Patent Application
20230317924
The present invention relates to a silicon and graphite containing composite material. More particularly, the composite material of the present invention is intended for use as an anode material in lithium-ion batteries.
In one highly preferred form, the present invention further relates to an anode composite comprising a silicon and graphite containing composite material.
The present invention still further relates to a method for producing a silicon and graphite containing composite material.
Presently, silicon/graphite composites are understood to show some promise as a lithium-ion anode material. However, there are number of well-known and understood disadvantages relating to silicon/graphite composites. These disadvantages include high levels of expansion, up to 400%, and poor cycle life. Any commercial application of silicon/graphite composites would need to address at least these issues.
The irreversible capacity loss of presently known and understood silicon-containing anodes is currently addressed through the use of nano-structured silicon particles as the electroactive material. It has been reported that silicon nanoparticles and nanostructured silicon are more tolerant of volume changes on charging and discharging when compared to microscale particles (XH Liu et al., “Size-Dependent Fracture of Silicon Nanoparticles During Lithiation”, ACS Nano, 2012, 6 (2), 1522-1531). However, nanoscale particles are not considered to be suitable for commercial scale applications as they are known to be difficult to prepare and handle. In addition to issues relating to silicon particle size, the nature of the silicon surfaces also plays an important role in the formation of the Solid Electrode Interface (SEI) and electronic conductivity. The SEI on the surface of the silicon is not stable and continuously consumes lithium, requiring the modification of the surface so as to avoid, or at least reduce, the exposure of silicon to the electrolyte. Further, silicon is not considered a particularly good conductive material.
A core-shell structured graphite/silicon@pyrolysed-carbon (Gr/Si@C) composite has been fabricated, including mechanical milling, spray drying, and the use of pitch (Li et al, “Scalable synthesis of a novel structured graphite/silicon/pyrolysed carbon composite as anode material for high-performance lithium-ion batteries”, Journal of Alloys and Compounds 688 (2016) 1072-1079). In this prior art process, what appears to be a relatively scalable and cost-effective method is demonstrated. Due to the carbon coating of the silicon and graphite present, the cyclability has been much improved relative to much prior art. However, the demonstrated low first cycle efficiency of 77.9% at a capacity of 637.7 mAh/g is far from the level required of the battery industry.
International Patent Application PCT/GB2018/051689 (WO 2018/229515) describes firstly the production of silicon nanoparticles through the ball milling of silicon microparticles in a solvent. A pyrolytic ‘amorphous’ carbon precursor containing at least one oxygen or nitrogen atom is added to silicon nanoparticles and a solvent, the solvent is removed, and the remaining silicon nanoparticles are coated with a thick layer of the pyrolytic carbon precursor. In turn these coated silicon nanoparticles are pyrolysed, forming composite particles comprising a plurality of silicon nanoparticles dispersed in a conductive pyrolytic carbon matrix. In this prior art process, due to the use of a large amount of amorphous carbon, significant First Cycle Loss (FCL) and expansion are still substantial problems. It is believed that the amorphous carbon contributes a large proportion of the unacceptable FCL and expansion experienced. In addition, once the Si@C expands, the connection between silicon and carbon weakens, as amorphous carbon is not elastic.
Using electroless plating of a thick layer of nickel on a micron size silicon, a graphene-caged silicon structure was formed and outstanding cell performance, including high capacity, small expansion, long cycle life and low FCL, was achieved (Li et al., “Growth of conformal graphene cages on micrometre-sized silicon particles as stable battery anodes”, Nature Energy, Vol. 1., Article No. 15029 (2016)).
Few-layer graphene-coated silicon nanoparticles have also been described as being formed by way of Chemical Vapour Deposition (CVD) (Son et al., “Silicon carbide-free graphene growth on silicon for lithium-ion battery with high volumetric energy density”, Nature Communications, Vol. 6., Article No. 7393 (2015)). Again, these coated silicon nanoparticles are said to provide outstanding cell performance, including high capacity, small expansion, long cycle life and low FCL. However, the processes by which these graphene-coated materials are formed are known to be expensive and are not scalable, particularly not to the level required for commercial application.
A more cost-effective method of coating few-layer graphene on silicon is described in the Patent Publication WO 2015/073674 A1, through the coating of silicon with graphene by way of bead-milling of a mixture of graphite and silicon. However, using this method does not yield a product with the required performance. For example, there is a substantial capacity drop (>45%) in the first 200 cycles.
US 2016/064731 (Jung Sung-Ho, et. al.) describes the manufacture of a carbon-silicon composite in which a silicon-carbon-polymer matrix is prepared and that is in turn heat-treated to carbonize the matrix. This carbonized matrix is pulverised and mixed with a carbon raw material, before then being carbonized to produce the carbon-silicon composite of the invention. This carbon-silicon composite is used as an anode slurry to provide an anode for a secondary battery.
US 2018/097229 (Jo Sungnim, et. al.) describes the manufacture of a negative active material comprising the formation of a silicon-carbon primary particle having an apparent density of about 2 grams per cubic centimetre or greater, thermally treating a plurality of the primary particles, a second carbonaceous material, and a foaming agent, to form a porous silicon-carbon secondary particle. This secondary particle may or may not be provided with a further coating layer.
The composite material and method of the present invention has as one object thereof to overcome substantially one or more of the above mentioned problems associated with prior art processes, or to at least provide a useful alternative thereto.
The preceding discussion of the background art is intended to facilitate an understanding of the present invention only. This discussion is not an acknowledgement or admission that any of the material referred to is or was part of the common general knowledge as at the priority date of the application.
Throughout the specification and claims, unless the context requires otherwise, the word “comprise” or variations such as “comprises” or “comprising”, will be understood to imply the inclusion of a stated integer or group of integers but not the exclusion of any other integer or group of integers.
Throughout the specification and claims, unless the context requires otherwise, references to “ball milling” are to be understood to include reference to “bead milling”, and references to “bead milling” are to be understood to include reference to “ball milling”. Similarly, unless the context requires otherwise, references to “ball milling” and/or “bead milling” are to be understood to include reference to “grinding”, and references to “grinding” are to be understood to include reference to “bead milling” and/or “ball milling” as the context requires.
Throughout the specification and claims, unless the context requires otherwise, references to “mechanofusion” are to be considered to refer to mixing that induces mechano-chemical reactions between multiple particles creating new particles having new characteristics. Similarly, references to “mixing” are to be understood to include reference to mechanofusion.
In accordance with the present invention there is provided a silicon and graphite containing composite material comprising a plurality of silicon nanoparticles coated with graphite particles, few-layer graphene particles, graphite nanoparticles, a carbon matrix, and an amorphous carbon external shell, wherein each of the graphite particle coated silicon nanoparticles, the few-layer graphene particles, and the graphite nanoparticles are held within the carbon matrix.
Preferably, the carbon matrix is provided in the form of an amorphous carbon matrix, a crystalline carbon matrix, or a combination of both an amorphous carbon matrix and a crystalline carbon matrix.
The graphite particles are preferably in the form of graphene-like nano-sheets.
In one form a further outside layer of amorphous carbon is provided about the plurality of silicon nanoparticles, graphite particles, and carbon matrix, but within the shell.
The outside layer of amorphous carbon may further comprise one or more oxides. The one or more oxides may preferably be present in the form of Al2O3, TiO2, ZrO2, BaTiO3, MgO, CuO, ZnO, Fe2O3, GeO2, Li2O, MnO, NiO, or zeolite, or any combination thereof.
Preferably, the oxides have a particle size in the range of about 20 nm to 1 micron.
Preferably, the composite material possesses a level of elastic properties conferred by the presence of one or more of the graphite particles, graphene, few-layer graphene and graphite nanoparticles that may be provided within the amorphous carbon matrix.
In accordance with the present invention there is still further provided an anode composite comprising a composite material as described hereinabove.
In accordance with the present invention there is yet still further provided a method for the production of a composite material, the method comprising the method steps of:
Preferably, the shell further comprises one or more oxides. Still preferably, the one or more oxides are provided in the form of Al2O3, TiO2, ZrO2, BaTiO3, MgO, CuO, ZnO, Fe2O3, GeO2, Li2O, MnO, NiO, or zeolite, or combination thereof.
In one form of the present invention, the method further comprises an initial step in which a silicon material is subjected to a size-reduction step, in a solvent, to produce the silicon nanoparticles of step (i).
Preferably, the silicon material of the initial step is provided in the form of micron-scale silicon particles.
In one form of the present invention, the size reduction step of step (i) provides silicon nanoparticles having a size of between about 20 to 200 nm.
Still preferably, the size-reduction steps of the initial step and step (i) are each a grinding step. Still further preferably, the grinding steps are conducted in one or more bead mills.
In one form of the present invention, the solvent is provided in the form of a non-aqueous solvent. Preferably, the solvent is provided in the form of isopropyl alcohol.
In one form of the present invention, the polymer is selected from the group of polyethylene oxide (PEO), polyvinyl alcohol (PVA), polyvinylidine fluoride (PVDF), poly(vinylidenefluoride-co-hexafluoropropylene) (PVDF-HFP), and poly(methyl methacrylate) (PMMA).
The processing of step (ii) may, in one form of the present invention, preferably be provided in the form of spray-drying, in the presence of a binder.
The processing of step (ii) may, in a further form of the present invention, be provided in the form of a mixing step. The mixing step preferably comprising a hybridising process whereby the secondary particles or product so produced is spheronised.
Preferably, the thermal treatments of steps (iii) and (v) are provided in the form of pyrolysis.
Still preferably, the thermal treatments of steps (iii) and (v) convert any binder present to amorphous carbon.
The temperature of the thermal treatment of step (iii) is preferably lower than that of step (v).
After the thermal treatment of step (iii), the composite material’s surface area (BET) is preferably in the range of about 70-120 m2/g. After the thermal treatment of step (v), the material’s BET is preferably in the range of about 10-30 m2/g.
Preferably, the graphite particles of the milling step (i) are provided in the form of pre-exfoliated graphite particles.
In one form of the present invention, the milling process of step (i) produces graphene that attaches to the silicon nanoparticles.
The thermal treatment of step (iii) is preferably conducted at a temperature in the range of about 500° C. to 700° C.
Still preferably, the thermal treatment of step (v) is conducted at a temperature in the range of about 750° C. to 1100° C.
Yet still preferably, the thermal treatment of step (v) is conducted at a temperature in the range of about 850° C. to 1000° C.
In accordance with the present invention there is further provided a method for the production of a composite material, the method comprising the method steps of:
Preferably, the processing of step (ii) is conducted by way of spray-drying or mechanofusion.
In accordance with the present invention there is still further provided a method for the production of an anode composite, the method comprising the method steps of:
In one form of the present invention, the method further comprises an initial step in which a silicon material is subjected to a size-reduction step, in a solvent, to produce the silicon particles of step (i).
Preferably, the silicon material of the initial step is provided in the form of micron-scale silicon particles.
Still preferably, the size-reduction steps of the initial step and step (i) are each a grinding step. Still further preferably, the grinding steps are conducted in one or more bead mills.
In one form of the present invention, the solvent is provided in the form of a non-aqueous solvent. Preferably, the solvent is provided in the form of isopropyl alcohol.
In one form of the present invention, the polymer is selected from the group of polyethylene oxide (PEO), polyvinyl alcohol (PVA), polyvinylidine fluoride (PVDF), poly(vinylidenefluoride-co-hexafluoropropylene) (PVDF-HFP), and poly(methyl methacrylate) (PMMA).
The processing of step (ii) may, in one form of the present invention, preferably be provided in the form of spray-drying, in the presence of a binder.
The processing of step (ii) may, in a further form of the present invention, be provided in the form of a mechanofusion or mixing step. The mixing step preferably comprising a hybridising process whereby the secondary particles or product so produced is spheronised.
Preferably, the thermal treatment of step (iii) is provided in the form of pyrolysis.
Still preferably, the thermal treatment of step (iii) converts any binder present to amorphous carbon.
Preferably, the graphite particles of the milling step (i) are provided in the form of pre-exfoliated graphite particles.
In one form of the present invention, the milling process of step (i) produces graphene that attaches to the silicon nanoparticles.
The thermal treatment of step (iii) is preferably conducted at a temperature in the range of about 500° C. to 700° C.
Still preferably, the thermal treatment of step (v) is conducted at a temperature in the range of about 750° C. to 1100° C.
Yet still preferably, the thermal treatment of step (v) is conducted at a temperature in the range of about 850° C. to 1000° C.
The present invention will now be described, by way of example only, with reference to two embodiments thereof and the accompanying drawings, in which:-
The present invention provides a silicon and graphite containing composite material comprising a plurality of silicon nanoparticles, graphite particles, a carbon matrix, and an external shell, wherein the silicon nanoparticles and graphite particles are held within the carbon matrix. The carbon matrix is provided in the form of an amorphous carbon matrix, a crystalline carbon matrix, or a combination of both an amorphous carbon matrix and a crystalline carbon matrix.
The silicon nanoparticles may be coated in the graphite particles. The graphite particles may be provided in the form of graphene-like nano-sheets. The composite material may further comprise a plurality of few-layer graphene particles. The composite material may still further comprise graphite particles at greater than nanoparticle scale. The composite material possesses a level of elastic properties conferred by the presence of one or more of the graphite particles, graphene, few-layer graphene and graphite nanoparticles (GNP) provided within the amorphous carbon matrix.
In one form a further outside layer of amorphous carbon is provided about the plurality of silicon nanoparticles, graphite particles, and carbon matrix, but within the shell.
The outside layer of amorphous carbon may further comprise one or more oxides. The one or more oxides may be present in the form of Al2O3, TiO2, ZrO2, BaTiO3, MgO, CuO, ZnO, Fe2O3, GeO2, Li2O, MnO, NiO, or zeolite, or a combination thereof. The oxides have, for example, a particle size in the range of 20 nm to 1 micron.
The present invention further provides an anode composite comprising a composite material in one of the forms as described hereinabove and/or hereinafter.
The present invention still further provides a method for the production of a composite material, the method comprising the method steps of:
The shell further comprises one or more oxides. For example, the one or more oxides are provided in the form of Al2O3, TiO2, ZrO2, BaTiO3, MgO, CuO, ZnO, Fe2O3, GeO2, Li2O, MnO, NiO, or zeolite, or a combination thereof.
In one form of the present invention, the method further comprises an initial step in which a silicon material is subjected to a size-reduction step, in a solvent, to produce the silicon nanoparticles of step (i).
The silicon material of the initial step is provided in the form of micron-scale silicon particles. The size-reduction steps of the initial step and step (i) are each a grinding step. Still further preferably, the grinding steps are conducted in one or more bead mills.
The solvent is provided in the form of a non-aqueous solvent. One suitable non-aqueous solvent is isopropyl alcohol (IPA).
If a polymer is present, the polymer is, for example, selected from the group of polyethylene oxide (PEO), polyvinyl alcohol (PVA), polyvinylidine fluoride (PVDF), poly(vinylidenefluoride-co-hexafluoropropylene) (PVDF-HFP), and poly(methyl methacrylate) (PMMA). The polymer is present in the range of 1 to 40% wt/wt, and the silicon particles present in the range of 1 to 80% wt/wt. In one preferred form of the present invention the polymer is present at 5% wt/wt and the silicon particles present at 10% wt/wt.
The processing of step (ii) may be provided in the form of spray-drying, in which the presence of a binder is preferred. Alternatively, the processing of step (ii) may be provided in the form of a mixing or mechanofusion step. The mixing step comprising a hybridising process whereby the secondary particles or product so produced is spheronised.
The thermal treatment of step (iii) is provided in the form of pyrolysis. The thermal treatment of step (iii) converts any binder present to amorphous carbon.
The graphite particles of the size reduction step (i) are provided in the form of pre-exfoliated graphite particles, whereby the size reduction process produces graphene that attaches to the silicon nanoparticles.
The thermal treatment of step (iii) is conducted at a temperature in the range of about 500° C. to 700° C. The thermal treatment of step (v) is conducted in the range of about 750° C. to 1100° C., or in one preferred form, in the range of about 850° C. to 1000° C.
The present invention further provides a method for the production of a composite material, the method comprising the method steps of:
The present invention still further provides a method for the production of an anode composite, the method comprising the method steps of:
In one form of the present invention, the method further comprises an initial step in which a silicon material is subjected to a size-reduction step, in a solvent, to produce the silicon nanoparticles of step (i). The silicon material of the initial step is provided in the form of micron-scale silicon particles.
The size-reduction steps of the initial step and step (i) are each a grinding step. The grinding steps are conducted in one or more bead mills.
In one form of the present invention, the solvent is provided in the form of a non-aqueous solvent. The solvent may be provided in the form of isopropyl alcohol.
Where present, the polymer is selected from the group of polyethylene oxide (PEO), polyvinyl alcohol (PVA), polyvinylidine fluoride (PVDF), poly(vinylidenefluoride-co-hexafluoropropylene) (PVDF-HFP), and poly(methyl methacrylate) (PMMA). The polymer is present in the range of 1 to 40% wt/wt, and the silicon particles present in the range of 1 to 80% wt/wt. In one preferred form of the present invention the polymer is present at 5% wt/wt and the silicon particles present at 10% wt/wt.
The processing of step (ii) may be provided in the form of spray-drying, in which the presence of a binder is preferred. Alternatively, the processing of step (ii) may be provided in the form of a mixing step. The mixing step comprising a hybridising process whereby the product is spheronised.
The thermal treatment of step (iii) is provided in the form of pyrolysis. The thermal treatment of step (iii) converts any binder present to amorphous carbon.
The graphite particles of the milling step (i) are provided in the form of pre-exfoliated graphite particles.
In one form of the present invention, the milling process of step (i) produces graphene that attaches to the silicon nanoparticles.
The thermal treatment of step (iii) is conducted at a temperature in the range of about 500° C. to 700° C. The thermal treatment of step (v) is conducted in the range of about 750° C. to 1100° C., or in one preferred form, in the range of about 850° C. to 1000° C.
In
The silicon nanoparticles are provided, for example, in the range of about 80 nm - 150 nm. The graphite particles 20 may be provided at a size of less than about 30 micron. In one form of the present invention the graphite particles are provided in the form of pre-exfoliated graphite.
The process 10 further comprises a processing step 28, for example a spray-drying or mechanofusion step, in which the product of the milling step 18, with the addition of a binder 30, is spray dried or mechanofused to produce secondary particles or composites 32. The binder 30 may be provided in the form of pitch. Alternatively, another organic carbon source may constitute the binder 30. The composites 32 produced by the processing step 28 are, for example, of a size between 1 and 40 micron.
The process 10 still further comprises a thermal treatment step, for example pyrolysis 34, of the composites 32, by which the binder 30 is converted to amorphous carbon thereby forming a first intermediate composite material 12. The pyrolysis 34 takes place at a temperature of between about 500° C. to 700° C.
A further coating is applied to the first intermediate composite material 12 with a binder 36, for example an organic source, to form a second intermediate composite 38. In one form the binder 36 is provided in the form of pitch. The binder 36 may in some forms contain one of, or mixtures of, oxide materials. The oxide materials may for example be Al2O3, TiO2, ZrO2, BaTiO3, MgO, CuO, ZnO, Fe2O3, GeO2, Li2O, MnO, NiO, or Zeolite, or a combination thereof.
The process 10 still further comprises a further thermal treatment step, for example a pyrolysis step 40, in which the second intermediate composite 38 is pyrolysed and the binder 36 converted to amorphous carbon, thereby forming the composite material 42. The pyrolysis step 40 takes place at a temperature of between 750° C. to 1100° C., for example between 800° C. to 1000° C.
Because of the presence of the graphene, FLG and GNP, it is understood by the Applicants that the composite material possesses some elastic properties, which will be helpful to keep the micron size anode composites integrated during expansion (lithiation) and prevent or at least reduce the direct exposure of the silicon surfaces to an electrolyte.
The Applicants envisage that the benefits of the composite material of the present invention may include one or more of the use of low cost bead milling to produce nanoscale silicon particles in the range of 20 nm - 200 nm, low cost of bead milling for the formation of the graphene-coated silicon particles, and the generation of FLG and GNP during bead-milling. The use of FLG and GNP in the composite material and anode composites of the present invention, for increasing the composite’s elasticity, is a further advantage that may be realised by the present invention.
In accordance with another embodiment of the present invention, the ‘another’ size reduction step comprises the mixing of graphite particles with the silicon nanoparticles in the presence of a polymer whilst undergoing mixing/size reduction. The polymer is, for example, selected from the group of polyethylene oxide (PEO), polyvinyl alcohol (PVA), polyvinylidine fluoride (PVDF), Poly(vinylidenefluoride-co-hexafluoropropylene) (PVDF-HFP), and poly(methyl methacrylate) (PMMA). The polymer is present in the range of 1 to 40% wt/wt, and the silicon particles present in the range of 1 to 80% wt/wt. In one preferred form of the present invention the polymer is present at 5% wt/wt and the silicon particles present at 10% wt/wt.
The mixture so produced is passed to the processing of step (ii). The processing step is provided in the form of a mixing step, comprising a hybridising process whereby the product is spheronised. This hybridisation, or spheronisation, process provides ‘potato’ shaped particles. The mixed or spheronised product is in turn the passed to a thermal treatment step as described hereinabove in accordance with the first embodiment of the present invention. However, in this second embodiment the polymer becomes the carbon matrix within which the graphite particles are held/located as they surround the silicon nanoparticles, without the need for the additional binder utilised in the first embodiment of the present invention.
The process of the present invention may be better understood with reference to the following non-limiting example.
The Applicants have developed a unique exfoliated-graphite (referred to by the Applicants as Talga HSA) for multiple applications, described in detail in International Patent Application PCT/GB2018/052095 (WO 2019/020999), the entire content of which is incorporated herein by reference.
The Applicant’s HSA has expanded gaps between the graphene layers in the graphite. So, compared to typical or ‘normal’ graphite, the graphene layers would be easier to peel off from the HSA and create FLG during bead milling. As shown in
In order to make silicon/graphite composites (Gr@Si@C1@C2) in accordance with the present invention, micron size silicon particles were initially bead-milled into nanoscale particles (d50, 50-200 nm) in the non-aqueous solvent (for example IPA). HSA was then added into the mixtures of the milled silicon/IPA and subjected to further milling, whereby HSA produced FLG, graphene, GNP (graphite nanoparticles) and thin flakes. Spray drying was used to convert the nano-mixtures into micron size secondary particles. Due to the use of organic binders during spray drying or bead-milling, thermal treatment was applied to convert them into amorphous carbon.
Half-cell testing was carried out on the Gr@Si@C1@C2and the graphite control sample.
As can be readily appreciated, each of the silicon/graphite composites in accordance with the present invention show a higher capacity compared to that of the original graphite material, and their capacity increases with the loading of Gr@Si@C1@C2.
Further details of the half-cell testing on the Si/graphite composites, the results of which are shown in
In both the above detail and Table 1 below, CMC designates carboxymethyl cellulose and SBR designates styrene butadiene rubber.
During the bead milling, 1,5-dihydroxynaphlene was used to completely replace the EG. After spray drying and pyrolysis, the product is called Si@C. A number of comparisons are listed in Table 2 below. As can be seen, the example with 2.5% Si in Gr@Si@C1@C2has higher capacity than that with 3.4% Si in Si@C. With similar Si content, for example 10%, about 12% higher capacity can be found in the material of Gr@Si@C1@C2compared to that from Si@C. According to the capacity data from 5% and 10% Si@C, the capacity for 5% Si content is about 460 mAh/g, which is also about 10% less than that from Gr@Si@C1@C2with similar silicon content. In addition, it also indicates that a better cycling life could reasonably be expected for Gr@Si@C1@C2when it has a similar capacity with that of Si@C.
In terms of the testing performed in respect of the calendering effect, two coatings with similar capacity (~490 mAh/g) were used. For comparison, a 2-ton press was applied after coating. As shown in
In order to form Gr@Si@C1@C2, a relative low temperature, for example 500-700° C., is used for converting the binder 30 into carbon with high surface area and form Gr@Si@C, followed by a further coating with a binder 36, such as pitch or dihydroxynaphthalene, via ordinary mixing in a solvent. Then, evaporate the solvent and apply a further heat treatment at a relative high temperature, such as 800-1000° C., to form the final Gr@Si@C1@C2. Binder 36 may contain one of the contents or mixtures of Al2O3, TiO2 and/or other ceramic material.
It is envisaged that the spray dryer described hereinabove may be advantageously replaced with a spouted fluidised bed system, for example, without departing from the scope of the invention.
It is further envisaged that the size reduction step (i) provides graphite particles that have a high or large “aspect ratio”. Such graphite particles may encompass all or some of any anticipated graphite nanoparticles and any few layer graphene (FLG) produced.
As can be seen with reference to the above description, the composite material and method of producing same of the present invention provide one or more advantages when compared with the prior art, including low cost ball or bead milling to produce nanoscale silicon particles, low cost ball or bead milling to produce formation of graphene coated silicon particles, the generation of few-layer graphene and graphite nanoparticles through the same low cost ball or bead milling, and the ability to provide a composite material with a relatively high level of elasticity. In one form of the present invention, the second embodiment thereof described hereinabove, it is envisaged that graphene need not be present, rather graphite particles are sufficient.
It is reasonably envisaged that the composite material and anode material of the present invention will provide improved capacity and better cycle life, at least in part as a result of multiple layers of graphene-like materials covering the silicon nanoparticles after grinding, which provides an improved expansion tolerance and improved conductivity, such as may be due to the ‘graphene sliding’ effect. Further, the FLG and GNP created during bead-milling are understood to maintain the secondary particle’s conductivity during lithiation/delithiation (expansion/extraction) due to their high flexibility.
It is further envisaged that the coating step (iv) and further thermal treatment step (v) provide an additional protection to the Gr@Si@C or the intermediate composite, with the composites of silicon graphene, graphite and carbon matrix. This additional layer or shell assists in providing a stable SEI, reducing the contact between silicon and electrolyte, and reducing outward expansion during lithiation.
Modifications and variations such as would be apparent to the skilled addressee are considered to fall within the scope of the present invention.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2019902306 | Jun 2019 | AU | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/IB2020/056050 | 6/26/2020 | WO |
