GB2529409A

GB2529409A - Electroactive materials for metal-ion batteries

Info

Publication number: GB2529409A
Application number: GB1414633.6A
Authority: GB
Inventors: William Macklin; Charles Mason; Christopher Michael Friend
Original assignee: Nexeon Ltd
Current assignee: Nexeon Ltd
Priority date: 2014-08-18
Filing date: 2014-08-18
Publication date: 2016-02-24
Also published as: WO2016027081A1; GB201414633D0

Abstract

A particulate material consists of a plurality of porous particles comprising a mixture of silicon and germanium, where the mole fraction of germanium is from 0.01 to 50%, where the porous particles have a D50 particle diameter in the range of from 500 nm to 25 Âµm, and where the porous particles have an intra-particle porosity in the range of from 30 to 90%. A process for the preparation of a particulate material comprises providing a plurality of alloy particles comprising from 11 to 45wt% of a mixture of silicon and germanium, where the mole fraction of germanium is from 0.01 to 50%, and a matrix metal component, and leaching the alloy particles to remove at least a portion of the matrix metal component and to at least partially expose the silicon and germanium containing structures, where the porous particles comprise no more than 40% by weight of the matrix metal component. The particulate composition may be used in an electrode composition in a rechargeable lithium-ion battery.

Description

Electroactive Materials for Metal-Ion Batteries This invention relates in general to electroactive materials for use in electrodes for metal-ion batteries and more specifically to particulate electroactive materials suitable for use as anode active materials in metal-ion batteries. Also provided are methods for the preparation of the particulate electroactive materials of the invention.

Rechargeable metal-ion batteries are widely used in portable electronic devices such as mobile telephones and laptops and are finding increasing application in electric or hybrid vehicles.

Rechargeable metal-ion batteries generally comprise an anode layer, a cathode layer, an electrolyte to transport metal ions between the anode and cathode layers, and a porous plastic spacer disposed between the anode and the cathode. The cathode typically comprises a metal current collector provided with a layer of metal ion containing metal oxide based composite, and the anode typically comprises a metal current collector provided with a layer of an electroactive material, defined herein as a material which is capable of inserting and releasing metal ions during the charging and discharging of a battery. For the avoidance of doubt, the terms "cathode" and "anode" are used herein in the sense that the battery is placed across a load, such that the cathode is the positive electrode and the anode is the negative electrode. When a metal-ion battery is charged, metal ions are transported from the metal-ion-containing cathode layer via the electrolyte to the anode and are inserted into the anode material. The term "battery" is used herein to refer both to a device containing a single anode and a single cathode and to devices containing a plurality of anodes and/or a plurality of cathodes.

There is interest in improving the gravimetric and/or volumetric capacities of rechargeable metal-ion batteries. The use of lithium-ion batteries has already provided a substantial improvement when compared to other battery technologies, but there remains scope for further development.

To date, commercial metal-ion batteries have largely been limited to the use of graphite as an anode active material. When a graphite anode is charged, lithium intercalates between the graphite layers to form a material with the empirical formula LiC5 (wherein x is greater than 0 and less than or equal to 1). Consequently, graphite has a maximum theoretical capacity of 372 mAh/g in a lithium-ion battery, with a practical capacity that is somewhat lower (ca. 340 to 360 mAh/g).

Other materials, such as silicon, tin and germanium, are capable of intercalating lithium with a significantly higher capacity than graphite but have yet to find widespread commercial use due to difficulties in maintaining sufficient capacity over numerous charge/discharge cycles.

Silicon in particular is attracting increasing attention as a potential alternative to graphite for the manufacture of rechargeable metal-ion batteries having high gravimetric and volumetric capacities because of its very high capacity for lithium (see, for example, Insertion Electrode Materials for Rechargeable Lithium Batteries, Winter, M. et aL in Adv. Mater. 1998, 10, No. 10). Silicon has a theoretical capacity in a lithium-ion battery of about 4,200 mAh/g (based on Li4 4Si). However its use as an anode material is complicated by large volumetric changes on charging and discharging.

Intercalation of lithium into bulk silicon leads to an increase in the volume of the anode material of up to 400% when silicon is lithiated to its maximum capacity, and repeated charge-discharge cycles cause significant mechanical strain in the silicon material, resulting in fracturing and delamination of the silicon anode material. Loss of electrical contact between the anode material and the current collector results in a significant loss of capacity in subsequent charge-discharge cycles.

The use of silicon as an electroactive material in metal-ion batteries is further complicated by the formation of a solid electrolyte interphase (SEI) layer at the anode surface during the first charge-discharge cycle of the battery. SEI layers are formed due to reaction of the electrolyte at the surface of the silicon during the first charging cycle, and it is believed that this reactivity can be attributed to the accumulation of metallic lithium at the silicon surface due to the low diffusion rate of lithium into the bulk of the silicon. The formation of an SEI layer can consume significant amounts of metal ions from the electrolyte during the first charge-discharge cycle (referred to herein as "first cycle loss", or "FCL'), thus depleting the capacity of the battery in subsequent charge-discharge cycles. In addition, any fracturing or delamination of the silicon during subsequent charge-discharge cycles exposes fresh silicon surfaces which then form SEI layers, further depleting the capacity of the battery.

The use of germanium as an anode active material is known in the art. Germanium has the advantages that it has higher electronic conductivity (by several orders of magnitude) and a higher lithium diffusion rate (by a factor of ca. 102), thus making it less susceptible to the formation of SEI layers. However, the use of germanium is also associated with significant disadvantages. Not only is germanium significantly more expensive than silicon, its theoretical maximum capacity of ca. 1625 mAh/g in a lithium-ion baftery is less than half that of silicon, due to the higher atomic mass of germanium. As with silicon, the insertion and release of metal ions by germanium is associated with large volumetric changes (up to 370% when germanium is lithiated to its maximum capacity). The associated mechanical stress on the germanium material may result in fracturing and delamination of the anode material and a loss of capacity.

A number of approaches have been proposed to overcome the problems associated with the volume change observed when charging silicon-containing anodes. These relate in general to silicon structures which are better able to tolerate volumetric changes than bulk silicon. For example, Ohara et 8/. (Journal of Power Sources 136 (2004) 303-306) have described the evaporation of silicon onto a nickel foil current collector as a thin film and the use of this structure as the anode of a lithium-ion baftery. Although this approach gives good capacity retention, the thin film structures do not give useful amounts of capacity per unit area, and any improvement is eliminated when the film thickness is increased. WO 2007/083155 discloses that improved capacity retention may be obtained through the use of silicon particles having high aspect ratio, i.e. the ratio of the largest dimension to the smallest dimension of the particle. The high aspect ratio, which may be as high as 100:1 or more, is thought to help to accommodate the large volume changes during charging and discharging without compromising the physical integrity of the particles.

Other approaches relate to the use of silicon structures that include void space to provide a buffer zone for the expansion that occurs when lithium is intercalated into silicon. For example, US 6,334,939 and US 6514,395 disclose silicon based nano-structures for use as anode materials in lithium ion secondary batteries. Such nano-structures include cage-like spherical particles and rods or wires having diameters in the range 1 to 50 nm and lengths in the range 500 nm to 10 pm.

WO 2012/175998 discloses particles comprising a plurality of silicon-containing pillars extending from a particle core which may be formed, for example, by chemical etching or by a sputtering process.

Porous silicon particles have also been investigated for use in lithium-ion battehes. Porous silicon particles are attractive candidates for use in metal-ion batteries as the cost of preparing these particles is generally less than the cost of manufacturing alternative silicon structures such as silicon fibres, ribbons or pillared particles. For example, US 2009/0186267 discloses an anode material for a lithium-ion battery, the anode material comprising porous silicon paiticles dispersed in a conductive matrix. The porous silicon particles have a diameter in the range 1 to 10 pm, pore diameters in the range 1 to 100 nm, a BET surface area in the range 140 to 250 m2/g and crystallite sizes in the range 1 to 20 nm. The porous silicon particles are mixed with a conductive material such as carbon black and a binder such as PVDF to form an electrode material which can be applied to a current collector to provide an electrode.

US 7,479,351 discloses porous silicon-containing particles containing microcrystalline silicon and having a particle diameter in the range of 0.2 to 50 pm. The particles are obtained by alloying silicon with an element X selected from the group consisting of Al, B, P, Ge, Sn, Pb, Ni, Co, Mn, Mo, Cr, V, Cu, Fe, W, Ti, Zn, alkali metals, alkaline earth metals and combinations thereof, followed by removal of the elementX by a chemical treatment.

Despite the effoits to date, known porous silicon materials do not meet the peiformance criteria required of electroactive materials for use in commercially viable lithium ion batteries. Foremost among these criteria is the requirement for an electroactive material that provides sufficient capacity retention over the lifetime of the battery. However, it is also desirable that the lifetime performance of the electroactive material be accompanied by handling properties which enable the electroactive material to be processed into an electrode layer. For instance, the electroactive material must retain its structural integrity during electrode manufacture, in particular during steps such as heat treatment and calendering of electrode active layers as are conventional in the art. In addition, the electroactive material should be readily dispersible into slurries in order that it may be distributed evenly in an electrode layer. In known porous silicon materials, it has been found that as capacity retention is improved, the processability of the porous silicon material deteriorates.

This is usually because the porous silicon is excessively fragile and disintegrates and/or because it forms agglomerates in slurries.

The performance requirements of electroactive materials are particularly exacting when the electroactive materials are used in "hybrid" electrodes, in which electroactive materials having high capacity, such as silicon, are used to supplement the capacity of graphite anodes. Hybrid electrodes are of particular interest to manufacturers focusing on incremental improvements to existing metal-ion battery technology rather than a wholesale transition from graphite anodes to silicon anodes.

For a hybrid electrode to be commercially viable, any additional electroactive material must be provided in a form which is compatible with the graphite particulate forms conventionally used in metal-ion batteries. For example, it must be possible to disperse the additional electroactive material throughout a matrix of graphite particles and the particles of the additional electroactive material must have sufficient structural integrity to withstand compounding with graphite particles and subsequent formation of an electrode layer, for example via steps such as compressing, drying and calendering. Differences in the metallation properties of graphite and other electroactive materials must also be taken into account when developing hybrid anodes. In the lithiation of a graphite-containing hybrid anode in which graphite constitutes at least 50 wt% of the electroactive material, a silicon-containing electroactive material needs to be lithiated to its maximum capacity to gain the capacity benefit from all the electroactive material. Whereas in a non-hybrid silicon electrode, the silicon material would generally be limited to Ca. 25 to 60% of its maximum gravimetric capacity during charge and discharge so as to avoid placing excessive mechanical stresses on the silicon material and a resultant reduction in the overall volumetric capacity retention of the cell, this option is not available in hybrid electrodes. Consequently, the electroactive material must be able to withstand very high levels of mechanical stress through repeated charge and discharge cycles.

Accordingly, there remains a need in the art to identify electroactive materials in which high gravimetric and volumetric capacity is obtained alongside commercially acceptable capacity retention of the electroactive material over multiple charge-discharge cycles. Preferably, the capacity retention over the lifetime of the electroactive material should not compromise the handling properties of the electroactive material. Furthermore, it would be desirable to identify electroactive materials having lifetime performance and handling properties meeting the criteria for hybrid anodes.

In a first aspect, the present invention provides a particulate material consisting of a plurality of porous particles comprising a mixture of silicon and germanium, wherein the mole fraction of germanium is from 0.01 to 50%, wherein the porous particles have a D50 particle diameter in the range of from 500 nm to 25 pm, and wherein the porous particles have an intra-particle porosity in the range of from 30 to 90%.

It has been found that the particulate material of the invention has particularly advantageous properties for use in metal-ion batteries. The use of a mixture of silicon and germanium as the electroactive material allows the gravimetric and volumetric capacity benefits of silicon to be realised alongside the increased conductivity and metal ion diffusion provided by gallium. In this way, the disadvantageous formation of SEI layers at the surface of silicon is reduced without the cost or loss of capacity due to the use of gallium becoming prohibitive. The porosity of the particles provides void space to accommodate expansion of the electroactive material during intercalation of metal ions, thereby avoiding excessive expansion of electrode layers comprising the particles. As a result, the reversible capacity of the particulate material over multiple charge-discharge cycles is maintained at a level which is commercially acceptable. The size of the porous particles is also controlled within a range that enables the particles to be dispersed readily and without agglomeration in slurries, facilitating their incorporation into electrode layers, without being so large as to prevent the formation of dense uniform electrode layers.

The particulate material of the invention preferably comprises at least 60 wt%, more preferably at least 70 wt%, more preferably at least 75 wt%, more preferably at least 80 wt%, and most preferably at least 85 wt% of the mixture of silicon and germanium. For example, the particulate material of the invention may comprise at least 90 wt%, at least 95 wt%, at least 98 wt% or at least 99 wt% of the mixture of silicon and germanium.

The properties of the particulate material may be tuned by adjusting the mole fraction of germanium in the mixture. For the avoidance of doubt, references herein to the mole fraction of germanium are based on the total molar amount of silicon and germanium in the particulate material. Suitably, the mole fraction of germanium may be at least 0.02%, at least 0.05%, at least 0.1%, at least 0.2%, at least 0.5%, at least 1%, at least 1.5%, at least 2% or at least 2.5%.

Suitably, the mole fraction of germanium may be no more than 40%, no more than 30%, no more than 25%, no more than 20%, no more than 15%, or no more than 10%.

Silicon and germanium may be present in combination with their oxides, for example due to the presence of a native oxide layer. As used herein, references to silicon and germanium shall be understood to include the oxides of silicon and germanium. Preferably, the oxides are present in an amount of no more than 30 wt%, preferably no more than 25 wt%, more preferably no more than 20 wt%, more preferably no more than 15 wt%, more preferably no more than 10 wt%, more preferably no more than 5 wt%, for example no more than 4 wt%, no more than 3 wt%, no more than 2 wt% or no more than 1 wt%, based on the total amount of silicon and germanium and the oxides thereof.

The particulate material of the invention may optionally comprise a minor amount of one or more additional elements other than silicon or germanium. For instance, the particulate material may comprise a minor amount of one or more additional elements selected from, Al, Sb, Cu, Mg, Zn, Mn, Cr, Co, Mo, Ni, Be, Zr, Fe, Na, Sr, P, Sn, Ru, Ag, Au and oxides thereof. Preferably the one or more additional elements, if present, are selected from one or more of Al, Ni, Ag and Cu, and most preferably Al. The one or more additional elements are preferably present in a total amount of no more than 40 wt%, more preferably no more than 30 wt%, more preferably no more than 25 wt%, more preferably no more than 20 wt%, more preferably no more than 15 wt%, more preferably no more than 10 wt%, and most preferably no more than 5 wt%, based on the total weight of the particulate material. Optionally, the one or more additional elements may be present in a total amount of at least 0.01 wt%, at least 0.05 wt%, at least 0.1 wt%, at least 0.2 wt%, at least 0.5 wt%, at least 1 wt%, at least 2 wt%, or at least 3 wt%, based on the total weight of the particulate material.

In some embodiments, the particulate material of the invention may comprise a minor amount of aluminium. For instance, the particulate material may comprise up to 40 wt% aluminium, more preferably up to 30 wt% aluminium, more preferably up to 25 wt% aluminium, more preferably up to 20 wt% aluminium, more preferably up to 15 wt% aluminium, more preferably up to 10 wt% aluminium, and most preferably up to 5 wt% aluminium. Optionally, the particulate material may comprise at least 0.01 wt% aluminium, at least 0.1 wt% aluminium, at least 0.5 wt% aluminium, at least 1 wt% aluminium, at least 2 wt% aluminium, or at least 3 wt% aluminium.

The porous particles have a D50 particle diameter in the range of from 500 nm to 25 pm.

Preferably, the D particle diameter is at least 1 pm, more preferably at least 1.5 pm, more preferably at least 2 pm, more preferably at least 2.5 pm, and most preferably at least 3 pm.

Preferably, the D50 particle diameter is no more than 20 pm, more preferably no more than 18 pm, more preferably no more than 15 pm, and most preferably no more than 12 pm.

The D10 particle diameter of the porous particles is preferably at least 200nm, more preferably at least 500 nm, and still more preferably at least 800 nm, for example at least 1 pm, at least 2 pm, or at least 3 pm. By maintaining the D10 particle diameter at 1 pm or more, the potential for undesirable agglomeration of sub-micron sized particles is reduced, resulting in improved dispersibility of the particulate material in slurries.

The 090 particle diameter of the porous particles is preferably no more than 40 pm, more preferably no more than 30 pm, more preferably no more than 25 pm, and most preferably no more than 20 pm.

The 099 particle diameter of the porous particles is preferably no more than 50 pm, more preferably no more than 40 pm, more preferably no more than 30 pm, and most preferably no more than 25 pm.

Within the general ranges of particle diameter provided above, two particular particle populations can be identified having particular (but not exclusive) suitability for use in hybrid anodes and non-hybrid/high-loading anodes, respectively.

For use in hybrid anodes, the porous particles suitably have a particle diameter in the range of from 1 to 7 pm. Preferably, the 050 particle diameter is at least 1.5 pm, more preferably at least 2 pm, more preferably at least 2.5 pm, and most preferably at least 3 pm. Preferably, the Dc, particle diameter is no more than 6 pm, more preferably no more than 5 pm, more preferably no more than 4.5 pm, more preferably no more than 4 pm, and most preferably no more than 3.5 pm. Particles having these dimensions are ideally suited to locate themselves in the void spaces between spheroidal synthetic graphite particles with particle diameters in the range of from 10 to 25 pm, as conventionally used to fabricate the anodes of commercial lithium-ion batteries.

For use in hybrid anodes, the porous particles preferably have a particle diameter of at least 500 nm, more preferably at least 800 nm. When the particle diameter is at least 1.5 pm, the D10 particle diameter is preferably at least 800 nm, more preferably at least 1 pm. When the D50 particle diameter is at least 2 pm, the D10 particle diameter is preferably at least 1 pm and still more preferably at least 1.5 pm.

For use in hybrid anodes, the porous particles preferably have a particle diameter of no more than 12 pm, more preferably no more than 10 pm, more preferably no more than 8 pm. When the D particle diameter is no more than 6 pm, the 090 particle diameter is preferably no more than 10 pm, more preferably no more than 8 pm. When the D50 particle diameter is no more than 5 pm, the particle diameter is preferably no more than 7.5 pm, more preferably no more than 7 pm.

When the D50 particle diameter is no more than 4 pm, the D90 particle diameter is preferably no more than 6 pm, more preferably no more than 5.5 pm.

For use in hybrid anodes, the porous particles preferably have a D99 particle diameter of no more than 20 pm, more preferably no more than 15 pm, and most preferably no more than 12 pm.

When the D50 particle diameter is no more than 6 pm, the D90 particle diameter is preferably no more than 15 pm, more preferably no more than 12 pm. When the Oso particle diameter is no more than 5 pm, the 090 particle diameter is preferably no more than 12 pm, more preferably no more than 9pm.

For use in non-hybrid anodes, the porous particles preferably have a 050 particle diameter in the range of from greater than 5 to 25 pm. Preferably, the 050 particle diameter is at least 6 pm, more preferably at least 7 pm, more preferably at least 8 pm, and most preferably at least 10 pm.

Preferably, the D50 particle diameter is no more than 20 pm, more preferably no more than 18 pm, more preferably no more than 15 pm, and most preferably no more than 12 pm. Particles within this size range are particularly suited to the formation of dense electrode layers of uniform thickness in the conventional range of from 20 to 50 pm.

For use in non-hybrid anodes, the D10 particle diameter of the porous particles is preferably at least 1 pm, more preferably at least 2 pm, and still more preferably at least 3 pm.

For use in non-hybrid anodes, the D90 particle diameter of the porous particles is preferably no more than 40 pm, more preferably no more than 30 pm, more preferably no more than 25 pm, and most preferably no more than 20 pm. It has been found that larger particles having a size above pm may be less physically robust and less resistant to mechanical stress during repeated charging and discharging cycles. In addition, larger particles are less suitable for forming dense electrode layers, particularly electrode layers having a thickness in the range of from 20 to 50 pm.

For use in non-hybrid anodes, the D99 particle diameter of the porous particles is preferably no more than 50 pm, more preferably no more than 40 pm, more preferably no more than 30 pm, and most preferably no more than 25 pm.

Preferably, the porous particles have a narrow size distribution span. For instance, the particle size distribution span (defined as (D90-D10)/D50) is preferably S or less, more preferably 4 or less, more preferably 3 or less, more preferably 2 or less and most preferably 1.5 or less. By maintaining a narrow size distribution span, the concentration of particles in the size range found by the inventors to be most favourable for use in electrodes is maximised.

For the avoidance of doubt, the term particle diameter" as used herein refers to the equivalent spherical diameter (esd), i.e. the diameter of a sphere having the same volume as a given particle, wherein the particle volume is understood to include the volume of the intra-particle pores. The terms "Do" and "D50 particle diameter" as used herein refer to the volume-based median particle diameter, i.e. the diameter below which 50% by volume of the particle population is found. The terms "D10" and "D10 particle diameter" as used herein refer to the 10th percentile volume-based median particle diameter, i.e. the diameter below which 10% by volume of the particle population is found. The terms "D90" and "D90 particle diameter" as used herein refer to the 90th percentile volume-based median particle diameter, i.e. the diameter below which 90% by volume of the particle population is found. The terms 099" and "0 particle diameter" as used herein refer to the 99th percentile volume-based median particle diameter, i.e. the diameter below which 99% by volume of the particle population is found.

Particle diameters and particle size distributions can be determined by routine laser diffraction techniques. Laser diffraction relies on the principle that a particle will scatter light at an angle that varies depending on the size the particle and a collection of particles will produce a pattern of scattered light defined by intensity and angle that can be correlated to a particle size distribution. A number of laser diffraction instruments are commercially available for the rapid and reliable determination of particle size distributions. Unless stated otherwise, particle size distribution measurements as specified or reported herein are as measured by the conventional Malvern Mastersizer 2000 particle size analyzer from Malvern Instruments. The Malvern Mastersizer 2000 particle size analyzer operates by projecting a helium-neon gas laser beam through a transparent cell containing the particles of interest suspended in an aqueous solution. Light rays which strike the particles are scattered through angles which are inversely proportional to the particle size and a photodetector array measures the intensity of light at several predetermined angles and the measured intensities at different angles are processed by a computer using standard theoretical principles to determine the particle size distribution. Laser diffraction values as reported herein are obtained using a wet dispersion of the particles in distilled water. The particle refractive index is taken to be 3.50 and the dispersant index is taken to be 1.330. Particle size distributions are calculated using the Mie scattering model.

As used herein, the term "porous particle" shall be understood as referring to a particle comprising a plurality of pores, voids or channels within a particle structure. The term "porous particle" shall be understood in particular to include particles comprising a random or ordered network of linear, branched or layered elongate structural elements, wherein interconnected void spaces or channels are defined between the elongate structural elements of the network, the elongate structural elements suitably including linear, branched or layered fibres, tubes, wires, pillars, rods, ribbons, plates or flakes. Preferably the porous particles have a substantially open porous structure such that substantially all of the pore volume of the porous particles is accessible to a fluid from the exterior of the particle, for instance to a gas or to an electrolyte. By a substantially open porous structure, it is meant that at least 90%, preferably at least 95%, preferably at least 98%, preferably at least 99% of the pore volume of the porous particles is accessible to a fluid from the exterior of the particles.

The intra-particle porosity of the porous particles should be distinguished from the inter-particle porosity of the particulate material of the invention. Intra-particle porosity is defined by the ratio of the volume of pores within a particle to the total volume of the particle. Inter-particle porosity is the volume of pores between discrete particles and is a function both of the size of the individual particles and of the packing density of the particulate material. The total porosity of the particulate material may be defined as the sum of the intra-particle and inter-particle porosity.

The intra-particle porosity of the porous particles is preferably at least 40%, preferably at least 50%, and most preferably at least 60. The intra-particle porosity is preferably no more than 87%, more preferably no more than 86%, more preferably no more than 85%, for example no more than 80%, or no more than 75%.

Where the porous particles are prepared by removal of an unwanted component from a starting material, e.g. by leaching of an alloy as discussed in further detail below, the intra-particle porosity can suitably be determined by determining the elemental composition of the particles before and after leaching and calculating the volume of material that is removed.

More preferably, the intra-particle porosity of the porous particles may be measured by mercury porosimetry. Mercury porosimetry is a technique that characterises the porosity of a material by applying varying levels of pressure to a sample of the material immersed in mercury. The pressure required to intrude mercury into the pores of the sample is inversely proportional to the size of the pores. More specifically, mercury porosimetry is based on the capillary law governing liquid penetration into small pores. This law, in the case of a non-wetting liquid such as mercury, is expressed by the Washburn equation: D = (1IP)4ycoscp wherein D is pore diameter, P is the applied pressure, y is the surface tension, and p is the contact angle between the liquid and the sample. The volume of mercury penetrating the pores of the sample is measured directly as a function of the applied pressure. As pressure increases during an analysis, pore size is calculated for each pressure point and the corresponding volume of mercury required to fill these pores is measured. These measurements, taken over a range of pressures, give the pore volume versus pore diameter distribution for the sample material. The Washburn equation assumes that all pores are cylindrical. While true cylindrical pores are rarely encountered in real materials, this assumption provides sufficiently useful representation of the pore structure for most materials. For the avoidance of doubt, references herein to pore diameter shall be understood as referring to the equivalent cylindrical dimensions as determined by mercury porosimetry. Values obtained by mercury porosimetry as reported herein are obtained in accordance with ASTM U0P574-1 1 with the surface tension y taken to be 480 mN/m and the contact angle q taken to be 140° for mercury at room temperature. The density of mercury is taken to be 13.5462 g/cm3 at room temperature.

For a sample in the form of a powder of porous particles, the total pore volume of the sample is the sum of intra-particle and inter-particle pores. This gives rise to an at least bimodal pore diameter distribution curve in a mercury porosimetry analysis, comprising a set of one or more peaks at lower pore sizes relating to the intra-particle pore diameter distribution and set of one or more peaks at larger pore sizes relating to the inter-particle pore diameter distribution. From the pore diameter distribution curve, the lowest point between the two sets of peaks indicates the diameter at which the intra-particle and inter-particle pore volumes can be separated. The pore volume at diameters greater than this is assumed to be the pore volume associated with inter-particle pores.

The total pore volume minus the inter-particle pore volume gives the intra-particle pore volume from which the intra-particle porosity can be calculated.

A number of high precision mercury porosimetry instruments are commercially available, such as the AutoPore IV series of automated mercury porosimeters available from Micromeritics Instrument Corporation, USA. For a complete review of mercury porosimetry reference may be made to P.A.

Webb and C. Orr in Analytical Methods in Fine Particle Technology, 1997, Micromeritics Instrument Corporation, ISBN 0-9656783-0.

It will be appreciated that mercury porosimetry and other intrusion techniques are effective only to determine the pore volume of pores that are accessible to mercury (or another fluid) from the exterior of the porous particles to be measured. As noted above, substantially all of the pore volume of the particles of the invention is accessible from the exterior of the particles, and thus porosity measurements by mercury porosimetry will generally be equivalent to the entire pore volume of the particles. Nonetheless, for the avoidance of doubt, intra-particle porosity values as specified or reported herein shall be understood as referring to the volume of open pores, i.e. pores that are accessible to a fluid from the exterior of the particles of the invention. Fully enclosed pores which cannot be identified by mercury porosimetry shall not be taken into account herein when specifying or reporting intra-particle porosity.

The particulate material of the invention is preferably characterised not only by the overall porosity of the porous particles, but also by the way that the porosity is distributed in the particles.

Preferably, the porosity is associated with a pore diameter distribution which ensures that the electroactive material structures in the particles are neither so fine as to be degraded during processing into electrode layers nor so large as to undergo unacceptable stress during charging and discharging of the electroactive material. Thus, the porous particles of the invention are sufficiently robust to survive manufacture and incorporation into an anode layer without loss of structural integrity, particularly when anode layers are calendered to produce a dense uniform layer as is conventional in the art, while also providing reversible capacity over multiple charge-discharge cycles at a level which is commercially acceptable.

The particulate material of the invention is characterised by having at least two peaks in the pore diameter distribution as determined by mercury porosimetry; at least one peak at lower pore size being associated with intra-particle pores and at least one peak at higher pore size being associated with inter-particle porosity. The particulate material of the invention preferably has a pore diameter distribution having a peak corresponding to the intra-particles pores in the range of from 50 nm to less than 500 nm as determined by mercury porosimetry.

The particulate material of the invention preferably has a pore diameter distribution having at least one peak at a pore size less than 460 nm, more preferably less than 420 nm, more preferably less than 400 nm, more preferably less than 380 nm, more preferably less than 360 nm, and most preferably less than 350 nm, as determined by mercury porosimetry. Preferably, the pore diameter distribution has at least one peak at a pore size of more than 60 nm, more preferably more than 80 nm, more preferably more than 100 nm, as determined by mercury porosimetry.

Preferably, the particulate material of the invention is also characterised by a peak in the pore diameter distribution of a loose packed plurality of particles relating to the inter-particle porosity at a pore diameter in the range of from 500 nm to 4 pm, as determined by mercury porosimetry.

In some embodiments, the particulate material of the invention may be characterised by the presence of particles comprising at least one pore, void or channel (accessible by electrolyte) having at least three dimensions of at least 150 nm.

The inventors have found that particles having peaks in the pore diameter distribution within these ranges and a porosity as set out above demonstrate particularly good charge-discharge cycling properties when used as electroactive materials in anodes for metal-ion batteries. Without being bound by theory, it is believed that the particulate material of the invention provides an optimum balance between overall porosity and pore size, thus providing sufficient void space within the particles to allow for inward expansion of the electroactive material during intercalation of metal ions, whilst also ensuring that the electroactive material architecture within the particles is sufficiently robust to withstand the mechanical strain during charging of the electroactive material to its maximum capacity and mechanical damage during particle manufacture and electrode assembly.

The porous particles are preferably spheroidal in shape. Spheroidal particles as defined herein may include both spherical and ellipsoidal particles and the shape of the particles of the invention may suitably be defined by reference to the sphericity and the aspect ratio of the particles of the invention. Spheroidal particles are found to be particularly well-suited to dispersion in slurries without the formation of agglomerates, particularly when the spheroidal particles have particle sizes falling within the ranges defined herein. In addition, the use of porous spheroidal particles is surprisingly found to provide a further improvement in capacity retention when compared to porous particles and porous particle fragments of more irregular morphology.

The sphericity of an object is conventionally defined as the ratio of the surface area of a sphere to the surface area of the object, wherein the object and the sphere have identical volume. However, in practice it is difficult to measure the surface area and volume of individual particles at the micron scale. However, it is possible to obtain highly accurate two-dimensional projections of micron scale particles by scanning electron microscopy (SEM) and by dynamic image analysis, in which a digital camera is used to record the shadow projected by a particle. The term "sphericity" as used herein shall be understood as the ratio of the area of the particle projection to the area of a circle, wherein the particle projection and circle have identical circumference. Thus, for an individual particle, the sphericity S may be defined as: -4 1.

S . ml

wherein Am is the measured area of the particle projection and C is the measured circumference of the particle projection. The average sphericity Say of a population of particles as used herein is defined as: n -tV [4 it. Am (Cm)2 wherein n represents the number of particles in the population.

As used herein, the term "spheroidal" as applied to the particles of the invention shall be understood to refer to a material having an average sphericity of at least 0.70. Preferably, the porous spheroidal particles of the invention have an average sphericity of at least 0.85, more preferably at least 0.90, more preferably at least 0.92, more preferably at least 0.93, more preferably at least 0.94, more preferably at least 0.95, more preferably at least 0.96, more preferably at least 0.97, more preferably at least 0.98 and most preferably at least 0.99.

The average aspect ratio of the porous particles is preferably less than 3:1, more preferably no more than 2.5:1, more preferably no more than 2:1, more preferably no more than 1.8:1, more preferably no more than 1.6:1, more preferably no more than 1.4:1 and most preferably no more than 1.2:1. As used herein, the term "aspect ratio" refers to the ratio of the longest dimension to the shortest dimension of a two-dimensional particle projection. The term "average aspect ratio" refers to a number-weighted mean average of the aspect ratios of the individual particles in the particle population.

It will be understood that the circumference and area of a two-dimensional particle projection will depend on the orientation of the particle in the case of any particle which is not perfectly spheroidal. However, the effect of particle orientation may be offset by reporting sphericity and aspect ratios as average values obtained from a plurality of particles having random orientation.

A number of SEM and dynamic image analysis instruments are commercially available, allowing the sphericity and aspect ratio of a particulate material to be determined rapidly and reliably.

Unless stated otherwise, sphericity values as specified or reported herein are as measured by a CamSizer XI particle analyzer from Retsch Technology GmbH. The CamSizer XT is a dynamic image analysis instrument which is capable of obtaining highly accurate distributions of the size and shape for particulate materials in sample volumes of from 100mg to 100 g, allowing properties such as average sphericity and aspect ratios to be calculated directly by the instrument.

The particulate material of the invention preferably has a BET surface area of less than 300 m2/g, more preferably less than 200 m2/g, more preferably less than 150 m2/g, more preferably less than m2/g. The particulate material of the invention may have a BET surface area of less than 100 m2/g, for example less than 80 m2/g. Suitably, the BET surface may be at least 10 m2/g, at least 15 m2/g, at least 20 m2/g, or at least 50 m2/g. The term "BET surface area" as used herein should be taken to refer to the surface area per unit mass calculated from a measurement of the physical adsorption of gas molecules on a solid surface, using the Brunauer-Emmett-Teller theory, in accordance with ASIM B922/10.

Control of the BET surface area of electroactive material is an important consideration in the design of anodes for metal ion bafteries. A BET surface area which is too low results in unacceptably low charging rate and capacity due to the inaccessibility of the bulk of the electroactive material to metal ions in the surrounding electrolyte. However, a very high BET surface area is also known to be disadvantageous due to the formation of a solid electrolyte interphase (SEI) layer at the anode surface during the first charge-discharge cycle of the battery.

SEI layers are formed due to reaction of the electrolyte at the surface of electroactive materials and can consume significant amounts of metal ions from the electrolyte, thus depleting the capacity of the battery in subsequent charge-discharge cycles. While previous teaching in the art focuses on an optimum BET surface area below about 10 m2/g, the present inventors have found that a much wider BET range can be tolerated when using the particulate material of the invention as an electroactive material, in particular due to the presence of germanium.

The particulate material of the invention may be distinguished in some embodiments by a specific microstructure of the structural elements that constitute the particulate material. Preferably, the porous particles comprise a network of interconnected irregular elongate structural elements comprising the electroactive material which may be described as acicular, flake-like, dendritic, or coral-like. These structural elements may include structures containing both silicon and germanium as well as structures containing substantially only silicon and substantially only germanium. This particle architecture is associated with an interconnected network of pores, preferably with a substantially even distribution of the pores throughout the particle. In preferred embodiments, the porous particles comprise networks of fine structural elements having an aspect ratio of at least 2:1 and more preferably at least 5:1. A high aspect ratio of the structural elements provides a high number of interconnections between the structural elements constituting the porous particles for electrical continuity.

The thickness of the structural elements constituting the porous particles is an important parameter in relation to the ability of the electroactive material to reversibly intercalate and release metal ions.

Structural elements which are too thin may result in excessive first cycle loss due to excessively high BET surface area the resulting formation of an SEI layer. However, structural elements which are too thick are placed under excessive stress during intercalation of metal ions and also impede the insertion of metal ions into the bulk of the silicon material. The particulate material of the invention provides an optimum balance of these competing factors due to the presence of structural elements of optimised size and proportions. Thus, the porous particles preferably comprise structural elements having a smallest dimension less than 300 nm, preferably less than nm, more preferably less than 150 nm, and a largest dimension at least twice, and preferably at least five times the smallest dimension. The smallest dimension is preferably at least 10 nm, more preferably at least 20 nm, and most preferably at least 30 nm.

The electroactive material containing structural elements constituting the porous particles preferably comprises amorphous or nanocrystalline material having a crystallite size of less than nm, preferably less than 50 nm. The structural elements may comprise a mixture of amorphous and nanocrystalline electroactive material. The crystallite size may be determined by X-ray diffraction spectrometry analysis using an X-ray wavelength of 1.5456 nm. The crystallite size is calculated using the Scherrer equation from a 29 XRD scan, where the crystallite size d = K.A / (B.cOSeB), the shape constant K is taken to be 0.94, the wavelength A is 1.5456 nm, B is the Bragg angle associated with the 220 silicon peak, and B is the full width half maximum (FWHM) of that peak. Preferably the crystallite size is at least 10 nm.

In preferred embodiments, at least a portion of the structural elements of the porous particles comprise both silicon and germanium, wherein the concentration of germanium at the surfaces of the structural elements is higher than the concentration at the centre of the structural elements.

Thus, there is a germanium concentration gradient from the interior of the structural elements to the surface of the structural elements, and the mole fraction of germanium at the pore surfaces of the porous particles is therefore higher on average than the mole fraction of germanium in the particulate material of the invention as a whole.

Structural elements having increased concentration of germanium at the surface facilitate faster kinetics of the intercalation of metal ions into the alloy structure and increase the electronic conductivity of the porous particles. Thus, the charge-discharge rate of the particulate material of the invention is improved in comparison to particles comprising silicon only. Furthermore, due to the faster intercalation of metal ions into the interior of the alloy, there is less accumulation of metal at the alloy surface and thus less reactivity with the electrolyte. As a result, first cycle loss (FCL) is significantly reduced in comparison to silicon particles, providing increased capacity in subsequent cycles.

The particulate material of the invention may suitably be obtained by processes in which unwanted material is removed from a particulate starting material comprising silicon and germanium.

Removal of unwanted material may create or expose the silicon and germanium structures defining the porous particles. For example, this may involve the removal of oxide components from a silicon or germanium structure, the etching of bulk silicon or germanium particles, or the leaching of a metal matrix from ternary alloy particles containing discrete silicon and germanium containing structures dispersed in a metal matrix.

The particulate material of the invention is preferably obtained by a process comprising leaching particles of a ternary alloy comprising discrete silicon and germanium containing structures in a metal matrix. This process relies on the observation that a network of crystalline silicon and/or germanium structures is precipitated within an alloy matrix when certain alloys containing these elements are cooled from the molten state. Suitably, the ternary alloys comprise matrix metals in which the solubility of silicon and germanium is low, and/or in which the formation of intermetallics between silicon and/or germanium and the matrix metal on cooling is negligible or non-existent.

Leaching of the metals constituting the metal matrix exposes the network of silicon and germanium structures. Thus, leaching particles of an alloy comprising silicon and germanium provides a suitable route to the porous particles defined above.

Accordingly, in a second aspect, the present invention provides a process for the preparation of a particulate material consisting of a plurality of porous particles comprising a mixture of silicon and germanium, the process comprising the steps of (a) providing a plurality of alloy particles comprising: (i) from 11 to 45 wt% of a mixture of silicon and germanium wherein the mole fraction of germanium is from 0.01 to 50%; and (ii) a matrix metal component; wherein said alloy particles have a 050 particle diameter in the range of from 500 nm to 25 pm, and wherein said alloy particles comprise discrete silicon and germanium containing structures dispersed in the matrix metal component; (b) leaching the alloy particles from step (a) to remove at least a portion of the matrix metal component and to at least partially expose the silicon and germanium containing structures; wherein the porous particles comprise no more than 40% by weight of the matrix metal component.

This aspect of the invention relies on the observation that crystalline silicon and germanium containing structures are precipitated within a matrix metal component when certain alloys are cooled. These alloys are those in which the solubility of the silicon and germanium in the matrix metal is low and in which there is little or no formation of intermetallics on cooling. By controlling the concentration of the silicon and germanium in the alloy in the range specified above, it is found that a particulate material is obtained having porosity and other structural properties that are particularly suitable for use in hybrid anodes for lithium ion batteries.

The alloy particles have a D50 particle diameter in the range of from 500 nm to 25 pm. Preferably, the D50 particle diameter may be at least 1 pm, more preferably at least 1.5 pm, more preferably at least 2 pm, more preferably at least 2.5 pm, and most preferably at least 3 pm. Preferably, the D50 particle diameter is no more than 20 pm, more preferably no more than 18 pm, more preferably no more than 15 pm, and most preferably no more than 12 pm.

The D10 particle diameter of the alloy particles is preferably at least 200nm, more preferably at least 500 nm, and still more preferably at least 800 nm, for example at least 1 pm, at least 2 pm, or at least 3 pm.

The D90 particle diameter of the alloy particles is preferably no more than 40 pm, more preferably no more than 30 pm, more preferably no more than 25 pm, and most preferably no more than 20 pm.

The D99 particle diameter of the alloy particles is preferably no more than 50 pm, more preferably no more than 40 pm, more preferably no more than 30 pm, and most preferably no more than 25 pm.

As discussed above, the particulate material of the invention encompasses two populations of particles having dimensions which are particularly (although not exclusively) suitable for use in hybrid and non-hybrid anodes, respectively. The dimensions disclosed above for each of these populations of particles are also applicable to the alloy particles used in the process according to the second aspect of the invention. Thus, the second aspect of the invention may be used for the preparation of a particulate material for use in both hybrid and non-hybrid electrodes by selection of the alloy particle dimensions within the ranges set out above.

The alloy particles preferably have a narrow size distribution span. Preferably, the particle size distribution span (defined as (D90-D10)/D50) of the alloy particles is 5 or less, more preferably 4 or less, more preferably 3 or less, and most preferably 2 or less, and most preferably 1.5 or less.

The alloy particles are preferably spheroidal particles. Thus, the alloy particles preferably have an average sphericity of at least 0.70, more preferably at least 0.85, more preferably at least 0.90, more preferably at least 0.92, more preferably at least 0.93, more preferably at least 0.94, more preferably at least 0.95, more preferably at least 0.96, more preferably at least 0.97, more preferably at least 0.98, and most preferably at least 0.99.

The average aspect ratio of the alloy particles is preferably less than 3:1, more preferably no more than 2.5:1, more preferably no more than 2:1, more preferably no more than 1.8:1, more preferably no more than 1.6:1, more preferably no more than 1.4:1 and most preferably no more than 1.2:1.

The mole fraction of germanium in the alloy particles may be at least 0.02%, at least 0.05%, at least 0.1%, at least 0.2%, at least 0.5%, at least 1%, at least 1.5%, at least 2% or at least 2.5%, based on the total molar amount of silicon and germanium. Suitably, the mole fraction of germanium in the alloy particles may be no more than 40%, no more than 30%, no more than 25%, no more than 20%, no more than 15%, or no more than 10%, based on the total molar amount of silicon and germanium.

The alloy particles preferably comprise at least 11.2 wt%, more preferably at least 11.5 wt%, more preferably at least 11.8 wt%, more preferably at least 12 wt%, and most preferably at least 12.2 wt% in total of silicon and germanium. For example, the alloy particles may comprise at least 12.4 wt%, more preferably at least 12.6 wt%, more preferably at least 12.8 wt%, and most preferably at least 13 wt% in total of silicon and germanium. Preferably the alloy particles comprise less than 40 wt%, preferably less than 35 wt%, more preferably less than 30 wt%, more preferably less than 25 wt%, more preferably less than 20 wt%, and most preferably less than 18 wt% in total of silicon and germanium. The total amount of silicon and germanium in the alloy particles is of course dictated by the desired structure of the porous particles, including the desired porosity and pore diameter distribution of the porous particles, and the dimension of the structural elements.

The matrix metal component is suitably selected from Al, Sb, Cu, Mg, Zn, Mn, Cr, Co, Mo, Ni, Be, Zr, Fe, Sn, Ru, Ag, Au and combinations thereof. Preferably, the matrix metal component comprises one or more of Al, Ni, Ag or Cu. More preferably, the matrix metal component comprises at least 50 wt%, more preferably at least 60 wt%, more preferably at least 70 wt%, more preferably at least 80 wt%, more preferably at least 90 wt% and most preferably at least 95 wt% of one or more of Al, Ni, Ag or Cu.

A preferred matrix metal component is aluminium. Thus, the matrix metal component may be aluminium, or a combination of aluminium with one or more additional metals or rare earths, for example one or more of Sb, Cu, Mg, Zn, Mn, Cr, Co, Mo, Ni, Be, Zr, Fe, Na, Sr, P, Sn, Ru, Ag and Au, wherein the combination comprises at least 50 wt%, more preferably at least 60 wt%, more preferably at least 70 wt%, more preferably at least 80 wt%, more preferably at least 90 wt%, more preferably at least 95 wt% aluminium. More preferably, the matrix metal component is selected from aluminium or a combination of aluminium with copper and/or silver and/or nickel, wherein the combination comprises at least 50 wt%, more preferably at least 60 wt%, more preferably at least wt%, more preferably at least 80 wt%, more preferably at least 90 wt% and most preferably at least 95 wt% aluminium.

Silicon and germanium have negligible solubility in solid aluminium and do not form intermetallics with aluminium. Thus, aluminium-silicon-germanium ternary alloy particles comprise discrete silicon and germanium structures dispersed in an aluminium matrix. These structures may include structures containing both silicon and germanium as well as structures containing substantially only silicon and substantially only germanium. By maintaining the concentration of silicon and germanium in the alloy particles in the ranges set out herein, it is found that the porous particles obtained after leaching have a specific microstructure which is particularly advantageous for use in hybrid anodes for metal ion batteries.

Where the amount of silicon and germanium in the alloy particles is in the range of 20 to 45 wt%, and particularly in the range of 24 to 45 wt%, coarse primary phase silicon and/or germanium domains may be observed following leaching of the matrix metal component. The size of such primary phase structures is dependent on the cooling rate during formation of the alloy particles from the molten alloy and can also be modified by adding further known additives to the alloy.

However, provided that the total amount of silicon in the alloy particles does not exceed 45 wt%, preferably 30 wt%, and more preferably 24 wt%, it is considered that the overall microstructure of the porous particles will be sufficiently fine to provide acceptable capacity retention during charging and discharging of hybrid anodes comprising the particulate material of the invention.

The shape and distribution of the discrete silicon and germanium containing structures within the alloy particles is a function of both the composition of the alloy particles and the process by which the alloy particles are made. If the amount of silicon and germanium is too low, then it is found that the porous particles obtained after removal of the matrix metal component have poor structural integrity, and tend to disintegrate during manufacture and/or subsequent incorporation into anodes.

In addition, the capacity retention of such particles may be inadequate for commercial applications due to insufficient resilience to the volumetric changes on charging and discharging.

The size and shape of the discrete silicon and germanium structures in the alloy particles may be influenced by controlling the rate of cooling of the alloy from the melt during production of the alloy particles. Chemical additives may also be added to the molten alloy to modify the morphology of the silicon and germanium structures in the alloy particles. In general, faster cooling will lead to the formation of smaller, more evenly distributed silicon and germanium structures. The rate of cooling, and thus the size and shape of the silicon and germanium containing structures formed, is a function of the process used to form the alloy particles. Thus, by the selection of an appropriate process, alloy particles may be obtained in which the discrete silicon and germanium structures have a morphology which, when exposed by leaching of the matrix metal, is particularly desirable for use in metal-ion batteries, in particular metal-ion batteries having hybrid electrodes.

The alloy particles used in the process of the invention are preferably obtained by cooling a molten alloy from the liquid state to the solid state at a cooling rate of at least 1 x io K/s, preferably at least 5 x i03 K/s, preferably at least 1 x i04 K/s, more preferably at least 5 x i04 K/s, for example at least 1 x i05 K/s, or at least 5 x io5 KIs, or at least 1 x io6 K/s, or at least 5 x 106 K/s, or at least 1 x i7 Kls. It is found that the pore diameter distribution of the porous particles obtained according to the process of the invention increases towards larger pore sizes with increased cooling rates.

Processes for cooling a molten alloy to form alloy particles with a cooling rate of at least i03 K/s include gas atomisation, water atomisation, melt-spinning, splat cooling and plasma phase atomisation. Preferred processes for cooling the molten alloy to form the alloy particles include gas atomisation and water atomisation. It is found that the rate of cooling of the particles obtained by gas and water atomisation processes may be correlated to the size of the alloy particles, and alloy particles having a particle size as specified herein cool at very high rates (i.e. in excess of 1 w3 K/s, and typically at least 1 x io K/s) and thus the silicon and germanium containing structures formed in the alloy particles have a morphology which is particularly preferred in accordance with the invention. If necessary, the alloy particles obtained by any particular cooling method may be classified to obtain an appropriate size distribution.

The metal matrix may be leached using any leachant which is suitable to remove at least a portion of the matrix metal component while leaving the silicon and germanium structures intact.

Leachants may be liquid or gas phase and may include additives or sub-processes to remove any by-product build up which might impede leaching. Leaching may suitably be carried out by a chemical or electrochemical process. Caustic leaching using sodium hydroxide may be used for leaching aluminium, although the concentration of sodium hydroxide in the leachant solution should be controlled below 10 to 20 wt% to avoid attack of silicon and germanium by the leachant.

Acidic leaching, for instance using hydrochloric acid or ferric chloride, is also a suitable technique.

Alternatively, the matrix metal may be leached electrochemically using salt electrolytes, e.g. copper sulfate or sodium chloride. Leaching is carried out until the desired porosity of the porous particles is achieved. For example, acid leaching using SM aqueous HCI at room temperature for a period of from 10 to 60 minutes is sufficient to leach substantially all of the leachable aluminium from the silicon-aluminium alloys described herein (noting that a minor amount of the matrix metal may not be leached).

Following leaching of the matrix metal component, the porous particles will be formed intact in the leachant. In general, it is appropriate to carry out cleaning and rinsing steps so as to remove by-products and residual leachant. The fine distribution of the silicon structural elements in the alloy particles is such that the porous particles obtained after leaching have particle dimensions and shape which are substantially equal to the particle dimensions and shape of the alloy particles.

It is not essential that the matrix metal component be removed in its entirety and a minor amount of matrix metal may remain even with extended leaching reaction times. Indeed, it may be desirable that the matrix metal component is not completely removed, since it may function as an additional electroactive material and/or as a dopant. Thus, the particulate material obtained according to the process of the invention may comprise residual matrix metal component as defined above in an amount of no more than 40 wt%, preferably no more than 30 wt%, more preferably no more than wt%, more preferably no more than 20 wt%, more preferably no more than 15 wt%, more preferably no more than 10 wt%, and most preferably no more than 5 wt%, relative to the total weight of the particulate material. Optionally, the particulate material obtained according to the process of the invention may comprise residual matrix metal component in an amount of at least 0.01 wt, at least 0.1 wt%, at least 0.5 wt%, at least 1 wt%, at least 2 wt%, or at least 3 wt%, relative to the total weight of the particulate material.

As discussed above, a preferred matrix metal component is aluminium, and thus the particulate material obtained according to the process of the invention may optionally comprise residual aluminium in an amount of no more than 40 wt%, more preferably no more than 30 wt%, more preferably no more than 25 wt%, more preferably no more than 20 wt%, more preferably no more than 15 wt%, more preferably no more than 10 wt%, and most preferably no more than 5 wt%, relative to the total weight of the particulate material. Optionally, the particulate material obtained according to the process of the invention may comprise residual aluminium in an amount of at least 0.01 wt, at least 0.1 wt%, at least 0.5 wt%, at least 1 wt%, at least 2 wt%, or at least 3 wt%, relative to the total weight of the particulate material. Residual aluminium is well-tolerated since it is itself capable of absorbing and releasing metal ions during charging and discharging of a metal-ion battery, and it may further aid in making electrical contact between the silicon structures and between the silicon structures and the anode current collector.

The process of the invention may optionally comprise an additional treatment to concentrate germanium at the surface of the alloy structures constituting the porous particle. Suitable treatments include thermal treatments and laser treatments.

In third aspect, the present invention provides a particulate material consisting of a plurality of porous particles comprising silicon and germanium, wherein the particulate material is obtainable by a process according to the second aspect of the invention. The process of the second aspect of the invention may be used to obtain the particulate material as defined with reference to the first aspect of the invention. Thus, the particulate material of the third aspect of the invention is preferably as defined with regard to the first aspect of the invention, and may have any of the features described as preferred or optional with regard to the first aspect of the invention.

In a fourth aspect of the invention, there is provided a composition comprising a particulate material according to the first and/or third aspect of the invention and at least one other component. In particular, the particulate material of the first and/or third aspects of the invention may be used as a component of an electrode composition. Thus, there is provided an electrode composition comprising a particulate material according to the first and/or third aspect of the invention and at least one other component selected from: (i) a binder; (ii) a conductive additive; and (iii) an additional particulate electroactive material. The particulate material used to prepare the electrode composition of the fourth aspect of the invention may have any of the features described as preferred or optional with regard to the first aspect of the invention and/or may be prepared by a process including any of the features described as preferred or optional with regard to the second aspect of the invention.

The electrode composition may optionally be a hybrid electrode composition which comprises a particulate material according to the first and/or third aspect of the invention and at least one additional particulate electroactive material. Examples of additional particulate electroactive materials include graphite, hard carbon, gallium, aluminium and lead. The at least one additional particulate electroactive material is preferably selected from graphite and hard carbon, and most preferably the at least one additional particulate electroactive material is graphite.

The at least one additional particulate electroactive material is preferably in the form of spheroidal particles having an average sphericity of at least 0.70, more preferably at least 0.85, more preferably at least 0.90, more preferably at least 0.92, more preferably at least 0.93, more preferably at least 0.94, and most preferably at least 0.95.

The at least one additional particulate electroactive material preferably has an average aspect ratio of less than 3:1, more preferably no more than 2.5:1, more preferably no more than 2:1, more preferably no more than 1.8:1, more preferably no more than 1.6:1, more preferably no more than 1.4:1 and most preferably no more than 1.2:1.

The at least one additional particulate electroactive material preferably has a 050 particle diameter in the range of from 10 to 50 pm, preferably from 10 to 40 pm, more preferably from 10 to 30 pm and most preferably from 10 to 25 pm, for example from 15 to 25 pm. Where the at least one additional particulate electroactive material has a D50 particle diameter within this range, the particulate material of the invention is advantageously adapted to occupy void space between the particles of the at least one additional particulate electroactive material, particularly where the particles of the at least one additional particulate electroactive material are spheroidal in shape.

In preferred embodiments, the at least one additional particulate electroactive material is selected from spheroidal carbon-comprising particles, preferably graphite particles and/or spheroidal hard carbon particles, wherein the graphite and hard carbon particles have a D50 particle diameter in the range of from 10 to 50 pm. Still more preferably, the at least one additional particulate electroactive material is selected from spheroidal graphite particles, wherein the graphite particles have a 050 particle diameter in the range of from 10 to 50 pm. Most preferably, the at least one additional particulate electroactive material is selected from spheroidal graphite particles, wherein the graphite particles have a D50 particle diameter in the range of from 10 to 50 pm, and the particulate material according to the first and/or third aspect of the invention consists of porous spheroidal particles, as described above.

Where the electrode composition is a hybrid electrode composition, the particulate material preferably has one or more of the preferred D50, Do, D90, and 099 particle diameters disclosed above as being particularly suitable for use in hybrid electrodes.

The ratio of the at least one additional particulate electroactive material to the particulate material of the invention is suitably in the range of from 50:50 to 99:1 by weight, more preferably from 60:40 to 98:2 by weight, more preferably 70:30 to 97:3 by weight, more preferably 80:20 to 96:4 by weight, and most preferably 85:15 to 95:5 by weight.

The at least one additional particulate electroactive material and the particulate material of the invention together preferably constitute at least 50 wt%, more preferably at least 60% by weight more preferably at least 70 wt%, and most preferably at least 80 wt%, for example at least 85 wt%, at least 90 wt%, or at least 95 wt% of the total weight of the electrode composition.

Where the electrode composition is a non-hybrid electrode composition, the particulate material of the invention preferably constitutes at least 50% by weight, more preferably at least 60% by weight of, more preferably at least 70 wt%, and most preferably at least 80 wt%, for example at least 85 wt%, at least 90 wt%, or at least 95 wt% of the total weight of the electrode composition.

Where the electrode composition is a non-hybrid electrode composition, the particulate material may have one or more of the preferred D50, D90, and D99 particle diameters disclosed above as being particularly suitable for use in non-hybrid electrodes.

The electrode compositions of the invention may optionally comprise a binder. A binder functions to adhere the electrode composition to a current collector and to maintain the integrity of the electrode composition. Examples of binders which may be used in accordance with the present invention include polyvinylidene fluoride (FVDF), polyacrylic acid (FAA) and alkali metal salts thereof, modified polyacrylic acid (mPAA) and alkali metal salts thereof, carboxymethylcellulose (CMC), modified carboxymethylcellulose (mCMC), sodium carboxymethylcellulose (Na-CMC), polyvinylalcohol (PVA), alginates and alkali metal salts thereof, styrene-butadiene rubber (SBR), and polyimide. The electrode composition may comprise a mixture of binders. Preferably, the binder comprises polymers selected from polyacrylic acid (FAA) and alkali metal salts thereof, and modified polyacrylic acid (mPAA) and alkali metal salts thereof, SBR and CMC.

The binder may suitably be present in an amount of from 0.5 to 20 wt%, preferably 1 to 15 wt% and most preferably 2 to 10 wt%, based on the total weight of the electrode composition.

The binder may optionally be present in combination with one or more additives that modify the properties of the binder, such as cross-linking accelerators, coupling agents and/or adhesive accelerators.

The electrode compositions of the invention may optionally comprise one or more conductive additives. Preferred conductive additives are non-electroactive materials which are included so as to improve electrical conductivity between the electroactive components of the electrode composition and between the electroactive components of the electrode composition and a current collector. The conductive additives may suitably be selected from carbon black, carbon fibres, carbon nanotubes, acetylene black, ketjen black, metal fibres, metal powders and conductive metal oxides. Preferred conductive additives include carbon black and carbon nanotubes.

The one or more conductive additives may suitably be present in a total amount of from 0.5 to 20 wt%, preferably 1 to 15 wt% and most preferably 2 to 10 wt%, based on the total weight of the electrode composition.

In a fifth aspect, the invention provides an electrode comprising a particulate material as defined with reference to the first and/or third aspect of the invention in electrical contact with a current collector. The particulate material used to prepare the electrode composition of the fifth aspect of the invention may have any of the features described as preferred or optional with regard to the first aspect of the invention and/or may be prepared by a process including any of the features described as preferred or optional with regard to the second aspect of the invention.

As used herein, the term current collector refers to any conductive substrate which is capable of carrying a current to and from the electroactive particles in the electrode composition. Examples of materials that can be used as the current collector include copper, aluminium, stainless steel, nickel, titanium and sintered carbon. Copper is a preferred material. The current collector is typically in the form of a foil or mesh having a thickness of between 3 to 500 pm. The particulate material of the invention may be applied to one or both surfaces of the current collector to a thickness which is preferably in the range of from 10 pm to 1 mm, for example from 20 to 500 pm, or from 50 to 200 pm.

Preferably, the electrode comprises an electrode composition as defined with reference to the fourth aspect of the invention in electrical contact with a current collector. The electrode composition may have any of the features described as preferred or optional with regard to the fourth aspect of the invention. In particular, it is preferred that the electrode composition comprises one or more additional particulate electroactive materials as defined above.

The electrode of the fifth aspect of the invention may suitably be fabricated by combining the particulate material of the invention (optionally in the form of the electrode composition of the invention) with a solvent and optionally one or more viscosity modifying additives to form a slurry.

The slurry is then cast onto the surface of a current collector and the solvent is removed, thereby forming an electrode layer on the surface of the current collector. Further steps, such as heat treatment to cure any binders and/or calendaring of the electrode layer may be carried out as appropriate. The electrode layer suitably has a thickness in the range of from 20 pm to 2 mm, preferably 20 pm to 1 mm, preferably 20 pm 10500 pm, preferably 20 pm to 200 pm, preferably 20 pm to 100 pm, preferably 20 pm to5O pm.

Alternatively, the slurry may be formed into a freestanding film or mat comprising the particulate material of the invention, for instance by casting the slurry onto a suitable casting template, removing the solvent and then removing the casting template. The resulting film or mat is in the form of a cohesive, freestanding mass which may then be bonded to a current collector by known methods.

The electrode of the fifth aspect of the invention may be used as the anode of a metal-ion battery.

Thus, in a sixth aspect, the present invention provides a rechargeable metal-ion battery comprising an anode, the anode comprising an electrode as described above, a cathode comprising a cathode active material capable of releasing and reabsorbing metal ions; and an electrolyte between the anode and the cathode.

The metal ions are preferably selected from lithium, sodium, potassium, calcium or magnesium.

More preferably the rechargeable metal-ion battery of the invention is a lithium-ion battery, and the cathode active material is capable of releasing and lithium ions.

The cathode active material is preferably a metal oxide-based composite. Examples of suitable cathode active materials include LiCoO2, LiCo099Al001O2, LiNiO2, LiMnO2, LiCo05Ni05O2, LiCo07Ni03O2, LiCo05Ni02O2, LiCo052Ni015O2, LiC005Ni015A1005O2, LiNi04Co03Mn03O2 and LiNi033Co033Mn034O2. The cathode current collector is generally of a thickness of between 3 to 500 pm. Examples of materials that can be used as the cathode current collector include aluminium, stainless steel, nickel, titanium and sintered carbon.

The electrolyte is suitably a non-aqueous electrolyte containing a metal salt, e.g. a lithium salt, and may include, without limitation, non-aqueous electrolytic solutions, solid electrolytes and inorganic solid electrolytes. Examples of non-aqueous electrolyte solutions that can be used include non-protic organic solvents such as propylene carbonate, ethylene carbonate, butylene carbonates, dimethyl carbonate, diethyl carbonate, gamma butyrolactone, 1,2-dimethoxyethane, 2-methyltetrahydrofuran, dimethylsulfoxide, 1,3-dioxolane, formamide, dimethylformamide, acetonitrile, nitromethane, methylformate, methyl acetate, phosphoric acid triesters, trimethoxymethane, sulfolane, methyl sulfolane and 1,3-dimethyl-2-imidazolidinone.

Examples of organic solid electrolytes include polyethylene derivatives polyethyleneoxide derivatives, polypropylene oxide derivatives, phosphoric acid ester polymers, polyester sulfide, polyvinylalcohols, polyvinylidine fluoride and polymers containing ionic dissociation groups.

Examples of inorganic solid electrolytes include nitrides, halides and sulfides of lithium salts such as Li5NI2, Li3N, Lil, LiSiO4, Li2SiS3, Li4SiO4, LiOH and Li3PO4.

The lithium salt is suitably soluble in the chosen solvent or mixture of solvents. Examples of suitable lithium salts include Lid, LiBr, Lil, LiCIO4, LiBF4, LiBC4O8, LiPF6, LiCF3SO3, LiA5F5, LiSbF6, LiAICI4, CH3SO3Li and CF3SO3Li.

Where the electrolyte is a non-aqueous organic solution, the battery is preferably provided with a separator interposed between the anode and the cathode. The separator is typically formed of an insulating material having high ion permeability and high mechanical strength. The separator typically has a pore diameter of between 0.01 and 100 pm and a thickness of between 5 and 300 pm. Examples of suitable electrode separators include a micro-porous polyethylene film.

The separator may be replaced by a polymer electrolyte material and in such cases the polymer electrolyte material is present within both the composite anode layer and the composite cathode layer. The polymer electrolyte material can be a solid polymer electrolyte or a gel-type polymer electrolyte.

In a seventh aspect, the invention provides the use of a particulate material as defined with reference to the first and/or third aspect of the invention as an anode active material. Preferably, the particulate material is in the form of an electrode composition as defined with reference to the fifth aspect of the invention, and most preferably the electrode composition comprises one or more additional particulate electroactive materials as defined above.

Claims

CLAIMS1. A particulate material consisting of a plurality of porous particles comprising comprising a mixture of silicon and germanium, wherein the mole fraction of germanium is from 0.01 to 50%, wherein the porous particles have a D50 particle diameter in the range of from 500 nm to 25 pm, and wherein the porous particles have an intra-particle porosity in the range of from 30 to 90%.
2. A particulate material according to claim 1, wherein the particulate material comprises at least 60 wt%, preferably at least 70 wt%, more preferably at least 75 wt%, more preferably at least wt%, and most preferably at least 85 wt% of the mixture of silicon and germanium.
3. A particulate material according to claim 1 or claim 2, wherein the mole fraction of germanium is at least 0.02%, at least 0.05%, at least 0.1%, at least 0.2%, at least 0.5%, at least 1%, at least 1.5%, at least 2% or at least 2.5%.
4. A particulate material according to any one of the preceding claims, wherein the mole fraction of germanium is no more than 40%, no more than 30%, no more than 25%, no more than 20%, no more than 15%, or no more than 10%.
5. A particulate material according to any one of the preceding claims, wherein the particulate material comprises a minor amount of one or more additional elements selected from aluminium, antimony, copper, magnesium, zinc, manganese, chromium, cobalt, molybdenum, nickel, beryllium, zirconium, iron, sodium, strontium, phosphorus, tin, ruthenium, gold, silver, and oxides thereof.
6. A particulate material according to claim 5, wherein the particulate material comprises a minor amount of aluminium, nickel, silver or copper, preferably aluminium.
7. A particulate material according to claim 6, wherein the particulate material comprises up to wt% aluminium, more preferably up to 30 wt% aluminium, more preferably up to 25 wt% aluminium, more preferably up to 20 wt% aluminium, more preferably up to 15 wt% aluminium, more preferably up to 10 wt% aluminium, and most preferably up to 5 wt% aluminium.
8. A particulate material according to claim 6 or claim 7, wherein the particulate material comprises at least 0.01 wt% aluminium, at least 0.1 wt% aluminium, at least 0.5 wt% aluminium, at least 1 wt% aluminium, at least 2 wt% aluminium, or at least 3 wt% aluminium.
9. A particulate material according to any one of the preceding claims, wherein the porous particles have a D50 particle diameter of at least 1 pm, preferably at least 1.5 pm, more preferably at least 2 pm, more preferably at least 2.5 pm, and most preferably at least 3 pm.
10. A particulate material according to any one of the preceding claims, wherein the porous particles have a 050 particle diameter of no more than 20 pm, preferably no more than 18 pm, more preferably no more than 15 pm, and most preferably no more than 12 pm.
11. A particulate material according to any one of the preceding claims, wherein the porous particles have a particle diameter of at least 200nm, preferably at least 500 nm, and still more preferably at least 800 nm, for example at least 1 pm, at least 2 pm, or at least 3 pm.
12. A particulate material according to any one of the preceding claims, wherein the porous particles have a 090 particle diameter of no more than 40 pm, preferably no more than 30 pm, more preferably no more than 25 pm, and most preferably no more than 20 pm.
13. A particulate material according to any one of the preceding claims, wherein the porous particles have a 099 particle diameter of no more than 50 pm, more preferably no more than 40 pm, more preferably no more than 30 pm, and most preferably no more than 25 pm.
14. A particulate material according to any one of the preceding claims, wherein the porous particles have a 050 particle diameter in the range of from ito 7 pm.
15. A particulate material according to claim 14, wherein the porous particles have a D particle diameter of at least 1.5 pm, preferably at least 2 pm, more preferably at least 2.5 pm, and most preferably at least 3 pm.
16. A particulate material according to claim 14 or claim 15, wherein the porous particles have a D5 particle diameter of no more than 6 pm, preferably no more than 5 pm, more preferably no more than 4.5 pm, more preferably no more than 4 pm, and most preferably no more than 3.5 pm.
17. A particulate material according to any one of claims 1 to 13, wherein the porous particles have a D50 particle diameter in the range of from greater than 5 to 25 pm.
18. A particulate material according to claim 17, wherein the porous particles have a 050 particle diameter of at least 6 pm, preferably at least 7 pm, more preferably at least 8 pm, and most preferably at least 10 pm.
19. A particulate material according to claim 17 or claim 18, wherein the porous particles have a D50 particle diameter of no more than 20 pm, preferably no more than 18 pm, more preferably no more than 15 pm, and most preferably no more than 12 pm.
20. A particulate material according to any one of the preceding claims, wherein the porous particles have a particle size distribution span of 5 or less, preferably 4 or less, more preferably 3 or less, more preferably 2 or less, and most preferably 1.5 or less.
21. A particulate material according to any one of the preceding claims, wherein the porous particles have an intra-particle porosity of at least 40%, preferably at least 50%, and more preferably at least 60%
22. A particulate material according to any one of the preceding claims, wherein the porous particles have an intra-particle porosity of no more than 87%, preferably no more than 86%, more preferably no more than 85%, more preferably no more than 80%, and most preferably no more than 75%.
23. A particulate material according to any one of the preceding claims, wherein the particulate material has a pore diameter distribution having a peak in the range of from 50 nm to less than 500 nm, as determined by mercury porosimetry.
24. A particulate material according to any one of the preceding claims, wherein the particulate material has a pore diameter distribution having at least one peak at a pore size less than 460 nm, preferably less than 420 nm, more preferably less than 400 nm, more preferably less than 380 nm, more preferably less than 360 nm, and most preferably less than 350 nm, as determined by mercury porosimetry.
25. A particulate material according to any one of the preceding claims, wherein the particulate material has a pore diameter distribution having at least one peak at a pore size of more than 60 nm, more preferably more than 80 nm, more preferably more than 100 nm, as determined by mercury porosimetry.
26. A particulate material according to any one of the preceding claims, wherein the porous particles are spheroidal particles having an average sphericity Say of at least 0.70, preferably at least 0.85, more preferably at least 0.90, preferably at least 0.92, more preferably at least 0.93, more preferably at least 0.94, more preferably at least 0.95, more preferably at least 0.96, more preferably at least 0.97, more preferably at least 0.98 and most preferably at least 0.99.
27. A particulate material according to any one of the preceding claims, wherein the porous particles have an average aspect ratio of less than 3:1, preferably no more than 2.5:1, more preferably no more than 2:1, preferably no more than 1.8:1, more preferably no more than 1.6:1, more preferably no more than 1.4:1 and most preferably no more than 1.2:1.
28. A particulate material according to any one of the preceding claims, having a BET surface area of less than 300 m2Ig, preferably less than 200 m2/g, more preferably less than 150 m2/g, more preferably less than 120 m2/g.
29. A particulate material according to any one of the preceding claims, having a BET surface area of at least 10 m2/g, at least 15 m2/g at least 20 m2!g, or at least 50 m2/g.
30. A particulate material according to any one of the preceding claims, wherein the porous particles comprise a network of interconnected irregular elongate structural elements, preferably wherein the porous particles comprise structural elements having an aspect ratio of at least 2:1 and more preferably at least 5:1.
31. A particulate material according to claim 30, wherein the porous particles comprise structural elements having a smallest dimension less than 300 nm, preferably less than 200 nm, more preferably less than 150 nm, and a largest dimension at least twice, and preferably at least five times the smallest dimension.
32. A particulate material according to claim 30 or claim 31, wherein the porous particles comprise structural elements having a smallest dimension of at least 10 nm, preferably at least 20 nm, preferably at least 30 nm.
33. A particulate material according to any one of the preceding claims, wherein at least a portion of the structural elements of the porous particles comprise both silicon and germanium, and wherein the concentration of germanium at the surfaces of the structural elements is higher than the concentration at the centre of the structural elements.
34. A process for the preparation of a particulate material consisting of a plurality of porous particles comprising a mixture of silicon and germanium, the process comprising the steps of: (a) providing a plurality of alloy particles comprising: (i) from 11 to 45 wt% of a mixture of silicon and germanium wherein the mole fraction of germanium is from 0.01 to 50%; and (ii) a matrix metal component; wherein said alloy particles have a D50 particle diameter in the range of from 500 nm to 25 pm, and wherein said alloy particles comprise discrete silicon and germanium containing structures dispersed in the matrix metal component; (b) leaching the alloy particles from step (a) to remove at least a portion of the matrix metal component and to at least partially expose the silicon and germanium containing structures; wherein the porous particles comprise no more than 40% by weight of the matrix metal component.
35. A process according to claim 34, wherein the alloy particles have a D50 particle diameter of at least 1 pm, preferably at least 1.5 pm, more preferably at least 2 pm, more preferably at least 2.5 pm, and most preferably at least 3 pm.
36. A process according to claim 34 or claim 35, wherein the alloy particles have a 050 particle diameter of no more than 20 pm, preferably no more than 18 pm, more preferably no more than 15 pm, and most preferably no more than 12 pm.
37. A process according to any one of claims 34 to 36, wherein the alloy particles have a 010 particle diameter of at least 200nm, preferably at least 500 nm, and still more preferably at least 800 nm, for example at least 1 pm, at least 2 pm, or at least 3 pm.
38. A process according to any one of claims 34 to 37, wherein the alloy particles have a D particle diameter of no more than 40 pm, preferably no more than 30 pm, more preferably no more than 25 pm, and most preferably no more than 20 pm.
39. A process according to any one of claims 34 to 38, wherein the alloy particles have a D particle diameter of no more than 50 pm, preferably no more than 40 pm, more preferably no more than 30 pm, and most preferably no more than 25 pm.
40. A process according to any one of claims 34 to 39, wherein the alloy particles have a particle size distribution span of 5 or less, preferably 4 or less, more preferably 3 or less, more preferably 2 or less, and most preferably 1.5 or less.
41. A process according to any one of claims 34 to 40, wherein the alloy particles have an average sphericity S8., of at least 0.70, preferably at least 0.85, more preferably at least 0.90, preferably at least 0.92, more preferably at least 0.93, more preferably at least 0.94, more preferably at least 0.95, more preferably at least 0.96, more preferably at least 0.97, more preferably at least 0.98, and most preferably at least 0.99.
42. A process according to any one of claims 34 to 41, wherein the alloy particles have an average aspect ratio of less than 3:1, preferably no more than 2.5:1, more preferably no more than 2:1, preferably no more than 1.8:1, more preferably no more than 1.6:1, more preferably no more than 1.4:1 and most preferably no more than 1.2:1.
43. A process according to any one of claims 34 to 42, wherein the mole fraction of germanium in the alloy particles is at least 0.02%, at least 0.05%, at least 0.1%, at least 0.2%, at least 0.5%, at least 1%, at least 1.5%, at least 2% or at least 2.5%, based on the total molar amount of silicon and germanium.
44. A process according to any one of claims 34 to 43, wherein the mole fraction of germanium in the alloy particles is no more than 40%, no more than 30%, no more than 25%, no more than 20%, no more than 15%, or no more than 10%, based on the total molar amount of silicon and germanium.
45. A process according to any one of claims 34 to 44, wherein the alloy particles comprise at least 11.2 wt%, more preferably at least 11.5 wt%, more preferably at least 11.8 wt%, more preferably at least 12 wt%, and most preferably at least 12.2 wt% in total of silicon and germanium.
46. A process according to any one of claims 34 to 45, wherein the alloy particles comprise less than 40 wt%, preferably less than 35 wt%, more preferably less than 30 wt%, more preferably less than 25 wt%, more preferably less than 20 wt%, and most preferably less than 18 wt% in total of silicon and germanium.
47. A process according to any one of claims 34 to 46, wherein the matrix metal component of the alloy particles is selected from aluminium, antimony, copper, magnesium zinc, manganese, chromium, cobalt, molybdenum, nickel, beryllium, zirconium, iron, tin, ruthenium, silver, gold and combinations thereof.
48. A process according to claim 47, wherein the matrix metal component of the alloy particles comprises at least 50 wt%, preferably at least 60 wt%, more preferably at least 70 wt%, more preferably at least 80 wt%, more preferably at least 90 wt% and most preferably at least 95 wt% of one or more of aluminium, nickel, silver or copper, preferably of aluminium.
49. A process according to any one of claims 34 to 48, wherein the particulate material comprises no more than 30 wt%, more preferably no more than 25 wt%, more preferably no more than 20 wt%, more preferably no more than 15 wt%, more preferably no more than 10 wt%, and most preferably no more than 5 wt% of the matrix metal component, relative to the total weight of the particulate material.
50. A process according to any one of claims 34 to 49, wherein the particulate material comprises at least 0.01 wt%, at least 0.1 wt%, at least 0.5 wt%, at least 1 wt%, at least 2 wt%, or at least 3 wt% of the matrix metal component, relative to the total weight of the particulate material.
51. A particulate material consisting of a plurality of porous particles comprising an electroactive material, wherein the particulate material is obtainable by a process as defined in any one of claims 34 to 50.
52. A particulate material according to claim 51, wherein the particulate material is as defined in any one of claims ito 33.
53. A composition comprising a particulate material as defined in any one of claims ito 33, 51 and 52, and at least one other component.
54. A composition according to claim 53, which is an electrode composition comprising a particulate material as defined in any one of claims 1 to 33, 51 and 52, and at least one other component selected from: (i) a binder; (ii) a conductive additive; and (iii) an additional particulate electroactive material.
55. An electrode composition according to claim 54, comprising at least one additional particulate electroactive material.56 An electrode composition according to claim 55, wherein the at least one additional particulate electroactive material is selected from graphite, hard carbon, gallium, aluminium and lead, preferably graphite.57. An electrode composition according to claim 55 or claim 56, wherein the at least one additional particulate electroactive material is in the form of spheroidal particles having an average sphericity of at least 0.70, preferably at least 0.85, more preferably at least 0.90, more preferably at least 0.92, more preferably at least 0.93, more preferably at least 0.94, and most preferably at least 0.95.58. An electrode composition according to any one of claims 55 to 57, wherein the at least one additional particulate electroactive material has an average aspect ratio of less than 3:1, preferably no more than 2.5:i, more preferably no more than 2:1, more preferably no more than 1.8:1, more preferably no more than 1.6:1, more preferably no more than 1.4:1 and most preferably no more than 1.2:1.59. An electrode composition according to any one of claims 55 to 58, wherein the at least one additional particulate electroactive material has a D50 particle diameter in the range of from 10 to pm, preferably from 10 to 40 pm, more preferably from 10 to 30 pm, more preferably from 10 to 25 pm, and most preferably from 15 to 25 pm.60. An electrode composition according to any one of claims 55 to 59, wherein the at least one additional particulate electroactive material has a D10 particle diameter of at least 5 pm, preferably at least 6 pm, more preferably at least 7 pm, more preferably at least 8 pm, more preferably at least 9 pm, and still more preferably at least 10pm.61. An electrode composition according to any one of claims 55 to 60, wherein the at least one additional particulate electroactive material has a D90 particle diameter of no more than 100 pm, preferably no more than 80 pm, more preferably no more than 60 pm, more preferably no more than 50 pm, and most preferably no more than 40 pm.62. An electrode composition according to any one of claims 55 to 61, wherein the particulate material of the invention is as defined in any one of claims 14 to 16.63. An electrode composition according to claim 62, wherein the ratio of the at least one additional particulate electroactive material to the particulate material of the invention is in the range of from 50:50 to 99:1 by weight, preferably from 60:40 to 98:2 by weight, more preferably 70:30 to 97:3 by weight, more preferably 80:20 to 96:4 by weight, and most preferably 85:15 to 95:5 by weight.64. An electrode composition according to any one of claims 55 to 63, wherein the particulate material of the invention and the at least one additional particulate material together constitute at least 50% by weight, preferably at least 60% by weight, more preferably at least 70 wt%, and most preferably at least 80 wt%, for example at least 85 wt%, at least 90 wt%, or at least 95 wt% of the total weight of the electrode composition.65. An electrode composition according to claim 54, wherein the particulate material of the invention is as defined in any one of claims 17 to 19.66. An electrode composition according to claim 65, wherein the particulate material of the invention constitutes at least 50% by weight, preferably at least 60% by weight, more preferably at least 70 wt%, and most preferably at least 80 wt%, for example at least 85 wt%, at least 90 wt%, or at least 95 wt% of the total weight of the electrode composition.67. An electrode composition according to any one of claims 54 to 66, comprising a binder, preferably in an amount of from 0.5 to 20 wt%, more preferably ito 15 wt% and most preferably 2 to 10 wt%, based on the total weight of the electrode composition.68. An electrode composition according to any one of claims 54 to 67, comprising one or more conductive additives, preferably in a total amount of from 0.5 to 20 wt%, more preferably ito 15 wt% and most preferably 2 to 10 wt%, based on the total weight of the electrode composition.69. An electrode comprising a particulate material as defined in any one of claims 1 to 33, 51 and 52 in electrical contact with a current collector.70. An electrode according to claim 69, wherein the particulate material is in the form of an electrode composition as defined in any one of claims 54 to 68.71. A rechargeable metal-ion battery comprising: (i) an anode, wherein the anode comprises an electrode as described in claim 69 or claim 70; (ii) a cathode comprising a cathode active material capable of releasing and reabsorbing metal ions; and (iH) an electrolyte between the anode and the cathode.72. Use of a particulate material as defined in any one of claims 1 to 33, 51 and 52 as an anode active material.73. Use according to claim 72, wherein the particulate material is in the form of an electrode composition as defined in any one of claims 54 to 68.