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 .
Continued Examination Under 37 CFR 1.114
A request for continued examination under 37 CFR 1.114, including the fee set forth in 37 CFR 1.17(e), was filed in this application after final rejection. Since this application is eligible for continued examination under 37 CFR 1.114, and the fee set forth in 37 CFR 1.17(e) has been timely paid, the finality of the previous Office action has been withdrawn pursuant to 37 CFR 1.114. Applicant's submission filed on 24 July 2025 has been entered.
Status of Claims
Claims 1 and 7 have been amended. Claims 11-18 stand withdrawn. Claims 1-7 and 9-10, as filed 24 July 2025, are examined herein. No new matter is included herein.
Response to Arguments
The objection to claim 7 is withdrawn in light of Applicant’s amendment.
Regarding the rejection under 35 USC 103, Applicant argues that the cited reference Joseph does not disclose which stage coating the carbon on the electrodes is executed, and specifically did not disclose coating with carbon then activation treating using plasma. This argument is moot in light of a new citation from Joseph which explicitly teaches the application of plasma treatment to a positive electrode comprising a positive active material, PVDF binder, and carbon.
Applicant further argues that Zhang does not disclose carbon coating then activation treatment. This argument is moot, in light of the new citation from Joseph.
Applicant further argues (page 7) that Zhang does not disclose that the NVP material is obtained by activation treating under cold plasma. Examiner notes that the instant claim 1 does not require NVP, and that the specification does not disclose forming the NVP using activation treatment under cold plasma. If Applicant intents to argue that the nitrogen doping of the carbon coating of Zhang’s NVP material is carried out prior to forming the positive electrode layer, Examiner agrees that Zhang’s disclosed 1-2% nitrogen doped carbon coating (formed by the introduction of melamine and sintering at 800˚C under Argon, see page 335 col. 1) is carried out prior to forming the positive electrode layer. However, Zhang is cited to provide motivation for the selection of NVP material and the selection of 1-2% nitrogen doped carbon coating, with the process to be carried out as taught by Joseph.
Applicant further argues (page 7 final paragraph) that in the instant invention, vanadium sodium phosphate, carbon black, and PVDF binder are coated onto Al foil, then activation treatment and doping is carried out. Examiner notes the instant specification at [0068] discloses “positive active material layer may also include a conductive agent and a binder.” The instant specification does not disclose that the conductive agent is carbon black, and does not disclose that the binder is PVDF. The instant specification appears to disclose two methods of adding carbon to the positive active material layer: the use of a conductive agent at [0068] and at [0047] (emphasis added) “The carbon layer 113 attached or coated on the surface of the cathode material layer 112 is doped by the high activity particle 114 generated by cold plasma, which can form more defects on the surface of the carbon layer 113 and improve the stability of the interface between the cathode material layer 112.” The limitation of claim 1 “wherein the positive electrode material to be treated is Na-containing and at least part of a surface of the positive electrode material to be treated is coated with a carbon layer, and the activation treating is performed under cold plasma to carry out active particle doping on the carbon layer” does not require the positive electrode material to be NVP, does not require the active particle doping to be nitrogen, and does not require that the carbon coating “layer” be coated onto the positive active material particle layer. Said differently, the limitations of claim 1 can be met with any of the following starting materials: a) a carbon coated, Na-containing positive active material particle b) a positive electrode having an aluminum current collector, and coated with a slurry of Na-containing positive active material particle, carbon-containing conductive additive, and binder; or c) a positive electrode having an aluminum current collector, and coated with a slurry of Na-containing positive active material particle and binder, then coated with a layer of carbon.
Applicant further argues that Choi makes the NaF layer by a different method. Applicant's argument is not persuasive. Choi is cited to provide evidence that a person of ordinary skill is aware of the desirability of the NaF layer.
Claim Rejections - 35 USC § 103
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.
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) 1-7 is/are rejected under 35 U.S.C. 103 as being unpatentable over Joseph (Joseph et. al., 2018, Plasma enabled synthesis and processing of materials for lithium‐ion batteries. Advanced Materials Technologies, 3(9), 1800070) and Zhang (Zhang, et. al., 2017, Effects of nitrogen doping on the structure and performance of carbon coated Na3V2 (PO4)3 cathodes for sodium-ion batteries. Carbon, 124, 334-341).
Regarding claim 1, Joseph teaches a method for treating positive electrode material of a battery, comprising:
Regarding the limitation “doping active particles on a positive electrode material to be treated and forming a NaF layer by activation treating the positive electrode material to be treated to obtain doped positive electrode material, wherein the positive electrode material to be treated is Na-containing and at least part of a surface of the positive electrode material to be treated is coated with a carbon layer,” the broadest reasonable interpretation of the instant claim limitation is determined to include “1) obtaining positive electrode material which comprises a carbon layer 2) activation treating the positive electrode material to obtain doped positive electrode material and form an NaF layer.”
Joseph teaches (page 2 col. 2) the influence of plasma treatments on crystal structure and conductivity. At (page 3 col 1-2), plasma synthesis “permits the inclusion of dopant species into the nanostructures
with ease” At (page 5 col. 1), (emphasis added) “LiMn2O4 [positive active material] was coated onto a substrate with PVDF and carbon black which was then treated with DC pulsed plasma for a few minutes. The morphology of the electrodes was transformed into a smooth interconnected surface compared to the untreated electrodes where the grain boundaries are clearly visible. The resultant smooth and dense
surface enhanced the overall performance by improving the conductivity and reducing the dissolution of manganese ions into the electrolyte.” Joseph explicitly teaches the use of plasma for nitrogen doping (page 7 col. 1) and (page 11 col. 2) the use of oxygen plasma to introduce oxygen functional groups, where the oxygen functional groups can “improve the wettability and increase the electrical insulating
property of the material and restrict the electronegative polysulfides to the cathode, this in turn reduces the polysulfide shuttling effect and enhances the battery stability.”
A person of ordinary skill in the art would have been motivated, as of before the effective filing date of the instant invention, to select a plasma treatment process for a positive electrode comprising positive active material, PVDF, and carbon black, in order to dope the carbon material, with a reasonable expectation of successfully improving electrode conductivity, improving wettability, and enhancing the battery stability.
Regarding the limitation “the activation treating is performed under cold plasma to carry out active particle doping on the carbon layer, wherein an doped amount of the active particles is not less than 50ppm, at least part of the surface of the doped positive electrode material is rod-like and comprises the NaF layer,” the broadest reasonable interpretation of the instant claim limitation is determined to include “wherein the activation treating is performed under cold plasma to dope the carbon layer at 50ppm or more, and at least part of the surface of the doped positive electrode material layer is rod-like and comprises the NaF layer.”
Joseph at (page 2 col. 1) discloses that plasma treatment includes thermal plasma and cold plasma, where cold plasma … provides a highly reactive environment which induces unique nanoarchitecture formation and assembly pathways. … crystalline nanoparticles of materials with high melting points can be formed at lower threshold temperatures, which avoids the need to heat the whole substrate unlike CVD methods.
A person of ordinary skill in the art would have been motivated, as of before the effective filing date of the instant invention, to select cold plasma treatment for the positive electrode of modified Joseph, with a reasonable expectation of obtaining the benefits of forming crystalline nanoparticles at lower threshold temperatures, which avoids the need to heat the whole substrate.
Joseph does not explicitly teach: “wherein the activation treating dopes the carbon layer at 50ppm or more, and at least part of the surface of the doped positive electrode material layer is rod-like and comprises the NaF layer.”
Zhang teaches (abstract) that sodium vanadium phosphate (NVP) is “a promising cathode material for sodium ion batteries due to the good electrochemical performance in terms of cycling stability and rate capability. However … a carbon coating is required to enhance the intrinsically poor material's conductivity. At (page 335 col. 1) Zhang teaches that a nitrogen-doped carbon coating improves the electrode electronic conductivity and electrode/electrolyte interface stability, both being extremely beneficial for the electrochemical performance. Zhang further teaches (page 336 col. 1, para 1) nitrogen-doped carbon, with a nitrogen content of 0.95 weight % and 1.94 weight %. ( This falls within claimed range of 50 ppm or more.)
Zhang teaches (page 336 col.2 para 1) an “appropriate amount of N-doping … enhances electrons conductivity.” At page 338, FIG. 4(b) an active material with nitrogen doping is shown to have improved capacity retention.) At page 340, “ With appropriate amount of N-doping, a superior electrochemical behavior is obtained as evident from the decreased voltage hysteresis, improved capacity and superior cycling stability with higher redox kinetic and lower solid electrolyte interface film resistance.”
A person of ordinary skill in the art would have been motivated, as of before the effective filing date of the instant invention, to select the sodium vanadium phosphate active material and the 0.95 weight % or higher nitrogen doping of Zhang for Joseph’s active material later, with a reasonable expectation of achieving the desirable properties of enhances electrical conductivity and improved capacity retention.
Joseph in view of Zhang does not explicitly teach wherein at least part of the surface of the doped positive electrode material is rod-like and comprises a NaF layer. However, the instant specification teaches that the process steps of claim 1 create a NaF layer when the positive electrode material to be treated contains Na. Because Joseph in view of Zhang has the appropriate positive electrode material and carries out the appropriate steps, it therefore creates a rod-like NaF layer.
Regarding claim 2, Joseph in view of Zhang teaches all of the limitations as set forth above, and Joseph teaches (FIG. 3) that a plasma process time could be 1-4 minutes, which falls within the range of the instant claim limitation, 1-60 minutes. Joseph does not explicitly teach wherein a power for activation treatment is 100 W-500 W, a cold plasma treating voltage is 50 V-150 V and a treating current is 0.4 A-2 A. A person of ordinary skill in the art would have been motivated, as of before the effective filing date of the instant invention, to optimize the operation parameters of the cold plasma treatment, in order to obtain successful active particle doping, with a reasonable expectation of success.
Regarding claim 3, Joseph in view of Zhang teaches all of the limitations as set forth above, and Joseph further teaches wherein a discharge to generate cold plasma is selected from one or a combination of radio-frequency plasma discharge, corona discharge, dielectric barrier discharge, and sliding arc discharge. (Page 7 col. 2 “radio frequency inductive coupled plasma”)
Regarding claim 4, Joseph in view of Zhang teaches all of the limitations as set forth above, and Joseph further teaches (page 6 col. 2 “DC-pulsed plasma in O2 atmosphere.”). However, Joseph does not explicitly teach wherein the active particle doping (of the carbon layer) is either oxygen doping or nitrogen doping or a combination thereof. Zhang teaches (abstract) the use of N-doped carbon coatings on active material. The motivation to use Zhang’s N-doped carbon coating as set forth in claim 1 is incorporated herein.
Regarding claim 5, Joseph in view of Zhang teaches all of the limitations as set forth above. Joseph in view of Zhang (as set forth in claim 1, above) teaches wherein in the cold plasma treatment includes inputting a precursor gas including one or a combination of oxygen and nitrogen into a cold plasma generator to generate active particles to be doped in the carbon layer. Joseph is silent on wherein a flow rate of the precursor gas is 1 ml/s~15 ml/s. A person of ordinary skill in the art would have been motivated, as of before the effective filing date of the instant invention, to optimize the flow rate of the gas for the cold plasma treatment, in order to obtain successful active particle doping, with a reasonable expectation of success.
Regarding claim 6, Joseph in view of Zhang teaches all of the limitations as set forth above, and Joseph further teaches wherein the positive electrode material is (Page 1 col. 2) “lithium metal oxide cathodes” or (page 3 col. 2) “crystalline nickel manganese cobalt (NMC) oxide”). These candidates are within the scope of the claimed list of alternatives.
Regarding claim 7, Joseph in view of Zhang teaches all of the limitations as set forth above. Joseph does not explicitly teach wherein the positive electrode material of the battery is vanadium phosphate sodium, sodium titanium phosphate, sodium fluoride phosphate, or NaMO2, wherein M is Co, Ni, Mn, V or Fe, and N may be Co, Ni, Mn or V.
Zhang teaches (abstract) the use of N-doped carbon coatings on positive active material and teaches (page 340 col. 1) the use of sodium vanadium phosphate active material. At page 340, “ With appropriate amount of N-doping, a superior electrochemical behavior is obtained as evident from the decreased voltage hysteresis, improved capacity and superior cycling stability with higher redox kinetic and lower solid electrolyte interface film resistance.” A person of ordinary skill in the art would have been motivated, as of before the effective filing date of the instant invention, to select the sodium vanadium phosphate active material of Joseph in view of Zhang, with a reasonable expectation of achieving desirable electrochemical behavior.
Alternatively, claim(s) 1-7 and 9-10 is/are rejected under 35 U.S.C. 103 as being unpatentable over Joseph (Joseph et. al., 2018, Plasma enabled synthesis and processing of materials for lithium‐ion batteries. Advanced Materials Technologies, 3(9), 1800070) and Zhang (Zhang, et. al., 2017, Effects of nitrogen doping on the structure and performance of carbon coated Na3V2 (PO4)3 cathodes for sodium-ion batteries. Carbon, 124, 334-341) and in further view of Choi (US 20230238538 A1.)
Regarding claim 1, Joseph teaches a method for treating positive electrode material of a battery, comprising:
Regarding the limitation “doping active particles on a positive electrode material to be treated and forming a NaF layer by activation treating the positive electrode material to be treated to obtain doped positive electrode material, wherein the positive electrode material to be treated is Na-containing and at least part of a surface of the positive electrode material to be treated is coated with a carbon layer,” the broadest reasonable interpretation of the instant claim limitation is determined to include “1) obtaining positive electrode material which comprises a carbon layer 2) activation treating the positive electrode material to obtain doped positive electrode material and form an NaF layer.”
Joseph teaches (page 2 col. 2) the influence of plasma treatments on crystal structure and conductivity. At (page 3 col 1-2), plasma synthesis “permits the inclusion of dopant species into the nanostructures
with ease” At (page 5 col. 1), (emphasis added) “LiMn2O4 [positive active material] was coated onto a substrate with PVDF and carbon black which was then treated with DC pulsed plasma for a few minutes. The morphology of the electrodes was transformed into a smooth interconnected surface compared to the untreated electrodes where the grain boundaries are clearly visible. The resultant smooth and dense
surface enhanced the overall performance by improving the conductivity and reducing the dissolution of manganese ions into the electrolyte.” Joseph explicitly teaches the use of plasma for nitrogen doping (page 7 col. 1) and (page 11 col. 2) the use of oxygen plasma to introduce oxygen functional groups, where the oxygen functional groups can “improve the wettability and increase the electrical insulating
property of the material and restrict the electronegative polysulfides to the cathode, this in turn reduces the polysulfide shuttling effect and enhances the battery stability.”
A person of ordinary skill in the art would have been motivated, as of before the effective filing date of the instant invention, to select a plasma treatment process for a positive electrode comprising positive active material, PVDF, and carbon black, in order to dope the carbon material, with a reasonable expectation of successfully improving electrode conductivity, improving wettability, and enhancing the battery stability.
Regarding the limitation “the activation treating is performed under cold plasma to carry out active particle doping on the carbon layer, wherein an doped amount of the active particles is not less than 50ppm, at least part of the surface of the doped positive electrode material is rod-like and comprises the NaF layer,” the broadest reasonable interpretation of the instant claim limitation is determined to include “wherein the activation treating is performed under cold plasma to dope the carbon layer at 50ppm or more, and at least part of the surface of the doped positive electrode material layer is rod-like and comprises the NaF layer.”
Joseph at (page 2 col. 1) discloses that plasma treatment includes thermal plasma and cold plasma, where cold plasma … provides a highly reactive environment which induces unique nanoarchitecture formation and assembly pathways. … crystalline nanoparticles of materials with high melting points can be formed at lower threshold temperatures, which avoids the need to heat the whole substrate unlike CVD methods.
A person of ordinary skill in the art would have been motivated, as of before the effective filing date of the instant invention, to select cold plasma treatment for the positive electrode of modified Joseph, with a reasonable expectation of obtaining the benefits of forming crystalline nanoparticles at lower threshold temperatures, which avoids the need to heat the whole substrate.
Joseph does not explicitly teach: “wherein the activation treating dopes the carbon layer at 50ppm or more, and at least part of the surface of the doped positive electrode material layer is rod-like and comprises the NaF layer.”
Zhang teaches (abstract) that sodium vanadium phosphate (NVP) is “a promising cathode material for sodium ion batteries due to the good electrochemical performance in terms of cycling stability and rate capability. However … a carbon coating is required to enhance the intrinsically poor material's conductivity. At (page 335 col. 1) Zhang teaches that a nitrogen-doped carbon coating improves the electrode electronic conductivity and electrode/electrolyte interface stability, both being extremely beneficial for the electrochemical performance. Zhang further teaches (page 336 col. 1, para 1) nitrogen-doped carbon, with a nitrogen content of 0.95 weight % and 1.94 weight %. ( This falls within claimed range of 50 ppm or more.)
Zhang teaches (page 336 col.2 para 1) an “appropriate amount of N-doping … enhances electrons conductivity.” At page 338, FIG. 4(b) an active material with nitrogen doping is shown to have improved capacity retention.) At page 340, “ With appropriate amount of N-doping, a superior electrochemical behavior is obtained as evident from the decreased voltage hysteresis, improved capacity and superior cycling stability with higher redox kinetic and lower solid electrolyte interface film resistance.”
A person of ordinary skill in the art would have been motivated, as of before the effective filing date of the instant invention, to select the sodium vanadium phosphate active material and the 0.95 weight % or higher nitrogen doping of Zhang for Joseph’s active material later, with a reasonable expectation of achieving the desirable properties of enhances electrical conductivity and improved capacity retention.
Joseph as modified by Zhang does not teach at least part of the surface of the doped positive electrode material is rod-like and comprises a NaF layer.
Choi teaches (FIG. 1) a rod-like material on the surface of a positive active material, and teaches [0010-0019] that the positive active material may include a metal fluoride disposed on the surface, which ([0018]) may be NaF. Choi teaches ([0008]) that the surface coatings provide the benefit of minimizing physical contact between the solid electrolyte and a conductive material.
A person of ordinary skill in the art would have been motivated, as of before the effective filing date of the instant invention, to modify Joseph as modified by Zhang with the carbon and NaF coating of Choi, with a reasonable expectation of successfully preventing contact between the solid electrolyte and the conductive material.
Regarding claim 2, Joseph in view of Zhang and Choi teaches all of the limitations as set forth above, and Joseph teaches (FIG. 3) that a plasma process time could be 1-4 minutes, which falls within the range of the instant claim limitation, 1-60 minutes. Joseph does not explicitly teach wherein a power for activation treatment is 100 W-500 W, a cold plasma treating voltage is 50 V-150 V and a treating current is 0.4 A-2 A. A person of ordinary skill in the art would have been motivated, as of before the effective filing date of the instant invention, to optimize the operation parameters of the cold plasma treatment, in order to obtain successful active particle doping, with a reasonable expectation of success.
Regarding claim 3, Joseph in view of Zhang and Choi teaches all of the limitations as set forth above, and Joseph further teaches wherein a discharge to generate cold plasma is selected from one or a combination of radio-frequency plasma discharge, corona discharge, dielectric barrier discharge, and sliding arc discharge. (Page 7 col. 2 “radio frequency inductive coupled plasma”)
Regarding claim 4, Joseph in view of Zhang and Choi teaches all of the limitations as set forth above, and Joseph further teaches (page 6 col. 2 “DC-pulsed plasma in O2 atmosphere.”). However, Joseph does not explicitly teach wherein the active particle doping (of the carbon layer) is either oxygen doping or nitrogen doping or a combination thereof. Zhang teaches (abstract) the use of N-doped carbon coatings on active material. The motivation to use Zhang’s N-doped carbon coating as set forth in claim 1 is incorporated herein.
Regarding claim 5, Joseph in view of Zhang and Choi teaches all of the limitations as set forth above. Joseph in view of Zhang (as set forth in claim 1, above) teaches wherein in the cold plasma treatment includes inputting a precursor gas including one or a combination of oxygen and nitrogen into a cold plasma generator to generate active particles to be doped in the carbon layer. Joseph is silent on wherein a flow rate of the precursor gas is 1 ml/s~15 ml/s. A person of ordinary skill in the art would have been motivated, as of before the effective filing date of the instant invention, to optimize the flow rate of the gas for the cold plasma treatment, in order to obtain successful active particle doping, with a reasonable expectation of success.
Regarding claim 6, Joseph in view of Zhang and Choi teaches all of the limitations as set forth above, and Joseph further teaches wherein the positive electrode material is a polyanionic compound, a layered oxide, a spinel compound, a Prussian blue, or a ternary lithium battery positive material. (Page 1 col. 2 “lithium metal oxide cathodes”; page 3 col. 2 “crystalline nickel manganese cobalt (NMC) oxide”)
Regarding claim 7, Joseph in view of Zhang and Choi teaches all of the limitations as set forth above. Joseph does not explicitly teach wherein the positive electrode material of the battery is vanadium phosphate sodium, sodium titanium phosphate, sodium fluoride phosphate, or NaMO2, wherein M is Co, Ni, Mn, V or Fe, and N may be Co, Ni, Mn or V.
Zhang teaches (abstract) the use of N-doped carbon coatings on positive active material and teaches (page 340 col. 1) the use of sodium vanadium phosphate active material. At page 340, “ With appropriate amount of N-doping, a superior electrochemical behavior is obtained as evident from the decreased voltage hysteresis, improved capacity and superior cycling stability with higher redox kinetic and lower solid electrolyte interface film resistance.” A person of ordinary skill in the art would have been motivated, as of before the effective filing date of the instant invention, to select the sodium vanadium phosphate active material modified Joseph’s plasma-doped, carbon-coated active material, with a reasonable expectation of achieving desirable electrochemical behavior.
Regarding claim 9, Joseph in view of Zhang and Choi teaches all of the limitations as set forth above, and Choi further teaches ([0015]) wherein an average length of the rod-like shape is 2 µm to 10 µm (overlaps the instant claim range of 1.5 µm to 3 µm) and an average diameter is from 100nm to 300nm (overlaps the instant claim range of 150nm to 300nm.)
Regarding claim 10, Joseph in view of Zhang and Choi teaches all of the limitations as set forth above, and further teaches the method of Claim 1, and Choi does not explicitly teach wherein the content of the NaF is not less than 500 ppm wherein the NaF layer has an average thickness of 6 nm-10 nm. However, Choi teaches ([0050]) that the NaF has an excellent insulating property, and minimizes contact between the carbon-based material and the solid electrolyte. A person of ordinary skill in the art would have been motivated, as of before the effective filing date of the instant invention, to optimize the coating amount of NaF to identify an NaF amount and thickness that is sufficient to provide insulation, with a reasonable expectation of obtaining a material which meets the current claim limitations.
Conclusion
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CLAIRE A. RUTISER
Examiner
Art Unit 1751
/C.A.R./Examiner, Art Unit 1751
/JONATHAN G LEONG/Supervisory Patent Examiner, Art Unit 1751 1/9/2026