rechargeable battery cells

Abstract

The present invention relates to a rechargeable battery cell (2, 20, 40) comprising an active metal, at least one positive electrode (4, 23, 44) having a conductor element (26), at least one negative electrode (5, 22, 45) having a conductor element (27), a housing (1, 28) and an electrolyte, wherein the conductor element (26) of the positive electrode (4, 23, 44) and the conductor element (27) of the negative electrode (5, 22, 45) are formed independently of one another by a material selected from the group formed by aluminum and copper, the electrolyte is based on SO2 and comprises at least one first conductive salt having formula (I), M is a metal selected from the group formed by alkali metals, alkaline earth metals, metals of group 12 of the periodic table of the elements and aluminum, x is an integer from 1 to 3 and is characterized by a substituent R 1 , R 2 , R 3 and R 4 are C1 to C 10 Alkyl, C2-C 10 Alkenyl, C2-C 10 Alkynyl, C3-C 10 Cycloalkyl, C6-C 14 Aryl and C5-C 14 heteroaryl; and Z is aluminum or boron. [Formula 1] JPEG2024504477000014.jpg42166

Description

[Technical Field]

[0001] The present invention relates to a rechargeable battery cell having an SO2-based electrolyte. [Background technology]

[0002] Rechargeable battery cells are extremely important in many technological fields. Often, these rechargeable cells are used in applications where only small rechargeable battery cells with relatively low currents are required, such as powering mobile phones. However, there is also a significant demand for larger rechargeable battery cells for high-energy applications, and for electric vehicle propulsion, storing large amounts of energy in the form of a battery cell is particularly important.

[0003] A key requirement for this type of rechargeable battery cell is high energy density. This means that the rechargeable battery cell must contain as much electrical energy as possible per unit weight and volume. For this reason, lithium has proven particularly advantageous as the active metal. Rechargeable battery cells containing lithium as the active metal are also called lithium-ion batteries. The energy density of such lithium-ion batteries can be increased by either increasing the specific capacity of the electrodes or increasing the cell voltage.

[0004] Both the positive and negative electrodes of a lithium-ion battery are formed as insertion electrodes. In the context of this invention, the term “insertion electrode” is understood to mean an electrode having a crystalline structure capable of accumulating or releasing ions of the active metal in the crystalline structure when the lithium-ion battery is operating. The active metal in a rechargeable battery cell refers to a metal whose ions in the electrolyte move to the negative or positive electrode during charging and discharging of the cell and participate in an electrochemical process there. In the case of an insertion electrode, this means that the electrode process can occur not only on the surface of the electrode but also within the crystalline structure. During charging of the lithium-ion battery, ions of the active metal are released from the positive electrode and accumulated in the negative electrode. The reverse process occurs during discharging of the lithium-ion battery. This electrochemical process directly or indirectly leads to the release of electrons to or acceptance of electrons from an external circuit. To enable the electrons to be released to or accepted from the external circuit, the positive and negative electrodes of the lithium-ion battery each have a conductive element. This conductive element is an important component of the positive and negative electrodes. In the electrode reaction of the first electrode, electrons (e -The electrons are released to the external circuit via their conductive elements. The electrons required for the electrode reaction of the second electrode are supplied from the external circuit by the conductive elements of the electrode. Good electron conductivity of both conductive elements is a prerequisite for the high current capacity of the electric cell. The conductive elements can be formed, for example, in a planar shape in the form of a metal sheet or in a three-dimensional shape in the form of a porous metal foam. The active material of the negative electrode or the positive electrode is introduced into the metal foam or coated onto the metal sheet. Since the active material in the metal foam and the coating of the planar metal sheet with the active material are porous, the electrolyte used can penetrate into their respective porous structures and thus come into contact with each of the conductive elements. A potential difference is formed between the electrodes when the battery cell is charged or discharged. The reaction between the conductive elements and the electrode active material or the electrolyte can be promoted by this potential difference. Therefore, the material of the conductive elements must be inert not only to the electrode active material used but also to the electrolyte used, without causing undesirable side reactions in the corresponding potential range. Therefore, when selecting an appropriate conducting element, it is necessary to consider the electrolyte used and the expected potential range. In the following text, the terms "conducting element," "conducting means," and "current conducting means" are synonymous.

[0005] The electrolyte is also an important functional element for a rechargeable battery cell. The electrolyte typically comprises a solvent or solvent mixture and at least one conductive salt. For example, a solid electrolyte or ionic solution contains only the conductive salt and no solvent. The electrolyte is in contact with the positive and negative electrodes of the battery cell. At least one ion (anion or cation) of the conductive salt is mobile within the electrolyte by ionic conduction, allowing for charge transport between electrodes, which is necessary for the function of the rechargeable battery cell. The electrolyte is electrochemically decomposed oxidatively when the rechargeable battery cell exceeds a predetermined upper cell voltage. This process often leads to irreversible destruction of the electrolyte components and, consequently, failure of the rechargeable battery cell. A reductive process can also destroy the electrolyte if the voltage falls below a predetermined lower cell voltage. To avoid this process, the positive and negative electrodes are selected such that the cell voltage is lower or higher than the electrolyte decomposition voltage. Therefore, the electrolyte determines the voltage window, and within that range, the rechargeable battery cell can be operated reversibly, that is, repeatedly charged or discharged.

[0006] Lithium-ion batteries known from the prior art include an electrolyte consisting of an organic solvent or solvent mixture and a conductive salt dissolved therein. The conductive salt is, for example, a lithium salt such as lithium hexafluorophosphate (LiPF6). The solvent mixture may include, for example, ethylene carbonate. Electrolyte LP57, having a composition of 1M LiPF6 at EC:EMC 3:7, is an example of such an electrolyte. By using the organic solvent or solvent mixture, this type of lithium-ion battery is also called an organic lithium-ion battery.

[0007] In addition to lithium hexafluorophosphate (LiPF6), which is frequently used as a conductive salt in the prior art, other conductive salts for organic lithium-ion batteries are described. For example, Japanese Patent No. 4306858 (hereinafter referred to as [V1]) describes conductive salts in the form of tetraalkoxy salts or tetraaryl oxyborate salts, which may be fluorinated or partially fluorinated. Japanese Patent Application Publication No. 2001-143750 (hereinafter referred to as [V2]) describes fluorinated or partially fluorinated tetraalkoxyborate and tetraalkoxyaluminate as conductive salts. The conductive salts described in both documents [V1] and [V2] are used in organic lithium-ion batteries by dissolving them in organic solvents or solvent mixtures.

[0008] It has long been known that unintentional overcharging of organic lithium-ion batteries can lead to irreversible decomposition of the electrolyte components. In this process, the oxidative decomposition of the organic solvent and / or the conductive salt occurs on the surface of the positive electrode. The reaction heat and gaseous products generated during this decomposition cause subsequent so-called "thermal runaway" and the resulting destruction of the organic lithium-ion battery. Most charging protocols for such organic lithium-ion batteries use cell voltage as an indicator of the end of charging. In this case, accidents due to thermal runaway are particularly likely to occur when using multi-cell battery packs in which multiple organic lithium-ion batteries of different capacities are connected in series.

[0009] Therefore, organic lithium-ion batteries have problems with their own stability and operational safety during long-term use. Safety risks also arise, in particular, from the flammability of the organic solvent or solvent mixture. If an organic lithium-ion battery ignites or even explodes, the organic solvent of the electrolyte forms a flammable substance. To avoid such safety risks, further measures are necessary. These measures include, in particular, extremely precise control of the charging and discharging processes of the organic lithium-ion battery and optimization of the battery structure. Furthermore, the organic lithium-ion battery contains components that melt when the temperature rises unintentionally, potentially filling the organic lithium-ion battery with molten plastic. This prevents further uncontrollable temperature increases. However, these measures lead to increased manufacturing costs and increases in volume and weight during the production of the organic lithium-ion battery. Furthermore, these measures reduce the energy density of the organic lithium-ion battery.

[0010] In known advanced forms from the prior art, sulfur dioxide (SO2)-based electrolytes are used in place of organic electrolytes in rechargeable battery cells. Rechargeable battery cells containing SO2-based electrolytes exhibit particularly high ionic conductivity. In the context of this invention, the term "SO2-based electrolyte" is understood to mean an electrolyte in which SO2 is not only present as an additive at a low concentration, but also in which the ionic mobility of the conductive salt contained in the electrolyte and which carries out charge transport is guaranteed at least partially, mostly, or completely by SO2. Thus, SO2 functions as a solvent for the conductive salt. The conductive salt is often lithium tetrachloroaluminate (LiAlCl4), which forms a liquid solvation compound complex with gaseous SO2, and in this process, the SO2 binds, significantly reducing the vapor pressure compared to pure SO2. An electrolyte with a lower vapor pressure is produced. This type of SO2-based electrolyte has the advantage of being non-flammable compared to the aforementioned organic electrolytes. Therefore, it is possible to eliminate the safety risks arising from the flammability of the electrolyte.

[0011] For example, European Patent No. 2534725 (hereinafter referred to as [V3]) describes a rechargeable battery cell having an SO2-based electrolyte, preferably containing tetrahaloluminic acid, particularly LiAlCl4, as the conductive salt.

[0012] Regarding conductive elements, [V3] states that "(...) nickel or nickel alloys are often used as current conductors to or from electrodes." Furthermore, the same document states that nickel foam is commonly used as a conductor for electrodes.

[0013] U.S. Patent Application Publication No. 2004 / 0157129 (hereinafter referred to as [V4]) also describes a rechargeable battery cell having an SO2-based electrolyte. The inventors of [V4] discovered that undesirable reactions occurred between the conductive element and the SO2-based electrolyte, particularly between conductive salts containing chlorides such as LiAlCl4. This problem occurred especially in battery cells that reached extremely high cell voltages (exceeding 4 volts) during charging. The problem is resolved by a battery cell in which at least one conductive electrode contains an alloy of chromium and another metal and / or a protective metal as a reaction-protecting material in the surface layer that protects the conductive element from undesirable reactions.

[0014] European Patent No. 2534719 (hereinafter referred to as [V5]) also discloses an SO2-based electrolyte that particularly contains LiAlCl4 as a conductive salt. The LiAlCl4 forms a composite with SO2, for example, having the formula LiAlCl4*1.5 moles SO2 or LiAlCl4*6 moles SO2. In [V5], lithium iron phosphate (LiFePO4) is used as the positive electrode. LiFePO4 has a lower charging termination voltage (3.7V) compared to LiCoO2 (4.2V). The reason why the problem of unintended reactions of the conductive elements does not occur in this rechargeable battery cell is that it does not reach the upper potential of 4.1 volts.

[0015] A further problem with SO2-based electrolytes is that many conductive salts, particularly those known in organic lithium-ion batteries, are insoluble in SO2.

[0016] [Table 2]

[0017] Measurements revealed that SO2 is a poor solvent for many conductive salts, such as: lithium fluoride (LiF), lithium bromide (LiBr), lithium sulfate (Li2SO4), lithium bis(oxalato)borate (LiBOB), lithium hexafluoroarsenate (LiAsF6), lithium tetrafluoroborate (LiBF4), trilithium hexafluoroaluminate (Li3AlF6), lithium hexafluoroantimonate (LiSbF6), lithium difluoro(oxalato)borate (LiBF2C2O4), lithium bis(trifluoromethanesulfonyl)imide (LiTFSl), lithium metaborate (LiBO2), lithium aluminate (LiAlO2), lithium triflate (LiCF3SO3), and lithium chlorosulfonate (LiSO3Cl). The solubility of these conductive salts in SO2 is approximately 10 -2 from 10 -4 The values ​​are moles / L (see Table 2). At these low salt concentrations, only low conductivity is present at best, and it can be assumed that this is insufficient for the useful operation of rechargeable battery cells. [Prior art documents] [Patent Documents]

[0018] [Patent Document 1] Patent No. 4306858 [Patent Document 2] Japanese Patent Publication No. 2001-143750 [Patent Document 3] European Patent No. 2534725 [Patent Document 4] U.S. Patent Application Publication No. 2004 / 0157129 [Patent Document 5] European Patent No. 2534719 [Overview of the project] [Problems that the invention aims to solve]

[0019] In order to further improve the applications and characteristics of rechargeable battery cells containing SO2-based electrolytes, the present invention is based on the objective of proposing a rechargeable battery cell having an SO2-based electrolyte that is superior to rechargeable battery cells known from the prior art, as follows: - The electrode has an inert conductive element that does not react with SO2-based electrolytes and remains stable even at higher charging potentials. - The electrode has a conductive element that does not dissolve at a higher potential or promote oxidative electrolyte decomposition. Furthermore, it must not inhibit the reaction for surface formation. - It has a wide electrochemical window so that oxidative electrolyte decomposition does not occur at the positive electrode. - The negative electrode has a stable surface layer, and the surface layer capacitance should be low, so that no further reductive electrolytic decomposition occurs on the negative electrode during subsequent operation. - It has an SO2-based electrolyte with good solubility of conductive salts, thereby being a good ion conductor and electronic insulator, and thus facilitating ion transport and minimizing self-discharge. - For example, it includes an SO2-based electrolyte that is inert to other components in a rechargeable battery cell, such as separators, electrode materials, and cell casing materials. - Robust against electrical, mechanical, or thermal misuse, - Contains an SO2-based electrolyte that has higher stability against residual water content in the cell components of a rechargeable battery cell, - Improved electrical performance data, especially with high energy density, - It has improved overcharge and deep discharge properties as well as lower self-discharge properties. - It exhibits a longer service life, especially a higher number of usable charge / discharge cycles, and furthermore - To be as inexpensive as possible and have high availability. This is particularly important in the case of large batteries or batteries that are widely distributed.

[0020] This type of rechargeable battery cell should have particularly excellent electrical energy data and performance data, high operating stability and service life, especially a high number of charge-discharge cycles that can be used, and in this case, the electrolyte should not be decomposed during the operation of the rechargeable battery cell.

Means for Solving the Problem

[0021] This problem is solved by a rechargeable battery cell having the features of claim 1. Claims 2 to 27 describe advantageous developments of the rechargeable battery cell according to the present invention.

[0022] The rechargeable battery cell according to the present invention comprises an active metal, at least one positive electrode having a conductor element, at least one negative electrode having a conductor element, a housing, and an electrolyte. The conductor element of the positive electrode and the conductor element of the negative electrode are each independently made of a material selected from the group consisting of aluminum and copper. The electrolyte is of the SO2 type and contains at least one first conductive salt. The first conductive salt has the formula (I).

[0023]

Chemical formula

[0024] In the formula (I), M is a metal selected from the group consisting of an alkali metal, an alkaline earth metal, a metal of Group 12 of the periodic table of elements, and aluminum. x is an integer from 1 、R 2 、R 3 and R 4 are each independently C1-C 10 alkyl, C2-C 10 alkenyl, C2-C 10 alkynyl, C3-C 10 cycloalkyl, C6-C14 Aryl and C5~C 14 Selected from the group formed by heteroaryl groups. The central atom Z is either aluminum or boron.

[0025] In the context of this invention, the term "conducting element" refers to an electron-conducting element used to enable the required electron-conductive connection between the active material of each electrode and the external circuit. For this purpose, each of the conductor elements is in electron-conductive contact with the active material involved in the electrode reaction of each of the electrodes.

[0026] The SO2-based electrolyte used in the rechargeable battery cell of the present invention not only contains SO2 at a low concentration as an additive, but also contains SO2 at a concentration such that the ion mobility of the first conductive salt contained in the electrolyte and responsible for charge transport is at least partially, mostly, or completely guaranteed by SO2. The first conductive salt is dissolved in the electrolyte and exhibits extremely good solubility within the electrolyte. The conductive salt can form a liquid solvated compound complex with gaseous SO2, and SO2 is bound to the solvated compound complex. In this case, the vapor pressure of the liquid solvated compound complex is significantly lower than that of pure SO2, resulting in an electrolyte with a lower vapor pressure. However, it is also within the scope of the present invention that a decrease in vapor pressure may not occur during the production of the electrolyte according to the present invention, depending on the chemical structure of the first conductive salt according to formula (I). In the latter case, it is preferable to work under low temperature or pressure during the production of the electrolyte according to the present invention. The electrolyte may also include a plurality of conductive salts according to formula (I) whose chemical structures differ from each other.

[0027] In the meaning of the present invention, "C1~C 10The term "alkyl" refers to a group comprising a linear or branched saturated hydrocarbon group having 1 to 10 carbon atoms. This includes, in particular, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, 2,2-dimethylpropyl, n-hexyl, isohexyl, 2-ethylhexyl, n-heptyl, isoheptyl, n-octyl, isooctyl, n-nonyl, and n-decyl.

[0028] In the meaning of the present invention, "C2~C 10 The term "alkenyl" refers to a hydrocarbon group comprising an unsaturated linear or branched hydrocarbon group having 2 to 10 carbon atoms, wherein the hydrocarbon group has at least one CC double bond. This includes, in particular, ethenyl, 1-propenyl, 2-propenyl, 1-n-butenyl, 2-n-butenyl, isobutenyl, 1-pentenyl, 1-hexenyl, 1-heptenyl, 1-octenyl, 1-nonenyl, and 1-decenyl.

[0029] In the meaning of the present invention, "C2~C 10 The term "alkynyl" refers to a hydrocarbon group comprising an unsaturated linear or branched hydrocarbon group having 2 to 10 carbon atoms, wherein the hydrocarbon group has at least one CC triple bond. This includes, in particular, ethynyl, 1-propynyl, 2-propynyl, 1-n-butynyl, 2-n-butynyl, isobutynyl, 1-pentynyl, 1-hexynyl, 1-heptynyl, 1-octinyl, 1-noninyl, and 1-decynyl.

[0030] In the meaning of the present invention, "C3~C 10 The term "cycloalkyl" refers to a cyclic saturated hydrocarbon group having 3 to 10 carbon atoms. This includes, in particular, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclohexyl, cyclononyl, and cyclodecanyl.

[0031] In the context of this invention, "C6~C 14The term "aryl" refers to an aromatic hydrocarbon group having 6 to 14 cyclic carbon atoms. This includes, in particular, phenyl (C6H5 group) and naphthyl (C6H5 group). 10 H7 group) and anthrasyl (C 14 H9 units are the ones that fall into this category.

[0032] In the meaning of the present invention, "C5~C 14 The term "heteroaryl" refers to an aromatic hydrocarbon group having 5 to 14 cyclic hydrocarbon atoms, wherein at least one of the hydrocarbon atoms is substituted or exchanged with a nitrogen atom, an oxygen atom, or a sulfur atom. This includes pyrrolyl, furanyl, thiophenyl, pyridinyl, pyranyl, and thiopyranyl, among others. All of the aforementioned hydrocarbon groups are bonded to the central atom according to formula (I) via the oxygen atom.

[0033] Rechargeable battery cells having this type of electrolyte have the advantage of virtually no decomposition at higher cell voltages compared to rechargeable battery cells containing electrolytes known from the prior art, because the first conductive salt contained in the electrolyte has higher oxidative stability. The electrolyte preferably exhibits oxidative stability up to an upper potential of at least 4.0 volts, more preferably up to an upper potential of at least 4.2 volts, more preferably up to an upper potential of at least 4.4 volts, more preferably up to an upper potential of at least 4.6 volts, more preferably up to an upper potential of at least 4.8 volts, and particularly preferably up to an upper potential of at least 5.0 volts. Therefore, when such an electrolyte is used in a rechargeable battery cell, electrolyte decomposition occurring within the working potential, i.e., in the range between the charging termination voltage and the discharging termination voltage of both electrodes of the rechargeable battery cell, is completely absent or extremely small. As a result, the rechargeable battery cell according to the present invention can have a charging termination voltage of at least 4.0 volts, more preferably 4.4 volts, more preferably at least 4.8 volts, more preferably at least 5.2 volts, more preferably at least 5.6 volts, and particularly preferably at least 6.0 volts. The service life of rechargeable battery cells containing this electrolyte is significantly longer than that of rechargeable battery cells containing electrolytes known from prior art.

[0034] Furthermore, rechargeable battery cells containing such electrolytes have low-temperature stability. For example, 61% of the charged capacity can still be discharged at a temperature of -40°C. The conductivity of the electrolyte at low temperatures is sufficient to operate the battery cell. Moreover, rechargeable battery cells containing such electrolytes have improved stability against residual water. If trace amounts of water (in the ppm range) remain in the electrolyte, the electrolyte or the first conductive salt, together with the water, form hydrolysis products that are significantly less corrosive to the cell components compared to SO2-based electrolytes known from the prior art. Therefore, the fact that the electrolyte does not contain water compared to SO2-based electrolytes known from the prior art does not play a particularly important role. The advantages of the electrolyte according to the present invention outweigh the disadvantages arising from the significantly larger anion size of the first conductive salt according to formula (I) compared to conductive salts known from the prior art. This larger anion size leads to lower conductivity of the first conductive salt according to formula (I) compared to the conductivity of LiAlCl4.

[0035] Conductor elements of the positive and negative electrodes In the following, advantageous developments of the rechargeable battery cell according to the present invention will be described with respect to the conductive elements of the positive electrode and the conductive elements of the negative electrode.

[0036] According to the present invention, not only the positive electrode but also the negative electrode has a conductive element. The conductive element is used to enable the necessary electron conduction connection of the active material of each electrode to an external circuit. For this purpose, the conductive element is in contact with the active material involved in the electrical reaction of each electrode. As described above, according to the present invention, the conductive element of the positive electrode and the conductive element of the negative electrode are formed independently of each other from a material selected from the group formed by aluminum and copper. In a preferred embodiment of the rechargeable battery cell according to the present invention, the conductive element of the positive electrode is made of aluminum. In another preferred embodiment of the rechargeable battery cell according to the present invention, the conductive element of the negative electrode is made of copper. The conductive element of the positive electrode and / or the conductive element of the negative electrode may be formed as a single unit or as a multi-part unit.

[0037] The conductive elements of the positive electrode and / or the negative electrode may be formed in a planar shape in the form of a thin metal sheet or thin metal foil. The thin metal foil may have a perforated or mesh structure. The planar conductive elements may also be formed from a metal-coated plastic foil. The metal coating preferably has a thickness in the range of 0.1 μm to 20 μm. The active material of each electrode is preferably applied to the surface of the thin metal sheet, the thin metal foil, or the metal-coated plastic foil. The active material may be applied to the front and / or back of the planar conductive element. This type of planar conductive element preferably has a thickness in the range of 0.5 μm to 50 μm, and particularly preferably 1 μm to 20 μm. When using planar conductive elements, the total thickness of each electrode may be at least 20 μm, preferably at least 40 μm, and particularly preferably at least 60 μm. The maximum thickness is preferably at most 300 μm, preferably at most 150 μm, and particularly preferably at most 100 μm.

[0038] Regarding the coating on one side of each of the aforementioned conductive elements, the positive electrode and / Alternatively, the area-specific capacitance of the negative electrode is preferably at least 0.5 mAh / cm² when a planar conductive element is used. 2 Furthermore, the following values ​​in this order are preferable: 1 mAh / cm² 2 , 3mAh / cm 2 5mAh / cm² 2 , 10mAh / cm 2 , 15mAh / cm 2 , 20mAh / cm 2 .

[0039] When the conductive element is formed in a planar shape in the form of a thin metal sheet, a thin metal foil, or a metal-coated plastic foil, the amount of the active material in the negative electrode or the positive electrode, i.e., the amount of the electrode filling with respect to the coating on one side, is preferably at least 1 mg / cm³. 2 Preferably at least 3 mg / cm³ 2 More preferably, at least 5 mg / cm³ 2 More preferably, at least 8 mg / cm³ 2 More preferably, at least 10 mg / cm³ 2 And especially preferably at least 20 mg / cm³ 2 That is the case.

[0040] The maximum filling amount of the electrode with respect to the coating on one of the aforementioned surfaces is preferably at most 150 mg / cm³. 2 More preferably, at most 100 mg / cm³ 2 And more preferably, at most 80 mg / cm³ 2 That is the case.

[0041] Furthermore, the conductive elements of the positive electrode and / or the conductive elements of the negative electrode may be formed in a three-dimensional porous metal structure, particularly in the form of a metal foam. The three-dimensional porous metal structure is porous so that the active material of each electrode can be incorporated into the pores of the metal structure. The amount of the active material incorporated or coated is the amount of filling in the electrode. When the conductive elements are formed in a three-dimensional porous metal structure, particularly in the form of a metal foam, each electrode has a thickness of preferably at least 0.2 mm, preferably at least 0.3 mm, more preferably at least 0.4 mm, still more preferably at least 0.5 mm, and particularly preferably at least 0.6 mm.

[0042] In another advantageous embodiment of the rechargeable battery cell according to the present invention, particularly when using three-dimensional conductive elements in the form of a metal foam, the area ratio capacity of the positive and / or negative electrode is preferably at least 2.5 mAh / cm². 2 The following values ​​are even more preferable in this order: 5mAh / cm² 2 , 15mAh / cm 2 , 25mAh / cm 2 , 35mAh / cm² 2 , 45mAh / cm 2 55mAh / cm² 2 65mAh / cm² 2 75mAh / cm² 2 If the conductive element is formed in a three-dimensional porous metal structure, particularly in the form of a metal foam, the amount of the active material in the positive electrode or the negative electrode, i.e., the amount of filling in each electrode on its own surface, is at least 10 mg / cm³. 2 Preferably at least 20 mg / cm³ 2 More preferably, at least 40 mg / cm³ 2 More preferably, at least 60 mg / cm³ 2 More preferably, at least 80 mg / cm³ 2 And especially preferably at least 100 mg / cm³ 2 The amount of filling in each electrode has a positive effect not only on the charging process of the rechargeable battery cell but also on the discharging process. Furthermore, the rechargeable battery cell may also include at least one positive electrode having a conductive element in the shape of a porous metal structure, particularly in the shape of a metal foam, and at least one negative electrode having a planar conductive element in the shape of a thin metal sheet, a thin metal foil, or a metal-coated plastic foil. Alternatively, the rechargeable battery cell may also include at least one negative electrode having a conductive element in the shape of a porous metal structure, particularly in the shape of a metal foam, and at least one positive electrode having a planar conductive element in the shape of a thin metal sheet, a thin metal foil, or a metal-coated plastic foil.

[0043] The active material of the positive electrode can at least partially or completely cover the conductive element. Furthermore, the active material of the negative electrode can at least partially or completely cover the conductive element. Both the planar conductive element and the three-dimensional conductive element can be formed as a multi-part mold. For contact of the conductive elements, the rechargeable battery cell may have further components attached to each of the conductive elements, such as lugs, wires, or sheets. These components may be formed from materials other than those of the respective conductive elements, i.e., aluminum or copper.

[0044] electrolyte The following describes the advantageous development of the rechargeable battery cell according to the present invention with respect to SO2-based electrolytes.

[0045] As described above, the substituent R in formula (I) of the first conductive salt 1 , R 2 , R 3 and R 4 These are C1~C, which are independent of each other. 10 Alkyl, C2~C 10 Alkenyl, C2~C 10 Alkinyl, C3~C 10 Cycloalkyl, C6~C 14 Aryl and C5~C 14 Selected from the group formed by heteroaryls. In another advantageous embodiment of the rechargeable battery cell, the substituent R of the first conductive salt 1 , R 2 , R 3 and R 4 The group is selected from the groups formed independently of each other by the following: - C1-C6 alkyl groups, preferably C2-C4 alkyl groups, particularly preferably 2-propyl, methyl, and ethyl alkyl groups, - C2-C6 alkenyl, preferably C2-C4 alkenyl, particularly preferably ethenyl and propenyl alkenyl groups, - C2-C6 alkynyl, preferably C2-C4 alkynyl, - C3~C6 cycloalkyl, - Phenyl, and - C5~C7 heteroaryl.

[0046] In the advantageous embodiment of the SO2-based electrolyte described above, the term "C1-C6 alkyl" includes linear or branched saturated hydrocarbon groups having 1 to 6 hydrocarbon groups, particularly methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, 2,2-dimethylpropyl, n-hexyl, and isohexyl. Of these, C2-C4 alkyl is preferred. Particularly preferred are 2-propyl, methyl, and ethyl C2-C4 alkyl groups.

[0047] In the advantageous embodiment of the SO2-based electrolyte described above, the term "C2-C6 alkenyl" comprises an unsaturated linear or branched hydrocarbon group having 2 to 6 carbon atoms, wherein the hydrocarbon group has at least one C-C double bond. This includes ethenyl, 1-propenyl, 2-propenyl, 1-n-butenyl, 2-n-butenyl, isobutenyl, 1-pentenyl, and 1-hexenyl, with C2-C4 alkenyl being preferred. Ethenyl and 1-propenyl are particularly preferred.

[0048] In the advantageous embodiment of the SO2-based electrolyte described above, the term "C2-C6 alkynyl" comprises an unsaturated linear or branched hydrocarbon group having 2 to 6 carbon atoms, wherein the hydrocarbon group has at least one C-C triple bond. This includes, in particular, ethynyl, 1-propynyl, 2-propynyl, 1-n-butynyl, 2-n-butynyl, isobutynyl, 1-pentynyl, and 1-hexynyl. Of these, C2-C4 alkynyls are preferred.

[0049] In the advantageous embodiment of the SO2-based electrolyte, the term "C3-C6 cycloalkyl" includes a cyclic saturated hydrocarbon group having 3 to 6 carbon atoms. This includes, in particular, cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl.

[0050] In the advantageous embodiment of the SO2-based electrolyte, the term "C5-C7 heteroaryl" includes phenyl and naphthyl.

[0051] In another preferred development of the rechargeable battery cell according to the present invention, the substituent R 1 , R 2 , R 3 and R 4 At least two of these are bridged to each other to form a bidentate chelate ligand. Such a bidentate chelate ligand may have a structure such as the following:

[0052] [ka]

[0053] The substituent R 1 , R 2 , R 3 and R 4 It is also preferable that three or four of these ligands can be bridged to each other to form a tridentate or tetradentate chelate ligand. After the formation of the chelate complex, the chelate ligands coordinate to the central atom Z. The term "chelate complex"—or simply "chelate"—refers to a complex compound in which a multidentate ligand (having more than one free electron pair) occupies at least two coordination sites (bonding sites) of the central atom. The central atom is a positively charged metal ion Al 3+ or B 3+ Therefore, the coordinate and the central atom are bonded by a coordinate covalent bond, which means that the bonded electron pair is composed solely of the coordinate.

[0054] Another preferred development of the rechargeable battery cell according to the present invention has a cell voltage of at least 4.0 volts, preferably at least 4.4 volts, more preferably at least 4.8 volts, even more preferably at least 5.2 volts, even more preferably at least 5.6 volts, and particularly preferably at least 6.0 volts.

[0055] In another preferred embodiment of the rechargeable battery cell according to the present invention, the substituent R is used to improve the solubility of the first conductive salt in the SO2-based electrolyte. 1 , R 2 , R 3 and R 4 The substituent R is substituted with at least one fluorine atom and / or at least one chemical group, the chemical group being selected from the group formed by C1-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, phenyl, and benzyl. The chemical groups C1-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, phenyl, and benzyl have similar properties or chemical structures to the hydrocarbon group described above. Substitution in this context refers to the substituent R 1 , R 2 , R 3 and R 4 This means that each individual atom or group of atoms is substituted by the fluorine atom and / or the chemical group.

[0056] The substituent R 1 , R 2 , R 3 and R 4 By having at least one of them be a CF3 group or an OSO2CF3 group, it is possible to obtain extremely high solubility of the first conductive salt in the SO2-based electrolyte.

[0057] In another advantageous development of the rechargeable battery cell, the first conductive salt is selected from the group formed by:

[0058] [ka]

[0059] The last mentioned first conductive salt having the molecular formula LiB(O2C2(CF3)4)2 is two bidentate chelate ligands having the following structure, wherein after the formation of the chelate complex, the central atom B 3+ It coordinates to the other side. Therefore, the two perfluoroalkoxy substituents are bridged to each other via CC single bonds.

[0060] [ka]

[0061] In another preferred embodiment of the rechargeable battery cell according to the present invention, in order to adapt the conductivity and / or further properties of the electrolyte to a desired value, the electrolyte has at least one second conductive salt different from the first conductive salt according to formula (I). This means that the electrolyte may contain, in addition to the first conductive salt, one or more second conductive salts that are different from the first conductive salt not only in its chemical composition but also in its chemical structure.

[0062] In another preferred embodiment of the rechargeable battery cell according to the present invention, the second conductive salt is an alkali metal compound, particularly a lithium compound. The alkali metal compound or the lithium compound is selected from the group formed by aluminates, halides, oxalates, borates, phosphates, arsenates, and gallates. The second conductive salt is preferably lithium tetrahalogenate, particularly LiAlCl4.

[0063] Furthermore, in another preferred embodiment of the rechargeable battery cell according to the present invention, the electrolyte comprises at least one additive. The additive is vinylene carbonate and its derivatives, vinylethylene carbonate and its derivatives, methylethylene carbonate and its derivatives, lithium (bisoxalato)boric acid, lithium difluoro(oxalato)borate, lithium tetrafluoro(oxalato)phosphate, lithium oxalate, 2-vinylpyridine, 4-vinylpyridine, cyclic exomethylene carbonate, sulfone, cyclic and acyclic sulfonates, acyclic sulfites, cyclic and acyclic sulfinic acid esters, organic esters of inorganic acids, acyclic and cyclic alkanes (the acyclic It is preferable to select from the group formed by aromatic compounds, cyclic and acyclic sulfonylimides, cyclic and acyclic phosphate esters, cyclic and acyclic phosphines, cyclic and acyclic phosphates, cyclic and acyclic phosphazenes, cyclic and acyclic silylamines, cyclic and acyclic halogenated esters, cyclic and acyclic amides, cyclic and acyclic anhydrides, and halogenated organic heterocycles (and cyclic alkanes having a boiling point of at least 36°C at 1 bar).

[0064] In another preferred development of the rechargeable battery cell according to the present invention, the electrolyte has the following composition with respect to the total weight of the electrolyte composition: (i) 5 to 99.4 wt% sulfur dioxide, (ii) 0.6 to 95 wt% of the first conductive salt, (iii) 0 to 25 wt% of the second conductive salt, and (iv) The additive in an amount of 0 to 10 wt%.

[0065] As described above, the electrolyte may contain not only one first conductive salt and one second conductive salt according to formula (I), but also multiple first conductive salts and multiple second conductive salts according to formula (I). In the latter case, the aforementioned proportions include multiple first conductive salts and multiple second conductive salts. The molar concentration of the first conductive 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 with respect to the total volume of the electrolyte.

[0066] In another preferred development of the rechargeable battery cell according to the present invention, the electrolyte comprises at least 0.1 moles of SO2, preferably at least 1 mole of SO2, more preferably at least 5 moles of SO2, even more preferably at least 10 moles of SO2, and particularly preferably at least 20 moles of SO2 per mole of conductive salt. The electrolyte may also contain SO2 in a very high molar ratio, with a preferred upper limit being 2600 moles of SO2 per mole of conductive salt, and further preferred upper limits being 1500, 1000, 500, and 100 moles of SO2 per mole of conductive salt, in that order. The term "per mole of conductive salt" refers to all conductive salts contained in the electrolyte. SO2-based electrolytes having this type of concentration ratio between SO2 and the conductive salt have the advantage that the electrolyte can dissolve a larger amount of conductive salt compared to electrolytes known from the prior art, such as organic solvent mixture-based electrolytes. Surprisingly, within the scope of the present invention, electrolytes having a relatively low conductive salt concentration have been found to be advantageous, particularly with respect to their own stability over numerous charge-discharge cycles of the rechargeable battery cell, despite the resulting increase in vapor pressure. The SO2 concentration in the electrolyte affects its conductivity. Therefore, by selecting the SO2 concentration, the conductivity of the electrolyte can be adapted to the intended use of the rechargeable battery cell operated by the electrolyte. The total weight of SO2 and the first conductive salt can be greater than 50 wt%, preferably more than 60 wt%, more preferably more than 70 wt%, more preferably more than 80 wt%, more preferably more than 85 wt%, more preferably more than 90 wt%, more preferably more than 95 wt%, or even more preferably more than 99 wt%.

[0067] The electrolyte may contain at least 5 wt% SO2 with respect to the total amount of the electrolyte contained in the rechargeable battery cell, and more preferably values ​​of 20 wt% SO2, 40 wt% SO2, and 60 wt% SO2. The electrolyte may contain up to 95 wt% SO2, and values ​​of 80 wt% SO2 and 90 wt% SO2 are preferred in that order.

[0068] The proportion of at least one organic solvent in the electrolyte may be small or nonexistent, which is also within the scope of the present invention. For example, the proportion of an organic solvent in the electrolyte, present in the form of a solvent or a mixture of several organic solvents, may be at most 50 wt% of the weight of the electrolyte. Particularly preferred are smaller proportions, at most 40 wt%, at most 30 wt%, at most 20 wt%, at most 15 wt%, at most 10 wt%, at most 5 wt%, or at most 1 wt%, relative to the weight of the electrolyte. It is even more preferable that the electrolyte does not contain any organic solvent. The small or nonexistent proportion of the organic solvent makes the electrolyte little to no flammability. This improves the operational safety of rechargeable battery cells that operate with this type of SO2-based electrolyte. It is particularly preferable that the SO2-based electrolyte is substantially free of organic solvents.

[0069] In another advantageous development of the rechargeable battery cell, the electrolyte has the following composition with respect to the total weight of the electrolyte composition: (i) 5 to 99.4 wt% sulfur dioxide, (ii) 0.6 to 95 wt% of the first conductive salt, (iii) 0 to 25 wt% of the second conductive salt, (iv) 0 to 10 wt% of the additive, and (v) 0 to 50 wt% organic solvent.

[0070] active metal The following describes advantageous developments of the rechargeable battery cell according to the present invention with respect to the active metal:

[0071] In an advantageous development of the rechargeable battery cell, the active metal is as follows: - Alkali metals, especially lithium or sodium, - Alkaline earth metals, especially calcium, - Metals of Group 12 of the periodic table, especially zinc, or - Aluminum.

[0072] positive electrode The following describes an advantageous development of the rechargeable battery cell according to the present invention with respect to the positive electrode:

[0073] In a first development of the rechargeable battery cell according to the present invention, the positive electrode is rechargeable to an upper limit potential of at least 4.0 volts, preferably to a potential of 4.4 volts, more preferably to a potential of at least 4.8 volts, even more preferably to a potential of at least 5.2 volts, even more preferably to a potential of at least 5.6 volts, and particularly preferably to a potential of at least 6.0 volts.

[0074] In another advantageous development of the rechargeable battery cell according to the present invention, the positive electrode comprises at least one active material, which is capable of storing ions of the active metal and releasing and reaccepting the ions of the active metal when the battery cell is in operation.

[0075] In another advantageous development of the rechargeable battery cell according to the present invention, the cathode comprises at least one intercalation compound. The term “intercalation compound” in the context of the present invention should be understood as a subcategory of the aforementioned insert material. The intercalation compound functions as a host matrix having interconnected cavities. During the discharge process of the rechargeable battery cell, the ions of the active metal may diffuse into and accumulate in these cavities. Structural changes in the host matrix during the accumulation of the ions of the active metal occur minimally or nowhere at all.

[0076] In another advantageous development aspect of the rechargeable battery cell according to the invention, the positive electrode comprises at least one conversion compound as the active material. The term "conversion compound" in the context of the present invention is to be understood as a material that forms another material during electrochemical activity, i.e., chemical bonds are broken and reformed during charge and discharge of the battery cell. Structural changes occur in the matrix of the conversion compound upon acceptance and release of the ions of the active metal.

[0077] In another advantageous development aspect of the rechargeable battery cell according to the invention, the active material is A x M’ y M” z O a has a composition of. The composition A x M’ y M” z O a in, - A is at least one metal selected from the group formed by an alkali metal, an alkaline earth metal, a metal of Group 12 of the periodic table of the elements 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 the elements, - x and y are each independently a number greater than 0, - z is a number greater than or equal to 0, and further - a is a number greater than 0.

[0078] A is preferably metallic lithium, i.e., the compound may have a composition of Li x M’ y M” z O a has.

[0079] Composition A x M’ y M” zO a In this example, the indices y and z represent the sum of the metals and elements represented by M' or M'', respectively. For example, if M' is two metals M'' 1 and M' 2 If it includes, the exponent y is y = y1 + y2, and y1 and y2 are metal M' 1 and M' 2 This represents the exponents. The exponents x, y, z, and a must be selected such that the charge in the composition is neutral. An example of a compound in which M' contains two metals is M' 1 =Ni, M' 2 Composition Li = Mn and M'' = Co x Ni y1 Mn y2 Co z It is lithium nickel manganese cobalt oxide in O2. An example of a compound where z=0, i.e., without another metal or element M'', is lithium cobalt oxide Li x Co y O a For example, M'' has two elements, one of which is metal. 1 On the other hand, M” 2 If it contains phosphorus, then for the exponent z, z = z1 + z2, where z1 and z2 are of the metal M''. 1 And Rin (M) 2 This represents the exponents of ). The exponents x, y, z, and a must be selected such that the charge in the composition is neutral. A is lithium, M'' is metal M'' 1 and M” 2 Examples of compounds containing phosphorus include A=Li, M'=Fe, M'' 1 =Mn, M” 2 Lithium iron manganese phosphate, where =P and z2=1. x Fe y Mn z1 P z2 O4 is present. In another composition, M'' is two nonmetals, for example M'' 1 Fluorine, M” 2 It is possible for it to contain sulfur. An example of such a compound is lithium iron fluorosulfate Li, where A=Li, M'=Fe, M''1=F, and M''2=P. x Fe yF z1 S z2 O4 is present.

[0080] In another advantageous development of the rechargeable battery cell according to the present invention, M' is made of nickel and manganese metals, and M'' is cobalt. In this case, the formula Li x Ni y1 Mn y2 Co z Lithium with a composition of O2(NMC), i.e., a layered oxide structure. Ni Kkel Ma Ngan Ko It may be a balt oxide. An example of such an active material consisting of lithium nickel manganese cobalt oxide is LiNi 1 / 3 Mn 1 / 3 Co 1 / 3 O2 (NMC111), LiNi 0.6 Mn 0.2 Co 0.2 O2 (NMC622) and LiNi 0.8 Mn 0.1 Co 0.1 It is O2 (NMC811). Other compounds consisting of lithium nickel manganese cobalt oxide have the composition LiNi 0.5 Mn 0.3 Co 0.2 O2, LiLiLi 0.5 Mn 0.25 Co 0.25 O2, LiLiLi 0.52 Mn 0.32 Co 0.16 O2, LiLiLi 0.55 Mn 0.30 Co 0.15 O2, LiLiLi 0.58 Mn 0.14 Co 0.28 O2, LiLiLi 0.64 Mn 0.18 Co 0.18 O2, LiLiLi 0.65 Mn 0.27 Co 0.08 O2, LiLiLi 0.7 Mn 0.2 Co 0.1 O2, LiLiLi 0.7 Mn 0.15 Co 0.15 O2, LiLiLi0.72 Mn 0.10 Co 0.18 O2, LiLiLi 0.76 Mn 0.14 Co 0.10 O2, LiLiLi 0.86 Mn 0.04 Co 0.10 O2, LiLiLi 0.90 Mn 0.05 Co 0.05 O2, LiLiLi 0.95 Mn 0.025 Co 0.025 It may contain O2 or a combination thereof. Using this compound, it is possible to manufacture a positive electrode for rechargeable battery cells with a cell voltage greater than 4.6 volts.

[0081] In another advantageous development of the rechargeable battery cell according to the present invention, the active material is a lithium- and manganese-rich metal oxide (or lithium- and manganese-rich oxide material in English). The metal oxide has a composition of Li x Mn y M" z O a It may have the above formula Li x M' y M" z O a Here, the exponent x is greater than or equal to 1, and the exponent y is greater than the exponent z or the sum of exponents z1 + z2 + z3, etc. For example, M'' represents two metallic M'' with exponents z1 and z2. 1 and M” 2 If it includes (for example, M") 1 =Ni z1=0.175 and M” 2 =Co z2=0.1 Li 1.2 Mn 0.525 Ni 0.175 Co 0.1O2), for the exponent y, y > z1 + z2 holds. The exponent z is 0 or greater, and the exponent a is greater than 0. The exponents x, y, z, and a must be selected such that the charge within the composition is neutral. The lithium- and manganese-rich metal oxide can also be represented by the formula mLi2MnO3(1 - m)LiM’O2 where 0 < m < 1. An example of this type of compound is Li 1.2 Mn 0.525 Ni 0.175 CO 0.1 O2, Li 1.2 Mn 0.6 Ni<{ 0.2 O2 or Li 1.2 Ni 0.13 CO 0.13 Mn<{ 0.54 O2.

[0082] In another advantageous development aspect of the rechargeable battery cell according to the present invention, the composition has the formula A x M’ y M” z O4. The said compound has a spinel structure. For example, A can be lithium, M’ can be cobalt, and M” can be manganese. In this case, the active material is lithium cobalt manganese oxide (LiCoMnO4). It is possible to manufacture a positive electrode for a rechargeable battery cell having a cell voltage greater than 4.6 volts using LiCoMnO4. Preferably, the said LiCoMnO4 does not contain Mn 3+ In another example, M’ can be nickel and M” can be manganese. In this case, the active material is lithium nickel manganese oxide (LiNiMnO4). The molar ratios of both metals M’ and M” may be different. Lithium nickel manganese oxide can have a composition such as LiNi 0.5 Mn 1.5 O4.

[0083] In another advantageous development of the rechargeable battery cell according to the present invention, the positive electrode comprises at least one active material, which is a conversion compound. The conversion compound undergoes a solid redox reaction upon accepting an active metal, such as lithium or sodium, during which the crystal structure of the material changes. This occurs under the decomposition and reformation of chemical bonds. A completely reversible reaction of the conversion compound may be, for example, as follows: Type A: MX z +yLi ⇔ M+zLi (y / z) X Type B: X + yLi ⇔ Li y X

[0084] Examples of conversion compounds include FeF2, FeF3, CoF2, CuF2, NiF2, BiF3, FeCl3, FeCl2, CoCl2, NiCl2, CuCl2, AgCl, LiCl, S, Li2S, Se, Li2Se, Te, I, and Lil.

[0085] In another advantageous developmental aspect, the compound is A x M' y M" 1 z1 M" 2 z2 It has the composition of O4, M” 1 It is selected from the group formed by elements of groups 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15 and 16 of the periodic table, and M” 2 The element is phosphorus, x and y are independent numbers greater than 0, z1 is a number greater than 0, and the value of z2 is 1. Composition A x M' y M" z1 M" z2 Compounds containing O4 are so-called metallic lithium phosphates. These compounds, in particular, have a Li x Fe' y Mn z1 P z2 It contains O4. Examples of metallic lithium phosphate are lithium iron phosphate (LiFePO4) or lithium iron manganese phosphate (Li(Fe y Mn z)PO4). An example of lithium iron manganese phosphate is Li(Fe 0.3 Mn 0.7 Examples include phosphates of PO4. An example is lithium iron manganese phosphate, which has the composition Li(Fe 0.3 Mn 0.7 It is a phosphate of PO4. It is also possible to use lithium metal phosphate having other compositions in the battery cell according to the present invention.

[0086] In another advantageous development of the rechargeable battery cell according to the present invention, the positive electrode comprises at least one metal compound. The metal compound is selected from the group formed by metal oxides, metal halides, and metal phosphates. The metal of the metal compound is preferably a transition metal with atomic numbers 22 to 28 of the periodic table, particularly cobalt, nickel, manganese, or iron.

[0087] In another advantageous development of the rechargeable battery cell according to the present invention, the positive electrode comprises at least one metal compound having the chemical structure of spinel, layered oxide, conversion compound, or polyanionic compound.

[0088] The positive electrode contains at least one of the aforementioned compounds or combinations of the aforementioned compounds as an active material, which falls within the scope of the present invention. The combination of the aforementioned compounds means a positive electrode containing at least two of the aforementioned materials.

[0089] In another advantageous development of the battery cell according to the present invention, the positive electrode has at least one binder. The binder is a fluorinated binder, particularly a terpolymer formed by polyvinylidene fluoride and / or tetrafluoroethylene, hexafluoropropylene, and vinylidene fluoride. However, the binder may be a polymer consisting of monomer structural units of a conjugated carboxylic acid or an alkali metal salt, alkaline earth metal salt, or ammonium salt of the conjugated carboxylic acid, or a combination thereof. Furthermore, the binder may consist of a monomeric styrene and butadiene structural unit polymer. Furthermore, the binder may be a binder consisting of carboxymethylcellulose group. The binder is preferably present in the positive electrode at a concentration of at most 20 wt%, more preferably at most 15 wt%, more preferably at most 10 wt%, more preferably at most 7 wt%, more preferably at most 5 wt%, and particularly preferably at most 2 wt%, relative to the total weight of the positive electrode.

[0090] negative electrode The following describes an advantageous development of the rechargeable battery cell according to the present invention with respect to the negative electrode:

[0091] In another advantageous development of the rechargeable battery cell, the negative electrode is an insertion electrode. The insertion electrode comprises an insertion material as an active material, and ions of the active metal can be accumulated in the insertion material when the rechargeable battery cell is charged, and released from the insertion material when the rechargeable battery cell is discharged. This means that the electrode process can be carried out not only on the surface of the negative electrode but also inside the negative electrode. For example, if a lithium-based conductive salt is used, lithium ions can be accumulated in the insertion material when the rechargeable battery cell is charged, and released from the insertion material when the rechargeable battery cell is discharged. The negative electrode preferably comprises carbon, particularly modified graphite, as an active material or insertion material. However, the carbon may also be in the form of natural graphite (flake-like accelerator or circular), synthetic graphite (mesophase graphite), graphitized mesocarbon microbeads (MCMB), carbon-coated graphite, or amorphous carbon, and this is also within the scope of the present invention.

[0092] In another advantageous development of the rechargeable battery cell according to the present invention, the negative electrode is, for example, lithium titanate (e.g., Li4Ti5O 12 ) and other materials containing a lithium intercalated negative electrode active material that does not contain carbon.

[0093] In another advantageous development embodiment of the rechargeable battery cell according to the present invention, the negative electrode comprises a negative electrode active material that forms an alloy with lithium. The negative electrode active material is, for example, a metal and metal alloy that stores lithium (e.g., Si, Ge, Sn, SnCo x C y , SnSi x (etc.) and oxides of metals and metal alloys that store lithium (e.g., SnO x SiO x Alternatively, it may be an oxide glass such as Sn or Si.

[0094] In another advantageous development embodiment of the rechargeable battery cell according to the present invention, the negative electrode comprises a conversion negative electrode active material. The conversion negative electrode active material is, for example, manganese oxide (MnO x ), iron oxide (FeO x ), cobalt oxide (CoOx ), nickel oxide (NiO x ), copper oxide (CuO x These can be transition metal oxides in the form of ), metal hydrides in the form of magnesium hydride (MgH2), titanium hydride (TiH2), aluminum hydride (AlH3), and boron-based, aluminum-based, and magnesium-based ternary hydrides.

[0095] In another advantageous development of the rechargeable battery cell according to the present invention, the negative electrode comprises a metal, particularly metallic lithium.

[0096] In another advantageous development of the rechargeable battery cell according to the present invention, the negative electrode is porous, with a porosity preferably at most 50%, more preferably at most 45%, more preferably at most 40%, more preferably at most 35%, more preferably at most 30%, more preferably at most 20%, and particularly preferably at most 10%. The porosity represents the void volume relative to the total volume of the negative electrode, which is formed by so-called pores or voids. The porosity results in an increase in the internal surface area of ​​the negative electrode. Furthermore, the porosity also reduces the density of the negative electrode and, consequently, the weight of the negative electrode. The individual pores of the negative electrode can preferably be completely filled with the electrolyte during operation.

[0097] In another advantageous development of the battery cell according to the present invention, the anode has at least one binder. The binder is a fluorinated binder, particularly a terpolymer formed by polyvinylidene fluoride and / or tetrafluoroethylene, hexafluoropropylene, and vinylidene fluoride. However, the binder may be a polymer consisting of monomer structural units of a conjugated carboxylic acid or an alkali metal salt, alkaline earth metal salt, or ammonium salt of the conjugated carboxylic acid, or a combination thereof. Furthermore, the binder may consist of monomeric styrene and butadiene structural unit polymers. Furthermore, the binder may be a binder consisting of carboxymethylcellulose group. The binder is present in the anode at a concentration of preferably at most 20 wt%, more preferably at most 15 wt%, more preferably at most 10 wt%, more preferably at most 7 wt%, more preferably at most 5 wt%, and particularly preferably at most 2 wt%, with respect to the total weight of the anode.

[0098] In another advantageous development embodiment of the battery cell according to the present invention, the negative electrode has at least one conductive additive. The conductive additive preferably has low weight, high chemical resistance and high specific surface area. Examples of the conductive additive are particulate carbon (carbon black, Super P, acetylene black), fibrous carbon (carbon nanotubes CNT, carbon (nano)fibers), finely divided graphite and graphene (nanosheets).

[0099] Structure of a rechargeable battery cell The following describes the advantageous developments of the rechargeable battery cell according to the present invention in relation to its structure:

[0100] To further improve the functionality of the rechargeable battery cell, in another advantageous development of the rechargeable battery cell according to the present invention, the rechargeable battery cell has a plurality of negative electrodes and a plurality of positive electrodes arranged alternately in a stack within a housing. Herein, it is preferable that the positive electrodes and the negative electrodes are electrically isolated from each other by separators.

[0101] However, the rechargeable battery cell may be formed as a coil cell, in which the electrodes are formed as a thin layer wound together with a separator material. The separator spatially and electrically separates the positive electrode and the negative electrode, on the one hand, and is permeable to ions of the active metal, in particular, on the other hand. This creates a large electrochemically effective surface, which enables a correspondingly high current yield. The separator can be formed using nonwoven fabrics, membranes, woven fabrics, knitted fabrics, organic materials, inorganic materials, or combinations thereof. Organic separators may consist of, for example, unsubstituted polyolefins (e.g., polypropylene or polyethylene), partially to fully halogen-substituted polyolefins (e.g., partially to fully fluorine-substituted, especially PVDF, ETFE, PTFE), polyesters, polyamides, or polysulfones. Separators including combinations of organic and inorganic materials are, for example, glass fiber woven materials in which a suitable polymer coating is provided on glass fibers. The coating is a fluorine-containing polymer such as polytetrafluoroethylene (PTFE), ethylenetetrafluoroethylene (ETFE), perfluoroethylene propylene (FEP), THV (a terpolymer consisting of tetrafluoroethylene, hexafluoroethylene, and vinylidene fluoride), perfluoroalkoxy polymer (PFA), aminosilane, polypropylene, or polyethylene (PE). The separator can also be provided folded in a so-called "Z-fold" shape, for example, within the housing of the rechargeable battery cell. In the case of the Z-fold, the strip-shaped separator is folded in a Z-shape so as to pass through the electrode or around the electrode. Furthermore, the separator may be formed as separator paper.

[0102] The separator may be formed as a coating, and the positive electrode or the negative electrode may be covered by the coating, which is also within the scope of the present invention. The coating can be formed using nonwoven fabric, film, woven fabric, knitted fabric, organic material, inorganic material, or a combination thereof.

[0103] The coating of the positive electrode ensures uniform ion movement and ion distribution in the rechargeable battery cell. In particular, a more uniform ion distribution at the negative electrode increases the possible amount of active material that can be packed into the negative electrode, thereby increasing the usable capacity of the rechargeable battery cell. At the same time, it avoids the risk of uneven packing and the resulting deposition of the active metal. This advantage is especially pronounced when the positive electrode of the rechargeable battery cell is covered by the coating.

[0104] Preferably, the surface dimensions of the electrode and the covering are adjusted to match each other such that the outer dimensions of the covering on the front electrode and the outer dimensions of the uncovered electrode match with respect to at least one dimension.

[0105] Preferably, the surface area of ​​the coating may be larger than the surface area of ​​the electrode. In this case, the coating extends beyond the boundary of the electrode. Thus, the two layers of the coating covering both sides of the electrode can be connected to each other by edge connections at the edge of the positive electrode.

[0106] In another advantageous embodiment of the rechargeable battery cell according to the present invention, the negative electrode has a coating while the positive electrode does not.

[0107] Further advantageous properties of the present invention are described and explained in detail below with reference to drawings, examples, and experiments. [Brief explanation of the drawing]

[0108] [Figure 1] This is a cross-sectional view of a first embodiment of a rechargeable battery cell according to the present invention. [Figure 2]Figure 1 is a detailed electron microscope image of the three-dimensional porous structure of a metal foam according to the first embodiment. [Figure 3] This is a cross-sectional view of a second embodiment of the rechargeable battery cell according to the present invention. [Figure 4] This figure shows a detailed view of the second embodiment of Figure 3. [Figure 5] This is an exploded view showing a third embodiment of the rechargeable battery cell according to the present invention. [Figure 6] This figure shows the potential (in [V]) in two complete experimental cells having graphite electrodes with copper or nickel conductive elements filled with the reference electrolyte according to Example 1 during charging, as a function of capacitance with respect to the theoretical capacitance of the negative electrode during surface layer formation. [Figure 7] This figure shows the discharge capacity as a function of the number of cycles in two complete experimental cells, each having a graphite electrode with copper or nickel conductive elements. The complete experimental cells are filled with a reference electrolyte. [Figure 8] This figure shows the potential (in [V]) in two complete experimental cells having graphite electrodes with copper or nickel conductive elements filled with electrolyte 1 during charging, as a function of capacitance with respect to the theoretical capacitance of the negative electrode while a surface layer is formed on the negative electrode. [Figure 9] This figure shows the discharge capacity as a function of the number of cycles in two complete experimental cells, each having a graphite electrode with copper or nickel conductive elements. The complete experimental cells are filled with electrolyte 1. [Figure 10] This is a photograph showing the copper conductor element after measurement in Figure 9. [Figure 11] The diagram shows the potential change (in volts) during charging and discharging as a function of the charge rate of a half-cell having a graphite electrode with a copper conductive element. The half-cell is filled with electrolyte 5. [Figure 12] This figure shows the potential and current as functions of time in a half-cell containing an aluminum conductor element. The half-cell is filled with either a reference electrolyte or electrolyte 1. [Figure 13]Figure 12 shows the aluminum conductive elements in a half-cell with a reference electrolyte before the experiment. [Figure 14] Figure 12 shows the aluminum conductive elements after the experiment in a half-cell with a reference electrolyte. [Figure 15] Figure 12 shows the aluminum conductive elements after the experiment in a half-cell containing electrolyte 1. [Figure 16] This figure shows the potential change (in volts) during charging and discharging as a function of the charge percentage in the first cycle of a half-cell having a positive electrode with an aluminum conductive element. The half-cell is filled with electrolyte 1. [Figure 17] This figure shows the discharge capacity as a function of the number of cycles in an experimental complete cell having a positive electrode with an aluminum conductive element. The experimental complete cell is filled with electrolyte 1. [Figure 18] This figure shows the discharge capacity as a function of the number of cycles for two complete cells, one having a positive electrode with an aluminum conductive element and the other a negative electrode with a copper conductive element. The complete cells are filled with electrolyte 1, and the end-of-charge voltage is 4.3 or 4.6 volts. [Figure 19] This figure shows the potential change (in volts) during charging and discharging as a function of the charge percentage in the first cycle of a half-cell having a positive electrode with an aluminum conductive element. The half-cell is filled with electrolyte 5. [Figure 20] The figure shows the potential (in [V]) in three complete experimental cells filled with electrolytes 1 and 3 according to Example 2 and the reference electrolyte according to Example 1 during charging of the negative electrode, as a function of capacity with respect to the theoretical capacity of the negative electrode while a surface layer is formed on the negative electrode. [Figure 21] This figure shows the potential progression (in volts) during discharge as a function of the charge percentage of four complete experimental cells, each filled with electrolytes 1, 3, 4, and 5 according to Example 2, and containing nickel-manganese-cobalt lithium oxide (NMC) as the electrode active material. [Figure 22]The figure shows the conductivity (in [mS / cm]) of electrolytes 1, 4, and 6 according to Example 2, depending on the concentrations of compounds 1, 4, and 6. [Figure 23] This figure shows the conductivity (in [mS / cm]) of electrolytes 3 and 5 according to Example 2, depending on the concentrations of compounds 3 and 5. [Modes for carrying out the invention]

[0109] Figure 1 shows a cross-sectional view of a first embodiment of a rechargeable battery cell 2 according to the present invention. The rechargeable battery cell 2 is formed as a prismatic cell and, in particular, has a housing 1. The housing 1 surrounds an electrode unit 3 comprising three positive electrodes 4 and four negative electrodes 5. The positive electrodes 4 and the negative electrodes 5 are arranged alternately in the electrode unit 3. However, the housing 1 can also accommodate more positive electrodes 4 and / or negative electrodes 5. Generally, it is preferable that the number of negative electrodes 5 is one greater than the number of positive electrodes 4. This ensures that the outer end face of the electrode stack is formed by the electrode surface of the negative electrodes 5. The electrodes 4 and 5 are connected to corresponding connection contacts 9 and 10 of the rechargeable battery cell 2 via electrode connections 6 and 7. The rechargeable battery cell 2 is filled with an SO2-based electrolyte, so that the electrolyte penetrates as completely as possible into all pores or cavities, especially inside the electrodes 4 and 5. The electrolyte is not shown in Figure 1. In this embodiment, the positive electrode 4 contains an intercalation compound as an active material. The interlayer compound is LiCoMnO4 having a spinel structure. In this embodiment, the electrodes 4 and 5 are formed as planar layers, i.e., layers with a small thickness relative to their surface area. The electrodes are separated from each other by a separator 11. The housing 1 of the rechargeable battery cell 2 is formed in a substantially cubic shape, and the electrodes 4 and 5 and the wall of the housing 1 shown in the cross-sectional view are formed substantially linearly and flat, extending perpendicular to the plane of the figure. However, the rechargeable battery cell 2 may also be formed as a coil cell, in which the electrodes are formed as thin layers wound together with the separator material. The separator 11 spatially and electrically separates the positive electrode 4 and the negative electrode 5 on the one hand, and on the other hand, is permeable to ions of the active metal in particular. This creates a large electrochemically effective surface, which enables a correspondingly high current yield. Furthermore, the electrodes 4 and 5 each have a conductive element used to enable the necessary electron conduction connection of the active material of each electrode.The conductive element is in contact with the active material (not shown in Figure 1) involved in the electrode reaction of each of the electrodes 4 and 5. The conductive element is formed in the shape of a porous metal foam 18. The metal foam 18 is stretched over the thickness dimension of the electrodes 4 and 5. The active material of the positive electrode 4 and the negative electrode 5 is incorporated into the pores of the metal foam 18, so that the active material uniformly fills the pores of the metal foam over the total thickness of the metal structure. To improve mechanical strength, the positive electrode 4 contains a binder. The binder is a fluoropolymer. The negative electrode 5 contains carbon as the active material in a shape suitable for receiving lithium ions as an insert material. The structure of the negative electrode 5 is the same as that of the positive electrode 4. In this first embodiment, the conductive element of the positive electrode 4 is made of aluminum, and the conductive element of the negative electrode 5 is made of copper.

[0110] Figure 2 shows an electron microscope image of the three-dimensional porous structure of the metal foam 18 in the first embodiment shown in Figure 1. Based on the displayed scale, it can be seen that the average diameter of the pores P is greater than 100 μm, i.e., relatively large.

[0111] Figure 3 shows a cross-sectional view of a second embodiment of the rechargeable battery cell 20 according to the present invention. This second embodiment differs from the first embodiment shown in Figure 1 in that the electrode unit includes one positive electrode 23 and two negative electrodes 22. The electrodes are separated from each other by a separator 21 and enclosed by a housing 28. The positive electrode 23 has a conductive element 26 in the form of a planar metal foil, and the active material 24 of the positive electrode 23 is coated on both sides of this conductive element. Similarly, the negative electrode 22 has a second conductive element 27 in the form of a planar metal foil, and the active material 25 of the negative electrode 22 is coated on both sides of this conductive element. Alternatively, it is possible to coat only one side of the planar conductive element of the edge electrode, i.e., the electrode that closes the electrode stack, with the active material. The uncoated side faces the wall of the housing 28. The electrodes 22 and 23 are connected to the corresponding connection contacts 31 and 32 of the rechargeable battery cell 20 via electrode connections 29 and 30.

[0112] Figure 4 illustrates the planar metal foil used as the conductive elements 26 and 27 of the positive electrode 23 and the negative electrode 22, respectively, in the second embodiment example of Figure 3. The metal foil has a perforated or mesh structure with a thickness of 20 μm.

[0113] Figure 5 shows an exploded view of a third embodiment of the rechargeable battery cell 40 according to the present invention. This third embodiment differs from the two embodiments described above in that the positive electrode 44 is covered by a coating 13. In this case, the surface area of ​​the coating 13 is larger than the surface area of ​​the positive electrode 44, and the boundary 14 of the positive electrode is indicated by a dashed line in Figure 5. The two layers 15 and 16 of the coating 13, which cover both sides of the positive electrode 44, are connected to each other by edge connections 17 at the periphery of the positive electrode 44. Both negative electrodes 45 are not covered. The electrodes 44 and 45 can be in contact via the electrode connections 46 and 47.

[0114] [Example 1] Production of reference electrolyte The reference electrolyte used in the following examples was prepared according to the method described in European Patent No. 2954588 (hereinafter referred to as [V6]). First, lithium chloride (LiCl) was dried under vacuum at 120°C for three days. Aluminum particles (Al) were dried under vacuum at 450°C for two days. LiCl, aluminum chloride (AlCl3), and Al were mixed together in a glass bottle with an opening for gas release so that the molar ratio of AlCl3:LiCl:Al was 1:1.06:0.35. The mixture was then heated in stages to produce a molten salt. After cooling, the formed molten salt was filtered, cooled to room temperature, and finally SO2 was added until the desired molar ratio of SO2 to LiAlCl4 was achieved. The thus formed reference electrolyte has the composition LiAlCl4*xSO2, where x depends on the amount of SO2 added.

[0115] [Example 2] Manufacturing of six embodiments of SO2-based electrolytes for battery cells: Examples 1, 2, 3, 4, 5 and 6 Six embodiments of SO2-based electrolytes, 1, 2, 3, 4, 5, and 6, were prepared for the experiments described below (hereinafter referred to as electrolytes 1, 2, 3, 4, 5, and 6). For this purpose, five different first conductive salts according to formula (I) were first prepared according to the manufacturing methods described in the following references [V7], [V8], and [V9]: [V7]I. Krossing, Chem. Eur. J. 2001, 7, 490 [V8]SM Ivanova et al., Chem. Eur. J. 2001, 7, 503 [V9]Tsujioka et al., J. Electrochem. Soc., 2004, 151, A1418

[0116] The six distinct first conductive salts according to formula (I) will be referred to below as compounds 1, 2, 3, 4, 5, and 6. These compounds belong to the polyfluoroalkoxyaluminic acid family and, in hexane, react with the corresponding alcohol R-OH(R) with LiAlH4. 1 =R 2 =R3 =R 4 It was manufactured starting from ) and following the reaction equation below.

[0117] [ka]

[0118] The chelate complex was prepared starting from the corresponding diol HO-R-OH according to the preparation method described in the following reference [V10]: [V10] Wu Xie et al., Electrochemical and Solid State Letters, 2000, 3, 366-368

[0119] This resulted in the formation of compounds 1, 2, 3, 4, 5, and 6, having the molecular or structural formulas shown below:

[0120] [ka]

[0121] For purification, compounds 1, 2, 3, 4, 5, and 6 were first recrystallized. This removed the residue of free LiAlH4 from the first conductive salt because the free LiAlH4 could potentially spark with trace amounts of water that may be present in the SO2.

[0122] Subsequently, compounds 1, 2, 3, 4, 5, and 6 were dissolved in SO2. It was found that compounds 1, 2, 3, 4, 5, and 6 dissolve well in SO2.

[0123] The production of electrolytes 1, 2, 3, 4, 5, and 6 is carried out by the following methods: The procedure was carried out under low temperature or pressure according to steps 1 through 4: 1) Place each compound 1, 2, 3, 4, 5, and 6 into a separate pressure flask with a riser pipe. 2) Empty the pressure flask. 3) Inflow of liquid SO2, 4) Repeat steps 2 and 3 until the target amount of SO2 has been added.

[0124] The concentrations of compounds 1, 2, 3, 4, 5, and 6 in electrolytes 1, 2, 3, 4, 5, and 6 were 0.6 mol / l (amount concentration per liter of electrolyte) unless otherwise specified in the following experimental description. The experiment described below was carried out using electrolytes 1, 2, 3, 4, 5, and 6 and the reference electrolyte.

[0125] [Example 3] Manufacturing of complete experimental cells The complete experimental cells used in the experiments described below are rechargeable battery cells having two negative electrodes and one positive electrode, each separated by a separator. The positive electrode contained an active material, a conductivity enhancer, and a binder. The active material is described in each experiment. The negative electrode also contained graphite as an active material, a binder, and a conductive element. Where described in the experiment, the negative electrode may further contain conductive additives. The materials of the conductive elements in the positive and negative electrodes are aluminum and copper, respectively, as described in each experiment. Nickel conductive element is used as the reference material according to the prior art. In particular, the purpose of the experiments is to demonstrate the use of aluminum and copper conductive elements in the positive and negative electrodes of the battery cell according to the present invention. Table 3 shows the experiments performed with different conductive elements.

[0126] Each of the experimental complete cells was filled with the electrolytes necessary for the experiment, namely the reference electrolyte or electrolytes 1, 2, 3, 4, 5, and 6. Multiple identical experimental complete cells, i.e., two to four, were prepared for the experiment. The results shown in the experiment are the average values ​​of the measurements obtained for each identical experimental complete cell.

[0127] [Example 4] Measurement in a complete experimental cell Surface capacity: The capacity consumed in the first cycle to form the surface layer on the negative electrode is an important criterion for the quality of the battery cell. This surface layer is formed on the negative electrode during the initial charging of the complete experimental cell. Because lithium ions are irreversibly consumed for this surface layer formation (surface capacity), the available cycleable capacity of the complete experimental cell in subsequent cycles is reduced. The surface capacity (in [%]) relative to the theoretical value used to form the surface layer on the negative electrode is calculated using the following formula:

[0128] Surface volume [percentage of theoretical value] = (Q lad (xmAh)-Q ent (ymAh) / Q NEL

[0129] Q lad This refers to the specified charge amount (in [mAh]) for each experiment, Q ent This is the amount of charge (in [mAh]) obtained during the subsequent discharge of the experimental complete cell. NEL This is the theoretical capacity of the negative electrode used. For example, in the case of graphite, the theoretical capacity is calculated using a value of 372 mAh / g.

[0130] Discharge capacity: In measurements using a complete experimental cell, for example, the discharge capacity is determined by the number of cycles. Therefore, the complete experimental cell is charged to a predetermined upper potential using a predetermined charging current. This upper potential is maintained until the charging current drops to a certain value. Then, discharge is performed using a predetermined discharge current until the predetermined discharge potential is reached. This charging method is called I / U charging. This process is repeated according to the desired number of cycles.

[0131] The aforementioned upper potential limit, discharge capacity, and respective charge / discharge currents are described in the experiment. The value that the charging current should reach is also described in the experiment.

[0132] The term "upper potential" is used synonymously with the terms "charging potential," "charging voltage," "charging termination voltage," and "upper potential limit." These terms indicate the voltage / potential that a cell or battery should reach when being charged by a battery charger.

[0133] It is preferable to charge the aforementioned battery at a current rate of C / 2 and a temperature of 22°C.

[0134] The term "discharge potential" is used synonymously with the term "lower cell voltage." This term indicates the voltage / potential that a cell or battery should reach when discharged by a battery charger.

[0135] It is preferable to discharge the aforementioned battery at a current rate of C / 2 and a temperature of 22°C.

[0136] The discharge capacity is obtained by the discharge current and the time until the criteria for terminating the discharge are met. In the diagrams related to these, the average value of the discharge capacity is shown as a function of the number of cycles. In many cases, this average value of the discharge capacity is standardized to 100% of the starting capacity and expressed as a percentage of the nominal capacity.

[0137] The following experiments investigate the properties of conductive elements formed from nickel, copper, or aluminum. According to [V3], conductive elements made of nickel are typically used in the prior art electrolyte LiAlCl4*xSO2, and will be referred to below as the reference electrolyte. Hereinafter, these conductive elements made of nickel will be referred to as nickel conductive elements (see Example 1). Therefore, experiments were conducted with the reference electrolyte LiAlCl4*xSO2 on the one hand, and with various electrolytes that can also be components of the rechargeable battery cell according to the present invention on the other hand. The electrical conductivity of copper and aluminum, which is known from the literature, is better than that of nickel (see Table 1). Therefore, conductive elements made of copper and aluminum are preferred within the scope of the present invention.

[0138] [Table 1]

[0139] [Experiment 1] Behavior of nickel and copper conductive elements in the negative electrode of an experimental complete cell having a reference electrolyte of composition LiAlCl4*4.5SO2 A negative electrode was manufactured using graphite as the active material. This negative electrode did not contain a binder. The conductive element of the first negative electrode consisted of copper in the form of a copper foam. The second negative electrode contained a nickel conductive element in the form of a nickel foam. Nickel is a material used for conductive elements in rechargeable battery cells having an electrolyte with the composition LiAlCl4*xSO2 according to prior art.

[0140] A first complete experimental cell 1 was formed according to Example 3 by assembling two negative electrodes having copper conductive elements and a positive electrode containing lithium iron phosphate as the electrode active material. A second complete experimental cell 2 was formed according to Example 3 using the negative electrode containing nickel conductive elements. Both complete experimental cells 1 and 2 were filled with the reference electrolyte according to Example 1, having the composition LiAlCl4*4.5SO2.

[0141] First, the surface capacitance was determined in the first cycle according to Example 4. Figure 6 shows the potential (in volts) of the experimental complete cell during charging of the negative electrode as a function of capacitance (in percent) with respect to the theoretical capacitance of the negative electrode, where the solid line corresponds to the curve of experimental complete cell 1 and the dashed line corresponds to the curve of experimental complete cell 2.

[0142] The two illustrated curves above show the results of multiple experiments conducted using the experimental complete cells 1 and 2 described above. First, 125mA(Q) was applied to the experimental complete cell. lad The cell was charged with a current of 15mA until it reached a potential of 2.5 volts. Then, the experimental complete cell was discharged at 15mA until it reached a potential of 2.5 volts. At that time, the discharge capacity (Q) was measured. ent ) was sought.

[0143] The calculated surface capacitance (unit [percentage of the theoretical capacitance of the negative electrode]) is higher than the surface capacitance obtained for an electrode containing a binder, for example, because the negative electrode does not contain a binder. In the case of experimental complete cell 1 having a graphite electrode with a copper foam conductive element, the surface capacitance is 19.8%, and in the case of experimental complete cell 2 having a graphite electrode with a nickel foam conductive element, it is 15.5%.

[0144] To determine the discharge capacity (see Example 4), both experimental complete cells 1 and 2 were charged to an upper limit potential of 3.8 volts at a charge rate of C / 2. Subsequently, they were discharged to a discharge potential of 2.5 volts at a discharge rate of C / 2.

[0145] Figure 7 shows the average discharge capacity of the two experimental complete cells 1 and 2 as a function of the number of cycles, with the solid line representing the curve for experimental complete cell 1 and the dashed line representing the curve for experimental complete cell 2. 190 cycles were performed. The average values ​​of the discharge capacity are expressed as a percentage of the nominal capacity (unit: [% of nominal capacity]).

[0146] The discharge capacity of the two experimental complete cells 1 and 2 shows a uniform decrease over time. However, the capacity decrease is significantly greater in the experimental complete cell containing a graphite electrode with a copper foam conductive element. Therefore, the capacity of experimental complete cell 1 (nickel conductive element) is still at 70% after 190 cycles, while the capacity of experimental complete cell 2 (copper conductive element) is only at 64% after 190 cycles.

[0147] In the aforementioned reference electrolyte, the negative electrode having a nickel conductive element exhibits lower surface capacitance and better cycle behavior compared to the negative electrode having a copper conductive element. This validates the [V3] statement that nickel is a common conductive element in LiAlCl4*xSO2 electrolytes.

[0148] [Experiment 2] Behavior of nickel and copper conductive elements for the negative electrode in an experimental complete cell using electrolyte 1 Again, a negative electrode having graphite as the active material was prepared. The conductor element of the first negative electrode was made of copper in the form of a porous copper foam. The second negative electrode included a nickel conductor element in the form of a porous nickel foam. Two negative electrodes having a copper foam as the conductor element were assembled into a first experimental full cell according to Example 3 together with a positive electrode containing lithium nickel manganese cobalt oxide (NMC622) as the electrode active material. A second experimental full cell was formed according to Example 3 using a negative electrode containing a nickel foam as the conductor element. Both experimental full cells were filled with electrolyte 1 according to Example 2.

[0149] First, the surface layer capacity was measured according to Example 4 in the first cycle.

[0150] FIG. 8 shows the potential (unit: [volt]) of both experimental full cells during charging of the negative electrode as a function of the capacity (unit: [%]) with respect to the theoretical capacity of the negative electrode. The two illustrated curves show the averaged results of a plurality of experiments respectively conducted using the aforementioned experimental full cells. The solid line curve corresponds to the experimental full cell having a graphite electrode with a copper conductor element, and the dashed-dotted line curve corresponds to the experimental full cell having a graphite electrode with a nickel conductor element. First, the experimental full cell was charged with a current of 15 mA until it reached 125 mA (Q lad ). Thereafter, the experimental full cell was discharged at 15 mA until it reached a potential of 2.5 volts. The discharge capacity (Q ent ) was determined at that time.

[0151] In the case of the experimental full cell having a graphite electrode with a copper conductor element, the surface layer capacity was 6.7%, and in the case of the experimental full cell having a graphite electrode with a nickel conductor element, it was 7.3%. The surface layer capacity is smaller when using a copper conductor element compared to when using a nickel conductor element.

[0152] To determine the discharge capacity (see Example 4), both experimental complete cells were charged to an upper limit potential of 4.4 volts at a charge level of C / 2. Subsequently, they were discharged to a discharge potential of 2.5 volts at a discharge level of C / 2.

[0153] Figure 9 illustrates the average discharge capacity of the two experimental complete cells as a function of the number of cycles. The solid line curve corresponds to the experimental complete cell with graphite electrodes having copper conductive elements, and the dashed line curve corresponds to the experimental complete cell with graphite electrodes having nickel conductive elements. The average discharge capacity is expressed as a percentage of the nominal capacity (unit: [% of nominal capacity]). The progression of the discharge capacity of the two experimental complete cells shows a uniform, almost linear progression. Only a slight decrease in capacity is observed in both experimental complete cells. Therefore, the capacity of both experimental complete cells is still approximately 95% (nickel conductive elements) or 94% (copper conductive elements) after 200 cycles.

[0154] Figure 10 is a photograph showing the copper conductor element after the aforementioned measurement in Figure 9. From Figure 10, it can be seen that no corrosion occurred in the copper conductor element during the experiment.

[0155] In the electrolyte 1, the negative electrode having a nickel conductive element and the negative electrode having a copper conductive element exhibit low surface capacitance and good cycle behavior. After the experiment, the negative electrode was not observed with the copper conductive element.

[0156] [Experiment 3] Behavior of the copper conductive element of the negative electrode in a half-cell having electrolytes 5 and 6 A negative electrode having graphite as the active material was manufactured again. The conductive element of the electrode was made of copper in the form of copper foil.

[0157] The experiment was conducted in a half-cell having metallic lithium as the return electrode and reference electrode. The working electrode was a graphite electrode with the copper conductive element under investigation. One half-cell was filled with electrolyte 5, and the other with electrolyte 6. The half-cell was charged to a potential of 0.03 volts at a charge / discharge rate of 0.02 C and discharged to a potential of 0.5 volts. Figure 11 illustrates the charge and discharge curves of the half-cell in the fourth cycle with electrolyte 5 and the second cycle with electrolyte 6, respectively, where the solid curve represents the potential of the charge curve and the dashed-dotted curve represents the potential of the discharge curve. The charge and discharge curves show stable, typical battery behavior. The copper conductive element is suitable as the negative electrode conductive element in electrolytes 5 and 6 and exhibits stable behavior.

[0158] [Experiment 4] Behavior of aluminum conductive elements in half-cell experiments using a reference electrolyte and electrolyte 1 according to the present invention. The purpose of this experiment was to investigate the long-term stability of aluminum conductive elements under current load in the reference electrolyte and electrolyte 1. The experiment was conducted in a half-cell having metallic lithium as the return electrode and reference electrode. The working electrode was an aluminum conductive element in the shape of the aluminum sheet under investigation. One half-cell was filled with the reference electrolyte having the composition of LiAlCl4*1.5SO2, and the other half was filled with electrolyte 1.

[0159] A constant current of 0.1 mA was applied to a half-cell containing an aluminum conductive element in a reference electrolyte for approximately 300 hours. The dashed line in Figure 12 shows the current (on the right side of the corresponding scale) and the corresponding potential (on the left side of the scale) over 90 hours. A potential of approximately 3.9 volts was observed throughout the entire time. After the experiment, the aluminum conductive element was removed from the half-cell and examined.

[0160] A constant current of 0.1 mA was initially applied to the half-cell containing the aluminum conductive element in electrolyte 1. The experimental target potential of 5.0 V was reached in approximately 2 minutes. Subsequently, the current was reduced to 0.5 μA and then sequentially increased to 1 μA, 2 μA, 3 μA, 4 μA, 6 μA, 8 μA, 10 μA, and 12 μA every 10 hours. The solid line in Figure 12 shows the current on the right-hand scale and the corresponding potential (on the left-hand scale) over 90 hours. After the experiment, the aluminum conductive element was again removed from the half-cell and investigated.

[0161] Figure 13 illustrates an example of aluminum conductive elements inserted into each half-cell at the start of the measurement. Figure 14 shows the aluminum conductive elements after the experiment in a half-cell with a reference electrolyte. Significant corrosion is observed on the edges and surface of the aluminum sheet after the experiment in the half-cell with the reference electrolyte. This corrosion is also reflected in the extremely large weight loss of 61.5% in the aluminum conductive elements. Aluminum is unstable in the reference electrolyte under current load. Figure 15 shows the aluminum conductive elements after the experiment in a half-cell with electrolyte 1. No change is observed in the aluminum sheet compared to the start of the measurement; that is, no corrosion is observed in the conductive elements. Aluminum is extremely stable in electrolyte 1 according to the present invention under current load.

[0162] [Experiment 5] Behavior of the conductive element made of aluminum in the positive electrode of experimental complete cells and half cells having electrolyte 1 To further investigate the conductive element made of aluminum, the conductive element was coated with a positive electrode active material. The active material used was LiNi 0.5 Mn 1.5A positive electrode containing O4(LNMO) was manufactured. LNMO is an active material that can be charged to a high upper limit potential, for example, 5 volts. The conductive elements of the electrode were made of aluminum in the form of an aluminum sheet. A half cell was formed using the positive electrode, with lithium electrodes as the return electrode and reference electrode. The half cell was filled with electrolyte 1. To determine the discharge capacity (see Example 4), the half cell was charged and discharged to a potential of 5 volts at a charge-discharge rate of 0.1C.

[0163] Figure 16 illustrates the potential of the first cycle of a half-cell with an aluminum conductor element, showing the charge curve (solid line) and discharge curve (dash-dotted line) as a function of capacitance.

[0164] The charge-discharge curve exhibits stable, typical battery behavior. The aluminum conductive element is extremely stable as the positive electrode conductive element in the electrolyte 1.

[0165] [Experiment 6] Behavior of the aluminum conductive element of the positive electrode in an experimental complete cell having electrolyte 1 Furthermore, to investigate the stability of the aluminum conductive element, an experimental complete cell was assembled using a positive electrode containing nickel manganese cobalt oxide (NMC622) and aluminum foil as conductive elements as active materials, and two negative electrodes. The negative electrodes contained graphite and nickel conductive elements as active materials. To determine the discharge capacity (see Example 4), the experimental complete cell was charged to an upper limit potential of 4.4 volts at a charge rate of 0.1 C. Then, it was discharged to a discharge potential of 2.8 volts at a discharge rate of 0.1 C. Figure 17 illustrates the progression of the discharge capacity over 200 cycles. The experimental complete cell exhibits extremely stable behavior with a nearly horizontal capacity progression. This demonstrates that the aluminum conductive element in the positive electrode is extremely stable in electrolyte 1.

[0166] [Experiment 7] Behavior of a conductive element made of aluminum as the positive electrode in combination with a conductive element made of copper as the negative electrode in a complete cell using electrolyte 1. To investigate the behavior of a conductive element made of aluminum as the positive electrode in combination with a conductive element made of copper as the negative electrode in a complete cell having electrolyte 1 according to the present invention, a complete cell was formed using 24 negative electrodes and 23 positive electrodes. The positive electrode contained nickel manganese cobalt oxide (NMC622) as the active material and aluminum foil as the conductive element. The negative electrode contained graphite as the active material and copper foil as the conductive element. To determine the discharge capacity (see Example 4), the complete cell was charged to various upper limit potentials of 4.3 volts or 4.6 volts at a charge rate of 0.1C. The charge capacity was limited to 50% of the theoretical cell capacity. Subsequently, discharge was performed to a discharge potential of 2.8 volts at a discharge rate of 0.1C. Figure 18 illustrates the progression of discharge capacity over 10 cycles, standardized to the maximum capacity of a complete cell with an upper limit potential of 4.3V and a complete cell with an upper limit potential of 4.6V. The complete cell exhibits extremely stable behavior, having a nearly horizontal capacitance curve even when measured at a higher upper potential limit. This demonstrates that the aluminum conductive element of the positive electrode, in combination with the copper conductive element of the negative electrode, is extremely stable in a complete cell having electrolyte 1.

[0167] [Experiment 8] Conductor made of aluminum for the positive electrode in a half cell having electrolyte 5 Element behavior A positive electrode was manufactured using nickel manganese cobalt oxide (NMC811) as the active material. The conductive element of the positive electrode consisted of aluminum in the form of aluminum foil. The experiment was conducted in a half-cell with metallic lithium as the return electrode and reference electrode. The working electrode was the positive electrode with the aluminum conductive element under investigation.

[0168] The half-cell was filled with electrolyte 5. To determine the discharge capacity (see Example 4), the half-cell was charged to a potential of 3.9 volts at a charge / discharge rate of 0.02 C and then discharged to a potential of 3 volts.

[0169] Figure 19 illustrates the potential of the second cycle of a half-cell having an aluminum conductor element during charging as a function of capacitance.

[0170] The charge-discharge curve shows stable behavior typical of a battery. The aluminum conductor element is extremely stable as the conductor element of the positive electrode in the electrolyte 5.

[0171] 〔Experiment 8〕Investigation of Electrolytes 1, 3, 4, and 5 Various experiments were carried out to investigate electrolytes 1, 3, 4, and 5. On the one hand, the surface capacitance of electrolytes 1 and 3 and the reference electrolyte was determined, and on the other hand, the discharge capacitance in electrolytes 1, 3, 4, and 5 was measured.

[0172] To determine the surface capacitance, three experimental full cells were filled with electrolyte 1 and 3 described in Example 2 and the reference electrolyte described in Example 1. The three experimental full cells contained lithium iron phosphate as the active material of the positive electrode.

[0173] Figure 20 illustrates the potential (unit: [volt]) of the experimental full cell during charging of the negative electrode as a function of the capacitance with respect to the theoretical capacitance of the negative electrode. The two illustrated curves show the results obtained from a plurality of experiments each carried out using the aforementioned experimental full cell. First, the experimental full cell was charged with a current of 15 mA until it reached 125 mA (Q lad ). Thereafter, the experimental full cell was discharged at 15 mA until a potential of 2.5 volts was reached. At that time, the discharge capacitance (Q ent ) was determined.

[0174] The absolute capacity loss was 7.58% and 11.51% for electrolytes 1 and 3, respectively, and 6.85% for the reference electrolyte. The capacity for surface formation is slightly higher for both electrolytes according to the present invention than for the reference electrolyte. The absolute capacity loss values ​​in the range of 7.5% to 11.5% are good results when combined with the possibility of using high-voltage cathodes up to 5 volts. For discharge experiments, four complete experimental cells according to Example 3 were filled with electrolytes 1, 3, 4, and 5 described in Example 2. The complete experimental cells contained nickel manganese cobalt lithium oxide (NMC) as the positive electrode active material. To determine the discharge capacity (see Example 4), the complete experimental cells were charged to a capacity of 125 mAh using a current of 15 mA. Then, discharge was performed to a discharge potential of 2.5 volts using a current of 15 mA.

[0175] Figure 21 illustrates the percentage of the potential change during discharge exceeding the discharged charge (unit: [% of maximum charge (discharge)]). All complete experimental cells exhibit a flat discharge curve, which is necessary for good battery cell operation.

[0176] [Experiment 9] Measurement of the conductivity of electrolytes 1, 3, 4, 5, and 6 Electrolytes 1, 3, 4, 5, and 6 were prepared with different concentrations of compounds 1, 3, 4, 5, and 6 for conductivity measurement. The conductivity of the electrolyte was measured for each of the different concentrations of the compounds using a conductivity measurement method. During this process, after tempering, the four-electrode sensor was held in contact with the solution and measurements were taken within a measurement range of 0.02 to 500 mS / cm.

[0177] Figure 22 illustrates the conductivity of electrolytes 1, 4, and 6 depending on the concentrations of compounds 1, 4, and 6. For electrolyte 1, a maximum conductivity of approximately 37.9 mS / cm is observed when the concentration of compound 1 is between 0.6 mol / L and 0.7 mol / L. In comparison, organic electrolytes known from prior art, such as LP30 (1M LiPF6 / EC-DMC (1:1 wt)), have a conductivity of only about 10 mS / cm. For electrolyte 4, a maximum conductivity of 18 mS / cm is obtained at a conductive salt concentration of 1 mol / L. Electrolyte 6 shows a maximum value of 11 mS / cm at a conductive salt concentration of 0.6 mol / L.

[0178] Figure 23 illustrates the conductivity of electrolytes 3 and 5 depending on their concentrations. For electrolyte 5, a maximum conductivity of 1.3 mS / cm is obtained when the conductive salt concentration is 0.8 mol / L. Electrolyte 3 exhibits a maximum conductivity of 0.5 mS / cm when the conductive salt concentration is 0.6 mol / L. Although the conductivity of electrolytes 3 and 5 was low, charging or discharging of the experimental half-cell described in Experiment 3 or the experimental full-cell described in Experiment 8 was still possible.

[0179] [Experiment 10] Low-temperature behavior Two complete experimental cells were prepared according to Example 3 to measure the low-temperature behavior of electrolyte 1 in comparison with the reference electrolyte. One complete experimental cell was filled with a reference electrolyte having the composition LiAlCl4*6SO2, and the other complete experimental cell was filled with electrolyte 1. The complete experimental cell containing the reference electrolyte contained lithium iron phosphate (LEP) as the positive electrode active material, and the complete experimental cell containing electrolyte 1 contained lithium nickel manganese cobalt oxide (NMC) as the active material. The complete experimental cells were charged to 3.6 volts (LEP) or 4.4 volts (NMC) at 20°C and discharged again to 2.5 volts at the respective temperatures under investigation. The discharge capacity achieved at 20°C was evaluated as 100%. The discharge temperature was lowered in 10°K temperature steps. The obtained discharge capacity was expressed as a percentage of the discharge capacity at 20°C. Since low-temperature discharge is largely independent of the positive and negative electrode active materials used, the results are applicable to all combinations of active materials. Table 5 shows the results.

[0180] The experimental complete cell using electrolyte 1 exhibits extremely good low-temperature behavior. At 20°C, it still reaches 82% of its capacity, and at -30°C, it still reaches 73%. Even at -40°C, it is still possible to discharge 61% of its capacity. In contrast, the experimental complete cell with the reference electrolyte can only discharge down to -10°C, reaching 21% of its capacity. At lower temperatures, it is no longer possible to discharge the cell with the reference electrolyte.

[0181] [Table 5]

Claims

1. A rechargeable battery cell (2, 20, 40) comprising an active metal, an active material and a conductive element (26) at least one positive electrode (4, 23, 44), a conductive element (27) at least one negative electrode (5, 22, 45), a housing (1, 28), and an electrolyte, The conductive element (26) of the positive electrode (4, 23, 44) and the conductive element (27) of the negative electrode (5, 22, 45) are formed independently of each other from a material selected from the group formed by aluminum and copper, and the electrolyte is SO ２ It is a system, 【Chemistry 1】 and 【Chemistry 2】 A rechargeable battery cell (2, 20, 40) characterized by comprising at least one first conductive salt selected from the group formed by the above.

2. The rechargeable battery cell (2, 20, 40) according to claim 1, characterized in that the conductive element (26) of the positive electrode (4, 23, 44) is made of aluminum.

3. The rechargeable battery cell (2, 20, 40) according to claim 1 or 2, characterized in that the conductive element (27) of the negative electrode (5, 22, 45) is made of copper.

4. The conductive element (26) of the positive electrode (4, 23, 44) and / or the conductive element (27) of the negative electrode (5, 22, 45) are - In the form of a thin metal sheet, thin metal foil, or metal-coated plastic foil, or, - In the three-dimensional shape of a porous metal structure A rechargeable battery cell (2, 20, 40) according to any one of claims 1 to 3, characterized in that it is formed as follows.

5. A rechargeable battery cell (2, 20, 40) according to any one of claims 1 to 4, characterized in that it has a cell voltage of at least 4.0 volts.

6. The rechargeable battery cell (2, 20, 40) according to any one of claims 1 to 5, characterized in that the electrolyte contains at least one second conductive salt different from the first conductive salt.

7. The rechargeable battery cell (2, 20, 40) according to claim 6, characterized in that the second conductive salt of the electrolyte is an alkali metal compound, and the alkali metal compound is selected from the group formed by aluminates, halides, oxalates, borates, phosphates, arsenates, and gallates.

8. The rechargeable battery cell (2, 20, 40) according to any one of claims 1 to 7, characterized in that the electrolyte contains at least one additive.

9. The additives in the electrolyte include vinylene carbonate and its derivatives, vinylethylene carbonate and its derivatives, methylethylene carbonate and its derivatives, lithium (bisoxalato)boric acid, lithium difluoro(oxalato)borate, lithium tetrafluoro(oxalato)phosphate, lithium oxalate, 2-vinylpyridine, 4-vinylpyridine, cyclic exomethylene carbonate, sulfones, cyclic and acyclic sulfonates, acyclic sulfites, cyclic and acyclic sulfinates, organic esters, inorganic acids, acyclic and cyclic alkanes (the acyclic and cyclic alkanes are 1 bar). A rechargeable battery cell (2, 20, 40) according to claim 8, characterized in that it is selected from the group formed by aromatic compounds, cyclic and acyclic sulfonylimides, cyclic and acyclic phosphate esters, cyclic and acyclic phosphines, cyclic and acyclic phosphates, cyclic and acyclic phosphazenes, cyclic and acyclic silylamines, cyclic and acyclic halogenated esters, cyclic and acyclic amides, cyclic and acyclic anhydrides, and halogenated organic heterocycles, having a boiling point of at least 36°C.

10. The rechargeable battery cell according to claim 8 or 9, directly or indirectly referencing claim 6 or 7, characterized in that the electrolyte has the following composition with respect to the total weight of the electrolyte composition: (i) 5 to 99.4 wt% sulfur dioxide, (ii) 0.6 to 95 wt% of the first conductive salt, (iii) 0 to 25 wt% of the second conductive salt, and (iv) The additive in an amount of 0 to 10 wt%.

11. The rechargeable battery cell according to any one of claims 1 to 10, characterized in that the molar concentration of the first conductive salt is in the range of 0.01 mol / l to 10 mol / l with respect to the total volume of the electrolyte (2, 20, 40).

12. The electrolyte contains at least 0.1 moles of SO per mole of conductive salt. ２ A rechargeable battery cell (2, 20, 40) according to any one of claims 1 to 11, characterized by including the following:

13. The rechargeable battery cell (2, 20, 40) according to any one of claims 1 to 12 is characterized in that the active metal is as follows: - Alkali metals, - Alkaline earth metals, - Metals of Group 12 of the periodic table, or - Aluminum.

14. The positive electrodes (4, 23, 44) are made of A as the active material. ｘ M' ｙ M" ｚ O ａ It comprises at least one compound having the following composition: - A is at least one metal selected from the group formed by 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 elements in groups 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, and 16 of the periodic table. -x and y are independent numbers greater than 0, -z is a number greater than or equal to 0, and furthermore -a is a number greater than 0. A rechargeable battery cell (2, 20, 40) according to any one of claims 1 to 13, characterized in that...

15. The compound is Li ｘ Ni ｙ１ Mn ｙ２ Co ｚ O ａ has a composition of, where x, y1, and y2 are each independently numbers greater than 0, z is a number greater than or equal to 0, and further a is a number greater than 0, and the rechargeable battery cell (2, 20, 40) according to claim 14.

16. The aforementioned compound is A ｘ M' ｙ M" １ ｚ１ M" ２ ｚ２ O ４ Having the composition, -M” １ It is selected from the group formed by elements of groups 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15 and 16 of the periodic table. -M” ２ It is the element phosphorus, -x and y are independent numbers greater than 0, -z1 is a number greater than 0, and further The value of -z² is 1. The rechargeable battery cell (2, 20, 40) according to claim 14, characterized in that it is a rechargeable battery cell (2, 20, 40) as described in claim 14.

17. The rechargeable battery cell (2, 20, 40) according to any one of claims 1 to 16, characterized in that the positive electrode (4, 23, 44) comprises at least one metal compound, the metal compound being selected from the group formed by metal oxides, metal halides, and metal phosphates.

18. The rechargeable battery cell (2, 20, 40) according to any one of claims 1 to 17, characterized in that the positive electrode (4, 23, 44) contains at least one metal compound having the chemical structure of spinel, layered oxide, conversion compound, or polyanion compound.

19. The rechargeable battery cell (2, 20, 40) according to any one of claims 1 to 18, characterized in that the negative electrode (5, 22, 45) is an insertion electrode.

20. The positive electrode (4, 23, 44) and / or the negative electrode (5, 22, 45) are provided with at least one fluorinated binder, or A binder consisting of a monomer structural unit of a conjugated carboxylic acid, or an alkali metal salt, alkaline earth metal salt, or ammonium salt of said conjugated carboxylic acid, or a polymer consisting of a combination thereof, The binder comprises a monomeric styrene and butadiene structural unit polymer or a binder composed of carboxymethylcellulose group, The rechargeable battery cell (2, 20, 40) according to any one of claims 1 to 19, characterized in that the binder is present at a concentration of at most 20 wt% with respect to the total weight of the positive electrode or the negative electrode.

21. A rechargeable battery cell (2, 20, 40) according to any one of claims 1 to 20, comprising a plurality of negative electrodes (5, 22, 45) and at least one positive electrode (4, 23, 44) arranged alternately in stacks within the housing (1, 28), wherein the positive electrode (4, 23, 44) and the negative electrode (5, 22, 45) are electrically isolated from each other by separators (11, 21, 13).

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