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EP-4736255-A2 - SPIROBISINDANE COPOLYMERS AND METHODS OF MAKING

EP4736255A2EP 4736255 A2EP4736255 A2EP 4736255A2EP-4736255-A2

Abstract

The invention describes spirobisindane and spirobischromane copolymers of intrinsic microporosity for use in separators in electrochemical cells.

Inventors

  • LYLE, Steven J.
  • GOLDEN, JESSICA H.
  • FRISCHMANN, PETER
  • RANGANATHAN, RANGA

Assignees

  • Sepion Technologies, Inc.

Dates

Publication Date
20260506
Application Date
20240627

Claims (20)

  1. 1. A copolymer comprising a plurality of repeat units A and B, wherein A and B are each independently a repeat unit having a structure of Formula I: or a structure of Formula II: wherein A and B are each different; R la and R lb are each independently hydrogen, Ci-6 alkyl, halogen, Ci-6 haloalkyl, - CH 2 R 1C orNR lal R lbl ; each R lal and R lbl are independently hydrogen, Ci-6 alkyl, C2-6 alkenyl, C2-6 alkynyl, C1-6 hydroxyalkyl, C2-6 alkoxyalkyl, C1-6 alkyl-NR la2 R lb2 , C3-10 cycloalkyd, or C1-6 alkj I-C3-10 cycloalkyl; each R la2 and R lb2 is independently hydrogen or C 1-6 alkyl; each R lc is independently NR lal R lbl , a 5-10 membered heterocycloalkyl having 1-4 heteroatoms each independently N, O or S, or a 5-10 membered heteroar l having 1-4 heteroatoms each independently N, O or S, wherein the heterocycloalky l and heteroaryl are each independently substituted with 0, 1, 2. 3, 4 or 5 R ld groups; each R ld is independently Ci-6 alkyl, C2-6 alkenyl, C2-6 alkynyl, Ci-6 hydroxy alkyl, C 2 .6 alkoxyalkyl, halogen, Ci-6 haloalky l, -OH, =0, =NH, -CN, -NO 2 , -C(O)H, - C(O)R le , -C(O)OR le , -S(O) 2 R le , -Ci-6 alkyl-(SO 3 ), -OP(=O)(OR le ) 2 , a 3-10 membered heterocycloalkyl having 1-4 heteroatoms each independently N, O or S, or a 3-10 membered heteroaryl having 1-4 heteroatoms each independently N, O or S; R le is Ci-6 alkyl or Ci-6 hydroxy alkyl: R 2a and R 2b are each independently hydrogen, Ci-6 alkyl, halogen, Ci-6 haloalkyl, - CH 2 R 2C or NR 2al R 2bl ; each R 2al and R 2bl are independently hydrogen, Ci-6 alkyl, C2-6 alkenyl, C2-6 alkynyl, C1-6 hydroxyalkyl, C2-6 alkoxyalkyl, C1-6 alkyl-NR 2a2 R 2b2 . C3-10 cycloalkyl, or C1-6 alkyl-Cs io cycloalkyl; each R 2a2 and R 2b2 is independently hydrogen or C 1-6 alkyl; each R 2C is independently NR 2a1 R 2bl , a 5-10 membered heterocycloalkyl having 1-4 heteroatoms each independently N, O or S, or a 5-10 membered heteroaryl having 1-4 heteroatoms each independently N, O or S, wherein the heterocycloalkyl and heteroaryl are each independently substituted with 0, 1, 2, 3, 4 or 5 R 2d groups; each R 2d is independently C1-6 alkyl, C2-6 alkenyl, C2-6 alkynyl, C1-6 hydroxy alkyl, C2-6 alkoxyalkyl, halogen, C1-6 haloalkyl, -OH, =0, =NH, -CN, -NO2, -C(O)H, - C(O)R 2e , -C(O)OR 2e , -S(O) 2 R 2e , -C1-6 alkyl-(SO 3 ), -OP(=O)(OR 2e ) 2 , a 3-10 membered heterocycloalkyl having 1-4 heteroatoms each independently N, O or S, or a 3-10 membered heteroaryl having 1-4 heteroatoms each independently N. O or S; R 2e is C1-6 alkyl or C1-6 hydroxy alkyl; X is -N= or C(R 3b )=; each R 3a and R 3b is independently hydrogen, C1-6 alkyl, halogen, Ci-6 haloalkyl, -CN, or -S(O) 2 R 3c ; and each R 3C is independently Ci-6 alkyl, C1-6 haloalkyl, or C6-12 aryl, wherein each aryl is independently substituted with 0, 1, 2, 3, 4 or 5 groups each independently Ci- 6 alkyl or Ci-6 haloalkyl.
  2. 2. The copolymer of claim 1, wherein the copolymer is a random copolymer.
  3. 3. The copolymer of claim 1 or 2. having the structure of Formula J: [A] x -[B] y -[C]zi-[D] z2 -[E] Z 3-[F] z4 (J) wherein: repeat units A, B, C, D, E and F are each independently the structure of Formula I or the structure of Formula II. wherein A. B, C. D, E and F are each different; subscript x and y are each independently an integer from 1 to 1000; and each subscript zl, z2, z3 and z4 is independently an integer from 0 to 1000.
  4. 4. The copolymer of claim 3, wherein A, B. C, D, E and F are each independently a repeat unit having the structure of Formula I.
  5. 5. The copolymer of claim 3 or 4, having the structure of Formula J- 1 : [A] x -[B] y -[C]zi (J-l) wherein A, B and C are each different; subscript x and y are each independently an integer from 1 to 1000; and subscript zl is independently an integer from 0 to 1000.
  6. 6. The copolymer of any one of claims 3 to 5, having the structure of Formula J-2: [A] x -[B] y (J-2) wherein A and B are each different; and subscript x and y are each independently an integer from 1 to 1000.
  7. 7. The copolymer of claim 1 or 6, wherein A is a repeat unit having the structure of Formula la:
  8. 8. The copolymer of claim 1 or 6, wherein each repeat unit of Formula I independently has the structure of Formula la:
  9. 9. The copolymer of any one of claims 1 to 8, wherein each R lc is independently NR lal R lbl , or a 5- or 6- membered heterocycloalkyl having 1 or 2 heteroatoms each independently N, O or S, wherein the heterocycloalkyl is independently substituted with 0 or 1 R ld groups.
  10. 10. The copolymer of any one of claims 1 to 9, wherein each R lc is independently a 6- membered heterocycloalkyl having 1 or 2 heteroatoms each independently N, O or S.
  11. 11. The copolymer of any one of claims 1 to 9 , wherein each R lal and R lbl are independently C1-3 alkyl or C2-4 alkenyl.
  12. 12. The copolymer of claim 1 or 9, wherein each R ld is independently - S(O) 2 — C1-3 alkyl.
  13. 13. The copolymer of any one of claims 1 to 12, wherein R 2a and R 2b are each hydrogen.
  14. 14. The copolymer of any one of claims 1 to 13, wherein R 3a is -CN.
  15. 15. The copolymer of any one of claims 1 to 14, wherein X is -C(R 3b )=.
  16. 16. The copolymer of any one of claims 1 to 15, wherein R ?b is -CN.
  17. 17. The copolymer of any one of claims 1 to 16, wherein A is PIM-13 having the structure: PIM-13S having the structure:
  18. 18. The copolymer of any one of claims 1 to 17, wherein B is PIM-1 :
  19. 19. The copolymer of any one of claims 1 to 17, wherein B is SBC:
  20. 20. The copolymer of any one of claims 1 to 17, wherein B is PIM-MAA:

Description

SPIROBISIND ANE COPOLYMERS AND METHODS OF MAKING CROSS-REFERENCES TO RELATED APPLICATIONS [0001] This application claims priority to U.S. Provisional Application No. 63/510,978, filed June 29, 2023, which is incorporated herein in its entirety for all purposes. BACKGROUND OF THE INVENTION [0002] Over the past decades, lithium-ion batteries (Li-ion batteries) have developed as the dominant high-energy chemistry due to their uniquely high energy density7 while maintaining high power and cyclability at acceptable prices. The energy density of current commercial Li- ion battery chemistries is however approaching the technology’s theoretical limit, whereas demand for higher energy density batteries at lower unit cost is increasing with the rapid trend towards electrification of the transport and energy7 industries. There is indeed a need for batteries with improved capacity, long cycle life and high stability7. Replacing graphite anodes in Li-ion with lithium metal anodes provides an opportunity to significantly increase the energy density of lithium batteries. However, after repetitive charge-discharge cycles, lithium metal batteries suffer from irreversible capacity loss driven by electrolyte depletion and loss of lithium inventory due to parasitic reactivity between the highly reactive lithium metal anode and the electrolyte components. This process contributes to local non-uniformities in the lithium anode surface, propagating further uneven plating and stripping and resulting in physically isolated “dead” lithium. Further, uneven lithium plating increases the risk of dendrite formation, which can cause thermal runaway resulting in catastrophic cell failure, posing a significant hurdle to the commercialization of lithium metal batteries. Mitigation of dendrite formation in lithium metal batteries is critical to enabling their safe, stable use in commercial applications. [0003] Battery separators are a critical component of Li-ion batteries since they isolate the electrodes, providing ion transport through large pores filled with electrolyte and insulating electronic conductivity that would otherwise induce a short circuit. Whereas separators are not involved directly in cell reactions, their physical properties play an important role in determining the performance of the battery including energy density, power density, and safety'. Importantly, separators’ mechanical integrity7 throughout the entire lifetime of the battery cell is critical for prevention of internal short circuit. [0004] Several porous membrane separator materials and composites are currently utilized in Li-ion batteries, such as separators made of made of polyolefin, for example polyethylene (PE), polypropylene (PP) and polypropylene-polyethylene-polypropylene (PP/PE/PP), as well as ceramic-coated separators, which include PP, PE or multilayer porous substrates with at least one surface coated with a ceramic composite layer. As described in US 6,432,583 (Celgard Inc.), the ceramic composite layer is intended to block dendrite growth and to prevent electronic shorting. Although ceramic coated separators have been successfully utilized in Li-ion batteries to improve mechanical properties, their utility is limited in lithium metal batteries due to parasitic reactions induced at the anode by the binding materials which host the ceramic coatings. [0005] WO 2018/106957 (Sepion Technologies, Inc et al.) describes the application of porous polymers (10-40% porosity, 0.5-2.0 nm pores) as templates that deliver solution- processed precursors of solid-state plus halide containing salts as a conformal coating between the Li-metal surface and the separator surface, in order to increase separator wettability and to increase Li-ion concentration and mobility at the separator-anode interface. The document also describes electrochemical cells including separators comprising several layers: a first polymer layer, comprising a planar species and a linker. The separator may also comprise a porous support made of PP or PE, laminated to the first polymer layer. The separator may also comprise a second membrane layer laminated to the porous support, such second layer comprising a ceramic material. [0006] The use of Polymers of Intrinsic Microporosity7 (PIMs) as a selective battery membrane has been investigated. PIMs are composed of fused rings providing rigidity and sites of contortion, which may be provided by spiro-centers, by bent or bridged ring moieties, or by similar structural components which serve as a barrier preventing conformational relaxation of polymer chains. PIMs have been described and studied since 2006, as they create continuous networks of interconnected voids used as gas separation membranes, hydrogen storage materials, adsorbents and heterogeneous catalysts. The intrinsic microporosity of PIMs is defined as a continuous network of interconnected intermolecular voids, which form as a direct consequence of the shape and rigidity7 of the com