Coating material based on functionalized organic molecules and use thereof in electrochemical applications

Abstract

The present technology relates to a coating material comprising at least one organic compound comprising a branched or linear unsaturated aliphatic group having 6 to 50 carbon atoms and having at least one carbon-carbon double or triple bond, and at least one non-carbon or hydrogen atom, a functional group containing at least one non-carbon or hydrogen atom or a group containing at least one optionally substituted ring or heterocyclic ring. The present technology also relates to coated particles comprising said coating material and to a method for the production thereof, to electrode materials, electrodes, electrolytes, current collector coating materials and current collectors comprising said coated particles, and to their use in electrochemical cells, for example in electrochemical batteries, in particular in all-solid-state batteries.

Description

[0001] Related applications

[0002] This application claims priority to Canadian Patent Application No. 3,208,410, filed August 4, 2023, the contents of which are incorporated herein by reference in their entirety for all purposes, in accordance with applicable law. Technical Field

[0003] This application relates to the field of coatings and their use in electrochemical applications. More specifically, this application relates to coatings for particles of ion-conducting inorganic materials, particles of electrochemically active materials, and particles of electronic conductors, methods for manufacturing them, and their use in electrochemical cells, particularly in all-solid-state battery packs.

[0004] Existing technology

[0005] Compared to their liquid electrolyte-based counterparts, all-solid-state electrochemical systems are significantly safer, lighter, more flexible, and perform better. However, the application range of solid-state electrolytes remains limited.

[0006] In fact, solid polymer electrolytes have problems associated with their limited electrochemical stability, their low mobility number, and their relatively low ionic conductivity at room temperature.

[0007] Ceramic-based solid electrolytes exhibit a wide electrochemical stability window and significantly higher ionic conductivity at room temperature. However, they are accompanied by issues related to their interfacial stability and stability in ambient air and humidity. Some ceramics, such as sulfide-based ceramics, may also react with other components of the battery pack, such as those present in the electrodes, which reduces battery life.

[0008] Furthermore, dispersion problems are frequently encountered in the fabrication of solid electrolytes and electrode materials for all-solid-state electrochemical systems, particularly during the formation of electrodes and composite electrolytes. More specifically, due to the different properties of the components (such as polymers and inorganic particles) in composite materials, solid components may tend to agglomerate within the polymer matrix or electrode binder, which can adversely affect the performance, efficiency, or stability of the system.

[0009] These dispersion problems can also be significantly limited by using adhesives, additives, or dispersion media that result in better particle dispersion.

[0010] Examples of dispersion media present in compositions of solid electrolytes are described in European Patent No. EP 3 467 845. Further examples are also described in International Patent Application WO2022 / 251968.

[0011] The manufacture of ceramic-based solid electrolytes is associated with cracking problems following dry compression processes. One strategy for addressing this issue involves encapsulating ceramic-based solid electrolyte particles with a fundamentally flexible (or elastic) polymer. For example, Korean Patent No. KR 10-2003300 describes a polymer coating comprising an acrylic-based, fluorinated, diene-based, organosilicon-based, or cellulose-based polymer applied to the surface of sulfide-based crystalline electrolyte particles. Besides minimizing the risk of solid electrolyte cracking, the polymer coating allows electrolyte particles to aggregate without reducing their ionic conductivity and is able to absorb volume changes during cycling. While this strategy yields advantageous properties, it does not solve the aforementioned dispersion problem.

[0012] Therefore, there is a need to develop all-solid-state electrochemical systems that do not have one or more of the drawbacks of conventional all-solid-state electrochemical systems. Summary of the Invention

[0013] In some respects, implementations of this technology include the following items: Project 1. A coating material for electrochemical batteries, comprising at least one unsaturated organic compound, said unsaturated organic compound comprising at least one branched or straight-chain unsaturated aliphatic group having 6 to 50 carbon atoms and having at least one carbon-carbon double or triple bond, and at least one atom of non-carbon or hydrogen, a functional group containing at least one atom of non-carbon or hydrogen, or a group containing at least one optionally substituted ring or heterocycle.

[0014] Project 2. The coating material according to Project 1, wherein the unsaturated organic compound has Formula I, or a salt of an unsaturated organic compound of Formula I: (R 1 ) n (X 1 ) m Formula I in: R 1 Each time it appears, it is independently an unsaturated branched or straight-chain aliphatic group having 6 to 50 carbon atoms; X 1 A group selected from halogen atoms, oxygen atoms, sulfur atoms, containing at least one atom selected from halogen, oxygen, sulfur, nitrogen, silicon, and phosphorus atoms, or containing at least one optionally substituted cycloalkyl, heterocycloalkyl, aryl, or heteroaryl functional group; and n and m are values ​​selected from the range 1 to 4.

[0015] Project 3. Based on the coating material of Project 2, where m is 1 and n is 2.

[0016] Project 4. Based on the coating material of Project 3, where X 1Selected from O, S, SS, O-Si(R) 2 )2、Si(R 2 2. O-Si(OR) 2 2. Si(OR) 2 2. NH, NR 2 and a functional group comprising at least one optionally substituted cycloalkyl, heterocycloalkyl, aryl, or heteroaryl group, wherein R 2 It can be an alkyl, alkenyl, or ynyl group that is optionally substituted.

[0017] Project 5. The coating material according to Project 3, wherein the unsaturated organic compound has Formula II: Formula II Where R 1 As defined above.

[0018] Project 6. The coating material according to Project 3, wherein the unsaturated organic compound has Formula III: Formula III Where R 1 As defined above, and p is 1 or 2.

[0019] Project 7. Based on the coating material of Project 6, where p is 1.

[0020] Project 8. The coating material according to Project 3, wherein the unsaturated organic compound has Formula IV: Formula IV Where R 1 As defined above, and X 2 The group is selected from cycloalkyl, heteroalkyl, aryl, heteroaryl, or contains at least two independently selected rings selected from cycloalkyl, heteroalkyl, aryl, and heteroaryl, said rings being fused together and linked together by carbon-carbon or carbon-heteroatom bonds or by heteroatoms, alkylene, alkenyl, ynylene, or combinations thereof, said cycloalkyl, heteroalkyl, aryl, and heteroaryl being optionally substituted.

[0021] Project 9. Based on the coating material of Project 8, where X 2 Having the following formula:

[0022] Where r is 0 or 1, q is 0, 1 or 2, and ---- indicates that it is related to R 1 The key can be in adjacent, intermediate, or opposite positions, preferably in opposite positions. It should be understood that when q is 0, there exists ----.

[0023] Project 10. Based on the coating material of Project 9, where q is 0.

[0024] Project 11. Based on the coating material of Project 9, where r is 1 and q is 2.

[0025] Project 12. Based on the coating material of Project 2, where m is 1 and n is 1.

[0026] Project 13. Based on the coating material of Project 12, where X 1 Selected from halogen atoms, OR 2 SR 2 S-SR 2 NH2, NHR 2 、N(R 2 )2、O-Si(R 2 3. Si(R) 2 3. O-Si(OR) 2 3. Si(OR) 2 )3、N3、P(O)(OR 2 2. SO2OR 2 OSO2R 2 SO2R 2 SO2NHR 2 NHSO2R 2 C(O)H, C(O)R 2 ,NHC(O)R 2 C(O)NHR 2 、NHC(O)NHR 2 OC(O)NHR 2 OC(O)R 2 C(O)OR 2 ,NHC(O)OR 2 OC(O)OR 2 C(S)R 2 The C(S)H group and a functional group comprising at least one optionally substituted cycloalkyl, heterocycloalkyl, aryl, or heteroaryl group, wherein R 2 It can be an alkyl, alkenyl, or ynyl group that is optionally substituted.

[0027] Project 14. Based on the coating material of Project 13, where X 1 Selected from P(O)(OR) 2 )2、O-Si(R 2 3. Optionally substituted aryl or heteroaryl groups, or a combination of the latter two, preferably O-Si(R 2 3. Optional substituted aryl or heteroaryl, or a combination of the latter two.

[0028] Item 15. Coating material according to any one of Items 2 to 14, wherein R1 It is an unsaturated aliphatic group containing 10 to 50 carbon atoms.

[0029] Item 16. Coating material according to any one of Items 2 to 15, wherein R 1 Each time it appears, it is independently selected from the following groups: decenyl, dodecenyl, undecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecanyl, octadecenyl, 1,9-decadienyl, dodecenyl, hexadecenyl, eicosene, tetradecenyl, squalene, farneyl, β-carotene, pinene, dicyclopentadienyl, camphenyl, α-phellandrényle, β-phellandrényle, terpinene. yle), β-myrcényle, limonényle, 2-carényle, sabinényle, α-cédrényle, copaényle, β-cédrényle, decanynyl, dodecanynyl, octadecynyl, hexadecynyl, tridecanynyl, tetradecynyl and docosynyl, and derivatives of any of these groups further comprising additional saturated or unsaturated carbon (such as (3E,7E)-4,8,12-trimethyltetadecacarbon-3,7,11-trienyl or (1E,3E,7E)-4,8,12-trimethyltetadecacarbon-1,3,7,11-tetraenyl), and combinations of at least two of them.

[0030] Item 17. The coating material according to Item 16, wherein the unsaturated aliphatic group, each time it appears, is independently selected from the following groups: decenyl, dodecenyl, undecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, 1,9-decadienyl, dodecenyl, hexadecenyl, eicosene, dodecenyl, squalene, farnesyl, β-caroteneyl, derivatives of one of these groups further comprising an additional saturated or unsaturated carbon, and combinations of at least two of them.

[0031] Item 18. The coating material according to Item 17, wherein the unsaturated aliphatic group, each time it appears, is independently selected from the following groups: decenyl, undecenyl, octadecenyl, squalene, farnesyl, β-caroteneyl, (3E,7E)-4,8,12-trimethyltetadeca-3,7,11-trienyl, (1E,3E,7E)-4,8,12-trimethyltetadeca-1,3,7,11-tetraenyl, and combinations of at least two of them.

[0032] Item 19. A coating material according to any one of Items 1 to 18, wherein the unsaturated aliphatic group comprises a squalene group.

[0033] Item 20. A coating material according to any one of Items 1 to 18, wherein the unsaturated aliphatic group comprises farnesyl.

[0034] Item 21. A coating material according to any one of Items 1 to 18, wherein the unsaturated aliphatic group comprises squalene and farnesyl.

[0035] Item 22. A coating material according to any one of Items 1 to 18, wherein the unsaturated aliphatic group comprises (3E,7E)-4,8,12-trimethyltridecane-3,7,11-trienyl or (1E,3E,7E)-4,8,12-trimethyltridecane-1,3,7,11-tetraenyl.

[0036] Item 23. The coating material according to Item 1, wherein the unsaturated organic compound is selected from the following compounds:

[0037] Compound 1

[0038] Compound 2

[0039] Compound 3

[0040] Compound 4

[0041] Compound 5

[0042] Compound 6

[0043] Compound 7

[0044] Compound 8

[0045] Compound 9

[0046] Compound 10

[0047] Compound 11

[0048] Compound 12

[0049] Compound 13

[0050] Compound 14

[0051] Compound 15

[0052] Or a salt of one of these, for example, the compound is selected from compounds 1 to 9, 11 to 15, or selected from compounds 1 to 5, 7 to 9, 11 to 15, or selected from compounds 1, 2, 4, 5, 7 to 9, 11 to 15.

[0053] Item 24. A coating material according to any one of items 1 to 23, comprising at least two of the unsaturated organic compounds.

[0054] Item 25. A coating material according to any one of items 1 to 23, wherein the unsaturated organic compound has a boiling point above 80°C or above 100°C.

[0055] Item 26. A coating material according to any one of items 1 to 25, wherein the unsaturated organic compound is in liquid form at 25°C.

[0056] Item 27. A coating material according to any one of items 1 to 25, wherein the unsaturated organic compound is in solid form at 25°C.

[0057] Item 28. A coating material according to any one of items 1 to 27, which is a mixture comprising the unsaturated organic compound and additional components.

[0058] Item 29. The coating material according to Item 28, wherein the additional component is a saturated or unsaturated aliphatic hydrocarbon, a solvent, or a combination thereof.

[0059] Item 30. The coating material according to Item 29, wherein the saturated or unsaturated aliphatic hydrocarbon contains 10 to 50 carbon atoms.

[0060] Item 31. The coating material according to Item 29 or 30, wherein the saturated or unsaturated aliphatic hydrocarbon comprises unsaturated aliphatic hydrocarbons.

[0061] Item 32. The coating material according to Item 31, wherein the unsaturated aliphatic hydrocarbon is selected from decene, dodecene, undecene, tridecene, tetradecene, pentadecene, hexadecene, heptadecene, octadecene, 1,9-decadiene, dodecene, hexadecene, eicosene, tetradecene, squalene, farne, β-carotene, pinene, dicyclopentadiene, camphene, α-phellandrène, β-phellandrène, terpinene, β-myrcene, limonene, 2-carene, and 1,9-saturated aliphatic hydrocarbon. sabinène, α-cedrene, copaène, β-cedrene, decanyne, dodecanyne, octadecyne, hexadecyne, tridecanyne, tetradecyne, docosylene, and combinations of at least two of these.

[0062] Item 33. The coating material according to Item 32, wherein the unsaturated aliphatic hydrocarbon is selected from decene, dodecene, undecene, tridecene, tetradecene, pentadecene, hexadecene, heptadecene, octadecene, 1,9-decadiene, dodecene, hexadecene, eicosene, tetradecene, squalene, farnesene, β-carotene, and combinations of at least two of them.

[0063] Item 34. The coating material according to Item 33, wherein the unsaturated aliphatic hydrocarbon is selected from decene, undecene, octadecene, squalene, farnesene, β-carotene, and combinations of at least two of them.

[0064] Item 35. The coating material according to Item 34, wherein the unsaturated aliphatic hydrocarbon comprises squalene.

[0065] Item 36. The coating material according to Item 34, wherein the unsaturated aliphatic hydrocarbon comprises farnesene.

[0066] Item 37. A coating material according to any one of Items 29 to 36, wherein the saturated or unsaturated aliphatic hydrocarbon comprises an alkane.

[0067] Item 38. The coating material according to Item 37, wherein the alkane is decane.

[0068] Item 39. A coating material according to any one of Items 29 to 38, wherein the solvent is selected from dichloromethane, tetrahydrofuran, dioxolane, xylene (ortho, meta, or para), toluene, benzene, methoxybenzene and other benzene derivatives, acetonitrile, N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, alkylene carbonate, dialkyl carbonate, and miscible combinations of at least two of these.

[0069] Item 40. A coating material according to any one of items 1 to 39, wherein the concentration of the unsaturated organic compound in the coating material is at least 2% by volume, or in the range of about 5% to 100%, or about 25% to 100%, or about 40% to 100%, or about 50% to 100%.

[0070] Item 41. Coated particles for use in electrochemical cells, said coated particles comprising: - A core comprising electrochemically active materials, electronically conductive materials, ionically conductive inorganic materials, or a combination of two or more of these; and - A coating material as defined in any one of items 1 to 40, the coating material being present on the surface of the core.

[0071] Item 42. The coated particles according to Item 41, wherein the coating material forms a homogeneous coating on the surface of the core.

[0072] Item 43. The coated particles according to Item 41, wherein the coating material forms a coating on at least a portion of the surface of the core.

[0073] Item 44. The coated particles according to Item 43, wherein the coating material is not uniformly dispersed on the surface of the core.

[0074] Item 45. Coated particles according to any one of Items 41 to 44, wherein the mass ratio of "coating material: core" is in the range of 0.2:100 to 50:100, or 0.5:100 to 40:100.

[0075] Item 46. The coated particles according to any one of items 41 to 45, wherein the core comprises an ion-conducting inorganic material.

[0076] Item 47. The coated particles according to Item 46, wherein the ion-conducting inorganic material is selected from glass, glass ceramics, ceramics, nanoceramics, and combinations of at least two of them.

[0077] Item 48. Coated particles according to Item 46 or 47, wherein the ion-conducting inorganic material comprises ceramics, glass or glass-ceramics based on fluorides, phosphides, sulfides, oxysulfides or oxides.

[0078] Item 49. The coated particles according to any one of Items 46 to 48, wherein the ion-conductive inorganic material is selected from crystalline and / or amorphous forms of LISICON, thio-LISICON, argyrodites, garnet, NASICON, perovskite, oxides, sulfides, oxysulfides, phosphides, fluorides, and combinations of at least two of them.

[0079] Item 50. The coated particles according to any one of Items 46 to 49, wherein the ion-conducting inorganic material is selected from inorganic compounds having the following formula: - MLZO (e.g., M7La3Zr2O) 12 M (7-a) La3Zr2Al b O 12 M (7-a) La3Zr2Ga b O 12 M (7-a) La3Zr (2-b) Ta b O 12 and M (7-a) La3Zr (2-b) Nb b O 12 ); - MLTaO (e.g., M7La3Ta2O) 12 M5La3Ta2O 12 and M6La3Ta 1.5 Y 0.5 O 12 ); - MLSnO (e.g., M7La3Sn2O) 12 ); - MAGP (e.g., M) 1+a Al a Ge 2-a (PO4)3); - MATP (e.g., M) 1+a Al a Ti 2-a (PO4)3); - MLTiO (e.g., M 3a La (2 / 3-a) TiO3); - MZP (e.g., M) a Zr b(PO4) c ); - MCZP (e.g., M) a Ca b Zr c (PO4) d ); - MGPS (e.g., M) a Ge b P c S d , such as M 10 GeP2S 12 ); - MGPSO (e.g., M) a Ge b P c S d O e ); - MSiPS (e.g., M) a Si b P c S d , such as M 10 SiP2S 12 ); - MSiPSO (e.g., M) a Si b P c S d O e ); - MSnPS (e.g., M) a Sn b P c S d , such as M 10 SnP2S 12 ); - MSnPSO (e.g., M) a Sn b P c S d O e ); - MPS (e.g., M) a P b S c such as M7P3S 11 ); - MPSO (e.g., M) a P b S c O d ); - MZPS (e.g., M) a Zn b P c S d ); - MZPSO (e.g., M) a Zn b P c S d O e ); - xM2S-yP2S5; - xM2S-yP2S5-zMX; - xM2S-yP2S5-zP2O5; - xM2S-yP2S5-zP2O5-wMX; - xM2S-yM2O-zP2S5; - xM2S-yM2O-zP2S5-wMX; - xM2S-yM2O-zP2S5-wP2O5; - xM2S-yM2O-zP2S5-wP2O5-vMX; - xM2S-ySiS2; - MPSX (e.g., M) a P b S c X d such as M7P3S 11 X, M7P2S8X and M6PS5X); - MPSOX (e.g., M) a P b S c O d X e ); - MGPSX (e.g., M) a Ge b P c S d X e ); - MGPSOX (e.g., M a Ge b P c S d O e X f ); - MSiPSX (e.g., M) a Si b P c S d X e ); - MSiPSOX (e.g., M) a Si b P c S d O e X f); - MSnPSX (e.g., M) a Sn b P c S d X e ); - MSnPSOX (e.g., M) a Sn b P c S d O e X f ); - MZPSX (e.g., M) a Zn b P c S d X e ); - MZPSOX (e.g., M) a Zn b P c S d O e X f ); - M3OX; - M2HOX; - M3PO4; - M3PS4; and - M a PO b N c (where a = 2b + 3c - 5); in, M is an alkali metal ion, an alkaline earth metal ion, or a combination thereof, wherein when M contains an alkaline earth metal ion, the amount of M is adjusted to achieve electroneutrality. X is selected from F, Cl, Br, I, or a combination of at least two of them; a, b, c, d, e, and f are non-zero values ​​and are chosen independently in each equation to achieve electrical neutrality; and v, w, x, y, and z are non-zero values ​​and are chosen independently in each formula to obtain a stable compound.

[0080] Item 51. The coated particles according to Item 50, wherein M is selected from Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, Ba or a combination of at least two of them.

[0081] Project 52. Coated particles according to Project 51, where M is Li.

[0082] Item 53. The coated particles according to any one of Items 46 to 52, wherein the ion-conducting inorganic material is selected from the formula Lia P b S c X d An inorganic compound, wherein X is Cl, Br, I or a combination of at least two of them, and a, b, c and d such that (a + 5b) = (2c + d).

[0083] Item 54. The coated particles according to Item 53, wherein the ion-conducting inorganic material is Li6PS5Cl.

[0084] Item 55. The coated particles according to any one of Items 46 to 52, wherein the ion-conducting inorganic material is selected from the formula Li a P b S c O d X e An inorganic compound, wherein X is Cl, Br, I or a combination of at least two of them, and a, b, c, d and e such that (a + 5b) = (2c + 2d + e).

[0085] Item 56. Coated particles according to Item 55, wherein a is selected from the range of 5 to 6, b is equal to 1, c is selected from the range of 3.5 to 4.8, and e is selected from the range of 1 to 2, preferably the ion-conducting inorganic material is Li. 5.4 PS 4.1 O 0.3 X 1.6 Or Li 5.4 PS 4.1 O 0.3 ClBr 0.5 I 0.1 .

[0086] Item 57. A coated particle according to any one of items 41 to 45, wherein the core comprises an electrochemically active material.

[0087] Item 58. The coated particles according to Item 57, wherein the electrochemically active material is selected from metal oxides, metal sulfides, metal oxysulfides, metal phosphates, metal fluorophosphates, metal oxyfluorophosphates, metal sulfates, metal halides, metal fluorides, sulfur, selenium, and combinations of at least two of them.

[0088] Item 59. The coated particles according to Item 58, wherein the metal of the electrochemically active material is selected from titanium (Ti), iron (Fe), manganese (Mn), vanadium (V), nickel (Ni), cobalt (Co), aluminum (Al), chromium (Cr), copper (Cu), zirconium (Zr), niobium (Nb), and combinations of at least two of them.

[0089] Item 60. The coated particles according to Item 58, wherein the metal of the electrochemically active material further comprises an alkali metal or alkaline earth metal selected from lithium (Li), sodium (Na), potassium (K) and magnesium (Mg).

[0090] Item 61. The coated particles according to any one of Items 58 to 60, wherein the electrochemically active material is a lithium-metal oxide.

[0091] Item 62. The coated particles according to Item 61, wherein the lithium-metal oxide is a mixed oxide (NCM) of lithium, nickel, manganese and cobalt.

[0092] Item 63. The coated particles according to any one of Items 57 to 60, wherein the electrochemically active material is a lithium-metal phosphate.

[0093] Item 64. The coated particles according to Item 63, wherein the lithium-metal phosphate is lithium iron phosphate.

[0094] Item 65. The coated particles according to Item 57, wherein the electrochemically active material is selected from non-alkali metals or non-alkaline earth metals, intermetallic compounds, metal oxides, metal nitrides, metal phosphides, metal phosphates, metal halides, metal fluorides, metal sulfides, metal oxysulfides, carbon, silicon (Si), silicon-carbon composites (Si-C), and silicon oxides (SiO). x ), silicon oxide-carbon composite material (SiO) x -C), tin (Sn), tin-carbon composites (Sn-C), tin oxides (SnO) x ), Tin oxide-carbon composite material (SnO) x -C), and combinations of at least two of them.

[0095] Item 66. The coated particles according to any one of items 57 to 65, wherein the electrochemically active material further comprises a dopant element.

[0096] Item 67. The coated particles according to any one of items 57 to 66, wherein the electrochemically active material further comprises a covering material.

[0097] Item 68. The coated particles according to Item 67, wherein the covering material forms a covering layer on the surface of the electrochemically active material, and the coating material is disposed on the surface of the covering layer.

[0098] Item 69. The coated particles according to Item 67 or 68, wherein the coating material is selected from Li2SiO3, LiTaO3, LiAlO2, Li2O-ZrO2, LiNbO3, other similar coating materials, and combinations of at least two of them.

[0099] Item 70. The coated particles according to any one of Items 67 to 69, wherein the coating material is LiNbO3.

[0100] Item 71. The coated particles according to Item 67 or 68, wherein the coating material is an electronically conductive material, preferably containing carbon.

[0101] Item 72. The coated particles according to any one of Items 41 to 45, wherein the core comprises an electronically conductive material.

[0102] Item 73. The coated particles according to Item 72, wherein the electronically conductive material is selected from carbon black, acetylene black, graphite, graphene, carbon fiber, carbon nanofiber, carbon nanotube, and combinations of at least two of them.

[0103] Item 74. The coated particles according to Item 73, wherein the electronically conductive material is carbon black.

[0104] Item 75. The coated particles according to any one of Items 72 to 74, wherein the surface of said electronically conductive material is grafted with at least one aryl group of Formula A: Formula A in, FG is a hydrophilic functional group; and h is an integer in the range of 1 to 5, h is preferably in the range of 1 to 3, h is preferably 1 or 2, and h is more preferably 1.

[0105] Item 76. The coated particles according to Item 75, wherein the hydrophilic functional group is a carboxylic acid or sulfonic acid functional group.

[0106] Item 77. The coated particles according to Item 75, wherein the aryl group of Formula A is benzoic acid or benzoylsulfonic acid.

[0107] Item 78. Coated particles according to any one of Items 46 to 77, used in electrode materials.

[0108] Item 79. Coated particles according to any one of Items 46 to 56, used in electrolytes.

[0109] Item 80. Coated particles according to any one of Items 72 to 77, used on current collectors.

[0110] Item 81. A method for preparing coated particles as defined in any one of Items 41 to 77, the method comprising at least the step of coating at least a portion of the surface of the core with the coating material.

[0111] Item 82. According to the method of Item 81, wherein the coating step is performed by a dry coating method.

[0112] Item 83. According to the method of Item 81, wherein the coating step is performed by a wet coating method.

[0113] Item 84. According to the method of Item 83, the wet coating method is a mechanical coating method.

[0114] Item 85. The method according to Item 84, wherein the mechanical coating method is a grinding, mechanical synthesis or mechanical melting method.

[0115] Item 86. The method according to any one of items 81 to 85, further comprising the step of grinding the core of the coated particles into an electrochemically active material, an electronically conductive material, or an ionically conductive inorganic material.

[0116] Item 87. The method of Item 86, wherein the coating and polishing steps are performed simultaneously, sequentially, or partially overlapping in time.

[0117] Item 88. The method according to Item 87, wherein the coating and polishing steps are performed simultaneously.

[0118] Item 89. Electrode materials comprising electrochemically active materials, electronically conductive materials, and optionally ionically conductive inorganic materials, wherein at least one of the electrochemically active materials, electronically conductive materials, or ionically conductive inorganic materials comprises coated particles as defined in Item 78.

[0119] Project 90. The electrode material according to Project 89 comprises ion-conducting inorganic materials.

[0120] Item 91. The electrode material according to Item 90, wherein the core of the coated particles comprises an ion-conducting inorganic material.

[0121] Item 92. The electrode material according to Item 90 or 91, wherein the ion-conducting inorganic material is as defined in any one of Items 47 to 56.

[0122] Item 93. An electrode material according to any one of Items 89 to 92, wherein the core of the coated particles comprises an electrochemically active material.

[0123] Item 94. An electrode material according to any one of Items 89 to 93, wherein the electrochemically active material is as defined in any one of Items 58 to 71.

[0124] Item 95. An electrode material according to any one of Items 89 to 94, wherein the core of the coated particles comprises an electronically conductive material.

[0125] Item 96. The electrode material according to any one of Items 89 to 95, wherein the electronically conductive material is as defined in any one of Items 73 to 77.

[0126] Item 97. The electrode material according to any one of items 89 to 96, further comprising an adhesive.

[0127] Item 98. The electrode material according to Item 97, wherein the adhesive is selected from polymer adhesives of the polyether, polycarbonate or polyester type, fluoropolymers, water-soluble adhesives and copolymers or compatible combinations thereof.

[0128] Item 99. The electrode material according to Item 97, wherein the binder comprises a mixture of a first polymer based on polybutadiene and a second polymer comprising a polymerized norbornene monomer unit containing a double bond derived from a compound of formula B: Formula B in, R a and R b Each time it appears, it is independently selected from hydrogen atom, carboxyl group (-COOH), sulfonic acid group (-SO3H), hydroxyl group (-OH), fluorine atom and chlorine atom.

[0129] Item 100. Electrode material according to Item 99, wherein the second polymer is a polymer of formula C: Formula C in, R a and R b As defined in Project 99, and j is an integer chosen such that the mass-average molecular weight of the polymer of formula C is between approximately 10,000 g / mol and approximately 100,000 g / mol, including the upper and lower limits.

[0130] Project 101. Electrode materials according to Project 99 or 100, where R a and R b Each time it appears, it is independently selected from hydrogen atoms and -COOH groups.

[0131] Project 102. Based on the electrode material of Project 101, where R a It is a -COOH group, and R b It is a hydrogen atom.

[0132] Project 103. Based on the electrode material of Project 101, where R a and R b They are all -COOH groups.

[0133] Item 104. An electrode material according to any one of items 99 to 103, wherein the first polymer is polybutadiene.

[0134] Item 105. The electrode material according to any one of items 99 to 103, wherein the first polymer is selected from epoxidized polybutadiene.

[0135] Item 106. Electrode material according to Item 105, wherein the epoxidized polybutadiene comprises repeating units of formulas E and D and / or F:

[0136] And two hydroxyl terminal groups.

[0137] Item 107. Electrode material according to Item 106, wherein the epoxidized polybutadiene has formula G: Formula G in, k is an integer, chosen such that the mass-average molecular weight of the epoxidized polybutadiene of formula G is between approximately 1,000 g / mol and approximately 1,500 g / mol, including both the upper and lower limits; and The epoxy equivalent weight is between approximately 100 g / mol and approximately 600 g / mol, including the upper and lower limits.

[0138] Project 108. The electrode material according to Project 107, wherein the mass-average molecular weight of the epoxidized polybutadiene of formula G is approximately 1,300 g / mol.

[0139] Item 109. Electrode materials according to Item 107 or 108, wherein the epoxy equivalent weight is between approximately 210 g / mol and approximately 550 g / mol, including the upper and lower limits.

[0140] Item 110. The electrode material according to any one of Items 107 to 109, wherein the epoxidized polybutadiene of formula G is Poly bd™ 600E resin having an average molecular weight of about 1,300 g / mol and an epoxy equivalent weight between about 400 g / mol and about 500 g / mol, including the upper and lower limits.

[0141] Item 111. The electrode material according to any one of Items 107 to 109, wherein the epoxy polybutadiene of formula G is Poly bd™ 605E resin having an average molecular weight of about 1,300 g / mol and an epoxy equivalent weight between about 260 g / mol and about 330 g / mol, including the upper and lower limits.

[0142] Item 112. An electrode material according to any one of Items 107 to 111, wherein the weight ratio of the first polymer to the second polymer is in the range of about 6:1 to about 2:3, including the upper and lower limits.

[0143] Item 113. The electrode material according to Item 112, wherein the weight ratio is in the range of about 5.5:1 to about 2:3, or about 5:1 to about 2:3, or about 4.5:1 to about 2:3, or about 4:1 to about 2:3, or about 6:1 to about 1:1, or about 5.5:1 to about 1:1, or about 5:1 to about 1:1, or about 5:1 to about 2:1, or about 4.5:1 to about 1:1, or about 4:1 to about 1:1, including the upper and lower limits.

[0144] Item 114. The electrode material according to Item 113, wherein the weight ratio is in the range of about 5:1 to about 2:1, including the upper and lower limits.

[0145] Item 115. Electrode, which is contained on a current collector as an electrode material as defined in any one of Items 89 to 114.

[0146] Item 116. A self-supporting electrode comprising an electrode material as defined in any one of Items 89 to 114.

[0147] Item 117. According to the electrode in Item 115 or 116, the electrode is a positive electrode.

[0148] Item 118. Electrolytes comprising coated particles as defined in Item 79, wherein the core of the coated particles comprises an ion-conducting inorganic material.

[0149] Item 119. The electrolyte according to Item 118 is a liquid electrolyte containing a solvent.

[0150] Item 120. The electrolyte according to Item 118 is a solid electrolyte that further comprises a solvated polymer.

[0151] Project 121. The electrolyte according to Project 120 is a hybrid polymer-ceramic solid electrolyte.

[0152] Item 122. According to Item 118, the electrolyte is an inorganic solid electrolyte.

[0153] Project 123. The electrolyte according to Project 122 is a ceramic-type inorganic solid electrolyte.

[0154] Item 124. The electrolyte according to any one of items 118 to 123 further comprises an alkali metal salt, preferably a lithium salt.

[0155] Item 125. An electrolyte according to any one of Items 118 to 124, further comprising at least one organic additive (e.g., ionic organic additive (liquid or solid), thiol, plasticizer, etc.).

[0156] Item 126. A coating material for a current collector comprising coating particles as defined in Item 80, wherein the core of the coating particles comprises an electronically conductive material.

[0157] Item 127. The coating material according to Item 126, wherein the electronically conductive material is carbon.

[0158] Item 128. Current collector, comprising a coating material as defined in Items 126 or 127 disposed on a metal sheet.

[0159] Item 129. An electrochemical cell comprising a negative electrode, a positive electrode and an electrolyte, wherein at least one of the positive or negative electrodes is as defined in any one of Items 115 to 117, or comprises an electrode material as defined in any one of Items 89 to 114.

[0160] Item 130. An electrochemical cell comprising a negative electrode, a positive electrode and an electrolyte, wherein the electrolyte is as defined in any one of Items 118 to 125.

[0161] Item 131. An electrochemical cell comprising a negative electrode, a positive electrode and an electrolyte, wherein at least one of the positive and negative electrodes is on a current collector as defined in Item 128 or on a current collector comprising a coating material as defined in Item 126 or 127.

[0162] Item 132. An electrochemical cell according to any one of Items 129 to 131, wherein the negative electrode comprises an electrochemically active material, the electrochemically active material comprising an alkali metal, an alkaline earth metal, an alloy containing at least one alkali metal or alkaline earth metal, a non-alkali metal and a non-alkaline earth metal, or an intermetallic alloy or compound.

[0163] Item 133. An electrochemical cell according to Item 132, wherein the electrochemically active material of the negative electrode comprises lithium metal or an alloy containing or based on lithium metal.

[0164] Item 134. An electrochemical cell according to Item 132 or 133, wherein the electrochemically active material of the negative electrode is in the form of a film with a thickness ranging from about 5 µm to about 500 µm, including the upper and lower limits.

[0165] Item 135. An electrochemical cell according to Item 134, wherein the thickness of the film of the electrochemically active material of the negative electrode is in the range of about 10 µm to about 100 µm, including the upper and lower limits.

[0166] Item 136. An electrochemical cell according to any one of Items 129 to 132, wherein the positive electrode is pre-lithiated and the negative electrode is substantially lithium-free.

[0167] Item 137. An electrochemical cell according to Item 136, wherein the negative electrode is lithium-ionized in situ during cycling of the electrochemical cell.

[0168] Item 138. An electrochemical storage battery comprising at least one electrochemical cell as defined in any one of Items 129 to 137.

[0169] Item 139. An electrochemical battery according to Item 138, wherein the electrochemical battery is a battery pack selected from lithium battery packs, lithium-ion battery packs, sodium battery packs, sodium-ion battery packs, magnesium battery packs and magnesium-ion battery packs.

[0170] Item 140. An electrochemical storage battery according to Item 138, wherein the battery pack is a lithium battery pack or a lithium-ion battery pack.

[0171] Item 141. An electrochemical battery according to Item 138, wherein the electrochemical battery is an all-solid-state battery pack. Attached Figure Description

[0172] Figure 1 The thermogravimetric analysis and impedance analysis results of the Li6PS5Cl coated particles PA (curve 1), P-4 (curve 2), P-2 (curve 3), P-3 (curve 4) and P-1 (curve 5) as described in Examples 2(b) and (c) are shown at 20°C.

[0173] Figure 2 The coating of Li as described in Examples 2(b) and (c) is shown. 5.4 PS 4.1 O 0.3 ClBr 0.5 I 0.1 Thermogravimetric analysis and impedance analysis results of particles PB (curve 6), P-6 (curve 7), P-5 (curve 8) and P-7 (curve 9) at 20℃.

[0174] Figure 3 The results of thermogravimetric analysis of coated Li6PS5Cl particles PA (curve 1), P-9 (curve 10), and P-10 (curve 11) as described in Example 2(b) are shown.

[0175] Figure 4Thermogravimetric analysis and impedance analysis results of Li6PS5Cl coated particles PA (curve 12) and P-11 (curve 13) as described in Examples 2(b) and (c) are shown at 20°C.

[0176] Figure 5 Thermogravimetric analysis and impedance analysis results of Li6PS5Cl coated particles PA (curve 12), P-12 (curve 14) and P-13 (curve 15) as described in Examples 2(b) and (c) are shown at 20°C.

[0177] Figure 6 Thermogravimetric analysis and impedance analysis results of Li6PS5Cl coated particles PA (curve 16) and P-15 (curve 17) as described in Examples 2(b) and (c) are shown at 20°C.

[0178] Figure 7 The solid-state magic angle rotation (MAS) of the P-4 particle (bottom) and farnesene (middle) and compound 2 (top) as references is shown. 1 H NMR spectrum.

[0179] Figure 8 Solid-state magic angle rotation (MAS) is shown for P-3 particles (bottom) and for reference for farnesene (middle) and compound 1 (top). 1 H NMR spectrum.

[0180] Figure 9 Solid-state magic angle rotation (MAS) is shown for P-11 particles (bottom) and squalene (middle) and compound 15 (top) as references. 1 H NMR spectrum.

[0181] Figure 10 The solid-state magic angle rotation (MAS) of P-9 particles (bottom) and squalene (middle) and compound 4 (top) as references is shown. 1 H NMR spectrum.

[0182] Figure 11 Solid-state magic angle rotation (MAS) is shown for P-10 particles (bottom) and squalene (middle) and compound 9 (top) as references. 1 H NMR spectrum.

[0183] Figure 12 Solid-state magic angle rotation (MAS) is shown for P-12 particles (bottom) and squalene (middle) and compound 11 (top) as references. 1 H NMR spectrum.

[0184] Figure 13Solid-state magic angle rotation (MAS) is shown for P-14 particles (bottom) and squalene (middle) and compound 3 (top) as references. 1 H NMR spectrum.

[0185] Figure 14 Solid-state magic angle rotation (MAS) of P-15 particles (bottom) and squalene (middle) and compound 14 (top) as references is shown. 1 H NMR spectrum.

[0186] Figure 15 The images show scanning electron microscopy (SEM) images of a section (a) of the positive electrode film F-1 as described in Example 3(b) and a section (b) of the positive electrode film F-2.

[0187] Figure 16 Displaying scanning electron microscopy (SEM) images of a slice of the positive electrode film F-5 as described in Example 3(b).

[0188] Figure 17 The graphs show the discharge and charge capacity (mAh / g) and coulombic efficiency (%) vs. cycle number of battery 1 (hollow symbol) and battery 2 (solid symbol) as described in Example 4(b).

[0189] Figure 18 The graphs show the discharge and charge capacity (mAh / g) and coulombic efficiency (%) vs. cycle number of batteries 1 (hollow circle symbol), 6 (star symbol), and 7 (hexagon symbol) as described in Example 4(b).

[0190] Figure 19 The graphs show the discharge capacity (mAh / g) and coulombic efficiency (%) vs. cycle number of batteries 3 (square), 4 (triangular), and 5 (circular) as described in Example 4(b).

[0191] Figure 20 The graphs show the discharge and charge capacity (mAh / g) and coulombic efficiency (%) vs. cycle number of battery 1 (hollow symbol) and battery 8 (solid symbol) as described in Example 4(b).

[0192] Figure 21 Photographs of particles in (a) PB, (b) P-8 and (c) P-7 after treatment in a toluene-tetrahydrofuran (80-20) solvent mixture as described in Example 5 are shown. Detailed Implementation

[0193] All technical and scientific terms and phrases used herein have the same definitions as commonly understood by one of ordinary skill in the art. Nevertheless, definitions of some terms and phrases used are provided below.

[0194] When the term “approximately” is used in this document, it means approximately, around, or near. For example, when the term “approximately” is used with respect to a numerical value, it modifies that the value varies by 10% above or below its nominal value. This term may also take into account, for example, experimental errors of measuring instruments or rounding.

[0195] When referring to a numerical range in this application, unless otherwise stated, the lower and upper limits of the range are always included in the definition. When referring to a numerical range in this application, all intermediate ranges and subranges, as well as individual values ​​included within these numerical ranges, are included in the definition.

[0196] When the articles "a" or "an" are used in this application to describe an element, it does not mean "only one," but rather "one or more." Of course, when the specification indicates that a particular step, component, element, or feature "may" or "may" be included, that particular step, component, element, or feature is not necessarily required to be included in each embodiment.

[0197] The chemical structures described herein are drawn according to conventions in the field. Therefore, when drawn atoms, such as carbon atoms, appear to include unsatisfied valences, it is presumed that the valence is satisfied by one or more hydrogen atoms, even if they are not explicitly drawn.

[0198] The term "aliphatic" generally refers to a straight-chain or branched hydrocarbon group that may include a non-aromatic ring. Unless otherwise specified, the term includes saturated groups (such as alkyl) and unsaturated groups (such as alkenyl or ynyl). Aliphatic groups may optionally be substituted.

[0199] As used herein, the term "alkyl" refers to a saturated hydrocarbon having 1 to 12 carbon atoms, including straight-chain or branched alkyl groups. Non-limiting examples of alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, isopropyl, tert-butyl, sec-butyl, isobutyl, etc. When the alkyl group is located between two functional groups, the term alkylene also includes alkylene compounds, such as methylene, ethylene, propylene, etc. The term "C"... m -C n "alkyl" and "C" m -C n "alkylene" refers to an alkyl or alkylene group having the indicated number of carbon atoms from "m" to "n".

[0200] As used herein, the term "alkenyl" refers to, for example, an optionally substituted unsaturated hydrocarbon having 2 to 60 carbon atoms and at least one double bond between two carbon atoms, including straight-chain or branched alkenyl groups. Non-limiting examples of alkenyl groups may include vinyl, allyl, 1-propen-2-yl, 1-buten-3-yl, 1-buten-4-yl, 2-buten-4-yl, 1-penten-5-yl, 1,3-pentadien-5-yl, unsaturated aliphatic groups of any alkenyl type described herein, etc. When the alkenyl group is located between two functional groups, the term alkenyl also includes alkenylides, such as vinylides, allylides, 1-propen-2-yl, 1-buten-3-yl, etc. The term "C m -C n "Alkenyl" and "C" m -C n "Alkenyl" refers to an alkenyl or alkenyl group having the indicated number of carbon atoms from "m" to "n".

[0201] As used herein, the term "alkynyl" refers to, for example, an optionally substituted unsaturated hydrocarbon having 2 to 60 carbon atoms and at least one triple bond between two carbon atoms, including straight-chain or branched alkynyl groups. Non-limiting examples of alkynyl groups may include ethynyl groups, 1-propyn-3-yl, 1-butyn-4-yl, 2-butyn-4-yl, 1-pentyn-5-yl, 1,3-pentadiyn-5-yl, one of the unsaturated aliphatic groups of the alkynyl types described herein, etc. When the alkynyl group is located between two functional groups, the term alkynyl also includes ynylene groups, such as ethynylene groups, 1-propyn-3-ylene, 1-butyn-4-ylene, etc. The term "C" m -C n "Alkyne" and "C" m -C n "Isomerynyl" refers to an ynyl or imynyl group having the indicated number of carbon atoms from "m" to "n".

[0202] Generally speaking, the terms "cyclic" and "heterocyclic" refer to "cycloalkyl" and "aryl" groups, and "heterocyclic alkyl" and "heteroaryl" groups, respectively.

[0203] As used herein, the term "cycloalkyl" refers to a group comprising one or more 3- to 15-membered saturated or partially unsaturated (non-aromatic) carbocyclic rings in a monocyclic or polycyclic system, including spirocyclic carbocyclic rings (comprising one atom), fused carbocyclic rings (comprising at least one bond), or bridged carbocyclic rings, which may optionally be substituted. Examples of cycloalkyl groups include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclopenten-1-yl, cyclopenten-2-yl, cyclopenten-3-yl, cyclohexyl, cyclohexen-1-yl, cyclohexen-2-yl, cyclohexen-3-yl, cycloheptyl, etc. The term cycloalkylene may also be used when the cycloalkyl group is located between two functional groups. The term "C" is also used. m -C n"Cycloalkyl" and "C" m -C n "Cycloalkylene" refers to a cycloalkylene or cycloalkylene group having the indicated number of carbon atoms from "m" to "n".

[0204] As used herein, the term "heterocyclic alkyl" refers to a group comprising 3 to 15 saturated or partially unsaturated (non-aromatic) carbocyclic rings in a monocyclic or polycyclic system, including spirocyclic (comprising one atom), fused-ring (comprising at least one bond), or bridged rings, which may optionally be substituted, and having a carbon atom and 1 to 4 heteroatoms (e.g., N, O, S, or P) or a group containing such heteroatoms (e.g., NH, NR). x (R) x Heterocyclic alkyl groups are alkyl, acyl, aryl, heteroaryl, or cycloalkyl groups (PO2, SO, SO2, and other similar groups). Where possible, heterocyclic alkyl groups may be bonded to a carbon atom or a heteroatom (e.g., via a nitrogen atom). The term heterocyclic alkyl includes both unsubstituted and substituted heterocyclic alkyl groups. The term hypocyclic alkyl may also be used when the heterocyclic alkyl group is located between two functional groups. The term "C" is used in this context. m -C n Heterocyclic alkyl groups and C m -C n "Hypo-heterocyclic alkyl" refers to a heterocyclic alkyl or hypo-heterocyclic alkyl having a number of ring atoms (including carbon atoms and heteroatoms) ranging from the indicated number "m" to the indicated number "n".

[0205] As used herein, the term "aryl" refers to a functional group comprising a ring with aromatic characteristics, having 6 to 14 ring atoms, preferably 6 ring atoms. The term "aryl" refers to monocyclic and conjugated polycyclic systems. The term "aryl" also includes substituted and unsubstituted groups. Examples of aryl groups include, but are not limited to, phenyl, benzyl, phenethyl, 1-phenylethyl, tolyl, naphthyl, biphenyl, terphenyl, indene, benzocyclooctenyl, benzocycloheptenyl, azulel, acenaphthel, fluorenyl, phenanthrene, anthracene, perylene, etc. The term "C" m -C n "Aryl" and "C" m -C n "Arylene" refers to an aryl or aryl group having the indicated number of carbon atoms from "m" to "n".

[0206] The term "heteroaryl" or "heteroaryl" refers to a group having 4n+2 conjugated π(pi) electrons (where n is a number from 1 to 3), for example having 5 to 18 ring atoms, preferably 5, 6, or 9 ring atoms; and having, in addition to carbon atoms, 1 to 5 heteroatoms selected from oxygen, nitrogen, and sulfur, or groups containing such heteroatoms (e.g., NH and NR). x (R) xA heteroaryl group is an aromatic group consisting of alkyl, acyl, aryl, heteroaryl, or cycloalkyl groups, SO, and other similar groups. A polycyclic system contains at least one heteroaryl ring. The heteroaryl group can be directly attached or linked via a C1-C3 alkyl group (also called a heteroarylalkyl or heteroarylalkyl group). Where possible, the heteroaryl group can be linked via a carbon atom or to a cyclic heteroatom (e.g., via a nitrogen atom). The term "C" is used in this context. m -C n "Hybrid aryl" and "C" m -C n "Hybrid aryl" refers to a heteroaryl or heteroaryl group having a number of ring atoms (including carbon atoms and heteroatoms) ranging from "m" to "n".

[0207] Generally, the term "substituted" means that one or more hydrogen atoms on a specified group are replaced by a suitable substituent. The substituents or combinations of substituents considered in this specification are those that result in the formation of chemically stable compounds. Examples of substituents include halogen atoms (such as F, Cl, Br, I) and hydroxyl, oxygen, alkyl, alkoxy, alkoxyalkyl, nitrile, azide, aldehyde, carboxylic acid, metal or alkyl carboxylate, ester, ketone, aldehyde, primary amine, secondary or tertiary amine, amide, urea, carbamate, carbonate, nitro, silane, siloxane, thiocarboxylate, thiol, disulfide, thionone, thioaldehyde, alkylthiol, sulfonyl, sulfonic acid, metal sulfonate or alkyl sulfonate, sulfonamide, metal dialkyl phosphate or dialkyl phosphate ester, metal dialkyl phosphonate or dialkyl phosphonate, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, heterocycloalkyl or combinations thereof.

[0208] As used herein, the term "salt" means a salt comprising at least one cation and at least one anion, wherein at least one of the cations or anions is organic (e.g., one of the organic compounds described herein), and the other is organic or inorganic. Unless otherwise specified, the term "salt" means a crystalline or amorphous solid salt, or a liquid salt such as an ionic liquid.

[0209] This technology relates to a coating material for electrochemical batteries, comprising at least one organic compound, said organic compound comprising at least one unsaturated branched or straight-chain aliphatic group preferably having 6 to 50 carbon atoms and having at least one carbon-carbon double or triple bond, said compound further comprising at least one atom that is not carbon or hydrogen, a functional group containing at least one atom that is not carbon or hydrogen, or a group containing at least one optionally substituted ring or heterocycle.

[0210] For example, the unsaturated and functionalized organic compound may have Formula I, or a salt of an unsaturated organic compound of Formula I: (R 1 ) n (X 1 ) m Formula I in: R 1 Each time it appears, it is independently a straight-chain or branched unsaturated aliphatic group having 6 to 50 carbon atoms; X 1 A group selected from halogen, oxygen, and sulfur atoms, containing at least one atom selected from halogen, oxygen, sulfur, nitrogen, silicon, and phosphorus atoms, or containing at least one optionally substituted cycloalkyl, heterocycloalkyl, aryl, or heteroaryl functional group; and n and m are values ​​selected from the range 1 to 4.

[0211] Based on some examples of compounds of formula I, where m is 1 and n is 2, group X 1 Preferably selected from O, S, SS, O-Si(R) 2 )2、Si(R 2 2. O-Si(OR) 2 2. Si(OR) 2 2. NH, NR 2 and a functional group comprising at least one optionally substituted cycloalkyl, heterocycloalkyl, aryl, or heteroaryl group, wherein R 2 It can be an alkyl, alkenyl, or ynyl group that is optionally substituted.

[0212] For example, m is 1 and n is 2, and the compound can have formula II: Formula II Where R 1 As defined above.

[0213] In an alternative, m is 1 and n is 2, and the compound has formula III: Formula III Where R 1 As defined above, and p is 1 or 2, preferably p is 1.

[0214] According to another alternative, m is 1 and n is 2, and the compound has formula IV: Formula IV Where R 1 As defined above, and X 2 The group is selected from cycloalkyl, heteroalkyl, aryl, heteroaryl, or contains at least two independently selected rings of cycloalkyl, heteroalkyl, aryl, and heteroaryl, said rings being fused together, linked together by carbon-carbon or carbon-heteroatom bonds or by heteroatoms, alkylene, alkenyl, ynylene, or combinations thereof, said cycloalkyl, heteroalkyl, aryl, and heteroaryl being optionally substituted.

[0215] In formula IV, group X 2 It can have, for example, the following formula:

[0216] Where r is 0 or 1, q is 0, 1 or 2, and ---- indicates that it is related to R 1 The connection can be adjacent, intermediate, or opposite, preferably opposite. It should be understood that when q is 0, ---- exists. According to some instances, q is 0. According to other instances, r is 1 and q is 2.

[0217] Based on some examples of compounds of formula I, m and n are 1, and the group X 1 Preferably selected from halogen atoms, groups OR 2 SR 2 S-SR 2 NH2, NHR 2 、N(R 2 )2、O-Si(R 2 3. Si(R) 2 3. O-Si(OR) 2 3. Si(OR) 2 )3、N3、P(O)(OR 2 2. SO2OR 2 OSO2R 2 SO2R 2 SO2NHR 2 NHSO2R 2 C(O)H, C(O)R 2 ,NHC(O)R 2 C(O)NHR 2 、NHC(O)NHR 2 OC(O)NHR 2 OC(O)R 2 C(O)OR 2 ,NHC(O)OR 2 OC(O)OR 2 C(S)R 2 C(S)H and a functional group comprising at least one optionally substituted cycloalkyl, heterocycloalkyl, aryl or heteroaryl group, wherein R 2 It can be an alkyl, alkenyl, or ynyl group that is optionally substituted. For example, X 1 It can be selected from halogen atoms and one of the following groups: OR 2 SR 2 S-SR 2 NH2, NHR 2 、N(R 2 )2、O-Si(R 2 3. Si(R)2 3. P(O)(OR) 2 2. SO2OR 2 OSO2R 2 SO2R 2 SO2NHR 2 NHSO2R 2 C(O)R 2 ,NHC(O)R 2 C(O)NHR 2 、NHC(O)NHR 2 OC(O)NHR 2 OC(O)R 2 C(O)OR 2 ,NHC(O)OR 2 OC(O)OR 2 C(S)R 2 and a functional group comprising at least one optionally substituted cycloalkyl, heterocycloalkyl, aryl, or heteroaryl group, wherein R 2 It can be an optionally substituted alkyl, alkenyl, or ynyl group. According to some examples, X 1 Selected from P(O)(OR) 2 )2、O-Si(R 2 3. Optionally substituted aryl or heteroaryl groups, or combinations of the latter two, preferably O-Si(R 2 3. Optional substituted aryl or heteroaryl, or a combination of the latter two.

[0218] According to one implementation scheme, group X as defined above 1 Excluding H2S trapping groups.

[0219] In some preferred instances, R 1 It is an unsaturated aliphatic group containing 10 to 50 carbon atoms.

[0220] According to some implementation schemes, unsaturated aliphatic groups (such as R) 1In each case, the group is independently selected from the following: decenyl, dodecenyl, undecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecanyl, octadecenyl, 1,9-decadienyl, dodecenyl, hexadecenyl, eicosene, tetradecenyl, squalene, farnesyl, β-carotene, pinenyl, dicyclopentadienyl, camphenyl, α-phellandrene, β-phellandrene, terpinenyl, β-myrcenyl, limonene, 2-carene. Derivatives of any of these groups, including argentyl, α-cedrenyl, cucurenyl, β-cedrenyl, decanynyl, dodecanynyl, octadecynyl, hexadecynyl, tridecanynyl, tetradecynyl, and docosynyl, further comprising additional saturated or unsaturated carbons (such as (3E,7E)-4,8,12-trimethyltridecane-3,7,11-trienyl or (1E,3E,7E)-4,8,12-trimethyltridecane-1,3,7,11-tetraenyl), and combinations of at least two of them. According to certain preferred embodiments, the unsaturated aliphatic group, each time it appears, is independently selected from the following groups: decenyl, dodecenyl, undecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, 1,9-decadienyl, dodecenyl, hexadecenyl, eicosene, tetradecenyl, squalene, farnesyl, β-caroteneyl, derivatives of one of these groups further comprising at least one additional saturated or unsaturated carbon, and combinations of at least two of them, preferably selected from the groups decenyl, undecenyl, octadecenyl, squalene, farnesyl, β-caroteneyl, (3E,7E)-4,8,12-trimethyltetracene-3,7,11-trienyl, (1E,3E,7E)-4,8,12-trimethyltetracene-1,3,7,11-tetraenyl, and combinations of at least two of them. According to some examples, the unsaturated aliphatic group contains squalene or farnesyl, or contains both squalene and farnesyl, or derivatives of one of them, such as (3E,7E)-4,8,12-trimethyltetadeca-3,7,11-trienyl or (1E,3E,7E)-4,8,12-trimethyltetadeca-1,3,7,11-tetraenyl.

[0221] Non-limiting examples of unsaturated aliphatic compounds include compounds 1 to 15 or their salts:

[0222] Compound 1

[0223] Compound 2

[0224] Compound 3

[0225] Compound 4

[0226] Compound 5

[0227] Compound 6

[0228] Compound 7

[0229] Compound 8

[0230] Compound 9

[0231] Compound 10

[0232] Compound 11

[0233] Compound 12

[0234] Compound 13

[0235] Compound 14

[0236] Compound 15.

[0237] For example, the compound may be selected from compounds 1 to 9 and 11 to 15, or from compounds 1 to 5, 7 to 9 and 11 to 15, or from compounds 1, 2, 4, 5, 7 to 9 and 11 to 15.

[0238] For example, the compound may be selected from compounds 1 to 9, 11, 12, 14 and 15, or from compounds 1 to 5, 7 to 9, 11, 12, 14 and 15, or from compounds 1, 2, 4, 5, 7 to 9, 11, 12, 14 and 15.

[0239] According to some embodiments, the coating material contains a single aliphatic organic compound. Alternatively, the coating material may contain two or more aliphatic organic compounds.

[0240] In one instance, an unsaturated organic compound, as defined herein, is characterized by a boiling point above about 80°C, or about 100°C, or about 150°C.

[0241] In some cases, the unsaturated organic compound can be in liquid form at 25°C. Alternatively, the unsaturated organic compound can be in solid form at 25°C.

[0242] According to another example, a coating material as defined herein is a mixture comprising an unsaturated organic compound as defined herein and at least one additional component, such as a saturated or unsaturated aliphatic hydrocarbon, a solvent, or a combination thereof.

[0243] As an example, the additional component can be a saturated or unsaturated aliphatic hydrocarbon, such as a saturated or unsaturated aliphatic hydrocarbon having 10 to 50 carbon atoms.

[0244] According to a preferred embodiment, the saturated or unsaturated aliphatic hydrocarbon comprises unsaturated aliphatic hydrocarbons, for example selected from decene, dodecene, undecene, tridecene, tetradecene, pentadecene, hexadecene, heptadecene, octadecene, 1,9-decadiene, dodecene, hexadecene, eicosene, tetradecene, squalene, farnesene, β-carotene, pinene, dicyclopentadiene, camphene, α-phellandrene, β-phellandrene, terpinene, β-myrcene, limonene, 2-carene, juniperene, α-cedrene, cobaene, β-cedrene, decyne, dodecanyne, octadecyne, hexadecyne, tridecanyne, tetradecanyne, dodecyne, and combinations of at least two of them. According to some examples, the unsaturated aliphatic hydrocarbon is selected from decene, dodecene, undecene, tridecene, tetradecene, pentadecene, hexadecene, heptadecene, octadecene, 1,9-decadiene, dodecene, hexadecene, eicosene, tetradecene, squalene, farnesene, β-carotene, and combinations of at least two thereof, preferably selected from decene, undecene, octadecene, squalene, farnesene, β-carotene, and combinations of at least two thereof. For example, the unsaturated aliphatic hydrocarbon may include squalene or farnesene, or combinations thereof.

[0245] According to some implementation schemes, saturated or unsaturated aliphatic hydrocarbons include alkanes, such as decane.

[0246] According to another example, the additional component may contain solvents, such as dichloromethane, tetrahydrofuran, dioxolane, xylene (ortho, meta, or para), toluene, benzene, methoxybenzene and other benzene derivatives, acetonitrile, N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, alkylene carbonate, dialkyl carbonate, and miscible combinations of at least two of these.

[0247] The coating material may contain an unsaturated organic compound at a concentration of at least 2% by volume, or in the range of about 5% to 100%, or about 25% to 100%, or about 40% to 100%, or about 50% to 100%. For example, the unsaturated organic compound may be in the coating material at a concentration of at least 2%, or 5% to 40%, or 5% to 25% when volatile solvents are present during the coating step, and then at a concentration of about 40% to 100%, or about 50% to 100%, after the coated particles have dried and the volatile solvents have been removed.

[0248] This technology also relates to coated particles for use in electrochemical cells. More specifically, the coated particles comprise: - A core comprising electrochemically active materials, electronically conductive materials, ionically conductive inorganic materials, or a combination of two or more of these; and - A coating material, as defined herein, is applied to the surface of the core.

[0249] As an example, the coating material can form a homogeneous coating on the core surface. That is, it can form a substantially uniform coating on the core surface.

[0250] In another example, the coating material can be formed on at least a portion of the core surface. For instance, it can be unevenly dispersed on the core surface.

[0251] It must be understood that the volume ratio or mass ratio of the coating material to the core material, as well as the conditions of the coating method, affect the coverage of the coating material on the surface of the core and / or the uniformity of the coated particle sample. For example, the mass ratio of "coating material:core" is in the range of 0.2:100 to 50:100, or 0.5:100 to 40:100.

[0252] According to some implementation schemes, the core comprises an ion-conducting inorganic material. For example, the ion-conducting inorganic material may be selected from glass, glass-ceramics, ceramics, nanoceramics, and combinations of at least two thereof, preferably ceramics, glasses, or glass-ceramics based on fluorides, phosphides, sulfides, oxysulfides, or oxides. The ion-conducting inorganic material may be a compound of the type of crystalline and / or amorphous LISICON, thio-LISICON, argyrodites, garnet, NASICON, perovskite, oxides, sulfides, oxysulfides, phosphides, fluorides, and combinations of at least two thereof.

[0253] Non-limiting examples of ion-conducting inorganic materials include inorganic compounds with the following formula: MLZO (e.g., M7La3Zr2O) 12 M (7-a) La3Zr2Al b O12 M (7-a) La3Zr2Ga b O 12 M (7-a) La3Zr (2-b) Ta b O 12 and M (7-a) La3Zr (2-b) Nb b O 12 ); MLTAO (e.g., M7La3Ta2O) 12 M5La3Ta2O 12 and M6La3Ta 1.5 Y 0.5 O 12 ); MLSnO (e.g., M7La3Sn2O) 12 ); MAGP (e.g., M 1+a Al a Ge 2-a (PO4)3); MATP (e.g., M) 1+a Al a Ti 2-a (PO4)3); MLTiO (e.g., M) 3a La (2 / 3-a) TiO3); MZP (e.g., M) a Zr b (PO4) c ); MCZP (e.g., M a Ca b Zr c (PO4) d ); MGPS (e.g., M a Ge b P c S d , such as M 10 GeP2S 12 ); MGPSO (e.g., M a Ge b P c S d O e ); MSiPS (e.g., M a Si b P c S d , such as M 10 SiP2S 12 ); MSiPSO (e.g., M a Si b P c S d O e ); MSnPS (e.g., M a Snb P c S d , such as M 10 SnP2S 12 ); MSnPSO (e.g., M a Sn b P c S d O e ); MPS (e.g., M a P b S c such as M7P3S 11 ); MPSO (e.g., M a P b S c O d ); MZPS (e.g., M a Zn b P c S d ); MZPSO (e.g., M a Zn b P c S d O e ); xM2S-yP2S5; xM2S-yP2S5-zMX; xM2S-yP2S5-zP2O5; 2S-yM2O-zP2S5-wMX; xM2S-yM2O-zP2S5-wP2O5; xM2S-yM2O-zP2S5-wP2O5-vMX; a P b S c X d such as M7P3S 11 X, M7P2S8X and M6PS5X (e.g., Li6PS5Cl); MPSOX (e.g., M a P b S c O d X e ); MGPSX (e.g., M a Ge b P c S d X e ); MGPSOX (e.g., M a Ge b P c S d O e X f ); MSiPSX (e.g., M a Sib P c S d X e ); MSiPSOX (e.g., M a Si b P c S d O e X f ); MSnPSX (e.g., M a Sn b P c S d X e ); MSnPSOX (e.g., M a Sn b P c S d O e X f ); MZPSX (e.g., M a Zn b P c S d X e ); MZPSOX (e.g., M a Zn b P c S d O e X f ); M3OX; M2HOX; M3PO4; M3PS4; and M a PO b N c (where a = 2b + 3c - 5); in: M is an alkali metal ion, an alkaline earth metal ion, or a combination thereof, wherein when M contains an alkaline earth metal ion, the amount of M is adjusted to achieve electroneutrality. X is selected from F, Cl, Br, I, or a combination of at least two of them; a, b, c, d, e, and f are values ​​other than 0 and are chosen independently in each formula to achieve electrical neutrality; and v, w, x, y, and z are numerical values ​​other than 0 and are chosen independently in each formula to obtain a stable compound.

[0254] For example, M can be selected from Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, Ba or a combination of at least two of them, preferably M is Li.

[0255] According to some implementation schemes, the ion-conducting inorganic material is selected from the formula Li a P b S c X dAn inorganic compound, wherein X is Cl, Br, I, or a combination of at least two of them, and a, b, c, and d such that (a + 5b) = (2c + d), for example, Li6PS5Cl. Alternatively, an ion-conducting inorganic material may be selected from the formula Li a P b S c O d X e An inorganic compound, wherein X is Cl, Br, I, or a combination of at least two of them, and a, b, c, d, and e such that (a + 5b) = (2c + 2d + e), for example, a is selected from the range of 5 to 6, b is equal to 1, c is selected from the range of 3.5 to 4.8, and e is selected from the range of 1 to 2; preferably, the ion-conducting inorganic material is Li. 5.4 PS 4.1 O 0.3 X 1.6 Or Li 5.4 PS 4.1 O 0.3 ClBr 0.5 I 0.1 .

[0256] According to other implementation schemes, the core contains electrochemically active materials.

[0257] In some cases, the electrochemically active material may be selected from metal oxides, metal sulfides, metal oxysulfides, metal phosphates, metal fluorophosphates, metal oxyfluorophosphates, metal sulfates, metal halides, metal fluorides, sulfur, selenium, and combinations of at least two of these. For example, the metal of the electrochemically active material may be selected from titanium (Ti), iron (Fe), manganese (Mn), vanadium (V), nickel (Ni), cobalt (Co), aluminum (Al), chromium (Cr), copper (Cu), zirconium (Zr), niobium (Nb), and combinations of at least two of these; it may further contain alkali metals or alkaline earth metals selected from lithium (Li), sodium (Na), potassium (K), and magnesium (Mg).

[0258] Non-limiting examples of electrochemically active materials include lithium-metal phosphates, composite oxides such as LiM'PO4 (where M' is Fe, Ni, Mn, Co or a combination thereof), LiV3O8, V2O5, LiMn2O4, LiM''O2 (where M'' is Mn, Co, Ni or a combination thereof), Li(NiM''')O2 (where M''' is Mn, Co, Al, Fe, Cr, Ti or Zr or a combination thereof), and compatible combinations thereof. In a preferred embodiment, the electrochemically active material is a lithium-metal oxide, such as a mixed lithium, nickel, manganese and cobalt oxide (NCM). Alternatively, the electrochemically active material is a lithium-metal phosphate, such as lithium iron phosphate. According to another alternative, the electrochemically active material is a manganese-containing lithium-metal phosphate, such as those mentioned above, for example, a manganese-containing lithium-metal phosphate is lithium iron manganese phosphate (LiMn... 1-x Fe x PO4, where x is between 0.2 and 0.5.

[0259] According to another example, the electrochemically active material is the negative electrode material, selected from non-alkali metals and non-alkaline earth metals (e.g., indium (In), germanium (Ge), and bismuth (Bi)), intermetallic compounds (e.g., SnSb, TiSnSb, Cu2Sb, AlSb, FeSb2, FeSn2, and CoSn2), metal oxides, metal nitrides, metal phosphides, metal phosphates (e.g., LiTi2(PO4)3), metal halides (e.g., metal fluorides), metal sulfides, metal oxysulfides, carbon (e.g., graphite, graphene, reduced graphene oxide, hard carbon, soft carbon, exfoliated graphite, and amorphous carbon), silicon (Si), silicon-carbon composites (Si-C), and silicon oxides (SiO2). x ), silicon oxide-carbon composite material (SiO) x -C), tin (Sn), tin-carbon composites (Sn-C), tin oxides (SnO) x ), Tin oxide-carbon composite material (SnO) x -C) and, when compatible, their combinations. For example, metal oxides can be selected from formula M'''' b O cCompounds (where M'''' is Ti, Mo, Mn, Ni, Co, Cu, V, Fe, Zn, Nb or combinations thereof; and b and c are values ​​such that the c:b ratio is in the range of 2 to 3) (e.g., MoO3, MoO2, MoS2, V2O5 and TiNb2O7), spinel oxides (e.g., NiCo2O4, ZnCo2O4, MnCo2O4, CuCo2O4 and CoFe2O4) and LiM''''O (where M''''' is Ti, Mo, Mn, Ni, Co, Cu, V, Fe, Zn, Nb or combinations thereof) (e.g., lithium titanate (such as Li4Ti5O) 12 ) or lithium molybdenum oxide (such as Li2Mo4O) 13 )).

[0260] Electrochemically active materials may further include dopant elements, which are additional elements present in a smaller proportion to partially replace the metal in the material, for example, to modulate or optimize its electrochemical properties. Electrochemically active materials can be doped by partially replacing the metal with other ions. For example, electrochemically active materials can be doped with transition metals (e.g., Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, or Y) and / or non-transition metals (e.g., Mg, Al, or Sb).

[0261] The electrochemically active material may further include a covering material. For example, when present, the covering material preferably forms a covering layer on the surface of the electrochemically active material, and the coating material is disposed on the surface of the covering layer.

[0262] In some instances, the coating material is selected from Li₂SiO₃, LiTaO₃, LiAlO₂, Li₂O-ZrO₂, LiNbO₃, other similar coating materials, and combinations of at least two of them, such as LiNbO₃. Alternatively, the coating material is an electronically conductive material, preferably containing carbon.

[0263] According to one implementation, the core of the coated particles contains an electronically conductive material.

[0264] Non-limiting examples of electronically conductive materials include carbon sources such as carbon black (e.g., Ketjen™ carbon and Super P™ carbon), acetylene black (e.g., Shawinigan carbon and Denka™ carbon black), graphite, graphene, carbon fibers (e.g., vapor-grown carbon fibers (VGCF)), carbon nanofibers, carbon nanotubes (CNTs), and combinations of at least two of these. According to one example, the electronically conductive material is carbon black.

[0265] According to another example, the electronically conductive material can be a modified electronically conductive material, such as those described in PCT patent application publication number WO2019 / 218067 (Delaporte et al.). For example, the modified electronically conductive material can be grafted with at least one aryl group of formula A: Formula A in: FG is a hydrophilic functional group; and h is an integer in the range of 1 to 5, h is preferably in the range of 1 to 3, h is preferably 1 or 2, and h is more preferably 1.

[0266] Examples of hydrophilic functional groups include hydroxyl, carboxyl, sulfonic acid, phosphonic acid, amine, amide, and other similar groups. For example, the hydrophilic functional group can be a carboxylic acid or a sulfonic acid. The functional group can optionally be lithiumized by exchanging a hydrogen atom with a lithium atom. Preferred examples of the aryl group of formula A are p-benzoic acid or p-benzenesulfonic acid.

[0267] According to one related variant, the electronically conductive material is carbon black optionally grafted with at least one aryl group of formula A. According to another related variant, the electronically conductive material can be a mixture comprising at least one modified electronically conductive material. For example, a mixture of carbon black grafted with at least one aryl group of formula A and carbon fibers (e.g., vapor-grown carbon fibers (VGCF)), carbon nanofibers, carbon nanotubes (CNTs), or combinations thereof.

[0268] This also relates to the use of coated particles in electrochemical applications as defined herein. For example, coated particles can be used in electrochemical cells and electrochemical storage batteries, particularly all-solid-state battery packs. For example, coated particles can be used in electrode materials, in electrolytes, as an additional layer at the interface between the two, or on current collectors.

[0269] This technology also relates to a method for manufacturing coated particles as defined herein, the method comprising the step of coating at least a portion of the surface of a core with the coating material. This coating step can be performed by any suitable coating method. For example, the coating step can be performed by a dry or wet coating method. According to a related variant, the coating step can be performed by a wet coating method, such as by a mechanical coating method, like mixing, grinding, mechanical synthesis, or mechanical fusion.

[0270] According to one example, the method further includes the step of grinding (or pulverizing) the electrochemically active material, electronically conductive material, or ionically conductive inorganic material of the core of the coated particles. For example, the coating and grinding steps can be performed simultaneously, sequentially, or partially overlap in time. When the coating and grinding steps are performed sequentially, the grinding step can be performed before the coating step. In another related variation, the coating and grinding steps are performed simultaneously, for example, using a planetary mill or a planetary micromill.

[0271] According to another example, the coating and grinding steps can be performed at a certain rotational speed for a defined time to achieve optimal particle size or diameter, desired coverage of the coating material on the surface of the particle nuclei, and / or desired uniformity of the coated particle sample.

[0272] According to some examples, the coating and polishing steps are performed at a rotational speed of about 300 rpm for about 7.5 hours to obtain coated particles with a final particle size of less than or equal to about 1 µm, for example, the average diameter of the particles is less than 500 nm, or less than 400 nm, or less than 300 nm.

[0273] According to another example, the method further includes a step of drying the coated particles. According to one example, the drying step may be performed to remove residual moisture and / or solvent. According to another example, the drying process may be carried out at a low temperature for a defined time to dry the coated particles without causing the coating material to evaporate or significantly evaporate. For example, the drying step may be carried out for a defined time at a temperature below the boiling point of the unsaturated aliphatic hydrocarbon in the coating material to avoid evaporation or significant evaporation. It is to be understood that when the coating material contains a mixture, at least one unsaturated aliphatic hydrocarbon will not completely evaporate during the drying step and thus remain present in the coating disposed on the surface of the particle core. For example, when the mixture includes additional components (such as alkanes as defined above or mixtures containing alkanes and polar solvents), this may partially or completely evaporate during the drying step. For example, the drying step may be carried out at a temperature of approximately 80°C for a duration of approximately 5 hours.

[0274] According to another example, when the coating material comprises a mixture, during the coating step, the mixture comprises at least about 2% by volume, between 5% by volume and 40% by volume, or between 5% by volume and 25% by volume of an unsaturated organic compound as defined herein.

[0275] In another example, the method further includes the step of coating (also called spreading) a suspension containing the coated particles, the spreading step being performed, for example, by at least one of blade coating, comma coating, reverse-comma coating, printing methods such as gravure coating, or slot die coating. In a related variant, the spreading step is performed by blade coating. According to one example, the suspension containing the coated particles can be coated onto a substrate or support film, followed by removal of the substrate or support film. According to another example, the suspension containing the particles can be directly coated onto a current collector.

[0276] This technology also relates to an electrode material comprising an electrochemically active material, an electronically conductive material, and optionally an ionically conductive inorganic material, wherein at least one of the electrochemically active material, the electronically conductive material, or the ionically conductive inorganic material comprises coated particles as defined above.

[0277] In some implementations, the electrode material comprises an ion-conducting inorganic material. According to some examples, the ion-conducting inorganic material may be contained within the core of the coated particles. Whether or not it is contained within the core of the coated particles, the ion-conducting inorganic material may be as defined above for the coated particles.

[0278] The electrochemically active material of the electrode material may be in the form of particles (e.g., microparticles and / or nanoparticles), which may be newly formed or from commercial sources. In some instances, the electrochemically active material may be incorporated into the core of the coated particles. The electrochemically active material, whether or not incorporated into the coated particles, can be as defined above.

[0279] According to some implementation schemes, the core of the coated particles contains an electronically conductive material. This electronically conductive material can be as defined above, whether or not it is included in the coated particles.

[0280] The electrode material may further comprise a binder. For example, the binder is selected based on its compatibility with various components of the electrochemical cell. Consider any known compatible binder. For example, the binder may be selected from polymeric binders such as polyethers, polyesters, polycarbonates, fluoropolymers, and water-soluble binders, or copolymers or compatible combinations of two or more of these. According to one example, the binder is a fluoropolymer such as polyvinylidene fluoride (PVDF) or polytetrafluoroethylene (PTFE). According to another example, the binder is a water-soluble binder such as styrene-butadiene rubber (SBR), acrylonitrile-butadiene rubber (NBR), hydrogenated NBR (HNBR), epichlorohydrin rubber (CHR), or acrylate rubber (ACM), and optionally contains a thickener such as carboxymethyl cellulose (CMC), or a polymer such as poly(acrylic acid) (PAA), poly(methyl methacrylate) (PMMA), or a combination of at least two of these. According to yet another example, the binder is a polyether-type polymeric binder. For example, polyether-type polymer adhesives are linear, branched, and / or crosslinked, and are based on poly(ethylene oxide) (POE), poly(propylene oxide) (POP), or a combination of both (such as OE / PO copolymers), and optionally contain crosslinkable units. For example, the crosslinkable segments of the polymer may be polymer segments containing at least one functional group that can be multidimensionally crosslinked by irradiation or heat treatment.

[0281] According to one related variant, the binder, if present in the electrode material, may comprise a mixture comprising a first polymer based on polybutadiene and a second polymer comprising norbornene monomer units obtained by polymerization of double bonds of compounds of formula B: Formula B in, R a and R b It is selected independently and each time it appears, from hydrogen atom, carboxyl group (-COOH), sulfonic acid group (-SO3H), hydroxyl group (-OH), fluorine atom and chlorine atom.

[0282] Based on an example, R a and R b At least one of them is selected from -COOH, -SO3H, -OH, -F and -Cl, which means that R a and R b At least one of them is different from a hydrogen atom. According to another example, R a or R b At least one of them is a -COOH group, and the norbornene monomer unit is a monomer unit based on carboxylic acid-functionalized norbornene. According to a related variant, R a It is a -COOH group, and R b It is a hydrogen atom. According to another related variant, Ra and R b Both are -COOH groups. According to another related variant, R... a and R b They are all hydrogen atoms.

[0283] According to another related variant, the binder, if present in the electrode material, may comprise a mixture including polybutadiene-based polymers and polymers of formula C: Formula C in, R a and R b As defined above, and j is an integer, chosen such that the mass-average molecular weight of the polymer of formula C, as determined by gel permeation chromatography (GPC), is between approximately 10,000 g / mol and approximately 100,000 g / mol, including the upper and lower limits.

[0284] According to another example, as determined by GPC, the mass-average molecular weight of the polymer of formula C is between about 12,000 g / mol and about 85,000 g / mol, or between about 15,000 g / mol and about 75,000 g / mol, or between about 20,000 g / mol and about 65,000 g / mol, or between about 25,000 g / mol and about 55,000 g / mol, or between about 25,000 g / mol and about 50,000 g / mol, including the upper and lower limits.

[0285] According to another example, polymers of norbornene based on formula B or polymers of formula C are homopolymers.

[0286] According to another example, the polymerization of norbornene monomers of formula B can be carried out by any known suitable polymerization method. According to a related variant, the polymerization of compounds of formula B can be carried out by the synthetic method described by Commarieu, B. et al. (Commarieu, Basile et al., "Ultrahigh T..."). g (Epoxy Thermosets Based on Insertion Polynorbornenes, Macromolecules, 49.3 (2016): 920-925). For example, the polymerization of compounds of formula B can also be carried out by addition polymerization.

[0287] For example, norbornene polymers prepared by addition polymerization are essentially stable under harsh conditions (e.g., acidic and alkaline conditions). Addition polymerization of norbornene polymers can be carried out using inexpensive norbornene monomers. The glass transition temperature (Tg) obtained using norbornene polymers prepared via this polymerization route is... v It can be equal to or higher than approximately 300°C, for example, up to 350°C.

[0288] According to another example, polybutadiene polymers can be characterized by significantly higher elasticity or flexibility and / or significantly lower glass transition temperature (T0) compared to norbornene polymers of formula C. v ).

[0289] In another example, the first polybutadiene polymer may be polybutadiene. Alternatively, the first polybutadiene polymer may be functionalized polybutadiene or a polybutadiene-derived polymer. For example, compared to non-functionalized polybutadiene, functionalized polybutadiene or polybutadiene-derived polymers may be characterized by significantly higher elasticity or flexibility, and / or a significantly lower glass transition temperature (Tg). v ), and / or may improve the mechanical or cohesive properties of the electrode adhesive.

[0290] According to another example, the first polybutadiene polymer is selected from epoxidized polybutadiene, such as epoxidized polybutadiene having reactive end groups. For example, the reactive end group may be hydroxyl. Epoxidized polybutadiene may comprise repeating units of formula E and repeating units of formula D and / or F and two hydroxyl end groups:

[0291] Formula D, Formula E, Formula F.

[0292] According to another example, as determined by GPC, the mass-average molecular weight of epoxidized polybutadiene containing repeating units of formulas E and D and / or F can be between about 1,000 g / mol and about 1,500 g / mol, including the upper and lower limits.

[0293] According to another example, as determined by GPC, the epoxy equivalent weight of epoxidized polybutadiene containing repeating units of formula E, D, and / or F is between about 100 g / mol and about 600 g / mol, including the upper and lower limits. The epoxy equivalent weight corresponds to the mass of resin containing 1 mole of epoxy functional group.

[0294] According to a related variant, epoxidized polybutadiene has formula G: Formula G in k is an integer chosen such that, as determined by GPC, the mass-average molecular weight of the epoxidized polybutadiene of formula G is between approximately 1,000 g / mol and approximately 1,500 g / mol, including both the upper and lower limits; and If determined by GPC, the epoxy equivalent weight is between approximately 100 g / mol and approximately 600 g / mol, including the upper and lower limits.

[0295] According to another example, as determined by GPC, the mass-average molecular weight of epoxidized polybutadiene containing repeating units of formulas E and D and / or F, or epoxidized polybutadiene of formula G, is between about 1,050 g / mol and about 1,450 g / mol, or between about 1,100 g / mol and about 1,400 g / mol, or between about 1,150 g / mol and about 1,350 g / mol, or between about 1,200 g / mol and about 1,350 g / mol, or between about 1,250 g / mol and about 1,350 g / mol, including the upper and lower limits. According to a related variant, as determined by GPC, the mass-average molecular weight of epoxidized polybutadiene containing repeating units of formulas E and D and / or F, or epoxidized polybutadiene of formula G, is about 1,300 g / mol.

[0296] According to another example, the epoxy equivalent weight of epoxidized polybutadiene containing repeating units of formulas E and D and / or F, or epoxidized polybutadiene of formula G, is between about 150 g / mol and about 550 g / mol, or between about 200 g / mol and about 550 g / mol, or between about 210 g / mol and about 550 g / mol, or between about 260 g / mol and about 500 g / mol, including the upper and lower limits. According to a related variant, as determined by GPC, the epoxy equivalent weight of epoxidized polybutadiene containing repeating units of formulas E and D and / or F, or epoxidized polybutadiene of formula G, is between about 400 g / mol and about 500 g / mol, or between about 260 g / mol and about 330 g / mol, including the upper and lower limits.

[0297] For example, the epoxidized polybutadiene of formula G is a commercially available epoxidized polybutadiene resin with hydroxyl end groups, such as Poly bd™ sold by CrayValley. 600E or 605E. The physicochemical properties of these resins are shown in Table 1.

[0298] Table 1. Physicochemical properties of Poly BD 600E and 605E resins

[0299] It should be understood that the electrode binder comprises a polymer blend including at least one first polymer and at least one second polymer. The first polymer is a polybutadiene polymer, and the second polymer is a polymer comprising norbornene monomer units polymerized from compounds derived from formula B or a polymer of formula C.

[0300] According to another example, the weight ratio of "first polymer:second polymer" is in the range of approximately 6:1 to approximately 2:3, including both the upper and lower limits. For example, the weight ratio of "first polymer:second polymer" is in the range of approximately 5.5:1 to approximately 2:3, or approximately 5:1 to approximately 2:3, or approximately 4.5:1 to approximately 2:3, or approximately 4:1 to approximately 2:3, or approximately 6:1 to approximately 1:1, or approximately 5.5:1 to approximately 1:1, or approximately 5:1 to approximately 1:1, or approximately 4.5:1 to approximately 1:1, or approximately 4:1 to approximately 1:1, including both the upper and lower limits. According to a related variant, the weight ratio of "first polymer:second polymer" is in the range of approximately 5:1 to approximately 2:1, including both the upper and lower limits.

[0301] This technology also relates to an electrode comprising an electrode material as defined herein. According to one example, the electrode may be on a current collector (e.g., an aluminum or copper sheet). Alternatively, the electrode may be self-supporting.

[0302] This technology also relates to an electrolyte comprising coated particles as defined herein, wherein the core of the coated particles comprises an ion-conducting inorganic material.

[0303] As an example, the electrolyte can be selected based on its compatibility with various components of the electrochemical cell. Consider any type of compatible electrolyte. In one example, the electrolyte is a liquid electrolyte comprising a solvent and an optional salt. Alternatively, the electrolyte is a gel electrolyte comprising a solvent, an optional solvated polymer, and an optional salt. Another alternative is a solid electrolyte further comprising a solvated polymer and an optional salt. For example, the electrolyte is a hybrid polymer-ceramic solid electrolyte. According to another alternative, the electrolyte is an inorganic solid electrolyte; for example, the electrolyte could be a ceramic-type solid electrolyte.

[0304] According to another example, the electrolyte may further comprise a salt. If present, this salt may be an ionic salt of an alkali metal, such as a lithium salt. Non-limiting examples of lithium salts include lithium hexafluorophosphate (LiPF6), lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), lithium bis(fluorosulfonyl)imide (LiFSI), lithium 2-trifluoromethyl-4,5-dicyanoimidazolium (LiTDI), lithium 4,5-dicyano-1,2,3-triazole (LiDCTA), lithium bis(pentafluoroethylsulfonyl)imide (LiBETI), lithium difluorophosphate (LiDFP), lithium tetrafluoroborate (LiBF4), lithium bis(oxalate)borate (LiBOB), lithium nitrate (LiNO3), lithium chloride (LiCl), and lithium bromide (LiBr). Lithium fluoride (LiF), lithium perchlorate (LiClO4), lithium hexafluoroarsenate (LiAsF6), lithium trifluoromethanesulfonate (LiSO3CF3) (LiOTf), lithium fluoroalkyl phosphate Li[PF3(CF2CF3)3] (LiFAP), lithium tetratetrafluoroacetoxy borate Li[B(OCOCF3)4] (LiTFAB), lithium bis(1,2-phenylene glycol (2-)-O,O')borate Li[B(C6O2)2] (LiBBB), lithium difluoro(oxalic acid)borate (LiBF2(C2O4)) (LiFOB), and LiBF2O4R x salt (of which R) x = C2-C4 alkyl), and combinations of at least two of them.

[0305] According to another example, if present in an electrolyte, the solvent can be a non-aqueous solvent. Non-limiting examples of solvents include cyclic carbonates such as ethylene carbonate (EC), propylene carbonate (PC), butyl carbonate (BC), and vinylene carbonate (VC); acyclic carbonates such as dimethyl carbonate (DMC), diethyl carbonate (DEC), ethyl methyl carbonate (EMC), and dipropyl carbonate (DPC); lactones such as γ-butyrolactone (γ-BL) and γ-valerolactone (γ-VL); and acyclic ethers such as 1,2-dimethoxyethane. (DME), 1,2-diethoxyethane (DEE), ethoxymethoxyethane (EME), trimethoxymethane and ethyl monoethylene glycol dimethyl ether; cyclic ethers, such as tetrahydrofuran, 2-methyltetrahydrofuran, 1,3-dioxolane and dioxolane derivatives; and other solvents, such as dimethyl sulfoxide, formamide, acetamide, dimethylformamide, acetonitrile, propionitrile, nitromethane, triphosphate, sulfolane, methylsulfolane, propylene carbonate derivatives and mixtures thereof.

[0306] According to another example, the electrolyte is a gel electrolyte or a polymeric gel electrolyte. A polymeric gel electrolyte may contain, for example, a polymeric precursor and a salt (e.g., a salt as previously defined), a solvent (e.g., a solvent as previously defined), and, if desired, a polymerization and / or crosslinking initiator. Examples of gel electrolytes include, but are not limited to, those described in PCT patent applications with publication numbers WO2009 / 111860 (Zaghib et al.) and WO2004 / 068610 (Zaghib et al.).

[0307] According to another example, gel electrolytes or liquid electrolytes, as previously defined, can also impregnate the membrane, such as polymer membranes. Examples of membranes include, but are not limited to, polyethylene (PE), polypropylene (PP), cellulose, polytetrafluoroethylene (PTFE), poly(vinylidene fluoride) (PVDF), and polypropylene-polyethylene-polypropylene (PP / PE / PP) membranes. For example, the membrane is a commercial polymer membrane of the Celgard™ type.

[0308] According to another example, the electrolyte is a solid polymer electrolyte. For example, the solid polymer electrolyte can be selected from any known solid polymer electrolyte and can be chosen based on its compatibility with various components of the electrochemical cell. Solid polymer electrolytes typically contain a salt and one or more optionally crosslinked solid polar polymers. Polyether-type polymers, such as those based on poly(ethylene oxide) (POE), can be used, but several other suitable polymers are also known for the preparation of solid polymer electrolytes and are considered. The polymer can be crosslinked. Examples of such polymers include branched polymers, such as star-shaped or comb-shaped polymers, as described in PCT patent application publication number WO2003 / 063287 (Zaghib et al.).

[0309] According to another example, the solid polymer electrolyte may comprise a sequenced copolymer consisting of at least one lithium-ion solvation segment and optionally at least one crosslinkable segment. Preferably, the lithium-ion solvation segment is selected from homopolymers or copolymers having repeating units having the following formula:

[0310] in, R is selected from hydrogen atoms and C1-C. 10 Alkyl or –(CH2-OR) x R y ) group; R x It is (CH2-CH2-O) i ; R y Selected from hydrogen atoms and C1-C 10alkyl; g is an integer selected from the range of 10 to 200,000; and i is an integer selected from the range 0 to 10.

[0311] According to another example, the crosslinkable segment of the copolymer is a polymer segment containing at least one functional group that can be multidimensionally crosslinked by irradiation or heat treatment.

[0312] When the electrolyte is a liquid electrolyte, gel electrolyte, or solid polymer electrolyte, coated particles, as defined herein, may be present as additives in the electrolyte.

[0313] When the electrolyte is a hybrid polymer-ceramic solid electrolyte or a ceramic-type solid electrolyte, the coated particles, as defined herein, can exist as inorganic solid electrolyte materials (e.g., as ceramics).

[0314] According to another example, the electrolyte may optionally include additional components such as ionicly conductive materials, inorganic particles, glass or ceramic particles as defined above, and other similar additives. The electrolyte may further include at least one organic additive (e.g., ionic organic additives (liquid or solid), thiols, plasticizers, etc.). In another example, the additional component may be a dicarbonyl compound, such as those described in PCT patent application publication number WO2018 / 116529 (Asakawa et al.). For example, the additional component may be poly(ethylene-alt-maleic anhydride) (PEMA). The additional component may be selected based on its compatibility with various elements of the electrochemical cell. In one example, the additional component may be substantially dispersed in the electrolyte. Alternatively, the additional component may be present in a separate layer.

[0315] This technology also relates to a coating material for a current collector comprising coating particles as defined herein, wherein the core of said coating particles comprises an electronically conductive material. For example, the coating particles may be coated conductive carbon particles that can be coated onto a metal current collector foil (e.g., an aluminum or copper sheet). Current collectors comprising a coating material coated onto a metal sheet have also been designed.

[0316] This technology also relates to an electrochemical battery comprising a negative electrode, a positive electrode, and an electrolyte, wherein at least one of the positive or negative electrodes is as defined herein or comprises an electrode material as defined herein.

[0317] According to a relevant variant, the negative electrode is as defined herein or comprises electrode materials as defined herein. For example, the electrochemical material of the negative electrode can be selected based on its electrochemical compatibility with various components of an electrochemical cell as defined herein. For example, the electrochemical material of the negative electrode may have a much lower redox potential than the electrochemically active material of the positive electrode.

[0318] According to another related variant, the positive electrode is as defined herein or comprises an electrode material as defined herein, and the negative electrode comprises an electrochemically active material selected from all known compatible electrochemically active materials. For example, the electrochemically active material of the negative electrode may be selected based on its electrochemical compatibility with various components of an electrochemical cell as defined herein. Non-limiting examples of electrochemically active materials for the negative electrode include alkali metals, alkaline earth metals, alloys comprising at least one alkali metal or alkaline earth metal, non-alkali metals and non-alkaline earth metals (e.g., indium (In), germanium (Ge), and bismuth (Bi)), and intermetallic alloys or compounds (e.g., SnSb, TiSnSb, Cu2Sb, AlSb, FeSb2, FeSn2, and CoSn2). For example, the electrochemically active material of the negative electrode may be in the form of a film with a thickness of about 5 µm to about 500 µm, preferably about 10 µm to about 100 µm (inclusive of the upper and lower limits). According to a related variant, the electrochemically active material of the negative electrode may comprise a film of lithium metal or an alloy containing or based on lithium metal.

[0319] In another example, the positive electrode may be pre-lithiated, while the negative electrode may initially (i.e., before electrochemical cell cycling) be substantially or completely lithium-free. The negative electrode may be in-situ lithiated during the cycling of the electrochemical cell, particularly during the first charge. In another example, metallic lithium may be deposited in-situ on a current collector (e.g., a copper current collector) or a non-lithiated material during the cycling of the electrochemical cell, particularly during the first charge. In yet another example, an alloy containing metallic lithium may be formed on the surface of a current collector (e.g., an aluminum current collector) or another metal during the cycling of the electrochemical cell, particularly during the first charge. It should be understood that the negative electrode may be formed in-situ during the cycling of the electrochemical cell, particularly during the first charge.

[0320] According to another related variant, both the positive and negative electrodes are as defined herein, or both contain electrode materials as defined herein.

[0321] This technology also relates to an electrochemical battery comprising a negative electrode, a positive electrode, and an electrolyte, wherein the electrolyte is as defined herein.

[0322] This technology also relates to an electrochemical cell comprising a negative electrode, a positive electrode, and an electrolyte, wherein at least one of the positive and negative electrodes is on a current collector as defined herein or comprising a coating material as defined herein.

[0323] This technology also relates to a battery pack comprising at least one electrochemical cell as defined herein. For example, the battery pack can be a primary battery pack (galvanic cell) or a secondary battery pack (rechargeable battery). According to one example, the battery pack is selected from lithium battery packs, lithium-ion battery packs, sodium battery packs, sodium-ion battery packs, magnesium battery packs, magnesium-ion battery packs, potassium battery packs, and potassium-ion battery packs. In another related variant, the battery pack is an all-solid-state battery pack.

[0324] As another example, this coating material can significantly reduce the number and size of particle agglomerates in a dispersion. For instance, it can significantly reduce the number and size of particle agglomerates in electrochemically active materials in electrode materials, electronically conductive materials in electrode materials or current collectors, or inorganic materials in electrolytes or electrode materials. Unrestricted by theory, for example, the repulsive interactions associated with this coating material can improve the dispersion of the positive electrode component within the dispersion, regardless of whether other components capable of achieving these types of interactions are modified. For example, the repulsive interactions can be π-π type and / or polar type interactions.

[0325] In some cases, this coating material also allows the use of solvents that are typically incompatible with the materials contained in the core of the coated particles.

[0326] According to another example, the coating material can also significantly limit parasitic reactions with other components of the electrochemical cell, and thus improve the cycle and aging stability of the electrochemical cell.

[0327] As another example, this coating material can also significantly limit charge transfer resistance and, due to the double or triple bonds present within the coating material, can significantly improve ionic and / or electronic conductivity. Unrestricted by theory, the π orbitals of the coating material, as defined herein, can allow orbital delocalization and thus interaction with the orbitals of ions and / or electrons.

[0328] As another example, this coating material can also significantly improve the safety of electrochemical cells, for instance, by reducing gas generation. For example, when applied to particles of sulfide-based ceramic electrolyte materials, the coating can significantly reduce the amount of hydrogen sulfide (H2S) generated due to the coated material being exposed to moisture or ambient air.

[0329] According to one example, the coating material may also include additional organic compounds or molecules to capture gas molecules (e.g., H2S) and / or form a barrier to reduce moisture intrusion and H2S formation.

[0330] Example

[0331] The following embodiments are for illustrative purposes only and should not be construed as further limiting the scope of the invention as intended. These embodiments are better understood with reference to the accompanying drawings.

[0332] Example 1 – Preparation of Unsaturated Organic Compounds

[0333] (a) Preparation of difarnesyl ether (compound 1)

[0334] The preparation of compound 1 was inspired by FM Istrate, F. Gagosz, Beilstein Journal of Organic Chemistry, 2011, 7, 878-885.

[0335] In a pre-dried Schlenk apparatus, 5.32 g of farnesol (23.91 mmol, 1 equivalent) was dissolved in 48 mL of anhydrous tetrahydrofuran (0.5 M), and the solution was cooled to 0 °C under an inert atmosphere. 1.15 g of sodium hydride (60% dispersed in mineral oil, 1.2 equivalent) was added, and the solution was stirred at room temperature for 10 to 15 minutes.

[0336] Next, the reaction mixture was cooled to 0°C, and 8.18 g of farnesyl bromide (1.2 equivalents) was added dropwise. The reaction was then stirred overnight at room temperature under an inert atmosphere.

[0337] The reaction was treated with a saturated ammonium chloride aqueous solution, the aqueous phase was extracted three times with diethyl ether, the combined organic phase was washed with water and brine, dried over anhydrous magnesium sulfate, filtered, and evaporated under vacuum.

[0338] The resulting oil was purified by rapid chromatography on silica (hexane / dichloromethane eluent) to give compound 1 (8.4 g) in the form of a pale yellow oil.

[0339] (b) Preparation of difarne sulfide (compound 2)

[0340] The preparation of compound 2 was inspired by TW Gaines et al., Macromol. Chem. Phys., 2016, 217, 2351-2359.

[0341] In a round-bottom flask, 12.63 g of sodium sulfide nonahydrate (52.58 mmol, 1.5 equivalents) was dissolved in 50 mL of anhydrous ethanol (1 mL / mmol sodium sulfide nonahydrate). 10 g of farnesyl bromide (35.5 mmol, 1.0 equivalents) was added, and the reaction was heated under reflux for 72 hours. Then, 50 mL of water was added, and the aqueous phase was extracted twice with hexane. The combined organic phases were washed three times with water and brine, dried over anhydrous magnesium sulfate, filtered, and evaporated under vacuum.

[0342] The resulting oil was purified by rapid chromatography on silica (hexane / dichloromethane eluent) to give compound 2 (6 g) in the form of a pale yellow oil.

[0343] (c) Preparation of diethyl farnesylphosphonate (compound 3)

[0344] A mixture of farnesyl bromide (4.3 g, 15.07 mmol) and triethyl phosphite (7 mL, 40.82 mmol) was heated at 80 °C for 3 hours with stirring. After returning to room temperature, 25 mL of diethyl ether was added, and the solution was washed with water (3 x 25 mL). The organic phase was dried over anhydrous magnesium sulfate, filtered, and evaporated. The resulting oil was purified by rapid chromatography on silica gel using hexane / ethyl acetate as eluent to give compound 3 (4.48 g) as a pale yellow oil.

[0345] (d) Preparation of 1-bromo-4-[(1E,3E,7E)-4,8,12-trimethyldecadec-1,3,7,11-tetraenyl]benzene (compound 4)

[0346] In a pre-dried Schlenk apparatus containing 10 mL of anhydrous tetrahydrofuran, compound 3 (4 g, 11.68 mmol) prepared in Example 1(c) was added, and the solution was cooled to 0 °C under an inert atmosphere. A potassium tert-butoxide solution (12.74 mL, 12.74 mmol) was added dropwise, and the mixture was stirred for 10 to 15 minutes. Then, a solution of 4-bromobenzaldehyde in 10 mL of anhydrous dichloromethane was added, and the mixture was stirred overnight at room temperature. The reaction was stopped with a saturated aqueous ammonium chloride solution, the aqueous phase was extracted three times with dichloromethane, the combined organic phases were washed with water and brine, dried over anhydrous magnesium sulfate, filtered, and evaporated under vacuum. The crude product was purified by rapid chromatography on silica gel (hexane eluent) to give compound 4 (3 g) in the form of a pale yellow oil.

[0347] (e) Preparation of 1,4-bis[(1E,3E,7E)-4,8,12-trimethyldecadec-1,3,7,11-tetraenyl]benzene (compound 5)

[0348] In a pre-dried Schlenk flask, compound 3 (3 g, 8.76 mmol) prepared in Example 1(c) and terephthalaldehyde (0.53 g, 3.98 mmol) were dissolved in 25 mL of anhydrous dichloromethane under an inert atmosphere, and the solution was cooled to 0 °C. Potassium tert-butoxide solution (9.56 mL, 9.56 mmol) was added dropwise, and the mixture was stirred overnight at room temperature. The reaction was then diluted with 50 mL of chloroform and washed with aqueous hydrochloric acid (0.1 M), water, and brine. The organic phase was dried over anhydrous magnesium sulfate, filtered, and evaporated under vacuum. The crude product was purified by rapid chromatography on silica gel (dry loading, hexane / dichloromethane eluent) to give compound 5 (0.93 g) in the heavy oil form.

[0349] (f) Preparation of 4-[(1E,3E,7E)-4,8,12-trimethyldecadec-1,3,7,11-tetraenyl]benzaldehyde (compound 6)

[0350] In a pre-dried Schlenk apparatus, compound 3 (2 g, 5.84 mmol) prepared in Example 1(c) and terephthalaldehyde (1.18 g, 8.76 mmol) were dissolved in 25 mL of anhydrous dichloromethane under an inert atmosphere, and the solution was cooled to 0 °C. Potassium tert-butoxide solution (7.01 mL, 7.01 mmol) was added dropwise, and the mixture was stirred overnight at room temperature. The reaction was then diluted with 50 mL of chloroform and washed with aqueous hydrochloric acid (0.1 M), water, and brine. The organic phase was dried over anhydrous magnesium sulfate, filtered, and evaporated under vacuum. The crude product was purified by rapid chromatography on silica gel (dry loading, hexane / dichloromethane eluent) to give compound 6 (1 g) in the form of a yellow oil.

[0351] (g) Preparation of 1,4-bis[2-((1E,3E,7E)-4,8,12-trimethyldecadec-1,3,7,11-tetraenyl)vinyl]benzene (compound 7)

[0352] Step 1 :

[0353] A mixture of 1,4-bis(bromomethyl)benzene (1 g, 3.79 mmol) and triethyl phosphite (5 mL, 29.16 mmol) was heated at 80 °C for 2 hours with stirring. After returning to room temperature, the mixture was poured into 200 mL of cold hexane. The resulting precipitate was filtered and washed with hexane to give tetraethyl terephthalamide diphosphonate (1.3 g) as a white solid.

[0354] Step 2 :

[0355] In a pre-dried Schlenk apparatus, compound 6 (1 g, 3.1 mmol) prepared in Example 1(f) and tetraethyl terephthalimide (0.53 g, 1.41 mmol) from step 1 were dissolved in 25 mL of anhydrous dichloromethane under an inert atmosphere, and the solution was cooled to 0 °C. Potassium tert-butoxide solution (3.1 mL, 3.1 mmol) was added dropwise, and the mixture was stirred overnight at room temperature. The reaction was then diluted with 50 mL of chloroform and washed with aqueous hydrochloric acid (0.1 M), water, and brine. The organic phase was dried over anhydrous magnesium sulfate, filtered, and evaporated under vacuum. The crude product was purified by rapid chromatography on silica gel (solid sediment, hexane / dichloromethane eluent) to give compound 7 (0.93 g) as a yellow solid.

[0356] (h) Preparation of difaryl disulfide (compound 8)

[0357] The preparation of compound 2 was inspired by H. Firouzabadi et al., Tetrahedron Lett., 2010, 51, 508-509.

[0358] Farnesyl bromide (570.5 mg, 2 mmol), manganese oxide (IV) (174 mg, 2 mmol), potassium carbonate (415 mg, 3 mmol), and 0.15 mL of water were added to a solution of thiourea (229 mg, 3 mmol) in 2 mL of PEG-200. The mixture was stirred overnight at 35 °C. Then 25 mL of water was added, and the mixture was extracted three times with diethyl ether. The combined organic phases were washed with water and brine, dried over anhydrous magnesium sulfate, filtered, and evaporated under vacuum. Purification was performed by silica gel rapid chromatography with hexane as eluent to give compound 8 (289 mg) as a pale yellow oil.

[0359] (i) Preparation of 2-((3E,7E)-4,8,12-trimethyldeca-3,7,11-trienyl)-6-methylpyridine (compound 9)

[0360] In a pre-dried Schlenk flask, 2,6-dimethylpyridine (1.84 g, 17.17 mmol) was added to 20 mL of anhydrous tetrahydrofuran, and the solution was cooled to -84 °C with a mixture of liquid nitrogen and ethyl acetate. Then, n-butyllithium (12.88 mL, 20.61 mmol) was added dropwise, and the solution was stirred at -30 °C for 2 hours. The solution was cooled again to -84 °C, and farnesyl bromide (5.88 g, 20.61 mmol) was added dropwise. The mixture was warmed to room temperature and stirred overnight. The reaction was gently quenched by adding a saturated aqueous solution of ammonium chloride. The aqueous phase was extracted three times with dichloromethane, and the combined organic phases were washed with water and brine, dried over anhydrous magnesium sulfate, filtered, and evaporated under vacuum. The crude product was purified by rapid silica gel chromatography (hexane / ethyl acetate eluent) to give compound 9 (4.1 g) as a pale yellow oil.

[0361] (j) Preparation of farnesyl azide (compound 10)

[0362] A suspension of farnesyl bromide (8.74 g, 30.64 mmol) and sodium azide (3.98 g, 61.28 mmol) was stirred overnight in 25 mL of acetonitrile. Then, 50 mL of water was added, and the acetonitrile was evaporated under vacuum. The aqueous phase was extracted three times with diethyl ether, and the combined organic phases were washed with water and brine, dried over anhydrous magnesium sulfate, filtered, and evaporated under vacuum. The resulting oil was purified by rapid chromatography on silica (hexane / dichloromethane eluent) to give compound 10 (6.32 g) as a clarified oil.

[0363] (k) Preparation of 1-farnilo-4-(4-butylphenyl)-1H-1,2,3-triazole (compound 11)

[0364] In a pre-dried Schlenk apparatus, nitrogen was bubbled through 10 mL of anhydrous dichloromethane for 5 minutes. Then, while bubbling, the following reagents were added: compound 10 (1 g, 4.04 mmol) from Example 1(j), 1-butyl-4-ethylbenzene (0.64 mg, 4.04 mmol), tetra(acetonitrile)copper hexafluorophosphate (I) (1.51 g, 4.04 mmol), and 2,6-dimethylpyridine (43.3 mg, 0.4 mmol). The mixture was stirred overnight at room temperature. Next, an aqueous solution of EDTA (1 M, pH 8, 25 mL) was added, and the mixture was stirred vigorously for 1 hour. The phases were separated, and the aqueous phase was extracted twice with dichloromethane. The combined organic phases were washed with water and brine, dried over anhydrous magnesium sulfate, filtered, and evaporated under vacuum. The crude product was purified by rapid chromatography on silica gel (solid sediment, 10% hexane / ethyl acetate eluent) to give compound 11 (1.35 g) as a pale yellow oil.

[0365] (l) Preparation of 1-farnil-1H-1,2,3-triazole (compound 12)

[0366] A suspension of 1H-1,2,3-triazole (0.6 g, 8.63 mmol), farnesyl bromide (3.69 g, 12.94 mmol), and potassium carbonate (2.39 g, 17.26 mmol) was stirred overnight in 20 mL of acetonitrile. The suspension was then filtered, and the filtrate was evaporated under vacuum. The crude product after evaporation was directly purified by rapid chromatography on silica (hexane / ethyl acetate eluent) to give compound 12 (1.31 g, 56% yield) as a pale yellow oil.

[0367] Preparation of (m) 3,7,11-trimethyl-2,6,10-dodecanetrien-1-thiol (compound 13)

[0368] A mixture of farnesyl bromide (4.37 g, 15.32 mmol) and thiourea (4.66 g, 61.28 mmol) in anhydrous ethanol (100 mL) was refluxed under an argon atmosphere for 24 hours. The solvent was then evaporated, and an aqueous solution of potassium hydroxide (2 M, 20 mL) was added to the residue, and the resulting mixture was stirred for 2 hours. The mixture was then acidified to pH 5–6 with hydrochloric acid, and the solution was extracted with dichloromethane (2 x 50 mL). The combined organic phases were washed with water and brine, dried over magnesium sulfate, filtered, and evaporated under vacuum. The crude product was purified by rapid chromatography on silica gel (hexane eluent) to give compound 13 (2 g) in the form of a colorless oil.

[0369] Preparation of (n) (1,1-dimethylethyl)dimethyl[(3,7,11-trimethyl-2,6,10-dodecathorienyl)oxy]silane (compound 14)

[0370] A mixture of farnesol (8.86 g, 39.84 mmol), tert-butyldimethylsilyl chloride (7.21 g, 47.81 mmol), and N,N-diisopropylethylamine (10.3 g, 79.69 mmol) in dichloromethane (1 mL / mmol) was stirred at room temperature for 16 hours. The reaction mixture was then washed with a saturated aqueous solution of ammonium chloride, sodium bicarbonate, and sodium chloride (saline). The organic phase was dried over magnesium sulfate, filtered, and concentrated under vacuum. The crude product was purified by rapid silica gel chromatography (hexane / ethyl acetate eluent 80 / 20) to give compound 14 (12.59 g) as a colorless oil.

[0371] Preparation of (o) (1E,3E,7E)-4,8,12-trimethyldecadec-1,3,7,11-tetraenylbenzene (compound 15)

[0372] Compound 3 (4 g, 11.68 mmol) was added to a pre-dried Schlenk apparatus containing 10 mL of anhydrous dichloromethane, and the solution was cooled to 0 °C under an inert atmosphere. A 1 M potassium tert-butoxide / THF solution (11.68 mL, 11.68 mmol) was added dropwise, and the mixture was stirred for 10 to 15 minutes. Benzaldehyde (1.13 g, 10.62 mmol) was then added, and the mixture was stirred overnight at room temperature. The reaction was stopped with a saturated aqueous ammonium chloride solution, the aqueous phase was extracted three times with dichloromethane, the combined organic phases were washed with water and brine, dried over magnesium sulfate, filtered, and evaporated under vacuum. The crude product was purified by rapid chromatography on silica gel (hexane eluent) to give a final product (1.39 g) in the form of a pale yellow oil.

[0373] Example 2 – Preparation and Characterization of Coated Ceramic Particles

[0374] (a) Preparation of coated particles (PA, PB, P1 to P-10)

[0375] Using PULVERISETTE TM 7. Planetary micro-mill for processing Li6PS5Cl or Li 5.4 PS 4.1 O 0.3 ClBr 0.5 I0.1 Particle coating. Apply Li6PS5Cl or Li 5.4 PS 4.1 O 0.3 ClBr 0.5 I 0.1 The particles (4 g) were placed in an 80 mL zirconium oxide (or zirconium oxide) grinding jar. A mixture containing 22 mL of anhydrous decane and the amounts of squalene, farnesene, and / or compounds 1, 2, 4, or 9 shown in Table 2, along with grinding beads of 2 mm diameter, was added to the jar. The Li6PS5Cl or Li... 5.4 PS 4.1 O 0.3 ClBr 0.5 I 0.1 The particles were combined with a mixture of decane and other compounds to produce Li6PS5Cl or Li coated with a mixture of decane and the compounds listed in Table 2. 5.4 PS 4.1 O 0.3 ClBr 0.5 I 0.1 The particles obtained were then dried under vacuum at a temperature of approximately 80°C to remove decane.

[0376] Table 2. Coated Particles

[0377] a. Ceramic 1: Li6PS5Cl, Ceramic 2: Li 5.4 PS 4.1 O 0.3 ClBr 0.5 I 0.1

[0378] (b) Thermogravimetric analysis (TGA)

[0379] Thermogravimetric analysis was performed at a heating rate of 10 °C / min.

[0380] Figure 1 The thermogravimetric curves (TGA) of Li6PS5Cl type solid sulfide electrolyte coated with a mixture of farnesene and squalene (P-4, curve 1), as described in Example 2(a), are shown below. -Curve 3), thermogravimetric curves (P-3, ---Curve 4) of Li6PS5Cl particles coated with a mixture of farnesene and compound 1, and thermogravimetric curves (P-1, ---Curve 4) of Li6PS5Cl particles coated with a mixture of compound 1 and squalene. Curve 5). Figure 1 The results show that the coating amount is similar for each sample, demonstrating the grafting of compound 2 or compound 1. It should be noted that the coating is more significant when compound 2 or compound 1 is combined with squalene than when combined with farnesene, confirming the excellent interaction between these novel coating molecules of the present invention and the sulfides.

[0381] Figure 2 As shown in Example 2(a), Li coated with a mixture of farnesene and squalene 5.4 PS 4.1 O 0.3 ClBr 0.5 I 0.1 Thermogravimetric curves (PB, curve 6) of solid sulfide electrolytes; Li coated with a mixture of farnesene and compound 2. 5.4 PS 4.1 O 0.3 ClBr 0.5 I 0.1 Thermogravimetric curves of particles (P-6, -- curve 7), Li coated with a mixture of farnesene and compound 1 5.4 PS 4.1 O 0.3 ClBr 0.5 I 0.1 Thermogravimetric curves of the particles (P-5, --- curve 8) and Li coated only with compound 1 5.4 PS 4.1 O 0.3 ClBr 0.5 I 0.1 Thermogravimetric curve of the particles (P-7, Curve 9). Figure 2 The results showed that the coating amount was similar for each sample when mixed with farnesene. Conversely, the coating amount was higher when compound 1 was used alone, confirming a stronger interaction between the sulfide and the organic molecules of the present invention. Therefore, the molecules of the present invention enable better coating of sulfide-type solid electrolytes, regardless of their composition.

[0382] Figure 3The thermogravimetric curves (TGA) of Li6PS5Cl type solid sulfide electrolyte coated with a farnesene-squalene mixture (PA, curve 1), Li6PS5Cl particles coated with a squalene-compound 4 mixture (P-9, curve 10), and Li6PS5Cl particles coated with a squalene-compound 9 mixture (P-10, curve 10) are shown, as described in Example 2(a). Curve 11). Figure 3 The results show that the coating amount is relatively similar for compound 4. For compound 9, a slight reduction in coating was observed, but it remained within the range of approximately 90%, demonstrating that each sample was coated. Therefore, the present invention is able to shape coatings and adjust their chemical properties according to desired effects.

[0383] Figure 4 The thermogravimetric curves (PA, curve 12) of a Li6PS5Cl type solid sulfide electrolyte coated with a mixture of farnesene and squalene as described in Example 2(a) and the thermogravimetric curves (P-11, curve 13) of Li6PS5Cl particles coated with a mixture of squalene and compound 15 are shown.

[0384] Figure 5 The thermogravimetric curves (TGA) of Li6PS5Cl type solid sulfide electrolyte coated with a mixture of farnesene and squalene (PA, curve 12) and Li6PS5Cl particles coated with a mixture of squalene and compound 11 (P-12, curve 14) or Li6PS5Cl particles coated with a mixture of squalene and compound 12 (P-13, curve 15) are shown, as described in Example 2(a).

[0385] Figure 6 The thermogravimetric curves (PA, curve 16) of a Li6PS5Cl type solid sulfide electrolyte coated with a mixture of farnesene and squalene as described in Example 2(a) and the thermogravimetric curves (P-15, curve 17) of Li6PS5Cl particles coated with a mixture of squalene and compound 14 are shown.

[0386] (c) Impedance

[0387] The powder prepared in Example 2 was formed into pellets with a diameter of 10 mm. 160 mg was placed in a mold with a diameter of 10 mm and compacted using a press at a pressure of 2.8 tons. The pellets were then placed in a closed conductivity cell under an inert argon atmosphere at a pressure of 5 MPa.

[0388] Using a VMP-300 multichannel potentiostat (Bio-Logic) TMThe ionic conductivity of the battery assembled in this embodiment was measured. Measurements were performed at an amplitude of 50 mV over a temperature range of -10°C to 70°C (in increments of 10°C) and a temperature range of 70°C to 20°C (in increments of 10°C).

[0389] Only results at 20℃ are shown Figure 1 , 2 And 4 to 6. In Figure 1 As previously described in (b), Li6PS5Cl sulfides with coatings produced by a combination of compound 1 or compound 2 and squalene exhibit higher electrical conductivity than those coated with a combination of compound 1 or compound 2 at the same and even higher coating rates. Therefore, these novel coating molecules of the present invention are able to maintain the high electrical conductivity of the sulfide while coating it, demonstrating a stronger interaction with the Li6PS5Cl sulfide. Figure 2 In the Li, a coating is produced by a combination of compound 1 or compound 2 and farnesene. 5.4 PS 4.1 O 0.3 ClBr 0.5 I 0.1 The sulfides exhibited higher conductivity at the same coating coverage. The sulfide coated with compound 1 alone showed the lowest ionic conductivity, confirming the higher coating amount of organic molecules. Nevertheless, this value of 0.33 mS / cm is still significant, as it exceeds the conductivity of 10 at 20°C. -4 S / cm. For Figures 4 to 6 The conductivity is on the same order of magnitude as the reference, proving that the conductivity properties of the powdered sulfide electrolyte prepared in this way are maintained.

[0390] (d) NMR spectroscopy

[0391] Through solid magic angle rotation (MAS) 1 The coated particle samples were analyzed by 1H NMR. These spectra were obtained on the coated particles after drying at 80 °C using a Bruker AVANCE NEO 500 MHz WB spectrometer with MAS (up to 15 kHz) and a 4 mm triple resonance probe.

[0392] Figure 7 This shows the results obtained using P-4 particles. P-4's... 1 The 1H NMR spectrum corresponds to a superposition of the previously recorded NMR spectra of farnesene and compound 2, where the characteristic signal of hydrogen is located near the sulfur atoms labeled 1 and 2. No signal corresponding to decane is present in this spectrum. Therefore, a combination of farnesene and compound 2 exists around the solid electrolyte particles.

[0393] Figure 8 This shows the results obtained using P-3 particles. P-3's... 1 The 1H NMR spectrum corresponds to a superposition of the previously recorded NMR spectra of farnesene and compound 1, where the characteristic signal of hydrogen is located near the oxygen atoms labeled 1 and 2. No signal corresponding to decane is present in this spectrum. Therefore, a combination of farnesene and compound 1 exists around the solid electrolyte particles.

[0394] Figure 9 This shows the results obtained using P-11 particles. P-11's... 1 The 1H NMR spectrum corresponds to a superposition of the previously recorded NMR spectra of squalene and compound 15, where the characteristic signals of hydrogen are located near the aromatic groups labeled 1, 2, and 3. No signal corresponding to decane is present in this spectrum. Therefore, a combination of squalene and compound 15 exists around the solid electrolyte particles.

[0395] Figure 10 This shows the results obtained using P-9 particles. P-9's... 1 The 1H NMR spectrum corresponds to the superposition of the previously recorded NMR spectra of squalene and compound 4, with characteristic signals of certain hydrogens labeled 1 to 5.

[0396] Figure 11 This shows the results obtained using P-10 particles. P-10's... 1 The 1H NMR spectrum corresponds to the superposition of the previously recorded NMR spectra of squalene and compound 9, with characteristic signals of certain hydrogens labeled 1 to 6.

[0397] Figure 12 This shows the results obtained using P-12 particles. P-12's... 1 The 1H NMR spectrum corresponds to the superposition of the previously recorded NMR spectra of squalene and compound 11, with characteristic signals of certain hydrogens labeled 1 to 8.

[0398] Figure 13 This shows the results obtained using P-14 particles. P-14's... 1 The 1H NMR spectrum corresponds to the superposition of the previously recorded NMR spectra of squalene and compound 3, with characteristic signals of certain hydrogens labeled 1 to 3.

[0399] Figure 14 This shows the results obtained using P-15 particles. P-15's... 1 The 1H NMR spectrum corresponds to the superposition of the previously recorded NMR spectra of squalene and compound 14, with characteristic signals of certain hydrogens labeled 1 to 4.

[0400] Example 3 – Preparation and Characterization of Positive Electrode Film

[0401] a) Preparation of the positive electrode film

[0402] 1.55 grams of commercially sourced LiNi coated with LiNbO3-type oxide with an average diameter of approximately 4 µm was used. 0.6 Mn 0.2 Co 0.2 O2 (NMC 622) particles were mixed with 0.40 g of PA, PB, P-4, P-5, P-7, P-9, P-10, or P-11 coated particles with an average diameter of approximately 200 nm prepared according to Example 2 (see Table 3) and 0.5 g of a mixture of modified carbon black (CB) and vapor-grown carbon fiber (VGCF) as described in International Patent Application WO2019 / 218067 to form a dry powder mixture. The dry powder was mixed using a vortex mixer for approximately 10 minutes. The dry powder mixture was further prepared by dissolving 0.04 g of polybutadiene and 0.01 g of polynorbornene in 0.94 g of a toluene-tetrahydrofuran (80-20) mixture in the presence of Li6PS5Cl (PA, P-4, P-9, P-10, and P-11) and in Li... 5.4 PS 4.1 O 0.1 ClBr 0.5 I 0.1 Polymer solutions were prepared separately by dissolving (PB, P-5, P7) in o-xylene-diethyl carbonate-tetrahydrofuran (70-20-10).

[0403] The polymer solution is added to the dry powder mixture. The resulting mixture is then blended using a planetary centrifugal mixer (Thinky Mixer) for approximately 5 minutes. The previously mentioned solvent mixture is added to achieve the optimal coating viscosity, approximately 10,000 cP. The resulting suspension is applied to an aluminum sheet using a doctor blade coating method to provide a positive electrode film applied to the current collector. The positive electrode film is then vacuum dried at approximately 120°C for approximately 5 hours.

[0404] The aluminum sheet may also be an unmodified carbon-coated aluminum sheet, or a carbon-coated aluminum sheet coated with a coating material as defined herein.

[0405] The composition of the positive electrode film is shown in Table 3.

[0406] Table 3. Composition of the positive electrode film NC / VGCF: Modified carbon black mixture / VGCF; PB: Polybutadiene; PNB: Polynorbornene b) Characterization of the prepared positive electrode film The morphology of different positive electrode films was studied using scanning electron microscopy (SEM).

[0407] Figure 15 SEM images of cross-sections of the positive electrode film prepared according to Example 3(a) are shown, wherein (a) a squalene-farnesene-coated Li6PS5Cl sulfide cathode electrolyte (F-1) and (b) a farnesene-compound 2 mixture (F-2) are used as the cathode electrolyte. Clearly, the use of the present invention eliminates the presence of small sulfide agglomerates observed during the squalene-farnesene coating process, even when the number of agglomerates is already very low. Therefore, coating Li6PS5Cl particles according to the present invention improves sulfide dispersion and significantly limits the presence of agglomerates.

[0408] Figure 16 The demonstration shows the use of a sulfide cathode electrolyte Li with a separate compound 1 coating prepared according to Example 5. 5.4 PS 4.1 O 0.3 ClBr 0.5 I 0.1 SEM image of the sliced ​​positive electrode film (F-5) prepared according to Example 3(a). No agglomerates of sulfides, carbon, or NMC active materials were observed. Clearly, the use of the present invention can eliminate the presence of agglomerates, regardless of the material onto which they are coated.

[0409] Example 4 – Electrochemical Properties

[0410] The electrochemical properties of the positive electrode film prepared in Example 3(a) were investigated.

[0411] a) Electrochemical cell configuration

[0412] Assemble an electrochemical cell according to the following procedure.

[0413] 10 mm diameter pellets were taken from the positive electrode film prepared in Example 3(a). An inorganic ceramic-type sulfide-based solid electrolyte was prepared by placing 80 mg of Li6PS5Cl sulfide-based ceramic on the surface of the positive electrode film pellets. The positive electrode film pellets, including the inorganic solid electrolyte layer, were then pressed at a pressure of 2.8 tons using a press. They were then assembled in a glove box into a CR2032 button cell casing with a 10 mm diameter lithium metal electrode facing a stainless steel current collector. The electrochemical cell was assembled according to the configuration given in Table 4.

[0414] Table 4. Electrochemical Cell Configuration

[0415] b) Battery behavior during cycling

[0416] This embodiment illustrates the electrochemical behavior of the electrochemical cell as described in Example 4(a).

[0417] The electrochemical cell assembled in Example 4(a) performed at 30°C at 4.3V and 2.5V vs Li / Li + The process involved cycling between two cycles. Formation cycling was performed at a constant charge / discharge current of C / 15. Then, four cycles were performed at a constant charge / discharge current of C / 10, followed by four cycles at a constant charge / discharge current of C / 5. Finally, aging tests were conducted at a constant charge / discharge current of C / 3.

[0418] Figure 17 The graphs show the discharge and charge capacity (mAh / g) and coulombic efficiency (%) vs. cycle number for battery 1 (hollow symbol) containing a Li6PS5Cl type sulfide solid electrolyte with a farnesene-squalene mixture as the cathode electrolyte and battery 2 (solid symbol) containing a Li6PS5Cl type sulfide solid electrolyte coated with a farnesene-compound 2 mixture as the cathode electrolyte.

[0419] Therefore, compared to coating with a squalene-farnesene mixture, coating the cathode electrolyte with farnesene-compound 2 improves the aging conditions of the positive electrode by reducing its capacity loss. Thus, the novel molecular coating of this invention provides improved electrochemical performance of the battery pack while reducing aging and parasitic reactions, demonstrating the excellent coating properties of our sulfide cathode electrolyte and improved interactions with various components within the positive electrode.

[0420] Figure 18 The graphs show the discharge and charge capacities (mAh / g) and coulombic efficiency (%) vs. cycle number for battery 1 (hollow circle symbol) with a Li6PS5Cl type sulfide solid electrolyte containing a farnesene-squalene mixture as the cathode electrolyte, battery 6 (star symbol) with a Li6PS5Cl type sulfide solid electrolyte coated with a squalene-compound 4 mixture as the cathode electrolyte, and battery 7 (hexagon symbol) with a Li6PS5Cl type sulfide solid electrolyte coated with a squalene-compound 9 mixture as the cathode electrolyte, as described in Example 4(a).

[0421] Therefore, compared to coating with a squalene-farnesene mixture, coating the cathode electrolyte with squalene-compound 4 or squalene-compound 9 significantly improves the aging conditions of the positive electrode by reducing its capacity loss. Thus, the novel molecular coating of this invention improves the electrochemical performance of the battery pack while reducing aging and parasitic reactions, demonstrating the excellent coating properties of our sulfide cathode electrolyte and its improved interaction with various components within the positive electrode.

[0422] Figure 19 The results show, as described in Example 2, the Li containing a favone-squalene mixture coating5.4 PS 4.1 O 0.3 ClBr 0.5 I 0.1 Battery 3 (square symbol) with sulfide as cathode electrolyte, containing Li coated with a mixture of farnesene and compound 1. 5.4 PS 4.1 O 0.3 ClBr 0.5 I 0.1 Battery 4 (triangle symbol) uses sulfides as the cathode electrolyte and contains Li coated with a separate compound 1. 5.4 PS 4.1 O 0.3 ClBr 0.5 I 0.1 A graph showing the discharge capacity (mAh / g) and coulombic efficiency (%) versus cycle number for battery 5 (circular symbol) with sulfide as the cathode electrolyte.

[0423] Therefore, compared with coating with a squalene-farnesene mixture, coating the cathode electrolyte Li with farnesene-compound 1 or compound 1 alone is more effective. 5.4 PS 4.1 O 0.3 ClBr 0.5 I 0.1 The aging of the positive electrode is improved by reducing its capacity loss. It should be noted that in the case of a cathode electrolyte coated with farnesene-compound 1, the cycling performance is greater. Nevertheless, using compound 1 alone is feasible and improves performance compared to coating with a squalene-farnesene mixture. Therefore, providing a coating with the novel molecule of the present invention enables improved electrochemical performance of the battery pack while reducing aging and parasitic reactions, reflecting the good coating of the sulfide cathode electrolyte and better interaction with various components within the positive electrode, regardless of the sulfide electrolyte used as the cathode electrolyte.

[0424] Figure 20 The graphs show the discharge and charge capacity (mAh / g) and coulombic efficiency (%) vs. cycle number for battery 1 (hollow symbol) containing a Li6PS5Cl type sulfide solid electrolyte with a farnesene-squalene mixture as the cathode electrolyte and battery 8 (solid symbol) containing a Li6PS5Cl type sulfide solid electrolyte coated with a squalene-compound 15 mixture as the cathode electrolyte.

[0425] Therefore, coating the cathode electrolyte with a squalene-compound 15 mixture yields similar electrochemical performance to that obtained with a farnesene-squalene mixture. Thus, it has been demonstrated that the performance of this type of battery pack can be maintained using novel coating compounds.

[0426] Example 5 – Solvent Compatibility

[0427] For the cathode electrolyte Li 5.4 PS 4.1 O 0.3 ClBr 0.5 I 0.1 The positive electrode as described in Example 3(a) must be prepared using o-xylene-diethyl carbonate-tetrahydrofuran solvent because degradation of electrochemical performance can be observed when using toluene-tetrahydrofuran solvent (e.g., 60-40).

[0428] To verify the effect of the coating on the stability of these halogen-doped lithium-deficient oxysulfide sulfides, 120 mg of sulfide was dispersed in a toluene-tetrahydrofuran (80-20) solvent mixture. After 30 minutes, the sulfide powder was decanted, and cathode electrolytes Li coated with (a) farnesene-squalene mixture (PB), (b) compound 2 (P-8), and (c) compound 1 (P-7) were photographed. 5.4 PS 4.1 O 0.3 ClBr 0.5 I 0.1 of Figure 21 The photograph shown in (a) reveals a bright yellow coloration, confirming the presence of the cathode electrolyte Li. 5.4 PS 4.1 O 0.3 ClBr 0.5 I 0.1 The sulfide exhibits deep degradation even with squalene-farnesene coating. However, in the case of coatings with compound 2 (in (b)) or compound 1 (in (c)), the sulfide remains suspended after 30 minutes, and the yellowing of the solvent is significantly reduced, demonstrating the protective effect of the novel coating molecules against the reaction of sulfides with various solvents. Therefore, due to the addition of these novel organic coating molecules and / or combinations, the use of NMP or other solvents previously prohibited due to their reaction with sulfides can be considered.

[0429] Various modifications may be made to any of the above embodiments without departing from the intended scope of the invention. All references, patents, or scientific literature mentioned in this application are incorporated herein by reference in their entirety for all purposes.

Claims

1. A coating material for an electrochemical cell comprising at least one unsaturated organic compound, the unsaturated organic compound comprising at least one branched or straight chain unsaturated aliphatic group having from 6 to 50 carbon atoms and having at least one carbon-carbon double or triple bond, and at least one atom other than carbon or hydrogen, a functional group containing at least one atom other than carbon or hydrogen, or a group containing at least one optionally substituted ring or heterocyclic ring.

2. The coating material of claim 1, wherein the unsaturated organic compound has the formula I, or is a salt of the unsaturated organic compound of formula I: ###0001### I wherein: n and m are numbers selected from the range of 1 to 4. (R 1 ) n (X 1 ) m Formula I 3. The coating material of claim 2, wherein m is 1 and n is 2. R 1 independently at each occurrence, is an unsaturated branched or straight chain aliphatic group having 6 to 50 carbon atoms; X 1 a functional group selected from a halogen atom, an oxygen atom, a sulfur atom, a group comprising at least one atom selected from halogen, oxygen, sulfur, nitrogen, silicon and phosphorus atoms, or a functional group comprising at least one optionally substituted cycloalkyl, heterocycloalkyl, aryl or heteroaryl group; and 5. The coating material of claim 3, wherein the unsaturated organic compound has the formula II: ###0002### II 6. The coating material of claim 3, wherein the unsaturated organic compound has the formula III: ###0003### III 4. The coating material according to claim 3, wherein X 1 is selected from O, S, S-S, O-Si(R 2 )2, Si(R 2 )2, O-Si(OR 2 )2, Si(OR 2 )2, NH, NR 2 and a functional group comprising at least one optionally substituted cycloalkyl, heterocycloalkyl, aryl or heteroaryl group, wherein R 2 is an optionally substituted alkyl, alkenyl or alkynyl group.

7. The coating material of claim 6, wherein p is 1. Formula II wherein R 1 As defined above.

8. The coating material of claim 3, wherein the unsaturated organic compound has the formula IV: ###0004### IV Formula III wherein R 1 As defined above, and p is 1 or 2.

10. The coating material of claim 9, wherein q is 0.

11. The coating material of claim 9, wherein r is 1 and q is 2. Formula IV wherein R 1 As defined above, and X 2 is selected from the group consisting of cycloalkylene, heterocycloalkylene, arylene, heteroarylene, or a group comprising at least two rings independently selected from cycloalkylene, heterocycloalkylene, arylene, and heteroarylene, said rings being fused, linked together by carbon-carbon or carbon-heteroatom bonds, or linked together by a heteroatom, alkylene, alkenylene, alkynylene, or a combination thereof, said cycloalkylene, heterocycloalkylene, arylene, and heteroarylene being optionally substituted.

9. The coating material of claim 8, wherein X 2 of the formula: wherein r is 0 or 1, q is 0, 1 or 2, and - - - represents a bond to R 1 and can be in ortho, meta or para position, preferably in para position, it being understood that - - - is present when q is 0.

12. The coating material of claim 2, wherein m is 1 and n is 1.

17. The coating material of claim 16, wherein the unsaturated aliphatic group is, at each occurrence, independently selected from the group consisting of decenyl, dodecenyl, undecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, 1,9-decadienyl, docosenyl, hexacosanenyl, eicosanenyl, tetracosanenyl, squalenyl, farnesyl, β-carotene, derivatives of one of these groups further comprising additional saturated or unsaturated carbons, and combinations of at least two thereof.

18. The coating material of claim 17, wherein the unsaturated aliphatic group is, at each occurrence, independently selected from the group consisting of decenyl, undecenyl, octadecenyl, squalenyl, farnesyl, β-carotene, (3E,7E)-4,8,12-trimethyltrideca-3,7,11-trienyl, (1E,3E,7E)-4,8,12-trimethyltrideca-1,3,7,11-tetraenyl, and combinations of at least two thereof.

13. The coating material according to claim 12, wherein X 1 is selected from the group consisting of halogen atoms, OR 2 , SR 2 , S-SR 2 , NH2, NHR 2 , N(R 2 )2, O-Si(R 2 )3, Si(R 2 )3, O-Si(OR 2 )3, Si(OR 2 )3, N3, P(O)(OR 2 )2, SO2OR 2 , OSO2R 2 , SO2R 2 , SO2NHR 2 , NHSO2R 2 , C(O)H, C(O)R 2 , NHC(O)R 2 , C(O)NHR 2 , NHC(O)NHR 2 , OC(O)NHR 2 , OC(O)R 2 , C(O)OR 2 , NHC(O)OR 2 , OC(O)OR 2 , C(S)R 2 , C(S)H groups and functional groups comprising at least one optionally substituted cycloalkyl, heterocycloalkyl, aryl or heteroaryl group, wherein R 2 is an optionally substituted alkyl, alkenyl or alkynyl group.

14. The coating material of claim 13, wherein X 1 is selected from P(O)(OR 2 )2, O-Si(R 2 )3, optionally substituted aryl or heteroaryl, or a combination of the latter two, preferably O-Si(R 2 )3, optionally substituted aryl or heteroaryl, or a combination of the latter two.

15. The coating material according to any one of claims 2 to 14, wherein R 1 is an unsaturated aliphatic group comprising 10 to 50 carbon atoms.

16. The coating material of any one of claims 2 to 15, wherein R 1 is independently at each occurrence selected from the group consisting of decenyl, dodecenyl, undecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, 1,9-decadienyl, docosenyl, hexacosanenyl, eicosanenyl, tetracosanenyl, squalenyl, farnesyl, β-carotenyi, pinenyl, dicyclopentadienyl, camphenyl, α-phellandrenyl, β-phellandrenyl, terpinenyl, β-myrcenyl, limonenenyl, 2-carenyl, sabinenyl, α-cedrenyl, cuperenyl, β-cedrenyl, decynyl, dodecynyl, octadecynyl, hexadecynyl, tridecynyl, tetradecynyl, and docosynyl, derivatives of any of these groups further comprising additional saturated or unsaturated carbons (such as (3E,7E)-4,8,12-trimethyltrideca-3,7,11-trienyl or (1E,3E,7E)-4,8,12-trimethyltrideca-1,3,7,11-tetraenyl), and combinations of at least two thereof.

19. The coating material of any one of claims 1 to 18, wherein the unsaturated aliphatic group comprises squalenyl.

20. The coating material of any one of claims 1 to 18, wherein the unsaturated aliphatic group comprises farnesyl.

21. The coating material of any one of claims 1 to 18, wherein the unsaturated aliphatic group comprises squalenyl and farnesyl. ​ ​ 22. The coating material according to any one of claims 1 to 18, wherein the unsaturated aliphatic group comprises (3E,7E)-4,8,12-trimethyltrideca-3,7,11-trienyl or (1E,3E,7E)-4,8,12-trimethyltrideca-1,3,7,11 -tetraenyl.

23. The coating material according to claim 1, wherein the unsaturated organic compound is selected from the following compounds: Compound 1 Compound 2 Compound 3 Compound 4 Compound 5 Compound 6 Compound 7 Compound 8 Compound 9 Compound 10 Compound 11 Compound 12 Compound 13 Compound 14 Compound 15 or a salt of one of these, for example the compound is selected from compounds 1 to 9, 11 to 15, or from compounds 1 to 5, 7 to 9, 11 to 15, or from compounds 1, 2, 4, 5, 7 to 9, 11 to 15.

24. The coating material according to any one of claims 1 to 23, comprising at least two of the unsaturated organic compounds.

25. The coating material according to any one of claims 1 to 23, wherein the unsaturated organic compound has a boiling point higher than 80 °C or higher than 100 °C.

26. The coating material according to any one of claims 1 to 25, wherein the unsaturated organic compound is in liquid form at 25 °C.

27. The coating material according to any one of claims 1 to 25, wherein the unsaturated organic compound is in solid form at 25 °C.

28. The coating material according to any one of claims 1 to 27, which is a mixture comprising the unsaturated organic compound and an additional component.

29. The coating material according to claim 28, wherein the additional component is a saturated or unsaturated aliphatic hydrocarbon, a solvent or a combination thereof.

30. The coating material according to claim 29, wherein the saturated or unsaturated aliphatic hydrocarbon comprises 10 to 50 carbon atoms.

31. The coating material according to claim 29 or 30, wherein the saturated or unsaturated aliphatic hydrocarbon comprises an unsaturated aliphatic hydrocarbon.

32. The coating material according to claim 31, wherein the unsaturated aliphatic hydrocarbon is selected from decene, dodecene, undecene, tridecene, tetradecene, pentadecene, hexadecene, heptadecene, octadecene, 1,9-decadiene, docosene, hexacosene, eicosene, tetracosene, squalene, farnesene, beta-carotene, pinene, dicyclopentadiene, camphene, alpha-phellandrene, beta-phellandrene, terpinene, beta-myrcene, limonene, 2-carene, sylvestrene, alpha-cedrene, coppedane, beta-cedrene, decyne, dodecyne, octadecyne, hexadecyne, tridecyne, tetradecyne, docosyne, and a combination of at least two of these.

33. The coating material of claim 32, wherein the unsaturated aliphatic hydrocarbon is selected from decene, dodecene, undecene, tridecene, tetradecene, pentadecene, hexadecene, heptadecene, octadecene, 1,9-decadiene, docosene, hexacosene, eicosene, tetracosene, squalene, farnesene, beta-carotene, and combinations of at least two thereof.

34. The coating material of claim 33, wherein the unsaturated aliphatic hydrocarbon is selected from decene, undecene, octadecene, squalene, farnesene, beta-carotene, and combinations of at least two thereof.

35. The coating material of claim 34, wherein the unsaturated aliphatic hydrocarbon comprises squalene.

36. The coating material of claim 34, wherein the unsaturated aliphatic hydrocarbon comprises farnesene.

37. The coating material of any one of claims 29 to 36, wherein the saturated or unsaturated aliphatic hydrocarbon comprises an alkane.

38. The coating material of claim 37, wherein the alkane is decane.

39. The coating material of any one of claims 29 to 38, wherein the solvent is selected from dichloromethane, tetrahydrofuran, dioxolane, xylene (ortho, meta, or para), toluene, benzene, methoxybenzene and other benzene derivatives, acetonitrile, N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, alkylene carbonates, dialkyl carbonates, and miscible combinations of at least two solvents.

40. The coating material of any one of claims 1 to 39, wherein the concentration of the unsaturated organic compound in the coating material is at least 2% by volume, or in the range of about 5% to 100%, or about 25% to 100%, or about 40% to 100%, or about 50% to 100%.

41. A coated particle for an electrochemical cell, the coated particle comprising: - a core comprising an electrochemically active material, an electronically conductive material, an ionically conductive inorganic material, or a combination of two or more thereof; and - a coating material according to any one of claims 1 to 40, the coating material being present on the surface of the core.

42. The coated particle of claim 41, wherein the coating material forms a uniform coating on the surface of the core.

43. The coated particle of claim 41, wherein the coating material forms a coating on at least a portion of the surface of the core.

44. The coated particle of claim 43, wherein the coating material is unevenly dispersed on the surface of the core.

45. The coated particle of any one of claims 41 to 44, wherein the mass ratio "coating material:core" is in the range of 0.2: 100 to 50: 100, or 0.5: 100 to 40:

100.

46. The coated particle of any one of claims 41 to 45, wherein the core comprises an ionically conductive inorganic material.

47. The coated particle of claim 46, wherein the ionically conductive inorganic material is selected from a glass, a glass-ceramic, a ceramic, a nanoceramic, and a combination of at least two of these.

48. The coated particle of claim 46 or 47, wherein the ionically conductive inorganic material comprises a fluoride-, phosphide-, sulfide-, oxysulfide- or oxide-based ceramic, glass or glass-ceramic.

49. The coated particle of any one of claims 46 to 48, wherein the ionically conductive inorganic material is selected from a compound of the LISICON, thio-LISICON, argyrodite, garnet, NASICON, perovskite, oxide, sulfide, oxysulfide, phosphide, fluoride type in crystalline and / or amorphous form, and a combination of at least two of these.

50. The coated particle of any one of claims 46 to 49, wherein the ionically conductive inorganic material is selected from an inorganic compound having the formula: - xM2S-yP2S5; - xM2S-yP2S5-zMX; - xM2S-yP2S5-zP2O5; - xM2S-yP2S5-zP2O5-wMX; - xM2S-yM2O-zP2S5; - xM2S-yM2O-zP2S5-wMX; - xM2S-yM2O-zP2S5-wP2O5; - xM2S-yM2O-zP2S5-wP2O5-vMX; - xM2S-ySiS2; - M3OX; - M2HOX; - M3PO4; - M3PS4; and wherein, M is an alkali metal ion, an alkaline earth metal ion or a combination thereof, and wherein when M comprises an alkaline earth metal ion, the amount of M is adjusted to achieve electrical neutrality; X is selected from F, CI, Br, I or a combination of at least two of these; a, b, c, d, e and f are non-zero values and are independently selected in each formula to achieve electrical neutrality; and v, w, x, y and z are non-zero values and are independently selected in each formula to obtain a stable compound. - MLZO (e.g. M7La3Zr2O 12 , M (7-a) La3Zr2Al b O 12 , M (7-a) La3Zr2Ga b O 12 , M (7-a) La3Zr (2-b) Ta b O 12 and M (7-a) La3Zr (2-b) Nb b O 12 ); - MLTaO (e.g. M7La3Ta2O 12 , M5La3Ta2O 12 and M6La3Ta 1.5 Y 0.5 O 12 ); - ML SnO (e.g. M7La3Sn2O 12 ); - MAGP (e.g. M 1+a Al a Ge 2-a (PO4)3) - MATP (e.g. M 1+a Al a Ti 2-a (PO4)3); - MLTiO (e.g. M 3a La (2 / 3-a) TiO3); - MZP (e.g. M a Zr b (PO4) c ) ; - MCZP (e.g. M a Ca b Zr c (PO4) d ) ; - MGPS (e.g. M a Ge b P c S d , as M 10 GeP2S 12 ); - MGPSO (e.g. M a Ge b P c S d O e ); - MSiPS (e.g. M a Si b P c S d , as M 10 SiP2S 12 ); - MSiPSO (e.g. M a Si b P c S d O e ); - MSnPS (e.g. M a Sn b P c S d , as M 10 SnP2S 12 ); - MSnPSO (e.g. M a Sn b P c S d O e ); - MPS (e.g. M a P b S c , such as M7P3S 11 ); - MPSO (e.g. M a P b S c O d ); - MZPS (e.g. M a Zn b P c S d ); - MZPSO (e.g. M a Zn b P c S d O e ) ; 51. The coated particle of claim 50, wherein M is selected from Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, Ba or a combination of at least two of these.

52. The coated particle of claim 51, wherein M is Li.

54. The coated particle of claim 53, wherein the ionically conductive inorganic material is Li6PS5CI.

57. The coated particle of any one of claims 41 to 45, wherein the core comprises an electrochemically active material.

58. The coated particle of claim 57, wherein the electrochemically active material is selected from a metal oxide, a metal sulfide, a metal oxysulfide, a metal phosphate, a metal fluorophosphate, a metal oxyfluorophosphate, a metal sulfate, a metal halide, a metal fluoride, sulfur, selenium, and a combination of at least two of these. ​ ​ ​ ​ - MPSX (e.g. M a P b S c X d such as M7P3S 11 X, M7P2S8X and M6PS5X); - MPSOX (e.g. M a P b S c O d X e ); - MGPSX (e.g. M a Ge b P c S d X e ); - MGPSOX (e.g. M a Ge b P c S d O e X f ) ; - MSiPSX (e.g. M a Si b P c S d X e ); - MSiPSOX (e.g. M a Si b P c S d O e X f ); - MSnPSX (e.g. M a Sn b P c S d X e ); - MSnPSOX (e.g. M a Sn b P c S d O e X f ); - MZPSX (e.g. M a Zn b P c S d X e ); - MZPSOX (e.g. M a Zn b P c S d O e X f ); ​ ​ ​ ​ - M a PO b N c (where a = 2b + 3c - 5); ​ ​ ​ ​ ​ ​ ​ ​ 53. The coated particle of any one of claims 46 to 52, wherein the ionically conductive inorganic material is selected from the group consisting of inorganic compounds of the formula Li a P b S c X d wherein X is CI, Br, I, or a combination of at least two of these, and a, b, c, and d are such that (a + 5b) = (2c + d). ​ 55. The coated particle of any one of claims 46 to 52, wherein the ionically conductive inorganic material is selected from the group consisting of inorganic compounds of the formula Li a P b S c O d X e wherein X is CI, Br, I, or a combination of at least two thereof, and a, b, c, d, and e are such that (a + 5b) = (2c + 2d + e).

56. The coated particle according to claim 55, wherein a is selected from the range of 5 to 6, b is equal to 1, c is selected from the range of 3.5 to 4.8, and e is selected from the range of 1 to 2, preferably the ionically conductive inorganic material is Li 5.4 PS 4.1 O 0.3 X 1.6 or Li 5.4 PS 4.1 O 0.3 ClBr 0.5 I 0.1 . ​ ​ 59. The coated particle of claim 58, wherein the metal of the electrochemically active material is selected from titanium (Ti), iron (Fe), manganese (Mn), vanadium (V), nickel (Ni), cobalt (Co), aluminum (Al), chromium (Cr), copper (Cu), zirconium (Zr), niobium (Nb), and combinations of at least two thereof.

60. The coated particle of claim 58, wherein the metal of the electrochemically active material further comprises an alkali metal or alkaline earth metal selected from lithium (Li), sodium (Na), potassium (K), and magnesium (Mg).

61. The coated particle of any one of claims 58 to 60, wherein the electrochemically active material is a lithium-metal oxide.

62. The coated particle of claim 61, wherein the lithium-metal oxide is a mixed oxide of lithium, nickel, manganese, and cobalt (NCM).

63. The coated particle of any one of claims 57 to 60, wherein the electrochemically active material is a lithium-metal phosphate.

64. The coated particle of claim 63, wherein the lithium-metal phosphate is lithium iron phosphate.

65. The coated particle of claim 57, wherein the electrochemically active material is selected from the group consisting of a non-alkali or non-alkaline earth metal, an intermetallic compound, a metal oxide, a metal nitride, a metal phosphide, a metal phosphate, a metal halide, a metal fluoride, a metal sulfide, a metal oxysulfide, carbon, silicon (Si), silicon-carbon composite (Si-C), silicon oxide (SiO x ), silicon oxide-carbon composite (SiO x -C), tin (Sn), tin-carbon composite (Sn-C), tin oxide (SnO x ), tin oxide-carbon composite (SnO x -C), and combinations of at least two thereof.

66. The coated particle of any one of claims 57 to 65, wherein the electrochemically active material further comprises a doping element.

67. The coated particle of any one of claims 57 to 66, wherein the electrochemically active material further comprises a capping material.

68. The coated particle of claim 67, wherein the capping material forms a capping layer on a surface of the electrochemically active material, and the coating material is disposed on a surface of the capping layer.

69. The coated particle of claim 67 or 68, wherein the capping material is selected from Li2SiO3, LiTaO3, LiAlO2, Li2O-ZrO2, LiNbO3, other similar capping materials, and combinations of at least two thereof.

70. The coated particle of any one of claims 67 to 69, wherein the capping material is LiNbO3.

71. The coated particle of claim 67 or 68, wherein the capping material is an electronically conductive material, preferably comprising carbon.

72. The coated particle of any one of claims 41 to 45, wherein the core comprises an electronically conductive material.

73. The coated particle of claim 72, wherein the electronically conductive material is selected from carbon black, acetylene black, graphite, graphene, carbon fibers, carbon nanofibers, carbon nanotubes, and combinations of at least two thereof.

74. The coated particle of claim 73, wherein the electronically conductive material is carbon black.

75. The coated particle of any one of claims 72 to 74, wherein the surface of the electronically conductive material is grafted with at least one aryl group of formula A: Formula A wherein, FG is a hydrophilic functional group; and h is an integer in the range of 1 to 5, h is preferably in the range of 1 to 3, h is preferably 1 or 2, h is more preferably 1.

76. The coated particle of claim 75, wherein the hydrophilic functional group is a carboxylic acid or sulfonic acid functional group. ​ 77. The coated particle according to claim 75, wherein the aryl group of Formula A is p- benzoic acid or p-benzenesulfonic acid.

78. The coated particle according to any one of claims 46 to 77 for use in an electrode material.

79. The coated particle according to any one of claims 46 to 56 for use in an electrolyte.

80. The coated particle according to any one of claims 72 to 77 for use on a current collector.

81. A method of manufacturing a coated particle according to any one of claims 41 to 77, the method comprising at least the step of coating at least a portion of the surface of the core with the coating material.

82. The method according to claim 81, wherein the coating step is performed by a dry coating method.

83. The method according to claim 81, wherein the coating step is performed by a wet coating method.

84. The method according to claim 83, wherein the wet coating method is a mechanical coating method.

85. The method according to claim 84, wherein the mechanical coating method is a milling, mechanical synthesis or mechanical fusion method.

86. The method according to any one of claims 81 to 85, further comprising the step of milling the electrochemically active material, electronically conductive material or ionically conductive inorganic material of the core of the coated particle.

87. The method according to claim 86, wherein the coating and milling steps are performed simultaneously, sequentially or partially overlapping in time.

88. The method according to claim 87, wherein the coating and milling steps are performed simultaneously.

89. An electrode material comprising an electrochemically active material, an electronically conductive material and optionally an ionically conductive inorganic material, wherein at least one of the electrochemically active material, electronically conductive material or ionically conductive inorganic material comprises a coated particle according to claim 78.

90. The electrode material according to claim 89, comprising an ionically conductive inorganic material.

91. The electrode material according to claim 90, wherein the core of the coated particle comprises an ionically conductive inorganic material.

92. The electrode material according to claim 90 or 91, wherein the ionically conductive inorganic material is as defined in any one of claims 47 to 56.

93. The electrode material according to any one of claims 89 to 92, wherein the core of the coated particle comprises an electrochemically active material.

94. The electrode material according to any one of claims 89 to 93, wherein the electrochemically active material is as defined in any one of claims 58 to 71.

95. The electrode material according to any one of claims 89 to 94, wherein the core of the coated particle comprises an electronically conductive material.

96. The electrode material according to any one of claims 89 to 95, wherein the electronically conductive material is as defined in any one of claims 73 to 77.

97. The electrode material according to any one of claims 89 to 96, further comprising a binder.

98. The electrode material of claim 97, wherein the binder is selected from the group consisting of polymeric binders of polyether, polycarbonate or polyester type, fluorinated polymers, water-soluble binders and copolymers or compatible combinations of two or more thereof.

99. The electrode material of claim 97, wherein the binder comprises a mixture of a first polymer based on polybutadiene and a second polymer containing polymerized units of a norbornene-based monomer containing double bonds derived from a compound of Formula B: Formula B wherein, Formula B 100. The electrode material of claim 99, wherein the second polymer is a polymer of Formula C: Formula C wherein, R a and R b is independently at each occurrence selected from a hydrogen atom, a carboxyl group (-COOH), a sulfonic acid group (-SO3H), a hydroxyl group (-OH), a fluorine atom, and a chlorine atom. j is an integer selected so that the mass average molecular weight of the polymer of Formula C is between about 10,000 g / mol and about 100,000 g / mol, inclusive. Formula C 104. The electrode material of any one of claims 99 to 103, wherein the first polymer is polybutadiene. R a and R b as defined in claim 99, and 105. The electrode material of any one of claims 99 to 103, wherein the first polymer is selected from epoxidized polybutadiene.

101. The electrode material of claim 99 or 100, wherein R a and R b is independently at each occurrence selected from a hydrogen atom and a -COOH group.

102. The electrode material of claim 101, wherein R a is a -COOH group, and R b is a hydrogen atom.

103. The electrode material of claim 101, wherein R a and R b are -COOH groups.

106. The electrode material of claim 105, wherein the epoxidized polybutadiene comprises repeating units of Formulae E and D and / or F: Formula E Formula D and two hydroxyl end groups.

107. The electrode material of claim 106, wherein the epoxidized polybutadiene is of Formula G: Formula G wherein, k is an integer selected so that the mass average molecular weight of the epoxidized polybutadiene of Formula G is between about 1,000 g / mol and about 1,500 g / mol, inclusive; and an epoxy equivalent weight of between about 100 g / mol and about 600 g / mol, inclusive. Formula G 108. The electrode material of claim 107, wherein the mass average molecular weight of the epoxidized polybutadiene of Formula G is about 1,300 g / mol.

109. The electrode material of claim 107 or 108, wherein the epoxy equivalent weight is between about 210 g / mol and about 550 g / mol, inclusive.

110. The electrode material of any one of claims 107 to 109, wherein the epoxidized polybutadiene of Formula G is a Poly bd™ 600E resin having an average molecular weight of about 1,300 g / mol and an epoxy equivalent weight of between about 400 g / mol and about 500 g / mol, inclusive.

111. The electrode material of any one of claims 107 to 109, wherein the epoxidized polybutadiene of Formula G is a Poly bd™ 605E resin having an average molecular weight of about 1,300 g / mol and an epoxy equivalent weight of between about 260 g / mol and about 330 g / mol, inclusive.

112. The electrode material of any one of claims 107 to 111, wherein the weight ratio of first polymer: second polymer is in the range of about 6: 1 to about 2:3, inclusive. ​ ​ ​ ​ 113. The electrode material of claim 112, wherein the weight ratio is in the range of about 5.5: 1 to about 2:3, or about 5: 1 to about 2:3, or about 4.5: 1 to about 2:3, or about 4: 1 to about 2:3, or about 6: 1 to about 1: 1, or about 5.5: 1 to about 1: 1, or about 5: 1 to about 1: 1, or about 5: 1 to about 2: 1, or about 4.5: 1 to about 1: 1, or about 4: 1 to about 1: 1, inclusive of the upper and lower limits.

114. The electrode material of claim 113, wherein the weight ratio is in the range of about 5: 1 to about 2: 1, inclusive of the upper and lower limits.

115. An electrode comprising the electrode material of any one of claims 89 to 114 on a current collector.

116. A self-supporting electrode comprising the electrode material of any one of claims 89 to 114.

117. The electrode of claim 115 or 116, which is a positive electrode.

118. An electrolyte comprising the coated particle of claim 79, wherein the core of the coated particle comprises an ionically conductive inorganic material.

119. The electrolyte of claim 118, which is a liquid electrolyte comprising a solvent.

120. The electrolyte of claim 118, which is a solid state electrolyte further comprising a solvating polymer.

121. The electrolyte of claim 120, which is a hybrid polymer-ceramic solid state electrolyte.

122. The electrolyte of claim 118, which is an inorganic solid state electrolyte.

123. The electrolyte of claim 122, which is a ceramic-type inorganic solid state electrolyte.

124. The electrolyte of any one of claims 118 to 123, further comprising an alkali metal salt, preferably a lithium salt.

125. The electrolyte of any one of claims 118 to 124, further comprising at least one organic additive (e.g., an ionic organic additive (liquid or solid), a mercaptan, a plasticizer, etc.).

126. A coating material for a current collector comprising the coated particle of claim 80, wherein the core of the coated particle comprises an electronically conductive material.

127. The coating material of claim 126, wherein the electronically conductive material is carbon.

128. A current collector comprising the coating material of claim 126 or 127 disposed on a metal sheet.

129. An electrochemical cell comprising a negative electrode, a positive electrode, and an electrolyte, wherein at least one of the positive electrode or the negative electrode is as defined in any one of claims 115 to 117, or comprises the electrode material as defined in any one of claims 89 to 114.

130. An electrochemical cell comprising a negative electrode, a positive electrode, and an electrolyte, wherein the electrolyte is as defined in any one of claims 118 to 125.

131. An electrochemical cell comprising a negative electrode, a positive electrode, and an electrolyte, wherein at least one of the positive electrode and the negative electrode is on a current collector as defined in claim 128 or a current collector comprising a coating material as defined in claim 126 or 127.

132. The electrochemical cell according to any one of claims 129 to 131, wherein the negative electrode comprises an electrochemically active material comprising an alkali metal, an alkaline earth metal, an alloy containing at least one alkali metal or alkaline earth metal, a non-alkali metal and non-alkaline earth metal, or an intermetallic alloy or compound.

133. The electrochemical cell according to claim 132, wherein the electrochemically active material of the negative electrode comprises metallic lithium or an alloy containing or based on metallic lithium.

134. The electrochemical cell according to claim 132 or 133, wherein the electrochemically active material of the negative electrode is in the form of a film having a thickness in the range of about 5 µm to about 500 µm, inclusive.

135. The electrochemical cell according to claim 134, wherein the electrochemically active material of the negative electrode is in the form of a film having a thickness in the range of about 10 µm to about 100 µm, inclusive.

136. The electrochemical cell according to any one of claims 129 to 132, wherein the positive electrode is pre-lithiated and the negative electrode is substantially free of lithium.

137. The electrochemical cell according to claim 136, wherein the negative electrode is lithiated in situ during cycling of the electrochemical cell.

138. An electrochemical battery comprising at least one electrochemical cell according to any one of claims 129 to 137.

139. The electrochemical battery according to claim 138, wherein the electrochemical battery is a battery selected from the group consisting of a lithium battery, a lithium-ion battery, a sodium battery, a sodium-ion battery, a magnesium battery, and a magnesium-ion battery.

140. The electrochemical battery according to claim 138, wherein the battery is a lithium battery or a lithium-ion battery.

141. The electrochemical battery according to claim 138, wherein the electrochemical battery is an all-solid-state battery.

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