture and porosity.Organic and inorganic electrolyte filled layer 200 is located in at least part on 100 surface of porous membrane substrate, is had
Machine-inorganic electrolyte filled layer 200 includes organic-inorganic electrolyte 210, and at least part organic and inorganic electrolyte 210
It being filled in porous membrane substrate 100, i.e., organic and inorganic electrolyte 210 can be filled in the hole in porous membrane substrate 100,
To significantly improve the consistency, mechanical strength and ionic conductivity of composite electrolyte membrane, porous membrane substrate can also filled
One layer of organic and inorganic electrolyte 210 is formed after hole in 100 on 100 surface of porous membrane substrate with higher-density,
To further increase the consistency, mechanical strength and ionic conductivity of composite electrolyte membrane.Simultaneously when composite electrolyte membrane by
When hot temperature reaches the fusing point of hot melt macromolecule filler particles 110, hot melt macromolecule filler particles 110 melt and penetrate into packet
210 surface of organic and inorganic electrolyte closed on is overlayed on, since hot melt macromolecule filler particles 110 do not have ionic conductance energy
Power reduces thermal runaway risk to achieve the effect that cut off conductive path, improves battery heat and abuses security performance.Electrostrictive polymer
Solution matter buffer layer 300 is located at least part of organic and inorganic electrolyte filled layer 200 and covers as the face contacted with electrode
It covers in porous membrane substrate 100, the compatibility of electrode and electrolyte interface in solid state lithium battery can be effectively improved, eliminate space
Charge effect layer.
According to one embodiment of present invention, porous membrane substrate can be for selected from polyolefin, polyimides, poly- terephthaldehyde
In sour second diester, polybutylene terephthalate, cellulose, polyamide, poly(p-phenylene terephthalamide) and spandex at least
One of.Inventors have found that above-mentioned porous membrane substrate is higher than conventional self-supporting dielectric film intensity, processing performance is good, while its hole
Gap rate and pore size are controllable, are conducive to the composite electrolyte membrane for preparing corresponding function according to actual needs.Further, porous
The thickness of film substrate can be 4-150 μm, such as can for 4 μm, 10 μm, 30 μm, 50 μm, 70 μm, 90 μm, 110 μm, 130 μm,
150 μm, porosity can be 80-95%, such as can be 80%, 82%, 86%, 90%, 93%, 95%, and average pore size can
Think 5-20 μm, such as can be 5 μm, 10 μm, 15 μm, 20 μm.Inventors have found that porosity it is too low easily lead to filling it is organic-
Inorganic electrolyte relative scale is low, and conductivity decline, the excessively high intensity that easily leads to is low, and then influences processing performance；Thickness is too low easily
Cause intensity low, reduces processing performance, it is excessively high to easily lead to the problems such as impedance is larger, and conductivity reduces；Average pore size is too low to be caused
Electrolyte filling is uneven, gap occurs, influences conductivity, excessively high to easily lead to reduction mechanical strength, reduces processing performance.According to
Yet another embodiment of the present invention, hot melt macromolecule filler particles can be for selected from polystyrene, polyvinyl chloride, polyacrylic acid
Ester, vinylacetate, polyethylene, polypropylene, polyacrylate copolymer, vinyl acetate co-polymer, in polypropylene copolymer
At least one of.Inventors have found that above-mentioned hot melt macromolecule filler particles have insulation performance, there is spherical shape mostly under room temperature
Particle, bulk density is controllable, and melting range can effectively reduce the risk of battery thermal runaway, and mobile performance is preferable after melting,
Can rapid osmotic expand to the bath surface closed on, play the role of Thermal shutdown.Further, hot melt macromolecule filling
Grain fusing point can be 100-135 DEG C, such as can for 100 DEG C, 105 DEG C, 110 DEG C, 115 DEG C, 120 DEG C, 125 DEG C, 130 DEG C,
135 DEG C, average grain diameter can be 0.2-2 μm, such as can be 0.2 μm, 0.6 μm, 1.0 μm, 1.4 μm, 1.8 μm, 2 μm.Invention
People's discovery, the fusing point of hot melt macromolecule filler particles is excessively high can not to play the role of Thermal shutdown, too low influence battery performance；Grain
Diameter is too low, excessively high can reduce processing performance.According to still another embodiment of the invention, the thickness of polymer dielectric buffer layer
It can be 0.5-50 μm, such as can be 0.5 μm, 5 μm, 10 μm, 20 μm, 30 μm, 40 μm, 50 μm.Inventors have found that polymer
The thickness of electrolyte buffer layer need to be matched with porous membrane substrate film thickness, excessively high, too low to be all unfavorable for processing performance.
Composite electrolyte membrane according to an embodiment of the present invention fills hot melt macromolecule filler particles in porous membrane substrate,
Aperture and the porosity of porous membrane substrate are advantageously reduced, while when the heating temperature of composite electrolyte membrane reaches hot melt high score
When the fusing point of sub- filler particles, hot melt macromolecule filler particles melt and penetrate into the organic and inorganic electrolyte for being coated on and closing on
Particle surface, to achieve the effect that cut off conductive path, is reduced since hot melt macromolecule filler particles have insulation performance
Thermal runaway risk improves battery heat and abuses security performance；Further, organic and inorganic electrolyte filled layer can make compound electric
Solving plasma membrane has high-compactness, and the mechanical strength and ionic conductivity of composite electrolyte membrane can be effectively ensured；It is outermost poly-
Polymer electrolyte buffer layer can be effectively improved the compatibility of electrode and electrolyte interface in solid state lithium battery, eliminate space charge
Effect layer.The composite electrolyte membrane has security performance height, mechanical strength, room-temperature conductivity high and and positive and negative electrode as a result,
The advantages that interface compatibility is good.
In another aspect of the invention, the invention proposes a kind of method for preparing above-mentioned composite electrolyte membrane, according to
The embodiment of the present invention, with reference to Fig. 2, this method comprises:
S100: hot melt macromolecule filler particles are mixed with the first solvent
In the step, hot melt macromolecule filler particles are mixed with binder, the first solvent, to obtain hot melt height
Molecule fills slurry.According to one embodiment of present invention, the first solvent can be for selected from N-Methyl pyrrolidone, dimethyl methyl
At least one of amide, acetonitrile, ethyl acetate and deionized water.Further, binder can for selected from PVDF, LA133,
At least one of SBR.Inventors have found that above-mentioned binder is that battery system often uses binder, chemistry, electrochemical stability
Good, side reaction is few, and adhesive property is good；Above-mentioned first solvent-dispersible can be good.Still another embodiment in accordance with the present invention, hot melt
Macromolecule fill slurry solid content can be 10-50wt%, such as can for 10wt%, 20wt%, 30wt%, 40wt%,
50wt%, viscosity can be 100-2000mPa.s, such as can for 100mPa.s, 400mPa.s, 700mPa.s,
1000mPa.s,1400mPa.s,1700mPa.s,2000mPa.s.Inventors have found that hot melt macromolecule consolidating for slurry of filling contains
Amount or excessively high easily lead to of viscosity fill difficulty, lead to occur gap inside porous membrane substrate, influence conductivity；Too low easily lead to is filled out
Degree of filling is insufficient, poor processability.It should be noted that the concrete type of hot melt macromolecule filler particles, fusing point and average grain
Diameter is consistent in above-mentioned composite electrolyte membrane, repeats no more to this.
S200: the filling slurry dip-coating of hot melt macromolecule is filled in porous membrane substrate
In the step, the filling slurry dip-coating of hot melt macromolecule is filled in porous membrane substrate, obtains composite base after drying
Bottom.Inventors have found that hot melt macromolecule filling slurry can be filled to the hole of porous membrane substrate after being filled by dip-coating
In, hot melt macromolecule filler particles are filled in porous membrane substrate, advantageously reduce aperture and the porosity of porous membrane substrate, together
When the heating temperature of composite electrolyte membrane reaches the fusing point of hot melt macromolecule filler particles, hot melt macromolecule filling
Grain melts and penetrates into the organic and inorganic electrolyte granular surface for being coated on and closing on, since hot melt macromolecule filler particles do not have
Standby ionic conductance ability reduces thermal runaway risk to achieve the effect that cut off conductive path, improves battery heat and abuses safety
Energy.According to one embodiment of present invention, the time of dip-coating can be 1-5min, such as can for 1min, 2min, 3min,
4min, 5min, drying temperature can be 60-80 DEG C, such as can be 60 DEG C, 65 DEG C, 70 DEG C, 75 DEG C, 80 DEG C.Invention human hair
Existing, time of immersion is too long to easily lead to that porosity is too low, influences the filling of subsequent organic and inorganic electrolyte, reduces conductivity；Dip-coating
Time, the too short hot melt macromolecule filler particles accounting that easily leads to was lower, reduced Thermal shutdown effect.It should be noted that perforated membrane
Substrate is consistent in composite electrolyte membrane, repeats no more to this.
S300: inorganic ceramic electrolyte, first polymer electrolyte, the first lithium salts and the second solvent are mixed
In the step, inorganic ceramic electrolyte, first polymer electrolyte, the first lithium salts and the second solvent are mixed, with
Just organic and inorganic electrolyte slurry is obtained.Specifically, can be first by inorganic ceramic electrolyte and first polymer electrolyte, the
One lithium salts is uniformly mixed, and then adds the second solvent to be uniformly mixed, to obtain organic and inorganic electrolyte slurry.According to
One embodiment of the present of invention, inorganic ceramic electrolyte can be for selected from titanium phosphate aluminium lithium, phosphoric acid germanium aluminium lithium, lithium lanthanum zirconium oxygen, lithium
At least one of lanthanum titanyl, lithium lanthanum zirconium tantalum oxygen and lithium lanthanum zirconium alumina.Further, first polymer electrolyte can for selected from
Polyether-based polymers, polyamine quasi polymer, polysulfide ether polymer, polyacrylate polymers and polyacrylonitrile quasi polymer
At least one of.Further, the first lithium salts can be for selected from lithium hexafluoro phosphate, double trifluoromethanesulfonimide lithiums, tetrafluoro
At least one of lithium borate and dioxalic acid lithium borate.Further, the second solvent can be selected from N-Methyl pyrrolidone, diformazan
At least one of base formamide, acetonitrile, ethyl acetate and deionized water.Inventors have found that inorganic ceramic electrolyte has electricity
The advantages that conductance is high, stability is good, first polymer electrolyte processing performance is good, flexible, mechanicalness after Organic-inorganic composite
Energy improves, conductivity is excellent.Still another embodiment in accordance with the present invention, inorganic ceramic electrolyte and first polymer electrolyte,
The mass ratio of first lithium salts is not particularly restricted, such as can be 5-50:10-85:5-40, such as can be 5/10/15/
20/25/30/35/40/45/50:10/20/30/40/50/60/70/80/85:5/10/15/ 20/25/30/35/40.Inventor
It was found that no matter who excessively high, too low can all influence organic-nothing for inorganic ceramic electrolyte and first polymer electrolyte, the first lithium salts
The conductivity and processing performance of machine electrolyte filled layer.
S400: organic and inorganic electrolyte slurry is filled in composite base in such a way that pressurization repeatedly is poured, dried repeatedly
Bottom simultaneously carries out hot pressing
In the step, organic and inorganic electrolyte slurry is filled in such a way that pressurization repeatedly is poured, dried repeatedly multiple
Substrate is closed, is pressurizeed after pouring, drying repeatedly repeatedly, organic and inorganic electrolyte slurry is filled in the hole of composite substrate,
It can also be formed in the composite substrate surface filled with organic and inorganic electrolyte slurry, modified combined electrolysis is obtained after hot pressing
Plasma membrane.Inventors have found that the filling of organic and inorganic electrolyte or the filling and covering of organic and inorganic electrolyte can make it is compound
Dielectric film has high-compactness, and the mechanical strength and ionic conductivity of composite electrolyte membrane can be effectively ensured.According to this hair
Bright one embodiment, dry actual conditions are not particularly limited, such as dry temperature can be 60-80 DEG C, such as can be with
For 60 DEG C, 65 DEG C, 70 DEG C, 75 DEG C, 80 DEG C, the time can be 6-12h, such as can be 6h, 7h, 8h, 9h, 10h, 11h, 12h, very
Reciprocal of duty cycle can be not more than -0.8MPa.Inventors have found that the excessively high destructible electrolysis of the too low influence processing efficiency of drying temperature, temperature
Plastidome component, drying time, vacuum degree is excessively high to easily lead to organic and inorganic electrolyte layer consistency drop with drying temperature correlation
Low, there is gap in inside.The condition of still another embodiment in accordance with the present invention, hot pressing is also not particularly limited, such as temperature can be with
It is 60-80 DEG C, such as can is 60 DEG C, 65 DEG C, 70 DEG C, 75 DEG C, 80 DEG C, pressure can be 0.1-0.8MPa, such as can be
0.1MPa,0.2MPa,0.3MPa,0.4MPa,0.5MPa,0.6MPa,0.7MPa,0.8MPa.Inventors have found that temperature it is excessively high,
Pressure is excessive to easily lead to the problems such as organic and inorganic dielectric film is damaged, material granule ruptures.Another implementation according to the present invention
Example, the consistency of modified composite electrolyte membrane can be 90-99%, for example, can for 90%, 92%, 94%, 96,98%,
99%.Inventors have found that the mechanical strength of composite electrolyte membrane can be reduced if the consistency of modified composite electrolyte membrane is too low,
Simultaneously because consistency is too low so that the polymer dielectric of subsequent coated some need to will affect for filling pore
The ionic conductivity of composite electrolyte membrane.
S500: second polymer electrolyte, the second lithium salts and third solvent are mixed, and mixed slurry is coated on
Two surfaces up and down of modified composite electrolyte membrane
In the step, second polymer electrolyte, the second lithium salts and third solvent are mixed, and mixed slurry is applied
Two surfaces up and down of modified composite electrolyte membrane are overlying on, composite electrolyte membrane, resulting composite electrolyte membrane are obtained after drying
In, the face contacted with electrode is polymer dielectric buffer layer.Specifically, can be first by second polymer electrolyte and the second lithium
Salt is uniformly mixed, and then adds the mixing of third solvent.Inventors have found that can be in the outermost layer of composite electrolyte membrane after coated
Polymer dielectric buffer layer is formed, which can be effectively improved electrode and electrolysis in solid state lithium battery
The compatibility at matter interface eliminates space charge effect layer.It should be noted that two surfaces up and down described herein, refer to multiple
Close two surfaces that can be contacted with battery electrode in dielectric film.According to one embodiment of present invention, second polymer is electrolysed
Matter can be for selected from polyether-based polymers, polyamine quasi polymer, polysulfide ether polymer, polyacrylate polymers and poly- third
At least one of alkene nitrile polymer.Further, the second lithium salts can be for selected from lithium hexafluoro phosphate, double fluoroform sulphonyl
At least one of imine lithium, LiBF4 and dioxalic acid lithium borate.Further, third solvent can be for selected from N- methyl
At least one of pyrrolidones, dimethylformamide, acetonitrile, ethyl acetate and deionized water.It is according to the present invention another
Embodiment, second polymer electrolyte and the mixing mass ratio of the second lithium salts are not particularly restricted, such as can be 50-85:
15-50 such as can be 50/55/60/65/70/75/80/85:15/20/25/30/35/40/45/50.Inventors have found that second
No matter who excessively high, too low conductivity and processing performance that can all influence composite electrolyte membrane of polymer dielectric, the second lithium salts.Root
According to another embodiment of the invention, the condition of drying is not particularly restricted, such as the temperature of drying can be 60-70 DEG C,
Such as can be 60 DEG C, 62 DEG C, 64 DEG C, 66 DEG C, 68 DEG C, 70 DEG C, the time can be 10-16h, such as can for 10h, 12h, 14h,
16h.Inventors have found that the too low influence processing efficiency of drying temperature, the excessively high destructible electrolyte system component of temperature, drying time
With drying temperature correlation.It should be noted that the thickness and above-mentioned compound electric of the polymer dielectric buffer layer formed after coating
It is consistent in solution plasma membrane, this is repeated no more.
The method according to an embodiment of the present invention for preparing composite electrolyte membrane fills hot melt macromolecule in porous membrane substrate
Filler particles advantageously reduce aperture and the porosity of porous membrane substrate, while when the heating temperature of composite electrolyte membrane reaches
When the fusing point of hot melt macromolecule filler particles, hot melt macromolecule filler particles melt and penetrate into be coated on close on it is organic-
Inorganic electrolyte particle surface, since hot melt macromolecule filler particles have insulation performance, to reach cutting conductive path
Effect, reduce thermal runaway risk, improve battery heat abuse security performance；Further, organic and inorganic electrolyte filled layer energy
So that composite electrolyte membrane has high-compactness, the mechanical strength and ionic conductivity of composite electrolyte membrane can be effectively ensured；
Outermost polymer dielectric buffer layer can be effectively improved the compatibility of electrode and electrolyte interface in solid state lithium battery, disappear
Except space charge effect layer.The composite electrolyte membrane has security performance height, mechanical strength, room-temperature conductivity high as a result,
And with positive and negative electrode interface compatibility it is good the advantages that.
It should be noted that the feature and advantage of above-mentioned composite electrolyte membrane are equally applicable to prepare composite electrolyte membrane
Method repeats no more this.Above-mentioned S100, S200, S300, S400, S500 might not specify the tandem of technique, ability
Field technique personnel can flexible choice according to actual needs during production practices.
In an additional aspect of the present invention, the invention proposes a kind of solid state batteries, according to an embodiment of the invention, this is solid
The combined electrolysis that state battery is had above-mentioned composite electrolyte membrane or is prepared using the above-mentioned method for preparing composite electrolyte membrane
Plasma membrane.Solid state battery according to an embodiment of the present invention, because the battery has above-mentioned composite electrolyte membrane, in the composite electrolyte membrane
Porous membrane substrate in fill hot melt macromolecule filler particles, advantageously reduce aperture and the porosity of porous membrane substrate, together
When the heating temperature of composite electrolyte membrane reaches the fusing point of hot melt macromolecule filler particles, hot melt macromolecule filling
Grain melts and penetrates into the organic and inorganic electrolyte granular surface for being coated on and closing on, since hot melt macromolecule filler particles have
Insulation performance reduces thermal runaway risk to achieve the effect that cut off conductive path, improves battery heat and abuses security performance；Into
One step, organic and inorganic electrolyte filled layer can make composite electrolyte membrane have high-compactness, and compound electric can be effectively ensured
Solve the mechanical strength and ionic conductivity of plasma membrane；Outermost polymer dielectric buffer layer can be effectively improved solid state lithium battery
The compatibility of middle electrode and electrolyte interface eliminates space charge effect layer.The composite electrolyte membrane has security performance as a result,
The advantages that height, mechanical strength, room-temperature conductivity are high and good with positive and negative electrode interface compatibility, significantly improves the property of battery
Energy.
Below with reference to specific embodiment, present invention is described, it should be noted that these embodiments are only to describe
Property, without limiting the invention in any way.
Embodiment 1
By fusing point is 125 DEG C, average grain diameter is 0.5 μm hot melt macromolecule filler particles it is ethene improved-vinyl acetate
Copolymer, binder SBR are mixed with the first solvent deionized water, are 20wt% to obtain solid content, viscosity 400mPa.s
Hot melt macromolecule fill slurry；
It is 10 μ that the filling slurry dip-coating of hot melt macromolecule, which is filled in a thickness of 15 μm, porosity 90%, average pore size,
In the porous membrane substrate polyimides electrostatic spinning of m, composite substrate is obtained after drying, wherein the time of dip-coating is 2min, drying
Temperature is 80 DEG C；
By inorganic ceramic electrolyte LAGP ceramic oxide and first polymer electrolyte modified PE O base organic polymer,
First lithium salts LiCLO4It is mixed with the second solvent acetonitrile, to obtain organic and inorganic electrolyte slurry.Wherein, inorganic ceramic electricity
Xie Zhiyu first polymer electrolyte, the first lithium salts mass ratio be 10:70:20；
Organic and inorganic electrolyte slurry is filled in composite substrate in such a way that pressurization repeatedly pours and dries repeatedly,
Organic and inorganic electrolyte slurry is filled in the hole of composite substrate, and it is multiple that the modification that consistency is 95% is obtained after hot pressing
Close dielectric film.Wherein, dry temperature is 80 DEG C, time 12h, and vacuum degree is -0.85MPa.The temperature of hot pressing is 80 DEG C,
Pressure is 0.6MPa；
By second polymer electrolyte modified PE O base organic polymer, the second lithium salts LiCLO4It is mixed with third solvent acetonitrile
It closes, and mixed slurry is coated on to two surfaces of modified composite electrolyte membrane by the way of rotogravure application, after drying
Obtain the composite electrolyte membrane with 5 μm of thickness of polymer dielectric buffer layer.Wherein, second polymer electrolyte and second
The mass ratio of lithium salts is 80:20；The temperature of drying is 65 DEG C, time 15h.
Embodiment 2
By fusing point is 130 DEG C, average grain diameter is 0.8 μm hot melt macromolecule filler particles modified poly ethylene, binder
LA133 is mixed with the first solvent deionized water, to obtain the hot melt high score that solid content is 15wt%, viscosity is 800mPa.s
Son filling slurry；
It is 6 μm that the filling slurry dip-coating of hot melt macromolecule, which is filled in a thickness of 20 μm, porosity 80%, average pore size,
Porous membrane substrate PET non-woven fabrics in, composite substrate is obtained after drying, wherein the time of dip-coating be 1min, drying temperature 70
℃；
By inorganic ceramic electrolyte LATP ceramic oxide, first polymer electrolyte MODIFIED PP C base organic polymer electricity
Xie Zhi, the first lithium salts LiTFSI and the mixing of the second solvent acetonitrile, to obtain organic and inorganic electrolyte slurry.Wherein, inorganic pottery
The mass ratio of porcelain electrolyte and first polymer electrolyte, the first lithium salts is 15:60:25；
Organic and inorganic electrolyte slurry is filled in composite substrate in such a way that pressurization repeatedly pours and dries repeatedly,
Organic and inorganic electrolyte slurry is filled in the hole of composite substrate, and it is multiple that the modification that consistency is 98% is obtained after hot pressing
Close dielectric film.Wherein, dry temperature is 60 DEG C, time 6h, and vacuum degree is not more than -0.9MPa.The temperature of hot pressing is 75
DEG C, pressure 0.8MPa；
By second polymer electrolyte modified PE O base organic polyelectrolyte, the second lithium salts LiTFSI and third solvent
Acetonitrile mixing, and mixed slurry is coated on to two surfaces for being modified composite electrolyte membrane, it is obtained after drying with thickness 4
μm polymer dielectric buffer layer composite electrolyte membrane.Wherein, the mass ratio of second polymer electrolyte and the second lithium salts
For 85:15；The temperature of drying is 70 DEG C, time 10h.
Embodiment 3
By fusing point is 135 DEG C, average grain diameter is 1 μm hot melt macromolecule filler particles modified polystyrene, binder
PVDF is mixed with the first solvent N-methyl pyrilidone, to obtain the hot melt that solid content is 25wt%, viscosity is 1000mPa.s
Property macromolecule fill slurry；
It is 6 μm that the filling slurry dip-coating of hot melt macromolecule, which is filled in a thickness of 15 μm, porosity 80%, average pore size,
Porous membrane substrate polyimides electrostatic spinning in, composite substrate is obtained after drying, wherein the time of dip-coating be 1.5min, dry
Dry temperature is 60 DEG C；
By inorganic ceramic electrolyte LLZTO, first polymer electrolyte modified PE O and PPO copolymer, the first lithium salts
LiCLO4It is mixed with the second solvent acetonitrile, to obtain organic and inorganic electrolyte slurry.Wherein, inorganic ceramic electrolyte and
One polymer dielectric, the first lithium salts mass ratio be 5:75:20；
Organic and inorganic electrolyte slurry is filled in composite substrate in such a way that pressurization repeatedly pours and dries repeatedly,
Organic and inorganic electrolyte slurry is filled in the hole of composite substrate, and it is multiple that the modification that consistency is 95% is obtained after hot pressing
Close dielectric film.Wherein, dry temperature is 75 DEG C, time 12h, and vacuum degree is not more than -0.8MPa.The temperature of hot pressing is 80
DEG C, pressure 0.7MPa；
By second polymer electrolyte modified PE O and PPO copolymer, the second lithium salts LiCLO4It is mixed with third solvent acetonitrile
It closes, and mixed slurry is coated on to two surfaces of modified composite electrolyte membrane, obtain having 2 μm of thickness poly- after drying
The composite electrolyte membrane of polymer electrolyte buffer layer.Wherein, the mass ratio of second polymer electrolyte and the second lithium salts is 85:
15；The temperature of drying is 70 DEG C, time 10h.
Comparative example 1 removes hot melt macromolecule filler particles filling work procedure
By inorganic ceramic electrolyte LAGP ceramic oxide and first polymer electrolyte modified PE O base organic polymer,
First lithium salts LiCLO4It is mixed with the second solvent acetonitrile, to obtain organic and inorganic electrolyte slurry.Wherein, inorganic ceramic electricity
Xie Zhiyu first polymer electrolyte, the first lithium salts mass ratio be 10:70:20；
Organic and inorganic electrolyte slurry is filled in such a way that pressurization repeatedly pours and dries repeatedly with a thickness of 15 μ
M, in the porous membrane substrate polyimides electrostatic spinning that porosity is 90%, average pore size is 10 μm, organic and inorganic is electrolysed chylema
Material is filled in the hole of porous membrane substrate, and the modification composite electrolyte membrane that consistency is 94% is obtained after hot pressing.Wherein,
Dry temperature is 80 DEG C, time 12h, and vacuum degree is -0.85MPa.The temperature of hot pressing is 80 DEG C, pressure 0.6MPa；
By second polymer electrolyte modified PE O base organic polymer, the second lithium salts LiCLO4It is mixed with third solvent acetonitrile
It closes, and mixed slurry is coated on to two surfaces of modified composite electrolyte membrane by the way of rotogravure application, after drying
Obtain the composite electrolyte membrane with 5 μm of thickness of polymer dielectric buffer layer.Wherein, second polymer electrolyte and second
The mass ratio of lithium salts is 80:20；The temperature of drying is 65 DEG C, time 15h.
The coating method of the change organic and inorganic electrolyte slurry of comparative example 2
By fusing point is 130 DEG C, average grain diameter is 0.8 μm hot melt macromolecule filler particles modified poly ethylene, binder
LA133 is mixed with the first solvent deionized water, to obtain the hot melt high score that solid content is 15wt%, viscosity is 800mPa.s
Son filling slurry；
It is 6 μm that the filling slurry dip-coating of hot melt macromolecule, which is filled in a thickness of 20 μm, porosity 80%, average pore size,
Porous membrane substrate PET non-woven fabrics in, composite substrate is obtained after drying, wherein the time of dip-coating be 1min, drying temperature 70
℃；
By inorganic ceramic electrolyte LATP ceramic oxide, first polymer electrolyte MODIFIED PP C base organic polymer electricity
Xie Zhi, the first lithium salts LiTFSI and the mixing of the second solvent acetonitrile, to obtain organic and inorganic electrolyte slurry.Wherein, inorganic pottery
The mass ratio of porcelain electrolyte and first polymer electrolyte, the first lithium salts is 15:60:25；
Organic and inorganic electrolyte slurry is coated in composite substrate by the way of rotogravure application, coating thickness is 4 μ
M obtains the modification composite electrolyte membrane that consistency is 85% after hot pressing.Wherein, dry temperature is 60 DEG C, time 6h,
Vacuum degree is not more than -0.9MPa.The temperature of hot pressing is 75 DEG C, pressure 0.8MPa；
By second polymer electrolyte modified PE O base organic polyelectrolyte, the second lithium salts LiTFSI and third solvent
Acetonitrile mixing, and mixed slurry is coated on to two surfaces for being modified composite electrolyte membrane, it is obtained after drying with thickness 4
μm polymer dielectric buffer layer composite electrolyte membrane.Wherein, the mass ratio of second polymer electrolyte and the second lithium salts
For 85:15；The temperature of drying is 70 DEG C, time 10h.
Comparative example 3 cancels hot pressing process
By fusing point is 135 DEG C, average grain diameter is 1 μm hot melt macromolecule filler particles modified polystyrene, binder
PVDF is mixed with the first solvent N-methyl pyrilidone, to obtain the hot melt that solid content is 25wt%, viscosity is 1000mPa.s
Property macromolecule fill slurry；
It is 6 μm that the filling slurry dip-coating of hot melt macromolecule, which is filled in a thickness of 15 μm, porosity 80%, average pore size,
Porous membrane substrate polyimides electrostatic spinning in, composite substrate is obtained after drying, wherein the time of dip-coating be 1.5min, dry
Dry temperature is 60 DEG C；
By inorganic ceramic electrolyte LLZTO, first polymer electrolyte modified PE O and PPO copolymer, the first lithium salts
LiCLO4It is mixed with the second solvent acetonitrile, to obtain organic and inorganic electrolyte slurry.Wherein, inorganic ceramic electrolyte and
One polymer dielectric, the first lithium salts mass ratio be 5:75:20；
Organic and inorganic electrolyte slurry is filled in composite substrate in such a way that pressurization repeatedly pours and dries repeatedly,
Organic and inorganic electrolyte slurry is filled in the hole of composite substrate, obtains the modification composite electrolyte that consistency is 80%
Film.Wherein, dry temperature is 75 DEG C, time 12h, and vacuum degree is not more than -0.8MPa.The temperature of hot pressing is 80 DEG C, pressure
For 0.7MPa；
By second polymer electrolyte modified PE O and PPO copolymer, the second lithium salts LiCLO4It is mixed with third solvent acetonitrile
It closes, and mixed slurry is coated on to two surfaces of modified composite electrolyte membrane, obtain having 2 μm of thickness poly- after drying
The composite electrolyte membrane of polymer electrolyte buffer layer.Wherein, the mass ratio of second polymer electrolyte and the second lithium salts is 85:
15；The temperature of drying is 70 DEG C, time 10h.
The conductivity and consistency of the resulting composite dielectrics film of embodiment 1-3 and comparative example 1-3 are as shown in table 1.By table 1
It is found that hot melt macromolecule filler particles can effectively improve the heat abuse security performance of composite electrolyte membrane, after reaching fusing point
Fusible and infiltration is coated on the organic-inorganic electrolyte particle surface that is connected, and since hot melt macromolecule filler particles do not have
Standby ionic conductance ability improves battery heat and abuses security performance so as to achieve the effect that cut off conductive path；Using coating
Mode carry out surface coat organic-inorganic electrolyte, the ionic conductance of resulting composite electrolyte membrane is significant lower, and passes through
High pressure filling, dry while repeatedly plate hot pressing mode can significantly improve the ionic conductivity of composite electrolyte membrane repeatedly.
The conductivity and consistency of composite electrolyte membrane obtained by 1 embodiment 1-3 of table and comparative example 1-3
| Composite electrolyte membrane | Conductivity (60 DEG C) | Conductivity (130 DEG C) | Consistency (%) |
| Embodiment 1 | 2.5*10-4S/cm | Plug-hole, without ionic conductivity | 95 |
| Comparative example 1 | 11*10-4S/cm | 35*10-4S/cm | 94 |
| Embodiment 2 | 3.7*10-4S/cm | Plug-hole, without ionic conductivity | 98 |
| Comparative example 2 | 2.4*10-6S/cm | Plug-hole, without ionic conductivity | 85 |
| Embodiment 3 | 1.5*10-4S/cm | Plug-hole, without ionic conductivity | 95 |
| Comparative example 3 | 47*10-6S/cm | Plug-hole, without ionic conductivity | 80 |
In the description of this specification, reference term " one embodiment ", " some embodiments ", " example ", " specifically show
The description of example " or " some examples " etc. means specific features, structure, material or spy described in conjunction with this embodiment or example
Point is included at least one embodiment or example of the invention.In the present specification, schematic expression of the above terms are not
It must be directed to identical embodiment or example.Moreover, particular features, structures, materials, or characteristics described can be in office
It can be combined in any suitable manner in one or more embodiment or examples.In addition, without conflicting with each other, the skill of this field
Art personnel can tie the feature of different embodiments or examples described in this specification and different embodiments or examples
It closes and combines.
Although the embodiments of the present invention has been shown and described above, it is to be understood that above-described embodiment is example
Property, it is not considered as limiting the invention, those skilled in the art within the scope of the invention can be to above-mentioned
Embodiment is changed, modifies, replacement and variant.
Claims (10)
1. a kind of composite electrolyte membrane characterized by comprising
Porous membrane substrate, the porous membrane substrate is interior to be filled with hot melt macromolecule filler particles；
Organic and inorganic electrolyte filled layer, the organic and inorganic electrolyte filled layer are located at the porous membrane substrate surface extremely
In few a part, the organic and inorganic electrolyte filled layer includes organic-inorganic electrolyte, and is had described at least part
Machine-inorganic electrolyte is filled in the porous membrane substrate；
Polymer dielectric buffer layer, the polymer dielectric buffer layer are located at the organic and inorganic electrolyte filled layer
It is covered in the porous membrane substrate at least part and as the face contacted with electrode.
2. composite electrolyte membrane according to claim 1, which is characterized in that the porous membrane substrate be selected from polyolefin,
Polyimides, polyethylene terephthalate, polybutylene terephthalate, cellulose, polyamide, poly- paraphenylene terephthalamide are to benzene
At least one of diamines and spandex.
3. composite electrolyte membrane according to claim 1 or 2, which is characterized in that the porous membrane substrate with a thickness of 4-
150 μm, porosity 80-95%, average pore size is 5-20 μm；
It is optional, the polymer dielectric buffer layer with a thickness of 0.5-50 μm.
4. composite electrolyte membrane according to claim 1, which is characterized in that the hot melt macromolecule filler particles are choosing
Self-polystyrene, polyvinyl chloride, polyacrylate, vinylacetate, polyethylene, polypropylene, polyacrylate copolymer, acetic acid
At least one of vinyl ester copolymers, polypropylene copolymer.
5. composite electrolyte membrane according to claim 1, which is characterized in that the hot melt macromolecule filler particles melt
Point is 100-135 DEG C, and average grain diameter is 0.2-2 μm.
6. a kind of method for preparing composite electrolyte membrane of any of claims 1-5 characterized by comprising
(1) hot melt macromolecule filler particles are mixed with binder, the first solvent, to obtain hot melt macromolecule filling slurry
Material；
(2) hot melt macromolecule filling slurry dip-coating is filled in porous membrane substrate, obtains composite substrate after drying；
(3) by inorganic ceramic electrolyte, first polymer electrolyte, the first lithium salts and the second solvent mix, so as to obtain it is organic-
Inorganic electrolyte slurry；
(4) the organic and inorganic electrolyte slurry is filled in such a way that pressurization repeatedly is poured, dried repeatedly described compound
Substrate obtains modified composite electrolyte membrane after hot pressing；
(5) second polymer electrolyte, the second lithium salts and third solvent are mixed, and mixed slurry is coated on described change
Two surfaces up and down of property composite electrolyte membrane, obtain composite electrolyte membrane after drying.
7. according to the method described in claim 6, it is characterized in that, in first solvent, step (3) in step (1)
The third solvent in second solvent and step (5) is separately selected from N-Methyl pyrrolidone, dimethyl formyl
At least one of amine, acetonitrile, ethyl acetate and deionized water；
Optional, in step (1), the solid content of the hot melt macromolecule filling slurry is 10-50wt%, viscosity 100-
2000mPa.s；
Optional, in step (2), the time of immersion is 1-5min, and drying temperature is 60-80 DEG C.
8. method according to claim 6 or 7, which is characterized in that in step (3), the inorganic ceramic electrolyte is
In titanium phosphate aluminium lithium, phosphoric acid germanium aluminium lithium, lithium lanthanum zirconium oxygen, Li-La-Ti oxygen, lithium lanthanum zirconium tantalum oxygen and lithium lanthanum zirconium alumina at least it
One；
Optional, the second polymer electrolyte in the first polymer electrolyte and step (5) in step (3) is
It birdss of the same feather flock together selected from polyether-based polymers, polyamine quasi polymer, polysulfide ether polymer, polyacrylate polymers and polyacrylonitrile
Close at least one of object；
It is optional, second lithium salts in first lithium salts and step (5) in step (3) be selected from lithium hexafluoro phosphate,
At least one of double trifluoromethanesulfonimide lithiums, LiBF4 and dioxalic acid lithium borate；
Optional, in step (3), the inorganic ceramic electrolyte and the first polymer electrolyte, first lithium salts
Mass ratio be 5-50:10-85:5-40.
9. according to the method described in claim 6, the temperature of the drying is 60-80 DEG C it is characterized in that, in step (4),
Time is 6-12h, and vacuum degree is not more than -0.8MPa；
Optional, in step (4), the temperature of the hot pressing is 60-80 DEG C, pressure 0.1-0.8Mpa；
Optional, in step (4), the consistency of the modified composite electrolyte membrane is 90-99%；
Optional, in step (5), the mass ratio of the second polymer electrolyte and second lithium salts is 50-85:15-
50；
Optional, in step (5), the temperature of the drying is 60-70 DEG C, time 10-16h.
10. a kind of solid state battery, which is characterized in that the solid state battery has of any of claims 1-5 compound
Dielectric film is prepared described multiple using the method for preparing composite electrolyte membrane described in any one of claim 6-9
Close dielectric film.
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