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and the fee set forth in 37 CFR 1.17(e) has been timely paid, the finality of the previous Office action has been withdrawn pursuant to 37 CFR 1.114.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 6/17/2025 has been entered.
DETAILED ACTION
This Office Action is responsive to the amendment filed on 5/26/2025. Claims 1-20 are pending. Applicant’s arguments have been considered. Claims 1-20 are non-finally rejected for reasons necessitated by applicant’s amendment.
Claim Rejections - 35 USC § 103
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.
Claims 1-5, 8-11, 13-20 are rejected under 35 U.S.C. 103 as being unpatentable over Chen (CN 114256448) in view of Chen (CN 114242988), Gao (WO 2018/032569), and Sato (JP 2007-242411), or in alternative, Chen (CN 114256448) in view of Chen (CN 114242988) and Gao (WO 2018/032569), Sato (JP 2007-242411), and Jang (LiFePO4 modified Li1.02(Co0.9Fe0.1)0.98PO4 cathodes with improved lithium storage properties, Journal of Materials Chemistry, 2011, 21, 6510-6514).
Regarding claim 1, Chen ‘448 discloses a secondary battery, comprising a positive electrode plate and a non-aqueous electrolytic solution, wherein
the positive electrode plate comprises a positive electrode active material, the positive electrode active material has a core-shell structure and comprises a core and a shell covering the core, wherein
the core has a chemical formula of LiMnxFe(1-x)PO4,
the core is electrically neutral.
Chen ‘448 discloses the shell comprises a first cladding layer covering the core, a second cladding layer covering the first cladding layer, and a third cladding layer covering the second cladding layer, wherein,
Chen ‘448 discloses the third cladding layer is carbon [0049].
Regarding claim 10, in the core the ratio of y to 1-y is from 1:10 to 1:1; and/or
in the core the ratio of z to 1-z is from 1:9 to 1:999 [0032].
Regarding claim 9, the first cladding layer has a thickness of 1 nm to 10 nm; and/or
the second cladding layer has a thickness of 2 nm to 15 nm; and/or
the third cladding layer has a thickness of 2 nm to 25 nm, Chen ‘448 clearly teaches that the second cladding layer is a result effective variable. It has been held by the courts that discovering an optimum value or workable ranges of a result-effective variable involves only routine skill in the art, and thus not novel. In re Boesch, 617 F.2d 272, 205 USPQ 215 (CCPA 1980). See MPEP 2144.05. It would have been obvious to one of ordinary skilled in the art at the time the invention was made to adjust the amount the second cladding layer of Chen ‘448 depending on the desired amount of protection of manganese dissolution.
Regarding claim 13, manganese is 10 wt% to 35 wt%, based on the weight of the positive electrode active material, Chen discloses by providing an inner core wrapped with a wrapping layer, the occurrence of manganese dissolution in the lithium iron manganese phosphate inner core with a high manganese content is effectively improved; the lithium iron manganese phosphate inner core with a high manganese content improves the energy density of the lithium iron manganese phosphate composite material; the barrier material layer blocks the dissolution of manganese in the inner core, thereby ensuring the structural stability and electrochemical stability of the lithium iron manganese phosphate composite material; the manganese content in the lithium iron manganese phosphate layer is low, thereby avoiding the occurrence of a large amount of manganese dissolution, and at the same time, the performance of the lithium iron manganese phosphate layer with a low manganese content is closer to the performance of lithium iron phosphate, which is beneficial to improving the high-rate charging and discharging of the lithium iron manganese phosphate composite material [0005]. It would have been obvious to one of ordinary skilled in the art at the time the invention was made to adjust the amount of manganese in the positive electrode active material for the benefit of having good energy density as well as to avoid manganese dissolution.
Regarding claim 1, Chen ‘448 discloses the core has a chemical formula of LiMnxFe(1-x)PO4,but does not disclose the core has a chemical formula as claimed in claim 1. Chen ‘988 teaches a lithium transition phosphate with a dopant. Doping creates defects inside the crystal which are beneficial to the diffusion of Li+. Moreover, due to the different charge valence states, a charge difference is generated, and cation vacancies are formed through a charge compensation mechanism, which improves the conductivity of the positive electrode material and improves the rate performance of the material [0036]. It would have been obvious to one of ordinary skilled in the art at the time the invention was made to add a dopant to the active material of Chen ‘448, as taught by Chen ‘988, for the benefit of having better diffusion of Li+.
Regarding claim 1, Chen ‘448 discloses a barrier layer comprising a pyrophosphate [0027, 0039], but does not disclose the first cladding layer comprises crystalline pyrophosphates LiaMP2O7 or Mb(P2O7)c as claimed in claim 1. Gao teaches a cathode active material comprising core having a lithium manganese iron phosphate having a shell comprising a mixture of carbon and one or more of LiFeP2O7, LiAlP2O7, Li3V2(PO4)3 [0010, 0012]. The addition of the lithium-containing metal phosphates and/or pyrophosphates can, on the one hand, increase the conductivity of the material ions, and on the other hand, effectively improve the effect of carbon coating, thereby reducing the carbon coating content, so that the rate performance and cycle performance of the core-shell structure positive electrode material are significantly improved, and it has a higher compaction density [0023].
It would have been obvious to one of ordinary skilled in the art at the time the invention was made to add a pyrophosphate of Gao as the pyrophosphate of Chen ‘448, as taught by Gao, for the benefit of having good conductivity of the active material.
Regarding claim 1, Chen ‘448 does not disclose the non-aqueous electrolytic solution comprises a first additive comprising one or more of a compound shown in Formula 1. Sato teaches a lithium secondary battery having an electrolyte with an additive aliphatic diisocyanate. See chemical formula 4. It forms a stable SEI on the negative electrode by charging and discharging during the initial period of use [0008].
Regarding claim 2, R1 represents at least one selected from the group consisting of the following groups substituted or unsubstituted by Ra: C2~C10 alkylidene [0009].
Regarding claim 3, the first additive comprises the compound H36 [0009].
Regarding claim 4, the first additive is W1% by weight, with W1 being 0.01 to 20, based on the total weight of the non-aqueous electrolytic solution; and/or
the first cladding layer is C1% by weight, with Cl being greater than 0 and less than or equal to 6, based on the weight of the core; and/or
the second cladding layer is C2% by weight, with C2 being greater than 0 and less than or equal to 6, based on the weight of the core; and/or
the third cladding layer is C3% by weight, with C3 being greater than 0 and less than or equal to 6, based on the weight of the core, Sato teaches the amount of the diisocyanate is 0.5 to 5% by weight [0009].
It would have been obvious to one of ordinary skilled in the art at the time the invention was made to add the additive of Sato to the electrolyte of Chen ‘448 for the benefit of forming a stable SEI on the negative electrode by charging and discharging during the initial period of use for the benefit of protecting the negative electrode.
Regarding claim 5, W1/(C1+C2+C3) is from 0.001 to 2, the diisocyanate additive forms a stable SEI on the negative electrode by charging and discharging during the initial period of use [0008]. Sato clearly teaches that additive is a result effective variable. It has been held by the courts that discovering an optimum value or workable ranges of a result-effective variable involves only routine skill in the art, and thus not novel. In re Boesch, 617 F.2d 272, 205 USPQ 215 (CCPA 1980). See MPEP 2144.05. It would have been obvious to one of ordinary skilled in the art at the time the invention was made to adjust the amount the additive of Sato to the electrolyte of Chen ‘448 depending on the desired thickness of SEI to stably form an SEI on the negative electrode.
Regarding claim 8, CN ‘448 does not disclose the non-aqueous electrolytic solution further comprises a third additive. Sato teaches and the third additive comprises one or more of a cyclic carbonate compound containing unsaturated bonds. With the additive, a decrease in capacity can be suppressed [0030]. It would have been obvious to one of ordinary skilled in the art at the time the invention was made to add a vinylene carbonate of Sato to the electrolyte of Chen ‘448 for the benefit of suppressing capacity decrease.
Regarding claim 18, the third additive is W3% by weight, with W3 being 0.01 to 10, based on the total weight of the non-aqueous electrolytic solution, Sato teaches and the third additive comprises one or more of a cyclic carbonate compound containing unsaturated bonds. With the additive, a decrease in capacity can be suppressed [0030]. Sato clearly teaches that additive is a result effective variable. It has been held by the courts that discovering an optimum value or workable ranges of a result-effective variable involves only routine skill in the art, and thus not novel. In re Boesch, 617 F.2d 272, 205 USPQ 215 (CCPA 1980). See MPEP 2144.05. It would have been obvious to one of ordinary skilled in the art at the time the invention was made to adjust the amount the additive of Sato to the electrolyte of Chen ‘448 for the benefit of suppressing capacity decrease.
Regarding claim 11, the crystalline pyrophosphate in the first cladding layer has an interplanar spacing ranging from 0.293 nm to 0.470 nm, and a crystal orientation angle ranging from 18.00° to 32.00°; and/or
the crystalline phosphate in the second cladding layer has an interplanar spacing ranging from 0.244 nm to 0.425 nm, and a crystal orientation angle ranging from 20.00° to 37.00°, it is noted that this is an intrinsic property of a material. Hence, it appears that the pyrophosphate of Park meets the limitation of claim 11.
MPEP 2112 V states that "once a reference teaching product appearing to be substantially identical is made the basis of a rejection, and the Examiner presents evidence or reasoning tending to show inherency, the burden shifts to the Applicant to show an unobvious difference."
Regarding claim 14, the positive electrode active material satisfies at least one of the following (1) to (4):
(1) before and after complete intercalation/deintercalation of lithium, the positive electrode active material has a lattice change rate of 4% or less;
(2) the positive electrode active material has a Li/Mn anti-site defect concentration of 4% or less;
(3) the positive electrode active material has a compaction density at 3T of 2.2 g/cm3 or more; and
(4) the positive electrode active material has a surface oxygen valence of -1.90 or less, the instant Specification states (emphasis added):
[0030] Crystalline pyrophosphates and crystalline phosphates having interplanar spacing and angle within the above ranges can more effectively inhibit the lattice change rate of lithium manganese phosphate and leaching of manganese ion during the process of deintercalation and intercalation of lithium, and thereby enhance the high-temperature cycling performance and the high-temperature storage performance of the secondary battery.
[0033] In embodiments of the present application, phosphorus is present in a content of from 12 wt% to 25 wt%, optionally in the range of 15 wt% to 20 wt%, based on the weight of the positive electrode active material. Thus, the following can be effectively avoided: if the content of the elemental phosphorus is too high, it may cause the covalency of P-O to be too strong and affect the conductivity of the small polarizers, thereby affecting the electrical conductivity of the positive electrode active material; if the content of the elemental phosphorus is too small, it may make the lattice structure of the pyrophosphate in the core, in the first cladding layer, and/or of the phosphate in the second cladding layer less stable, thereby affecting the positive electrode active material's overall stability.
[0084] The inventors have found after conducting a large number of researches that by doping modification of lithium manganese phosphate and cladding lithium manganese phosphate with multiple layers, a new type of positive electrode active material having a core-shell structure can be obtained, and the positive electrode active material is capable of realizing a reduced leaching out of manganese ion and a reduced lattice change rate, so as to be able to improve rate performance, cycling performance, storage performance, safety performance of secondary batteries, and to increase the capacity exertion of the secondary batteries.
It appears that the structure of pyrophosphate, the amount of phosphorus, and the presence of dopant in the active material of Chen ‘448 modified by Gao and Chen ‘988 reads on Applicant’s lattice limitation of claim 11.
Regarding claim 15, CN ’448 modified by CN ‘988, Gao, and Sato teaches a battery module, comprising the secondary battery according to claim 1.
Regarding claim 16, CN ’448 modified by CN ‘988, Gao, and Sato teaches a battery pack, comprising the battery module according to claim 15.
Regarding claim 17, CN ’448 modified by CN ‘988, Gao, and Sato teaches an electrical device comprising the secondary battery according to claim 1.
Regarding claim 19, phosphorus is 12 wt% to 25 wt%, based on the weight of the positive electrode active material, it is noted that Chen ‘448 modified by Chen ‘988 and Sato meet the compounds of claim 1, and hence meets the phosphorus amount of the positive electrode active material. It is noted that the phosphorus amount is not patentable unless the amount is critical.
Regarding claim 20, secondary battery according to claim 1, wherein a weight ratio of manganese to phosphorus is in the range of 0.90 to 1.25 [0074].
Regarding claim 1, the second cladding layer comprises crystalline phosphate XPO4, X is one or more elements selected from Li, Fe, Ni, Mg, Co, Cu, Zn, Ti, Ag, Zr, Nb and Al, Chen ‘448 discloses the second cladding layer comprises LiMnyFe(1-y)O4 [0004]. Chen ‘448 discloses the manganese content in the lithium iron manganese phosphate layer is low, thereby avoiding the occurrence of a large amount of manganese dissolution, and at the same time, the performance of the lithium iron manganese phosphate layer with a low manganese content is closer to the performance of lithium iron phosphate, which is beneficial to improving the high-rate charging and discharging of the lithium iron manganese phosphate composite material [0005]. The amount of manganese is 0<y<0.65 [0007]. It would have been obvious to one of ordinary skilled in the art at the time the invention was made to have no manganese on the second cladding layer for the benefit of forming LiFePO4 and hence, avoiding any manganese dissolution and having high-rate charging and discharging of lithium iron phosphate. LiFePO4 of Chen ‘445 would read on Applicant's second cladding material.
Should it not be obvious, Jang teaches a LiFePO4 modified Li1.02(Co0.9Fe0.1)0.98PO4. LiFePO4 coating renders good thermal stability at elevated temperatures, provide long-term capacity retention and reduce reactivity towards electrolytes at high voltages (page 6512). It would have been obvious to one of ordinary skilled in the art at the time the invention was made to replace the lithium manganese phosphate layer of Chen ‘448 with Jang’s LiFePO4 since either phosphate layer provides good cycle performance, as well as to prevent the core from further contact with the electrolyte.
Claims 6-7 are rejected under 35 U.S.C. 103 as being unpatentable over Chen (CN 114256448) in view of Chen (CN 114242988), Gao (WO 2018/032569), and Sato (JP 2007-242411), or in alternative, Chen (CN 114256448) in view of Chen (CN 114242988) and Gao (WO 2018/032569), Sato (JP 2007-242411), and Jang (LiFePO4 modified Li1.02(Co0.9Fe0.1)0.98PO4 cathodes with improved lithium storage properties, Journal of Materials Chemistry, 2011, 21, 6510-6514) as applied to claim 1, further in view of Tsujioka (US 2010/0323240).
Regarding claim 6, Chen ‘448 modified by Chen ‘988, Gao and Sato does not teach the non-aqueous electrolytic solution further comprises a second additive as claimed, and regarding claim 7, Chen ‘448 modified by Chen ‘988, Gao and Sato does not teach the second additive is W2% by weight, with W2 being 0.01 to 20, based on the total weight of the non-aqueous electrolytic solution.
Tsujioka teaches an electrolyte having an additive comprising lithium difluorophosphate. The additive contains a concentration of lower than 0.01 wt % reduces the nonaqueous electrolyte solution in durability resulting from lithium difluorophosphate, such as cycle characteristics and high-temperature storage characteristics, and does not sufficiently produce the effect of suppressing gasification. Meanwhile, if a lithium difluorophosphate concentration in the electrolyte solution for the nonaqueous electrolyte battery exceeds 5.0 wt %, there may arise a fear that the electrolyte solution decreases in ionic conduction and increases in internal resistance [0029]. It would have been obvious to one of ordinary skilled in the art at the time the invention was made to add and adjust the amount of lithium difluorophosphate in the electrolyte of Chen ‘448 modified by Chen ‘988, Gao and Sato, as taught by Tsujioka, for the benefit of having good battery cycle characteristics.
Claim 12 is rejected under 35 U.S.C. 103 as being unpatentable over Chen (CN 114256448) in view of Chen (CN 114242988), Gao (WO 2018/032569), and Sato (JP 2007-242411), or in alternative, Chen (CN 114256448) in view of Chen (CN 114242988) and Gao (WO 2018/032569), Sato (JP 2007-242411), and Jang (LiFePO4 modified Li1.02(Co0.9Fe0.1)0.98PO4 cathodes with improved lithium storage properties, Journal of Materials Chemistry, 2011, 21, 6510-6514) as applied to claim 1, further in view of Takei (US 2016/0099464).
Regarding claim 12, Chen ‘448 modified by Chen ‘988, Gao, and Sato does not teach the carbon of the third cladding layer is a mixture of SP2 carbon and SP3 carbon. Takei teaches a lithium nickel-based oxide particle and a coating on the particle comprising diamond-like carbon. An sp2/sp3 ratio of the coating layer is about 50/50 to 60/40. See Abstract. The SP2 carbon atom contributes to conductivity of the diamond-like carbon, and the SP3 carbon atom contributes to oxidation resistance and abrasion resistance of the diamond-like carbon [0054]. It would have been obvious to one of ordinary skilled in the art at the time the invention was made to use a mixture of SP2 and SP3 carbon as the carbon layer of Chen ‘448, as taught by Takei, for the benefit of having good conductivity as well as oxidation resistance and abrasion resistance.
Response to Arguments
Arguments dated 5/26/2025 are addressed below:
Applicant asserts that the material of the lithium iron manganese phosphate layer comprises LiMnyFe1-yPO4, wherein y < x.” In addition, Chen describes at paragraph [0007] that “ y is more than 0 and less than or equal to 0.65.” It is clear that Chen specifically defines that y could not be 0. Thus, Chen intends that the lithium iron manganese phosphate LiMnyFe1-yPO4 could not be phosphate. Page 10 of Arguments.
In response, Chen discloses that 0<y<0.65 is optional. Chen ‘448 discloses the manganese content in the lithium iron manganese phosphate layer is low, thereby avoiding the occurrence of a large amount of manganese dissolution, and at the same time, the performance of the lithium iron manganese phosphate layer with a low manganese content is closer to the performance of lithium iron phosphate, which is beneficial to improving the high-rate charging and discharging of the lithium iron manganese phosphate composite material [0005]. It would have been obvious to one of ordinary skilled in the art at the time the invention was made to have no manganese on the second cladding layer for the benefit of forming LiFePO4 and hence, avoiding any manganese dissolution and having high-rate charging and discharging of lithium iron phosphate. LiFePO4 of Chen ‘445 would read on Applicant's second cladding material.
It is noted that Chen does not necessarily teach away from y to equal 0.
Applicant asserts that it is evident that Chen specifically includes the lithium iron manganese phosphate layer over the barrier layer for a technological purpose. If, as asserted by the Office, y could be 0, then the lithium iron manganese phosphate layer LiMnyFe1-yPO4 would be reduced to the same or similar materials as the barrier material layer discussed in the Chen. It directly frustrates the intended purpose of Chen. Page 11 of Arguments.
The Examiner respectfully disagrees. The barrier layer of Chen is made of a completely different composition from the phosphate layer. The barrier layer is made of a metal oxide, metaphosphate, or a pyrophosphate [0039]. Assuming that y is 0 to the lithium iron phosphate layer would not form a similar layer as the barrier layer. Hence, the rejection is proper.
Conclusion
Any inquiry concerning this communication or earlier communications from the examiner should be directed to CYNTHIA KYUNG SOO WALLS whose telephone number is (571)272-8699. The examiner can normally be reached on M-F until 5pm.
If attempts to reach the examiner by telephone are unsuccessful, the examiner’s supervisor, Jonathan Leong can be reached at 571-270-1292. The fax phone number for the organization where this application or proceeding is assigned is 571-273-8300.
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/CYNTHIA K WALLS/ Primary Examiner, Art Unit 1751