CN118281307A - Halogen-rich sulfide electrolyte and preparation method thereof, composition for composite electrolyte membrane, preparation method of composite electrolyte membrane and lithium ion battery - Google Patents
Halogen-rich sulfide electrolyte and preparation method thereof, composition for composite electrolyte membrane, preparation method of composite electrolyte membrane and lithium ion battery Download PDFInfo
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- CN118281307A CN118281307A CN202410713324.3A CN202410713324A CN118281307A CN 118281307 A CN118281307 A CN 118281307A CN 202410713324 A CN202410713324 A CN 202410713324A CN 118281307 A CN118281307 A CN 118281307A
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 181
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 title claims abstract description 116
- 229910052736 halogen Inorganic materials 0.000 title claims abstract description 76
- 150000002367 halogens Chemical class 0.000 title claims abstract description 74
- 239000000203 mixture Substances 0.000 title claims abstract description 56
- 239000002131 composite material Substances 0.000 title claims abstract description 50
- 239000012528 membrane Substances 0.000 title claims abstract description 47
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title abstract description 10
- 239000013078 crystal Substances 0.000 claims abstract description 15
- ISJNWFZGNBZPQE-UHFFFAOYSA-N germanium;sulfanylidenesilver Chemical compound [Ge].[Ag]=S ISJNWFZGNBZPQE-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000000126 substance Substances 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims description 43
- 229910052744 lithium Inorganic materials 0.000 claims description 16
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 claims description 16
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 12
- 229910052717 sulfur Inorganic materials 0.000 claims description 11
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 10
- 229910052760 oxygen Inorganic materials 0.000 claims description 10
- 229910052785 arsenic Inorganic materials 0.000 claims description 9
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims description 9
- 239000011593 sulfur Substances 0.000 claims description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 239000011230 binding agent Substances 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 7
- 238000000935 solvent evaporation Methods 0.000 claims description 6
- UKUVVAMSXXBMRX-UHFFFAOYSA-N 2,4,5-trithia-1,3-diarsabicyclo[1.1.1]pentane Chemical compound S1[As]2S[As]1S2 UKUVVAMSXXBMRX-UHFFFAOYSA-N 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- AYRZLUSHOXJGKY-UHFFFAOYSA-N [bis(sulfanylidene)-$l^{5}-arsanyl]sulfanyl-bis(sulfanylidene)-$l^{5}-arsane Chemical compound S=[As](=S)S[As](=S)=S AYRZLUSHOXJGKY-UHFFFAOYSA-N 0.000 claims description 4
- 229940052288 arsenic trisulfide Drugs 0.000 claims description 4
- 238000005266 casting Methods 0.000 claims description 4
- 239000006185 dispersion Substances 0.000 claims description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 4
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Chemical compound [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 claims description 4
- 238000011282 treatment Methods 0.000 claims description 4
- 238000007731 hot pressing Methods 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 238000010345 tape casting Methods 0.000 claims description 3
- LULLIKNODDLMDQ-UHFFFAOYSA-N arsenic(3+) Chemical compound [As+3] LULLIKNODDLMDQ-UHFFFAOYSA-N 0.000 claims description 2
- 230000000052 comparative effect Effects 0.000 description 25
- 150000002500 ions Chemical class 0.000 description 14
- 239000007774 positive electrode material Substances 0.000 description 14
- 239000006258 conductive agent Substances 0.000 description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 11
- 239000007784 solid electrolyte Substances 0.000 description 11
- 238000002441 X-ray diffraction Methods 0.000 description 10
- 238000007580 dry-mixing Methods 0.000 description 10
- 239000007789 gas Substances 0.000 description 10
- 239000002245 particle Substances 0.000 description 9
- 229920000459 Nitrile rubber Polymers 0.000 description 8
- 239000011883 electrode binding agent Substances 0.000 description 8
- -1 halogen ions Chemical class 0.000 description 8
- 238000001453 impedance spectrum Methods 0.000 description 8
- 239000010416 ion conductor Substances 0.000 description 8
- 229910018068 Li 2 O Inorganic materials 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000007773 negative electrode material Substances 0.000 description 6
- 229910052958 orpiment Inorganic materials 0.000 description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 description 6
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 4
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 4
- GLNWILHOFOBOFD-UHFFFAOYSA-N lithium sulfide Chemical compound [Li+].[Li+].[S-2] GLNWILHOFOBOFD-UHFFFAOYSA-N 0.000 description 4
- 239000002109 single walled nanotube Substances 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000011267 electrode slurry Substances 0.000 description 3
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 3
- 229910001947 lithium oxide Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 229920006132 styrene block copolymer Polymers 0.000 description 3
- 229920003048 styrene butadiene rubber Polymers 0.000 description 3
- 239000002203 sulfidic glass Substances 0.000 description 3
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- 239000006245 Carbon black Super-P Substances 0.000 description 2
- 229910000733 Li alloy Inorganic materials 0.000 description 2
- 229910000676 Si alloy Inorganic materials 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 239000006183 anode active material Substances 0.000 description 2
- COHDHYZHOPQOFD-UHFFFAOYSA-N arsenic pentoxide Chemical compound O=[As](=O)O[As](=O)=O COHDHYZHOPQOFD-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 239000002134 carbon nanofiber Substances 0.000 description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 238000005098 hot rolling Methods 0.000 description 2
- 239000011244 liquid electrolyte Substances 0.000 description 2
- 239000001989 lithium alloy Substances 0.000 description 2
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- HJTAZXHBEBIQQX-UHFFFAOYSA-N 1,5-bis(chloromethyl)naphthalene Chemical compound C1=CC=C2C(CCl)=CC=CC2=C1CCl HJTAZXHBEBIQQX-UHFFFAOYSA-N 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 229910001152 Bi alloy Inorganic materials 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910000846 In alloy Inorganic materials 0.000 description 1
- 239000002227 LISICON Substances 0.000 description 1
- 229910013716 LiNi Inorganic materials 0.000 description 1
- 229910014330 LiNi1-x-yCoxAlyO2 Inorganic materials 0.000 description 1
- 229910014360 LiNi1−x−yCoxAlyO2 Inorganic materials 0.000 description 1
- 229910013677 LiNixMnyCo1-x-yO2 Inorganic materials 0.000 description 1
- 229910013686 LiNixMnyCo1−x−yO2 Inorganic materials 0.000 description 1
- 239000002228 NASICON Substances 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910001128 Sn alloy Inorganic materials 0.000 description 1
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 1
- JDUMCRPZQXLCDV-UHFFFAOYSA-N [Ge]=S.[Ag] Chemical compound [Ge]=S.[Ag] JDUMCRPZQXLCDV-UHFFFAOYSA-N 0.000 description 1
- JFBZPFYRPYOZCQ-UHFFFAOYSA-N [Li].[Al] Chemical compound [Li].[Al] JFBZPFYRPYOZCQ-UHFFFAOYSA-N 0.000 description 1
- ZVLDJSZFKQJMKD-UHFFFAOYSA-N [Li].[Si] Chemical compound [Li].[Si] ZVLDJSZFKQJMKD-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000011884 anode binding agent Substances 0.000 description 1
- GOLCXWYRSKYTSP-UHFFFAOYSA-N arsenic trioxide Inorganic materials O1[As]2O[As]1O2 GOLCXWYRSKYTSP-UHFFFAOYSA-N 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- JYPVGDJNZGAXBB-UHFFFAOYSA-N bismuth lithium Chemical compound [Li].[Bi] JYPVGDJNZGAXBB-UHFFFAOYSA-N 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000011263 electroactive material Substances 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000002223 garnet Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- LHJOPRPDWDXEIY-UHFFFAOYSA-N indium lithium Chemical compound [Li].[In] LHJOPRPDWDXEIY-UHFFFAOYSA-N 0.000 description 1
- 229910003480 inorganic solid Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- UIDWHMKSOZZDAV-UHFFFAOYSA-N lithium tin Chemical compound [Li].[Sn] UIDWHMKSOZZDAV-UHFFFAOYSA-N 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 229910052960 marcasite Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- CYQAYERJWZKYML-UHFFFAOYSA-N phosphorus pentasulfide Chemical compound S1P(S2)(=S)SP3(=S)SP1(=S)SP2(=S)S3 CYQAYERJWZKYML-UHFFFAOYSA-N 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder 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
- 238000005096 rolling process Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000011871 silicon-based negative electrode active material Substances 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- RYYWUUFWQRZTIU-UHFFFAOYSA-K thiophosphate Chemical compound [O-]P([O-])([O-])=S RYYWUUFWQRZTIU-UHFFFAOYSA-K 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- VKJKOXNPYVUXNC-UHFFFAOYSA-K trilithium;trioxido(oxo)-$l^{5}-arsane Chemical compound [Li+].[Li+].[Li+].[O-][As]([O-])([O-])=O VKJKOXNPYVUXNC-UHFFFAOYSA-K 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 238000001238 wet grinding Methods 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
Landscapes
- Conductive Materials (AREA)
Abstract
The invention relates to the field of lithium ion batteries, and discloses a halogen-rich sulfide electrolyte and a preparation method thereof, a composition for a composite electrolyte membrane, a preparation method of the composite electrolyte membrane and a lithium ion battery. The halogen-rich sulfide electrolyte has a cubic sulfur silver germanium ore type crystal structure, and has a chemical formula shown as Li 6‑xAsS5‑x‑yM1+xOy; wherein 0< x <0.7, 0.ltoreq.y <0.5, and 0.02< x+y <1; m is selected from at least one of Cl, br and I. The halogen-rich sulfide electrolyte provided by the invention has higher stability in air, higher ionic conductivity and wide application prospect.
Description
Technical Field
The invention relates to the field of lithium ion batteries, in particular to a halogen-rich sulfide electrolyte and a preparation method thereof, a composite electrolyte membrane and a preparation method thereof, and a lithium ion battery.
Background
Lithium ion batteries are widely used in the field of portable electronic devices such as electric automobiles, mobile phones, tablet computers and the like due to the advantages of high energy density and the like. However, the conventional lithium ion battery uses an organic inflammable liquid electrolyte, which may cause combustion and explosion of the electrolyte in case of abnormal conditions such as high-rate charge and discharge, overcharge, short circuit, external impact, etc., thereby causing serious safety problems.
The solid lithium ion battery adopts nonflammable solid electrolyte to replace organic flammable electrolyte and a diaphragm, so that the safety problem of the lithium ion battery can be fundamentally solved. In recent years, related studies on solid-state lithium ion batteries have attracted extensive attention in academia and industry. Among them, sulfide electrolytes are favored for their higher room temperature ionic conductivity and easy processability, such as some groups conducted studies on ionic conductivity of Li 10GeP2S12 system (Noriaki Kamaya, et al, "A lithium superionic conductor." Nature materials 10.9 (2011): 682-686.) which was invented for the ionic conductivity of 12ms·cm -1; there have also been some studies （Shenghao Li, et al. "High-Entropy Lithium Argyrodite Solid Electrolytes Enabling Stable All-Solid-State Batteries." Angewandte Chemie International Edition 62.50 (2023): e202314155.）, on the ionic conductivity of the Li 5.5PS4.5Cl0.8Br0.7 system, which invented an ionic conductivity of 9.6 mS.cm -1. The ionic conductivity at room temperature of the above system etc. thus reaches even the level of the liquid electrolyte.
However, most of the thiophosphate sulfide electrolytes are poor in air stability and easily react with moisture in the air to cause structural destruction, thereby causing a decrease in ion conductivity. This is because the center ion P 5+ of most sulfide electrolytes is a hard acid that reacts more readily with the hard base O 2- in moisture to form P-O bonds than the soft base S 2-, while the soft base S 2- in sulfide electrolytes reacts more readily with H + in air to produce H 2 S gas. For example, CN 114852980a discloses a solid electrolyte Li 5+xPS4+xCl2-x-y-zBryIz for lithium batteries, which has poor air stability.
At present, some documents report that the air stability of sulfide electrolyte can be obviously improved by doping Li 3PS4 with ZnO or Bi 2O3, and also report that the air stability can be improved to a certain extent by co-doping Li 7P3S11 electrolyte with Nb-O, sb-I, sn-O, sb-O, but the improvement effect of the modification on the air stability is limited. Li 3.875Sn0.875As0.125S4 electrolytes have been reported to exhibit excellent stability to water, however the modified electrolyte has a relatively low ionic conductivity at room temperature (< 3mS cm -1).
As another example, CN109526242a discloses a sulfide solid electrolyte having a sulfur-silver-germanium ore type crystal structure, which contains lithium, phosphorus, sulfur, one or more elements X selected from the group consisting of oxygen group elements other than sulfur and halogen group elements, and has a composition of Li a(P1-zMz)SbXc. The electrolyte has improved room temperature ionic conductivity but still has poor air stability.
Therefore, a sulfide electrolyte with good air stability and high ionic conductivity is needed to meet the requirements of high specific energy long-cycle solid-state lithium ion batteries.
Disclosure of Invention
The invention aims to provide a sulfide electrolyte with good air stability on the premise of keeping the ionic conductivity higher than 8mS cm -1.
In order to achieve the above object, a first aspect of the present invention provides a halogen-rich sulfide electrolyte having a cubic sulfur silver germanium ore type crystal structure, and having a chemical formula shown in formula I:
Li 6-xAsS5-x-yM1+xOy formula I;
Wherein 0< x <0.7, 0.ltoreq.y <0.5, and 0.02< x+y <1;
M is selected from at least one of Cl, br and I.
A second aspect of the present invention provides a method of preparing the halogen-rich sulfide electrolyte of the first aspect, the method comprising:
(1) Stirring and mixing a lithium source, an arsenic source, a sulfur source, a halogen source and an oxygen source to obtain a mixture;
(2) And carrying out heat treatment on the mixture to obtain the halogen-rich sulfide electrolyte.
A third aspect of the present invention provides a composition for a composite electrolyte membrane, the composition comprising a halogen-rich sulfide electrolyte and a binder; the content of the halogen-rich sulfide electrolyte is 80-99wt% based on the total mass of the composition, and the content of the binder is 1-20wt%;
the halogen-rich sulfide electrolyte is the halogen-rich sulfide electrolyte of the first aspect.
A fourth aspect of the present invention provides a method of producing a composite electrolyte membrane, the method comprising:
Sequentially carrying out wet mixing, casting and solvent evaporation on each component in the composition for the composite electrolyte membrane, and optionally carrying out hot pressing treatment after solvent evaporation to obtain the composite electrolyte membrane;
The composition for a composite electrolyte membrane is the composition for a composite electrolyte membrane according to the third aspect.
A fifth aspect of the present invention provides a method of producing a composite electrolyte membrane, the method comprising:
Dispersing each component in the composition for the composite electrolyte membrane in the presence of an organic solvent, and then sequentially carrying out tape casting and drying on the obtained dispersion liquid to obtain the composite electrolyte membrane;
The composition for a composite electrolyte membrane is the composition for a composite electrolyte membrane according to the third aspect.
A sixth aspect of the present invention provides a lithium ion battery comprising a positive electrode, a negative electrode, and a composite electrolyte membrane; the thickness of the composite electrolyte membrane is 8-30 mu m;
The composite electrolyte membrane is prepared by the method of the fourth aspect and/or the fifth aspect.
Through the technical scheme, the invention has at least the following advantages:
The halogen-rich sulfide electrolyte provided by the invention has a cubic sulfur silver germanium ore type crystal structure, and has a chemical formula shown as Li 6-xAsS5-x-yM1+xOy. The solid electrolyte material has higher stability in air and higher ionic conductivity, and has wide application prospect.
Specifically, based on a soft and hard acid-base theory, as 5+ soft acid is adopted to completely replace P 5+ hard acid, and hard base O 2- and more halogen X - are adopted to partially replace soft base S 2- in the electrolyte, so that the generation of H 2 S gas by the reaction of S 2- in the sulfide electrolyte and H + in the air is avoided, and the air stability of the sulfide electrolyte can be improved. In addition, S 2− is partially substituted with X - (especially X - is Br -), which not only weakens the interactions within the "cage" built by Li +, thereby facilitating movement of lithium ions throughout the unit cell; and an additional T4 Li + site is provided, which provides a lower energy barrier for Li + to jump between cages, thereby realizing high room temperature ion conductivity.
Drawings
FIG. 1 is a flow chart of a method for preparing a halogen-rich sulfide electrolyte provided by the invention;
FIG. 2 is an XRD pattern of sulfide electrolyte prepared in example 1 of the present invention;
FIG. 3 is a graph showing the impedance spectrum of the sulfide electrolyte prepared in example 1 of the present invention;
FIG. 4 is an XRD pattern of sulfide electrolyte prepared in example 2 of the present invention;
FIG. 5 is a graph showing the impedance spectrum of sulfide electrolyte obtained in example 2 of the present invention;
FIG. 6 is an XRD pattern of a sulfide electrolyte prepared in comparative example 1 of the present invention;
FIG. 7 is a graph showing the impedance of sulfide electrolyte obtained in comparative example 1 of the present invention;
FIG. 8 is an XRD pattern of a sulfide electrolyte prepared in comparative example 2 of the present invention;
FIG. 9 is a graph showing the impedance of sulfide electrolyte obtained in comparative example 2 of the present invention;
FIG. 10 is an XRD pattern of sulfide electrolyte prepared in comparative example 3 of the present invention;
FIG. 11 is a graph showing the impedance of sulfide electrolyte obtained in comparative example 3 of the present invention;
FIG. 12 is a graph showing the change in the amount of H 2 S gas generated by the sulfide electrolyte produced in example 1 and comparative examples 1 to 3 according to the present invention, as a function of time when it is exposed to nitrogen gas having a relative humidity of 40%;
fig. 13 is a graph showing changes in ionic conductivity of sulfide electrolytes prepared in example 1 and comparative examples 1 to 3 according to the present invention when exposed to air of the same humidity for different times.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
The "sulfide solid electrolyte" refers to a sulfur-containing solid electrolyte. The halogen-rich sulfide electrolyte belongs to the category of sulfide solid electrolyte, the crystal structure is a sulfur silver germanium ore crystal structure, halogen ions X - and free S 2− ions are positioned at Wyckoff a and 4d sites, as 5+ and a part of S or O form an AsS 4 3−、AsS3O3− tetrahedron and the like, and the rest of gaps can be used for lithium occupation.
The "oxide solid electrolyte" refers to a solid electrolyte containing mainly oxygen, and its general crystal structure includes NASICON structure, garnet structure and perovskite structure.
The "halide solid electrolyte" mainly refers to a solid electrolyte composed of lithium, transition metal elements and halogen elements, and cations are mainly filled in the pores of the polyhedral structure of MX 6 or MX 9 (M is a transition metal and X is a halogen element). The halide solid electrolyte containing a small amount of oxygen element therein is also called oxyhalide electrolyte.
In the present invention, li 2 S represents "lithium sulfide", li 2 O represents "lithium oxide", P 2S5 represents "phosphorus pentasulfide", as 2S3 represents "arsenic trisulfide", as 2S5 represents "arsenic pentasulfide", S represents "sulfur", and LiBr represents "lithium bromide".
As previously described, a first aspect of the present invention provides a halogen-rich sulfide electrolyte having a cubic sulfur silver germanium ore type crystal structure, and the electrolyte has a chemical formula shown in formula I:
Li 6-xAsS5-x-yM1+xOy formula I;
Wherein 0< x <0.7, 0.ltoreq.y <0.5, and 0.02< x+y <1;
M is selected from at least one of Cl, br and I.
Preferably, in the formula I, 0.1< x <0.6, 0.ltoreq.y <0.2, and 0.02< x+y <1.
Preferably, M is Br. The inventors found that in this preferred case, a sulfide electrolyte having good air stability and higher room temperature ion conductivity can be obtained.
Preferably, the halogen-rich sulfide electrolyte has a D 50 of 0.1-5 μm.
Preferably, the halogen-rich sulfide electrolyte has a D 50 of 0.3-5 μm.
In the present invention, D 50 refers to the particle size corresponding to 50% of the cumulative particle size volume distribution of the sulfide electrolyte measured using a Mastersizer3000 laser particle sizer, that is, particles having a particle size less than (or greater than) 50% of the particle size.
Preferably, in the formula I, 0.3.ltoreq.x <0.6,0.ltoreq.y <0.05, and 0.02< x+y <1. The inventors found that in this preferred case, a sulfide electrolyte having good air stability and higher room temperature ion conductivity can be obtained.
According to a particularly preferred embodiment, the halogen-rich sulfide electrolyte is selected from at least one of Li5.5AsS4.49Br1.5O0.01、Li5.7AsS4.68Br1.3O0.02、Li5.44AsS4.4Br1.56O0.04、Li5.35AsS4.1Br1.65O0.25 and Li 5.77AsS4.7Br1.23O0.07.
As previously described, a second aspect of the present invention provides a method of preparing the halogen-rich sulfide electrolyte of the first aspect, the method comprising:
(1) Stirring and mixing a lithium source, an arsenic source, a sulfur source, a halogen source and an oxygen source to obtain a mixture;
(2) And carrying out heat treatment on the mixture to obtain the halogen-rich sulfide electrolyte.
Preferably, the present invention provides a flowchart of a preparation method of the above halogen-rich sulfide electrolyte in fig. 1, the preparation method comprising:
(1) Mixing a lithium source, an arsenic source, a sulfur source, a halogen source and an oxygen source according to a preset molar ratio to obtain a mixture;
(2) And carrying out heat treatment on the mixture to obtain the Li 6-xAsS5-x-yM1+xOy (M is at least one of Cl, br and I, 0< x <0.7, 0.ltoreq.y <0.5, and 0.02< x+y < 1) halogen-rich sulfide electrolyte.
Preferably, in step (1), the lithium source is selected from at least one of lithium sulfide, lithium polysulfide, lithium hydroxide, lithium carbonate, and elemental lithium, more preferably lithium sulfide.
Preferably, in step (1), the arsenic source is selected from at least one of arsenic pentasulfide, arsenic trisulfide and elemental arsenic; the halogen source is selected from at least one of lithium chloride, lithium bromide and lithium iodide.
More preferably, in step (1), the arsenic source is arsenic trisulfide and/or arsenic pentasulfide; the halogen source is lithium bromide.
Preferably, in step (1), the sulfur source is selected from at least one of elemental sulfur, lithium sulfide, and arsenic sulfide.
Preferably, in step (1), the oxygen source is selected from at least one of lithium oxide, arsenic trioxide, arsenic pentoxide and lithium arsenate, more preferably lithium oxide.
Preferably, in step (1), the stirring and mixing conditions include: the rotation speed is 10000-20000rpm, and the time is 3-20min.
Preferably, in step (1), the mixing and stirring means is at least one selected from dry mixing, mechanical vibration, ball milling and wet milling.
Preferably, in step (2), the conditions of the heat treatment include: the temperature is 420-550deg.C, preferably 440-500deg.C; the time is 1-20h, preferably 5-10h.
As described above, the third aspect of the present invention provides a composition for a composite electrolyte membrane, the composition comprising a halogen-rich sulfide electrolyte and a binder; the content of the halogen-rich sulfide electrolyte is 80-99wt% based on the total mass of the composition, and the content of the binder is 1-20wt%;
the halogen-rich sulfide electrolyte is the halogen-rich sulfide electrolyte of the first aspect.
The binder of the present invention serves to bind the electrolyte particles. Preferably, the binder is selected from at least one of Polytetrafluoroethylene (PTFE), styrene-butadiene rubber (SBR), hydrogenated nitrile-butadiene rubber (HNBR), nitrile-butadiene rubber (NBR), styrene-ethylene-butylene-styrene block copolymer (SEBS), styrene-butadiene-styrene block copolymer (SBS).
As described above, the fourth aspect of the present invention provides a method of preparing a composite electrolyte membrane, the method comprising:
Sequentially carrying out wet mixing, casting and solvent evaporation on each component in the composition for the composite electrolyte membrane, and optionally carrying out hot pressing treatment after solvent evaporation to obtain the composite electrolyte membrane;
The composition for a composite electrolyte membrane is the composition for a composite electrolyte membrane according to the third aspect.
Preferably, the wet mixing conditions include: the temperature is 20-50 ℃ and the rotating speed is 100-600rpm.
Preferably, the conditions of the autoclave include: the temperature is 60-300 ℃, the pressure is 50-300MPa, and the time is 1-10min.
As described above, the fifth aspect of the present invention provides a method of preparing a composite electrolyte membrane, the method comprising:
Dispersing each component in the composition for the composite electrolyte membrane in the presence of an organic solvent, and then sequentially carrying out tape casting and drying on the obtained dispersion liquid to obtain the composite electrolyte membrane;
The composition for a composite electrolyte membrane is the composition for a composite electrolyte membrane according to the third aspect.
Preferably, the organic solvent is selected from at least one of toluene, para-xylene, and anisole.
The dispersion treatment, casting and drying are not particularly limited in the present invention, and may be carried out by those skilled in the art by methods known in the art.
As described above, the sixth aspect of the present invention provides a lithium ion battery including a positive electrode, a negative electrode, and a composite electrolyte membrane; the thickness of the composite electrolyte membrane is 8-30 mu m;
The composite electrolyte membrane is prepared by the method of the fourth aspect and/or the fifth aspect.
Preferably, the positive electrode includes a positive electrode current collector and a positive electrode active material layer covering the surface of the positive electrode current collector, and the positive electrode active material layer includes a positive electrode active material, a positive electrode binder, a positive electrode electron conductive agent, and a positive electrode ion conductor.
According to a preferred embodiment, the positive electrode is prepared by a method comprising the steps of:
mixing the positive electrode active material, the positive electrode binder, the positive electrode electron conductive agent, the positive electrode ion conductor and the solvent I to obtain positive electrode slurry; and coating the positive electrode slurry on the surface of the positive electrode current collector, and drying and rolling to obtain the positive electrode plate.
Preferably, the solvent I is an organic solvent. For example: toluene, para-xylene, anisole, acetonitrile, tetrahydrofuran, ethyl acetate, butyl acetate, etc., in such an amount that a desired viscosity of a positive electrode slurry containing a positive electrode active material, a positive electrode binder, a positive electrode ion conductive agent, a positive electrode electron conductive agent is obtained.
According to another preferred embodiment, the positive electrode is prepared by a method comprising the steps of:
Dry-mixing the positive electrode active material, the positive electrode binder, the positive electrode electron conductive agent and the positive electrode ion conductor to obtain a composite material; and pressing the composite material to the surface of the positive electrode current collector in a hot rolling or hot rolling mode to obtain the positive electrode.
Preferably, the content of the positive electrode active material is 60wt% to 95wt% and the content of the positive electrode electron conductive agent is 1wt% to 5wt% based on the total weight of the composite material.
The positive electrode current collector is not particularly limited as long as it has conductivity without causing chemical changes in the battery. For example: the positive electrode current collector is selected from any one of an aluminum simple substance, stainless steel or a nickel simple substance.
The positive electrode active material in the present invention is a compound that reversibly intercalates and deintercalates lithium ions, or a compound that can participate in a conversion reaction.
Preferably, the positive electrode active material is a lithium-based positive electrode material having electrochemical activity or a compound capable of participating in a conversion reaction. For example: the layered oxide positive electrode comprises one or more lithium-based positive electrode electroactive materials selected from the group consisting of: liCoO 2(LCO)、LiNixMnyCo1-x-yO2 (wherein 0.ltoreq.x.ltoreq.1 and 0.ltoreq.y.ltoreq.1), liNi 1-x-yCoxAlyO2 (wherein 0.ltoreq.x.ltoreq.1 and 0.ltoreq.y.ltoreq.1), liNi xMn1-xO2 (wherein 0.ltoreq.x.ltoreq.1), li 1+xMO2 (wherein M is one of Mn, ni, co and Al, 0.ltoreq.x.ltoreq.1). The spinel positive electrode comprises one or more lithium-based positive electrode active materials selected from the group consisting of: liMn 2O4 (LMO) and LiNi xMn1.5O4. The conversion positive electrode is selected from at least one of S, li 2S、FeS2、VS2 and CuS.
The positive electrode ion conductor in the present invention provides lithium ion conduction in the positive electrode and may be a common inorganic solid electrolyte including, but not limited to, the above-mentioned halogen-rich sulfide electrolyte.
The positive electrode binder in the present invention includes, but is not limited to, at least one of Polytetrafluoroethylene (PTFE), styrene-butadiene rubber (SBR), hydrogenated nitrile-butadiene rubber (HNBR), nitrile-butadiene rubber (NBR), styrene-ethylene-butylene-styrene block copolymer (SEBS), styrene-butadiene-styrene block copolymer (SBS).
The positive electrode electron conductive agent in the present invention is a material that provides conductivity without causing adverse chemical reactions in the battery. Preferably, the positive electrode electron conductive agent is selected from at least one of Super-P, acetylene black, conductive carbon black Super C65, carbon fiber (VGCF), multi-wall carbon tube (MWCNT), single-wall carbon nanotube (SWCNT), and graphene.
The above materials are merely illustrative examples of the selected positive electrode materials, and any known positive electrode materials including positive electrode binders, positive electrode active materials, positive electrode conductive agents, and other additives can be used in the present embodiment without departing from the spirit of the present application.
Preferably, the negative electrode includes a negative electrode current collector and a negative electrode active material layer covering a surface of the negative electrode current collector.
The negative electrode current collector is not particularly limited as long as it has conductivity without causing chemical changes in the battery. For example: the negative electrode current collector is selected from any one of simple substance copper, stainless steel and simple substance nickel.
According to a preferred embodiment, the negative electrode active material layer is lithium metal and/or a lithium alloy, wherein the lithium alloy is selected from any one of a lithium indium alloy, a lithium aluminum alloy, a lithium bismuth alloy, a lithium tin alloy, and a lithium silicon alloy.
According to another preferred embodiment, the anode active material layer includes an anode active material, an anode ion conductor, an anode binder, and an anode electron conductive agent.
Preferably, the negative electrode active material is a silicon-based negative electrode active material and/or graphite. More preferably, the negative electrode active material is selected from at least one of silicon, silicon alloy, silicon oxide, silicon carbon, artificial graphite, and natural graphite.
The negative electrode ion conductor provides lithium ion conduction in the negative electrode, and can be a common sulfide electrolyte with a sulfur silver germanium ore crystal structure, including but not limited to Li 7P2S8 I and/or xLi 2S-(100-x)P2S5 (x is more than or equal to 70 and less than or equal to 80).
The negative electrode binder is used for binding a negative electrode active material, a negative electrode ion conductor and a negative electrode electron conductive agent, and adhering the negative electrode active material, the negative electrode ion conductor and the negative electrode electron conductive agent to a negative electrode current collector.
The negative electrode binder in the present invention includes, but is not limited to, at least one of Polytetrafluoroethylene (PTFE), sodium carboxymethylcellulose (CMC), styrene-butadiene rubber (SBR), nitrile-butadiene rubber (NBR), styrene-ethylene-butylene-styrene block copolymer (SEBS), styrene-butadiene-styrene block copolymer (SBS).
Preferably, the negative electrode electron conductive agent is selected from at least one of conductive carbon black Super-P, acetylene black, conductive carbon black Super C65, carbon fiber (VGCF), multi-wall carbon tube (MWCNT), single-wall carbon nanotube (SWCNT), and graphene.
The invention will be described in detail below by way of examples. In the following examples, unless otherwise specified, the instruments, reagents, materials and the like referred to are conventional instruments, reagents, materials and the like, and are commercially available.
Example 1
A method for preparing a Li 5.5AsS4.49Br1.5O0.01 halogen-rich sulfide electrolyte, the method comprising the steps of:
(1) At 15000rpm, li 2S、As2S3, S, liBr and Li 2 O were mixed in a molar ratio of 1.99:0.5:1:1.5:0.01, carrying out dry mixing for 3 min to obtain a mixture;
(2) And carrying out heat treatment on the mixture for 8 hours at the temperature of 450 ℃ to obtain the Li 5.5AsS4.49Br1.5O0.01 halogen-rich sulfide electrolyte.
Example 2
A method for preparing a Li 5.7AsS4.68Br1.3O0.02 halogen-rich sulfide electrolyte, the method comprising the steps of:
(1) At 15000rpm, li 2S、As2S3, S, liBr and Li 2 O were mixed in a molar ratio of 2.18:0.5:1.0:1.3:0.02, dry-mixing 3 min to obtain a mixture;
(2) And carrying out heat treatment on the mixture at 460 ℃ for 8 hours to obtain the Li 5.7AsS4.68Br1.3O0.02 halogen-rich sulfide electrolyte.
Example 3
A method for preparing a Li 5.44AsS4.4Br1.56O0.04 halogen-rich sulfide electrolyte, the method comprising the steps of:
(1) At 20000rpm, li 2S、As2S5, liBr, and Li 2 O were mixed in a molar ratio of 1.9:0.5:1.56:0.04, dry-mixing for 10min to obtain a mixture;
(2) And carrying out heat treatment on the mixture at 450 ℃ for 6 hours to obtain the Li 5.44AsS4.4Br1.56O0.04 halogen-rich sulfide electrolyte.
Example 4
A method for preparing a Li 5.35AsS4.1Br1.65O0.25 halogen-rich sulfide electrolyte, the method comprising the steps of:
(1) At 15000rpm, li 2S、As2S3, S, liBr and Li 2 O were mixed in a molar ratio of 1.6:0.5:1:1.65: dry-mixing 3 min with 0.25 to obtain a mixture;
(2) And carrying out heat treatment on the mixture for 8 hours at the temperature of 450 ℃ to obtain the Li 5.35AsS4.1Br1.65O0.25 halogen-rich sulfide electrolyte.
Example 5
A method for preparing a Li 5.77AsS4.7Br1.23O0.07 halogen-rich sulfide electrolyte, the method comprising the steps of:
(1) At 15000rpm, li 2S、As2S3, S, liBr and Li 2 O were mixed in a molar ratio of 2.2:0.5:1:1.23:0.07 to dry blend 3 min to obtain a mixture;
(2) And carrying out heat treatment on the mixture for 8 hours at the temperature of 450 ℃ to obtain the Li 5.77AsS4.7Br1.23O0.07 halogen-rich sulfide electrolyte.
Comparative example 1
A method for preparing a halogen-rich sulfide electrolyte of Li 6PS5 Br, which comprises the following steps:
(1) At 15000rpm, li 2S、P2S5 and LiBr were mixed in a molar ratio of 5:1:2, dry-mixing 3 min to obtain a mixture;
(2) And carrying out heat treatment on the mixture for 8 hours at 550 ℃ to obtain the Li 6PS5 Br halogen-rich sulfide electrolyte.
Comparative example 2
A method for preparing a Li 5.5PS4.5Br1.5 halogen-rich sulfide electrolyte, the method comprising the steps of:
(1) At 15000rpm, li 2S、P2S5 and LiBr were mixed in a molar ratio of 4:1:3, dry-mixing 3 min to obtain a mixture;
(2) And carrying out heat treatment on the mixture for 8 hours at the temperature of 450 ℃ to obtain the Li 5.5PS4.5Br1.5 halogen-rich sulfide electrolyte.
Comparative example 3
A method for preparing a halogen-rich sulfide electrolyte of Li 6AsS5 Br, which comprises the following steps:
(1) At 15000rpm, li 2S、As2S3, S and LiBr were mixed in a molar ratio of 2.5:0.5:1:1, dry-mixing 3 min to obtain a mixture;
(2) And carrying out heat treatment on the mixture for 8 hours at 550 ℃ to obtain the Li 6AsS5 Br halogen-rich sulfide electrolyte.
Comparative example 4
A method for preparing a Li 5.5P0.7As0.3S4.49Br1.5O0.01 halogen-rich sulfide electrolyte, the method comprising the steps of:
(1) At 15000rpm, li 2S、P2S5、As2S3, S, liBr and Li 2 O were mixed in a molar ratio of 1.99:0.35:0.15:0.3:1.5:0.01, carrying out dry mixing for 3 min to obtain a mixture;
(2) And carrying out heat treatment on the mixture for 8 hours at the temperature of 450 ℃ to obtain the Li 5.5P0.7As0.3S4.49Br1.5O0.01 halogen-rich sulfide electrolyte.
Test case
The halogen-rich sulfide electrolyte prepared in the above examples was subjected to performance tests, including: d 50, ionic conductivity, air stability, impedance. The results of the ion conductivity and air stability tests are shown in table 1. Wherein,
The ionic conductivity was tested with reference to the following standard method:
(i) Weighing 0.12g of halogen-rich sulfide electrolyte, and pressing under 150MPa to obtain a halogen-rich sulfide electrolyte ceramic sheet;
(ii) Stainless steel is stuck on two sides of the halogen-rich sulfide electrolyte ceramic plate to serve as a current collector, and a sample I to be detected is obtained;
(iii) The impedance of the sample I to be tested is tested by using an electrochemical workstation to obtain an alternating current impedance spectrum shown in figure 3, the impedance of the electrolyte ceramic sheet is obtained, and then the room temperature ion conductivity of the electrolyte is obtained by calculation according to a formula ①:
sigma=l/RS formula ①
In formula ①, L is the thickness of the electrolyte in mm; r is the impedance of the electrolyte in Ohm; s is the contact area, and the unit is cm 2; sigma is room temperature ionic conductivity in mS.cm -1.
Air stability (amount of H 2 S gas generated by electrolyte release) was tested with reference to the following method:
First 100mg of the halogen-rich sulfide electrolyte powder was pressed into 10mm particles at 150MPa, and then the particles were placed in a sealed container (40000 cm 3 in volume) and exposed to humid nitrogen (40% relative humidity) gas for 30 minutes, and the amount of H 2 S gas generated was calculated from the H 2 S concentration measured by the H 2 S gas sensor.
In addition, all samples were exposed to humid air (20% relative humidity) for ion conductivity measurements and again tested for air stability.
TABLE 1
The present invention provides an XRD pattern of the sulfide electrolyte prepared in example 1, as exemplified in fig. 2, and it can be seen from fig. 2 that the sulfide electrolyte prepared in this example has a crystal structure of sulfur silver germanium ore.
The present invention provides an impedance spectrum of the sulfide electrolyte prepared in example 1 as exemplified in fig. 3, and it can be calculated from fig. 3 that the sulfide electrolyte has a room temperature ion conductivity of 14.2ms·cm -1.
The XRD pattern of the sulfide electrolyte prepared in example 2 is exemplarily provided in fig. 4, and it can be seen from fig. 4 that the sulfide electrolyte prepared in this example has a crystal structure of sulfur silver germanium ore.
The present invention provides an impedance spectrum of the sulfide electrolyte prepared in example 2 as exemplified in fig. 5, and it can be calculated from fig. 5 that the room temperature ion conductivity of the sulfide electrolyte is 12.5ms·cm -1.
The XRD pattern of the sulfide electrolyte prepared in comparative example 1 is exemplarily provided in fig. 6, and it can be seen from fig. 6 that the sulfide electrolyte prepared in this comparative example has a crystal structure of silver germanium sulfide ore.
The present invention provides an impedance spectrum of the sulfide electrolyte prepared in comparative example 1 exemplarily in fig. 7, and it can be calculated from fig. 7 that the sulfide electrolyte has a room temperature ion conductivity of 2.0ms·cm -1.
The present invention illustratively provides the XRD pattern of the sulfide electrolyte prepared in comparative example 2 in fig. 8, and it can be seen from fig. 8 that the sulfide electrolyte prepared in this comparative example has a crystal structure of sulfur silver germanium ore.
The present invention provides an impedance spectrum of the sulfide electrolyte prepared in comparative example 2 exemplarily in fig. 9, and it can be calculated from fig. 9 that the sulfide electrolyte has a room temperature ion conductivity of 4.8ms·cm -1.
The present invention illustratively provides XRD patterns of the sulfide electrolyte prepared in comparative example 3 in fig. 10, and it can be seen from fig. 10 that the sulfide electrolyte prepared in this comparative example has a crystal structure of sulfur silver germanium ore.
The present invention provides an impedance spectrum of the sulfide electrolyte prepared in comparative example 3 exemplarily in fig. 11, from which it can be calculated that the room temperature ion conductivity of the sulfide electrolyte is 1.9ms·cm -1.
The present invention provides a graph of the amount of H 2 S gas produced released by the sulfide electrolytes prepared in example 1 and comparative examples 1-3 as a function of time during which they were exposed to nitrogen having a relative humidity of 40% in fig. 12 by way of example. As can be seen from fig. 12, the sulfide electrolytes of comparative examples 1 to 3 were poor in air stability, and a large amount of H 2 S gas was generated in the test time of 30 minutes, whereas the sulfide electrolyte of example 1 was relatively small in the amount of H 2 S gas generated.
The present invention provides a graph of changes in ionic conductivity of sulfide electrolytes prepared in example 1 and comparative examples 1 to 3 exposed to air of the same humidity for different times, as exemplarily shown in fig. 13, and it can be seen from fig. 13 that the ionic conductivity retention rate of example 1 is significantly higher than that of comparative examples 1 to 3, which means that the use of As element completely replaces P element, and the use of hard base O 2- and more halogen X - partially replaces soft base S 2- in the electrolyte, so that the air stability of sulfide electrolyte is significantly improved.
From the above results, it can be seen that the sulfide electrolyte provided by the invention can maintain the sulfide electrolyte with higher ionic conductivity while improving the air stability of the sulfide electrolyte by adopting As 5+ soft acid to completely replace P 5+ hard acid and adopting hard base O 2- and more halogen X - to partially replace soft base S 2- in the electrolyte.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (10)
1. A halogen-rich sulfide electrolyte, characterized in that the halogen-rich sulfide electrolyte has a cubic sulfur silver germanium ore type crystal structure, and the electrolyte has a chemical formula shown in formula I:
Li 6-xAsS5-x-yM1+xOy formula I;
Wherein 0< x <0.7, 0.ltoreq.y <0.5, and 0.02< x+y <1;
M is selected from at least one of Cl, br and I.
2. The halogen-rich sulfide electrolyte of claim 1 wherein in the formula I, 0.1< x <0.6, 0.ltoreq.y <0.2, and 0.02< x+y <1;
And/or M is Br;
and/or the D 50 of the halogen-rich sulfide electrolyte is 0.1-5 μm.
3. The halogen-rich sulfide electrolyte of claim 1 wherein in the formula I, 0.3-x <0.6,0-y <0.05, and 0.02< x+y <1;
And/or the halogen-rich sulfide electrolyte is selected from at least one of Li5.5AsS4.49Br1.5O0.01、Li5.7AsS4.68Br1.3O0.02、Li5.44AsS4.4Br1.56O0.04、Li5.35AsS4.1Br1.65O0.25 and Li 5.77AsS4.7Br1.23O0.07.
4. A method of preparing the halogen-rich sulfide electrolyte of any one of claims 1-3, comprising:
(1) Stirring and mixing a lithium source, an arsenic source, a sulfur source, a halogen source and an oxygen source to obtain a mixture;
(2) And carrying out heat treatment on the mixture to obtain the halogen-rich sulfide electrolyte.
5. The method of claim 4, wherein in step (1), the arsenic source is selected from at least one of arsenic pentasulfide, arsenic trisulfide, and elemental arsenic; the halogen source is selected from at least one of lithium chloride, lithium bromide and lithium iodide.
6. A composition for a composite electrolyte membrane, characterized in that the composition contains a halogen-rich sulfide electrolyte and a binder; the content of the halogen-rich sulfide electrolyte is 80-99wt% based on the total mass of the composition, and the content of the binder is 1-20wt%;
The halogen-rich sulfide electrolyte according to any one of claims 1 to 3.
7. A method of preparing a composite electrolyte membrane, the method comprising:
Sequentially carrying out wet mixing, casting and solvent evaporation on each component in the composition for the composite electrolyte membrane, and optionally carrying out hot pressing treatment after solvent evaporation to obtain the composite electrolyte membrane;
the composition for a composite electrolyte membrane according to claim 6.
8. The method of claim 7, wherein the wet mixing conditions comprise: the temperature is 20-50 ℃ and the rotating speed is 100-600rpm;
and/or, the conditions of the autoclave include: the temperature is 60-300 ℃, the pressure is 50-300MPa, and the time is 1-10min.
9. A method of preparing a composite electrolyte membrane, the method comprising:
Dispersing each component in the composition for the composite electrolyte membrane in the presence of an organic solvent, and then sequentially carrying out tape casting and drying on the obtained dispersion liquid to obtain the composite electrolyte membrane;
the composition for a composite electrolyte membrane according to claim 6.
10. A lithium ion battery is characterized in that the lithium ion battery comprises a positive electrode, a negative electrode and a composite electrolyte membrane; the thickness of the composite electrolyte membrane is 8-30 mu m;
The composite electrolyte membrane is prepared by the method according to any one of claims 7 to 9.
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| DE102014221737A1 (en) * | 2014-10-24 | 2016-04-28 | Robert Bosch Gmbh | Electrolyte for lithium-sulfur cell |
| CN113097560A (en) * | 2021-04-09 | 2021-07-09 | 浙江大学山东工业技术研究院 | High-air-stability nanocrystalline sulfide solid electrolyte, solid-state battery and preparation method of solid-state battery |
| US20220093966A1 (en) * | 2020-09-23 | 2022-03-24 | Solid Power, Inc. | Solid electrolyte material and solid-state battery made therewith |
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2024
- 2024-06-04 CN CN202410713324.3A patent/CN118281307B/en active Active
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|---|---|---|---|---|
| DE102014221737A1 (en) * | 2014-10-24 | 2016-04-28 | Robert Bosch Gmbh | Electrolyte for lithium-sulfur cell |
| US20220093966A1 (en) * | 2020-09-23 | 2022-03-24 | Solid Power, Inc. | Solid electrolyte material and solid-state battery made therewith |
| CN113097560A (en) * | 2021-04-09 | 2021-07-09 | 浙江大学山东工业技术研究院 | High-air-stability nanocrystalline sulfide solid electrolyte, solid-state battery and preparation method of solid-state battery |
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| Title |
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| 马玉林: "《电化学综合实验》", 30 September 2019, 哈尔滨工业大学出版社, pages: 187 * |
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Effective date of registration: 20240923 Address after: Building A, Zhongshi Building, No. 10 Wenxiu Street, Hongshan Street, Hongshan District, Wuhan City, Hubei Province 430070 Patentee after: Wuhan Tianshi Kefeng New Energy Technology Co.,Ltd. Country or region after: China Address before: Room 07-0001, 7th Floor, No. 53 Gongchen Street, Gongchen Street, Fangshan District, Beijing, 102401 Patentee before: Beijing Ziyue Zhixin Technology Co.,Ltd. Country or region before: China |