Manufacture of solid state batteries using molten solid electrolyte
By using a method of combining molten solid electrolyte with an active material layer, the problem of complex and costly manufacturing process of the battery pack system is solved, and the effect of simplifying the manufacturing process, reducing costs and improving battery performance is achieved.
Patent Information
- Application Number
- CN202410174684.0
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Priority Date
- 2023-10-09
- Filing Date
- 2024-02-07
- Publication Date
- 2025-04-11
AI Technical Summary
Existing battery pack systems have complex and costly manufacturing processes in improving power density and range, especially when manufacturing composite solid electrolytes/electrodes.
The molten solid electrolyte is used to combine with the active material layer, by melting the solid electrolyte and coating it on the active material layer, or by laying the solid electrolyte on the active material layer and heating it to produce the molten solid electrolyte, and then solid electrolyte is solidified to form the solid electrolyte layer.
This method simplifies the manufacturing process, reduces capital investment needs, avoids the need to manufacture fragile thin layers, and enables the manufacture of solid electrolytes at a thinner thickness, creating low interfacial resistance.
Smart Images
Figure CN119812423A_ABST
Abstract
Description
Technical Field
[0001] The present disclosure relates to the fabrication of battery cells, and more particularly to the fabrication of composite solid electrolyte / electrodes using molten solid electrolytes. Background Art
[0002] The information provided in this section is for the purpose of generally introducing the background of the present disclosure. No admission is made, either explicitly or implicitly, that the work of the presently named inventors described in this section is prior art to the present disclosure, nor is it admitted that the work is prior art to the present disclosure, as described in this section, which may not otherwise be identified as prior art at the time of filing.
[0003] Electric vehicles (EVs), such as battery electric vehicles (BEVs), hybrid electric vehicles, and / or fuel cell vehicles, include one or more motors and a battery system, which includes one or more battery cells, modules, and / or packs. A battery control module is used to control the charging and / or discharging of the battery system during charging and / or driving. Electric vehicle manufacturers are seeking to increase power density to increase the range of electric vehicles. Summary of the invention
[0004] A method for making a composite solid electrolyte (SSE) / electrode for a battery cell, comprising providing an electrode comprising an active material layer. The method comprises one of the steps of melting a solid electrolyte to produce a molten solid electrolyte and coating the active material layer with the molten solid electrolyte, and disposing a solid electrolyte on the active material layer and heating the electrode and the solid electrolyte to produce a molten solid electrolyte. The method comprises solidifying the molten solid electrolyte to form a solid electrolyte layer.
[0005] In other features, the active material layer is disposed on a current collector. The molten solid electrolyte penetrates into open areas between particles of the active material layer. The melting temperature of the solid electrolyte is less than or equal to 300° C. The solid electrolyte is selected from a polymer, an antiperovskite, a lithium metal halide, a lithium hydride, a lithium closo-borate, and / or a combination thereof.
[0006] In other features, the melting comprises one or more methods selected from induction heating, warm isostatic pressing (WIP), infrared light, ultrafast high temperature sintering (UHS), flash heating, microwave heating and discharge plasma. The molten solid electrolyte is applied to the active material layer using a method selected from injection, ultrasonic, hot rolling / pressing and / or spraying. The active material layer further comprises an active material, a binder and a conductive filler.
[0007] In other features, the electrode comprises an anode electrode, the active material in the active material layer comprises an anode active material, and the current collector comprises an anode current collector.
[0008] In other features, the electrode comprises a cathode electrode, the active material in the active material layer comprises a cathode active material, and the current collector comprises a cathode current collector.
[0009] A method for making a composite solid electrolyte (SSE) / electrode for a battery cell includes providing an electrode including an active material layer and a wetting layer disposed on the active material layer. The method includes one of: melting a solid electrolyte to produce a molten solid electrolyte and coating the wetting layer with the molten solid electrolyte, and disposing a solid electrolyte on the wetting layer and heating the electrode, the wetting layer, and the solid electrolyte to produce a molten solid electrolyte. The method includes solidifying the molten solid electrolyte to form a solid electrolyte layer.
[0010] In other features, the active material layer is disposed on a current collector. The wetting layer comprises aluminum oxide. The melting temperature of the solid electrolyte is less than or equal to 300° C. The solid electrolyte is selected from polymers, antiperovskites, lithium metal halides, lithium hydrides, lithium borate, and / or combinations thereof.
[0011] In other features, the melting comprises one or more methods selected from induction heating, warm isostatic pressing (WIP), infrared light, ultrafast high temperature sintering (UHS), flash heating, microwave heating and discharge plasma. The molten solid electrolyte is applied to the active material layer using a method selected from injection, ultrasonic, hot rolling / pressing and / or spraying. The active material layer further comprises an active material, a binder and a conductive filler.
[0012] In other features, the electrode comprises an anode electrode, the active material in the active material layer comprises an anode active material, and the current collector comprises an anode current collector.
[0013] In other features, the electrode comprises a cathode electrode, the active material in the active material layer comprises a cathode active material, and the current collector comprises a cathode current collector.
[0014] The present invention discloses the following scheme:
[0015] Scheme 1. A method for making a composite solid electrolyte (SSE) / electrode for a battery cell, comprising:
[0016] providing an electrode including an active material layer;
[0017] Do one of the following:
[0018] melting a solid electrolyte to produce a molten solid electrolyte, and coating the active material layer with the molten solid electrolyte, and
[0019] disposing a solid electrolyte on the active material layer, and heating the electrode and the solid electrolyte to produce a molten solid electrolyte; and
[0020] The molten solid electrolyte is solidified to form a solid electrolyte layer.
[0021] Option 2. The method according to Option 1, wherein the active material layer is arranged on a current collector.
[0022] Option 3. A method according to Option 1, wherein the molten solid electrolyte penetrates into open areas between particles of the active material layer.
[0023] Option 4. A method according to Option 1, wherein the melting temperature of the solid electrolyte is less than or equal to 300°C.
[0024] Option 5. A method according to Option 1, wherein the solid-state electrolyte is selected from polymers, antiperovskites, lithium metal halides, lithium hydrides, lithium closo-borate and / or combinations thereof.
[0025] Option 6. A method according to Option 1, wherein the melting includes one or more methods selected from induction heating, warm isostatic pressing (WIP), infrared light, ultrafast high temperature sintering (UHS), flash heating, microwave heating and discharge plasma.
[0026] Option 7. A method according to Option 1, wherein the molten solid electrolyte is applied to the active material layer using a method selected from injection, ultrasound, hot rolling / pressing and / or spraying.
[0027] Option 8. The method according to Option 1, wherein the active material layer further comprises an active material, a binder and a conductive filler.
[0028] Scheme 9. The method according to Scheme 2, wherein:
[0029] The electrodes include an anode electrode,
[0030] The active material in the active material layer includes an anode active material, and
[0031] The current collector includes an anode current collector.
[0032] Scheme 10. The method according to Scheme 2, wherein:
[0033] The electrodes include a cathode electrode,
[0034] The active material in the active material layer includes a cathode active material, and
[0035] The current collector includes a cathode current collector.
[0036] 11. A method for making a composite solid electrolyte (SSE) / electrode for a battery cell, comprising:
[0037] providing an electrode including an active material layer and a wetting layer disposed on the active material layer;
[0038] Do one of the following:
[0039] melting a solid electrolyte to produce a molten solid electrolyte, and coating the wetting layer with the molten solid electrolyte, and
[0040] disposing a solid electrolyte on the wetting layer, and heating the electrode, the wetting layer, and the solid electrolyte to produce a molten solid electrolyte; and
[0041] The molten solid electrolyte is solidified to form a solid electrolyte layer.
[0042] Option 12. The method according to Option 11, wherein the active material layer is arranged on a current collector.
[0043] Option 13. The method according to Option 11, wherein the wetting layer comprises aluminum oxide.
[0044] Option 14. A method according to Option 11, wherein the melting temperature of the solid electrolyte is less than or equal to 300°C.
[0045] Option 15. A method according to Option 11, wherein the solid-state electrolyte is selected from polymers, antiperovskites, lithium metal halides, lithium hydrides, lithium borate and / or combinations thereof.
[0046] Option 16. A method according to Option 11, wherein the melting includes one or more methods selected from induction heating, warm isostatic pressing (WIP), infrared light, ultrafast high temperature sintering (UHS), flash heating, microwave heating and discharge plasma.
[0047] Option 17. A method according to Option 11, wherein the molten solid electrolyte is applied to the active material layer using a method selected from injection, ultrasound, hot rolling / pressing and / or spraying.
[0048] Option 18. The method according to Option 11, wherein the active material layer further comprises an active material, a binder and a conductive filler.
[0049] Embodiment 19. The method according to embodiment 12, wherein:
[0050] The electrodes include an anode electrode,
[0051] The active material in the active material layer includes an anode active material, and
[0052] The current collector includes an anode current collector.
[0053] Option 20. The method according to Option 12, wherein:
[0054] The electrodes include a cathode electrode,
[0055] The active material in the active material layer includes a cathode active material, and
[0056] The current collector includes a cathode current collector.
[0057] Further areas of applicability of the present disclosure will become apparent from the detailed description, claims and drawings.The detailed description and specific examples are intended for purposes of illustration only and are not intended to limit the scope of the present disclosure. BRIEF DESCRIPTION OF THE DRAWINGS
[0058] The present disclosure will be more fully understood from the detailed description and accompanying drawings, in which:
[0059] Figure 1 is a side cross-sectional view of an example of a solid-state battery cell including an electrode fabricated using a molten solid electrolyte according to the present disclosure;
[0060] Figure 2 is a side cross-sectional view of a battery pack including a solid-state battery cell according to the present disclosure;
[0061] Figure 3A , Figure 3B and Figure 3C is a perspective view of an example of a method for melting a powdered solid state electrolyte (SSE) onto an active material layer of an electrode according to the present disclosure;
[0062] Figure 4 is a perspective view of an example of a method for spraying a molten solid electrolyte (SSE) onto an active material layer of an electrode to form a composite SSE / electrode according to the present disclosure;
[0063] Figure 5A and Figure 5B is an example of an electrode according to the present invention before application of a molten solid electrolyte; and
[0064] Figure 6 is a flow chart of an example of a method of making a composite SSE / electrode using a molten solid electrolyte according to the present disclosure.
[0065] In the drawings, reference numerals may be repeated to designate similar and / or identical elements. DETAILED DESCRIPTION
[0066] Although solid-state battery cells according to the present disclosure are illustrated herein in the context of electric vehicles, the solid-state battery cells may be used in stationary applications and / or other types of battery applications.
[0067] Solid-state batteries (SSBs) have higher energy density and improved safety performance compared to liquid electrolyte battery systems. However, the manufacturing process of SSBs is complex and costly due to high temperature and high pressure procedures, including sintering ceramic solid electrolyte membranes, manufacturing of cathode / SSE composite electrodes, anode / SSE composite electrodes, and stacking and sintering layers between current collectors. Understandably, this manufacturing method requires a large amount of capital investment.
[0068] The present disclosure relates to the manufacture of SSBs using molten solid electrolytes (SSEs). The molten SSE is distributed (or melted in situ) onto a cathode electrode and / or an anode electrode to form a composite SSE / cathode electrode and / or SSE / anode electrode, respectively. In some examples, the molten SSE is applied to the active material layer of the electrode using one or more methods such as injection, ultrasonic heating, hot rolling / pressing, and / or spraying. In some examples, the heating source for melting the SSE uses induction heating, warm isostatic pressing, infrared light, ultrafast high temperature sintering, flash heating, microwave heating, and / or discharge plasma heating.
[0069] In some examples, the melting temperature of the SSE is less than or equal to 300° C. Examples of SSEs include polymers, antiperovskites, lithium metal halides, lithium hydrides, lithium borates, and / or complexes thereof. In some examples, an interlayer may be disposed between the SSE and the active material layer of the electrode to improve wettability of the molten SSE with the active material layer of the electrode. In some examples, the interlayer comprises aluminum oxide (Al2O3).
[0070] A liquefied / molten SSE with a low melting point (less than or equal to 300°C) is absorbed into the active material layer of the electrode and then solidifies during cooling. This method requires less capital investment than previous methods. Using this method eliminates the need to manufacture a fragile and thin SSE layer. In addition, the SSE can be formed on current lithium-ion cathode or anode electrodes. Since the SSE does not need to be processed, it can be manufactured in a relatively thin thickness compared to other methods. In addition, this method produces low interfacial resistance.
[0071] Reference now Figure 1 and Figure 2, the battery cell 10 includes cathode electrodes 20-1, 20-2, ..., and 20-C, where C is an integer greater than 1. The cathode electrode 20 includes a cathode active material layer 24 arranged on one side or both sides of the cathode current collector 26. The battery cell 10 includes anode electrodes 40-1, 40-2, ..., and 40-A, where A is an integer greater than 1. The anode electrode 40 includes an anode active material layer 42 arranged on one side or both sides of the anode current collector 46. The cathode electrode 20, the anode electrode 40 and S separators 32 are arranged in a predetermined order in the battery cell stack 12, and the battery cell stack 12 is arranged in the housing 50, where S is an integer greater than 1. For example, the separator 32 is arranged between the cathode electrode 20 and the anode electrode 40. The outer tabs 28 and 48 of the cathode electrode 20 and the anode electrode 40 may be arranged on the same side, different sides and / or opposite sides. The external tabs 28 and 48 allow for connection between the cathode electrode 20 and the anode electrode 40 and the terminals of the battery cell 10 .
[0072] exist Figure 2 , the battery pack 58 includes M battery modules 56 - 1 , 56 - 2 , . . . , and 56 -M, each battery module including B battery cells 10 (eg, battery cells 10 - 1 , 10 - 2 , . . . , and 10 -B), where B and M are integers greater than 1.
[0073] Reference now FIG. 3A to FIG. 3C , shows an example of melting SSE powder 80 onto an electrode 81 including an active material layer 82 and a current collector 84. Figure 3A In the process, SSE powder 80 is placed on active material layer 82 and heated to a temperature greater than the melting temperature of the SSE powder. Figure 3B In the process, the molten SSE powder 80' begins to infiltrate the open areas between the particles of the active material layer 82 (as shown at 86). After heating is completed, the molten SSE powder 80' substantially fills the open volume, as shown at 86. Figure 3C As will be further described below, in other examples, the SSE is melted prior to contacting the electrode.
[0074] Referring now to FIG. 4 , an example of a manufacturing method is shown. A delivery system 90 supplies an electrode 91 (discrete or continuous) to a housing 93, which includes a dispenser 92 (e.g., a syringe or sprayer) that dispenses molten SSE into the electrode 91. A leveling device 96 levels the thickness of the molten SSE on the electrode 91 to form a composite SSE / electrode 97 having an SSE layer 98 (e.g., having a predetermined thickness of less than 50 μm in some examples).
[0075] Reference now Figure 5A and 5B, shows an example of an electrode before adding molten SSE. Figure 5A In the embodiment, an electrode 120 (e.g., a cathode electrode and / or an anode electrode) includes an active material layer 122 disposed on one or both sides of a current collector 126. The active material layer 122 includes different types of particles, which contain one or more active materials 132, conductive fillers 134, binders 136, and / or other materials. After manufacturing the electrode 120 having the active material layer 122, a portion of the molten solid electrolyte infiltrates into the open area of the active material layer 122 and the other portion forms the SSE layer 98 ( Figure 4 ).
[0076] exist Figure 5B In the embodiment, an electrode 140 (e.g., a cathode electrode and / or an anode electrode) includes an active material layer 142 disposed on one or both sides of a current collector 146. The active material layer 142 includes different types of particles, the particles including one or more active materials 152, conductive fillers 154, binders 156, and / or other materials. In some examples, a wetting layer 160 is applied on the outer surface of the active material layer 142. In some examples, the wetting layer 160 includes aluminum oxide (Al2O3). After manufacturing the electrode 140 with the active material layer 142, a portion of the molten solid electrolyte 138 penetrates into the open area of the active material layer 122 and the other portion forms the SSE layer 98 ( Figure 4 ).
[0077] Reference now Figure 6 , a method 250 for making electrodes and battery cells using a molten solid electrolyte is shown. At 260, the electrode includes one or more active material layers arranged on a current collector. In some instances, the active material layer includes an optional wetting layer. At 264, the solid electrolyte is either melted in situ on the electrode into a molten solid electrolyte, or melted to a molten state before coating the electrode. In some instances, the melting temperature of the solid electrolyte is less than or equal to 300°C. In some instances, the solid electrolyte is selected from polymers, antiperovskites, lithium metal halides, lithium metal hydrides, closed lithium borates and / or combinations thereof. In some instances, melting includes one or more methods selected from induction heating, warm isostatic pressing (WIP), infrared light, ultrafast high temperature sintering (UHS), flash heating, microwaves and / or discharge plasma.
[0078] At 266, a portion of the molten solid electrolyte infiltrates one or more active material layers and the other portion forms SSE layer 98 ( Figure 4). In some examples, the molten solid electrolyte is applied to the one or more active material layers using a method selected from injection, ultrasonic, hot rolling / pressing and / or spraying. At 270, the electrode is arranged with other electrodes (cathode electrode and / or anode electrode) and separators to form a battery cell stack and arranged in a housing.
[0079] The foregoing description is merely exemplary and is absolutely not intended to limit the present disclosure, its application or use. The broad teachings of the present disclosure can be implemented in various forms. Therefore, although the present disclosure includes specific examples, the true scope of the present disclosure should not be limited thereto, because after studying the drawings, the specification and the following claims, other modifications will become apparent. It should be understood that one or more steps in the method may be implemented in different orders (or simultaneously) without changing the principles of the present disclosure. In addition, although each embodiment is described above as having certain features, any one or more features described with respect to any embodiment of the present disclosure may be implemented in any other embodiment and / or combined with the features of any other embodiment, even if the combination is not explicitly described. In other words, the embodiments are not mutually exclusive, and the mutual replacement of one or more embodiments is still within the scope of the present disclosure.
[0080] Various terms are used to describe the spatial and functional relationships between elements (e.g., between modules, circuit elements, semiconductor layers, etc.), including "connected," "engaged," "coupled," "adjacent," "next to," "on top of," "on," "under," and "disposed." Unless explicitly described as "directly," when describing the relationship between a first element and a second element in the above disclosure, the relationship can be a direct relationship in which there are no other intervening elements between the first element and the second element, or an indirect relationship in which there are one or more intervening elements (spatially or functionally) between the first element and the second element. The phrase "at least one of A, B, and C" as used herein should be interpreted to mean a logical (A or B or C) using a non-exclusive logical OR, and should not be interpreted to mean "at least one of A, at least one of B, and at least one of C."
[0081] In the drawings, the direction of the arrows, as shown by the arrows, generally shows the flow of information (such as data or instructions) that the illustration is concerned with. For example, when component A and component B exchange various information but the information sent from component A to component B is relevant to the illustration, the arrow may point from component A to component B. Such a one-way arrow does not mean that no other information is sent from component B to component A. In addition, for information transmitted from component A to component B, component B may send a request for the information or a receipt to component A.
Claims
1. A method for making a composite solid electrolyte (SSE) / electrode for a battery cell, comprising: providing an electrode including an active material layer; Do one of the following: melting a solid electrolyte to produce a molten solid electrolyte, and coating the active material layer with the molten solid electrolyte, and disposing a solid electrolyte on the active material layer, and heating the electrode and the solid electrolyte to produce a molten solid electrolyte; and The molten solid electrolyte is solidified to form a solid electrolyte layer. The method according to claim 1 , wherein the active material layer is disposed on a current collector. 3 . The method according to claim 1 , wherein the molten solid electrolyte infiltrates open areas between particles of the active material layer. The method according to claim 1 , wherein the melting temperature of the solid electrolyte is less than or equal to 300° C. .
5. The method according to claim 1, wherein the solid electrolyte is selected from polymers, antiperovskites, lithium metal halides, lithium hydrides, lithium closo-borate and / or combinations thereof.
6. The method of claim 1, wherein the melting comprises one or more methods selected from induction heating, warm isostatic pressing (WIP), infrared light, ultrafast high temperature sintering (UHS), flash heating, microwave heating, and discharge plasma.
7. The method of claim 1, wherein the molten solid electrolyte is applied to the active material layer using a method selected from injection, ultrasound, hot rolling / pressing and / or spraying. 8 . The method according to claim 1 , wherein the active material layer further comprises an active material, a binder, and a conductive filler.
9. The method according to claim 2, wherein: The electrodes include an anode electrode, The active material in the active material layer includes an anode active material, and The current collector includes an anode current collector.
10. The method according to claim 2, wherein: The electrodes include a cathode electrode, The active material in the active material layer includes a cathode active material, and the current collector includes a cathode current collector.