CN115483432A - Composite solid electrolyte and preparation method thereof - Google Patents
Composite solid electrolyte and preparation method thereof Download PDFInfo
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- CN115483432A CN115483432A CN202211192533.5A CN202211192533A CN115483432A CN 115483432 A CN115483432 A CN 115483432A CN 202211192533 A CN202211192533 A CN 202211192533A CN 115483432 A CN115483432 A CN 115483432A
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- 239000002131 composite material Substances 0.000 title claims abstract description 127
- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 115
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000002070 nanowire Substances 0.000 claims abstract description 89
- 229910003480 inorganic solid Inorganic materials 0.000 claims abstract description 40
- 239000005518 polymer electrolyte Substances 0.000 claims abstract description 23
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 17
- 238000005516 engineering process Methods 0.000 claims abstract description 13
- 239000000463 material Substances 0.000 claims abstract description 13
- 238000011065 in-situ storage Methods 0.000 claims abstract description 12
- 239000002243 precursor Substances 0.000 claims abstract description 9
- 239000011258 core-shell material Substances 0.000 claims abstract description 8
- 239000011159 matrix material Substances 0.000 claims abstract description 8
- 239000007787 solid Substances 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims description 45
- 239000012456 homogeneous solution Substances 0.000 claims description 39
- 239000000178 monomer Substances 0.000 claims description 20
- 230000000977 initiatory effect Effects 0.000 claims description 17
- 230000003647 oxidation Effects 0.000 claims description 15
- 238000007254 oxidation reaction Methods 0.000 claims description 15
- 150000003839 salts Chemical class 0.000 claims description 15
- 239000003792 electrolyte Substances 0.000 claims description 13
- 239000012071 phase Substances 0.000 claims description 11
- 230000009471 action Effects 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 10
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 claims description 8
- 239000003999 initiator Substances 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 238000005245 sintering Methods 0.000 claims description 8
- 239000003431 cross linking reagent Substances 0.000 claims description 6
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 6
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- 238000010894 electron beam technology Methods 0.000 claims description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910044991 metal oxide Inorganic materials 0.000 claims description 4
- 150000004706 metal oxides Chemical class 0.000 claims description 4
- 238000007740 vapor deposition Methods 0.000 claims description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 229910052744 lithium Inorganic materials 0.000 claims description 3
- 230000000379 polymerizing effect Effects 0.000 claims description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 2
- 239000011575 calcium Substances 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 238000000151 deposition Methods 0.000 claims description 2
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 150000004678 hydrides Chemical class 0.000 claims description 2
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 2
- -1 ion salt Chemical class 0.000 claims description 2
- 239000007791 liquid phase Substances 0.000 claims description 2
- 230000005389 magnetism Effects 0.000 claims description 2
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 2
- 150000002825 nitriles Chemical class 0.000 claims description 2
- 150000003457 sulfones Chemical class 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 4
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims 1
- 239000002203 sulfidic glass Substances 0.000 claims 1
- 150000002500 ions Chemical class 0.000 description 33
- 230000000052 comparative effect Effects 0.000 description 12
- 230000005012 migration Effects 0.000 description 12
- 238000013508 migration Methods 0.000 description 12
- 238000004502 linear sweep voltammetry Methods 0.000 description 10
- 239000011734 sodium Substances 0.000 description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 230000037427 ion transport Effects 0.000 description 6
- 238000003760 magnetic stirring Methods 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- QJVKUMXDEUEQLH-UHFFFAOYSA-N [B].[Fe].[Nd] Chemical compound [B].[Fe].[Nd] QJVKUMXDEUEQLH-UHFFFAOYSA-N 0.000 description 5
- JEIPFZHSYJVQDO-UHFFFAOYSA-N ferric oxide Chemical compound O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 5
- 238000011049 filling Methods 0.000 description 5
- 230000006698 induction Effects 0.000 description 5
- 239000011777 magnesium Substances 0.000 description 5
- 229910001172 neodymium magnet Inorganic materials 0.000 description 5
- 229910001220 stainless steel Inorganic materials 0.000 description 5
- 239000010935 stainless steel Substances 0.000 description 5
- 238000009210 therapy by ultrasound Methods 0.000 description 5
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 2
- 238000009791 electrochemical migration reaction Methods 0.000 description 2
- 239000002001 electrolyte material Substances 0.000 description 2
- 239000011244 liquid electrolyte Substances 0.000 description 2
- 239000000696 magnetic material Substances 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910009511 Li1.5Al0.5Ge1.5(PO4)3 Inorganic materials 0.000 description 1
- 229910010941 LiFSI Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- MHEBVKPOSBNNAC-UHFFFAOYSA-N potassium;bis(fluorosulfonyl)azanide Chemical compound [K+].FS(=O)(=O)[N-]S(F)(=O)=O MHEBVKPOSBNNAC-UHFFFAOYSA-N 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 description 1
- 229910001488 sodium perchlorate Inorganic materials 0.000 description 1
- YLKTWKVVQDCJFL-UHFFFAOYSA-N sodium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Na+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F YLKTWKVVQDCJFL-UHFFFAOYSA-N 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001291 vacuum drying 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F114/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
- C08F114/02—Monomers containing chlorine
- C08F114/04—Monomers containing two carbon atoms
- C08F114/06—Vinyl chloride
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
- C08F220/285—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing a polyether chain in the alcohol moiety
- C08F220/286—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing a polyether chain in the alcohol moiety and containing polyethylene oxide in the alcohol moiety, e.g. methoxy polyethylene glycol (meth)acrylate
-
- 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- 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
- H01M2300/0085—Immobilising or gelification of electrolyte
-
- 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
- H01M2300/0091—Composites in the form of mixtures
-
- 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)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Electrochemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Conductive Materials (AREA)
- Secondary Cells (AREA)
Abstract
A composite solid electrolyte and a preparation method thereof belong to the technical field of solid batteries, and the specific scheme is as follows: a composite solid electrolyte comprises a polymer electrolyte and composite inorganic nanowires which are directionally arrayed inside a polymer electrolyte matrix, wherein the composite inorganic nanowires comprise an inorganic solid electrolyte material and magnetic nanowires, and the surface of the magnetic nanowires is coated with the inorganic solid electrolyte material. The magnetic nanowires and the inorganic solid electrolyte material are compounded to form composite inorganic nanowires with a core-shell structure, the composite inorganic nanowires are directionally arrayed in a polymer electrolyte precursor solution in a magnetic field environment, an in-situ curing technology is combined to enable an inorganic solid electrolyte and polymer electrolyte contact interface to form a continuously conducted interface seepage layer, and the interface seepage layer has ultrahigh room-temperature ionic conductivity and can efficiently and quickly conduct metal ions.
Description
Technical Field
The invention belongs to the technical field of solid-state batteries, and particularly relates to a composite solid electrolyte and a preparation method thereof.
Background
The rocking chair type ion battery is widely applied to the fields of various electronic products, electric automobiles, power grid energy storage and the like. However, because of the low saturated vapor pressure and high flammability of liquid electrolyte solvents, the scaling up of commercial ion batteries still presents a significant safety concern. The solid-state battery adopts a solid-state electrolyte material with high intrinsic safety to replace a flammable organic liquid electrolyte, so that the safety of a battery system is greatly improved. Common single solid electrolytes are inorganic solid electrolytes and polymer electrolytes. The inorganic solid electrolyte has excellent mechanical strength, high room-temperature ionic conductivity, and a wide electrochemical window, but is poor in flexibility, easily broken, and large in interfacial resistance. Although the polymer electrolyte has good flexibility, easy processing and low cost, the electrochemical window is narrow, and the room-temperature ionic conductivity is low.
Therefore, the composite solid electrolyte obtained by adding the inorganic solid electrolyte into the polymer electrolyte matrix has excellent mechanical property and electrochemical property, and realizes 'making up for the weakness' of a single solid electrolyte system, and is regarded as the most promising solid electrolyte material. The high room temperature ionic conductivity of the composite solid electrolyte benefits from an interface seepage layer with high ionic conductivity formed between the inorganic solid electrolyte and the polymer matrix, however, the inorganic solid electrolyte filling particles in the composite electrolyte obtained by a common filling method are low in arrangement order degree, the interface seepage layer between the inorganic solid electrolyte filling particles and the polymer matrix is in point distribution and difficult to be tightly connected, and the randomly dispersed inorganic solid electrolyte filling particles are easy to agglomerate, so that the ionic conduction is hindered, the room temperature ionic conductivity of the composite solid electrolyte is reduced, and the ideal electrochemical performance is difficult to obtain.
Disclosure of Invention
The invention aims to solve the problems that inorganic solid electrolyte filling particles in a composite solid electrolyte are easy to agglomerate and are discontinuous with a high-ionic-conductivity seepage layer formed between polymer electrolyte matrixes, and provides the composite solid electrolyte.
In order to achieve the purpose, the invention adopts the following technical scheme:
a composite solid electrolyte comprises a polymer electrolyte and composite inorganic nanowires which are arranged inside a polymer electrolyte matrix in a directional array mode, wherein the composite inorganic nanowires comprise an inorganic solid electrolyte material and magnetic nanowires, and the surface of the magnetic nanowires is coated with the inorganic solid electrolyte material.
The preparation method of the composite solid electrolyte comprises the following steps:
step one, preparing a magnetic nanowire, and coating an inorganic solid electrolyte on the surface of the magnetic nanowire to obtain a composite inorganic nanowire;
step two, uniformly mixing a polymerizable monomer, a cross-linking agent, an initiator and a metal ion salt to prepare a polymer electrolyte precursor solution I;
adding the composite inorganic nanowire into the polymer electrolyte precursor solution I, and uniformly dispersing to obtain a homogeneous phase solution II;
placing the homogeneous solution II in a magnetic field vertical to the liquid surface, and directionally arranging the composite inorganic nanowires in an array according to the direction of the magnetic field under the action of the magnetic field to obtain a homogeneous solution III;
and step five, carrying out in-situ initiation on the homogeneous phase solution III under the condition of keeping the action of the magnetic field, and fully polymerizing the polymerizable monomer to obtain the composite solid electrolyte with the composite inorganic nanowires in directional array arrangement.
Compared with the prior art, the invention has the beneficial effects that:
the magnetic nanowires and the inorganic solid electrolyte material are compounded to form composite inorganic nanowires with a core-shell structure, the composite inorganic nanowires are directionally arrayed in a polymer electrolyte precursor solution in a magnetic field environment, an in-situ curing technology is combined to enable an inorganic solid electrolyte and polymer electrolyte contact interface to form a continuously conducted interface seepage layer, and the interface seepage layer has ultrahigh room-temperature ionic conductivity and can efficiently and quickly conduct metal ions. In the prior art, the magnetic material is adsorbed on the surface of the inorganic solid electrolyte material, and the oriented array arrangement of the inorganic solid electrolyte in the polymer matrix can be realized under the action of a magnetic field, but the magnetic material can cause the interruption of an interface seepage layer, and the improvement effect of the ionic conductivity is limited. In addition, the mechanical strength of the composite solid electrolyte, the electrochemical window and the interface stability between the electrochemical window and the electrode can be improved through the composition of the composite inorganic nanowire and the polymer electrolyte, and the service life of the battery is further prolonged.
Detailed Description
The technical solutions in the present invention will be clearly and completely described below with reference to the embodiments, and it is obvious that the described embodiments are only a part of the embodiments of the invention, rather than all embodiments, and all other embodiments obtained by those skilled in the art without any inventive work based on the embodiments in the present invention belong to the protection scope of the present invention.
Detailed description of the invention
A composite solid electrolyte comprises a polymer electrolyte and composite inorganic nanowires which are arranged inside a polymer electrolyte matrix in a directional array mode, wherein the composite inorganic nanowires comprise an inorganic solid electrolyte material and magnetic nanowires, and the surface of the magnetic nanowires is coated with the inorganic solid electrolyte material.
Furthermore, the magnetic nanowire is an inorganic metal oxide nanowire with magnetism, and the inorganic metal oxide comprises one or a combination of more of ferroferric oxide, ferric oxide, nickel oxide, cobaltosic oxide and cobaltosic oxide.
Further, the inorganic solid state electrolyte material includes one or a combination of more of an oxide solid state electrolyte, a sulfide solid state electrolyte, a cyanide solid state electrolyte, a chloride solid state electrolyte, and a complex hydride solid state electrolyte.
Furthermore, the composite inorganic nanowire accounts for 5-50 wt% of the composite solid electrolyte.
Detailed description of the invention
A method of preparing a composite solid electrolyte comprising the steps of:
step one, preparing a magnetic nanowire, and coating an inorganic solid electrolyte on the surface of the magnetic nanowire to obtain a composite inorganic nanowire;
step two, uniformly mixing a polymerizable monomer, a cross-linking agent, an initiator and a metal ion salt to prepare a polymer electrolyte precursor solution I;
adding the composite inorganic nanowire into the polymer electrolyte precursor solution I, and uniformly dispersing by ultrasonic to obtain a homogeneous phase solution II;
placing the homogeneous solution II in a magnetic field vertical to the liquid surface, and directionally arranging the composite inorganic nanowires in an array according to the direction of the magnetic field under the action of the magnetic field to obtain a homogeneous solution III;
and step five, carrying out in-situ initiation on the homogeneous phase solution III under the condition of keeping the action of the magnetic field, and fully polymerizing the polymerizable monomer to obtain the composite solid electrolyte in the directional array arrangement of the composite inorganic nanowires.
Further, in the first step, the preparation method of the magnetic nanowire is a template method, a template method assisted vapor deposition method, a template method assisted liquid phase deposition method, a hydrothermal synthesis method or an electrochemical anodic oxidation method, and the magnetic nanowire is coated with an inorganic solid electrolyte by a sol-gel technology and a high-temperature sintering technology to form the composite inorganic nanowire with a core-shell structure. Specifically, a precursor of an inorganic solid electrolyte is wrapped on the surface of the magnetic nanowire by a sol-gel technology; then obtaining the magnetic nanowire coated by the inorganic solid electrolyte by a high-temperature sintering technology.
Further, in the second step, the polymerizable monomer includes at least one of an ester monomer, an ether monomer, a nitrile monomer, a sulfone monomer, and a siloxane monomer.
Further, in the second step, the metal ion salt includes one of a lithium metal ion salt, a sodium metal ion salt, a potassium metal ion salt, a magnesium metal ion salt and a calcium metal ion salt, and corresponds to the lithium ion battery composite solid electrolyte, the sodium ion battery composite solid electrolyte, the potassium ion battery composite solid electrolyte, the magnesium ion battery composite solid electrolyte and the calcium ion battery composite solid electrolyte, respectively.
Further, in the second step, the molar ratio of the polymerizable monomer to the metal ion salt is 3.
Further, in the fourth step, the homogeneous solution II is placed in a groove with the depth of 100-300 microns, the direction of a magnetic field is vertical to the liquid level, and the magnetic field intensity is 0.2T-1.0T.
Furthermore, in the fifth step, the in-situ initiation mode is one of thermal initiation, ultraviolet light initiation, electric initiation or electron beam irradiation initiation.
Example 1
A preparation method of a composite solid electrolyte specifically comprises the following steps:
the method comprises the following steps: preparing magnetic nickel oxide nano-wire by adopting template casting and vapor deposition technology, and preparing Li by using sol-gel technology and high-temperature sintering technology 1.5 Al 0.5 Ge 1.5 (PO 4 ) 3 (LAGP) solid electrolyte particles are coated on the magnetic nickel oxide nanowire to prepare the composite inorganic nanowire with the core-shell structure.
Step two: ultrasonically mixing PEGMEA (polyethylene glycol methacrylate) and LiFSI (lithium bis (fluoromethanesulfonylimide)) according to a molar ratio of 10.
Step three: and (3) mixing the composite inorganic nanowire prepared in the step one with the homogeneous phase solution I, and performing ultrasonic treatment for 30min at 50-60 ℃ to obtain a homogeneous phase solution II, wherein the addition amount of the composite inorganic nanowire is 5wt%.
Step four: and (3) injecting the homogeneous solution II into a mold groove with the depth of 300 microns, then placing the mold groove between two nickel-plated neodymium-iron-boron magnets, wherein the direction of a magnetic field is vertical to the liquid level, the size of the magnetic field is 1.0T, and the composite inorganic nanowires form directional array arrangement under the induction of the magnetic field, namely the homogeneous solution III.
Step five: and under the condition of keeping the action of the magnetic field, putting the homogeneous phase solution III and the whole mould into a vacuum drying oven for thermal initiation and solidification at the temperature of 70 ℃, removing the magnet after the homogeneous phase solution III is completely solidified, and demoulding the solidified electrolyte to obtain the composite solid electrolyte.
And (3) carrying out ion conductivity, ion migration number and electrochemical window tests on the prepared composite solid electrolyte. Carrying out ion conductivity test on the composite solid electrolyte by adopting an alternating current impedance method; assembling the Li/composite solid electrolyte/Li symmetrical battery, and performing an ion migration number test by adopting a steady-state current method; and performing electrochemical window test on the composite solid electrolyte by adopting a linear sweep voltammetry test (LSV), wherein the test structure is Li/composite solid electrolyte/stainless steel sheet, the test potential interval is from open circuit potential to 6V, and the sweep speed is 0.5mV/s. The room-temperature ionic conductivity of the composite solid electrolyte with the structure reaches 8.51mS/cm, the ionic migration number reaches 0.83, and the oxidation voltage window is 4.85V.
Example 2
A preparation method of a composite solid electrolyte specifically comprises the following steps:
the method comprises the following steps: preparing magnetic iron trioxide nano-wire by electrochemical anode oxidation method, and preparing Na-beta' -Al by auxiliary sol-gel technique and high-temperature sintering technique 2 O 3 The inorganic solid electrolyte is coated on the magnetic ferric oxide nanowire to prepare the composite inorganic nanowire with the core-shell structure.
Step two: mixing VC (vinyl chloride) and NaClO 4 (sodium perchlorate) was ultrasonically mixed at a molar ratio of 5After the liquid dispersion, 5vol% of crosslinking agent EG (ethylene glycol) is added, after the magnetic stirring dispersion, 1wt% of initiator HMPP (alpha-hydroxyisobutyrophenone) is added, and the magnetic stirring is carried out for 30min to obtain homogeneous phase solution I.
Step three: and (3) mixing the homogeneous solution I with the composite inorganic nanowire prepared in the step one, and performing ultrasonic treatment at 50-60 ℃ for 30min to obtain a homogeneous solution II, wherein the addition amount of the composite inorganic nanowire is 30wt%.
Step four: and (3) injecting the homogeneous solution II into a mold groove with the depth of 300 microns, then placing the mold groove between two nickel-plated neodymium-iron-boron magnets, wherein the direction of a magnetic field is vertical to the liquid level, the size of the magnetic field is 0.6T, and the composite inorganic nanowires form directional array arrangement under the induction of the magnetic field, namely the homogeneous solution III.
Step five: and under the condition of keeping the action of the magnetic field, carrying out ultraviolet irradiation on the homogeneous solution III and the whole mould to cure the homogeneous solution III in situ, removing the magnet after the homogeneous solution III is completely cured, and demoulding the cured electrolyte to obtain the composite solid electrolyte.
And (3) carrying out ion conductivity, ion migration number and electrochemical window tests on the prepared composite solid electrolyte. Carrying out ion conductivity test on the composite solid electrolyte by adopting an alternating current impedance method; assembling a Na/composite solid electrolyte/Na symmetrical battery, and performing an ion migration number test by adopting a steady-state current method; and performing electrochemical window test on the composite solid electrolyte by adopting a linear sweep voltammetry test (LSV), wherein the test structure is Na/composite solid electrolyte/stainless steel sheet, the test potential interval is from open circuit potential to 6V, and the sweep speed is 0.5mV/s. The room-temperature ion conductivity of the composite solid electrolyte with the structure reaches 6.1mS/cm, the ion migration number reaches 0.75, and the oxidation voltage window is 4.92V.
Example 3
A method of preparing a composite solid electrolyte comprising the steps of:
the method comprises the following steps: preparing magnetic ferroferric oxide nano-wire by adopting a wet template method, and adding Na by using an auxiliary sol-gel technology and a high-temperature sintering technology 3 SbS 4 The inorganic solid electrolyte is coated on the magnetic ferroferric oxide nanowire to prepare the magnetic ferroferric oxide nanowire with the core shellA composite inorganic nanowire of the structure.
Step two: PEGMEA and NaTFSI (sodium bis (trifluoromethanesulfonylimide)) are ultrasonically mixed according to a molar ratio of 10 to 1, 5vol% of cross-linking agent PEGDA is added after the solution is dispersed, magnetic stirring is carried out for 30min, then 2wt% of initiator HMPP is added, and the magnetic stirring is continued for 30min until the initiator is completely dissolved, so that homogeneous solution I is obtained.
Step three: and (3) performing ultrasonic treatment on the homogeneous solution I and the composite inorganic nanowire prepared in the step one at 50-60 ℃ for 1h to obtain a homogeneous solution II, wherein the adding amount of the composite inorganic nanowire is 50wt%.
Step four: and (3) injecting the homogeneous solution II into a mold groove with the depth of 300 microns, then placing the mold groove between two nickel-plated neodymium-iron-boron magnets, wherein the direction of a magnetic field is vertical to the liquid level, the size of the magnetic field is 0.2T, and the composite inorganic nanowires form directional array arrangement under the induction of the magnetic field, namely the homogeneous solution III.
Step five: and (3) carrying out electron beam irradiation radiation initiation on the homogeneous solution III and the whole mould to enable the homogeneous solution III to be cured in situ, removing the magnet after the homogeneous solution III is completely cured, and demoulding the cured electrolyte.
And (3) carrying out ion conductivity, ion migration number and electrochemical window tests on the prepared composite solid electrolyte. Carrying out ion conductivity test on the composite solid electrolyte by adopting an alternating current impedance method; assembling a Na/composite solid electrolyte/Na symmetrical battery, and performing an ion migration number test by adopting a steady-state current method; and performing electrochemical window test on the composite solid electrolyte by adopting a linear sweep voltammetry test (LSV), wherein the test structure is Na/composite solid electrolyte/stainless steel sheet, the test potential interval is from open circuit potential to 6V, and the sweep speed is 0.5mV/s. The room-temperature ion conductivity of the composite solid electrolyte with the structure reaches 9.12mS/cm, the ion transport number reaches 0.72, and the oxidation voltage window is 5.2V.
Example 4
A method of preparing a composite solid electrolyte comprising the steps of:
the method comprises the following steps: preparing magnetic nickel oxide nano-wire by template method assisted vapor deposition method, assisted sol-gel technique and high-temperature sintering techniqueGeneral procedure K 2 Mg 2 TeO 6 The inorganic solid electrolyte is coated on the magnetic nickel oxide nanowire to prepare the composite inorganic nanowire with the core-shell structure.
Step two: PEGMEA and KFSI (potassium bis (trifluoromethanesulfonylimide)) are ultrasonically mixed according to a molar ratio of 20 to 1, after the solution is dispersed, 5vol% of a cross-linking agent PEGDA is added, magnetic stirring is carried out for 30min, then 1.5wt% of an initiator HMPP is added, and the magnetic stirring is continued for 30min until the initiator is completely dissolved, so that a homogeneous solution I is obtained.
Step three: and (3) performing ultrasonic treatment on the homogeneous solution I and the composite inorganic nanowire prepared in the step one at 50-60 ℃ for 1h to obtain a homogeneous solution II, wherein the adding amount of the composite inorganic nanowire is 40wt%.
Step four: and (3) injecting the homogeneous solution II into a mold groove with the depth of 300 microns, then placing the mold groove between two nickel-plated neodymium-iron-boron magnets, wherein the direction of a magnetic field is vertical to the liquid level, the size of the magnetic field is 0.2T, and the composite inorganic nanowires form directional array arrangement under the induction of the magnetic field, namely the homogeneous solution III.
Step five: and (3) carrying out electron beam irradiation radiation initiation on the homogeneous solution III and the whole mould to cure the homogeneous solution III in situ, removing the magnet after the homogeneous solution III is completely cured, and demoulding the cured electrolyte.
And (3) carrying out ion conductivity, ion migration number and electrochemical window tests on the prepared composite solid electrolyte. Carrying out ion conductivity test on the composite solid electrolyte by adopting an alternating current impedance method; assembling a K/composite solid electrolyte/K symmetrical battery, and performing an ion migration number test by adopting a steady-state current method; and performing electrochemical window test on the composite solid electrolyte by adopting a linear sweep voltammetry test (LSV), wherein the test structure is K/composite solid electrolyte/stainless steel sheet, the test potential interval is from open circuit potential to 6V, and the sweep speed is 0.5mV/s. The room-temperature ion conductivity of the composite solid electrolyte with the structure reaches 8.34mS/cm, the ion transport number reaches 0.82, and the oxidation voltage window is 4.85V.
Example 5
A preparation method of a composite solid electrolyte specifically comprises the following steps:
the method comprises the following steps: preparing magnetic iron trioxide nano-wire by electrochemical anode oxidation method, and preparing MgY by auxiliary sol-gel technique and high-temperature sintering technique 2 S 4 The inorganic solid electrolyte is coated on the magnetic ferric oxide nanowire to prepare the composite inorganic nanowire with the core-shell structure.
Step two: VC (vinyl chloride) and MgTFSI are ultrasonically mixed according to a molar ratio of 10.
Step three: and (3) mixing the homogeneous solution I with the composite inorganic nanowire prepared in the step one, and performing ultrasonic treatment at 50-60 ℃ for 30min to obtain a homogeneous solution II, wherein the adding amount of the composite inorganic nanowire is 50wt%.
Step four: and (3) injecting the homogeneous solution II into a mold groove with the depth of 300 microns, then placing the mold groove between two nickel-plated neodymium-iron-boron magnets, wherein the direction of a magnetic field is vertical to the liquid level, the size of the magnetic field is 0.6T, and the composite inorganic nanowires form directional array arrangement under the induction of the magnetic field, namely the homogeneous solution III.
Step five: and under the condition of keeping the action of the magnetic field, carrying out ultraviolet irradiation on the homogeneous solution III and the whole mould to cure the homogeneous solution III in situ, removing the magnet after the homogeneous solution III is completely cured, and demoulding the cured electrolyte to obtain the composite solid electrolyte.
And (3) carrying out ion conductivity, ion migration number and electrochemical window tests on the prepared composite solid electrolyte. Carrying out ion conductivity test on the composite solid electrolyte by adopting an alternating current impedance method; assembling the Mg/composite solid electrolyte/Mg symmetrical battery, and performing an ion migration number test by adopting a steady-state current method; and performing electrochemical window test on the composite solid electrolyte by adopting a linear sweep voltammetry test (LSV), wherein the test structure is Mg/composite solid electrolyte/stainless steel sheet, the test potential interval is from open circuit potential to 6V, and the sweep speed is 0.5mV/s. The room-temperature ion conductivity of the composite solid electrolyte with the structure reaches 7.05mS/cm, the ion migration number reaches 0.79, and the oxidation voltage window is 4.85V.
Comparative example 1
This comparative example is different from example 1 in that the composite inorganic nanowire in example 1 was replaced with Li 1.5 Al 0.5 Ge 1.5 (PO 4 ) 3 (LAGP) inorganic solid electrolyte particles, the same procedures as in example 1 were repeated, and the composite solid electrolyte was measured to have an ion conductivity of 0.72mS/cm at room temperature, an ion transference number of 0.45 and an oxidation voltage window of 4.3V.
Comparative example 2
The difference between the comparative example and the example 1 is that the filled composite inorganic nanowire is not induced by a magnetic field, but is directly cured by in-situ initiation, and the room-temperature ionic conductivity of the composite solid electrolyte is measured to reach 0.82mS/cm, the ionic migration number reaches 0.55, and the oxidation voltage window is 4.35V.
Comparative example 3
The comparative example is different from example 2 in that the composite inorganic nanowire of example 2 is replaced with Na-beta' -Al 2 O 3 The inorganic solid electrolyte, the rest being the same as in example 2, was found to have an ion conductivity of 1.05mS/cm at room temperature, an ion transport number of 0.45 and an oxidation voltage window of 4.35V.
Comparative example 4
This comparative example is different from example 3 in that the composite inorganic nanowire in example 3 was replaced with Na 3 SbS 4 The inorganic solid electrolyte, the rest being the same as in example 3, was measured to have an ion conductivity of 0.55mS/cm at room temperature, an ion transport number of 0.52 and an oxidation voltage window of 4.25V.
Comparative example 5
This comparative example is different from example 4 in that the composite inorganic nanowire in example 4 is replaced with K 2 Mg 2 TeO 6 The inorganic solid electrolyte, the rest being the same as in example 4, was found to have an ionic conductivity of 0.35mS/cm at room temperature, an ion transport number of 0.42 and an oxidation voltage window of 4.35V.
Comparative example 6
This comparative example is different from example 5 in that the composite inorganic nanowire in example 5 was replaced with MgY 2 S 4 The inorganic solid electrolyte, the rest being the same as in example 5, was measured to have an ion conductivity of 0.68mS/cm at room temperature, an ion transport number of 0.45 and an oxidation voltage window of 4.32V.
Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should integrate the description, and the embodiments may be combined as appropriate to form other embodiments understood by those skilled in the art.
Claims (10)
1. A composite solid electrolyte characterized by: the composite inorganic nanowire array comprises a polymer electrolyte and composite inorganic nanowires which are directionally arrayed inside a polymer electrolyte matrix, wherein the composite inorganic nanowires comprise an inorganic solid electrolyte material and magnetic nanowires, and the surface of the magnetic nanowires is coated with the inorganic solid electrolyte material.
2. The composite solid electrolyte according to claim 1, wherein: the magnetic nanowire is an inorganic metal oxide nanowire with magnetism, and the inorganic metal oxide comprises one or a combination of more of ferroferric oxide, ferric oxide, nickel oxide, cobaltosic oxide and cobaltosic oxide.
3. A composite solid state electrolyte as claimed in claim 1, wherein: the inorganic solid electrolyte material includes one or more of an oxide solid electrolyte, a sulfide solid electrolyte, a cyanide solid electrolyte, a chloride solid electrolyte, and a complex hydride solid electrolyte in combination.
4. A composite solid state electrolyte as claimed in claim 1, wherein: the composite inorganic nanowire accounts for 5-50 wt% of the composite solid electrolyte.
5. A method for producing the composite solid electrolyte according to any one of claims 1 to 4, comprising the steps of:
step one, preparing a magnetic nanowire, and coating an inorganic solid electrolyte on the surface of the magnetic nanowire to obtain a composite inorganic nanowire;
step two, uniformly mixing a polymerizable monomer, a cross-linking agent, an initiator and a metal ion salt to prepare a polymer electrolyte precursor solution I;
adding the composite inorganic nanowire into the polymer electrolyte precursor solution I, and uniformly dispersing to obtain a homogeneous phase solution II;
placing the homogeneous solution II in a magnetic field vertical to the liquid surface, and directionally arranging the composite inorganic nanowires in an array according to the direction of the magnetic field under the action of the magnetic field to obtain a homogeneous solution III;
and step five, carrying out in-situ initiation on the homogeneous phase solution III under the condition of keeping the action of the magnetic field, and fully polymerizing the polymerizable monomer to obtain the composite solid electrolyte with the composite inorganic nanowires in directional array arrangement.
6. The method of claim 5, wherein: in the first step, the preparation method of the magnetic nanowire is a template method, a template method assisted vapor deposition method, a template method assisted liquid phase deposition method, a hydrothermal synthesis method or an electrochemical anodic oxidation method, and the magnetic nanowire is coated with an inorganic solid electrolyte by a sol-gel technology and a high-temperature sintering technology to form the composite inorganic nanowire with the core-shell structure.
7. The production method according to claim 5, characterized in that: in the second step, the polymerizable monomer comprises at least one of an ester monomer, an ether monomer, a nitrile monomer, a sulfone monomer and a siloxane monomer.
8. The production method according to claim 5, characterized in that: in the second step, the metal ion salt includes one of a lithium metal ion salt, a sodium metal ion salt, a potassium metal ion salt, a magnesium metal ion salt and a calcium metal ion salt.
9. The method of claim 5, wherein: in the second step: the molar ratio of the polymerizable monomer to the metal ion salt is 3-20.
10. The production method according to claim 5, characterized in that: in the fifth step, the in-situ initiation mode is one of thermal initiation, ultraviolet light initiation, electric initiation or electron beam irradiation initiation.
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