WO2023000604A1 - Membrane électrolytique solide au sulfure et batterie au lithium-ion solide - Google Patents

Membrane électrolytique solide au sulfure et batterie au lithium-ion solide Download PDF

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WO2023000604A1
WO2023000604A1 PCT/CN2021/138978 CN2021138978W WO2023000604A1 WO 2023000604 A1 WO2023000604 A1 WO 2023000604A1 CN 2021138978 W CN2021138978 W CN 2021138978W WO 2023000604 A1 WO2023000604 A1 WO 2023000604A1
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sulfide solid
solid electrolyte
electrolyte membrane
membrane
polymer
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PCT/CN2021/138978
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Chinese (zh)
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冯玉川
刘思捷
何泓材
李峥
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清陶(昆山)能源发展股份有限公司
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    • 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
    • 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
    • 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
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • 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 embodiments of the present application relate to the field of lithium batteries, such as a sulfide solid-state electrolyte membrane and a solid-state lithium-ion battery.
  • Existing solid-state electrolytes are mainly divided into three types: oxide solid-state electrolytes, sulfide solid-state electrolytes and polymer solid-state electrolytes, and sulfide solid-state electrolytes are considered to be a kind with broad industrialization prospects because of their high ionic conductivity. Material. However, it is difficult to form the sulfide solid-state electrolyte membrane. The thickness of the pure sulfide solid-state electrolyte membrane is about 0.5-1 mm. Excessive film thickness leads to low volumetric energy density of the battery. Therefore, at present, sulfide solid-state electrolytes can only be used in laboratory-scale batteries, and the energy density is much lower than that of industrial liquid batteries.
  • the present application provides a sulfide solid electrolyte membrane and a solid lithium ion battery.
  • an embodiment of the present application provides a sulfide solid-state electrolyte membrane
  • the sulfide solid-state electrolyte membrane includes a polymer film having a three-dimensional skeleton structure and a sulfide solid-state electrolyte material forming a continuous phase; the sulfide solid-state electrolyte
  • the ion conductivity of the membrane is greater than 10 -4 S/cm, and the thickness of the sulfide solid electrolyte membrane is less than or equal to 40 ⁇ m.
  • the ionic conductivity of the sulfide solid electrolyte membrane can be, for example, 5 ⁇ 10 -4 S/cm, 5.5 ⁇ 10 -4 S/cm, 6 ⁇ 10 -4 S/cm or 10 -3 S/cm cm, etc.; the thickness of the sulfide solid electrolyte membrane can be, for example, 40 ⁇ m, 35 ⁇ m, 30 ⁇ m, or 25 ⁇ m.
  • the flexible polymer membrane is used as a skeleton support, and the sulfide forms a continuous phase in the polymer membrane, which ensures the ion conductivity of the sulfide solid electrolyte membrane and greatly reduces the thickness of the solid electrolyte membrane.
  • the polymer film is a PVDF film or a PVDF-based polymer film, and the molecular structure of the PVDF-based polymer film is P(VDF-B) or P(VDF-B-A);
  • B is selected from any one or a combination of at least two of trifluoroethylene (Trifluoroethylene, TrFE), hexafluoropropylene (hexafluoropropylene, HFP) or methyl methacrylate (MMA);
  • A is selected from three Any one or a combination of at least two of chlorofluoroethylene (chlorotrifluoroethylene, CTFE), 1,1-chlorofluoroethylene (1,1-chlorofluoroethylene, CFE) or chlorodifluoroethylene (Chlorodifluoroethylene cdfe, CDFE);
  • the mass fraction of structural units based on VDF monomers in the PVDF-based polymer film is a, where a ⁇ 50%, such as 50%, 55%, 60%, 65%, 70%, 75% or 80%;
  • the mass fraction of structural units based on A monomer in the PVDF-based polymer film is b, b ⁇ 20%, such as 20%, 18%, 15%, 10%, 7%, 6%, 5%, 3% or 1% etc.
  • the PVDF-based polymerization The mass fraction of the structural unit based on the B monomer in the film is less than or equal to 50%, for example, it can be 50%, 45%, 40%, 35%, 30%, 25% or 20%; for the molecules of the PVDF-based polymer film
  • the sum of the mass fraction of the structural unit based on the B monomer and the mass fraction of the structural unit based on the A monomer in the PVDF-based polymer film is less than or equal to 50%, for example, it can be 50% , 45%, 40%, 35%, 30% or 25%, etc.
  • c for example, can be 0.5%, 1%, 3%, 5%, 8%, 10%, 15%, 20%, 25%
  • the polymer membrane of the present application has good flexibility and can provide a good skeleton support effect, which is beneficial to ensure the continuity of the sulfide solid electrolyte membrane, so that the sulfide solid electrolyte membrane can obtain high ion conductivity at a very thin thickness .
  • This application uses the method of electrospinning to prepare polymer membranes, forming a three-dimensional skeleton structure through fibers, and making the mesh holes non-directional, which ensures good mechanical properties on the one hand, and facilitates the formation of a continuous phase of sulfide solid electrolytes on the other hand And better play the advantage of improving the ionic conductivity of the sulfide solid electrolyte membrane.
  • the polymer membrane is a PVDF-based polymer membrane
  • the molecular structure is P(VDF-B)
  • B is trifluoroethylene
  • the mass fraction of the structural unit based on the trifluoroethylene monomer is c, and c ⁇ 50%.
  • the molecular structure of the polymer film is also P(VDF-TrFE).
  • P(VDF-TrFE) Compared with other types of PVDF-based polymers, P(VDF-TrFE) has interaction and bonding with sulfide solid electrolytes such as Li 6 PS 5 Cl, which makes the position where the sulfide and polymer combine also form a conductive structure. Lithium pathways that enhance the performance of solid-state electrolyte membranes.
  • the polymer membrane has a maximum mesh pore size of 30 ⁇ m.
  • the "grid aperture” mentioned in this application refers to the equivalent diameter of the through holes in the three-dimensional skeleton structure.
  • the equivalent diameter refers to the diameter of a local hole.
  • the equivalent diameter is indicated by the double-headed arrow.
  • the mesh pore size D50 of the polymer membrane is 10 ⁇ m ⁇ 18 ⁇ m, such as 10 ⁇ m, 12 ⁇ m, 14 ⁇ m, 15 ⁇ m, 16 ⁇ m or 18 ⁇ m. More preferably, the mesh pore size D90 of the polymer membrane is 10 ⁇ m ⁇ 18 ⁇ m.
  • the grid aperture D50 is A to B, which means that more than 50% of the grid apertures are within the range of A to B.
  • the grid aperture D90 is A to B, which means that more than 90% of the grid apertures are in the range of A to B.
  • the topography can be obtained by SEM, then the dimensions can be measured, and the results can be obtained statistically.
  • the mesh pores of the polymer film have no orientation.
  • the polymer film is prepared by electrospinning.
  • the sulfide solid electrolyte material includes Li 2 SP 2 S 5 , Li 2 SP 2 S 5 -MS x , Li 3.4 Si 0.4 P 0.6 S 4 , Li 10 GeP 2 S 11.7 O 0.3 , Li 9.6 P 3 S 12 , Li 7 P 3 S 11 , Li 9 P 3 S 9 O 3 , Li 10.35 Si 1.35 P 1.65 S 12 , Li 9.81 Sn 0.81 P 2.19 S 12 , Li 10 (Si 0.5 Ge 0.5 )P 2 S 12 , Li(Ge 0.5 Sn 0.5 )P 2 S 12 , Li(Si 0.5 Sn 0.5 )PsS 12 , Li 10 GeP 2 S 12 (LGPS), Li 6 PS 5 X, Li 7 P 2 S 8 I, Li 10.35 Ge 1.35 Any one or at least two of P 1.65 S 12 , Li 3.25 Ge 0.25 P 0.75 S 4 , Li 10 SnP 2 S 12 , Li 10 SiP 2 S 12 or Li 9.54 Si 1.74
  • the sulfide solid electrolyte material is Li 6 PS 5 X , wherein X is Cl, Br or I.
  • the sulfide solid electrolyte material forms a continuous phase in the polymer membrane by making a solution and pouring it onto the polymer membrane.
  • the particle size of the sulfide solid electrolyte material is smaller than the maximum mesh pore size of the polymer membrane.
  • the particle size of the sulfide solid electrolyte material is 50%-70% of the largest mesh pore size of the polymer membrane, such as 50%, 55%, 60%, 65% or 70%.
  • the sulfide solid electrolyte membrane contains lithium salt.
  • the lithium salt accounts for 0%-30% by mass of the polymer in the polymer film and does not contain 0%, more preferably 5%-20%, particularly preferably 5%-15%.
  • the present application provides a method for preparing the above-mentioned sulfide solid electrolyte membrane, the method for preparing the sulfide solid electrolyte membrane includes the following steps:
  • step S2 pouring a solution containing sulfide solid electrolyte particles onto the polymer film obtained in step S1;
  • the ionic conductivity of the sulfide solid electrolyte membrane is >10 -4 S/cm, and the thickness of the sulfide solid electrolyte membrane is ⁇ 40 ⁇ m;
  • the maximum mesh pore size of the prepared polymer membrane is larger than the particle size of the sulfide solid electrolyte particles in the step S2.
  • the polymer membrane is an internal three-dimensional interconnected structure.
  • the polymer film is prepared by electrospinning.
  • step S2 a step of thickness control is also included.
  • an embodiment of the present application provides a solid-state lithium-ion battery, which includes a positive electrode, a negative electrode, and the sulfide solid-state electrolyte membrane described in the first aspect.
  • the present application does not specifically limit the type of the solid-state lithium-ion battery, for example, it may be a lithium-sulfur battery, a lithium-ion battery, a lithium-iron disulfide battery or a lithium-titanium sulfide battery.
  • the negative electrode in the lithium-sulfur battery can be lithium metal, and the positive electrode active material used in the positive electrode in the lithium-sulfur battery can be a sulfur-carbon composite material.
  • the formula and composition of the lithium-sulfur battery will not be repeated here.
  • the present application provides a method for preparing the above-mentioned sulfur-carbon composite material, including: mixing sulfur vapor and conductive additives, wherein the mass ratio of sulfur vapor to conductive additives can be adjusted according to actual use needs, and the After sulfur vapor is mixed with conductive additives, it is heated at 145-160°C to obtain sulfur-carbon composites.
  • the conductive additives used in the preparation of sulfur-carbon composite materials include but are not limited to any of carbon black materials such as acetylene black, SuperP, SuperS, 350G, carbon fiber (VGCF), carbon nanotubes (CNTs) or Ketjen Black.
  • carbon black materials such as acetylene black, SuperP, SuperS, 350G, carbon fiber (VGCF), carbon nanotubes (CNTs) or Ketjen Black.
  • VGCF carbon fiber
  • CNTs carbon nanotubes
  • Ketjen Black Ketjen Black
  • a polymer film with a three-dimensional skeleton structure is combined with a continuous phase sulfide solid electrolyte material, which can obtain high ion conductivity while reducing the thickness.
  • the embodiment of the present application provides a preferred preparation method of the sulfide solid electrolyte membrane.
  • the copolymer is prepared into a polymer film by electrospinning, and the three-dimensional through-hole structure in the polymer film forms a three-dimensional skeleton, so that the entire The support membrane becomes flexible, and then through perfusion, hot pressing and other methods, the sulfide solid electrolyte particles can form a continuous phase in the network, forming a three-dimensional percolation network, and a sulfide solid electrolyte membrane with high ion conductivity and thin thickness is prepared. .
  • the embodiment of the present application preferably uses PVDF-based polymer as the main component of the polymer membrane.
  • the PVDF-based polymer has a good match with the sulfide solid electrolyte, and the formed solid electrolyte membrane has high ion conductivity and relatively Thin thickness helps to improve battery performance.
  • P(VDF-TrFE) has interaction and bonding with sulfide solid electrolytes such as Li 6 PS 5 Cl, which makes the binding position of sulfide and polymer also form The lithium-conducting pathway improves the performance of the solid electrolyte membrane.
  • Fig. 1 is the physical picture of the sulfide solid electrolyte membrane prepared in embodiment 1;
  • Fig. 2A is the SEM figure of the P (VDF-TrFE) electrospun membrane prepared in embodiment 1;
  • Fig. 2B is the SEM figure of the P (VDF-TrFE) electrospun membrane prepared in embodiment 2;
  • Fig. 2 C is the SEM picture of the P (VDF-TrFE) electrospun membrane prepared in embodiment 3;
  • Fig. 3 A is the SEM picture of the P (VDF-TrFE) electrospun membrane prepared in embodiment 4;
  • Fig. 3 B is the SEM picture of the P (VDF-TrFE) electrospun membrane prepared in embodiment 5;
  • Fig. 4 is the SEM picture of the solid electrolyte membrane prepared in embodiment 1;
  • Figure 5 is a cycle performance diagram of Example 7 and Comparative Example 1, wherein Li 6 PS 5 Cl@P(VDF-TrFe) corresponds to Example 7, and Li 6 PS 5 Cl corresponds to Comparative Example 1;
  • Fig. 6 is a comparison diagram of NMR spectra of Li 6 PS 5 Cl@PVDF solid electrolyte membrane and PVDF membrane in Example 6;
  • Fig. 7 is a comparison chart of the nuclear magnetic resonance spectra of the Li 6 PS 5 Cl@P(VDF-TrFE) solid electrolyte membrane and the P(VDF-TrFE) membrane in Example 1.
  • this embodiment provides a sulfide solid electrolyte membrane, the sulfide solid electrolyte membrane includes a polymer film having a three-dimensional skeleton structure and a sulfide solid electrolyte material forming a continuous phase; the sulfide solid electrolyte membrane
  • the ionic conductivity is >10 -4 S/cm, and the thickness of the sulfide solid electrolyte membrane is ⁇ 40 ⁇ m.
  • the flexible polymer membrane is used as a skeleton support, and the sulfide forms a continuous phase in the polymer membrane, which ensures the ionic conductivity of the sulfide solid electrolyte membrane and greatly reduces the thickness of the solid electrolyte membrane.
  • the molecular structure of the polymer film is P(VDF-B), and B is selected from any one or a combination of at least two of trifluoroethylene, hexafluoropropylene or methyl methacrylate,
  • the mass fraction of structural units based on VDF monomer in the polymer film is ⁇ 50%
  • the mass fraction of structural units based on B monomer in the polymer film is ⁇ 50%.
  • the molecular structure of the polymer film is P(VDF-B-A), and B is selected from any one or a combination of at least two of trifluoroethylene, hexafluoropropylene or methyl methacrylate, A is selected from any one or a combination of at least two of chlorotrifluoroethylene, 1,1-chlorofluoroethylene or difluorochloroethylene, and the mass fraction of structural units based on VDF monomer in the polymer film is ⁇ 50% , the mass fraction of structural units based on monomer A in the polymer film is ⁇ 20%, the mass fraction of structural units based on monomer A in the polymer film is the same as the mass fraction of structural units based on monomer B in the polymer film The sum of the scores ⁇ 50%.
  • the molecular structure of the polymer film is P(VDF-TrFE), and the mass fraction of structural units based on TrFE monomers in the polymer film is ⁇ 50%.
  • the ionic conductivity is mainly provided by the sulfide solid electrolyte in the continuous phase. Therefore, as an implementation mode, the examples of the present application have no special requirements on the molar ratio of each monomer in the raw materials for polymer membrane preparation.
  • the present application has no special requirements on the molecular weight of the polymer, as long as the polymer can form a film normally and form a three-dimensional skeleton.
  • the polymer membrane is an internal three-dimensional interconnected structure.
  • the maximum mesh pore size of the polymer membrane is 30 ⁇ m.
  • the mesh pore size D50 of the polymer membrane is 10 ⁇ m to 18 ⁇ m, more preferably the mesh pore size D90 of the polymer membrane is 10 ⁇ m to 18 ⁇ m.
  • the preparation method of the polymer film there is no special requirement for the preparation method of the polymer film, only a polymer skeleton forming a three-dimensional network structure is required.
  • the polymer skeleton needs to be able to accommodate sulfide solid electrolyte particles, so that the sulfide solid electrolyte particles A continuous phase is formed in the three-dimensional network structure to provide lithium-conducting pathways.
  • the mesh pores of the polymer film have no orientation.
  • the polymer membrane is prepared by electrospinning.
  • the polymer membrane is prepared by electrospinning, and the three-dimensional skeleton structure is formed through the fibers, and the mesh holes are not oriented. Make good use of the advantages of improving the ionic conductivity of the sulfide solid electrolyte membrane.
  • the embodiment of the present application does not specifically limit the type of sulfide solid-state electrolytes. All sulfide solid-state electrolytes known in the related art can be used in this application.
  • Li 2 SP 2 S 5 Li 2 SP 2 S 5 -MS x , Li 3.4 Si 0.4 P 0.6 S 4 , Li 10 GeP 2 S 11.7 O 0.3 , Li 9.6 P 3 S 12 , Li 7 P 3 S 11 , Li 9 P 3 S 9 O 3 , Li 10.35 Si 1.35 P 1.65 S 12 , Li 9.81 Sn 0.81 P 2.19 S 12 , Li 10 (Si 0.5 Ge 0.5 )P 2 S 12 , Li(Ge 0.5 Sn 0.5 ) P 2 S 12 , Li(Si 0.5 Sn 0.5 )PsS 12 , Li 10 GeP 2 S 12 , Li 6 PS 5 X, Li 7 P 2 S 8 I, Li 10.35 Ge 1.35 P 1.65 S 12 , Li 3.25 Ge 0.25 P Any one or a combination of at least two of 0.75 S 4 , Li 10 SnP 2 S 12 , Li 10 SiP 2 S 12 or Li 9.54 Si 1.74 P 1.44 S 11.7 C 10.3
  • the sulfide solid electrolyte material forms a continuous phase in the polymer membrane by making a solution and pouring it onto the polymer membrane.
  • the particle size of the sulfide solid electrolyte material is smaller than the maximum mesh pore size of the polymer membrane. Further preferably, the particle size of the sulfide solid electrolyte particles is 50% to 70% of the maximum mesh pore size of the polymer membrane, most preferably 60%.
  • the mesh pore size of an appropriate size is conducive to the formation of a continuous phase by the sulfide solid electrolyte particles being made into a solution to perfuse the polymer membrane; if the mesh pore size is too small, the sulfide solid electrolyte cannot be completely poured into the polymer, which affects the final phase. Ionic conductivity of shaped sulfide solid electrolyte membranes.
  • the sulfide solid electrolyte membrane includes a lithium salt, which can effectively improve the ion conductivity of the sulfide solid electrolyte membrane.
  • lithium salts include inorganic lithium salts, organic lithium salts or mixtures of inorganic lithium salts and organic lithium salts
  • inorganic lithium salts include but not limited to lithium perchlorate (LiClO 4 ), lithium tetrafluoroborate (LiBF 4 ), hexa Any one or a combination of at least two of lithium fluoroarsenate (LiAsF 6 ) or lithium hexafluorophosphate (LiPF 6 );
  • organic lithium salts include but are not limited to lithium bisoxalate borate (LiBOB), lithium difluorooxalate borate (LIFOB), Lithium bisfluorosulfonyl imide (LiFSI), lithium bistrifluoromethylsulfonyl imide (MSDS), lithium trifluoromethanesulf
  • the mass ratio of the lithium salt to the polymer in the polymer film is 0%-30% and does not contain 0%, more preferably 5%-20%, particularly preferably 5%-15%.
  • the sulfide solid electrolyte membrane finally prepared according to the embodiment of the present application has an ionic conductivity of 10 -4 S/cm and a thickness of less than 40 ⁇ m. For the first time, a relatively complete sulfide solid electrolyte membrane with high ionic conductivity and thin thickness has been produced.
  • the embodiment of the present application further provides a method for preparing the above-mentioned sulfide solid electrolyte membrane, including:
  • step S2 pouring a solution containing sulfide solid electrolyte particles onto the polymer film obtained in step S1;
  • the ionic conductivity of the sulfide solid electrolyte membrane is >10 -4 S/cm, and the thickness of the sulfide solid electrolyte membrane is ⁇ 40 ⁇ m;
  • the maximum mesh pore size of the prepared polymer membrane is larger than the particle size of the sulfide solid electrolyte particles in the step S2.
  • the polymer film is a PVDF film.
  • the molecular structure of the polymer film is P(VDF-B), and B is selected from any one or at least two of trifluoroethylene, hexafluoropropylene or methyl methacrylate.
  • the molecular structure of the polymer film is P(VDF-B-A), and B is selected from any one or at least two of trifluoroethylene, hexafluoropropylene or methyl methacrylate.
  • A is selected from any one or a combination of at least two of chlorotrifluoroethylene, 1,1-chlorofluoroethylene or difluorochloroethylene, and the mass fraction of structural units based on VDF monomer in the polymer film is ⁇ 50%, the mass fraction of structural units based on monomer A in the polymer film is ⁇ 20%, the mass fraction of structural units based on monomer A in the polymer film is the same as the structural unit based on monomer B in the polymer film The sum of the mass fractions is ⁇ 50%.
  • step S1 the polymer film is an internal three-dimensional interconnected structure.
  • step S1 the maximum mesh pore size of the polymer membrane is 30 ⁇ m.
  • the mesh pore diameter D50 of the polymer membrane is 10 ⁇ m ⁇ 18 ⁇ m, more preferably the mesh pore diameter D90 of the polymer membrane is 10 ⁇ m ⁇ 18 ⁇ m.
  • step S1 a polymer film is prepared by electrospinning.
  • the preparation method of electrospinning is not particularly limited.
  • polymer particles can be dissolved in a solvent to obtain a polymer precursor solution, and then electrospinning is performed under the action of an electric field. filaments to prepare corresponding polymer electrospun membranes.
  • the polymer in the polymer precursor solution is P(VDF-TrFE).
  • the solvent in the polymer precursor solution is not particularly limited, as long as the polymer particles can be uniformly dissolved.
  • it can be N,N-dimethylamide, acetone, Ethanol or, ethylene glycol monomethyl ether, etc.
  • the concentration of the precursor solution prepared during electrospinning, the time and speed of electrospinning will affect the thickness of the spinning membrane.
  • the embodiment of the present application has no special limitation on the process parameters of the electrospinning, as long as the corresponding spinning membrane is prepared.
  • the electric field strength should be greater than the critical electric field strength of electrospinning.
  • the electric field strength is 0.5kV/cm-2kV/cm, preferably 1kV /cm ⁇ 1.6kV/cm.
  • a lithium salt is added during the preparation of the polymer film in step S1, the lithium salt is mixed with the polymer in the step S1 to prepare a precursor solution, and electrospinning is used to prepare the polymer film.
  • the premixing of lithium salt and polymer before film formation is beneficial to the uniformity of mixing and improving the interaction between the two.
  • the type of lithium salt added to the precursor solution is not particularly limited, and any known lithium salt can be used in the present application without departing from the concept of the application.
  • Known lithium salts include inorganic lithium salts, organic lithium salts or mixtures of inorganic lithium salts and organic lithium salts, inorganic lithium salts include but not limited to lithium perchlorate (LiClO 4 ), lithium tetrafluoroborate (LiBF 4 ), hexa Any one or a combination of at least two of lithium fluoroarsenate (LiAsF 6 ) or lithium hexafluorophosphate (LiPF 6 ); organic lithium salts include but are not limited to lithium bisoxalate borate (LiBOB), lithium difluorooxalate borate (LIFOB), Lithium bisfluorosulfonyl imide (LiFSI), lithium bistrifluoromethylsulfonyl imide (MSDS), lithium trifluoromethanes
  • the lithium salt in the precursor solution accounts for 0%-30% by mass of the polymer in the polymer film and does not contain 0%, such as 0.5%, 1%, 2%, 2.5% , 3%, 4%, 5%, 5.5%, 6%, 8%, 9%, 10%, 12%, 15%, 17%, 20%, 22%, 25%, 27% or 30%, etc., More preferably, it is 5%-20%, Especially preferably, it is 5%-15%.
  • the amount of the lithium salt used is within an appropriate range.
  • Orientation means that in the polymer film, the polymer spinning is arranged in a fixed direction to form a regular grid hole arrangement.
  • step S1 the mesh pores of the polymer film have no orientation.
  • the particle size of the sulfide solid electrolyte particles is 50% to 70% of the maximum pore size of the polymer membrane, most preferably 60%.
  • sulfide solid electrolyte particles in step S2 there is no particular limitation on the type of sulfide solid electrolyte particles in step S2.
  • All sulfide solid electrolytes known in the related art can be used in this application, including but not limited to Li 2 SP 2 S 5 , Li 2 SP 2 S 5 -MS x , Li 3.4 Si 0.4 P 0.6 S 4 , Li 10 GeP 2 S 11.7 O 0.3 , Li 9.6 P 3 S 12 , Li 7 P 3 S 11 , Li 9 P 3 S 9 O 3 , Li 10.35 Si 1.35 P 1.65 S 12 , Li 9.81 Sn 0.81 P 2.19 S 12 , Li 10 (Si 0.5 Ge 0.5 )P 2 S 12 , Li(Ge 0.5 Sn 0.5 )P 2 S 12 , Li(Si 0.5 Sn 0.5 )PsS 12 , Li 10 GeP 2 S 12 , Li 6 PS 5 X, Li 7 P 2 S 8 I, Li 10.35 Ge 1.35 P
  • step S2 it also includes putting the sulfide solid electrolyte particles into the solvent and dispersing to form a homogeneous solution.
  • Solvents capable of uniformly dispersing sulfide solid electrolyte particles are known, including but not limited to benzene, toluene, xylene, pentane, hexane, octane, cyclohexane, cyclohexanone, chlorobenzene, dichlorobenzene, Any one or a combination of at least two of methanol, ethanol, isopropanol or ether.
  • the dispersion method there is no particular limitation on the dispersion method, and a mechanical dispersion method, such as mechanical stirring, can be used, as long as the sulfide electrolyte particles are formed into a homogeneous solution in a solvent.
  • step S2 a step of thickness control is also included.
  • the thickness control refers to controlling the thickness of the polymer film perfused with the sulfide solid electrolyte within a specific thickness range, for example, within 40 ⁇ m.
  • the method of thickness control in the embodiment of the present application is not particularly limited.
  • scraping can be performed by using a scraper with a thickness adjustment knob.
  • step S3 the purpose of drying is to remove excess solvent, and the drying method is known, for example, the electrolyte membrane obtained by perfusion is dried in a constant temperature dryer.
  • drying temperature and drying time for example, drying may be performed at 100° C. to 150° C. for 1 h to 10 h.
  • this embodiment provides a solid-state lithium-ion battery, which includes a positive electrode, a negative electrode, and the sulfide solid-state electrolyte membrane prepared in the above-mentioned embodiment.
  • the negative electrode is formed of a lithium host material that can be used as a negative terminal of a lithium ion battery.
  • the negative electrode may comprise a lithium host material capable of serving as the negative terminal of the battery.
  • the negative electrode can be defined by a variety of negative active material particles, and such negative active material particles can be disposed in one or more layers so as to define the three-dimensional structure of the negative electrode.
  • the negative electrode can also include an electrolyte material, the type of electrolyte material is known in the art, and can be any one of an oxide solid electrolyte, a sulfide solid electrolyte, a halide solid electrolyte or a polymer solid electrolyte. one or a combination of at least two.
  • the negative electrode may include a lithium-based negative electrode active material including, for example, lithium metal and/or a lithium alloy.
  • the anode is a silicon-based anode active material comprising silicon, such as a silicon alloy and/or silicon oxide.
  • the silicon-based negative active material may also be mixed with graphite.
  • the negative electrode may include a carbonaceous-based negative electrode active material including any one or a combination of at least two of graphite, graphene, or carbon nanotubes (CNTs).
  • a carbonaceous-based negative electrode active material including any one or a combination of at least two of graphite, graphene, or carbon nanotubes (CNTs).
  • the negative electrode includes one or more negative electrode active materials that accept lithium, such as lithium titanium oxide (Li 4 Ti 5 O 12 ), transition metals (such as Sn), metal oxides (such as V 2 O 5 ), tin oxide (SnO), titanium dioxide (TiO 2 ), titanium niobium oxide (Ti x Nb y O z , where 0 ⁇ x ⁇ 2, 0 ⁇ y ⁇ 24, 0 ⁇ z ⁇ 64), metal alloy ( For example, any one or a combination of at least two of copper-tin alloys (Cu 6 Sn 5 )) or metal sulfides (such as iron sulfide (FeS)).
  • lithium titanium oxide Li 4 Ti 5 O 12
  • transition metals such as Sn
  • metal oxides such as V 2 O 5
  • TiO 2 titanium dioxide
  • Ti niobium oxide Ti x Nb y O z , where 0 ⁇ x ⁇ 2, 0 ⁇ y ⁇ 24, 0 ⁇ z ⁇ 64
  • the negative active material in the negative electrode can be doped with one or more conductive materials that provide electron conduction paths and/or at least one polymeric binder material that improves the structural integrity of the negative electrode.
  • the negative electrode active material can be doped with conductive materials such as: any one or a combination of at least two of carbon-based materials, powdered nickel, other metal particles or conductive polymers.
  • the carbon-based material may include, for example, at least one particle of carbon black, graphite, superP, acetylene black (such as KETCHENTM black or DENKATM black), carbon fiber, carbon nanotube, or graphene.
  • the conductive polymer may include at least one of polyaniline, polythiophene, polyacetylene, polypyrrole, poly(3,4-ethylenedioxythiophene) polysulfonylstyrene, and the like.
  • the negative active material can be doped with binders such as: poly(tetrafluoroethylene) (PTFE), sodium carboxymethylcellulose (CMC), styrene-butadiene rubber (SBR), polyvinylidene Vinyl fluoride (PVDF), nitrile rubber (NBR), styrene ethylene butylene styrene copolymer (SEBS), styrene butadiene styrene copolymer (SBS), lithium polyacrylate (LiPAA), sodium polyacrylate ( NaPAA), sodium alginate, lithium alginate, and combinations thereof.
  • binders such as: poly(tetrafluoroethylene) (PTFE), sodium carboxymethylcellulose (CMC), styrene-butadiene rubber (SBR), polyvinylidene Vinyl fluoride (PVDF), nitrile rubber (NBR), styrene ethylene butylene styrene copolymer (SE
  • the negative electrode may include 50% to 97% of negative electrode active materials, optional 0% to 60% of solid electrolytes, optional 0% to 15% of conductive materials, and optional 0% to 10% binder. It should be noted that “optional” means that the corresponding substance may or may not be included, and when the content is 0%, it means that the corresponding substance is not included.
  • the positive electrode includes a positive electrode electroactive material layer, and the positive electrode electroactive material layer includes a lithium-based positive electrode electroactive material.
  • the positive electrode electroactive material layer has a thickness of 1 ⁇ m ⁇ 1000 ⁇ m.
  • the positive electrode electroactive material layer is formed by a plurality of positive electrode active particles containing one or more transition metal cations, such as manganese (Mn), nickel (Ni), cobalt (Co), Any one or a combination of at least two of chromium (Cr), iron (Fe) or vanadium (V).
  • transition metal cations such as manganese (Mn), nickel (Ni), cobalt (Co), Any one or a combination of at least two of chromium (Cr), iron (Fe) or vanadium (V).
  • the positive electroactive material layer is one of a layered oxide cathode, a spinel cathode, an olivine cathode or a polyanion cathode.
  • the layered oxide cathode (eg, rock salt layered oxide cathode) comprises one or more lithium-based positive electrode electroactive materials selected from the group consisting of: LiCoO 2 (LCO), LiNi a Mn b Co 1 -ab O 2 (where 0 ⁇ a ⁇ 1, 0 ⁇ b ⁇ 1), LiNi 1-cd Co c Al d O 2 (where 0 ⁇ c ⁇ 1 and 0 ⁇ d ⁇ 1), LiNi e Mn 1-e Any one of O 2 (where 0 ⁇ e ⁇ 1) or Li 1+f MO 2 (where M is any one or a combination of at least two of Mn, Ni, Co or Al, 0 ⁇ f ⁇ 1) one or a combination of at least two.
  • LiCoO 2 LiCoO 2
  • LiNi a Mn b Co 1 -ab O 2 where 0 ⁇ a ⁇ 1, 0 ⁇ b ⁇ 1
  • LiNi 1-cd Co c Al d O 2 where 0 ⁇ c ⁇ 1 and 0 ⁇ d ⁇ 1
  • the spinel cathode comprises one or more lithium-based positive electrode electroactive materials selected from LiMn 2 O 4 (LMO) and LiNi 0.5 Mn 1.5 O 4 .
  • the olivine-type cathode comprises one or more lithium-based positive electrode electroactive materials LiMPO 4 (where M is at least one of Fe, Ni, Co, and Mn).
  • the polyanionic cathode comprises one or more lithium-based positive electrode electroactive materials: phosphates and/or silicates, phosphates such as LiV2 ( PO4 ) 3 , silicates such as LiFeSiO4 .
  • the positive electroactive material layer further includes an electrolyte, such as a plurality of electrolyte particles.
  • one or more lithium-based positive electrode electroactive materials can optionally be coated and/or can be doped.
  • one or more lithium-based cathode electroactive materials are coated by LiNbO 3 and/or Al 2 O 3 .
  • one or more lithium-based positive electrode electroactive materials are doped with magnesium (Mg).
  • one or more lithium-based positive electrode electroactive materials can optionally be mixed with one or more conductive materials that provide electron conduction paths and/or at least one polymeric material that improves the structural integrity of the positive electrode. adhesive material.
  • the positive electrode electroactive material layer may comprise 30% to 98% of one or more lithium-based positive electrode electroactive materials, 0% to 30% of a conductive material and 0% to 20% of a binder , in some embodiments, comprising 1% to 20% of binder.
  • the lithium-based positive electrode electroactive material can optionally be mixed with the following binders: polytetrafluoroethylene (PTFE), sodium carboxymethylcellulose (CMC), styrene-butadiene rubber (SBR), polyvinylidene fluoride (PVDF), nitrile rubber (NBR), styrene-ethylene-butylene-styrene copolymer (SEBS), styrene-butadiene-styrene copolymer (SBS) , lithium polyacrylate (LiPAA), sodium polyacrylate (NaPAA), sodium alginate or lithium alginate, or any one or a combination of at least two.
  • binders polytetrafluoroethylene (PTFE), sodium carboxymethylcellulose (CMC), styrene-butadiene rubber (SBR), polyvinylidene fluoride (PVDF), nitrile rubber (NBR), styrene-ethylene-butylene-
  • the lithium-based positive electrode electroactive material can optionally be mixed with a conductive material that can include any one of carbon-based materials, powdered nickel, other metal particles, or conductive polymers or at least A combination of the two.
  • the carbon-based material may include, for example, any one or a combination of at least two of carbon black, graphite, acetylene black (such as KETCHENTM black or DENKATM black), carbon fibers, carbon nanotubes, or graphene.
  • the conductive polymer may include, for example, any one or a combination of at least two of polyaniline, polythiophene, polyacetylene or polypyrrole.
  • the positive current collector facilitates the flow of electrons between the positive electrode and the external circuit.
  • the positive current collector may comprise metal such as metal foil, metal grid or metal mesh.
  • the positive electrode current collector may be formed of any one or at least two of aluminum, stainless steel, nickel, or any other suitable conductive material known to those skilled in the art.
  • Li 2 S (purity 99.9%), P 2 S 5 (purity 99%), LiCl (purity 99.9%) powders were weighed according to mass ratio 5:1:2 and mixed in planetary ball mill, mixing speed 100rpm, mixing time 1h. Subsequently, the mixture was calcined in a crucible at 400 °C for 10 h, and then slowly cooled to room temperature.
  • the calcined Li 6 PS 5 Cl powder was passed through a 400-mesh sieve to obtain electrolyte powder particles with uniform particle size.
  • the P(VDF-TrFE) precursor solution was electrospun under the conditions of an electric field strength of 1kV/cm and a flow rate of 1mL/h to prepare a P(VDF-TrFE) electrospun membrane.
  • the SEM image is shown in Figure 2A.
  • the mesh pore size D50 of P(VDF-TrFE) electrospun membrane is 10 ⁇ m ⁇ 18 ⁇ m;
  • the Li 6 PS 5 Cl particles obtained in Step 1 were dissolved in toluene (purity 99.9%), and mechanically stirred at 30° C. for 1 h to obtain a homogeneous Li 6 PS 5 Cl solution.
  • the sulfide solid electrolyte membrane obtained by perfusion was dried in a constant temperature dryer at 120°C for 2 hours to remove excess solvent, and two composite solid electrolyte membranes were obtained. Then, the two composite solid electrolytes were stacked and hot-pressed at 200 °C and 10 MPa for 2 h. All operations are carried out in an argon atmosphere to obtain a sulfide solid electrolyte membrane.
  • the finally obtained sulfide solid electrolyte membrane had a thickness of 37 ⁇ m and an ion conductivity of 1.2 mS cm ⁇ 1 .
  • FIG. 1 is a physical diagram of the sulfide solid electrolyte membrane prepared in Example 1.
  • FIG. 2A is an SEM image of the P(VDF-TrFE) electrospun membrane prepared in Example 1.
  • FIG. 4 is an SEM image of the solid electrolyte membrane prepared in Example 1.
  • FIG. 7 is the NMR spectrum of the Li 6 PS 5 Cl@P(VDF-TrFE) solid electrolyte membrane in Example 1.
  • the quality of P(VDF-TrFE) polymer particles is 0.6g
  • Fig. 2B is the prepared P( VDF-TrFE) electrospun membrane SEM figure
  • the grid aperture D50 of the obtained P (VDF-TrFE) electrospun membrane is 1 ⁇ m ⁇ 5 ⁇ m, other is the same as embodiment 1.
  • the finally obtained sulfide solid electrolyte membrane had a thickness of 37 ⁇ m and an ion conductivity of 1.01 ⁇ 10 ⁇ 4 S/cm.
  • the quality of P(VDF-TrFE) polymer particles is 0.8g
  • Fig. 2C shows the prepared P( VDF-TrFE) SEM image of the electrospun membrane
  • the grid aperture D50 of the obtained P (VDF-TrFE) electrospun membrane is 5 ⁇ m ⁇ 10 ⁇ m, and the others are the same as in Example 1.
  • the finally obtained sulfide solid electrolyte membrane had a thickness of 37 ⁇ m and an ion conductivity of 5.3 ⁇ 10 ⁇ 4 S/cm.
  • FIG. 3A is an SEM image of the P(VDF-TrFE) electrospun membrane prepared in Example 4.
  • FIG. 3A is an SEM image of the P(VDF-TrFE) electrospun membrane prepared in Example 4.
  • the finally obtained P(VDF-TrFE) electrospun membrane has a certain orientation, and the perfusion of the oriented electrospun membrane is difficult.
  • FIG. 3B is an SEM image of the P(VDF-TrFE) electrospun membrane prepared in Example 5.
  • the finally obtained P(VDF-TrFE) electrospun membrane has improved orientation, that is, weakened orientation, and reduced perfusion difficulty.
  • Example 1 The same electrospinning process as in Example 1 was used to prepare a PVDF membrane, and the others were the same as in Example 1.
  • Li 6 PS 5 Cl@PVDF solid electrolyte membrane has a thickness of 37 ⁇ m and an ion conductivity of 5 ⁇ 10 -4 S/cm.
  • Fig. 6 is a comparison diagram of NMR spectra of Li 6 PS 5 Cl@PVDF solid electrolyte membrane and PVDF membrane in Example 6;
  • This embodiment provides a method for preparing a S@C
  • the multi-walled carbon nanotubes were dissolved in a 1% sodium dodecylbenzenesulfonate solution, and the sulfur was dissolved in tetrahydrofuran to form a protective solution.
  • the protection solution was added to the multi-walled carbon nanotube solution, and vigorously stirred. The suspension was separated and washed several times with distilled water to remove sodium dodecylbenzenesulfonate.
  • the obtained sulfur-carbon nanotube composites were dried to obtain S@C composite particles, wherein the mass ratio of nano-sulfur and multi-walled carbon nanotubes was 6:4.
  • the synthesized S@C composite particles and Li 6 PS 5 Cl were stirred in a ball mill at a stirring speed of 300 rpm for 1 h at a mass ratio of 4:6, and the obtained product was prepared to form a positive electrode.
  • This embodiment provides a Li 6 PS 5 Cl@C
  • Li 6 PS 5 Cl and multi-walled carbon nanotubes were mixed at a mass ratio of 7:3 and ball milled in a ball mill at a speed of 100 rpm for one hour, and the obtained product was prepared to form a positive electrode.
  • This embodiment provides a method for preparing an NCM@LNO
  • NCM811 particles were heated at 90°C for twelve hours before use, LiOC 2 H 5 and Nb(OC 2 H5) 5 were dissolved in absolute ethanol, then NCM811 was added to the above solution and stirred for 3 h. The slurry was dried at 150 °C for 12 h, and heated at 400 °C for 1 h in an oxygen atmosphere to form LNO-coated NCM particles, and the obtained product was prepared to form a positive electrode.
  • Li 2 S was used as the positive electrode active material, and the others were the same as in Example 7.
  • Adopt FeS 2 as positive electrode active material others are identical with embodiment 7.
  • Example 7 Compared with Example 7, the difference is that the P(VDF-TrFE) sulfide solid electrolyte membrane is replaced by a pure Li 6 PS 5 Cl sulfide solid electrolyte membrane.
  • the mesh pore size of the polymer membrane is too small, it is limited by the particle size of the sulfide solid electrolyte particles, which makes the infusion effect unsatisfactory, and it is difficult for larger sulfide particles to be completely poured into the spinning net, which makes the implementation
  • the ionic conductivity of the sulfide solid electrolyte membrane prepared in Example 2-3 is low, and the ionic conductivity is significantly improved when the mesh pore size of the polymer membrane reaches 10 ⁇ m or more.
  • the thickness of the sulfide solid electrolyte membrane prepared in Example 1 reaches 37 ⁇ m, and the surface of the sulfide solid electrolyte membrane is evenly distributed, and the particles are evenly poured into the polymer membrane, and the particles cover the polymer membrane. whole.
  • Figure 6 is a comparison of the NMR spectra of the Li 6 PS 5 Cl@PVDF solid electrolyte membrane and the PVDF membrane in Example 6
  • Figure 7 is the Li 6 PS 5 Cl@P(VDF-TrFE) solid electrolyte membrane and the PVDF membrane in Example 1
  • the NMR spectrum comparison chart of P(VDF-TrFE) membrane comparing Figure 6 and Figure 7, it can be seen that the solid electrolyte membrane formed by pure PVDF and sulfide solid electrolyte is the same as the NMR spectrum of pure PVDF, which proves that pure PVDF and There is no interaction between the sulfide solid electrolytes; and the solid electrolyte membrane formed by P(VDF-TrFE) and sulfide solid electrolytes has a different peak shape than pure P(VDF-TrFE), which shows that the sulfide solid state
  • the electrolyte membrane has a strong interaction with P(VDF-TrFE), not purely physical mixing.
  • FIG. 5 is a cycle performance diagram of Example 7 and Comparative Example 1, wherein Li 6 PS 5 Cl@P(VDF-TrFe) corresponds to Example 7, Li 6 PS 5 Cl corresponds to Comparative Example 1, from Figure 5 and Example 7 Compared with Comparative Example 1, it can be seen that the capacity of the battery using the pure Li 6 PS 5 Cl sulfide solid electrolyte membrane declines faster, which is due to the fact that the too thick sulfide solid electrolyte membrane prolongs the ion conduction path, making the interface problem of the battery in the It's even worse during charging and discharging.
  • the present application illustrates the detailed method of the present application through the above-mentioned examples, but the present application is not limited to the above-mentioned detailed method, that is, it does not mean that the application must rely on the above-mentioned detailed method to be implemented.
  • Those skilled in the art should understand that any improvement to the present application, the equivalent replacement of each raw material of the product of the present application, the addition of auxiliary components, the selection of specific methods, etc., all fall within the scope of protection and disclosure of the present application.

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Abstract

La présente invention concerne le domaine des batteries au lithium, et fournit une membrane électrolytique solide au sulfure et une batterie au lithium-ion solide. La membrane électrolytique solide à base de sulfure comprend une membrane polymère ayant une structure d'ossature tridimensionnelle et un matériau d'électrolyte solide à base de sulfure formant une phase continue. La conductivité ionique de la membrane électrolytique solide au sulfure est supérieure à 10 −4S/cm, et l'épaisseur de la membrane électrolytique solide au sulfure est inférieure ou égale à 40 μm. la membrane polymère flexible fait office de cadre de support, et un sulfure forme une phase continue dans la membrane polymère, garantissant ainsi la conductivité ionique de la membrane électrolytique solide au sulfure et réduisant significativement l'épaisseur de la membrane électrolytique solide.
PCT/CN2021/138978 2021-07-22 2021-12-17 Membrane électrolytique solide au sulfure et batterie au lithium-ion solide WO2023000604A1 (fr)

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CN115149092A (zh) * 2022-06-20 2022-10-04 上海屹锂新能源科技有限公司 硫化物固态电解质薄膜制备方法、包含其的全固态电池
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