Abstract
The invention relates to a method for producing a battery cell (10), in particular a solid-state battery cell, wherein material particles (1) are provided with a first coating (3), wherein in a deposition step the material particles (1) having the first coating (3) are accelerated toward a substrate (112) in such a way that the first coating (3) of the material particles (1) joins with the first coating (3) of further material particles (1) upon hitting the substrate (112) such that a first layer (30) is formed, in particular without an input of heat from outside.
Claims
1. A method for producing a battery cell (10), the method comprising providing, in a coating step, material particles (1) having a first coating (3), and, in a deposition step, accelerating the material particles (1) having the first coating (3) toward a substrate (112) in such a way that the first coating (3) of the material particles (1) bonds on impact on the substrate (112) with the first coating (3) of further material particles (1) so that a first layer (30) is formed.
2. The method as claimed in claim 1, characterized in that at least one second coating (5) is applied to the first coating (3) of the material particles (1).
3. The method as claimed in claim 2, characterized in that the first coating (3) of the material particles (1) and/or the second coating (5) breaks open on impact on the substrate (112) and/or fuses with the first coating (3) of further material particles (1) and/or the second coating (5).
4. The method as claimed in claim 2, characterized in that the first coating (3) and/or the second coating (5) is configured to be an ion-conducting coating and/or electron-conducting coating.
5. The method as claimed in claim 4, characterized in that the ion-conducting coating (3, 5) comprises a garnet, a sulfidic or phosphatic glass, and/or an argyrodite.
6. The method as claimed in claim 2, characterized in that the first coating (3) and/or the second coating (5) is/are an active material and/or the first coating (3) and/or the second coating (5) is/are a protective material.
7. The method as claimed in claim 1, characterized in that the material particles (1) are active material particles of an electrode of the battery cell (10) or conducting material particles of an electrode of the battery cell (10).
8. The method as claimed in claim 2, characterized in that the coating step, in which the material particles (1) having the first coating (3) and/or the second coating (5) are provided, and the deposition step take place in the same device (100).
9. The method as claimed in claim 2, characterized in that the coating step is conducted immediately prior to the deposition step.
10. The method as claimed in claim 1, characterized in that the method comprises an aerosol deposition method (ADM).
11. A battery cell (10) comprising a plurality of layers (20, 21, 22, 23, 24, 25) configured such that a first coating (3) of material particles (1) of the respective layer (20, 21, 22, 23, 24, 25) bonds with the first coating (3) of further material particles (1) of the respective layer (20, 21, 22, 23, 24, 25).
12. The battery cell (10) as claimed in claim 11, characterized in that at least one layer (20, 21, 22, 23, 24, 25) of the battery cell (10) comprises a gradient.
13. (canceled)
14. The method as claimed in claim 1 wherein the first layer (30) is formed without an input of heat from outside.
15. The method as claimed in claim 4, characterized in that the ion-conducting coating (3, 5) comprises LiLaZrO, Li.sub.10XP.sub.2S.sub.12, where X=Ge, Sn, and/or Li.sub.6PS.sub.5CI.
16. The method as claimed in claim 2, characterized in that the coating step is conducted immediately prior to the deposition step in order to prevent reaction of the coating (3) and/or the second coating (5) with atmospheric components.
17. The battery cell (10) as claimed in claim 11, wherein the layers (20, 21, 22, 23, 24, 25) of the battery cell (10) are an anode conductor layer (20), an anode-active material layer (21) of an anode, an electrolyte layer (22), a cathode conductor layer (24), a cathode-active material layer (23) of a cathode, and/or a protective layer (25).
18. The battery cell (10) as claimed in claim 11, characterized in that at least one layer (20, 21, 22, 23, 24, 25) of the battery cell (10) comprises an anode-active material layer (21) and/or a cathode-active material layer (23), wherein an ion-conducting portion of the anode-active material layer (21) and/or the cathode-active material layer (23) varies over the thickness of the anode-active material layer (21) and/or the cathode-active material layer (23).
Description
BRIEF DESCRIPTION OF THE DRAWINGS
[0038] Embodiments of the present invention are shown in the drawings and explained in further detail in the following description of the figures, which show the following:
[0039] FIG. 1: A schematic cross-sectional view of a device for producing a battery cell according to the invention with a coating chamber, a deposition chamber, and a plurality of nozzles,
[0040] FIG. 2a: A schematic cross-sectional view of a material particle having a first coating before a deposition step of the method according to the invention in a first embodiment,
[0041] FIG. 2b: A schematic cross-sectional view of material particles having a first coating according to FIG. 2a after the deposition step of the method according to the invention in the first embodiment,
[0042] FIG. 3a: A schematic cross-sectional view of a material particle with a first and a second coating before a deposition step of the method according to the invention in a second embodiment,
[0043] FIG. 3b: A schematic cross-sectional view of material particles with a first and a second coating according to FIG. 3a after the deposition step of the method according to the invention in a first variant of the second embodiment,
[0044] FIG. 3c: A schematic three-dimensional view of the material particles with a first and a second coating according to FIG. 3b,
[0045] FIG. 3d: A schematic cross-sectional view of material particles with a first and a second coating according to FIG. 3a after the deposition step of the method according to the invention in the second variant of the second embodiment,
[0046] FIG. 4a: A schematic cross-sectional view of a material particle with a first and a second coating before a deposition step of the method according to the invention in a third variant of the second embodiment,
[0047] FIG. 4b: A schematic cross-sectional view of material particles with a first and a second coating according to FIG. 4a after a deposition step of the method according to the invention in a third variant of the second embodiment,
[0048] FIG. 5a: A schematic cross-sectional view of a battery cell according to the invention with a plurality of layers in a first embodiment, and
[0049] FIG. 5b: A schematic cross-sectional view of the battery cell of the present invention according to FIG. 3a in a second embodiment.
DETAILED DESCRIPTION
[0050] FIG. 1 shows a device 100 for producing a battery cell, in particular a lithium-ion battery cell. Beginning from a gas storage unit 102, a gas flow 104, for example, is regulated by means of a flow controller 103 and fed into a material particle reservoir 105 in which material particles 1 are present, for example in powder form. The material particles 1, for example, are active material particles of an electrode of a battery cell, or conducting material particles of an electrode of a battery cell. In an embodiment, the powder composed of material particles 1 is synthesized in a system installed upstream of the device 100, which is not shown, for example from the gas phase, e.g. by condensation of gas phase components. The material particles 1 are transported by the gas flow 104, for example filtered through a filter 106 and e.g. classified by means of a classifier 107, for example according to size, shape, or charge characteristics. The material particles 1 are then transported by the gas flow 104 into a coating chamber 109. In the coating chamber 109, for example, a first nozzle 108a and a second nozzle 108b are arranged, and the material particles 1 flow by these nozzles. By means of the first nozzles 108a, a first coating 3, for example, is applied to the material particles 1. FIG. 1 shows a first substance 33 sprayed by the first nozzle 108a for forming the first coating 3. By means of the second nozzle 108b, for example, a second coating 5 is applied to the first coating 3 of the material particles 1. FIG. 1 shows a second substance 55 sprayed by the second nozzle 108b for forming the second coating 5. Alternatively, a second coating 5 is applied to the first coating 3 of the material particles 1, said coating corresponding to the first coating 3, so that the latter is made thicker. In an alternative embodiment, only a first coating 3 is applied to the material particles 1 by a first nozzle 108a. In a further alternative embodiment, the coating chamber 109 comprises multiple nozzles (108a, 108b) so that a plurality of the same or different coatings 3, 5 is applied to the material particles 1. For example, the coating chamber 109 is configured as a vacuum coating chamber in which the coating(s) 3, 5 is/are applied under a vacuum to the material particles 1. Alternatively, the coating chamber 109, for example, is a sputtering chamber in which the coating(s) 3, 5 is/are sputtered onto the material particles 1. Further alternatively, the coating chamber 109 is for example a vapor deposition chamber in which the coating(s) 3, 5 is/are vapor-deposited on the material particles 1. Further alternatively, the coating chamber 109 is for example an ALD/CVD chamber in which the coating(s) 3, 5 is/are applied to the material particles 1 by means of an ALD/CVD process. The nozzles 108a, 108b are for example slot nozzles and/or air blades, which for example are installed in parallel or in series with respect to one another so that a plurality of coatings 3, 5 can be applied simultaneously or successively. A first or second coating 3, 5 can thus for example also comprise two or more different materials if the nozzles installed in parallel to each other 108a, 108b simultaneously coat the material particles 1. For example, the coating 3, 5 is configured as an open coating that does not completely surround the material particles 1 and is applied, for example, by means of a vapor deposition process. Alternatively, for example, the coating 3, 5 is a closed coating, which completely surrounds the material particles 1 and is applied to the material particles 1, for example, by means of an ALD/CVD method. The gas flow 104 is fed through the coating chamber 109 one or multiple times. Alternatively, the device 100 comprises a plurality of coating chambers 109 though which the gas flow 104 is fed one or multiple times. In this manner, for example, thicker coatings 3, 5 and/or a plurality of different coatings 3, 5 can be obtained. In a further step, the material particles 1 having a coating 3, 5 are for example filtered through a filter 106 and classified by means of a classifier 107. The gas flow 104 with the material particles 1 having a coating 3, 5 is supplied to a deposition chamber 110, in which the coated material particles 1 are deposited on a substrate 112 in a deposition step.
[0051] The substrate 112, for example, is an anode or cathode conductor layer of a battery cell or a ceramic layer, such as e.g. an electrolyte layer of a battery cell, in particular a solid-state electrolyte layer. Alternatively, the substrate 112 is an anode- or cathode-active material layer of a battery cell, a protective layer of a battery cell composed of a protective material, or a layer that is not a component of a battery cell, and for example only fulfills carrier functions. Alternatively, the substrate 112 is composed of multiple layers, for example various functional or carrier layers.
[0052] In order to deposit the coated material particles 1 on the substrate 112, for example, a vacuum is produced in the deposition chamber 110, for example by means of a pump 115. Because of the difference in pressure produced by the vacuum before and after the deposition nozzle 113, the coated material particles 1 are accelerated in the deposition nozzle 113 so that a material particle flow 114 is deposited on the substrate 112. Here, the position of the substrate 112 can be modified, for example by means of a movable frame 116. Deposition of the material particles is preferably carried out by means of an aerosol deposition method (ADM) or alternatively by means of a plasma spray method.
[0053] FIG. 2a shows an individual material particle 1 having a first coating 3 in a first embodiment before a step of deposition on a substrate 112. The first coating 3 is completely formed around the material particles 1.
[0054] FIG. 2b shows coated material particles 1 in the first embodiment according to FIG. 2a after the step of deposition on the substrate 112. In the deposition step, the material particles 1 having the first coating 3 are accelerated toward the substrate 112 in such a way that the first coating 3 of the material particles 1 bonds with the first coating 3 of further material particles 1 on impact on the substrate 112 so that a first layer 30 is formed. The first layer 30 is completely formed around the material particles 1. On impact of the coated material particles 1 on the substrate 112, the first coating 3, for example, breaks open and/or fuses with the coating 3 of further material particles 1, wherein in particular no heat is added from outside.
[0055] FIG. 3a shows an individual material particle 1 having a first coating 3 and a second coating 5 in a second embodiment prior to the step of deposition on the substrate 112. The first coating 3 is completely formed around the material particles 1, and the second coating 5 is completely formed around the first coating 3.
[0056] FIG. 3b shows coated material particles 1 according to FIG. 3a after the step of deposition on the substrate 112 in a first variant of the second embodiment. In the deposition step, the material particles 1 having the first coating 3 and the second coating 5 are accelerated toward the substrate 112 in such a way that the second coating 5 of the material particles 1 bonds with the second coating 5 of further material particles 1 on impact on the substrate 112, so that a second layer 50 is formed. In this case, the first coating 3 of the material particles 1 remains completely intact around the material particles 1 and bonds at least partially with the first coating 3 of further material particles 1 so that a first layer 30 is formed. On impact of the coated material particles 1 on the substrate 112, the second coating 5, for example, breaks open and/or fuses with the second coating 5 of further material particles 1, wherein in particular no heat is added from outside. In this case, the second layer 50 in particular surrounds the entirety of the material particles 1 with the first layer 30 so that the outermost layer is continuously formed by the second layer 50. On impact on the substrate 112, for example, the first coating 3 also at least partially breaks open and/or at least partially fuses with the first coating 3 of further material particles 1. In an alternative variant not shown in the figures, the first coating 3 does not break open and also does not fuse with the first coating 3 of further material particles 1, but in particular is completely surrounded by the second layer 50.
[0057] FIG. 3c shows the coated material particles 1 after the deposition step according to FIG. 3b in a three-dimensional view.
[0058] FIG. 3d shows coated material particles 1 according to FIG. 3a after the step of deposition on the substrate 112 in a second variant of the second embodiment. In the deposition step, the material particles 1 having the first coating 3 and the second coating 5 are accelerated toward the substrate 112 in such a way that the second coating 5 of the material particles 1 bonds with the second coating 5 of further material particles 1 on impact on the substrate 112 so that a second layer 50 is formed. In this case, the first coating 3 of the material particles 1 bonds with the first coating 3 of further material particles 1 so that a first layer 30 is formed. Here, the first layer 30 of the material particles 1 remains only partially intact around the material particles 1 so that the material particles 1 at least partially come into contact with one another. However, the first layer 30 surrounds the material particles 1, for example, in their entirety so that they do not come into contact with the second layer 50. On impact of the coated material particles 1 on the substrate 112, the second coating 5, for example, breaks open and/or fuses with the second coating 5 of further material particles 1, wherein in particular no heat is added from outside. In this case, for example, the first coating 3 also at least partially breaks open and/or at least partially fuses with the first coating 3 of further material particles 1.
[0059] FIG. 4a shows an individual material particle 1 having a first coating 3 and a second coating 5 in a third variant of the second embodiment prior to the step of deposition on the substrate 112. The first coating 3 is only partially formed around the material particles 1. The second coating 5 is entirely formed around the material particles 1 with the partial first coating 3.
[0060] FIG. 4b shows coated material particles 1 according to FIG. 4a after the step of deposition on the substrate 112 in the third variant of the second embodiment. In the deposition step, the material particles 1 with the partial first coating 3 and the second coating 5 are accelerated toward the substrate 112 in such a way that the second coating 5 of the material particles 1 bonds with the second coating 5 of further material particles 1 on impact on the substrate 112 so that a second layer 50 is formed. Here, the partial first coating 3 of the material particles 1 bonds with the partial first coating 3 of further material particles 1 so that a first layer 30 is formed. In this case, the first layer 30 of the material particles 1 remains partially intact around the material particles 1. Here, the material particles 1 do not come into contact with one another. Moreover, they are partially surrounded by the first layer 30 and partially by the second layer 50. The second layer 50 preferably surrounds the material particles 1 and the first layer 30 in their entirety so that the outermost layer is formed by the second layer 50.
[0061] In an alternative embodiment not shown in the figures, the material particles 1 come at least partially into contact with one another.
[0062] On impact of the coated material particles 1 on the substrate 112, the second coating 5, for example, breaks open and/or fuses with the second coating 5 of further material particles 1, wherein in particular, no heat is added from outside. In this case, for example, the first coating 3 also at least partially breaks open and/or at least partially fuses with the first coating 3 of further material particles 1.
[0063] The following explanations pertain to all of the aforementioned embodiments and variants of FIGS. 2a through 4b and the explanations thereof.
[0064] On impact of the coated material particles 1 on the substrate 112, it is possible, for example, that the material particles 1 will undergo chemical reactions with the first coating 3 and/or that chemical or physical bonds will form. It is additionally or alternatively possible that the first coating 3 will undergo chemical reactions with a second coating 5 and/or that chemical or physical bonds will form. In embodiments with a plurality of coatings, this also applies to these coatings.
[0065] The material particles 1 are for example active material particles of an electrode of a battery cell, for example lithium metal oxides such as lithium cobalt dioxide (LiCoO.sub.2) or lithium nickel cobalt manganese oxides, in particular LiNi.sub.1/3Co.sub.1/3Mn.sub.1/3O.sub.2, or a lithium iron phosphate (LiFePO.sub.4) or conducting material particles of an electrode of a battery cell, for example carbon-containing material particles 1 such as soot, graphite, or graphene.
[0066] The first coating 3 and/or the second coating 5 is configured for example to be ion-conducting; in particular, the first coating 3 and/or the second coating 5 comprises a garnet, in particular LiLaZrO, a sulfidic or a phosphatic glass, in particular Li.sub.10XP.sub.2S.sub.12, where X=Ge, Sn, and/or an argyrodite, in particular Li.sub.6PS.sub.5CI. Alternatively or additionally, the first coating 3 and/or the second coating 5 is configured to be electron-conducting, preferably by means of carbon-containing compounds such as soot, graphite, and graphene.
[0067] In an alternative or additional embodiment, the first coating 3 and/or the second coating 5 is an active material of an electrode of a battery cell, for example a lithium metal oxide, such as e.g. lithium cobalt dioxide (LiCoO.sub.2) or lithium nickel cobalt manganese oxides, in particular LiNi.sub.1/3Co.sub.1/3Mn.sub.1/3O.sub.2, or a lithium iron phosphate (LiFePO.sub.4). Alternatively, the first coating 3 and/or the second coating 5 is a protective material of a battery cell, for example an aluminum oxide (AI.sub.2O.sub.3), a zirconium oxide (ZrO.sub.2), LiloSnP.sub.2S.sub.12, LiTi.sub.2(PO.sub.4).sub.3, a lithium niobate (LiNbO.sub.3), a lithium phosphate (Li.sub.3PO.sub.4) or (LiSn.sub.2(PO.sub.4).sub.3).
[0068] In a particularly preferred embodiment, the material particles 1 comprise an active material of a battery cell, in particular a lithium nickel cobalt manganese oxide (LiNi.sub.xCo.sub.yMn.sub.zO.sub.2) or a lithium nickel cobalt aluminum oxide (LiNi.sub.xCo.sub.yAI.sub.zO.sub.2). A first coating 3 is applied to the material particles 1, which in particular is configured to be ion-conducting. The ion-conducting first coating 3 comprises for example a garnet, in particular LiLaZrO, a sulfidic or a phosphatic glass, in particular Li.sub.2SyP.sub.2S.sub.5, where x,y=Ge, Sn, and/or an argyrodite, in particular Li.sub.6PS.sub.5CI. A second coating 5, for example, is applied to the first coating 3, which for example contains carbon, and in particular comprises a soot, a graphite, or a graphene.
[0069] For example, a further coating or an alternative second coating 5 comprises on the one hand carbon-containing components, in particular soot, a graphite, or a graphene, and on the other elastic components, in particular a polyethylene oxide. Elastic components are used for example to absorb volume changes in the battery cell and alleviate them.
[0070] FIG. 5a shows a battery cell 10, in particular a solid-state battery cell, immediately after the step of deposition on the substrate 112. The battery cell 10 comprises a plurality of layers 20, 21, 22, 23, 24, 25 that are configured such that a first coating 3 of material particles 1 of the respective layer 20, 21, 22, 23, 24, 25 bonds with the first coating 3 of further material particles 1 of this respective layer 20, 21, 22, 23, 24, 25 as shown in FIGS. 2a-4b. These layers 20, 21, 22, 23, 24, 25 of the battery cell 10, for example, are an anode conductor layer 20, an anode-active material layer 21, and electrolyte layer 22 configured as a solid body that functions as a separator, among other functions, a cathode-active material layer 23, a cathode conductor layer 24, and/or a protective layer 25 composed of a protective material. The various layers 20, 21, 22, 23, 24, 25 are applied, for example, by means of a method that in particular comprises an aerosol coating method, such as e.g. shown in FIG. 1. In an embodiment, in this process, the anode conductor layer 20 is first deposited on the substrate 112 as shown in FIG. 5a. In an alternative embodiment, the cathode conductor layer 24 is first deposited on the substrate 112.
[0071] The anode conductor layer 20 comprises for example a copper, and the anode-active material layer 21 of the anode comprises for example lithium, a graphite, in particular a natural or a synthetic graphite, silicon, and/or a titanate. The electrolyte layer 22, which functions as a separator, among other functions, comprises for example a garnet and/or a sulfidic glass. The cathode-active material layer 23 of the cathode comprises for example a lithium metal oxide or a lithium metal phosphate, and the cathode conductor layer 24 comprises for example an aluminum or a nickel. The protective layer 25 composed of a protective material comprises for example a metal nitride or a metal oxide.
[0072] In an embodiment, at least one of the layers 20, 21, 22, 23, 24, 25 of the battery cell 10 comprises a gradient, in particular an anode-active material layer 21 and/or a cathode-active material layer 23, wherein an ion-conducting portion of the anode-active material layer 21 and/or the cathode-active material layer 23 varies over the thickness of the anode-active material layer 21 and/or the cathode-active material layer 23.
[0073] FIG. 5b shows the battery cell 10 according to FIG. 3a in a second embodiment. The electrolyte layer 22 also surrounds the anode-active material layer 21 laterally so that the anode-active material layer 21 is surrounded on all sides by the electrolyte layer 22 with the exception of the surface on which the anode-active material layer 21 is deposited on the substrate 112. Moreover, the cathode-active material layer 23 surrounds the electrolyte layer 22 on all sides with the exception of the surface on which the electrolyte layer 22 is deposited on the anode-active material layer 21 and the surface on which the electrolyte layer 22 lies on the substrate 112. The protective layer 25 surrounds the aforementioned layer stacks on all surfaces that are not adjacent to the substrate 112. In this manner, the layers lying under the protective layer 25 are protected.
