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    • 专利摘要:
    rechargeable lithium battery cell. The present invention relates to a rechargeable lithium battery cell with a box, a positive electrode, a negative electrode and an electrolyte, which contains a conductive salt, the electrolyte being based on SO2 and the positive electrode containing a alkali metal of the composition lixm'ym''z(xo4)afb, wherein m' is at least one metal, selected from the group consisting of the elements ti, v, cr, mn, fe, co, ni, cu and zn, m '' is at least one metal, selected from the group consisting of the metals of groups ii to iii a, iv a, va, via, ib, iib, iiib, ivb, vb, vib and viiib, x is selected from the group consisting of the elements p, si and s, x is greater than 0, y is greater than 0, z is greater than or equal to 0, a is greater than 0, and b is greater than or equal to 0.
    公开号:BR112012020118B1
    申请号:R112012020118-2
    申请日:2011-02-04
    公开日:2021-06-29
    发明作者:Laurent Zinck；Christian Pszolla；Christiane Ripp；Markus Borck；Claudia Wollfahrt
    申请人:Innolith Assets Ag；
    IPC主号:
    专利说明:

    [001] The present invention relates to a rechargeable lithium battery cell with a positive electrode, a negative electrode and an electrolyte, which contains a conductive salt.
    [002] Rechargeable battery cells are of great importance in many technical fields. They are often used for applications where only relatively low current intensities are needed, such as, for example, mobile phones. Furthermore, there is a great need for battery cells for high voltage current applications, where the electrical drive of vehicles is of particular importance. The present invention is especially concerned with cells, which are also suitable for high voltage current applications.
    [003] An important requirement is a high energy density. The cell must contain the maximum amount of electrical energy per unit of weight and volume. In this regard, lithium is particularly advantageous as an active metal.
    [004] Rechargeable cells are, in practice, almost exclusively lithium-ion cells. Its negative electrode consists of coated carbon over copper, in which lithium ions are incorporated when charged. The positive electrode also consists of an insert material, which is suitable for absorbing active metal ions. As a rule, the positive electrode is based on lithium cobalt oxide, which is coated over an aluminum deflector element. Both electrodes are very thin (the thickness, as a rule, is less than 100 µm) . Upon charging, active metal ions are discharged from the positive electrode and inserted into the negative electrode. When downloading, the reverse process takes place. The transport of ions between the electrodes is carried out through the electrolyte, which guarantees the necessary ionic mobility. Lithium ion cells contain an electrolyte, which consists of a lithium salt (eg LiPF6) dissolved in an organic solvent or mixture of solvents (eg based on ethylene carbonate). Hereinafter, they are also referred to as "organic lithium ion cells".
    [005] Problematic are the organic lithium ion cells with respect to safety. Safety risks are especially caused by organic electrolyte. When a lithium-ion cell catches fire or even explodes, the organic solvent in the electrolyte forms the combustible material. To avoid such risks, additional measures must be taken, especially with regard to very exact regulation of the charging and discharging procedures and with regard to additional safety measures in the construction of batteries. For example, the cell contains components, which fuse in the event of an error and flood the battery with molten plastic material. These measures, however, lead to an increase in costs and an increase in volume and weight, thus reducing energy density.
    [006] The problems are particularly serious when battery cells must be developed for high voltage applications. Demands for long-term stability and confidence are, in this case, particularly high. As high voltage cells here are designated cells which (at rated voltage) have a maximum permissible current intensity, in relation to the electrode area (hereinafter "specific maximum permissible current intensity"), of at least 10 mA µg/cm2, preferably at least 50 mA/cm2 and particularly preferably at least 150 mA/cm2.
    [007] There is a great need for improved rechargeable battery cells, which especially fulfill the following requirements: - very good electrical performance data, especially high energy density with simultaneously high withdrawable currents (power density). - Confidence, even in difficult environmental conditions in a vehicle. - Long service life, especially high number of loading and unloading cycles. - The lowest possible price, that is, low cost materials and the simplest production processes. - Other important requirements for practice, such as overload capacity and full discharge capacity.
    [008] The invention is based on the technical problem of making a battery cell available, which fulfills these partly controversial requirements - considered as a whole - better than before.
    [009] The technical problem is solved by a rechargeable electrochemical lithium battery cell with a box, a positive electrode, a negative electrode and an electrolyte, which contains a conductive salt, in which the electrolyte is based on SO2 and the positive electrode contains an active material of the composition LixM'yM''z(XO4)aFb, where M' is at least one metal, selected from the group consisting of the elements Ti, V, Cr, Mn, Fe, Co, Ni, Cu and Zn, M'' is at least one metal, selected from the group consisting of the metals of groups II A, III A, IV A, VA, VI A, IB, IIB, IIIB, IVB, VB, VIB and VIIIB, X is selected from the group consisting of the elements P, Si, and S, x is greater than 0, y is greater than 0, z is greater than or equal to 0, a is greater than 0, and b is greater than or equal to 0.
    [010] Preferably, the active material is a phosphate, the X component, therefore, is phosphorus. Particularly preferably, the metal M' is iron. According to another preferred embodiment, a is 0, the active material therefore does not contain any fluorine.
    [011] "At least one metal" is to be understood, that the components M' and M'' may respectively consist of two or more of the materials mentioned. The suffixes y and z here refer to all metals, which are represented by M' or M''. Of course, one must observe the condition of charge neutrality. The sum of the positive charges of the components Li, M' and M'', therefore, must equal the sum of the negative charges of the components (XO4) and (optionally) F.
    [012] For reasons of simplification, hereinafter, in substitution also to the other compounds that fall under the definition mentioned above and without restriction of generality, reference is made to lithium-iron phosphate and, for this, the abbreviation "LEP" is used .
    [013] As "SO2 based electrolyte" (SO2 based electrolyte) is meant in the context of the invention an electrolyte, which does not contain SO2 only as an additive in low concentration, but in which the mobility of the conducting salt ions, which is contained in the electrolyte and carries the charge, is at least partially guaranteed by SO2. Preferably, the electrolyte is substantially free of organic materials, whereby "substantially" is understood to mean that the amount of organic materials optionally present is so low that they pose no safety risk. Lithium cells with an SO2-based electrolyte are referred to in the following as Li-SO2 cells.
    [014] For a long time now, SO2-based electrolytes for lithium cells have been discussed. In (1) "Handbook of Batteries", David Linden (editor), 2nd edition, McGraw-Hill, 1994 reference is made especially to the high ionic conductivity of an inorganic electrolyte based on SO2. This electrolyte would also be advantageous with respect to other electrical data. Therefore, systems with an SO2-based electrolyte would have been researched for a longer period and would still be of interest for special applications. The other commercial applicability would, however, be limited, especially as the electrolyte is toxic and strongly corrosive.
    [015] Battery cells with SO2 electrolytes are described, for example, in the following documents: (2) US patent 5,213,914 (3) WO 00/44061 and US patent 6,709,789 (4) WO 00/ 79631 and US patent 6,730,441 (5) WO 2005/031908 and US 2007/0065714 (6) L. Zinck et al., "Purification process for an inorganic rechargeable lithium battery and new safety concepts", J. Appl. Electrochem., 2006, 1291-1295 (7) WO 2008/058685 and US patent application 2010/0062341 (8) WO 2009/007140
    [016] In the examples of execution of these documents, positive electrodes based on a lithium metal oxide are always used, especially based on lithium cobalt oxide.
    [017] Lithium metal phosphates have also long been known for lithium ion cells with organic electrolytes. Regarding previous experimental research, it is reported in (9) North American patent 5,910,382 (10) Padhi et al., "Phospho-olivines as Positive-Electrode Materials for Rechargeable Lithium Batteries", J. Electrochem. soc. 1997, 1188-1194
    [018] In (9) and (10) cathode materials for lithium cells, which contain the polyanion (PO4)3-, are investigated. The research refers to compounds with the metals Mn, Fe, Co and Ni, which are present in two different structures, namely, the olivine structure and the NASICON structure. We describe the influence of structures on lithium storage and report on tests with battery cells, with which a large number of charge cycles (maximum 25 cycles) were performed.
    [019] In (9) and (10) reference is also made to the problems, which are associated with the use of LEP electrodes in lithium ion cells. On the other hand, for an electrical charge with a very small specific surface of 0.05 mA/cm2 a cell voltage of only 3.5 V is indicated. In comparison, the cell voltage with a lithium-cobalt oxide electrode would be 4 V, therefore, about 14% higher. Also, the electrical conductivity of LEP is very poor. This leads to a strong decrease in cell voltage already at relatively low current loads. Cell capacity is also heavily dependent on electrical charge and already drops with a specific surface electrical charge of less than 0.2 mA/cm2 for values, which render the cell considerably useless.
    [020] According to (11) US patent 7,338,734, these problems must be solved in a lithium ion cell with organic electrolyte due to the fact that the specific surface of the active material of the positive electrode is increased (in others words, the material consists of very small particles) and instead of a pure lithium-iron phosphate, a material is used, which is endowed with one of the elements of groups II A, III A, IV A, VA, VI A and III B of the periodic system, especially niobium.
    [021] This, compared to the above known organic lithium ion cells with a positive LEP electrode, substantially improved electrical data is obtained. However, the production of cells is very expensive, especially due to the necessary doping of the LEP material, due to the production of very thin LEP fractions, due to the casting of thin electrode layers (in film form) and due to the assembly of the cells with the thin electrode layers.
    [022] In the context of the present invention, it has surprisingly been found that very good electrical power data, also for high voltage applications, can be obtained quite simply, when a positive LEP electrode is used in a Li cell -SO2. In this case, it is possible to use lithium-iron phosphate also without doping and nevertheless guarantee a high maximum permissible current intensity. It is also not necessary to use an extremely fine-grained LEP. In the context of the invention, an LEP is advantageously used with a specific surface, measured according to the Brunauer-Emmett-Teller (BET) method, of a maximum of 40 m2/g, and materials with no. maximum 30 m2/g and even materials with a maximum of 15 m2/g. The preferred average particle size amounts to at least 0.2 µm, whereby materials with an average particle size of at least 0.5 µm, at least 1 µm or even at least 2 µm can advantageously also be used.
    [023] The positive electrode according to the invention is preferably porous. Preferably, however, the porosity should not be too high. Therefore, the following maximum porosity values in that order are particularly preferred: 50%, 45%, 40%, 35%, 30%, 25%, 20%.
    [024] The pores of the positive electrode in operation are preferably completely filled with electrolyte. Suitable conducting salts of the electrolyte are in particular aluminates, halides, oxalates, borates, phosphates, arsenates and gallates of an alkali metal or alkaline earth metal. In the context of the invention, a lithium tetrahaloaluminate, particularly preferably a lithium tetrachloroaluminate, is preferably used.
    [025] The electrolyte preferably contains at least 2.0 moles of SO2 per mole of conductive salt, with the following values in that order being more preferred: at least 2.5 moles of SO2 per mole of conductive salt, at least 3, 0 moles SO2 per mole of conductive salt, at least 4.0 moles of SO2 per mole of conductive salt. In the context of the invention, it has surprisingly been found that an electrolyte with a relatively low concentration of conductive salt, despite the higher vapor pressure associated with it, is advantageous, especially with respect to stability over many cycles.
    [026] Particular advantages have a cell according to the invention, if the thickness of the positive electrode matters at least 0.25 mm, preferably at least 0.3 mm, more preferably at least 0.4 mm, so even more Preferred is at least 0.5 mm and particularly preferably at least 0.6 mm. In this case, the amount of active material, relative to the surface of the positive electrode ("charge"), must be high. Preferably, this amounts to at least 30 mg/cm3, and the following values in that order are even more preferred: 40 mg/cm2, 60 mg/cm2, 80 mg/cm2, 100 mg/cm2. 120 mg/cm2 and 140 mg/cm2.
    [027] Essential advantages are associated with the large thickness of the positive electrode and the correspondingly high charge with active material. Especially the capacity, in relation to the surface of the positive electrode ("surface specific capacity"), is very high. The theoretical capacity of LEP amounts to 169 mAh/g. In the experimental test of the invention, it was verified that this theoretical value in a Li-SO2 cell is obtained with a very good feed (more than 90%). The specific surface capacity of the positive electrode is preferably at least 5 mAh/cm2, with the following minimum values in that order being even more preferred: 7.5 mAh/cm2, 10 mAh/cm2, 12.5 mAh/cm2, 15 mAh/cm2, 20 mAh/cm2, 25 mAh/cm2.
    [028] In the context of the invention, it was found that through the combination of an LEP electrode and an SO2-based electrolyte, an electrochemical battery cell can be produced which, with respect to the totality of the initially mentioned requirements, is substantially improved, as it is especially suitable for electromobility applications (eg battery-powered and hybrid cars): - the high charge of the positive electrode and the associated high specific surface capacity make it possible to produce cells, which with high total capacity, have a surface of the electrode relatively small. The load can clearly exceed the minimum values mentioned above and reach more than 100 mg/cm2. For a capacity of 1 A-h, then, only a surface of 60 cm2 is needed. The electrode surface required is smaller by a factor of 3 than the conventional LEP electrodes described for organic lithium ion cells, which have a thickness of 50 to 90 µm and a surface charge of 4 to 6 mAh/cm2 and, therefore, to provide a capacity of 1 Ah, they need a total electrode surface of 170 to 250 cm2. Due to the smaller surface of the positive electrode, less separator and negative electrode surface is also required. In addition, for example, in prismatic cells with several electrodes, a smaller number of discharge conductor panels is needed for the connection with the cell poles and the connection of the electrodes in the box is substantially simpler with a small number of electrodes . - The maximum allowable current intensity is too high. Positive electrodes according to the invention can provide, for example, a specific surface electrical charge of 300 mA/cm2. - The theoretical capacity of the positive electrode is practically useful at least 90%. Therefore, the lithium ions, on charging, can be almost completely removed from the positive electrode and on discharge, again stored in the positive electrode. Also with respect to the capacity dependence of the maximum permissible current intensity, good values are obtained according to the invention. In other words, in the case of a high electrical charge there is still a large part of the original capacity of the cells available. Altogether - during the useful life of the cell - the practically useful capacity of the cell according to the invention is greater than with a lithium-cobalt oxide electrode, although the theoretical capacity of LEP, in comparison with lithium oxide- cobalt matters at only 60%. - The high number of charge and discharge cycles required for electromobility applications is possible. In the experimental text, more than 9000 complete cycles were obtained. - It is not necessary to regenerate the electrolyte due to cell overload, as described, for example, in document (8). As a result, the colorimetric effectiveness increases. However, the cell according to the invention is superchargeable, should this be necessary in a specific application case. - The spontaneous discharge of the cell according to the invention is extraordinarily low. Therefore, it can be stored in the charged state for a long time and immediately used without recharging. Furthermore, the safety risk associated with a spontaneous discharge, for example, described in (2), is exempted from a "thermal runaway". - The stability of a negative carbon electrode, as preferably used in the context of the invention, is substantially improved. The negative electrode can be produced even without bonding agent. - It is not necessary to use in the active material of the positive electrode a relatively high fraction of carbon-based conductivity improver as described in documents (9), (10) and (11). On the contrary, relatively low amounts of conductivity improver are sufficient. Preferably, the carbon content of the positive electrode amounts to less than 10% by weight, with the following maximum values in that order being more preferred: 7% by weight, 5% by weight, 2% by weight. - The adhesive fraction can also be very low. Preferably, the positive electrode contains at most 10% adhesive, with the following values in that order being more preferred: 7% by weight, 5% by weight, 2% by weight.
    [029] Based on the information present before the invention, it was not possible to expect that a Li-SO2 cell with LEP as active material of the positive electrode would be able to work and even be particularly advantageous.
    [030] - As mentioned, the cell voltage of a lithium ion cell with LEP is almost 15% below the cell voltage of a lithium ion cell with lithium cobalt oxide. As a result, a corresponding worsening in energy density was expected.
    [031] - In documents published so far for Li-SO2 cells, a positive electrode based on an oxide was always shown, especially of lithium cobalt oxide, as an ideal combination with the SO2 electrolyte. To improve the properties of the electrode, an activating purification was recommended in (5).
    [032] - The electrodes are in contact with the electrolyte in the cell and therefore, primarily, they can only react with it. Therefore, the electrolyte is decisive for possible reactions of the materials contained in the electrodes. A problematic characteristic of an SO2-based electrolyte, as already shown in document (1), is its high corrosion. From the chemical behavior of LEP in an organic electrolyte, nothing can be deviated from the resistance in a fundamentally different inorganic electrolyte based on SO2. Since lithium cobalt oxide was proven in a Li-SO2 cell, alternatives were sought, at best, in chemically related oxidic compounds.
    [033] - The most important advantage of an SO2-based electrolyte was considered its good conductivity. On the other hand, it is known that LEP is a very poor conductive electrode material. On that basis, it did not seem logical, in developing a battery cell also suitable for high voltage applications, to combine the advantageous electrolyte with respect to the internal resistance of the cell with an electrode material visibly disadvantageous in that respect.
    [034] - In document (1), it is pointed out that the selection of positive electrode materials for a Li-SO2 cell is restricted to those compounds, which are reduced in potentials above the reduction potential of SO2.Since the reduction potential of LEP at 2.9 Volt is considerably lower than that of lithium-cobalt oxide (3.5 Volt), only a narrow voltage range remains, within which the cell must be loaded and unloaded as completely as possible. In the LEP test in an organic cell according to document (9) and (10), only about 60% of the lithium in the LEP was extracted, although it was charged and discharged with an extremely low surface specific electrical charge of 50 μA /cm2.
    [035] Both the positive electrode based on LEP, as well as the negative electrode based on carbon are intercalating electrodes, which absorb the active metal lithium in the charge or discharge in its grid structure. In these intercalation electrodes and generally also in other insertion electrodes suitable for the absorption of lithium in their interior, refers to a preferred embodiment of the invention, according to which in battery cells, whose electrolyte is based on SO2, at least one of the electrodes is an insert electrode suitable for the absorption of lithium ions, which is pretreated to reduce the covering layer. Such an embodiment is advantageous for the rechargeable lithium battery cell with a positive LEP electrode explained above, but it is also, in addition, of importance for all insert electrodes in an SO2-based electrolyte.
    [036] The pretreatment to reduce the covering layer refers to the formation of covering layers on the surface of insertion electrodes, which form in the first charge cycles. The formation of the covering layer not only uses up charging current, but also leads to an irreversible drain on the active components of the battery system and, therefore, to a decrease in capacity during the additional useful life of the battery. By means of the cover layer thinning pretreatment, the capacity loss associated with the formation of the cover layer is reduced.
    [037] Below, the invention is illustrated in detail based on the figures. The features shown and described can be used individually or in combination to produce preferred embodiments of the invention. They show: figure 1 a cross-sectional representation of a battery cell according to the invention; 2 is a cross-sectional representation of a metallic foam suitable for the invention; Figure 3 is a cross-sectional representation of a positive electrode; figure 4 the dependence of the charge capacity on the number of cycles in a test performed with a positive electrode; Figure 5 the dependence of the discharge capacity on the discharge rate in a test performed with a positive electrode compared to published results; figure 6 the dependence of the electrical resistance of an electrode on the number of cycles in a test performed with a positive electrode; figure 7 the capacity dependence of the number of cycles in a test performed with two different positive electrodes; figure 8 the capacity dependence of the number of cycles in another test performed with two different positive electrodes; figure 9 the dependence of the discharge capacity on the number of cycles in a test carried out with two different cells; figure 10 the dependence of the capacity on the number of cycles in a long-term trial; figure 11 the dependence of the electrical voltage on the charge capacity for three negative electrodes previously treated in a different way.
    [038] The case 1 of the rechargeable battery cell 2 shown in figure 1 involves an electrode arrangement 3, which includes several positive electrodes 4 (in the case shown, three) and several negative electrodes 5 (in the case shown, four). Electrodes 4, 5 are, as usual, connected via electrode connections 6, 7 with corresponding connection contacts 9, 10 of the battery. The cell is filled with an SO2-based electrolyte not shown in the figures in such a way that it penetrates as completely as possible into all pores, especially inside electrodes 4, 5.
    [039] The electrodes 4, 5 are structured flat in the usual way, that is, as layers with a small thickness in relation to their area expansion. They are respectively separated from each other by spacers 11. The box 1 of the prismatic cell shown is substantially cuboid, the electrodes and walls shown in the cross section of Figure 1 extending vertically to the plane of the drawing and running substantially straight and flat. . The cell according to the invention, however, can also be structured as a winder cell.
    [040] The electrodes 4, 5 present, as usual, a deflection element, which consists of metal and serves to allow the necessary electronically conductive connection of the active material of the respective electrode. The deviation element is in contact with the active material participating in the reaction of the electron of the respective electrode. Preferably, the positive electrode deflection element, particularly preferably also the negative electrode deflection element, is structured in the form of a three-dimensional porous metal structure, especially in the form of a metal foam. The term "three-dimensional porous metal structure" in this case designates each structure consisting of metal, which extends not only, such as a thin sheet, along the length and width of the flat electrode, but also along its thickness dimension, which is so porous, that the active material of the electrode can be incorporated into the pores.
    [041] Figure 2 shows an electron micrograph of a cross-sectional surface of a metallic structure suitable for the invention. Based on the scale indicated, it is recognized that pores P have a diameter of more than 100 µm in the centre, ie they are relatively large. Instead of metallic foam, another three-dimensional metallic structure can also be used, for example in the form of a metallic nonwoven or metallic fabric.
    [042] In the production of electrodes, the LEP material is so incorporated into the porous structure of the deflection element, that this fills its pores evenly throughout the thickness of the metallic structure. The material is then pressed under high pressure, the thickness after the pressing process being preferably at most 50%, particularly preferably at most 40%, of the exit thickness.
    [043] The structure of the resulting electrode in this case can be recognized in Figure 3, again in the form of an electron micrograph. To prevent the structural features from being falsified by a cutting procedure, the electrode material was cooled in liquid nitrogen and then broken down. Despite certain damage to the material caused by the rupture process, the essential characteristics of the structure of a positive electrode according to the invention can be well recognized in figure 3.
    [044] Compared to LEP electrodes, the electrode is very thick. In the case shown, the thickness d is about 0.6 mm. The three-dimensional porous metal structure 13 of the deflector element extends substantially throughout the thickness d of the deflector element and the active LEP material 15 is substantially evenly distributed therein. "Substantially" with respect to the two conditions mentioned is to be understood in the sense that cellular function is only negligibly impaired by eventual deviations. In any case, the porous metal structure extends over at least 70%, preferably at least about 80%, of the electrode thickness.
    [045] To improve mechanical stability, the positive electrode contains an adhesive. In the context of the invention, fluorinated adhesives have been proven, especially THV (tetrafluoroethylene, hexafluoropropylene and vinylidene fluoride terpolymer) and PVDF (polyvinylidene fluoride). Advantageously, it is sufficient for the adhesive to be contained in a relatively low concentration in the electrode.
    [046] The negative electrode contains as active material preferably carbon in a form suitable as an insert material for the absorption of lithium ions. The structure is preferably similar to the positive electrode with the following characteristics: - in the negative electrode, the deflection element also preferably has a three-dimensional porous metallic structure, especially in the form of a metallic foam. - This is relatively thick, its thickness being at least 0.2 mm and the following values in that order are more preferred: 0.3 mm, 0.4 mm, 0.5 mm, 0.6 mm. - The amount of active material of the negative electrode, in relation to its surface, is at least 10 mg/cm2, with the following values in that order being more preferred: 20 mg/cm2, 40 mg/cm2, 60 mg/cm2 , 80 mg/cm2, 100 mg/cm2. - The surface specific capacity preferably matters in at least 2.5 mAh/cm2, with the following values in that order being more preferred: 5 mAh/cm2, 10 mAh/cm2, 15 mAh/cm2, 20 mAh/cm2, 25 mAh /cm2, 30 mAh/cm2. - This is preferably porous, and its porosity matters at most 50% and the following values in that order are more preferred: 45%, 40%, 35%, 30%. The proportion of adhesive amounts to at most 5% by weight, more preferably at most 3% by weight and particularly preferably at most 1% by weight. Most particularly preferred is a negative electrode, which does not contain any adhesive.
    [047] Further information about the invention and its preferred embodiments result from the tests described below. Test 1:
    [048] From the following components 94% by weight of lithium iron phosphate not provided with a carbon surface coating; average particle size is approximately 2 - 3 µm 2% by weight, carbon black as conductivity promoter 4% by weight, THV as binding agent A slurry was prepared, the binding agent being initially dissolved in acetone, then carbon black was added to the solution under stirring and finally the active mass, in exchange for another solvent, was also added under stirring.
    [049] The paste was homogeneously introduced into a metallic foam with a starting porosity of more than 90% and dried for one hour at 50°C. After cooling, the electrode material was compressed by means of a calender from a starting thickness of 1.6 mm to a thickness of 0.6 mm. Afterwards, this was subjected to a heating process at 180°C. The resulting electrode material had a cross-section corresponding to figure 3.
    [050] Large pieces of 1 cm2 were cut out of the electrode material. They had a capacity of about 13 mAh. They were examined in an E-cell with a three-electrode arrangement, in which the reference electrode and the counter-electrode consisted of metallic lithium. The electrolyte used in cell E had the composition LiAlCl4 * 1.5 SO2.
    [051] To determine the discharge capacities of electrodes with different electrical charges, 40 charge and discharge cycles were performed in cells E, and the charge was carried out in each case with the same charge rate of 1 C ("C" " indicates how many times the rated capacity is charged or discharged within one hour). After each loading procedure, it was unloaded, and cells in 40 cycles were unloaded at the following rates: 10 cycles 1 C each 4 cycles 2 C, 4 C, 8 C, 10 C, 15 C 10 cycles 1 C.
    [052] Charging was carried out to a voltage of 3.7 V. Discharging was completed with a voltage of 3.2 V.
    [053] Figure 4 shows as mean values during eight tests, the dependence of the QD discharge capacity in mAh/g on the cycle number. It can be seen that also at very high discharge rates, a large part of the nominal capacity is available. When, for example, the cell is discharged so fast that it is zeroed in six minutes (10 C), two thirds of the nominal capacity can still be withdrawn.
    [054] Figure 5 shows the results presented in Figure 4 as a dependence of the discharge capacity QD on the discharge rate C (curve A). Curve B shows values from the publication (12) W. Porcher et al, "Design of Aqueous Processed Thick LiFePO4 Composite Electrodes for High-Energy Lithium Battery, J. Electrochem. Soc. 2009, A133 - A144.
    [055] This publication describes the production of relatively thick electrodes for lithium ion cells, where a thickness of 0.2 mm is already considered as thick (compared to what has been commonly used). They are produced with a water-soluble binding agent in aqueous suspension. The surface specific capacity ("capacity density") obtained in this case is indicated as 3 mAh/cm2 with a load of 20 mg/cm2 and an electrode thickness of 200 μm. The measurement data recorded in figure 5 were read from figure 1 on page A135 of the publication for your best material ("CMC"). It is recognized that the capacity decreases much faster than in the electrode according to the invention with the rate of discharge. For example, for a discharge rate of 10 C, the positive electrode described in the publication for a lithium ion cell has a discharge capacity of 18 mAh/g compared to 100 mAh/g in the present invention. The comparison is summarized in the following table 1:

    [056] In figure 6, the resistance R values of the electrode are represented as a function of the number of cycles, which were measured in cells E after charging. Despite the very high discharge rates, the electrode resistance remains largely stable and is in the range of 0.6 to 0.8 Ohm. Test 2:
    [057] For this test, a subC-type coil cell was produced, whose electrodes have a capacity of 17 mAh/cm2 (positive electrode with LEP mass as in test 1).
    [058] The electrodes were wound together with a separator interposed between them to form a coil and introduced into the SubC box. Then, it was filled with an electrolyte solution of the composition LiAlCl4.6SO2.
    [059] The cell was charged at a charge rate of 0.7 C with 831 mA-h. The discharge current imported at 10 A, which corresponds to a discharge rate of 7 C. The discharge was interrupted with a cell voltage of 2 Volt and a draw capacity of 728 mAh. This corresponds to 88% of the loaded capacity. The high current carrying capacity could therefore be justified. Test 3:
    [060] With a positive electrode according to the invention and a positive electrode analogous to the other characteristics, which contained lithium-cobalt oxide as active material, the dependence of the capacity on the number of charge and discharge cycles (in each case with1 C) in a cell E.
    [061] Figure 7 shows the resulting products in this case with the use of an SO2 electrolyte, which contained 1.5 mol of SO2 per mol of conductive salt (lithium tetrachloroaluminate). The discharge capacity QD is applied in percent of the theoretical value of the number of charge and discharge cycles performed, with curve A referring to the LEP electrode and curve B to the lithium-cobalt oxide electrode. It is recognized that with the LEP electrode almost all the theoretical capacity can be practically used, whereas with the comparative electrode, in practice, on average only about 60% of the theoretical capacity is available. Thus, the higher theoretical capacity of lithium cobalt oxide (273 mAh/g) is practically balanced compared to LEP (170 mAh/g).
    [062] Figure 8 shows the results of a test, which differs from the test that serves as the basis for Figure 7 only with respect to the concentration of conductive salt in the electrolyte. In this case, it imported 4.5 moles of SO2 per mole of LiAlCl4. It is recognized that the LEP electrode also in the electrolyte containing a lower concentration of conductive salt behaves very well (curve A), whereas for the lithium-cobalt oxide electrode the capacity drops rapidly to unacceptably low values ( curve B). Test 4:
    [063] Figure 9 shows the results of an assay, in which the function of a complete cell with a negative carbon electrode, an SO2 electrolyte and a positive electrode according to the invention with a capacity of 19 mAh/cm2 ( curve A) was compared with an analogous cell in the remaining values, however, with a positive electrode based on lithium cobalt oxide (curve B). In this case, the electrolyte contained 6 moles of SO2 per mole of LiAlCl4.
    [064] The QD discharge capacity is applied as a percent of the nominal value as a function of the number of cycles. After an initial reduction, the available capacity in the cell according to the invention is almost constant, whereas in the comparative cell it rapidly decreases to unacceptably low values. This confirms the superiority of the cell according to the invention, especially in combination with an electrolyte, which contains a relatively high fraction of SO2.
    [065] Altogether, in the context of the invention it was found that it is advantageous to employ an electrolyte with a relatively low content of conductive salt, in relation to the amount of SO2. This is in contrast to the recommendations preponderantly contained so far in publications on lithium-SO2 cells, especially with respect to the vapor pressure of an electrolyte with a relatively low SO2 fraction.
    [066] Alternatively or in addition to the high fraction of SO2, the stability of the invention to capacity can be improved by the fact that it contains a lithium halide, preferably a lithium chloride, this salt according to another form of preferred embodiment, is especially contained with mixing in the active mass of the positive electrode.
    [067] Figure 10 shows the results of a long-term test with a cell, as in figure 9, curve A, in which again the available QD capacity was applied as a function of the number of cycles. The figure shows around 9700 cycles, where the available capacity reduction for every 100 cycles is remarkably low at less than 0.4%.
    [068] Reducing pre-treatment of the cover layer: As shown above, an improvement in the stability to capacity of lithium-SO2 cells with at least one insert electrode, especially intercalation electrode, can be obtained by a pre-treatment reducer of the covering layer of at least one insertion electrode. For this, there are several possibilities.
    [069] A first possibility is to submit the insertion electrode to a temperature treatment. This applies especially for carbon electrodes, which are tempered to a temperature of at least 900°C under oxygen exclusion (preferably under protective gas) for a prolonged period (at least 10, preferably at least 20 and particularly preferably at least 40 hours).
    [070] Alternatively or additionally, the formation of the covering layer can be reduced in a negative carbon electrode by using a graphite material with relatively low specific surface.
    [071] According to another preferred embodiment, the reducing pre-treatment of the covering layer is carried out by the fact that the corresponding electrode is provided with a thin surface coating.
    [072] Such a surface coating can be specially performed by means of atomic layer deposition (Atomic Layer Deposition). This process is recently applied for numerous purposes. A synopsis is given, for example, by the publication (13) S.M. George "Atomic Layer Deposition: An Oberview", Chem. Rev. 2010, 111-131.
    [073] In this case, the process parameters can be adjusted to the needs of the electrode. In the context of the invention, it was found that particular advantages are obtained when the carbon electrode is pretreated by means of NO2-TMA (ok - nitric oxide-trimethylaluminum). With this, a first functional layer is applied on the carbon, which is advantageous for the subsequent treatment of ALD. For this, complementary reference can be made to (14) G.M. Sundaram et al, "Leading Edge Atomic Layer Deposition Applications", ECS Transactions, 2008, 1927.
    [074] Preferably, by means of ALD a thin layer of Al2O3 is applied. According to current knowledge, the application of SiO2 is also possible.
    [075] Another possibility of applying a suitable surface coating for the reduction of the covering layer is the Dip coating. For this, either the active insert material provided for processing in the electrode or the entire electrode is brought into contact with a reaction solution, which contains starting materials for forming a suitable layer. Then, a temperature treatment is carried out to form and fix the layer. For example, it is possible to process as follows: isopropanol, water, 1 molar hydrochloric acid and tetraethyl orthosilicate are mixed in a molar ratio of 3:1:1:1. The solution is kept at room temperature. It is then diluted with isopropanol in a volume ratio of 1:1. The electrodes to be treated are immersed in the reaction solution for 30 seconds or, if bubbles are observed, until they diminish. They are then dried for 48 hours in a drying oven at 200°C without vacuum.
    [076] Figure 11 shows the results of a test with the following electrode materials: A negative electrode without pre-treatment reducing the covering layer B negative electrode, in which the active material, before being introduced into the electrode, was pre -treated by dip-coating with formation of a layer of SiO2 C negative electrode, which was pretreated as a whole by means of Dip coating with formation of a layer of SiO2.
    [077] The three experimental electrodes were examined by means of an E cell, and when charging the electrode, the course of the voltage U in Volt was applied against lithium through the charge state Q in relation to the nominal capacity QN. The three groups of curves presented show the results in each case of several tests with the electrodes described above. In Figure 11, the surface under the curve corresponds to the cell capacity lost due to the formation of the covering layer. It is recognized that the loss of capacity in the two pre-treated electrodes is substantially less than in the untreated electrode, and between the two pre-treated electrodes, the pre-treated electrode in its entirety is a little better.
    权利要求:
    Claims (21)
    [0001]
    1. Rechargeable lithium battery cell, which has a box, a positive electrode, a negative electrode and an electrolyte that contains a conductive salt, characterized in that the electrolyte is based on SO2 and the electrolyte contains at least 2 moles of SO2 per mol of conductive salt, the positive electrode contains an active material having the composition LiFePO4.
    [0002]
    2. Rechargeable lithium battery cell, according to claim 1, characterized in that the positive electrode has a thickness of at least 0.25 mm.
    [0003]
    3. Rechargeable lithium battery cell, according to any one of claims 1 or 2, characterized by the positive electrode in relation to its surface, containing an amount per unit of at least 30 mg/cm2 of active material.
    [0004]
    4. Rechargeable lithium battery cell, according to any one of claims 1 to 3, characterized in that the positive electrode is porous.
    [0005]
    5. Rechargeable lithium battery cell, according to any one of claims 1 to 4, characterized in that the positive electrode has a deflection element with a three-dimensional porous metallic structure.
    [0006]
    6. Rechargeable lithium battery cell, according to claim 5, characterized in that the porous metal structure extends substantially over the entire thickness of the positive electrode.
    [0007]
    7. Rechargeable lithium battery cell, according to any one of claims 5 or 6, characterized in that the active material is substantially homogeneously distributed in the positive metallic structure.
    [0008]
    8. Rechargeable lithium battery cell according to any one of claims 1 to 7, characterized in that the negative electrode has a thickness of at least 0.2 mm.
    [0009]
    9. Rechargeable lithium battery cell, according to any one of claims 1 to 8, characterized in that the positive electrode contains an adhesive.
    [0010]
    10. Rechargeable lithium battery cell, according to any one of claims 1 to 9, characterized in that the negative electrode contains carbon for the absorption of lithium ions.
    [0011]
    11. Rechargeable lithium battery cell, according to any one of claims 1 to 10, characterized in that the amount of active material of the negative electrode, in relation to its surface, amounts to at least 10 mg/cm2 per unit.
    [0012]
    12. Rechargeable lithium battery cell according to any one of claims 1 to 11, characterized in that the negative electrode is porous.
    [0013]
    13. Rechargeable lithium battery cell according to any one of claims 1 to 12, characterized in that the negative electrode contains an adhesive.
    [0014]
    Rechargeable lithium battery cell according to any one of claims 1 to 13, characterized in that the electrolyte contains at least 2.5 moles of SO2.
    [0015]
    15. Rechargeable lithium battery cell, according to any one of claims 1 to 14, characterized in that the electrolyte contains as conductive salt a halide, oxalate, borate, phosphate, arsenate or gallate.
    [0016]
    16. Rechargeable lithium battery cell according to any one of claims 1 to 15, characterized in that the cell has a maximum permissible current intensity, in relation to the surface of the positive electrode, of at least 10 mA/cm2.
    [0017]
    Rechargeable lithium battery cell according to any one of claims 1 to 16, characterized in that it contains a lithium halide.
    [0018]
    18. Rechargeable lithium battery cell, which contains a box, a positive electrode, a negative electrode and an electrolyte that contains a conductive salt, according to any one of claims 1 to 17, characterized in that the electrolyte is based on SO2 and at least one of the electrodes is an insertion electrode suitable for insertion of lithium ions, which is pretreated to reduce the covering layers.
    [0019]
    19. Rechargeable lithium battery cell according to claim 18, characterized in that at least one electrode is pretreated to reduce the covering layers by a surface coating of the active material.
    [0020]
    20. Rechargeable lithium battery cell, according to claim 19, characterized in that the surface coating is applied by means of atomic layer deposition (ALD) or dip coating and the surface coating contains Al2O3 or SiO2.
    [0021]
    21. Process for the production of an electrode for a rechargeable lithium battery cell, as defined in any one of claims 1 to 20, characterized by the following steps: - production of a pasty mass of active material with optional addition of an adhesive and /or a conductivity improving material; - homogeneous incorporation of the pasty mass into the three-dimensional porous metallic structure; - pressing of the three-dimensional metallic structure containing the porous mass in such a way that its thickness is reduced.
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    同族专利:
    公开号 | 公开日
    EP3611788A1|2020-02-19|
    EP3208869B1|2019-10-09|
    AU2011214615B2|2015-05-21|
    ES2536892T3|2015-05-29|
    PL2534719T3|2017-05-31|
    KR101909084B1|2018-10-17|
    JP5901539B2|2016-04-13|
    CN102742062A|2012-10-17|
    US10892487B2|2021-01-12|
    CN102742049A|2012-10-17|
    US20140113182A1|2014-04-24|
    CA2787918C|2019-08-27|
    WO2011098233A3|2011-10-27|
    EP2534725A1|2012-12-19|
    KR102043247B1|2019-11-11|
    MX2012008872A|2012-08-31|
    DK2534719T3|2017-05-01|
    EP3611788B1|2021-05-12|
    IL221368D0|2012-10-31|
    US20110287304A1|2011-11-24|
    EP2534719B1|2017-01-25|
    CN102742049B|2015-11-25|
    MX349280B|2017-07-20|
    HUE047163T2|2020-04-28|
    KR20130006614A|2013-01-17|
    PL3208869T3|2020-05-18|
    KR20120129960A|2012-11-28|
    WO2011098233A9|2012-06-07|
    EP3208869A1|2017-08-23|
    RU2560717C2|2015-08-20|
    RU2012136194A|2014-02-27|
    HUE055534T2|2021-12-28|
    CN102742062B|2015-09-16|
    DK3208869T3|2020-01-20|
    EP2534725B1|2015-04-08|
    WO2011098233A2|2011-08-18|
    WO2011098232A1|2011-08-18|
    JP2013519968A|2013-05-30|
    BR112012020118A2|2016-06-07|
    EP2360772A1|2011-08-24|
    RU2569328C2|2015-11-20|
    IL221368A|2016-09-29|
    KR102128405B1|2020-07-01|
    ES2764205T3|2020-06-02|
    KR20180114256A|2018-10-17|
    RU2012137863A|2014-03-20|
    AU2011214615A1|2012-08-02|
    ES2617354T3|2017-06-16|
    HK1173854A1|2013-05-24|
    CA2787918A1|2011-08-18|
    US20120308876A1|2012-12-06|
    HK1173267A1|2013-05-10|
    EP2534719A2|2012-12-19|
    ZA201206696B|2013-05-29|
    JP2013519967A|2013-05-30|
    US9263745B2|2016-02-16|
    JP6083078B2|2017-02-22|
    PL3611788T3|2021-11-02|
    ES2880692T3|2021-11-25|
    KR20190128089A|2019-11-14|
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    法律状态:
    2018-01-02| B25A| Requested transfer of rights approved|Owner name: ALEVO RESEARCH AG (CH) |
    2018-01-23| B25A| Requested transfer of rights approved|Owner name: ALEVO INTERNATIONAL S.A. (CH) |
    2018-04-10| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
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    优先权:
    申请号 | 申请日 | 专利标题
    EP10001458.8|2010-02-12|
    EP10001458A|EP2360772A1|2010-02-12|2010-02-12|Rechargeable and electrochemical cell|
    PCT/EP2011/000507|WO2011098233A2|2010-02-12|2011-02-04|Rechargeable electrochemical cell|
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