GB2597983A - An electrode architecture and method of making the electrode architecture - Google Patents

An electrode architecture and method of making the electrode architecture Download PDF

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GB2597983A
GB2597983A GB2012666.0A GB202012666A GB2597983A GB 2597983 A GB2597983 A GB 2597983A GB 202012666 A GB202012666 A GB 202012666A GB 2597983 A GB2597983 A GB 2597983A
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electrode
alkali metal
layer
anode
current collector
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Ian Joseph Gruar Robert
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Dyson Technology Ltd
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Dyson Technology Ltd
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Priority to GB2012666.0A priority Critical patent/GB2597983A/en
Publication of GB202012666D0 publication Critical patent/GB202012666D0/en
Priority to CN202180055419.5A priority patent/CN116018697A/en
Priority to PCT/GB2021/052065 priority patent/WO2022034308A1/en
Publication of GB2597983A publication Critical patent/GB2597983A/en
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    • H01M4/044—Activating, forming or electrochemical attack of the supporting material
    • H01M4/0445—Forming after manufacture of the electrode, e.g. first charge, cycling
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Abstract

An electrode architecture for use in an alkali metal ion cell comprises a solid electrolyte 116 capable of carrying ions of an alkali metal, an electrode 114 adjacent to the solid electrolyte and transitionable between a first state in which the electrode has a first alkali metal ion content and a second state in which the electrode has a second alkali metal ion content higher than the first alkali metal ion content, and an electrode current collector 122 adjacent to the electrode. The electrode comprises a first electrode layer 124 adjacent to the solid electrolyte, comprising an alloy of a first electrode material and the alkali metal and a second electrode layer 128 between the first electrode layer and the electrode current collector, the second electrode layer comprising the alkali metal. In the first state the second electrode layer has a thickness t1, and in the second state, the second electrode layer has a thickness t2 that is greater than t1. A method of making the electrode architecture is also described in which the first electrode layer, second electrode layer and electrode current collector layer are sequentially deposited on the electrolyte layer.

Description

An electrode architecture and method of making the electrode architecture The present invention relates to an electrode architecture for an alkali metal ion cell, a cell incorporating the electrode architecture, and a method of making such an electrode architecture.
Introduction
Solid cell architectures typically comprise anode and cathode layers, separated by a solid electrolyte. The solid electrolyte contains alkali metal ions, for example lithium ions, and upon charge and discharge of the cell, the alkali metal ions migrate between the anode and the cathode, via the solid electrolyte. Current collectors may be used at each of the anode and the cathode, to collect and conduct current to an appropriate point within the cell. The current collector is usually made of a conducting material such as a transition metal, and is often provided as a foil that is placed over and in electrical contact with the electrode.
The anode may consist for example of a layer of the alkali metal. In this case, during charging of the cell, alkali metal ions from the electrolyte add to the volume of the alkali metal anode.
However, alkali metals are highly reactive materials that are difficult to handle. Manufacturing an electrode containing an alkali metal is therefore difficult, and can be both hazardous and costly.
It would be desirable to produce a cell that avoids one or more of the problems associated with known cell architectures.
Summary of invention
Against this background, the invention resides in an electrode architecture for use in an alkali metal ion cell, the electrode architecture comprising: a solid electrolyte capable of carrying ions of an alkali metal; an electrode adjacent to the solid electrolyte and transitionable between a first state in which the electrode has a first alkali metal ion content and a second state in which the electrode has a second alkali metal ion content that is higher than the second alkali metal content; and an electrode current collector adjacent to the electrode. The electrode comprises a first electrode layer adjacent to the solid electrolyte, comprising an alloy of a first electrode material and the alkali metal; and a second electrode layer between the first electrode layer and the electrode current collector, the second electrode layer comprising the alkali metal. In the first state the second electrode layer has a thickness ti, and in the second state, the second electrode layer has a thickness t2 that is greater than Forming a plated layer of the alkali metal at a boundary between the first electrode layer and the electrode current collector layer is a particularly advantageous way of forming the alkali metal layer. The first electrode layer acts as a 'buffer' that controls the rate of formation of the alkali metal layer. Because the first electrode material alloys with the alkali metal, to reach the boundary, alkali metal ions need not only to diffuse through the first anode layer, but also to alloy with the material in the layer, which significantly slows the kinetics of the plating process, whilst being thermodynamically stable. The slower rate of growth of the plated layer provides a uniform alkali metal layer which avoids dendrite growth, which results in a uniform plating, improving the electrode's efficiency and performance.
The transition between the first electrode material and the second electrode material, which results from an alloying mechanism, may be considered to take effect when the crystal structure, particularly the crystal system, of the first electrode material. This may also be expresses as a change in space group or point group. Thus the first and second electrode materials can be distinguished in that they have a different crystal system, space group or point group.
The electrode may be an anode. The electrode architecture described is particularly appropriate for an anode architecture that is to be incorporated into an electrochemical cell. When the electrode is an anode, the first state may correspond to a 'discharged' (or partially-discharged) state, and the second state may correspond to a 'charged' (or partially-charged) state.
The first electrode material is preferably selected from the group consisting of: Sn, Sn-Ge, Bi, Ag, Al, Zn, Ge, or lithium phosphide. Such materials are safe, effective and relatively easy to fabricate, for example using physical vapour deposition (PVD) techniques.
The first electrode layer may be a PVD-deposited layer. PVD is a particularly convenient method for producing a cell architecture, and particularly for producing a layered architecture.
The electrode current collector preferably comprises a deposited layer that is deposited over the electrode. This provides intimate contact between the electrode current collector and the electrode, which maximises efficiency and effectiveness of the electrode current collector layer, minimises losses, and also allows the electrode current collector layer to provide particularly effective protection against loss of the alkali metal through reactions at the electrode surface.
The electrode current collector layer may be resistant to forming an alloy with the alkali metal. In this way, the alkali metal will not be taken into the current collector layer, where it would no longer contribute to the capacity of the cell, but will remain in the first and second anode layers. This also guards against loss of the alkali metal through the electrode current collector layer. Preferably the electrode current collector layer comprises a transition metal, most preferably selected from the group consisting of: Cu, Pt, Ni, Mo, and W. Such materials are effective current collector layers that are easy to produce.
The solid electrode may contain ions of the alkali metal.
The alkali metal may be for example lithium and/or sodium. Lithium and sodium are particularly preferred because they are light but highly reactive and hence provide a high energy density cell. Sodium and lithium also advantageously intercalate. In some circumstances, lithium may be particularly preferred for it particularly high energy density. In other circumstances, sodium may be particularly preferred for because it is a less reactive, and hence hazardous, material that is easier to work with.
The invention also extends to an alkali metal ion cell comprising the electrode architecture above, and a further electrode adjacent to the solid electrolyte. VVhere the electrode is an anode, the further electrode may be a cathode. In this way, the electrode may be incorporated into a cell that can be used to power a device.
The invention also extends to a method of making an electrode architecture for use in an alkali metal ion cell, the method comprising: providing a solid electrolyte layer comprising ions of an alkali metal; depositing a first electrode layer on the solid electrolyte layer, the first electrode layer comprising either i) a first electrode material capable of alloying with the alkali metal or ii) an alloy of the alkali metal and a first electrode material; depositing a second electrode layer on the first electrode layer, the second electrode layer comprising a layer of the alkali metal; and depositing an electrode current collector layer on the second electrode layer, the electrode current collector layer comprising a material that is resistant to alloying with the alkali metal. This method provides a convenient method of making the electrode described above.
The method may comprise depositing the electrode layer(s) and/or the electrode current collector layer using a physical vapour deposition method. PVD is a particularly convenient method for producing a cell architecture, and particularly for producing a layered architecture.
The method may comprise making the electrode architecture in the first state. This advantageously allows the electrode to be made with a comparatively low alkali metal ion content. This may correspond, for example, to a discharged state, which may be a less hazardous state for fabrication of the electrode, and may allow the electrode to be handled and sold without the need for additional discharging steps.
In embodiments where the first electrode layer comprises i) a first electrode material capable of alloying with the alkali metal, the method may further comprise a step of increasing the alkali metal ion content of the electrode, thereby causing the first electrode material to alloy with the alkali metal to form a second electrode material. This advantageously allows the electrode to be fabricated initially with the first electrode layer in an un-alloyed state, which may be easier than fabricating the layer in an alloyed state, and for the first electrode layer to undergo a subsequent alloying process. The step of increasing the alkali metal ion content of the electrode may comprise charging the electrode.
The invention also encompasses an electrode architecture for use in an alkali metal ion cell, the electrode architecture comprising: a solid electrolyte capable of carrying ions of an alkali metal; an electrode adjacent to the solid electrolyte and transifionable between a first state in which the electrode has a first alkali metal ion content and a second state in which the electrode has a second alkali metal ion content that is higher than the second alkali metal content and an electrode current collector adjacent to the electrode. In the first state the electrode comprises a first electrode layer comprising a first material adjacent to the electrolyte that is capable of alloying with the alkali metal, the first material having a first alkali metal ion content Al; and in the second state, the electrode comprises a first electrode layer comprising an alloy of the first material and the alkali metal, the alloy having a second alkali metal ion content A2 that is higher than the first alkali metal ion content A1, and a second electrode layer between the first electrode layer and the electrode current collector, the second electrode layer comprising the alkali metal.
Forming a plated layer of the alkali metal at a boundary between the first electrode layer and the electrode current collector layer is a particularly advantageous way of forming the alkali metal layer. The first electrode layer acts as a 'buffer' that controls the rate of formation of the alkali metal layer. Because the first electrode material alloys with the alkali metal, to reach the boundary, alkali metal ions need not only to diffuse through the first anode layer, but also to alloy with the material in the layer, which significantly slows the kinetics of the plating process, whilst being thermodynamically stable. The slower rate of growth of the plated layer provides a uniform alkali metal layer which avoids dendrite growth, which results in a uniform plating, improving the electrode's efficiency and performance.
The transition between the first electrode material and the second electrode material, which results from an alloying mechanism, may be considered to take effect when the crystal structure, particularly the crystal system, of the first electrode material. This may also be expresses as a change in space group or point group. Thus the first and second electrode materials can be distinguished in that they have a different crystal system, space group or point group.
The electrode may be an anode. The electrode architecture described is particularly appropriate for an anode architecture that is to be incorporated into an electrochemical cell. When the electrode is an anode, the first state may correspond to a 'discharged' (or partially-discharged) state, and the second state may correspond to a 'charged' (or partially-charged) state.
The first electrode material is preferably selected from the group consisting of: Sn, Sn-Ge, Bi, Ag, Al, Zn, Ge, or lithium phosphide. Such materials are safe, effective and relatively easy to fabricate, for example using physical vapour deposition (PVD) techniques.
The first electrode layer may be a PVD-deposited layer. PVD is a particularly convenient method for producing a cell architecture, and particularly for producing a layered architecture.
The electrode current collector preferably comprises a deposited layer that is deposited over the electrode. This provides intimate contact between the electrode current collector and the electrode, which maximises efficiency and effectiveness of the electrode current collector layer, minimises losses, and also allows the electrode current collector layer to provide particularly effective protection against loss of the alkali metal through reactions at the electrode surface.
The electrode current collector layer may be resistant to forming an alloy with the alkali metal. In this way, the alkali metal will not be taken into the current collector layer, where it would no longer contribute to the capacity of the cell, but will remain in the first and second anode layers. This also guards against loss of the alkali metal through the electrode current collector layer. Preferably the electrode current collector layer comprises a transition metal, most preferably selected from the group consisting of Cu, Pt, Ni, Mo, and W. Such materials are effective current collector layers that are easy to produce.
In the first state, the electrode may comprise a second electrode layer between the first electrode layer and the electrode current collector, the second electrode layer comprising the alkali metal. A thickness of the second layer may be greater in the first state than in the second state. In this case, some portion of the second electrode layer (i.e. the alkali metal layer) remains in the first state. This may be because of parasitic losses that result in some amount of the second layer remaining at all times. Alternatively, this may be because the first state is a state in which only a part of the alkali metal content has been removed from the electrode (for example by charge or discharge of the electrode), such that some alkali metal layer remains. In this case, further removal of alkali metal ions could occur at a future point if desired, in which case the alkali metal layer may be removed.
In the first state, the alkali metal content Al of the first electrode material may be less than 1 at%, preferably substantially 0 at%. In other words, in the first state the first electrode layer may be substantially free of the alkali metal ions in the first state. This is advantageous in that it maximises capacity of the electrode, and hence the cell into which it is incorporated.
The alkali metal may be for example lithium and/or sodium. Lithium and sodium are particularly preferred because they are light but highly reactive and hence provide a high energy density cell. Sodium and lithium also advantageously intercalate. In some circumstances, lithium may be particularly preferred for it particularly high energy density. In other circumstances, sodium may be particularly preferred for because it is a less reactive, and hence hazardous, material that is easier to work with.
The invention also extends to an alkali metal ion cell comprising the electrode architecture above, and a further electrode adjacent to the solid electrolyte. Where the electrode is an anode, the further electrode may be a cathode. In this way, the electrode may be incorporated into a cell that can be used to power a device.
The first electrode layer may have a first alkali metal ion inventory // that is determined by the first electrode material and/or the thickness of the first electrode layer. The further electrode may have a second alkali metal ion inventory /2 that is determined by the further electrode material and/or the thickness of the further electrode layer. // and /2 may be selected such that /1 0.5 /2. In this way, the alkali metal ion inventory of the first electrode layer is less than or equal to half of the alkali metal ion inventory of the further electrode. This means that when all the alkali metal ions have been transferred from the further electrode to the electrode, a maximum of half the alkali metal ion inventory is taken up with the first electrode layer, and hence with the alloying mechanism, and a minimum of half of the alkali metal ion inventory is available to form the second electrode layer, i.e. the alkali metal layer. Ensuring that at least half of the alkali metal inventory is available for the alkali metal layer provides a high cell capacity, since greater capacity is achieved by the plating of the alkali metal than by the alloying mechanism.
The invention extends further to a method of making an electrode architecture for use in an alkali metal ion cell, the method comprising: providing a solid electrolyte layer comprising ions of an alkali metal; depositing an electrode on the solid electrolyte layer, the electrode comprising a first electrode layer comprising a first electrode material capable of alloying with the alkali metal; and depositing an electrode current collector layer on the electrode.
This provides a convenient and effective method of making the electrode architecture described above.
The method may comprise depositing the electrode layer(s) and/or the electrode current collector layer using a physical vapour deposition method. PVD is a particularly convenient method for producing a cell architecture, and particularly for producing a layered architecture.
The method may comprise making the electrode architecture in a state that is substantially free of alkali metal. This advantageously allows the electrode to be made without the need to form any alkali metal layer or component, which would otherwise be comparatively costly and hazardous. This state that is substantially free of alkali metal may correspond, for example, to a discharged state, which may be a less hazardous state for fabrication of the electrode, and may allow the electrode to be handled and sold without the need for additional discharging steps.
Features of any one aspect or embodiment described above may apply alone or in appropriate combination to features of other aspects and embodiments also.
Description of the Figures
In order that the present invention may be more readily understood, embodiments of the invention will now be described, by way of example, with reference to the accompanying Figures, in which: Figure 1 is a schematic view of a cell according to a first embodiment in a discharged state; Figure 2 is a schematic view of the cell of Figure 1 in a charged state; Figures 3a to 3c are schematic views of stages in a method of making the cell of Figure 1; Figure 4 is a schematic view of a cell according to a second embodiment in a discharged state; Figure 5 is a schematic view of the cell of Figure 4 in a charged state; Figure 6 is a schematic view of the cell of Figures 4 and 5 in an alternative discharged state at the point of its manufacture; and Figures 7a to 7c are schematic views of stages in a method of making the cell of Figure 6.
Description of specific embodiments of the invention Figures 1 and 2 illustrates a cell 10 for use in alkali metal-ion cell such as a lithium-ion or sodium-ion battery.
The cell comprises two electrodes: a first electrode, which is referred to here as an anode 14, and a further or second electrode, which is referred to here as a cathode 12. The electrodes 12, 14 are separated by a solid electrolyte 16. The solid electrolyte 16 is made of a material through which alkali metal ions can diffuse, such that alkali metal ions can move back and forth between the anode 14 and cathode 12 for charge and discharge of the cell 10. The solid electrolyte may be any suitable solid or semi-solid material, such as an ion-conducting polymer, ceramic, gel, or a material comprising a soild or semi-solid matrix material.
An anode current collector layer 22 overlies the anode 14. In this example, the anode current collector layer 22 is deposited directly onto the anode 14, such that it is in intimate contact with the anode 14.
The anode 14 can be transitioned between a first state in which the anode 14 has a relatively low alkali metal ion content, referred to here as the discharged state and shown in Figure 1, and a second state in which the anode 14 has a relatively high alkali metal ion content, referred to here as the charged state, and shown in Figure 2. In this case, Figure 1 shows a fully-discharged state, and Figure 2 shows a fully-charged state, though it will be appreciated that the anode may also be in partially-charged states. Where the alkali metal is lithium, the first or discharged state may also be referred to as a de-lithiated state, and the second or charged state may also be referred to as a lithiated state.
In the discharged state, the anode 14 comprises a first anode layer 24 that is adjacent to the electrolyte 16. The first anode layer 24 comprises a first material 26 that is capable of forming an alloy with the alkali metal of the cell. The first material 26 has a first alkali metal ion content A/.
In the charged state, the anode 14 comprises the first anode layer 24 that is adjacent to the electrolyte 16 and a second anode layer 28 that is between the first anode layer 24 and the anode current collector layer 22. In this charged state, the first anode layer 24 comprises a second material 29 different to the first material 26, and that in particular is an alloy of the first material 26 and the alkali metal. The second material 29 has a second alkali metal ion content A2 that is higher than the first alkali metal ion content A1.
The second anode layer 28 comprises the alkali metal.
As will be explained in more detail below, the cell 10 can advantageously be manufactured in the discharged state of Figure 1, in which the anode 14 is substantially free of the alkali metal. In this state, the anode 14 comprises only the first anode layer 24 with an alkali ion content Al that is substantially 0. In other words, the first anode layer 24 is substantially free from the alkali metal, but is capable of forming an alloy with the alkali metal.
As the cell is charged, the anode undergoes two anodic charging mechanisms. The mechanisms are described here sequentially, however it should be appreciated that the mechanisms may occur to some extent in parallel.
The first anodic charging mechanism is an alloying mechanism. By this mechanism, alkali metal ions diffuse from the electrolyte 16 into the first anode layer 24, and alloy with the first material 26. Eventually, when sufficient alkali metal ions have diffused into the first anode layer 24, the first anode material 26 will have alloyed with the alkali metal ions to the fullest extent possible, and the first anode layer 24 will be saturated with alkali metal ions. In this state, the first anode layer 24 will now comprise the second anode material 29, which is an alloy of the first anode material 26 and the alkali metal.
The second anode material 29 is distinguished from the first anode material in that it has an alkali ion content A2 that is greater than the first alkali ion content A/ of the first anode material. The second anode material 29 is also distinguished in that, having undergone an alloying process, the second anode material has a different crystal structure, and in particular a different crystal system. By way of non-limiting example, the crystal system of the first anode material 26 may be cubic and the crystal system of the second anode material 29 may be trigonal. Said another way, the space group or point group of the alloying material changes between the first material 26 and the second material 29. The transition between the first and second anode materials 26, 29 may therefore be said to occur when the crystal system, space group or point group of the material changes. This alloying mechanism is particularly advantageous because it is thermodynamically stable.
The second anodic charging mechanism is an alkali metal plating mechanism. As charging continues, more alkali metal ions diffuse into the first anode layer 24. However, once the first anode layer 24 is saturated with alkali metal ions, these ions can no longer accommodated in the first anode layer 24. Instead, the alkali metal ions will diffuse to the boundary 30 between the first anode layer 24 and the current collector layer 22. The material of the current collector layer 22 is selected such that it is resistant to forming an alloy with the alkali metal, and resistant to diffusion of the alkali metal ions. The alkali metal will therefore be plated' at the boundary 30 between the first anode layer 24 and the current collector layer 22. This plating forms the second anode layer 28 which comprises the alkali metal.
Charging is complete when the substantially the entire alkali metal ion inventory of the cathode has been transferred to the anode: either as part of the alloy of the first anode layer 24, or as part of the plated alkali metal of the second anode layer 28. In this state, the cell is ready for discharge.
During discharge, the reverse anodic mechanisms will occur: specifically i) a de-alloying mechanism by which alkali metal ions will diffuse out of the first anode layer 24 to the solid electrolyte 16, eventually de-alloying the second material 29 back to the first material 26, and ii) a de-plating mechanism, by which the alkali metal of the second anode layer 28 diffuses back through the first anode layer 24 to the solid electrolyte 16. This reduces a thickness of the second anode layer 28 from a thickness t2 in the charged state to a thickness ti in the discharged state. In this example, the thickness t1 is substantially 0.
Forming a plated layer of the alkali metal at the boundary 30 between the first anode layer 24 and the anode current collector layer 22 is a particularly advantageous way of forming the alkali metal layer 28. The first anode layer 24 acts as a 'buffer' that controls the rate of formation of the alkali metal layer 28. In particular, to reach the boundary 30, alkali metal ions need not only to diffuse through the first anode layer, but also to alloy with the material in the layer, which significantly slows the kinetics of the plating process. The slower rate of growth of the plated layer provides a uniform alkali metal layer which avoids dendrite growth. This is particularly advantageous because dendrites would otherwise 'block' the surface area of the electrolyte, preventing diffusion and reducing efficiency of the plating process and hence efficiency of the electrode. Dendrites also have a higher surface energy than the surrounding surface, such that when dendrites are present, plating preferentially occurs on the dendrites, resulting in non-uniform layers. The absence of dendrites therefore improves the cell's efficiency and performance.
Considering the anode layers in more detail: The first material 26 of the first anode layer 24 is selected so as to be capable of alloying with the alkali metal. The nature of the first material can therefore depend on the alkali metal of the cell. Suitable materials include for example: silicon (Si), tin (Sn), germanium (Ge), lead (Pb), Arsenic (As), Indium (In), gold (Au), silver (Ag), cadmium (Cd), aluminium (Al), zinc (Zn), bismuth (Si), bismuth-containing compounds, lithium phosphates (LixP), fin, germanium, or silicon based alloys (Sn-M, Ge-M, Si-M, where M is a G2-G7 atom) transition-metal based compounds (e.g. Tm-P, TmSby, Tm-Zn, where Tm is a transition metal), and conductive transition metal oxides (e.g. Fe.0y, NiO, Co°, Mn02, Cr2O3, Cu0).
Particularly preferred materials, which may be particularly suitable for a lithium-ion cell, include for example: tin (Sn), Sn-M (where M is a G2-G7 atom), TmSby (where Tm is a transition metal), bismuth (Bi), silver (Ag), aluminium (Al), and zinc (Zn). In these cases, the second material 29 of the first anode layer 24 would be correspondingly (where AM designates the alkali metal), an Sn -AM alloy, Sn-M-AM alloy (where M is a G2-G7 atom), TmSby -AM alloy (where Tm is a transition metal), Bi-AM alloy, Ag-AM alloy, Al-AM alloy, or a Zn-AM alloy.
The first anode layer will have capacity for a first alkali metal ion inventory b that is determined by the first anode material and/or the thickness of the first anode layer. When the first anode layer is completely alloyed, such that it is saturated with alkali metal ions, and has formed the second anode material, this inventory 11 will completely accommodated in the first anode layer.
The first anode material is preferably selected such that it forms an alloy with the alkali metal that has a relatively low alkali metal inventory h, i.e. when the alloy is saturated with the alkali metal, it has a relatively low alkali metal content A2. Selecting a relatively low alkali metal inventory means that relatively little alkali metal is contained within the alloy of the second anode material, and more is available for plating of the alkali metal at the boundary 30 between the first anode layer 24 and the anode current collector layer 22. By ensuring that a high amount of alkali metal is available for the plating mechanism, the capacity of the cell can be maximised.
When the anode 14 is incorporated into a cell 10 with a cathode 12, as in Figures 1 and 2, the cathode will have a second alkali metal ion inventory /2 that is determined by the cathode material and/or the thickness of the cathode layer. The parameters of the first anode layer (specifically, the first anode material and the thickness of the first anode layer) are preferably specifically selected so that 11 0.5 /2. This means that first anode layer will be saturated with alkali metal ions when the inventory of the cathode is discharged by 50% or less. The remaining inventory of the cathode 12 (/2 -/y) will then be accommodated in the second anode layer 26 as pure alkali metal.
Although a relatively low alkali metal inventory b is desirable for the first anode layer 24, it should be noted that because the second anode material 29 is an alloyed mixture of the alkali metal and the first alloy material 26, (rather than, for example, a non-alloy material through which some small number of alkali metal ions might diffuse) the alkali metal content of the alloy will still be sufficiently high as to constitute an alloy. For example, the alkali metal ion content of the second anode material may be at last 10 at%, preferably at least 20 at%.
The first material is preferably deposited directly onto the solid electrolyte by means of physical vapour deposition.
The thickness of the layer of the first material is tailored according to the requirements of the cell, and may be influenced by factors including the inventory of the cathode as explained above, and also by the material of the electrolyte, and the choice of the first anode material.
A typical thickness, depending on the parameters and materials of the electrode and the cell into which it is incorporated, would be for example between approximately 5 nm and approximately 100 microns. Generally it is desirable for the layer of first material to be as thin as possible. A particularly preferred thickness would be a thickness that can provide for approximately 20% over-capacity of the lithium inventory of the cathode.
The material of the anode current collector layer is selected such that it is resistant to forming an alloy with the alkali metal, and resistant to diffusion of the alkali metal through the layer. This ensures that the alkali metal will be plated at the boundary between the first anode layer and the current collector layer, rather than alloying with or diffusing through the current collector layer, which would otherwise allow the alkali metal ions to escape, depleting the capacity of the cell. The material of the anode current collector layer is also selected to be electrically conductive.
Suitable materials for the anode current collector include transition metals that are resistant to alloying with the alkali metal ions of the cell: for example, copper (Cu), platinum (Pt), nickel (Ni), molybdenum (Mo), and tungsten (1A0.
The solid electrolyte may be any suitable material that is capable of carrying alkali metal ions.
For example, where the alkali metal of the cell is lithium, the solid electrolyte may be LiPON.
The anode may be made using a physical vapour deposition (PVD) method that will now be described with reference to Figures 3a to 3c.
Preferably, the anode 14 is made in the uncharged state shown in Figure 1. Making the anode 14 in the uncharged state is particularly advantageous because in this state the anode 14 is substantially free from the highly reactive alkali metal, making it easy to manufacture and handle. There is no need to deposit any layer of the pure alkali metal, which facilitates fabrication.
As shown in Figure 3a, the solid electrolyte 16 is first provided. In the example of Figure 3a, the solid electrolyte 16 is the top layer of an architecture that also includes the cathode layer and cathode current collector. The solid electrolyte 16 defines a substrate onto which the anode 14 will subsequently be deposited.
Next, as shown in Figure 3n, a first anode layer 24, comprising the first anode material 26, is deposited onto the solid electrolyte 16. The material is deposited using a PVD method, such as for example sputtering. Accordingly, the solid electrode 16 is arranged in a vacuum chamber of a sputtering apparatus prior to deposition.
With first anode layer 24 in place, the anode current collector layer 22 is deposited over the first anode layer 24. The first anode current collector layer 22 is also deposited using a PVD method, such as for example sputtering.
In this example, there is no need to deposit any further anode layers before the anode current collector layer 22. In particular, there is no need to deposit a second anode layer comprising the alkali metal, since this layer can be formed during a subsequent charging process.
With the anode current collector layer 22 in place, the anode 14 is complete in its uncharged state, and can be removed from the deposition apparatus. The anode is then ready for use in a cell, where it may be charged and discharged according to the mechanisms described above.
The anode architecture describes provides a cell of high energy density, that can be manufactured exclusively in the discharged state, thereby allowing for safe and easy manufacture. Because the primary anodic charging mechanism is plating of the alkali metal, the cell has a high capacity. Plating the alkali metal beneath a deposited current collector layer means that alkali metal is not lost from the cell, and capacity is maintained. The presence of the alloying material means that the lithium plating occurs at a low rate, encouraging uniform plating and reducing dendrite growth which would otherwise hinder cell capacity.
Another embodiment of the invention will now be described with reference to Figures 4, 5, 6 and 7a to 7d.
Figures 4 and 5 illustrate an anode 114 that is similar to the anode 14 of Figures 1 and 2, except that i) the second anode layer 128 comprising the alkali metal is present in both the charged and discharged states and ii) the first alloy layer 124 comprises the second material 129 in both the charged and discharged states. In this embodiment, a total volume, and hence total thickness, of the second anode layer 128 is greater in the charged state than in the discharged state.
Referring to Figure 4, which illustrates the discharged state, in the discharged state, the anode 114 comprises a first anode layer 124 that is adjacent to the electrolyte 116 and a second anode layer 128 that is between the first anode layer 124 and the anode current collector layer 122. In this embodiment, the first anode layer 124 comprises the second material 129 that is an alloy including the alkali metal of the cell, having an alkali metal ion content Az. The second anode layer 128 comprises the alkali metal, and had a first thickness In the charged state shown in Figure 5, the anode 114 comprises the first anode layer 124 that is adjacent to the electrolyte 116 and the second anode layer 128 that is between the first anode layer 124 and the anode current collector layer 122. In this charged state, the first anode layer 124 also comprises the second material 129. The second anode layer 128 comprises the alkali metal, and has a second thickness t2 that is greater than the first thickness t, As with the anode of Figures 1 and 2, the anode of Figures 4 and 5 can be manufactured in a discharged state. However, in this case the anode is not made in precisely the discharged state of Figure 4 but is made instead in an alternative discharged state shown in Figure 6. This state is substantially the same as the discharged state of Figure 4, except that the first anode layer 124 comprises the first material 126 of the same type as the embodiment of Figure 1, i.e. a material capable of alloying with alkali metal ions, and having an alkali ion content Al that is less than A2, which in this case is substantially 0.
The first time the cell is charged after manufacture, the anode is charged from the alternative discharged state of Figure 6 to the charged state of Figure 5. The anode undergoes the same two anodic charging mechanisms as the anode of Figures 1 and 2: an alloying mechanism and a plating mechanism. The alloying mechanism is substantially the same as that described above. The alkali metal plating mechanism is similar to that described above, but in this case, some alkali metal is already present in the second anode layer 128 between the first anode layer 124 and the current collector layer 122. In this case, as the alkali metal is 'plated' during charging, the thickness of the alkali metal of the second anode layer 128 increases from the uncharged thickness t1 to the charged thickness tz. In this way, by virtue of the plating mechanism, the total volume of the alkali metal and hence the second anode layer 128 increases during charging.
During the first (and all subsequent) discharge cycle, the anode is discharged from the charged state of Figure 5 to the discharged state of Figure 4. A de-plating mechanism will occur, by which at least some of the alkali metal of the second anode layer 128 diffuses back through the first anode layer 124 to the solid electrolyte 116 via the alloying mechanism, so that the thickness of the second anode layer decreases from t2 to ti. In this embodiment the discharge cycle does not involve de-alloying of the first anode layer 124.
During subsequent charging cycles, the anode is charged from the discharged state of Figure 4 to the charged state of Figure 5. In this charge cycle, the anode does not undergo the alloying mechanism, but undergoes only the alkali metal plating mechanism described above, in which the thickness increases from the thickness of the alkali metal of the second anode layer 128 increases from the uncharged thickness ti to the charged thickness t2.
Subsequent charge and discharge cycles continue as described above, with the anode being charged and discharged between the discharged state of Figure 4 and the charged state of Figure 5. The anode does not return to the alternative discharge state of Figure 6, since the first anode layer 124 does not undergo de-alloying.
Figures 7a to 7d illustrate stages in making the anode of Figure 6. The process is generally similar to the process described in conjunction with Figures 3a to 3c, except that in an additional step, a layer of alkali metal is deposited.
As shown in Figure 7a, the solid electrolyte 116 is first provided. In the example of Figure 7a, the solid electrolyte 116 is the top layer of an architecture that also includes the cathode layer and cathode current collector. The solid electrolyte 116 defines a substrate onto which the anode 114 will subsequently be deposited.
Next, as shown in Figure 7b, a first anode layer 124, comprising the first anode material 126, is deposited onto the solid electrolyte 116. The material is deposited using a PVD method, such as for example sputtering. Accordingly, the solid electrode 116 is arranged in a vacuum chamber of a sputtering apparatus prior to deposition.
With first anode layer 124 in place, as shown in Figure 7c, a second anode layer 128 comprising the alkali metal is deposited on top of the first anode layer 124, also using a PVD method such as sputtering.
Next, the anode current collector layer 122 is deposited over the second anode layer 128, as shown in Figure 7d. The anode current collector layer 122 is also deposited using a PVD method, such as for example sputtering.
With the anode current collector layer 122 in place, the anode is complete in its alternative discharged state, and can be removed from the deposition apparatus. The anode is then ready for use in a cell, where it may be charged and discharged according to the mechanisms described above.
It will be appreciated that sub-layers may be present in any of the anode layers described above. For example, the first anode layer may comprise sub-layers of different materials, some or all of which sub-layers may be capable of alloying with the alkali metal.
In the examples above, the anode architectures have been described in fully charged and fully discharged states. However, it will be appreciated that the anode architectures may also exist in partially charged states. It will also be appreciated that due to parasitic reactions and kinetic limitations within a cell, in practice a cell may not achieve perfectly charged and discharged states. For example, in the first embodiment, de-alloying may not be complete, so that in a discharged state, a small amount of alkali metal ions may remain present in the first anode layer, for example such that Al may not be 0, but may be a small value such as at%. De-plating may also be incomplete, so that a small amount of the second anode layer is present in the discharged state.
Other variations will be apparent to the skilled person without departing form the scope of the appended claims.

Claims (1)

  1. Claims 1. An electrode architecture for use in an alkali metal ion cell, the electrode architecture comprising: a solid electrolyte capable of carrying ions of an alkali metal; an electrode adjacent to the solid electrolyte and transitionable between a first state in which the electrode has a first alkali metal ion content and a second state in which the electrode has a second alkali metal ion content that is higher than the second alkali metal content; and an electrode current collector adjacent to the electrode; characterised in that the electrode comprises: a first electrode layer adjacent to the solid electrolyte, comprising an alloy of a first electrode material and the alkali metal; a second electrode layer between the first electrode layer and the electrode current collector, the second electrode layer comprising the alkali metal; wherein in the first state the second electrode layer has a thickness t1, and in the second state, the second electrode layer has a thickness t2 that is greater than 2. The electrode architecture of Claim 1, wherein the electrode is an anode.3. The electrode architecture of Claim 3, wherein the first electrode material is selected from the group consisting of: Sn, Sn-Ge, Bi, Ag, Al, Zn, Ge or lithium phosphide.4. The electrode architecture of any preceding claim, wherein the first electrode layer is a PVD-deposited layer.5. The electrode architecture of any preceding claim, wherein the electrode current collector comprises a deposited layer that is deposited over the electrode, optionally a PVDdeposited layer.6. The electrode architecture of any preceding claim wherein the electrode current collector layer is resistant to forming an alloy with the alkali metal, and preferably comprises a transition metal, most preferably selected from the group consisting of: Cu, Pt, Ni, Mo, and W. 7. The electrode architecture of any preceding claim, wherein the solid electrode contains ions of the alkali metal.8. The electrode architecture of any preceding claim, wherein the alkali metal is lithium or sodium.9. An alkali metal ion cell comprising the electrode architecture of any preceding claim and a further electrode adjacent to the solid electrode.10. The alkali metal ion cell of Claim 9, wherein the further electrode is a cathode.11. A method of making an electrode architecture for use in an alkali metal ion cell, the method comprising: providing a solid electrolyte layer comprising ions of an alkali metal; depositing a first electrode layer on the solid electrolyte layer, the first electrode layer comprising either i) a first electrode material capable of alloying with the alkali metal or ii) an alloy of the alkali metal and a first electrode material; depositing a second electrode layer on the first electrode layer, the second electrode layer comprising a layer of the alkali metal; and depositing an electrode current collector layer on the second electrode layer, the electrode current collector layer comprising a material that is resistant to alloying with the alkali metal.12. The method of Claim 11, comprising depositing the electrode layer(s) and/or the electrode current collector layer using a physical vapour deposition method.13. The method of Claim 11 or Claim 12, comprising depositing the layers to provide an electrode that is in the first state.14. The method of Claim 13, wherein the first electrode layer comprises i) a first electrode material capable of alloying with the alkali metal, and wherein the method further comprises increasing the alkali metal ion content of the electrode, thereby causing the first electrode material to alloy with the alkali metal to form a second electrode material.
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