CN118040019A - Water-stable inorganic sulfide electrolyte, preparation method thereof and battery - Google Patents
Water-stable inorganic sulfide electrolyte, preparation method thereof and battery Download PDFInfo
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 58
- 229910052945 inorganic sulfide Inorganic materials 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title abstract description 11
- -1 polyoxy silane Polymers 0.000 claims abstract description 48
- 239000002001 electrolyte material Substances 0.000 claims abstract description 46
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 30
- 239000006185 dispersion Substances 0.000 claims description 38
- 239000002904 solvent Substances 0.000 claims description 35
- 238000000034 method Methods 0.000 claims description 29
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 18
- 239000007788 liquid Substances 0.000 claims description 18
- 239000007784 solid electrolyte Substances 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 229910052744 lithium Inorganic materials 0.000 claims description 11
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 8
- 125000003545 alkoxy group Chemical group 0.000 claims description 7
- 229910052736 halogen Inorganic materials 0.000 claims description 7
- 150000002367 halogens Chemical class 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 238000000967 suction filtration Methods 0.000 claims description 7
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 claims description 6
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- 125000005369 trialkoxysilyl group Chemical group 0.000 claims description 6
- 125000004665 trialkylsilyl group Chemical group 0.000 claims description 6
- 239000002798 polar solvent Substances 0.000 claims description 5
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 4
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 claims description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- 239000004593 Epoxy Substances 0.000 claims description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 4
- 125000004423 acyloxy group Chemical group 0.000 claims description 4
- 125000003368 amide group Chemical group 0.000 claims description 4
- 125000001951 carbamoylamino group Chemical group C(N)(=O)N* 0.000 claims description 4
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 239000012046 mixed solvent Substances 0.000 claims description 4
- 239000012454 non-polar solvent Substances 0.000 claims description 4
- 125000001424 substituent group Chemical group 0.000 claims description 4
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 claims description 3
- 229910052731 fluorine Inorganic materials 0.000 claims description 3
- ISJNWFZGNBZPQE-UHFFFAOYSA-N germanium;sulfanylidenesilver Chemical compound [Ge].[Ag]=S ISJNWFZGNBZPQE-UHFFFAOYSA-N 0.000 claims description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 3
- FLTJDUOFAQWHDF-UHFFFAOYSA-N trimethyl pentane Natural products CCCCC(C)(C)C FLTJDUOFAQWHDF-UHFFFAOYSA-N 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052732 germanium Inorganic materials 0.000 claims description 2
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052740 iodine Inorganic materials 0.000 claims description 2
- 239000003208 petroleum Substances 0.000 claims description 2
- 239000002203 sulfidic glass Substances 0.000 abstract description 31
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 abstract description 24
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 8
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 8
- 238000006243 chemical reaction Methods 0.000 abstract description 6
- 230000000903 blocking effect Effects 0.000 abstract description 4
- 239000002245 particle Substances 0.000 abstract description 4
- 239000010410 layer Substances 0.000 description 29
- 239000000463 material Substances 0.000 description 21
- 239000007787 solid Substances 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 15
- 150000002500 ions Chemical class 0.000 description 11
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 3
- 239000011247 coating layer Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 239000004814 polyurethane Substances 0.000 description 3
- 229920002635 polyurethane Polymers 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000003917 TEM image Methods 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910001251 solid state electrolyte alloy Inorganic materials 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 229910008029 Li-In Inorganic materials 0.000 description 1
- 229910015950 LiNi0.90Co0.05Mn0.05O2 Inorganic materials 0.000 description 1
- 229910006670 Li—In Inorganic materials 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910003480 inorganic solid Inorganic materials 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002052 molecular layer Substances 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000002345 surface coating layer Substances 0.000 description 1
- 125000000101 thioether group Chemical group 0.000 description 1
- PZJJKWKADRNWSW-UHFFFAOYSA-N trimethoxysilicon Chemical group CO[Si](OC)OC PZJJKWKADRNWSW-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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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Abstract
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a water-stable inorganic sulfide solid electrolyte, a preparation method thereof and a battery. The water-stable inorganic sulfide electrolyte comprises an inorganic sulfide electrolyte material and a hydrophobic layer coated on the surface of the inorganic sulfide electrolyte material; wherein the hydrophobic layer is hydroxyl-terminated polyoxy silane, and the thickness of the hydrophobic layer is 1-20 nm. The hydroxyl-terminated polyoxy silane provided by the invention is used for treating sulfide solid electrolyte, the polyoxy silane shell plays a role in blocking air and moisture, and the polyoxy silane can be anchored on the surface of electrolyte particles by utilizing the reaction between the hydroxyl-terminated polyoxy silane and the sulfide electrolyte, so that the wet air stability of the sulfide solid electrolyte is obviously improved.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a water-stable inorganic sulfide electrolyte, a preparation method thereof and a battery.
Background
Lithium ion secondary batteries play an extremely important role in modern society, and especially, new energy automobiles and the development of large-scale energy storage are pushed to unprecedented heights. Along with the continuous improvement of the energy density and safety requirements of the power battery, the existing liquid lithium ion battery system is close to the upper limit of the energy density, and the potential safety hazard of the high-specific-energy liquid lithium ion battery is more prominent due to the combustible organic electrolyte. The all-solid-state battery using the nonflammable inorganic solid material as the electrolyte not only can eliminate potential safety hazards caused by leakage of the electrolyte and thermal runaway in the battery in the use process, but also can be used under extreme conditions of high temperature, low temperature and the like. The use of lithium metal anodes will also further increase the energy density of all-solid lithium secondary batteries. Solid-state electrolytes are the most critical materials in all-solid batteries, and the development of inorganic solid-state electrolytes with high stability and high lithium ion conductivity is a key in the development of all-solid batteries with high performance.
Among the many solid electrolyte materials currently being studied are sulfide solid electrolytes with great potential for use. The main reason is that sulfide electrolytes have ion conductivity comparable to liquid electrolytes. However, sulfide solid electrolytes are sensitive to water and generate toxic H 2 S gas when meeting water, and the ion conductivity is reduced. Therefore, the use condition of the sulfide solid electrolyte is very harsh, which is unfavorable for large-scale application. Therefore, there is a need to develop a sulfide electrolyte material stable to humid air, which satisfies the practical demands. The use of other elements to dope and replace P, S and other elements in the sulfide solid electrolyte can effectively improve the wet air stability of the sulfide solid electrolyte, and articles and invention patents are reported, such as ACSSustainable chem.eng.2020,8,3321-3327,ACS Appl.Mater.Interfaces 2022,14,4179-4185, CN110085908A, CN113097560A and the like. However, there is still a limitation that the introduction of doping elements inevitably affects the ion conductivity of the electrolyte material. The elements involved in the introduction of the sulfide solid electrolyte are mainly Li, P, S and cheap elements of the halogen lamp, are considered to have natural competitive advantages in terms of cost, and the doping elements lead to the fact that the price advantages of the sulfide solid electrolyte are not existed to a certain extent, so that the large-scale application of the sulfide solid electrolyte is necessarily limited. Some doping elements (As) are even toxic, which is clearly contrary to the green development of lithium ion batteries and new energy automobiles. The invention CN115377481A reports an organic-inorganic composite solid electrolyte, and the shell polyurethane can improve the air stability of a core sulfide electrolyte, and has the defects that the shell is too thick (30-50 mu m), the polyurethane is an unstable organic matter, the risk of firing when the polyurethane is heated is different from the original purpose of high safety of an all-solid battery, and the low-ion conducting shell inevitably leads to the reduction of the whole ion conduction of an electrolyte material. In addition, studies have shown that sulfide solid electrolytes have serious side reactions with polar solvents (e.g., nano letters,2017,17,3013-3020), and thus the disclosed methods clearly fail to obtain high performance electrolyte materials. The invention CN112018458a discloses an aqueous sulfide-polymer composite solid electrolyte which is still organic-inorganic composite in nature, and the template method cannot provide a powder electrolyte material with wider applicability according to the use requirement of all solid-state batteries. The invention CN111129579a discloses a sulfide solid state electrolyte without Li hydrophobic molecular layer coating, but the melting point of the alkyl phosphoric acid adopted by the electrolyte is only about 100 ℃, and the risk of coating failure exists when the working temperature of the all solid state battery exceeds 100 ℃. In addition, the above scheme can not effectively solve the problem of close contact between the organic coating layer and the sulfide core, and the risk of shell falling exists.
Disclosure of Invention
In order to solve the technical problems, the invention provides an inorganic sulfide solid electrolyte which is stable in water, namely under the condition of wet air, a preparation method thereof and a battery. The research of the invention finds that the technical difficulties can be solved by adopting hydroxyl-terminated polyoxy silane to treat sulfide solid electrolyte. The polyoxy silane shell plays a role in blocking air and moisture, and the polyoxy silane can be anchored on the surface of electrolyte particles by utilizing the reaction between the hydroxyl end groups and sulfide electrolyte, so that the falling risk is avoided; and the water stability (wet air stability) of the sulfide solid electrolyte is obviously improved.
Specifically, the water-stable inorganic sulfide electrolyte provided by the first aspect of the invention comprises an inorganic sulfide electrolyte material and a hydrophobic layer coated on the surface of the inorganic sulfide electrolyte material; wherein the hydrophobic layer is hydroxyl-terminated polyoxy silane, and the thickness of the hydrophobic layer is 1-20 nm. The invention adopts hydroxyl-terminated polyoxy silane as the surface hydrophobic layer of the water-stable inorganic sulfide electrolyte, the polyoxy silane shell plays a role in blocking air and water, and meanwhile, the hydroxyl-terminated polyoxy silane reacts with the sulfide electrolyte, so that the polyoxy silane can be well anchored on the surface of electrolyte particles, and the falling risk is avoided. The wet air stability of the sulfide solid electrolyte provided by the invention is obviously improved. The present inventors have found that the effect is optimal when the thickness of the specific hydrophobic layer is in the range of 1 to 20nm. The hydrophobic layer is too small in thickness, so that the water stability is not high, and the too large thickness of the hydrophobic layer influences the ion conduction of sulfide.
Preferably, the hydroxyl-terminated polyoxysilanes have the structural formula (1):
Wherein R1 and R2 are respectively selected from one or more of halogen, methyl, methoxy, ethyl, ethoxy, vinyl, epoxy, amido, acyloxy, aminopropyl and ureido, R3 is selected from one or more of hydroxyl, solvoyl, amino, trialkylsilyl, trialkoxysilyl and alkoxy, and n is an integer of 10-1000.
Or, the structural formula of the hydroxyl-terminated polyoxy silane is shown as formula (2):
Wherein R4 is selected from one or more of F, CF 3, R5 is selected from one or more of trialkylsilyl, trialkoxysilyl and alkoxy, and n is an integer of 10-1000.
Further preferably, the thickness of the water-repellent layer is preferably 5 to 15nm.
Preferably, the hydroxyl value of the hydroxyl-terminated polyoxysilanes is 10.0 or less, preferably from 1 to 8. The research of the invention finds that the surface hydrophobic treatment of the sulfide solid electrolyte by using the polyoxy silane which contains halogen, methyl, methoxy, ethyl, ethoxy, vinyl, epoxy, amido, acyloxy, aminopropyl and/or ureido groups and is blocked by the alkoxy of hydroxyl, solo, amino, trimethylsilyl and/or trimethoxy silyl can effectively improve the water stability, the reaction between the blocked hydroxyl and the sulfide solid electrolyte can ensure the compactness and compactness of the hydrophobic layer, and the reaction does not have obvious influence on the ion conduction of the sulfide electrolyte when the hydroxyl value is less than or equal to 10.0, and particularly, the comprehensive performance is optimal when the hydroxyl value of the hydroxyl-blocked polyoxy silane is 1-8.
The state of the inorganic sulfide electrolyte material is not limited to the method of the present invention, and may be amorphous, glassy, crystalline, or any combination of the three forms.
Preferably, the number of carbon atoms in each of the R1, R2, R3, R4 and R5 substituents is not more than 8.
In the invention, the inorganic sulfide electrolyte material is prepared or commercialized.
Further preferably, the inorganic sulfide electrolyte material contains P and/or halogen; the inorganic sulfide electrolyte material is amorphous, glassy, crystalline or any combination of the three forms;
preferably, the inorganic sulfide electrolyte material is a sulfur silver germanium ore type crystalline state.
Further preferably, the inorganic sulfide electrolyte material is Li 6±aP1-bMbS5±a-cOcXd, wherein a is more than or equal to 0 and less than 1.0, b is more than or equal to 0 and less than or equal to 1.0, c is more than or equal to 0 and less than or equal to 1.0,0.6 and d is more than or equal to 2.0, M is one or more of Ge, si, sn, sb, al, and X is one or more of Cl, br and I.
The preparation method of the water-stable inorganic sulfide electrolyte provided by the second aspect of the invention comprises the following steps:
1) Dispersing an inorganic sulfide electrolyte material in a first solvent to obtain a first dispersion;
2) Dissolving hydroxyl-terminated polyoxy silane in a second solvent to obtain a second dispersion;
3) Mixing the first dispersion liquid and the second dispersion liquid, and stirring for 30-120 min at 25-70 ℃;
4) And removing the solvent to obtain the water-stable inorganic sulfide electrolyte.
Preferably, the first solvent is one or more selected from nonpolar solvents, polar solvents with polarity not more than 0.1, and mixed solvents with polarity not more than 0.1; preferably, the first solvent is selected from one or more of isopentane, n-pentane, hexane, cyclohexane, isooctane and trimethylpentane;
and/or the second solvent is selected from one or more of nonpolar solvents, polar solvents with polarity not more than 0.2 and mixed solvents with polarity not more than 0.2; preferably, the second solvent is selected from one or more of petroleum ether, trifluoroacetic acid, cyclopentane and n-heptane.
Further preferably, in the step 1), the mass ratio of the inorganic sulfide electrolyte to the first solvent is (10 to 40): 100;
And/or in step 2), the mass ratio of the hydroxyl-terminated polyoxy silane to the second solvent is (0.5-10): 100.
Preferably, in step 4), the method for removing solvent comprises suction filtration; and/or vacuum heat treatment at 80-120 deg.c for 8-24 hr.
In the invention, the water-stable inorganic sulfide electrolyte prepared by adopting the process and the preferable conditions further improves the water stability and the cycle performance.
The invention also provides application of any sulfide solid electrolyte in preparation of an all-solid-state lithium secondary battery.
The third aspect of the present invention also provides a lithium secondary battery comprising a positive electrode layer, a negative electrode layer and a solid electrolyte layer, wherein the lithium secondary battery contains the water-stable inorganic sulfide electrolyte prepared by the water-stable inorganic sulfide electrolyte or any one of the preparation methods of the water-stable inorganic sulfide electrolyte materials. In the invention, the lithium secondary battery prepared by adopting the hydroxyl-terminated polyoxy silane is more stable in the use process and excellent in performance, and after long circulation, the battery using the sulfide solid electrolyte shows more excellent circulation performance.
The invention has the advantages that:
1) The hydroxyl-terminated polyoxy silane provided by the invention is used for treating the sulfide solid electrolyte, the polyoxy silane shell plays a role in blocking air and moisture, and the polyoxy silane can be better anchored on the surface of electrolyte particles by utilizing the reaction between the hydroxyl-terminated polyoxy silane and the sulfide electrolyte, and meanwhile, the wet air stability of the sulfide solid electrolyte is obviously improved.
2) The invention has wide application range, can be used for various solid electrolyte materials containing S element, and does not limit the crystal form of sulfide electrolyte. The method is suitable for the preparation process of sulfide electrolyte and is also suitable for further treatment of the commercially purchased sulfide electrolyte material. The preparation method is simple, efficient and low in cost.
3) The water-stable sulfide solid electrolyte provided by the invention is beneficial to understanding and further improving the stability problem of the electrolyte in the aspect of theoretical research, and can be used for obtaining various electrolyte materials with high stability in practical application.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the following description will briefly explain the drawings needed in the embodiments or the prior art, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and other drawings can be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a TEM image of a solid electrolyte material obtained in example 1 of the present invention;
FIG. 2 is an XRD diffraction pattern of the solid electrolyte material obtained in example 1 and comparative example 1 of the present invention;
fig. 3 is a graph showing battery cycle performance of sulfide solid electrolyte of solid electrolyte materials provided in example 1 and comparative example 11 of the present invention.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be clearly and completely described below, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The embodiments of the present invention are not to be construed as specific techniques or conditions, according to techniques or conditions described in the literature in this field, or according to product specifications. The devices, instruments, reagents, etc. used are conventional products available for purchase by regular vendors, not identified to the manufacturer. The raw materials used in the invention can be conveniently purchased in domestic product market. The hydroxyl-terminated polyoxysilanes used in the examples and comparative examples of the present invention were purchased from domestic product markets. The structural formula of the hydroxyl-terminated polyoxy silane is represented by the formula (1):
Wherein R1 and R2 are respectively selected from one or more of halogen, methyl, methoxy, ethyl, ethoxy, vinyl, epoxy, amido, acyloxy, aminopropyl and ureido, R3 is selected from one or more of hydroxyl, solvoyl, amino, trialkylsilyl, trialkoxysilyl and alkoxy, and n is an integer of 10-1000;
or a hydroxyl-terminated polyoxysilane having the structural formula (2):
Wherein R4 is selected from one or more of F, CF 3, R5 is selected from one or more of trialkylsilyl, trialkoxysilyl and alkoxy, and n is an integer of 10-1000.
Example 1
This example provides a water stable inorganic sulfide electrolyte and a method of making the same.
The sulfide solid electrolyte material used was prepared as follows: in a glove box, li 2S、P2S5 and LiCl were weighed according to the element ratio in Li 5.5PS4.5Cl1.5, the above raw materials were placed in a 50ml zirconia ball mill pot, and 50g zirconia pellets with a diameter of 5mm were added. And placing the sealed ball milling tank on a ball mill, and grinding and mixing uniformly. And collecting the ball-milled sample, and sealing the ball-milled sample in a vacuum quartz tube for calcination. The calcination temperature is controlled by adopting temperature programming, and is raised from room temperature to 540 ℃ at a speed of 3 ℃/min, and the temperature is kept for 12 hours. And cooling to 50 ℃ after sintering is completed, and obtaining the target sulfide solid electrolyte material Li 5.5PS4.5Cl1.5 which is a sulfur silver germanium ore type crystalline state. (the examples of the present invention are merely illustrative of one of conventional methods for producing a sulfide solid state electrolyte material, and are not intended to limit the sulfide solid state electrolyte material used in the present invention.
Dispersing sulfide solid electrolyte material in cyclohexane, wherein the mass ratio of the electrolyte to the solvent is 20:100, so as to obtain a dispersion liquid 1;
dispersing the hydroxyl-terminated polyoxysilane shown in formula 1 used in the present example in table 1 in n-heptane, wherein the mass ratio of the hydroxyl-terminated polyoxysilane to the solvent is 0.8:100, to obtain a dispersion 2; the concentration ratio of dispersion 2 to dispersion 1 was 4.0:100;
And mixing the dispersion liquid 1 and the dispersion liquid 2 according to the proportion of 1:1, stirring at 60 ℃ for 60min, removing most of the solvent by suction filtration after stirring, and heating in a vacuum oven at 115 ℃ for 24h to obtain the target electrolyte material with the hydrophobic layer thickness of 12 nm. The TEM image of the solid electrolyte material obtained in this example is shown in fig. 1, the coating layer of the solid electrolyte material is in close contact with the electrolyte, and the XRD diffraction pattern of the solid electrolyte material is shown in fig. 2.
Example 2
The same procedure as in example 1 was used except that the hydroxyl-terminated polyoxysilanes used in Table 1 were different. The target electrolyte material with the hydrophobic layer thickness of 12nm is obtained.
Example 3
The same procedure as in example 1 was employed, except that a sulfide solid electrolyte material was dispersed in cyclohexane at a mass ratio of electrolyte to solvent of 35:100 to obtain a dispersion 1;
dispersing the hydroxyl-terminated polyoxosilane used in the present example in table 1 in n-heptane at a mass ratio of hydroxyl-terminated polyoxosilane to solvent of 1.0:100 to give dispersion 2; the concentration ratio of dispersion 2 to dispersion 1 was 2.9:100;
And mixing the dispersion liquid 1 and the dispersion liquid 2 according to the proportion of 1:1, stirring at 60 ℃ for 60min, removing most of the solvent by suction filtration after stirring, and heating in a vacuum oven at 115 ℃ for 24h to obtain the target electrolyte material with the hydrophobic layer thickness of 8 nm.
Example 4
The same procedure as in example 1 was employed, except that a sulfide solid electrolyte material was dispersed in trimethylpentane at a mass ratio of electrolyte to solvent of 15:100 to obtain a dispersion 1;
Dispersing the hydroxyl-terminated polyoxosilane used in the present example in table 1 in n-heptane, the mass ratio of hydroxyl-terminated polyoxosilane to solvent being 0.7:100, to give dispersion 2; the concentration ratio of dispersion 2 to dispersion 1 was 4.7:100;
and mixing the dispersion liquid 1 and the dispersion liquid 2 according to the proportion of 1:1, stirring at 60 ℃ for 60min, removing most of the solvent by suction filtration after stirring, and heating in a vacuum oven at 115 ℃ for 24h to obtain the target electrolyte material with the hydrophobic layer thickness of 14nm.
Example 5
The same procedure as in example 1 was employed, except that a sulfide solid electrolyte material was dispersed in isooctane at a mass ratio of electrolyte to solvent of 40:100 to obtain a dispersion 1;
Dispersing the hydroxyl-terminated polyoxosilane used in the present example in table 1 in n-heptane at a mass ratio of hydroxyl-terminated polyoxosilane to solvent of 0.5:100 to give dispersion 2; the concentration ratio of dispersion 2 to dispersion 1 was 1.25:100;
And mixing the dispersion liquid 1 and the dispersion liquid 2 according to the proportion of 1:1, stirring at 60 ℃ for 60min, removing most of the solvent by suction filtration after stirring, and heating in a vacuum oven at 115 ℃ for 24h to obtain the target electrolyte material with the hydrophobic layer thickness of 6 nm.
Example 6
The same procedure as in example 1 was used except that the hydroxyl-terminated polyoxy silane used was different and the solvent of dispersion 2 was replaced with trifluoroacetic acid. The target electrolyte material with the hydrophobic layer thickness of 12nm is obtained.
Example 7
The same procedure as in example 1 was used, except that the hydroxyl-terminated polyoxysilanes used were different. The target electrolyte material with the hydrophobic layer thickness of 12nm is obtained.
Example 8
The same procedure as in example 1 was employed except that the sulfide solid state electrolyte was replaced with Li 6PS5 Cl. The target electrolyte material with the hydrophobic layer thickness of 12nm is obtained.
Example 9
The same procedure as in example 1 was employed except that the sulfide solid state electrolyte was replaced with Li 6P0.95Sn0.05S5 Cl. The target electrolyte material with the hydrophobic layer thickness of 12nm is obtained.
Example 10
The same procedure as in example 1 was employed except that the sulfide solid state electrolyte was replaced with Li 6P0.98Sn0.02S4.98O0.02 Cl. The target electrolyte material with the hydrophobic layer thickness of 12nm is obtained.
Comparative examples 1 to 10
The same procedure as in example 1 was followed except that the hydroxyl-terminated polyoxysilanes used were varied and that the R1, R2 and R3 groups were as indicated in Table 1. The target electrolyte material with the hydrophobic layer thickness of 12nm is obtained.
Comparative example 11
The same procedure as in example 1 was used, except that the hydroxyl-terminated polyoxysilanes were replaced with: The R1, R2 and R3 substituents are shown in the table 1.
Comparative example 12
The same procedure as in example 1 was used, except that the hydroxyl-terminated polyoxysilanes used were different. Simultaneously, the mass ratio of the hydroxyl-terminated polyoxy silane to the solvent is 1.7:100, so as to obtain a dispersion liquid 2; the concentration ratio of dispersion 2 to dispersion 1 was 8.5:100;
And mixing the dispersion liquid 1 and the dispersion liquid 2 according to the proportion of 1:1, stirring at 60 ℃ for 60min, removing most of the solvent by suction filtration after stirring, and heating in a vacuum oven at 115 ℃ for 24h to obtain the target electrolyte material with the hydrophobic layer thickness of 25 nm.
Examples 11 to 19
The same procedure as in example 1 was followed except that the hydroxyl-terminated polyoxysilanes of the formula (2) were used, and the R4, R5 groups, n values and hydroxyl values were as shown in Table 2. A target electrolyte material having a hydrophobic layer thickness of 12nm was prepared.
Comparative examples 12 to 17
The same procedure as in example 1 was followed except that the hydroxyl-terminated polyoxysilanes of the formula (2) were used, and the R4, R5 groups, n values and hydroxyl values were as shown in Table 2. A target electrolyte material having a hydrophobic layer thickness of 12nm was prepared.
Experimental example 1
Solid electrolyte material wet air stability test
The obtained solid electrolyte material was subjected to a wet air stability test. In a glove box, 300mg of solid electrolyte material was weighed into a 5ml open glass bottle. The vial was then placed in a reaction chamber with a flow of air of a specified humidity and allowed to stand at room temperature. The relative humidity of the dry air was 10% and the air flow was 100ml/min. After 24h samples were taken for ion conductivity testing. The data for each example and comparative example are summarized in tables 1 and 2.
Table 1 summary of data for examples 1-10 and comparative examples 1-12
Table 2 summary of data for examples 11 to 19 and comparative examples 1 to 4, 13 to 18
It can be seen from tables 1 and 2 that the sulfide solid state electrolyte material treated with the hydroxyl-terminated polyoxysilanes provided by the present invention has only a slight decrease in ion conductivity compared to untreated bare samples, but a substantial decrease in the extent of decrease after exposure to humid air, i.e., a substantial increase in water stability. When the hydroxyl-terminated polyoxysilanes and their substituents are not required in the present invention, the ion guide is greatly reduced and the water stability is not significantly improved compared to the untreated sulfide solid state electrolyte material (comparative example 1). When the surface coating layer thickness was >20nm (comparative example 12), although the stability could be ensured, the ion guide was greatly reduced (5.84. Fwdarw.3.22 mS/cm) compared with the bare sample without coating treatment.
The invention has the advantages of simple material composition, easily obtained raw materials, simple preparation method, low production cost, better air stability and high lithium ion conductivity, and is expected to solve the practical application problem of inorganic sulfide electrolyte as high-performance all-solid-state lithium secondary battery electrolyte.
The solid electrolyte material of sulfide provided by the embodiment of the invention has good stability In the use process, and the all-solid lithium secondary battery provided by the solid electrolyte material of sulfide has better cycle performance than the prior art after long cycle, taking the sulfide solid electrolytes of the embodiment 1 and the comparative example 11 as the solid electrolyte layers respectively, and the mixture of the LiNi 0.90Co0.05Mn0.05O2 ultra-high nickel oxide positive electrode and the embodiment 1 or the comparative example 11 as the positive electrode layers respectively, and adopting the Li-In alloy as the negative electrode layer, and assembling to obtain the all-solid lithium secondary battery.
And (3) carrying out charge-discharge cycle test, wherein the charge-discharge current is 0.1C, the voltage range is 2.5-4.3V (vs Li/Li +), and the temperature is room temperature (25 ℃).
The results show that although the electrolyte materials of example 1 and comparative example 11 were very close in ion conductivity and wet air stability, the first 10 weeks cycles of the die cell using both electrolytes were also substantially identical, but after long cycles, the cell using the sulfide solid state electrolyte of the present invention showed more excellent cycle performance (fig. 3). This indicates that the coating layer of the sulfide solid state electrolyte material of the present invention is more stable during use.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and are not limiting; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit and scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. A water-stable inorganic sulfide electrolyte, characterized by comprising an inorganic sulfide electrolyte material and a hydrophobic layer coated on the surface of the inorganic sulfide electrolyte material; wherein the hydrophobic layer is hydroxyl-terminated polyoxy silane, and the thickness of the hydrophobic layer is 1-20 nm.
2. The water stable inorganic sulfide electrolyte according to claim 1, wherein the hydroxyl-terminated polyoxysilane has a structural formula as shown in formula (1):
Wherein R1 and R2 are respectively selected from one or more of halogen, methyl, methoxy, ethyl, ethoxy, vinyl, epoxy, amido, acyloxy, aminopropyl and ureido, R3 is selected from one or more of hydroxyl, solvoyl, amino, trialkylsilyl, trialkoxysilyl and alkoxy, and n is an integer of 10-1000;
or, the structural formula of the hydroxyl-terminated polyoxy silane is shown as formula (2):
Wherein R4 is selected from one or more of F, CF 3, R5 is selected from one or more of trialkylsilyl, trialkoxysilyl and alkoxy, and n is an integer of 10-1000.
3. The water-stable inorganic sulfide electrolyte according to claim 2, wherein the hydroxyl value of the hydroxyl-terminated polyoxy silane is 10.0 or less, preferably 1 to 8.
4. The water-stable inorganic sulfide electrolyte according to claim 1, wherein the number of carbon atoms in each of the substituents R1, R2, R3, R4, and R5 is not more than 8.
5. The water stable inorganic sulfide electrolyte as claimed in claim 4, wherein the inorganic sulfide electrolyte material contains P and/or halogen; the inorganic sulfide electrolyte material is amorphous, glassy, crystalline or any combination of the three forms;
preferably, the inorganic sulfide electrolyte material is a sulfur silver germanium ore type crystalline state;
And/or the inorganic sulfide electrolyte material is Li 6±aP1-bMbS5±a-cOcXd, wherein a is more than or equal to 0 and less than or equal to 1.0, b is more than or equal to 0 and less than or equal to 1.0, c is more than or equal to 0 and less than or equal to 1.0,0.6 and d is more than or equal to 2.0, M is one or more of Ge, si, sn, sb, al, and X is one or more of Cl, br and I.
6. A method for preparing the water-stable inorganic sulfide electrolyte as claimed in any one of claims 1 to 5, comprising:
1) Dispersing an inorganic sulfide electrolyte material in a first solvent to obtain a first dispersion;
2) Dissolving hydroxyl-terminated polyoxy silane in a second solvent to obtain a second dispersion;
3) Mixing the first dispersion liquid and the second dispersion liquid, and stirring for 30-120 min at 25-70 ℃;
4) And removing the solvent to obtain the water-stable inorganic sulfide electrolyte.
7. The method for producing a water-stable inorganic sulfide electrolyte according to claim 6, wherein the first solvent is one or more selected from a nonpolar solvent, a polar solvent having a polarity of not more than 0.1, and a mixed solvent having a polarity of not more than 0.1; preferably, the first solvent is selected from one or more of isopentane, n-pentane, hexane, cyclohexane, isooctane and trimethylpentane;
and/or the second solvent is selected from one or more of nonpolar solvents, polar solvents with polarity not more than 0.2 and mixed solvents with polarity not more than 0.2; preferably, the second solvent is selected from one or more of petroleum ether, trifluoroacetic acid, cyclopentane and n-heptane.
8. The method for producing a water-stable inorganic sulfide electrolyte according to claim 6 or 7, wherein in step 1), a mass ratio of the inorganic sulfide electrolyte to the first solvent is (10 to 40): 100;
And/or in step 2), the mass ratio of the hydroxyl-terminated polyoxy silane to the second solvent is (0.5-10): 100.
9. The method for preparing a water-stable inorganic sulfide electrolyte according to claim 6, wherein in the step 4), the method for removing the solvent includes suction filtration; and/or vacuum heat treatment at 80-120 deg.c for 8-24 hr.
10. A lithium secondary battery comprising a positive electrode layer, a negative electrode layer and a solid electrolyte layer, wherein the lithium secondary battery contains the water-stable inorganic sulfide electrolyte prepared by the water-stable inorganic sulfide electrolyte according to any one of claims 1 to 5 or the water-stable inorganic sulfide electrolyte prepared by the method for preparing the water-stable inorganic sulfide electrolyte according to any one of claims 6 to 9.
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