Segmented cell architecture for solid-state batteries

Abstract

A new cell architecture and manufacturing method is provided that makes solid-state batteries flexible and allows them to be rolled or folded into stacked configurations. [Solution] An electrochemical device is provided that includes a cathode, an anode, and a solid electrolyte disposed between the cathode and the anode, wherein at least one of the cathode and the anode includes an array (15) of segments (11) embedded within a structural matrix, the segments including a lithium host material.

Description

[Technical Field]

[0001] [CROSS-REFERENCE TO RELATED APPLICATIONS] This application is a continuation of U.S. patent application Ser. No. 62 / 289,559, filed February 1, 2016. Claim priority to the

[0002] [STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT] Not applicable.

[0003] The present invention relates to a lithium ion battery electrode, a lithium ion conductive solid electrolyte, and and solid-state lithium-ion batteries and other electrochemical devices containing the electrodes and solid electrolytes. The present invention also relates to a method for making such an electrochemical device, more particularly The present invention makes the solid-state battery flexible and allows it to be rolled or folded into a stack structure. This paper relates to a segmented cell architecture that enables [Background technology]

[0004] Lithium-ion (Li-ion) battery technology has made significant advances, reaching $10.5 billion in 2019 The current state-of-the-art lithium-ion battery has two electrodes (an and cathode) and the Li + Separator material that allows ions to pass through , and an electrolyte (an organic liquid containing lithium salt). + Ions flow between the electrodes It will be replaced.

[0005] State-of-the-art lithium-ion technology is currently used in low-volume plug-in hybrid vehicles and niche applications. It is used in high-performance vehicles. However, the penetration of electrified powertrains is expected to reach 25%. cost reduction, four times better performance, and safer batteries that don't have the potential to catch fire. Therefore, future energy storage requires safer, cheaper, and higher-performance energy storage means. to be needed.

[0006] One strategy is to develop solid-state batteries in which the liquid electrolyte is replaced with a solid material that is conductive to Li + ions and can provide three to four times the energy density while reducing the cost of the battery pack by about 20%. Despite these attractive features, the manufacture and testing of solid-state batteries for bulk-scale applications such as electric vehicles have not been demonstrated. The main challenges associated with solid-state batteries are the development of new manufacturing technologies for thin ceramic layers and their assembly into new cell architectures. Regardless of how the layers of a solid-state battery can be formed, these layers must be assembled into an architecture. Current liquid-based technologies stack the components of a battery, namely the anode, separator, and cathode, into a stack and wind or fold this stack. In this type of roll or fold stack structure, each layer must be flexible and able to bend significantly. The layers for typical solid-state batteries are not as flexible as those of current liquid-based technologies, so a roll or fold structure was impossible.

[0007] Therefore, new cell architectures and manufacturing methods are needed to make solid-state batteries flexible and enable a roll or fold stack structure.

Summary of the Invention

[0008]

Problems to be Solved by the Invention

[0009] This disclosure reports on a segmented cell architecture that enables a solid-state battery to be flexible and take on a roll or foldable stack structure. This disclosure also provides a method for forming a segmented cell architecture for a solid-state battery. In one aspect, the present invention provides an electrochemical device comprising a cathode, an anode, and a solid electrolyte disposed between the cathode and the anode. Either or both of the cathode and the anode may comprise an array of segments embedded within a structural matrix. The segments of the cathode or anode may comprise a lithium host material. The structural matrix may comprise a flexible material. The structural matrix may comprise a polymeric material. The polymeric material may be selected from the group consisting of polyolefins, polystyrene, divinylbenzene, and styrene-divinylbenzene copolymers. The structural matrix may comprise polypropylene or polyethylene. In the electrochemical device, the anode may comprise an array of segments embedded within the structural matrix, and the lithium host material may be selected from the group consisting of graphite, lithium metal, lithium titanate, hard carbon, tin / cobalt alloy, or silicon / carbon. In the electrochemical device, the cathode may comprise an array of segments embedded within the structural matrix, and the lithium host material may be a lithium metal oxide in which the metal is one or more of aluminum, cobalt, iron, manganese, nickel, and vanadium.

Means for Solving the Problems

[0010] In one aspect, the present invention provides an electrochemical device comprising a cathode, an anode, and a solid electrolyte disposed between the cathode and the anode. Either or both of the cathode and the anode may comprise an array of segments embedded within a structural matrix. The segments of the cathode or anode may comprise a lithium host material. The structural matrix may comprise a flexible material. The structural matrix may comprise a polymeric material. The polymeric material may be selected from the group consisting of polyolefins, polystyrene, divinylbenzene, and styrene-divinylbenzene copolymers. The structural matrix may comprise polypropylene or polyethylene. In the electrochemical device, the anode may comprise an array of segments embedded within the structural matrix, and the lithium host material may be selected from the group consisting of graphite, lithium metal, lithium titanate, hard carbon, tin / cobalt alloy, or silicon / carbon. In the electrochemical device, the cathode may comprise an array of segments embedded within the structural matrix, and the lithium host material may be a lithium metal oxide in which the metal is one or more of aluminum, cobalt, iron, manganese, nickel, and vanadium. ​​​​​​​​​​​​​​and optionally having the general formula LiMPO4, where M is cobalt, iron, manganese, and nickel and may be selected from the group consisting of lithium-containing phosphates, where M is one or more of cobalt, iron, manganese, and nickel. Lithium host materials may be selected from lithium manganese nickel oxides. Lithium host materials may be selected from lithium titanium oxides.

[0011] In another aspect, the present invention provides an electrochemical device comprising a cathode, an anode, and a solid electrolyte disposed between the cathode and the anode, the solid electrolyte comprising an array of segments. The segments of the solid electrolyte may comprise a solid electrolyte material and may be embedded within a structural matrix. The structural matrix may comprise a flexible material. The structural matrix may comprise a polymeric material. The polymeric material may be selected from the group consisting of polyolefins, polystyrenes, divinylbenzenes, and styrene-divinylbenzene copolymers. The structural matrix may comprise polypropylene or polyethylene. In the electrochemical device, the solid electrolyte material may be an oxide or phosphate material in any combination with garnet, perovskite, NaSICON, or LiSICON phases. The garnet phase may have the formula Li Re M A O where Re may be any combination of elements having a nominal atomic valence of +3, including La, Nd, Pr, Pm, Sm, Sc, Eu, Gd, Tb, Dy, Y, u Re v M w A x O y and M may be Zr, Ta, Nb, Sb, W, Hf, Sn, Ti, V, Ho, Er, Tm, Yb, and Lu, and A may be any combination of elements having a nominal atomic valence of +3, including La, Nd, Pr, Pm, Sm, Sc, Eu, Gd, Tb, Dy, Y, Ho, Er, Tm, Yb, and Lu. The perovskite phase may have the formula ABO3, where A may be any combination of elements having a nominal atomic valence of +2, including Ca, Sr, Ba, Pb, and Eu, and B may be any combination of elements having a nominal atomic valence of +4, including Ti, Zr, Hf, Sn, Ce, Th, and Pr. The NaSICON phase may have the formula Na1+xZr2-xSixPO4, where x may be any value between 0 and 2. The LiSICON phase may have the formula Li1+xZr2-xSixPO4, where x may be any value between 0 and 2. The solid electrolyte material may be a composite material comprising any combination of the above phases. The solid electrolyte segments may be in the form of thin films, fibers, particles, or any other suitable shape. The structural matrix may be in the form of a porous material, a non-porous material, or a combination of both. The electrochemical device may be a battery, a fuel cell, a supercapacitor, or any other type of electrochemical device. The cathode may comprise a cathode active material, a conductive additive, and a binder. The cathode active material may be selected from the group consisting of lithium transition metal oxides, lithium manganese oxides, lithium cobalt oxides, lithium nickel oxides, and lithium iron phosphates. The conductive additive may be selected from the group consisting of carbon black, graphite, carbon nanotubes, and graphene. The binder may be selected from the group consisting of polyvinylidene fluoride, polyacrylonitrile, and polytetrafluoroethylene. The anode may comprise an anode active material, a conductive additive, and a binder. The anode active material may be selected from the group consisting of lithium metal, lithium alloys, carbonaceous materials, and titanium oxides. The conductive additive may be selected from the group consisting of carbon black, graphite, carbon nanotubes, and graphene. The binder may be selected from the group consisting of polyvinylidene fluoride, polyacrylonitrile, and polytetrafluoroethylene. The electrochemical device may further comprise a separator disposed between the cathode and the anode. The separator may be a porous material that allows the flow of ions but prevents the flow of electrons. The separator may be selected from the group consisting of polyolefin membranes, ceramic membranes, and composite membranes. The electrochemical device may be assembled by any suitable method, including physical vapor deposition, chemical vapor deposition, sol-gel processing, and electrochemical deposition. The electrochemical device may be tested and characterized by any suitable method, including cyclic voltammetry, galvanostatic charge-discharge cycling, impedance spectroscopy, and scanning electron microscopy. The electrochemical device may be optimized by adjusting the composition, structure, and processing conditions of the cathode, anode, solid electrolyte, and separator. The electrochemical device may be used in a variety of applications, including portable electronics, electric vehicles, and renewable energy storage systems. and A may be any combination of elements having a nominal atomic valence of +3, including La, Nd, Pr, Pm, Sm, Sc, Eu, Gd, Tb, Dy, Y, Metals having a nominal valence of +3, +4, +5, or +6 and containing Bi, Ge, and Si may be any combination thereof, and A is H, Na, K, Rb, Cs, Ba, Sr, C a, Mg, Fe, Co, Ni, Cu, Zn, Ga, Al, B, and Mn, any combination of dopant atoms having a nominal valence of +1, + 2, +3, or +4; u may vary from 3 to 7.5; v may vary from 0 to 3; w may vary from 0 to 2; and y may vary from 11 to 12.5. The garnet is a ceramic oxide exhibiting a combination of high ionic conductivity (4×10 S / cm at room temperature) and chemical stability with respect to metallic lithium, and may be a lithium lanthanum zirconium oxide having the formula Li -4 La3Zr2Al 6.25 0.25 O 12 O 12 (LLZO).

[0012] In another aspect, the present invention provides a method of forming a segmented electrode. The method comprises (a) forming an array comprising spaced segments, and (b) depositing a flexible material between the segments, the segments comprising a lithium host material . Step (a) may comprise casting a slurry onto a surface to form an array of spaced segments and sintering the segments . Each segment may have a thickness in the range of 10 to 100 microns . Step (a) may comprise sintering the layer at a temperature in the range of 600°C to 1100°C . In this method, the lithium host material is graphite ​​, lithium metal, lithium titanate, hard carbon, tin / cobalt alloy, or may be selected from the group consisting of silicon / carbon. The lithium host material is such that the metal is 1 or more of aluminum, cobalt, iron, manganese, nickel, and vanadium, the lithium metal oxide, and a lithium-containing phosphate having the general formula LiMPO4, where M is one or more of cobalt, iron, manganese and nickel, may be selected from the group consisting of. The lithium host material may be selected from lithium manganese nickel oxide . The lithium host material may be selected from lithium titanate. In another aspect, the present invention provides a method of forming a segmented solid electrolyte array.

[0013] The method may include (a) forming an array comprising spaced segments, and (b ) depositing a flexible material between the segments, the segments comprising a solid electrolyte material. Step (a) may include molding a slurry onto a surface to form an array comprising spaced segments, and sintering the segments to form a solid electrolyte material. The slurry comprises a solid electrolyte material precursor. In this method, each segment may have a thickness in the range of 10 to 100 microns. The slurry is 40 wt% to 60 wt% solid electrolyte material, a solid electrolyte material comprising a lithium lanthanum zirconium oxide having the formula Li La3Zr2Al O Li 6.25 La3Zr2Al 0.25 O 12 , 0.1 wt% to 2 wt% dispersant, 1 wt% to 5 wt% binder, 1 wt% to 5 wt% plasticizer, and 20 wt% to 45 wt% solvent ​ and may include all weight percentages are based on the weight of the total slurry. Step (a) may include a step of sintering the layer at a temperature in the range of 600°C to 1100°C .

[0014] In another aspect, the present invention provides a method of forming an electrochemical device. The method includes (a) forming a first layer of an array comprising spaced segments, the segments comprising a first lithium host material, a step; (b) forming a second layer of the array over the first layer of the array, the second layer comprising a solid electrolyte material, a step; and (c) forming a third layer of the array over the second layer of the array, the third layer comprising a second lithium host material, a step; and (d) depositing a flexible material between the segments to form an electrochemical device. This method may include. In this method, step (a) may include forming a first slurry on a surface to form a first layer of an array comprising spaced segments, the first slurry comprising a first lithium host material, step (b) may include forming a second slurry over the first layer of the array to form a second layer of the array, the second slurry comprising a solid electrolyte material, step (c) may include forming a third slurry over the second layer of the array to form a third layer of the array, the third slurry comprising a second lithium host material, and step (d) may include sintering the array before depositing the flexible material between the segments. In this method, each of the first layer, the second layer, and the third layer may have a thickness in the range of 10 to 100 microns. In this method, the surface is may include forming a second slurry over the first layer of the array to form a second layer of the array, the second slurry comprising a solid electrolyte material, step (c) may include forming a third slurry over the second layer of the array to form a third layer of the array, the third slurry comprising a second lithium host material, and step (d) may include sintering the array before depositing the flexible material between the segments. In this method, each of the first layer, the second layer, and the third layer may have a thickness in the range of 10 to 100 microns. In this method, the surface is sintered, and each of the first layer, the second layer, and the third layer may have a thickness in the range of 10 to 100 microns. In this method, the surface is may be flexible. It may include the surface of the flexible current collector. The flexible material deposited between the segments may include a polymer material. The polymer material may include polyolefin, polystyrene, divinylbenzene, and styrene-divinylbenzene copolymer. The polymer material may be selected from polypropylene and polyethylene. In this method, the first lithium host material is (i) a lithium metal oxide in which the metal is one or more of aluminum, cobalt, iron, manganese, nickel, and vanadium, and a lithium-containing phosphate having the general formula LiMPO4, where M is one or more of cobalt, iron, manganese, and nickel, and (ii) selected from the second group consisting of graphite, lithium metal, lithium titanium oxide, hard carbon, tin / cobalt alloy, or silicon / carbon. When the first lithium host material is selected from the first group, the second lithium host material is selected from the second group, and when the first lithium host material is selected from the second group, the second lithium host material is selected from the first group. Step (d) may include sintering the array at a temperature in the range of 600 °C to 1100 °C. In this method, step (a) may include first forming a layer of the polymer material and forming indentations in the layer, where the indentations provide space in the array for the spaced segments. This method may further include stacking an electrochemical device on a similar electrochemical device, thereby forming a bipolar stacked battery. In this method, the second slurry is 40 wt% to 60 wt% of a solid electrolyte material having the formula Li La3Zr2Al and stacking the electrochemical device on a similar electrochemical device to form a bipolar stacked battery. This method may further include stacking an electrochemical device on a similar electrochemical device to form a bipolar stacked battery. In this method, the second slurry is 40 wt% to 60 wt% of a solid electrolyte material, which is a material of the formula Li 6.25 La3Zr2Al0.25 O 12 Rich a solid electrolyte material comprising lanthanum zirconium oxide and 0.1 wt. % to 2 wt. % % of a dispersant, 1% to 5% by weight of a binder, 1% to 5% by weight of a plasticizer, and 20 % to 45% by weight of the solvent, all weight percentages being based on the weight of the total slurry. In this method, the solid electrolyte material is an oxide having a garnet phase. The solid electrolyte material may be selected from the group consisting of lithium lanthanum zirconium The solid electrolyte material may be a lithium oxide of the formula Li 6.25 La3Zr2Al 0.2 5O 12 The solid electrolyte material may have the formula Li u Re v M w A x O y Having where Re is La, Nd, Pr, Pm, Sm, Sc, Eu, Gd, Tb, Dy, +3 nominal valence, including Y, Ho, Er, Tm, Yb, and Lu M may be any combination of elements having a valence of Zr, Ta, +3, +4, + including Nb, Sb, W, Hf, Sn, Ti, V, Bi, Ge, and Si A may be any combination of metals with a nominal valence of +5, or +6, and A is H , Na, K, Rb, Cs, Ba, Sr, Ca, Mg, Fe, Co, Ni, Cu, Zn, G Dopants with a nominal valence of +1, +2, +3, or +4, including Al, Al, B, and Mn It may be any combination of alkyl groups and u may vary from 3 to 7.5. where v may vary from 0 to 3, w may vary from 0 to 2, and y may vary from 11 to May vary up to 12.5.

[0015] In another aspect, the present invention provides a method of forming a segmented electrochemical device. The method includes (a) forming a first layer comprising a first lithium host material; (b) forming a second layer over the first layer, the second layer comprising a solid electrolyte material; (c) forming a third layer over the second layer to form a continuous stack, the third layer comprising a second lithium host material; (d) dividing the continuous stack into segments, each segment comprising a portion of the first, second, and third layers of the continuous stack; (e) dispersing the segments in an array; and (f) depositing a flexible material between the segments to form a segmented electrochemical device. In this method, step (a) may include shaping a first slurry on a surface to form the first layer, the first slurry comprising the first lithium host material; step (b) may include shaping a second slurry over the first layer to form the second layer, the second slurry comprising the solid electrolyte material; step (c) may include shaping a third slurry over the second layer to form the third layer and sintering the first, second, and third layers to form the continuous stack, the third slurry comprising the second lithium host material. The method may further include stacking an electrochemical device over a similar electrochemical device to form a bipolar stacked battery. In this method, each of the first, second, and third layers is 10 microns or less in thickness. It may have a thickness in the range of 100 microns. The surface may comprise the surface of the flexible current collector. The flexible material deposited between segments may comprise a polymer material. The polymer material may be selected from polyolefin, polystyrene, divinylbenzene, and styrene - divinyl benzene copolymer. The polymer material may be selected from polypropylene and poly ethylene. In this method, the first lithium host material is (i) a lithium metal oxide in which the metal is one or more of aluminum, cobalt, iron, manganese, nickel, and vanadium, and a first group consisting of lithium - containing phosphates having the general formula LiMPO4, where M is one or more of cobalt, iron, manganese, and nickel, and (ii) a second group consisting of graphite, lithium metal, lithium titanate, hard carbon an, tin / cobalt alloy, or silicon / carbon. It may be selected. When the first lithium host material is selected from the first group, the second lithium host material is selected from the second group, and when the first lithium host material is selected from the second group, the second lithium host material is selected from the first group. Step (d) may comprise sintering the first, second, and third layers at a temperature in the range of 600 °C to 1100 °C. The second slurry may be 40 wt% to 60 wt% of a solid electrolyte material, which is a lithium lanthanum zirconium oxide having the formula Li La3Zr 2Al O 6.25 La3Zr 2Al 0.25 O 12 and may comprise a dispersant of 0.1 wt% to 2 wt%, a binder of 1 wt% to 5 wt%, a plasticizer of 1 wt% to 5 wt%, and a solvent of 20 wt% to 45 wt%, all by weight. by weight. The weight percentage is the weight percentage of the total slurry. The solid electrolyte material may be selected from the group consisting of oxide materials having a garnet phase. The solid electrolyte material may be lithium lanthanum zirconium oxide. The solid electrolyte material has the formula Li 6.25 La3Z r2Al 0.25 O 12 and may have. The solid electrolyte material has the formula Li u Re v M w A x O y with a nominal valence of +3, including Tb, Dy, Y, Ho, Er, Tm, Yb, and Lu. Any combination of elements having may be, M is any combination of metals having a nominal valence of +3, +4, +5, or +6, including Zr, Ta, Nb, Sb, W, Hf s, Ba, Sr, Ca, Mg, Fe, Co, Ni, Cu, Zn, Ga, Al, B, and Any combination of dopant atoms having a nominal valence of +1, +2, +3, or +4, including Mn, may be, u may vary from 3 to 7.5, v may vary from 0 to 3 Any combination of dopant atoms having a nominal valence of +1, +2, +3, or +4, including Mn, may be, u may vary from 3 to 7.5, v may vary from 0 to 3 Any combination of dopant atoms having a nominal valence of +1, +2, +3, or +4, including Mn, may be, u may vary from 3 to 7.5, v may vary from 0 to 3 Any combination of dopant atoms having a nominal valence of +1, +2, +3, or +4, including Mn, may be, u may vary from 3 to 7.5, v may vary from 0 to 3 Any combination of dopant atoms having a nominal valence of +1, +2, +3, or +4, including Mn, may be, u may vary from 3 to 7.5, v may vary from 0 to 3

[0016] Solid-state batteries manufactured using the methods and cell architectures of the present invention have many advantages For example, solid-state batteries manufactured using the methods and cell architectures of the present invention are safer (i.e., non-flammable) than liquid electrolyte batteries, and the methods and cells of the present invention Solid-state batteries are safer (i.e., non-flammable) than liquid electrolyte batteries, and the methods and cells of the present invention ​Solid-state batteries manufactured using a luer architecture provide a higher energy density, Solid-state batteries manufactured using the methods and cell architectures of the present invention reduce battery costs (e.g., simpler packaging is used), and solid-state batteries manufactured using the methods and cell architectures of the present invention allow ceramics to be used in various structures. Furthermore, solid-state batteries manufactured using the methods and cell architectures of the present invention allow the battery to be flexible and take a roll or foldable stack structure.

[0017] These and other features, aspects, and advantages of the present invention will be better understood by considering the following detailed description, drawings, and accompanying claims. BRIEF DESCRIPTION OF THE DRAWINGS

[0018]

Figure 1

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DETAILED DESCRIPTION OF THE INVENTION

[0019] Similar reference numerals are used to refer to similar parts throughout the following description of the drawings. for each figure.

[0020] The present invention provides a new cell architecture suitable for use in solid-state batteries and a method for manufacturing the same, which make the battery flexible and capable of taking a roll-shaped or foldable stack structure.

[0021] As used throughout this specification, the active material refers to the material in the battery layer that participates in the electrochemical reaction. This may include substances that transport or store Li atoms, but may exclude substances such as additives for increasing electronic conductivity. As used throughout this specification, formation means a process or state in which all substances within the cell are activated and the device functions as a battery. For example, formation may be to bond all three layers (anode, electrolyte, and cathode) together so that an electrochemical reaction occurs. electrolyte, and cathode) together so that an electrochemical reaction occurs.

[0022] Currently, liquid-based batteries are manufactured in two steps. First, for each electrode type​​​​​ The layer is formed from a slurry onto a metal foil or current collector. The formed slurry on the metal current collector is several meters in length, and this process is suitable for continuous roll-to-roll processing. The dried electrode from the slurry is a composite containing a flexible polymer binder in addition to the active material is. Then, a stack is formed with three components: an anode, a separator, and a cathode. This stack is wound, folded, and placed in a container. When placed in the container, a liquid electrolyte is added to form a battery. The combination of discrete layers within a rolled or folded geometric shape is called a cell architecture.

[0023] The above-described cell architecture is advantageous from a manufacturing perspective because the process is suitable for roll-to-roll continuous processing and is thus inexpensive. Thus, new inexpensive battery technologies, including solid-state batteries, must be capable of some degree of continuous processing in order to have cost competitiveness with existing technologies. This continuous processing of solid-state batteries may include forming each of the three layers of the anode, electrolyte, and cathode from a slurry. However, unlike liquid electrolyte batteries, a high-temperature sintering step is required to form solid-state batteries. At such high temperatures, polymers that can impart flexibility to the film may be lost. In this way, the resulting film is less flexible and cannot be wound as a continuous sheet. Furthermore, the materials for solid-state batteries are ceramics and are inherently brittle, so such a high aspect ratio of a large area for a small thickness within a continuous sheet can lead to cracking. To overcome these disadvantages, the new cell architecture disclosed herein is disclosed. In addition, the materials for solid-state batteries are ceramics and are inherently brittle, so such a high aspect ratio of a large area for a small thickness within a continuous sheet can lead to cracking. To overcome these disadvantages, the new cell architecture disclosed herein is minimizes layer fragmentation and enables the use of inherently brittle materials in a roll-to-roll continuous process to be possible.

[0024] As described above, the cell architecture is an integration of how the cell pieces (anode, electrolyte, and cathode ) are assembled into a package. For example, the winding or folding of the discrete composite layer constitutes different package assemblies. Several different techniques such as film deposition may be utilized to form the disclosed cell architecture. may be.

[0025] Instead of forming a continuous sheet on the current collector 13, as seen in electrode 10 of FIG. 1, the layer material may be divided into regularly repeating subunits similar to tiles or segments 11. The repeating pattern of segments 11 may form an array 15. These segments 11 offer advantages such as reducing the aspect ratio to make fragmentation less likely, i.e., each segment 11 has an area small compared to its thickness. Another benefit of the segments 11 is the acceptable flexibility of the resulting structure such as segments 11 dispersed on the flexible current collector 13. The flexible structure or array 15 may be used in roll-to-roll processing.

[0026] Extending the tile similarity, the space 17 between the tiles or segments 11 may be filled back with a second material (such as a polymer or other flexible material). As seen in FIG. 2, this second material filling the space 17 between the segments 11 forms a structural matrix 19. The structural matrix 19 can provide structural support to the segments 11.​​ It is okay whether the structural matrix material is electrochemically active or not.

[0027] The segment 11 embedded in the structural matrix 19 can form a "tile" structure with a polymer "grout" which may be a composite material. However, this novel cell architecture provides distinct advantages for solid-state batteries. Each layer of the anode, electrolyte, and cathode may be formed as described above. Then, these layers are repeatedly laminated and bonded to each other to form a monolithic battery. The segment 11 can be of any size. For example, the segment 11 can be as small as 1 to 5 micrometers or as large as 1 to 5 centimeters. Further, the segment 11 can have a thickness ranging from 1 to 5 micrometers up to a maximum of 1

[0028] 00 micrometers. The segment 11 can be of any shape. For example, as shown in FIGS. 1 to 2, the segment 11 can be formed in the shape of a polyhedron or other self-similar shapes that can be closely packed. These closest-packed structures can advantageously minimize the space 17 between each segment 11 and thus save the space that would otherwise be occupied by the entire array 15. For example, the segment 11 can be formed as a hexagon, square, triangle, disk (as seen in FIGS. 5 to 6), or any combination thereof. Alternatively, the segment 11 can be formed randomly or crushed into various shapes,

[0029] which can reduce the processing cost. For example, the anode, solid electrolyte The segment 11 can be of any shape. For example, as shown in FIGS. 1 to 2, the segment 11 can be formed in the shape of a polyhedron or other self-similar shapes that can be closely packed. These closest-packed structures can advantageously minimize the space 17 between each segment 11 and thus save the space that would otherwise be occupied by the entire array 15. For example, the segment 11 can be formed as a hexagon, square, triangle, disk (as seen in FIGS. 5 to 6), or any combination thereof. Alternatively, the segment 11 can be formed randomly or crushed into various shapes, which can reduce the processing cost. For example, the anode, solid electrolyte The segment 11 can be of any shape. For example, as shown in FIGS. 1 to 2, the segment 11 can be formed in the shape of a polyhedron or other self-similar shapes that can be closely packed. These closest-packed structures can advantageously minimize the space 17 between each segment 11 and thus save the space that would otherwise be occupied by the entire array 15. For example, the segment 11 can be formed as a hexagon, square, triangle, disk (as seen in FIGS. 5 to 6), or any combination thereof. Alternatively, the segment 11 can be formed randomly or crushed into various shapes, which can reduce the processing cost. For example, the anode, solid electrolyte The segment 11 can be of any shape. For example, as shown in FIGS. 1 to 2, the segment 11 can be formed in the shape of a polyhedron or other self-similar shapes that can be closely packed. These closest-packed structures can advantageously minimize the space 17 between each segment 11 and thus save the space that would otherwise be occupied by the entire array 15. For example, the segment 11 can be formed as a hexagon, square, triangle, disk (as seen in FIGS. 5 to 6), or any combination thereof. Alternatively, the segment 11 can be formed randomly or crushed into various shapes, which can reduce the processing cost. For example, the anode, solid electrolyte or any combination thereof. Alternatively, the segment 11 can be formed randomly or crushed into various shapes, which can reduce the processing cost. For example, the anode, solid electrolyte and cathode layers can be formed from segments 11 of various shapes, sizes, and thicknesses. and the three - layer continuous sheet of the anode, cathode, and cathode are molded, sintered, and then crushed to form the array 15 This may be done. The randomly occurring fractures or spaces 17 along the three - layer continuous sheet, for example by spraying or pouring a liquid flexible material onto the sheet and curing it to form the structural matrix 19, can be filled with the flexible material.

[0030] The segments 11 may be spaced apart from each other by any distance. For example, the segments 11 may be 100 to 900 nanometers, 1 to 9 micrometers, or 10 to 50 micrometers apart from each other.

[0031] The segments 11 may have any composition. The composition of the segments 11 may be different in the deposited state compared to the as - formed state. For example, the composition of the deposited material may contain additives in addition to the active material to facilitate deposition. Similarly, the composition of the deposited material may contain additives to improve the battery performance after formation.

[0032] The structural matrix 19 may be of any composition. The structural matrix 19 may advantageously be formed of a flexible polymer - based material that can improve the mechanical properties of the sheet . However, the structural matrix 19 may be formed of any material such as a thermoplastic polymer, an inorganic polymer, a metal, glass, or ceramic. Non - limiting exemplary polymer materials include polyolefins (e.g., polypropylene or polyethylene) , polystyrene, divinylbenzene, and styrene - divinylbenzene copolymers. ​​​​

[0033] As shown in FIG. 3, segment 111 may be formed from a layer of cathode 123, solid electrolyte 125, and anode 127. These layers are sintered together in a continuous sheet, segmented into segments 111, and then dispersed in an array (not shown) on the first current collector 113. The space between segments 111 may be filled with a structural matrix 119. The structural matrix 119 may be made of a polymer or other flexible material . Alternatively, the structural matrix 119 may be any other material. The second current collector 131 may be applied over an array of three-layer segments 111 within the structural matrix . The first and second current collectors 113, 131 may be made of a flexible material or a thin foil having some degree of flexibility. For example, the first current collector 113 may comprise a conductive aluminum foil , and the second current collector 131 may be a conductive fabric having a metal thread or mesh .

[0034] The layers of the first current collector 113, cathode 123, solid electrolyte 125, anode 127, and second current collector 131 can form a single cell 121. Multiple layers of the single cell 121 may be wound, stacked, or arranged to form a battery. As shown in FIG. 3, between each anode 127 and cathode 123 in adjacent half-cells, a bipolar laminated battery 129 having a two-layer current collector (formed by the second and first current collectors 131, 113) can be formed by stacking the single cells 121 in series. By stacking the single cells 121 in series, the voltage of the bipolar battery 129 is increased. The number of stacked single cells 121 Provided is a modular battery system that, by being made different, advantageously satisfies changing needs. This can be done. The layer of single cells 121 with an array of segments 111 can be stored in a roll and, if necessary, distributed, cut, and laminated.

[0035] In another embodiment, the single cell 121 may form a monopole by laminating an insulator between the first current collector 113 and the second current collector 131 instead of a bipolar arrangement. In this stack, a higher cell capacity in the battery is provided by the parallel connection of the first current collectors 113 and the parallel connection of the second current collectors 131.

[0036] FIG. 4 shows a bipolar stack 229 of single cells 221 similar to that of FIG. 3. The segments 211 of the anode 223 surrounded by the current collector 213 and the structural matrix 219 can together form electrodes similar to those seen in the embodiments of FIGS. 1 to 2. A layer of an array (not shown) of segments 211 of the solid electrolyte 225 surrounded by the electrolyte structural matrix 220 may be formed separately from this electrode. Further, an array of materials of the cathode 227 that are separated into segments 211 are formed separately and surrounded by the structural matrix 219. These layers may be laminated to form the single cell 221. These single cells 221 may be further laminated, wound, or otherwise arranged to form the electrochemical device 229. Within the bipolar stack 229 shown in FIG. 4, the current collector 213 of the electrode adjacent to the anode 223 can function as a conductor for the cathode 227 of the adjacent single cell 221. The last current collector 231 is for the stack of single cells 221 to form a bipolar battery ​ It may be placed thereon or connected by other means.

[0037] FIG. 5 shows an exploded view of a method in which a single cell 221 (similar to that shown in FIG. 4) having an array of segments 211 for forming a bipolar battery 229 is stacked and a current collector 231 is placed thereon. FIG. 6 shows a stack of two single cell 221 arrays with the top quarter shown in dashed lines to show one possible arrangement of segments 211 of each single cell 221 directly on top of each other. Alternatively, the single cells 221 may be arranged such that the segments 211 of adjacent single cells 221 are offset from each other. The particular arrangement of segments 211 within the stack 229 can contribute to the structural stability or flexibility of the stack 229. For purposes of visualization, FIGS. 5 - 6 are shown without the structural matrix 219, but the segments 211 may be embedded within the structural matrix material in each single cell 221 layer within the bipolar battery stack 229. As seen in FIG. 7, the single cell 521 may be formed from layers of a polymer composite anode 523, a solid electrolyte 525, and a polymer composite cathode 527. One or both of the current collectors 513, 531 may be applied to the top and / or bottom of the single cell 521. The layers of the polymer composite anode 523, the solid electrolyte 525, and the polymer composite cathode 527 may be arranged within an array of segments 511 within a structural matrix 519 that may comprise a polymer material. The structural matrix 519 may support the segments 511 by applying the current collectors 513, 531 separately. The polymer composite anode 523 may be mixed with a polymer.

[0038] ​​​​​​​​​​​​​It may include the formed anode active material. Similarly, the polymer composite cathode 527 may include a cathode active material mixed with a polymer. The solid electrolyte 525 may include lithium lanthanum titanium zirconium oxide or any other solid electrolyte material.

[0039] As also seen in FIG. 7, the single cell 621 may be formed from a layer of a current collector 613, a ceramic composite anode 6 23, a solid electrolyte 625, a ceramic composite cathode 627, and a current collector 631. The layers of the ceramic composite anode 623, the solid electrolyte 625, and the ceramic composite cathode 627 may be disposed within an array of segments 611. The segments 611 may be supported within the array by either or both of the current collectors 613, 631 such that a structural matrix between the segments 611 is not required and these gaps may be filled with air or other substances. Alternatively, either or both of the structural matrix and the current collectors 613, 6 31 may help support the segments 611 within the array. Similar to the single cell 521, the solid electrolyte 625 may include a solid electrolyte material such as, for example, lithium lanthanum titanate oxide. The ceramic composite anode 623 may include an anode active material mixed with a ceramic to form a composite. Similarly, the ceramic composite cathode 627 may include a cathode active material mixed with a ceramic to form a composite.

[0040] As also shown in FIG. 7, the single cell 721 may be formed from a layer of a current collector 713, a lithium metal anode 73 5, a solid electrolyte 725, a ceramic composite cathode 727, and a current collector 731. It may be formed. As shown, segment 711 may be a current collector that is a metal foil supported by 713, but as described above, the structural matrix can also support segment 711 within the array. Lithium metal can replace any of the electrodes within a single cell. Here, FIG. 7 shows an anode comprising lithium metal 735.

[0041] FIG. 8 shows an exemplary roll-shaped distribution system for a sheet of single cells 521 similar to that shown in FIG. 7. The sheet of single cells 521 may comprise an array of segments 511 supported by a structural matrix 519. The sheet may be wound around a cylindrical dispenser or drum 550 for easy access. The length and width of a particular cell stack may be cut from the sheet after being pulled from drum 550. Additionally, drum 550 may be arranged with other drums supplying sheets of other single cells and / or current collectors such as metal foils. This arrangement can provide a system for the continuous roll manufacturing of batteries. This can be advantageous for rapidly mass-producing laminated, folded, or wound batteries while utilizing electroplating spray of components or other techniques suitable for continuous roll or sheet manufacturing. The roll-shaped single cells 521 arranged around drum 550 can also be advantageous for custom battery sizes where the length and width are cut or folded from an array of larger segments 511 within the sheet. In addition, drum 550 may be arranged with other drums supplying sheets of other single cells and / or current collectors such as metal foils. This arrangement can provide a system for the continuous roll manufacturing of batteries. This can be advantageous for rapidly mass-producing laminated, folded, or rolled batteries while utilizing electroplating spray of components or other techniques suitable for continuous roll or sheet manufacturing. The roll-shaped single cells 521 arranged around drum 550 can also be advantageous for custom battery sizes where the length and width are cut or folded from an array of larger segments 511 within the sheet. wound batteries while utilizing electroplating spray of components or other techniques suitable for continuous roll or sheet manufacturing. The roll-shaped single cells 521 arranged around drum 550 can also be advantageous for custom battery sizes where the length and width are cut or folded from an array of larger segments 511 within the sheet.

[0042] As seen in FIG. 9, bipolar laminated battery 629 may be formed from layers of single cells similar to those shown in FIG. 7. Here, current collector 613 is a segment 6 within its array supported by 713, but as described above, the structural matrix can also support segment Provide support for 11. The current collector 613 can function as a conductor for both the anode of one single cell 621 and the cathode of the adjacent single cell. The current collector 631 can fill the battery stack and provide a good conductor to one terminal of the bipolar stacked battery 629.

[0043] As seen from FIGS. 10 to 11, a single cell 621 similar to the embodiment shown in FIG. 7 may be formed by laminating segments 611 of the electrolyte layer 625 between electrode layers in the array. The single cell array 621 may be disposed between current collectors 613, 631. The electrode layer may include a layer of ceramic composite anode material 623 and a layer of ceramic composite cathode material 627. Alternatively, the electrode layer may be any suitable anode or cathode material as seen in FIG. 12, for example, individual cathode material 627A, polymer composite cathode material 527, individual anode material 623A, polymer composite anode material 523 and lithium metal 735.

[0044] The method for forming the electrode or solid electrolyte of the present invention may include: (a) forming an array comprising spaced segments; and (b) depositing a flexible material between the segments. In one non-limiting example version of this method, an array comprising spaced segments can be formed by molding a slurry on a surface to form an array comprising spaced segments and sintering the segments. Non-limiting examples of slurry formulations for forming the segments include: (i) one or more active battery materials (e.g., lithium lanthanum zirconium oxide as a component of a solid electrolyte, or an anode of a lithium-ion battery) ​​​​​​​​​​(ii) one or more binders; (iii) one or more lithium host materials for the electrode or cathode; one or more dispersants (used to prevent suspended powders, such as active battery materials, from settling); (iv) one or more plasticizers (to enhance the processability of the molded segments); (v) one or more Sintering aids (i.e., other components of the liquid phase) are used to sinter and rearrange the particles into a more favorable packing arrangement. ,materials added to the system that dissolve before creating attraction between particles through capillary action and (vi) one or more solvents. The slurry components are mixed and then The layers are cast to form ceramic layers that are sintered to form ceramic layers suitable for use in solid state batteries.

[0045] The slurry formulation used to form the segments is such that the lithium in the slurry is removed during sintering. It can be tailored for solid-state batteries by addressing the issue of lithium volatility. These changes in material formulation can have adverse effects on battery performance (especially when using electrolytes). In one version of the method of the present invention, lithium loss is described. Excess lithium is added to the system to clarify the sintering process. Lithium boron oxide acts as a sintering aid. However, instead of adding lithium boron oxide directly, , precursors (e.g., boron containing alkoxides including tri-isopropyl borate, Any source of borate ions may be added, and the precursor converts excess lithium to lithium Forms boron oxide.

[0046] When forming the solid electrolyte, anode, or cathode, the slurry components become uniform. The mixture is mixed until the desired consistency is achieved, and then a continuous layer or a segmented layer is cast. The thickness of the cast layer can be controlled. is capable, and a layer having a thickness of 10 to 150 microns is suitable for the solid electrolyte or anode or cathode of a solid-state battery. The subsequent layers can be molded by being stacked on top of each other. For example, the anode may be molded first, then the electrolyte, and finally the cathode. Or, the cathode may be molded first, then the electrolyte, and finally the anode. These molded layers can be processed individually or integrally so that a solid-state battery is formed. For example, the anode may be molded first, then the electrolyte, and finally the cathode. Or, the cathode may be molded first, then the electrolyte, and finally the anode. These molded layers can be processed individually or integrally so that a solid-state battery is formed.

[0047] The slurry formulation used to form segment 11 can be utilized in a low-temperature co-firing ceramic process. Additional constraints that do not exist in related fields must be considered for electrochemical applications such as solid-state batteries. Primarily, many solid battery materials contain most of the element lithium that becomes volatile at the high temperatures required for sintering. Loss of lithium, and thus changes in the battery material formulation, result in negative consequences for the performance of the battery. This is particularly relevant in the case of solid electrolytes such as LLZO. Therefore, any means of achieving (i.e., sintering) a dense layer at a lower temperature serves to alleviate the lithium loss problem. The slurry formulations described herein are specifically adjusted to address lithium loss during sintering.

[0048] Each component of the exemplary slurry formulation used to form segment 11 (i.e., active battery material, sintering aid, dispersant, plasticizer, binder, and solvent) is discussed below.

[0049] Active battery material - The slurry formulation manufactures a solid electrolyte or anode or cathode ​Depending on whether it is used or not, the active battery material can be (i) a component of the solid electrolyte, or (ii) a lithium host material for the anode or cathode of a lithium-ion battery. The active battery material may be in the form of fine particles. Suitable fine particles can have an average particle size ranging from 1 nanometer to 500 micrometers. The fine particles may have any suitable shape, including spherical. In another embodiment, suitable fine particles can have two or more shapes. The active battery material may be in the form of fibers.

[0050] Suitable solid electrolyte active materials are Li-ion fast-conducting materials. The solid electrolyte can be any combination of garnet, perovskite, NaSICON, or LiSICON phase oxide or phosphate materials. The garnet phase can have the formula Li Re u Re v M w A x O y where Re can be any combination of elements with a nominal valence of +3, including La, Nd, Pr, Pm, Sm, Sc, Eu, G d, Tb, Dy, Y, Ho, Er, Tm, Yb, and Lu, M can be any combination of metals with a nominal valence of +3, +4, +5, or +6, including Zr, Ta, Nb, Sb, W, H f, Sn, Ti, V, Bi, Ge, and Si, A can be any combination of dopant atoms with a nominal valence of +1, +2, +3, or +4, including H, Na, K, Rb, Cs, Ba, Sr, Ca, Mg, Fe, Co, Ni, Cu, Zn, Ga, Al, B, and Mn, and u can vary from 3 to 7.5 and v can vary from 0 to 3. Cs, Ba, Sr, Ca, Mg, Fe, Co, Ni, Cu, Zn, Ga, Al, B, and Mn, and u can vary from 3 to 7.5 and v can vary from 0 to 3. The value of u may vary from 3 to 7.5 and the value of v may vary from 0 to 3. may also vary, w may vary from 0 to 2, and y may vary from 11 to 12.5 The garnet may be a lithium lanthanum zirconium oxide having the formula Li 6.25 La3Zr2Al 0.25 O 12 (LLZO) When a solid electrolyte is used, the disadvantages associated with the deterioration of the liquid electrolyte can be eliminated. In order to match or exceed the current ionic conductivity value of the liquid electrolyte, the solid electrolyte needs to be close to the theoretical density and thermally and chemically stable in air and against metallic lithium. The formation of lithium dendrites in the solid electrolyte after the charge cycle should be minimized or eliminated. The high-density solid electrolyte can be manufactured through the optimization of the slurry sintering conditions, namely time, temperature, pressure, atmosphere, and chemical composition. The optimization of the ceramic powder processing of the sintering temperature and sintering mechanism is shown here to increase the density and Li ion conductivity in the garnet lithium lanthanum zirconium oxide electrolyte Li and the disadvantages associated with the deterioration of the liquid electrolyte can be eliminated. In order to match or exceed the current ionic conductivity value of the liquid electrolyte, the solid electrolyte needs to be close to the theoretical density and thermally and chemically stable in air and against metallic lithium. The formation of lithium dendrites in the solid electrolyte after the charge cycle should be minimized or eliminated. The high-density solid electrolyte can be manufactured through the optimization of the slurry sintering conditions, namely time, temperature, pressure, atmosphere, and chemical composition. The optimization of the ceramic powder processing of the sintering temperature and sintering mechanism is shown here to increase the density and Li ion conductivity in the garnet lithium lanthanum zirconium oxide electrolyte Li and the disadvantages associated with the deterioration of the liquid electrolyte can be eliminated. In order to match or exceed the current ionic conductivity value of the liquid electrolyte, the solid electrolyte needs to be close to the theoretical density and thermally and chemically stable in air and against metallic lithium. The formation of lithium dendrites in the solid electrolyte after the charge cycle should be minimized or eliminated. The high-density solid electrolyte can be manufactured through the optimization of the slurry sintering conditions, namely time, temperature, pressure, atmosphere, and chemical composition. The optimization of the ceramic powder processing of the sintering temperature and sintering mechanism is shown here to increase the density and Li ion conductivity in the garnet lithium lanthanum zirconium oxide electrolyte Li and the disadvantages associated with the deterioration of the liquid electrolyte can be eliminated. In order to match or exceed the current ionic conductivity value of the liquid electrolyte, the solid electrolyte needs to be close to the theoretical density and thermally and chemically stable in air and against metallic lithium. The formation of lithium dendrites in the solid electrolyte after the charge cycle should be minimized or eliminated. The high-density solid electrolyte can be manufactured through the optimization of the slurry sintering conditions, namely time, temperature, pressure, atmosphere, and chemical composition. The optimization of the ceramic powder processing of the sintering temperature and sintering mechanism is shown here to increase the density and Li ion conductivity in the garnet lithium lanthanum zirconium oxide electrolyte Li and the disadvantages associated with the deterioration of the liquid electrolyte can be eliminated. In order to match or exceed the current ionic conductivity value of the liquid electrolyte, the solid electrolyte needs to be close to the theoretical density and thermally and chemically stable in air and against metallic lithium. The formation of lithium dendrites in the solid electrolyte after the charge cycle should be minimized or eliminated. The high-density solid electrolyte can be manufactured through the optimization of the slurry sintering conditions, namely time, temperature, pressure, atmosphere, and chemical composition. The optimization of the ceramic powder processing of the sintering temperature and sintering mechanism is shown here to increase the density and Li ion conductivity in the garnet lithium lanthanum zirconium oxide electrolyte Li and the disadvantages associated with the deterioration of the liquid electrolyte can be eliminated. In order to match or exceed the current ionic conductivity value of the liquid electrolyte, the solid electrolyte needs to be close to the theoretical density and thermally and chemically stable in air and against metallic lithium. The formation of lithium dendrites in the solid electrolyte after the charge cycle should be minimized or eliminated. The high-density solid electrolyte can be manufactured through the optimization of the slurry sintering conditions, namely time, temperature, pressure, atmosphere, and chemical composition. The optimization of the ceramic powder processing of the sintering temperature and sintering mechanism is shown here to increase the density and Li ion conductivity in the garnet lithium lanthanum zirconium oxide electrolyte Li and the disadvantages associated with the deterioration of the liquid electrolyte can be eliminated. In order to match or exceed the current ionic conductivity value of the liquid electrolyte, the solid electrolyte needs to be close to the theoretical density and thermally and chemically stable in air and against metallic lithium. The formation of lithium dendrites in the solid electrolyte after the charge cycle should be minimized or eliminated. The high-density solid electrolyte can be manufactured through the optimization of the slurry sintering conditions, namely time, temperature, pressure, atmosphere, and chemical composition. The optimization of the ceramic powder processing of the sintering temperature and sintering mechanism is shown here to increase the density and Li ion conductivity in the garnet lithium lanthanum zirconium oxide electrolyte Li and the disadvantages associated with the deterioration of the liquid electrolyte can be eliminated. In order to match or exceed the current ionic conductivity value of the liquid electrolyte, the solid electrolyte needs to be close to the theoretical density and thermally and chemically stable in air and against metallic lithium. The formation of lithium dendrites in the solid electrolyte after the charge cycle should be minimized or eliminated. The high-density solid electrolyte can be manufactured through the optimization of the slurry sintering conditions, namely time, temperature, pressure, atmosphere, and chemical composition. The optimization of the ceramic powder processing of the sintering temperature and sintering mechanism is shown here to increase the density and Li ion conductivity in the garnet lithium lanthanum zirconium oxide electrolyte Li The appropriate cathode active material is a lithium host material capable of storing and subsequently releasing lithium ions. Exemplary cathode active materials are lithium metal oxides in which the metal is one or more of aluminum, cobalt, iron, manganese, nickel, and vanadium. Non-limiting exemplary lithium metal oxides are LiCoO2 (LCO), LiFeO2, L 6.25 La3Zr2Al 0.25 O 12 (LLZO). The optimization of the ceramic powder processing of the sintering temperature and sintering mechanism is shown here to increase the density and Li ion conductivity in the garnet lithium lanthanum zirconium oxide electrolyte Li and Li ion conductivity as shown here.

[0051] The appropriate cathode active material is a lithium host material capable of storing and subsequently releasing lithium ions. Exemplary cathode active materials are lithium metal oxides in which the metal is one or more of aluminum, cobalt, iron, manganese, nickel, and vanadium. Non-limiting exemplary lithium metal oxides are LiCoO2 (LCO), LiFeO2, L and Li ion conductivity as shown here. The appropriate cathode active material is a lithium host material capable of storing and subsequently releasing lithium ions. Exemplary cathode active materials are lithium metal oxides in which the metal is one or more of aluminum, cobalt, iron, manganese, nickel, and vanadium. Non-limiting exemplary lithium metal oxides are LiCoO2 (LCO), LiFeO2, L and Li ion conductivity as shown here. The appropriate cathode active material is a lithium host material capable of storing and subsequently releasing lithium ions. Exemplary cathode active materials are lithium metal oxides in which the metal is one or more of aluminum, cobalt, iron, manganese, nickel, and vanadium. Non-limiting exemplary lithium metal oxides are LiCoO2 (LCO), LiFeO2, L iMnO2 (LMO), LiMn2O4, LiNiO2 (LNO), LiNi iMnO2 (LMO), LiMn2O4, LiNiO2 (LNO), LiNi x Co y O 2, LiMnx Co y O2, LiMn x Ni y O2, LiMn x Ni y O4, LiNi x Co y Al z O2, LiNi 1 / 3 Mn 1 / 3 Co 1 / 3 O2, etc. Cathode active material Other examples of materials include lithium iron phosphate (LFP) and lithium iron fluorophosphate. Lithium-containing phosphates having the general formula LiMPO4, where M is cobalt, iron, The cathode material is one or more of manganese and nickel. For example, Co, Many different elements such as Mn, Ni, Cr, Al or Li can be substituted or added to the structure The cathode active material may be a mixture of any number of these cathode active materials. may be also possible.

[0052] Suitable anode active materials include graphite, lithium metal, lithium titanium oxide, and hard Lithium ion-capturing materials such as silicon / carbon, tin / cobalt alloy, or silicon / carbon The anode active material is a lithium host material that can absorb and subsequently release lithium. The anode active material may be a mixture of any number of these anode active materials.

[0053] Sintering aids - Any sintering aids that melt to form a liquid can be used to form a sintered material in Segment 1 via liquid phase sintering. This can aid in sintering of the molding slurry formulation used to form 1. In one version of the slurry formulation, the sintering aid provides a source of borate ions. In another version of the slurry formulation, the sintering aid provides a source of phosphate ions. S In another version of the slurry formulation, the sintering aid provides a source of silicate ions. Sla In another version of the slurry formulation, the sintering aid provides a source of aluminate ions. E xemplary sintering aids include lithium borate oxide (LBO), lithium phosphate, lithium silicate and boric acid, borates, borate esters, boron alkoxides, phosphoric acid, phosphates, phosphate esters, silicic acid, silicates, sily nols, silicon alkoxides, aluminum alkoxides, and mixtures thereof, which help in the formation of lithium aluminum oxide phase. For example, excess lithium reacts with the sintering aid to form in situ a lithium borate phase between LLZO particles during heating. In the methods described herein a liquid source of the sintering aid (e.g., triisopropyl borate as a source of borate ions) can be included in the slurry formulation. Since the source of borate ions is liquid it uniformly and evenly coats the active battery material in the slurry, thereby forming an interphase layer during sintering In the case of LLZO, to account for lithium loss occurring during high temperature processing, excess lithium is added to the system. Excess lithium functions as a source for forming the LBO phase from a source of borate ions (e.g., tri-isopropyl borate). LLZO with excess lithium ions can provide the lithium ions necessary to react with the source of borate ions to form the LBO phase. Dispersant - The slurry formulation may optionally include a dispersant. One purpose of the dispersant is to

[0054]

[0054] ​is to stabilize the slurry and prevent the suspended active battery material microparticles from precipitating. The dispersant can also provide a source of lithium ions necessary to react with the sintering aid. In the slurry formulation, the selected dispersant may contain lithium ions and be soluble in the solvent. This means that the dispersant can stabilize the particles in the slurry during molding, and when the temperature is raised after the molded segment has dried, it can also function as a source of lithium ions. The dispersant may be selected from the group consisting of salts of lithium and fatty acids. The fatty acid may be selected from lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, arachidic acid, and behenic acid. In one non-limiting example of the slurry formulation, the dispersant is lithium stearate.

[0055] The plasticizer-slurry formulation may optionally contain a plasticizer. The purpose of the plasticizer is to enhance the processability of the as-molded segments. Preferably, the plasticizer is a naturally derived vegetable oil. The plasticizer may be selected from the group consisting of coconut oil, castor oil, soybean oil, palm kernel oil, almond oil, corn oil, canola oil, rapeseed oil, and mixtures thereof. Petroleum derivatives can also be used as plasticizers, but the choice of vegetable oil is sustainable. The plasticizer is also selected to reduce the evaporation rate of the solvent and increase the mechanical ductility of the dried slurry. In one non-limiting example of the slurry formulation, coconut oil is used as the plasticizer.

[0056] The binder-slurry formulation may optionally contain a binder. Non-limiting examples of the binder are poly(methyl methacrylate), poly(vinyl acetate), polyvinyl alcohol, ​​​​​​​​​​​​​Ethylene oxide, polyvinylpyrrolidone, polyvinyl ether, polyvinyl chloride, poly acrylonitrile, polyvinylpyridine, styrene-butadiene rubber, acrylonitrile butadiene rubber, polyethylene, polypropylene, ethylene-propylene-diene terpoly mer (EPDM), cellulose, carboxymethyl cellulose, starch, hydroxy propyl cellulose, and mixtures thereof. The binder is preferably a non-fluorinated poly mer material. Fluorinated polymers such as polytetrafluoroethylene (Teflon®) and polyvinylidene fluoride are often used as binders in current lithium-ion batteries. However, unlike current lithium-ion batteries, the molded ceramic segment layer of the present invention is sintered. The temperature rise and the presence of fluorine in the polymer result in the inevitable formation of the compound LiF and a decrease in battery performance. In one non-limiting exemplary slurry formulation, acrylic polymers, poly(methyl methacrylate) are selected because they leave little or no residue when heated. The solvent-solvent is useful in the slurry formulation to dissolve the binder and to act as a medium for mixing other additives. Any suitable solvent may be used to mix the active battery material fine particles, dispersant, and binder into a uniform slurry. Suitable solvents include alkanols (e.g., ethanol), nitriles (e.g., acetonitrile), alkyl carbonates, alkylene carbonates (e.g., propylene carbonate), alkyl acetates, sulfoxides, glycol ethers, ethers, N-methyl-2-pyrrolidone, dimethyl sulfoxide, and mixtures thereof. In one non-limiting exemplary slurry formulation, acrylic polymers, poly(methyl methacrylate) are added because they leave little or no residue when heated, so these polymers can be selected.

[0057] The solvent-solvent acts as a medium for dissolving the binder and mixing other additives, and is useful in the slurry formulation. Any suitable solvent can be used to mix the active battery material fine particles, dispersant, and binder into a uniform slurry. Suitable solvents include alkanols (e.g., ethanol), nitriles (e.g., acetonitrile), alkyl carbonates, alkylene carbonates (e.g., propylene carbonate), alkyl acetates, sulfoxides, glycol ethers, ethers, N-methyl-2-pyrrolidone, dimethyl sulfoxide, and mixtures thereof. To mix the active battery material fine particles, dispersant, and binder into a uniform slurry, any suitable solvent can be used. Suitable solvents include alkanols (e.g., ethanol), nitriles (e.g., acetonitrile), alkyl carbonates, alkylene carbonates (e.g., propylene carbonate), alkyl acetates, sulfoxides, glycol ethers, ethers, N-methyl-2-pyrrolidone, dimethyl sulfoxide, and mixtures thereof. alkyl, sulfoxide, glycol ether, ether, N-methyl-2-pyrrolidone, dimethyl ​It may contain N-methylformamide, dimethylacetamide, tetrahydrofuran, or a mixture of these solvents. As one non-limiting exemplary slurry formulation, a mixture of two solvents can be selected. First, a solvent can be selected to dissolve the binder and the dispersant. A second solvent is added, and the proportion of the plasticizer may be changed to adjust the evaporation rate and the resulting molded slurry segment. In one non-limiting exemplary slurry formulation, a mixture of ethanol and acetonitrile may be used as the solvent.

[0058] Other additive - slurry formulations may contain other additives. For example, cathode or anode active battery material fine particles may be mixed with other fine particles such as conductive fine particles. Any conductive material may be used without particular limitation as long as it has appropriate conductivity without causing chemical changes in the manufactured battery. Examples of conductive materials include graphite; carbon blacks such as carbon black, acetylene black, ketjen black, channel black, furnace black, lamp black, and thermal black; conductive fibers such as carbon fibers and metal fibers; metal powders such as aluminum powder and nickel powder; conductive whiskers such as zinc oxide and potassium titanate; conductive metal oxides such as titanium oxide; and polyphenylene derivatives.

[0059] Any suitable method may be used to mix the active battery material fine particles and / or other particles with the sintering aid, plasticizer, binder, and solvent to form a homogeneous slurry. Suitable mixing methods include ultrasonic treatment, mechanical stirring, physical vibration, vortex, ball mill, and It may also include any other suitable means.

[0060] After a uniform slurry is obtained, in order to form a molding layer or a molding layer of a segment, the composition is molded on the substrate surface. The substrate may include any stable conductive metal suitable as a current collector for a battery. After a uniform slurry is obtained, in order to form a molding layer or a molding layer of a segment, the composition is molded on the substrate surface. The substrate may include any stable conductive metal suitable as a current collector for a battery. Suitable metal substrates may include aluminum, copper, silver, iron, gold, nickel, cobalt, titanium, molybdenum, steel, zirconium, tantalum, and stainless steel. Suitable metal substrates may include aluminum, copper, silver, iron, gold, nickel, cobalt, titanium, molybdenum, steel, zirconium, tantalum, and stainless steel. In one embodiment, the metal substrate is aluminum.

[0061] The slurry layer molded on the surface can have a thickness in the range of several micrometers to several centimeters. In one embodiment, the thickness of the molded slurry layer is from 10 micrometers to 150 micrometers, preferably from 10 micrometers to 100 micrometers, more preferably in the range of 10 micrometers to 50 micrometers. The slurry layer molded on the surface can have a thickness in the range of several micrometers to several centimeters. In one embodiment, the thickness of the molded slurry layer is from 10 micrometers to 150 micrometers, preferably from 10 micrometers to 100 micrometers, more preferably in the range of 10 micrometers to 50 micrometers. The slurry layer molded on the surface can have a thickness in the range of several micrometers to several centimeters. In one embodiment, the thickness of the molded slurry layer is from 10 micrometers to 150 micrometers, preferably from 10 micrometers to 100 micrometers, more preferably in the range of 10 micrometers to 50 micrometers. The slurry layer molded on the surface can have a thickness in the range of several micrometers to several centimeters. In one embodiment, the thickness of the molded slurry layer is from 10 micrometers to 150 micrometers, preferably from 10 micrometers to 100 micrometers, more preferably in the range of 10 micrometers to 50 micrometers. The slurry layer molded on the surface can have a thickness in the range of several micrometers to several centimeters. In one embodiment, the thickness of the molded slurry layer is from 10 micrometers to 150 micrometers, preferably from 10 micrometers to 100 micrometers, more preferably in the range of 10 micrometers to 50 micrometers.

[0062] After the slurry is molded on the substrate surface to form a molding layer or a molding layer of a segment, the green layer or the green layer of the segment is dried and sintered at a temperature in the range of 300 °C to 1200 °C, more preferably 600 °C to 1000 °C, to achieve the required electrochemical properties. Optionally, multiple layers can be molded on top of each other. For example, first the anode can be molded on the metal substrate, then the electrolyte can be molded on the anode, and finally the cathode can be molded on the electrolyte. Alternatively, the cathode can be molded on the metal substrate first, followed by the electrolyte, and finally the anode can be molded. After the slurry is molded on the substrate surface to form a molding layer or a molding layer of a segment, the green layer or the green layer of the segment is dried and sintered at a temperature in the range of 300 °C to 1200 °C, more preferably 600 °C to 1000 °C, to achieve the required electrochemical properties. Optionally, multiple layers can be molded on top of each other. For example, first the anode can be molded on the metal substrate, then the electrolyte can be molded on the anode, and finally the cathode can be molded on the electrolyte. Alternatively, the cathode can be molded on the metal substrate first, followed by the electrolyte, and finally the anode can be molded. After the slurry is molded on the substrate surface to form a molding layer or a molding layer of a segment, the green layer or the green layer of the segment is dried and sintered at a temperature in the range of 300 °C to 1200 °C, more preferably 600 °C to 1000 °C, to achieve the required electrochemical properties. Optionally, multiple layers can be molded on top of each other. For example, first the anode can be molded on the metal substrate, then the electrolyte can be molded on the anode, and finally the cathode can be molded on the electrolyte. Alternatively, the cathode can be molded on the metal substrate first, followed by the electrolyte, and finally the anode can be molded. After the slurry is molded on the substrate surface to form a molding layer or a molding layer of a segment, the green layer or the green layer of the segment is dried and sintered at a temperature in the range of 300 °C to 1200 °C, more preferably 600 °C to 1000 °C, to achieve the required electrochemical properties. Optionally, multiple layers can be molded on top of each other. For example, first the anode can be molded on the metal substrate, then the electrolyte can be molded on the anode, and finally the cathode can be molded on the electrolyte. Alternatively, the cathode can be molded on the metal substrate first, followed by the electrolyte, and finally the anode can be molded. After the slurry is molded on the substrate surface to form a molding layer or a molding layer of a segment, the green layer or the green layer of the segment is dried and sintered at a temperature in the range of 300 °C to 1200 °C, more preferably 600 °C to 1000 °C, to achieve the required electrochemical properties. Optionally, multiple layers can be molded on top of each other. For example, first the anode can be molded on the metal substrate, then the electrolyte can be molded on the anode, and finally the cathode can be molded on the electrolyte. Alternatively, the cathode can be molded on the metal substrate first, followed by the electrolyte, and finally the anode can be molded. After the slurry is molded on the substrate surface to form a molding layer or a molding layer of a segment, the green layer or the green layer of the segment is dried and sintered at a temperature in the range of 300 °C to 1200 °C, more preferably 600 °C to 1000 °C, to achieve the required electrochemical properties. Optionally, multiple layers can be molded on top of each other. For example, first the anode can be molded on the metal substrate, then the electrolyte can be molded on the anode, and finally the cathode can be molded on the electrolyte. Alternatively, the cathode can be molded on the metal substrate first, followed by the electrolyte, and finally the anode can be molded. After the slurry is molded on the substrate surface to form a molding layer or a molding layer of a segment, the green layer or the green layer of the segment is dried and sintered at a temperature in the range of 300 °C to 1200 °C, more preferably 600 °C to 1000 °C, to achieve the required electrochemical properties. Optionally, multiple layers can be molded on top of each other. For example, first the anode can be molded on the metal substrate, then the electrolyte can be molded on the anode, and finally the cathode can be molded on the electrolyte. Alternatively, the cathode can be molded on the metal substrate first, followed by the electrolyte, and finally the anode can be molded. is possible. The green molding layer of the multilayer green molding layer or segment can achieve the required electrical chemical properties, and can be sintered at a temperature in the range of 300°C to 1200°C, more preferably 600°C to 1 000°C.

[0063] The following Table 1, Table 2, and Table 3 provide the general formulas of the slurries for molding the molding layer or segment layer according to the present invention.

[0064] [Table 1]

[0065] [Table 2]

[0066] [Table 3]

[0067] Therefore, the present invention provides a method and structure for manufacturing a solid battery such as a lithium-ion solid battery into a segmented cell architecture.

[0068] Although the present invention has been described in considerable detail with reference to specific embodiments, those skilled in the art will understand that the described embodiments are presented for illustrative purposes and are not limiting, and that the present invention can be practiced otherwise. Therefore, the scope of the appended claims should not be limited to the description of the embodiments included herein. ​​

Claims

1. a first layer including a cathode including a first array of first segments embedded within a first structural matrix; a second layer including an anode including a second array of second segments embedded within a second structural matrix; a third layer including a solid-state electrolyte including a third array of third segments embedded within a third structural matrix; and An electrochemical device comprising: the first layer, the second layer, and the third layer are stacked and adhered to one another to form a unit cell, with the third layer being located between the first layer and the second layer; At least one of the cathode first segment and the anode second segment is in contact with a current collector; each of the first structural matrix, the second structural matrix, and the third structural matrix comprises a flexible material; the first segment of the cathode contacts the third segment of the solid-state electrolyte within the unit cell; the second segment of the anode contacting the third segment of the solid-state electrolyte within the unit cell; the first structural matrix is in contact with the third structural matrix within the unit cell; the second structural matrix is in contact with the third structural matrix within the unit cell; Electrochemical devices.

2. 10. The electrochemical device of claim 1, wherein the first structural matrix, the second structural matrix, and the third structural matrix each comprise a polymeric material.

3. 3. The electrochemical device of claim 2, wherein the polymeric material is selected from the group consisting of polyolefins, polystyrene, divinylbenzene, and styrene-divinylbenzene copolymers.

4. the second segment comprises a lithium host material selected from the group consisting of graphite, lithium metal, lithium titanium oxide, hard carbon, tin / cobalt alloy, or silicon / carbon; The electrochemical device of claim 1 .

5. The first segment includes a lithium metal oxide in which the metal is one or more of aluminum, cobalt, iron, manganese, nickel, and vanadium, and a lithium host material selected from the group consisting of lithium-containing phosphates having the general formula LiMPO ４ where M is one or more of cobalt, iron, manganese, and nickel. The electrochemical device of claim 1 .

6. 6. The electrochemical device of claim 5 wherein the lithium host material is selected from the group consisting of lithium manganese nickel oxides.

7. 5. The electrochemical device of claim 4 wherein the lithium host material is selected from the group consisting of lithium titanium oxides.

8. 1. A method of forming an electrochemical device, comprising: (a) forming a first layer including a cathode including a first array of first segments embedded in a first structural matrix; (b) forming a second layer including an anode including a second array of second segments embedded within a second structural matrix; (c) forming a third layer comprising a solid-state electrolyte comprising a third array of third segments embedded within a third structural matrix; (d) stacking and adhering the first layer, the second layer, and the third layer together to form a unit cell in which the third layer is located between the first layer and the second layer; Equipped with the first segment of the cathode contacts the third segment of the solid-state electrolyte within the unit cell; the second segment of the anode contacting the third segment of the solid-state electrolyte within the unit cell; the first structural matrix is in contact with the third structural matrix within the unit cell; the second structural matrix is in contact with the third structural matrix within the unit cell; The method, wherein the first structural matrix, the second structural matrix, and the third structural matrix each comprise a flexible material.

9. the second segment comprises a lithium host material selected from the group consisting of graphite, lithium metal, lithium titanium oxide, hard carbon, tin / cobalt alloy, or silicon / carbon; The method of claim 8.

10. The first segment comprises a lithium metal oxide in which the metals are one or more of aluminum, cobalt, iron, manganese, nickel, and vanadium, and a metal of the general formula LiMPO ４ wherein M is one or more of cobalt, iron, manganese, and nickel; The method of claim 8.

11. 11. The method of claim 10, wherein the lithium host material is selected from the group consisting of lithium manganese nickel oxides.

12. The method of claim 8, wherein the first segment of the cathode, the second segment of the anode, and the third segment of the solid electrolyte are aligned within the unit cell.

13. The electrochemical device of claim 1, wherein the first segment of the cathode, the second segment of the anode, and the third segment of the solid electrolyte are aligned within the unit cell.

14. The electrochemical device according to claim 1, which can have a folded stack structure.

15. The electrochemical device according to claim 1, wherein the first segment of the cathode, the second segment of the anode, and the third segment of the solid electrolyte are disk-shaped.

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