Method of preparing battery assembly with subunits beginning and ending with cathode

Abstract

Disclosed is a method for preparing a battery assembly based on multiple pre-pressed subunits each of which begins and ends with a cathode layer. In some embodiments, the battery assembly prepared by the method as disclosed herein can lead to a longer cycle life in comparison to one prepared by pre-pressed subunits beginning and ending with an anode layer.

Description

METHOD OF PREPARING BATTERY ASSEMBLY WITH SUBUNITS BEGINNING AND ENDING WITH CATHODECROSS-REFERENCE

[0001] The present application claims the benefit of US Serial No. 63 / 690,445, filed September 4, 2024, the entire content of which is incorporated herein by reference into this application.FIELD

[0002] This disclosure generally relates to a method for preparing a battery assembly and battery assemblies prepared thereby.BACKGROUND

[0003] Assembly of solid electrolyte (SE) with electrodes is challenging due to solid-solid interface. To reduce the SE / electrode interfacial resistance, a compression is usually applied to a stack of cell components during assembly to keep the solid electrolyte and electrode in intimate contact with each other. In general, a mechanical pressing or an isostatic pressing is performed to bring multiple subunits together, wherein the subunits usually begin and end with anode. Such isostatic pressing based on subunits beginning and ending with anode, however, leads to a low yield and / or poor cycling performance. Thus, there remains a need for a new design and method to prepare cell assembly with a high yield and / or cycling performance.SUMMARY

[0004] The present disclosure provides a method for preparing a battery assembly based on multiple subunits each of which begins and ends with cathode instead of anode. In some embodiments, the battery assembly prepared by the method as disclosed herein can lead to an improved cycle life.BRIEF DESCRIPTION OF THE FIGURES

[0005] Non-limiting embodiments of the present disclosure will be described by way of example with reference to the accompanying figures, which are schematic and are not intended to be drawn to scale. In the figures, each identical or nearly identical component illustrated istypically represented by a single numeral. For purposes of clarity, not every component is labeled in every figure, nor is every component of each embodiment of the disclosure shown where illustration is not necessary to allow those of ordinary skill in the art to understand the disclosure.

[0006] Fig. 1 shows a conventional configuration of a subunit beginning and ending with an anode.

[0007] Fig. 2 shows a typical configuration of a subunit beginning and ending with a cathode according to one embodiment of the present disclosure.

[0008] Fig. 3 shows a representative configuration of a subunit beginning and ending with a cathode according to one embodiment of the present disclosure.]0009[ Fig. 4 shows a representative configuration of an assembly prepared with subunits beginning and ending with a cathode according to one embodiment of the present disclosure.DETAILED DESCRIPTION

[0010] Disclosed herein is a method for preparing a battery assembly. The method comprises laminating multiple subunits each ending with a cathode.

[0011] Fig. 1 shows a conventional subunit comprising a cathode (1) with a cathode tab (1-1), two anodes (2) each configured with an anode tab (2-1), and two solid electrolyte layers (3), wherein the subunit ends with two anodes (2). In some embodiments, the cathode (1) comprises a cathode active material layer and a cathode current collector. In some embodiments, an anode (2) comprises an optional anode active material layer and an anode current collector. In some embodiments, an anode further comprises an anode protective layer (alternatively anode interlayer or anode sublayer) disposed between a solid electrolyte (SE) layer and an anode active material layer or between an SE layer and an anode current collector.

[0012] As shown in Fig. 2 according to one embodiment of the present disclosure, a subunit comprises two cathodes (1) each configurated with a cathode tab (1-1), an anode (2) with ananode tab (2-1), and two solid electrolyte layers (3), wherein the subunit begins and ends with cathode (1).100131 In one aspect, the present disclosure provides a method of preparing an assembly of a battery comprising multiple cathodes, multiple anodes, and multiple solid electrolyte (SE) layers each SE layer disposed between a cathode and an anode, the method comprising: a) having multiple pre-pressed subunits, wherein each subunit begins and ends with a cathode and each subunit is compressed by an isostatic compression, b) laminating the multiple pre-pressed subunits into a pre-assembly, and c) pressurizing the pre-assembly, thereby obtaining an assembly.

[0014] In some embodiments, a battery assembly assembled with multiple subunits exhibits an improved cycle life. In some embodiments, the battery assembly exhibits an average cycle life of at least 10% longer than the one prepared by subunits beginning and ending with anode

[0015] In some embodiments, the isostatic pressing for preparing a subunit is independently conducted at a temperature range. In some embodiments, the isostatic pressing is a cold isostatic pressing (CIP) or warm isostatic pressing (WIP). In some embodiments, the isostatic pressing is conducted at a temperature in a range from 0 °C to 150 °C, from 0 °C to 140 °C, from 0 °C to 130 °C, from 0 °C to 120 °C, from 0 °C to 110 °C, from 0 °C to 100 °C, from 0 °C to 80 °C, from 0 °C to 60 °C, from 0 °C to 40 °C, 10 °C to 150 °C, from 10 °C to 140 °C, from 10 °C to 130 °C, from 10°C to 120 °C, from 10 °C to 110 °C, from 10 °C to 100 °C, from 10 °C to 80 °C, from 10 °C to 60 °C, from 10 °C to 40 °C, 20°C to 150 °C, from 20 °C to 140 °C, from 20 °C to 130 °C, from 20 °C to 120 °C, from 20 °C to 110 °C, from 20 °C to 100 °C, from 20 °C to 80 °C, from 20 °C to 60 °C, from 20 °C to 40 °C, 30 °C to 150 °C, from 30 °C to 140 °C, from30 °C to 130 °C, from 30 °C to 120 °C, from 30 °C to 110 °C, from 30 °C to 100 °C, from 30 °C to 80 °C, from 30 °C to 60 °C, or any and all ranges and subranges therebetween.

[0016] In some embodiments, the isostatic pressing for each subunit has a working pressure in a range from 10 MPa to 1000 MPa, from 10 MPa to 800 MPa, from 10 MPa to 600 MPa, from10 MPa to 400 MPa, from 10 MPa to 200 MPa, from 10 MPa to 150 MPa, from 10 MPa to 125 MPa, from 10 MPa to 100 MPa, from 10 MPa to 75 MPa, from 10 MPa to 50 MPa, from 20 MPa to 1000 MPa, from 20 MPa to 800 MPa, from 20 MPa to 600 MPa, from 20 MPa to 400 MPa, from 20 MPa to 200 MPa, from 20 MPa to 150 MPa, from 20 MPa to 125 MPa, from 20 MPa to 100 MPa, from 20 MPa to 75 MPa, from 20 MPa to 50 MPa, from 30 MPa to 1000 MPa, from 30 MPa to 800 MPa, from 30 MPa to 600 MPa, from 30 MPa to 400 MPa, from 30 MPa to 200 MPa, from 30 MPa to 150 MPa, from 30 MPa to 125 MPa, from 30 MPa to 100 MPa, from 30 MPa to 75 MPa, from 30 MPa to 50 MPa, from 50 MPa to 1000 MPa, from 50 MPa to 800 MPa, from 50 MPa to 600 MPa, from 50 MPa to 400 MPa, from 50 MPa to 200 MPa, from 50 MPa to 150 MPa, from 50 MPa to 125 MPa, from 50 MPa to 100 MPa, from 50 MPa to 75 MPa, or any and all ranges and subranges therebetween.

[0017] In some embodiments, the working pressure is loaded at a controlled rate to allow slow deformation of cell pouch and the cell laminations therein, which is critical in avoiding stress concentration thus achieving desirable consistency and uniformity. In some embodiments, the working pressure of a working fluid is increased at a rate in a range from 0.1 MPa / min to 20.0 MPa / min, from 0.1 MPa / min to 15.0 MPa / min, from 0.1 MPa / min to 10.0 MPa / min, from 0.1 MPa / min to 7.5 MPa / min, from 0.1 MPa / min to 5.0 MPa / min, from 0.1 MPa / min to 2.5 MPa / min, from 0.1 MPa / min to 1.0 MPa / min, from 0.1 MPa / min to 0.75 MPa / min, from 0.1 MPa / min to 0.5 MPa / min, 0.25 MPa / min to 20.0 MPa / min, from 0.25 MPa / min to 15.0 MPa / min, from 0.25 MPa / min to 10.0 MPa / min, from 0.25 MPa / min to 7.5 MPa / min, from 0.25 MPa / min to 5.0 MPa / min, from 0.25 MPa / min to 2.5 MPa / min, from 0.25 MPa / min to 1.0 MPa / min, from 0.25 MPa / min to 0.75 MPa / min, from 0.5 MPa / min to 20.0 MPa / min, from 0.5 MPa / min to 15.0 MPa / min, from 0.5 MPa / min to 10.0 MPa / min, from 0.5 MPa / min to 7.5 MPa / min, from 0.5 MPa / min to 5.0 MPa / min, from 0.5 MPa / min to 2.5 MPa / min, from 0.5MPa / min to 1.0 MPa / min, from 1.0 MPa / min to 20.0 MPa / min, from 1.0 MPa / min to 15.0MPa / min, from 1.0 MPa / min to 10.0 MPa / min, from 1.0 MPa / min to 7.5 MPa / min, from 1.0MPa / min to 5.0 MPa / min, from 1.0 MPa / min to 2.5 MPa / min, from 2.0 MPa / min to 20.0MPa / min, from 2.0 MPa / min to 15.0 MPa / min, from 2.0 MPa / min to 10.0 MPa / min, from 2.0 MPa / min to 7.5 MPa / min, from 2.0 MPa / min to 5.0 MPa / min, or any and all ranges and subranges therebetween.

[0018] In some embodiments, the working pressure for each subunit is independently maintained for a period of time in a range from 1 min to 60 min, from 2 min to 60 min, from 3 min to 60 min, from 5 min to 60 min, from 10 min to 60 min, from 1 min to 50 min, from 2 min to 50 min, from 3 min to 50 min, from 5 min to 50 min, from 10 min to 50 min, from 1 min to 40 min, from 2 min to 40 min, from 3 min to 40 min, from 5 min to 40 min, from 10 min to 40 min, from 1 min to 30 min, from 2 min to 30 min, from 3 min to 30 min, from 5 min to 30 min, from 10 min to 30 min, from 1 min to 20 min, from 2 min to 20 min, from 3 min to 20 min, from 5 min to 20 min, from 10 min to 20 min, or any and all ranges and subranges therebetween.

[0019] In some embodiments, the isostatic compression for each subunit is independently conducted prior to, concurrently with, or after heating to an elevated temperature in a range from 20 °C to 150 °C, from 30 °C to 150 °C, from 40 °C to 150 °C, from 50 °C to 150 °C, from 60 °C to 150 °C, from 70 °C to 150 °C, from 20 °C to 120 °C, from 30 °C to 120 °C, from 40 °C to 120 °C, from 50 °C to 120 °C, from 60 °C to 120 °C, from 70 °C to 120 °C, from 20 °C to 100 °C, from 30 °C to 100 °C, from 40 °C to 100 °C, from 50 °C to 100 °C, from 60 °C to 100 °C, from 70 °C to 120 °C, or any and all ranges and subranges therebetween .

[0020] In some embodiments, the cathodes are substantially parallel to anodes.

[0021] In some embodiments, the pre-assembly is pressurized by placing the pre-assembly into a vacuuming bag followed by vacuuming the vacuuming bag to a preset vacuum percentage. Vacuum percentage is a relative value of the pressure difference between atmospheric pressure (Patm) and pressure in the evacuated system (Pv) over the atmospheric pressure as the base value multiplied by 100%, i.e., (Patm - Pv) / Patm x 100%.

[0022] In some embodiments, the preset vacuum percentage is at least 99.0%, at least 99.5%, at least 99.6%, at least 99.7%, at least 99.8%, or at least 99.9%.

[0023] In some embodiments, the vacuuming bag is made of a flexible material. In some embodiments, the vacuuming bag comprises at least one selected from the group consisting of polyethene (PE), polyvinylidene chloride (PVDC), polypropylene (PP), polyvinyl chloride (PVC), polyester such as polyethylene terephthalate (PET), and polyamide (PA). In some embodiments, the vacuuming bag comprises a film made of biaxially oriented PET (BoPET) (also known as Mylar).

[0024] In some embodiments, the cell assembly may comprise a number of layers. In some embodiments, a cell assembly comprising a cell pouch and a cell stack has a thickness in a range from 1 mm to 20 mm, from 1 mm to 15 mm, from 1 mm to 10 mm, from 1 mm to 7.5 mm, from 1 mm to 5 mm, from 1 mm to 4 mm, from 1 mm to 3 mm, from 1 mm to 2.5 mm, from 1.0 mm to 2.0 mm, from 2 mm to 20 mm, from 2 mm to 15 mm, from 2 mm to 10 mm, from 2 mm to 7.5 mm, from 2 mm to 5 mm, from 2 mm to 4 mm, from 2 mm to 3 mm, from 2 mm to 2.5 mm, from 3 mm to 20 mm, from 3 mm to 15 mm, from 3 mm to 10 mm, from 3 mm to 7.5 mm, from 3 mm to 5 mm, from 3 mm to 4 mm, or any and all ranges and subranges therebetween. In some embodiments, the cell assembly has a thickness smaller than the original cell assembly. In some embodiments, the cell assembly has a thickness around 5%, 10%, 15%, or 20% lower than that of the original cell assembly prior to the isostatic pressing.

[0025] In some embodiments, the cathode tabs are made of a metal or an alloy for electrically connecting the cell assembly with an external circuit. In some embodiments, non-limiting specific metals include aluminum and copper.

[0026] In some embodiments, the cell pouch is airtight. In some embodiments, the cell pouch is made of a material selected from the group consisting of aluminum foil, aluminum foil with one surface coated with at least one polymer layer, aluminum foil with two surfaces each coated with at least one polymer layer and a combination thereof.

[0027] In some embodiments, the working fluid in the chamber does not infiltrate into the cell pouch. In some embodiments, the working fluid in the chamber does not infiltrate into a pressing bag under the isostatic pressing.

[0028] In some embodiments, the pressing bag is made of a material that can seal the bag from the working fluid. In some embodiments, the bag is made of a film. In some embodiments, the film is made of polyethylene terephthalate (PET), polyethylene (PE), PU, latex, or a mixture thereof. In some embodiments, the film is made of biaxially oriented PET (BoPET) (also known as Mylar). In some embodiments, the film of the pressing bag has a thickness in a range from 0.01 mm to 0.5 mm, from 0.01 mm to 0.4 mm, from 0.01 mm to 0.3 mm, from 0.01 mm to 0.2 mm, from 0.01 mm to 0.15 mm, from 0.01 mm to 0.10 mm, from 0.01 mm to 0.08 mm, from 0.01 mm to 0.06 mm, from 0.01 mm to 0.04 mm, from 0.02 mm to 0.5 mm, from 0.02 mm to 0.4 mm, from 0.02 mm to 0.3 mm, from 0.02 mm to 0.2 mm, from 0.02 mm to 0.15 mm, from 0.02 mm to 0.10 mm, from 0.02 mm to 0.08 mm, from 0.02 mm to 0.06 mm, from 0.02 mm to 0.04 mm, from 0.04 mm to 0.5 mm, from 0.04 mm to 0.4 mm, from 0.04 mm to 0.3 mm, from 0.04 mm to 0.2 mm, from 0.04 mm to 0.15 mm, from 0.04 mm to 0.10 mm, from 0.04 mm to 0.08 mm, from 0.04 mm to 0.06 mm, from 0.05 mm to 0.5 mm, from 0.05 mm to 0.4 mm, from 0.05 mm to 0.3 mm, from 0.05 mm to 0.2 mm, from 0.05 mm to 0.15 mm, from 0.05 mm to 0.10 mm, from 0.05 mm to 0.08 mm, or any and all ranges and subranges therebetween.

[0029] In some embodiments, the film comprises PE reinforced with a polymer fiber such as nylon with a diameter in a range from 5 pm to 1000 pm, from 5 pm to 750 pm, from 5 pm to 500 pm, from 5 pm to 250 pm, from 5 pm to 100 pm, from 5 pm to 75 pm, from 5 pm to 50 pm, from 5 pm to 25 pm, from 10 pm to 1000 pm, from 10 pm to 750 pm, from 10 pm to 500 pm, from 10 pm to 250 pm, from 10 pm to 100 pm, from 10 pm to 75 pm, from 10 pm to 50 pm, from 10 pm to 25 pm, from 25 pm to 1000 pm, from 25 pm to 750 pm, from 25 pm to 500 pm, from 25 pm to 250 pm, from 25 pm to 100 pm, from 25 pm to 75 pm, from 25 pm to 50 pm, or any and all ranges and subranges therebetween.

[0030] In some embodiments, the working fluid is a liquid or a gas. Non-limiting specific fluids include water, oil, argon, air, nitrogen, carbon dioxide, and a mixture thereof.

[0031] In some embodiments, the cell assembly is a cell assembly of an all solid-state battery (ASSB). In some embodiments, the method as described herein is for preparing a cell assembly of an ASSB.

[0032] In some embodiments, the ASSB comprises a cell stack containing a solid electrolyte in at least one of the one or more electrolyte layers.

[0033] In some embodiments, the solid electrolyte includes a polymer solid electrolyte, an oxide-based solid electrolyte, a sulfide-based solid electrolyte, and any combination thereof.

[0034] In some embodiments, the solid electrolyte is an oxide-based solid electrolyte or a sulfide-based electrolyte. In one embodiment, the solid electrolyte has a formula LixMlyM2zPi-PM3pS6-a-b-qOqClaBrb (Formula I), wherein 4<x<8, 0<y<l, 0<z <1, 0<p<l, 0<q<l, 0<a<2, 0<b<2, 0<6-a-b-q<6, 0<l-p<l, wherein Ml is at least one element of Group 1 or Group 11 other than H or Li of the periodic table, M2 is at least one element of Group 2 of the periodic table, and M3 is at least one element of Group 14 of the periodic table.

[0035] In some embodiments, the solid electrolytes has a formula LixMlyM2zPi-pM3PS6-a-b- qOqClaBrb (Formula I), wherein 4<x<8, 0<y<l, 0<z <1, 0<p<l, 0<q<l, 0<a<2, 0<b<2, 0<6-a- b-q<6, 0<l -p<l , and wherein Ml is at least one element of Group 1 or Group 11 other than H or Li of the periodic table, M2 is at least one element of Group 2 of the periodic table, and M3 is at least one element of Group 14 of the periodic table.

[0036] In some embodiments, Ml is at least one selected from the group consisting of Na, K, Rb, Cs, Cu, Ag, and Au. In some embodiments, M2 is at least one selected from the group consisting of Be, Mg, Ca, Sr, and Ba. In some embodiments, M3 is at least one selected from the group consisting of Si, Ge, Sn, and Pb.

[0037] In some embodiments, b / a has a value in a range from 0 to 20, i.e, 0<b / a<20.

[0038] In some embodiments, the formula of sulfide solid electrolyte in the electrolyte layer, i.e., LixMlyM2zPi-pM3pS6-a-b-qOqClaBrb, does not comprise any of Ml, M2, M3 or O, i.e., y=z=p=q=0, corresponding to a formula of LixPSe-a-bClaBrb.

[0039] In some embodiments, the formula of the sulfide electrolyte comprises at least one element selected from the group consisting of Ml, M2, M3 and O. In some embodiments, the Formula (I) contains one element selected from the group consisting of Ml, M2, M3 and O. In some embodiments, Formula I is selected from the group consisting of:1) LixMlyPSe-a-bClaBrb, where 4<x<8, 0<y<l, 0<a<2, 0<b<2, 0<6-a-b<6;2) LixM2zPS6-a-bClaBrb, where 4<x<8, 0<z<l, 0<a<2, 0<b<2, 0<6-a-b<6;3) LixPi-pM3PS6-a-bClaBrb, where 4<x<8, 0<p<l, 0<a<2, 0<b<2, 0<6-a-b<6, 0<l-p<l; and4) LixPSe-a-b-qOqClaBrb, where 4<x<8, 0<q<l, 0<a<2, 0<b<2, 0<6-a-b-q<6.

[0040] In some embodiments, the Formula (I) contains O and one element selected from the group consisting of Ml, M2, and M3. In some embodiments, the sulfide solid electrolyte has a formula selected from the group consisting of LixMlyPSe-a-b-qOqClaBrb (4<x<8, 0<y< 10<q<l, 0<a<2, 0<b<2, 0<6-a-b-q<6), LixM2zPiS6-a-b-qOqClaBrb (4<x<8, 0<z<l, 0<q<l, 0<a<2, 0<b<2, 0<6-a-b-q<6,), and LixPi-pM3pS6-a-b-qOqClaBrb (4<x<8, 0<p<l, 0<q<l, 0<a<2, 0<b<2, 0<6-a-b-q<6, 0<l-p<l). In one embodiment, the Formula (I) contains O without Ml, M2, or M3. In one embodiment, the formula of the sulfide electrolyte is LixPSe-a-b-qOqClaBrb (4<x<8, 0<q<l, 0<a<2, 0<b<2, 0<6-a-b-q<6). In some embodiments, Ml is at least one element of Group 1 or Group 11 other than H or Li of the periodic table. In some embodiments, Ml is at least one selected from the group consisting of Na, K, Rb, Cs, Cu, Ag, and Au. In some embodiments, M2 is at least one element of Group 2 of the periodic table. In some embodiments, M2 is at least one selected from the group consisting of Be, Mg, Ca, Sr, and Ba. In some embodiments, M3 is at least one element of Group 14 of the periodic table. In some embodiments, M3 is at least one selected from the group consisting of Si, Ge, Sn, and Pb.

[0041] In one embodiment, the sulfide solid electrolyte has a formula of LixPSe-a-b-qOqClaBrb, where 4<x<8, 0<q<l, 0<a<2, 0<b<2, 0<6-a-b-q<6. The incorporation of oxygen into the formula makes such material more stable. In some embodiments, the molar amount of O with q having a value in a range from 0 to 0.1, from 0 to 0.2, from 0 to 0.3, from 0 to 0.4, from 0 to0.5, from 0 to 0.6, from 0.001 to 0.1, from 0.001 to 0.2, from 0.001 to 0.3, from 0.001 to 0.4, from 0.001 to 0.5, from 0.001 to 0.6, from 0.002 to 0.1, from 0.002 to 0.2, from 0.002 to 0.3, from 0.002 to 0.4, from 0.002 to 0.5, from 0.002 to 0.6, from 0.005 to 0.1, from 0.005 to 0.2, from 0.005 to 0.3, from 0.005 to 0.4, from 0.005 to 0.5, from 0.005 to 0.6, or any and all ranges and subranges therebetween. In one embodiment, the formula is Li5.8PS4.70o.iCli.2.

[0042] In some embodiments, the formula is LixPSe-a-b-qOqClaBrb, wherein 4<x<8, 0<q<l, 0<a<2, 0<b<2, 0<6-a-b-q<6. In some embodiments, b / a has a value higher than zero. In some embodiments, b / a has a value in a range from 0 to 3.5. In some embodiments, b / a has a value in a range from 0 to 7. In some embodiments, b / a has a value in a range from 0 to 10, from 0 to 15, or from 0 to 20.

[0043] In some embodiments, when the formula is LixMlyPSe-a-b-qClaBrb, 4<x<8, 0<y<l, 0<a<2, 0<b<2, 0<6-a-b<6, b / a has a value in a range from 0 to 3.5. In some embodiments, b / a has a value in a range from 0 to 7. In some embodiments, b / a has a value in a range from 0 to 10, from 0 to 15, or from 0 to 20. In some embodiments, b / a has a value higher than zero.|0044| In some embodiments, when the formula is LixM2zPS6-a-bClaBrb, where 4<x<8, 0<z<l, 0<a<2, 0<b<2, 0<6-a-b<6, b / a has a value in a range from 0 to 3.5. In some embodiments, b / a has a value in a range from 0 to 7. In some embodiments, b / a has a value in a range from 0 to 10, from 0 to 15, or from 0 to 20. In some embodiments, b / a has a value higher than zero.

[0045] In one embodiment, when the formula is LixPi-pM3PS6-a-bClaBrb, 4<x<8, 0<p<l, 0<a<2, 0<b<2, 0<6-a-b<6, 0<l-p<l, b / a has a value in a range from 0 to 3.5. In some embodiments, b / a has a value in a range from 0 to 7. In some embodiments, b / a has a value in a range from 0 to 10, from 0 to 15, or from 0 to 20. In some embodiments, b / a has a value higher than zero.

[0046] In some embodiments, the Formula (I) contains O and one element selected from the group consisting of Ml, M2, and M3. In some embodiments, the sulfide solid electrolyte has a formula selected from the group consisting of LixMlyPSe-a-b-qOqClaBrb (4<x<8, 0<y<l,0<q<l, 0<a<2, 0<b<2, 0<6-a-b-q<6), LixM2zPS6-a-b-qOqClaBrb (4<x<8, 0<z<l, 0<q<l, 0<a<2, 0<b<2, 0<6-a-b-q<6,), and LixPi-pM3pS6-a-b-qOqClaBrb (4<x<8, 0<p<l, 0<q<l, 0<a<2, 0<b<2, 0<6-a- b-q<6, 0<l-p<l). In one embodiment, the Formula (I) contains O without Ml, M2, or M3. In one embodiment, the formula of the sulfide electrolyte is LixPSe-a-b-qOqClaBrb (4<x<8, 0<q<l, 0«2. 0<b<2, 0<6-a-b-q<6). In some embodiments, the molar amount of Br in the formula has a value higher than zero, i.e., b>0.

[0047] In some embodiments, the total molar amount of the halogen in the formula of sulfide electrolyte is no more than 2, i.e., a+b<2. In one embodiment, the total molar amount of the halogen in the formula is no less than 2 and no more than 3, i.e., 2<a+b<3. In one embodiment, the total molar amount of the halogen in the formula is no less than 2 and less than 4, i.e., 2<a+b<4. In one embodiment, the total molar amount of Br and Cl in the formula is no more than 2, i.e., a+b<2, no less than 2 and no more than 3, i.e., 2<a+b<3, or no less than 2 and less than 4, i.e., 2<a+b<4.

[0048] In some embodiments, the sulfide solid electrolyte has a formula selected from the group consisting of:1) LixPSe-a-bClaBrb, where 4<x<8, 0<a<2, 0<b<2, 0<6-a-b<6;2) LixMlyPSe-a-bClaBrb, where 4<x<8, 0<y<l, 0<a<2, 0<b<2, 0<6-a-b<6;3) LixM2zPS6-a-bClaBrb, where 4<x<8, 0<z<l, 0<a<2, 0<b<2, 0<6-a-b<6;4) LixPi-pM3pS6-a-bClaBrb, where 4<x<8, 0<p<l, 0<a<2, 0<b<2, 0<6-a-b<6, 0<l-p<l;5) LixPSe-a-b-qOqClaBrb, where 4<x<8, 0<q<l, 0<a<2, 0<b<2, 0<6-a-b-q<6;6) LixMlyPSe-a-b-qOqClaBrb, where 4<x<8, 0<y<l,0<q<l, 0<a<2, 0<b<2, 0<6-a-b-q<6;7) LixM2zPS6-a-b-qOqClaBrb, where 4<x<8, 0<z<l, 0<q<l, 0<a<2, 0<b<2, 0<6-a-b-q<6;8) LixPi-pM3pS6-a-b-qOqClaBrb, where 4<x<8, 0<p<l, 0<q<l, 0<a<2, 0<b<2, 0<6-a-b-q<6, 0<l-p<l; and9) mixtures thereof.10049] In some embodiments, the anode comprises lithium metal or lithium alloy.

[0050] In some embodiments, the battery prepared by the present method exhibits an average cycle life of at least 10%, at least 25%, at least 50%, at least 70%, at least 100%, at least 150%, at least 200%, at least 250%, at least 300%, at least 350% or at least 400% longer than the one prepared with subunits beginning and ending with anode.

[0051] Without wishing to be bound by any theory, the improved cycling performance is probably ascribed to the protected anodes with less defects, damage and / or impurities. The conventional method may introduce scratches and / or dents to the anode surface.

[0052] In some embodiments, the present disclosure provides a battery prepared according to any method disclosed herein.

[0053] In some embodiments, each pre-pressed subunit (alternatively unit) may comprise 2n layers of SE, wherein n is an integer greater than 0. In some embodiments, a pre-pressed subunit comprises 2, 4, 6, 8, 10, or 12 layers of SE. In some embodiments, a pre-pressed subunit comprises 2n layers of SE and n+1 layers of cathode. In some embodiments, a pre-pressed subunit comprises 2n layers of SE and n+1 layers of anode. A representative subunit as shown in Fig. 2 includes two SE layers, two cathode layers and one anode layer. A representative subunit as shown in Fig. 3 includes four SE layers, three cathode layers and two anode layers.

[0054] As representatively shown in Fig. 4, a battery assembly is prepared by two pre-pressed subunits in Fig. 2. No further isostatic pressing is conducted for this battery assembly. As shown in Fig. 4, a battery assembly includes four cathode layers each with a cathode tab (1-1) (1), four SE layers (3), and two anode layers (2) each with an anode tab (2-1). In some embodiments, the two cathode layers between two SE layers as shown in Fig. 4 comprise an ending cathode layer of the subunit on the top and a beginning cathode layer on the bottom. Insome embodiments, the cathode layer between two SE layers as shown in Fig. 4 bridges the top subunit and the bottom subunit and is referred to as a bridging cathode layer.

[0055] In some embodiments, a cathode layer comprises a cathode active material. In some embodiments, a cathode layer comprises a cathode current collector and a cathode active material layer on one side of the cathode current collector. In some embodiments, a cathode layer comprises a cathode current collector and a cathode active material layer on each side of the cathode current collector.

[0056] In some embodiments, a bridging cathode layer comprises one cathode current collector from either subunit. In some embodiments, the bridging cathode layer comprises two cathode current collectors from adjacent subunits.

[0057] In some embodiments, atop subunit comprises a beginning cathode layer and an ending cathode layer. In some embodiments, the beginning cathode layer comprises a beginning cathode current collector and a cathode active material layer on the inner side of the cathode current collector, wherein the beginning cathode current collector is the outside component of the top subunit. In some embodiments, the ending cathode layer in the top subunit is complementary to a beginning cathode layer in a bottom subunit, wherein the ending cathode layer in the top subunit and the beginning cathode layer in the bottom subunit, via a pressurization process, form a bridging cathode layer with only one cathode current collector. In some embodiments, the bridging cathode layer comprises one cathode current collector with one cathode active material layer on each side (two cathode active material layers in total). In some embodiments, the bottom subunit further comprises an ending cathode layer.

[0058] In some embodiments, the only one cathode current collector in a bridging cathode layer may be from either of the adjacent pre-pressed subunits. In some embodiments, when the bridging cathode layer comprises two cathode current collectors, these two cathode current collectors are from the adjacent pre-pressed subunits. In some embodiments, the two cathodecurrent collectors from the adjacent pre-pressed subunits are assemblable into a single cathode current collector via a pressurization process.100591 In some embodiments, an ending cathode layer of a top subunit of two adjacent subunits comprises an ending cathode active material layer and a cathode current collector, while the beginning cathode layer of a bottom subunit comprises a beginning cathode active material layer. And after the two adjacent subunits, i.e., the top and bottom subunits, are connected via a pressurization, the ending cathode active material layer and cathode current collector of the top subunit and the beginning cathode active material layer of the bottom subunit form to a single cathode layer, i.e., a bridging cathode layer. In some embodiments, the cathode current collector in the bridging cathode layer may be from the bottom subunit.(0060] In some embodiments, each anode (2) may comprise an anode current collector and an optional anode active material layer. In some embodiments, each anode (2) may comprise an anode current collector and an anode active material layer on each side of the anode current collector. In some embodiments, the anode active material layer is a lithium foil or a lithium alloy foil.

[0061] In some embodiments, a pre-pressed unit includes 4 layers of cathode, 6 layers of solid electrolyte, and 3 layers of anode.100621 In some embodiments, the method comprises laminating multiple pre-pressed subunits, each pre-pressed subunit beginning and ending with cathode.

[0063] In some embodiments, the battery is an anode-less or anode-free battery, wherein an anode active material layer is formed after the first charge.

[0064] In some embodiments, an assembly of a battery comprises two pre-pressed subunits, three pre-pressed subunits, four pre-pressed subunits or five pre-pressed subunits. In some embodiments, an assembly of a battery comprises six pre-pressed subunits, eight pre-pressed subunits, ten pre-pressed subunits, twelve pre-pressed subunits or fifteen pre-pressed subunits.In some embodiments, an assembly of a battery comprises twenty pre-pressed subunits, twenty- five pre-pressed subunits or thirty pre-pressed subunits.|0065| Capacity refers to the amount of energy a battery that can store and deliver, usually expressed in ampere-hours (Ah), milliampere-hours (mAh) or watt-hours (Wh). In some embodiments, an assembly of a battery has a capacity of at least 4 Ah, at least 8 Ah, at least 10 Ah, at least 15 Ah, at least 20 Ah, at least 25 Ah, at least 30 Ah, at least 40 Ah, at least 45 Ah or at least 50 Ah.

[0066] Although the disclosed teachings have been described with reference to various applications, methods, compounds, compositions, and materials, it will be appreciated that various changes and modifications to them may be made without departing from the teachings herein. The following examples are provided to better illustrate the disclosed teachings and are not intended to limit the scope of the teachings presented herein. As described herein, when a part such as a layer, subunit, unit, component, etc. is described as "on", "above" or “over” another, this includes both the scenario where the part is directly on top of another part and the scenario where a third part is located between these two parts. Terms such as first and second may be used to describe various components, but the components should not be limited by the terms. Terms such as top and bottom are used to distinguish one component from another in view of their relative locations, rather than limiting to a fixed configuration wherein a top component is on the top of a bottom component.|0067| While the present teachings have been described in terms of these exemplary embodiments, the skilled artisan will readily understand that numerous variations and modifications of these exemplary embodiments are possible without undue experimentation. All such variations and modifications are within the scope of the teachings of this disclosure.ExamplesPreparation of cell assemblies

[0068] A pre-pressed subunit was prepared by stacking a top cathode current collector, a top cathode active material layer, a top solid electrolyte (SE) layer, an anode, a bottom SE layer, a bottom cathode active material layer and a bottom cathode current collector in the order into a bag, conducting an isostatic pressing, and removing the stacked subunit from the bag. In some embodiments, the anode is anode-less, i.e., including an anode current collector without any anode active material layer. In some embodiments, the anode comprises an anode current collector and an anode active material layer on either or both sides of the anode current collector.

[0069] A cell assembly with a capacity of 4Ah was prepared by laminating two pre-pressed subunits followed by a pressurization on a vacuuming machine to reach a vacuum percentage of at least 99.8%.Table 1 Average cycle life of assemblies prepared by different methodsa: Average cycle life is the average cycle number of assemblies to reach 80% of the original capacity and was determined by testing at least 8 assemblies.

[0070] A comparative cell assembly with a capacity of 4Ah was similarly assembled with two comparative pre-pressed subunits wherein each comparative pre-pressed subunit begins and ends with an anode current collector.

[0071] As shown in Table 1, the average cycle life of 4Ah cell assemblies is around 55 cycles when assembled with pre-pressed subunits beginning and ending with anode. In contrast, the present method unexpectedly led to an average cycle life of about 198 cycles, which is about 2.6 times higher than the conventional method.Aspects

[0072] In a first aspect of the present disclosure, a method of preparing an assembly of a battery comprising multiple cathode layers, multiple anode layers, and multiple solid electrolyte (SE)layers each SE layer disposed between a cathode layer and an anode layer. The method comprises: a) having multiple pre-pressed subunits, wherein each subunit begins and ends with a cathode layer and each subunit is compressed by an isostatic compression, b) laminating the multiple pre-pressed subunits into a pre-assembly, and c) pressurizing the pre-assembly, thereby obtaining an assembly, wherein the assembly begins and ends with a cathode layer.

[0073] In a second aspect according to the first aspect, the isostatic compression for each subunit is conducted at a temperature in a range from 0 °C to 150 °C at a pressure normal to the surface of the cathode layer in a range from 10 MPa to 1000 MPa.

[0074] In a third aspect according to any preceding aspect, the isostatic compression is conducted prior to, concurrently with, or after heating to an elevated temperature in a range from 20 °C to 150 °C.

[0075] In a fourth aspect according to any preceding aspect, the multiple cathode layers are substantially parallel to the multiple anode layers.

[0076] In a fifth aspect according to any preceding aspect, the pre-assembly is pressurized by placing the pre-assembly into a vacuuming bag followed by vacuuming the vacuuming bag to a preset vacuum percentage.

[0077] In a sixth aspect according to the fifth aspect, the preset vacuum percentage is at least 99.0%.

[0078] In a seven aspect according to any preceding aspect, the anode layer comprises an anode current collector without an anode active material layer.

[0079] In an eighth aspect according to any of the first through sixth aspects, the anode layer comprises an anode current collector and an anode active material layer.

[0080] In a nineth aspect according to the eighth aspect, the anode active material layer comprises lithium metal or lithium alloy.100811 In a tenth aspect according to any preceding aspect, at least one of the multiple cathode layers comprises a cathode current collector and a cathode active material layer.10082 [ In an eleventh aspect according to any preceding aspect, the battery is an all solid-state battery (ASSB) and the multiple SE layers comprise at least one selected from the group consisting of an all-solid-state polymer electrolyte, gel polymer electrolyte, an inorganic oxide electrolyte, an inorganic sulfide electrolyte and a combination thereof.

[0083] In a twelfth aspect according to the eleventh aspect, the inorganic sulfide electrolyte has a formula (I) LixMlyM2zPi-pM3pS6-a-b-qOqClaBrb (Formula I), wherein 4<x<8, 0<y<l, 0<z <1, 0<p<l, 0<q<l, 0<a<2, 0<b<2, 0<6-a-b-q<6, 0<l-p<l, wherein Ml is at least one element of Group 1 or Group 11 other than H or Li of the periodic table, M2 is at least one element of Group 2 of the periodic table, and M3 is at least one element of Group 14 of the periodic table.

[0084] In a thirteenth aspect, the present disclosure provides an assembly of a battery prepared according to any preceding aspect. In some embodiments, the battery exhibits an average cycle life of at least 10% longer than the one prepared with multiple subunits beginning and ending with anode.

[0085] In a fourteenth aspect, the present disclosure provides a battery assembly comprising multiple pre-pressed subunits each beginning and ending with a cathode layer, wherein• each pre-pressed subunit is compressed by an isostatic compression and comprises multiple cathode layers, multiple solid electrolyte (SE) layers and one or more anode layers, wherein each SE layer is sandwiched between one of the cathode layers and one of the anode layer; and• two adjacent pre-pressed subunits of the multiple pre-pressed subunits are connected via a bridging cathode layer comprising one cathode current collector from either of two adjacent pre-pressed subunits or two cathode current collectors from two adjacent pre-pressed subunits.

[0086] In some embodiments, each pre-pressed subunit is compressed by an isostatic pressing.

[0087] In a fifteenth aspect according to the fourteenth aspect, the multiple SE layers comprise at least one selected from the group consisting of an all-solid-state polymer electrolyte, an inorganic oxide electrolyte, an inorganic sulfide electrolyte and combinations thereof.

[0088] All transitional phrases such as “comprising,” “including,” “carrying,” “having,” “containing,” “involving,” “holding,” “composed of,” and the like are to be understood to be open-ended, i.e., to mean including but not limited to. Only the transitional phrases “consisting of’ and “consisting essentially of’ shall be closed or semi-closed transitional phrases, respectively.

[0089] The terms such as “above”, “below”, “top” and “bottom” may be used to indicate relative positions for elements, for example, stacked components or layers of a subunit and stacked subunits of a battery assembly, and are not limiting embodiments to either of a horizontal or vertical stack orientation.

[0090] Certain features that are described in this specification in the context of separate embodiments can also be implemented in combination in a single embodiment. Conversely, various features that are described in the context of a single embodiment can also be implemented in multiple embodiments separately or in any suitable subcombination. Moreover, although features may be described above as acting in certain combinations and even initially claimed as such, one or more features from a claimed combination can in some cases be excised from the combination, and the claimed combination may be directed to a subcombination or variation of a subcombination.

[0091] Various embodiments of the features of this disclosure are described herein. However, it should be understood that such embodiments are provided merely by way of example, and numerous variations, changes, and substitutions can occur to those skilled in the art without departing from the scope of this disclosure. It should also be understood that various alternative to the specific embodiments described herein are also within the scope of this disclosure.

Claims

What is claimed is:

1. A method of preparing an assembly of a battery comprising multiple cathode layers, multiple anode layers, and multiple solid electrolyte (SE) layers each SE layer disposed between a cathode layer and an anode layer, the method comprising: a) having multiple pre-pressed subunits, wherein each pre-pressed subunit begins and ends with a cathode layer and each pre-pressed subunit is compressed by an isostatic compression, b) laminating the multiple pre-pressed subunits into a pre-assembly, and c) pressurizing the pre-assembly, thereby obtaining an assembly, wherein the assembly begins and ends with a cathode layer.

2. The method of claim 1, wherein the isostatic compression for each pre-pressed subunit is conducted at a temperature in a range from 0 °C to 150 °C and at a pressure normal to the surface of the cathode layer in a range from 10 MPa to 1000 MPa.

3. The method of claim 1, wherein the isostatic compression is conducted prior to, concurrently with, or after heating to an elevated temperature in a range from 20 °C to 150 °C.

4. The method of claim 1, wherein the multiple cathode layers are substantially parallel to the multiple anode layers.

5. The method of claim 1, wherein the pre-assembly is pressurized by placing the preassembly into a vacuuming bag followed by vacuuming the vacuuming bag to a preset vacuum percentage.

6. The method of claim 5, wherein the preset vacuum percentage is at least 99.0%.

7. The method of claim 1, wherein the anode layer comprises an anode current collector without an anode active material layer.

8. The method of claim 1, wherein the anode layer comprises an anode current collector and an anode active material layer.

9. The method of claim 8, wherein the anode active material layer comprises lithium metal or lithium alloy.

10. The method of claim 1, wherein at least one of the multiple cathode layers comprises a cathode current collector and a cathode active material layer.

11. The method of claim 1, wherein the battery is an all solid-state battery (ASSB) and the multiple SE layers comprise at least one selected from the group consisting of an all- solid-state polymer electrolyte, gel polymer electrolyte, an inorganic oxide electrolyte, an inorganic sulfide electrolyte and a combination thereof.

12. The method of claim 11, wherein the inorganic sulfide electrolyte has a formula (I) LixMlyM2zPi-pM3pS6-a-b-qOqClaBrb (Formula I), wherein 4<x<8, 0<y<l, 0<z <1, 0<p<l, 0<q<l, 0<a<2, 0<b<2, 0<6-a-b-q<6, 0<l -p<l , wherein Ml is at least one element of Group 1 or Group 11 other than H or Li of the periodic table, M2 is at least one element of Group 2 of the periodic table, and M3 is at least one element of Group 14 of the periodic table.

13. An assembly of a battery prepared according to any preceding claim.

14. A battery assembly comprising multiple pre-pressed subunits each beginning and ending with a cathode layer, wherein• each pre-pressed subunit is compressed by an isostatic compression and comprises multiple cathode layers, multiple solid electrolyte (SE) layers and one or more anode layers, wherein each SE layer is sandwiched between one of the cathode layers and one of the anode layer; and• two adjacent pre-pressed subunits of the multiple pre-pressed subunits are connected via a bridging cathode layer comprising one cathode current collector from either of two adjacent pre-pressed subunits or two cathode current collectors from two adjacent pre-pressed subunits.

15. The battery assembly of claim 14, wherein the multiple SE layers comprise at least one selected from the group consisting of an all-solid-state polymer electrolyte, an inorganic oxide electrolyte, an inorganic sulfide electrolyte and combinations thereof.

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