CN112909328A - Ultrathin sulfide solid electrolyte layer and preparation method and application thereof - Google Patents
Ultrathin sulfide solid electrolyte layer and preparation method and application thereof Download PDFInfo
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- CN112909328A CN112909328A CN201911229155.1A CN201911229155A CN112909328A CN 112909328 A CN112909328 A CN 112909328A CN 201911229155 A CN201911229155 A CN 201911229155A CN 112909328 A CN112909328 A CN 112909328A
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- sulfide solid
- polydopamine
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- 239000002203 sulfidic glass Substances 0.000 title claims abstract description 227
- 238000002360 preparation method Methods 0.000 title claims abstract description 35
- 229920001690 polydopamine Polymers 0.000 claims abstract description 88
- 239000000843 powder Substances 0.000 claims abstract description 51
- 239000002002 slurry Substances 0.000 claims abstract description 43
- 239000002904 solvent Substances 0.000 claims abstract description 31
- 238000001035 drying Methods 0.000 claims abstract description 28
- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229960001149 dopamine hydrochloride Drugs 0.000 claims abstract description 26
- 238000001816 cooling Methods 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 238000002156 mixing Methods 0.000 claims abstract description 15
- 238000004146 energy storage Methods 0.000 claims abstract description 12
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 claims description 44
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 27
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 27
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 24
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 24
- FEWLNYSYJNLUOO-UHFFFAOYSA-N 1-Piperidinecarboxaldehyde Chemical compound O=CN1CCCCC1 FEWLNYSYJNLUOO-UHFFFAOYSA-N 0.000 claims description 18
- 229910052698 phosphorus Inorganic materials 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 16
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 16
- XUPYJHCZDLZNFP-UHFFFAOYSA-N butyl butanoate Chemical compound CCCCOC(=O)CCC XUPYJHCZDLZNFP-UHFFFAOYSA-N 0.000 claims description 16
- 229910052787 antimony Inorganic materials 0.000 claims description 15
- 239000007784 solid electrolyte Substances 0.000 claims description 13
- 229910052717 sulfur Inorganic materials 0.000 claims description 12
- 229910052794 bromium Inorganic materials 0.000 claims description 11
- 229910052801 chlorine Inorganic materials 0.000 claims description 11
- 229910052710 silicon Inorganic materials 0.000 claims description 10
- 229910052718 tin Inorganic materials 0.000 claims description 10
- VUNPWIPIOOMCPT-UHFFFAOYSA-N piperidin-3-ylmethanol Chemical compound OCC1CCCNC1 VUNPWIPIOOMCPT-UHFFFAOYSA-N 0.000 claims description 9
- XBXHCBLBYQEYTI-UHFFFAOYSA-N piperidin-4-ylmethanol Chemical compound OCC1CCNCC1 XBXHCBLBYQEYTI-UHFFFAOYSA-N 0.000 claims description 9
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 8
- 229910052740 iodine Inorganic materials 0.000 claims description 8
- 150000001450 anions Chemical group 0.000 claims description 7
- 150000001768 cations Chemical group 0.000 claims description 7
- 239000003607 modifier Substances 0.000 claims description 7
- 230000001105 regulatory effect Effects 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 4
- 229910052732 germanium Inorganic materials 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 229910052711 selenium Inorganic materials 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- 239000007891 compressed tablet Substances 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 6
- 239000000243 solution Substances 0.000 description 28
- 238000007599 discharging Methods 0.000 description 18
- 239000011734 sodium Substances 0.000 description 13
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 12
- 229910052744 lithium Inorganic materials 0.000 description 12
- 238000003825 pressing Methods 0.000 description 11
- 238000000498 ball milling Methods 0.000 description 10
- 238000001514 detection method Methods 0.000 description 10
- 230000014759 maintenance of location Effects 0.000 description 10
- 238000011056 performance test Methods 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 239000012046 mixed solvent Substances 0.000 description 6
- 229910000921 lithium phosphorous sulfides (LPS) Inorganic materials 0.000 description 5
- 238000003892 spreading Methods 0.000 description 5
- 230000007480 spreading Effects 0.000 description 5
- 229910003405 Li10GeP2S12 Inorganic materials 0.000 description 4
- 229910012820 LiCoO Inorganic materials 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 4
- 238000000462 isostatic pressing Methods 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 239000011812 mixed powder Substances 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000005096 rolling process Methods 0.000 description 4
- 229910011328 LiNi0.6Co0.2Mn0.2O2 Inorganic materials 0.000 description 3
- 229910002995 LiNi0.8Co0.15Al0.05O2 Inorganic materials 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000003801 milling Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 229910011201 Li7P3S11 Inorganic materials 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 229910003480 inorganic solid Inorganic materials 0.000 description 2
- 238000010907 mechanical stirring Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 238000001132 ultrasonic dispersion Methods 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 208000032953 Device battery issue Diseases 0.000 description 1
- 229910005870 GeS3 Inorganic materials 0.000 description 1
- 229910004956 Li10SiP2S12 Inorganic materials 0.000 description 1
- 229910011788 Li4GeS4 Inorganic materials 0.000 description 1
- 229910012007 Li4P2S6 Inorganic materials 0.000 description 1
- 229910011889 Li4SiS4 Inorganic materials 0.000 description 1
- 229910011899 Li4SnS4 Inorganic materials 0.000 description 1
- 229910010854 Li6PS5Br Inorganic materials 0.000 description 1
- 229910010848 Li6PS5Cl Inorganic materials 0.000 description 1
- 229910010850 Li6PS5X Inorganic materials 0.000 description 1
- 229910011187 Li7PS6 Inorganic materials 0.000 description 1
- 229910002099 LiNi0.5Mn1.5O4 Inorganic materials 0.000 description 1
- 229910004663 Na10SnP2S12 Inorganic materials 0.000 description 1
- 229910020657 Na3V2(PO4)3 Inorganic materials 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- MVPPADPHJFYWMZ-IDEBNGHGSA-N chlorobenzene Chemical group Cl[13C]1=[13CH][13CH]=[13CH][13CH]=[13CH]1 MVPPADPHJFYWMZ-IDEBNGHGSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000007590 electrostatic spraying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910021385 hard carbon Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910000614 lithium tin phosphorous sulfides (LSPS) Inorganic materials 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 229910052960 marcasite Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 description 1
- 229910052683 pyrite Inorganic materials 0.000 description 1
- 229910052952 pyrrhotite Inorganic materials 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- -1 sulfide compound Chemical class 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0561—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
- 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
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Secondary Cells (AREA)
Abstract
The invention provides a preparation method of an ultrathin sulfide solid electrolyte layer, which comprises the following steps: a) adding the reaction solution into a solvent, and then sequentially adding a sulfide solid electrolyte and dopamine hydrochloride for mixing to obtain polydopamine-coated sulfide solid electrolyte slurry; b) drying the polydopamine-coated sulfide solid electrolyte slurry obtained in the step a), and cooling to obtain polydopamine-coated sulfide solid electrolyte powder; c) tabletting the polydopamine-coated sulfide solid electrolyte powder obtained in the step b) to obtain the ultrathin sulfide solid electrolyte layer. Compared with the prior art, the preparation method provided by the invention can better improve the cohesiveness of the sulfide solid electrolyte to obtain an ultrathin sulfide solid electrolyte layer with higher ionic conductivity, thereby realizing the preparation of a high-energy-density all-solid-state energy storage device; the preparation method has the advantages of simple process, easy control, high repeatability and low cost.
Description
Technical Field
The invention relates to the technical field of all-solid-state energy storage devices, in particular to an ultrathin sulfide solid electrolyte layer and a preparation method and application thereof.
Background
Commercial lithium ion batteries are now widely used in the fields of transportation, communication, portable electronic products, electric tools, and the like, and are expanding in the field of large-scale storage. However, the organic electrolyte used in the current commercial lithium ion battery is easy to leak, easy to burn and explode and brings great potential safety hazard. Meanwhile, the dendritic grown metal lithium easily pierces a diaphragm in the liquid battery to cause short circuit of the battery, so that the battery is out of work and even explodes, the use of the metal lithium in the liquid lithium ion battery is limited, and the improvement of the energy density of the liquid battery is limited. The inorganic solid electrolyte is nonflammable, has strong temperature adaptability, has the advantages of strong mechanical property, capability of effectively blocking lithium dendrite and the like, can fundamentally solve the safety problem of the liquid electrolyte, simplifies the structure of the battery, reduces the manufacturing cost, and improves the cycle life and the energy density of the battery.
Among inorganic solid electrolytes, sulfide solid electrolytes have the advantages of high ionic conductivity, good machining performance, simple preparation and the like. At present, a sulfide solid electrolyte layer for an all-solid battery is mainly prepared by a method of directly pressing sulfide solid electrolyte powder, and the solid electrolyte layer obtained by the method is relatively thick (0.5-1 mm) due to poor cohesiveness among sulfide powder, so that the preparation of a high-energy-density battery is difficult to realize; the sulfide solid electrolyte layer used for the all-solid-state battery at present is brittle and has poor flexibility, and the battery is easy to crack to cause battery failure; at present, the sulfide electrolyte thin layer can be prepared by pulse laser deposition and chemical vapor deposition, but the technology is very expensive and has low yield, and is difficult to apply in practical production.
Disclosure of Invention
In view of the above, the present invention provides an ultra-thin sulfide solid electrolyte layer, and a preparation method and an application thereof, and the preparation method provided by the present invention has the advantages of simple process, easy control, high repeatability and low cost, and can prepare an ultra-thin sulfide solid electrolyte layer with high ionic conductivity, thereby realizing the preparation of a high energy density all-solid-state energy storage device.
The invention provides a preparation method of an ultrathin sulfide solid electrolyte layer, which comprises the following steps:
a) adding the reaction solution into a solvent, and then sequentially adding a sulfide solid electrolyte and dopamine hydrochloride for mixing to obtain polydopamine-coated sulfide solid electrolyte slurry;
b) drying the polydopamine-coated sulfide solid electrolyte slurry obtained in the step a), and cooling to obtain polydopamine-coated sulfide solid electrolyte powder;
c) tabletting the polydopamine-coated sulfide solid electrolyte powder obtained in the step b) to obtain the ultrathin sulfide solid electrolyte layer.
Preferably, the reaction solution in step a) is selected from one or more of piperidine, 3-piperidinemethanol, 4-piperidinemethanol and 1-formylpiperidine.
Preferably, the solvent in step a) is selected from one or more of ethanol, isopropanol, n-butanol, toluene, chlorobenzene, ethyl acetate, butyl butyrate, n-heptane and cyclohexanone.
Preferably, the sulfide solid electrolyte in step a) comprises one or more of a general formula sulfide solid electrolyte of formula I, a modified compound of a general formula sulfide solid electrolyte of formula I, a general formula sulfide solid electrolyte of formula II, and a modified compound of a general formula sulfide solid electrolyte of formula II;
the modifier of the sulfide solid electrolyte with the general formula I is preferably selected from sulfide solid electrolytes with the general formula I, wherein the sulfide solid electrolytes are substituted by anions and cations, doped or regulated by vacancies;
the modifier of the sulfide solid electrolyte with the general formula II is preferably selected from sulfide solid electrolytes with the general formula II, which are substituted by anions and cations, doped or regulated by vacancies;
xLiaB·yCcDd·zP2S5formula I;
in formula I, x is 0-100, y is 0-100, z is 0-100, a is 1 or 2, C is 1 or 2, D is 1, 2 or 5, B is S, Cl, Br or I, C is Li, Si, Ge, P, Sn or Sb, D is Cl, Br, I, O, S or Se;
rNapEe·sMmNn·tJjQquV formula II;
in formula II, 0 ≦ r <100, 0 ≦ S <100, 0 ≦ t <100, 0 ≦ u <100, P ≦ 1 or 2, E ≦ 0, 1, 2, or 5, M ≦ 1 or 2, N ≦ 0, 1, 2, or 5, J ≦ 1 or 2, Q ≦ 0, 1, 2, or 5, E is S, Cl, Br, or I, M is P, Sb, Se, Ge, Si, or Sn, N is P, Sb, Se, Si, or Sn, J is P, Sb, Se, Ge, Si, or Sn, Q is P, Sb, Se, Ge, Si, or Sn, V is S or P, and at least one of E and V is S.
Preferably, the mass ratio of the reaction solution, the solvent, the sulfide solid electrolyte and the dopamine hydrochloride in step a) is 1: (5-100): (0.5-10): (0.1-10).
Preferably, the mixing temperature in the step a) is 10-100 ℃, and the mixing time is 0.1-12 h.
Preferably, the drying temperature in the step b) is 40-100 ℃, and the drying time is 1-48 h.
Preferably, the pressure of the tabletting in the step c) is 50MPa to 500MPa, and the temperature is 10 ℃ to 500 ℃.
The invention also provides an ultrathin sulfide solid electrolyte layer, which comprises at least one ultrathin sulfide solid electrolyte layer prepared by the preparation method in the technical scheme;
the thickness of the ultrathin sulfide solid electrolyte layer is 1-500 mu m, and the conductivity is 10-6S·cm-1～10- 1S·cm-1。
The invention also provides an all-solid-state energy storage device which is formed by assembling the solid electrolyte layer and the electrode, wherein the solid electrolyte layer is the ultrathin sulfide solid electrolyte layer in the technical scheme.
The invention provides a preparation method of an ultrathin sulfide solid electrolyte layer, which comprises the following steps: a) adding the reaction solution into a solvent, and then sequentially adding a sulfide solid electrolyte and dopamine hydrochloride for mixing to obtain polydopamine-coated sulfide solid electrolyte slurry; b) drying the polydopamine-coated sulfide solid electrolyte slurry obtained in the step a), and cooling to obtain polydopamine-coated sulfide solid electrolyte powder; c) tabletting the polydopamine-coated sulfide solid electrolyte powder obtained in the step b) to obtain the ultrathin sulfide solid electrolyte layer. Compared with the prior art, the preparation method provided by the invention adopts specific process steps and conditions, can better improve the cohesiveness of the sulfide solid electrolyte, and obtains the ultrathin sulfide solid electrolyte layer with higher ionic conductivity, thereby realizing the preparation of the high-energy-density all-solid-state energy storage device; meanwhile, the preparation method provided by the invention has the advantages of simple process, easiness in control, high repeatability, wide and easily obtained raw materials, low cost and wide application prospect.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a preparation method of an ultrathin sulfide solid electrolyte layer, which comprises the following steps:
a) adding the reaction solution into a solvent, and then sequentially adding a sulfide solid electrolyte and dopamine hydrochloride for mixing to obtain polydopamine-coated sulfide solid electrolyte slurry;
b) drying the polydopamine-coated sulfide solid electrolyte slurry obtained in the step a), and cooling to obtain polydopamine-coated sulfide solid electrolyte powder;
c) tabletting the polydopamine-coated sulfide solid electrolyte powder obtained in the step b) to obtain the ultrathin sulfide solid electrolyte layer.
According to the preparation method, firstly, a reaction solution is added into a solvent, and then sulfide solid electrolyte and dopamine hydrochloride are sequentially added and mixed to obtain polydopamine-coated sulfide solid electrolyte slurry. In the present invention, the reaction solution is preferably selected from one or more of piperidine, 3-piperidinemethanol, 4-piperidinemethanol and 1-formylpiperidine, and more preferably from one or two of piperidine, 3-piperidinemethanol, 4-piperidinemethanol and 1-formylpiperidine. In a preferred embodiment of the present invention, the reaction solution is a mixed solution of piperidine and 3-piperidinemethanol, wherein the volume ratio of piperidine to 3-piperidinemethanol is 1: 1; in another preferred embodiment of the present invention, the reaction solution is a mixed solution of 4-piperidinemethanol and 1-formylpiperidine, wherein the volume ratio of 4-piperidinemethanol to 1-formylpiperidine is 1: 2; in another preferred embodiment of the present invention, the reaction solution is piperidine. The present invention is not particularly limited with respect to the source of the reaction solution, and commercially available products of the above-mentioned piperidine, 3-piperidinemethanol, 4-piperidinemethanol and 1-formylpiperidine, which are well known to those skilled in the art, may be used.
In the present invention, the solvent is preferably selected from one or more of ethanol, isopropanol, n-butanol, toluene, chlorobenzene, ethyl acetate, butyl butyrate, n-heptane, and cyclohexanone. In a preferred embodiment of the present invention, the solvent is a mixed solvent of ethanol, isopropanol and n-butanol, wherein the volume ratio of ethanol, isopropanol and n-butanol is 1: 1: 2; in another preferred embodiment of the present invention, the solvent is a mixed solvent of toluene and chlorobenzene, wherein the volume ratio of toluene to chlorobenzene is 1: 2; in another preferred embodiment of the present invention, the solvent is a mixed solvent of ethyl acetate and butyl butyrate, wherein the volume ratio of ethyl acetate to butyl butyrate is 1: 2; in another preferred embodiment of the present invention, the solvent is an n-heptane solvent; in another preferred embodiment of the present invention, the solvent is a chlorobenzene solvent; in another preferred embodiment of the present invention, the solvent is a toluene solvent. The source of the solvent is not particularly limited in the present invention, and commercially available products of the above-mentioned ethanol, isopropanol, n-butanol, toluene, chlorobenzene, ethyl acetate, butyl butyrate, n-heptane and cyclohexanone, which are well known to those skilled in the art, may be used.
In the invention, the sulfide solid electrolyte comprises one or more of a sulfide solid electrolyte of a general formula I, a modified substance of the sulfide solid electrolyte of the general formula I, a sulfide solid electrolyte of a general formula II and a modified substance of the sulfide solid electrolyte of the general formula II;
the modifier of the sulfide solid electrolyte with the general formula I is preferably selected from sulfide solid electrolytes with the general formula I, wherein the sulfide solid electrolytes are substituted by anions and cations, doped or regulated by vacancies;
the modifier of the sulfide solid electrolyte with the general formula II is preferably selected from sulfide solid electrolytes with the general formula II, which are substituted by anions and cations, doped or regulated by vacancies;
xLiaB·yCcDd·zP2S5formula I;
in formula I, x is 0-100, y is 0-100, z is 0-100, a is 1 or 2, C is 1 or 2, D is 1, 2 or 5, B is S, Cl, Br or I, C is Li, Si, Ge, P, Sn or Sb, D is Cl, Br, I, O, S or Se;
rNapEe·sMmNn·tJjQquV formula II;
formula II wherein 0 ≦ r <100, 0 ≦ S <100, 0 ≦ t <100, 0 ≦ u <100, P ═ 1 or 2, E ═ 0, 1, 2, or 5, M ═ 1 or 2, N ═ 0, 1, 2, or 5, J ═ 1 or 2, Q ═ 0, 1, 2, or 5, E is S, Cl, Br, or I, M is P, Sb, Se, Ge, Si, or Sn, N is P, Sb, Se, Si, or Sn, J is P, Sb, Se, Ge, Si, or Sn, Q is P, Sb, Se, Ge, Si, or Sn, V is S or P, and at least one of E and V is S;
more preferably Li3PS4System, Li2P2S6System, Li7PS6System, Li4P2S6System, Li7P3S11System, Li7P2S8X (X ═ Cl, Br, I) system, Li4SiS4System, Li4SnS4System, Li7Ge3PS12System, Li2GeS3System, Li4GeS4System, Li2ZnGeS4System, Li5GaS4System, Li10GeP2S12System, Li6PS5X (X ═ Cl, Br, I) system, Li11Si2PS12System, Li10SiP2S12System, Li11Sn2PS12System, Li10SnP2S12System, Na3PS4System, Na3SbS4System, Na11Sn2PS12System, Na10SnP2S12The system also includes modifier of the sulfide system, such as sulfide electrolyte system with anion and cation substitution, doping or vacancy regulation, such as Li6-xPS5-xCl1+x(x is not less than 0 and not more than 6) system and Li6+xMxSb1-xS5I (M ═ Si, Ge, Sn) (0 ≦ x ≦ 1) system, Li3+3xP1-xZnxS4-xOx(x is not less than 0 and not more than 1) system, Li9.54Si1.74P1.44S11.7Cl0.3、Li3InCl6System, Na3PSe4System, Na11Sn2PSe12System, Na3SbS4-xSex(x is more than or equal to 0 and less than or equal to 4), and the like. The source of the sulfide solid electrolyte is not particularly limited in the present invention, and any commercially available or self-produced product using the above sulfide solid electrolyte material known to those skilled in the art may be used.
In the invention, the dopamine hydrochloride can be coated by a simple liquid phase chemical method to improve the caking property among the sulfide solid electrolyte particles, so that the sulfide solid electrolyte can be pressed into a sheet, and the thickness of the sulfide solid electrolyte layer is reduced and the ionic conductivity of the sulfide solid electrolyte layer is improved. The source of the dopamine hydrochloride is not particularly limited in the present invention, and commercially available products well known to those skilled in the art may be used.
In the present invention, the mass ratio of the reaction solution, the solvent, the sulfide solid electrolyte, and dopamine hydrochloride is preferably 1: (5-100): (0.5-10): (0.1-10).
In the present invention, the mixing means preferably includes one or more of mechanical stirring, mechanical shaking, ultrasonic dispersion, ball milling and roll milling. In the present invention, the mixing temperature is preferably 10 to 100 ℃; the mixing time is preferably 0.1 to 12 hours.
After the solid electrolyte slurry coated with the polydopamine is obtained, the solid electrolyte slurry coated with the polydopamine is dried and cooled to obtain solid electrolyte powder coated with the polydopamine. The drying method is not particularly limited in the present invention, and the drying method can be performed by a drying method known to those skilled in the art. In the present invention, the drying temperature is preferably 40 ℃ to 100 ℃; the drying time is preferably 1 to 48 hours.
In the present invention, the cooling process is preferably performed at room temperature.
After the polydopamine-coated sulfide solid electrolyte powder is obtained, the obtained polydopamine-coated sulfide solid electrolyte powder is tabletted to obtain the ultrathin sulfide solid electrolyte layer. In the present invention, it is preferable that the tablet further comprises, before the tabletting:
and tiling the polydopamine-coated sulfide solid electrolyte powder. In the present invention, the spreading manner preferably includes one or more of scraper type powder spreading, electrostatic spraying, roller type powder spreading, hopper type powder spreading, electrostatic screen printing and oscillation type powder spreading. In a preferred embodiment of the present invention, the polydopamine-coated sulfide solid electrolyte powder includes a plurality of sulfide solid electrolyte materials, and before being tiled, the sulfide solid electrolyte materials are directly and uniformly mixed. The mixing method is not particularly limited, and mechanical stirring, ball milling or roller milling methods well known to those skilled in the art can be used.
In the present invention, the means of tabletting preferably comprises one or more of flat-bed pressing, isostatic pressing, rolling and stamping. In the present invention, the pressure of the tablet is preferably 50 to 500 MPa; the temperature of the tablet is preferably 10 ℃ to 500 ℃.
In the invention, the ultrathin sulfide solid electrolyte layer comprises at least one ultrathin sulfide solid electrolyte layer prepared by the preparation method of the technical scheme. In a preferred embodiment of the present invention, the ultrathin sulfide solid electrolyte layer includes an ultrathin sulfide solid electrolyte layer prepared by the preparation method according to the above technical solution; in another preferred embodiment of the present invention, the ultrathin sulfide solid electrolyte layer includes a plurality of ultrathin sulfide solid electrolyte layers prepared by the preparation method according to the above technical solution, and the ultrathin sulfide solid electrolyte layer is formed by stacking and tabletting. In the invention, the layers of the ultrathin sulfide solid electrolyte layer prepared by the preparation method of the multilayer according to the technical scheme can be the same or different, and the invention is not limited in particular.
The preparation method provided by the invention adopts specific process steps and conditions, can better improve the cohesiveness of the sulfide solid electrolyte, and obtains the ultrathin sulfide solid electrolyte layer with higher ionic conductivity, thereby realizing the preparation of the high-energy-density all-solid-state energy storage device; meanwhile, the preparation method provided by the invention has the advantages of simple process, easiness in control, high repeatability, wide and easily obtained raw materials, low cost and wide application prospect.
The invention also provides an ultrathin sulfide solid electrolyte layer which comprises at least one ultrathin sulfide solid electrolyte layer prepared by the preparation method of the technical scheme. In the present invention, the thickness of the ultra-thin sulfide solid electrolyte layer is 1 μm to 500 μm, preferably 1 μm to 100 μm, and more preferably 1 μm to 50 μm; the conductivity of the ultrathin sulfide solid electrolyte layer is 10-6S·cm-1～10-1S·cm-1Preferably 10-5S·cm-1～5×10-2S·cm-1。
The invention also provides an all-solid-state energy storage device which is formed by assembling the solid electrolyte layer and the electrode, wherein the solid electrolyte layer is the ultrathin sulfide solid electrolyte layer in the technical scheme. In the present invention, the all-solid-state energy storage device preferably includes an all-solid-state battery and an all-solid-state supercapacitor. The electrode is not particularly limited in the present invention, and is a common electrode material in energy storage devices, preferably LiCoO, well known to those skilled in the art2、LiNi0.8Co0.15Al0.05O2、LiNi0.6Co0.2Mn0.2O2、LiNi0.5Mn1.5O4、FeS2、Fe1-xS(0≤x≤0.125)、WS2、Co9S8NiS, surface-modified Na3V2(PO4)3Graphite, hard carbon, metallic lithium, metallic sodium, carbon nanotubes and other common electrode materials. The assembly method is not particularly limited by the present invention, and a corresponding assembly method known to those skilled in the art may be adopted according to the kind of the specific all-solid-state energy storage device.
The invention provides a preparation method of an ultrathin sulfide solid electrolyte layer, which comprises the following steps: a) adding the reaction solution into a solvent, and then sequentially adding a sulfide solid electrolyte and dopamine hydrochloride for mixing to obtain polydopamine-coated sulfide solid electrolyte slurry; b) drying the polydopamine-coated sulfide solid electrolyte slurry obtained in the step a), and cooling to obtain polydopamine-coated sulfide solid electrolyte powder; c) tabletting the polydopamine-coated sulfide solid electrolyte powder obtained in the step b) to obtain the ultrathin sulfide solid electrolyte layer. Compared with the prior art, the preparation method provided by the invention adopts specific process steps and conditions, can better improve the cohesiveness of the sulfide solid electrolyte, and obtains the ultrathin sulfide solid electrolyte layer with higher ionic conductivity, thereby realizing the preparation of the high-energy-density all-solid-state energy storage device; meanwhile, the preparation method provided by the invention has the advantages of simple process, easiness in control, high repeatability, wide and easily obtained raw materials, low cost and wide application prospect.
To further illustrate the present invention, the following examples are provided for illustration. The reagents and raw materials used in the following examples of the present invention are commercially available or self-made.
Example 1
(1) Adding 1 weight part of mixed solution of piperidine and 3-piperidinemethanol (the volume ratio of the piperidine to the 3-piperidinemethanol is 1: 1) into 5 weight parts of mixed solvent of ethanol, isopropanol and n-butanol (the volume ratio of the ethanol, the isopropanol and the n-butanol is 1: 1: 2), and adding 0.5 weight part of Li6PS5Br sulfide solid electrolyte, 0.1 weight part dopamine hydrochloride, mechanically stirring at 10 deg.CAnd (5) obtaining the polydopamine coated sulfide solid electrolyte slurry after 0.1 h.
(2) And (2) drying the polydopamine-coated sulfide solid electrolyte slurry obtained in the step (1) at 40 ℃ for 1h, and naturally cooling to room temperature to obtain polydopamine-coated sulfide solid electrolyte powder.
(3) Performing flat-plate static pressure tabletting on the polydopamine-coated sulfide solid electrolyte powder obtained in the step (2) at 50MPa and 500 ℃ to obtain an ultrathin sulfide solid electrolyte layer; the thickness of the ultrathin sulfide solid electrolyte layer is 100 mu m, and the conductivity is 2 multiplied by 10-4S·cm-1。
The ultra-thin sulfide solid electrolyte layer and LiCoO provided in example 12The positive electrode and the metallic lithium negative electrode are assembled into an all-solid-state battery.
The battery adopts a blue CT2001A battery test system to carry out electrochemical performance test, the voltage range of charging and discharging is 3.1V-4.2V, and the charging and discharging are carried out at room temperature at 0.1C multiplying power. Through detection, the capacity retention rate of the battery after 100 cycles is 91.2%.
Example 2
(1) Adding 1 part by weight of 4-piperidinemethanol and 1-formylpiperidine mixed solution (the volume ratio of 4-piperidinemethanol to 1-formylpiperidine is 1: 2) into 50 parts by weight of toluene and chlorobenzene mixed solvent (the volume ratio of toluene to chlorobenzene is 1: 2), and adding 5 parts by weight of Li10GeP2S12And mechanically shaking the sulfide solid electrolyte and 5 parts by weight of dopamine hydrochloride at 50 ℃ for 6 hours to obtain the polydopamine-coated sulfide solid electrolyte slurry.
(2) And (2) drying the polydopamine-coated sulfide solid electrolyte slurry obtained in the step (1) at 80 ℃ for 24h, and naturally cooling to room temperature to obtain polydopamine-coated sulfide solid electrolyte powder.
(3) Performing flat-plate static pressure tabletting on the polydopamine-coated sulfide solid electrolyte powder obtained in the step (2) at 150MPa and 400 ℃ to obtain an ultrathin sulfide solid electrolyte layer; the thickness of the ultrathin sulfide solid electrolyte layer is 50 mu m, and the conductivity is 1.01 multiplied by 10-2S·cm-1。
The ultra-thin sulfide solid electrolyte layer and LiCoO provided in example 22The positive electrode and the metallic lithium negative electrode are assembled into an all-solid-state battery.
The battery adopts a blue CT2001A battery test system to carry out electrochemical performance test, the voltage range of charging and discharging is 3.1V-4.2V, and the charging and discharging are carried out at room temperature at 0.5C multiplying power. Through detection, the capacity retention rate of the battery after 500 cycles is 82.5%.
Example 3
(1) Adding 1 part by weight of piperidine solution into 100 parts by weight of mixed solvent of ethyl acetate and butyl butyrate (the volume ratio of ethyl acetate to butyl butyrate is 1: 2), and adding 10 parts by weight of Li3PS4And (3) performing ultrasonic dispersion on the sulfide solid electrolyte and 10 parts by weight of dopamine hydrochloride at 70 ℃ for 12 hours to obtain polydopamine-coated sulfide solid electrolyte slurry.
(2) And (2) drying the polydopamine-coated sulfide solid electrolyte slurry obtained in the step (1) at 100 ℃ for 48h, and naturally cooling to room temperature to obtain polydopamine-coated sulfide solid electrolyte powder.
(3) Performing isostatic pressing on the polydopamine-coated sulfide solid electrolyte powder obtained in the step (2) at 500MPa and 10 ℃ to obtain an ultrathin sulfide solid electrolyte layer; the thickness of the ultrathin sulfide solid electrolyte layer is 5 mu m, and the conductivity is 4.12 multiplied by 10-4S·cm-1。
The ultrathin sulfide solid electrolyte layer provided in example 3 and LiNi0.8Co0.15Al0.05O2The positive electrode and the metallic lithium negative electrode are assembled into an all-solid-state battery.
The battery adopts a blue CT2001A battery test system to carry out electrochemical performance test, the voltage range of charging and discharging is 3.0V-4.2V, and the charging and discharging are carried out at room temperature at 0.1C multiplying power. Through detection, the capacity retention rate of the battery after 50 cycles is 84.9%.
Example 4
(1) 1 part by weight of a piperidine solution was added to 80 parts by weight of an n-heptane solvent, and 10 parts by weight of Li was added7P3S11A solid electrolyte of a sulfide compound, a lithium ion battery,and (3) carrying out ball milling on 10 parts by weight of dopamine hydrochloride at the temperature of 30 ℃ for 12 hours to obtain the polydopamine-coated sulfide solid electrolyte slurry.
(2) And (2) drying the polydopamine-coated sulfide solid electrolyte slurry obtained in the step (1) at 100 ℃ for 48h, and naturally cooling to room temperature to obtain polydopamine-coated sulfide solid electrolyte powder.
(3) Pressing and tabletting the polydopamine-coated sulfide solid electrolyte powder obtained in the step (2) under 250MPa and 200 ℃ to obtain an ultrathin sulfide solid electrolyte layer; the thickness of the ultrathin sulfide solid electrolyte layer is 180 mu m, and the conductivity is 1.3 multiplied by 10-3S·cm-1。
The ultrathin sulfide solid electrolyte layer provided in example 4 and LiNi0.6Co0.2Mn0.2O2The positive electrode and the metallic lithium negative electrode are assembled into an all-solid-state battery.
The battery adopts a blue CT2001A battery test system to carry out electrochemical performance test, the voltage range of charging and discharging is 3.0V-4.2V, and the charging and discharging are carried out at room temperature at 1C multiplying power. Through detection, the capacity retention rate of the battery after 1000 cycles is 83.1%.
Example 5
(1) Adding 1 weight part of piperidine solution into 80 weight parts of chlorobenzene solvent, and adding 2 weight parts of Li6PS5And (3) rolling and grinding the Cl sulfide solid electrolyte and 1 part by weight of dopamine hydrochloride at 60 ℃ for 3 hours to obtain polydopamine-coated sulfide solid electrolyte slurry.
(2) And (2) drying the polydopamine-coated sulfide solid electrolyte slurry obtained in the step (1) at 80 ℃ for 24h, and naturally cooling to room temperature to obtain polydopamine-coated sulfide solid electrolyte powder.
(3) Pressing and tabletting the polydopamine-coated sulfide solid electrolyte powder obtained in the step (2) at 350MPa and 100 ℃ to obtain an ultrathin sulfide solid electrolyte layer; the thickness of the ultrathin sulfide solid electrolyte layer is 60 mu m, and the conductivity is 3.2 multiplied by 10-3S·cm-1。
The ultra-thin sulfide solid electrolyte layer provided in example 5 and LiNi0.6Co0.2Mn0.2O2The positive electrode and the metallic lithium negative electrode are assembled into an all-solid-state battery.
The battery adopts a blue CT2001A battery test system to carry out electrochemical performance test, the voltage range of charging and discharging is 3.0V-4.2V, and the charging and discharging are carried out at room temperature at 0.1C multiplying power. Through detection, the capacity retention rate of the battery after 500 cycles is 86.4%.
Example 6
(1) Adding 1 weight part of piperidine solution into 80 weight parts of chlorobenzene solvent, and adding 2 weight parts of Li6PS5And (3) rolling and grinding the Cl sulfide solid electrolyte and 1 part by weight of dopamine hydrochloride at 60 ℃ for 3 hours to obtain polydopamine-coated sulfide solid electrolyte slurry.
(2) Drying the polydopamine-coated sulfide solid electrolyte slurry obtained in the step (1) at 80 ℃ for 24h, and naturally cooling to room temperature to obtain polydopamine-coated Li6PS5Cl sulfide solid electrolyte powder.
(3) 1 part by weight of a piperidine solution was added to 80 parts by weight of an n-heptane solvent, and 10 parts by weight of Li was added7P3S11And (3) carrying out ball milling on the sulfide solid electrolyte and 10 parts by weight of dopamine hydrochloride at the temperature of 30 ℃ for 12h to obtain polydopamine-coated sulfide solid electrolyte slurry.
(4) Drying the polydopamine-coated sulfide solid electrolyte slurry obtained in the step (3) at 100 ℃ for 48h, and naturally cooling to room temperature to obtain polydopamine-coated Li7P3S11Sulfide solid electrolyte powder.
(5) Li coated with polydopamine obtained in step (2)6PS5Cl sulfide solid electrolyte powder and polydopamine-coated Li obtained in step (4)7P3S11And (3) rolling and mixing the sulfide solid electrolyte powder to obtain mixed powder.
(6) Pressing and tabletting the mixed powder obtained in the step (5) at 350MPa and 100 ℃ to obtain an ultrathin sulfide solid electrolyte layer; the thickness of the ultrathin sulfide solid electrolyte layer is 30 mu m, and the conductivity is 1.8 multiplied by 10-3S·cm-1。
The ultra-thin sulfide solid electrolyte layer and LiCoO provided in example 62The positive electrode and the metallic lithium negative electrode are assembled into an all-solid-state battery.
The battery adopts a blue CT2001A battery test system to carry out electrochemical performance test, the voltage range of charging and discharging is 3.1V-4.2V, and the charging and discharging are carried out at 60 ℃ and 0.1C multiplying power. Through detection, the capacity retention rate of the battery after 50 cycles is 94.3%.
Example 7
(1) Adding 1 weight part of piperidine solution into 80 weight parts of chlorobenzene solvent, and adding 2 weight parts of Li10GeP2S12And (3) carrying out roller milling on the sulfide solid electrolyte and 1 part by weight of dopamine hydrochloride at 70 ℃ for 3 hours to obtain polydopamine-coated sulfide solid electrolyte slurry.
(2) Drying the polydopamine-coated sulfide solid electrolyte slurry obtained in the step (1) at 80 ℃ for 24h, and naturally cooling to room temperature to obtain polydopamine-coated Li10GeP2S12Sulfide solid electrolyte powder.
(3) 1 part by weight of a piperidine solution was added to 80 parts by weight of a toluene solvent, and 10 parts by weight of Li was added3PS4And (3) carrying out ball milling on the sulfide solid electrolyte and 10 parts by weight of dopamine hydrochloride at the temperature of 30 ℃ for 12h to obtain polydopamine-coated sulfide solid electrolyte slurry.
(4) Drying the polydopamine-coated sulfide solid electrolyte slurry obtained in the step (3) at 100 ℃ for 48h, and naturally cooling to room temperature to obtain polydopamine-coated Li3PS4Sulfide solid electrolyte powder.
(5) Li coated with polydopamine obtained in step (2)10GeP2S12Pressing the sulfide solid electrolyte powder into tablets at 350MPa and 100 ℃; coating the polydopamine obtained in the step (4) with Li3PS4Pressing the sulfide solid electrolyte powder into tablets under 450MPa and 50 ℃; then, carrying out isostatic pressing on the obtained two layers of sheets at 500MPa and 60 ℃ to obtain an ultrathin sulfide solid electrolyte layer; said ultra-thinThe sulfide solid electrolyte layer had a thickness of 230 μm and an electrical conductivity of 1.03X 10- 3S·cm-1。
The ultrathin sulfide solid electrolyte layer provided in example 7 and LiNi0.8Co0.15Al0.05O2The positive electrode and the metallic lithium negative electrode are assembled into an all-solid-state battery.
The battery adopts a blue CT2001A battery test system to carry out electrochemical performance test, the voltage range of charging and discharging is 3.0V-4.2V, and the charging and discharging are carried out at room temperature at 0.2C multiplying power. Through detection, the capacity retention rate of the battery after 500 cycles is 81.4%.
Example 8
(1) 1 part by weight of the piperidine solution was added to 80 parts by weight of an n-heptane solvent, and 2 parts by weight of Na was added3PS4And (3) carrying out ball milling on the sulfide solid electrolyte and 10 parts by weight of dopamine hydrochloride at the temperature of 30 ℃ for 6 hours to obtain polydopamine-coated sulfide solid electrolyte slurry.
(2) Drying the polydopamine-coated sulfide solid electrolyte slurry obtained in the step (1) at 80 ℃ for 24h, and naturally cooling to room temperature to obtain polydopamine-coated Na3PS4Sulfide solid electrolyte powder.
(3) Adding 1 weight part of piperidine solution into 80 weight parts of toluene solvent, and adding 10 weight parts of Na3SbS4And (3) carrying out ball milling on the sulfide solid electrolyte and 10 parts by weight of dopamine hydrochloride at the temperature of 30 ℃ for 6 hours to obtain polydopamine-coated sulfide solid electrolyte slurry.
(4) Drying the polydopamine-coated sulfide solid electrolyte slurry obtained in the step (3) at 100 ℃ for 48h, and naturally cooling to room temperature to obtain polydopamine-coated Na3SbS4Sulfide solid electrolyte powder.
(5) Na coated by polydopamine obtained in step (2)3PS4Pressing the sulfide solid electrolyte powder into tablets at 350MPa and 100 ℃; na coated by polydopamine obtained in step (4)3SbS4Pressing the sulfide solid electrolyte powder into tablets under 350MPa and 50 ℃; and laminating the obtained two layers onPerforming isostatic pressing at 500MPa and 60 ℃ to obtain an ultrathin sulfide solid electrolyte layer; the thickness of the ultrathin sulfide solid electrolyte layer is 400 mu m, and the conductivity is 7.3 multiplied by 10-4S·cm-1。
The ultra-thin sulfide solid electrolyte layer and FeS provided in example 82The positive electrode and the metallic sodium negative electrode are assembled into an all-solid-state battery.
The battery adopts a blue CT2001A battery test system to carry out electrochemical performance test, the voltage range of charging and discharging is 0.8V-3.0V, and the charging and discharging are carried out at room temperature at 0.1C multiplying power. Through detection, the capacity retention rate of the battery after 500 cycles is 82.9%.
Example 9
(1) Adding 1 weight part of piperidine solution into 80 weight parts of chlorobenzene solvent, and adding 2 weight parts of Li3PS4And (3) carrying out ball milling on the sulfide solid electrolyte and 1 part by weight of dopamine hydrochloride at 60 ℃ for 3h to obtain polydopamine-coated sulfide solid electrolyte slurry.
(2) And (2) drying the polydopamine-coated sulfide solid electrolyte slurry obtained in the step (1) at 80 ℃ for 24h, and naturally cooling to room temperature to obtain polydopamine-coated sulfide solid electrolyte powder.
(3) Pressing and tabletting the polydopamine-coated sulfide solid electrolyte powder obtained in the step (2) at 350MPa and 100 ℃ to obtain an ultrathin sulfide solid electrolyte layer; the thickness of the ultrathin sulfide solid electrolyte layer is 45 mu m, and the conductivity is 6.7 multiplied by 10-4S·cm-1。
The ultra-thin sulfide solid electrolyte layer and the carbon nanotube electrode provided in example 9 were assembled into an all-solid-state supercapacitor.
Through detection, the all-solid-state supercapacitor has good cycle performance, and the capacity retention rate is 88.3% after 500 cycles at room temperature.
Example 10
(1) Adding 1 weight part of piperidine solution into 80 weight parts of chlorobenzene solvent, and adding 10 weight parts of Li3InCl6Sulfide solid electrolyte and 1 part by weight of dopamine hydrochloride are subjected to ball milling for 6 hours at the temperature of 30 DEG CAnd obtaining the polydopamine-coated sulfide solid electrolyte slurry.
(2) Drying the polydopamine-coated sulfide solid electrolyte slurry obtained in the step (1) at 80 ℃ for 24h, and naturally cooling to room temperature to obtain polydopamine-coated Li3InCl6Sulfide solid electrolyte powder.
(3) 1 part by weight of a piperidine solution was added to 80 parts by weight of a cyclohexane solvent, and 10 parts by weight of Li was added6.6Sn0.3Sb0.7S5And (3) carrying out ball milling on the sulfide solid electrolyte I and 10 parts by weight of dopamine hydrochloride at the temperature of 30 ℃ for 6 hours to obtain polydopamine-coated sulfide solid electrolyte slurry.
(4) Drying the polydopamine-coated sulfide solid electrolyte slurry obtained in the step (3) at 80 ℃ for 48h, and naturally cooling to room temperature to obtain polydopamine-coated Li6.6Sn0.3Sb0.7S5I sulfide solid electrolyte powder.
(5) Li coated with polydopamine obtained in step (2)3InCl6Sulfide solid electrolyte powder and polydopamine-coated Li obtained in step (4)6.6Sn0.3Sb0.7S5And I, grinding and mixing the sulfide solid electrolyte powder by a roller to obtain mixed powder.
(6) Pressing and tabletting the mixed powder obtained in the step (5) at 300MPa and 100 ℃ to obtain an ultrathin sulfide solid electrolyte layer; the thickness of the ultrathin sulfide solid electrolyte layer is 310 mu m, and the conductivity is 2.4 multiplied by 10-3S·cm-1。
The ultra-thin sulfide solid electrolyte layer and Co provided in example 109S8The positive electrode and the metallic lithium negative electrode are assembled into an all-solid-state battery.
The battery adopts a blue CT2001A battery test system to carry out electrochemical performance test, the voltage range of charging and discharging is 0.5V-3.0V, and the charging and discharging are carried out at room temperature at 1C multiplying power. Through detection, the capacity retention rate of the battery after 100 cycles is 93.2%.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. A preparation method of an ultrathin sulfide solid electrolyte layer comprises the following steps:
a) adding the reaction solution into a solvent, and then sequentially adding a sulfide solid electrolyte and dopamine hydrochloride for mixing to obtain polydopamine-coated sulfide solid electrolyte slurry;
b) drying the polydopamine-coated sulfide solid electrolyte slurry obtained in the step a), and cooling to obtain polydopamine-coated sulfide solid electrolyte powder;
c) tabletting the polydopamine-coated sulfide solid electrolyte powder obtained in the step b) to obtain the ultrathin sulfide solid electrolyte layer.
2. The method according to claim 1, wherein the reaction solution in step a) is one or more selected from the group consisting of piperidine, 3-piperidinemethanol, 4-piperidinemethanol and 1-formylpiperidine.
3. The method according to claim 1, wherein the solvent in step a) is one or more selected from the group consisting of ethanol, isopropanol, n-butanol, toluene, chlorobenzene, ethyl acetate, butyl butyrate, n-heptane and cyclohexanone.
4. The preparation method according to claim 1, wherein the sulfide solid electrolyte in step a) comprises one or more of a general formula sulfide solid electrolyte of formula I, a modified compound of the general formula sulfide solid electrolyte of formula I, a general formula sulfide solid electrolyte of formula II, and a modified compound of the general formula sulfide solid electrolyte of formula II;
the modifier of the sulfide solid electrolyte with the general formula I is preferably selected from sulfide solid electrolytes with the general formula I, wherein the sulfide solid electrolytes are substituted by anions and cations, doped or regulated by vacancies;
the modifier of the sulfide solid electrolyte with the general formula II is preferably selected from sulfide solid electrolytes with the general formula II, which are substituted by anions and cations, doped or regulated by vacancies;
xLiaB·yCcDd·zP2S5formula I;
in formula I, x is 0-100, y is 0-100, z is 0-100, a is 1 or 2, C is 1 or 2, D is 1, 2 or 5, B is S, Cl, Br or I, C is Li, Si, Ge, P, Sn or Sb, D is Cl, Br, I, O, S or Se;
rNapEe·sMmNn·tJjQquV formula II;
in formula II, 0 ≦ r <100, 0 ≦ S <100, 0 ≦ t <100, 0 ≦ u <100, P ≦ 1 or 2, E ≦ 0, 1, 2, or 5, M ≦ 1 or 2, N ≦ 0, 1, 2, or 5, J ≦ 1 or 2, Q ≦ 0, 1, 2, or 5, E is S, Cl, Br, or I, M is P, Sb, Se, Ge, Si, or Sn, N is P, Sb, Se, Si, or Sn, J is P, Sb, Se, Ge, Si, or Sn, Q is P, Sb, Se, Ge, Si, or Sn, V is S or P, and at least one of E and V is S.
5. The preparation method according to claim 1, wherein the mass ratio of the reaction solution, the solvent, the sulfide solid electrolyte and the dopamine hydrochloride in step a) is 1: (5-100): (0.5-10): (0.1-10).
6. The method of claim 1, wherein the mixing in step a) is carried out at a temperature of 10 ℃ to 100 ℃ for a time of 0.1h to 12 h.
7. The method according to claim 1, wherein the drying in step b) is carried out at a temperature of 40 ℃ to 100 ℃ for a time of 1h to 48 h.
8. The method of claim 1, wherein the pressure of the compressed tablet in step c) is 50 to 500MPa and the temperature is 10 to 500 ℃.
9. An ultrathin sulfide solid electrolyte layer, characterized by comprising at least one ultrathin sulfide solid electrolyte layer produced by the production method according to any one of claims 1 to 8;
the thickness of the ultrathin sulfide solid electrolyte layer is 1-500 mu m, and the conductivity is 10-6S·cm-1～10-1S·cm-1。
10. An all-solid-state energy storage device assembled from a solid electrolyte layer and an electrode, wherein the solid electrolyte layer is the ultra-thin sulfide solid electrolyte layer of claim 9.
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Application publication date: 20210604 |