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 .
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and the fee set forth in 37 CFR 1.17(e) has been timely paid, the finality of the previous Office action has been withdrawn pursuant to 37 CFR 1.114.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 01/23/2026 has been entered.
Response to Amendment
Examiner notes the following amendments made to the claims:
Claim 1 amended to further limit the molar ratio of TiNb2O7 to LiH2PO4 to being (1-8):1
Claim 27 amended to limit the ratio of total mass TiNb2O7 and LiH2PO4 to the cobalt-free single crystal material being 0.1-0.5 wt%
Claim 39 amended to limit the ratio of total mass TiNb2O7 and LiH2PO4 to the cobalt-free single crystal material being 0.1-0.5 wt%
Response to Arguments
Applicant’s arguments, filed 1/23/2026, with respect to the rejection of claim 27 under 35 USC 112 (b) have been fully considered and are persuasive. The rejection of claim 27 under 35 USC 112 (b) has been withdrawn.
Applicant's arguments filed 1/23/2026 regarding the rejections of claims 1, 5, 8, 11-16, 27-29, 40-41 under 35 USC 103, and additionally the rejections of all further dependent claims, have been fully considered but they are not persuasive. Specifically, examiner finds that all of the limitations of the claims are met by the previously applied prior art, including the new limitations added in amendment. Examiner will respond to applicant arguments in order:
First, applicant argues that because He provided numerous options for organic filler as well as other additives, and that it provides numerous possible options for a niobium-containing composite metal oxide, that it is not specifically limited to a combination of TiNb2O7 and a conductive lithium salt. Examiner does not find this argument persuasive as He clearly teaches TiNbO7 as the niobium-containing composite metal oxide and teaches the inclusion of a lithium salt, and therefore, given the further modification of Park, which teaches LiH2PO4 as a lithium salt, it would be within the ambit of one of ordinary skill in the art, prior to the effective filing date of the invention, to produce a layer including TiNb2O7 and a conductive lithium salt. Applicant states that the shell of the cobalt-free single crystal composite material excludes other components, but this is not present in the claims, as claim 1 recites “the shell layer is of a material formulation comprised of TiNb2O7 and LiH2PO4.” The usage of the term “comprised” allows for the inclusion of additional materials. If this were change to “consists of,” then the shell would be limited to only these two materials.
Second, applicant argues that the molar ratio of niobium to titanium in He is 3, rather than 2. Examiner does not find this convincing, as He explicitly teaches the usage of specifically TiNb2O7 both in broad terms in the specification (“The niobium-containing composite metal oxide for use as an inorganic filler in the encapsulating elastomer shell may be selected from the group consisting of TiNb2O7” He [0084]) as well as in the specific examples (See examples 1 and 2 of He). Applicant then argues further that the ratio of lithium to titanium in He is outside of the claimed range. However, examiner does not find this convincing for two reasons. First, He teaches a niobium-containing composite metal oxide that includes lithium in addition to TiNb2O7, LixTiNb2O7, where x is between 0 and 5 (He [0084] and He example 1). This alone teaches the desired ratio of Li to niobium, as argued. Secondly, when explicitly referring to the molar ratio of TiNb2O7 to LiH2PO4, He teaches the inclusion of a lithium salt in a quantity of 0.1-40% by weight. (“In certain embodiments, the inorganic filler-reinforced elastomer further contains from 0.1% to 40% by weight (preferably from 1% to 30% by weight) of a lithium ion-conducting additive dispersed in the elastomer matrix material,” He [0035]. He states that this lithium ion-conducting additive mat be a lithium salt “In some embodiments, the inorganic filler-reinforced elastomer further contains a lithium ion-conducting additive dispersed in a sulfonated elastomer matrix material, wherein the lithium ion-conducting additive contains a lithium salt” He [0038]). He additionally teaches that the mass of its inorganic filler, which can be the niobium-containing composite metal oxide, is 0.01-50% by weight of the elastomer shell (“a thin layer of inorganic filler-reinforced elastomer having from 0.01% to 50% by weight of particles of an inorganic filler” He [0014] and “The niobium-containing composite metal oxide for use as an inorganic filler in the encapsulating elastomer shell may be selected from the group consisting of TiNb2O7-” He [0084]). Given the molar masses of TiNb2O7 (345.68 g/mol) and LiH2PO4 (103.93 g/mol), if there were an equivalent weight % of both, for example, 30% metal oxide inorganic filler and 30% lithium salt, then the molar ratio of TiNb2O7 to LiH2PO4 would be 3.32, which would fall within the claimed range. This would be the case if the masses of inorganic filler and lithium salt were the same, which could be anywhere from 0.1%-40% of each.
Based on the above statements, the arguments presented are not considered to be persuasive, and the rejection of claim 1 stands in view of Liu, He, and Park. Given that there are no further arguments presented regarding the dependent claims, the rejections also stand. Therefore, there is currently not considered to be any allowable subject matter present in the claims.
Claim Rejections - 35 USC § 112
The following is a quotation of 35 U.S.C. 112(d):
(d) REFERENCE IN DEPENDENT FORMS.—Subject to subsection (e), a claim in dependent form shall contain a reference to a claim previously set forth and then specify a further limitation of the subject matter claimed. A claim in dependent form shall be construed to incorporate by reference all the limitations of the claim to which it refers.
The following is a quotation of pre-AIA 35 U.S.C. 112, fourth paragraph:
Subject to the following paragraph [i.e., the fifth paragraph of pre-AIA 35 U.S.C. 112], a claim in dependent form shall contain a reference to a claim previously set forth and then specify a further limitation of the subject matter claimed. A claim in dependent form shall be construed to incorporate by reference all the limitations of the claim to which it refers.
Claim 28 rejected under 35 U.S.C. 112(d) or pre-AIA 35 U.S.C. 112, 4th paragraph, as being of improper dependent form for failing to further limit the subject matter of the claim upon which it depends, or for failing to include all the limitations of the claim upon which it depends. Specifically, claim 28 does not provide any further limitation of claim 1, as claim 1 requires the molar ratio of TiNb2O7 to LiH2PO4 to be (1-8):1, and claim 28 requires the same ratio to be (0.1-10):1. Applicant may cancel the claim(s), amend the claim(s) to place the claim(s) in proper dependent form, rewrite the claim(s) in independent form, or present a sufficient showing that the dependent claim(s) complies with the statutory requirements.
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, 8, 11-16, 27-29, 40-41 is/are rejected under 35 U.S.C. 103 as being unpatentable over Liu (US 20210226203 A1) in view of He (20200067079 A1) and further in view of Park (US 20170179484 A1).
Regarding claim 1, Liu teaches the following elements:
A cobalt-free single crystal composite material having a core-shell structure, wherein the core layer is of a cobalt-free single crystal material, (“Also provided are methods for preparing the cathode active materials with different composition structures, such as uniform compositions, full concentration gradient compositions, and core-shell structures. Finally, processes are described to suppress cation mixing (Li/Ni disorder), and further improve electrochemical performance of lithium ion batteries or sodium ion batteries that are cobalt-free.” Liu [0027])
Liu is silent on the following elements of claim 1:
and the shell layer is of a material formulation comprised of TiNb207 and LiH2PO4.
and a molar ratio of TiNb207 to LiH2PO4 is (1-8): 1.
However, He teaches some of the elements of claim 1 that are not found in Liu. Specifically, He teaches a shell layer for a cathode material containing titanium niobium oxide and a conductive lithium salt. Park teaches that LiH2PO4 can be used as a conductive lithium salt, which could therefore be a simple substitution for that of He. When the lithium salt of He is substituted with LiH2PO4, as taught by Park, the limitation regarding the molar ratio would be met.
and the shell layer is of a material formulation comprises TiNb207 and LiH2PO4. (The niobium-containing composite metal oxide for use as an inorganic filler in the encapsulating elastomer shell may be selected from the group consisting of TiNb2O7 [He 0084]), and (The inorganic filler is preferably nitride… of a transition metal. Preferably, the transition metal is selected from Ti [He 0015]).
and a molar ratio of TiNb207 to LiH2PO4 is (1-8): 1. (He teaches the inclusion of a lithium salt in a quantity of 0.1-40% by weight. (“In certain embodiments, the inorganic filler-reinforced elastomer further contains from 0.1% to 40% by weight (preferably from 1% to 30% by weight) of a lithium ion-conducting additive dispersed in the elastomer matrix material,” He [0035]. He states that this lithium ion-conducting additive mat be a lithium salt “In some embodiments, the inorganic filler-reinforced elastomer further contains a lithium ion-conducting additive dispersed in a sulfonated elastomer matrix material, wherein the lithium ion-conducting additive contains a lithium salt” He [0038]). He additionally teaches that the mass of its inorganic filler, which can be the niobium-containing composite metal oxide, is 0.01-50% by weight of the elastomer shell (“a thin layer of inorganic filler-reinforced elastomer having from 0.01% to 50% by weight of particles of an inorganic filler” He [0014] and “The niobium-containing composite metal oxide for use as an inorganic filler in the encapsulating elastomer shell may be selected from the group consisting of TiNb2O7-” He [0084]). Given the molar masses of TiNb2O7 (345.68 g/mol) and LiH2PO4 (103.93 g/mol), if there were an equivalent weight % of both, for example, 30% metal oxide inorganic filler and 30% lithium salt, then the molar ratio of TiNb2O7 to LiH2PO4 would be 3.32, which would fall within the claimed range. This would be the case if the masses of inorganic filler and lithium salt were the same, which could be anywhere from 0.1%-40% of each.)
He and Liu are considered to be analogous because they are both within the same field of cathode materials for secondary batteries. Therefore, It would have been obvious to one of ordinary skill before the effective filing date of the claimed invention to modify the core-shell structure of Liu to include the shell structure of He in order to improve the obtain a desirable lithium intercalation potential of higher than 1.1 V vs Li/Li+. (He paragraph 0083) This would be desirable in a shell for an electrode material as having a higher intercalation potential on the shell than the core of a core-shell material reduces the formation of SEI on the shell material, which helps to avoid rapid decay of battery capacity. (He paragraph 0082).
He is silent on the use of LiH2PO4 as the conductive lithium salt in the shell layer. However, Park teaches the use of LiH2PO4 as a conductive lithium salt (“The co-precipitated precursor of a metal oxide thus obtained may be mixed with a lithium salt to prepare a lithium compound, and a precursor including the lithium compound may be heat-treated at a temperature in a range of about 600° C. to about 1200° C. to prepare the core material.” Park [0126] and “The lithium salt may be included at least one selected from Li.sub.2CO.sub.3, LiNO.sub.3, LiBr, LiCl, Lil, LiOH, Li(CH.sub.3CO.sub.2), LiH.sub.2PO.sub.4, LiOH.H.sub.2O, and Li(CH.sub.3CO.sub.2).2H.sub.2O.” Park [0127]).
He and Park are considered to be analogous because they are both within the same field of cathode materials containing conductive materials combined with metal oxides. Therefore, it would have been obvious to one of ordinary skill before the effective filing date of the claimed invention to modify the shell of He containing titanium niobium oxide to substitute the inorganic filler of He with the LiH2-PO4 salt of Park as they are both used as materials mixed with metal oxides in electrode materials, and the simple substitution of one known element for another is likely to be obvious when predictable results are achieved. (see MPEP § 2143, B.).
By combining the shell of He including the lithium salt of Park into the invention of Liu, and the methods used by those references to produce such modifications, the dependent claims rejected under Liu, He, and Park are all done so without requiring any further modification or motivation.
Regarding claim 8, modified Liu teaches the following elements:
The cobalt-free single crystal composite material according to claim 1, wherein the cobalt-free single crystal composite material has a particle size D50 of 1-5 µm. (“Para. 8. The particle of Para. 6 or 7, wherein the particle is generally spherical and wherein a single crystal or a single particle has a diameter of about 10 nm to about 5 μm.” Liu [0086].)
The examiner takes note of the fact that the prior art ranges of 10nm-5 μm for the particle size of the single crystal compositive material encompasses the claimed range of 1-5 μm for the same parameter. Absent any additional and more specific information in the prior art, a prima facie case of obviousness exists. In re Peterson, 315 F.3d 1325, 1330, 65 USPQ2d 1379 (Fed. Cir. 2003). MPEP 2144.05.
Regarding claim 11, modified Liu teaches the following elements:
A method for preparing the cobalt-free single crystal composite material according to claim 1 comprising: (“These cobalt-free materials deliver competitive or superior electrochemical performance when compared to cobalt-containing counterpart materials. The cathode active materials may be single crystals, single particle materials, or composite materials having a secondary particle that is composed of smaller, primary particles. Also provided are methods/processes for preparing the new compositions of cathode active materials.” Liu [0027])
mixing a cobalt-free single crystal material, TiNb2O7, and LiH2PO4, (“The process for the single particle may be prepared by one-step or multiple steps (at least two-step). The one-step method includes mixing the precursor (synthesized by the above co-precipitant method) or solid transition metal salts of Ni, Mn, Al, and M or M′, and the lithium/sodium salts in an appropriate stoichiometric ratio, and simultaneously adding appropriate amount of co-solvent. The mixture is then sintered followed by a first and a second (or more) calcination step at a temperature of about 680° C. to about 1200° C. for a time period of about 5 hours to about 30 hours, cooling of the reaction.” Liu [0045]. By using the methods of Liu and replacing the shell with that of modified He containing TiNb2O7, the above limitation would be met.)
and carrying out sintering to obtain the cobalt-free single crystal composite material. (“The heat-treating may include pre-sintering at a temperature of about 300° C. to about 600° C., maintaining this temperature for about 0 to about 10 hours, and then sintering at a temperature of about 680° C. to about 1200° C.” Liu paragraph 0041 and “The cathode active materials may be single crystals, single particle materials, or composite materials having a secondary particle that is composed of smaller, primary particles. Also provided are methods/processes for preparing the new compositions of cathode active materials.” Liu paragraph 0027)
Regarding claim 12, modified Liu teaches the following elements:
The method according to claim 11, wherein a method for preparing the cobalt-free single crystal material comprises: mixing a lithium salt and a precursor of the cobalt- free single crystal material, and carrying out calcination to obtain the cobalt-free single crystal material. (“The process for the single particle may be prepared by one-step or multiple steps (at least two-step). The one-step method includes mixing the precursor (synthesized by the above co-precipitant method) or solid transition metal salts of Ni, Mn, Al, and M or M′, and the lithium/sodium salts in an appropriate stoichiometric ratio, and simultaneously adding appropriate amount of co-solvent. The mixture is then sintered followed by a first and a second (or more) calcination step at a temperature of about 680° C. to about 1200° C.” Liu [0045])
Regarding claim 13, modified Liu teaches the following elements:
The method according to claim 12, wherein the precursor of the cobalt-free single crystal material has a chemical formula of NiaMnb(OH)2, wherein 0.4 < a < 0.95 and 0.05 <b<0.6. (“the concentration gradient precursor was prepared by two metal solutions. The solution for preparing the core component contains Ni and Mn at a ratio of 85:15 wt % basis;” Liu [0056] and “0.5 M NaOH aqueous solution was supplied to maintain pH in the reactor at 11. In the whole synthesis process, the stirring speed of the reactor was kept at 1000 rpm, and the reaction temperature was set at 60° C. The co-precipitation reaction was conducted around 20 hours; hereafter, the precipitant was kept at the steady state for 4 hours to obtain a co-precipitated compound with higher density. Soon afterwards, the compound was filtered, washed with water, and dried with 110° C. with nitrogen gas for 15 hours to obtain a cathode active material precursor” Liu [0058]. Liu uses a precursor for the cobalt free single crystal material having a ratio of 85:15 Ni to Mn. It then mixes this metal solution with NaOH, which would form the claimed precursor material. Based on the weight to mole conversions, the precursor compound would have a formula of Ni0.84-Mn0.16(OH)2.)
Regarding claim 14, modified Liu teaches the following elements:
The method according to claim 12, wherein the lithium salt comprises lithium hydroxide and/or lithium carbonate. (“The precursor was mixed with lithium hydroxide at a ratio of 1:1.03, and then heated to 450° C. at a rate of 2° C./min, and then maintain at 450° C. for 5 hours followed by calcining at 750° C. for 12 hours to obtain a final cathode active material particle.” Liu [0059])
Regarding claim 15, modified Liu teaches the following elements:
The method according to claim 12, wherein a ratio of a molar amount of lithium in the lithium salt to a molar amount of total metal elements in the precursor of the cobalt-free single crystal material is 1.05-1.5. (“The cathode active material may be prepared by mixing a cathode active material precursor with a lithium salt at an appropriate ratio (i.e. based upon the range of provided stoichiometry), and heat-treating at a temperature of about 300° C. to about 1200° C. Illustrative lithium salts include, but are not limited to, lithium hydroxide, lithium carbonate, lithium nitrate, lithium chloride, lithium fluoride, lithium oxide, and the combination of any two or more thereof. A ratio of the lithium salt and the metal of the precursor may be from about 0.9 to 1.1 on a mol basis.” Liu [0041] and “The process of any one of Paras. 24-40, wherein the lithium salt is lithium hydroxide, lithium carbonate, lithium oxalate, lithium nitrate, or a mixture of any two or more thereof; and wherein a ratio of the lithium to precipitate is 1.0 to 1.1 on a mol basis.” Liu [0123])
The examiner takes note of the fact that the prior art ranges of 0.9 to 1.1 for the ratio of lithium hydroxide to precursor in a method for producing a single crystal cathode material overlaps the claimed range of 1.05-1.5 for the same parameter. Absent any additional and more specific information in the prior art, a prima facie case of obviousness exists. In re Peterson, 315 F.3d 1325, 1330, 65 USPQ2d 1379 (Fed. Cir. 2003). MPEP 2144.05.
Regarding claim 16, modified Liu teaches the following elements:
The method according to claim 12, wherein the lithium salt and the precursor of the cobalt-free single crystal material are mixed under stirring. (“Further, the content of precipitating agent, NaOH, was controlled by pH value. 5 M NaOH aqueous solution was supplied to maintain pH in the reactor at 11. In the whole synthesis process, the stirring speed of the reactor was kept at 1000 rpm, and the reaction temperature was set at 60° C. The co-precipitation reaction was conducted around 20 hours; hereafter, the precipitant was kept at the steady state for 4 hours to obtain a co-precipitated compound with higher density. Soon afterwards, the compound was filtered, washed with water, and dried with 110° C. with nitrogen gas for 15 hours to obtain a cathode active material precursor.” Liu [0058])
Regarding claim 27, Liu is silent on the following elements:
The method according to claim 11, wherein a ratio of a total mass of TiNb207 and LiH2PO4 to a weight of the cobalt-free single crystal material is 0.1-0.5wt %
However, Park teaches all of the elements of claim 27 that are not found in Liu
The method according to claim 11, wherein a ratio of a total mass of TiNb207 and LiH2PO4 to a weight of the cobalt-free single crystal material is 0.1-0.5wt % (“In one specific embodiment, a weight of the shell relative to a weight of the core may be 0.1% by weight to 3.0% by weight.” Park [0019]. In this case, if the shell is a composition of the niobium-containing composite metal oxide and the lithium salt, as is taught in He and applied in claim 1, these components would be present in a 0.1-3wt% of the cobalt-free single crystal material as a whole, thus encompassing the claimed range.)
The examiner takes note of the fact that the prior art range of 0.1-3 wt% of TiNb2O7 and LiH2PO4 (in this case, the mass of the shell) to the total weight of the cobalt-free single crystal material (the core and the shell) encompasses the claimed range of 0.1-0.5 wt% for the same parameter. Absent any additional and more specific information in the prior art, a prima facie case of obviousness exists. In re Peterson, 315 F.3d 1325, 1330, 65 USPQ2d 1379 (Fed. Cir. 2003). MPEP 2144.05.
Regarding claim 28, Liu is silent on the following elements:
The method according to claim 11, wherein a molar ratio of TiNb207 to LiH2PO4 is (0.1-10): 1.
However, Park teaches all of the elements of claim 28 not found in Liu. Specifically, Park teaches a mixture ratio of metal oxide to LiH2PO4 that meats the claimed range.
The method according to claim 11, wherein a molar ratio of TiNb207 to LiH2PO4 is (0.1-10): 1. (“The metal oxide compound precursor and the phosphate compound precursor may be mixed together at an appropriate stoichiometric molar ratio to obtain a mixture.” Park [0132] and “and a weight ratio of the phosphate compound to the metal oxide compound in a range of greater than 0 to about 1 may be prepared.” Park [0135]. In this case, if a there were a 3.3:1 weight ratio of TiNb2O7 to LiH2PO4, which would be 0.303:1 phosphate to metal oxide, within the teachings of Park, there would be a 1:1 molar ratio of TiNb2O7 to LiH2PO4, which falls within the claimed range.)
The examiner takes note of the fact that the prior art ranges of 0.3:1 (in the case of a 1:1 weight ratio) to nearly infinite (in the case of a 0.00001:1 weight ratio) for the molar ratio of TiNb2O7 to LiH2PO4 in the shell overlaps the claimed range of (0.1-10):1 for the same parameter. Absent any additional and more specific information in the prior art, a prima facie case of obviousness exists. In re Peterson, 315 F.3d 1325, 1330, 65 USPQ2d 1379 (Fed. Cir. 2003). MPEP 2144.05.
*Additionally, see claim 1 for how the weight ratios taught by He would also meet this limitation, given the inclusion of LiH2PO4 as the lithium salt.
Regarding claim 29, Liu teaches the following elements:
and mixing the mixture and the cobalt-free single crystal material. (“In another aspect, a process for preparing a cathode active material includes a solid state reaction, the process including mixing solid transition metal salts of Ni, Mn, Al and M and M′ with appropriate ratio of a lithium or sodium salt to form a mixture; and calcining the mixture at a temperature of about 680° C. to about 1200° C., for a time period of about 5 hours to about 30 hours, in an atmosphere of oxygen, air, or oxygen-enriched air.” Liu [0011]. In this case, the lithium salt of Liu would be replaced with the metal oxide/lithium phosphate material of modified He, as shown below.)
Liu is silent on the following elements of claim 29:
The method according to claim 11, wherein a process of mixing the cobalt-free single crystal material, TiNb207 and LiH2PO4 comprises: mixing and dissolving TiNb207 and LiH2PO4 in deionized water, drying the mixture,
However, He teaches all of the elements of claim 29 that are not found in Liu
The method according to claim 11, wherein a process of mixing the cobalt-free single crystal material, TiNb207 and LiH2PO4 comprises: mixing and dissolving TiNb207 and LiH2PO4 in deionized water, drying the mixture, (“The niobium oxide (Nb2O5) and titanate proton compounds… was dispersed in pure water, followed by vigorous mixing. The obtained mixture was placed in a heat-resistant container and was subjected to hydrothermal synthesis under conditions of 180 C for a total of 24 hours. The obtained sample was washed in pure water three times, and then dried.” He [0145] If the titanate proton of He were replaced with the lithium phosphate of Park, as described in claim 1, then the method of He would meet all of the above limitations of claim 29. Then, if this mixture were included in the method of Liu, all of the portions of claim 29 would be met.)
Regarding claim 40, modified Liu teaches the following elements:
A cathode sheet, comprising the cobalt-free single crystal composite material according to claim 1. (“Para. 47. An electrochemical device comprising an anode, a non-aqueous electrolyte, and a cathode; the cathode comprising a cathode active material” Liu [0129]. While Liu doesn’t explicitly state that the cathode is a sheet, one of ordinary skill in the art would understand that a sheet is a common form of an electrode and therefore it would be obvious to use the methods of Liu to make a cathode sheet.)
Regarding claim 41, modified Liu teaches the following elements:
A lithium-ion battery, comprising the cathode sheet according to claim 40. (“The electrochemical device of Para. 46, wherein the electrochemical device is a lithium ion battery”)
Claim(s) 2 is/are rejected under 35 U.S.C. 103 as being unpatentable over Liu (US 20210226203 A1) in view of He (20200067079 A1), further in view of Park (US 20170179484 A1), and further in view of Manthiram (US 7678503 B2).
Regarding claim 2, Liu is silent on the following elements:
The cobalt-free single crystal composite material according to claim 1, wherein the cobalt-free single crystal material has a chemical formula of LimNixMnyO2, wherein 0.4<x<0.95,0.05<y<0.6, and m is 1.05 to 1.5.
However, Manthiram teaches all of the elements of claim 2 that are not found in Liu:
The cobalt-free single crystal composite material according to claim 1, wherein the cobalt-free single crystal material has a chemical formula of LimNixMnyO2, wherein 0.4<x<0.95,0.05<y<0.6, and m is 1.05 to 1.5. (“All the samples have the O3 type structure of LiCoO2 similar to that found previously for Li[Li0.17Mn0.58Ni0.25]O-2 ,.sup.3-7 and TABLE 1 gives the lattice parameter values of the layered oxide compositions.” Manthiram page 11 column 7 line 5”. Manthiram table 1 teaches a composition that is within the claimed range of claim 2.)
Manthiram and Liu are considered to be analogous because they are both within the same field of cobalt-free cathode materials. Therefore, it would have been obvious to one of ordinary skill before the effective filing date of the claimed invention to modify the cathode material of Liu to have the composition of Manthiram, as it is a known cobalt-free cathode material in the art with desirable properties (Manthiram table 2 shows comparable and improved properties compared to cobalt-containing substances), and the selection of a known material, which is based upon its suitability for the intended use, is within the ambit of one of ordinary skill in the art. See In re Leshin, 125 USPQ 416 (CCPA 1960) (see MPEP § 2144.07).
Claim(s) 6 is/are rejected under 35 U.S.C. 103 as being unpatentable over Liu (US 20210226203 A1) in view of He (20200067079 A1), further in view of Park (US 20170179484 A1), and further in view of Park (US 20190312260 A1), hereinafter referred to as Park ‘260.
Regarding claim 6, modified Liu is silent on the following elements:
The cobalt-free single crystal composite material according to claim 1, wherein the shell layer accounts for a ratio of 0.1-0.5wt% in the cobalt-free single crystal composite material and/or the core layer accounts for a ratio of 99.5-99.9wt% in the cobalt-free single crystal composite material.
However, Park ‘260 teaches all of the elements of claim 6 that are not found in Liu. Specifically, Park ‘260 teaches a weight ratio of core-shell in a core-shell cathode material that meets the claimed limitations of claim 6.
The cobalt-free single crystal composite material according to claim 1, wherein the shell layer accounts for a ratio of 0.1-0.5wt% in the cobalt-free single crystal composite material and/or the core layer accounts for a ratio of 99.5-99.9wt% in the cobalt-free single crystal composite material. (“In one specific embodiment, a weight of the shell relative to a weight of the core may be 0.1% by weight to 3.0% by weight.” Park ‘260 [0019])
The examiner takes note of the fact that the prior art range of 0.1-3% for the weight of the shell in the core-shell material encompasses the claimed range of 0.1-0.5%. Absent any additional and more specific information in the prior art, a prima facie case of obviousness exists. In re Peterson, 315 F.3d 1325, 1330, 65 USPQ2d 1379 (Fed. Cir. 2003). MPEP 2144.05.
Park ‘260 is considered to be analogous to modified Liu, specifically, He, because it is within the same field of core-shell materials used in electrodes. Therefore, it would have been obvious to one of ordinary skill before the effective filing date of the claimed invention to modify the core-shell structure of He using the single crystal material of Liu to have the weight ratio of core to shell as taught by Park ‘260, in order to optimize the desirable effects of the shell without sacrificing capacity of the electrode (“When the weight of the shell relative to the weight of the core is less than 0.1% by weight, the ratio of the shell in the positive electrode active material particle is excessively low, and thus desired effects may not be sufficiently achieved. On the contrary, when the weight of the shell relative to the weight of the core is more than 3.0% by weight, the ratio of the shell in the positive electrode active material particle is excessively high, and thus there is a problem in that the overall capacity of the positive electrode active material may be relatively reduced.” Park ‘260 [0020]).
Claim(s) 9 is/are rejected under 35 U.S.C. 103 as being unpatentable over Liu (US 20210226203 A1) in view of He (20200067079 A1), further in view of Park (US 20170179484 A1), and further in view of Du (US 20220077464 A1)
Regarding claim 9, modified Liu is silent on the following elements:
The cobalt-free single crystal composite material according to claim 1, wherein the cobalt-free single crystal composite material has a specific surface area of 0.3-1.5 m2/g.
However, Du teaches all of the elements of claim 9 that are not found in modified Liu. Specifically, Du teaches a single crystal cathode material with the desired specific surface area range:
The cobalt-free single crystal composite material according to claim 1, wherein the cobalt-free single crystal composite material has a specific surface area of 0.3-1.5 m2/g. (“Preferably, the actual specific surface area BET.sub.2 of the positive active material is 0.5 m.sup.2/g to 1.5 m.sup.2/g.” Du [0051] and “The positive active material in the first aspect of this application is further a ternary material … with single crystal or quasi-single crystal particle morphology” Du [0038])
Du is considered to be analogous to Liu because they are both within the same field of single crystal materials used in electrodes. Therefore, it would have been obvious to one of ordinary skill before the effective filing date of the claimed invention to modify the single crystal of Liu to have the specific surface area of Du in order to optimize contact between electrolyte solution and active material, which can inhibit side reactions and reduce the chance of swelling. (“When the actual specific surface area of the positive active material is within the foregoing range, a contact area between the electrolyte solution and the positive active material is relatively small. This is helpful in inhibiting side reactions, and avoiding that the swelling problem of the electrochemical energy storage apparatus is aggravated because of corrosion damage caused by the electrolyte solution to the crystal structure of the positive active material. In addition, when the actual specific surface area of the positive active material is within the foregoing range, it is further helpful in achieving relatively strong adhesion of the positive active material to the binder and the conductive agent with fewer auxiliary materials in making a positive slurry through mixing, thereby helping to increase the energy density of the electrochemical energy storage apparatus.” Du [0051]) Even though the crystal of Du is not identical to that of Liu, Du teaches the clear benefits of using this specific surface area in a single crystal cathode material, and therefore it would be obvious to use these parameters in any single crystal cathode material.
Regarding claim 10, modified Liu teaches the following elements:
The cobalt-free single crystal composite material according to claim 1, wherein the cobalt-free single crystal composite material has a surface pH of 11.8 or below and 3500 ppm or below of total alkalis. (Given that modified Liu teaches a cobalt-free single crystal material with the same chemical formula, particle size, and specific surface area as that in the instant application, it is inherent that the cobalt-free single crystal material would have the same surface pH and alkali content as that of the instant application, as these are intensive properties that would be the same even if it was not explicitly stated in the prior art. See MPEP 2112. II. or Schering Corp. v. Geneva Pharm. Inc., for case law regarding the fact that an inherent feature need not be recognized at the relevant time in order for it to still anticipate the feature, which is later recognized. See claims 1, 2, 8 and 9 for how the material of the prior art is the same as that of the instant application.)
Claim(s) 39 is/are rejected under 35 U.S.C. 103 as being unpatentable over Liu (US 20210226203 A1) in view of He (20200067079 A1), further in view of Park (US 20170179484 A1), further in view of Lu (US 20180190970 A1), further in view of Kwak (US 20150037678 A1), and further in view of Stuart et Al (Paul A. Stuart et Al, the synthesis and sintering behaviour of BaZr0.9Y0.1O3−δ powders prepared by spray pyrolysis, Journal of the European Ceramic Society, Volume 29, Issue 4, 2009, Pages 697-702,).
Regarding claim 39, Liu teaches the following elements:
The method according to claim 11, comprising the following steps: (See claim 11, above)
wherein a ratio of a molar amount of lithium in the lithium salt to a molar amount of total metal elements in the precursor of the cobalt- free single crystal material is 1.05-1.5; (“The ratio of the lithium or sodium salt and the total metal salt may vary from 0.5 to 1.1,” Liu [0045])
The examiner takes note of the fact that the prior art ranges of 0.5 to 1.1 for the ratio of lithium hydroxide to precursor in a method for producing a single crystal cathode material overlaps the claimed range of 1.05-1.5 for the same parameter. Absent any additional and more specific information in the prior art, a prima facie case of obviousness exists. In re Peterson, 315 F.3d 1325, 1330, 65 USPQ2d 1379 (Fed. Cir. 2003). MPEP 2144.05.
carrying out calcination for 8-20 h at a temperature of 850-1000 °C and in an oxygen atmosphere (“In another aspect, a process for preparing a cathode active material includes a solid state reaction, the process including mixing solid transition metal salts of Ni, Mn, Al and M and M′ with appropriate ratio of a lithium or sodium salt to form a mixture; and calcining the mixture at a temperature of about 680° C. to about 1200° C., for a time period of about 5 hours to about 30 hours, in an atmosphere of oxygen, air, or oxygen-enriched air.” Liu [0011])
The examiner takes note of the fact that the prior art ranges of ------680-1200 C for the calcining temperature and 5 to 30 hours for the calcining time encompass the claimed range of 850-1000C and 8-20 hours for the same parameters. Absent any additional and more specific information in the prior art, a prima facie case of obviousness exists. In re Peterson, 315 F.3d 1325, 1330, 65 USPQ2d 1379 (Fed. Cir. 2003). MPEP 2144.05.
wherein the calcination is carried out at a temperature ramp rate of 3-5 °C/min; (“The heating rate may be from about 0.1° C./min to about 20° C./min, and the cooling rate may be from about 0.1° C./min to about 20° C./min, or it may be natural cooling or rapid quenching.” Liu [0045])
The examiner takes note of the fact that the prior art range of 0.1-20 C/min for the ramp rate of calcination encompasses the claimed range of 3-5C/min for the same parameter. Absent any additional and more specific information in the prior art, a prima facie case of obviousness exists. In re Peterson, 315 F.3d 1325, 1330, 65 USPQ2d 1379 (Fed. Cir. 2003). MPEP 2144.05.
carrying out sintering for 6-12 h at a temperature of 300-700 °C and in an oxygen atmosphere (“The heat-treating may include pre-sintering at a temperature of about 300° C. to about 600° C., maintaining this temperature for about 0 to about 10 hours, and then sintering at a temperature of about 680° C. to about 1200° C., and maintaining this temperature for about 5 to about 30 hours. The sintering/calcining may be conducted in an atmosphere of oxygen, air, or oxygen-enriched air.” Liu [0041])
The examiner takes note of the fact that the prior art range of 0-10 hours for the time of sintering overlaps the claimed range of 6-12 hours for the same parameter. Absent any additional and more specific information in the prior art, a prima facie case of obviousness exists. In re Peterson, 315 F.3d 1325, 1330, 65 USPQ2d 1379 (Fed. Cir. 2003). MPEP 2144.05.
wherein the sintering is carried out at a temperature ramp rate of 3-5 °C/min; (“The mixture is then sintered followed by a first and a second (or more) calcination step at a temperature of about 680° C. to about 1200° C. for a time period of about 5 hours to about 30 hours, cooling of the reaction. The heating rate may be from about 0.1° C./min to about 20° C./min,” Liu [0045])
The examiner takes note of the fact that the prior art range of 0.1-20 C/min for the ramp rate of sintering encompasses the claimed range of 3-5C/min for the same parameter. Absent any additional and more specific information in the prior art, a prima facie case of obviousness exists. In re Peterson, 315 F.3d 1325, 1330, 65 USPQ2d 1379 (Fed. Cir. 2003). MPEP 2144.05.
Liu is silent on the following elements of claim 39:
(1) mixing a lithium salt and a precursor of the cobalt-free single crystal material under stirring at a rotational speed of 1500-2500 rpm for 5-15 min,
[calcining] with a flowrate of 5-10 L/min,
and cooling, crushing and sieving with a 300- 400 mesh sieve to obtain the cobalt-free single crystal material; and
(2) mixing and dissolving TiNb207 and LiH2PO4 at a molar ratio of (0.1-10): 1 in deionized water,
drying the mixture, and mixing the mixture and the cobalt-free single crystal material for 10-20 min in a handheld stirrer,
wherein a ratio of a total mass of TiNb207 and LiH2PO4 to a weight of the cobalt-free single crystal material is 0.1-0.5wt%;
[sintering] with a flowrate of 5-10 L/min,
and cooling, crushing and sieving to obtain the cobalt-free single crystal composite material.
He teaches the following elements of claim 39:
(2) mixing and dissolving TiNb207 and LiH2PO4 at a molar ratio of (0.1-10): 1 in deionized water, (niobium oxide (Nb2O5), a titanate proton compound, and iron oxide (Fe2O3) were weighed such that the molar ratio of niobium to titanium and of iron to titanium in the synthesized compound was 3 and 0.3, respectively [He 0147] In this example, iron oxide is used in the inorganic filler, but as shown in paragraph 0015, Titanium Nitride is used as an equivalent material to be used in the inorganic filler. In this case, if the titanium nitride were replaced with the lithium phosphate salt of Park, as described in claim 1, the claimed ratio would be met. Additionally, He teaches “The niobium oxide (Nb2O5) and titanate proton compounds… was dispersed in pure water, followed by vigorous mixing. The obtained mixture was placed in a heat-resistant container and was subjected to hydrothermal synthesis under conditions of 180 C for a total of 24 hours. The obtained sample was washed in pure water three times, and then dried.” He [0145] If the titanate proton of He were replaced with the lithium phosphate of Park, as described in claim 1, then the method of He would meet all of the above limitations of claim 29. Then, if this mixture were included in the method of Liu, all of the portions of claim 29 would be met.)
He and Liu are silent on the following elements of claim 39:
(1) mixing a lithium salt and a precursor of the cobalt-free single crystal material under stirring at a rotational speed of 1500-2500 rpm for 5-15 min,
[calcining] with a flowrate of 5-10 L/min,
and cooling, crushing and sieving with a 300- 400 mesh sieve to obtain the cobalt-free single crystal material; and
drying the mixture, and mixing the mixture and the cobalt-free single crystal material for 10-20 min in a handheld stirrer,
wherein a ratio of a total mass of TiNb207 and LiH2PO4 to a weight of the cobalt-free single crystal material is 0.1-0.5wt%;
[sintering] with a flowrate of 5-10 L/min,
and cooling, crushing and sieving to obtain the cobalt-free single crystal composite material.
Park teaches the following elements of claim 39 that are not found in Liu or He:
wherein a ratio of a total mass of TiNb207 and LiH2PO4 to a weight of the cobalt-free single crystal material is 0.1-0.5wt%; (“In one specific embodiment, a weight of the shell relative to a weight of the core may be 0.1% by weight to 3.0% by weight.” Park [0019]. In this case, if the shell is a composition of the niobium-containing composite metal oxide and the lithium salt, these components would be present in a 0.1-3wt% of the cobalt-free single crystal material as a whole, thus encompassing the claimed range.)
The examiner takes note of the fact that the prior art range of 0.1-3 wt% of TiNb2O7 and LiH2PO4 (in this case, the mass of the shell) to the total weight of the cobalt-free single crystal material (the core and the shell) encompasses the claimed range of 0.1-0.5 wt% for the same parameter. Absent any additional and more specific information in the prior art, a prima facie case of obviousness exists. In re Peterson, 315 F.3d 1325, 1330, 65 USPQ2d 1379 (Fed. Cir. 2003). MPEP 2144.05.
drying the mixture, and mixing the mixture and the cobalt-free single crystal material for 10-20 min in a handheld stirrer, (“a method of preparing a cathode active material includes: adding a metal oxide compound precursor and a phosphate compound precursor to a core material capable of intercalating and deintercalating lithium ions to obtain a mixture; drying the mixture; and heat-treating the dried mixture to prepare a cathode active material,” Park [0016]. By incorporating the phosphate metal oxide of Park and method of producing it into the material of Liu, this limitation would be met. It would be obvious to one skilled in the art to perform this mixing via a handheld stirrer or another method, and the time of stirring would be a result effective variable, as it would be optimizable based on the material and how long it takes for it to be fully homogenized and would be well within the bounds of routine experimentation.)
Park, Liu, and He are silent on the following elements of claim 39:
(1) mixing a lithium salt and a precursor of the cobalt-free single crystal material under stirring at a rotational speed of 1500-2500 rpm for 5-15 min
[calcining] with a flowrate of 5-10 L/min,
and cooling, crushing and sieving with a 300- 400 mesh sieve to obtain the cobalt-free single crystal material; and
[sintering] with a flowrate of 5-10 L/min,
and cooling, crushing and sieving to obtain the cobalt-free single crystal composite material.
Lu teaches the following elements of claim 39 that are not found in the aforementioned references:
(1) mixing a lithium salt and a precursor of the cobalt-free single crystal material under stirring at a rotational speed of 1500-2500 rpm for 5-15 min,
(“In another embodiment of the disclosure, a preparation method of a high-voltage positive electrode material for a lithium battery includes preparing a precursor using a coprecipitation method and then mixing and sintering the precursor and lithium salt to produce the material represented by formula (1) above.” Lu [0006] and “the stirring speed is, for instance, between 800 rpm and 2000 rpm.” Lu [0041]. As for the time of stirring, this would be a result effective variable as it would within obvious/routine experimentation to stir at this speed until the mixture is properly homogenized.)
The examiner takes note of the fact that the prior art range 800-2000rpm for the stirring speed of mixing overlaps the claimed range of 1500-2500 for the same parameter. Absent any additional and more specific information in the prior art, a prima facie case of obviousness exists. In re Peterson, 315 F.3d 1325, 1330, 65 USPQ2d 1379 (Fed. Cir. 2003). MPEP 2144.05.
Lu is considered to be analogous to Liu because they are both within the same field of mixing precursors and lithium salts to form cathode materials. Therefore, it would have been obvious to one of ordinary skill before the effective filing date of the claimed invention to modify Liu to use the rotational speed of stirring of Lu as this is a known method in the art to form a desirable material.
Lu is silent on the following elements of claim 39:
[calcining] with a flowrate of 5-10 L/min,
and cooling, crushing and sieving with a 300- 400 mesh sieve to obtain the cobalt-free single crystal material; and
[sintering] with a flowrate of 5-10 L/min,
and cooling, crushing and sieving to obtain the cobalt-free single crystal composite material.
Kwak teaches the following elements of claim 39 that are not found in the aforementioned references:
and cooling, crushing and sieving with a 300- 400 mesh sieve to obtain the cobalt-free single crystal material; and (“A cake obtained after the sintering was ground in a mortar and then classified using a 400 mesh sieve” Kwak [0109])
and cooling, crushing and sieving to obtain the cobalt-free single crystal composite material. (“A cake obtained after the sintering was ground in a mortar and then classified using a 400 mesh sieve” Kwak [0109])
Kwak is considered to be analogous to Liu because it is within the same field of methods for producing particulate cathode materials. Therefore, it would have been obvious to one of ordinary skill before the effective filing date of the claimed invention to modify the method of Liu to include the crushing and sieving portion of Kwak in order to produce particles of a desired size to form an optimal electrode material. Additionally, this method is known in the art and therefore would be obvious to draw from when choosing a method for producing a single crystal cathode material.
Kwak is silent on the following elements of claim 39:
[calcining] with a flowrate of 5-10 L/min,
[sintering] with a flowrate of 5-10 L/min,
Stuart et al teaches all of the remaining elements of claim 39,
[calcining] with a flowrate of 5-10 L/min,
[sintering] with a flowrate of 5-10 L/min,
Start et al teaches a sintering process for an electrode material precursor having a flow rate of 6L/min (Stuart et Al, table 1). Stuart et Al and Liu are considered to be analogous because they are all related to the preparation of electrode materials. Therefore, it would have been obvious to one of ordinary skill before the effective filing date of the claimed invention to modify, or include, the flow rate of 6L/min from Stuart et Al into the sintering and calcining steps of Liu, in order to optimize the sintering conditions and not risk lowering yield rate--Stuart et al page 3 paragraph 2 states that lowering the flow rate from 6L/min to 3L/min was deemed undesirable as it was directly proportional to the powder yield rate. This would be desirable in a sintering process as decreasing the powder yield would make the process as a whole less efficient.
Conclusion
Any inquiry concerning this communication or earlier communications from the examiner should be directed to BENJAMIN ELI KASS-MULLET whose telephone number is (571)272-0156. The examiner can normally be reached Monday-Friday 8:30am-6pm except for the first Friday of bi-week.
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/BENJAMIN ELI KASS-MULLET/Examiner, Art Unit 1752
/NICHOLAS A SMITH/Supervisory Primary Examiner, Art Unit 1752