CN106898811B - A kind of solid electrolyte and preparation method thereof with dual diversion sub-network - Google Patents
A kind of solid electrolyte and preparation method thereof with dual diversion sub-network Download PDFInfo
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- CN106898811B CN106898811B CN201710316645.XA CN201710316645A CN106898811B CN 106898811 B CN106898811 B CN 106898811B CN 201710316645 A CN201710316645 A CN 201710316645A CN 106898811 B CN106898811 B CN 106898811B
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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
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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
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The present invention relates to a kind of solid electrolytes and preparation method thereof with dual diversion sub-network, which solve the low technical problems of existing polyphosphazene solid electrolyte poor mechanical property, conductivity, it is made of porous membrane and polyphosphazene electrolyte, porous membrane is made of polymer, inorganic solid electrolyte and lithium salts, and porous membrane is the skeleton of the polyphosphazene electrolyte；Polyphosphazene electrolyte is the carrier of lithium ion.Invention also provides preparation methods.It invention can be widely used in the preparation field of electrolyte.
Description
Technical field
The present invention relates to lithium ion battery solid electrolyte fields, relate in particular to a kind of with dual diversion sub-network
Solid electrolyte and preparation method thereof.
Background technique
As lithium ion battery is in the application of energy storage field, the safety of battery becomes focus concerned by people, big at present
Most lithium ion batteries all use organic liquid electrolytes, and organic liquid electrolytes are easily revealed, inflammable problem threatens
The safety of battery.In order to solve this problem, solid electrolyte comes into being.It is solidifying that current solid electrolyte can be divided into polymer
Glue electrolyte, polymer all solid state electrolyte, inorganic solid electrolyte etc. are several.
The shortcomings that solid polyelectrolyte is inflammable because there is no organic liquid electrolytes, easy leakage, and also have one
Fixed flexibility, so being increasingly becoming focus concerned by people.
In solid polyelectrolyte, poly- phosphorus eyeball electrolyte because of its special structure so that polyphosphazene can have compared with
Low glass transition temperature (Tg), rotary freedom and thermal stability to a certain extent, are conducive to the transmission of ion.But
It is on the other hand, because the poly- lower glass transition temperature of phosphorus eyeball material causes its mechanical property poor, to become viscous under high temperature
Fluidised form is easy to flow under the effect of the pressure, makes battery short circuit.
In order to solve the problems, such as polyphosphazene solid electrolyte poor mechanical property, somebody uses the side of ultraviolet radioactive crosslinking
Method improves its mechanical strength, and also somebody uses the method that nanofiller is added, and provides physical crosslinking point, but these methods
The conductivity of material can be had an impact, and mechanical property is not met by the requirement of practical application.
Summary of the invention
The present invention be exactly in order to solve the low technical problem of existing poly- phosphorus eyeball solid electrolyte poor mechanical property, conductivity,
There is provided it is a kind of with preferable mechanical property, excellent film forming and compared with high ion conductivity with dual diversion sub-network
Solid electrolyte and preparation method thereof.
For this purpose, the present invention provides a kind of solid electrolyte with dual diversion sub-network, by porous membrane and poly- phosphorus
Nitrile electrolyte is constituted, and the porous membrane is made of polymer, inorganic solid electrolyte and lithium salts, and the porous membrane is
The skeleton of the polyphosphazene electrolyte；The polyphosphazene electrolyte is the carrier of lithium ion.
Preferably, polymer be polyacrylonitrile (PAN), polymethyl methacrylate (PMMA), Kynoar (PVDF),
Polyethylene glycol oxide (PEO) it is one or more.
Preferably, inorganic solid electrolyte is the solid electrolyte of oxide system or the solid state electrolysis of sulfide systems
Matter.
Preferably, the solid electrolyte of oxide system is the one or more of LLTO, LATP, LLZO, LATP, LAGP.
Preferably, solid electrolyte LGPS, LPS, LS-BS-LI's of sulfide systems is one or more.
Present invention simultaneously provides a kind of preparation methods of solid electrolyte with dual diversion sub-network comprising as follows
Step: (1) high molecular polymer, lithium salts and inorganic solid electrolyte (nano wire, nanotube or nano particle) is put into appearance
In device, and solvent is added and is made into spinning solution, carries out electrostatic spinning, obtain porous membrane；(2) linear polyphosphazene is dissolved in tetrahydro
In furans (THF) solution, it is added thereto containing heteroatom oxygen atom, sub- amide functional group and mercaptan sulphur atom functional group
Polymer lateral chain is coordinated lithium ion as electron donor, while the intermediate product that acid-releasing agent removes dereaction is added, and obtains concentrate；
Sufficiently after reaction, THF is removed, the concentrate is instilled in petroleum ether, precipitated product is obtained, precipitated product is put into bag filter
In, it dialyses, water removal obtains polyphosphazene electrolyte；(3) solution is made in the polyphosphazene electrolyte that step (2) obtains,
Lithium salts is added；Porous membrane obtained in the step (1) is laid on glass or polytetrafluoroethylene, to its upper
One strata phosphonitrile electrolyte solution, covers one layer of porous membrane again on it later, sufficiently after drying, obtains sandwich structure
Electrolytic thin-membrane.
Preferably, in step (1), the mass ratio of the lithium salts and the high molecular polymer is (0.1-0.6): 1；It is described
Quality of the inorganic solid electrolyte filler in the mixture of the high molecular polymer and the inorganic solid electrolyte filler
Score is 5-25%.
Preferably, in step (3), polyphosphazene electrolyte is dissolved in dehydrated alcohol mass fraction 10- is made first
30% solution, then according to molar ratio lithium salts (Li+X-): ether oxygen functional group (~O~) or imino functionalities (~NH~) or
=1:(4~14 thioether functional group (~S~)) proportion be added lithium salts, be sufficiently stirred, dissolve electrolyte sufficiently.
The copolymer solid electrolyte system of sandwich structure provided by the invention, it is porous as prepared by electrostatic spinning
Film and polyphosphazene electrolyte are constituted, and layer structure of the electrostatic spinning porous membrane as sandwich structure electrolyte is
The polyphosphazene dielectric film of sandwich layer provides support frame, improves the mechanical property of polyphosphazene electrolyte；Meanwhile electrostatic spinning is porous
Membrane material itself joined a certain amount of inorganic solid electrolyte, has certain ionic conductivity, can effectively mitigate three
Influence of Mingzhi's layer structure to polyphosphazene electrolyte ion conductivity (uses the electrostatic spinning perforated membrane that solid electrolyte is added
Sandwich structure electrolytic conductivity as skeleton is more not plus the structure of inorganic solid electrolyte improves an order of magnitude),
Improve poly- phosphorus eyeball electrolyte film forming.In addition, polyphosphazene solid electrolyte is during use, become viscosity flow under high temperature
State is easy to flow under the effect of the pressure, the presence of electrostatic spinning film, and the protection for playing isolation battery plus-negative plate is made
With；The polyphosphazene electrolyte is cooperateed with to play the role of transmitting lithium ion as the carrier of lithium ion simultaneously.
The solid polyelectrolyte of sandwich structure prepared by the present invention has shape and size designability；Have
It is preferable flexible.Preparation process of the present invention is simple, it is environmental-friendly, low in cost, be easy to realize industrial production and commercial applications.
Detailed description of the invention
Fig. 1 is electrostatic spinning film schematic diagram of the present invention；
Fig. 2 is sandwich structure schematic diagram of the present invention；
Fig. 3 is poly- phosphorus eyeball electrolyte of the present invention；
Fig. 4 A, Fig. 4 B and Fig. 4 C are the curved schematics of sandwich structure electrolyte of the present invention.
Specific embodiment
According to following embodiments, the present invention may be better understood.However, as it will be easily appreciated by one skilled in the art that real
It applies content described in example and is merely to illustrate the present invention, without this hair described in claims should will not be limited
It is bright.
Embodiment 1
(1) lithium perchlorate and PAN (mass ratio 0.1:1) are put into conical flask and suitable solvent is added, be made into high polymer
The spinning solution of mass fraction 10%；Then by inorganic solid-state that mass fraction is 5% (quality that gross mass is PAN and filler) electricity
Nanometer rods made of solution matter are added in above-mentioned solution, and being sufficiently stirred makes to be uniformly mixed.
(2) the injection speed of 1ml/h, 20kv spinning voltage, use roller receive (roller revolving speed 1000r/min) item
Electrostatic spinning is carried out under part；
(3) electrostatic spinning film is put into baking oven after spinning, dry 3~48h keeps solvent complete under the conditions of 60 DEG C
Full volatilization.Obtained film is spare.
(4) a certain amount of linear polyphosphazene (PDCP) is dissolved in quantitative THF solution, to PDCP after completely dissolution to
Diethylene glycol monomethyl ether (Diethylene Glycol Monomethyl Ether) wherein is added, while a certain amount of tie up is added
Sour agent triethylamine (TEA) removes the intermediate product of dereaction, molar ratio n (PDCP): n (DGME): n (TEA)=1:2.2 of raw material:
2.4。
(5) after sufficiently reacting 10~40h, major part THF is removed using rotary evaporation, the concentrate in previous step is slow
Instillation petroleum ether in and ceaselessly stir, obtaining precipitated product is poly- phosphorus eyeball electrolyte.
(6) precipitated product of previous step is put into bag filter (molecular cut off 1000~10000), in deionized water
Dialysis 5~10 days.
Most of water in product is removed using rotary evaporation, recycles freeze-drying 48h to remove water therein, so far
The higher poly- phosphorus eyeball electrolyte of purity can be obtained.
(7) polyphosphazene electrolyte described in previous step is dissolved in dehydrated alcohol and the molten of mass fraction 30% is made
Liquid, then according to molar ratio Li+: lithium salts is added in~O~=1:8 proportion, and 1~10h is sufficiently stirred, keeps electrolyte abundant
Dissolution.
(8) porous membrane described in third step is laid on glass polytetrafluoroethylene, to its one strata of upper
Plate is placed in baking oven and heats 5 minutes, covers one layer of porous membrane again on it later by phosphonitrile electrolyte solution, sufficiently dry
The electrolytic thin-membrane of sandwich structure is placed between two blocks of tetrafluoroethene plates or glass plate after dry, this sandwich is placed on
On tablet press machine, apply the pressure pressure maintaining of 1MPa 5 minutes.Sandwich is put into -20 in refrigerator~0 DEG C freeze 1~5 hour, so
The electrolyte of sandwich structure is taken out from interlayer afterwards, is assembled into battery in the glove box full of argon gas.
(9) AC impedance method is used, the conductivity for the solid electrolyte for testing the sandwich structure under the conditions of 25 DEG C is
1.4×10-4s/cm。
Embodiment 2
(1) lithium perchlorate and PAN (mass ratio 0.1:1) are put into conical flask and suitable solvent is added, be made into high polymer
The spinning solution of mass fraction 10%；It then is the inorganic solid-state of 15% (quality that gross mass is PAN and filler) by mass fraction
Nanometer rods made of electrolyte are added in above-mentioned solution, and being sufficiently stirred makes to be uniformly mixed.
(2) the injection speed of 1ml/h, 20kv spinning voltage, use roller receive (roller revolving speed 1000r/min) item
Electrostatic spinning is carried out under part；
(3) electrostatic spinning film is put into baking oven after spinning, dry 3~48h keeps solvent complete under the conditions of 60 DEG C
Full volatilization.Obtained film is spare.
(4) a certain amount of linear polyphosphazene (PDCP) is dissolved in quantitative THF solution, to PDCP after completely dissolution to
Diethylene glycol monomethyl ether (Diethylene Glycol Monomethyl Ether) wherein is added, while a certain amount of tie up is added
Sour agent triethylamine (TEA) removes the intermediate product of dereaction, molar ratio n (PDCP): n (DGME): n (TEA)=1:2.2 of raw material:
2.4。
(5) after sufficiently reacting 10~40h, major part THF is removed using rotary evaporation, the concentrate in previous step is slow
Instillation petroleum ether in and ceaselessly stir, obtaining precipitated product is poly- phosphorus eyeball electrolyte.
(6) precipitated product of previous step is put into bag filter (molecular cut off 1000~10000), in deionized water
Dialysis 5~10 days.
Most of water in product is removed using rotary evaporation, recycles freeze-drying 48h to remove water therein, so far
The higher poly- phosphorus eyeball electrolyte of purity can be obtained.
(7) polyphosphazene electrolyte described in previous step is dissolved in dehydrated alcohol and the molten of mass fraction 30% is made
Liquid, then according to molar ratio Li+: lithium salts is added in~O~=1:8 proportion, and 1~10h is sufficiently stirred, keeps electrolyte abundant
Dissolution.
(8) porous membrane described in third step is laid on glass polytetrafluoroethylene, to its one strata of upper
Plate is placed in baking oven and heats 5 minutes, covers one layer of porous membrane again on it later by phosphonitrile electrolyte solution, sufficiently dry
The electrolytic thin-membrane of sandwich structure is placed between two blocks of tetrafluoroethene plates or glass plate after dry, this sandwich is placed on
On tablet press machine, apply the pressure pressure maintaining of 1MPa 5 minutes.Sandwich is put into -20 in refrigerator~0 DEG C freeze 1~5 hour, so
The electrolyte of sandwich structure is taken out from interlayer afterwards, is assembled into battery in the glove box full of argon gas.
(9) AC impedance method is used, the conductivity for the solid electrolyte for testing the sandwich structure under the conditions of 25 DEG C is
2.2×10-4s/cm。
Embodiment 3
(1) lithium perchlorate and PAN (mass ratio 0.1:1) are put into conical flask and suitable solvent is added, be made into high polymer
The spinning solution of mass fraction 10%；It then is the inorganic solid-state of 25% (quality that gross mass is PAN and filler) by mass fraction
Nanometer rods made of electrolyte are added in above-mentioned solution, and being sufficiently stirred makes to be uniformly mixed.
(2) the injection speed of 1ml/h, 20kv spinning voltage, use roller receive (roller revolving speed 1000r/min) item
Electrostatic spinning is carried out under part；
(3) electrostatic spinning film is put into baking oven after spinning, dry 3~48h keeps solvent complete under the conditions of 60 DEG C
Full volatilization.Obtained film is spare.
(4) a certain amount of linear polyphosphazene (PDCP) is dissolved in quantitative THF solution, to PDCP after completely dissolution to
Diethylene glycol monomethyl ether (Diethylene Glycol Monomethyl Ether) wherein is added, while a certain amount of tie up is added
Sour agent triethylamine (TEA) removes the intermediate product of dereaction, molar ratio n (PDCP): n (DGME): n (TEA)=1:2.2 of raw material:
2.4。
(5) after sufficiently reacting 10~40h, major part THF is removed using rotary evaporation, the concentrate in previous step is slow
Instillation petroleum ether in and ceaselessly stir, obtaining precipitated product is poly- phosphorus eyeball electrolyte.
(6) precipitated product of previous step is put into bag filter (molecular cut off 1000~10000), in deionized water
Dialysis 5~10 days.
Most of water in product is removed using rotary evaporation, recycles freeze-drying 48h to remove water therein, so far
The higher poly- phosphorus eyeball electrolyte of purity can be obtained.
(7) polyphosphazene electrolyte described in previous step is dissolved in dehydrated alcohol and the molten of mass fraction 30% is made
Liquid, then according to molar ratio Li+: lithium salts is added in~O~=1:8 proportion, and 1~10h is sufficiently stirred, keeps electrolyte abundant
Dissolution.
(8) porous membrane described in third step is laid on glass polytetrafluoroethylene, to its one strata of upper
Plate is placed in baking oven and heats 5 minutes, covers one layer of porous membrane again on it later by phosphonitrile electrolyte solution, sufficiently dry
The electrolytic thin-membrane of sandwich structure is placed between two blocks of tetrafluoroethene plates or glass plate after dry, this sandwich is placed on
On tablet press machine, apply the pressure pressure maintaining of 1MPa 5 minutes.Sandwich is put into -20 in refrigerator~0 DEG C freeze 1~5 hour, so
The electrolyte of sandwich structure is taken out from interlayer afterwards, is assembled into battery in the glove box full of argon gas.
(9) AC impedance method is used, the conductivity for the solid electrolyte for testing the sandwich structure under the conditions of 25 DEG C is
1.7×10-4s/cm。
Embodiment 4
(1) lithium perchlorate and PAN (mass ratio 0.33:1) are put into conical flask and suitable solvent is added, be made into high polymer
The spinning solution of mass fraction 10%；Then by inorganic solid-state that mass fraction is 5% (quality that gross mass is PAN and filler) electricity
Nanometer rods made of solution matter are added in above-mentioned solution, and being sufficiently stirred makes to be uniformly mixed.
(2) the injection speed of 1ml/h, 20kv spinning voltage, use roller receive (roller revolving speed 1000r/min) item
Electrostatic spinning is carried out under part；
(3) electrostatic spinning film is put into baking oven after spinning, dry 3~48h keeps solvent complete under the conditions of 60 DEG C
Full volatilization.Obtained film is spare.
(4) a certain amount of linear polyphosphazene (PDCP) is dissolved in quantitative THF solution, to PDCP after completely dissolution to
Diethylene glycol monomethyl ether (Diethylene Glycol Monomethyl Ether) wherein is added, while a certain amount of tie up is added
Sour agent triethylamine (TEA) removes the intermediate product of dereaction, molar ratio n (PDCP): n (DGME): n (TEA)=1:2.2 of raw material:
2.4。
(5) after sufficiently reacting 10~40h, major part THF is removed using rotary evaporation, the concentrate in previous step is slow
Instillation petroleum ether in and ceaselessly stir, obtaining precipitated product is poly- phosphorus eyeball electrolyte.
(6) precipitated product of previous step is put into bag filter (molecular cut off 1000~10000), in deionized water
Dialysis 5~10 days.
Most of water in product is removed using rotary evaporation, recycles freeze-drying 48h to remove water therein, so far
The higher poly- phosphorus eyeball electrolyte of purity can be obtained.
(7) polyphosphazene electrolyte described in previous step is dissolved in dehydrated alcohol and the molten of mass fraction 30% is made
Liquid, then according to molar ratio Li+: lithium salts is added in~O~=1:8 proportion, and 1~10h is sufficiently stirred, keeps electrolyte abundant
Dissolution.
(8) porous membrane described in third step is laid on glass polytetrafluoroethylene, to its one strata of upper
Plate is placed in baking oven and heats 5 minutes, covers one layer of porous membrane again on it later by phosphonitrile electrolyte solution, sufficiently dry
The electrolytic thin-membrane of sandwich structure is placed between two blocks of tetrafluoroethene plates or glass plate after dry, this sandwich is placed on
On tablet press machine, apply the pressure pressure maintaining of 1MPa 5 minutes.Sandwich is put into -20 in refrigerator~0 DEG C freeze 1~5 hour, so
The electrolyte of sandwich structure is taken out from interlayer afterwards, is assembled into battery in the glove box full of argon gas.
(9) AC impedance method is used, the conductivity for the solid electrolyte for testing the sandwich structure under the conditions of 25 DEG C is
1.9×10-4s/cm。
Embodiment 5
(1) lithium perchlorate and PAN (mass ratio 0.33:1) are put into conical flask and suitable solvent is added, be made into high polymer
The spinning solution of mass fraction 10%；It then is the inorganic solid-state of 15% (quality that gross mass is PAN and filler) by mass fraction
Nanometer rods made of electrolyte are added in above-mentioned solution, and being sufficiently stirred makes to be uniformly mixed.
(2) the injection speed of 1ml/h, 20kv spinning voltage, use roller receive (roller revolving speed 1000r/min) item
Electrostatic spinning is carried out under part；
(3) electrostatic spinning film is put into baking oven after spinning, dry 3~48h keeps solvent complete under the conditions of 60 DEG C
Full volatilization.Obtained film is spare.
(4) a certain amount of linear polyphosphazene (PDCP) is dissolved in quantitative THF solution, to PDCP after completely dissolution to
Diethylene glycol monomethyl ether (Diethylene Glycol Monomethyl Ether) wherein is added, while a certain amount of tie up is added
Sour agent triethylamine (TEA) removes the intermediate product of dereaction, molar ratio n (PDCP): n (DGME): n (TEA)=1:2.2 of raw material:
2.4。
(5) after sufficiently reacting 10~40h, major part THF is removed using rotary evaporation, the concentrate in previous step is slow
Instillation petroleum ether in and ceaselessly stir, obtaining precipitated product is poly- phosphorus eyeball electrolyte.
(6) precipitated product of previous step is put into bag filter (molecular cut off 1000~10000), in deionized water
Dialysis 5~10 days.
Most of water in product is removed using rotary evaporation, recycles freeze-drying 48h to remove water therein, so far
The higher poly- phosphorus eyeball electrolyte of purity can be obtained.
(7) polyphosphazene electrolyte described in previous step is dissolved in dehydrated alcohol and the molten of mass fraction 30% is made
Liquid, then according to molar ratio Li+: lithium salts is added in~O~=1:8 proportion, and 1~10h is sufficiently stirred, keeps electrolyte abundant
Dissolution.
(8) porous membrane described in third step is laid on glass polytetrafluoroethylene, to its one strata of upper
Plate is placed in baking oven and heats 5 minutes, covers one layer of porous membrane again on it later by phosphonitrile electrolyte solution, sufficiently dry
The electrolytic thin-membrane of sandwich structure is placed between two blocks of tetrafluoroethene plates or glass plate after dry, this sandwich is placed on
On tablet press machine, apply the pressure pressure maintaining of 1MPa 5 minutes.Sandwich is put into -20 in refrigerator~0 DEG C freeze 1~5 hour, so
The electrolyte of sandwich structure is taken out from interlayer afterwards, is assembled into battery in the glove box full of argon gas.
(9) AC impedance method is used, the conductivity for the solid electrolyte for testing the sandwich structure under the conditions of 25 DEG C is
2.6×10-4s/cm。
Embodiment 6
(1) lithium perchlorate and PAN (mass ratio 0.33:1) are put into conical flask and suitable solvent is added, be made into high polymer
The spinning solution of mass fraction 10%；It then is the inorganic solid-state of 25% (quality that gross mass is PAN and filler) by mass fraction
Nanometer rods made of electrolyte are added in above-mentioned solution, and being sufficiently stirred makes to be uniformly mixed.
(2) the injection speed of 1ml/h, 20kv spinning voltage, use roller receive (roller revolving speed 1000r/min) item
Electrostatic spinning is carried out under part；
(3) electrostatic spinning film is put into baking oven after spinning, dry 3~48h keeps solvent complete under the conditions of 60 DEG C
Full volatilization.Obtained film is spare.
(4) a certain amount of linear polyphosphazene (PDCP) is dissolved in quantitative THF solution, to PDCP after completely dissolution to
Diethylene glycol monomethyl ether (Diethylene Glycol Monomethyl Ether) wherein is added, while a certain amount of tie up is added
Sour agent triethylamine (TEA) removes the intermediate product of dereaction, molar ratio n (PDCP): n (DGME): n (TEA)=1:2.2 of raw material:
2.4。
(5) after sufficiently reacting 10~40h, major part THF is removed using rotary evaporation, the concentrate in previous step is slow
Instillation petroleum ether in and ceaselessly stir, obtaining precipitated product is poly- phosphorus eyeball electrolyte.
(6) precipitated product of previous step is put into bag filter (molecular cut off 1000~10000), in deionized water
Dialysis 5~10 days.
Most of water in product is removed using rotary evaporation, recycles freeze-drying 48h to remove water therein, so far
The higher poly- phosphorus eyeball electrolyte of purity can be obtained.
(7) polyphosphazene electrolyte described in previous step is dissolved in dehydrated alcohol and the molten of mass fraction 30% is made
Liquid, then according to molar ratio Li+: lithium salts is added in~O~=1:8 proportion, and 1~10h is sufficiently stirred, keeps electrolyte abundant
Dissolution.
(8) porous membrane described in third step is laid on glass polytetrafluoroethylene, to its one strata of upper
Plate is placed in baking oven and heats 5 minutes, covers one layer of porous membrane again on it later by phosphonitrile electrolyte solution, sufficiently dry
The electrolytic thin-membrane of sandwich structure is placed between two blocks of tetrafluoroethene plates or glass plate after dry, this sandwich is placed on
On tablet press machine, apply the pressure pressure maintaining of 1MPa 5 minutes.Sandwich is put into -20 in refrigerator~0 DEG C freeze 1~5 hour, so
The electrolyte of sandwich structure is taken out from interlayer afterwards, is assembled into battery in the glove box full of argon gas.
(9) AC impedance method is used, the conductivity for the solid electrolyte for testing the sandwich structure under the conditions of 25 DEG C is
2.2×10-4s/cm。
Embodiment 7
(1) lithium perchlorate and PAN (mass ratio 0.4:1) are put into conical flask and suitable solvent is added, be made into high polymer
The spinning solution of mass fraction 10%；Then by inorganic solid-state that mass fraction is 5% (quality that gross mass is PAN and filler) electricity
Nanometer rods made of solution matter are added in above-mentioned solution, and being sufficiently stirred makes to be uniformly mixed.
(2) the injection speed of 1ml/h, 20kv spinning voltage, use roller receive (roller revolving speed 1000r/min) item
Electrostatic spinning is carried out under part；
(3) electrostatic spinning film is put into baking oven after spinning, dry 3~48h keeps solvent complete under the conditions of 60 DEG C
Full volatilization.Obtained film is spare.
(4) a certain amount of linear polyphosphazene (PDCP) is dissolved in quantitative THF solution, to PDCP after completely dissolution to
Diethylene glycol monomethyl ether (Diethylene Glycol Monomethyl Ether) wherein is added, while a certain amount of tie up is added
Sour agent triethylamine (TEA) removes the intermediate product of dereaction, molar ratio n (PDCP): n (DGME): n (TEA)=1:2.2 of raw material:
2.4。
(5) after sufficiently reacting 10~40h, major part THF is removed using rotary evaporation, the concentrate in previous step is slow
Instillation petroleum ether in and ceaselessly stir, obtaining precipitated product is poly- phosphorus eyeball electrolyte.
(6) precipitated product of previous step is put into bag filter (molecular cut off 1000~10000), in deionized water
Dialysis 5~10 days.
Most of water in product is removed using rotary evaporation, recycles freeze-drying 48h to remove water therein, so far
The higher poly- phosphorus eyeball electrolyte of purity can be obtained.
(7) polyphosphazene electrolyte described in previous step is dissolved in dehydrated alcohol and the molten of mass fraction 30% is made
Liquid, then according to molar ratio Li+: lithium salts is added in~O~=1:8 proportion, and 1~10h is sufficiently stirred, keeps electrolyte abundant
Dissolution.
(8) porous membrane described in third step is laid on glass polytetrafluoroethylene, to its one strata of upper
Plate is placed in baking oven and heats 5 minutes, covers one layer of porous membrane again on it later by phosphonitrile electrolyte solution, sufficiently dry
The electrolytic thin-membrane of sandwich structure is placed between two blocks of tetrafluoroethene plates or glass plate after dry, this sandwich is placed on
On tablet press machine, apply the pressure pressure maintaining of 1MPa 5 minutes.Sandwich is put into -20 in refrigerator~0 DEG C freeze 1~5 hour, so
The electrolyte of sandwich structure is taken out from interlayer afterwards, is assembled into battery in the glove box full of argon gas.
(9) AC impedance method is used, the conductivity for the solid electrolyte for testing the sandwich structure under the conditions of 25 DEG C is
1.2×10-4s/cm。
Embodiment 8
(1) lithium perchlorate and PAN (mass ratio 0.4:1) are put into conical flask and suitable solvent is added, be made into high polymer
The spinning solution of mass fraction 10%；It then is the inorganic solid-state of 15% (quality that gross mass is PAN and filler) by mass fraction
Nanometer rods made of electrolyte are added in above-mentioned solution, and being sufficiently stirred makes to be uniformly mixed.
(2) the injection speed of 1ml/h, 20kv spinning voltage, use roller receive (roller revolving speed 1000r/min) item
Electrostatic spinning is carried out under part；
(3) electrostatic spinning film is put into baking oven after spinning, dry 3~48h keeps solvent complete under the conditions of 60 DEG C
Full volatilization.Obtained film is spare.
(4) a certain amount of linear polyphosphazene (PDCP) is dissolved in quantitative THF solution, to PDCP after completely dissolution to
Diethylene glycol monomethyl ether (Diethylene Glycol Monomethyl Ether) wherein is added, while a certain amount of tie up is added
Sour agent triethylamine (TEA) removes the intermediate product of dereaction, molar ratio n (PDCP): n (DGME): n (TEA)=1:2.2 of raw material:
2.4。
(5) after sufficiently reacting 10~40h, major part THF is removed using rotary evaporation, the concentrate in previous step is slow
Instillation petroleum ether in and ceaselessly stir, obtaining precipitated product is poly- phosphorus eyeball electrolyte.
(6) precipitated product of previous step is put into bag filter (molecular cut off 1000~10000), in deionized water
Dialysis 5~10 days.
Most of water in product is removed using rotary evaporation, recycles freeze-drying 48h to remove water therein, so far
The higher poly- phosphorus eyeball electrolyte of purity can be obtained.
(7) polyphosphazene electrolyte described in previous step is dissolved in dehydrated alcohol and the molten of mass fraction 30% is made
Liquid, then according to molar ratio Li+: lithium salts is added in~O~=1:8 proportion, and 1~10h is sufficiently stirred, keeps electrolyte abundant
Dissolution.
(8) porous membrane described in third step is laid on glass polytetrafluoroethylene, to its one strata of upper
Plate is placed in baking oven and heats 5 minutes, covers one layer of porous membrane again on it later by phosphonitrile electrolyte solution, sufficiently dry
The electrolytic thin-membrane of sandwich structure is placed between two blocks of tetrafluoroethene plates or glass plate after dry, this sandwich is placed on
On tablet press machine, apply the pressure pressure maintaining of 1MPa 5 minutes.Sandwich is put into -20 in refrigerator~0 DEG C freeze 1~5 hour, so
The electrolyte of sandwich structure is taken out from interlayer afterwards, is assembled into battery in the glove box full of argon gas.
(9) AC impedance method is used, the conductivity for the solid electrolyte for testing the sandwich structure under the conditions of 25 DEG C is
2.0×10-4s/cm。
Embodiment 9
(1) lithium perchlorate and PAN (mass ratio 0.4:1) are put into conical flask and suitable solvent is added, be made into high polymer
The spinning solution of mass fraction 10%；It then is the inorganic solid-state of 25% (quality that gross mass is PAN and filler) by mass fraction
Nanometer rods made of electrolyte are added in above-mentioned solution, and being sufficiently stirred makes to be uniformly mixed.
(2) the injection speed of 1ml/h, 20kv spinning voltage, use roller receive (roller revolving speed 1000r/min) item
Electrostatic spinning is carried out under part；
(3) electrostatic spinning film is put into baking oven after spinning, dry 3~48h keeps solvent complete under the conditions of 60 DEG C
Full volatilization.Obtained film is spare.
(4) a certain amount of linear polyphosphazene (PDCP) is dissolved in quantitative THF solution, to PDCP after completely dissolution to
Diethylene glycol monomethyl ether (Diethylene Glycol Monomethyl Ether) wherein is added, while a certain amount of tie up is added
Sour agent triethylamine (TEA) removes the intermediate product of dereaction, molar ratio n (PDCP): n (DGME): n (TEA)=1:2.2 of raw material:
2.4。
(5) after sufficiently reacting 10~40h, major part THF is removed using rotary evaporation, the concentrate in previous step is slow
Instillation petroleum ether in and ceaselessly stir, obtaining precipitated product is poly- phosphorus eyeball electrolyte.
(6) precipitated product of previous step is put into bag filter (molecular cut off 1000~10000), in deionized water
Dialysis 5~10 days.
Most of water in product is removed using rotary evaporation, recycles freeze-drying 48h to remove water therein, so far
The higher poly- phosphorus eyeball electrolyte of purity can be obtained.
(7) polyphosphazene electrolyte described in previous step is dissolved in dehydrated alcohol and the molten of mass fraction 30% is made
Liquid, then according to molar ratio Li+: lithium salts is added in~O~=1:8 proportion, and 1~10h is sufficiently stirred, keeps electrolyte abundant
Dissolution.
(8) porous membrane described in third step is laid on glass polytetrafluoroethylene, to its one strata of upper
Plate is placed in baking oven and heats 5 minutes, covers one layer of porous membrane again on it later by phosphonitrile electrolyte solution, sufficiently dry
The electrolytic thin-membrane of sandwich structure is placed between two blocks of tetrafluoroethene plates or glass plate after dry, this sandwich is placed on
On tablet press machine, apply the pressure pressure maintaining of 1MPa 5 minutes.Sandwich is put into -20 in refrigerator~0 DEG C freeze 1~5 hour, so
The electrolyte of sandwich structure is taken out from interlayer afterwards, is assembled into battery in the glove box full of argon gas.
(9) AC impedance method is used, the conductivity for the solid electrolyte for testing the sandwich structure under the conditions of 25 DEG C is
1.8×10-4s/cm。
Claims (3)
1. a kind of preparation method of the solid electrolyte with dual diversion sub-network, it is characterized in that including the following steps:
(1) high molecular polymer, lithium salts and inorganic solid electrolyte are put into container, and solvent is added and is made into spinning solution, into
Row electrostatic spinning, obtains porous membrane；
(2) linear polyphosphazene is dissolved in tetrahydrofuran solution, is added thereto containing heteroatom oxygen atom, sub- amide official
It can roll into a ball and the polymer lateral chain of mercaptan sulphur atom functional group is as electron donor's coordination lithium ion, while it is anti-that acid-releasing agent removing is added
The intermediate product answered, obtains concentrate；Sufficiently after reaction, tetrahydrofuran is removed, the concentrate is instilled in petroleum ether, is obtained
Precipitated product is put into bag filter by precipitated product, is dialysed, and water removal obtains polyphosphazene electrolyte；
(3) solution is made in the polyphosphazene electrolyte that step (2) obtains, lithium salts is added；It will be obtained in the step (1)
Porous membrane is laid on glass or polytetrafluoroethylene, to its one strata phosphonitrile electrolyte solution of upper, later at it
On cover one layer of porous membrane again, after sufficiently dry, obtain the electrolytic thin-membrane of sandwich structure.
2. the preparation method of the solid electrolyte according to claim 1 with dual diversion sub-network, it is characterised in that
In the step (1), the mass ratio of the lithium salts and the high molecular polymer is (0.1-0.6): 1；The inoganic solids electricity
Solving mass fraction of the matter filler in the mixture of the high molecular polymer and the inorganic solid electrolyte filler is 5-
25%.
3. the preparation method of the solid electrolyte according to claim 1 with dual diversion sub-network, it is characterised in that
In the step (3), polyphosphazene electrolyte is dissolved in dehydrated alcohol to the solution that mass fraction 10~30% is made first,
Then according to molar ratio lithium salts: ether oxygen functional group or imino functionalities or thioether functional group=1:(4~14) proportion be added
Lithium salts dissolves electrolyte sufficiently.
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| TWI722747B (en) * | 2019-12-18 | 2021-03-21 | 財團法人工業技術研究院 | Battery |
| CN111180788B (en) * | 2020-03-02 | 2022-03-22 | 珠海冠宇电池股份有限公司 | All-solid-state electrolyte, preparation method thereof and lithium ion battery |
| CN111900468B (en) * | 2020-08-11 | 2022-08-30 | 珠海冠宇电池股份有限公司 | Solid electrolyte, preparation method thereof and lithium ion battery |
| CN111910283A (en) * | 2020-08-14 | 2020-11-10 | 浙江理工大学 | Oxide type ceramic composite nanofiber solid electrolyte and electrostatic spinning preparation method thereof |
| CN116130759B (en) * | 2023-04-17 | 2023-06-23 | 江苏华富储能新技术股份有限公司 | Preparation method of sandwich structure composite solid polymer electrolyte |
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