CN111082136B - Power lithium battery fiber membrane solid electrolyte and preparation method thereof - Google Patents
Power lithium battery fiber membrane solid electrolyte and preparation method thereof Download PDFInfo
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- 239000000835 fiber Substances 0.000 title claims abstract description 52
- 239000012528 membrane Substances 0.000 title claims abstract description 48
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 34
- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 238000009987 spinning Methods 0.000 claims abstract description 107
- 239000000243 solution Substances 0.000 claims abstract description 82
- PAZHGORSDKKUPI-UHFFFAOYSA-N lithium metasilicate Chemical compound [Li+].[Li+].[O-][Si]([O-])=O PAZHGORSDKKUPI-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910052912 lithium silicate Inorganic materials 0.000 claims abstract description 28
- 150000002642 lithium compounds Chemical class 0.000 claims abstract description 26
- 229920000642 polymer Polymers 0.000 claims abstract description 21
- 238000002844 melting Methods 0.000 claims abstract description 19
- 230000008018 melting Effects 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 19
- 239000007864 aqueous solution Substances 0.000 claims abstract description 14
- 239000002608 ionic liquid Substances 0.000 claims abstract description 12
- 238000003825 pressing Methods 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 11
- 238000000151 deposition Methods 0.000 claims abstract description 9
- 239000002253 acid Substances 0.000 claims abstract description 7
- 238000005507 spraying Methods 0.000 claims abstract description 7
- -1 1-propyl-3-methylimidazole bistrifluoromethane sulfimide salt Chemical compound 0.000 claims description 29
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 21
- 239000002202 Polyethylene glycol Substances 0.000 claims description 17
- 229920001223 polyethylene glycol Polymers 0.000 claims description 17
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 14
- 239000007787 solid Substances 0.000 claims description 11
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 10
- 238000000227 grinding Methods 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 229910002984 Li7La3Zr2O12 Inorganic materials 0.000 claims description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 229910010854 Li6PS5Br Inorganic materials 0.000 claims description 3
- 229910006939 Si0.5Ge0.5 Inorganic materials 0.000 claims description 3
- 229910000921 lithium phosphorous sulfides (LPS) Inorganic materials 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 235000012239 silicon dioxide Nutrition 0.000 claims description 3
- 229910009178 Li1.3Al0.3Ti1.7(PO4)3 Inorganic materials 0.000 claims description 2
- 229910003405 Li10GeP2S12 Inorganic materials 0.000 claims description 2
- 229910004956 Li10SiP2S12 Inorganic materials 0.000 claims description 2
- 229910010408 Li2NH Inorganic materials 0.000 claims description 2
- 229910011201 Li7P3S11 Inorganic materials 0.000 claims description 2
- 229910011195 Li7PN4 Inorganic materials 0.000 claims description 2
- 229910011187 Li7PS6 Inorganic materials 0.000 claims description 2
- 229910010084 LiAlH4 Inorganic materials 0.000 claims description 2
- 229910013698 LiNH2 Inorganic materials 0.000 claims description 2
- 239000012448 Lithium borohydride Substances 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 239000012280 lithium aluminium hydride Substances 0.000 claims description 2
- AFRJJFRNGGLMDW-UHFFFAOYSA-N lithium amide Chemical compound [Li+].[NH2-] AFRJJFRNGGLMDW-UHFFFAOYSA-N 0.000 claims description 2
- IDBFBDSKYCUNPW-UHFFFAOYSA-N lithium nitride Chemical compound [Li]N([Li])[Li] IDBFBDSKYCUNPW-UHFFFAOYSA-N 0.000 claims description 2
- 229910000614 lithium tin phosphorous sulfides (LSPS) Inorganic materials 0.000 claims description 2
- UFHGFEBWRZMIAT-UHFFFAOYSA-N [SH2]=N.FC(F)F.FC(F)F.C(C)N1CN(C=C1)C Chemical compound [SH2]=N.FC(F)F.FC(F)F.C(C)N1CN(C=C1)C UFHGFEBWRZMIAT-UHFFFAOYSA-N 0.000 claims 1
- 230000008021 deposition Effects 0.000 abstract description 6
- 230000008569 process Effects 0.000 abstract description 6
- 239000002131 composite material Substances 0.000 abstract description 3
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 3
- 238000001879 gelation Methods 0.000 abstract description 2
- 238000010041 electrostatic spinning Methods 0.000 abstract 1
- 239000011148 porous material Substances 0.000 abstract 1
- 229910001416 lithium ion Inorganic materials 0.000 description 12
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 11
- 239000003792 electrolyte Substances 0.000 description 9
- 239000005518 polymer electrolyte Substances 0.000 description 9
- 238000007493 shaping process Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000002791 soaking Methods 0.000 description 5
- 239000011159 matrix material Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- RFJSVARKFQELLL-UHFFFAOYSA-N 1-ethyl-3-methyl-2h-imidazole;1,1,1-trifluoro-n-(trifluoromethylsulfonyl)methanesulfonamide Chemical compound CCN1CN(C)C=C1.FC(F)(F)S(=O)(=O)NS(=O)(=O)C(F)(F)F RFJSVARKFQELLL-UHFFFAOYSA-N 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 229910003002 lithium salt Inorganic materials 0.000 description 3
- 159000000002 lithium salts Chemical class 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- JFYZBXKLRPWSGV-UHFFFAOYSA-N 1-methyl-3-propyl-2h-imidazole Chemical compound CCCN1CN(C)C=C1 JFYZBXKLRPWSGV-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000011244 liquid electrolyte Substances 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920000379 polypropylene carbonate Polymers 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- KAIPKTYOBMEXRR-UHFFFAOYSA-N 1-butyl-3-methyl-2h-imidazole Chemical compound CCCCN1CN(C)C=C1 KAIPKTYOBMEXRR-UHFFFAOYSA-N 0.000 description 1
- AXWLKJWVMMAXBD-UHFFFAOYSA-N 1-butylpiperidine Chemical compound CCCCN1CCCCC1 AXWLKJWVMMAXBD-UHFFFAOYSA-N 0.000 description 1
- JSHASCFKOSDFHY-UHFFFAOYSA-N 1-butylpyrrolidine Chemical compound CCCCN1CCCC1 JSHASCFKOSDFHY-UHFFFAOYSA-N 0.000 description 1
- IBZJNLWLRUHZIX-UHFFFAOYSA-N 1-ethyl-3-methyl-2h-imidazole Chemical compound CCN1CN(C)C=C1 IBZJNLWLRUHZIX-UHFFFAOYSA-N 0.000 description 1
- VTDIWMPYBAVEDY-UHFFFAOYSA-N 1-propylpiperidine Chemical compound CCCN1CCCCC1 VTDIWMPYBAVEDY-UHFFFAOYSA-N 0.000 description 1
- HLNRRPIYRBBHSQ-UHFFFAOYSA-N 1-propylpyrrolidine Chemical compound CCCN1CCCC1 HLNRRPIYRBBHSQ-UHFFFAOYSA-N 0.000 description 1
- GBHTUZMELHJUSG-UHFFFAOYSA-N CCCN1CCCCC1.O=S(C(F)(F)F)(NS(C(F)(F)F)(=O)=O)=O Chemical compound CCCN1CCCCC1.O=S(C(F)(F)F)(NS(C(F)(F)F)(=O)=O)=O GBHTUZMELHJUSG-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000010416 ion conductor Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000010295 mobile communication Methods 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
- H01M2300/0082—Organic polymers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Dispersion Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Secondary Cells (AREA)
Abstract
The invention provides a preparation method of a fiber membrane solid electrolyte of a power lithium battery, which comprises the steps of dispersing and melting an ionic liquid and a polymer to prepare a spinning solution A; adding the spinning solution A and the spinning solution B into a spinning channel, and carrying out coaxial electrostatic spinning to ensure that the spinning solution A is on the outer layer and the spinning solution B is on the inner layer; and spraying lithium silicate aqueous solution on the surface of the outer layer, spraying the lithium silicate aqueous solution on a roller for deposition, treating the lithium silicate aqueous solution in weak acid solution, pressing and drying to obtain the power lithium battery fiber membrane solid electrolyte. According to the invention, the lithium compound is encapsulated in the inner layer of the fiber through coaxial spinning, so that the inorganic lithium compound is stabilized, the surface of the composite fiber forms loose and micro-pores through gelation of lithium silicate, and the conductivity is greatly improved due to good interface performance. The preparation process of the invention has easily controlled and stable process and is suitable for large-scale production.
Description
Technical Field
The invention relates to the field of lithium battery materials, in particular to a power lithium battery fiber membrane solid electrolyte and a preparation method thereof.
Background
With the progress of economic globalization and the increasing demand for energy, finding new energy storage devices has become a focus of attention in the field related to new energy. Lithium Ion Battery (Li-Ion, Lithium Ion Battery): is a secondary battery (rechargeable battery) that operates by mainly relying on lithium ions moving between a positive electrode and a negative electrode. During charging and discharging, Li + is inserted and extracted back and forth between two electrodes: during charging, Li + is extracted from the positive electrode and is inserted into the negative electrode through the electrolyte, and the negative electrode is in a lithium-rich state; the opposite is true during discharge. Compared with nickel-cadmium and nickel-hydrogen batteries, the lithium ion battery has the advantages of high voltage, large specific energy, long cycle life, good safety performance, small self-discharge, no memory effect, rapid charge and discharge, wide working temperature range and the like, and is widely applied to various fields of electric automobiles, electric bicycles, electric motorcycles, solar photovoltaic and wind power generation energy storage systems, intelligent power grid energy storage systems, mobile communication base stations, electric power, chemical engineering, hospital standby UPS, EPS power supplies, security and protection lighting, portable mobile power supplies, mine safety equipment and the like.
With the application of lithium batteries in the field of power, the safety, high capacity and long life of lithium ion batteries become critical. However, the organic liquid electrolyte is easy to leak and burn, so that potential safety hazards exist, and the raw materials are high in price. In recent years, solid electrolytes have been rapidly developed for use in lithium ion batteries. With the application of lithium batteries in the field of power, the safety, high capacity and long life of lithium ion batteries become critical. The electrolyte of the lithium ion secondary battery is a flammable liquid organic matter which is widely adopted at present, and when the size of the battery is further enlarged and the charging and discharging power is further improved, the electrolyte brings a lot of unpredictable potential safety hazards to the use of the battery. In recent years, inorganic solid-phase electrolytes are proposed to replace organic liquid-phase electrolytes, so that potential safety hazards in the large-scale application process of lithium ion batteries are eliminated.
Among them, the replacement of liquid electrolyte with solid polymer electrolyte is a great progress in the development of lithium ion batteries. The solid polymer electrolyte is a novel electrolyte formed by compounding a polymer body and metal salt, does not contain an organic solvent, does not have the safety problems of leakage and the like, has good flexibility, can relieve the volume change of active substances in the charge and discharge process, and obviously improves the cycle life and the safety performance of the battery. The polymer electrolyte is easy to process into a film and can be made into a full-plastic structure, so that ultra-thin batteries with various shapes can be manufactured, and the volume change of electrodes in the charging and discharging processes of the batteries can be well adapted.
An ideal lithium battery polymer electrolyte matrix should have: firstly, the polymer matrix has high dielectric constant, and the chain segment contains polar groups capable of complexing with metal ions, and the groups can dissolve lithium salt and form a polymer/salt composite system; secondly, the polymer can provide a channel for the migration of ions, and a polymer chain has more amorphous areas and better flexibility according to the conductive mechanism of polymer electrolyte; the polymer has better electrochemical stability; and fourthly, the polymer has good mechanical property, can inhibit the growth of lithium dendrite and endows the battery with good processing performance. In recent years, a large number of different types of polymer electrolytes such as polyethylene oxide (PEO), polypropylene carbonate (PPC), Polysiloxane (PSLICs), and polyvinylidene fluoride (PVDF) have been reported.
The solid polymer electrolyte is mostly prepared by compounding a polymer matrix and lithium salt, however, lithium ions and counter ions provided by the lithium salt can migrate under the action of an electric field force, and significant concentration polarization can be caused by simultaneous migration of anions and cations, so that the conductivity of a system is attenuated, the impedance of the system is increased, the transmission efficiency of the electrolyte is low, and the application of the polymer electrolyte in the field of a power battery with quick start is hindered. Therefore, designing and developing a polymer matrix with a novel structure and optimizing the composition of the polymer electrolyte and the structure of the all-solid-state battery are the key points for preparing the high-performance all-solid-state lithium battery.
Disclosure of Invention
Aiming at the defect of low transmission efficiency of the existing polymer solid electrolyte, the invention provides the fiber membrane solid electrolyte of the power lithium battery and the preparation method thereof.
In order to solve the problems, the invention adopts a power lithium battery fiber membrane solid electrolyte and a preparation method thereof.
A preparation method of a power lithium battery fiber membrane solid electrolyte comprises the following steps:
(1) dispersing and melting the ionic liquid and the polymer to prepare spinning solution A;
(2) grinding the lithium compound to a nano level, and forming a spinning solution B by the lithium compound, the silicon dioxide sol and polyethylene glycol;
(3) adding the spinning solution A and the spinning solution B into a spinning channel, carrying out coaxial spinning, enabling the spinning solution A to be on the outer layer and the spinning solution B to be on the inner layer, spraying a lithium silicate aqueous solution on the surface of the outer layer through a nozzle, and carrying out spinning and depositing on a roller to obtain a felt-shaped fiber membrane;
(4) and (4) treating the felt-shaped fiber membrane obtained in the step (3) with weak acid liquid to enable lithium silicate on the surface to be gelatinized, and further pressing and drying to obtain the loose power lithium battery fiber membrane solid electrolyte with micropores on the surface.
Preferably, the ionic liquid is one of 1-ethyl-3-methylimidazole bistrifluoromethylsulfonyl imide salt, 1-propyl-3-methylimidazole bistrifluoromethylsulfonyl imide salt, 1-butyl-3-methylimidazole bistrifluoromethylsulfonyl imide salt, N-methyl, propyl piperidine bistrifluoromethylsulfonyl imide salt, N-methyl, butyl piperidine bistrifluoromethylsulfonyl imide salt, N-methyl, propyl pyrrolidine bistrifluoromethylsulfonyl imide salt, N-methyl, butyl pyrrolidine bistrifluoromethylsulfonyl imide salt; the polymer is polyoxyethylene.
Preferably, the mass ratio of the ionic liquid to the polymer is (0.05-0.08) to (0.95-0.92), the melting temperature is set to be 100 ℃, and the ionic liquid and the polymer are uniformly mixed and melted in a high-speed mixer to prepare the spinning solution A.
Preferably, the lithium compound is Li7La3Zr2O12、Li1.3Al0.3Ti1.7(PO4)3、Li3PS4、Li9.6P3S12、Li7P3S11、Li11Si2PS12、Li10SiP2S12、Li10SnP2S12、Li10GeP2S12、Li10Si0.5Ge0.5P2S12、Li10Ge0.5Sn0.5P2S12、Li10Si0.5Sn0.5P2S12、Li9.54Si1.74P1.44S11.7Cl0.3、 Li6PS5Br、Li6PS5Br、Li7PS6、Li7PS5I、Li7PO5Cl、Li3N、Li7PN4、LiSi2N3、LiPN2、Li2NH、Li3(NH2)2I、LiBH4、LiAlH4、LiNH2、Li2CdCl4The particle size of the lithium compound is 20-800 nm.
Preferably, the mass ratio of the lithium compound to the silica sol to the polyethylene glycol is (10-15): (77-88): (2-8), wherein the solid content of the silica sol is 10-20%.
Preferably, the modulus of the lithium silicate aqueous solution in the step (3) is 2.2 to 4.5. And coating a lithium silicate aqueous solution to wet the surface of the fiber.
Preferably, the coaxial spinning parameters in the step (3) are 12-30KV and 10-20cm of positive and negative electrode spacing.
Preferably, the weak acid solution in the step (4) is one of phosphoric acid and acetic acid with pH of 4-6.
The invention also provides a power lithium battery fiber membrane solid electrolyte prepared by the method.
Aiming at the defect of low transmission efficiency of the existing polymer solid electrolyte, the invention provides a preparation method of a fiber membrane solid electrolyte of a power lithium battery, which comprises the steps of preparing a spinning solution A by dispersing and melting an ionic liquid and a polymer; grinding the lithium compound to a nano level, and forming a spinning solution B by the lithium compound, the silicon dioxide sol and polyethylene glycol; adding the spinning solution A and the spinning solution B into a spinning channel, and carrying out coaxial spinning to ensure that the spinning solution A is on the outer layer and the spinning solution B is on the inner layer; spraying lithium silicate solution on the surface of the outer layer through a nozzle, and spraying the lithium silicate solution on a roller for deposition to obtain a felt-like fibrous membrane; and (3) treating with weak acid solution to gelatinize lithium silicate on the surface, further pressing and drying to obtain loose power lithium battery fiber membrane solid electrolyte with micropores on the surface. Adopting electrostatic coaxial spinning, when the electric field force is large enough, polymer liquid drops overcome the surface tension to form jet trickle, and finally fall on a roller rotating continuously to form a fiber film similar to a felt shape; the fiber is sprayed with lithium silicate solution and further treated in weak acid solution to gelatinize the lithium silicate on the surface, and the solid electrolyte of the fiber membrane of the power lithium battery is obtained after pressing and drying.
Compared with the prior art, the fiber membrane solid electrolyte for the power lithium battery and the preparation method thereof have the outstanding characteristics and excellent effects that:
1. the invention combines organic and inorganic through spinning, and encapsulates lithium compound in the inner layer of the fiber, thereby not only stabilizing the inorganic lithium compound, but also forming loose and micropore on the surface of the composite fiber through lithium silicate gelation, and having good boundaryThe surface performance greatly improves the conductivity. The conductivity of the obtained fiber membrane solid electrolyte at room temperature of the ionic conductor is more than 10-3S/cm and excellent mechanical property.
2. The invention has simple process method and easily controlled and stable preparation process, and is suitable for large-scale production and manufacture.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments, but it should not be construed that the scope of the present invention is limited to the following examples. Various substitutions and alterations can be made by those skilled in the art and by conventional means without departing from the spirit of the method of the invention described above.
Example 1
(1) Preparing 1-ethyl-3-methylimidazole bistrifluoromethanesulfonimide salt and polyoxyethylene according to the mass ratio of 0.05: 0.95, setting the melting temperature to be 100 ℃, and uniformly mixing and melting in a high-speed mixer to prepare a spinning solution A;
(2) mixing Li7La3Zr2O12Grinding until the particle size is 200nm, the solid content is 15% of silica sol and polyethylene glycol to form a spinning solution B, wherein the mass ratio of the lithium compound to the silica sol to the polyethylene glycol is 12: 80: 8;
(3) adding the spinning solution A and the spinning solution B into a spinning channel, wherein the feeding mass ratio of the spinning solution A to the spinning solution B is 1:3, carrying out coaxial spinning, wherein the coaxial spinning parameters are 30KV and the positive and negative electrode spacing is 10cm, so that the spinning solution A is on the outer layer, the spinning solution B is on the inner layer, the surface of the outer layer is sprayed with a lithium silicate aqueous solution with the modulus of 2.5 through a nozzle, and the spinning is carried out on a continuously rotating roller for deposition, thus obtaining a felt-shaped fiber membrane;
(4) and (4) soaking the felty fiber membrane obtained in the step (3) in an acetic acid solution with the pH value of 5 for 5min to gelatinize lithium silicate on the surface, further performing roller pressing and shaping, and drying at 70 ℃ to obtain the loose power lithium battery fiber membrane solid electrolyte with micropores on the surface.
Example 2
(1) Preparing ionic liquid 1-propyl-3-methylimidazole bistrifluoromethane sulfimide salt and polyoxyethylene according to the mass ratio of 0.07: 0.93, setting the melting temperature to be 100 ℃, and uniformly mixing and melting in a high-speed mixer to prepare spinning solution A;
(2) mixing lithium compound Li10Si0.5Ge0.5P2S12Grinding until the particle size is 800nm, the solid content is 20 percent, and the spinning solution B is composed of silica sol and polyethylene glycol, wherein the mass ratio of the lithium compound to the silica sol to the polyethylene glycol is 13: 81: 6;
(3) adding the spinning solution A and the spinning solution B into a spinning channel, wherein the feeding mass ratio of the spinning solution A to the spinning solution B is 1:3, carrying out coaxial spinning, wherein the coaxial spinning parameters are 30KV and the positive and negative electrode spacing is 10cm, so that the spinning solution A is on the outer layer, the spinning solution B is on the inner layer, the surface of the outer layer is sprayed with a lithium silicate aqueous solution with the modulus of 2.5 through a nozzle, and the spinning is carried out on a continuously rotating roller for deposition, thus obtaining a felt-shaped fiber membrane;
(4) and (4) soaking the felty fiber membrane obtained in the step (3) in an acetic acid solution with the pH value of 5 for 8min to gelatinize lithium silicate on the surface, further performing roller pressing and shaping, and drying at 70 ℃ to obtain the loose power lithium battery fiber membrane solid electrolyte with micropores on the surface.
Example 3
(1) Preparing ionic liquid N-methyl, propyl piperidine bistrifluoromethanesulfonimide salt and polyoxyethylene according to the mass ratio of 0.06: 0.94, setting the melting temperature to be 100 ℃, and uniformly mixing and melting in a high-speed mixer to prepare spinning solution A;
(2) mixing lithium compound LiSi2N3Grinding until the particle size is 20nm, the solid content is 10% of silica sol and polyethylene glycol to form a spinning solution B, wherein the mass ratio of the lithium compound to the silica sol to the polyethylene glycol is 10: 88: 2;
(3) adding the spinning solution A and the spinning solution B into a spinning channel, wherein the feeding mass ratio of the spinning solution A to the spinning solution B is 1:3, carrying out coaxial spinning, wherein the coaxial spinning parameters are 30KV and the positive and negative electrode spacing is 10cm, so that the spinning solution A is on the outer layer, the spinning solution B is on the inner layer, the surface of the outer layer is sprayed with a lithium silicate aqueous solution with the modulus of 2.5 through a nozzle, and the spinning is carried out on a continuously rotating roller for deposition, thus obtaining a felt-shaped fiber membrane;
(4) and (4) soaking the felty fiber membrane obtained in the step (3) in an acetic acid solution with the pH value of 5 for 10min to gelatinize lithium silicate on the surface, further performing roller pressing and shaping, and drying at 70 ℃ to obtain the loose power lithium battery fiber membrane solid electrolyte with micropores on the surface.
Example 4
(1) Uniformly mixing and melting ionic liquid 1-propyl-3-methylimidazole bistrifluoromethanesulfonylimide salt and polyoxyethylene in a high-speed mixer at a melting temperature of 149 ℃ according to a mass ratio of 0.07: 0.93 to prepare a spinning solution A;
(2) mixing lithium compound Li3PS4Grinding until the particle size is 700nm, the solid content is 14 percent, and the spinning solution B is composed of silica sol and polyethylene glycol, wherein the mass ratio of the lithium compound to the silica sol to the polyethylene glycol is 15: 77: 8;
(3) adding the spinning solution A and the spinning solution B into a spinning channel, wherein the feeding mass ratio of the spinning solution A to the spinning solution B is 1:3, carrying out coaxial spinning, wherein the coaxial spinning parameters are 30KV and the positive and negative electrode spacing is 10cm, so that the spinning solution A is on the outer layer, the spinning solution B is on the inner layer, the surface of the outer layer is sprayed with a lithium silicate aqueous solution with the modulus of 2.5 through a nozzle, and the spinning is carried out on a continuously rotating roller for deposition, thus obtaining a felt-shaped fiber membrane;
(4) and (4) soaking the felty fiber membrane obtained in the step (3) in an acetic acid solution with the pH value of 5 for 5min to gelatinize lithium silicate on the surface, further performing roller pressing and shaping, and drying at 70 ℃ to obtain the loose power lithium battery fiber membrane solid electrolyte with micropores on the surface.
Comparative example 1
(1) Preparing 1-ethyl-3-methylimidazole bistrifluoromethanesulfonimide salt and polyoxyethylene according to the mass ratio of 0.05: 0.95, setting the melting temperature to be 100 ℃, and uniformly mixing and melting in a high-speed mixer to prepare a spinning solution A;
(2) mixing Li7La3Zr2O12Grinding to obtain powder with particle diameter of 200nm and solid content of 15%The spinning solution B consists of silica sol and polyethylene glycol, and the mass ratio of the lithium compound to the silica sol to the polyethylene glycol is 12: 80: 8;
(3) mixing the spinning solution A and the spinning solution B according to the mass ratio of 1:3, directly spinning, wherein the spinning parameters are 30KV and the distance between a positive electrode and a negative electrode is 10cm, spraying a lithium silicate aqueous solution with the modulus of 2.5 on the surface of an outer layer through a nozzle, and depositing the lithium silicate aqueous solution on a roller which continuously rotates through spinning to obtain a felt-shaped fibrous membrane;
(4) and (4) soaking the felty fiber membrane obtained in the step (3) in an acetic acid solution with the pH value of 5 for 5min to gelatinize lithium silicate on the surface, further performing roller pressing and shaping, and drying at 70 ℃ to obtain the loose power lithium battery fiber membrane solid electrolyte with micropores on the surface.
Comparative example 1 compared to example 1, no co-axial spinning was performed and no lithium compound was encapsulated in the inner layer of the fiber, affecting the interfacial properties.
Comparative example 2
(1) Preparing 1-ethyl-3-methylimidazole bistrifluoromethanesulfonimide salt and polyoxyethylene according to the mass ratio of 0.05: 0.95, setting the melting temperature to be 100 ℃, and uniformly mixing and melting in a high-speed mixer to prepare a spinning solution A;
(2) mixing Li7La3Zr2O12Grinding until the particle size is 200nm, the solid content is 15% of silica sol and polyethylene glycol to form a spinning solution B, wherein the mass ratio of the lithium compound to the silica sol to the polyethylene glycol is 12: 80: 8;
(3) adding the spinning solution A and the spinning solution B into a spinning channel, wherein the feeding mass ratio of the spinning solution A to the spinning solution B is 1:3, and carrying out coaxial spinning, wherein the coaxial spinning parameters are 30KV, the distance between positive and negative electrodes is 10cm, the spinning solution A is on the outer layer, the spinning solution B is on the inner layer, and the spinning is deposited on a roller which continuously rotates to obtain a felt-shaped fiber membrane;
(4) and (4) further pressing and shaping the felt-shaped fiber membrane obtained in the step (3) through a roller, and drying at 70 ℃ to obtain the power lithium battery fiber membrane solid electrolyte.
Comparative example 2 did not loosen the fiber membrane, affecting the interfacial properties.
And (3) performance testing:
1. conductivity test
For qualitative comparison, examples 1-4 and comparative examples 1-2 were tested for conductivity performance under equivalent conditions. The test method adopts an electrochemical impedance method, and comprises the following specific steps: the electrolyte membrane and the non-steel sheet are assembled into a sandwich-type blocking cell, and electrochemical impedance test is carried out at 25 ℃ in the frequency range of 1-10 MHz. Ionic conductivity σ = l/RS, where R is the bulk impedance measured by electrochemical impedance method; s is the contact area of the electrolyte and the stainless steel sheet, the test is repeated for 3 times, and the average value is calculated; as in table 1.
2. Mechanical properties:
the thickness of the solid electrolyte of the battery fiber membrane is controlled by a roller which continuously rotates, so that the thickness after pressing is 1mm, and the tensile test is carried out under the condition of 10mm/min by referring to GB1040-92 plastic tensile property test method. The equipment adopts an XLS electronic tension meter of Chengdu detection instrument company, 5 samples of each sample are tested, and the average value of the three middle values is taken. As shown in table 1.
Table 1:
Claims (9)
1. the preparation method of the power lithium battery fiber membrane solid electrolyte is characterized by comprising the following steps:
(1) dispersing and melting the ionic liquid and the polymer to prepare spinning solution A;
(2) grinding the lithium compound to a nano level, and forming a spinning solution B by the lithium compound, the silicon dioxide sol and polyethylene glycol;
(3) adding the spinning solution A and the spinning solution B into a spinning channel, carrying out coaxial spinning, enabling the spinning solution A to be on the outer layer and the spinning solution B to be on the inner layer, spraying a lithium silicate aqueous solution on the surface of the outer layer through a nozzle, and carrying out spinning and depositing on a roller to obtain a felt-shaped fiber membrane;
(4) and (4) treating the felt-shaped fiber membrane obtained in the step (3) with weak acid liquid to enable lithium silicate on the surface to be gelatinized, and further pressing and drying to obtain the loose power lithium battery fiber membrane solid electrolyte with micropores on the surface.
2. The method of claim 1, wherein the ionic liquid is one of 1-ethyl-3-methylimidazole bistrifluoromethane sulfimide salt, 1-propyl-3-methylimidazole bistrifluoromethane sulfimide salt, 1-butyl-3-methylimidazole bistrifluoromethane sulfimide salt, N-methyl, propylpiperidine bistrifluoromethane sulfimide salt, N-methyl, butylpiperidine bistrifluoromethane sulfimide salt, N-methyl, propylpyrrolidine bistrifluoromethane sulfimide salt, N-methyl, butylpyrrolidine bistrifluoromethane sulfimide salt; the polymer is polyoxyethylene.
3. The method for preparing the fiber membrane solid electrolyte of the power lithium battery as claimed in claim 1, wherein the mass ratio of the ionic liquid to the polymer is (0.05-0.08) to (0.95-0.92), the melting temperature is set to be 100 ℃, and the spinning solution A is prepared by uniformly mixing and melting in a high-speed mixer.
4. The method of claim 1, wherein the lithium compound is Li7La3Zr2O12、Li1.3Al0.3Ti1.7(PO4)3、Li3PS4、Li9.6P3S12、Li7P3S11、Li11Si2PS12、Li10SiP2S12、Li10SnP2S12、Li10GeP2S12、 Li10Si0.5Ge0.5P2S12、Li10Ge0.5Sn0.5P2S12、Li10Si0.5Sn0.5P2S12、Li9.54Si1.74P1.44S11.7Cl0.3、Li6PS5Br、Li7PS6、Li7PS5I、Li7PO5Cl、Li3N、Li7PN4、LiSi2N3、LiPN2、Li2NH、Li3(NH2)2I、LiBH4、LiAlH4、LiNH2、Li2CdCl4The particle size of the lithium compound is 20-800 nm.
5. The method for preparing the power lithium battery fiber membrane solid electrolyte as claimed in claim 1, wherein the mass ratio of the lithium compound to the silica sol to the polyethylene glycol is (10-15): (77-88): (2-8), wherein the solid content of the silica sol is 10-20%.
6. The method as claimed in claim 1, wherein the modulus of the aqueous solution of lithium silicate in step (3) is 2.2-4.5.
7. The method for preparing the fiber membrane solid electrolyte of the power lithium battery as claimed in claim 1, wherein the coaxial spinning parameters in the step (3) are voltage of 12-30KV and positive-negative electrode spacing of 10-20 cm.
8. The method for preparing a fiber membrane solid electrolyte of a power lithium battery as claimed in claim 1, wherein the weak acid solution in step (4) is one of phosphoric acid and acetic acid with pH 4-6.
9. A power lithium battery fibrous membrane solid electrolyte, characterized by being prepared by the method of any one of claims 1 to 8.
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