CN115224352A - Dry-method prepared hydrophobic solid electrolyte and preparation method and application thereof - Google Patents
Dry-method prepared hydrophobic solid electrolyte and preparation method and application thereof Download PDFInfo
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- CN115224352A CN115224352A CN202210951615.7A CN202210951615A CN115224352A CN 115224352 A CN115224352 A CN 115224352A CN 202210951615 A CN202210951615 A CN 202210951615A CN 115224352 A CN115224352 A CN 115224352A
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- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 104
- 230000002209 hydrophobic effect Effects 0.000 title claims abstract description 44
- 238000000034 method Methods 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 67
- 239000000843 powder Substances 0.000 claims abstract description 47
- 239000000463 material Substances 0.000 claims abstract description 43
- 238000003756 stirring Methods 0.000 claims abstract description 35
- 238000005507 spraying Methods 0.000 claims abstract description 31
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000007822 coupling agent Substances 0.000 claims abstract description 19
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 18
- 239000000243 solution Substances 0.000 claims abstract description 16
- 238000001035 drying Methods 0.000 claims abstract description 15
- 239000011259 mixed solution Substances 0.000 claims abstract description 11
- 239000002904 solvent Substances 0.000 claims abstract description 10
- 230000008569 process Effects 0.000 claims abstract description 8
- 230000002378 acidificating effect Effects 0.000 claims abstract description 7
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 7
- 238000001291 vacuum drying Methods 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 5
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 claims description 20
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 11
- 239000005977 Ethylene Substances 0.000 claims description 11
- 239000003792 electrolyte Substances 0.000 claims description 11
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 10
- 230000004048 modification Effects 0.000 claims description 10
- 238000012986 modification Methods 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- -1 acyloxy titanate Chemical compound 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 229960000583 acetic acid Drugs 0.000 claims description 6
- 239000012362 glacial acetic acid Substances 0.000 claims description 6
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 6
- 239000002228 NASICON Substances 0.000 claims description 5
- 125000004423 acyloxy group Chemical group 0.000 claims description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 5
- 239000002223 garnet Substances 0.000 claims description 4
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 claims description 3
- 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 claims description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 3
- 239000005662 Paraffin oil Substances 0.000 claims description 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 3
- PAHNBNDPQWLRQX-UHFFFAOYSA-N [N].[O].[P].[Li] Chemical compound [N].[O].[P].[Li] PAHNBNDPQWLRQX-UHFFFAOYSA-N 0.000 claims description 3
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 claims description 3
- 239000006185 dispersion Substances 0.000 claims description 3
- 239000010416 ion conductor Substances 0.000 claims description 3
- 239000002480 mineral oil Substances 0.000 claims description 3
- 235000010446 mineral oil Nutrition 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- ZQZCOBSUOFHDEE-UHFFFAOYSA-N tetrapropyl silicate Chemical compound CCCO[Si](OCCC)(OCCC)OCCC ZQZCOBSUOFHDEE-UHFFFAOYSA-N 0.000 claims description 3
- 239000008096 xylene Substances 0.000 claims description 3
- 239000002203 sulfidic glass Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims 7
- 239000010936 titanium Substances 0.000 claims 7
- 238000004519 manufacturing process Methods 0.000 claims 3
- 229910012305 LiPON Inorganic materials 0.000 claims 1
- AXCZRQHGMPTZPR-UHFFFAOYSA-N ethane-1,1,2,2-tetrol Chemical compound OC(O)C(O)O AXCZRQHGMPTZPR-UHFFFAOYSA-N 0.000 claims 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims 1
- 229940095070 tetrapropyl orthosilicate Drugs 0.000 claims 1
- 229910000664 lithium aluminum titanium phosphates (LATP) Inorganic materials 0.000 description 14
- 239000002245 particle Substances 0.000 description 14
- 239000002105 nanoparticle Substances 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 238000002441 X-ray diffraction Methods 0.000 description 6
- HTDKEJXHILZNPP-UHFFFAOYSA-N dioctyl hydrogen phosphate Chemical compound CCCCCCCCOP(O)(=O)OCCCCCCCC HTDKEJXHILZNPP-UHFFFAOYSA-N 0.000 description 6
- 239000007921 spray Substances 0.000 description 6
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 5
- 230000003068 static effect Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 238000002715 modification method Methods 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- QBCOASQOMILNBN-UHFFFAOYSA-N didodecoxy(oxo)phosphanium Chemical compound CCCCCCCCCCCCO[P+](=O)OCCCCCCCCCCCC QBCOASQOMILNBN-UHFFFAOYSA-N 0.000 description 2
- 239000002001 electrolyte material Substances 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000011244 liquid electrolyte 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
- CVJYOKLQNGVTIS-UHFFFAOYSA-K aluminum;lithium;titanium(4+);phosphate Chemical compound [Li+].[Al+3].[Ti+4].[O-]P([O-])([O-])=O CVJYOKLQNGVTIS-UHFFFAOYSA-K 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
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- 230000007062 hydrolysis Effects 0.000 description 1
- CEMTZIYRXLSOGI-UHFFFAOYSA-N lithium lanthanum(3+) oxygen(2-) titanium(4+) Chemical compound [Li+].[O--].[O--].[O--].[O--].[Ti+4].[La+3] CEMTZIYRXLSOGI-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
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- 239000002184 metal Substances 0.000 description 1
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- 230000009467 reduction Effects 0.000 description 1
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical group [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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Images
Classifications
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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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/54—Electrolytes
- H01G11/56—Solid electrolytes, e.g. gels; Additives therein
-
- 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
- H01M2300/00—Electrolytes
- H01M2300/0088—Composites
-
- 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)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Manufacturing & Machinery (AREA)
- General Chemical & Material Sciences (AREA)
- Power Engineering (AREA)
- Inorganic Chemistry (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Conductive Materials (AREA)
Abstract
The invention relates to a hydrophobic solid electrolyte prepared by a dry method, a preparation method and application thereof. The dry preparation method of the hydrophobic solid electrolyte comprises the following steps: putting the solid electrolyte material into mixing equipment, and stirring and dispersing; in the stirring and dispersing process, spraying a silicate treating agent on the surface of the solid electrolyte material, and continuously stirring for a first preset time to form a first powder material; preparing a mixed solution by using a titanate coupling agent and a solvent, and adding an acidic auxiliary agent to adjust the pH value to 3-6 to form a spraying solution; spraying the spraying solution on the surface of the first powder material in a spraying mode, and continuously stirring at a first set temperature for a second preset time to obtain wet powder; and putting the wet powder into a vacuum drying box, and drying at a second set temperature to obtain the hydrophobic solid electrolyte.
Description
Technical Field
The invention relates to the technical field of new energy material preparation, in particular to a hydrophobic solid electrolyte prepared by a dry method and a preparation method and application thereof.
Background
Currently, commercial lithium ion batteries mainly use organic electrolyte and graphite carbon negative electrodes, and the energy density of the lithium ion batteries almost reaches a theoretical limit value, so that the lithium ion batteries are difficult to meet the increasing energy storage requirement. Metallic lithium is an ideal anode material with the highest specific energy and the lowest reduction potential. However, the problems of pulverization, dendritic crystal growth, volume expansion, continuous reaction with the electrolyte and the like of the metal lithium cathode in the repeated charge-discharge process are solved, and more importantly, the traditional liquid electrolyte has the characteristics of easy volatilization, easy leakage, easy combustion and the like, so that the lithium battery is easy to catch fire or even explode, and serious safety accidents can be caused.
The development of solid-state batteries using a solid electrolyte instead of a liquid electrolyte is a final solution that is considered to solve the above-mentioned problems. The solid electrolyte has high safety and reliability due to the advantages of no leakage, good thermal stability and the like. Most importantly, the solid electrolyte has high mechanical strength and can effectively inhibit the growth of dendrites during the cycling process of the battery. Meanwhile, the solid-state battery has a simple structure, and the electrodes and the electrolyte are solid, so that the battery is convenient to process and package. Therefore, the solid-state battery has the characteristics of high safety and high energy density, and is an ideal scheme for developing a new generation of energy storage battery.
However, the solid electrolyte is highly sensitive to water. Upon contact with water, the solid electrolyte undergoes a significant decrease in ionic conductivity, and even microcracks, grain shape deformation, nanoparticle formation, chemical composition transformation, cell shrinkage, internal structure polyhedrons, and strain changes. The surface of the nano solid electrolyte contains polar hydrophilic groups which are easy to absorb water, and has extremely small particle size and extremely high specific surface area, and a pore structure exists among particles, so that the nano solid electrolyte is easy to absorb water, and the final performance of the solid battery is influenced. Therefore, it is necessary to find a method for preparing a hydrophobic solid electrolyte, thereby blocking the adsorption of moisture in the environment and maintaining a stable and high-performance state of the solid electrolyte.
Disclosure of Invention
The embodiment of the invention provides a hydrophobic solid electrolyte prepared by a dry method, and a preparation method and application thereof. The dry preparation method of the hydrophobic solid electrolyte can prevent the solid electrolyte from contacting and adsorbing moisture in the environment and keep the high performance stability of the solid electrolyte. The dry modification method greatly improves the operability.
In a first aspect, an embodiment of the present invention provides a dry-process preparation method of a hydrophobic solid electrolyte, including:
putting the solid electrolyte material into mixing equipment, and stirring and dispersing;
in the stirring and dispersing process, spraying a silicate treating agent on the surface of the solid electrolyte material, and continuously stirring for a first preset time to form a first powder material;
preparing a mixed solution by using a titanate coupling agent and a solvent, and adding an acidic auxiliary agent to adjust the pH value to 3-6 to form a spraying solution;
spraying the spraying solution on the surface of the first powder material in a spraying mode, and continuously stirring for a second preset time at a first set temperature to obtain wet powder;
and putting the wet powder into a vacuum drying box, and drying at a second set temperature to obtain the hydrophobic solid electrolyte.
Preferably, the amount of the silicate treating agent is 1-20% of the mass of the solid electrolyte material;
in the mixed solution, the mass ratio of the titanate coupling agent to the solvent is 1-10;
the mass ratio of the titanate coupling agent to the silicate treating agent is 1-1.
Preferably, the solid state electrolyte material includes: at least one of garnet type solid electrolyte, sulfide solid electrolyte, sodium fast ion conductor NASICON type solid electrolyte, lithium phosphorus oxygen nitrogen LiPON type electrolyte or perovskite type solid electrolyte;
the silicate treating agent comprises: one or more of tetramethyl silicate, tetraethyl silicate and tetrapropyl silicate;
the titanate coupling agent comprises: one or more of isopropyldioleate acyloxy (dioctylphosphate) titanate, isopropyltris (dioctylphosphate) titanate, isopropyltrioleate acyloxy titanate, isopropyltris (dioctylphosphate) titanate, triisostearate isopropyl titanate, bis (dioctyloxypyrophosphate) ethylene titanate, tetraisopropylbis (dioctylphosphato) titanate, isopropyl trihydroxyacyl titanate, isopropyl tristearate titanate, tri (dioctylphosphato) isopropyl titanate, di (dioctylphosphato) ethylene titanate, di (dioctylphosphato) glycolic acid titanate, dihydroxyacyl ethylene titanate, alkylol diphosphato glycolic acid titanate, alkylol amine diphosphato glycolic acid titanate, alkylol diphosphato glycolic acid titanate, tri (dodecylbenzenesulfonyl) isopropyl titanate, isopropyltris (isostearyl) titanate, isopropyltris (dioctylphosphato) titanate, tetraisopropylbis (dilauryl phosphite) titanate;
the solvent comprises: one or more of isopropanol, acetone, ethyl acetate, paraffin oil, dioctyl phthalate, xylene, toluene or mineral oil;
the acidic auxiliary agent comprises one or more of hydrochloric acid, citric acid and glacial acetic acid.
Preferably, the stirring speed of the stirring dispersion is 800rpm-1600rpm; the first preset time is 0.5-3 hours;
the first set temperature is 80-100 ℃, and the second set time is 1-24 hours;
the second set temperature is 70-200 ℃, and the drying time is 1-24 hours.
Preferably, the solid electrolyte material contains moisture adsorbed from the environment, the silicate treating agent reacts with the moisture to hydrolyze to form active alcohol, and the active alcohol is condensed with hydroxyl on the surface of the first powder, and the titanate coupling agent is condensed with free groups on the surface of the first powder, so that the solid electrolyte material is subjected to surface modification to form the hydrophobic solid electrolyte.
In a second aspect, the embodiment of the present invention provides a hydrophobic solid-state electrolyte prepared by the dry method for preparing a hydrophobic solid-state electrolyte according to the first aspect.
In a third aspect, embodiments of the present invention provide an all-solid battery, including the hydrophobic solid electrolyte according to the second aspect.
In a fourth aspect, embodiments of the present invention provide a semi-solid battery comprising a hydrophobic solid-state electrolyte as described in the second aspect above.
In a fifth aspect, embodiments of the present invention provide a supercapacitor including the hydrophobic solid-state electrolyte according to the second aspect.
According to the dry preparation method of the hydrophobic solid electrolyte provided by the embodiment of the invention, the surface of the solid electrolyte is modified by adopting a dry process, so that the contact adsorption of the solid electrolyte and moisture in the environment can be prevented through modification, the moisture adsorbed from the environment in the solid electrolyte material can be further reduced, the solid electrolyte material is hydrolyzed under the action of a silicate treating agent and the moisture to form active alcohol, the active alcohol is condensed with hydroxyl on the surface of solid electrolyte powder, and the titanate coupling agent is condensed with free radicals on the surface of the solid electrolyte powder to obtain the hydrophobic solid electrolyte. The method enhances the hydrophobicity of the material and prevents the solid electrolyte material from absorbing moisture in the environment under the condition of not changing the original particle size of the solid electrolyte material particles, so that the solid electrolyte material has a stable and high-performance state. In addition, the dry modification method greatly improves the operability.
Drawings
The technical solutions of the embodiments of the present invention are further described in detail below with reference to the accompanying drawings and embodiments.
Fig. 1 is a flowchart of a dry method for preparing a hydrophobic solid electrolyte according to an embodiment of the present invention;
fig. 2 is an X-ray diffraction (XRD) pattern of hydrophobically modified NASICON-type solid electrolyte LATP nanoparticles prepared in example 1 of the present invention and an XRD pattern of untreated LATP nanoparticles.
Detailed Description
The invention is further illustrated by the following figures and specific examples, but it will be understood that these examples are given solely for the purpose of illustration and are not to be construed as limiting the invention in any way, i.e., not as limiting the scope of the invention.
The invention provides a dry preparation method of a hydrophobic solid electrolyte, which comprises the following steps as shown in figure 1:
specifically, the mixing device may be a device for stirring and dispersing powder, such as a high-speed disperser, a planetary mixer, a mixer, etc., which are commonly used in the art, and is not limited herein.
Solid state electrolyte materials useful in the present invention include: at least one of a garnet-type solid electrolyte, a sulfide-type solid electrolyte, a sodium fast ion conductor (NASICON) -type solid electrolyte, a lithium phosphorus oxygen nitrogen (LiPON) -type electrolyte, or a perovskite-type solid electrolyte.
Preferably, the solid electrolyte material is in powder form when added. However, since the solid electrolyte is easy to agglomerate, the solid electrolyte is stirred and dispersed in advance, so that the subsequent spraying can be more uniform.
preferably, the stirring speed of stirring dispersion is 800rpm-1600rpm; the first preset time is 0.5-3 hours;
the silicate-based treating agent includes: one or more of tetramethyl silicate, tetraethyl silicate and tetrapropyl silicate. The dosage of the silicate treating agent is 1-20% of the mass of the solid electrolyte material.
titanate coupling agents include: one or more of isopropyldioleate acyloxy (dioctylphosphate) titanate, isopropyltris (dioctylphosphate) titanate, isopropyltrioleate acyloxy titanate, isopropyltris (dioctylphosphate) titanate, triisostearate isopropyl titanate, bis (dioctyloxypyrophosphate) ethylene titanate, tetraisopropylbis (dioctylphosphato) titanate, isopropyl trihydroxyacyl titanate, isopropyl tristearate titanate, tri (dioctylphosphato) isopropyl titanate, di (dioctylphosphato) ethylene titanate, di (dioctylphosphato) glycolic acid titanate, dihydroxyacyl ethylene titanate, alkylol diphosphato glycolic acid titanate, alkylol amine diphosphato glycolic acid titanate, alkylol diphosphato glycolic acid titanate, tri (dodecylbenzenesulfonyl) isopropyl titanate, isopropyltris (isostearyl) titanate, isopropyltris (dioctylphosphato) titanate, tetraisopropylbis (dilauryl phosphite) titanate;
the solvent comprises: one or more of isopropanol, acetone, ethyl acetate, paraffin oil, dioctyl phthalate, xylene, toluene or mineral oil;
the acidic auxiliary agent comprises one or more of hydrochloric acid, citric acid and glacial acetic acid.
This step may be performed before the entire method is performed, or may be performed in synchronization with any of the above steps 110, 120 of the method, as long as it is performed before spraying.
In the mixed solution, the mass ratio of the titanate coupling agent to the solvent is 1. In addition, the mass ratio of the titanate coupling agent to the silicate treating agent is 1-1.
preferably, the first set temperature is 80 ℃ to 100 ℃, and the second preset time for continuous stirring is 1 hour to 24 hours.
And 150, putting the wet powder into a vacuum drying box, and drying at a second set temperature to obtain the hydrophobic solid electrolyte.
Preferably, the second set temperature is 70-200 ℃, and the drying time is 1-24 hours.
In the preparation process, because the solid electrolyte material contains moisture adsorbed from the environment, the solid electrolyte material is hydrolyzed under the action of a silicate treating agent and the moisture to form active alcohol to be condensed with hydroxyl on the surface of the first powder, and then the active alcohol is condensed with free groups on the surface of the first powder through a titanate coupling agent, so that the solid electrolyte material is subjected to surface modification to form the hydrophobic solid electrolyte. In addition, the titanate coupling agent can further consume moisture in the first powder to generate a hydrolysis reaction to generate titanyl oxide, and the titanyl oxide reacts with a silicate hydrolysis product.
The hydrophobic solid electrolyte prepared by the method can be applied to all-solid batteries, semi-solid batteries or super capacitors.
The surface of the solid electrolyte is modified by adopting a dry process, so that the contact adsorption of the solid electrolyte and moisture in the environment can be prevented through modification, the moisture adsorbed from the environment in the solid electrolyte material can be further reduced, the solid electrolyte material is hydrolyzed under the action of a silicate treating agent and the moisture to form active alcohol, the active alcohol is condensed with hydroxyl on the surface of solid electrolyte powder, and the titanate coupling agent is condensed with free radicals on the surface of the solid electrolyte powder to obtain the hydrophobic solid electrolyte. The method enhances the hydrophobicity of the material and prevents the solid electrolyte material from absorbing moisture in the environment under the condition of not changing the original particle size of the solid electrolyte material particles, so that the solid electrolyte material has a stable and high-performance state. In addition, the dry modification method greatly improves the operability.
In order to better understand the technical scheme provided by the present invention, the following description respectively illustrates specific processes and characteristics of preparing a hydrophobic solid electrolyte by applying the method provided by the above embodiments of the present invention with a plurality of specific examples.
Example 1
1000g NASICON type solid electrolyte lithium titanium aluminum phosphate (LATP) nano particles are put into a mixer to be stirred and dispersed for 1 hour at the rotating speed of 1200rpm to obtain powder;
spraying 10g of tetramethyl silicate on the surface of the powder in a spraying mode, and continuously stirring for 1 hour to obtain powder to be sprayed;
preparing a mixed solution of 10g of isopropyl tri (dioctyl pyrophosphato acyloxy) titanate and 10g of isopropanol, adding glacial acetic acid to adjust the pH value to 4, and filling the mixed solution into a spray bottle for later use;
spraying the solution in the spray bottle on the powder to be sprayed, and stirring for 2 hours at the constant temperature of 90 ℃ at the same stirring speed to obtain wet modified LATP powder;
and (3) putting the wet modified LATP powder into a vacuum drying oven, keeping the temperature of 80 ℃ and drying for 12 hours to obtain the hydrophobic LATP nano-particles.
FIG. 2 is an X-ray diffraction (XRD) pattern of the hydrophobically modified NASICON type solid electrolyte LATP nanoparticles prepared in example 1 of the present invention and an XRD pattern of the untreated LATP nanoparticles, as compared to standard card PDF #82-0297, from which the XRD diffraction peaks of the untreated LATP solid electrolyte match the standard diffraction peaks of the standard card, indicating that the untreated LATP is a pure phase LATP; the XRD diffraction peaks of the hydrophobic LATP solid electrolyte obtained in the examples coincided with those of the untreated LATP solid electrolyte, indicating that the phase of the hydrophobic LATP solid electrolyte was not changed.
Example 2
Putting 1000g garnet type Lithium Lanthanum Zirconium Oxide (LLZO) nano particles into a mixer, and stirring and dispersing for 1 hour at the rotating speed of 1200rpm to obtain powder;
spraying 12g of tetramethyl silicate on the surface of the powder in a spraying mode, and stirring for 1 hour to obtain powder to be sprayed;
preparing a mixed solution of 12g of bis (dioctyloxypyrophosphate) ethylene titanate and 12g of toluene, adding glacial acetic acid to adjust the pH value to 4, and filling the solution into a spray bottle for later use;
spraying the solution in the spray bottle on the powder to be sprayed, and stirring for 4 hours at the constant temperature of 85 ℃ at the same stirring speed to obtain wet modified LLZO powder;
and (3) putting the wet modified LLZO powder into a vacuum drying oven, keeping the temperature of 100 ℃ and drying for 8 hours to obtain the hydrophobic LLZO nano-particles.
Example 3
Putting 1500g garnet type Lithium Lanthanum Titanium Oxide (LLTO) nanoparticles into a mixer, stirring and dispersing for 1 hour at the rotating speed of 1400rpm to obtain powder;
spraying 20g of tetramethyl silicate on the surface of the powder in a spraying mode, and continuously stirring for 1 hour to obtain powder to be sprayed;
preparing a mixed solution of 22g of bis (dioctyloxypyrophosphate) ethylene titanate and 26g of isopropanol, adding glacial acetic acid to adjust the pH value to 4, and filling the solution into a spray bottle for later use;
spraying the solution in the spray bottle on the powder to be sprayed, and stirring for 4 hours at a constant temperature of 90 ℃ at the same stirring speed to obtain wet modified LLZO powder;
and (3) putting the wet modified LLZO powder into a vacuum drying oven, keeping the temperature at 150 ℃ and drying for 10 hours to obtain the hydrophobic LLTO nano-particles.
The solid electrolyte materials before and after modification in the above three examples were compared, respectively. The comparison was made with the original solid electrolyte as a comparative example sample and the solid electrolyte after the modification as an example sample. The results are as follows.
| Sample (I) | Comparative example 1 | Example 1 | Comparative example 2 | Example 2 | Comparative example 3 | Example 3 |
| Particle size/nm | 315 | 317 | 402 | 410 | 601 | 620 |
| Contact Angle/° | 12 | 151 | 16 | 138 | 22 | 110 |
TABLE 1
It can be seen that the particle diameters and the static contact angles with water of the hydrophobic solid electrolytes prepared in the above 3 examples are shown in table 1. Wherein the particle size of the prepared hydrophobic solid electrolyte is detected by a Malvern particle size analyzer. Particle size detection shows that the particle size of the solid electrolyte before and after modification is not changed. The static contact angle of the solid electrolyte nanoparticles with water was tested by an OCA 40Micro contact angle meter. The hydrophobic property of the solid electrolyte particles is characterized by the static contact angle of the particles and water, and the larger the static contact angle with water, the better the hydrophobic property of the nano solid electrolyte. The measurement shows that the static antenna is obviously enlarged after the dry hydrophobic modification of the invention, which shows that the hydrophobicity of the material is obviously improved.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are merely exemplary embodiments of the present invention, and are not intended to limit the scope of the present invention, and any modifications, equivalent substitutions, improvements and the like made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (9)
1. A dry-process production method for a hydrophobic solid electrolyte, characterized by comprising:
putting the solid electrolyte material into mixing equipment, and stirring and dispersing;
in the stirring and dispersing process, spraying a silicate treating agent on the surface of the solid electrolyte material, and continuously stirring for a first preset time to form a first powder material;
preparing a mixed solution by using a titanate coupling agent and a solvent, and adding an acidic auxiliary agent to adjust the pH value to 3-6 to form a spraying solution;
spraying the spraying solution on the surface of the first powder material in a spraying mode, and continuously stirring for a second preset time at a first set temperature to obtain wet powder;
and putting the wet powder into a vacuum drying box, and drying at a second set temperature to obtain the hydrophobic solid electrolyte.
2. The dry preparation method according to claim 1, wherein the amount of the silicate treating agent is 1-20% of the mass of the solid electrolyte material;
in the mixed solution, the mass ratio of the titanate coupling agent to the solvent is 1-10;
the mass ratio of the titanate coupling agent to the silicate treating agent is 1-1.
3. The dry-process production method according to claim 1, wherein the solid electrolyte material comprises: at least one of garnet type solid electrolyte, sulfide solid electrolyte, sodium fast ion conductor NASICON type solid electrolyte, lithium phosphorus oxygen nitrogen LiPON type electrolyte or perovskite type solid electrolyte;
the silicate treating agent comprises: one or more of tetramethyl orthosilicate, tetraethyl orthosilicate and tetrapropyl orthosilicate;
the titanate coupling agent comprises: one or more of isopropyldioleate acyloxy (dioctylphosphate acyloxy) titanate, isopropyltris (dioctylphosphate acyloxy) titanate, isopropyltrioleate acyloxy titanate, isopropyltris (dioctylphosphate acyloxy) titanate, triisostearate titanium isopropyl, bis (dioctylphosphato) ethylene titanate, tetraisopropylbis (dioctylphosphato acyloxy) titanate, trihydroxyacyl titanium isopropyl, tristearate titanium isopropyl, trioctylphosphato) titanium isopropyl, dioctylphosphato ethylene titanate, trioctylphosphato titanium isopropyl, trioctylphosphato ethylene titanate, trioctylphosphato titanium isopropyl tri (dioctylphosphato) titanium isopropyl, dioctylphosphato glycolic acid titanate, dihydroxyethylene glycol titanate, alkylol diphosphato glycolic acid titanate, tridodecylbenzenesulfonyl titanium isopropyl, isopropyltris (isostearyl) titanate, isopropyltris (dioctylphosphato) titanate, tetraisopropyldilaurate phosphite titanate;
the solvent comprises: one or more of isopropanol, acetone, ethyl acetate, paraffin oil, dioctyl phthalate, xylene, toluene or mineral oil;
the acidic auxiliary agent comprises one or more of hydrochloric acid, citric acid and glacial acetic acid.
4. The dry production method according to claim 1,
the stirring speed of the stirring dispersion is 800rpm-1600rpm; the first preset time is 0.5-3 hours;
the first set temperature is 80-100 ℃, and the second set time is 1-24 hours;
the second set temperature is 70-200 ℃, and the drying time is 1-24 hours.
5. The dry preparation method according to claim 1, wherein the solid electrolyte material contains moisture adsorbed from the environment, the silicate treating agent reacts with the moisture to hydrolyze and form active alcohol to condense with hydroxyl groups on the surface of the first powder, and the titanate coupling agent condenses with free groups on the surface of the first powder, so that the solid electrolyte material is subjected to surface modification to form the hydrophobic solid electrolyte.
6. A hydrophobic solid electrolyte prepared by the dry preparation method of a hydrophobic solid electrolyte according to any one of claims 1 to 5.
7. An all-solid battery comprising the hydrophobic solid electrolyte according to claim 6.
8. A semi-solid battery, characterized in that it comprises a hydrophobic solid-state electrolyte according to claim 6.
9. A supercapacitor characterized in that it comprises the hydrophobic solid-state electrolyte of claim 5.
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| CN111342117B (en) * | 2020-02-02 | 2022-10-28 | 江苏大学 | Super-hydrophobic solid electrolyte of lithium-air battery and preparation method thereof |
| US20220131184A1 (en) * | 2020-10-23 | 2022-04-28 | Battelle Memorial Institute | Air-stable solid-state sulfide electrolyte |
| CN112421119A (en) * | 2020-11-23 | 2021-02-26 | 成都新柯力化工科技有限公司 | Preparation method of all-solid-state sulfide electrolyte for lithium ion battery |
| CN112701345B (en) * | 2020-12-29 | 2022-04-12 | 长三角物理研究中心有限公司 | Super-hydrophobic material capable of conducting lithium ions as well as preparation method and application thereof |
| CN115224352A (en) * | 2022-08-09 | 2022-10-21 | 南木纳米科技(北京)有限公司 | Dry-method prepared hydrophobic solid electrolyte and preparation method and application thereof |
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