CN113839078A - Solid state battery pack - Google Patents
Solid state battery pack Download PDFInfo
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- CN113839078A CN113839078A CN202110434510.XA CN202110434510A CN113839078A CN 113839078 A CN113839078 A CN 113839078A CN 202110434510 A CN202110434510 A CN 202110434510A CN 113839078 A CN113839078 A CN 113839078A
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- 239000007787 solid Substances 0.000 title claims description 18
- 239000004020 conductor Substances 0.000 claims abstract description 183
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 41
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 41
- 238000000034 method Methods 0.000 claims abstract description 21
- 238000004519 manufacturing process Methods 0.000 claims description 21
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 239000012799 electrically-conductive coating Substances 0.000 claims description 4
- 239000010439 graphite Substances 0.000 claims description 4
- 229910002804 graphite Inorganic materials 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 3
- 239000002223 garnet Substances 0.000 claims description 3
- 239000003792 electrolyte Substances 0.000 description 19
- 239000011248 coating agent Substances 0.000 description 13
- 238000000576 coating method Methods 0.000 description 13
- 239000000463 material Substances 0.000 description 11
- 238000009825 accumulation Methods 0.000 description 6
- 238000007650 screen-printing Methods 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 238000010146 3D printing Methods 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 239000013067 intermediate product Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 229910002984 Li7La3Zr2O12 Inorganic materials 0.000 description 2
- RJEIKIOYHOOKDL-UHFFFAOYSA-N [Li].[La] Chemical compound [Li].[La] RJEIKIOYHOOKDL-UHFFFAOYSA-N 0.000 description 2
- 239000010426 asphalt Substances 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
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- 150000002642 lithium compounds Chemical class 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
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- 238000001556 precipitation Methods 0.000 description 2
- 238000004549 pulsed laser deposition Methods 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000007784 solid electrolyte Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 239000011345 viscous material Substances 0.000 description 2
- QNRATNLHPGXHMA-XZHTYLCXSA-N (r)-(6-ethoxyquinolin-4-yl)-[(2s,4s,5r)-5-ethyl-1-azabicyclo[2.2.2]octan-2-yl]methanol;hydrochloride Chemical compound Cl.C([C@H]([C@H](C1)CC)C2)CN1[C@@H]2[C@H](O)C1=CC=NC2=CC=C(OCC)C=C21 QNRATNLHPGXHMA-XZHTYLCXSA-N 0.000 description 1
- 239000005279 LLTO - Lithium Lanthanum Titanium Oxide Substances 0.000 description 1
- 229910009297 Li2S-P2S5 Inorganic materials 0.000 description 1
- 229910009228 Li2S—P2S5 Inorganic materials 0.000 description 1
- 239000002224 Li5La3Nb2O12 Substances 0.000 description 1
- 229910010709 Li5La3Nb2O12 Inorganic materials 0.000 description 1
- 229910010886 Li7-xLa3Zr2-xTaxO12 Inorganic materials 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
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- 230000001070 adhesive effect Effects 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000006182 cathode active material Substances 0.000 description 1
- 239000002800 charge carrier Substances 0.000 description 1
- 230000001427 coherent effect Effects 0.000 description 1
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- 229910000204 garnet group Inorganic materials 0.000 description 1
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- 229910000664 lithium aluminum titanium phosphates (LATP) Inorganic materials 0.000 description 1
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- 238000007740 vapor deposition Methods 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/04—Construction or manufacture in general
- H01M10/0413—Large-sized flat cells or batteries for motive or stationary systems with plate-like electrodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/04—Construction or manufacture in general
- H01M10/0472—Vertically superposed cells with vertically disposed plates
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
- H01M10/0562—Solid materials
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/463—Separators, membranes or diaphragms characterised by their shape
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2220/00—Batteries for particular applications
- H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Secondary Cells (AREA)
Abstract
The invention relates to a solid-state battery (14) having a plurality of cells (22) stacked one above the other in a stacking direction (14), wherein each cell (22) has a cathode conductor layer (24) arranged perpendicular to the stacking direction (16) and an anode conductor layer (26) arranged perpendicular to the stacking direction (16). The cathode conductor layer (24) and the anode conductor layer (26) are mechanically connected to each other by a lithium-containing cathode layer (28) and a separator layer (32). The cathode layer (28) is left empty by means of a plurality of blanks (30) running parallel to the stacking direction (16). The invention also relates to a method (34) for producing a battery (22) of a solid-state battery (14) and to a battery (20) of a solid-state battery (14).
Description
Technical Field
The present invention relates to a solid-state battery pack having a plurality of cells stacked one on another in a stacking direction. The invention also relates to a method for manufacturing a battery of a solid state battery and to a battery of a solid state battery. The solid-state battery is expediently a component of a motor vehicle and preferably a component of a high-voltage battery.
Background
Motor vehicles are increasingly being driven at least partially by means of electric machines, so that these are designed as electric or hybrid vehicles. For energizing the electric machine, a high-voltage battery pack is generally used, which has a plurality of individual battery packs. The battery packs are electrically connected in series and/or in parallel with each other such that the voltage attached to the high voltage battery pack corresponds to a multiple of the voltage provided by means of each of the battery packs.
Each battery pack in turn has a plurality of cells, which are likewise connected electrically in series and/or in parallel with one another. Each cell has an anode, a cathode, and an electrolyte disposed between the anode and the cathode, the electrolyte including freely movable charge carriers. For example, a liquid is used as such an electrolyte. However, to simplify maintenance, the electrolyte is preferably designed as a solid. In this case, no liquid leaks out even in the case of a failure of the battery cell, which improves safety. Such batteries are also referred to as solid state batteries.
Graphite is mostly used as the anode material. However, it is also known to use lithium for this purpose. In this case, the energy density of the solid-state battery is also increased, which leads to a reduction in the volume of the solid-state battery with the same capacity or an increase in the capacity with the same volume. Such solid-state batteries are therefore particularly suitable for use in motor vehicles. In this case, a lithium-containing cathode layer, a lithium-containing electrolyte layer, which also forms a required separator, and a conductor, which are stacked in an overlapping manner in the stacking direction, are often provided in each cell. When charging a solid-state battery, lithium migrates from the cathode layer through the electrolyte layer and accumulates on the current conductor, so that the volume required there increases. Due to the lithium layer formed and grown in this manner, the electric conductor is spaced apart from the electrolyte layer. When the battery is subsequently discharged, lithium re-enters the cathode layer through the separator layer and the distance between the electrical conductor and the electrolyte layer decreases.
Therefore, in the case of multiple charging/discharging, the electric conductor is moved, and it is possible that: lithium is not constantly removed/accumulated. It is thus possible to: mechanically separating the separator layer from the electrical conductor, which results in an increase in the resistance of the cell or complete failure of the cell. To prevent this, provision is made for: the individual cells are mechanically forced in the stacking direction such that the conductor layer is not moved from the beginning, or at least such that the accumulation or removal of lithium is constant over substantially the entire area of the conductor layer. Therefore, a comparatively stable design of the solid-state battery is required, which leads to an increase in the structural space and an increase in weight.
Disclosure of Invention
The invention is based on the task of: a particularly suitable solid-state battery, a particularly suitable method for producing a cell of a solid-state battery, and a cell of a particularly suitable solid-state battery are specified, wherein advantageously the weight and/or volume is reduced, and wherein advantageously the production is simplified and/or the service life is increased.
With regard to the solid-state battery, this object is achieved according to the invention, with regard to the method, this object is achieved according to the invention, and with regard to the battery, this object is achieved according to the invention. Advantageous embodiments and embodiments are the subject matter of the respective dependent claims.
The solid-state battery pack has a plurality of cells stacked one on another in a stacking direction. In this case, the individual cells are expediently connected to one another at least partially in series as a result of the stacking direction. Each cell has a cathode conductor layer which is arranged perpendicular to the stacking direction. Each cell also has an anode conductor layer that is also arranged perpendicular to the stacking direction. The two conductor layers each serve as a current conductor for conducting electrons and are expediently made of metal. The thickness of the two conductor layers, i.e. the extent parallel to the stacking direction, is comparatively small here, for example, so that the two conductor layers are designed in the form of a foil. Alternatively, the thickness of the at least one conductor layer is greater, and in particular greater than 0.5 mm.
A cathode layer is disposed between the anode conductor layer and the cathode conductor layer. Between the cathode and anode conductor layers there is also a separator layer, also referred to as electrolyte layer. In this case, the individual layers are arranged such that the cathode conductor layer is mechanically connected to the anode conductor layer via the cathode layer and the separator layer/electrolyte layer. Thus, the cathode conductor layer is held in mechanical contact with the anode conductor layer via the cathode layer and the separator layer, and no other constituent parts are mechanically arranged therebetween. In particular, the cathode layer mechanically abuts directly against the cathode conductor layer, and the cathode layer mechanically abuts directly against the anode conductor layer, preferably via the separator layer. Due to the mechanical direct contact, charge transfer can be achieved, thus reducing the electrical resistance. The mechanical stability is also improved.
The electrolyte of the battery, which in particular forms a galvanic cell, is provided by means of the separator layer/electrolyte layer. Since the electrolyte is a constituent of the solid-state battery, it is likewise a solid or at least viscous substance and is also referred to as a solid electrolyte, a solid electrolyte or a solid ion conductor, for example. Suitably, lithium is used as the electrolyte. The cathode layer is preferably likewise arranged substantially perpendicularly to the stacking direction and comprisesLithium, for example pure lithium or lithium compounds. In particular, the cathode layer or at least the lithium compound comprised by the cathode layer is designed to be mechanically and chemically stable. For example, the anode conductor layer is made of metal, preferably copper, which has a relatively high stability. In this case, also, lithium accumulation from the cathode layer can be achieved. In another alternative, the anode conductor layer comprises, for example, at least in part, lithium. Suitably, the anode conductor layer at least partially forms the anode of the cell or an electrical conductor corresponding to the anode. The cathode layer is for example likewise made of lithium or at least partially comprises lithium. In an alternative thereto, the cathode conductor layer is made of a different material, for example aluminum. In this case, the cathode conductor layer serves in particular only as a current collector. Preferably, the cathode layer is made of LCO, NCM, NCA, LFP, LNMO, or the cathode layer at least partially comprises these components. In one embodiment, the cathode of the battery is formed at least partially by means of a cathode layer, and the cathode layer therefore contains active material and/or is designed as a composite material. In another alternative, Li is used5La3Ta2O12、Li5La3Nb2O12、Li7-XLa3Zr2O12-X/2、Li7-XLa3Zr2Nb2、Al 2*(Li7La3Zr2O12)、Ga 2*(Li7La3Zr2O12)、Li7-XLa3Zr2-XTaXO12。
The cathode layer is left empty by means of a plurality of blanks which run parallel to the stacking direction. In other words, recesses are introduced into the cathode layer, which recesses extend in particular up to the surface of the cathode layer. Suitably, the openings of these vacant portions are assigned to the anode conductor layer. Preferably, in this case, the separator layer is spaced apart from the anode conductor layer in the region of the recess.
Therefore, due to the vacant portions, a space is provided for lithium that moves from the cathode layer through the electrolyte layer/separator layer when charging the solid-state battery, and therefore the anode conductor layer does not move relative to the cathode conductor layer in the stacking direction. In other words, during charging of the solid-state battery, lithium is therefore moved at least partially into the recesses perpendicular to the stacking direction. When the solid-state battery is discharged, lithium from these recesses passes through the separator layer and re-enters the cathode layer, wherein no movement of the anode conductor layer relative to the cathode conductor layer occurs again. Therefore, the solid-state battery pack does not change in volume at different states of charge, and does not require a force in the stacking direction or in other directions so as not to change the volume. Therefore, the battery housing of the solid-state battery within which the individual cells are arranged can be designed to be comparatively thin, so that the weight and the structural size are reduced. Since a movement of the anode conductor layer relative to the cathode conductor layer is avoided, it is also ensured that the mechanical contact of the individual layers is maintained and thus also that the layers are kept in electrical contact with each other. Thus, the service life is increased. Furthermore, since no forces have to be applied to the individual layers in the stacking direction, the individual layers do not need to have a comparatively high mechanical stability and thus higher manufacturing tolerances can be selected. Thus, manufacturing is simplified.
For example, these voids are filled with a specific gas. Preferably, however, a vacuum is present in these recesses, which simplifies the process of lithium entering these recesses. In this way, no pressure rise occurs within the solid-state battery. For example, a negative pressure or a rough vacuum is used as the vacuum. Thus, manufacturing is simplified. The vacuum is expediently maintained here by means of a possible battery housing.
Particularly preferably, the solid-state battery is a component of a motor vehicle. In other words, the solid-state battery is a component of the motor vehicle in the normal state. The solid-state battery is suitable for this purpose, in particular is provided and set up for this purpose. In the normal state, the solid-state battery is, for example, a component of an energy store of a motor vehicle, which has a plurality of such solid-state batteries. These solid-state batteries are arranged in particular in the housing of the energy accumulator and are electrically connected in parallel and/or in series with one another. Thus, the voltage attached to the accumulator is a multiple of the voltage provided by each of these solid state battery packs. Expediently, all solid-state batteries are identical to one another in construction here, which simplifies the production. The housing is preferably made of metal, for example steel, such as stainless steel or aluminum, and/or is made in a die-casting process. In particular, the housing is designed to be closed. Expediently, an interface is introduced into the housing, which interface forms the connection end of the energy store. The interface is electrically contacted to the solid-state battery pack, so that electrical energy can be fed out of the energy store and/or extracted from the solid-state battery pack as soon as a corresponding plug is plugged into the connection.
The motor vehicle is preferably land-based and preferably has a plurality of wheels, at least one, preferably a plurality or all of which are driven by means of a drive device. Suitably, one of the wheels, preferably a plurality of wheels, is designed in a controllable manner. Thus, the motor vehicle can be moved independently of a specific lane, for example a track or the like. In this case, it is advantageously possible to position the motor vehicle substantially at will on a roadway, which is made in particular of asphalt, asphalt or concrete. The motor vehicle is, for example, a commercial vehicle, such as a truck (Lkw) or a bus. However, the motor vehicle is particularly preferably a passenger car (Pkw).
The motor vehicle has in particular a drive device, by means of which the travel of the motor vehicle is effected. For example, the drive, in particular the main drive, is designed at least partially electrically, and the motor vehicle is, for example, an electric vehicle. The electric machine is operated, for example, by means of an energy accumulator, which is suitably designed as a high-voltage battery. Suitably, the direct voltage is provided by means of a high voltage battery, wherein the voltage is for example between 200V and 800V and for example approximately 400V. Preferably, an electrical converter is arranged between the high-voltage battery pack and the electric machine, by means of which converter the energization of the electric machine is regulated. In an alternative, the drive additionally has a combustion engine, so that the motor vehicle is designed as a hybrid motor vehicle. In an alternative, the low-voltage on-board system of the motor vehicle is supplied with power by means of an energy store, and a dc voltage of, in particular, 12V, 24V or 48V is provided by means of the energy store.
In the following, in particular only some of the cells of the solid-state battery are discussed. However, these embodiments are particularly applicable to all batteries herein. Preferably, the cells are structurally identical to one another here, preferably all or at least some of these cells are structurally identical to one another. Suitably, all the cells except the cells forming the boundary of the solid-state battery pack on both sides in the stacking direction are structurally identical to each other, or the cells between them are divided into different types, wherein at least two cells are assigned to each type, in particular. In this case, all the batteries assigned to the same type are structurally identical to each other. Particularly preferably, there are only two types of batteries, which further simplifies the manufacture.
Suitably, these recesses are at least partially separated from the cathode conductor layer by means of a separator layer, and the recesses are closed, for example, substantially by means of an anode conductor layer, so that lithium that has precipitated from the cathode layer can directly accumulate on the anode conductor layer. For example, these recesses are only designed in the shape of blind holes and therefore have a bottom. However, it is particularly preferred that these recesses project through the entire cathode layer. In this case, the cathode layer is, for example, designed to be coherent or to have a plurality of regions spaced apart from one another, so that the cathode layer is formed from individual components, between which the recesses are present. Thus, a comparatively large volume is provided for the lithium, so that the existing pressure does not increase too much even if the solid-state battery is fully charged. Since these recesses are continuous, the production is also simplified. These recesses are, for example, only introduced into the cathode layer afterwards, or the cathode layer has been manufactured such that these recesses are present.
Preferably, these vacant sections are identical in structure to each other. Thus, common parts and/or the same manufacturing method can be used, which simplifies the manufacturing. In this way, a uniform charging and discharging of the solid-state battery pack can also be achieved, which avoids local overloads. For example, the shape of these cutouts is partly rhombic or trapezoidal, or the cutouts have a honeycomb structure in a cross section perpendicular to the stacking direction. It is particularly preferred that all the lateral lengths of the cross section of the recess perpendicular to the stacking direction are equally long, irrespective of the respective shape of the recess, so that an overload of one of the walls forming the boundary of the recess, which could lead to a mechanical overload on one side and a subsequent failure of the solid-state battery, is avoided. Therefore, the service life is further increased.
Particularly preferably, each of the cutouts has a truncated pyramid shape. The height of the truncated pyramids expediently corresponds to the distance between the cathode conductor layer and the anode conductor layer, in particular to the distance between the cathode conductor layer and the anode conductor layer as long as these recesses project over the entire cathode layer. In other words, the truncated pyramids run in the stacking direction. Suitably, the base of the truncated pyramid is here assigned to the anode conductor layer, and the blunt end of the pyramid is suitably directed towards the cathode conductor layer. Therefore, the accumulation of lithium on the anode conductor layer is further simplified. In an alternative thereto, the arrangement directions of the truncated pyramids are different with respect to one another, so that the blunt ends or bases of the respective truncated pyramids are alternately assigned to the anode conductor layer or the cathode conductor layer. Due to the design of the truncated pyramid shape, lithium can enter the hollow portion from the cathode layer in the entire circumferential direction of the hollow portion, so that the charging and discharging processes are accelerated. Suitably, in this case, the cutouts are arranged checkerboard-like in a top view along the stacking direction such that the volume of the cathode layer is substantially equal to the volume of the cutouts. Therefore, lithium can be caused to enter and exit these vacant portions from all the circumferential sides of each vacant portion. Stability is also improved in this way.
In particular, the separator layer is applied to the cathode conductor layer in the region of these recesses. In particular, the cathode conductor layer is coated in the region of these recesses by means of a separator layer. In this case, these recesses expediently project through the entire cathode layer. A comparatively large volume of these recesses is thus achieved, so that an excessive pressure build-up is avoided during charging/discharging. The mechanical stability is also improved due to the coating of the separator layer onto the cathode conductor layer, in particular by means of a coating.
Alternatively or particularly preferably in combination therewith, the separator layer is electrically bonded to the anode conductor layer in a region spaced apart from the recesses. The separator layer thus bears directly against the anode conductor layer in the region spaced apart from these recesses, i.e. where the cathode layer is present, so that charge transfer from the cathode layer via the separator layer to the anode conductor layer is possible. In this case, the anode conductor layer can be provided after the cathode layer and the separator layer are manufactured in a relatively simple manner due to the conductive adhesion, and therefore the manufacturing is simplified.
Particularly preferably, these recesses are completely lined with a separator layer, so that the entire volume of these recesses is available for the precipitation of lithium. Therefore, pressure accumulation is reduced at the time of lithium deposition, which improves stability. In this way, electrical short circuits are also avoided and manufacturing is also simplified. For this purpose, the entire intermediate product is coated with a separator layer during production, in particular after the cathode layer has been applied to the cathode conductor layer.
In a particularly preferred embodiment of the invention, the separator layer is coated with an electrically conductive layer in the region of the recesses, preferably on the side opposite the cathode layer, i.e. on the side of the anode conductor layer. In other words, the electrically conductive coating on the separator layer is arranged on the anode side in these recesses. For example, in this case, the separator layer is provided with a conductive coating only in the region of the recesses or over the entire surface, so that the separator layer bears against the anode conductor layer via the conductive coating. Alternatively, the coating in the regions of the separator layer which are in direct contact with the anode conductor layer differs from the coating in the regions of these recesses. Due to the electrically conductive coating, in particular the accumulation of lithium in these recesses is facilitated. The conductive coating is for example carbon-based and particularly preferably graphite.
Particularly preferably, a garnet-group compound is used as the lithium-containing cathode layer. That is, a material that forms garnet and contains lithium is used. The material is a mechanically and chemically stable material, so that the precipitation of lithium after passing through the separator layer is simplified. Particularly preferably, LLZO (lanthanum lithium zirconate) is used here as the material of the cathode layer. In an alternative thereto, LLTO, LATP are used, i.e. oxides, polymers, such as polyethylene oxide, sulphides, such as LGPS, LI, respectively7P3S11、Li2S-P2S5A gas.
For example, the recesses of all directly adjacent cells, i.e. cells directly adjoining one another in the stacking direction, are arranged flush or randomly with respect to one another. However, it is particularly preferred if the recesses of directly adjacent cells are offset relative to one another perpendicular to the stacking direction. Therefore, the empty spaces of these directly adjacent cells do not overlap. In particular, in this case, the cross-section of these cutouts perpendicular to the stacking direction is rectangular, and the cutouts of each cell are arranged in a checkerboard fashion relative to one another. Thus, in the stacking direction, there is a cathode layer on each side opposite to these empty portions with respect to the anode conductor layer or the cathode conductor layer, respectively. In the case of lithium accumulation in these recesses, the pressure acting on the cathode conductor layer or anode conductor layer bordering the recesses is therefore compensated on the opposite side by means of the cathode layer, or these layers are at least stabilized, so that no damage of the anode conductor layer or cathode conductor layer occurs even in the case of excessive pressure within these recesses. Therefore, the stability is further improved. For example, the cutouts of all directly adjacent cells are offset relative to one another perpendicular to the stacking direction. However, it is particularly preferred if only the recesses of the cells directly adjacent in one direction with respect to each of the cells are offset perpendicularly to the stacking direction with respect to one another. While the empty spaces of the directly adjacent cells in opposite directions of the respective cells are flush with respect to each other. Thus, on the one hand, the stability is improved. On the other hand, the manufacture is simplified and there is a comparatively short electrical connection between adjacent cathode layers, so that the electrical resistance is reduced.
For example, one of the anode conductor layers of the solid-state battery is stacked on each cathode conductor layer on the side opposite to the cathode layer in the stacking direction and is, for example, directly fixed to the cathode layer and is thus directly electrically contacted. Therefore, all the cells of the solid-state battery pack are electrically connected in series with each other. Particularly preferably, however, a plurality of cathode conductor layers and a plurality of anode conductor layers are each assigned to two directly adjacent cells. In this case, the cathode conductor layer and the anode conductor layer of the same cell are each assigned to a different cell. In other words, the cathode conductor layer is assigned to the cell adjacent in the stacking direction on one side thereof and the anode conductor layer is assigned to the cell adjacent in the stacking direction on the other side thereof. Suitably, all of the cathode conductor layers or the anode conductor layers except the cathode conductor layer or the anode conductor layer forming the boundary of the solid-state battery in the stacking direction are respectively assigned to two of the cells. In other words, the cathode conductor layer of each of these cells is arranged between two cathode layers, wherein these cathode layers are assigned to different cells. Preferably, the cathode layers are in this case in direct electrical contact with the respective cathode conductor layer. Therefore, two of the cells of the solid-state battery pack are always electrically connected in parallel with each other, and the capacity of each solid-state battery pack is thus increased.
The method is used to manufacture a battery of a solid-state battery having a plurality of batteries stacked one on another in a stacking direction. The cells are identical to one another in particular in terms of construction. In this case, the solid-state battery is suitable, in particular, for use in a high-voltage battery or other energy store of a motor vehicle, for example a land vehicle, which is expediently designed as a multi-rail vehicle. Alternatively thereto, the motor vehicle is for example a monorail and in particular a motorcycle. Suitably, the motor vehicle comprises an electric drive which is electrically connected with the high voltage battery pack, preferably via a converter. The drive means is therefore energized by means of the high-voltage battery pack. In this way, energy can also be fed into the high-voltage battery, in particular as long as the drive is operated as a generator. The drive device acts in particular on possible wheels of the motor vehicle. The drive means are formed, for example, by means of a motor or a plurality of motors. Alternatively thereto, the electric machine additionally comprises a combustion engine by means of which the one or more electric machines are assisted.
The battery has a cathode conductor layer arranged perpendicular to the stacking direction and an anode conductor layer arranged perpendicular to the stacking direction, the cathode conductor layer and the anode conductor layer being mechanically connected to each other by a cathode layer containing lithium and a separator layer. Here, the electrolyte is provided by means of a cathode layer, wherein the electrolyte is a solid or at least viscous substance. The cathode layer is left empty by means of a plurality of empty spaces running parallel to the stacking direction.
The method for manufacturing the battery provides for: first, a cathode conductor layer is provided. In particular, the cathode conductor layer is made of aluminum, for example, stamped. In a further working step, a cathode layer which is left free by means of a plurality of blanks running parallel to the stacking direction is applied to the cathode conductor layer. The cathode layer here in particular already has lithium. The cathode layer is applied on the cathode conductor layer, for example by means of 3D printing or by means of a screen printing process. Suitably, the cathode conductor layer is first provided with a template before the cathode layer is applied, in particular in the areas where these voids should be present. This is preferably achieved by means of a coating template or by means of a polymer, which is in particular applied in the form of a matrix and/or dots. Then, a material forming the cathode layer is coated on the cathode conductor layer. This is achieved, for example, by means of a printing process, for example a screen printing process, or by means of casting, for example a casting based on a paste. The coating is carried out, for example, by means of a doctor blade. Preferably, the material is subsequently dried, so that there is a cathode layer which does not yet have a void. In particular, subsequent sintering is carried out, thus improving the mechanical stability. The placeholder or template is then suitably removed, wherein this is effected, for example, in a solvent-based manner, thermally or mechanically. In summary, a coating of the cathode layer is thus achieved, which in particular comprises a cathode active material. For this purpose, for example, screen printing, 3D printing or sintering is used. In particular, a subsequent drying step is carried out in each case. Alternatively, the coating is effected by means of sputtering or by means of Laser Deposition, for example Pulsed Laser Deposition (Pulsed Laser Deposition) or ALD.
In a subsequent working step, a separator layer is applied to the exposed portions of the cathode conductor layer and the cathode layer, i.e. the exposed portions of the cathode layer. This is effected, for example, in a wet-chemical manner, by means of screen printing, by means of 3D printing or by vapor deposition. The coated membrane layer is then expediently dried and/or sintered. Thus, the exposed portions of the electrolyte layer and the cathode conductor layer are completely wetted by the separator layer and are thus provided with the separator layer.
In a subsequent working step, an anode conductor layer is provided, which is present in particular as a plate, suitably as a copper plate. The anode conductor layer is fixed to the separator layer, suitably by means of an electrically conductive adhesive. In particular, the anode conductor layer is fixed here only at a region of the separator layer which is spaced apart from the cathode conductor layer, in particular at the free end of the cathode layer provided with the separator layer.
Due to this method, a comparatively time-saving manufacture of the battery can be achieved. In addition, in particular, cathode layers are applied to both sides of the cathode conductor layer, so that the cathode conductor layer is assigned to two cells adjacent to one another. In this way, two cathode layers can be applied in one working step, which are each assigned to a directly adjacent cell. It is also possible to produce a plurality of modules in one working step, each module having a common cathode conductor layer, two cathode layers and two separator layers. In a subsequent operating step, the individual modules are stacked on top of one another by means of the respectively assigned anode conductor layer, so that two cells connected in parallel with one another are connected electrically in series to produce the solid-state battery.
The cell is a constituent of a solid-state battery and has a cathode conductor layer arranged perpendicular to the stacking direction and an anode conductor layer arranged perpendicular to the stacking direction, which are mechanically connected to one another by a lithium-containing cathode layer and a separator layer. The cathode layer is left empty by means of a plurality of empty spaces running parallel to the stacking direction. Preferably, the cell is produced in a method in which a cathode conductor layer is provided and a cathode layer which is left empty by means of a plurality of blanks running parallel to the stacking direction is applied to the cathode conductor layer. A separator layer is applied to the cathode conductor layer and the exposed portions of the cathode layer, and an anode conductor layer is at least partially secured to the separator layer.
In contrast, the advantages and embodiments described in connection with the solid-state battery can also be transferred to the method/the battery and to each other and vice versa.
Drawings
Subsequently, embodiments of the invention are explained in more detail on the basis of the figures. Wherein:
fig. 1 schematically and in a simplified manner shows a motor vehicle having a high-voltage battery pack with a plurality of solid-state battery packs;
fig. 2 schematically shows one of the solid-state battery packs in a sectional view along the stacking direction;
fig. 3 shows a solid-state battery in a sectional view perpendicular to the stacking direction;
fig. 4 shows a variant of the solid-state battery according to fig. 3; and
fig. 5 shows a method for manufacturing a battery of a solid-state battery.
Parts corresponding to each other are provided with the same reference numerals throughout the drawings.
Detailed Description
In fig. 1, a motor vehicle 2 in the form of a passenger vehicle (Pkw) is schematically shown. The motor vehicle 2 has a plurality of wheels 4, at least some of which are driven by means of a drive device 6, which comprises an electric motor. Thus, the automobile 2 is an electric vehicle or a hybrid vehicle. The drive 6 also has a current transformer by means of which the electric motor is energized. The converter of the drive 6 is in turn energized by means of an energy accumulator 8 in the form of a high-voltage battery. For this purpose, the drive 6 is connected to an interface 10 of the energy store 8, which is inserted into a housing 12 of the energy store 8, which is made of stainless steel. Disposed within housing 12 are a plurality of solid state battery packs 14, two of which are shown. The solid-state battery packs 14 are in electrical contact with each other, wherein a portion of the solid-state battery packs 14 are electrically connected in series with each other and the portion and other portions of the solid-state battery packs 14 are electrically connected in parallel with each other. The electrical connections of the solid-state battery packs 14 are in electrical contact with the interface 10, so that the solid-state battery packs 14 are discharged when the drive 6 is operated. Due to this electrical connection, the voltage of 400V provided at the interface 10 is in this case a multiple of the voltage provided by the solid-state battery packs 14 which are identical in construction to one another.
In fig. 2, one of the solid-state battery packs 14 is schematically and simply shown in a sectional view along the stacking direction 16. The solid-state battery 14 has a battery housing 18 which is made of metal and into which two connection terminals 20 are introduced. In operation, a dc voltage is present at these connections 20. Inside the outer casing 18, a plurality of cells 22 are stacked one on top of the other in the stacking direction 16, wherein each of the cells 22 outermost in the stacking direction 16 is electrically contacted to one of the connection terminals 20.
Each of the cells 22 has a cathode conductor layer 24, which is arranged in each case perpendicularly to the stacking direction 16 and is in each case formed as an aluminum plate. Each of the cells 22 also has an anode conductor layer 26, which is formed by means of a copper plate and is arranged perpendicularly to the stacking direction 16. The cathode conductor layer 24 and the anode conductor layer 26 coincide with each other in the stacking direction 16. Along stacking direction 16, the stack of cells 22 is bounded on one side by one of the cathode conductor layers 24 and on the opposite side by one of the anode conductor layers 26. Here, the cathode conductor layer 24 and the anode conductor layer 26 are respectively assigned only to the cells 22 that are outermost in the stacking direction 16. While the remaining anode conductor layer 26 and cathode conductor layer 24 are respectively assigned to two of the cells 22, that is to say respectively two cells which are adjacent in the stacking direction 16. In summary, a plurality of cathode conductor layers 24 and a plurality of anode conductor layers 26 are thus respectively assigned to two directly adjacent cells 22. Here, the number of cathode conductor layers and anode conductor layers is one minus ("1") the number of cells 22.
Between each of the cathode conductor layers 24 and the respectively associated anode conductor layer 26 of the same cell 22, a lithium-containing cathode layer 28 is arranged, which is left free by means of a plurality of recesses 30 running parallel to the stacking direction 16. Cathode layer 28 has lithium and is a compound of garnet groups. In this case, LLZO, i.e., lanthanum lithium zirconate, is used as the material of the cathode layer 28.
The hollow 30 is filled with a negative pressure or rough vacuum and protrudes completely through the respective allocated cathode layer 28. The shape of the recesses 30 is respectively a truncated pyramid running in the stacking direction 16. In other words, the hollow 30 is a truncated pyramid. In this case, the widened ones of the ends are each closed by means of the assigned anode conductor layer 26.
As shown in a cross-sectional view perpendicular to stacking direction 16 in fig. 3, cutouts 30 are arranged in a checkerboard pattern such that cathode layer 28 of each cell 22 is also checkerboard-shaped. In this case, the cutouts 30 of the cells 22 adjacent with respect to the respective anode conductor layers 26 are vertically offset from each other in the stacking direction 16. Whereas the cutouts 30 of adjacent cells 22 are arranged flush with respect to one another with respect to the cathode conductor layers 24 respectively arranged therebetween.
When charging the solid-state battery 14, a voltage is applied to the connection 20, so that a voltage is also formed between the cathode conductor layer 24 and the anode conductor layer 26 of each cell 22. Thus, lithium enters the corresponding void 30 of each of cells 22 from the respective cathode layer 28 and accumulates there on the respective anode conductor layer 26. Here, the already existing possible forces acting between adjacent cathode conductor layers 24 and anode conductor layers 26 in the stacking direction 16 do not change, so that the solid-state battery 14 is comparatively stable. When battery 14 is discharged, lithium re-enters cathode layer 28 from void 30 through separator layer 32.
Fig. 4 shows a variant of the solid-state battery 14. In this case, the cross section of the recesses 30 perpendicular to the stacking direction 16 is honeycomb-shaped, and the cathode layer 28 is at least partially designed as a continuous surface. While the arrangement of the cathode conductor layer 24, the anode conductor layer 26, and the separator layer 32 in the stacking direction 16 is unchanged.
A method for manufacturing one of the cells 22 of the solid-state battery 14 is shown in fig. 5. In a first working step 36, the cathode conductor layer 24 is provided. For this purpose, the cathode conductor layer 24 is stamped from an aluminum sheet.
In a subsequent second work step 38, a template is applied to the cathode conductor layer 24. The template is coated, for example by means of 3D printing, or the template is a solid body which is fixed on the cathode conductor layer 24. In another alternative, the template is a matrix of placeholders, e.g., polymers, coated onto the cathode conductor layer 24. By means of the template/placeholder, the cathode conductor layer 24 is covered in the area where the space 30 should later be present. In this case, the cathode conductor layer 24 is covered on opposite sides in the stacking direction 16 by means of a stencil. Preferably, two such templates are used for this purpose.
In an immediately third working step 40, a cathode layer 28 with electrolyte is applied to the cathode conductor layer 24 covered by means of a template. A cathode layer 28 is also applied to cathode conductor layer 24 on the opposite side. Thus, cathode layers 28 are coated on both sides of cathode conductor layer 24, respectively. The coating is performed by means of a screen printing process, for example a paste-based screen printing process. In this case, the material of cathode layer 28 adheres to the template in the region of the recesses 30 to be produced and otherwise to cathode conductor layer 24. Once the material of cathode layer 28 is dried, the material is additionally sintered, which improves mechanical stability.
In a subsequent fourth work step 42, the template/templates is/are removed from both sides of the cathode conductor layer 24, for which purpose a solvent is used, for example. In an alternative, the template/templates are mechanically removed. Therefore, only the cathode conductor layer 24 is present, and one of the cathode layers 28 is present on both sides of the cathode conductor layer, and is left empty by the empty portions 30.
In a fifth work step 44, the existing intermediate product of cathode conductor layer 24 and two cathode layers 28 is provided with two separator layers 32. Thus, the separator layers 32 are applied to the exposed portions of the cathode conductor layer 24 and possibly the cathode layer 28, respectively, so that there are now two separator layers 32, between which the two cathode layers 28 and the cathode conductor layer 24 are arranged. To improve the mechanical stability, the membrane layer 32 is not only dried but also sintered.
In a following sixth work step 46, the anode conductor layer 26 is fixed and for this purpose electrically conductively bonded to one of the separator layers 32. Thus making one of the cells 22. If a further anode conductor layer 26 is fastened to a further separator layer 32 on the side opposite in the stacking direction 16, two cells 22 are thus produced which are electrically connected in parallel with one another between the two anode conductor layers 26 and the common cathode conductor layer 24.
The intermediate products present after the fifth operating step 44 can be prefabricated into modules, wherein a corresponding number of modules are assembled to form the solid-state battery 14, if necessary. In an alternative, the template, the cathode layer 28, the separator layer 32 and the anode conductor layer 26 are applied only on a single one of the sides of the cathode conductor layer 24, so that only a single cell 22 is produced by means of the method 34, which accordingly has only a single cathode layer 28, separator layer 32, anode conductor layer 26 and cathode conductor layer 4.
The invention is not limited to the embodiments described above. Rather, other variants of the invention can be derived therefrom by those skilled in the art without departing from the subject matter of the invention. Furthermore, all individual features described in connection with the individual embodiments can furthermore also be combined with one another in other ways without departing from the subject matter of the invention.
List of reference numerals
2 Motor vehicle
4 wheel
6 drive device
8 energy accumulator
10 interface
12 outer cover
14 solid state battery
16 stacking direction
18 Battery pack case
20 connecting end
22 cell
24 cathode conductor layer
26 anode conductor layer
28 cathode layer
30 hollow part
32 diaphragm layer
34 method
36 first working step
38 second working step
40 third working step
42 fourth working step
44 fifth working step
46 sixth work step.
Claims (11)
1. A solid-state battery (14) having a plurality of cells (22) stacked one above the other in a stacking direction (16), wherein each cell (22) has a cathode conductor layer (24) arranged perpendicular to the stacking direction (16) and an anode conductor layer (26) arranged perpendicular to the stacking direction (16), which are mechanically connected to one another by a lithium-containing cathode layer (28) and a separator layer (32), wherein the cathode layer (28) is left free by means of a plurality of recesses (30) running parallel to the stacking direction (16).
2. The solid state battery (14) of claim 1, wherein the void (30) extends through the entire cathode layer (28).
3. The solid state battery (14) of claim 1 or 2, wherein each hollow (30) is in the shape of a truncated pyramid.
4. The solid-state battery (14) according to any one of claims 1 to 3, characterized in that the separator layer (32) is applied to the cathode conductor layer (24) in the region of the recess (30).
5. The solid state battery (14) of any of claims 1 to 4, wherein the separator layer (32) is conductively bonded to the anode conductor layer (26) in a region spaced from the void (30).
6. The solid-state battery (14) according to one of claims 1 to 5, characterized in that an electrically conductive coating, in particular graphite, on the separator layer (32) is provided on the anode side in the recess (30).
7. The solid-state battery (14) according to any one of claims 1 to 6, characterized in that a compound of garnet groups is used as the lithium-containing cathode layer (28).
8. Solid-state battery (14) according to one of claims 1 to 7, characterized in that the cutouts (30) of directly adjacent cells (22) are staggered with respect to one another perpendicular to the stacking direction (16).
9. The solid-state battery (14) according to any one of claims 1 to 8, characterized in that a plurality of the cathode conductor layers (24) and a plurality of the anode conductor layers (26) are respectively assigned to two directly adjacent cells (22).
10. Method (34) for manufacturing a battery (22) of a solid state battery (14) according to any of claims 1 to 9, wherein
-providing a cathode conductor layer (24);
-applying a cathode layer (28) which is left empty by means of a plurality of blanks (30) running parallel to the stacking direction (16) to the cathode conductor layer (24);
-applying a separator layer (32) onto exposed portions of said cathode conductor layer (24) and said cathode layer (28); and is
-partially fixing an anode conductor layer (26) on the separator layer (32).
11. A battery (22) of a solid state battery (14) according to any one of claims 1 to 9.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102020205065 | 2020-04-22 | ||
| DE102020205065.1 | 2020-04-22 |
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| CN113839078A true CN113839078A (en) | 2021-12-24 |
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| CN202110434510.XA Pending CN113839078A (en) | 2020-04-22 | 2021-04-22 | Solid state battery pack |
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| DE (1) | DE102021203235A1 (en) |
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