CN114300743A - Method and solution for treating solid electrolyte surface and solid interface in solid battery - Google Patents
Method and solution for treating solid electrolyte surface and solid interface in solid battery Download PDFInfo
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- CN114300743A CN114300743A CN202111663910.4A CN202111663910A CN114300743A CN 114300743 A CN114300743 A CN 114300743A CN 202111663910 A CN202111663910 A CN 202111663910A CN 114300743 A CN114300743 A CN 114300743A
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- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 85
- 239000007787 solid Substances 0.000 title claims abstract description 46
- 238000000034 method Methods 0.000 title claims abstract description 39
- -1 lithium hexafluorophosphate Chemical compound 0.000 claims abstract description 50
- 239000002904 solvent Substances 0.000 claims abstract description 41
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 21
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 15
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 7
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims abstract description 5
- OGYGAYICMFHAFR-UHFFFAOYSA-N B([O-])(O)O.FC(C(=O)O)C(=O)O.FC(C(=O)O)C(=O)O.[Li+] Chemical compound B([O-])(O)O.FC(C(=O)O)C(=O)O.FC(C(=O)O)C(=O)O.[Li+] OGYGAYICMFHAFR-UHFFFAOYSA-N 0.000 claims abstract description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 4
- 229920001774 Perfluoroether Polymers 0.000 claims abstract description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims abstract description 4
- SYRDSFGUUQPYOB-UHFFFAOYSA-N [Li+].[Li+].[Li+].[O-]B([O-])[O-].FC(=O)C(F)=O Chemical compound [Li+].[Li+].[Li+].[O-]B([O-])[O-].FC(=O)C(F)=O SYRDSFGUUQPYOB-UHFFFAOYSA-N 0.000 claims abstract description 4
- ABDBNWQRPYOPDF-UHFFFAOYSA-N carbonofluoridic acid Chemical compound OC(F)=O ABDBNWQRPYOPDF-UHFFFAOYSA-N 0.000 claims abstract description 4
- 150000007942 carboxylates Chemical class 0.000 claims abstract description 4
- PGRMNXHYAZYNPG-UHFFFAOYSA-N fluoro hydrogen carbonate Chemical compound OC(=O)OF PGRMNXHYAZYNPG-UHFFFAOYSA-N 0.000 claims abstract description 4
- XPBBUZJBQWWFFJ-UHFFFAOYSA-N fluorosilane Chemical compound [SiH3]F XPBBUZJBQWWFFJ-UHFFFAOYSA-N 0.000 claims abstract description 4
- UQSQSQZYBQSBJZ-UHFFFAOYSA-M fluorosulfonate Chemical compound [O-]S(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-M 0.000 claims abstract description 4
- 150000003949 imides Chemical class 0.000 claims abstract description 4
- DEUISMFZZMAAOJ-UHFFFAOYSA-N lithium dihydrogen borate oxalic acid Chemical compound B([O-])(O)O.C(C(=O)O)(=O)O.C(C(=O)O)(=O)O.[Li+] DEUISMFZZMAAOJ-UHFFFAOYSA-N 0.000 claims abstract description 4
- XKLXIRVJABJBLQ-UHFFFAOYSA-N lithium;2-(trifluoromethyl)-1h-imidazole-4,5-dicarbonitrile Chemical compound [Li].FC(F)(F)C1=NC(C#N)=C(C#N)N1 XKLXIRVJABJBLQ-UHFFFAOYSA-N 0.000 claims abstract description 4
- ACFSQHQYDZIPRL-UHFFFAOYSA-N lithium;bis(1,1,2,2,2-pentafluoroethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)C(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)C(F)(F)F ACFSQHQYDZIPRL-UHFFFAOYSA-N 0.000 claims abstract description 4
- IGILRSKEFZLPKG-UHFFFAOYSA-M lithium;difluorophosphinate Chemical compound [Li+].[O-]P(F)(F)=O IGILRSKEFZLPKG-UHFFFAOYSA-M 0.000 claims abstract description 4
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 0.000 claims abstract description 4
- 150000002825 nitriles Chemical class 0.000 claims abstract description 4
- UJMWVICAENGCRF-UHFFFAOYSA-N oxygen difluoride Chemical compound FOF UJMWVICAENGCRF-UHFFFAOYSA-N 0.000 claims abstract description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 4
- 239000010452 phosphate Substances 0.000 claims abstract description 4
- 150000003457 sulfones Chemical class 0.000 claims abstract description 4
- OBTWBSRJZRCYQV-UHFFFAOYSA-N sulfuryl difluoride Chemical compound FS(F)(=O)=O OBTWBSRJZRCYQV-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000001035 drying Methods 0.000 claims description 19
- 239000003792 electrolyte Substances 0.000 claims description 16
- 239000007774 positive electrode material Substances 0.000 claims description 16
- 239000002841 Lewis acid Substances 0.000 claims description 14
- 150000007517 lewis acids Chemical class 0.000 claims description 14
- 238000002791 soaking Methods 0.000 claims description 13
- 229920000642 polymer Polymers 0.000 claims description 11
- 230000008569 process Effects 0.000 claims description 11
- 238000005507 spraying Methods 0.000 claims description 9
- 150000001768 cations Chemical class 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- 238000007151 ring opening polymerisation reaction Methods 0.000 claims description 7
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 6
- 239000011247 coating layer Substances 0.000 claims description 6
- 238000011049 filling Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 229910052731 fluorine Inorganic materials 0.000 claims description 4
- 239000011737 fluorine Substances 0.000 claims description 4
- 238000003672 processing method Methods 0.000 claims description 2
- 239000002041 carbon nanotube Substances 0.000 description 19
- 239000011248 coating agent Substances 0.000 description 19
- 238000000576 coating method Methods 0.000 description 19
- 229910021393 carbon nanotube Inorganic materials 0.000 description 18
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 17
- 229910052782 aluminium Inorganic materials 0.000 description 17
- 238000012360 testing method Methods 0.000 description 16
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 15
- 239000011889 copper foil Substances 0.000 description 15
- 239000011888 foil Substances 0.000 description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 13
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 10
- 239000002033 PVDF binder Substances 0.000 description 10
- 239000002174 Styrene-butadiene Substances 0.000 description 10
- 229910021383 artificial graphite Inorganic materials 0.000 description 10
- 239000001768 carboxy methyl cellulose Substances 0.000 description 10
- 230000001351 cycling effect Effects 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- 238000005096 rolling process Methods 0.000 description 10
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 8
- 229910009274 Li1.4Al0.4Ti1.6 (PO4)3 Inorganic materials 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- 229910015872 LiNi0.8Co0.1Mn0.1O2 Inorganic materials 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 5
- 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 5
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 5
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 5
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 5
- 239000007773 negative electrode material Substances 0.000 description 5
- 229920002857 polybutadiene Polymers 0.000 description 5
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 5
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 5
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 5
- 239000011115 styrene butadiene Substances 0.000 description 5
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 4
- 238000002955 isolation Methods 0.000 description 4
- 238000003475 lamination Methods 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 3
- XKTYXVDYIKIYJP-UHFFFAOYSA-N 3h-dioxole Chemical compound C1OOC=C1 XKTYXVDYIKIYJP-UHFFFAOYSA-N 0.000 description 3
- 229910013716 LiNi Inorganic materials 0.000 description 3
- 229910013872 LiPF Inorganic materials 0.000 description 3
- 101150058243 Lipf gene Proteins 0.000 description 3
- 229910010252 TiO3 Inorganic materials 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 description 2
- 229910002984 Li7La3Zr2O12 Inorganic materials 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000004880 explosion Methods 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229910013075 LiBF Inorganic materials 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 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
Abstract
The invention relates to a method and a solution for treating the surface of a solid electrolyte and a solid interface in a solid battery. The solution comprises: solutes, solvents and trace amounts of water; the solute comprises: one or more of lithium hexafluorophosphate, lithium hexafluoroarsenate, lithium tetrafluoroborate, lithium difluorophosphate, lithium dioxalate borate, lithium difluorooxalate borate, lithium bis (trifluoromethylsulfonyl imide), lithium bis (fluorosulfonyl imide), lithium difluorodioxalate phosphate, lithium trifluoromethylsulfonate, lithium fluorosulfonyl (n-perfluorobutylsulfonyl) imide, lithium bis (pentafluoroethylsulfonyl) imide, lithium bis (fluoromalonate) borate, lithium bis (2-methyl-2-fluoromalonate) borate, lithium 4, 5-dicyano-2-trifluoromethyl-imidazole; the solvent comprises: carbonate, sulfate, carboxylate, nitrile solvent, sulfone solvent, ether solvent, fluoro carbonate, fluoro ether solvent, fluoro sulfate, fluoro carboxylate, fluoro nitrile solvent, fluoro sulfone solvent or fluoro silane.
Description
Technical Field
The invention relates to the technical field of energy storage, in particular to a method and a solution for treating a solid electrolyte surface and a solid interface in a solid battery.
Background
Lithium ion batteries have been widely used in our lives, playing an important role in numerous applications, from consumer electronics and electric vehicles to aerospace products. With the continuous increase in the demand for electrification, the use of lithium ion batteries has also grown exponentially. Therefore, it is very necessary to use a high-safety, high-energy-density battery.
At present, because the electrolyte used by the lithium ion battery contains flammable organic solvents, the risk of fire or even explosion exists. The solid electrolyte, instead of the liquid electrolyte, increases the safety of the battery, and the solid electrolyte may use metallic lithium as a negative electrode, which greatly increases the energy density of the battery. Therefore, the all-solid-state battery is considered as one of the key technologies in the future, and continues to receive wide attention in recent years.
After the electrolyte in the solid-state battery is changed from a liquid state to a solid state, the lithium battery system is converted from the solid-liquid interface of the electrode material-electrolyte to the solid-solid interface of the electrode material-solid-state electrolyte. The difference is that there is no wettability between the solid and the solid, and the interface is more likely to form higher contact resistance. The solid electrolyte/electrode interface has the phenomena of difficult full contact, mutual diffusion and even reaction of components, formation of a space charge layer and the like, so that the internal resistance of the all-solid-state lithium ion battery is increased rapidly, and the cycle performance of the battery is deteriorated.
At present, the interface high resistance problem caused by a solid interface in the industry is generally improved by the following two ways:
1. the composite system is adopted, the organic polymer is compounded with the solid electrolyte material, and the polymer with flexibility is utilized to solve the problem of rigid contact of a solid-solid interface;
2. solid-liquid mixing is adopted, a certain amount of liquid is reserved in the solid-state battery, and the problem of rigid contact of a solid-solid interface is solved by utilizing the liquidity of the liquid
However, both of the above two approaches also have their own disadvantages. In the first mode, if a single polymer is used in the composite system, the requirements of oxidation resistance, reduction resistance and high conductivity are difficult to simultaneously satisfy, so that multiple substances are generally used in a composite way, but the process is complex and is not beneficial to industrial application; in the second mode, a certain amount of liquid generally exists in the solid-liquid mixing mode, the risk of possibly causing combustion or explosion still exists, and the problem cannot be really solved.
Disclosure of Invention
The embodiment of the invention provides a method and a solution for treating a solid-solid interface on the surface of a solid electrolyte and in a solid battery.
In a first aspect, embodiments of the present invention provide a solution for treating a solid electrolyte surface and a solid interface in a solid-state battery, the solution comprising: solutes, solvents and trace amounts of water; the water content of the solution is 0.1 mu g/g-10 mg/g;
the solute comprises: one or more of lithium hexafluorophosphate, lithium hexafluoroarsenate, lithium tetrafluoroborate, lithium difluorophosphate, lithium dioxalate borate, lithium difluorooxalate borate, lithium bis (trifluoromethylsulfonyl imide), lithium bis (fluorosulfonyl imide), lithium difluorodioxalate phosphate, lithium trifluoromethylsulfonate, lithium fluorosulfonyl (n-perfluorobutylsulfonyl) imide, lithium bis (pentafluoroethylsulfonyl) imide, lithium bis (fluoromalonate) borate, lithium bis (2-methyl-2-fluoromalonate) borate, lithium 4, 5-dicyano-2-trifluoromethyl-imidazole;
the solvent comprises: one or more of carbonate, sulfate, carboxylate, nitrile solvent, sulfone solvent, ether solvent, fluoro carbonate, fluoro ether solvent, fluoro sulfate, fluoro carboxylate, fluoro nitrile solvent, fluoro sulfone solvent or fluoro silane;
in the solution, the content of solute is 0.01mol/L-2.0 mol/L.
In a second aspect, an embodiment of the present invention provides a method for treating a surface of a solid electrolyte, the method comprising:
soaking a product to be treated containing the solid electrolyte in the solution of the first aspect, or spraying or washing the product with the solution of the first aspect, and drying to obtain a surface-treated product.
Preferably, the temperature of soaking, spraying or washing is between 25 and 100 ℃, and the treatment time is between 0.01 and 48 hours.
Preferably, the solid electrolyte-containing product includes: a solid electrolyte diaphragm, a diaphragm with a solid electrolyte coating layer, a solid electrolyte-coated positive electrode material or a solid electrolyte material for filling a gap between pole pieces.
Preferably, the solid electrolyte is a solid electrolyte containing Li element, and during the soaking, spraying or rinsing process, the solute is hydrolyzed by trace water in the solution and decomposed into cations, fluoride anions and Lewis acid; wherein the fluorine anion combines with hydrogen ions in water to generate HF, and the HF reacts with LiOH and/or Li on the surface of the solid electrolyte2CO3Reacting to form LiF; the lewis acid initiates ring-opening polymerization of the solvent to produce the organoalkyllithium and polymer on the surface of the solid electrolyte.
In a third aspect, an embodiment of the present invention provides a method for processing a solid-solid interface in a solid-state battery, where the method includes:
and (3) injecting the solution in the first aspect into a solid-state battery of a product containing solid electrolyte or soaking a solid-state battery cell in the solution, standing, and drying to remove the solution to obtain the solid-state battery with a solid-solid interface.
Preferably, the standing temperature is 25-100 ℃, and the standing time is 0.01-48 hours.
Preferably, the solid electrolyte-containing product includes: a solid electrolyte diaphragm, a diaphragm with a solid electrolyte coating layer, a solid electrolyte-coated positive electrode material or a solid electrolyte material for filling a gap between pole pieces.
Preferably, the solid electrolyte is a solid electrolyte containing Li element, and during the standing process, the solute is hydrolyzed by trace water in the solution and decomposed into cations, fluorine anions and Lewis acid; wherein the fluorine anion combines with hydrogen ions in water to generate HF, and the HF reacts with LiOH and/or Li on the surface of the solid electrolyte2CO3Reacting to form LiF; the lewis acid initiates ring-opening polymerization of the solvent to produce the organoalkyllithium and polymer on the surface of the solid electrolyte.
In a fourth aspect, the present invention provides a solid-state battery, including the solid-state electrolyte processed by the method for processing the surface of the solid-state electrolyte according to the second aspect, or including the solid-state interface processed by the method for processing the solid-state interface in the solid-state battery according to the third aspect
The trace amount of water in the solution for treating the surface of the solid electrolyte and the solid-solid interface in the solid-state battery, which is provided by the invention, enables the solute to be hydrolyzed and decomposed into cations, fluoride anions and Lewis acid; the fluorine anions then combine with hydrogen ions in the water to produce HF, which in turn combines with LiOH and/or Li at the surface of the solid electrolyte2CO3Reacting to form LiF; the lewis acid initiates the ring-opening polymerization of the solvent to produce the organoalkyllithium and polymer on the surface of the solid electrolyte. LiF, organic alkyl lithium and polymer generated on the surface of the solid electrolyte or the surface interface of the solid electrolyte and the active material can effectively improve the rigid contact of the solid-solid interface and achieve the effect of improving the electrochemical performance of the solid battery.
Detailed Description
The invention is further illustrated by the following specific examples, but it will be understood that these examples are for the purpose of illustration only and are not to be construed as in any way limiting the scope of the present invention, i.e., are not intended to be limiting.
The solution for treating the solid electrolyte surface and the solid interface in the solid battery can be used for treating the solid electrolyte surface and the solid interface in the solid battery. The solution comprises: solutes, solvents and trace amounts of water; wherein the trace water is water content in the solution of 0.1 mu g/g-10 mg/g;
the solute comprises: one or more of lithium hexafluorophosphate, lithium hexafluoroarsenate, lithium tetrafluoroborate, lithium difluorophosphate, lithium dioxalate borate, lithium difluorooxalate borate, lithium bis (trifluoromethylsulfonyl imide), lithium bis (fluorosulfonyl imide), lithium difluorodioxalate phosphate, lithium trifluoromethylsulfonate, lithium fluorosulfonyl (n-perfluorobutylsulfonyl) imide, lithium bis (pentafluoroethylsulfonyl) imide, lithium bis (fluoromalonate) borate, lithium bis (2-methyl-2-fluoromalonate) borate, lithium 4, 5-dicyano-2-trifluoromethyl-imidazole;
the solvent comprises: one or more of carbonate, sulfate, carboxylate, nitrile solvent, sulfone solvent, ether solvent, fluoro carbonate, fluoro ether solvent, fluoro sulfate, fluoro carboxylate, fluoro nitrile solvent, fluoro sulfone solvent or fluoro silane;
the solute content in the solution is 0.01mol/L-2.0 mol/L.
The method for treating the surface of the solid electrolyte by using the above solution comprises the following steps: and soaking the product containing the solid electrolyte to be treated in the solution, or spraying or washing the product with the solution, and drying to obtain the product after surface treatment. The temperature of soaking, spraying or washing is 25-100 ℃, and the treatment time is 0.01-48 hours. Solid electrolyte-containing products that can be treated by the present method include, but are not limited to: a solid electrolyte diaphragm, a diaphragm with a solid electrolyte coating layer, a solid electrolyte-coated positive electrode material or a solid electrolyte material for filling a gap between pole pieces.
The solid electrolyte treated by the method is specifically a solid electrolyte containing Li; during the process of soaking, spraying or washing, the solute is hydrolyzed by trace water in the solution and is decomposed into cations, fluorine anions and Lewis acid; wherein the fluorine anion combines with hydrogen ions in water to generate HF, and the HF combines with LiOH and/or Li on the surface of the solid electrolyte2CO3Reacting to form LiF; the lewis acid initiates the ring-opening polymerization of the solvent to produce the organoalkyllithium and polymer on the surface of the solid electrolyte.
The method for treating the solid-solid interface in the solid-state battery by using the solution comprises the following steps: and injecting the solution into a solid battery of a product containing solid electrolyte or soaking a solid battery cell in the solution, standing, and drying to remove the solution to obtain the solid battery with the solid-solid interface treated. The standing temperature is 25-100 ℃, and the standing time is 0.01-48 hours. Solid state batteries of solid electrolyte containing products that can be treated by the present method include, but are not limited to: the solid-state battery comprises a solid electrolyte diaphragm, a diaphragm with a solid electrolyte coating layer, a positive electrode material coated by a solid electrolyte or a solid electrolyte material for filling a pole piece gap.
The solid electrolyte of the present invention is specifically a solid electrolyte containing LiA solid electrolyte of an element; during the standing process, the solute is hydrolyzed by trace water in the solution and is decomposed into cations, fluoride anions and Lewis acid; wherein the fluorine anion combines with hydrogen ions in water to generate HF, and the HF combines with LiOH and/or Li on the surface of the solid electrolyte2CO3Reacting to form LiF; the lewis acid initiates the ring-opening polymerization of the solvent to produce the organoalkyllithium and polymer on the surface of the solid electrolyte.
The method can effectively improve the rigid contact of the solid-solid interface through LiF, organic alkyl lithium and the polymer generated on the surface of the solid electrolyte or the surface interface of the solid electrolyte and the active substance, thereby achieving the effect of improving the electrochemical performance of the solid battery.
In order to better understand the technical solution provided by the present invention, the following description will respectively illustrate the specific processes and the performances achieved by applying the methods provided by the above embodiments of the present invention to the solid electrolyte surface or solid-solid interface treatment.
Example 1
Selecting LiNi0.8Co0.1Mn0.1O2As a positive electrode material, LiNi is used as a positive electrode material0.8Co0.1Mn0.1O2Carbon Nanotube (CNT), Li1.4Al0.4Ti1.6(PO4)3Polyvinylidene fluoride (PVDF) as in 92.5: 1.5: 4.5: 1.5, coating the mixture on an aluminum foil current collector, drying the aluminum foil current collector by an oven, and rolling the aluminum foil current collector on a roller press to obtain the required positive plate;
selecting artificial graphite as a negative electrode material, and mixing the artificial graphite, sodium carboxymethyl cellulose (CMC), Carbon Nano Tubes (CNT) and Li1.4Al0.4Ti1.6(PO4)3Styrene Butadiene Rubber (SBR) as 91.8: 1.4: 0.8: 4.0: 2.0, coating the mixture on a copper foil current collector, drying the copper foil current collector by an oven, and rolling the copper foil current collector on a roller press to obtain the required negative plate;
selecting 9um PE as a base film, and coating 2um Li on two sides of the base film1.4Al0.4Ti1.6(PO4)3To obtain a (2+9+2) coated separatorManufacturing the pole piece into a small soft package battery of 2Ah by a lamination method;
mixing Ethylene Carbonate (EC), 1, 3-Dioxolane (DOL) according to a volume ratio of 1: 1 proportion, adding lithium hexafluorophosphate (LiPF)6) Adding trace water with the water content of 100 mu g/g to obtain solution A, wherein the solute concentration is 1 mol/L;
and (3) injecting 6g of the solution A into the prepared soft package battery, standing for 4 hours at 80 ℃, and drying in vacuum to remove the solution to obtain the solid battery. After capacity grading and cycle performance testing, the charge-discharge voltage window is 2.75-4.2V; the cycling test of the battery is 25 ℃ at room temperature, and the cycling charge-discharge current is 1C. The specific test results are shown in table 1.
Example 2
Selecting LiNi0.8Co0.1Mn0.1O2Is a positive electrode material, the surface of the positive electrode is coated with 100nm Li7La3Zr2O12Coating the positive electrode material LiNi0.8Co0.1Mn0.1O2Carbon Nanotube (CNT), Li1.4Al0.4Ti1.6(PO4)3Polyvinylidene fluoride (PVDF) as 93.0: 1.5: 4.0: 1.5, coating the mixture on an aluminum foil current collector, drying the aluminum foil current collector by an oven, and rolling the aluminum foil current collector on a roller press to obtain the required positive plate;
selecting artificial graphite as a negative electrode material, and mixing the artificial graphite, sodium carboxymethyl cellulose (CMC), Carbon Nano Tubes (CNT) and Li0.30La0.567TiO3Styrene Butadiene Rubber (SBR) as 91.8: 1.4: 0.8: 4.0: 2.0, coating the mixture on a copper foil current collector, drying the copper foil current collector by an oven, and rolling the copper foil current collector on a roller press to obtain the required negative plate;
selecting 9um PE as a base film, and coating 2um Li on two sides of the base film1.4Al0.4Ti1.6(PO4)3Obtaining a (2+9+2) coating isolation film, and manufacturing a pole piece into a 2Ah small soft package battery by a lamination method;
fluoroethylene carbonate (FEC), 1, 3-Dioxolane (DOL) and a solvent are mixed according to a volume ratio of 1: 1 ratio ofMixing, adding lithium tetrafluoroborate (LiBF)4) Adding trace water with the water content of 50 mu g/g into the solution B with the solute concentration of 0.5mol/L to obtain solution B;
and (3) injecting 6g of the solution B into a soft package battery, standing for 4 hours at 80 ℃, and drying in vacuum to remove the solution to obtain the solid battery. After capacity grading and cycle performance testing, the charge-discharge voltage window is 2.75-4.2V; the cycling test of the battery is 25 ℃ at room temperature, and the cycling charge-discharge current is 1C. The specific test results are shown in table 1.
Example 3
Selecting LiNi0.8Co0.1Mn0.1O2Is a positive electrode material, the surface of the positive electrode is coated with 50nm Li1.4Al0.4Ti1.6(PO4)3Coating the positive electrode material LiNi0.8Co0.1Mn0.1O2Carbon Nanotube (CNT), Li7La3Zr2O12Polyvinylidene fluoride (PVDF) as 93.0: 1.5: 4.0: 1.5, coating the mixture on an aluminum foil current collector, drying the aluminum foil current collector by an oven, and rolling the aluminum foil current collector on a roller press to obtain the required positive plate;
selecting artificial graphite as a negative electrode material, and mixing the artificial graphite, sodium carboxymethyl cellulose (CMC), Carbon Nanotubes (CNTs) and Li0.30La0.567TiO3Styrene Butadiene Rubber (SBR) as 91.8: 1.4: 0.8: 4.0: 2.0, coating the mixture on a copper foil current collector, drying the copper foil current collector by an oven, and rolling the copper foil current collector on a roller press to obtain the required negative plate;
selecting 9um PE as a base film, and coating 2um Li on two sides of the base film0.30La0.567TiO3Obtaining a (2+9+2) coating isolation film;
vinylene Carbonate (VC), 1, 3-Dioxolane (DOL) and a solvent are mixed according to a volume ratio of 1: 1, adding lithium bis (fluorosulfonyl imide) (LiFSI) with solute concentration of 1.5mol/L, and adding trace water with water content of 60 mu g/g to obtain a solution C;
and sequentially laminating the positive pole piece, the isolating membrane and the negative pole piece, applying certain pressure to ensure that the positive pole piece, the isolating membrane and the negative pole piece are fixed and kept in close contact, soaking in the solution C, standing for 5 hours at 60 ℃, drying in vacuum to remove the solution, and packaging by using an aluminum plastic membrane or an aluminum shell. After capacity grading and cycle performance testing, the charge-discharge voltage window is 2.75-4.2V; the cycling test of the battery is 25 ℃ at room temperature, and the cycling charge-discharge current is 1C. The specific test results are shown in table 1.
For the purpose of explaining the technical effects of the present invention, comparative examples 1 and 2 are described below.
Comparative example 1
Selecting LiNi0.8Co0.1Mn0.1O2As a positive electrode material, LiNi is used as a positive electrode material0.8Co0.1Mn0.1O2Carbon Nanotube (CNT), Li1.4Al0.4Ti1.6(PO4)3Polyvinylidene fluoride (PVDF) as in 92.5: 1.5: 4.5: 1.5, coating the mixture on an aluminum foil current collector, drying the aluminum foil current collector by an oven, and rolling the aluminum foil current collector on a roller press to obtain the required positive plate;
selecting artificial graphite as a negative electrode material, and mixing the artificial graphite, sodium carboxymethyl cellulose (CMC), Carbon Nano Tubes (CNT) and Li1.4Al0.4Ti1.6(PO4)3Styrene Butadiene Rubber (SBR) as 91.8: 1.4: 0.8: 4.0: 2.0, coating the mixture on a copper foil current collector, drying the copper foil current collector by an oven, and rolling the copper foil current collector on a roller press to obtain the required negative plate;
selecting Al2O3The coated PE film is an isolation film (2+9+2) um, and the pole piece is manufactured into a small soft package battery of 2Ah by a lamination method;
in a glove box with water content less than 0.1ppm and oxygen content less than 0.1ppm and filled with argon, Ethylene Carbonate (EC), diethyl carbonate (DEC) and Ethyl Methyl Carbonate (EMC) are mixed according to the volume ratio of 3: 2: 5, and adding lithium hexafluorophosphate (LiPF)6) And adding auxiliary additives of fluoroethylene carbonate (FEC), ethylene carbonate (VC) and 1, 3-Propane Sultone (PS) into the electrolyte at the concentration of 1mol/L according to the mass percent of 1%, 1% and 1% of the total mass of the electrolyte respectively to obtain an electrolyte D.
Injecting the electrolyte D into a small soft package battery of 2Ah according to the amount of 3g/Ah, and carrying out formation, capacity grading and cycle performance testing, wherein the charge-discharge voltage window is 2.75-4.2V; the cycling test of the battery is 25 ℃ at room temperature, and the cycling charge-discharge current is 1C. The specific test results are shown in table 1.
Comparative example 2
Selecting LiNi0.8Co0.1Mn0.1O2As a positive electrode material, LiNi is used as a positive electrode material0.8Co0.1Mn0.1O2Carbon Nanotube (CNT), Li1.4Al0.4Ti1.6(PO4)3Polyvinylidene fluoride (PVDF) as in 92.5: 1.5: 4.5: 1.5, coating the mixture on an aluminum foil current collector, drying the aluminum foil current collector by an oven, and rolling the aluminum foil current collector on a roller press to obtain the required positive plate;
selecting artificial graphite as a negative electrode material, and mixing the artificial graphite, sodium carboxymethyl cellulose (CMC), Carbon Nano Tubes (CNT) and Li1.4Al0.4Ti1.6(PO4)3Styrene Butadiene Rubber (SBR) as 91.8: 1.4: 0.8: 4.0: 2.0, coating the mixture on a copper foil current collector, drying the copper foil current collector by an oven, and rolling the copper foil current collector on a roller press to obtain the required negative plate;
selecting 9um PE as a base film, and coating 2um Li on two sides of the base film1.4Al0.4Ti1.6(PO4)3Obtaining a (2+9+2) coating isolation film, and manufacturing a pole piece into a 2Ah small soft package battery by a lamination method;
in a glove box with water content less than 0.1ppm and oxygen content less than 0.1ppm and filled with argon, Ethylene Carbonate (EC), diethyl carbonate (DEC) and Ethyl Methyl Carbonate (EMC) are mixed according to the volume ratio of 3: 2: 5, and adding lithium hexafluorophosphate (LiPF)6) And adding auxiliary additives of fluoroethylene carbonate (FEC), ethylene carbonate (VC) and 1, 3-Propane Sultone (PS) into the electrolyte at the concentration of 1mol/L according to the mass percent of 1%, 1% and 1% of the total mass of the electrolyte respectively to obtain the electrolyte E. Injecting the electrolyte E into a small soft package battery of 2Ah according to the amount of 3g/Ah, and carrying out formation, capacity grading, cycle performance testing, charging and dischargingThe voltage window is 2.75-4.2V; the cycling test of the battery is 25 ℃ at room temperature, and the cycling charge-discharge current is 1C. The specific test results are shown in table 1.
Table 1 shows the results of the electrical property tests of examples 1 to 3 and comparative examples 1 and 2.
| Group of | Capacity retention rate of 1000 cycles at 25 DEG C | 1000 cycles of DC impedance at 25 DEG C |
| Example 1 | 87.25％ | 10.2mΩ |
| Example 2 | 86.32％ | 10.5mΩ |
| Example 3 | 86.62％ | 10.4mΩ |
| Comparative example 1 | 80.62％ | 15.6mΩ |
| Comparative example 2 | 81.45％ | 15.3mΩ |
TABLE 1
The data show that after the solution disclosed by the invention is used for processing, the capacity retention rate of the solid-state battery is improved, and the direct-current impedance is obviously reduced, so that the solution and the corresponding processing method disclosed by the invention can be used for effectively improving the rigid contact of a solid-solid interface and achieving the effect of improving the electrochemical performance of the solid-state battery.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are merely exemplary embodiments of the present invention, and are not intended to limit the scope of the present invention, and any modifications, equivalent substitutions, improvements and the like made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (10)
1. A solution for treating a solid electrolyte surface and a solid interface in a solid state battery, the solution comprising: solutes, solvents and trace amounts of water; the water content of the solution is 0.1 mu g/g-10 mg/g;
the solute comprises: one or more of lithium hexafluorophosphate, lithium hexafluoroarsenate, lithium tetrafluoroborate, lithium difluorophosphate, lithium dioxalate borate, lithium difluorooxalate borate, lithium bis (trifluoromethylsulfonyl imide), lithium bis (fluorosulfonyl imide), lithium difluorodioxalate phosphate, lithium trifluoromethylsulfonate, lithium fluorosulfonyl (n-perfluorobutylsulfonyl) imide, lithium bis (pentafluoroethylsulfonyl) imide, lithium bis (fluoromalonate) borate, lithium bis (2-methyl-2-fluoromalonate) borate, lithium 4, 5-dicyano-2-trifluoromethyl-imidazole;
the solvent comprises: one or more of carbonate, sulfate, carboxylate, nitrile solvent, sulfone solvent, ether solvent, fluoro carbonate, fluoro ether solvent, fluoro sulfate, fluoro carboxylate, fluoro nitrile solvent, fluoro sulfone solvent or fluoro silane;
in the solution, the content of solute is 0.01mol/L-2.0 mol/L.
2. A method of treating a surface of a solid electrolyte, the method comprising:
soaking the product containing the solid electrolyte to be treated in the solution of claim 1, or spraying or washing the product with the solution of claim 1, and drying to obtain the surface-treated product.
3. The treatment process according to claim 2, wherein the soaking, spraying or rinsing temperature is between 25 ℃ and 100 ℃ and the treatment time is between 0.01 hour and 48 hours.
4. The process of claim 2, wherein the solid electrolyte-containing product comprises: a solid electrolyte diaphragm, a diaphragm with a solid electrolyte coating layer, a solid electrolyte-coated positive electrode material or a solid electrolyte material for filling a gap between pole pieces.
5. The treatment method according to claim 2, wherein the solid electrolyte is a solid electrolyte containing Li element, and during the soaking, spraying or rinsing, the solute is hydrolyzed by a trace amount of water in the solution and decomposed into cations, fluoride anions and Lewis acid; wherein the fluorine anion combines with hydrogen ions in water to generate HF, and the HF is bonded with Li OH and/or Li on the surface of the solid electrolyte2CO3Reacting to obtain Li F; the lewis acid initiates ring-opening polymerization of the solvent to produce the organoalkyllithium and polymer on the surface of the solid electrolyte.
6. A processing method of a solid-solid interface in a solid-state battery is characterized by comprising the following steps:
and (2) injecting the solution of claim 1 into a solid battery of a product containing solid electrolyte or soaking a solid battery cell in the solution, standing, and drying to remove the solution to obtain the solid battery with the solid-solid interface treated.
7. The treatment process according to claim 6, wherein the temperature of the standing is between 25 ℃ and 100 ℃ and the time of the standing is between 0.01 hour and 48 hours.
8. The process of claim 6, wherein the solid electrolyte-containing product comprises: a solid electrolyte diaphragm, a diaphragm with a solid electrolyte coating layer, a solid electrolyte-coated positive electrode material or a solid electrolyte material for filling a gap between pole pieces.
9. The treatment method according to claim 6, wherein the solid electrolyte is a solid electrolyte containing Li element, and during the standing process, the solute is hydrolyzed by the trace amount of water in the solution and decomposed into cations, fluorine anions and Lewis acid; wherein the fluorine anion combines with hydrogen ions in water to generate HF, and the HF is bonded with Li OH and/or Li on the surface of the solid electrolyte2CO3Reacting to form LiF; the lewis acid initiates ring-opening polymerization of the solvent to produce the organoalkyllithium and polymer on the surface of the solid electrolyte.
10. A solid-state battery comprising the solid-state electrolyte treated by the method for treating the surface of the solid-state electrolyte according to any one of claims 2 to 5, or comprising the solid-state interface treated by the method for treating the solid-state interface in the solid-state battery according to any one of claims 6 to 9.
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| JPH052804B2 (en) * | 1989-11-17 | 1993-01-13 | Yamaha Motor Co Ltd | |
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