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WO2025217411A1 - Impression combinatoire d'électrolytes solides à gradient fonctionnel pour batteries au lithium-métal haute tension - Google Patents

Impression combinatoire d'électrolytes solides à gradient fonctionnel pour batteries au lithium-métal haute tension

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Publication number
WO2025217411A1
WO2025217411A1 PCT/US2025/024089 US2025024089W WO2025217411A1 WO 2025217411 A1 WO2025217411 A1 WO 2025217411A1 US 2025024089 W US2025024089 W US 2025024089W WO 2025217411 A1 WO2025217411 A1 WO 2025217411A1
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Prior art keywords
electrolyte
polymer
polymer electrolyte
solid
content
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English (en)
Inventor
Yanliang Zhang
Qiang Jiang
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University of Notre Dame
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University of Notre Dame
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Classifications

    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—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
    • H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/1041—Polymer electrolyte composites, mixtures or blends
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
    • H01M8/1025—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having only carbon and oxygen, e.g. polyethers, sulfonated polyetheretherketones [S-PEEK], sulfonated polysaccharides, sulfonated celluloses or sulfonated polyesters
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
    • H01M8/103—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having nitrogen, e.g. sulfonated polybenzimidazoles [S-PBI], polybenzimidazoles with phosphoric acid, sulfonated polyamides [S-PA] or sulfonated polyphosphazenes [S-PPh]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
    • H01M8/1032—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having sulfur, e.g. sulfonated-polyethersulfones [S-PES]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
    • H01M8/1034—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having phosphorus, e.g. sulfonated polyphosphazenes [S-PPh]
    • 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

  • SSLMBs High-voltage solid-state lithium metal batteries
  • SSEs solid-state electrolytes
  • SSEs exhibit good stability when paired with a reducing Li metal anode, but their limited resistance to oxidation makes them incompatible with high-voltage cathodes, thereby restricting the energy density of SSLMBs.
  • SSEs that are compatible with high-voltage cathodes often suffer from instability when used with a Li metal anode, significantly limiting their versatility and practicality. Considering that each SSE has its own advantages and drawbacks, it becomes a daunting task to identify a single SSE with the ability to withstand both reduction and oxidation simultaneously.
  • heterogeneous multilayered solid-state electrolyte (HMSSE) strategy is introduced to solve this dilemma.
  • HMSSE multilayered solid-state electrolyte
  • researchers have applied this strategy via a dual-layered solid electrolyte consisting of polyethylene oxide (PEO) polymer contacting the lithium-metal anode and a poly(A/-methyl-malonic amide) (PMA) contacting the cathode.
  • PEO polyethylene oxide
  • PMA poly(A/-methyl-malonic amide)
  • Others constructed a dual-layered SSE by leveraging the oxidation resistance of poly(acrylonitrile) (PAN) and reduction compatibility of poly(vinylidene fluoride) (PVDF) layer.
  • Sandwich structure was also proposed in addition to the bilayer structure.
  • the HMSSE strategy can potentially broaden the working voltage windows
  • the newly introduced interface between electrolyte layers which is unavoidable in the HMSSE prepared by traditional manufacturing methods such as casting, has raised new challenges when considering the ion transport in the electrolyte.
  • the ion transport resistance at the interface can be much higher than that from bulk electrolyte, leading to the inferior performance of the HMSSE.
  • EIS electrochemical impedance spectroscopy
  • electrolyte/electrolyte interfacial resistance can be 100 times of that of the bulk electrolyte in the PEO-LATP multilayer model.
  • new manufacturing strategies are imperative to reduce the interfacial resistance and further improve the conductivity and the overall performance of the high-voltage SSLMBs.
  • AM additive manufacturing
  • aerosol jet printing has gained widespread attention due to its high resolution in material deposition and its wide applicability, encompassing materials such as polymers, ceramics, metals, semiconductors, adhesives, and biomaterials.
  • One embodiment described herein is a functionally graded solid-state electrolyte, comprising a multi-polymer electrolyte gradient extending between a first electrolyte end and a second electrolyte end, the first electrolyte end comprising a first polymer electrolyte content, the second electrolyte end comprising a second polymer electrolyte content, and the multi-polymer electrolyte gradient comprising a graded weight ratio of the first polymer electrolyte content to the second polymer electrolyte content of between 1 :0 and 0: 1 from the first electrolyte end to the second electrolyte end.
  • the first polymer electrolyte content and the second polymer electrolyte content comprise a polynitrile polymer, a polyether polymer, a polyalcohol polymer, a polyethylene oxide polymer, a polyethylene glycol polymer, a polyacrylate polymer, a polyester polymer, a polyvinyl polymer, a polyphosphazene polymer, a polysulfone polymer, a polysiloxane polymer, a fluoropolymer, or combinations thereof.
  • the electrolyte further comprises one or more ionic conducting materials evenly distributed throughout the electrolyte.
  • the one or more ionic conducting materials comprises lithium b/s(trifluoromethanesulfonyl)imide (LiTFSI) salt, Li6.4La3Zr1.4Tao.6O12 (LLZTO) nanoparticles, succinonitrile (SN), or combinations thereof.
  • the electrolyte comprises about 5 wt% to about 90 wt% of the one or more ionic conducting materials.
  • the electrolyte comprises about 15 wt% to about 70 wt% of the one or more ionic conducting materials.
  • the electrolyte has reduced resistance and improved lithium-ion transport and conductivity relative to a conventional heterogeneous multilayered solid-state electrolyte (HMSSE).
  • HMSSE heterogeneous multilayered solid-state electrolyte
  • a lithium-ion solid-state battery comprising: a positive electrode positioned on a positive electrode current collector; a negative electrode positioned on a negative electrode current collector; and a functionally graded solid-state electrolyte positioned between the positive electrode and the negative electrode, the functionally graded solid-state electrolyte comprising a multi-polymer electrolyte gradient extending between a first electrolyte end and a second electrolyte end, the first electrolyte end being in contact with the positive electrode and comprising a first polymer electrolyte content, the second electrolyte end being in contact with the negative electrode and comprising a second polymer electrolyte content, and the multi-polymer electrolyte gradient comprising a graded weight ratio of the first polymer electrolyte content to the second polymer electrolyte content of between 1 :0 and 0:1 from the first electrolyte end to the second electrolyte end.
  • the positive electrode comprises a cathode active material comprising lithium nickel cobalt aluminum oxide (NCA), LiCoO2, LiMn2C>4, LiNiO2, LiFePCU, LiNio.5Mn1.5O4, or LiNio.6Mno.2Coo.2O2 (NCM622).
  • the negative electrode comprises a lithium metal anode.
  • the battery operates at voltages greater than 5.5 V.
  • the battery maintains a discharge capacity of greater than 90 mAh g -1 after 200 cycles.
  • the battery has an improved rate performance relative to a battery having a conventional heterogeneous multilayered solid-state electrolyte (HMSSE).
  • HMSSE heterogeneous multilayered solid-state electrolyte
  • Another embodiment described herein is a method of making a functionally graded solid- state electrolyte, the method comprising: mixing a first aerosolized ink stream comprising a first polymer electrolyte and a second aerosolized ink stream comprising a second polymer electrolyte using a nitrogen carrier gas to form an aerosolized electrolyte mixture; and aerosol jet printing the aerosolized electrolyte mixture onto a substrate using a sheath gas such that the first aerosolized ink stream comprising the first polymer electrolyte is first deposited onto the substrate to form a first electrolyte end comprising the first polymer electrolyte; wherein flow rates of the first aerosolized ink stream and the second aerosolized ink stream are continuously adjusted to form a multi-polymer electrolyte gradient extending between the first electrolyte end and a second electrolyte end comprising the second polymer electrolyte, the multi-polymer electrolyte gradient comprising a graded weight ratio of the first
  • the method is performed in an environment comprising argon gas.
  • the substrate comprises a high-voltage cathode substrate.
  • the substrate is maintained at a temperature of about 50 °C to about 70 °C.
  • the method further comprises drying the functionally graded solid-state electrolyte to remove any solvent.
  • the method further comprises adding a lithium metal anode to the second electrolyte end.
  • the method comprises a sheath gas flow rate of about 50 seem to about 70 seem.
  • the method comprises an aerosol jet print speed of about 1 mm/s to about 10 mm/s.
  • the first polymer electrolyte and the second polymer electrolyte comprise a polynitrile polymer, a polyether polymer, a polyalcohol polymer, a polyethylene oxide polymer, a polyethylene glycol polymer, a polyacrylate polymer, a polyester polymer, a polyvinyl polymer, a polyphosphazene polymer, a polysulfone polymer, a polysiloxane polymer, a fluoropolymer, or combinations thereof.
  • the first polymer electrolyte comprises poly(acrylonitrile) (PAN) polymer and the second polymer electrolyte comprises polyethylene oxide) (PEO) polymer.
  • one or more of the first aerosolized ink stream and the second aerosolized ink stream further comprise one or more of lithium b/s(trifluoromethanesulfonyl)imide (LiTFSI) salt, Li6.4La3Zr1.4Tao.6O12 (LLZTO) nanoparticles, succinonitrile (SN), dimethylformamide (DMF), or /V-methylpyrrolidone (NMP).
  • LiTFSI lithium b/s(trifluoromethanesulfonyl)imide
  • LLZTO Li6.4La3Zr1.4Tao.6O12
  • SN succinonitrile
  • DMF dimethylformamide
  • NMP /V-methylpyrrolidone
  • FIG. 1A-E show schematic illustrations and SEM images of an exemplary functionally graded solid-state electrolyte (FGSSE) as described herein.
  • FIG. 1A shows a schematic illustration of an exemplary combinatorial aerosol jet printing method of FGSSE using aerosolized inks.
  • FIG. 1 B shows a schematic illustration of the FGSSE with enhanced ion transport capability.
  • FIG. 1C shows a cross-sectional SEM image of the FGSSE.
  • FIG. 1 D shows a schematic illustration of an HMSSE with impeded ion transport capability.
  • FIG. 1 E shows a cross-sectional SEM image of the HMSSE.
  • FIG. 2 shows an image of PEG and PAN inks for use in the combinatorial aerosol jet printing methods described herein.
  • FIG. 3 shows the relationship between the printed layer number and electrolyte film thickness.
  • the average thickness of one layer was ⁇ 1.6 pm.
  • the total thickness of the printed electrolyte film can be precisely controlled by the printed layer number.
  • FIG. 4 shows an SEM image of the surface of a gradient electrolyte film.
  • a smooth and crack-free surface of the gradient electrolyte film can be obtained after optimizing the printing process which can afford the good contact between an electrode and the electrolyte.
  • FIG. 5A-D show energy dispersive spectroscopy (EDS) results for FGSSE.
  • FIG. 5A shows an EDS of N and O signals of FGSSE.
  • FIG. 5B shows an EDS of Zr signal of FGSSE.
  • FIG. 50 shows a Raman spectra at every 5 pm along the Z-axis of the FGSSE.
  • FIG. 5D shows the normalized intensity of C N peak at different locations for varied PAN content.
  • FIG. 6A-B show an SEM (FIG. 6A) and EDS (FIG. 6B) image of an HMSSE film.
  • the EDS N and O distributions show that there is a composition change, which will lead to a sharp interface between polymers causing the discontinuous transport of ions in the film.
  • the diffusion of the PEG ink led to some PEG entry into the PAN film, but this had limited effect on diminishing the interface.
  • FIG. 7 shows a Raman spectra of the gradient electrolyte film at different locations.
  • FIG. 8 shows the relative intensity of Raman peak at 2244.7 cm -1 of gradient electrolyte film at different locations.
  • the intensity at 2244.7 cm -1 of the spectrum at 30 pm was 201.9, which was similar to the baseline. So, this value was taken as baseline when normalizing the intensity at different locations.
  • FIG. 9 shows Raman spectra for LiTFSI salt and PEO-based and PAN-based inks.
  • the TFSI’ peak at 749.5 cm -1 from LiTFSI is very sensitive to the complex environment and shifts to 744.5 cm -1 and 742.6 cm -1 for the TFSI’ in PAN and PEG electrolytes.
  • FIG. 10A-B show the FT-IR spectra of ink components.
  • FIG. 10A shows the spectra
  • FIG. 10B shows an expanded view with assignments.
  • FTIR shows the vibrational shifts of LiTFSI in the electrolyte.
  • the asymmetric S-N-S stretching [va(SNS)] at 1063 cm -1 shifts to 1057 cm -1 .
  • the va(CF3) shifts from 1200 cm -1 to 1186-1190 cm -1 .
  • FIG. 11A-B show XRD data.
  • FIG. 11 A shows XRD patterns of PEG, PEG ink, and LLZTO nanoparticles.
  • FIG. 11 B shows XRD patterns of PAN, PAN ink, and LLZTO nanoparticles.
  • the XRD measurement manifested the interaction between polymer electrolytes and the LLZTO nanoparticles.
  • the disappearance of characteristic peaks (19.5° and 23.5° for PEG and 16.9° for PAN) after the introduce of LLZTO nanoparticles indicates that the incorporation of LLZTO nanoparticles efficaciously decreases the crystallinity of the PEO and PAN matrix, and greatly enhance the movement of the polymer chain which is beneficial to the ion transport.
  • FIG. 12A-D show measured parameters for FGSSE.
  • FIG. 12A shows real conductivity as a function of frequency and temperature for FGSSE.
  • FIG. 12B shows temperature-dependent conductivity of FGSSE and HMSSE.
  • FIG. 12C shows impedance spectra and DC polarization curve of Li/FGSSE/Li cell for Li + transference number test.
  • FIG. 12D shows linear scan voltammetry of Li/FGSSE/SS. Inset is the zoom-in image of the onset of the oxidation process.
  • FIG. 13 shows real conductivity as a function of frequency and temperature for HMSSE. The value at the plateau was extracted as the bulk conductivity.
  • FIG. 14 shows impedance spectra and DC polarization curve of Li/HMSSE/Li for Li + transference number tests.
  • FIG. 15 shows linear scan voltammogram of Li/PEO electrolyte/SS to determine oxidative stability.
  • FIG. 16 shows linear scan voltammogram of Li/HMSSE/SS to determine oxidative stability. Inset is the zoom-in image of the onset of the oxidation process.
  • FIG. 17A-D shows data for Li/HMSSE/NCM622 cells.
  • FIG. 17A shows Nyquist plots of the Li/FGSSE/NCM622 and Li/HMSSE/NCM622 cells.
  • FIG. 17B shows the equivalent circuit model used to fit the EIS spectra.
  • FIG. 17C shows CV curves of the Li/FGSSE/NCM622 cell.
  • FIG. 17D shows rate performance of the Li/FGSSE/NCM622 and Li/HMSSE/NCM622 cells. All measurements were conducted at 60 °C.
  • FIG. 18A-D show data for Li/FGSSE/NCM622 and Li/HMSSE/NCM622 cells.
  • FIG. 18A shows long-term cycling performance of Li/FGSSE/NCM622 and Li/HMSSE/NCM622 cells at 1 C at 60°C.
  • FIG. 18B shows SEM image of the Li anode before cycling.
  • FIG. 18C-D show SEM images of the Li anode after 200 cycles with FGSSE (FIG. 18C) and HMSSE electrolytes (FIG. 18D).
  • FIG. 19 shows Nyquist plots of the LI/FGSSE/NCM622 cell at different cycles.
  • the term “substantially” means to a great or significant extent, but not completely.
  • the term “about” or “approximately” as applied to one or more values of interest refers to a value that is similar to a stated reference value, or within an acceptable error range for the particular value as determined by one of ordinary skill in the art, which will depend in part on how the value is measured or determined, such as the limitations of the measurement system.
  • the term “about” refers to any values, including both integers and fractional components that are within a variation of up to ⁇ 10% of the value modified by the term “about.”
  • “about” can mean within 3 or more standard deviations, per the practice in the art.
  • the term “about” can mean within an order of magnitude, in some embodiments within 5-fold, and in some embodiments within 2-fold, of a value.
  • the symbol means “about” or “approximately.”
  • ranges disclosed herein include both end points as discrete values as well as all integers and fractions specified within the range.
  • a range of 0.1-2.0 includes 0.1 , 0.2, 0.3, 0.4 . . . 2.0. If the end points are modified by the term “about,” the range specified is expanded by a variation of up to ⁇ 10% of any value within the range or within 3 or more standard deviations, including the end points, or as described above in the definition of “about.”
  • room temperature refers to the typical temperature in an indoor laboratory setting.
  • the laboratory setting is climate controlled to maintain the temperature at a substantially uniform temperature or with a specific range of temperatures.
  • room temperature refers a temperature of about 15-30 °C, including all integers and endpoints within the specified range.
  • room temperature refers a temperature of about 15-30 °C; about 20-30 °C; about 22-30 °C; about 25-30 °C; about 27-30 °C; about 15-22 °C; about 15-25 °C; about 15-27 °C; about 20-22 °C; about 20-25 °C; about 20-27 °C; about 22-25 °C; about 22-27 °C; about 25-27 °C; about 15 °C ⁇ 10%; about 20 °C ⁇ 10%; about 22 °C ⁇ 10%; about 25 °C ⁇ 10%; about 27 °C ⁇ 10%; ⁇ 20 °C, ⁇ 22 °C, ⁇ 25 °C, or ⁇ 27 °C, at standard atmospheric pressure.
  • control As used herein, the terms “control,” or “reference” are used herein interchangeably.
  • a “reference” or “control” level may be a predetermined value or range, which is employed as a baseline or benchmark against which to assess a measured result.
  • Control also refers to control experiments.
  • Heterogeneous multilayered solid-state electrolyte has been widely explored for its broadened working voltage range and compatibility with electrodes.
  • the interface between electrolyte layers in HMSSE can severely decrease the ionic conductivity.
  • a combinatory aerosol jet printing (CAJP) method is introduced to fabricate functionally graded solid-state electrolytes (FGSSE) without any sharp interface between different polymer electrolyte/electrolyte layers. Owing to CAJP’s unique ability of in-situ mixing and instantaneous tuning of the mixing ratios, an FGSSE with smooth microscale compositional gradation is achieved.
  • FGSSE has excellent oxidative stability exceeding 5.5 V and improved conductivity (>7 times of an analogous HMSSE).
  • the resistance from the electrolyte/electrolyte interface of HMSSE was found to be 5.7-times the total resistance of FGSSE.
  • a Li/FGSSE/NCM622 cell can be stably run for more than 200 cycles with improved rate performance.
  • a multi-polymer FGSSE comprises a multipolymer electrolyte gradient extending between a first electrolyte end and a second electrolyte end, where the multi-polymer electrolyte gradient comprises a first polymer electrolyte content and a second polymer electrolyte content, the first and second polymer electrolyte contents being distinct from one another, where a compositional ratio of the first polymer electrolyte content to the second polymer electrolyte content gradually changes from 1 :0 to 0: 1 from the first electrolyte end to the second electrolyte end.
  • the first polymer electrolyte content and the second polymer electrolyte content include, but are not limited to, a polynitrile polymer, a polyether polymer, a polyalcohol polymer, a polyester polymer, or a fluoropolymer.
  • Non-limiting exemplary polymer electrolytes include polyolefins (e.g., polyethylenes, poly(butene-l), poly(n-pentene-2), polypropylene, polytetrafluoroethylene), polyamines (e.g., polyethylene imine) and polypropylene imine (PPI)); polyamides (e.g., polyamide (Nylon), poly(E-caprolactam) (Nylon 6), poly(hexamethylene adipamide) (Nylon 66)), polyimides (e.g., polyimide, polynitrile, poly(acrylonitrile) (PAN), and poly(pyromellitimide-1 ,4-diphenyl ether) (Kapton®) (NOMEX®) (KEVLAR®)); polyether ether ketone (PEEK); vinyl polymers (e.g., polyacrylamide, poly(2-vinyl pyridine), poly(N- vinylpyrrolidone), poly(methylcyanoacrylate),
  • the first polymer electrolyte content comprises poly(acrylonitrile) (PAN) polymer and the second polymer electrolyte content comprises polyethylene oxide) (PEO) polymer.
  • PAN poly(acrylonitrile)
  • PEO polyethylene oxide
  • the multi-polymer FGSSEs described herein may further comprise one or more ionic conducting materials evenly distributed throughout the electrolyte.
  • the FGSSE may further comprise an ionic conducting salt, including, but not limited to, lithium b/s(trifluoromethanesulfonyl)imide (LiTFSI) and lithium bis(fluorosulfonyl)imide (LiFSI), lithium bis(oxalato)borate (LiBOB), lithium Difluro(oxalato)borate (LiDFOB), LiSCN, LiBr, Lil, LiCIO 4 , LiAsF 6 , LiSO 3 CF 3 , LiSO 3 CH 3 , LiBF 4 , LiB(Ph) 4 , LiPF 6 , LiC(SO 2 CF 3 ) 3 , LiN(SO 2 CF 3 ) 2 ), LiNO 3 , sodium bis(trifluoromethanesulfonyl)imide (NaTFSI) and sodium bis(fluorosulfonyl)imide (NaFSI), sodium bis(oxalato)boride (
  • the FGSSE may further comprise oxide-based solid-state electrolytes including, but not limited to, Li?La 3 Zr 2 0i 2 (LLZO), LATP, LAGP, LLTO, LiPON, LiBON, lithium borate, or Li6. 4 La 3 Zri. 4 Tao.50i 2 (LLZTO) nanoparticles.
  • LLZTO is a tantalum-doped version of LLZO.
  • LLZTO nanoparticles have high ionic conductivity and are chemically stable with lithium metal.
  • the FGSSEs described herein may comprise one or more plasticizers, binders, or fillers. Plasticizers help to facilitate lithium-ion transport and conductivity within polymer electrolyte materials.
  • Non-limiting exemplary plasticizers include plastic- crystal plasticizers such as succinonitrile (SN).
  • the one or more ionic conducting materials comprises lithium b/s(trifluoromethanesulfonyl)imide (LiTFSI) salt, Li 6.4 La 3 Zri. 4 Tao.60i 2 (LLZTO) nanoparticles, succinonitrile (SN), or combinations thereof.
  • Non-limiting exemplary binders include polyvinylidene fluoride (PVDF), polyacrylic acid, carboxymethyl cellulose, styrene-butadiene rubber, sodium alginate, and the like.
  • a lithium metal solid-state battery comprising: a positive electrode positioned on a positive electrode current collector; a negative electrode positioned on a negative electrode current collector; and a functionally graded solid- state electrolyte positioned between the positive electrode and the negative electrode, the functionally graded solid-state electrolyte comprising a multi-polymer electrolyte gradient extending between a first electrolyte end adjacent to the positive electrode and a second electrolyte end adjacent to the negative electrode, the multi-polymer electrolyte gradient comprising a first polymer electrolyte content and a second polymer electrolyte content, wherein a compositional ratio of the first polymer electrolyte content to the second polymer electrolyte content gradually changes from 1 :0 to 0:1 from the first electrolyte end to the second electrolyte end.
  • the positive electrode i.e., cathode
  • the positive electrode comprises a cathode active material comprising lithium nickel cobalt aluminum oxide (NCA), LiCoO 2 , LiMn 2 O4, LiNiO 2 , LiFePO4, LiNio.5Mn1.5O4, or LiNio.6Mno. 2 Coo. 2 0 2 (NCM622).
  • NCA lithium nickel cobalt aluminum oxide
  • LiCoO 2 LiMn 2 O4
  • LiNiO 2 LiFePO4, LiNio.5Mn1.5O4, or LiNio.6Mno. 2 Coo. 2 0 2
  • NCM622 lithium nickel cobalt aluminum oxide
  • the negative electrode i.e., anode
  • the anode comprises a lithium (Li) metal anode material.
  • the anode may incorporate dense Li metal or a Li metal alloy.
  • an active anode material may include, for example, lithium powder, titanium oxide, silicon, tin oxide, germanium, antimony, silicon oxide, iron oxide, cobalt oxide, ruthenium oxide, molybdenum oxide, molybdenum sulfide, chromium oxide, nickel oxide, manganese oxide, carbon-based materials (hard carbons, soft carbons, graphene, graphite, carbon nanofibers, carbon nanotubes, etc.), or a combination thereof.
  • the positive electrode current collector comprises aluminum foil, which can optionally be surface treated (e.g., carbon coating).
  • the negative electrode current collector comprises copper foil, which can optionally be surface treated.
  • One embodiment described herein is a functionally graded solid-state electrolyte, comprising a multi-polymer electrolyte gradient extending between a first electrolyte end and a second electrolyte end, the first electrolyte end comprising a first polymer electrolyte content, the second electrolyte end comprising a second polymer electrolyte content, and the multi-polymer electrolyte gradient comprising a graded weight ratio of the first polymer electrolyte content to the second polymer electrolyte content of between 1 :0 and 0:1 from the first electrolyte end to the second electrolyte end.
  • the first polymer electrolyte content and the second polymer electrolyte content comprise a polynitrile polymer, a polyether polymer, a polyalcohol polymer, a polyethylene oxide polymer, a polyethylene glycol polymer, a polyacrylate polymer, a polyester polymer, a polyvinyl polymer, a polyphosphazene polymer, a polysulfone polymer, a polysiloxane polymer, a fluoropolymer, or combinations thereof.
  • the electrolyte further comprises one or more ionic conducting materials evenly distributed throughout the electrolyte.
  • the one or more ionic conducting materials comprises lithium b/s(trifluoromethanesulfonyl)imide (LiTFSI) salt, Li6.4La3Zr1.4Tao.6O12 (LLZTO) nanoparticles, succinonitrile (SN), or combinations thereof.
  • the electrolyte comprises about 5 wt% to about 90 wt% of the one or more ionic conducting materials.
  • the electrolyte comprises about 15 wt% to about 70 wt% of the one or more ionic conducting materials.
  • the electrolyte has reduced resistance and improved lithium-ion transport and conductivity relative to a conventional heterogeneous multilayered solid-state electrolyte (HMSSE).
  • HMSSE heterogeneous multilayered solid-state electrolyte
  • a lithium-ion solid-state battery comprising: a positive electrode positioned on a positive electrode current collector; a negative electrode positioned on a negative electrode current collector; and a functionally graded solid-state electrolyte positioned between the positive electrode and the negative electrode, the functionally graded solid-state electrolyte comprising a multi-polymer electrolyte gradient extending between a first electrolyte end and a second electrolyte end, the first electrolyte end being in contact with the positive electrode and comprising a first polymer electrolyte content, the second electrolyte end being in contact with the negative electrode and comprising of a second polymer electrolyte content, and the multi-polymer electrolyte gradient comprising a graded weight ratio of the first polymer electrolyte content to the second polymer electrolyte content of between 1 :0 and 0:1 from the first electrolyte end to the second electrolyte end.
  • the positive electrode comprises a cathode active material comprising lithium nickel cobalt aluminum oxide (NCA), LiCoCh, LiM C , LiNiC>2, LiFePCU, LiNio.5Mn1.5O4, or LiNi0.6Mn0.2Co0.2O2 (NCM622).
  • the negative electrode comprises a lithium metal anode.
  • the battery operates at voltages greater than 5.5 V.
  • the battery maintains a discharge capacity of greater than 90 mAh g -1 after 200 cycles.
  • the battery has an improved rate performance relative to a battery having a conventional heterogeneous multilayered solid-state electrolyte (HMSSE).
  • HMSSE heterogeneous multilayered solid-state electrolyte
  • Another embodiment described herein is a method of making a functionally graded solid- state electrolyte, the method comprising: mixing a first aerosolized ink stream comprising a first polymer electrolyte and a second aerosolized ink stream comprising a second polymer electrolyte using a nitrogen carrier gas to form an aerosolized electrolyte mixture; and aerosol jet printing the aerosolized electrolyte mixture onto a substrate using a sheath gas such that the first aerosolized ink stream comprising the first polymer electrolyte is first deposited onto the substrate to form a first electrolyte end comprising of the first polymer electrolyte; wherein flow rates of the first aerosolized ink stream and the second aerosolized ink stream are continuously adjusted to form a multi-polymer electrolyte gradient extending between the first electrolyte end and a second electrolyte end comprising of the second polymer electrolyte, the multi-polymer electrolyte gradient comprising a graded weight ratio of
  • the method is performed in an environment comprising argon gas.
  • the substrate comprises a high-voltage cathode substrate.
  • the substrate is maintained at a temperature of about 50 °C to about 70 °C.
  • the method further comprises drying the functionally graded solid-state electrolyte to remove any solvent.
  • the method further comprises adding a lithium metal anode to the second electrolyte end.
  • the method comprises a sheath gas flow rate of about 50 seem to about 70 seem.
  • the method comprises an aerosol jet print speed of about 1 mm/s to about 10 mm/s.
  • the first polymer electrolyte and the second polymer electrolyte comprise a polynitrile polymer, a polyether polymer, a polyalcohol polymer, a polyethylene oxide polymer, a polyethylene glycol polymer, a polyacrylate polymer, a polyester polymer, a polyvinyl polymer, a polyphosphazene polymer, a polysulfone polymer, a polysiloxane polymer, a fluoropolymer, or combinations thereof.
  • the first polymer electrolyte comprises poly(acrylonitrile) (PAN) polymer and the second polymer electrolyte comprises polyethylene oxide) (PEO) polymer.
  • one or more of the first aerosolized ink stream and the second aerosolized ink stream further comprise one or more of lithium b/s(trifluoromethanesulfonyl)imide (LiTFSI) salt, Li6.4La3Zr1.4Tao.6O12 (LLZTO) nanoparticles, succinonitrile (SN), dimethylformamide (DMF), or /V-methylpyrrolidone (NMP).
  • LiTFSI lithium b/s(trifluoromethanesulfonyl)imide
  • LLZTO Li6.4La3Zr1.4Tao.6O12
  • SN succinonitrile
  • DMF dimethylformamide
  • NMP /V-methylpyrrolidone
  • compositions and methods provided are exemplary and are not intended to limit the scope of any of the specified embodiments. All of the various embodiments, aspects, and options disclosed herein can be combined in any variations or iterations.
  • the scope of the compositions, formulations, methods, and processes described herein include all actual or potential combinations of embodiments, aspects, options, examples, and preferences herein described.
  • the exemplary compositions and formulations described herein may omit any component, substitute any component disclosed herein, or include any component disclosed elsewhere herein.
  • a functionally graded solid-state electrolyte comprising a multi-polymer electrolyte gradient extending between a first electrolyte end and a second electrolyte end, the first electrolyte end comprising a first polymer electrolyte content, the second electrolyte end comprising a second polymer electrolyte content, and the multi-polymer electrolyte gradient comprising a graded weight ratio of the first polymer electrolyte content to the second polymer electrolyte content of between 1 :0 and 0:1 from the first electrolyte end to the second electrolyte end.
  • Clause 2 The electrolyte of clause 1, wherein the first polymer electrolyte content and the second polymer electrolyte content comprise a polynitrile polymer, a polyether polymer, a polyalcohol polymer, a polyethylene oxide polymer, a polyethylene glycol polymer, a polyacrylate polymer, a polyester polymer, a polyvinyl polymer, a polyphosphazene polymer, a polysulfone polymer, a polysiloxane polymer, a fluoropolymer, or combinations thereof.
  • the first polymer electrolyte content and the second polymer electrolyte content comprise a polynitrile polymer, a polyether polymer, a polyalcohol polymer, a polyethylene oxide polymer, a polyethylene glycol polymer, a polyacrylate polymer, a polyester polymer, a polyvinyl polymer, a polyphosphazene polymer, a polysulfone polymer, a poly
  • Clause 3 The electrolyte of clause 1 or 2, wherein the first polymer electrolyte content comprises poly(acrylonitrile) (PAN) polymer and the second polymer electrolyte content comprises poly(ethylene oxide) (PEO) polymer.
  • PAN poly(acrylonitrile)
  • PEO poly(ethylene oxide)
  • Clause 4 The electrolyte of any one of clauses 1-3, further comprising one or more ionic conducting materials evenly distributed throughout the electrolyte.
  • Clause 5 The electrolyte of clause any one of clauses 1-4, wherein the one or more ionic conducting materials comprises lithium b/s(trifluoromethanesulfonyl)imide (LiTFSI) salt, Li6.4La3Zr1.4Tao6O12 (LLZTO) nanoparticles, succinonitrile (SN), or combinations thereof.
  • LiTFSI lithium b/s(trifluoromethanesulfonyl)imide
  • LLZTO Li6.4La3Zr1.4Tao6O12
  • SN succinonitrile
  • Clause 6 The electrolyte of clause any one of clauses 1-4, wherein the electrolyte comprises about 5 wt% to about 90 wt% of the one or more ionic conducting materials.
  • Clause 7 The electrolyte of clause any one of clauses 1-4, wherein the electrolyte comprises about 15 wt% to about 70 wt% of the one or more ionic conducting materials.
  • Clause 8 The electrolyte of any one of clauses 1-7, wherein the electrolyte comprises a thickness of about 20 pm to about 40 pm.
  • Clause 9 The electrolyte of any one of clauses 1-8, wherein the electrolyte has reduced resistance and improved lithium-ion transport and conductivity relative to a conventional heterogeneous multilayered solid-state electrolyte (HMSSE).
  • HMSSE heterogeneous multilayered solid-state electrolyte
  • a lithium-ion solid-state battery comprising: a positive electrode positioned on a positive electrode current collector; a negative electrode positioned on a negative electrode current collector; and a functionally graded solid-state electrolyte positioned between the positive electrode and the negative electrode, the functionally graded solid-state electrolyte comprising a multi-polymer electrolyte gradient extending between a first electrolyte end and a second electrolyte end, the first electrolyte end being in contact with the positive electrode and comprising a first polymer electrolyte content, the second electrolyte end being in contact with the negative electrode and comprising a second polymer electrolyte content, and the multi-polymer electrolyte gradient comprising a graded weight ratio of the first polymer electrolyte content to the second polymer electrolyte content of between 1 :0 and 0:1 from the first electrolyte end to the second electrolyte end.
  • the positive electrode comprises a cathode active material comprising lithium nickel cobalt aluminum oxide (NCA), LiCoO2, LiMn2O4, LiNiC>2, LiFePC , LiNio.5Mn1.5O4, or LiNi06Mn0.2Co0.2O2 (NCM622).
  • NCA lithium nickel cobalt aluminum oxide
  • LiCoO2 LiMn2O4
  • LiFePC LiNio.5Mn1.5O4
  • LiNi06Mn0.2Co0.2O2 NCM622
  • Clause 12 The battery of clause 10 or 11 , wherein the negative electrode comprises a lithium metal anode.
  • Clause 13 The battery of any one of clauses 10-12, wherein the battery operates at voltages greater than 5.5 V.
  • Clause 14 The battery of any one of clauses 10-13, wherein the battery maintains a discharge capacity of greater than 90 mAh g -1 after 200 cycles.
  • Clause 15 The battery of any one of clauses 10-14, wherein the battery has an improved rate performance relative to a battery having a conventional heterogeneous multilayered solid- state electrolyte (HMSSE).
  • HMSSE heterogeneous multilayered solid- state electrolyte
  • a method of making a functionally graded solid-state electrolyte comprising: mixing a first aerosolized ink stream comprising a first polymer electrolyte and a second aerosolized ink stream comprising a second polymer electrolyte using a nitrogen carrier gas to form an aerosolized electrolyte mixture; and aerosol jet printing the aerosolized electrolyte mixture onto a substrate using a sheath gas such that the first aerosolized ink stream comprising the first polymer electrolyte is first deposited onto the substrate to form a first electrolyte end comprising the first polymer electrolyte; wherein flow rates of the first aerosolized ink stream and the second aerosolized ink stream are continuously adjusted to form a multi-polymer electrolyte gradient extending between the first electrolyte end and a second electrolyte end comprising the second polymer electrolyte, the multi-polymer electrolyte gradient comprising a graded weight ratio of the first polymer electrolyt
  • Clause 17 The method of clause 16, wherein the method is performed in an environment comprising argon gas.
  • Clause 18 The method of clause 16 or 17, wherein the substrate comprises a high-voltage cathode substrate.
  • Clause 19 The method of any one of clauses 16-18, wherein the substrate is maintained at a temperature of about 50 °C to about 70 °C.
  • Clause 20 The method of any one of clauses 16-19, further comprising drying the functionally graded solid-state electrolyte to remove any solvent.
  • Clause 21 The method of any one of clauses 16-20, further comprising adding a lithium metal anode to the second electrolyte end.
  • Clause 22 The method of any one of clauses 16-21 , wherein the method comprises a sheath gas flow rate of about 50 seem to about 70 seem.
  • Clause 23 The method of any one of clauses 16-22, wherein the method comprises an aerosol jet print speed of about 1 mm/s to about 10 mm/s.
  • Clause 24 The method of any one of clauses 16-23, wherein the first polymer electrolyte and the second polymer electrolyte comprise a polynitrile polymer, a polyether polymer, a polyalcohol polymer, a polyethylene oxide polymer, a polyethylene glycol polymer, a polyacrylate polymer, a polyester polymer, a polyvinyl polymer, a polyphosphazene polymer, a polysulfone polymer, a polysiloxane polymer, a fluoropolymer, or combinations thereof.
  • the first polymer electrolyte and the second polymer electrolyte comprise a polynitrile polymer, a polyether polymer, a polyalcohol polymer, a polyethylene oxide polymer, a polyethylene glycol polymer, a polyacrylate polymer, a polyester polymer, a polyvinyl polymer, a polyphosphazene polymer, a polysulfone polymer, a poly
  • Clause 25 The method of any one of clauses 16-24, wherein the first polymer electrolyte comprises poly(acrylonitrile) (PAN) polymer and the second polymer electrolyte comprises polyethylene oxide) (PEO) polymer.
  • PAN poly(acrylonitrile)
  • PEO polyethylene oxide
  • Clause 26 The method of any one of clauses 16-25, wherein one or more of the first aerosolized ink stream and the second aerosolized ink stream further comprise one or more of lithium b/s(trifluoromethanesulfonyl)imide (LiTFSI) salt, Li6.4La3Zr1.4Tao.5O12 (LLZTO) nanoparticles, succinonitrile (SN), dimethylformamide (DMF), or /V- methylpyrrolidone (NMP).
  • LiTFSI lithium b/s(trifluoromethanesulfonyl)imide
  • LLZTO Li6.4La3Zr1.4Tao.5O
  • Lithium b/s(trifluoromethanesulfonyl)imide LiTFSI was obtained from TCI chemicals.
  • LLZTO 300 nm was obtained from Neware.
  • Lithium chips, LiNi06Mn02Co02O2 (NCM622), and Super P were obtained from MSE supplies. All chemicals were used without further purification.
  • X-ray diffraction (XRD) patterns were performed by D8 Discover, Bruker (40 kV, 40 mA) with the scan angle from 10° to 60°.
  • the morphologies and energy-dispersive spectral (EDS) images of the SPEs were investigated with a scanning electron microscope (SEM) Helios G4 L)X.
  • SEM scanning electron microscope
  • FT-IR Fourier transform infrared spectroscopy
  • Ionic conductivity measurements were conducted on a Novocontrol Broadband Dielectric spectrometer equipped with an alpha-A high performance frequency analyzer and Quatro temperature control system with a cryostat. Data was collected in a frequency range from 1 * 10 6 Hz to 0.1 Hz at an AC voltage amplitude of 0.1 V from 25 to 85 °C at intervals of 15 °C. The temperature was ramped at 5 °C/min with 5 min of stabilization time at each measurement temperature. Cycling tests of the coin cell were conducted by a Neware battery test system with a voltage range of 2.8-4.3 V.
  • Cyclic voltammetry was conducted using a Parstat, AMETEK potentiostat/galvanostat with a scanning rate of 0.1 mV s -1 and a voltage range of 2.8-4.3 V.
  • Electrochemical impedance spectroscopy (EIS) measurement was conducted using a Gamry Interface 1010E Potentiostat with frequency range from 1 * 10 6 Hz to 0.1 Hz at an AC voltage amplitude of 0.1 V.
  • Linear sweep voltammetry (LSV) measurements were conducted using a Parstat, AMETEK potentiostat/galvanostat with a scanning rate of 0.2 mV s -1 . All the electrochemical tests were conducted at 60 °C.
  • PEO-based ink 20 mg of PEO, 20 mg of LLZTO, and 10 mg of LiTFSI were added into a glass vial with 2 mL DMF. The glass vial was sonicated for 1 h in a bath sonicator before use.
  • FIG. 2 shows an image of the PEO and PAN inks.
  • the inks used for the printing of HMSSE were the same as the inks used for the printing of functionally graded solid-state electrolyte (FGSSE).
  • the overall composition of the HMSSE was the same as FGSSE.
  • the difference between FGSSE and HMSSE is that the FGSSE had a functionally graded layer within the electrolyte.
  • the thickness of FGSSE was 32 pm and the thickness of the HMSSE was 33 pm. All the electrolyte films were dried for 48 hours in a vacuum oven at 65 °C to remove the solvent.
  • the specific parameters of the aerosol jet printing method are provided in Table 1 .
  • FIG. 3 shows the relationship between the printed layer number and electrolyte film thickness.
  • the average thickness of one layer was ⁇ 1.6 pm/layer.
  • the total thickness of the printed electrolyte film can be precisely controlled by the printed layer number.
  • FIG. 4 shows an SEM image of the surface of a gradient electrolyte film.
  • a smooth and crack-free surface of the gradient electrolyte film can be obtained after optimizing the printing process which can afford the good contact between an electrode and the electrolyte.
  • the cathode was prepared by casting onto a carbon coated aluminum current collector from a NMP slurry.
  • the NMP slurry was prepared by mixing and stirring the LiNi0.6Mn0.2Co0.2O2 (NCM622) active material (70%), conductive carbon (Super P) (15%), PVDF binder (15%) and NMP in a vial overnight.
  • the electrode was vacuum dried at 120 °C for 24 h.
  • the mass loading of the cathode material was ⁇ 2 mg cm -2 .
  • the cathode was cut into small squares with length of ⁇ 6 mm and cold pressed at ⁇ 10 MPa.
  • the obtained cathodes were used as the substrate during the printing of electrolyte. 2032 coin cells were assembled in an argon-filled glovebox with Li metal anode, NMC622 cathode, and the in-situ printed solid-state electrolyte.
  • Described herein is a novel combinatory aerosol jet printing (CAJP) method that was introduced to fabricate a functionally graded solid-state electrolyte (FGSSE).
  • CAJP solid-state electrolyte
  • oxidation-tolerant PAN and reduction-resistant PEG were separately dissolved and used as two inks in the CAJP.
  • LiTFSI Lithium b/s(trifluoromethane)sulfonimide
  • LLZTO nano-size Li6.4 a3Zr1.4Tao.6O12
  • the composition could be finely tuned along with the thickness direction of the printed materials to realize the FGSSE.
  • the generated FGSSE displayed an excellent oxidative stability exceeding 5.5 V and improved ionic conductivity (over 7 times that of HMSSE).
  • a high-voltage lithium metal cell with the FGSSE was found to stably run for more than 200 cycles.
  • the pure PAN-LLZTO electrolyte contacts the high-voltage cathode which avoids the oxidation of PEO electrolyte when the batteries are run at high-voltage.
  • the pure PEO-LLZTO contacts the lithium metal which can separate the PAN from lithium metal avoiding the side reaction between PAN and the lithium metal.
  • the compositional ratio between PAN and PEO was gradually changed from 1 :0 to 0:1 during the printing process along the Z-axis of the FGSSE. The gradual and smooth compositional modulations avoid the sharp compositional changes and render the electrolyte merging very well between different layers of printing. In this FGSSE, the Li + can transfer efficiently across the whole electrolyte.
  • FIG. 6A-B show an SEM (FIG. 6A) and EDS (FIG. 6B) image of the HMSSE film.
  • the EDS N and O distributions show that there is a composition change, which will lead to a sharp interface between polymers causing the discontinuous transport of ions in the film.
  • the diffusion of the PEO ink led to some PEO entry into the PAN film but this had limited effect on diminishing the interface.
  • FIG. 5A shows N and O distributions along the cross-section of FGSSE film.
  • N signal indicating the bottom layer was composed of PAN.
  • the N signal decreased, and the O signal increased gradually along the Z axis from the bottom to the top, which indicates the content of PAN decreased and the content of PEO increased gradually.
  • This smooth compositional change can be attributed to the in-situ mixing and accurate modulation of the ink mixing ratio during deposition.
  • FIG. 5B shows the homogeneous distribution of Zr element, indicating the good dispersion of the LLZTO nanoparticles within the polymer electrolyte.
  • the confocal Raman microscope can distinguish different polymers and their spatial distribution by revealing the organic functionalities information. So, Raman spectra were collected at every 5 pm along the Z-axis of the electrolyte film to verify the spatial distribution of the polymers.
  • FIG. 7 shows a Raman spectra of the gradient electrolyte film at different locations.
  • FIG. 8 shows the relative intensity of Raman peak at 2244.7 cm -1 of gradient electrolyte film at different locations.
  • the intensity at 2244.7 cm -1 of the spectrum at 30 pm was 201.9, which was similar to the baseline. So, this value was taken as baseline when normalizing the intensity at different locations.
  • the ionic conductivity of the FGSSE and HMSSE was systematically studied by dielectric spectroscopy at different temperatures from 25 to 85°C. As shown in FIG. 12A and FIG. 13, the ionic conductivity increased with the increase of the temperature for both electrolytes. The conductivities at different temperatures are summarized and compared in FIG. 12B.
  • the FGSSE displayed a conductivity of 2.0 x 10 -5 S cm -1 at 25 °C which is over 7 times of that of HMSSE (2.8 x 1Q-6 s cm -1 at 25 °C). This revealed that the FGSSE has an improved ion transport capability compared with the HMSSE.
  • FIG. 12C and FIG. 14 show the EIS and DC polarization experimental results of symmetric lithium cells with FGSSE and HMSSE for Li + transference measurements. Based on these results and according to the Bruce-Vincent-Evans equation, the Li + transference number (t Li +) of FGSSE was estimated to be 0.32 and the t Li + of the HMSSE was about 0.28. These values were within the range of t Li + of PEO, PAN, and LLZTO-containing composite electrolytes.
  • the electrochemical stability window is an important property that determines whether an electrolyte is suitable for high-voltage Li metal batteries.
  • the electrochemical window of the electrolyte was investigated by linear sweep voltammetry (LSV) test in Li/electrolyte/stainless steel (SS) cells at a scan rate of 0.2 mV s -1 . Adverse reactions started to occur for the PEO electrolyte when the voltage went above 3.8 V, indicating its poor antioxidation performance (FIG. 15). For FGSSE (FIG. 12D), the excellent anti-oxidation capability was observed as with HMSSE (FIG. 16). No clear onset of current was observed until 5.5 V versus Li/Li + , indicating its exceptional high-voltage stability.
  • FIG. 17A presents the EIS spectra recorded at 60 °C for the cells Li/FGSSE/NCM622 and Li/HMSSE/NCM622.
  • the spectra can be divided into high-frequency (HF, the first semicircle), medium-frequency (MF, the second semicircle) and low-frequency domains (LF, linear tail).
  • the HF, MF, and LF contributions were, respectively, assigned to the bulk electrolyte response, the interface response comprising both the polymer/polymer electrolyte interface and electrode/electrolyte interfaces, and the diffusion process.
  • the Rb, Ret, and RM are well decoupled in frequencies, thus the R c t from different cells could be extracted from the EIS and compared directly.
  • the R c t included Li/PEO and PAN/cathode interfaces.
  • the R c t of cells with HMSSE was composed of Li/PEO, PAN/cathode, and the polymer/polymer electrolyte interfaces.
  • the polymer/polymer interface resistance in the HMSSE can be deduced by subtracting the R c t of FGSSE from the R c t of HMSSE.
  • the equivalent electrical circuit presented in FIG. 17B was applied to fit the impedance spectra.
  • the equivalent circuit is composed of the cable contribution [resistance R c ) and inductance (L c )] in series with the bulk electrolyte and charge transfer response (modeled by F?b//CPE b and F? C f//CPE cf ), and the Warburg impedance (Z w ).
  • the R c t from HMSSE was 397.4 ⁇ 4.2 Qcm 2
  • the R ct from FGSSE was 64.3 ⁇ 0.4 Qcm 2
  • polymer/polymer interface resistance in the HMSSE was calculated to be 333.1 ⁇ 4.2 Qcm 2 , which is 5.7 times the total resistance of FGSSE (58.6 Qcm 2 ). This revealed that the significant charge transfer resistance arising from polymer/polymer interface can be dramatically reduced via the CAJP process described herein.
  • FIG. 17C Cyclic voltammetry (CV) measurements of the cells showed a typical NCM622 oxidization peak at 3.9 V and a reduction peak at 3.58 (FIG. 17C).
  • the oxidation peak shifted to 4.06 V because of the formation of interphase layer. No other redox peak could be found, which also confirmed the high stability of gradient electrolyte when it was paired with high- voltage cathode.
  • FIG. 17D shows the performance of the cells at various cycling rates from 0.2- 5 C.
  • the cell with FGSSE displayed discharge capacities of 161 , 153, 136, 110, and 44 mAh g -1 at current rates of 0.2, 0.5, 1 , 2, and 5 C, respectively.
  • the cell with HMSSE displayed discharge capacities of 160, 136, 103, 43, and 0.3 mAh g -1 at corresponding rates. After the end of cycling at a high current rate of 5 C, the discharge capacity of FGSSE cell could still be boosted to 155 mAh g -1 when the current rate returned to 0.2 C, reaching 96% of the initial discharge capacity at 0.2 C. While cells with different electrolytes exhibit similar capacity at relatively low currents, the cell with HMSSE displayed significantly lower capacity once the current exceeded 1 C. Especially, when the current was increased to 5 C, the cell with HMSSE showed almost no capacity while the cell with FGSSE could still run and deliver a capacity of 44 mAh g -1 . This demonstrated the battery with FGSSE had much better rate performance.
  • the long-term cycling performance of the cells is presented in FIG. 18A in terms of the discharge capacity and Coulombic efficiency as a function of cycle number.
  • the battery with FGSSE delivered a capacity of 142 mAh g -1 after a few cycles of activation and maintained a capacity of 97 mAh g -1 after 200 cycles, while the capacity of the cell with HMSSE was about 113 mAh g -1 after activation and just 40 mAh g -1 after 200 cycles.
  • the cell with FGSSE upheld a stable Coulombic efficiency throughout the cycling test at a level of 98.6-100% after the initial activation.
  • the EIS of the cell with FGSSE electrolyte at the 0, 25 th , 50 th , and 200 th cycles were compared (FIG.
  • the FGSSE described herein with an expanded electrochemical window and an improved ionic conductivity was successfully prepared via an innovative CAJP method for the first time.
  • FGSSE was printed with oxidation-tolerant PAN deposited in contact with the cathode followed by a gradual and smooth transition to reduction-resistant PEO. In this way, the side reactions among the electrodes and electrolyte could be avoided.
  • the electrochemical window of the electrolyte was expanded to 0-5.5 V.
  • the continuous compositional gradation of the electrolyte within the FGSSE improved the conductivity by avoiding the sharp compositional changes and the associated interfacial barrier for ion transport.
  • the overall conductivity of the FGSSE was over 7-times that of HMSSE at 25 °C.
  • the EIS analysis revealed the resistance from the electrolyte/electrolyte interface in the HMSSE was 5.7-times the total resistance of FGSSE.
  • the cell with FGSSE displayed a capacity of 142 mAh g -1 at 1 C and could stably run for more than 200 cycles with an improved rate performance.
  • This innovative CAJP method opens new opportunities to produce FGSSEs with enhanced properties and facilitates the development of high-performance solid-state batteries. The possibility of scaling up and integrating the FGSSEs with roll-to-roll processing for large-scale Li-ion battery production will be explored.

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Abstract

L'invention concerne des électrolytes solides à gradient fonctionnel et leurs procédés de fabrication. Dans certains modes de réalisation, les électrolytes comprennent un gradient d'électrolyte multipolymère comprenant un polymère de poly(acrylonitrile) (PAN) et un polymère de poly(oxyde d'éthylène) (PEO). Dans certains modes de réalisation, les procédés de fabrication de ces électrolytes reposent sur des techniques combinatoires d'impression par jet d'aérosol qui font intervenir des flux d'encre en aérosol comprenant des électrolytes polymères. Les électrolytes solides à gradient fonctionnel décrits ici ont une résistance réduite et un transport et une conductivité du lithium-ion améliorés par rapport aux électrolytes solides multicouches hétérogènes classiques. L'invention concerne également des batteries solides au lithium-ion comprenant des électrolytes solides à gradient fonctionnel.
PCT/US2025/024089 2024-04-11 2025-04-10 Impression combinatoire d'électrolytes solides à gradient fonctionnel pour batteries au lithium-métal haute tension Pending WO2025217411A1 (fr)

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Citations (7)

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