Patent Application
20250070171
The present invention relates to an anode material. More particularly, the present invention further relates to an anode material comprising graphite particles of predominantly two distinct sizes.
The present invention still further relates to a method for producing an anode comprising an anode material in accordance with the present invention.
It is presently known that the mixing of natural with synthetic graphite products in the preparation of anode materials provides a cost benefit. However, it is also known that such mixed anode materials provide a relative loss of performance compared to anode materials prepared from natural graphite products alone. Such natural graphite products provide a typical particle sizing of about 10 μm. Specifically, the cycle and capacity performance metrics are typically diminished in mixed anode materials of the prior art.
The anode material and method of the present invention have as one object thereof to overcome substantially one or more of the above-mentioned problems associated with the prior art, 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, the word “graphite” or related terms such as “graphite particle(s)” will be understood to refer to natural graphite.
Throughout the specification and claims, unless the context requires otherwise, D50 is to be understood to refer to the median value of the particle size distribution. Put another way, it is the value of the particle diameter at 50% in a cumulative distribution. For example, if the D50 of a sample is a value X, 50% of the particles in that sample are smaller than the value X, and 50% of the particles in that sample are larger than the value X. Similarly, it is to be understood that reference to D50, unless the context requires otherwise, may include reference to volume, mass and number D50.
It is to be understood that the ranges provided herein include the stated range and any value or sub-range within the stated range. For example, a range from about 1 micrometer (μm) to about 2 μm, or about 1 μm to 2 μm, should be interpreted to include not only the explicitly recited limits of from between from about 1 μm to about 2 μm, but also to include individual values, such as about 1.2 μm, about 1.5 μm, about 1.8 μm, etc., and sub-ranges, such as from about 1.1 μm to about 1.9 μm, from about 1.25 μm to about 1.75 μm, etc. Furthermore, when “about” and/or “substantially” are/is utilised to describe a value, they are meant to encompass minor variations (up to +/−10%) from the stated value.
In accordance with the present invention there is provided an anode material comprising graphite particles of predominantly two distinct sizes.
Preferably, the two distinct sizes of the graphite particles have a D50 of:
In one preferred form of the present invention the two distinct sizes have a D50 of about:
Preferably, the ratio of smaller particles to larger particles is between about 10:90 to 50:50.
In a preferred form, the ratio of smaller particles to larger particles is about 30:70.
In one form, the larger graphite particles may be provided in the form of a synthetic graphite material. In another form, the larger graphite particles may be provided in the form of a natural graphitic material.
Still preferably, the smaller graphite particles are provided in the form of a natural graphite material.
In one preferred form of the present invention the smaller graphite particles are provided in the form of secondary graphite particles that preferably approximate an oblate spheroid.
Preferably, the secondary graphite particles comprise an aggregate of ground primary graphite particles providing the approximate oblate spheroid form.
The secondary graphite particles preferably have a D50 of less than:
The ground primary graphite particles are preferably spheronised and coated with a carbon-based material, being one or more of pitch, polyethylene oxide and polyvinyl oxide, then pyrolysed at a temperature between 880° C. to 1100° C. for a time in the range of 12 to 40 hours. The amount of carbon-based material in the secondary graphite particles is preferably in the range of 2 to 10 wt % relative to graphite.
The ground primary graphite particles preferably have a D50 of:
Preferably, the ground primary graphite particles have a surface area of:
Preferably, the ground primary graphite particles have XRD characteristics of one or more of a d002 of >3.35 Å, an Lc of >1000 Å and an La of >1000 Å. In a preferred form, the ground primary graphite particles have XRD characteristics of each of a d002 of >3.35 Å, an Lc of >1000 Å and an La of >1000 Å, and a purity of >99.9%.
In accordance with the present invention there is further provided a method for producing an anode material comprising graphite particles of predominantly two distinct sizes as described hereinabove.
In accordance with the present invention there is still further provided a method for the production of a battery comprising an anode material produced in accordance with the method described hereinabove.
The present invention will now be described, by way of example only, with reference to one embodiment thereof and the accompanying drawings, in which: —
The present invention provides an anode material comprising graphite particles of predominantly two distinct sizes.
The two distinct sizes of the graphite particles have a D50 of:
For example, the two distinct sizes have a D50 of about:
The ratio of smaller particles to larger particles is between about 10:90 to 50:50. In a preferred form, the ratio of smaller particles to larger particles is about 30:70.
The larger graphite particles may be provided in the form of either a synthetic graphite material or a natural graphitic material. The smaller graphite particles are provided in the form of a natural graphite material.
In one preferred form of the present invention the smaller graphite particles are provided in the form of secondary graphite particles that preferably approximate an oblate spheroid. The Applicant has previously described these secondary graphite particles in International Patent Application PCT/IB2020/058910 (WO2021/059171) and the entire content thereof is incorporated herein by reference. These secondary graphite particles are referred to by the Applicant as Talnode C™ or Talnode-C™.
The secondary graphite particles comprise an aggregate of ground primary graphite particles. The ground primary graphite particles are preferably spheronised and coated with a carbon-based material, being one or more of pitch, polyethylene oxide and polyvinyl oxide, then pyrolysed at a temperature between 880° C. to 1100° C. for a time in the range of 12 to 40 hours. The amount of carbon-based material in the secondary graphite particles is preferably in the range of 2 to 10 wt % relative to graphite.
The ground primary graphite particles may have a D50 of:
The ground primary graphite particles have a surface area of about 2 to 9 m2/g, for example 7 to 9 m2/g or 7 m2/g. Further, the ground primary graphite particles have XRD characteristics of one or more of a d002 of >3.35 Å, an Lc of >1000 Å and an La of >1000 Å. In a preferred form, the ground primary graphite particles have XRD characteristics of each of a d002 of >3.35 Å, an Lc of >1000 Å and an La of >1000 Å, and a purity of >99.9%.
The Applicant further envisages that the small graphite particles may be provided in the form of the ground primary graphite particle described herein or in the form of the silicon and graphite containing composite material described in the Applicant's International Patent Application PCT/IB2020/056050 (WO2020/261194), the entire content of which is hereby incorporated by reference.
The present invention further provides a method for producing an anode material comprising graphite particles of predominantly two distinct sizes as described hereinabove and described hereinafter.
The present invention still further provides a method for the production of a battery comprising an anode material prepared in accordance with the method described hereinabove and described hereinafter.
Table 1 below provides an example of an appropriate ground primary graphite particle for use in/as used in the method of the present invention, whilst Table 2 provides the elemental analysis thereof.
The process of the present invention may be better understood with reference to the following non-limiting example.
The procedure employed for the preparation of an anode, incorporating an anode material 10 in accordance with the present invention, is shown in
The anode material of the present invention employed, as is evidenced by
The electrode was prepared by using a CMC aqueous solution (BSH-12/1% aqueous solution), SBR (TRD2001™) binder. The slurry preparation procedure, the slurry solid content, and the viscosity of the prepared electrode are shown in
The minimum strength of the electrode was checked as to whether the electrode can be used in electrochemical testing.
The electrode was evaluated by winding it to the stainless steel rods of 4 mm in diameter. If cracking and peel-off occurred on the electrode, the strength of the electrode was judged to be insufficient. In such a case, the compounding ratio of the electrode would need to be re-evaluated.
The electrode was evaluated by impregnation to acetone (lower viscosity and more rapid permeability in electrolyte solutions) and checked whether peel-off from the current collector foil had occurred. If there was no peel-off nor any other problem evident from the acetone impregnation test, the strength of the electrode is considered to be sufficient. Note, peel-off and other problems in the reliability testing cannot be checked.
The surface of the electrode was rubbed with a paper waste to check for the presence of powder.
The prepared electrodes were adjusted to have the loading of 10.8 m/cm2 and a density of 1.44 g/cm3. There is no problem in terms of strength, and the conductivity is almost the same level as other samples. GTK1/ZH-16HY=30/70 shows some spring back effect during electrode preparation. Comparative details of properties of electrodes prepared either in accordance with the present invention (first column) or from a graphite material of a single size distribution (second column) are shown in Table 5 below.
The piece of sample electrode (size: 50 mm×20 mm, 10 cm2) was dried for 10 hr at 120° C. The electrode density was calculated after measuring the thickness and the weight without blank value of current collecting foils.
Half cell configuration is as shown in Table 6 below, and the half cell for evaluation is a three-pole type cell using Li metal as a counter electrode and a reference electrode. The evaluation electrode was punched a size of 17 mm Φ and then vacuum dried at 120° C.×10 h, cell preparation was performed in a dry box with a dew point of −80° C. or less. Moreover, the half cell characteristic was measured on the charging/discharging conditions, again as shown in Table 6 below.
The first cycle efficiency for GTK1/ZH-16HY is shown in
A single layer laminate cell was punched out with positive electrode (30 mm×50 mm) and negative electrode (32 mm×52 mm). The dried positive electrode (170° C.×10 h drying), and negative electrode (120° C.×10 h drying) are opposed through a separator (70° C.×10 h drying), and inserted into the Al laminate outer package. An electrolyte was then poured into the cell, followed by vacuum impregnation. Finally, the cell was sealed in a vacuum. The cell configuration is shown in
After preparation of the cell, the evaluation cell was subjected to charge/discharge tests of 3 cycles in a voltage range of 4.2V-2.7V at 25° C. Detailed test conditions are shown in
In battery/capacitor evaluation, the input/output characteristics, which greatly affect the resistance characteristics, are important. The input/output characteristics are directly related to the internal resistance of the device, and the DC internal resistance evaluation was conducted using “Current-Rest-Method” (C.R.M.) proposed by Dr. S. Yata as an input/output evaluation method (S. Yata, Practical evaluation technology on lithium ion batteries and capacitors (No. 1357), Technical Information Institute Co., Ltd. (2006); and S. Yata, The sequel to practical evaluation technology on lithium ion batteries and capacitors (No. 1516) Technical Information Institute Co., Ltd. (2009)).
In this method, it is possible to evaluate the resistance corresponding to the input/output of about up to 60 seconds, however, it is necessary to pay attention to the consideration when there are effects of relaxation (diffusion) due to at least concentration polarization, heterogeneous reaction, and resistance heating effect during charge/discharge (low temperature).
Charge process; Repeat “charge 12 min-rest 1 min” pattern up to upper limit of 4.2V, Current 0.5 C, Rest width ΔSOC10% equivalent.
Discharge process; Repeat “discharge 12 min-rest 1 min” pattern up to lower limit of 2.7V, Current 0.5 C, Rest width ΔSOC10% equivalent.
Measurement temperature; 25° C., 0° C. (only discharge process)
C.R.M. resistance; Resistance calculated from voltage change from 0 sec to 60 sec. Measure time-rate resistance up to 60 seconds for each SOC.
Ohmic component; Resistance calculated from voltage change from 0 sec to 1 sec. (1 second rate resistance).
Relaxation component; Resistance calculated from voltage change from 1 sec to 60 sec. Equilibrium/relaxation resistance from 1 sec to 60 sec.
A summary of the CRM resistance and A.C. Resistance is provided in Table 8 below:
The measurement conditions of discharge rate characteristics were:
In the case of the GTK1/ZH-16HY electrode the maintenance rate of the 2 C rate is 86.6%, which is slightly lower than that of Talnode-C (GTK1) but relatively maintained. There is no significant reduction due to the mixing or ‘bi-modal’ distribution. The comparative discharge rate characteristics are shown in
Storage characteristics of the anode material of the present invention were investigated under the following conditions:
60° C. storage test conditions
After storage: checking OCV, remaining capacity, recovery capacity, AC resistance, gas volume measurement (volumetric measurement before the test and at each test period, measuring the amount of gas generated).
After storage, 25° C. for characterization.
25° C. Test conditions
A summary of the storage characteristics are provided in Table 10 below.
V(V)
The discharge capacity change of the anode material Talnode C (GTK1) is shown with reference to
The capacity retention for 100 cycles is 91.8%, as seen in
A comparison of the cycle characteristics of the Applicant's Talnode C (GTK-1) graphite material, the anode material of the present invention (referenced again as GTK1/ZH-16HY=30/70) and the ZH-16HY synthetic graphite product is shown in
The cycle characteristics of ZH-16HY alone show a maintenance rate of 86% at 200 cycles, which is slightly inferior to that of Talnode C (CGK-1). The results for GTK1/ZH-16HY=30/70, the anode material of the present invention, are demonstrably better than those of Talnode C (CGK-1) and ZH-16HY, and are considered excellent by the Applicant.
The Applicant has attributed the cause of the improvement to the bimodal particle distribution effect and it is further understood to potentially be due to the particle size balance and the relative binder ratio. The bimodal distribution optimises the electrode loading and the stress absorbed by the particles during calendaring, giving an improved and substantially homogeneous distribution of particles into the electrode. This in turn keeps the conduction path into the electrode while long cycling, hence the improvement in cycling performance.
A summary of durability (50° C. cycle, 60° C. storage) characteristics is provided in Table 11 below for comparison purposes. Included in the comparison is the Applicant's Talnode C (GTK-1) graphite material and the anode material of the present invention (referenced again as GTK1/ZH-16HY=30/70).
As can be seen with reference to the above description, the anode composition of the present invention can achieve a loading of up to 1.7 gr/cm2 and significantly improve cycle life relative to anode compositions of the prior art.
It is further readily apparent that the anode material of the present invention, being a combination of graphite particles of predominantly two distinct sizes, provides improved performance relative to anode materials comprised of only one or other of those two distinctly sized anode materials. The Applicant refers to this effect as a ‘bimodal effect’. This ‘bimodal effect’ can be assigned a numerical value based on the ratio of the larger particles to the smaller particles in the combination. For example, the product referenced throughout as GTK1/ZH-16HY=30/70 is composed of the GTK1 particles at a size of about 5 μm and the ZH-16HY particles at a size of about 20 μm, giving a ‘bimodal effect’ of 4.
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 |
|---|---|---|---|
| 2021904147 | Dec 2021 | AU | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/IB2022/062514 | 12/20/2022 | WO |
