Parallel battery with multilayer ceramic structure

Abstract

The utility model relates to a parallel battery with a multilayer ceramic structure. The parallel battery with the multilayer ceramic structure comprises a plurality of battery units which are longitudinally stacked in parallel, and each battery unit comprises a positive current collector, a positive electrode, a polymer composite electrolyte layer, a negative electrode and a negative current collector which are sequentially stacked, the positive electrode comprises a multi-layer ceramic structure formed by co-firing a positive electrode material and a solid electrolyte material, and the negative electrode is a metal lithium negative electrode. The utility model provides a parallel battery with a multi-layer ceramic structure, in each battery unit of the parallel battery, a positive electrode comprising the multi-layer ceramic structure is connected with a metal lithium negative electrode through a polymer composite electrolyte layer, and wide application is facilitated.

Description

TECHNICAL FIELD

[0001] The utility model relates to battery technology field especially, and relates to a kind of parallel connection battery with multilayer ceramic structure. BACKGROUND

[0002] As next-generation energy storage system, all-solid-state metal battery is more and more concerned by academia and industry, which is mainly due to its good safety, and is expected to achieve high energy density. Multilayer ceramic battery (MLCB) is often referred to as the battery version of multilayer ceramic capacitor (MLCC). In the prior art, the positive electrode material and the solid electrolyte material are co-fired to form a positive electrode including a multilayer ceramic structure. However, how to connect the positive electrode including the multilayer ceramic structure with the metal lithium negative electrode is a problem to be solved in the field. SUMMARY

[0003] Therefore, it is necessary to provide a parallel connection battery with a multilayer ceramic structure. The positive electrode including the multilayer ceramic structure in the parallel connection battery is connected with the metal lithium negative electrode through a polymer composite electrolyte layer.

[0004] A parallel connection battery with a multilayer ceramic structure includes a plurality of battery units stacked longitudinally in parallel. Each battery unit includes, in order, a positive electrode current collector, a positive electrode, a polymer composite electrolyte layer, a negative electrode, and a negative electrode current collector. The positive electrode includes a multilayer ceramic structure formed by co-firing a positive electrode material and a solid electrolyte material. The negative electrode is a metal lithium negative electrode.

[0005] The utility model provides a parallel connection battery with a multilayer ceramic structure. In each battery unit of the parallel connection battery, the positive electrode including the multilayer ceramic structure is connected with the metal lithium negative electrode through the polymer composite electrolyte layer, which is beneficial to wide application.

[0006] In a feasible implementation, the positive electrode further includes a solid electrolyte layer. The solid electrolyte layer is located between the multilayer ceramic structure and the polymer composite electrolyte layer.

[0007] In a feasible implementation, the solid electrolyte layer is an oxide electrolyte layer.

[0008] In a feasible implementation, the thickness of the solid electrolyte layer is 10 μm to 1000 μm.

[0009] In a feasible implementation, the positive electrode material is NCM532, NCM622, or NCM811.

[0010] In a feasible implementation, the solid electrolyte material is LLZO, LLTO, or LLZTO.

[0011] In one possible implementation, the polymer composite electrolyte layer comprises a polymer matrix, and the polymer matrix is a PEO matrix, a PU matrix, a PTFE matrix or a PMMA matrix.

[0012] In one possible implementation, the polymer composite electrolyte layer has a thickness of 3 μm to 1000 μm.

[0013] In one possible implementation, the positive current collector is a stainless steel foil, a nickel foil, a porous nickel current collector or an aluminum foil.

[0014] In one possible implementation, the negative current collector is a copper foil or a porous copper foil. BRIEF DESCRIPTION OF DRAWINGS

[0015] Figure 1 A stack schematic diagram of the parallel battery with the multilayer ceramic structure according to one embodiment of the present application;

[0016] Figure 2 A schematic diagram of a battery cell in the parallel battery with the multilayer ceramic structure according to one embodiment of the present application;

[0017] Figure 3 A stack schematic diagram of the parallel battery with the multilayer ceramic structure according to another embodiment of the present application;

[0018] Figure 4 A schematic diagram of a battery cell in the parallel battery with the multilayer ceramic structure according to another embodiment of the present application;

[0019] Figure 5 A schematic diagram of a double-layer positive composite electrode monomer in the preparation method of the parallel battery according to Embodiment 1 of the present application;

[0020] Figure 6 A schematic diagram of a double-layer negative lithium monomer in the preparation method of the parallel battery according to Embodiment 1 of the present application;

[0021] Figure 7 A schematic diagram of a double-layer positive composite electrode monomer in the preparation method of the parallel battery according to Embodiment 2 of the present application;

[0022] Figure 8 A schematic diagram of a double-layer negative lithium monomer in the preparation method of the parallel battery according to Embodiment 2 of the present application. DETAILED DESCRIPTION

[0023] In order to make the above objectives, features and advantages of the present application more obvious and easy to understand, the specific embodiments of the present application will be described in detail below with reference to the drawings. In the following description, many specific details are set forth in order to provide a thorough understanding of the present application. However, the present application can be practiced in a variety of ways other than those described herein, and those skilled in the art can make similar improvements without departing from the spirit of the present application, so the present application is not limited to the specific embodiments disclosed below.

[0024] It should be noted that when an element is referred to as being "fixed" to another element, it can be directly on the other element or there can be an intervening element. When an element is referred to as being "connected" to another element, it can be directly connected to the other element or there can be an intervening element. The terms "vertical", "horizontal", "left", "right", and similar expressions used herein are for illustrative purposes only.

[0025] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the present application belongs. The terminology used in the description of the present application herein only for the purpose of describing specific embodiments and is not intended to limit the present application. The term "and / or" as used herein includes any and all combinations of one or more of the associated listed items.

[0026] Please refer to Figure 1 and Figure 2 , the parallel battery 100 with a multi-layer ceramic structure of an embodiment of the present application includes a plurality of battery units 110 stacked longitudinally in parallel, each battery unit 110 includes a positive current collector 111, a positive electrode 112, a polymer composite electrolyte layer 113, a negative electrode 114 and a negative current collector 115 stacked in sequence, the positive electrode 112 includes a multi-layer ceramic structure 116 co-fired from a positive electrode material and a solid-state electrolyte material, and the negative electrode 114 is a metal lithium negative electrode.

[0027] Specifically, the battery units 110 are stacked longitudinally in parallel in the following manner: the negative current collector 115 of a subsequent battery unit 110 is completely attached to the negative current collector 115 of a previous battery unit 110; or, the positive current collector 111 of a subsequent battery unit 110 is completely attached to the positive current collector 111 of a previous battery unit 110, to achieve parallel stacking of the battery units 110.

[0028] On the basis of the foregoing embodiment, the positive electrode material is NCM532, NCM622 or NCM811.

[0029] On the basis of the foregoing embodiment, the solid-state electrolyte material is LLZO, LLTO or LLZTO.

[0030] On the basis of the foregoing embodiment, the polymer composite electrolyte layer 113 comprises a polymer matrix, and the polymer matrix is a PEO matrix, a PU matrix, a PTFE matrix or a PMMA matrix.

[0031] On the basis of the foregoing embodiment, the thickness of the polymer composite electrolyte layer 113 is 3 μm to 1000 μm. Further, the thickness of the polymer composite electrolyte layer 113 can be, but is not limited to, 3 μm, 10 μm, 100 μm, 200 μm, 300 μm, 400 μm, 500 μm, 600 μm, 700 μm, 800 μm, 900 μm or 1000 μm.

[0032] On the basis of the foregoing embodiment, the positive current collector 111 is a stainless steel foil, a nickel foil, a porous nickel current collector or an aluminum foil.

[0033] On the basis of the foregoing embodiment, the negative current collector 115 is a copper foil or a porous copper foil.

[0034] In each battery cell 110 of the parallel battery 100 with the multilayer ceramic structure of the embodiment, the positive electrode 112 with the multilayer ceramic structure and the lithium metal negative electrode are connected through the polymer composite electrolyte layer 113, which is conducive to wide application.

[0035] In addition, it should be noted that in the parallel battery with the multilayer ceramic structure of the utility model, a solid electrolyte layer can also be arranged on the side of the multilayer ceramic structure away from the positive current collector.

[0036] Please refer to Figure 3 and Figure 4 The parallel battery 100 with the multilayer ceramic structure of another embodiment of the utility model comprises a plurality of battery cells 110 stacked in parallel, each battery cell 110 comprises a positive current collector 111, a positive electrode 112, a polymer composite electrolyte layer 113, a negative electrode 114 and a negative current collector 115 stacked in sequence, the positive electrode 112 comprises a multilayer ceramic structure 116 formed by co-firing of a positive electrode material and a solid electrolyte material, and the negative electrode 114 is a lithium metal negative electrode.

[0037] In the parallel battery 100 of the utility model, the positive electrode 112 further comprises a solid electrolyte layer 117, and the solid electrolyte layer 117 is located between the multilayer ceramic structure 116 and the polymer composite electrolyte layer 113.

[0038] On the basis of the foregoing embodiment, the solid electrolyte layer 117 is an oxide electrolyte layer, and further for example can be an LLZO electrolyte layer.

[0039] On the basis of the foregoing embodiment, the thickness of the solid electrolyte layer 117 is 10 μm to 1000 μm. The thickness of the solid electrolyte layer 117 can be, but is not limited to, 10 μm, 100 μm, 200 μm, 300 μm, 400 μm, 500 μm, 600 μm, 700 μm, 800 μm, 900 μm, or 1000 μm.

[0040] The utility model provides a kind of parallel connection battery with multilayer ceramic structure, in each battery unit of the parallel connection battery, including multilayer ceramic structure's anode and metal lithium cathode are connected by polymer composite electrolyte layer, it is conducive to wide application.

[0041] With reference to the foregoing implementation, in order to make the technical scheme of the utility model more specific and clear, easy to understand, the technical scheme of the utility model will be exemplified, but it needs to be explained that the content to be protected by the utility model is not limited to the following examples.

[0042] Example 1

[0043] The embodiment provides a kind of parallel connection battery with multilayer ceramic structure and preparation method thereof, the structure of parallel connection battery is as shown in Figure 1 Please combine Figure 1 、 Figure 5 And Figure 6 The preparation method of parallel connection battery of the embodiment is as follows:

[0044] (1) preparation of anode composite electrolyte ceramic sheet

[0045] Raw material preparation and mixing: NCM532 powder with an average particle size of 10 μm and LLZO powder with a particle size of 500 nm are added to a ball mill tank in a mass ratio of 97:3, and ball milling is carried out at a speed of 500 rpm for 24 hours. After ball milling, the mixture is placed in an oven at 80°C for 6 hours to dry, obtaining dried powder.

[0046] Powder forming: the dried powder is loaded into a mold and formed by hydraulic pressure under a pressure of 20 MPa, obtaining an anode green body.

[0047] Cold isostatic pressing: the anode green body is placed in a cold isostatic pressing device and cold isostatic pressed under a pressure of 200 MPa to improve the density of the anode green body, and the processing time is about 10 minutes.

[0048] Sintering: the anode green body subjected to cold isostatic pressing is placed in a tube-type sintering furnace, and vacuumized to a vacuum degree of 6×10^-4 Pa. Sintering is carried out at 900°C for 5 hours to densify the multilayer ceramic structure. Cooling to room temperature obtains a multilayer ceramic structure 116 with co-sintering.

[0049] (2) preparation of anode composite electrode

[0050] Current collector coating: One side of the multilayer ceramic structure 116 prepared in step (1) is coated with a 10-μm-thick metal Al film by magnetron sputtering under Ar gas protection, serving as the positive current collector 111 of the composite electrode.

[0051] Double-layer positive composite electrode monomer: Two pieces of the positive composite electrode coated with the metal Al film are pasted on both sides of the aluminum foil by conductive glue to form a double-layer positive composite electrode monomer 120, as shown in Figure 5 , and the tab is led out for subsequent assembly.

[0052] (3) Assembly of multilayer ceramic battery

[0053] Parallel high-capacity battery assembly: The double-layer positive composite electrode monomer 120 prepared above and the double-layer negative lithium monomer 130 with the surface coated with the flexible polymer composite electrolyte layer 113, as shown in Figure 6 , are stacked in sequence, and the number of stacks can be set according to the battery capacity requirement. The warm isostatic pressing equipment is used to apply a pressure of 100 MPa at 120°C for 30 minutes. After warm isostatic pressing, the flexible polymer composite electrolyte layer 113 is ensured to be in close contact with the multilayer ceramic structure 116 in the double-layer positive composite electrode monomer 120, obtaining the parallel battery 100, as shown in Figure 1 .

[0054] Example 2

[0055] This example provides a parallel battery with a multilayer ceramic structure and a preparation method thereof. The structure of the parallel battery is as shown in Figure 3 ; please refer to Figure 3 , Figure 7 and Figure 8 , the preparation method of the parallel battery of this example is as follows:

[0056] (1) Preparation of composite positive electrode

[0057] Raw material preparation and mixing: NCM532 powder with an average particle size of 10 μm and LLZO powder with a particle size of 500 nm are added to a ball mill jar in a mass ratio of 97:3, and ball milling is performed at a speed of 500 rpm for 24 hours. After ball milling, the mixture is dried in an oven at 80°C for 6 hours to obtain dried powder.

[0058] Powder molding: The dried powder is loaded into a mold and hydraulically formed under a pressure of 20 MPa to obtain a positive electrode green body.

[0059] Spraying electrolyte and cold isostatic pressing: spray a layer of 10 μm thick LLZO electrolyte powder on one surface of the positive electrode green body. Place the sprayed positive electrode green body in a cold isostatic pressing device and cold isostatic pressing at a pressure of 200 MPa to improve the density of the positive electrode green body, and the processing time is about 10 minutes.

[0060] Sintering: place the green body after cold isostatic pressing in a tube sintering furnace, and vacuumize to a vacuum degree of 6*10^-4 Pa. Sinter at 900°C for 5 hours to densify the multilayer ceramic structure. Cool to room temperature to obtain a co-sintered positive electrode composite electrolyte ceramic sheet 112.

[0061] (2) Preparation of positive electrode composite electrode

[0062] Current collector plating: the positive electrode composite electrolyte ceramic sheet 112 prepared in step (1) is plated with a 10 μm thick metal Al film on the side without spraying LLZO electrolyte powder as the positive electrode current collector 111 of the composite electrode by magnetron sputtering under the protection of Ar gas.

[0063] Double-layer composite electrode monomer: two pieces of positive electrode composite electrode plated with metal Al film are pasted on both sides of the aluminum foil to form a double-layer positive electrode composite electrode monomer 120 as shown in Figure 7 , and the tab is drawn out for subsequent assembly.

[0064] (3) Assembly of multilayer ceramic battery

[0065] Parallel high-capacity battery assembly: stack the positive electrode composite electrode monomer 120 prepared above and the double-layer negative lithium monomer 130 with a flexible polymer composite electrolyte layer 113 coated on the surface as shown in Figure 8 in sequence, and the number of stacks can be set according to the battery capacity requirement. Use a warm isostatic pressing device to apply a pressure of 100 MPa at a heating temperature of 120°C for isostatic pressing, and the time is controlled to be 30 minutes. After warm isostatic pressing, ensure that the flexible polymer composite electrolyte layer 113 is in close contact with the solid electrolyte layer 117 (i.e. LLZO layer) in the double-layer positive electrode composite electrode monomer 120, to obtain a parallel battery 100 as shown in Figure 3 .

[0066] The technical features of the above-described embodiments can be combined in any way. In order to make the description concise, not all possible combinations of the technical features in the above-described embodiments are described, however, as long as the combinations of the technical features do not contradict each other, they should be considered to be within the scope of the present disclosure.

[0067] The above-described embodiments only express several implementation manners of the utility model, the description is more specific and detailed, but can not therefore be understood as the limitation of the utility model patent range. It should be pointed out that for ordinary skilled person in the art, without departing from the utility model concept, several modifications and improvements can be made, which belong to the protection range of the utility model. Therefore, the protection range of the utility model patent should be subject to the appended claims.

Claims

1. A parallel cell having a multi-layer ceramic structure, characterized by, The parallel battery comprises a plurality of battery units stacked longitudinally in parallel, each of the battery units comprising, in sequence, a positive current collector, a positive electrode, a polymer composite electrolyte layer, a negative electrode, and a negative current collector, the positive electrode comprising a multilayer ceramic structure co-fired from a positive electrode material and a solid-state electrolyte material, and the negative electrode being a metal lithium negative electrode.

2. The parallel battery having a multi-layer ceramic structure according to claim 1, characterized by, The positive electrode further comprises a solid-state electrolyte layer between the multilayer ceramic structure and the polymer composite electrolyte layer.

3. The parallel battery having a multi-layer ceramic structure according to claim 2, characterized by, The solid electrolyte layer is an oxide electrolyte layer 。 4. The parallel battery having a multi-layer ceramic structure according to claim 2, characterized by, The solid-state electrolyte layer has a thickness of 10-1000 μm.

5. The parallel battery having a multi-layer ceramic structure according to claim 1, characterized by, The positive electrode material is NCM532, NCM622, or NCM811.

6. The parallel battery having a multi-layer ceramic structure according to claim 1, characterized by, The solid-state electrolyte material is LLZO, LLTO, or LLZTO.

7. The parallel battery having a multi-layer ceramic structure according to claim 1, characterized by, The polymer composite electrolyte layer comprises a polymer matrix, which is a PEO matrix, a PU matrix, a PTFE matrix, or a PMMA matrix.

8. The parallel battery having a multi-layer ceramic structure according to claim 1, characterized by, The polymer composite electrolyte layer has a thickness of 3-1000 μm.

9. The parallel battery having a multi-layer ceramic structure according to claim 1, characterized by, The positive current collector is a stainless steel foil, a nickel foil, a porous nickel current collector, or an aluminum foil.

10. The parallel battery having a multi-layer ceramic structure according to claim 1, characterized by, The negative current collector is a copper foil or a porous copper foil.

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