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 .
Election/Restrictions
Applicant’s election of Group I (Claims 1-5 and 8-10) in the reply filed on 4/9/26 is acknowledged. Because applicant did not distinctly and specifically point out the supposed errors in the restriction requirement, the election has been treated as an election without traverse (MPEP § 818.01(a)).
Priority
Receipt is acknowledged of certified copies of papers required by 37 CFR 1.55.
Information Disclosure Statement
The information disclosure statements (IDS) submitted on 2/5/25 and 7/27/23 was filed. The submission is in compliance with the provisions of 37 CFR 1.97. Accordingly, the information disclosure statements have been considered by the examiner.
Drawings
The drawings were received on 7/27/23. These drawings are acceptable.
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.
The factual inquiries for establishing a background for determining obviousness under 35 U.S.C. 103 are summarized as follows:
1. Determining the scope and contents of the prior art.
2. Ascertaining the differences between the prior art and the claims at issue.
3. Resolving the level of ordinary skill in the pertinent art.
4. Considering objective evidence present in the application indicating obviousness or nonobviousness.
This application currently names joint inventors. In considering patentability of the claims the examiner presumes that the subject matter of the various claims was commonly owned as of the effective filing date of the claimed invention(s) absent any evidence to the contrary. Applicant is advised of the obligation under 37 CFR 1.56 to point out the inventor and effective filing dates of each claim that was not commonly owned as of the effective filing date of the later invention in order for the examiner to consider the applicability of 35 U.S.C. 102(b)(2)(C) for any potential 35 U.S.C. 102(a)(2) prior art against the later invention.
Claims 1-5 and 8-10 are rejected under 35 U.S.C. 103 as being unpatentable over US 2020/0176760 A1 (US'760) in view of US 2018/0219221 A1 (US'221) and JP 2015103386 A (JP'386).
As to Claim 1:US'760 discloses an active material comprising:
silicon and oxygen (Abstract; US'760 [0007], [0032]);
a first element including boron, phosphorus, or both (US'760 [0007], [0032], [0061], disclosing a second element group including B and P);
a second element including at least one of an alkali metal element, a transition element, or a typical element (US'760 [0007], [0032], [0061], disclosing Cu, Li, and Na);
wherein a content of silicon with respect to the active material and excluding oxygen and carbon is greater than or equal to 60 atomic percent and less than or equal to 98 atomic percent (US'760 [0040], [0202], Table 1, disclosing a Si content of 30–70 at% of the total Si+additive+O system, and Example 1-1 having Si:O:Cu = 42.5:52.5:5 at%, which corresponds to about 89.5 at% Si when oxygen is excluded);
a content of the first element with respect to the active material and excluding oxygen and carbon is greater than or equal to 1 atomic percent and less than or equal to 25 atomic percent (US'760 [0040], [0061], disclosing additive amounts of 1–30 at% and B/P as selectable second elements); and
a first peak is detectable in an XPS spectrum of Si2p relating to the active material... having an apex within a range... of 102 electronvolts to 105 electronvolts (US'760 [0028], [0173]–[0176], [0206]–[0207], FIG. 11A–11D, disclosing XPS spectra of vapor-deposited films and narrow scanning of Si2p).
However, US'760 does not explicitly disclose a third element including an alkaline earth metal element in a range of 0 to 6 atomic percent; the XPS peak having a shoulder on a smaller binding energy side; a second peak detectable in a Raman spectrum having an apex within a range of 435 to 465 wavenumbers; and the active material having fine pores with a third peak detectable in a fine pore distribution measured by a mercury intrusion method having an apex within a range of 0.01 to 10 micrometers.
US'221 teaches that a negative electrode active material based on silicon and oxygen may further contain a third element including an alkaline earth metal element (at least one of Mg, Ca, Ba, or Sr) to stabilize the amorphous glass network (US'221 [0010]–[0013], [0029], [0039], [0049]; see also Tables 2–6, disclosing BaO, MgO, CaO, and SrO-containing compositions). JP'386 teaches that an electrode material comprising silicon and oxygen should be manufactured to have fine pores to accommodate volume expansion during lithiation, wherein a peak is detectable in a fine pore distribution measured by a mercury intrusion method having an apex within the range of 0.01 to 2.0 micrometers (JP'386, p. 1, Abstract; p. 2, describing Si/Sn oxide negative electrode materials and a mercury-intrusion pore-distribution peak in the range of 0.001 μm to 0.2 μm; p. 3, disclosing pores of 0.01–0.3 μm and 0.3–2.0 μm measured by mercury porosimetry and the AutoPore IV 9500 mercury-intrusion measurement). The specific XPS shoulder and the Raman shift apex are inherent physical properties of the amorphous silicate glass structure resulting from the synthesis and carbon-reduction methods disclosed in US'760 (US'760 [0032]–[0033], [0044]–[0047], [0167]–[0176], [0202]–[0207).
US'760, US'221, and JP'386 are analogous arts because they are all directed to the field of negative electrode active materials for lithium-ion secondary batteries and address the common technical problem of improving the structural stability and cycle characteristics of silicon-based materials (US'760 [0002]–[0007], [0032]; US'221 [0001]–[0002], [0008]–[0013], [0023], [0029]; JP'386, pp. 1–3).
It would have been obvious to a person skilled in the art before the effective filing date of the instant application to incorporate the alkaline earth metal stabilizers of US'221 into the silicon-oxide matrix of US'760 to improve electrochemical stability, and to further provide the active material with the fine pore structure taught by JP'386 to provide a physical buffer for silicon volume expansion, thereby achieving a battery with higher capacity and better cycle life.
As to Claim 2:US'760 discloses an active material comprising: silicon and oxygen (Abstract; US'760 [0007], [0032]); a first element including boron, phosphorus, or both (US'760 [0007], [0032], [0061], disclosing a second element group including B and P); a second element including at least one of an alkali metal element, a transition element, or a typical element (US'760 [0007], [0032], [0061], disclosing Cu, Li, and Na); wherein a content of silicon with respect to the active material and excluding oxygen and carbon is 60–98 at% (US'760 [0040], [0202]–[0203], disclosing Si content of 30–70 at% in the total Si+additive+O system, and Example 1-1 having Si:O:Cu = 42.5:52.5:5 at%, which corresponds to about 89.5 at% Si when oxygen is excluded); and a first peak is detectable in an XPS spectrum of Si2p relating to the active material... having an apex within a range... of 102 to 105 electronvolts (US'760 [0028], [0173]–[0176], FIG. 11D, disclosing XPS spectra of insides of vapor-deposited films and Si2p narrow scanning). Regarding the further limitation of claim 2, US'760 discloses that the active material comprises an amorphous matrix where silicon is bonded to oxygen and other elements, resulting in a broad XPS Si2p peak distribution that encompasses multiple valence states (Si1+ through Si4+) as shown in Figure 11D (US'760 [0032]–[0033], [0040]–[0043], [0173]–[0176], FIG. 11D).
However, US'760 does not explicitly disclose a third element including an alkaline earth metal element; the active material having fine pores measured by mercury intrusion; the specific Raman apex shift; and the first peak having a half-width of 4.0 electronvolts or greater.
US'221 teaches that a negative electrode active material for a power storage device may contain an amorphous phase and further include a third element including an alkaline earth metal element such as Mg, Ca, Ba, or Sr to stabilize the structural network (US'221 [0010]–[0013], [0016]–[0018], [0029], [0039], [0049], disclosing R′ as Mg, Ca, Ba, Zn, or Sr and teaching that the negative electrode active material preferably contains an amorphous phase). JP'386 teaches that an electrode material comprising silicon and oxygen should have a fine pore structure to alleviate stress during lithium occlusion, wherein a peak is detectable in a fine pore distribution measured by a mercury intrusion method having an apex within a range of 0.01 to 2.0 micrometers (JP'386, p. 1, Abstract; p. 2, describing Si/Sn oxide negative electrode materials, volume-change problems, and a mercury-intrusion pore-distribution peak in the range of 0.001 μm to 0.2 μm; p. 3, disclosing pores of 0.01–0.3 μm and 0.3–2.0 μm measured by mercury porosimetry and that pores of 0.3–2.0 μm buffer volume change; p. 8, disclosing pore characteristics measured by mercury porosimetry using AutoPore IV 9500). The limitation of claim 2 requiring a half-width of 4.0 eV or greater is an inherent physical property of the amorphous silicon sub-oxide matrix synthesized via the methods of US'760; paragraph [0043] and Fig. 11D of US'760 describe a peak that is broadened due to the co-existence of varied silicon-oxygen-metal bonding environments, which results in the broad half-width signature claimed.
It would have been obvious to a person skilled in the art before the effective filing date of the instant application to incorporate the alkaline earth metal stabilizers of US'221 into the silicon-oxide matrix of US'760 to improve electrochemical stability, and to further provide the active material with the fine pore structure taught by JP'386 to provide a physical buffer for silicon volume expansion. Furthermore, it would have been obvious to arrive at the XPS peak half-width of claim 2, as this broad peak profile is a structural consequence of the amorphous sub-oxide material synthesized according to the primary reference to achieve high capacity and flexibility.
As to Claim 3:US'760 discloses an active material according to claim 1, comprising: silicon and oxygen (Abstract; US'760 [0007], [0032]); a first element including boron or phosphorus (US'760 [0007], [0032], [0061], [0210]); a second element including at least one of an alkali metal element or a transition element (US'760 [0007], [0032], [0061], disclosing Cu, Li, and Na); wherein a content of silicon excluding oxygen and carbon is within the claimed range (US'760 [0040], [0202]–[0203], disclosing Si content of 30–70 at% in the total Si+additive+O system and Example 1-1 having Si:O:Cu = 42.5:52.5:5 at%, corresponding to about 89.5 at% Si when oxygen is excluded); and an XPS spectrum of Si2p having a first peak with an apex within a range of 102 electronvolts to 105 electronvolts (US'760 [0028], [0173]–[0176], [0206]–[0208], Fig. 11D; [0043]). US'760 further discloses that the Si2p peak represents a distribution of multiple valence states, including Si⁰, Si¹⁺, Si²⁺, Si³⁺, and Si⁴⁺ species, which arise from the varied bonding environments in the amorphous silicon sub-oxide matrix (US'760 [0032]–[0033], [0173]–[0176], [0206]–[0208]; [0043]; Fig. 11D).
However, US'760 does not explicitly disclose a third element including an alkaline earth metal element; the first peak having a shoulder on a smaller binding energy side; a second peak detectable in a Raman spectrum within a range of 435 to 465 wavenumbers; the active material having fine pores with a distribution measured by a mercury intrusion method; and the area ratio S2/S1 of 0.85 or greater.
US'221 teaches that a negative electrode active material comprising silicon and oxygen may further contain a third element including an alkaline earth metal element (such as Mg, Ca, Ba, or Sr) to stabilize the structural network and improve conductivity (US'221 [0010]–[0013], [0016]–[0018], [0038]–[0040], [0049]). JP'386 teaches that an electrode material comprising silicon and oxygen should possess a fine pore structure to alleviate stress during lithium occlusion, wherein a peak is detectable in a fine pore distribution measured by a mercury intrusion method having an apex within the range of 0.01 to 2.0 micrometers (JP'386, p. 1, Abstract; p. 2, describing Si/Sn oxide negative electrode materials, volume-change problems, and a mercury-intrusion pore-distribution peak in the range of 0.001 μm to 0.2 μm; p. 3, disclosing pores of 0.01–0.3 μm and 0.3–2.0 μm measured by mercury porosimetry and that pores of 0.3–2.0 μm buffer volume change; p. 8, disclosing pore characteristics measured by mercury porosimetry using AutoPore IV 9500). Regarding the area ratio of Claim 3, the specific numerical ratio S2/S1 of 0.85 or greater is an inherent physical property of the amorphous silicon sub-oxide material synthesized following the co-deposition and oxidation-control teachings of US'760; the broad XPS peak distribution shown in Figure 11D of US'760 inherently encompasses the ratio of low-valence species to Si⁴⁺ that is required to achieve high electrochemical capacity.
It would have been obvious to a person skilled in the art before the effective filing date of the instant application to incorporate the alkaline earth metal stabilizers of US'221 into the silicate-based active material of US'760 and to further provide the material with the fine pore structure taught by JP'386 to provide a physical buffer for silicon volume expansion. Furthermore, it would have been obvious to arrive at the XPS peak area ratio of Claim 3, as the ratio S2/S1 is a structural consequence of the degree of reduction in the amorphous sub-oxide matrix, and optimizing the amount of Si⁰ through Si³⁺ relative to Si⁴⁺ is a routine design variable used to maximize lithium storage capacity.
As to Claim 4:US'760 discloses an active material comprising: a center part including silicon and oxygen (Abstract; US'760 [0007], [0032]–[0034], disclosing a matrix 111 including Si and O and a cluster 112 including Si dispersed in the matrix); a first element including boron, phosphorus, or both (US'760 [0007], [0032], [0061], disclosing B and P in the second-element group); a second element including transition or alkali metals (US'760 [0007], [0032], [0061], disclosing Cu, Li, and Na); wherein a content of silicon with respect to the active material and excluding oxygen and carbon is within the claimed range (US'760 [0040], [0202]–[0203], disclosing Si:O:Cu = 42.5:52.5:5 at% in Example 1-1 and Si:O:Cu = 41.7:54.6:3.7 at% in Example 1-3, corresponding to about 89.5 at% Si and about 91.9 at% Si, respectively, when oxygen is excluded); a first peak is detectable in an XPS spectrum of Si2p relating to the center part having an apex within a range of 102 to 105 electronvolts (US'760 [0028], [0173]–[0176], [0206]–[0208], Fig. 11D; [0043]); and a covering part covering at least a portion of a surface of the center part and including carbon as a constituent element ([0066], discussing carbon coating peaks in Raman spectroscopy; see also US'221 [0059]–[0066], teaching coating or mixing the negative electrode active material with electrically conductive carbon, carbon coating thickness, and Raman D/G/F carbon-coating peaks; JP'386, pp. 2–4, disclosing an electrode material containing a Si or Si oxide component and a carbon material).
However, US'760 does not explicitly disclose a third element including an alkaline earth metal element; the XPS peak having a shoulder on a smaller binding energy side; a second peak detectable in a Raman spectrum relating to the center part with an apex within 435 to 465 wavenumbers; and the center part having fine pores measured by a mercury intrusion method.
US'221 teaches that a negative electrode active material based on silicon and oxygen may further contain a third element including an alkaline earth metal element (Mg, Ca, Ba, or Sr) to stabilize the structural network and improve initial efficiency (US'221 [0010]–[0013], [0039]–[0040], [0049], disclosing R′ as at least one selected from Mg, Ca, Ba, Zn, and Sr and teaching R₂O+R′O components). JP'386 teaches an electrode material comprising a particle (center part) containing silicon and an oxide thereof, and a carbon material (covering part) covering the particle, wherein the center part has a fine pore structure to alleviate stress during volume expansion, with a peak detectable in a fine pore distribution measured by a mercury intrusion method having an apex within a range of 0.01 to 2.0 micrometers (JP'386, p. 1, Abstract, disclosing particles containing a metal/semimetal or oxide capable of occluding lithium and carbon material; JP'386, p. 2, disclosing Si or Sn and oxides thereof as preferred lithium-occluding materials and discussing a mercury-intrusion pore-distribution peak in the range of 0.001 μm to 0.2 μm; JP'386, p. 3, disclosing pore diameters of 0.01–0.3 μm and 0.3–2.0 μm measured by mercury porosimetry and explaining that pores of 0.3–2.0 μm buffer volume change; JP'386, p. 4, disclosing manufacture by mixing porous Si with an organic compound to become carbon material). The specific XPS shoulder and the Raman apex shift of 435–465 cm⁻¹ are inherent physical signatures of the amorphous silicate glass structure resulting from the controlled oxidation and carbon-reduction synthesis methods taught by US'760 and JP'386.
It would have been obvious to a person skilled in the art before the effective filing date of the instant application to incorporate the alkaline earth metal stabilizers of US'221 into the silicon-oxide core of US'760 to improve structural stability, and to further provide the core particle (center part) with the fine pore structure taught by JP'386 to provide a physical buffer for silicon volume expansion. Furthermore, it would have been obvious to provide a carbon coating (covering part) on the surface of the center part as taught by US'760 and JP'386 to improve the electrical conductivity and rate characteristics of the resulting porous active material.
As to Claim 5: US'760 discloses an active material comprising: a center part including silicon and oxygen (Abstract; US'760 [0007], [0032]–[0034], disclosing a matrix 111 including Si and O and a cluster 112 including Si dispersed in the matrix); a first element including boron or phosphorus (US'760 [0007], [0032], [0061]); a second element including alkali or transition metals (US'760 [0007], [0032], [0061], disclosing Cu, Li, and Na); elemental content ranges within the claimed ranges (US'760 [0040], [0202]–[0203], disclosing Si:O:Cu = 42.5:52.5:5 at% in Example 1-1 and Si:O:Cu = 41.7:54.6:3.7 at% in Example 1-3, corresponding to about 89.5 at% Si and about 91.9 at% Si, respectively, when oxygen is excluded); a first peak detectable in an XPS spectrum of Si2p relating to the center part having an apex within a range of 102 to 105 electronvolts (US'760 [0028], [0173]–[0176], [0206]–[0208], Fig. 11D; [0043]); and a covering part covering at least a portion of a surface of the center part and including carbon as a constituent element ([0066]; see also US'221 [0059]–[0066], teaching coating or mixing the negative electrode active material with electrically conductive carbon, carbon coating thickness, and Raman D/G/F carbon-coating peaks; JP'386, pp. 1–4, disclosing an electrode material containing a particle including Si or Si oxide and a carbon material, and manufacture by mixing porous Si with an organic compound to become carbon material).
However, US'760 does not explicitly disclose a third element including an alkaline earth metal element; the XPS peak having a shoulder; a Raman peak within the 435–465 wavenumber range; a third peak in a fine pore distribution measured by a mercury intrusion method; and the center part and the covering part each having the fine pores.
US'221 teaches that a silicon-oxide-based negative electrode active material may further contain a third element including an alkaline earth metal element (Mg, Ca, Ba, or Sr) to stabilize the structural network (US'221 [0010]–[0013], [0039]–[0040], [0049], disclosing R′ as at least one selected from Mg, Ca, Ba, Zn, and Sr and teaching R₂O+R′O components). JP'386 teaches an electrode material comprising a particle (center part) and a carbon material (covering part), wherein the material has a fine pore structure to alleviate stress during volume expansion, with a peak detectable in a fine pore distribution measured by a mercury intrusion method having an apex within a range of 0.01 to 2.0 micrometers (JP'386, p. 1, Abstract, disclosing particles containing a metal/semimetal or oxide capable of occluding lithium and carbon material; JP'386, p. 2, disclosing Si or Sn and oxides thereof as preferred lithium-occluding materials and discussing a mercury-intrusion pore-distribution peak in the range of 0.001 μm to 0.2 μm; JP'386, p. 3, disclosing pore diameters of 0.01–0.3 μm and 0.3–2.0 μm measured by mercury porosimetry and explaining that pores of 0.3–2.0 μm buffer volume change; JP'386, p. 4, disclosing manufacture by mixing porous Si with an organic compound to become carbon material). Because JP'386 discloses that the composite particle formed of the silicon-based core and the carbon coating contains these fine pores to allow for electrolyte penetration and stress relief, JP'386 teaches the limitation that the center part and the covering part each have the fine pores.
It would have been obvious to a person skilled in the art before the effective filing date of the instant application to incorporate the alkaline earth metal stabilizers of US'221 into the silicate-based core of US'760 and to further provide the composite particle with the fine pore structure taught by JP'386. Specifically, it would have been obvious to design the active material such that the center part and the covering part each have the fine pores, as taught by JP'386, to provide a physical buffer for silicon volume expansion while ensuring that the entire particle remains accessible to the electrolytic solution.
As to Claim 8:
US'760 discloses an electrode comprising an active material (Abstract; [0007, 0009, 0014, 0032, 0087-0090].
As to Claim 9:
US'760 discloses a secondary battery comprising: a positive electrode; a negative electrode including an active material according to claim 1; and an electrolytic solution (Abstract; [0010, 0015, 0071-0084]).
As to Claim 10:
US'760 further discloses that the secondary battery comprises a lithium-ion secondary battery (Abstract; [0015]; see also US'760 [0003], [0032], [0067], [0216]).
Conclusion
The prior art made of record and not relied upon is considered pertinent to applicant's disclosure.
JP 2013067543 A discloses a method for producing a silicate compound whose composition and particle size are easily controlled.
Any inquiry concerning this communication or earlier communications from the examiner should be directed to JIMMY K VO whose telephone number is (571)272-3242. The examiner can normally be reached Monday - Friday, 8 am to 6 pm EST.
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If attempts to reach the examiner by telephone are unsuccessful, the examiner’s supervisor, Tong Guo can be reached at (571) 272-3066. The fax phone number for the organization where this application or proceeding is assigned is 571-273-8300.
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/JIMMY VO/
Primary Examiner
Art Unit 1723
/JIMMY VO/ Primary Examiner, Art Unit 1723
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