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 .
Claim Rejections - 35 USC § 112
The following is a quotation of 35 U.S.C. 112(b):
(b) CONCLUSION.—The specification shall conclude with one or more claims particularly pointing out and distinctly claiming the subject matter which the inventor or a joint inventor regards as the invention.
Claims 9, 18 and 20 are rejected under 35 U.S.C. 112(b) or 35 U.S.C. 112 (pre-AIA ), second paragraph, as being indefinite for failing to particularly point out and distinctly claim the subject matter which the inventor or a joint inventor (or for applications subject to pre-AIA 35 U.S.C. 112, the applicant), regards as the invention.
Claim 9: Claim 9 recites “a cell volume of the single phase crystalline solution increases with increasing content of the second borate cluster anion.” This phrase is indefinite because the claim refers to a solid state electrolyte which contains a specific concentration of an anion at a given time and the concentration does not change once formed. For examination purposes, the phrase “a cell volume of the single phase crystalline solution increases with increasing content of the second borate cluster anion” will be interpreted as “wherein a different electrolyte could have been chosen with more of the second anion and a greater cell volume”.
Claim 18: Claim 18 recites “wherein a cell volume of the single phase crystalline solution increases with increasing content of the halogenated closo-borate cluster anion”. This phrase is indefinite because the claim refers to a solid state electrolyte which contains a specific concentration of an anion at a given time and the concentration does not change once formed. For examination purposes, the phrase “wherein a cell volume of the single phase crystalline solution increases with increasing content of the halogenated closo-borate cluster anion” will be interpreted as “wherein a different electrolyte could have been chosen with more of the second anion and a greater cell volume”.
Claim 20: Claim 20 recites “wherein a cell volume of the single phase crystalline solution increases with increasing content of the at least one second borate cluster anion”. This phrase is indefinite because the claim refers to a solid state electrolyte which contains a specific concentration of an anion at a given time and the concentration does not change once formed. For examination purposes, the phrase “wherein a cell volume of the single phase crystalline solution increases with increasing content of the at least one second borate cluster anion” will be interpreted as “wherein a different electrolyte could have been chosen with more of the second anion and a greater cell volume”.
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.
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.
Claims 1-4 and 19-20 are rejected under 35 U.S.C. 103 as being unpatentable over Tutusaus et al. (US 20220017375 AI), further in view of Yushin et al. (US 20200343580 A1) .
Claim 1-2: Tutusaus ‘375 teaches solvent-free closo-borate electrolytes (i.e., inorganic solid electrolyte) comprising a lithium closo-borate wherein the closo-borate can be a mixed salt having a single anion structure or a mixed salt having a mixture of different anion structures with the formula Li2B12H12-xZx, where x ≤ 6; and Z is a halogen [0006, 0011, 0018], such as a mixture comprising Li2B12H12 and Li2B12H11F.
Tutusaus ‘375 does not explicitly teach that the mixed closo-borate salts are single phase crystalline solutions or the elastic modulus of the solid state electrolytes. However, Yushin teaches solid state electrolytes including hydride solid state electrolytes comprising closo-borate-based salts of Li and their mixtures [0107-0109, 0112], wherein some solid electrolytes are single phase (solid solution) in a solid state (i.e., a single phase crystalline solution) [0059, 0060], and the preferred Young’s modulus (i.e., elastic modulus) at room temperature is in the range 0.1 GPa to 100.0 GPa [0067]. Yushin teaches too high or too low values may lead to reduced stability and performance characteristics of solid electrolyte -based cells [0067]. Yushin does not identically teach the range of less than 15 GPa. However, overlapping ranges have been held to support a case of obviousness (see MPEP 2144.05.I).
Therefore, it would have been obvious to one of ordinary skill in the art at the time of filling the instant invention to have made Tutusaus solid state electrolyte with an elastic modulus of less than 15 GPa because Yushin teaches solid electrolytes in this range have favorable stability and performance characteristics.
Claim 3: Tutusaus ‘375 teaches a lithium closo-borate wherein the closo-borate can be a mixed salt having a mixture of different anion structures with the formula Li2B12H12-xZx, where x ≤ 6; and Z is a halogen [0006, 0011, 0018], such as a mixture comprising Li2B12H11F and Li2B12H10F2 (i.e., Li4[B12H11F2-][ B12H10F22-] ) wherein both anions are halogenated.
Claim 4: Tutusaus ‘375 teaches a lithium closo-borate wherein the closo-borate can be a mixed salt having a mixture of different anion structures with the formula Li2B12H12-xZx, where x ≤ 6; and Z is a halogen [0006, 0011, 0018], such as a mixture comprising Li2B12H12 and Li2B12H11F (i.e., Li4[B12H122-][ B12H11F2-] ) wherein the first borate cluster anion is non-halogenated and the second borate cluster anion is halogenated.
Claim 19: Tutusaus ‘375 further teaches an electrochemical device (i.e, electrochemical cell) comprising an anode, a cathode and an electrolyte (i.e., inorganic solid state electrolyte) that is a solvent-free alkali metal or alkali earth metal closo-borate salt in contact with the anode and the cathode. [0009, 0033], wherein the anode can be an alloy (i.e. Si, Sn) anode [0034],
and the cathode can undergo insertion of the cathode material (i.e., an insertion cathode) [0035].
Claim 20: Tutusaus ‘375 teaches solid-electrolyte a mixed salt comprising LiCB11H12 and one of closo-borate salts with the formula LiCB11H12-xZx, wherein Z is a halogen [0018, 0032], wherein the first anion is CB11H12- , and for x = 1, the second anion is chosen from CB11H11Z-, wherein Z is X- is F-, Cl-, Br-, or I-. Tutusaus ‘375 does not teach the change in cell volume of the single phase crystalline solution of the salt with respect to the content of the second borate cluster anion. However, Tutusaus ‘375’s closo-borate salt is identical to the claimed salt in claim 15.If a first sample of Tutusaus ‘375’s solid electrolyte comprising Li2[CB11H12-][CB11H11F-] was prepared with an arbitrary content of the second borate, [CB11H11F-], and a second sample of the same salt was prepared with a greater content of [CB11H11F-], the second sample would have shown a larger volume of the cell of the of the single phase solid solution.
Claims 5-6, 8-10 are rejected under 35 U.S.C. 103 as being unpatentable over Tutusaus et al. (US 20220017375 AI) and Yushin et al. (US 20200343580 A1) as applied to claim 4 above, and further in view Tang et al. (ACS Energy. Lett., 2016, 1, 4, 659-664) and Bjarne et al. (Chem. Mater. 2017, 29, 3423-3430).
Claim 5: Tutusaus ‘375 teaches the composition of the mixed closo-borate salt. Tutusaus ‘375 does not teach the borate anions have different crystalline phases. However, Tang teaches pure Na and Li closo-carbopolyborate-based salts exhibit high conductivities above ambient temperatures because of entropically driven disordered crystalline phases promoted by high temperatures [page 659 abstract]. Tang further teaches that it is possible to improve ion conductivity of these pure salts at lower or ambient temperatures by suppressing the formation of ordered structures characteristic of pure closo-borate salts. This can be done by mixing two different closo-borate salt anions to promote formation of disordered structures at lower or ambient temperatures. Tang teaches mixing anions of slightly different geometric “flavors” entail an enthalpic penalty upon formation of any possible ordered phase, thus formation of the disordered phase is favored [page 663 para 1]. Tang teaches non-halogenated closo-borate, and Na2B12H12 and NaCB11H12, which exhibit superionic conductivity at elevated temperatures on their own [p 659 abstract, p 660], and combinations of these salts with other non-halogenated salt, Na2B10H10, that have a stabilized disordered structure and retains superionic conductivity at ambient temperature [page 663 para 2 and 3]. Bjarne teaches the high conductivity of closo-boranes such as Na2B12H12 is linked to the highly disordered high temperature polymorphs, where partially occupied cation sites and fast reorientational dynamics promote excellent cation mobility [page 3423 para 2].
Tang does not teach mixed salts comprising non-halogenated closo-borate and a halogenated closo-borate, but Bjarne teaches halogenated closo-borates, such as Na2B12Cl12, which are isostructural to B12H122- salts at room temperature [3424 para 11] but have very different order-disorder phase transition temperature (Fig. 5, table 2), such that at high temperatures between 270-450 ̊C, Na2B12H12 assumes a bcc structure with a disordered phase while the halogenated Na2B12Cl12 retains its fcc ordered phase (Table 1 and 2) (Fig. 5). According to Tang mixing these two salts at any temperature within the range of 270-450 ̊C would result in a solid solution salt with a disordered crystalline phase.
Therefore, it would have been obvious to one of ordinary skill in the art at the time of filling the instant invention to have mixed two different crystalline phase anions with different order-disorder phases to make Tutusaus ’375’s solid electrolyte because this would ensure the electrolyte salt would have a disordered phase with superionic conducting properties.
Claim 6 and 8: Tutusaus ‘375 teaches Li containing solvent-free closo-borate electrolytes (i.e., inorganic solid electrolyte) comprising combinations of anions such as LiCB11H12 and LiCB11H12-xZx, wherein Z is a halogen [0018, 0032], wherein the borate cluster ions include CB11H12- and CB11H11F-. Therefore, it would have been obvious to one pf ordinary skill to have prepared an electrolyte comprising the anions CB11H12- and CB11H11F-.
Claim 9: As discussed above, if a sample of Tutusaus ‘375’s solid electrolyte comprising Li2[CB11H12-][CB11H11F-] was prepared with an arbitrary content of [CB11H11F-], and a second sample of the same salt was prepared with a greater content of the second borate, [CB11H11F-], the second sample would have shown a larger volume of the cell of the of the single phase solid solution.
Claim 10: As discussed above, Yushin teaches the Young’s modulus (i.e., elastic modulus) at room temperature is in the range 0.1 GPa to 100.0 GPa [0067].
Claims 7 is rejected under 35 U.S.C. 103 as being unpatentable over Tutusaus et al. (US 20220017375 AI), Yushin et al. (US 20200343580 A1), Tang et al. (ACS Energy. Lett., 2016, 1, 4, 659-664) and Bjarne et al. (Chem. Mater. 2017, 29, 3423-3430) as applied to claim 5 above, and further in view of Mohtadi et al (US 20220246980 A1).
Claim 7: Tutusaus ‘375 teaches mixed anion closo-borates [0018, 0032]. Tutusaus ‘375 does not teach the concentration of the second borate cluster ion is between 1mol% and 90mol%. However, Mohtadi ‘980 teaches an ultrahigh closo-borate concentration solid-state electrolyte comprising a combined salt of a lithium closo-borate, LiCB11H12, and a conductivity enhancing organic plastic crystal material (SISE), Pyr14CB11H12, wherein a composition that is 80 mole% LiCB11H12 exhibits approximately two-fold higher conductivity over that of neat LiCB11H12 at room temperature, and compositions between 20 mole% and 81 mole% generally display higher conductivity than neat LiCB11H12 at temperatures below 60 ̊C (Fig. 1) [0014, 0022]. Therefore, it would have been obvious to one of ordinary skill in the art at the time of filling the instant invention that a mixed borate anion solid state electrolyte comprising LiCB11H12 would have more enhanced conductivity than the neat LiCB11H12 if the second anion was present with a concentration within the range 19 mole% and 80 mole%. Thus, it would have been obvious to have made Tutusaus solid state electrolyte comprising the anions CB11H12- and CB11H11F- with the concentration of the second borate anion, CB11H11F-, between 19 mole% and 80 mole% because Mohtadi ‘980 teaches such a concentration would enhance the conductivity of the mixed borate solid state electrolyte, at least above that of neat salt ofCB11H12-.
Claims 11 is rejected under 35 U.S.C. 103 as being unpatentable over Tutusaus et al. (US 20220017375 AI), further in view of Yushin et al. (US 20200343580 A1) and Mohtadi et al (US 20210408587 A1).
Claim 11: Tutusaus ’375 teaches the solvent-free alkali metal or alkali earth metal closo-borate can be combined as a solvent-free electrolyte with one or more additional alkali metal or alkali earth metal salts with second salt anions selected from be ClO4-, SO4-2, F-, Cl-, or any other anion the enhances the metal ion mobility (i.e., ion conductivity) in the electrolyte. [0019, 0031]. Tutusaus ‘375 does not teach the mole fraction of the additional anions. However, Mohtadi ‘587 teaches a solid state electrolyte comprising a combination of an alkali metal or alkali earth metal closo-borate and an alkali metal or alkali earth metal conductivity enhancing anion salt such as ClO4-, SO4-2, F- or Cl- [0005], wherein the mole fraction of the conductivity enhancing anion to the total anions in the combined salt can be 0.01 to 0.9 in the combined salt [0006], wherein the closo-borate salt and the conductivity enhancing salt can be combined in solid-state by ball milling, and heating to melt and fuse the salts into a single combined lattice or solid solution (i.e., single phase crystalline solution) [0007, 0017, 0018].
Therefore, it would have been obvious to one of ordinary skill in the art at the time of filling the instant invention to have made Tutusaus ‘375 solid state electrolyte with a conductivity enhancing anion mole fraction between 0.01 and 0.9 because Mohtadi ‘587 teaches solid electrolytes containing a mole fraction of the additive anion in this range are functional.
Claims 12-15 and 17-18 are rejected under 35 U.S.C. 103 as being unpatentable over Tutusaus et al. (US 20220017375 AI), further in view of Yushin et al. (US 20200343580 A1),Tang et al. (ACS Energy. Lett., 2016, 1, 4, 659-664), Bjarne et al. (Chem. Mater. 2017, 29, 3423-3430) and Tutusaus et al (US 20170117585 A1).
Claim 12: Tutusaus ‘375 in combination with Yushin, Tang and Bjarne teach the limitations of claims 1 and 5 as described above, however, they do not teach a coulombic efficiency of metal or silicone anode charge/discharge greater than 99%.
Tutusaus ‘585 teaches a magnesium electrochemical cell comprising a closo-borate containing magnesium boron cluster electrolyte in communication with an anode containing magnesium metal [0032, 0033, 0034] exhibiting coulombic efficiency exceeding 95% net efficiency per cycle over 100 cycles (Fig. 4) [0040]. Tutusaus ‘585 does not identically teach the range of greater than 99%. However, overlapping ranges have been held to support a case of obviousness (see MPEP 2144.05.I).
Therefore, it would have been obvious to one of ordinary skill in the art at the time of filling the instant invention to have made Tutusaus ‘375 solid state electrolyte cell with a coulombic efficiency exceeding 99% because Tutusaus ‘585 teaches such is an operable cell.
Claim 13-14: Tutusaus teaches a lithium closo-borate wherein the closo-borate can be a mixed salt having a mixture of different anion structures with the formula Li2B12H12-xZx, where x ≤ 6; and Z is a halogen [0006, 0011, 0018], such as a mixture comprising non-halogenated closo-borate, Li2B12H12 , and halogenated closo-borate, Li2B12H11F, (i.e., Li4[B12H122-][ B12H11F2-] ).
Claim 15 and 17: Tutusaus teaches Li containing solvent-free closo-borate electrolytes (i.e., inorganic solid electrolyte) comprising combinations of anions such as LiCB11H12 and LiCB11H12-xZx, wherein Z is a halogen [0018, 0032], wherein the borate cluster ions include CB11H12- and CB11H11F-. Therefore, it would have been obvious to one pf ordinary skill to have prepared an electrolyte comprising the anions CB11H12- and CB11H11F-.
Claim 18: As described above, if a first sample of Tutusaus ‘375’s solid electrolyte comprising Li2[CB11H12-][CB11H11F-] was prepared with an arbitrary content of the halogenated borate, [CB11H11F-], and a second sample of the same salt was prepared with a greater content of [CB11H11F-], the second sample would have shown a larger volume of the cell of the of the single phase solid solution.
Claims 16 is rejected under 35 U.S.C. 103 as being unpatentable over Tutusaus et al. (US 20220017375 AI), Yushin et al. (US 20200343580 A1), Tang et al. (ACS Energy. Lett., 2016, 1, 4, 659-664), Bjarne et al. (Chem. Mater. 2017, 29, 3423-3430), and Tutusaus et al (US 20170117585 A1) as applied to claim 15 above, and further in view of Mohtadi et al (US 20220246980 A1).
Claim 16: Tutusaus ‘375 teaches mixed anion closo-borates [0018, 0032]. Tutusaus ‘375 does not teach the concentration of the second borate cluster ion is between 1mol% and 90mol%. However, Mohtadi ‘980 teaches an ultrahigh closo-borate concentration solid-state electrolyte comprising a combined salt of a lithium closo-borate, LiCB11H12, and a conductivity enhancing organic plastic crystal material (SISE), Pyr14CB11H12, wherein a composition that is 80 mole% LiCB11H12 exhibits approximately two-fold higher conductivity over that of neat LiCB11H12 at room temperature, and compositions between 20 mole% and 81 mole% generally display higher conductivity than neat LiCB11H12 at temperatures below 60 ̊C (Fig. 1) [0014, 0022]. Therefore, it would have been obvious to one of ordinary skill in the art at the time of filling the instant invention that a mixed borate anion solid state electrolyte comprising LiCB11H12 would have more enhanced conductivity than the neat LiCB11H12 if the second anion was present with a concentration within the range 19 mole% and 80 mole%. Thus, it would have been obvious to have made Tutusaus ‘375 solid state electrolyte comprising the anions CB11H12- and CB11H11F- with the concentration of the second borate anion, CB11H11F-, between 19 mole% and 80 mole% because Mohtadi ‘980 teaches such a concentration would enhance the conductivity of the mixed borate solid state electrolyte, at least above that of neat salt ofCB11H12-. Mohtadi ‘980 does not identically teach the range of 1 mole% to 90 mole%. However, overlapping ranges have been held to support a case of obviousness (see MPEP 2144.05.I).
Conclusion
The prior art made of record and not relied upon is considered pertinent to applicant's disclosure. Ivanov et al. (US 20060027789 A1) teaches proton conducting electrolytes for electrochemical cells comprising fluoroheteroborates [0015].
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/L.N.R./Examiner, Art Unit 1712
/MICHAEL B CLEVELAND/Supervisory Patent Examiner, Art Unit 1712
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