Patent Application
20230395845
This disclosure relates to an SO2-based electrolyte for a rechargeable battery cell and a rechargeable battery cell.
Rechargeable battery cells are of great importance in many technical fields. In many cases, they are used for applications in which only small rechargeable battery cells with relatively low current ratings are required, such as in the operation of cell phones. In addition, however, there is also a great need for larger rechargeable battery cells for high-energy applications, where mass storage of energy in the form of battery cells is of particular importance for the electric drive of vehicles.
An important requirement for such rechargeable battery cells is high energy density. This means that the rechargeable battery cell should contain as much electrical energy as possible per unit of weight and volume. Lithium has proved particularly advantageous as the active metal for this purpose. The active metal of a rechargeable battery cell is the metal whose ions migrate within the electrolyte to the negative or positive electrode during charging or discharging of the cell and participate in electrochemical processes there. These electrochemical processes lead directly or indirectly to the release of electrons into the external circuit or to the acceptance of electrons from the external circuit. Rechargeable battery cells that contain lithium as the active metal are also known as lithium-ion cells. The energy density of these lithium-ion cells can be increased either by increasing the specific capacity of the electrodes or by increasing the cell voltage.
Both the positive and negative electrodes of lithium-ion cells are designed as insertion electrodes. The term “insertion electrode” as used in this disclosure refers to electrodes that have a crystal structure into which ions of the active material can be inserted and removed during operation of the lithium-ion cell. This means that the electrode processes can take place not only on the surface of the electrodes, but also within the crystal structure. When the lithium-ion cell is charged, the ions of the active metal are removed from the positive electrode and inserted into the negative electrode. When discharging the lithium-ion cell, the reverse process takes place.
The electrolyte is an important functional element of every rechargeable battery cell. It usually contains a solvent or solvent mixture and at least one conducting salt. Solid electrolytes or ionic liquids, for example, contain no solvent but only a conducting salt. The electrolyte is in contact with the positive and negative electrodes of the battery cell. At least one ion of the conducting salt (anion or cation) is mobile in the electrolyte in such a way that, by ionic conduction, a charge transport necessary for the function of the rechargeable battery cell can take place between the electrodes. The electrolyte undergoes oxidative electrochemical decomposition above a certain upper cell voltage of the rechargeable battery cell. This process often leads to irreversible destruction of components of the electrolyte and thus to failure of the rechargeable battery cell. Reductive processes can also decompose the electrolyte above a certain lower cell voltage. To avoid these processes, the positive and negative electrodes are selected so that the cell voltage is below or above the decomposition voltage of the electrolyte. The electrolyte thus determines the voltage window within which a rechargeable battery cell can be operated reversibly.
The lithium-ion cells known from the prior art contain an electrolyte consisting of a conducting salt dissolved in an organic solvent or solvent mixture. The conducting salt is a lithium salt such as lithium hexafluorophosphate (LiPF6). The solvent mixture may contain, for example, ethylene carbonate. Because of the organic solvent or solvent mixture, such lithium-ion cells are also called organic lithium-ion cells. The negative electrode of these organic lithium-ion cells consists of a carbon coating applied to a copper conducting element. The conducting element provides the necessary electronically conductive connection between the carbon coating and the external circuit. The positive electrode consists of lithium cobalt oxide (LiCoO2), which is applied to an aluminum conducting element. Both electrodes have a thickness of generally less than 100 μm and are therefore very thin.
It has long been known that the unintentional overcharging of organic lithium-ion cells leads to irreversible decomposition of electrolyte components. In this process, the oxidative decomposition of the organic solvent and/or the conducting salt takes place on the surface of the positive electrode. The heat of reaction generated during this decomposition and the resulting gaseous products are responsible for the subsequent so-called “thermal runaway” and the resulting destruction of the organic lithium-ion cell. The vast majority of charging protocols for these organic lithium-ion cells use the cell voltage as an indicator for the end of charge. Here, accidents due to thermal runaway are particularly likely when using multi-cell battery packs in which several organic lithium-ion cells with mismatching capacities are connected in series.
Therefore, organic lithium-ion cells are problematic with regard to their stability as well as long-term operational safety. Safety risks are also caused in particular by the flammability of the organic solvent or solvent mixture. If an organic lithium-ion cell catches fire or even explodes, the organic solvent of the electrolyte forms a flammable material. To avoid such safety risks, additional measures must be taken. These measures include, in particular, very precise control of the charging and discharging processes of the organic lithium-ion cell and optimized battery design. Furthermore, the organic lithium-ion cell contains components that can melt in the event of an unwanted increase in temperature, thereby flooding the organic lithium-ion cell with molten plastic. This prevents a further uncontrolled temperature increase. However, these measures lead to increased production costs in the manufacture of the organic lithium-ion cell as well as to increased volume and weight. Furthermore, these measures reduce the energy density of the organic lithium-ion cell.
Another disadvantage of organic lithium-ion cells is that any hydrolysis products formed in the presence of residual water are very aggressive towards the cell components of the rechargeable battery cell. For example, the LiPF6 conducting salt often used in organic cells produces very reactive, aggressive hydrogen fluoride (HF) by reacting with traces of water. Because of this, care must be taken to minimize the residual water content in the electrolyte and cell components when manufacturing such rechargeable battery cells with an organic electrolyte. Production therefore often takes place in cost-intensive drying rooms with extremely low humidity. The problems described above with regard to stability and long-term operational reliability are particularly serious in the development of organic lithium-ion cells, which have, on the one hand, very good electrical energy and performance data and, on the other hand, very high operational reliability and service life, in particular, a high number of usable charge and discharge cycles.
A further development known from the prior art therefore provides for the use of a sulfur dioxide (SO2)-based electrolyte instead of an organic electrolyte for rechargeable battery cells. Rechargeable battery cells containing an SO2-based electrolyte exhibit, among other things, high ionic conductivity. The term “SO2-based electrolyte” is to be understood as an electrolyte which contains SO2 not only as an additive in low concentration, but in which the mobility of the ions of the conducting salt, which is contained in the electrolyte and causes charge transport, is ensured at least partially, largely, or even completely by SO2. The SO2 thus serves as a solvent for the conducting salt. The conducting salt can form a liquid solvate complex with the gaseous SO2, whereby the SO2 is bound and the vapor pressure is noticeably lowered compared to pure SO2. Electrolytes with low vapor pressure are formed. Such SO2-based electrolytes have the advantage of non-flammability compared to the organic electrolytes described above. This eliminates the safety risks associated with the flammability of the electrolyte.
For example, EP 1 201 004 B1 (hereinafter referred to as [V1]) discloses an SO2-based electrolyte with the composition LiAlCl4*SO2 in combination with a positive electrode of LiCoO2. To avoid disruptive decomposition reactions during overcharging of the rechargeable battery cell from a potential of 4.1 to 4.2 volts, such as the undesirable formation of chlorine (Cl2) from lithium tetrachloroaluminate (LiAlCl4), EP 1 201 004 B1 proposes the use of an additional salt.
EP 2534719 B1 (hereinafter referred to as [V2]) also discloses an SO2-based electrolyte with, among other things, LiAlCl4 as the conducting salt. This LiAlCl4 forms with the SO2, for example, complexes of the formula LiAlCl4*1.5 mol SO2 or LiAlCl4*6 mol SO2. Lithium iron phosphate (LiFePO4) is used as the positive electrode. LiFePO4 has a lower charging potential (3.7 V) compared to LiCoO2 (4.2 V). The problem of undesirable overcharge reactions does not occur in this rechargeable battery cell, since potentials of 4.1 volts, which are harmful to the electrolyte, are not reached.
In order to further improve the possible applications and properties of SO2-based electrolytes and rechargeable battery cells containing this electrolyte, this disclosure is based, on the one hand, on the task of providing an SO2-based electrolyte which, compared with electrolytes known from the prior art,
Such electrolytes are intended to be applicable in particular in rechargeable battery cells, which at the same time have very good electrical energy and performance characteristics, high operational reliability and service life, in particular a high number of usable charging and discharging cycles, all without the electrolyte thereby decomposing during operation of the rechargeable battery cell.
On the other hand, it is the object of this disclosure to specify a rechargeable battery cell which contains an SO2-based electrolyte and, compared with the rechargeable battery cells known from the prior art, exhibits
This task is solved by an SO2-based electrolyte having the features of claim 1 and by a rechargeable battery cell having the features of claim 9. Advantageous embodiments of the electrolyte according to this disclosure are defined in claims 2 to 8. Claims 10 to 19 describe advantageous further embodiments of the rechargeable battery cell according to this disclosure.
An SO2-based electrolyte for a rechargeable battery cell according to this disclosure comprises at least a first conducting salt, which has the formula (I)
MaBmXn formula (I)
In 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. B represents the element boron of the periodic table of the elements. X stands for a halogen, i.e., an element of the seventh main group or the 17th group of the periodic table of the elements. A, m, and n are integers independent of each other.
The SO2-based electrolyte according to this disclosure contains SO2 not only as an additive in low concentration, but in concentrations at which the mobility of the ions of the first conducting salt, which is contained in the electrolyte and causes the charge transport, is at least partially, largely, or even completely ensured by the SO2. The first conducting salt is dissolved in the electrolyte and shows very good solubility therein. It can form a liquid solvate complex with the gaseous SO2, in which the SO2 is bound. In this case, the vapor pressure of the liquid solvate complex drops significantly compared with pure SO2, and electrolytes with a low vapor pressure are formed. However, it is also within the scope of this disclosure that, depending on the chemical structure of the first conducting salt according to formula (I), no vapor pressure drop may occur during the preparation of the electrolyte according to this disclosure. In the latter case, it is preferred that the preparation of the electrolyte according to this disclosure is carried out at cryogenic temperature or under pressure, preferably using liquid SO2. The electrolyte may also contain several conducting salts of formula (I), which differ from each other in their chemical structure.
Another aspect of this disclosure provides for a rechargeable battery cell. This rechargeable battery cell comprises the electrolyte according to this disclosure described above or an electrolyte according to one of the advantageous embodiments of the electrolyte according to this disclosure described below. Further, the rechargeable battery cell according to this disclosure comprises an active metal, at least one positive electrode, at least one negative electrode, and a housing.
An electrolyte according to this disclosure and a rechargeable battery cell according to this disclosure containing such an electrolyte have the advantage over electrolytes and rechargeable battery cells known in the prior art that the first conducting salt contained in the electrolyte has a higher oxidation stability and, as a result, shows essentially no or only very little decomposition at higher cell voltages. This leads to increased long-term stability of the electrolyte as well as the rechargeable battery cell.
Advantageous embodiments of the electrolyte according to this disclosure are described below.
A first advantageous embodiment of the SO2-based electrolyte provides that M is lithium (Li). Such lithium compounds of formula (I) have the composition LiaBmXn, wherein A, m, and n are independent integers, as previously described. In another advantageous further embodiment, X is selected from the group formed by fluorine (F), chlorine (Cl), bromine (Br), and iodine (I). Preferably, X is fluorine or chlorine. A further advantageous embodiment of the SO2-based electrolyte provides that M is lithium and X is chlorine. Such compounds have the composition LiaBmCln, wherein a, m, and n are independent integers, as previously described. Examples of compounds of this composition are Li2B10Cl10 or Li2B12Cl12. Furthermore, in the previously mentioned formula (I), M can be lithium and X can be fluorine. Such compounds have the composition LiaBmFn, wherein a, m, and n are independent integers, as previously described. Examples of compounds of this composition are Li2B10F10 or Li2B12F12.
A further advantageous embodiment of the rechargeable battery cell according to this disclosure provides that the electrolyte contains at least 1 mol of SO2, preferably at least 10 mol of SO2, further preferably at least 30 mol of SO2, and particularly preferably at least 50 mol of SO2 per mol of conducting salt. The electrolyte may also contain very high molar proportions of SO2, the preferred upper limit being 2600 moles of SO2 per mole of conducting salt, and upper limits of 1500, 1000, 500, and 100 moles of SO2 per mole of conducting salt being further preferred in that order. In this context, the term “per mole of conducting salt” refers to all conducting salts contained in the electrolyte. SO2-based electrolytes with such a concentration ratio between SO2 and the conducting salt have the advantage that they can dissolve a larger amount of conducting salt compared to electrolytes known from the prior art, which are based on an organic solvent mixture, for example. The concentration of SO2 in the electrolyte affects its conductivity. Thus, by selecting the SO2 concentration, the conductivity of the electrolyte can be adapted to the intended use of a rechargeable battery cell operated with this electrolyte.
The total content of SO2 and the first conducting salt may be greater than 50% by weight (percent by weight) of the weight of the electrolyte, preferably greater than 60% by weight, more preferably greater than 70% by weight, more preferably greater than 80% by weight, more preferably greater than 85% by weight, more preferably greater than 90% by weight, more preferably greater than 95% by weight, or more preferably greater than 99% by weight.
The electrolyte may contain at least 5% by weight of SO2 based on the total amount of electrolyte contained in the rechargeable battery cell, with values of 20% by weight of SO2, 40% SO2, and 60% by weight of SO2 being further preferred. The electrolyte may also contain up to 95% by weight of SO2, with maximum values of 80% by weight of SO2 and 90% by weight of SO2 being preferred in that order.
In order to adapt the conductivity and/or other properties of the electrolyte to a desired value, in another advantageous further embodiment, the electrolyte comprises at least a second conducting salt different from the first conducting salt according to formula (I). This means that, in addition to the first conducting salt, the electrolyte can contain one or also further second conducting salts which differ from the first conducting salt in their chemical composition as well as their chemical structure. The second conducting salt is preferably an alkali metal compound, in particular a lithium compound. The alkali metal compound or the lithium compound are selected from the group formed by an aluminate, a halide, an oxalate, a borate, a phosphate, an arsenate, and a gallate. Further preferably, the second conducting salt is a lithium tetrahaloaluminate, in particular LiAlCl4.
The electrolyte may have the following composition based on the total weight of the electrolyte composition:
As previously mentioned, the electrolyte may contain not only a first conducting salt according to formula (I) and a second conducting salt, but also a plurality of first conducting salts according to formula (I) and a plurality of second conducting salts, respectively. In the latter case, the aforementioned percentages also include a plurality of first conducting salts and a plurality of second conducting salts.
Preferably, the electrolyte has only a small percentage or even no percentage of at least one organic solvent. The percentage of organic solvents in the electrolyte, which is present, for example, in the form of a solvent or a mixture of several organic solvents, may be at most 50% by weight of the weight of the electrolyte. Preferred are lower proportions of at most 40% by weight, more preferably at most 30% by weight, more preferably at most 20% by weight, more preferably at most 15% by weight, more preferably at most 10% by weight, more preferably at most 5% by weight or more preferably at most 1% by weight of the weight of the electrolyte. Particularly preferably, the electrolyte is substantially free of organic solvents. Due to the only small proportion of organic solvents or even their complete absence, the electrolyte is either hardly combustible or not combustible at all. This increases the operational safety of a rechargeable battery cell operated with such an SO2-based electrolyte. Based on the total weight of the electrolyte composition, in another advantageous further embodiment, the electrolyte has the following composition:
Advantageous further embodiments of the rechargeable battery cell according to this disclosure with respect to the active metal are described below:
In a first advantageous further embodiment of the rechargeable battery cell, the active metal is
Advantageous further embodiments of the rechargeable battery cell according to this disclosure with respect to the negative electrode are described below:
Another advantageous further embodiment of the rechargeable battery cell provides that the negative electrode is an insertion electrode. This insertion electrode contains an insertion material as active material, into which the ions of the active metal can be stored during charging of the rechargeable battery cell and from which the ions of the active metal can be removed during discharging of the rechargeable battery cell. This means that electrode processes can occur not only on the surface of the negative electrode, but also inside the negative electrode. For example, if a lithium-based conducting salt is used, lithium ions can be stored in the insertion material during charging of the rechargeable battery cell and can be removed from it during discharging of the rechargeable battery cell. Preferably, the negative electrode contains carbon as the active material or insertion material, in particular in the modification graphite. However, it is also within the scope of this disclosure for the carbon to be in the form of natural graphite (flake-feed or rounded), synthetic graphite (mesophase graphite), graphitized MesoCarbon MicroBeads (MCMB), carbon coated graphite, or amorphous carbon.
In another advantageous further embodiment of the rechargeable battery cell according to this disclosure, the negative electrode comprises lithium intercalation anode active materials that do not contain carbon, such as lithium titanates (e.g., Li4Ti5O12).
Another advantageous further development of the rechargeable battery cell according to this disclosure provides that the negative electrode comprises lithium alloy-forming anode active materials. These are, for example, lithium storing metals and metal alloys (e.g., Si, Ge, Sn, SnCoxCy, SnSix, and the like) and oxides of the lithium storing metals and metal alloys (e.g., SnOx, SiOx, oxide glasses of Sn, Si, and the like).
In another advantageous further embodiment of the rechargeable battery cell according to this disclosure, the negative electrode includes conversion anode active materials. These conversion anode active materials may be, for example, transition metal oxides in the form of manganese oxides (MnOx), iron oxides (FeOx), cobalt oxides (CoOx), nickel oxides (NiOx), copper oxides (CuOx), or metal hydrides in the form of magnesium hydride (MgH2), titanium hydride (TiH2), aluminum hydride (AlH3), and boron, aluminum, and magnesium-based ternary hydrides and the like.
In another advantageous further embodiment of the rechargeable battery cell according to this disclosure, the negative electrode comprises a metal, in particular metallic lithium.
Another advantageous further embodiment of the rechargeable battery cell according to this disclosure provides that the negative electrode is porous, wherein the porosity is preferably at most 50%, further preferably at most 45%, further preferably at most 40%, further preferably at most 35%, further preferably at most 30%, further preferably at most 20%, and particularly preferably at most 10%. The porosity represents the void volume to total volume of the negative electrode, where the void volume is formed by so-called pores or voids. This porosity leads to an increase of the inner surface of the negative electrode. Furthermore, the porosity reduces the density of the negative electrode and thus its weight. The individual pores of the negative electrode can preferably be completely filled with the electrolyte during operation.
Another advantageous further development of the battery cell according to this disclosure provides that the negative electrode has a conducting element. This means that, in addition to the active material or insertion material, the negative electrode also comprises a conducting element. This conducting element serves to enable the required electronically conductive connection of the active material of the negative electrode. For this purpose, the conducting element is in contact with the active material involved in the electrode reaction of the negative electrode. This conducting element can be planar in the form of a thin metal sheet or a thin metal foil. The thin metal foil preferably has an openwork or mesh-like structure. The active material of the negative electrode is preferably applied to the surface of the thin metal sheet or foil. Such planar conducting elements have a thickness in the range of 5 μm to 50 μm. A thickness of the planar conducting element in the range of 10 μm to 30 μm is preferred. When using planar conducting elements, the negative electrode can have a total thickness of at least 20 μm, preferably at least 40 μm and particularly preferably at least 60 μm. The maximum thickness is at most 200 μm, preferably at most 150 μm, and particularly preferably at most 100 μm. The area-specific capacity of the negative electrode preferably has at least 0.5 mAh/cm2 when a planar conducting element is used, with the following values being further preferred in this order: 1 mAh/cm2, 3 mAh/cm2, 5 mAh/cm2, 10 mAh/cm2.
Furthermore, there is also the possibility that the conducting element can be formed three-dimensionally in the form of a porous metal structure, in particular in the form of a metal foam. In this context, the term “three-dimensional porous metal structure” refers to any structure consisting of metal that extends not only over the length and width of the planar electrode like the thin metal sheet or metal foil, but also over its thickness dimension. The three-dimensional porous metal structure is so porous that the active material of the negative electrode can be incorporated into the pores of the metal structure. The amount of incorporated or applied active material is the charging of the negative electrode. If the conducting element is formed three-dimensionally in the form of a porous metal structure, in particular in the form of a metal foam, then the negative electrode preferably has a thickness of at least 0.2 mm, preferably at least 0.3 mm, more preferably at least 0.4 mm, further preferably at least 0.5 mm and particularly preferably at least 0.6 mm. The thickness of the electrodes in this case is significantly greater compared to negative electrodes, which are used in organic lithium-ion cells. A further advantageous embodiment provides that the area-specific capacity of the negative electrode is preferably at least 2.5 mAh/cm2 when a three-dimensional conducting element in the form of a metal foam is used, in particular in the form of a metal foam, the following values being further preferred in this order: 5 mAh/cm2, 10 mAh/cm2, 15 mAh/cm2, 20 mAh/cm2, 25 mAh/cm2, 30 mAh/cm2. If the conducting element is formed three-dimensionally in the form of a porous metal structure, in particular in the form of a metal foam, the amount of active material of the negative electrode, i.e., the charging of the electrode, relative to its area, is at least 10 mg/cm2, preferably at least 20 mg/cm2, more preferably at least 40 mg/cm2, more preferably at least 60 mg/cm2, more preferably at least 80 mg/cm2 and particularly preferably at least 100 mg/cm2. This charging of the negative electrode has a positive effect on the charging process as well as the discharging process of the rechargeable battery cell.
In another advantageous further embodiment of the battery cell according to this disclosure, the negative electrode comprises at least one binder. This binder is preferably a fluorinated binder, in particular a polyvinylidene fluoride and/or a terpolymer formed from tetrafluoroethylene, hexafluoropropylene, and vinylidene fluoride. However, it can also be a binder consisting of a polymer built up from monomeric structural units of a conjugated carboxylic acid or from the alkali metal, alkaline earth metal, or ammonium salt of this conjugated carboxylic acid or from a combination thereof. Furthermore, the binder may also comprise a polymer based on monomeric styrene and butadiene structural units. Furthermore, the binder can also be a binder from the group of carboxymethyl celluloses. The binder is preferably present in the negative electrode in a concentration of at most 20% by weight, further preferably at most 15% by weight, further preferably at most 10% by weight, further preferably at most 7% by weight, further preferably at most 5% by weight, and particularly preferably at most 2% by weight based on the total weight of the negative electrode.
Advantageous further embodiments of the rechargeable battery cell according to this disclosure with respect to the positive electrode are described below:
A first advantageous further embodiment of the rechargeable battery cell according to this disclosure provides that the positive electrode is chargeable at least up to an upper potential of 4.0 volts, preferably up to a potential of 4.4 volts, more preferably of at least a potential of 4.8 volts, more preferably at least up to a potential of 5.2 volts, more preferably at least up to a potential of 5.6 volts, and particularly preferably at least up to a potential of 6.0 volts.
In another advantageous further embodiment of the rechargeable battery cell according to this disclosure, the positive electrode comprises at least one active material. This can store ions of the active metal and release and reabsorb the ions of the active metal during operation of the battery cell.
In another advantageous further embodiment of the rechargeable battery cell according to this disclosure, the positive electrode comprises at least one intercalation compound. For the purposes of this disclosure, the term “intercalation compound” is to be understood as a subcategory of the insertion materials previously described. This intercalation compound acts as a host matrix which has vacancies that are interconnected. The ions of the active metal can diffuse into these vacancies during the discharge process of the rechargeable battery cell and be intercalated there. In the course of this intercalation of the ions of the active metal, only minor or no structural changes occur in the host matrix.
In another further advantageous embodiment of the rechargeable battery cell according to this disclosure, the positive electrode contains at least one conversion compound as active material. For the purposes of this disclosure, the term “conversion compounds” means materials that form other materials during electrochemical activity; i.e., chemical bonds are broken and reestablished during charging and discharging of the battery cell. During the absorption or release of the ions of the active metal, structural changes occur in the matrix of the conversion compound.
In another advantageous further embodiment of the rechargeable battery cell according to this disclosure, the active material has the composition AxM′yM″zOa. In this composition AxM′yM″zOa:
A is preferably the metal lithium, i.e., the compound may have the composition LixM′yM″zOa.
The indices y and z in the composition AxM′yM″zOa refer to the totality of metals and elements represented by M′ and M″, respectively. For example, if M′ comprises two metals M′ 1 and M′2, the following applies to the index y: y=y1+y2, where y1 and y2 represent the indices of the metals and M′2. The indices x, y, z, and a must be selected so that there is charge neutrality within the composition. Examples of compounds in which M′ comprises two metals are lithium nickel manganese cobalt oxides of the composition LixNiy1Mny2CozO2 with M′1=Ni, M′2=Mn, and M″=Co. Examples of compounds in which z=0, i.e., those which have no further metal or element M″, are lithium cobalt oxides LixCoyOa. For example, if M″ comprises two elements, one being a metal M″1 and the other phosphorus as M″2, the index z is: z=z1+z2, where z1 and z2 are the indices of the metal M″1 and the phosphorus (M″2). The indices x, y, z, and a must be selected so that there is charge neutrality within the composition. Examples of compounds in which A comprises lithium, M″, a metal M″1, and phosphorus as M″2 are lithium iron manganese phosphates LixFeyMnz1Pz2O4 with A=Li, M′=Fe, M″1=Mn, and M″2=P and z2=1. In another composition, M″ may comprise two nonmetals, for example fluorine as M″1 and sulfur as M″2. Examples of such compounds are lithium iron fluorosulfates LixFeyFz1Sz2O4 with A=Li, M′=Fe, M″1=Mn, and M″2=P.
Another advantageous further embodiment of the rechargeable battery cell according to this disclosure provides that M′ consists of the metals nickel and manganese, and M″ is cobalt. These may be compositions of the formula LixNiy1Mny2CozO2 (NMC), i.e., lithium nickel manganese cobalt oxides having the structure of layered oxides. Examples of these lithium nickel manganese cobalt oxide active materials include LiNi1/3Mn1/3Co1/3O2 (NMC111), LiNi0.6Mn0.2Co0.2O2 (NMC622), and LiNi0.8Mn0.1Co0.1O2 (NMC811). Other compounds of lithium nickel manganese cobalt oxide may have the composition LiNi0.5Mn0.3Co0.2O2, LiNi0.5Mn0.25Co0.25O2, LiNi0.52Mn0.32Co0.16O2, LiNi0.55Mn0.30Co0.15O2, LiNi0.58Mn0.14Co0.28O2, LiNi0.64Mn0.18Co0.18O2, LiNi0.65Mn0.27Co0.08O2, LiNi0.7Mn0.2Co0.1O2, LiNi0.7Mn0.15Co0.15O2, LiNi0.72Mn0.10Co0.18O2, LiNi0.76Mn0.14Co0.10O2, LiNi0.86Mn0.04Co0.10O2, LiNi0.90Mn0.05Co0.05O2, LiNi0.95Mn0.025Co0.025O2, or any combination thereof. These compounds can be used to produce positive electrodes for rechargeable battery cells with a cell voltage above 4.6 volts.
Another advantageous further embodiment of the rechargeable battery cell according to this disclosure provides that the active material is a metal oxide rich in lithium and manganese (Lithium- and Manganese-Rich Oxide Material). This metal oxide may have the composition LixMnyM“zOa. M′ thus represents the metal manganese (Mn) in the formula LixM′yM”zOa described above. Here, the index x is greater than or equal to 1, the index y is greater than the index z or greater than the sum of the indices z1+z2+z3, etc., respectively. If, for example, M″ comprises two metals M″1 and M″2 with indices z1 and z2 (e.g., Li1/2Mn0.525Ni0.175Co0.1O2 with M″1=Ni z1=0.175 and M″2=Co z2=0.1) then the following applies to the index y: y>z1+z2. The index z is greater than or equal to 0 and the index a is greater than 0. The indices x, y, z, and a must be selected so that there is charge neutrality within the composition. Metal oxides rich in lithium and manganese can also be described by the formula mLi2MnO3·(1−m)LiM′O2 with 0<m<1. Examples of such compounds are Li1.2Mn0.525Ni0.175Co0.1O2, Li1.2Mn0.6Ni0.2O2 or Li1.2Ni0.13Co0.13Mn0.54O2.
Another advantageous further embodiment of the rechargeable battery cell according to this disclosure provides that the composition has the formula AxM′yM“zO4. These compounds are spinel structures. For example, A may be lithium, M′ may be cobalt, and M” may be manganese. In this case, the active material is lithium cobalt manganese oxide (LiCoMnO4). LiCoMnO4 can be used to produce positive electrodes for rechargeable battery cells with a cell voltage above 4.6 volts. This LiCoMnO4 is preferably free of Mn3+. 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 proportions of the two metals M′ and M″ may vary. Lithium nickel manganese oxide, for example, can have the composition LiNi0.5Mn1.5O4.
In another advantageous further embodiment of the rechargeable battery cell according to this disclosure, the positive electrode contains as active material at least one active material which is a conversion compound. Conversion compounds undergo a solid-state redox reaction during the absorption of the active metal, e.g., lithium or sodium, in which the crystal structure of the material changes. This occurs with the breaking and recombination of chemical bonds. Fully reversible reactions of transformation compounds can be, for example, as follows:
Examples of conversion are FeF2, FeF3, CoF2, CuF2, NiF2, BiF3, FeCl3, FeCl2, CoCl2, NiCl2, CuCl2, AgCl, LiCl, S, Li2S, Se, Li2Se, Te, I, and LiI.
In another advantageous further embodiment, the compound has the composition AxM′yM″z1M″z2O4, where M″ is phosphorus and z2 has the value 1. The compound having the composition LixM′yM″z1M″z2O4 is so-called lithium metal phosphates. In particular, this compound has the composition LixFeyMnz1Pz2O4. Examples of lithium metal phosphates are lithium iron phosphate (LiFePO4) or lithium iron manganese phosphates (Li(FeyMnz)PO4). An example of a lithium iron manganese phosphate is the phosphate of composition Li(Fe0.3Mn0.7)PO4. An example of a lithium iron manganese phosphate is the phosphate of composition Li(Fe0.3Mn0.7)PO4. Lithium metal phosphates of other compositions can also be used for the battery cell according to this disclosure.
Many of the positive electrode active materials described are high voltage active materials. This means that they can be used to produce electrodes which are chargeable at least up to an upper potential of 4.0 volts, preferably up to an upper potential of 4.4 volts.
Another advantageous further embodiment of the rechargeable battery cell according to this disclosure provides that the positive electrode comprises at least one metal compound. This metal compound is selected from the group formed by a metal oxide, a metal halide, and a metal phosphate. Preferably, the metal of this metal compound is a transition metal of atomic numbers 22 to 28 of the periodic table of the elements, in particular cobalt, nickel, manganese, or iron.
Another advantageous further embodiment of the rechargeable battery cell according to this disclosure provides that the positive electrode comprises at least one metal compound having the chemical structure of a spinel, a layer oxide, a conversion compound, or a polyanionic compound.
It is within the scope of this disclosure that the positive electrode contains as active material at least one of the described compounds or a combination of the compounds. A combination of the compounds means a positive electrode containing at least two of the described materials.
Another advantageous further embodiment of the battery cell according to this disclosure provides that the positive electrode comprises a conducting element. This means that, in addition to the active material, the positive electrode also comprises a conducting element. This conducting element serves to enable the required electronically conductive connection of the active material of the positive electrode. For this purpose, the conducting element is in contact with the active material involved in the electrode reaction of the positive electrode.
This conducting element can be planar in the form of a thin metal sheet or a thin metal foil. The thin metal foil preferably has an openwork or mesh-like structure. The planar conducting element can also be made of a plastic film coated with metal. These metal coatings have a thickness in the range of 0.1 μm to 20 μm. The active material of the positive electrode is preferably deposited on the surface of the thin metal sheet, the thin metal foil, or the metal-coated plastic foil. The active material may be deposited on the front and/or back surface of the planar conducting element. Such planar conducting elements have a thickness in the range of 5 μm to 50 μm. A thickness of the planar conducting element in the range of 10 μm to 30 μm is preferred. When planar conducting elements are used, the positive electrode may have a total thickness of at least 20 μm, preferably at least 40 μm, and particularly preferably at least 60 μm. The maximum thickness is at most 200 μm, preferably at most 150 μm, and particularly preferably at most 100 μm. The area-specific capacity of the positive electrode relative to the coating of one side preferably has at least 0.5 mAh/cm2 when a planar conducting element is used, the following values being further preferred in this order: 1 mAh/cm2, 3 mAh/cm2, 5 mAh/cm2, 10 mAh/cm2, 15 mAh/cm2, 20 mAh/cm2.
Furthermore, there is also the possibility that the conducting element of the positive electrode is formed three-dimensionally in the form of a porous metal structure, in particular in the form of a metal foam. The three-dimensional porous metal structure is so porous that the active material of the positive electrode can be incorporated into the pores of the metal structure. The amount of incorporated or applied active material is the loading of the positive electrode. If the conducting element is formed three-dimensionally in the form of a porous metal structure, in particular in the form of a metal foam, then the positive electrode preferably has a thickness of at least 0.2 mm, preferably at least 0.3 mm, more preferably at least 0.4 mm, further preferably at least 0.5 mm, and particularly preferably at least 0.6 mm. A further advantageous embodiment provides that the area-specific capacity of the positive electrode is preferably at least 2.5 mAh/cm2 when a three-dimensional conducting element is used, in particular in the form of a metal foam, the following values being further preferred in this order: 5 mAh/cm2, 15 mAh/cm2, 25 mAh/cm2, 35 mAh/cm2, 45 mAh/cm2, 55 mAh/cm2, 65 mAh/cm2, 75 mAh/cm2. If the conducting element is formed three-dimensionally in the form of a porous metal structure, in particular in the form of a metal foam, the amount of active material of the positive electrode, i.e., the loading of the electrode, relative to its area, is at least 10 mg/cm′, preferably at least 20 mg/cm′, further preferably at least 40 mg/cm′, further preferably at least 60 mg/cm′, further preferably at least 80 mg/cm2, and particularly preferably at least 100 mg/cm′. This loading of the positive electrode has a positive effect on the charging process as well as the discharging process of the rechargeable battery cell.
In another advantageous further embodiment of the battery cell according to this disclosure, the positive electrode comprises at least one binder. This binder is preferably a fluorinated binder, in particular a polyvinylidene fluoride and/or a terpolymer formed from tetrafluoroethylene, hexafluoropropylene, and vinylidene fluoride. However, it can also be a binder consisting of a polymer built up from monomeric structural units of a conjugated carboxylic acid or from the alkali metal, alkaline earth metal, or ammonium salt of this conjugated carboxylic acid or from a combination thereof. Furthermore, the binder may also comprise a polymer based on monomeric styrene and butadiene structural units. Furthermore, the binder can also be a binder from the group of carboxymethyl celluloses. The binder is preferably present in the positive electrode in a concentration of at most 20% by weight, further preferably at most 15% by weight, further preferably at most 10% by weight, further preferably at most 7% by weight, further preferably at most 5% by weight, and particularly preferably at most 2% by weight based on the total weight of the positive electrode.
Advantageous further embodiments of the rechargeable battery cell according to this disclosure are described below with regard to its structure:
In order to further improve the function of the rechargeable battery cell, another advantageous further embodiment of the rechargeable battery cell according to this disclosure provides that the rechargeable battery cell comprises a plurality of negative electrodes and a plurality of positive electrodes which are arranged alternately stacked in the housing. Here, the positive electrodes and the negative electrodes are preferably electrically separated from each other by separators.
The separator may be formed of a nonwoven fabric, a membrane, a woven fabric, a knitted fabric, an organic material, an inorganic material, or a combination thereof. Organic separators can be made of 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 containing a combination of organic and inorganic materials include glass fiber textile materials in which the glass fibers are coated with a suitable polymeric coating. The coating preferably contains a fluorine-containing polymer such as polytetrafluoroethylene (PTFE), ethylene tetrafluoroethylene (ETFE), perfluoroethylene propylene (FEP), THV (terpolymer of tetrafluoroethylene, hexafluoroethylene, and vinylidene fluoride), a perfluoroalkoxy polymer (PFA), aminosilane, polypropylene, or polyethylene (PE). The separator may also be present folded in the rechargeable battery cell housing, for example in the form of a so-called “Z-folding.” In this Z-folding, a strip-shaped separator is folded through or around the electrodes in a Z-shaped manner. Furthermore, the separator can also be in the form of separator paper.
It is also within the scope of this disclosure that the separator may be formed as coating, wherein each positive electrode or each negative electrode is enveloped by the coating. The coating may be formed of a nonwoven material, a membrane, a woven fabric, a knitted fabric, an organic material, an inorganic material, or a combination thereof.
Coating the positive electrode results in more uniform ion migration and ion distribution in the rechargeable battery cell. The more uniform the ion distribution, especially in the negative electrode, the higher the possible loading of the negative electrode with active material and consequently the usable capacity of the rechargeable battery cell can be. At the same time, risks that may be associated with uneven loading and resulting deposition of the active metal are avoided. These advantages are particularly effective when the positive electrodes of the rechargeable battery cell are encased in the coating.
Preferably, the areal dimensions of the electrodes and the coating may be matched such that the outer dimensions of the coating of the electrodes and the outer dimensions of the non-clad electrodes match in at least one dimension.
Preferably, the areal extent of the coating may be greater than the areal extent of the electrode. In this case, the coating extends beyond a boundary of the electrode. Two layers of the coating covering the electrode on both sides can therefore be joined together at the edge of the positive electrode by an edge joint.
In a further advantageous embodiment of the rechargeable battery cell according to this disclosure, the negative electrodes have a coating, while the positive electrodes have no coating.
The above-mentioned aspects of exemplary embodiments will become more apparent and will be better understood by reference to the following description of the embodiments taken in conjunction with the accompanying drawings, wherein:
The embodiments described below are not intended to be exhaustive or to limit the invention to the precise forms disclosed in the following detailed description. Rather, the embodiments are chosen and described so that others skilled in the art may appreciate and understand the principles and practices of this disclosure.
In the present embodiment, the electrodes 4, 5 are flat, i.e., as layers with a smaller thickness in relation to their surface area. They are each separated from each other by separators 11. The housing 1 of the rechargeable battery cell 2 is substantially cuboidal in shape, with the electrodes 4, 5 and the walls of the housing 1 shown in sectional view extending perpendicularly to the drawing plane and being substantially straight and planar in shape. However, the rechargeable battery cell 2 may also be formed as a wound cell, in which the electrodes are formed as thin layers wound together with a separator material. The separators 11 separate the positive electrode 4 and the negative electrode 5 spatially and electrically on the one hand and are permeable to the ions of the active metal, among other things, on the other hand. In this way, large electrochemically effective surfaces are created which enable a correspondingly high current yield.
The electrodes 4, 5 further comprise a conductive element which serves to enable the required electronically conductive connection of the active material of the respective electrode. This conductive element is in contact with the active material involved in the electrode reaction of the respective electrode 4, 5 (not shown in
A reference electrolyte used for the examples described below was prepared according to the method described in patent specification EP 2 954 588 B1. 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 in a molar ratio AlCl3:LiCl:Al of 1:1.06:0.35 mixed together in a glass bottle with an opening that allowed gas to escape. Then, this mixture was heat-treated stepwise to produce a molten salt. After cooling, the formed molten salt was filtered, then cooled to room temperature, and finally SO2 was added until the desired molar ratio of SO2 to LiAlCl4 was formed. The reference electrolyte thus formed had the composition LiAlCl4*x SO2, where x is dependent on the amount of SO2 added.
For the experiments described below, two embodiments 1 and 2 of the electrolyte according to this disclosure were prepared (hereinafter referred to as electrolytes 1 and 2).
For this purpose, two different first conducting salts according to formula (I) were first prepared according to a preparation procedure described in the following documents [V3], [V4] and [V5]:
Synth. 1967, 9, 16
The two first conducting salts thus prepared according to formula (I) had the molecular formulae Li2B12Cl12 (compound 1) and Li2B10Cl10 (compound 2).
After the synthesis of the conducting salts, the solution of compounds 1 and 2 in SO2 was carried out to prepare electrolytes 1 and 2. The preparation of the electrolytes was carried out at cryogenic temperature or under pressure according to the following listed process steps 1 to 4:
The respective concentration of compounds 1 and 2 in electrolytes 1 and 2 was 0.25 mol/1 (molar concentration based on 1 liter of the electrolyte) unless otherwise described in the following experimental description. The experiments described below were carried out with electrolytes 1 and 2 and the reference electrolyte.
The test full cells used in the experiments described below were rechargeable battery cells with two negative electrodes and one positive electrode, each of which was separated by a separator. The positive electrodes had an active material, a conductivity mediator, and a binder. The active material is named in the respective experiment. The negative electrodes contained graphite as the active material and also a binder. The test full cells were each filled with the electrolyte required for the experiments, i.e., either the reference electrolyte or electrolytes 1 or 2.
One or more, e.g., two to four identical test full cells, were prepared for each experiment. The results presented in the experiments are, where available, averages of the measured values obtained for the identical test full cells.
A capacity consumed in the first cycle for the formation of a top layer on the negative electrode is an important criterion for the quality of a battery cell. This top layer is formed on the negative electrode during the first charge of the test full cell. For this top layer formation, lithium ions are irreversibly consumed (top layer capacity), so that less cycling capacity is available to the test full cell for the subsequent cycles. The top layer capacity in % of the theory consumed to form the top layer on the negative electrode is calculated according to the following formula:
Top layer capacity [in % of theory]=(Qlad(x mAh)−Qent(y mAh))/QNEL
Qlad describes the amount of charge in mAh specified in the respective experiment; Qent describes the amount of charge in mAh obtained when the test full cell was subsequently discharged. QNEL is the theoretical capacity of the negative electrode used. For example, the theoretical capacity is calculated to be 372 mAh/g in the case of graphite.
For measurements in test full cells, for example, a discharge capacity is determined via the cycle number. For this purpose, the test full cells are charged with a certain charge current up to a certain upper potential. The corresponding upper potential is held until the charge current has dropped to a certain value. Discharge then takes place with a specific discharge rate up to a specific discharge potential. This charging method is referred to as I/U charging. This process is repeated depending on the desired number of cycles.
The upper potentials or the discharge potential and the respective charge or discharge rates are named in the experiments. The value to which the charge current must have dropped is also described in the experiments.
The term “upper potential” is used synonymously with the terms “charge potential,” “charge voltage,” “charge end voltage,” and “upper potential limit.” The terms refer to the voltage or potential to which a test full cell or battery is charged using a battery charging device.
Preferably, the battery is charged at a current rate of C/2 and at a temperature of 22° C. By definition, with a charge or discharge rate of 1 C, the nominal capacity of a test full cell is charged or discharged in one hour. A charge rate of C/2 therefore means a charge time of 2 hours.
The term “discharge potential” is used synonymously with the term “lower cell voltage.” This refers to the voltage or potential up to which a test full cell or battery is discharged using a battery charging device.
Preferably, the battery is discharged at a current rate of C/2 and at a temperature of 22° C.
The discharge capacity is obtained from the discharge current and the time until the criteria for termination of discharge are met. The accompanying figures show average values for the discharge capacities as a function of cycle number. These average values of discharge capacities are often normed to the maximum capacity reached in the particular experiment, each expressed as a percentage of the nominal capacity.
Experiment 1: Examination of the Top Layer Capacity in Test Full Cells with Either Electrolyte 1 or the Reference Electrolyte
In a first experiment, the capacity consumed in the first cycle for the formation of a top layer on the negative electrode was examined. For this purpose, test full cells according to example 3 were filled with either reference electrolyte or electrolyte 1. Electrolyte 1 contained the conducting salt Li2B12Cl12 at a concentration of 0.25 mol/L. The reference electrolyte had the composition LiAlCl4*6 SO2. The active material of the positive electrode both when using the reference electrolyte and when using electrolyte 1 was nickel manganese cobalt oxide (NMC622).
The capacity for the top layer formation is 6.9% of the theoretical capacity of the negative electrode for electrolyte 1, which is slightly lower than for the reference electrolyte, which has a value of 7.1%.
Experiment 2: Examination of the Potential Curve in Test Full Cells with Electrolyte 1 and with Nickel Manganese Cobalt Oxide as the Active Material of the Positive Electrode
The test full cell can be charged to a high upper potential of 4.4 volts and then discharged again. Nickel manganese cobalt oxide is a high-voltage active material and, accordingly, can be cycled well in electrolyte 1. No electrolyte decomposition, even at high potentials, is evident.
Experiment 3: Examination of the Capacity Curve in Test Full Cells with Electrolyte 1 and with Nickel Manganese Cobalt Oxide as the Active Material of the Positive Electrode
The examination of the discharge capacity curve was carried out with the test full cells from experiment 1, which were filled with either reference electrolyte or electrolyte 1.
To determine the discharge capacities (see example 4), the test full cells were charged with a current of 100 mA to an upper potential of 4.4 volts. This was followed by discharging with a current of 100 mA to a discharge potential of 2.5 volts.
Experiment 4: Examination of the Capacity Curve in Test Full Cells with Electrolyte 2 and with Lithium Iron Phosphate as the Active Material of the Positive Electrode
To examine the discharge capacity curve, test full cells were filled with either reference electrolyte or electrolyte 2 as shown in example 3. Electrolyte 2 contained the conducting salt Li2B10Cl10 at a concentration of 0.25 mol/L. The reference electrolyte used had the composition LiAlCl4*6 SO2. The active material of the positive electrode was lithium iron phosphate. To determine the discharge capacities (see example 4), the test full cells were charged with a current of 100 mA to an upper potential of 3.6 volts. This was followed by discharging with a current of 100 mA to a discharge potential of 2.5 volts.
To determine the conductivity, electrolytes 1 and 2 were prepared with different concentrations of the compounds Li2B12Cl12 or Li2B10Cl10. For each concentration of the different compounds, the conductivities of the electrolytes were determined by using a conductive measurement method. In this method, a four-electrode sensor was held in contact with the solution after tempering and measured in a measuring range of 0.02-500 mS/cm.
In comparison, prior art organic electrolytes such as LP30 (1 M LiPF6/EC-DMC (1:1 wt.)) have a conductivity of only about 10 mS/cm.
While exemplary embodiments have been disclosed hereinabove, the present invention is not limited to the disclosed embodiments. Instead, this application is intended to cover any variations, uses, or adaptations of this disclosure using its general principles. Further, this application is intended to cover such departures from the present disclosure as come within known or customary practice in the art to which this invention pertains and which fall within the limits of the appended claims.
| Number | Date | Country | Kind |
|---|---|---|---|
| 20 212 727.0 | Dec 2020 | EP | regional |
This application is a continuation of PCT/EP2021/079062, filed Oct. 20, 2021, which claims priority to EP 20 212 727.0, filed Dec. 9, 2020, the entire disclosures of both of which are hereby incorporated herein by reference.
| Number | Date | Country | |
|---|---|---|---|
| Parent | PCT/EP2021/079062 | Oct 2021 | US |
| Child | 18330904 | US |
