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 .
Summary
Since the Office Action mailed on 10 September 2025, claim 1 and withdrawn claim 31 has been amended, and claims 1, 4, 8, 11-13, 18, 24, 28 and 63-69 currently remain in the application for further examination with full consideration of applicant remarks.
The 103 rejections are maintained, and applicant remarks responded to, in this Office Action.
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 Rejections - 35 USC § 103
Claims 1, 4, 8, 11-13, 28, 63 and 66-67 are rejected under 35 U.S.C. 103 as being unpatentable over Xu et al (“Energetic Zinc Ion Chemistry: The Rechargeable Zinc Ion Battery”, Angewandte Chemie Int. Ed., 2012, 51 & “Supporting Information”, Wiley-VCH 2012) in view of Phillips et al (US 2010/0092857 A1). Hereinafter referred to as Xu and Phillips, respectively.
Regarding claim 1, Xu discloses a secondary electrochemical cell for storing and delivering electrical energy (“zinc ion battery … can deliver a high capacity” article p. 933, first paragraph, last sentence), the secondary electrochemical cell comprising:
a zinc metal negative electrode (“zinc anode” article p. 933, third paragraph, first sentence) having a thickness less than 500 micrometers (“100μm in thickness” supporting information p. 1, second paragraph), comprising:
a negative electrode current collector (“current collector, stainless steel foil (30μm)” supporting information p. 1, third sentence); and
a zinc metal layer applied to the negative electrode current collector (“For the negative electrode, Zn power (64%), activated carbon (6%), carbon black (20%) and PVDF binder (10%) were mixed to obtain the slurry at an appropriate viscosity, which was coated on conductive layer and then dried” supporting information, p. 1, seventh sentence);
a positive electrode (“α-MnO2 cathode” article p. 933, third paragraph, first sentence) having a thickness less than one millimeter (“100μm in thickness” supporting information p. 1, second paragraph), comprising:
a positive electrode current collector (“current collector, stainless steel foil (30μm)” supporting information p. 1, third paragraph); and
an active material layer applied to the positive electrode current collector (“MnO2 (70%), carbon black (20%) and PVDF binder (10%) were mixed to obtain the slurry at an appropriate viscosity, which was coated on conductive layer and then dried” supporting information p. 1, third paragraph);
wherein the active material layer electrochemically reacts reversibly with Zn2+ cations (“Zn2+ ions can be reversibly intercalated into tunnels of α-MnO2” article p. 933, third paragraph, fourth sentence) and over 90% of charge transferred during a discharge reaction is recovered when the cell is fully charged (“the discharge capacity of the ZIB still remains near 100% of original values” article p. 935, first paragraph);
an aqueous electrolyte (“a mild ZnSO4 or Zn(NO3)2 aqueous electrolyte” article p. 933, third paragraph, first sentence) comprising the Zn2+ cations (“in a mild aqueous solution containing Zn2+ ions” article p. 933, third paragraph, third sentence);
wherein the aqueous electrolyte comprises only a single electrolyte composition (“a mild ZnSO4 or Zn(NO3)2 aqueous electrolyte” article p. 933, third paragraph, first sentence, which is exclusive language and intends use of one composition or the other, and never a combination of both) ionically coupling both the negative and the positive electrode (as cited in the limitation above - “in a mild aqueous solution containing Zn2+ ions” article p. 933, third paragraph, third sentence, and Xu supplemental reference Figure SI2 shows the battery chemistry, which involves Zn2+ of the anode reacting with OH- compounds, and therefore couples the negative and positive electrodes); and
a separator (“filter paper was used as the separator” supporting information p. 1, third paragraph, last sentence) disposed between the negative electrode and the positive electrode (Supporting information Figure SI1 (b));
wherein the zinc metal layer has an areal capacity greater than an areal capacity of the positive electrode (see calculations for theoretical negative and positive electrode capacity, Qtheoretical, below, which results in the zinc metal layer of the negative electrode capacity being greater than the positive electrode)
Q
t
h
e
o
r
e
t
i
c
a
l
=
n
F
3600
∙
M
w
=
n
∙
(
96485.333
C
m
o
l
)
3600
∙
M
w
(Eq. 1)
where n is the charge number of the active material ion, F is the Faraday constant, and Mw is the active material molecular weight, yielding Qtheoretical in units of Ah/g.
For Zn in the slurry disclosed in the supporting information of Xu,
Q
z
i
n
c
m
e
t
a
l
l
a
y
e
r
=
2
∙
(
96485.333
C
m
o
l
)
3600
∙
65.38
g
m
o
l
=
0.82
A
h
g
(Eq. 2)
By factoring in the density of Zn into Eq. 2 and the thickness of the negative electrode active material or Zn foil used in the battery assembled in Xu, the following is obtained.
Q
z
i
n
c
m
e
t
a
l
l
a
y
e
r
=
0.82
A
h
g
∙
7.14
g
c
m
3
∙
0.0065
c
m
=
0.038
A
h
c
m
2
∴
Q
z
i
n
c
m
e
t
a
l
l
a
y
e
r
=
38
m
A
h
c
m
2
Similarly,
Q
p
o
s
i
t
i
v
e
e
l
e
c
t
r
o
d
e
=
2
∙
(
96485.333
C
m
o
l
)
3600
∙
86.937
g
m
o
l
=
0.62
A
h
g
(Eq. 3)
Q
p
o
s
i
t
i
v
e
e
l
e
c
t
r
o
d
e
=
0.62
A
h
⁄
g
∙
5.03
g
c
m
3
∙
0.0065
c
m
=
0.020
∴
Q
p
o
s
i
t
i
v
e
e
l
e
c
t
r
o
d
e
=
20
m
A
h
c
m
2
;
wherein the zinc metal negative electrode has a first face and a second face (the faces of ‘Negative Zn electrodes’ extending in the vertical and width direction of Figure SI1(b) in Supporting Information), and wherein the areal capacity of the zinc metal layer is greater than or equal to 1 mAh/cm2 on each of the first face and the second face of the negative electrode (results from Eq 2 above, divided by 2 for each face of the negative electrode, which further results in 19 mAh/cm2); and
wherein during normal operation, the Zn2+ cations are consumed by each electrode at approximately an identical rate as the Zn2+ cations are produced by the other electrode (“Cyclic
voltammogram of integral cell indicated that the insertion and extraction potentials of zinc ion occur in accordance with the single α-MnO2 electrode measurements” supporting information p. 18, last sentence) such that discharging the cell to a capacity and charging the cell to the capacity in a discharge-charge cycle results in a concentration of the Zn2+ cations in the separator being within 10% of the concentration of the Zn2+ cations in the separator prior to the discharge-charge cycle (“The continuous rechargeability of ZIB has been investigated by the galvanostatic charge/discharge cycling tests at 100% depth of discharge.” supporting information p. 20, first sentence).
Xu does not disclose the separator having a thickness less than 200 micrometers, wherein the separator is wetted by the aqueous electrolyte comprising only the single electrolyte composition as a bridge between the negative electrode and the positive electrode.
However, Phillips discloses a secondary electrochemical cell for storing an delivering electrical energy (“power cell” [0030]) that comprises a zinc metal negative electrode (“negative electrode includes one or more electroactive sources of zinc or zincate ions” [0037]) comprising of a zinc metal layer applied to a negative electrode current collector (“current collector contains a core metal layer coated (fully or partially) with a zinc alloy” [0113]), a positive electrode (“positive electrode” [0068]) comprising an active material layer applied to a positive electrode current collector (“A nickel foam matrix is preferably used to support the electroactive nickel (e.g., Ni(OH)2) electrode material” [0070]) wherein the active material layer electrochemically reacts reversibly with Zn2+ cations (“zinc-nickel battery has excellent properties, such as … good reversibility” [0005]), and a separator disposed between the negative electrode and the positive electrode (“negative electrode-separator-positive electrode sandwich structure … The separator 305 mechanically separates the negative electrode (components 301 and 303) from the positive electrode ( components 307 and309) while allowing ionic exchange to occur between the electrodes and the electrolyte” [0105]). Phillips teaches the separator having a thickness less than 200 micrometers (“This material is 20 microns thick” [0081]), and wherein the separator is wetted by an aqueous electrolyte comprising only a single electrolyte composition (“Soaking for several hours in a dilute aqueous solution” [0082] with italics added for emphasis addressing “only a single electrolyte composition” limitation of the claim) as a bridge between the negative electrode and the positive electrode (“a single separator material may be used to block zinc penetration and to keep the cell wet with electrolyte” [0080]). Phillips further teaches that this embodiment of the separator blocks zinc dendrite formation that occurs in the aqueous electrolyte of the electrochemical cell during the lifetime of the cell, which bridges the negative electrode and the positive electrode that results in shorts and subsequent loss of battery function ([0073]).
Therefore, it would have been obvious for a person of ordinary skill in the art to modify the separator of the secondary electrochemical cell of Xu in a way that the separator has a thickness less than 200 micrometers and is wetted by the aqueous electrolyte comprising only the single electrolyte composition as a bridge between the negative electrode and the positive electrode, in view of Phillips. The person of ordinary skill in the art would be able to achieve a separator that blocks zinc dendrite formation that occurs in the aqueous electrolyte of the electrochemical cell during the lifetime of the cell, preventing the occurrence of shorts and loss of battery function.
Regarding claim 4, modified Xu discloses all the limitations for the secondary electrochemical cell as set forth in claim 1 above, but does not disclose wherein the negative electrode current collector has a thickness less than or equal to 50 µm (Xu supporting information “current collector, stainless steel foil (30μm)” p. 1, third paragraph, third sentence).
Regarding claim 8, modified Xu discloses all the limitations for the secondary electrochemical cell as set forth in claim 1 above, and wherein the aqueous electrolyte comprises a zinc salt dissolved in water (Xu “a mild ZnSO4 or Zn(NO3)2 aqueous electrolyte” p. 933, third paragraph, first sentence).
Regarding claim 11, modified Xu discloses all the limitations for the secondary electrochemical cell as set forth in claim 8 above, and wherein the zinc salt is selected from a group consisting of zinc sulfate (Xu “ZnSO4” p. 933, third paragraph, first sentence), zinc acetate, zinc citrate, zinc iodide, zinc chloride, zinc perchlorate, zinc bis(trifluoromethanesulfonyl)imide, zinc nitrate (Xu “Zn(NO3)2” p. 933, third paragraph, first sentence), zinc phosphate, zinc triflate, zinc tetrafluoroborate, and zinc bromide.
Regarding claim 12, modified Xu discloses all the limitations for the secondary electrochemical cell as set forth in claim 1 above, and wherein the aqueous electrolyte has a pH value between 4 and 6 (Xu “(pH 5.2)” Figure 2.).
Regarding claim 13, modified Xu discloses all the limitations for the secondary electrochemical cell as set forth in claim 1 above, but does not disclose wherein the aqueous electrolyte comprises a gelling agent for increasing the viscosity of the aqueous electrolyte.
However, Phillips teaches wherein the aqueous electrolyte comprises a gelling agent for increasing the viscosity of the aqueous electrolyte (“the electrolyte may comprise a liquid and a gel. The gel electrolyte may comprise a thickening agent” [0089]), and that this embodiment of the aqueous electrolyte limits dendrite formation and other forms of material redistribution in the zinc metal negative electrode ([0086]).
Therefore, it would have been obvious for a person of ordinary skill in the art to further modify the electrochemical cell of modified Xu in view of Phillips wherein the aqueous electrolyte comprises a gelling agent for increasing the viscosity of the aqueous electrolyte, in order to further ensure the electrochemical cell prevents dendrite formation, and other forms of material redistribution in the zinc metal negative electrode.
Regarding claim 24, modified Xu discloses all the limitations for the secondary electrochemical cell as set forth in claim 1 above, and wherein the positive electrode has a first face and a second face (Xu supporting information Figure SI1 (b) where the ‘Positive MnO2 electrodes’ have two faces opposite of one another that extends in the vertical and the width direction of the electrodes), and wherein the storage capacity per electrode area is between 1 mAh/cm2 and 10 mAh/cm2 on each of the first face and the second face of the positive electrode (results from Eq 3 above, divided by 2 for each face of the positive electrode, which further results in 10 mAh/cm2).
Regarding claim 28, modified Xu discloses all the limitations for the secondary electrochemical cell as set forth in claim 1 above, but does not disclose wherein the positive electrode current collector has a thickness less than or equal to 50 µm (Xu supporting information “current collector, stainless steel foil (30μm)” p. 1, third paragraph, third sentence).
Regarding claim 63, modified Xu discloses all the limitations for the secondary electrochemical cell as set forth in claim 1 above, and wherein the active material layer comprises manganese dioxide (Xu “an α-MnO2 cathode” p. 933, third paragraph, first sentence).
Regarding claim 66, modified Xu discloses all the limitations for the secondary electrochemical cell as set forth in claim 1 above, and wherein the number of Zn2+ ions produced or consumed in electrochemical reactions at the negative and positive electrode is greater than the number of Zn2+ ions in the separator when the cell is charged or discharged to the full storage capacity of the cell (Xu “the charge storage mechanism is based on the migration of Zn2+ ions between cathode and anode” p. 933 second column, first paragraph, last sentence, and supporting information p. 20 first sentence states that “The continuous rechargeability of ZIB has been investigated by the galvanostatic charge/discharge cycling tests at 100% depth of discharge” where about all of the Zn2+ ions are migrating between the cathode and the anode only).
Regarding claim 67, modified Xu discloses all the limitations for the secondary electrochemical cell as set forth in claim 63 above, and wherein the manganese dioxide has a tunneled crystal structure (u “an α-MnO2 cathode” p. 933, third paragraph, first sentence, which α-MnO2 is known in the art to have a tunneled crystal structure).
Claim 18 is rejected under 35 U.S.C. 103 as being unpatentable over Xu et al (“Energetic Zinc Ion Chemistry: The Rechargeable Zinc Ion Battery”, Angewandte Chemie Int. Ed., 2012, 51 & “Supporting Information”, Wiley-VCH 2012) in view of Phillips et al (US 2010/0092857 A1), and further in view of Frischmann et al (WO 2018/106957 A1). Hereinafter referred to as Frischmann.
Regarding claim 18, modified Xu discloses all the limitations for the secondary electrochemical cell as set forth in claim 1 above, but does not disclose wherein the separator comprises ceramic or glass particles embedded in a polymeric matrix of textile fibers.
However, Frischmann discloses a secondary electrochemical cell (“lithium-ion (Li-ion) batteries” [0003]) comprising an aqueous electrolyte (“Electrolyte solvent 134 include may be aqueous” [0114]) and a separator (“separator 140 may include second membrane layer 146. The position of second membrane layer 146 may be such that membrane support 142 is disposed between first membrane layer 144 and second membrane layer 146 as, for example, is shown in FIG. 5 and FIG. 6. … Furthermore, first membrane layer 144 and second membrane layer 146 may be used without membrane support 142 as noted above.” [0106] where the first and second membrane layer corresponds to the claimed separator) that is wetted by the aqueous electrolyte (“At least a portion of the electrolyte is disposed within the separator” [0008]). Frischmann teaches wherein the separator comprises ceramic or glass particles embedded in a polymeric matrix of textile fibers (“the first membrane layer includes a microporous polymer” [0090] and “second membrane layer 146 is a ceramic separator coating. Some examples of ceramic materials that can be used in second membrane layer 146 include, but are not limited to, aluminum oxide, silicon oxide, silicon carbide, titanium dioxide, magnesium oxide, tin oxide, cerium oxide, zirconium oxide, barium titanite, yttrium oxide, boron nitride, ion conducting ceramic (e.g., (Li,La)Ti03, Li-La-Zr-O, sulfide based electrolytes), and combinations thereof. These ceramic materials may be present in the form of particles” [0107]). Frischmann further teaches that this separator provides physical separation between the positive electrode and the negative electrode of the electrochemical cell and prevents an electrical short between these electrodes while allowing for ion migration between the electrodes ([0111]), and that the polymeric matrix of textile fibers defines permeability characteristics of the separator ([0058]) and the ceramic particles enhances the thermal shutdown, high temperature stability and oxidative stability characteristics of the separator ([0108]).
Therefore, it would have been obvious for a person of ordinary skill in the art to modify the separator of the electrochemical cell of modified Xu in view of Frischmann wherein the separator comprises ceramic or glass particles embedded in a polymeric matrix of textile fibers in order to achieve a separator that provides physical separation between the positive electrode and the negative electrode of the electrochemical cell and prevents an electrical short between these electrodes while allowing for ion migration between the electrodes while featuring proper permeability characteristics and thermal shutdown, high temperature stability and oxidative stability characteristics.
Claims 64 and 65 are rejected under 35 U.S.C. 103 as being unpatentable over Xu et al (“Energetic Zinc Ion Chemistry: The Rechargeable Zinc Ion Battery”, Angewandte Chemie Int. Ed., 2012, 51 & “Supporting Information”, Wiley-VCH 2012) in view of Phillips et al (US 2010/0092857 A1), and further in view of Ueda (US 2013/0260214 A1). Hereinafter referred to as Ueda.
Regarding claim 64, modified Xu discloses all the limitations for the secondary electrochemical cell as set forth in claim 24 above, and wherein the positive electrode has a first face and a second face (Xu supporting information Figure SI1 (b) where the ‘Positive MnO2 electrodes’ have two faces opposite of one another that extends in the vertical and the width direction of the electrodes), but does not disclose wherein the storage capacity per electrode area is between 3 mAh/cm2 and 8 mAh/cm2 on each of the first face and the second face of the positive electrode (In addressing this limitation, the examiner recognizes that the storage capacity per electrode area can be modified or varied based on modifying or varying the thickness of the positive electrode active material layer such that, based on Eq 3, this storage capacity range corresponds to a thickness range of 10 µm to 26 µm).
However, Ueda discloses a secondary electrochemical cell (“electronic device” [0026]) comprising a negative electrode (“negative electrode” [0041]) that comprises a negative electrode current collector (“negative electrode current collector” [0041]) and a metal layer applied to the negative electrode current collector (“negative electrode active material layer” [0041] or “metal foil” [0084]), and a positive electrode (“positive electrode” [0041]) that comprises a positive electrode current collector (“positive electrode current collector” [0041]) and an active material layer applied to the positive electrode current collector (“electrode active material layer 2” [0041]). Ueda teaches wherein the storage capacity per electrode area is between 3 mAh/cm2 and 8 mAh/cm2 on each of the first face and the second face of the positive electrode (“The thickness of the positive electrode active material layer is, for example, 10 to 200 µm” [0044]). Ueda further teaches that by arranging one of the electrodes to have a high flexural modulus (i.er µm., low flexibility) compared to the flexural modulus of the other electrode, the flexural modulus of the electrochemical cell is reduced, or the flexibility is improved ([0111]).
Therefore, it would have been obvious for a person of ordinary skill in the art to modify the positive electrode of the secondary electrochemical cell of modified Xu in view of Ueda wherein the storage capacity per electrode area is between 3 mAh/cm2 and 8 mAh/cm2 on each of the first face and the second face of the positive electrode, in order to achieve improved flexibility in the electrochemical cell.
Regarding claim 65, modified Xu discloses all the limitations for the secondary electrochemical cell as set forth in claim 64 above, and wherein the positive electrode has a first face and a second face (Xu supporting information Figure SI1 (b) where the ‘Positive MnO2 electrodes’ have two faces opposite of one another that extends in the vertical and the width direction of the electrodes), and wherein the storage capacity per electrode area is between 4 mAh/cm2 and 7 mAh/cm2 on each of the first face and the second face of the positive electrode (“The thickness of the positive electrode active material layer is, for example, 10 to 200 µm” [0044] where the disclosed thickness range overlaps the claimed thickness range that corresponds to the electrode capacity per unit area of the positive electrode).
Response to Arguments
Applicant's arguments filed 12 January 2026 have been fully considered but they are not persuasive.
Applicant appears to remark that none of the prior art references disclose or teach the limitations amended into currently cited claim 1.
In response to applicant remark above, the Xu reference discloses “wherein the aqueous electrolyte comprises only a single electrolyte composition” in p. 933, third paragraph, first sentence such that “a mild ZnSO4 or Zn(NO3)2 aqueous electrolyte” (italics added for emphasis), which is exclusive language and intends use of one composition or the other, and never a combination of both. Furthermore, Xu also discloses “ionically coupling both the negative and the positive electrode” in p. 933, third paragraph, third sentence such that “in a mild aqueous solution containing Zn2+ ions” (italics added for emphasis) where Xu supplemental reference Figure SI2 shows the battery chemistry, involving Zn2+ of the anode reacting with OH- compounds and therefore coupling the negative and positive electrodes.
Conclusion
THIS ACTION IS MADE FINAL. 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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/CHARLENE BERMUDEZ/Examiner, Art Unit 1721
/ALLISON BOURKE/Supervisory Patent Examiner, Art Unit 1721