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BR-112021022989-B1 - Rechargeable battery cell

BR112021022989B1BR 112021022989 B1BR112021022989 B1BR 112021022989B1BR-112021022989-B1

Abstract

RECHARGEABLE BATTERY CELL. The invention relates to a rechargeable battery cell (2, 20, 40), containing an active metal, at least one positive electrode (4, 23, 44), at least one negative electrode (5, 22, 45), a casing (1, 28) and an electrolyte, wherein the positive electrode (4, 23, 44) contains at least one compound in the form of a layered oxide as the active material and wherein the electrolyte is based on SO2, and contains at least one first conductive salt, which has formula (I), wherein M is a metal that is selected from the group that is formed by alkali metals, alkaline earth metals, metals of group 12 of the periodic table of elements and aluminum; x is an integer from 1 to 3; The substituents R1, R2, R3, and R4 are selected independently of each other from the group consisting of C1-C10 alkyl, C2-C10 alkenyl, C2-C10 alkynyl, C3-C10 cycloalkyl, C6-C14 aryl, and C5-C14 heteroaryl; wherein Z is aluminum or boron.

Inventors

  • Laurent Zinck
  • Christian Pszolla
  • Markus Borck

Assignees

  • Innolith Technology AG

Dates

Publication Date
20260310
Application Date
20200730
Priority Date
20190731

Claims (20)

  1. 1. Rechargeable battery cell (2, 20, 40), containing an active metal, at least one positive electrode (4, 23, 44), at least one negative electrode (5, 22, 45), a casing (1, 28) and an electrolyte, wherein the positive electrode (4, 23, 44) contains at least one compound in the form of a layered oxide as the active material and characterized in that the electrolyte is based on SO2 and contains at least one first conductive salt, which has the formula (I) where: - M is a metal that is selected from the group that is formed by alkali metals, alkaline earth metals, metals of group 12 of the periodic table of elements and aluminum; - x is an integer from 1 to 3; - the substituents R1, R2, R3 and R4 are, independently of each other, and selected from the group that is formed by C1-C10 alkyl, C2-C10 alkenyl, C2-C10 alkynyl, C3-C10 cycloalkyl, C6-C14 aryl and C5-C14 heteroaryl; and - where Z is aluminum or boron.
  2. 2. Rechargeable battery cell (2, 20, 40), according to claim 1, characterized in that the compound has the composition AxM'yM"zOa, wherein: - A is at least one metal selected from the group formed by the alkali metals, alkaline earth metals, metals of group 12 of the periodic table or aluminum; - M' is at least one metal selected from the group formed by the elements Ti, V, Cr, Mn, Fe, Co, Ni, Cu and Zn; - M" is at least one element selected from the group formed by the elements of groups 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15 and 16 of the periodic table of elements; - x and y are, independently of each other, numbers greater than 0; - z is a number greater than or equal to 0; e- a is a number greater than 0.
  3. 3. Rechargeable battery cell (2, 20, 40), according to claim 2, characterized in that the compound has the composition AxM'yM"zOa, wherein A is lithium and M' is cobalt and wherein x and y are preferably equal to 1, z is equal to 0 and a is preferably equal to 2.
  4. 4. Rechargeable battery cell (2, 20, 40), according to claim 2, characterized in that the compound has the composition AxM'yM"zOa, wherein A is lithium, M' comprises nickel and manganese and M" is cobalt.
  5. 5. Rechargeable battery cell, according to claim 4, characterized in that the compound has the composition LixNiyiMny2CozOa, wherein x, y1 and y2 are, independently of each other, numbers greater than 0 and z is a number greater than or equal to 0 and a is a number greater than 0.
  6. 6. Rechargeable battery cell (2, 20, 40), according to claim 5, characterized in that the compound has the composition LiNi0.33Mn0.33Co0.33O2, LiNi0.5Mn0.3Co0.2O2, LiNi0.5Mn0.25Co0.25O2, LiNi0.52Mn0.32Co0.16O2, LiNi0.55Mn0.30Co0.15O2, LiNi0.58Mn0.14Co0.28O2, LiNi0.6Mn0.2Co0.2O2, LiNi0.64Mn0.18Co0.18O2, LiNi0.65Mn0.27Co0.08O2, LiNi0.7Mn0.2Co0.1O2, LiNi0.7Mn0.15Co0.15O2, LiNi0.72Mn0.10Co0.1sO2, LiNi0.76Mn0.14Co0.10O2, LiNi0.8Mn0.1Co0.1O2, LiNi0.86Mn0.04Co0.10O2, LiNi0.90Mn0.05Co0.05O2, LiNi0.95Mn0.025Co0.025O2 or a combination thereof.
  7. 7. Rechargeable battery cell, according to claim 2, characterized in that the compound has the compositions LixMnyM"zOa, wherein x is a number greater than or equal to 1 and y is a number greater than the number z.
  8. 8. Rechargeable battery cell (2, 20, 40), according to claim 7, characterized in that the compound has the composition LixMnyM"zOa, wherein M" is nickel and/or cobalt, in which the compound preferably has the composition Li1.2Mn0.525Ni0.175Co0.1O2, Li1.2Mn0.6Ni0.2O2, Li1.16Mn0.61Ni0.15Co0.16O2 or Li1.2Mn0.54Ni0.13Co0.13O2.
  9. 9. Rechargeable battery cell (2, 20, 40), according to any of the preceding claims, characterized in that the substituents R1, R2, R3 and R4 of the first conducting salt are selected independently of each other from the group formed by: - C1-C6 alkyl; preferably, C2-C4 alkyl; particularly preferably, 2-propyl, methyl and ethyl alkyl groups; - C2-C6 alkenyl; preferably, C2-C4 alkenyl; particularly preferably, alkenyl, ethenyl and propenyl groups; - C2-C6 alkynyl; preferably, C2-C4 alkynyl; - C3-C6 cycloalkyl; - phenyl; and - C5-C7 heteroaryl.
  10. 10. Rechargeable battery cell (2, 20, 40), according to any of the preceding claims, characterized in that at least one of the substituents R1, R2, R3 and R4 of the first conducting salt is replaced by at least one fluorine atom and/or by a chemical group, wherein the chemical group is selected from the group that is formed by C1-C4-alkyl, C2-C4-alkenyl, C2-C4-alkynyl, phenyl and benzyl.
  11. 11. Rechargeable battery cell (2, 20, 40), according to any of the preceding claims, characterized in that at least one of the substituents R1, R2, R3 and R4 of the first conducting salt is a CF3 group or an 0S02CF3 group.
  12. 12. Rechargeable battery cell (2, 20, 40), according to any of the preceding claims, characterized in that the first conductive salt is selected from the group, which is formed by
  13. 13. Rechargeable battery cell (2, 20, 40), according to any one of the preceding claims, characterized in that the electrolyte contains at least one second conductive salt that differs from the first conductive salt according to formula (I).
  14. 14. Rechargeable battery cell (2, 20, 40), according to claim 13, characterized in that the second conductive salt of the electrolyte is an alkali metal compound, particularly a lithium compound, which is selected from the group that is formed by an aluminate, a halide, an oxalate, a borate, a phosphate, an arsenate and a gallate.
  15. 15. Rechargeable battery cell (2, 20, 40), according to claim 13 or 14, characterized in that the second conductive salt of the electrolyte is a lithium tetrahaloaluminate, particularly lithium tetrachloroaluminate.
  16. 16. Rechargeable battery cell (2, 20, 40), according to any one of the preceding claims, characterized in that the electrolyte contains at least one additive.
  17. 17. Rechargeable battery cell (2, 20, 40), according to claim 16, characterized in that the electrolyte additive is selected from the group consisting of vinylene carbonate and its derivatives, vinylethylene carbonate and its derivatives, methylene carbonate and its derivatives, lithium (bisoxalate) borate, lithium difluoro(oxalate) borate, lithium tetrafluoro(oxalate) phosphate, lithium oxalate, 2-vinylpyridine, 4-vinylpyridine, cyclic exomethylene carbonates, sultones, acyclic cyclic sulfonates and cyclic sulfonates, organic esters, inorganic acids, acyclic and cyclic alkanes, acyclic and cyclic alkanes having a boiling point at 1 bar of at least 36 °C, aromatic compounds, cyclic sulfonylamides and Halogenated acyclic compounds, halogenated cyclic and acyclic phosphate esters, halogenated cyclic and acyclic phosphines, halogenated cyclic and acyclic phosphites, halogenated cyclic and acyclic phosphazenes, halogenated cyclic and acyclic silylamines, halogenated cyclic and acyclic esters, halogenated cyclic and acyclic amides, halogenated cyclic and acyclic anhydrides, and halogenated organic heterocycles.
  18. 18. Rechargeable battery cell (2, 20, 40), according to any of the preceding claims, characterized in that the electrolyte has the composition (i) 5 to 99.4% by weight sulfur dioxide, (ii) 0.6 to 95% by weight of the first conductive salt, (iii) 0 to 25% by weight of the second conductive salt and (iv) 0 to 10% by weight of additive, relative to the total weight of the electrolyte composition.
  19. 19. Rechargeable battery cell (2, 20, 40), according to any of the preceding claims, characterized in that the quantity concentration of the first conducting salt is in the range of 0.01 mol/l to 10 mol/l, preferably 0.05 mol/l to 10 mol/l, more preferably 0.1 mol/l to 6 mol/l and particularly preferably 0.2 mol/l to 3.5 mol/l relative to the total volume of the electrolyte.
  20. 20. Rechargeable battery cell (2, 20, 40), according to any of the preceding claims, characterized in that the electrolyte contains at least 0.1 mol of SO2, preferably at least 1 mol of SO2, more preferably at least 5 mol of SO2, more preferably at least 10 mol of SO2 and particularly preferably at least 20 mol of SO2 for each mol of the conducting salt.

Description

[0001] The invention relates to a rechargeable battery cell with an electrolyte based on SO2. [0002] Rechargeable battery cells are of great importance in various technical sectors. In many cases, they are used for applications where only small rechargeable battery cells with relatively low currents are needed, such as in mobile phone operations. However, there is also a greater need for larger rechargeable battery cells for high-energy applications, where mass energy storage in the form of battery cells for the electric drive of vehicles is of great importance. [0003] An important requirement in such rechargeable battery cells is a high energy density. This means that the rechargeable battery cell must contain as much electrical energy as possible per unit of weight and volume. For this, lithium has proven to be the most advantageous active metal. As the active metal in a rechargeable battery cell, metals stand out whose ions within the electrolyte, during the charging or discharging of the cell, migrate to the negative or positive electrode and, at that location, participate in electrochemical processes. These electrochemical processes directly lead to the release of electrons into the external electrical circuit or to the absorption of electrons from the external electrical current. Rechargeable battery cells containing lithium as the active metal are also referred to as lithium-ion cells. The energy density of these lithium-ion cells can be increased either by increasing the specific capacitance of the electrodes or by increasing the cell voltage. [0004] Both the positive and negative electrodes of lithium-ion cells are formed as insertion electrodes. The term "insertion electrode," in the sense of the present invention, refers to electrodes that possess a crystal structure in which the ions of the active material can be internalized and externalized during the operation of the lithium-ion cell. This means that the electrode processes can occur not only on the surface of the electrodes but also within the crystal structure. Both electrodes typically have a density of less than 100 μm and are therefore formed very thinly. When charging the lithium-ion cell, the ions of the active metal are externalized from the positive electrode and internalized in the negative electrodes. When discharging the lithium-ion cell, the reverse process occurs. [0005] The electrolyte is also an important functional element of each rechargeable battery cell. It usually contains a solvent or solvent mixture and at least one conductive salt. Solid or liquid ionic electrolytes, for example, do not contain any solvent, but only a conductive salt. The electrolyte comes into contact with the positive and negative electrodes of the battery cell. At least one ion of the conductive salt (anion or cation) is mobile in the electrolyte, so that, through ion conduction, charge transport between the electrodes can occur, which is necessary for the function of the rechargeable battery cell. The electrolyte is decomposed electrochemically and oxidatively from a certain higher cell voltage of the rechargeable battery cell. This process often leads to irreversible destruction of the electrolyte components and, consequently, to failure of the rechargeable battery cell. Reduction processes can also decompose electrolytes from a certain lower cell voltage. To avoid these processes, the positive and negative electrodes are selected in such a way that the cell voltage is below or above the electrolyte's decomposition voltage. The electrolyte thus determines the voltage window within which a rechargeable battery cell can be operated reversibly, that is, charged and discharged repeatedly. [0006] Known lithium-ion cells in the prior art contain an electrolyte, which consists of a conductive salt dissolved in an organic solvent or a mixture of solvent and dissolved in a conductive salt. Such a conductive salt is a lithium salt, such as, for example, lithium hexafluorophosphate (LiPFe). The solvent mixture may contain, for example, ethylene carbonate. The electrolyte LP57, which has the composition 1 M LiPF6 in EC:EMC 3:7, is an example of such an electrolyte. Due to the organic solvent or solvent mixture, such lithium-ion cells are also designated as organic lithium-ion cells. [0007] The negative electrodes of these organic lithium-ion cells consist of a carbon coating, which is applied to a copper discharge element. The discharge element produces the necessary conductive electrical conduction between the discharge coating and the external electric current. The positive electrode consists of lithium cobalt oxide (UC0O2), which is applied to an aluminum discharge element. [0008] It has long been known that undesirable overcharging of organic lithium-ion cells leads to irreversible decomposition of the electrolyte components. In this case, oxidative decomposition of the organic solvent and/or conductive salt occurs on the surface of the positive electrode