Sulfide-based solid electrolyte with a glass-ceramic structure, its production and use, and a solid-state battery cell containing this

Abstract

The invention relates to a sulfide-based solid electrolyte with a glass-ceramic structure, comprising or consisting of the general chemical formula (I): Li7P2S8X1xX2yX3z, formula (I), wherein X1, X2, and X3 are each independently selected from the group consisting of Cl, Br, and I; where: x > 0, y > 0, and z ≥ 0, and 1 < x + y + z ≤ 1.7; with the proviso that for z > 0, X1 ≠ X2 ≠ X3 and X1 ≠ X3, and for z = 0, X1 ≠ X2. The sulfide-based solid electrolyte with a glass-ceramic structure is characterized by a similarly high electrochemical performance, such as high ionic conductivity and (electro)chemical stability, compared to similar crystalline sulfide-based solid electrolytes (LGPS, argyrodite).However, the inventive sulfide-based solid electrolyte with a glass-ceramic structure can be produced at lower sintering temperatures and in a shorter time than the known crystalline sulfide-based solid electrolytes, which significantly reduces the time, energy and cost expenditure.

Description

The invention relates to a sulfide-based solid electrolyte having a glass-ceramic structure, its production and use, and to a solid-state battery cell comprising the same.In battery technology, lithium ion-based battery systems have become increasingly prevalent in recent years. These are distinguished in particular by their high energy density and expected long service life, so that more efficient battery configurations are possible. The high chemical reactivity and the low mass of lithium ions and their high mobility play a central role here. In all-solid-state batteries, both electrodes and the electrolyte are made of solid material. In lithium ion batteries, lithium compounds are present in all three phases of the electrochemical cell, i.e. the negative electrode, the positive electrode and the electrolyte contain lithium ions from solid-state lithium ion conductors. The general advantage of lithium-based solid-state batteries is that a liquid electrolyte, which is frequently easily flammable or toxic and tends to decompose, is replaced and an improvement in the safety and reliability of lithium-based batteries is thus possible.In particular for electric vehicles, the development of lithium-based solid-state batteries with high power output, high capacity and good (electro)chemical stability is of great interest. For high battery performance, a solid electrolyte material having good ionic conductivity is generally desirable in view of achieving as high a power output as possible of a battery.A problem in the production of known sulfidic solid-state electrolytes with a crystalline structure for solid-state batteries is that the method is time-intensive, energy-intensive and costly.Thus, conventional solid state sulphide electrolytes for solid state batteries are produced by a so-called solid state synthesis consisting of two steps: 1. the starting materials are ground in a ball mill for more than 40 hours to obtain a homogeneous powder mixture, whereby a powder with amorphous morphology is obtained. 2. the obtained powder is heated to about 550° C. for 20 hours and more under vacuum or argon. By heating the powder, the powder becomes crystalline, wherein the degree of crystallization can generally be increased with increasing heating temperature and longer duration of the heating step. The disadvantageous cost, time and energy expenditure must therefore be accepted in order to obtain the desired material properties.Representative of conventional solid-state synthesis to produce crystalline, sulfidic solid electrolytes, reference is made, for example, to Thragen Krauskopf et al. (1) where the starting mixture for producing a solid-state electrolyte is ball milled at 400 U / min for 48 hours, and then heated under vacuum to 773 K (499.85° C.) as a pellet and annealed for 20 hours.Although Laidong Zhou et al. (2) does not use a conventional ball milling method, a high temperature and a long period of time are also required to produce the solid electrolyte. Thus, the starting materials as mixtures for preparing Li 6+x Si x Sb 1-x S 5 I are heated in vacuofor 7 days to 550° C. (0.5≤x≤0.7) or 500° C. (0.1≤x≤0.4), in each case at a ramp rate of 5° C. / min. To produce Li 6 Sb x P 1-x S 5 I, heating is carried out at 550° C. (0.1≤x≤0.4) or 500° C. (0.5≤x≤1) for 100 h at a ramp rate of 5° C. / min, and to produce Li 6+x Ge x Sb 1-x S 5 I, heating is carried out at 550° C. for 50 hours at the same ramp rate.Furthermore, Subin Song et al. (3) describes solid electrolyte of the Li 10 GeP 2 S 12- type. For their preparation, the starting materials Li 2 S, P 2 S 5, LiBr and LiI were weighed out in the molar ratios provided and ground by planetary ball milling for 40 h and then sealed as pellets in a quartz tube at 5 Pa and heated in an oven in the temperature range of 463-493 K (189.85° C.-219.85° C.) for 4 h. For example, the solid electrolytes Li 10 P 3 S 12 Br, and Li 10.25 P 3 S 12.25 I 0.75 are described.There are approaches in the prior art to improve manufacturing conditions. For example, Tomoyuki Tsujimura et al. (4) discloses the compounds (1-x)LiCl-xLiBr-2Li 3 PS 4( x = 0, 0.25, 0.50, 0.75 and 1.0) prepared by high energy ball milling, wherein milling was carried out under argon for 16.5 hours and crystallizing in an oven at various heat treatment temperatures for 12 hours under vacuum. For example, Li 7 P 2 S 8 I, Li 7 P 2 S 8 Br 0.5 I 0.5, Li 7 P 2 S8I0.5Cl0.5or Li7P2S8I0.75Br0.25were thus produced.There is still a great need to provide sulfide-based solid electrolyte with improved manufacturing process and at the same time good performance.The object of the present invention is therefore to avoid the disadvantages from the prior art and to provide a sulfide-based solid electrolyte which has comparable electrochemical performance, in particular ionic conductivity and (electro)chemical stability, to crystalline, sulfidic solid electrolytes, but does not require the adverse conditions for the production process which are known from the prior art.According to the invention, the above object is achieved by a sulfide-based solid electrolyte having a glass-ceramic structure, comprising or consisting of the general chemical formula (I): Li 7 P 2 S 8 X1 x X2 y X3 z formula (I), wherein X1, X2and X3are each independently selected from the group consisting of Cl, Br and I; wherein the following applies: with the proviso that z>0: X1≠ X2≠ X3and X1≠ X3and z=0: X1≠ X2.Therefore, a sulfide-based solid electrolyte having the general chemical formula (I) is provided. The terms "sulfide-based solid electrolyte", "sulfide solid electrolyte" and "sulfide solid electrolyte" are intended to be synonymous and interchangeable.The sulfide-based solid electrolyte of the invention is a novel solid electrolyte which has a glass ceramic morphology, i.e., both crystalline and amorphous portions are present simultaneously.It is known that crystalline, sulfidic solid electrolytes, such as Li 10 GeP 2 S 12( LGPS) and Li 6 PS 5 Cl (argyrodite) (see Subin Song et al. (3) and Laidong Zhou et al. (2)), typically have a higher electrochemical performance than amorphous or glass-ceramic solid electrolytes, i.e. solid electrolytes having crystalline and amorphous fractions. It is therefore surprising that the sulfide-based solid electrolyte according to the invention with glass ceramic structure has a similar high electrical performance to comparable crystalline solid electrolytes, for example Li 10 GePS 12( LGPS) and Li 6 PS 5 Cl (argyrodite). The sulfide-based solid electrolyte has high ion conductivity at 25° C. (σ RT) >4 mS*cm -1. Stable high current densities of 1 mA* cm -2 or more were also measured. Such good properties are otherwise observed only with purely crystalline solid electrolyte based on sulfide.In the general chemical formula (I), X1is selected from Cl, Br or I; X2is selected from Cl, Br or I; and X3is selected from Cl, Br or I. However, X1, X2and X3should be selected differently from each other such that X1≠X2≠X3. This means that X1≠X2and X2≠X3, wherein X1≠X3should also be used, so that in the case of z>0, the chemical formula (I) is constructed, for example, as follows: Li 7 P 2 S 8 Cl x Br y I z.X1≠X2, if X1=Cl, then X2may not be Cl, but only Br or I.This applies analogously to X1≠X3and X2≠X3.If X1≠X2≠X3and X1=Cl and X2=Br, then X3=I.x>0 means that x has a numerical value above zero, but is selected such that the sum of x+y+z is in the specified range. For example, x=0.1. Larger values are also possible.y>0 means that y has a numerical value above zero, but is selected such that the sum of x+y+z is in the specified range. For example, y=0.1. Larger values are also possible.When z = 0, X3 is absent in formula (I).If z>0, this means that x has a numerical value above zero, but is selected such that the sum of x+y+z lies in the specified range. For example, z=0.1. Larger values are also possible.According to a preferred embodiment, the general chemical formula (I) is followed by 1.05<x+y+z≤1.7 or 1.1<x+y+z≤1.65 or 1.1<x+y+z≤1.6 or 1.15<x+y+z≤1.6 or 1.2<x+y+z≤1.55 or 1.25<x+y+z≤1.5, in particular 1.3<x+y+z≤1.5.According to one embodiment of the invention, z=0. In this case, X3is not present in the chemical formula (I). The chemical formula (Ia) is then present, according to which the sulfide-based solid electrolyte having a glass-ceramic structure comprises or consists of the following general chemical formula: Li 7 P 2 S 8 X1 x X2 y formula (Ia), wherein X1, X2 are each independently selected from the group consisting of Cl, Br and I, with the proviso that X1≠ X2, wherein the following applies: x>0 and y>0 and 1<x+y≤1.7.According to a preferred embodiment, the general chemical formula (Ia) is followed by 1.05<x+y≤1.7 or 1.1<x+y≤1.65 or 1.1<x+y≤1.6 or 1.15<x+y≤1.6 or 1.2<x+y≤1.55 or 1.25<x+y≤1.5, in particular 1.3<x+y≤1.5.It has been found to be particularly advantageous if the halogens in the general chemical formula (I) or (Ia) are present in superstoichiometric amounts, i.e. (x+y) >1 or (x+y+z) >1. It is precisely if this is observed that the advantageous electrochemical properties, in particular the high ionic conductivity and stable high current density, are achieved.The invention also relates to a process for the production of the sulfide-based solid electrolyte having a glass ceramic structure, comprising the following steps: (a) providing the starting materials of the sulfide-based solid electrolyte, preferably in the form of sulfide and / or halide salts, (b) weighing the starting materials in stoichiometric amounts according to the general formula (I) or (la) of the sulfide-based solid electrolyte of the present invention; (c) grinding the weighed amounts of the starting materials in a ball mill for 35 h to 45 h; (d) heating the ground mixture obtained in step (c) to a temperature in the range of 150 to 200°C for less than 20 hours, and (e) after cooling, obtaining the sulfide-based solid electrolyte having a glass ceramic structure, wherein steps (b), (c) and (d) are carried out in an inert gas atmosphere with exclusion of moisture or in a vacuum with exclusion of moisture.In step (a), first, the starting materials of the sulfide-based solid electrolyte are provided. These are, for example, commercially available salts, preferably in the form of sulfide and / or halide salts. The salts are each preferably used in a purity of ≥98%, more preferably ≥98.5%, even more preferably ≥99.0%, in particular ≥99.5% or ≥99.9% purity.In step (b), the weighing of the starting materials is then carried out in stoichiometric amounts according to the general formula (I) or (Ia). The weighing is carried out under an inert gas atmosphere or under reduced pressure, i.e. without the presence of oxygen, and with exclusion of moisture. An inert gas atmosphere is, for example, an inert gas such as argon or nitrogen gas and the like. With exclusion of moisture, for example, a content of H 2 means O<0.6 ppm. Compliance with an O 2- content<0.6 ppm may also be expedient.After weighing in step (b), optionally, mixing of the starting materials can be carried out or else a direct transition can be made to step (c). If mixing is carried out, this is likewise carried out under an inert gas atmosphere or under vacuum, i.e. without the presence of oxygen, and in each case with exclusion of moisture.In the subsequent step (c), the weighed amounts of the starting materials are ground. The mixture is ground in a ball mill for 35 h to 45 h. Preferably 38 h to 42 h, in particular about 40 h, it is possible to use any type of ball mill for this purpose, in which grinding can be carried out under an inert gas atmosphere or under vacuum, i.e. without the presence of oxygen, and with exclusion of moisture. According to the invention, a planetary ball mill is particularly preferably used. The balls of the ball mill may be selected from, for example, steel, stone, porcelain or ceramic. Preference is given to balls made of ceramic materials, for example made of ZrO 2. Particularly preferably, the grinding takes place in the range from 350 U / min to 450 U / min or in the range from 380 to 420 U / min or 390 to 410 U / min, in particular at about 400 U / min.Optionally, after step (c) and before step (d), the resulting ground mixture may be pressed in the form of pellets. This is preferably carried out again under an inert gas atmosphere or vacuum and with exclusion of moisture.In step (d), the ground mixture or the pellets obtained in step (c) are heated to a temperature in the range from 150° C. to 200° C. in an inert gas atmosphere or under vacuum and exclusion of moisture for less than 20 h. A duration of 10 h to less than 20 h or 10 h to 18 h, in particular 12 h to 15 h, is particularly preferred.After cooling, in step (e), the sulfide-based solid electrolyte is obtained as a glass ceramic. Cooling is preferably carried out by leaving the solid electrolyte based on sulfide at room temperature (25° C.), preferably under an inert gas atmosphere or under vacuum and with exclusion of moisture.The form in which the sulfide-based solid electrolyte having a glass ceramic structure may be present is not limited any more. Preferably, the sulfide-based solid electrolyte obtained in the step (e) is subjected to another milling step to obtain a powder. Preferably, the average particle diameter (d50) of the powder is in the range of 0.1 μm to 50 μm. The grinding is preferably carried out under an inert gas atmosphere or under vacuum and with exclusion of moisture.The method according to the invention enables a distinct lowering of the heating temperature in step (d) in order to obtain the glass-ceramic solid electrolyte of the invention. In addition, a significantly shortened time period is necessary in order to provide the glass-ceramic solid electrolyte. This means a significant reduction in energy consumption. This has a particularly severe effect, particularly on an industrial scale. Overall, the method of the invention is improved compared with the known methods from the prior art both in terms of time, energy and cost. This simultaneously means a distinct improvement in the CO 2- balance.The production of the novel sulfide-based solid-state electrolytes for solid-state batteries having a glass-ceramic morphology is therefore distinguished in particular by low and short sintering temperatures of the starting mixture. In addition, the sulfide-based solid electrolytes exhibit a similarly high electrochemical performance as compared to corresponding sulfide-based crystalline solid electrolytes (LGPS, Argyrodite) known for their high electrochemical performance (ionic conductivity / (electro)chemical stability).The invention also relates to the use of the sulfide-based solid electrolyte having a glass ceramic structure in a solid-state battery cell.The invention also relates to a solid-state battery cell comprising the sulfide-based solid electrolyte having a glass ceramic structure according to the present invention. Preferably, the all-solid-state battery cell is a high power output cell.The all-solid-state battery cell of the present invention may be a primary battery or a secondary battery, preferably a secondary battery that can be repeatedly charged and discharged. Primary batteries can only be discharged once and cannot be recharged thereafter. Secondary batteries, which are also referred to as accumulators, are rechargeable. For example, the solid-state battery cell according to the invention can be mounted in a motor vehicle.A solid-state battery cell preferably has a cathode material layer, an anode material layer and an electrolyte layer arranged therebetween, wherein the sulfide-based solid-state electrolyte according to the invention is present in one, two or all three layers.The anode material layer of an all-solid-state battery cell includes, for example, at least one anode active material, and may include an all-solid electrolyte material, a conductive material, and a binder. The anode-active material layer preferably comprises the sulfide-based solid electrolyte according to the invention having a glass-ceramic structure, for example in a proportion of from 0.1 to 80% by volume. Furthermore, a metal such as In, Al, Si and Sn may be present as anode-active materials. The anode material layer may further include a conductive material selected from carbon black, graphitized carbon black, graphite, carbon nanotubes, and carbon nanofibers, or combinations thereof. In addition, the anode material layer may include a binder such as polyvinylidene fluoride (PVDF). The thickness of the anode material layer is preferably in a range of 0.1 μm to 1000 μm.The cathode material layer of an all-solid-state battery cell includes, for example, at least one cathode active material, and may include an all-solid electrolyte material, a conductive material, and a binder. The cathode-active material layer preferably comprises the sulfide-based solid electrolyte according to the invention, for example in a proportion of from 0.1 to 80% by volume. For example, a cathode active material may comprise LiCoO 2, LiNiO 2 or Li y Ni (1-p-w) M p N w O 2 where 0.8≤y≤1.2, 0≤p≤0.33, 0 sw≤0.33, where M and N are selected from Mn, Co, Al. Further, a conductive material and a binder are present as in the anode material layer. The thickness of the cathode material layer is preferably in the range from 0.1 μm to 1000 μm.The electrolyte layer of a solid-state battery cell is present between the cathode material layer and the anode material layer, and enables ion conduction. The electrolyte layer preferably contains the sulfide-based solid electrolyte according to the invention, which is present in a proportion of 10 to 100% by volume. The thickness of the electrolyte layer is preferably in the range from 0.1 μm to 1000 μm, for example in the range from 0.1 μm to 300 μm.The all-solid-state battery cell has a separator which spatially and electrically separates the anode and cathode from one another. According to a preferred embodiment, the separator of the all-solid-state battery cell comprises a sulfide-based solid-state electrolyte having a glass-ceramic structure.It is further preferred that the particle size (d50) of the sulfide-based solid electrolyte of the cathode composition is smaller than the particle size (d50) of the cathode active material. Further, it is preferable that the particle size (d50) of the sulfide-based solid electrolyte used in the cathode composition is smaller than the particle size (d50) of the sulfide-based solid electrolyte used for the separator.The sulfide-based solid electrolyte with a glass-ceramic structure thus exhibits particularly good properties and can therefore be used particularly advantageously in solid-state battery cells.Production Example:Sulfide-based solid electrolyte materials of the present invention represented by the formula (I) were prepared by a mechanical ball mill and then solid-state reaction at elevated temperatures as described below.For this purpose, Li 2 S (99.9%+ purity), P 2 S 5(99,9 %+ purity), LiCl (99.9%+ purity), LiBr (99.9%+ purity) and LiI (99.9%+ purity) were weighed in stoichiometric amounts in an argon gas-filled glove box containing <0.6 ppm of H 2 O and <0.6 ppm of O 2. The weighed chemicals were mixed and loaded in a zirconia planetary ball mill for 40 hours with a Premium 7 Series Pulverizer from Fa. Ground in fritsch. The ground powder was formed into cylindrical pellets in a glove box filled with argon gas. The pellets were filled into fused silica vials and evacuated to <10 Pa. The sealed ampoules were heated from 25°C to 150°C, and the temperature was then maintained for 15 hours. After the reaction, the ampoules were naturally cooled to room temperature, and the desired sulfide-based solid electrolyte having a glass ceramic structure was obtained.List of Literature:(1) Thorden Krauskopf et al.: "Bottleneck of Diffusion and Inductive Effects in Li 10 Ge 1-x Sn x P 2 S 12 " in Chem. Mater. 2018, 30, pp. 1791-1798; (2) Laidong Zhou et al.: "New Family of Argyrodite Thioantimonate Lithium Anionic Conductors" in J. Am. Chem. Soc. 2019, 141, pp 19002-19013; (3) Subin Song et al.: "Material Search for a Li 10 GeP 2 S 12- Type Solid Electrolyte in the Li-P-S-X (X=Br, I) System via Classification of the Composition-Structure-Property Relationships" in Chem Mat. 2022, 34, pp. 8237-8247; and (4) Tomoyuki Tsujimura et al.: "Synthesis and characterization of low-temperature lithium-ion conductive phase of LiX(X=Cl, Br)-Li 3 PS 4 solid electrolytes" in Solid State Ionics 383, 2022, 115970, pp. 1-8.References included in the specificationThis list of documents cited by the applicant has been produced in an automated manner and is only included for the better information of the reader. The list is not part of the German patent application or utility model application. The DPMA does not take any adhesion for any faults or omissions.Cited Non-Patent LiteratureThorden Krauskopf et al.: "Bottleneck of Diffusion and Inductive Effects in Li 10 Ge 1-x Sn x P 2 S 12 " in Chem. Mater. 2018, 30, pp. 1791-1798

[0049] Laidong Zhou et al.: "New Family of Argyrodite Thioantimonate Lithium Superionic Conductors" in J. Am. Chem. Soc. 2019, 141, pp 19002-19013

[0049] Subin Song et al.: "Material Search for a Li 10 GeP 2 S 12- Type Solid Electrolyte in the Li-P-S-X (X=Br, I) System via Classification of the Composition-Structure-Property Relationships" in Chem Mater. 2022, 34, pp. 8237-8247

[0049] Tomoyuki Tsujimura et al.: "Synthesis and characterization of low-temperature lithium-ion conductive phase of LiX(X=Cl, Br)-Li 3 PS 4 solid electrolytes" in Solid State Ionics 383, 2022, 115970, pp. 1-8

[0049]

Claims

A sulfide-based solid electrolyte having a glass-ceramic structure, comprising or consisting of the general chemical formula (I): Li 7 P 2 S 8 X1 x X2 y X3 z formula (I), wherein X1, X2 and X3 are each independently selected from the group consisting of Cl, Br and I; wherein x > 0, y > 0 and z ≥ 0 and 1 < x + y + z ≤ 1.7; with the proviso that z > 0: X1 ≠ X2 ≠ X3 and X1 ≠ X3 and z = 0: X1 ≠ X2.Solid electrolyte according to Claim 1, characterized in that the sulfide-based solid electrolyte having a glass-ceramic structure, which comprises or consists of the following general chemical formula (Ia): Li 7 P 2 S 8 X1 x X2 y formula (Ia), where X1, X2 are each independently selected from the group consisting of Cl, Br and I, with the proviso X1 ≠ X2, where the following applies: x > 0 and y > 0 and 1 < x + y ≤ 1.7.Solid electrolyte according to Claim 1 or 2, characterized in that the following applies in the general chemical formula (I): 1.05 < x + y + z ≤ 1.7 or 1.1 < x + y + z ≤ 1.65 or 1.1 < x + y + z ≤ 1.6 or 1.15 < x + y + z ≤ 1.6 or 1.2 < x + y + z ≤ 1.55 or 1.25 < x + y + z ≤ 1.5, in particular - re 1.3 < x + y + z ≤ 1.5 or the following applies in the general chemical formula (Ia): 1.05 < x + y ≤ 1.7 or 1.1 < x + y ≤ 1.65 or 1.1 < x + y ≤ 1.6 or 1.15 < x + y ≤ 1.6 or 1.2 < x + y ≤ 1.55 or 1.25 < x + y ≤ 1.5, in particular 1.3 < x + y ≤ 1.

5. A process for the production of the sulfide-based solid electrolyte having a glass-ceramic structure according to any one of claims 1 to 3, comprising the steps of: (a) providing the starting materials of the sulfide-based solid electrolyte, preferably in the form of sulfide and / or halide salts, (b) weighing the starting materials in stoichiometric amounts according to the general formula (I) of claim 1 or the general formula (Ia) of claim 2; (c) grinding the weighed amounts of the starting materials in a ball mill for 35 h to 45 h; (d) heating the ground mixture obtained in step (c) to a temperature in the range of 150 to 200°C for less than 20 hours, and (e) after cooling, obtaining the sulfide-based solid electrolyte having a glass ceramic structure, wherein steps (b), (c) and (d) are carried out in an inert gas atmosphere with exclusion of moisture or in a vacuum with exclusion of moisture.Process according to Claim 4, characterized in that, after step (b) and before step (c), the starting materials are mixed under an inert gas atmosphere and moisture exclusion or in vacuo with moisture exclusion, and / or, after step (c) and before step (d), the ground mixture obtained is pressed into the form of pellets under an inert gas atmosphere with moisture exclusion or in vacuo with moisture exclusion.Method according to claim 4 or 5, characterised in that in step (c) the ball milling is carried out in the range from 350 U / min to 450 U / min or in the range from 380 to 420 U / min or 390 to 410 U / min, in particular at about 400 U / min.Method according to one of Claims 4 to 6, characterized in that in step (c) the ball milling is carried out for a duration of 36 h to 44 h or 38 h to 42 h, in particular 40 h.Process according to any of Claims 4 to 7, characterized in that in step (d) heating is carried out to a temperature in the range from 150°C to 200°C for 10 h to less than 20 h or 10 h to 18 h, in particular 12 h to 15 h.Use of the sulfide-based solid electrolyte having a glass ceramic structure according to any one of claims 1 to 3 in a solid-state battery cell.An all-solid-state battery cell comprising the sulfide-based solid electrolyte having a glass-ceramic structure according to any one of claims 1 to 3, wherein the all-solid-state battery cell is particularly a high output cell.The all-solid-state battery cell according to claim 10, characterized in that the all-solid-state battery cell has a cathode material layer, an anode material layer and an electrolyte layer arranged therebetween, wherein the sulfide-based all-solid electrolyte having a glass ceramic structure according to any one of claims 1 to 3 is present in one, two or all three layers.The all-solid-state battery cell according to claim 10 or 11, in the form of a primary battery or a secondary battery.