WO2025019663A2 - Électrolytes à base de sulfonamide fluoré pour batteries sans lithium correspondantes - Google Patents

Électrolytes à base de sulfonamide fluoré pour batteries sans lithium correspondantes Download PDF

Info

Publication number
WO2025019663A2
WO2025019663A2 PCT/US2024/038532 US2024038532W WO2025019663A2 WO 2025019663 A2 WO2025019663 A2 WO 2025019663A2 US 2024038532 W US2024038532 W US 2024038532W WO 2025019663 A2 WO2025019663 A2 WO 2025019663A2
Authority
WO
WIPO (PCT)
Prior art keywords
composition
battery
sodium
halogenated
alkyl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/US2024/038532
Other languages
English (en)
Other versions
WO2025019663A3 (fr
Inventor
Yang Shao-Horn
Jeremiah A. Johnson
Daniel Wang
Ju Li
Weiyin CHEN
Christian Orlando Plaza RIVERA
Jin-Sung Park
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Massachusetts Institute of Technology
Original Assignee
Massachusetts Institute of Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Massachusetts Institute of Technology filed Critical Massachusetts Institute of Technology
Publication of WO2025019663A2 publication Critical patent/WO2025019663A2/fr
Publication of WO2025019663A3 publication Critical patent/WO2025019663A3/fr
Anticipated expiration legal-status Critical
Pending legal-status Critical Current

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0568—Liquid materials characterised by the solutes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0569—Liquid materials characterised by the solvents
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • 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

Definitions

  • the commonly used electrolytes use strongly solvating solvents, which enhance the cation-dipole interaction and facilitate the formation of solvent- separated ion pairs (SSIPs) as shown in Fig. 1A, allowing solubility and high ion conductivity (ACS Nano 18, 8350-8359 (2024)).
  • SSIPs solvent- separated ion pairs
  • the free solvent molecules can be vulnerable to parasitic reactions with the electrode during cycling (Chem 9, 2943-2955 (2023)).
  • weakly solvating solvents allow the incorporation of anions within the first solvation sheath, contributing to the accumulation of contact-ion pairs (CIPs) and ion aggregates (AGGs) with higher electrochemical stability against sodium metal anodes and cathodes.
  • compositions comprising: a halogenated sodium salt; a halogenated sulfonate; and a co-solvent.
  • the term “optionally substituted” refers to the replacement of one to six hydrogen radicals in a given structure with the radical of a specified substituent including, but not limited to: hydroxyl, hydroxyalkyl, alkoxy, halogen, alkyl, nitro, silyl, acyl, acyloxy, aryl, cycloalkyl, heterocyclyl, amino, aminoalkyl, cyano, haloalkyl, haloalkoxy, -OCO-CH2-O- alkyl, -OP(O)(O-alkyl)2 or -CH2-OP(O)(O-alkyl)2.
  • “optionally substituted” refers to the replacement of one to four hydrogen radicals in a given structure with the substituents mentioned above. More preferably, one to three hydrogen radicals are replaced by the substituents as mentioned above. It is understood that the substituent can be further substituted.
  • acyl is art-recognized and refers to a group represented by the general formula hydrocarbylC(O)-, preferably alkylC(O)-.
  • acyloxy is art-recognized and refers to a group represented by the general formula hydrocarbylC(O)O-, preferably alkylC(O)O-.
  • alkoxyalkyl refers to an alkyl group substituted with an alkoxy group and may be represented by the general formula alkyl-O-alkyl.
  • alkyl refers to saturated aliphatic groups, including straight-chain alkyl groups, branched-chain alkyl groups, cycloalkyl (alicyclic) groups, alkyl-substituted cycloalkyl groups, and cycloalkyl-substituted alkyl groups.
  • a straight chain or branched chain alkyl has 30 or fewer carbon atoms in its backbone (e.g., Ci- 30 for straight chains, C3-30 for branched chains), and more preferably 20 or fewer.
  • alkyl as used throughout the specification, examples, and claims is intended to include both unsubstituted and substituted alkyl groups, the latter of which refers to alkyl moieties having substituents replacing a hydrogen on one or more carbons of the hydrocarbon backbone, including haloalkyl groups such as trifluoromethyl and 2,2,2- trifluoroethyl, etc.
  • C x.y or “C x -C y ”, when used in conjunction with a chemical moiety, such as, acyl, acyloxy, alkyl, alkenyl, alkynyl, or alkoxy is meant to include groups that contain from x to y carbons in the chain.
  • Coalkyl indicates a hydrogen where the group is in a terminal position, a bond if internal.
  • a C i -ealkyl group for example, contains from one to six carbon atoms in the chain.
  • alkylamino refers to an amino group substituted with at least one alkyl group.
  • alkylthio refers to a thiol group substituted with an alkyl group and may be represented by the general formula alkylS-.
  • amido refers to a group wherein R 9 and R 10 each independently represent a hydrogen or hydrocarbyl group, or R 9 and R 10 taken together with the N atom to which they are attached complete a heterocycle having from 4 to 8 atoms in the ring structure.
  • amine and “amino” are art-recognized and refer to both unsubstituted and substituted amines and salts thereof, e.g., a moiety that can be represented by wherein R 9 , R 10 , and R 10 ’ each independently represent a hydrogen or a hydrocarbyl group, or R 9 and R 10 taken together with the N atom to which they are attached complete a heterocycle having from 4 to 8 atoms in the ring structure.
  • aminoalkyl refers to an alkyl group substituted with an amino group.
  • aralkyl refers to an alkyl group substituted with an aryl group.
  • aryl as used herein include substituted or unsubstituted single-ring aromatic groups in which each atom of the ring is carbon.
  • the ring is a 5- to 7-membered ring, more preferably a 6-membered ring.
  • aryl also includes polycyclic ring systems having two or more cyclic rings in which two or more carbons are common to two adjoining rings wherein at least one of the rings is aromatic, e.g., the other cyclic rings can be cycloalkyls, cycloalkenyls, cycloalkynyls, aryls, heteroaryls, and/or heterocyclyls.
  • Aryl groups include benzene, naphthalene, phenanthrene, phenol, aniline, and the like.
  • carboxylate is art-recognized and refers to a group wherein R 9 and R 10 independently represent hydrogen or a hydrocarbyl group.
  • Carbocyclylalkyl refers to an alkyl group substituted with a carbocycle group.
  • Carbocycle includes 5-7 membered monocyclic and 8-12 membered bicyclic rings. Each ring of a bicyclic carbocycle may be selected from saturated, unsaturated and aromatic rings. Carbocycle includes bicyclic molecules in which one, two or three or more atoms are shared between the two rings.
  • fused carbocycle refers to a bicyclic carbocycle in which each of the rings shares two adjacent atoms with the other ring. Each ring of a fused carbocycle may be selected from saturated, unsaturated and aromatic rings.
  • an aromatic ring e.g., phenyl
  • a saturated or unsaturated ring e.g., cyclohexane, cyclopentane, or cyclohexene.
  • Exemplary “carbocycles” include cyclopentane, cyclohexane, bicyclo[2.2.1]heptane, 1,5-cyclooctadiene, 1,2,3,4-tetrahydronaphthalene, bicyclo[4.2.0]oct- 3-ene, naphthalene and adamantane.
  • Exemplary fused carbocycles include decalin, naphthalene, 1,2,3,4-tetrahydronaphthalene, bicyclo[4.2.0]octane, 4,5,6,7-tetrahydro-lH- indene and bicyclo[4.1.0]hept-3-ene.
  • “Carbocycles” may be substituted at any one or more positions capable of bearing a hydrogen atom.
  • Carbocyclylalkyl refers to an alkyl group substituted with a carbocycle group.
  • carbonate is art-recognized and refers to a group -OCO2-.
  • cycloalkyl includes substituted or unsubstituted non-aromatic single ring structures, preferably 4- to 8-membered rings, more preferably 4- to 6-membered rings.
  • cycloalkyl also includes polycyclic ring systems having two or more cyclic rings in which two or more carbons are common to two adjoining rings wherein at least one of the rings is cycloalkyl and the substituent (e.g., R 100 ) is attached to the cycloalkyl ring, e.g., the other cyclic rings can be cycloalkyls, cycloalkenyls, cycloalkynyls, aryls, heteroaryls, and/or heterocyclyls.
  • Heteroaryl groups include, for example, pyrrole, furan, thiophene, imidazole, oxazole, thiazole, pyrazole, pyridine, pyrazine, pyridazine, pyrimidine, denzodioxane, tetrahydroquinoline, and the like.
  • esters refers to a group -C(O)OR 9 wherein R 9 represents a hydrocarbyl group.
  • ether refers to a hydrocarbyl group linked through an oxygen to another hydrocarbyl group. Accordingly, an ether substituent of a hydrocarbyl group may be hydrocarbyl-O-. Ethers may be either symmetrical or unsymmetrical. Examples of ethers include, but are not limited to, heterocycle-O-heterocycle and aryl-O-heterocycle. Ethers include “alkoxyalkyl” groups, which may be represented by the general formula alkyl-O-alkyl.
  • halo and “halogen” as used herein means halogen and includes chloro, fluoro, bromo, and iodo.
  • heteroalkyl and “heteroaralkyl”, as used herein, refers to an alkyl group substituted with a hetaryl group.
  • heteroaryl and “hetaryl” include substituted or unsubstituted aromatic single ring structures, preferably 5- to 7-membered rings, more preferably 5- to 6-membered rings, whose ring structures include at least one heteroatom, preferably one to four heteroatoms, more preferably one or two heteroatoms.
  • heteroaryl and “hetaryl” also include polycyclic ring systems having two or more cyclic rings in which two or more carbons are common to two adjoining rings wherein at least one of the rings is heteroaromatic, e.g., the other cyclic rings can be cycloalkyls, cycloalkenyls, cycloalkynyls, aryls, heteroaryls, and/or heterocyclyls.
  • Heteroaryl groups include, for example, pyrrole, furan, thiophene, imidazole, oxazole, thiazole, pyrazole, pyridine, pyrazine, pyridazine, and pyrimidine, and the like.
  • heteroatom as used herein means an atom of any element other than carbon or hydrogen. Preferred heteroatoms are nitrogen, oxygen, and sulfur.
  • heterocyclylalkyl refers to an alkyl group substituted with a heterocycle group.
  • heterocyclyl refers to substituted or unsubstituted non-aromatic ring structures, preferably 3- to 10-membered rings, more preferably 3- to 7-membered rings, whose ring structures include at least one heteroatom, preferably one to four heteroatoms, more preferably one or two heteroatoms.
  • heterocyclyl and “heterocyclic” also include polycyclic ring systems having two or more cyclic rings in which two or more carbons are common to two adjoining rings wherein at least one of the rings is heterocyclic, e.g., the other cyclic rings can be cycloalkyls, cycloalkenyls, cycloalkynyls, aryls, heteroaryls, and/or heterocyclyls.
  • Heterocyclyl groups include, for example, piperidine, piperazine, pyrrolidine, morpholine, lactones, lactams, and the like.
  • Hydrocarbyl groups include, but are not limited to aryl, heteroaryl, carbocycle, heterocycle, alkyl, alkenyl, alkynyl, and combinations thereof.
  • hydroxyalkyl refers to an alkyl group substituted with a hydroxy group.
  • lower when used in conjunction with a chemical moiety, such as, acyl, acyloxy, alkyl, alkenyl, alkynyl, or alkoxy is meant to include groups where there are ten or fewer atoms in the substituent, preferably six or fewer.
  • acyl, acyloxy, alkyl, alkenyl, alkynyl, or alkoxy substituents defined herein are respectively lower acyl, lower acyloxy, lower alkyl, lower alkenyl, lower alkynyl, or lower alkoxy, whether they appear alone or in combination with other substituents, such as in the recitations hydroxyalkyl and aralkyl (in which case, for example, the atoms within the aryl group are not counted when counting the carbon atoms in the alkyl substituent).
  • polycyclyl refers to two or more rings (e.g., cycloalkyls, cycloalkenyls, cycloalkynyls, aryls, heteroaryls, and/or heterocyclyls) in which two or more atoms are common to two adjoining rings, e.g., the rings are “fused rings”.
  • Each of the rings of the polycycle can be substituted or unsubstituted.
  • each ring of the polycycle contains from 3 to 10 atoms in the ring, preferably from 5 to 7.
  • sulfate is art-recognized and refers to the group -OSO3H, or a pharmaceutically acceptable salt thereof.
  • sulfonamido is art-recognized and refers to the group represented by the general formulae wherein R 9 and R 10 independently represents hydrogen or hydrocarbyl.
  • sulfoxide is art-recognized and refers to the group-S(O)-.
  • sulfonate is art-recognized and refers to the group SO3H, or a pharmaceutically acceptable salt thereof.
  • substituted refers to moieties having substituents replacing a hydrogen on one or more carbons of the backbone. It will be understood that “substitution” or “substituted with” includes the implicit proviso that such substitution is in accordance with permitted valence of the substituted atom and the substituent, and that the substitution results in a stable compound, e.g., which does not spontaneously undergo transformation such as by rearrangement, cyclization, elimination, etc. As used herein, the term “substituted” is contemplated to include all permissible substituents of organic compounds.
  • the permissible substituents include acyclic and cyclic, branched and unbranched, carbocyclic and heterocyclic, aromatic and non-aromatic substituents of organic compounds.
  • the permissible substituents can be one or more and the same or different for appropriate organic compounds.
  • the heteroatoms such as nitrogen may have hydrogen substituents and/or any permissible substituents of organic compounds described herein which satisfy the valences of the heteroatoms.
  • Substituents can include any substituents described herein, for example, a halogen, a hydroxyl, a carbonyl (such as a carboxyl, an alkoxycarbonyl, a formyl, or an acyl), a thiocarbonyl (such as a thioester, a thioacetate, or a thioformate), an alkoxyl, a phosphoryl, a phosphate, a phosphonate, a phosphinate, an amino, an amido, an amidine, an imine, a cyano, a nitro, an azido, a sulfhydryl, an alkylthio, a sulfate, a sulfonate, a sulfamoyl, a sulfonamido, a sulfonyl, a heterocyclyl, an aralkyl, or an aromatic or heteroaromatic mo
  • thioalkyl refers to an alkyl group substituted with a thiol group.
  • thioester refers to a group -C(O)SR 9 or -SC(O)R 9 wherein R 9 represents a hydrocarbyl.
  • urea is art-recognized and may be represented by the general formula wherein R 9 and R 10 independently represent hydrogen or a hydrocarbyl.
  • stereogenic center in their structure.
  • This stereogenic center may be present in a R or a S configuration, said R and S notation is used in correspondence with the rules described in Pure Appl. Chem. (1976), 45, 11-30.
  • the disclosure contemplates all stereoisomeric forms such as enantiomeric and diastereoisomeric forms of the compounds, salts.
  • DMTMSA and THF were chosen for demonstration, since DMTMSA is a weakly solvating solvent with favorable molecular structure (Nat. Energy 6, 495-505 (2021)), and THF can dissolve NaFSI to form -7 m solution.
  • THF can dissolve NaFSI to form -7 m solution.
  • the average CEs and cycling overpotentials at 1.0 mA cm' 2 over 100 cycles were calculated to evaluate their electrochemical performance.
  • the average cycling overpotential firstly decreased from >600 mV to -72 mV, and then increased to -156 mV (FIG. 8C).
  • the average CE initially increased from -92.60% to -99.30%, followed by a decrease to -64.02% (FIG. 8D), which was matched with the trend observed by using the Aurbach method at 1.0 mA cm' 2 with areal capacity of 1.0 mAh cm' 2 (FIG. 10).
  • the non-monotonic dependence between the average CEs and cycling overpotentials guided our electrolyte HSE design, where the optimized molar ratio between DMTMSA and THF is 4:1 when NaFSI is used as the salt, and is called “1 m NaFSI DMTMSA/THF” afterwards.
  • LSV Linear sweep voltammetry
  • Ionic conductivity was measured using electrochemical impedance spectroscopy (EIS) results.
  • the ionic conductivity of 1 m NaFSI DMTMSA/THF is -220% greater than for the DMTMSA only electrolyte at room temperature (FIG. 13).
  • Activation energy was calculated using the Arrhenius fitting model; the value of 1 m NaFSI DMTMSA/THF was 14.90 kJ mol' 1 , which is lower than common HCE and LHCE with only strong solvating solvents (Angew. Chem. Int. Ed. 63, e202400406 (2024)).
  • the viscosity of 1 m NaFSI DMTMSA/THF is -5.3 cP at room temperature (FIG. 14), which is close to the value of advanced electrolytes with similar concentrations (ACS Energy Eett. 3, 315-321 (2016), Nat. Energy 6, 495-505 (2021)), and the value remains consistent for more than 3 weeks.
  • the observed greater ionic conductivity and stability are important factors to achieve fast cycling (>3.0 mA cm' 2 ) and high cut-off voltage (-4.0 V) for sodium metal batteries (SMBs).
  • the fast activation was also observed when the current density increased to 3.0 mA cm' 2 and when the areal capacity increases to 3.0 mAh cm' 2 .
  • the cycling CE exceeded 99.0%, which is the fastest activation observed so far in this work and in the literature (Table 1).
  • the fast activation of this HSE suggested the rapid formation of a passivation layer and minimized dissolution of reduced electrolyte products (Nat. Energy 7, 718-725 (2022)), which is one of the important electrolyte design principles.
  • the average CE was -99.3% over 100 cycles with stable cycling overpotential of -80 mV using an areal capacity of 3.0 mAh cm' 2 .
  • Rate performance was also conducted to evaluate this HSE.
  • 1 m NaFSI THF poor cycling reversibility was observed for all current densities; however, there is a relatively high CE of -97% with a low cycling overpotential of ⁇ 100 mV using a current density of ⁇ 0.5 mA cm' 2 for the DMTMSA-only electrolyte.
  • the current density reached 1.5 mA cm' 2 , a sharp voltage drop with a potential minimum of -2.4 V can be observed during the sodium- metal plating process and soft short-circuiting happened afterwards.
  • Nao.44Mn02 as the cathode with an areal capacity of -1.0 mAh cm' 2 .
  • 1 m NaFSI DMTMSA/THF enabled a capacity retention of -77.9 % over 600 cycles with an average CE of >99.9% (FIG. 18).
  • the capacity retention is -98.1 % over 500 cycles with an average CE of >99.9%. Further increasing the cycling rate to 5.0 C (-5.0 mA cm' 2 ) and cut-off voltage to 4.0 V was achieved with an initial specific capacity of -92.9 mAh g’ 1 .
  • 1 m NaFSI DMTMSA/THF enables a capacity retention of -70% over 1500 cycles with an average CE of -99.9% (FIG. 20).
  • a pouch cell with the configuration of NallNa3V2(PO4)3 was assembled to test 1 m NaFSI DMTMSA/THF. A uniaxial pressure of -50 kPa was applied. After 125 cycles, capacity retention was -95.8% and the average CE was -99.9%.
  • Na metal deposition morphology was studied for these different electrolytes.
  • metal deposition is compact while the particle size is small (FIG. 21A).
  • the average area and perimeter are 0.43 pm 2 and 3.11 pm, respectively, as calculated from -1700 individual microparticles labeled using a computer vision method (FIG. 22).
  • the high particle density can be attributed to the high nucleation density, as confirmed by the large nucleation overpotential at 1.0 mA cm' 1 .
  • the DMTMSA only electrolyte induces the formation of an inorganic -rich SEI, which can stabilize the electrode-electrolyte interface, leading to a compact deposition morphology.
  • microparticles show larger values as shown in the distribution of structure factor using 1 m NaFSI DMTMSA/THF, and the average structure factor value is ⁇ 4x and ⁇ 15x larger than 1 m NaFSI THF and DMTMSA only electrolyte, respectively.
  • the improved deposition behavior can be explained by the optimized solvation structure of HSEs.
  • the cation-dipole interaction becomes weaker.
  • the downshift of 23 Na NMR peak from -6.8 ppm to -11.0 ppm can be observed (FIG. 23A), reflecting the shielding effect induced by the increase of electron density near the cation and suggesting greater anion-cation association.
  • the peak width for different HSEs is larger than 1 m NaFSI THF and DMTMSA-only electrolyte, which is consistent with a mix of cation solvation environments within the HSEs.
  • the interaction between solvents, induced by the dipole-dipole interaction, can also be distinguished by the proton chemical shift for both THF and DMTMSA (FIG. 23B), together with the 19 F NMR chemical shift from DMTMSA (FIG. 23C).
  • Raman spectroscopy was used to further show how the combination of ion-dipole and dipole-dipole interactions in HSEs can tune solvation structures. The blueshift of Raman peaks can be seen when the molar ratio between DMTMSA and THF increases from -1.35 to -6.43.
  • THF shows a stronger interaction with Na + than DMTMSA and FST
  • the partial replacement of FST and modification of the primary solvation sheath can be achieved by controlling the THF amounts.
  • the CN for DMTMSA, FST and THF are 2.07, 2.46 and 0.66, respectively for 1 m NaFSI DMTMSA/THF.
  • the reduction of Na + -anion cluster and increasing Na + -anion single pair can maintain the preferred anion decomposition at the metal anode to form stable SEI and increase the ionic conductivity simultaneously.
  • extra THF can form the over solvated electrolytes and solvent surrounded Na + becomes dominant.
  • sodium bis(trifluoromethanesulfonyl)imide NaTFSI
  • sodium bis(trifluoromethanesulfonyl)imide NaTFSI
  • the HSEs can achieve the fastest activation, maintain low overpotentials and high reversibility even when cycled with a practical current density (-3.0 mA cm' 2 ), owing to the favored solvation structures contributing from the fine- tuning between strong and weak solvating solvents.
  • the default working electrode is Cu foil unless otherwise specified.

Landscapes

  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Materials Engineering (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Primary Cells (AREA)
  • Secondary Cells (AREA)

Abstract

L'invention concerne des compositions, des électrolytes, des cellules électrochimiques et des batteries comprenant un sel de sodium halogéné ; un sulfonate halogéné ; et un co-solvant.
PCT/US2024/038532 2023-07-18 2024-07-18 Électrolytes à base de sulfonamide fluoré pour batteries sans lithium correspondantes Pending WO2025019663A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US202363514181P 2023-07-18 2023-07-18
US63/514,181 2023-07-18

Publications (2)

Publication Number Publication Date
WO2025019663A2 true WO2025019663A2 (fr) 2025-01-23
WO2025019663A3 WO2025019663A3 (fr) 2025-05-01

Family

ID=94282597

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2024/038532 Pending WO2025019663A2 (fr) 2023-07-18 2024-07-18 Électrolytes à base de sulfonamide fluoré pour batteries sans lithium correspondantes

Country Status (1)

Country Link
WO (1) WO2025019663A2 (fr)

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4823401B2 (ja) * 1996-12-30 2011-11-24 イドロ―ケベック 過フッ化アミド塩及びイオン伝導物質としてのその使用方法
KR102818684B1 (ko) * 2015-09-28 2025-06-10 더 유나이티드 스테이츠 오브 어메리카 애즈 레프리젠티드 바이 더 세크러테리 오브 디 아미 광범위한 전기화학적 안정성 윈도우가 있는 수성 및 혼성 전해질
US20230100910A1 (en) * 2021-08-25 2023-03-30 Uchicago Argonne, Llc Non-flammable electrolytes
EP4420180A4 (fr) * 2021-10-21 2026-05-06 Univ Leland Stanford Junior Solvants d'électrolyte et procédés pour des batteries lithium-ion et lithium-métal
CN116169363A (zh) * 2023-03-24 2023-05-26 西安交通大学 一种钠离子电池电解液及钠离子电池

Also Published As

Publication number Publication date
WO2025019663A3 (fr) 2025-05-01

Similar Documents

Publication Publication Date Title
Togasaki et al. Enhanced cycling performance of a Li metal anode in a dimethylsulfoxide-based electrolyte using highly concentrated lithium salt for a lithium− oxygen battery
CN102786443B (zh) 二元或三元含氟磺酰亚胺的碱金属盐和离子液体及其应用
KR100867535B1 (ko) 비수 전해액 첨가제 및 이를 이용한 이차 전지
CN103641751B (zh) 二元或三元含氟磺酰亚胺的碱金属盐和离子液体及其应用
JP2021106161A (ja) 非水電解質組成物
US11038196B2 (en) Electrolytes containing six membered ring cyclic sulfates
TWI634688B (zh) 電化學裝置用電解液及電化學裝置
US11302924B2 (en) Dual electron-ion conductive polymer composite
US7749660B2 (en) Electrolyte for improving life characteristics at high temperature and lithium secondary battery comprising the same
CN107531600A (zh) 锂盐化合物、及使用了其的非水电解液、锂离子二次电池及锂离子电容器
CN110312726A (zh) 基于硼族元素的化合物及其在电解质组合物中的用途
CN114614088A (zh) 一种容量补偿型电解液添加剂、制备方法、应用以及含有该添加剂的电解液和二次电池
Schkeryantz et al. Designing potassium battery salts through a solvent-in-anion concept for concentrated electrolytes and mimicking solvation structures
Henderson Nonaqueous electrolytes: advances in lithium salts
US20210313583A1 (en) Stable metal anodes and batteries utilizing the same
EP3373379B1 (fr) Additif pour solutions électrolytiques non aqueuses, solution électrolytique non aqueuse et dispositif de stockage d'électricité
JP2024540368A (ja) 非水電解質組成物
US12571112B2 (en) Method of continuous electrochemical dinitrogen reduction
EP1236732B1 (fr) Sels de Phosphates de fluoroalkyl ET PREPARATION DE CEUX-CI
WO2025019663A2 (fr) Électrolytes à base de sulfonamide fluoré pour batteries sans lithium correspondantes
CN105609878B (zh) 一种锂离子电池高电压电解液
CN104193655A (zh) 一种二元含氟磺酰亚胺及其碱金属盐的制备方法
KR20150028770A (ko) Li-이온 전지용 2환 방향족 음이온염
US12046716B2 (en) Calcium salt for calcium batteries
KR100566915B1 (ko) 전극 접착력을 향상시킨 리튬망간산화물을 포함하는리튬이차전지용 양극

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 24843954

Country of ref document: EP

Kind code of ref document: A2

NENP Non-entry into the national phase

Ref country code: DE