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 .
Claim Rejections - 35 USC § 103
The text of those sections of Title 35, U.S. Code not included in this action can be found in a prior Office action.
Claim(s) 1-2 and 6 is/are rejected under 35 U.S.C. 103 as being unpatentable over Morimoto et al. (US-20150357639-A1) in view of Wang et al. (US-20170279109-A1) and in further view of Banerjee et al. (Angew. Chem. Int. Ed. 2016, 55, 9634-9638; see NPL provided 09/13/2023 for citations).
Regarding Claim 1, Morimoto discloses a lithium-ion secondary battery (20, Fig. 2; [0065-0067, 0091-0092]) comprising a negative electrode [0067-0068, 0076-0079] for use in the lithium-ion secondary battery, a positive electrode [0067-0068, 0072-0075] for use in the lithium-ion secondary battery, and a separator [0090, 0118].
Morimoto further discloses that the negative electrode comprises a negative electrode material mixture layer (anode active material layer 12, Fig. 2) comprising a negative electrode active material (active substance 1; Fig. 1) and an inorganic solid (Na ion conductor; 2, Fig. 1) [0029, 0067-0068, 0078].
Morimoto discloses that the material for the negative electrode current collector can be selected from a group of materials that include copper [0089]. Therefore, although not Morimoto does not disclose a specific embodiment wherein the negative electrode current collector is selected to be copper, it would have been obvious to one of ordinary skill in the art, before the effective filing date of the claimed invention, to have selected copper as the negative electrode current collector with a reasonable expectation that such a selection would result in a successful negative electrode for a lithium secondary battery (MPEP 2144.07).
Morimoto discloses that the positive electrode comprises a positive electrode material mixture layer (cathode active material layer 11, Fig. 2) which is coated on a positive electrode current collector (cathode current collector 14, Fig. 2) [0067-0068, 0072]. In a specific example (Example 1), Morimoto discloses that the positive electrode current collector is formed of aluminum, and the positive electrode material mixture layer includes LiNi0.5Mn1.5O4 as a positive electrode active material [0115-0166].
Morimoto does not disclose that the positive electrode material mixture layer comprises Li1Ni0.6Co0.2Mn0.2O2 as a positive electrode active material.
Wang teaches lithium metal oxide composites for use as cathode materials in electrodes for lithium ion batteries [0002, 0012, 0023, 0041]. Wang teaches that the lithium metal oxide can include LiNi0.5Mn1.5O4 or Li1Ni0.6Co0.2Mn0.2O2 [0048]. Examiner notes that this establishes Li1Ni0.6Co0.2Mn0.2O2 as a substitutable alternative to LiNi0.5Mn1.5O4 for cathode materials in lithium ion batteries (MPEP 2144.06, II).
Therefore, it would have been obvious to one of ordinary skill in the art, before the effective filing date of the claimed invention, to have substituted the LiNi0.5Mn1.5O4 cathode material disclosed by Morimoto for Li1Ni0.6Co0.2Mn0.2O2 with a reasonable expectation that such a substitution would result in a successful positive electrode for use in a lithium ion secondary battery (MPEP 2144.06, II).
Morimoto teaches that the negative electrode active material can include a metal active substance or a carbon active substance [0078]. Examples of the carbon active substance include high orientation property graphite (HOPG) [0078].
Therefore, although not disclosed in a specific example, one of ordinary skill in the art, before the effective filing date of the claimed invention, would have found it obvious to have selected the negative electrode active material to be HOPG with a reasonable expectation that such a selection would result in a successful negative electrode active material for use in a lithium ion battery. HOPG is a form of graphite, and therefore reads on the recited limitation of “graphite as the negative electrode active material”.
Morimoto further teaches that the negative electrode material mixture layer can include at least one of a conductive material, a binding material, and a solid electrolyte material in addition to the negative electrode active material [0077, 0079]. Examples of the conductive material include acetylene black [0074, 0079]. Examples of the binder include styrene-butadiene rubber (SBR) [0074, 0079].
Therefore, although not disclosed in a specific example, one of ordinary skill in the art, before the effective filing date of the claimed invention, would have found it obvious to have include acetylene black and SBR in the negative electrode material mixture layer with a reasonable expectation that such a selection would result in a successful negative electrode material mixture layer for use in a lithium ion battery.
Morimoto discloses that the binder is not particularly limited, and can include fluorine-containing materials such as polyvinylidene fluoride (PVdF) [0074]. Modified Morimoto does not disclose the use of carboxymethyl cellulose in the negative electrode material mixture.
Wang teaches an electrode material for a lithium ion secondary battery which includes a binder [0038, 0130]. Wang teaches that any binder known in the art which is appropriate for use in preparing electrodes of batteries is suitable [0131]. Specific examples include PVdF, carboxymethyl cellulose (CMC), or combinations thereof [0131]. Examiner notes that this establishes CMC as a suitable binder for use in electrode materials for lithium ion batteries and a substitutable alternative to PVdF (MPEP 2144.06, I-II; MPEP 21440.7).
Therefore, it would have been obvious to one of ordinary skill in the art, before the effective filing date of the claimed invention, to have included CMC as a binder in the negative electrode material mixture layer of modified Morimoto with a reasonable expectation that such an addition would result in a successful negative electrode material mixture layer for use in a lithium ion secondary battery.
Modified Morimoto teaches that the negative electrode material mixture layer (12, Fig. 2) comprises the negative electrode active material [0078]. The negative electrode material mixture layer (12, Fig. 2) contacts an electrolyte layer (13, Fig. 2) [0068, 0082, 0090]. The electrolyte layer can include a liquid electrolyte [0082, 0118] and a separator [0090]. The liquid electrolyte reads on the recited limitation of an electrolytic solution.
Since the negative electrode material mixture layer comprising the negative electrode active material contacts the electrolyte layer, a portion of the negative electrode active material (active substance 1, Fig. 1) located at the interface of the electrolyte layer would necessarily contact both the electrolytic solution and the inorganic solid (Na ion conductor 2, Fig. 2; see Figs. 1-2).
Morimoto discloses that the active material is designed to have a high-capacity [0054]. Morimoto further discloses that the Na ion conductor preferably has Na ion conductivity of 10-5 S/cm or more [0050] and preferably has stability in air [0048]. Morimoto teaches that the particle diameter of the Na ion conductor is not limited so long as it is capable of being disposed on the surface of an active substance [0051]. Modified Morimoto does not disclose that the inorganic solid comprises Na3SbS4.
Banerjee teaches Na3SbS4 as a superionic conductor (Pg. 9635, Left column, Par. 2). Banerjee teaches that Na3SbS4 can be coated on an active material (i.e. NCO particles; Pg. 9637, Right column, Par. 2), and that the coated material exhibited a high discharge capacity (Pg. 9637, Right column, Par. 1). Furthermore, Banerjee teaches that the Na3SbS4 material has a high ionic conductivity of 0.1 mS/cm to 0.3 mS/cm (Pg. 9635, Left column, Par. 2) and was found to have good stability in air (Pg. 9635, Right column, Par.3 - Pg. 9636, Left column, Par. 1).
Therefore, in seeking to increase the ion conductivity of the Na ion conductor of modified Morimoto, it would have been obvious to one of ordinary skill in the art, before the effective filing date of the claimed invention, to have selected the Na ion conductor material of modified Morimoto to comprise Na3SbS4. One of ordinary skill in the art would have a reasonable expectation that using an Na ion conductor comprising Na3SbS4 would result in a successful negative electrode active material with high ionic conductivity, stability in air, and capable of being successfully coated on an active material surface, as well as providing other potential benefits, such as high capacity.
The use of an Na ion conductor comprising Na3SbS4 reads on the recited limitation of an inorganic solid which comprises Na3SbS4 and further reads on the recited limitation of an inorganic solid with a relative permittivity of 10 or higher as evidenced by the instant specification [instant specification: 0070, 0076].
Morimoto discloses that the active material is designed to have a high-capacity [0054] and the Na ion conductor has ion conductivity [0050]. Morimoto discloses that the ratio of the Na ion conductor to the active substance is preferably in the range of 0.1% by weight to 30% by weight [0056]. Morimoto further discloses that the ratio of Na ion conductor to active substance can be varied depending on whether the Na ion conductor coats the entire active substance, or a portion of the active substance [0059-0061].
While Morimoto does not explicitly disclose that the negative electrode material mixture layer comprises 0.1 wt% or more and 0.5 wt% or less of the inorganic solid, in seeking to achieve a balance between ion conductivity and capacity, one of ordinary skill in the art, before the effective filing date of the claimed invention, would have found it obvious to have optimized the ratio of Na ion conductor to active substance, including optimizing the content of inorganic solid to be 0.1 wt.% to 0.5 wt.%, with a reasonable expectation that such a content would result in a successful active material for a lithium ion battery capable of achieving high capacity while retaining ion conductivity (MPEP 2144.05, II).
Regarding Claim 2, modified Morimoto renders obvious all of the limitations as set forth above. Morimoto further teaches that the inorganic solid (2, Fig. 1) is provided in gaps between the negative electrode active material or on the surface of the electrode active material (Fig. 3; the mixing of the active substance and the Na ion conductor would necessarily result in inorganic solid between active substance particles).
Regarding Claim 6, modified Morimoto renders obvious all of the limitations as set forth above. Modified Morimoto teaches that the inorganic solid is Na3SbS4 which corresponds to the use of an inorganic solid with a reductive decomposition potential of 1.5V or less relative to a Li/Li+ equilibrium potential (1.5V vs Li/Li+) as evidenced by [0076, 0087] of the instant specification (MPEP 2112.01, I-II).
Claim(s) 1-2 and 6 is/are under 35 U.S.C. 103 as being unpatentable over Fujino et al. (WO-2019225437-A1; see English equivalent US-20210202984-A1 for citations) in view of Hintennach et al. (DE-102016011895-A1; see English translation provided 09/13/2023 for citations) and in further view of Banerjee et al. (Angew. Chem. Int. Ed. 2016, 55, 9634-9638; see NPL provided 09/13/2023 for citations).
Regarding Claim 1, Fujino discloses a lithium-ion secondary battery (1, Fig. 1) comprising a negative electrode (7, Fig. 1) for use in the lithium-ion secondary battery, a positive electrode (4, Fig. 1) for use in the lithium-ion secondary battery, and a separator (8, Fig. 1) [Abstract].
The negative electrode comprises a negative electrode material mixture layer (6, Fig. 1) comprising a negative electrode active material (12, Fig. 2) and an inorganic solid (high dielectric solids 13, Fig. 2) [0047]. Fujino discloses an embodiment wherein the negative electrode current collector is copper [0101].
Fujino discloses that the positive electrode comprises a positive electrode material mixture layer comprises Li1Ni0.6Co0.2Mn0.2O2 as a positive electrode active material [0063, 0096], and aluminum as a positive electrode current collector [0098].
Fujino further discloses that the negative electrode material mixture layer comprises graphite (artificial graphite) as the negative electrode active material, carboxymethyl cellulose, styrene butadiene rubber, and acetylene black [0100].
Fujino discloses that the negative electrode active material (12, Fig. 2) has a surface site in contact with the inorganic solid (13, Fig. 2) and has another surface site to be in contact with an electrolytic solution (9, Fig. 2) [0048].
Fujino discloses that the inorganic solid is preferably an oxide solid electrolyte having lithium ion conductivity [0080]. The inorganic solid is designed to contact portions of the negative electrode active material (see Fig. 2) in order to reduce interfacial resistance of lithium ions between the negative electrode active material and the inorganic solid [0047-0049]. Fujino does not teach that the inorganic solid comprises Na3SbS4.
Hintennach teaches a solid electrolyte with a coating comprising aluminum oxide or an ion-conducting glass [0016]. The coating is formed between the solid electrolyte and the anode/cathode [0016]. Hintennach teaches that this coating is an improvement on a previous coating applied directly to an anode [014-0015]. Hintennach further teaches that the coating necessarily has metal ion conductivity for the metal of the active material (e.g. lithium in the case of a lithium or lithium ion battery) [0036].
Advantageously, Hintennach teaches that if the coating is also conductive for other metal ions such as sodium or magnesium, which are almost always present, clogging of the coating by the foreign ions can be avoided [0036].
Therefore, in seeking to prevent the clogging by sodium or magnesium ions, it would have been obvious to one of ordinary skill in the art, before the effective filing date of the claimed invention, to have added a sodium ion conductor to the electrode material mixture layer of Fujino. One of ordinary skill in the art would have a reasonable expectation that adding a Na-ion conductor to the negative electrode material mixture layer of Fujino would result in a successful coating capable of preventing clogging due to Na ions.
Modified Fujino does not teach Na3SbS4 as an identity for the Na-ion conductor.
Banerjee teaches Na3SbS4 as a superionic conductor (Pg. 9635, Left column, Par. 2). Banerjee teaches that Na3SbS4 can be coated on an active material (i.e. NCO particles; Pg. 9637, Right column, Par. 2), and that the coated material exhibited a high discharge capacity (Pg. 9637, Right column, Par. 1). Furthermore, Banerjee teaches that the Na3SbS4 material has a high ionic conductivity of 0.1 mS/cm to 0.3 mS/cm (Pg. 9635, Left column, Par. 2) and was found to have good stability in air (Pg. 9635, Right column, Par.3 - Pg. 9636, Left column, Par. 1).
Therefore, one of ordinary skill in the art, before the effective filing date of the claimed invention, would have found it obvious to have added the sodium-based inorganic taught by Banerjee to the electrode active material of modified Fujino. One of ordinary skill in the art would have a reasonable expectation that the addition of Na3SbS4 to the electrode material mixture layer taught by modified Fujino would result in a successful electrode material mixture layer for an electrode in a lithium secondary battery which is capable of preventing clogging of the coating due to Na ions.
The addition of Na3SbS4 to the electrode active material layer reads on the recited limitation of an inorganic solid which comprises Na3SbS4, and further reads on an inorganic solid with a relative permittivity of 10 or higher as evidenced by the instant specification [instant specification: 0070, 0076].
Fujino discloses that the inorganic solids are included in the range of 0.1 to 5 % by mass with respect to the total amount of electrode mixture layer [0056]. Fujino also discloses that if the inorganic solids cover too much (i.e. more than 80%) of the surface of the negative electrode active material, the resistance of the electrode material becomes excessively large and the durability is lowered [0057]. On the other hand, if the inorganic solids cover too little (i.e. less than 1%) of the surface of the negative electrode active material, the advantageous effects of the high dielectric inorganic solid (i.e. increasing the amount of charge at low temperatures and improving the quick charge capability and durability; [0055]) cannot be obtained [0057].
Therefore, although Fujino does not explicitly disclose that the negative electrode material mixture layer comprises 0.1 wt% or more and 0.5 wt% or less of the inorganic solid, in seeking to cover an optimal amount of the surface area of the negative electrode active material such that the advantageous effects of quick charge capability and durability are achieved without increasing the resistance of the negative electrode active material, one of ordinary skill in the art, before the effective filing date of the claimed invention, would have found it obvious to have optimized the content of inorganic solid, including selecting the content of inorganic solid to be 0.1 to 0.5 wt%, with a reasonable expectation that such a content of inorganic solid would result in a successful negative electrode material mixture layer for use in a lithium ion secondary battery MPEP 2144.05, II).
Regarding Claim 2, modified Fujino renders obvious all of the limitations as set forth above. Fujino further teaches that the high-dielectric inorganic solid (13, Fig. 2) is provided on a surface of a particle of the negative electrode active material (12, Fig. 2) .
Regarding Claim 6, modified Fujino renders obvious all of the limitations as set forth above. Since modified Fujino teaches the use of Na3SbS4, it necessarily has a reductive decomposition potential of 1.5V or less relative to a Li/Li+ equilibrium potential (1.5V vs Li/Li+) as evidenced by [0076, 0087] of the instant specification (MPEP 2112.01, I-II).
Response to Arguments
Applicant’s arguments filed 05/29/2025 have been fully considered but are not persuasive. Applicant has argued the criticality of the wt% of inorganic solid and the criticality of the identity of the inorganic solid in achieving the allegedly unexpected results (Remarks, Pg. 6). Specifically, Applicant has argued that Examples 4-5 (which include 0.1 wt% and 0.5 wt% of NSS) exhibit a higher capacity retention than Example 6 (which includes 1.0 wt% NSS), thus demonstrating that there is an upper limit for the ratio of NSS included in the negative electrode (Remarks, Pg. 6).
Examiner has carefully considered this argument, but does not find it persuasive. As an initial matter, Examiner notes that Claim 1, as written, requires 0.1 wt% or more and 0.5 wt% or less of the inorganic solid (lines 20-21), and recites that the inorganic solid comprises NSS (line 17). Therefore, Claim 1 is open to a configuration wherein the inorganic solid comprises a combination of NSS and an any additional inorganic solid, as long as the combined wt% falls within the claimed range. For example, an embodiment wherein the inorganic solid comprises 0.05 wt% of NSS and 0.15 wt% of Al2O3 would be within the scope of Claim 1, and yet such an embodiment is not within the scope of the showing of evidence.
Examiner also notes that Example 7 contains 0.5 wt% of NSS, which is within the claimed range of 0.1 wt% to 0.5 wt%, yet exhibits a lower capacity retention (see annotation of instant Table 1, below) than Example 6 (which contains 1.0 wt% NSS), thereby casting doubt on the criticality of the claimed wt% of inorganic solid in achieving the allegedly unexpected results. Examiner notes that Example 7 appears to be within the scope of independent Claim 1.
Applicant has further argued that Na3SbS4 (NSS) exhibits unexpectedly improved results over MSP, as evidenced by Examples 5 and 9 (Remarks, Pg. 6). Specifically, Applicant has argued that Example 5, which contains 0.5 wt% of NSS, exhibits a higher capacity retention than Example 9, which contains 0.5 wt% of MSP, thereby evidencing the criticality in the selection of NSS (Remarks, Pg. 6).
Examiner has carefully considered this argument, but does not find it persuasive. Examiner notes the Example 5 exhibits a capacity retention of 91.2%, while Example 9 exhibits a capacity retention of 90.3% (Table 1). Although Examiner acknowledges that this represents a difference of 0.9%, it is not clear that this difference is statistically significant since no error bars are included to provide context as to what constitutes an unexpected change (MPEP 716.02, b, I).
Furthermore, Examiner notes that Example 7 (which includes 0.5 wt% of NSS) exhibits a capacity retention of 88.3% (Table 1), which represents a 2.0% decrease in capacity retention compared to Example 9 (which includes 0.5 wt% MSP). Since the use of NSS in Example 7 did not result in improved capacity retention over Example 9 which uses MSP, doubt is thereby cast on the criticality of NSS in achieving the allegedly unexpected results.
Examiner notes that Example 7 appears to be within the scope of Claim 1. Since Example 7 does not exhibit the allegedly unexpected improvement in capacity retention, it appears that Claim 1 is broader than the showing of evidence, and the allegedly unexpected results would not be expected within the entire scope of Claim 1 (MPEP 716.02, d). Accordingly, Claim 1 is not commensurate in scope with the showing of evidence.
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Annotation of instant Table 1.
Although Examiner acknowledges that Applicant’s amendment places the independent claim closer in scope to the showing of evidence, Examiner notes that independent Claim 1 still does not appear to require all of the elements which, absent persuasive evidence or discussion to the contrary, appear to be necessary in order to achieve the allegedly unexpected results.
For instance, the showing of evidence (understood in light of Applicant’s arguments as Examples 4-5; Remarks Pg. 6) appears to require at least the following elements, which are currently not required in independent Claim 1:
A positive electrode material consisting of Li1Ni0.6Co0.2Mn0.2O2 (NCM622), acetylene black (AB) and polyvinylidene fluoride (PVdF) such that the ratio of NCM622 : AB : PVdF is 94 : 4.2 : 1.8 [0097];
NCM622 with a median diameter of 12 µm [0097];
A negative electrode active material mixture layer comprising graphite particles, 1 wt% acetylene black, 1 wt% carboxymethyl cellulose, 1.5 wt% styrene butadiene rubber and 0.1 to 0.5 wt% of an inorganic solid, wherein the inorganic solid consists of NSS (Table 1);
Natural graphite with a median diameter of graphite of 12 µm as the negative electrode active material [0098];
A polyethylene microporous membrane as the separator, with one side coated with alumina particles of about 5 µm [0100];
An electrolytic solution comprising LiPF6 as an electrolyte salt and a mixed solvent of ethylene carbonate, ethyl methyl carbonate, and dimethyl carbonate in a volume ratio of 30:30:40 [0100].
For at least these reasons, Claim 1 appears to be broader in scope than the showing of evidence. Examiner notes that each of these differences appears critical absent persuasive discussion/evidence to the contrary. The missing elements noted above are provided as non-limiting examples.
Conclusion
Applicant's amendment necessitated the new ground(s) of rejection presented in this Office action. Accordingly, THIS ACTION IS MADE FINAL. See MPEP § 706.07(a). Applicant is reminded of the extension of time policy as set forth in 37 CFR 1.136(a).
A shortened statutory period for reply to this final action is set to expire THREE MONTHS from the mailing date of this action. In the event a first reply is filed within TWO MONTHS of the mailing date of this final action and the advisory action is not mailed until after the end of the THREE-MONTH shortened statutory period, then the shortened statutory period will expire on the date the advisory action is mailed, and any nonprovisional extension fee (37 CFR 1.17(a)) pursuant to 37 CFR 1.136(a) will be calculated from the mailing date of the advisory action. In no event, however, will the statutory period for reply expire later than SIX MONTHS from the mailing date of this final action.
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/D.C.N./Examiner, Art Unit 1751
/JONATHAN G LEONG/Supervisory Patent Examiner, Art Unit 1751 8/6/2025