# Patent

## Title
Silicon anode for a rechargeable battery

## Abstract

An electrode and electrode assembly, for example for use as an anode in a lithium-ion rechargeable cell that uses silicon or silicon-based elements of specific dimensions and geometry as its active material, is provided, as well as methods for manufacturing the same. The active silicon or silicon-based material may include fibers, sheets, flakes, tubes or ribbons, for example.

## Background
This invention relates to an electrode for a rechargeable battery cell that uses silicon or a silicon-based material as its active ingredient, in particular although not exclusively for use as the anode in a lithium-ion battery cell.
The recent increase in the use of portable electronic devices such as mobile telephones and notebook computers has created a need for smaller, lighter, longer lasting rechargeable batteries to provide the power to the above mentioned and other battery powered devices. During the 1990s, lithium rechargeable batteries, specifically lithium-ion batteries, became popular and, in terms of units sold, now dominate the portable electronics marketplace. However, as more and more power hungry functions are added to the above mentioned devices (e.g. cameras on mobile phones), improved batteries that store more energy per unit mass and per unit volume are required.
It is well known that silicon can be used as the active anode material of a rechargeable lithium-ion electrochemical battery cell (see, for example, Insertion Electrode Materials for Rechargeable Lithium Batteries, M. Winter, J. O. Besenhard, M. E. Spahr, and P. Novuk in Adv. Mater. 1998, 10, No. 10). The basic composition of a conventional lithium-ion rechargeable battery cell is shown in FIG. 1 including a graphite-based anode electrode, the component to be replaced by the silicon-based anode. The battery cell includes a single cell but may also include more than one cell.
The battery cell generally comprises a copper current collector for the anode 10 and an aluminium current collector for the cathode 12 which are externally connectable to a load or to a recharging source as appropriate. A graphite-based composite anode layer 14 overlays the current collector 10 and a lithium containing metal oxide-based composite cathode layer 16 overlays the current collector 12. A porous plastic spacer or separator 20 is provided between the graphite-based composite anode layer 14 and the lithium containing metal oxide-based composite cathode layer 16 and a liquid electrolyte material is dispersed within porous plastic spacer or separator 20, the composite anode layer 14 and the composite cathode layer 16. In some cases, the porous plastic spacer or separator 20 may be replaced by a polymer electrolyte material and in such cases the polymer electrolyte material is present within both the composite anode layer 14 and the composite cathode layer 16.
When the battery cell is fully charged, lithium has been transported from the lithium containing metal oxide via the electrolyte into the graphite-based layer where it reacts with the graphite to create the compound, LiC6. The graphite, being the electrochemically active material in the composite anode layer, has a maximum capacity of 372 mAh/g. It will be noted that the terms “anode” and “cathode” are used in the sense that the battery is placed across a load.
It is generally believed that silicon, when used as an active anode material in a lithium-ion rechargeable cell, provides a significantly higher capacity than the currently used graphite. Silicon, when converted to the compound Li21Si5 by reaction with lithium in an electrochemical cell, has a maximum capacity of 4,200 mAh/g, considerably higher than the maximum capacity for graphite. Thus, if graphite can be replaced by silicon in a lithium rechargeable battery the desired increase in stored energy per unit mass and per unit volume can be achieved.
Existing approaches of using a silicon or silicon-based active anode material in a lithium-ion electrochemical cell have failed to show sustained capacity over the required number of charge/discharge cycles and are thus not commercially viable.
One approach disclosed in the art uses silicon in the form of a powder (say as particles or spherical elements with a 10 μm diameter), in some instances made into a composite with or without an electronic additive and containing an appropriate binder such as polyvinylidene difluoride coated onto a copper current collector. However, this electrode system fails to show sustained capacity when subjected to repeated charge/discharge cycles. It is believed that this capacity loss is due to partial mechanical isolation of the silicon powder mass arising from the volumetric expansion/contraction associated with lithium insertion/extraction to and from the host silicon. In turn this gives rise to electrical isolation of the silicon elements from both the copper current collector and themselves. In addition, the volumetric expansion/contraction causes the spherical elements to be broken up causing a loss of electrical contact within the spherical element itself.
Another approach known in the art designed to deal with the problem of the large volume changes during successive cycles is to make the size of the silicon elements that make up the silicon powder very small, that is to use spherical particles that have diameters in the 1-10 nm range. This strategy assumes that the nano-sized elements can undergo the large volumetric expansion/contraction associated with lithium insertion/extraction without being broken up or destroyed. However, this approach is problematic in that it requires the handling of very fine, nano-sized powder that may pose a health and safety risk and it does not prevent the electrical isolation of the spherical elements from both the copper current collector and themselves as the silicon powder undergoes the volumetric expansion/contraction associated with lithium insertion/extraction. Importantly, since a lithium-containing surface film is typically created during lithium insertion and the lithium ions that make up this surface film are trapped and can not be removed during the deinstertion process, the large surface area of the nano-sized elements can give introduce large irreversible capacity into the lithium-ion battery cell. In addition, the large number of small silicon particles creates a large number of particle-to-particle contacts for a given mass of silicon and these each have a contact resistance and may thus cause the electrical resistance of the silicon mass to be too high. The above problems have thus prevented silicon particles from becoming a commercially viable replacement for graphite in lithium rechargeable batteries and specifically lithium-ion batteries.
In another approach described by Ohara et al. in Journal of Power Sources 136 (2004) 303-306 silicon is evaporated onto a nickel foil current collector as a thin film and this structure is then used to form the anode of a lithium-ion cell. However, although this approach gives good capacity retention, this is only the case for very thin films (say  ̃50 nm) and thus these electrode structures do not give usable amounts of capacity per unit area. Increasing the film thickness (say >250 nm) causes the good capacity retention to be eliminated. The good capacity retention of these thin films is considered by the present inventors to be due to the ability of the thin film to absorb the volumetric expansion/contraction associated with lithium insertion/extraction from the host silicon without the film being broken up or destroyed. Also, the thin film has a much lower surface area than the equivalent mass of nano-sized particles and thus the amount of irreversible capacity due to the formation of a lithium-containing surface film is reduced. The above problems have thus prevented a thin film of silicon on a metal foil current collector from becoming a commercially viable replacement for graphite in lithium rechargeable batteries and specifically lithium-ion batteries.
In another approach described in U.S. Pat. No. 6,887,511, silicon is evaporated onto a roughened copper substrate to create medium-thickness films of up to 10 μm. During the initial lithium ion insertion process, the silicon film breaks up to form pillars of silicon. These pillars can then reversibly react with lithium ions and good capacity retention is achieved. However, the process does not function well with thicker films and the creation of the medium-thickness film is an expensive process, thus limiting this concept's commercially viability. Also, the pillared structure created by the break up of the film has no inherent porosity and thus the long terms capacity retention is questionable.
In another approach described in US2004/0126659, silicon is evaporated onto nickel fibres which are then used to form the anode of a lithium battery. However this is found to provide an uneven distribution of silicon on the nickel fibres hence significantly affecting operation. In addition, these structures have a high ratio of nickel current collector mass to active silicon mass and thus do not give usable amounts of capacity per unit area or per unit mass.
A review of nano- and bulk-silicon-based insertion anodes for lithium-ion secondary cells has been provided by Kasavajjula et al (J. Power Sources (2006), doi:10.1016/jpowsour.2006.09.84), herewith incorporated by reference herein.
The invention is set out in the independent claims.
Advantageously, some embodiments provide an electrode containing as its active material an interconnected array of high-aspect ratio silicon or silicon-based elements. Cycle life is improved as the structure of the elements, in conjunction with an upper limit of the smallest dimension of the elements, allows for accommodation of the volume expansion associated with insertion/extraction (charging and discharging) of the silicon or silicon-based elements while a lower limit on the smallest dimension controls the ratio of surface area for a given volume of silicon or silicon-based and thus minimises the surface-related irreversible capacity. At least one other dimension is chosen sufficiently large such as to ensure multiple contacts between elements for good electronic conductivity.
The high-aspect ratio elements may be elongate, for example ribbon-like such that a first larger dimension is larger than the smallest dimension and a second larger dimension is larger than the first larger dimension. High-aspect ratio elements may also be sheet-like or flake-like, wherein the first and second larger dimensions are larger than the first dimension but comparable to each other.


The invention is now described, by way of example only and with reference to the accompanying FIG. 1, schematically showing a lithium ion rechargeable cell including an anode electrode in accordance with embodiments of the invention.
It has been realised by the inventors that the above-mentioned problems and drawbacks of the prior art may be addressed by carefully selecting the dimensions and geometry of the silicon or silicon-based elements that are the active ingredient of an electrode for a rechargeable battery. For elongate elements which have two comparable dimensions smaller than a third dimension (referred to as fibres in the remainder), to a first approximation, the irreversible capacity loss is inversely proportional to the diameter of the fibre. Similarly, for an elongate structure for which one of the two smaller dimensions is larger, than the other one, for example twice as large or more as the smaller dimension (referred to below as a ribbon) and for a element which has two comparable largest dimension and a single dimension smaller than that (referred to as a sheet or flake below) the irreversible capacity can be shown to be approximately inversely proportional to the thickness of the ribbon or sheet (that is the smallest dimension), ignoring the sides of the ribbon or the sheet. Thus, for fibres, ribbons, flakes or sheets, a ten-fold decrease in the smallest dimension approximately is expected to result in a ten-fold increase in the irreversible capacity loss. These considerations impose a lower limit on the smallest dimension for these structures if they are to be used as silicon elements in a composite electrode with limited irreversible capacity loss.
As discussed above, one significant problem in the use of silicon or silicon-based materials as the active anode material for a lithium-ion rechargeable battery cell is the large volume changes associated with the charging and discharging of the cell. The associated stresses lead to crack formation in bulk silicon; as described above. Experimental work on pillar-shaped silicon substrates has shown that silicon pillars of close to 1 micrometer diameter (approximately 0.8 micrometer) can be formed which can accommodate the volume changes without cracking [Mino Green, Elizabeth Fielder, Bruno Scrosati, Mario Wachtler and Judith Serra Moreno, “Structured Silicon Anodes for Lithium Battery Applications”, Electrochemical and Solid-State Letters: 6, A75-A79 (2003).] Furthermore, experimental work on silicon plates has shown that even in thick plates (350 microns thickness) stress fractures have a characteristic length of 10 microns.
Based on the foregoing considerations, the smallest dimension of silicon or silicon-based elements in a electrode in accordance with an embodiment of the invention may be in the range of 0.08 to 1 preferably 0.2 μm to 0.3 μm or within the range therebetween. To further ensure a favourable surface area to volume ratio, the second largest dimension should be at least two times as large as the smallest dimension.
Another consideration is the number of electrical interconnections between the elements. For elongate elements such as fibres or ribbons, the larger the largest dimension, the more likely the individual members are to criss-cross each other and form multiple connections there between. Similarly, for sheet or flake-like members, the larger the flakes or sheets, the more likely they will be to mutually overlap. Moreover, the larger the one or two largest dimensions, the more mass of silicon will be arranged for a given surface area, further reducing irreversible capacity. Based on these considerations, the largest, or largest two dimensions are chosen to be larger than ten times the smallest dimension, preferable 100 or 200 times larger or within the range therebetween. The total length or largest dimension may be as large as 500 μm, for example.
It will be appreciated, of course, that any appropriate approach can be adopted in order to fabricate the silicon or silicon-based elements discussed above.
For example, fibres can be manufactured by forming pillars on a suitable silicon or silicon-based substrate and detaching these pillars to create fibres by a suitable method. Pillars of silicon can be manufactured as described in PCT/GB2007/000211 or as described in U.S. application Ser. No. 10/049,736.
Ribbons of silicon can be manufactured via a lithography process such that suitably shaped structure are made on a silicon or silicon-based substrate and then detached from the substrate using a suitable detachment method.
Sheets (or also flakes) may be manufactured using thin film deposition of silicon on poorly adhering substrates leading to detachable sheets of silicon. If the detachable sheet is broken up, flakes result.
Once the silicon or silicon-based elements have been manufactured they can be used as the active material in a composite anode for lithium-ion electrochemical cells. To fabricate a composite anode, the elements can be mixed with polyvinylidene difluoride and made into a slurry with a casting solvent such as n-methyl pyrrolidinone. This slurry can then be applied or coated onto a metal foil or other conducting substrate for example physically with a blade or in any other appropriate manner to yield a coated film of the required thickness and the casting solvent is then evaporated from this film using an appropriate drying system which may employ elevated temperatures in the range of 50 degrees C. to 140 degrees C. to leave the composite film free or substantially from casting solvent. The resulting composite film has a porous structure in which the mass of silicon or silicon-based elements is typically between 70 percent and 95 percent. The composite film will have a percentage pore volume of 10-30 percent, preferably about 20 percent.
Fabrication of the lithium-ion battery cell thereafter can be carried out in any appropriate manner for example following the general structure shown in FIG. 1 but with a silicon or silicon based active anode material rather than a graphite active anode material. For example the silicon elements-based composite anode layer is covered by the porous spacer 18, the electrolyte added to the final structure saturating all the available pore volume. The electrolyte addition is done after placing the electrodes in an appropriate casing and may include vacuum filling of the anode to ensure the pore volume is filled with the liquid electrolyte.
A particular advantage of the approach described herein is that large sheets of silicon-based anode can be fabricated and then rolled or stamped out subsequently as is currently the case in graphite-based anodes for lithium-ion battery cells meaning that the approach described herein can be retrofitted with the existing manufacturing capability.
It will be appreciated, of course, that any appropriate approach can be adopted in order to arrive at the approaches and apparatus described above. For example the element manufacture can comprise any of a suitable method employed in the silicon processing industry. The cathode material can be of any appropriate material, typically a lithium-based metal oxide material. The elements can have any appropriate dimension and can for example be pure silicon or doped silicon or other silicon-based material such as a silicon-germanium mixture or any other appropriate mixture.
The above description is by way of example only and not intended to be limiting on the scope of the claimed subject matter which is intended to cover any such modifications, juxtapositions or alterations of the above-described embodiments as may appear to the skilled person. For example, although the specific description has been presented in terms of silicon as an electrode material, other silicon-based materials may be employed in place of undoped silicon, such as doped silicon, for example SiGe.
The present invention resulted from work undertaken under a joint research agreement between Nexeon Ltd and Imperial Innovations Ltd in the field of batteries, rechargeable cells and associated energy storage devices.

## Claims

1. An electrochemical cell anode comprising
a porous composite film containing a plurality of discrete silicon or silicon-based elements as an active material, each having a first dimension in the range of 0.08 μm to 0.3 μm and a second dimension of at least five times as large as the first dimension, the composite film having a mass of silicon or silicon-based elements between 70 and 95 percent,
wherein the silicon or silicon-based elements form an interconnected array,
wherein the silicon or silicon-based elements are capable of lithium insertion and removal, and
wherein the silicon or silicon-based elements are selected from the group consisting of hollow tubes, ribbons and flakes.

2. An electrochemical cell anode as claimed in claim 1, in which the silicon or silicon-based elements are elongate.

3. An electrochemical cell anode as claimed in claim 1 further comprising a copper current collector.

4. An electrochemical cell containing an electrochemical cell anode as claimed in claim 1.

5. An electrochemical cell as claimed in claim 4 in which a cathode of the electrochemical cell comprises lithium-based compound as its active material.

6. An electrochemical cell as claimed in claim 5 in which the cathode comprises lithium-based metal oxide as its active material.

7. A device powered by an electrochemical cell as claimed in claim 4.

8. An electrochemical cell anode as claimed in claim 1 wherein the elements have a third dimension oriented transverse to each of the first and second dimensions, the third dimension being at least ten times as large as the first dimension.

9. An electrochemical cell anode as claimed in claim 1 wherein the elements have a third dimension oriented transverse to each of the first and second dimensions, the third dimension being at least 100 times as large as the first dimension.

10. An electrochemical cell anode as claimed in claim 1 wherein members of the interconnected array form multiple connections therebetween.

11. An electrochemical cell anode as claimed in claim 1 wherein members of the interconnected array criss-cross one another.

12. An electrochemical cell anode as claimed in claim 1 wherein the first dimension is in the range of 0.2 μm to 0.3 μm.

13. An electrochemical cell anode as claimed in claim 1 wherein the silicon or silicon-based elements are hollow tubes.

14. An electrochemical cell anode as claimed in claim 1 wherein the silicon or silicon-based elements are ribbons.

15. An electrochemical cell anode as claimed in claim 1 wherein the silicon or silicon-based elements are flakes.

16. An electrochemical cell anode as claimed in claim 1 wherein the second dimension is at least 10 times as large as the first dimension.

17. An electrochemical cell anode as claimed in claim 1 wherein the elements further comprise a third dimension that is at least 10 times as large as the first dimension.

18. An electrochemical cell anode as claimed in claim 4 further comprising an electrolyte saturating the available electrode pore volume.

19. A lithium-ion rechargeable battery cell containing an electrochemical cell anode as claimed in claim 1.

20. An electrochemical anode as claimed in claim 1, wherein the composite film has a pore volume between 10% and 30%.

21. An electrochemical cell as claimed in claim 6, wherein the active material of the cathode comprises LiCoO2.

22. An electrochemical anode as claimed in claim 1, wherein the elements have a largest dimension that is no larger than 500 μm.