CN112490495A - Inorganic-organic composite solid electrolyte, preparation method and solid lithium battery - Google Patents
Inorganic-organic composite solid electrolyte, preparation method and solid lithium battery Download PDFInfo
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 47
- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 45
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 239000002131 composite material Substances 0.000 title claims abstract description 30
- 239000007787 solid Substances 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title abstract description 15
- 239000002105 nanoparticle Substances 0.000 claims abstract description 24
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 23
- 239000003792 electrolyte Substances 0.000 claims abstract description 15
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 13
- 229920005596 polymer binder Polymers 0.000 claims abstract description 11
- 239000002491 polymer binding agent Substances 0.000 claims abstract description 11
- 150000002170 ethers Chemical class 0.000 claims abstract description 5
- -1 Lithium tetrafluoroborate Chemical compound 0.000 claims description 27
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 18
- 239000002002 slurry Substances 0.000 claims description 18
- 239000012528 membrane Substances 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 12
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- 239000011248 coating agent Substances 0.000 claims description 10
- 238000000576 coating method Methods 0.000 claims description 10
- 239000012266 salt solution Substances 0.000 claims description 10
- 229920000459 Nitrile rubber Polymers 0.000 claims description 9
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 9
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 9
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 9
- 229920000642 polymer Polymers 0.000 claims description 8
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 7
- 239000002033 PVDF binder Substances 0.000 claims description 6
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 6
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 5
- 239000002270 dispersing agent Substances 0.000 claims description 5
- 239000002612 dispersion medium Substances 0.000 claims description 5
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 claims description 5
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 claims description 5
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 4
- 229910001220 stainless steel Inorganic materials 0.000 claims description 4
- 239000010935 stainless steel Substances 0.000 claims description 4
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910006210 Li1+xAlxTi2-x(PO4)3 Inorganic materials 0.000 claims description 3
- 229910006212 Li1+xAlxTi2−x(PO4)3 Inorganic materials 0.000 claims description 3
- 229910002984 Li7La3Zr2O12 Inorganic materials 0.000 claims description 3
- 229910010092 LiAlO2 Inorganic materials 0.000 claims description 3
- 229910000552 LiCF3SO3 Inorganic materials 0.000 claims description 3
- 229910010941 LiFSI Inorganic materials 0.000 claims description 3
- 229910001290 LiPF6 Inorganic materials 0.000 claims description 3
- 239000005062 Polybutadiene Substances 0.000 claims description 3
- KEUXFMZOCWOGGS-UHFFFAOYSA-N [Li+].O=[S-](=O)F Chemical compound [Li+].O=[S-](=O)F KEUXFMZOCWOGGS-UHFFFAOYSA-N 0.000 claims description 3
- 150000003949 imides Chemical class 0.000 claims description 3
- 239000010416 ion conductor Substances 0.000 claims description 3
- 229910052758 niobium Inorganic materials 0.000 claims description 3
- 229920002857 polybutadiene Polymers 0.000 claims description 3
- 239000004814 polyurethane Substances 0.000 claims description 3
- 229920002635 polyurethane Polymers 0.000 claims description 3
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 3
- 229910052715 tantalum Inorganic materials 0.000 claims description 3
- 238000007664 blowing Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 6
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 6
- 230000005540 biological transmission Effects 0.000 abstract description 3
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 abstract 1
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 abstract 1
- 150000002825 nitriles Chemical class 0.000 description 13
- 238000007605 air drying Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 3
- 238000011031 large-scale manufacturing process Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 238000009210 therapy by ultrasound Methods 0.000 description 3
- 229910012820 LiCoO Inorganic materials 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 2
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- NRJJZXGPUXHHTC-UHFFFAOYSA-N [Li+].[O--].[O--].[O--].[O--].[Zr+4].[La+3] Chemical compound [Li+].[O--].[O--].[O--].[O--].[Zr+4].[La+3] NRJJZXGPUXHHTC-UHFFFAOYSA-N 0.000 description 1
- 238000000627 alternating current impedance spectroscopy Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000001453 impedance spectrum Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000005240 physical vapour deposition Methods 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0561—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
- H01M10/0562—Solid materials
-
- 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
-
- 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
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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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- 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
- H01M2300/0088—Composites
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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
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- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
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Abstract
The invention belongs to the technical field of lithium batteries, in particular to an inorganic-organic composite solid electrolyte, a preparation method thereof and a solid lithium battery, and the invention is especially suitable for a 4.5V system. The composite solid electrolyte comprises the following components: 1 part by mass of a polymer binder, 1.8 to 12 parts by mass of a lithium salt having ionic conductivity; 0.9-3.6 parts by mass of inorganic nano particles and 2-7.4 parts by mass of ether compounds. The composite solid electrolyte has higher mechanical property and excellent electrochemical stability, and can be applied to solid batteries adopting high-voltage anodes such as 4.5V-grade lithium cobalt oxide. The solid lithium battery assembled by the electrolyte has higher room-temperature ionic conductivity, higher capacity exertion and stable cycle performance, wider electrochemical window and better mechanical property; the pole piece and the electrolyte layer have good physical contact, and interface lithium ion rapid transmission can be realized.
Description
Technical Field
The invention belongs to the technical field of lithium batteries, in particular to an inorganic-organic composite solid electrolyte, a preparation method thereof and a solid lithium battery, and the invention is especially suitable for a 4.5V system.
Background
At present, a combustible liquid organic solvent is generally used as an electrolyte of a commercial lithium ion battery, so that the electrolyte is volatile and easy to burn, and potential safety hazards exist in the lithium ion battery due to a chemical system. The solid lithium battery adopts non-volatile and non-flammable solid electrolyte to replace liquid electrolyte, so that the safety problem of the lithium battery can be improved.
One of the difficulties of the solid lithium battery technology is the preparation of an all-solid electrolyte layer with high ionic conductivity and easy film formation, and the common method of directly coating solid electrolyte slurry on the surface of an electrode often has difficulty in forming a solid electrolyte film with good mechanical and electrochemical properties. The mature vacuum physical vapor deposition method has high cost and low efficiency, and the capacity of the prepared battery is generally only microampere time level and can not meet the requirement of large-scale production. Therefore, it is important and urgent to develop a solid-state battery electrolyte layer having excellent characteristics such as high performance and easy preparation.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides an inorganic-organic composite solid electrolyte applicable to a 4.5V system, a preparation method and a solid lithium battery, so that a pole piece and an electrolyte layer have good physical contact, and interface lithium ion rapid transmission is realized. The electrolyte layer provided by the invention is simple to prepare, has excellent performance and is suitable for large-scale production.
The technical scheme adopted by the invention for solving the technical problems in the prior art is as follows:
an inorganic-organic composite solid electrolyte comprising the following components by mass: 1 part by mass of a polymer binder, 1.8 to 12 parts by mass of a lithium salt having ionic conductivity; 0.9-3.6 parts of inorganic nano particles and 2-7.4 parts of ether compounds.
Further, the polymer binder comprises one or more of nitrile rubber, butadiene rubber, styrene butadiene rubber, hydrogenated nitrile rubber, polyvinylidene fluoride, polyurethane or derivatives thereof.
Further, the lithium salt is LiClO (lithium perchlorate)4Lithium tetrafluoroborate LiBF4Lithium hexafluorophosphate LiPF6Lithium triflate LiCF3SO3One or more of bis (trifluoromethanesulfonic acid) lithium imide LiTFSi, bis (fluorosulfonyl) lithium imide LiFSI and lithium difluorooxalato borate LiODFB.
Further, the inorganic nanoparticles are active fast ion conductors and are Li7La3Zr2O12，LixLa2/3-xTi03，Li1+xAlxTi2-x(PO4)3，LiAlO2，Li7-xLa3Zr2-xMxO12Where M ═ Ta, Nb; 0.25<x<2；30≤y≤70。
Further, the ether compound is triethylene glycol dimethyl ether or tetraethylene glycol dimethyl ether.
Further, the ionic conductivity of the solid electrolyte membrane is measured by the formula of sigma-L/Arb, wherein L is the thickness of the electrolyte, A is the area of the stainless steel sheet, and Rb is the measured impedance; the ionic conductivity of the lithium salt at room temperature was calculated to be 9.5X 10 by test-5S/cm。
Further, the present invention also provides a method for preparing the inorganic-organic composite solid electrolyte, comprising the steps of:
adding a certain mass part of polymer binder and lithium salt into a certain mass part of tetrahydrofuran dispersant under the protection of argon in a glove box for neutralization, stirring at room temperature, and ultrasonically preparing a uniform polymer binder-lithium salt solution;
adding a certain mass part of inorganic nano particles and an ether compound into the polymer adhesive-lithium salt solution obtained in the step one, and stirring at room temperature to obtain uniform polymer adhesive-lithium salt-inorganic nano particle slurry;
and step three, coating the slurry obtained in the step two on a polytetrafluoroethylene board, drying by blowing at 100 ℃ for 12-24h, and stripping the solid electrolyte membrane from the polytetrafluoroethylene board after fully drying and removing the dispersion medium tetrahydrofuran to obtain the solid electrolyte membrane.
Furthermore, the invention protects the solid-state lithium battery assembled by the inorganic-organic composite solid-state electrolyte.
Furthermore, the invention protects the characteristics of the lithium battery, namely the solid-state lithium battery has the maximum specific discharge capacity of 168mAh/g within the voltage range of 3.0V-4.5V at the multiplying power of 0.1C.
The invention has the advantages and positive effects that:
the invention discloses an inorganic-organic composite solid electrolyte which has higher mechanical property and excellent electrochemical stability, and can be applied to a solid battery adopting a high-voltage anode such as 4.5V-grade lithium cobaltate. Tests show that the solid lithium battery assembled by using the electrolyte has higher room-temperature ionic conductivity, higher capacity exertion and stable cycle performance, wider electrochemical window and better mechanical performance; the pole piece and the electrolyte layer have good physical contact, so that interface lithium ion rapid transmission can be realized; the preparation method of the composite solid electrolyte is simple in preparation, excellent in performance and suitable for large-scale production.
Drawings
FIG. 1 is an AC impedance spectrum of a composite solid electrolyte membrane according to a first embodiment of the present invention;
FIG. 2 is a graph showing the first charge and discharge curves at 0.1C rate of the discharge voltage of the composite solid electrolyte membrane according to the present invention (lithium cobaltate LiCoO)2Lithium metal);
Detailed Description
For a further understanding of the invention, its nature and utility, reference should be made to the following examples, which are set forth in the following detailed description, taken in conjunction with the accompanying drawings, in which:
the invention discloses an inorganic-organic composite solid electrolyte, which comprises the following components:
5-60 wt% of a polymeric binder; 10 wt% to 80 wt% of a lithium salt having ionic conductivity; 10 wt% to 40 wt% of inorganic nanoparticles; 10-40 wt% of ether compound;
preferably, the polymer binder comprises one or more of nitrile rubber, butadiene rubber, styrene butadiene rubber, hydrogenated nitrile rubber, polyvinylidene fluoride, polyurethane or derivatives thereof;
the lithium salt with ionic conductivity is lithium perchlorate LiClO4Lithium tetrafluoroborate LiBF4Lithium hexafluorophosphate LiPF6Lithium triflate LiCF3SO3One or more of bis (trifluoromethanesulfonic acid) lithium imide LiTFSi, bis (fluorosulfonyl) lithium imide LiFSI and lithium difluorooxalato borate LiODFB;
the inorganic nano-particles are active fast ion conductors and are Li7La3Zr2O12，LixLa2/3-xTi03，Li1+ xAlxTi2-x(PO4)3，LiAlO2，Li7-xLa3Zr2-xMxO12Where M ═ Ta, Nb; 0.25<x<2；30≤y≤70；
The ether compound is triethylene glycol dimethyl ether or tetraethylene glycol dimethyl ether.
The preparation method of the inorganic-organic composite solid electrolyte comprises the following steps:
step one, adding a polymer binder into a dispersion medium tetrahydrofuran according to a certain mass ratio, stirring and ultrasonically preparing a uniform polymer binder solution at room temperature;
adding lithium salt, ether compounds and inorganic nano particles into the polymer binder solution prepared in the step one, and stirring to obtain uniform polymer binder-lithium salt-inorganic nano particle slurry;
and step three, coating the polymer binder-lithium salt-inorganic nanoparticle slurry obtained in the step two on a polytetrafluoroethylene plate, drying at 100 ℃ in an inert atmosphere, and stripping the solid electrolyte membrane from the polytetrafluoroethylene plate after fully drying and removing the dispersion medium tetrahydrofuran to obtain the solid electrolyte membrane.
The dispersion medium is one or more of carbonic ester, aromatic hydrocarbon, tertiary amine and ether.
And the coating mode in the third step adopts blade coating, spray coating or spin coating.
The following examples are provided to illustrate the preparation of the new system lithium battery of the present invention:
example 1
The embodiment provides a preparation method of a composite solid electrolyte, which comprises the following steps:
mixing 1g of nitrile rubber, 7.2g of lithium bis (fluorosulfonyl) imide and 20g of tetrahydrofuran dispersant under the protection of argon in a glove box, stirring at room temperature, and ultrasonically preparing a uniform nitrile rubber-lithium salt solution;
step two, 1.8g of inorganic nano-particle lithium lanthanum zirconium oxide (Li)7La3Zr2O12) Adding 2g of triethylene glycol dimethyl ether into the nitrile rubber-lithium salt solution, stirring at room temperature, and performing ultrasonic treatment for 12 hours to obtain uniform nitrile rubber-lithium salt-inorganic nanoparticle slurry;
and step three, coating the nitrile rubber-lithium salt-inorganic nanoparticle slurry obtained in the step two on a polytetrafluoroethylene plate through a scraper, performing forced air drying at the temperature of 100 ℃ for 12 hours, and stripping the slurry from the surface of the substrate to obtain the solid electrolyte membrane independently formed into the membrane.
Example 2
Mixing 2g of nitrile rubber, 3.6g of lithium bis (fluorosulfonyl) imide and 20g of tetrahydrofuran serving as a dispersing agent in the preparation process under the protection of argon in a glove box, stirring at room temperature, and ultrasonically preparing a uniform nitrile rubber-lithium salt solution;
step two, 1.8g of inorganic nano particles are addedLithium aluminum titanium phosphorus oxygen (LiAlTi (PO)4)3) Adding 4.6g of triethylene glycol dimethyl ether into the nitrile rubber-lithium salt solution, stirring at room temperature, and performing ultrasonic treatment for 12 hours to obtain uniform nitrile rubber-lithium salt-inorganic nanoparticle slurry;
and step three, coating the nitrile rubber-lithium salt-inorganic nanoparticle slurry obtained in the step two on a polytetrafluoroethylene plate through a scraper, performing forced air drying at 100 ℃ for 24 hours, and stripping the slurry from the surface of the substrate to obtain the solid electrolyte membrane independently formed into the membrane.
Example 3
Mixing 0.5g of nitrile rubber, 6g of lithium bis (trifluoromethanesulfonate) imide and 20g of tetrahydrofuran serving as a dispersing agent in the preparation process under the protection of argon in a glove box, stirring at room temperature, and ultrasonically preparing a uniform nitrile rubber-lithium salt solution;
step two, 1.8g of inorganic nano-particle lithium aluminum titanium phosphorus oxygen (LiAlTi (PO)4)3) Adding 3.7g of tetraethylene glycol dimethyl ether into the nitrile rubber-lithium salt solution, stirring and carrying out ultrasonic treatment for 12 hours at room temperature to obtain uniform nitrile rubber-lithium salt-inorganic nanoparticle slurry;
and step three, coating the nitrile rubber-lithium salt-inorganic nanoparticle slurry obtained in the step two on a polytetrafluoroethylene plate through a scraper, performing forced air drying at 100 ℃ for 48 hours, and stripping the slurry from the surface of the substrate to obtain the solid electrolyte membrane independently formed into the membrane.
Test examples
The ion conductivity of the solid electrolyte film obtained in example 1 above was tested by sandwiching the solid electrolyte between two sheets of stainless steel and placing it in a 2432 type battery can. The ionic conductivity was measured by electrochemical ac impedance spectroscopy using the formula σ ═ L/ARb, where L is the thickness of the electrolyte, a is the area of the stainless steel sheet, and Rb is the measured impedance. The ionic conductivity of the lithium salt at room temperature was calculated to be 9.5X 10 by test-5S/cm, the nitrile rubber-lithium salt-inorganic nanoparticle electrolyte membrane obtained as shown in figure 1 is used for assembling a solid lithium battery and measuring the specific charge-discharge capacity.
Battery performance characterization
The all-solid-state lithium battery assembled by the inorganic-organic composite solid electrolyte comprises a positive electrode, a negative electrode and the inorganic-organic composite solid electrolyte between the positive electrode and the negative electrode, wherein the positive electrode comprises a positive electrode current collector, a positive electrode active material, a conductive agent and a binder; the negative electrode is lithium metal; the positive electrode active material is lithium cobaltate.
(1) Preparation of positive plate
Dissolving polyvinylidene fluoride (PVDF) in N-methyl pyrrolidone (NMP) with the mass fraction of 5%; PVDF/NMP solution, lithium cobaltate (LiCoO)2) And uniformly mixing the conductive carbon black by ball milling according to a certain proportion to prepare slurry, coating the slurry on an aluminum box by using a scraper with the diameter of 100 microns, and then drying in a forced air drying box at the temperature of 120 ℃ for later use.
(2) Electrochemical performance test
A button cell was assembled from the lithium metal as a negative electrode and the lithium cobaltate as a positive electrode in example 1, and a charge and discharge test was performed using a LAND charge and discharge tester. Tests show that under the condition of 25 ℃, the charging and discharging curve of the lithium ion battery assembled by the composite electrolyte at the rate of 0.1C in the voltage range of 3.0V-4.5V is shown in figure 2. The result shows that the maximum specific discharge capacity of the battery is 168 mAh/g.
Similarly, the solid electrolyte membranes of examples 2 and 3 were used for assembling and measuring the specific charge/discharge capacity of the solid lithium battery, and the data in table 1 were obtained:
TABLE 1
| Content of measurement | Example 1 | Example 2 | Example 3 |
| Specific discharge capacity (mAh/g) | 168 | 165 | 162 |
It can be seen from table 1 that the inorganic-organic composite solid electrolyte prepared by the present invention is applied to a button cell with a structure of positive electrode-composite solid electrolyte-lithium negative electrode, the battery capacity performance at room temperature can reach the design value, and the performance of the solid secondary lithium battery is improved.
The embodiments described herein are only some, and not all, embodiments of the invention. Based on the above explanations and guidance, those skilled in the art can make modifications, improvements, substitutions, and the like on the embodiments based on the present invention and examples, but all other embodiments obtained without innovative research fall within the scope of the present invention.
Claims (9)
1. An inorganic-organic composite solid electrolyte, characterized in that it comprises the following components by mass: 1 part by mass of a polymer binder, 1.8 to 12 parts by mass of a lithium salt having ionic conductivity; 0.9-3.6 parts by mass of inorganic nano particles and 2-7.4 parts by mass of ether compounds.
2. The inorganic-organic composite solid electrolyte of claim 1, wherein: the polymer binder comprises one or more of nitrile rubber, butadiene rubber, styrene butadiene rubber, hydrogenated nitrile rubber, polyvinylidene fluoride, polyurethane or derivatives thereof.
3. The inorganic-organic composite solid electrolyte of claim 1, wherein: the lithium salt is LiClO4Lithium tetrafluoroborate LiBF4Lithium hexafluorophosphate LiPF6Trifluoromethyl radicalLithium sulfonate LiCF3SO3One or more of bis (trifluoromethanesulfonic acid) lithium imide LiTFSi, bis (fluorosulfonyl) lithium imide LiFSI and lithium difluorooxalato borate LiODFB.
4. The inorganic-organic composite solid electrolyte of claim 1, wherein: the inorganic nano-particles are active fast ion conductors and are Li7La3Zr2O12，LixLa2/3-xTi03，Li1+xAlxTi2-x(PO4)3，LiAlO2，Li7-xLa3Zr2- xMxO12Where M ═ Ta, Nb; 0.25<x<2；30≤y≤70。
5. The inorganic-organic composite solid electrolyte of claim 1, wherein: the ether compound is triethylene glycol dimethyl ether or tetraethylene glycol dimethyl ether.
6. The inorganic-organic composite solid electrolyte according to claim 1, wherein the ionic conductivity of the solid electrolyte is measured using the formula σ ═ L/Arb, where L is the thickness of the electrolyte, a is the area of the stainless steel sheet, and Rb is the measured resistance; the ionic conductivity of the lithium salt at room temperature was calculated to be 9.5 × 10 by the test-5S/cm。
7. The method for producing an inorganic-organic composite solid electrolyte according to any one of claims 1 to 5, comprising the steps of:
adding a certain mass part of polymer binder and lithium salt into a tetrahydrofuran dispersant under the protection of argon in a glove box, stirring at room temperature, and ultrasonically preparing a uniform polymer binder-lithium salt solution;
adding a certain mass part of inorganic nano-particles and ether compounds into the polymer adhesive-lithium salt solution obtained in the step one, and stirring at room temperature to obtain uniform polymer adhesive-lithium salt-inorganic nano-particle slurry;
and step three, coating the slurry obtained in the step two on a polytetrafluoroethylene board, drying by blowing at 100 ℃ for 12-24h, and stripping the solid electrolyte membrane from the polytetrafluoroethylene board after fully drying and removing the dispersion medium tetrahydrofuran to obtain the solid electrolyte membrane.
8. A solid state lithium battery characterized by: the solid lithium battery is assembled by using the inorganic-organic composite solid electrolyte according to any one of claims 1 to 5.
9. The solid state lithium battery of claim 8, wherein: the solid lithium battery has the maximum specific discharge capacity of 168mAh/g within the voltage range of 3.0V-4.5V at the multiplying power of 0.1C.
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