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 . Election/Restrictions
Applicant's election with traverse of Species (Claims 1 – 14) in the reply filed on (1 – 23 – 2026) is acknowledged. The traversal is on the ground(s) that the claims are not referenced at all, and that the restriction is not based on what is claimed. This is not found persuasive because as detailed in the restriction requirement of (12 – 18 – 2025) each species had the associated claim, i.e, (A I) was marked as Claim 1, and (A II) was marked as Claim 11, with Claim 1 reciting second calcining conducted at a second temperature range from 1000 °C to 1300 °C, which is not claimed in Claim 15, which only requires a single sintering at a first temperature higher predetermined temperature for example, at from 1000° C. to 1300° C, ([0067]). As such, The requirement is still deemed proper and is therefore made FINAL. Accordingly, claim(s) 15 – 20 are withdrawn from further consideration pursuant to 37 CFR 1.142(b), as being drawn to a nonelected species, there being no allowable generic or linking claim. Applicant timely traversed the restriction (election) requirement in the same reply filed on (1 – 23 – 2026).
Claim Rejections - 35 USC § 103
In the event the determination of the status of the application as subject to AIA 35 U.S.C. 102 and 103 (or as subject to pre-AIA 35 U.S.C. 102 and 103) is incorrect, any correction of the statutory basis (i.e., changing from AIA to pre-AIA ) for the rejection will not be considered a new ground of rejection if the prior art relied upon, and the rationale supporting the rejection, would be the same under either status.
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.
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.
A.) Claim(s) 1 – 15, is/are rejected under 35 U.S.C. 103 as being unpatentable over Badding et al. (US 20180301754 A1, hereinafter Badding) Regarding claim 1,
A method of making a composite ceramic, comprising:
A first mixing of inorganic source materials to form a mixture, including a lithium source compound and
at least one transition metal compound;
a first calcining conducted at a first temperature range from 800 °C to 1200 °C
a second calcining conducted at a second temperature range from 1000 °C to 1300 °C
milling the mixture to reduce particle size;
sieving to obtain a powder having at least one dimension in a range from 0.01 µm to 1 µm;
passivating the powder by at least one of an air carbonation or an acid treatment;
heating a metal oxide at a third temperature range from 500 °C to 1500 °C
a second mixing of the passivated powder, the metal oxide, and at least one solvent to form a slip composition;
tape casting the slip composition to form a green tape; and
sintering the green tape at a fourth temperature range from 950 °C to 1500 °C to form the composite ceramic,
wherein the second calcining is conducted at a temperature greater than the first calcining.
Badding teaches the following:
& b.) (Claim 7) teaches a first mixing of inorganic source materials to form a mixture, including a lithium source compound, and other suitable inorganic source materials to make the desired garnet composition. ([0003]) teaches the disclosure provides a composite Li-garnet ceramic electrolyte of the formula Li7-xLa3(Zr2-xMx)O12-SA, where M is, for example, Al, Ga, In, Si, Ge, Sn, Sb, Bi, Sc, Y, Ti, Hf, V, Nb, Ta, W, or a mixture thereof; “SA” refers to a second additive (SA) oxide selected from the group MgO, CaO, ZrO2, HfO2, or mixtures thereof. Where, Ta, Sc, Y, Ti and ZrO2, HfO2 amongst others listed are known transition metals. ([0128]) teaches mixing the lithium compound and Ta2O5 (99.99%) following the stoichiometry ratio of the desired empirical formula were mixed together by a wet grinding process with isopropanol and zirconia balls used as the milling media. As such, the mixing of inorganic compounds including a including a lithium source compound and a transition metal source compound are understood to be disclosed.
, d.) (Claim 7) teaches calcining the milled mixture to form a garnet oxide at from 800 °C to 1200 °C. Highlighting, performing calcination at temperatures between 1000 °C and below 1300 °C inherently encompasses an initial thermal treatment within the 800 °C to 1200 °C range. Due to when achieving a calcination temperature such as 1001 °C or 1299 °C it requires the system to first traverse the lower temperature bracket i.e., the 800 °C to 1200 °C. As such, the requirements for a first calcining stage are effectively satisfied during the heating phase to the desired calcination temperature. Accordingly, while no discrepancies are perceived to exist regarding implementing a first calcining conducted at a first temperature range from 800 °C to 1200 °C and a second calcining conducted at a second temperature range from 1000 °C to 1300 °C. However, if there any supposed inconsistencies the case law for sequential vs. simulations steps may be recited. Where, in general, the transposition of process steps or the splitting of one step into two, where the processes are substantially identical or equivalent in terms of function, manner and result, was held to be not patentably distinguish the processes. Ex parte Rubin, 128 USPQ 440 (Bd. Pat. App. 1959). Additionally, ([0128]) teaches that the reaction of the mixture of reactants was accomplished by twice calcining at 950 °C. for 6 hr for improving the uniformity of the synthesis powder, as such twice calcining is understood to impact the uniformity of the synthesis powder. Accordingly, the case law for result effective variables may be recited. Where, a particular parameter namely, the number of calcination treatments, must first be recognized as a result-effective variable, i.e., a variable which achieves a recognized result, before the determination of the optimum or workable ranges of said variable might be characterized as routine experimentation.
(Claim 7) teaches a second mixing of the milled and calcined garnet oxide and a second additive to provide a second mixture; a second milling of the second mixture to reduce the particle size of constituents of the second mixture. As such, milling the calcined garnet oxide powder is understood to be disclosed.
& g.) ([0081]) teaches that classifying the milled powder to a mono-modal distribution having a particle size of from 0.3 to 0.7 microns. ([0142]) teaches that a mono-modal fine powder, e.g., 3 microns, can be achieved by air classification of the ball milled powder. Where the classifying of the milled powder via air classification / jetting air at the particles is understood to act as applicant’s sieving, while simultaneously providing for passivating the powder by at least one of an air carbonation. As such, obtaining a milled powder having at least one dimension in a range from 0.01 µm to 1 µm and passivating the powder by at least one of an air carbonation is understood to be disclosed.
([0128]) teaches that the reaction of the mixture of reactants was accomplished by twice calcining at 950° C for 6 hr for improving the uniformity of the synthesis powder. Finally, the synthesized powder, having from 0 to 9 wt. % added MgO, was ground again to a fine powder by a wet grinding with isopropanol and zirconia balls as the milling media. The mixture was dried at 80 °C. for 16 hrs and then heated at 500 °C. As such, after calcining the lithium source compound and the transition metal compound twice, the secondary additive MgO was included into the mixture followed by heat treatment at 500° C. As such, the secondary additive MgO was heat treated at 500 °C, which is found to overlap with applicant’s range of heating a metal oxide at a third temperature range from 500 °C to 1500 °C. Accordingly, while no discrepancies are perceived to exist regarding heating a metal oxide at a third temperature range from 500 °C to 1500 °C. However, if there any supposed inconsistencies the case law for sequential vs. simulations steps may be recited. Where, in general, the transposition of process steps or the splitting of one step into two, where the processes are substantially identical or equivalent in terms of function, manner and result, was held to be not patentably distinguish the processes. Ex parte Rubin, 128 USPQ 440 (Bd. Pat. App. 1959).
([0128]) teaches that the dried mixture was then dry-milled to produce a homogeneous fine powder. ([0087]) teaches that the tape casting process begins by making an aqueous garnet slip. The aqueous slip contains DI water, water soluble organic binder, a plasticizer, and a lithium garnet powder. As such, a second mixing that comprises a lithium garnet powder, i.e, the passivated powder / lithium source compound with the transition metal compound, and the secondary additive oxide / the metal oxide (Li7-xLa3(Zr2-x,Mx)O12-SA), with a solvent / DI water to form a slip composition is understood to be disclosed.
([0154]) teaches that after mixing, the slip was immediately cast on a Mylar surface with a blade of 14 mil gap. As such, tape casting the slip composition to form a green tape is understood to be disclosed.
([0156]) teaches the laminated stack of sheets was sintered at 1075 °C. As such, the green tape is sintered at a fourth temperature range that falls within applicant’s range of 950 °C to 1500 °C to form the composite ceramic.
([0128]) teaches that the reaction of the mixture of reactants was accomplished by twice calcining at 950 °C. for 6 hr for improving the uniformity of the synthesis powder, as such twice calcining is understood to impact the uniformity of the synthesis powder. ([0118]) teaches that the mixture of inorganic material, after the mixing step, is calcined at a predetermined temperature, for example, at from 800 to 1200° C., including intermediate values and ranges, to react and form the target Li-garnet oxides. The predetermined temperature depends on the type of the garnet oxides. As such, the calcination temperature are also understood to impact the type of the garnet oxides that can be used and/or produced. Accordingly, the case law for result effective variables may be recited. Where, a particular parameter namely, the calcination temperature and the number of calcination treatments, must first be recognized as a result-effective variable, i.e., a variable which achieves a recognized result, before the determination of the optimum or workable ranges of said variable might be characterized as routine experimentation.
Regarding claim 2 as applied to claim 1,
Wherein the air carbonation comprises exposing the powder to air to form a protonated powder with an overlaying Li2CO3 shell.
Badding teaches the following:
([0142]) teaches that a mono-modal fine powder, e.g., 3 microns, can be achieved by air classification of the ball milled powder. Three powders were produced after air classification and their particle size distributions are shown in FIGS. 11A and 11B. As such, exposing the ball milled powder to air, via air classification / jetting of air is understood to be disclosed and acts as applicant’s air carbonation process which comprises exposing the powder to air. Highlighting, while Badding may not mention forming a protonated powder with an overlaying Li2CO3 shell. The case law for
Regarding claim 3 as applied to claim 1,
Wherein the acid treatment comprises exposing the powder to an acid solution to form a protonated powder.
Badding teaches the following:
([0144]) teaches that Garnet powder is reported to be more stable in acid and basic aqueous solution than LTAP. ([0146]) teaches that the polymer is soluble in water when the pH is alkaline, and can be achieved by, for example, the addition of a small percentage (e.g., 0.1 to 3 wt %) of ammonia hydroxide. Accordingly, implementing a solvent that comprises either a water, acidic or basic aqueous solution is understood to be disclosed. As such, during the second mixing of the composite ceramic comprising a lithium source compound and at least one transition metal compound along with the metal oxide is understood to include exposure of the powder to an acid solution to form a protonated powder. Accordingly, while no discrepancies are perceived to exist regarding acid treatment comprises exposing the powder to an acid solution to form a protonated powder. However, if there any supposed inconsistencies the case law for sequential vs. simulations steps may be recited. Where, in general, the transposition of process steps or the splitting of one step into two, where the processes are substantially identical or equivalent in terms of function, manner and result, was held to be not patentably distinguish the processes. Ex parte Rubin, 128 USPQ 440 (Bd. Pat. App. 1959).
Regarding claim 4 as applied to claim 1,
Wherein the second mixing further includes at least one of:
organic binder, plasticizer, an excess lithium source, dispersant, or combinations thereof.
Badding teaches the following:
([0144]) teaches that Table 3 shows the information of aqueous binders used in the slips. The slip making includes the steps of: dispersing the garnet powder in de-ionized water to form a garnet suspension; adding binder to the garnet suspension. ([0146]) teaches the binder can include, for example, an aqueous solution of a proprietary acrylic polymer having copolymerized polar functional groups. ([0147]) notes that the binder system also comprise a plasticizer. As such, the second mixing is understood to comprise including an organic binder (polymer) and a plasticizer.
Regarding claim 5 as applied to claim 5,
Wherein the composite ceramic comprises:
a lithium-garnet major phase; and
a grain growth inhibitor minor phase,
wherein the composite ceramic comprises at least one of:
a Li-ion conductivity of at least 10-4 S/cm; or
a relative density of at least 90% of a theoretical maximum density of composite ceramic.
Badding teaches the following:
([0041]) teaches that the ceramic composite comprises a lithium garnet major phase.
([0042]) teaches that the ceramic composite comprises a grain growth inhibitor minor phase.
([0049]) the ceramic has an ion conductivity, for example, of from 1×10−4 S/cm to 6×104 S/cm such as 1×104 S/cm to 3×104 S/cm, including intermediate values and ranges. ([0082]) teaches the ion conductivity of the tape can be, for example, higher than 10−4 S/cm whether sintered in air or in an inert atmosphere. As such, the composite ceramic comprises a Li-ion conductivity of at least 10-4 S/cm.
Highlighting, that only one limitation amongst (c) and (d) is required. However, ([0051]) teaches that the density of the ceramic is at least 95 to 98% of a theoretical maximum density of the ceramic. ([0082]) teaches that in embodiments, the tape can have a thickness from 20 to 300 microns, and a high density of about 95%. As such, the composite ceramic comprises a relative density of at least 90% of a theoretical maximum density of composite ceramic.
Regarding claim 6 as applied to claim 5,
Wherein the grain growth inhibitor minor phase comprises the metal oxide in a range from 0.1 wt.% to 10 wt.% based on a total weight of the composite ceramic.
Badding teaches the following:
([0006]) teaches that the resulting composite Li-garnet oxide contains the second additive in an amount up to 9 wt. % such as from 1 to 9 wt % based on the total weight of the composite. ([0029]) teaches that “SA,” “second additive,” “second phase additive,” “second phase additive oxide,” “phase additive oxide,” “additive oxide,” “additive,” or like terms refer to an additive oxide that produces a minor phase or second minor phase within the major phase (i.e., the first phase) when included in the disclosed compositions. As such, the grain growth inhibitor minor phase comprises the metal oxide in a range from 0.1 wt.% to 10 wt.% based on a total weight of the composite ceramic.
Regarding claim 7 as applied to claim 5,
Wherein the lithium-garnet major phase comprises at least one of:
(i) Li7 – 3aLa3Zr2LaO12, with L = Al, Ga or Fe and 0 < a < 0.33;
(ii) Li7La3 – bZr2MbO12, with M = Bi, Ca, or Y and 0 < b < 1;
(iii) Li7 – cLa3(Zr2 – c, Nc)O12, with N = In, Si, Ge, Sn, Sb, Sc, Ti, Hf, V, W, Te, Nb, Ta, Al, Ga, Fe, Bi, Y, Mg, Ca, or combinations thereof and 0 < c < 1, or a combination thereof.
Badding teaches the following:
It should be noted that only one limitation amongst (a), (b) or (c) is required. However, ([0098]) teaches that (i) cation substitutions of Li7La3Zr2O12 in the formula of Li7-xLa3(Zr2-xMx)O12 wherein M is, for example, Al, Ga, In, Si, Ge, Sn, Sb, Bi, Sc, Y, Ti, Hf, V, Nb, Ta, and W. ([0153]) teaches a Li6.5La2.8Ga0.2Zr1.75Nb0.25O12 composition. As such, the use of Li7 – 3aLa3Zr2LaO12 with L = Al or Nb and a = 0.2, (which falls within applicant’s range of a = 0 < a < 0.33) is understood to be disclosed.
It should be noted that only one limitation amongst (a), (b) or (c) is required. ([0003]) teaches that he disclosure provides a composite Li-garnet ceramic electrolyte of the formula Li7-xLa3(Zr2-xMx)O12-SA, where M is, for example, Al, Ga, In, Si, Ge, Sn, Sb, Bi, Sc, Y, Ti, Hf, V, Nb, Ta, W. As such, Y is understood to be disclosed to be used in a formula comprising Li7La3 – bZr2MbO12.
([0095]) teaches that Lithium-containing Garnets, such as Li5La3M2O12 (M=Ta, Nb), Li7La3Zr2O12, etc., can accommodate a greater concentration of Li+ cations in the [La3M2O12]5− framework. ([0128]) teaches that The garnet-type oxides were synthesized as follows: a garnet-type oxide Ta-doped Li7La3Zr2O12 was prepared via a conventional solid-state reaction method, having the formula Li6.4La3Ta0.6Zr14O12 (LLTZO). ([0125]) teaches that a suitable setter composition is a Ta doped garnet with a formula of Li6.5La3Zr1.5Ta0.5O12. As such, the use of a Li7 – cLa3(Zr2 – c, Nc)O12, with N = Ta, and C = 0.6 or 0.5 (which falls within applicant’s range of 0 < c < 1) is understood to be disclosed.
Regarding claim 8 as applied to claim 7,
Wherein the lithium-garnet major phase comprises:
Li7 – cLa3(Zr2-e, Ne)O12, with N = Ta, Mg, or combinations thereof, and 0 < c < 1.
Badding teaches the following:
([0095]) teaches that Lithium-containing Garnets, such as Li5La3M2O12 (M=Ta, Nb), Li7La3Zr2O12, etc., can accommodate a greater concentration of Li+ cations in the [La3M2O12]5− framework. ([0128]) teaches that The garnet-type oxides were synthesized as follows: a garnet-type oxide Ta-doped Li7La3Zr2O12 was prepared via a conventional solid-state reaction method, having the formula Li6.4La3Ta0.6Zr14O12 (LLTZO). ([0125]) teaches that a suitable setter composition is a Ta doped garnet with a formula of Li6.5La3Zr1.5Ta0.5O12. As such, the use of a Li7 – cLa3(Zr2 – c, Nc)O12, with N = Ta, and C = 0.6 or 0.5 (which falls within applicant’s range of 0 < c < 1) is understood to be disclosed.
Regarding claim 9 as applied to claim 5,
Wherein the metal oxide comprises:
MgO, CaO, ZrO2, HfO2, or a combination thereof.
Badding teaches the following:
([0003]) teaches that the disclosure provides a composite Li-garnet ceramic electrolyte of the formula Li7-xLa3(Zr2-xMx)O12-SA, where M is, for example, Al, Ga, In, Si, Ge, Sn, Sb, Bi, Sc, Y, Ti, Hf, V, Nb, Ta, W, or a mixture thereof; “SA” refers to a second additive (SA) oxide selected from the group MgO, CaO, ZrO2, HfO2, or mixtures thereof. As such, the metal oxide comprises MgO, CaO, ZrO2, HfO2, and/or a combination thereof.
Regarding claim 10 as applied to claim 9,
Wherein the metal oxide comprises MgO.
Badding teaches the following:
([0003]) teaches that the disclosure provides a composite Li-garnet ceramic electrolyte of the formula Li7-xLa3(Zr2-xMx)O12-SA, where M is, for example, Al, Ga, In, Si, Ge, Sn, Sb, Bi, Sc, Y, Ti, Hf, V, Nb, Ta, W, or a mixture thereof; “SA” refers to a second additive (SA) oxide selected from the group MgO, CaO, ZrO2, HfO2, or mixtures thereof. As such, the metal oxide comprises MgO.
Regarding claim 11 as applied to claim 5,
Wherein a maximum grain size measured for a population of grains of the lithium-garnet major phase representing at least 5% of a total grain population does not exceed an average grain size of the total grain population by more than a multiple of 20.
Badding teaches the following:
([0039]) teaches that for example, the maximum grain size measured for a population of grains representing at least 5% of the total grains should not exceed the average grain size by more than a multiple of 20.
Regarding claim 12 as applied to claim 5,
Wherein the composite ceramic comprises a membrane having a thickness in a range from 30 µm to 150 µm.
Badding teaches the following:
([0082]) teaches that in embodiments, the tape can have a thickness from 20 to 300 microns, and a high density of about 95%. As such, the composite ceramic comprises a membrane having a thickness in a range from 30 µm to 150 µm.
Regarding claim 13 as applied to claim 1,
Wherein the sintering comprises:
heating from room temperature to the fourth temperature range;
holding at the fourth temperature range for a time in a range from 1 minute to 20 minutes;
cooling from the fourth temperature range to room temperature,
wherein: a heating ramp rate (HRR) for the heating is 100°C/min < HRR < 1000°C/min, and
a cooling rate (CR) for the cooling is 100°C/min < CR < 1000°C/min.
Badding teaches the following:
, b.) & d.) ([0159]) teaches that the sintering profile was as follows: heating rate is 100° C./hr from ambient (e.g., 25 °C.) to 600° C., and hold for 1 hr to remove any organic residues in the green tape, and after that the temperature continues to rise to the sintering temperature of 1200 °C at the same heating rate of 100 °C/h, and then a hold for 2 to 3 hrs to sinter the tape. As such, heating from heating from ambient (e.g., 25° C.) / room temperature to the fourth sintering temperature range of 1200 °C and holding for 2 to 3 hrs is understood to be disclosed. Highlighting, that applicant’s holding time is slightly lower than that of Badding’s holding time. With ([0088]) adding that the holding time at the top sintering temperature can vary from 2 to 6 hrs depending on the size of samples. ([00148]) expanding on this stating that the dwell time on the sintering temperature can be, for example, from 2 to 10 hrs depending on the composition, the mass of sample, and the grain size target. As such, the holding time is understood to impact the composition utilized, the grain size target the mass, and size of the sample provided. Accordingly, the case law for result effective variables may be recited. Where, it is well settled that determination of optimum values of cause effective variables such as these process parameters is within the skill of one practicing in the art. In re Boesch, 205 USPQ 215 (CCPA 1980). In re Antonie, 559 F.2d 618, 195 USPQ 6 (CCPA 1977), MPEP 2143 II (B).
& e.) ([0159]) teaches that finally the tape is cooled to ambient or about 25° C. with a cooling rate of 300 °C/hr. As such, cooling to room / ambient temperature (25° C) at a rate of 300 °C/hr (which falls within applicant’s cooling rate range of 100°C/min < CR < 1000°C/min) is understood to be disclosed.
Regarding claim 14 as applied to claim 13,
Wherein:
the HRR is 250 °C/min < HRR < 750 °C/min,
the CR is 250 °C/min < CR < 750 °C/min, and
the fourth temperature range is from 1100 °C to 1300 °C.
Badding teaches the following:
([0148]) teaches that a slow heating rate below 400 °C is preferred such as from 60 to 90 °C/hr due to the binder burn out. Above 400 °C, the heating rate can be, for example, above 100 °C/hr, such as set at 120 °C/hr, until at the top sintering temperature. As such, the use of a heating rate above 100 °C/hr (which falls within applicant’s cooling rate range of 250°C/min < HRR < 750°C/min) is understood to be disclosed.
([0159]) teaches that finally the tape is cooled to ambient or about 25° C. with a cooling rate of 300 °C/hr. As such, a cooling rate of 300 °C/hr (which falls within applicant’s cooling rate range of 250°C/min < CR < 750°C/min) is understood to be disclosed.
([0148]) teaches that the top sintering temperature depends on the composition, and can vary, for example, from 1000 to 1250 °C. As such, a sintering temperature of 1000 to 1250 °C is found to overlap with applicant’s fourth temperature range of 1100 °C to 1300 °C.B.) Claim(s) 13, is/are rejected under 35 U.S.C. 103 as being unpatentable over Badding in view of Xu et al. (Effect of Acid Treatment of Li7La3Zr2O12 on Ionic Conductivity of Composite Solid Electrolytes, 2020, hereinafter Xu)
Regarding claim 3 as applied to claim 1,
Wherein the acid treatment comprises exposing the powder to an acid solution to form a protonated powder.
Badding teaches the following:
([0144]) teaches that Garnet powder is reported to be more stable in acid and basic aqueous solution than LTAP. ([0146]) teaches that the polymer is soluble in water when the pH is alkaline, and can be achieved by, for example, the addition of a small percentage (e.g., 0.1 to 3 wt %) of ammonia hydroxide. Accordingly, implementing a solvent that comprises either a water, acidic or basic aqueous solution is understood to be disclosed. As such, during the second mixing of the composite ceramic comprising a lithium source compound and at least one transition metal compound along with the metal oxide is understood to include exposure of the powder to an acid solution to form a protonated powder. Accordingly, while no discrepancies are perceived to exist regarding acid treatment comprises exposing the powder to an acid solution to form a protonated powder. However, if there any supposed inconsistencies the case law for sequential vs. simulations steps may be recited. Where, in general, the transposition of process steps or the splitting of one step into two, where the processes are substantially identical or equivalent in terms of function, manner and result, was held to be not patentably distinguish the processes. Ex parte Rubin, 128 USPQ 440 (Bd. Pat. App. 1959).
Regarding Claim 3, Badding is silent on the acid treatment comprises exposing the powder to an acid solution. In analogous art for forming a Li7La3Zr2O12 ceramic composite solid electrolyte (Abstract), Xu suggests details regarding implementing an acid treatment comprises exposing the powder to an acid solution, and in this regard, Xu teaches the following:
(Abstract) teaches that LLZO is unstable in humid air and easily forms Li2CO3 on the surface, which leads to the decrease of ion conductivity. In this paper, chemical treatment by oxalic acid is carried out to remove the lithium carbonate on the surface of LLZO. The results show that oxalic acid with a concentration ratio of 5% can completely remove lithium carbonate. Composite polymer electrolyte membranes fabricated by the polyvinylidene fluoride (PVDF)and LLZO before and after the acid treatment are prepared to evaluate the effect on ionic conductivity. The ionic conductivity is 1.4 × 10 – 4 S/cm and 9.0 x 10 – 4 S/cm for samples added the LLZO before and after the acid treatment, respectively. As such, implementation of an acid treatment comprises exposing the powder to an acid solution is understood to be disclosed.
It would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to modify the production method and apparatus for manufacturing a composite ceramic solid electrolyte and tapes thereof, including a lithium garnet major phase; and a grain growth inhibitor minor phase of Badding. By modifying the process to include an acid treatment comprising exposing the powder to an acid solution, as taught by Xu. Highlighting, one would be motivated to implement an acid treatment comprising exposing the powder to an acid solution as it provides for tailoring for the ionic conductivity of the of lithium composite ceramic solid electrolyte. Highlighting, due to the acid treatment comprising exposing the powder to an acid solution impact the ionic conductivity of the of lithium composite ceramic solid electrolyte. The case law for result effective variables may be recited. Where, a particular parameter, namely an acid treatment comprising exposing the powder to an acid solution, must first be recognized as a result-effective variable, i.e., a variable which achieves a recognized result, before the determination of the optimum or workable ranges of said variable might be characterized as routine experimentation. Additionally, the use of known technique to improve similar devices (methods, or products) in the same way and/or the applying a known technique to a known device (method, or product) ready for improvement to yield predictable results provides for the recitation of KSR case law. Where, "A person of ordinary skill has good reason to pursue the known option within his or her technical grasp. If this leads to the anticipated success, it is likely the product not of innovation but of ordinary skill and common sense." KSR int'l Co. v. Teleflex Inc., 127 S. Ct. 1727, 82 USPQ2d 1385 (2007), MPEP 2143.
C.) Claim(s) 13, is/are rejected under 35 U.S.C. 103 as being unpatentable over Badding in view of Hitz et al. (US 20170155169 A1, hereinafter Hitz)Regarding claim 13 as applied to claim 1,
Wherein the sintering comprises:
heating from room temperature to the fourth temperature range;
holding at the fourth temperature range for a time in a range from 1 minute to 20 minutes;
cooling from the fourth temperature range to room temperature,
wherein: a heating ramp rate (HRR) for the heating is 100°C/min < HRR < 1000°C/min, and
a cooling rate (CR) for the cooling is 100°C/min < CR < 1000°C/min.
Badding teaches the following:
, b.) & d.) ([0159]) teaches that the sintering profile was as follows: heating rate is 100° C./hr from ambient (e.g., 25 °C.) to 600° C., and hold for 1 hr to remove any organic residues in the green tape, and after that the temperature continues to rise to the sintering temperature of 1200 °C at the same heating rate of 100 °C/h, and then a hold for 2 to 3 hrs to sinter the tape. As such, heating from heating from ambient (e.g., 25° C.) / room temperature to the fourth sintering temperature range of 1200 °C and holding for 2 to 3 hrs is understood to be disclosed. Highlighting, that applicant’s holding time is slightly lower than that of Badding’s holding time. With ([0088]) adding that the holding time at the top sintering temperature can vary from 2 to 6 hrs depending on the size of samples. ([00148]) expanding on this stating that the dwell time on the sintering temperature can be, for example, from 2 to 10 hrs depending on the composition, the mass of sample, and the grain size target. As such, the holding time is understood to impact the composition utilized, the grain size target the mass, and size of the sample provided. Accordingly, the case law for result effective variables may be recited. Where, it is well settled that determination of optimum values of cause effective variables such as these process parameters is within the skill of one practicing in the art. In re Boesch, 205 USPQ 215 (CCPA 1980). In re Antonie, 559 F.2d 618, 195 USPQ 6 (CCPA 1977), MPEP 2143 II (B).
& e.) ([0159]) teaches that finally the tape is cooled to ambient or about 25° C. with a cooling rate of 300 °C/hr. As such, cooling to room / ambient temperature (25° C) at a rate of 300 °C/hr (which falls within applicant’s cooling rate range of 100°C/min < CR < 1000°C/min) is understood to be disclosed.
Regarding Claim 13, Badding is silent on sintering and holding at the fourth temperature range for a time in a range from 1 minute to 20 minutes. In analogous art for ceramic ion-conducing structures, the structures can be in the form of a single layer or multilayer structures comprising lithium garnet materials, (Abstract & [0107]), Hitz suggests details regarding sintering and holding at the fourth temperature range for a time in a range from 1 minute to 20 minutes, and in this regard, Hitz teaches the following:
([0107]) teaches that the ionically conductive material can have, among other materials, various members of the lithium garnet family. ([0054]) teaches fabricating ceramic-ionic conducing structures comprises sintering a layer of a slurry. The sintering can be carried out in discrete steps (e.g., pre-sintering (burn out) and sintering steps) or in single continuous step.
([0055]) teaches that for example, sintering is carried out at 800° C. to 1200° C., including all integer ° C. values and ranges therebetween. In an example, sintering is carried out at 1000° C. to 1000° C. The sintering can be carried out for 1 minute to 24 hours, including all integer minute values and ranges therebetween. ([0127]) expands on this stating that a dilatometric study, shown in (FIG. 4b), indicates that a significant amount of sintering occurs before 1000° C., where lithium loss starts to be a significant factor. This is the rationale behind the longer 5-hour sintering time at 950° C. or short 20-minute hold at 1050 °C., which both promote sintering. As such, sintering either at a 20-minute hold at 1050 °C and/or 5-hour sintering time at 950 °C is understood to be disclosed, with the range being expanding as low as 1 minute and as high as 24 hours.
It would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to modify the production method and apparatus for manufacturing a composite ceramic solid electrolyte and tapes thereof, including a lithium garnet major phase; and a grain growth inhibitor minor phase of Badding. By modifying the sintering to comprise a holding time of 1 minute to 20 minutes, as taught by Hitz. Highlighting, one would be motivated to implement sintering holding time of 1 minute to 20 minutes as it provides for using a shorter holding time using low-cost nichrome heating elements, ([0124]). Accordingly, sintering at 20 minute or less is understood to overlap with applicant’s range, in particular 20 minutes is understood to overlap with applicant’s range upper end point, i.e,. 1 minute to 20 minutes. As such, the case law for overlapping ranges are prima facie evidence of obviousness. It would have been obvious to one having ordinary skill in the art to have selected the portion of Hitz sintering holding time range that corresponds to the claimed range. In re Malagari, 184 USPQ 549 (CCPA 1974).
Conclusion
The prior art made of record and not relied upon is considered pertinent to applicant's disclosure.
Beck et al. (US 20210194045 A1) – teaches in the (Abstract) that the instant disclosure sets forth multiphase lithium-stuffed garnet electrolytes having secondary phase inclusions, wherein these secondary phase inclusions are material(s) which is/are not a cubic phase lithium-stuffed garnet, but which is/are entrapped or enclosed within a lithium-stuffed garnet.
Iyer et al. (US 20180045465 A1) – teaches in the (Abstract) setter plates are fabricated from Li-stuffed garnet materials having the same, or substantially similar, compositions as a garnet Li-stuffed solid electrolyte. The Li-stuffed garnet setter plates, set forth herein, reduce the evaporation of Li during a sintering treatment step and/or reduce the loss of Li caused by diffusion out of the sintering electrolyte.
Holme et al. (US 20150099190 A1) – teaches in the (Abstract) Set forth herein are garnet material compositions, e.g., lithium-stuffed garnets and lithium-stuffed garnets doped with alumina, which are suitable for use as electrolytes and catholytes in solid state battery applications. Set forth herein are lithium-stuffed garnet thin films having fine grains therein.
Badding et al. (US 20220359908 A1) – teaches in the (Abstract) A composite ceramic including: a lithium garnet major phase; and a grain growth inhibitor minor phase, as defined herein. Also disclosed is a method of making composite ceramic, pellets and tapes thereof, a solid electrolyte, and an electrochemical device including the solid electrolyte, as defined herein.
Badding et al. (US 20230369641 A1) – teaches in the (Abstract) A composite ceramic including: a lithium garnet major phase; and a grain growth inhibitor minor phase, as defined herein. Also disclosed is a method of making composite ceramic, pellets and tapes thereof, a solid electrolyte, and an electrochemical device including the solid electrolyte, as defined herein.
Badding et al. (US 20160149260 A1) An air stable solid garnet composition, comprising: a bulk composition and a surface protonated composition on at least a portion of the bulk composition as defined herein, and the protonated surface composition is present on at least a portion of the exterior surface of the bulk composition at a thickness of from 0.1 to 10,000 nm. Also disclosed is a composite electrolyte structure, and methods of making and using the composition and the composite electrolyte structure.
Badding et al. (US 20190148770 A1) – teaches in the (Abstract) An air stable solid garnet composition, comprising: a bulk composition and a surface protonated composition on at least a portion of the bulk composition as defined herein, and the protonated surface composition is present on at least a portion of the exterior surface of the bulk composition at a thickness of from 0.1 to 10,000 nm. Also disclosed is a composite electrolyte structure, and methods of making and using the composition and the composite electrolyte structure.
Badding et al. (US 20220209289 A1) – teaches in the (Abstract) An air stable solid garnet composition, comprising: a bulk composition and a surface protonated composition on at least a portion of the bulk composition as defined herein, and the protonated surface composition is present on at least a portion of the exterior surface of the bulk composition at a thickness of from 0.1 to 10,000 nm. Also disclosed is a composite electrolyte structure, and methods of making and using the composition and the composite electrolyte structure.
Badding et al. (US 20220209288 A1) – teaches in the (Abstract) An air stable solid garnet composition, comprising: a bulk composition and a surface protonated composition on at least a portion of the bulk composition as defined herein, and the protonated surface composition is present on at least a portion of the exterior surface of the bulk composition at a thickness of from 0.1 to 10,000 nm. Also disclosed is a composite electrolyte structure, and methods of making and using the composition and the composite electrolyte structure.
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/Andrés E. Behrens Jr./Examiner, Art Unit 1741
/JaMel M Nelson/Primary Examiner, Art Unit 1743