DETAILED ACTION
Notice of Pre-AIA or AIA Status
The present application, filed on or after March 16, 2013, is being examined under the first inventor to file provisions of the AIA .
Status of Claims
Claims 1-20 are pending.
Claim Rejections - 35 USC § 103
In the event the determination of the status of the application as subject to AIA 35 U.S.C. 102 and 103 (or as subject to pre-AIA 35 U.S.C. 102 and 103) is incorrect, any correction of the statutory basis (i.e., changing from AIA to pre-AIA ) for the rejection will not be considered a new ground of rejection if the prior art relied upon, and the rationale supporting the rejection, would be the same under either status.
The following is a quotation of 35 U.S.C. 103 which forms the basis for all obviousness rejections set forth in this Office action:
A patent for a claimed invention may not be obtained, notwithstanding that the claimed invention is not identically disclosed as set forth in section 102, if the differences between the claimed invention and the prior art are such that the claimed invention as a whole would have been obvious before the effective filing date of the claimed invention to a person having ordinary skill in the art to which the claimed invention pertains. Patentability shall not be negated by the manner in which the invention was made.
Claim(s) 1-8, 16 are rejected under 35 U.S.C. 103 as being unpatentable over Kim et al (US 20160322666 A1) in view of Lu et al (Penghao Lu, Fei Ding, Zhibin Xu, Jiaquan Liu, Xingjiang Liu, Qiang Xu, Study on (100-x)(70Li2S-30P2S5)-xLi2ZrO3 glass-ceramic electrolyte for all-solid-state lithium-ion batteries, Journal of Power Sources, Volume 356, 2017, Pages 163-171).
Regarding Claim 1,
Kim teaches a positive electrode for an all-solid-state rechargeable battery (Paragraph 0051), the positive electrode comprising: a current collector (Paragraph 0056); and a positive electrode active material layer on the current collector (Paragraph 0056). Kim states that the constitution of the battery is commonly used, and therefore the detailed description is omitted. A commonly used constitution of the battery is wherein the positive electrode active material layer is on the current collector.
Kim teaches that the positive electrode active material layer includes a positive electrode active material and a solid electrolyte (Paragraph 0052).
Kim teaches that the solid electrolyte is in the form of a particle with a core and a coating (Paragraph 0009). The core comprises sulfide-based compound such as Li2S-P2S5 (Paragraph 0010, 0012; this is a sulfide based solid electrolyte). The coating comprises an oxide based lithium ion conductor such as LiNbO3, Li2ZrO3, Li2WO4, Li4SiO4 (Paragraph 0011, 0013; a lithium-metal-oxide on a surface of the sulfide solid electrolyte particles).
Kim does not specifically teach that in an X-ray diffraction analysis of the solid electrolyte, a full width at half maximum of a main peak is less than or equal to about 0.160. The instant specification states that as the crystallinity of the solid electrolyte increases or the size of the crystal increases, a full width at half maximum (FWHM) of a main peak may decrease in an X-ray diffraction analysis. Sulfide solid electrolytes may have aggregated particles or may have a large particle size immediately after synthesis. They may be subjected to a process such as pulverization to adjust them to a particle size usable in a battery, the crystallinity may be lowered, and the ion conductivity may be lowered. In the solid electrolyte according to some example embodiments, by heating sulfide solid electrolyte particles in a specific temperature range while coating a lithium-metal-oxide thereon, the crystallinity may be increased to adjust the full width at half maximum of the main peak to less than or equal to about 0.160.
Hence, based on the instant specification the X-ray diffraction FWHM is dependent on parameters such as particle size, and heating temperature.
Kim teaches a particle size of the sulfide solid electrolyte to be about 10 nm to 20 µm (Paragraph 0009). The instant specification states that the D50 of the sulfide solid electrolyte is about 0.1 to 2 µm. This range is included within the range of Kim.
Kim also teaches that the thickness of the coating layer is about 1 to 100 nm. This means that the overall particle size would be about 11 nm to 20.1 µm. The instant specification states that the D50 of the solid electrolyte is about 0.1 to 5 µm. This range is included within the range of Kim. Hence, it would have been obvious to one of ordinary skill in the art prior to the effective filing date of the claimed invention to have particles sizes for both sulfide solid electrolyte and the overall solid electrolyte within the claimed ranges in order to efficiently reduce interface resistance and protect the core from oxygen and moisture (Paragraph 0048).
Kim is silent about heating temperature applied in the process of making the solid electrolyte particle. However, Lu teaches a method of making glass-ceramic electrolyte (100-x)(70Li2S-30P2S5)-xLi2ZrO3 (x = 0, 1, 2, 5) which comprises the sulfide solid electrolyte, and the lithium metal oxide. The solid electrolyte of Lu has the same components overlapping with the claimed weight ratio (i.e. lithium metal oxide at about 0.01-3 wt% of the total weight of the solid electrolyte). Lu also teaches varying ball milling time to determine an appropriate preparing process of the solid electrolyte. Ball milling time controls the particle size of the electrolyte. Further, Lu teaches that the crystallization heating temperature was chosen at 285 ˚C. The instant specification states that the heating treatment may be performed in a temperature range of about 250 to 350 ˚C while coating lithium metal oxide on the pulverized sulfide solid electrolyte particles, and the crystallinity and ion conductivity may be increased (Paragraph 0078). The temperature of Lu lies within the temperature range of instant specification. Hence, it would have been obvious to one of ordinary skill in the art prior to the effective filing date of the claimed invention to use the heat treatment method of Lu in order to form a solid electrolyte with high ionic conductivity and improved discharge capacities.
A combination of the solid electrolyte structure used in positive electrode material as taught in Kim, and the heat treatment crystallization method as taught in Lu enable the formation of a solid electrolyte particle such that it would demonstrate in an X-ray diffraction analysis of the solid electrolyte, a full width at half maximum of a main peak is less than or equal to about 0.160. Per MPEP 2112.01, where the claimed and prior art products are identical or substantially identical in structure or composition, or are produced by identical or substantially identical processes, a prima facie case of either anticipation or obviousness has been established. Hence, it would have been obvious to one of ordinary skill in the art prior to the effective filing date of the claimed invention to combine the teachings of Kim and Lu to reach the FWHM XRD measurement as claimed in order to form a solid electrolyte with high ionic conductivity and improved discharge capacities.
Regarding Claim 2,
Kim teaches that the coating comprises an oxide based lithium ion conductor such as LiNbO3, Li2ZrO3, Li2WO4, Li4SiO4 (Paragraph 0011, 0013; a lithium-metal-oxide on a surface of the sulfide solid electrolyte particles) wherein the metal in the lithium metal oxide is Nb, Zr, W, Si which are in the claimed list.
Regarding Claim 3, and Claim 4,
Kim does not specifically teach that the lithium metal oxide is included in the solid electrolyte in an amount of about 0.01 wt% to about 3 wt %, or 0.01 wt% to about 0.8 wt% based on total weight of the electrolyte. Kim teaches the thickness of the coating layer of lithium metal oxide which can in turn be translated to the wt% in the electrolyte.
However, Lu teaches glass-ceramic electrolyte (100-x)(70Li2S-30P2S5)-xLi2ZrO3 (x = 0, 1, 2, 5). When x= 1, then that translates to an amount of lithium metal oxide about 1 wt % compared to the total weight of the solid electrolyte. Hence, there is an overlapping range of wt% between Lu and the claimed range.
Furthermore, Figure 2 shows a continuous graph of x (mol %) to temperature of the solid electrolyte composition. Since the chart is continuous it hints to the wt% of the lithium metal oxide being varied between 0 to 5 %. This would result in an overlapping range between the claimed range of 0.01 to 0.8 wt%.
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Hence, it would have been obvious to one of ordinary skill in the art prior to the effective filing date of the claimed invention to choose a wt% value from the overlapping range in Lu in order to form a solid electrolyte with high ionic conductivity and improved discharge capacities.
Regarding Claim 5,
Kim does not specifically teach that the lithium metal oxide used is amorphous. However, Lu states that the glass -ceramic electrolyte is obtained after steadily heating the amorphous powders which includes the lithium metal oxide as explained in rejection of Claim 1 above. Hence, it would have been obvious to one of ordinary skill in the art prior to the effective filing date of the claimed invention that the lithium metal oxide is amorphous as a characteristic of the powders being blended to make the solid electrolyte.
Regarding Claim 6,
Kim teaches the use of sulfide based compound such as Li6PS5Cl which is an argyrodite type sulfide. This compound is taught in the instant specification as well.
Regarding Claim 7, and Claim 8,
Kim teaches a particle size of the sulfide solid electrolyte to be about 10 nm to 20 µm (Paragraph 0009). The instant specification states that the D50 of the sulfide solid electrolyte is about 0.1 to 2 µm. This range is included within the range of Kim.
Kim also teaches that the thickness of the coating layer is about 1 to 100 nm. This means that the overall particle size would be about 11 nm to 20.1 µm. The instant specification states that the D50 of the solid electrolyte is about 0.1 to 5 µm. This range is included within the range of Kim. Hence, it would have been obvious to one of ordinary skill in the art prior to the effective filing date of the claimed invention to have particles sizes for both sulfide solid electrolyte and the overall solid electrolyte within the claimed ranges in order to efficiently reduce interface resistance and protect the core from oxygen and moisture (Paragraph 0048).
Regarding Claim 16,
Kim teaches an all-solid state battery comprises a positive electrode, a negative electrode, and a solid electrolyte which is interposed between the electrodes (Paragraph 0051, 0055).
Claim(s) 9 is rejected under 35 U.S.C. 103 as being unpatentable over Kim and Lu in view of Sugiura et al (US 20140295260 A1).
Regarding Claim 9,
Kim teaches the size of the sulfide solid electrolyte particle, and the thickness of the coating layer. Kim does not specifically teach that a value of (D90-D10)/D50 in a particle size distribution for the solid electrolyte is greater than about 1 and less than or equal to about 5. Lu teaches varying ball milling time to determine an appropriate preparing process of the solid electrolyte. Ball milling time controls the particle size distribution of the electrolyte.
However, since Lu does not provide any additional details related to ball milling process conditions, the prior art reference of Sugiura teaches a method for producing a sulfide solid electrolyte having a small average particle diameter which can be utilized in a cathode as well (Paragraph 0044). Sugiura provides examples of milled sulfide solid electrolyte with the following D10, D50, D90 particle diameters as shown in Table 1.
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The values of the D10, D50 and D90 shown satisfy the claimed conditions of the particle size distribution. Hence, it would have been obvious to one of ordinary skill in the art prior to the effective filing date of the claimed invention to utilize a value of (D90-D10)/D50 in a particle size distribution for the solid electrolyte greater than about 1 and less than or equal to about 5 in order to improve the productivity and ion conductivity of the solid electrolyte.
Claim(s) 10-15, 17, 18 are rejected under 35 U.S.C. 103 as being unpatentable over Kim and Lu in view of Meguro et al (US 20170125842 A1).
Regarding Claim 10,
Kim states that the solid electrolyte is used as a material in the positive electrode in an amount of commonly used level when manufacturing the all-solid state battery (Paragraph 0053), and that the positive electrode may comprise the positive electrode active material, a conductive material, a binder and the solid electrolyte (Paragraph 0052). The positive electrode active material may be the oxide-based compound, and the conductive material and the binder may be any material, which can be commonly used to an all-solid state battery without limitation (Paragraph 0052).
Kim does not teach that the solid electrolyte is included in the positive electrode active material layer in an amount of about 0.5 wt% to about 35 wt%, based on a total weight of the positive electrode active material layer.
However, Meguro teaches an all-solid state battery in which the concentration of the positive electrode active material is preferably 10 to 90% by mass (Paragraph 0229). Hence, it would have been obvious to one of ordinary skill in the art prior to the effective filing date of the claimed invention to use the range in Meguro that overlaps with the claimed range into the invention of Kim in order to form a battery capable of exhibiting an improved ion-conducting property (Paragraph 0011).
Regarding Claim 11,
Kim teaches that there is no buffer layer in the positive electrode active particles because the Kim’s invention provides a coating on the sulfide based core which acts as a buffer between core and the active material. The positive electrode as claimed in claim 1, wherein: the positive electrode active material is in the form of particles, and the particles do not include a buffer layer.
Meguro teaches that the positive electrode active material is in the form of particles (Paragraph 0228).
Regarding Claim 12, and Claim 13,
Kim does not teach that the positive electrode active material includes a lithium cobalt oxide, lithium nickel oxide, a lithium nickel cobalt oxide, a lithium nickel cobalt aluminum oxide, a lithium nickel cobalt manganese oxide, a lithium nickel manganese oxide, a lithium manganese oxide, a lithium iron phosphate, or a combination thereof. Kim does not teach a lithium nickel oxide represented by Chemical Formula 1, a lithium cobalt oxide represented by Chemical Formula 2, a lithium iron phosphate compound represented by Chemical Formula 3, or a combination thereof (as shown in claim 13).
However, Meguro teaches lithium cobalt oxide, lithium nickel oxide, a lithium nickel cobalt aluminum oxide, a lithium nickel cobalt manganese oxide, a lithium nickel manganese oxide used as positive electrode active material (Paragraph 0223). Furthermore, Meguro provides formulas such as LiNi0.85Co0.10Al0.05O2 which meets the claimed formula (claim 13). Hence, it would have been obvious to one of ordinary skill in the art prior to the effective filing date of the claimed invention to use these compounds as positive active materials in order to be capable of reversibly intercalating and deintercalating lithium ions (Paragraph 0220)
Regarding Claim 14,
Kim does not teach an average particle diameter (D50) of the positive electrode active material is about 3 um to about 25 um.
However, Meguro teaches that the volume average particle diameter is 0.1 to 50 um. This includes the claimed range of particle diameter values. Hence, it would have been obvious to one of ordinary skill in the art prior to the effective filing date of the claimed invention to use the particle diameter as taught in Meguro into Kim in order to form a positive electrode capable of reversibly intercalating and deintercalating lithium ions (Paragraph 0220).
Regarding Claim 15,
Kim does not teach that the positive electrode active material layer includes: about 50 wt% to about 99.5 wt% of the positive electrode active material, about 0.5 wt% to about 35 wt% of the solid electrolyte, about 0 wt% to about 10 wt% of a binder, and about 0 wt% to about 5 wt% of a conductive material, based on a total weight of the positive electrode active material layer.
However, in the example shown in Meguro the positive electrode is made of Lithium cobaltate (100 parts), acetylene black (5 parts), the solid electrolyte composition obtained above (75 parts). This translates to 22% active material, 1.11% conductive material, 16% of solid electrolyte. These values lie within the claimed range. Meguro also teaches a high-molecular-weight compound can be applied as a binder for positive electrode active materials (Paragraph 0301). Meguro suggests that the binder is added 0.1% to 50% by mass in the solid content (Paragraph 0181).
Hence, it would have been obvious to one of ordinary skill in the art prior to the effective filing date of the claimed invention to use the positive electrode materials in the claimed range in order to form a positive electrode capable of reversibly intercalating and deintercalating lithium ions (Paragraph 0220).
Regarding Claim 17, and Claim 18,
Kim does not teach that the all-solid state battery wherein the negative electrode includes a current collector and a negative electrode active material layer or a negative electrode catalyst layer on the current collector.
However, Meguro teaches an all solid-state secondary battery that has a metal foil current collector with a layer of negative electrode material on it comprising the active material (Paragraph 0248).
Kim does not teach that the negative electrode includes: a current collector, a negative electrode catalyst layer on the current collector, and a lithium metal layer formed during initial charging between the current collector and the negative electrode catalyst layer. Meguro teaches the structure of the current collector and the negative electrode active material layer on the collector. Hence, based on a combination of Kim, Lu and Meguro, it would be obvious that a lithium metal layer is formed during the initial charging between the current collector and the negative electrode active layer. The lithium metal layer is a result of the structure and composition and would be inherent to the structure and composition as taught in Kim, Lu and Meguro.
Claim(s) 19,20 are rejected under 35 U.S.C. 103 as being unpatentable over Kim and Lu in view of Sugiyo et al (US 20210367265 A1).
Regarding Claim 19, and claim 20,
Kim does not teach that the solid electrolyte layer includes a solid electrolyte, and an average particle diameter (D50) of the solid electrolyte included in the positive electrode is smaller than an average particle diameter (D50) of the solid electrolyte included in the solid electrolyte layer, and that : the average particle diameter (D50) of the solid electrolyte included in the positive electrode is about 0.5 um to about 2.0 um, and the average particle diameter (D50) of the solid electrolyte included in the solid electrolyte layer is about 2.1 um to about 5.0 um.
However, Sugiyo teaches that in an all-solid state battery wherein a positive electrode contains first solid electrolyte particles (Paragraph 0009), and the solid electrolyte layer contains second solid electrolyte particles (Paragraph 0010), the average particle diameter of first solid electrolyte particles is less than the average particle diameter of the second solid electrolyte particles (Paragraph 0011). The average particle diameter of the first solid electrolyte particle is 0.01 to 10 um (Paragraph 0069), and the average particle diameter of the second solid electrolyte particles is 1 to 50 um. These values in Sugiyo overlap with the claimed ranges (Claim 20). Hence, it would have been obvious to one of ordinary skill in the art prior to the effective filing date of the claimed invention to use the overlapping particle diameter values in Sugiyo into Kim in order to secure high ion conductivity in the solid electrolyte layer, and suppress warpage of the solid electrolyte layer (Paragraph 0018).
Conclusion
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/SUHANI JITENDRA PATEL/Examiner, Art Unit 1783
/MARIA V EWALD/Supervisory Patent Examiner, Art Unit 1783
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