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 .
Specification
The specification is objected to because it lacks subject matter recited in the claims. Specifically, claims 8, 12, 14, and 15 each recite a “small molecule alkali metal salt dopant.” The disclosure fails to describe “a small molecule alkali metal salt” or a “dopant.” The objection can be overcome by amending the specification to include the claimed subject matter. See MPEP 608.01(l).
Appropriate correction is required.
Claim Objections
Claims 12, 13, and 15 are objected to because of the following informalities:
The claims are missing a period at the end of each claim. To overcome the objection, amend the claims to include proper punctuation.
Appropriate correction is required.
Claim 20 is objected to because the upper endpoint of the temperature range is missing the unit °C.
Appropriate correction is required.
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.
The following is a quotation of 35 U.S.C. 112 (pre-AIA ), second paragraph:
The specification shall conclude with one or more claims particularly pointing out and distinctly claiming the subject matter which the applicant regards as his invention.
Claims 1-20 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 1 recites:
A composite electrolyte comprising:
a) an alkali metal salt of an aromatic polyimide polymer; and
b) an ionic liquid;
wherein the composite is a solid at 25°C and at a temperature of about 200°c. Emphasis added.
Claim 1 is indefinite because the claim recites “an alkali metal salt of an aromatic polyimide polymer.” However, dependent claim 11 further limits the aromatic polyimide polymer to poly(2,2’-disulfonyl-4,4’-benzidineterephthalamide) (PBDT) or a derivative thereof. The specification states that PBDT is a rigid-rod highly sulfonated aromatic polyamide (Spec. [34]). Therefore, it is unclear whether the aromatic polymer required by claim 1 is a polyimide polymer or a polyamide polymer. For the purpose of compact prosecution, claim 1 is interpreted as requiring an aromatic polyamide polymer.
Claims 2-20 are indefinite because they depend from claim 1.
Claim 10 recites:
The composite electrolyte according to claim 1, wherein the alkali metal is selected from the group consisting of sodium, lithium, and potassium, preferably lithium. Emphasis added.
Claim 10 is indefinite because “preferably” is exemplary claim language that leads to confusion over the intended scope of the claim. See MPEP 2173.05(d).
Claim 11 recites:
The composite electrolyte according to claim 1, wherein the aromatic polyimide polymer is poly(2,2'-disulfonyl-4,4'-benzidine terephthalamide) or a derivative thereof. Emphasis added.
Claim 11 is indefinite because the claim recites an “aromatic polyimide polymer” but further identifies the polymer as poly(2,2'-disulfonyl-4,4'-benzidine terephthalamide which indicates an amide-containing polymer. Therefore, it is unclear whether the claimed polymer is a polyimide or polyamide. For the purpose of compact prosecution, claim 11 is interpreted as requiring a polyamide polymer.
Claim 12 recites:
The composite electrolyte according to claim 1, wherein the small molecule alkali metal salt dopant is LiTFSI. Emphasis added.
Claim 14 recites:
The composite electrolyte according to claim 1, wherein the electrolyte is made by a process comprising casting an aqueous solution of the alkali metal salt of the aromatic polyimide polymer; the ionic liquid, and optionally the small molecule alkali metal salt dopant to form the composite electrolyte. Emphasis added.
Claim 15 recites:
The composite electrolyte of according to claim 1, wherein the aromatic polyimide polymer is poly(2,2’-disulfonyl-4,4’-benzidineterephthalamide) or a derivative thereof: wherein the small molecule alkali metal salt dopant is LiTFSI; and wherein the ionic liquid comprises Pyr14TFSI. Emphasis added.
Claims 12, 14, and 15 each recite “the small molecule alkali metal salt dopant.” This limitation renders each claim indefinite because “the small molecule alkali metal salt dopant” lacks antecedent basis.
Claim 16 recites:
A battery comprising an alkali metal anode, a composite electrolyte according to claim 1, and a suitable cathode. Emphasis added.
Claim 16 is indefinite because “suitable” in “suitable cathode” is subjective. See MPEP 2173.05(b), subsection IV.
Claim 17 recites:
The battery according to claim 16, wherein the alkali metal is lithium and the alkali metal anode is a lithium anode. Emphasis added.
Claim 17 is indefinite because it is unclear if “the alkali metal” refers to the alkali metal of the “alkali metal salt of an aromatic polyimide” (claim 1) or to the alkali metal of the “alkali metal anode” (claim 16).
Claim Rejections - 35 USC § 102
The following is a quotation of the appropriate paragraphs of 35 U.S.C. 102 that form the basis for the rejections under this section made in this Office action:
A person shall be entitled to a patent unless –
(a)(1) the claimed invention was patented, described in a printed publication, or in public use, on sale, or otherwise available to the public before the effective filing date of the claimed invention.
Claims 1, 2, 6, 7, 10 and 11 are rejected under 35 U.S.C. 102(a)(1) as being anticipated by Wang et al., (Highly Conductive and Thermally Stable Ion Gels with Tunable Anisotropy and Modulus, Advanced Materials, January 2016) (herein after referred to as Wang) and evidenced by Wang et al., US 2020/0373578 A1 (herein after referred to as Wang-578).
Regarding claims 1, 10 and 11, Wang teaches an ion gel electrolyte (p. 1), which reads on the claimed “composite electrolyte.” The ion gel electrolyte comprises:
A rigid-rod polyanion of poly(2,2’-disulfonyl-4,4’-benzidine terephthalamide) (PBDT) with Na+ counterions (ps. 1, 7). This reads on “an alkali metal salt of an aromatic polyamide polymer (claim 1)…wherein the alkali metal is…sodium (claim 10)…wherein the aromatic polyamide polymer is poly(2,2’-disulfonyl-4,4’-benzidine terephthalamide) (claim 11)”; and
An ionic liquid (p.1), which reads on the claimed “ionic liquid.”
The ion gel is “solid,” as claimed, because Wang-578 teaches that gel polymer electrolytes are semi-solid (Wang-578, [0096]). The ion gel is solid at 25°C and at a temperature of about 200°C, as claimed, because the ion gel exhibits thermal stability up to 300°C (p. 1) and has a decomposition temperature of about 350°C (p. 2).
Regarding claim 2, Wang teaches dynamic mechanical thermal analysis (DMTA) in tension mode for the ion gels (p. 6; Fig. 4f). Wang further teaches that the 21% PBDT ion gel has an elastic modulus of 3 GPa, while the 5% PBDT ion gel has an elastic modulus of 30 MPa (0.03 GPa) (p.6; Fig. 4f). The disclosed elastic modulus reads on the claimed “wherein the composite has a tensile modulus of about 0.03 GPa to about 3 GPa at a temperature of about 23°C.”
Regarding claims 6 and 7, Wang teaches preparing ion gel samples with increasing PBDT mass percentages relative to the total gel mass of 5 wt.%, 11 wt.%, 15 wt.%, and 21 wt.% (p.2), which reads on the claimed “wherein the alkali metal salt of the aromatic polyamide polymer is present in an amount from about 5 weight percent to about 25 weight percent based on a total weight of the composite electrolyte.” Because Wang defines the PBDT mass percentage relative to the total gel mass (PBDT + ionic liquid) (p.1, p.2), the corresponding ionic liquid contents are 95 wt.%, 89 wt.%, 85 wt.%, and 79 wt.%, which reads on the claimed “wherein the ionic liquid is present in an amount from about 50 weight percent to about 95 weight percent based on a total weight of the composite electrolyte” (Claim 7).
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 3, 8, 12, and 13-20 are rejected under 35 U.S.C. 103 as being unpatentable over Wang et al., (Highly Conductive and Thermally Stable Ion Gels with Tunable Anisotropy and Modulus, Advanced Materials, January 2016) (herein after referred to as Wang) in view of Lee et al., US 2016/0336618 A1 as evidenced by Wang et al., US 2020/0373578 A1 (herein after referred to as Wang-578).
Regarding claim 3, Wang differs from claim 3 because it is silent to the ion gel having a tensile strength of about 1 MPa to about 100 MPa at a temperature of about 23°C, as claimed. But the ion gel exhibits excellent mechanical properties, including high thermal stability, tunable elastic modulus, and that the modulus may be tuned to provide the desired device stiffness and mechanical response (p. 5-6; Fig.4).
With this in mind, Lee, which is directed to electrolyte compositions for lithium batteries including electrolyte composites having liquid electrolytes, polymer ionic liquids, solid electrolytes, and gel electrolytes ([0104]-[0107]). Lee also teaches that the electrolyte composite may have a tensile strength of about 2.0 MPa or greater at a temperature of 25°C ([0143]), which overlaps with the claimed tensile strength range. The mechanical properties of the electrolyte composite, including ductility and elasticity, are beneficial because they are satisfactory for battery performance ([0142]).
It would have been prima facie obvious to one of ordinary skill, in the art as of the effective filing date, to modify the ion gel tensile strength of Wang to the electrolyte composite tensile strength of Lee to improve battery performance.
Regarding claims 8 and 12, Wang differs from claims 8 and 12 because it is silent as to the ion gel electrolyte comprising a small molecule alkali salt dopant. But Wang teaches that the ion gel electrolyte comprises an ionic liquid. With this in mind, Lee teaches an electrolyte composition comprising an ionic liquid and an alkali metal salt where the alkali metal salt can be LiN(SO2CF3)2 (i.e., LiTFSI). The alkali metal salt is beneficial because when the composite includes an ionic liquid and a lithium salt, the electrolyte composite exhibits high lithium mobility, high ionic conductivity, and improved mechanical properties ([0139]). It would have been prima facie obvious to one of ordinary skill, in the art as of the effective filing date, to modify the composite electrolyte of Wang to include the LiTFSI taught by Lee to provide high lithium mobility, high ionic conductivity, and improved mechanical properties ([0139]).
With this modification, the alkali metal salt read on the claimed “wherein the small molecule alkali metal salt dopant is LiTFSI” (Claim 12).
Wang in view of Lee also teaches that the small alkali metal salt is present in an amount of 10-70 parts by weight based on 100 parts by weight of a first block copolymer ([0135]). Lee further teaches an ionic liquid amount of about 5 to about 40 parts by weight on 100 parts of the first block copolymer ([133]) These amounts correspond to about 6.7 wt.% to about 40 wt.% of alkali metal salt based on the total composite electrolyte, which overlaps with the claimed range of about 1 wt. % to about 20 wt.% (Claim 8), establishing a prima facie case of obviousness.
Regarding claim 13, Wang as modified differs from claim 13 because the ionic liquid comprises 1-ethyl-3-methyl imidazolium (C2mim)+ and trifluoromethanesulfonate (TfO)- but is silent to the ionic liquid comprising Pyr14TFSI.
But Lee teaches an electrolyte composition for a battery comprising an ionic liquid where the ionic liquid is N-butyl-N-methylpyrrolidiniumbis(3 trifluoromethylsulfonyl)imide (i.e., Pyr14TFSI) ([0132]). The ionic liquid comprising Pyr14TFSI is beneficial because when present ionic conductivity and mechanical properties are improved ([0133]).
It would have been obvious to one of ordinary skill, in the art as of the effective filing date, to substitute Wang’s ionic liquid with the Pyr14TFSI taught by Lee in order to provide improved mechanical properties and improved ionic conductivity ([0133]).
With this modification, the ionic liquid read on the claimed “wherein the ionic liquid comprises Pyr14TFSI.”
Regarding claim 14, Wang differs from claim 14 because it is silent to the electrolyte being made by a process comprising casting.
But Lee teaches that a solid electrolyte composite in the form of a sheet, film, or membrane may be formed using casting ([0182]). It is beneficial to provide an electrolyte composition in the form of a sheet through casting to have improved intensity, elasticity, ductility, ionic conductivity, lithium-ion mobility, and improved stability against the liquid electrolyte ([0183]).
It would have been obvious to one or ordinary skill in the art at the time of the invention to prepare Wang’s composite electrolyte using the casting process taught by Lee because casting is a known technique in the art ([0182]) and to have improved intensity, elasticity, ductility, ionic conductivity, lithium-ion mobility, and improved stability against the liquid electrolyte ([0183]).
With this modification, the composite electrolyte making process reads on the claimed “wherein the electrolyte is made by a process comprising casting an aqueous solution of the alkali metal salt of the aromatic polyamide polymer; the ionic liquid, and optionally the small molecule alkali metal salt dopant to form the composite electrolyte.”
Regarding claim 15, Wang teaches an ion gel electrolyte (p. 1), which reads on the claimed “composite electrolyte.” The ion gel electrolyte comprises a rigid-rod polyanion of poly(2,2’-disulfonyl-4,4’-benzidine terephthalamide) (PBDT) (p. 1). This reads on “wherein the aromatic polyamide polymer is poly(2,2'-disulfonyl-4,4'-benzidine terephthalamide) or a derivative thereof.”
Wang also teaches that the ion gel electrolyte comprises an ionic liquid. With this in mind, Lee teaches an electrolyte composition comprising an ionic liquid and an alkali metal salt where the alkali metal salt can be LiN(SO2CF3)2 (i.e., LiTFSI). The alkali metal salt is beneficial because when the composite includes an ionic liquid and a lithium salt, the electrolyte composite exhibits high lithium mobility, high ionic conductivity, and improved mechanical properties ([0139]). It would have been prima facie obvious to one of ordinary skill, in the art as of the effective filing date, to modify the composite electrolyte of Wang to include the LiTFSI taught by Lee to provide high lithium mobility, high ionic conductivity, and improved mechanical properties ([0139]).
With this modification, the alkali metal salt read on the claimed “wherein the small molecule alkali metal salt dopant is LiTFSI.”
Lee further teaches an electrolyte composition for a battery comprising an ionic liquid where the ionic liquid is N-butyl-N-methylpyrrolidiniumbis(3 trifluoromethylsulfonyl)imide (i.e., Pyr14TFSI) ([0132]). The ionic liquid comprising Pyr14TFSI is beneficial because when present ionic conductivity and mechanical properties are improved ([0133]).
It would have been obvious to one of ordinary skill, in the art as of the effective filing date, to substitute Wang’s ionic liquid with the Pyr14TFSI taught by Lee in order to provide improved mechanical properties and improved ionic conductivity ([0133]).
With this modification, the ionic liquid read on the claimed “wherein the ionic liquid comprises Pyr14TFSI.”
Regarding claims 16, 17, and 18, Wang teaches that the composite electrolyte is suitable for use in battery applications and in lithium-ion batteries (p. 1). Wang differs from claim 16 and 18 because it is silent to a battery comprising an alkali metal anode, the composite electrolyte, and a suitable cathode, wherein the cathode is LiFePO4.
But Lee teaches a lithium secondary battery ([0195]). The lithium secondary battery reads on the claimed “battery.”
The battery comprises a positive electrode ([0196]), and a negative electrode ([0197]). The negative electrode may be a lithium metal ([0199]) and reads on the claimed “alkali metal anode” and “wherein the alkali metal is lithium and the alkali metal anode is lithium anode” (claim 17).
The battery comprises an electrolyte composition disposed between the positive and negative electrode ([0198]) that reads on the claimed “composite electrolyte” Lee further teaches that the positive electrode active material may include lithium iron phosphate (LiFePO4) ([0227]-[0228]), that reads on the claimed “suitable cathode” and “wherein the suitable cathode is LiFePO4” (claim 18).
It is beneficial to have a lithium secondary battery because they have good voltage characteristics such as high capacity and high energy density ([0201]).
It would have been prima facie obvious to one of ordinary skill, in the art as of the effective filing date, to include the electrolyte composition of Wang into the lithium battery taught by Lee in order to have good voltage characteristics such as high capacity and energy density ([0201]).
Regarding claims 19 and 20, Wang differs from claims 19 and 20 because it is silent to the battery having a discharge capacity of about 120 to about 170 mAh/g at a 1 C rate when measured at 100°C to about 150°C and further silent to the battery having a discharge capacity retention of at least 90% or at least 95% or at least 99% when measured over 50, 100, or 150 cycles at a temperature of about 100°C to about 150.
Lee teaches measuring discharge capacity during repeated charge/discharge cycling ([289]-[300]), calculating discharge retention after repeated cycling ([299]-[301]), and recognizing improved discharge capacity retention as indicative of improved battery performance ([301]-[302]).
It would have been prima facie obvious to one of ordinary skill, in the art as of the effective filing date to optimize the battery components and operating conditions of Wang to obtain the claimed discharge capacity and discharge capacity retention as they are result-effective variables for improving battery performance, cycle life, and stability ([289]-[302]).
Claim 4 is rejected under 35 U.S.C. 103 as being unpatentable over Wang et al., (Highly Conductive and Thermally Stable Ion Gels with Tunable Anisotropy and Modulus, Advanced Materials, January 2016) (herein after referred to as Wang) in view of Fox et al., (Nanofibrillar Ionic Polymer Composite Enable High Modulus Ion-Conducting Membranes, September 2019) (herein after referred to as Fox) as evidenced by Wang et al., US 2020/0373578 A1 (herein after referred to as Wang-578).
Regarding claim 4, Wang differs from claim 4 because it is silent to the ion gel having a strain at break of about 0.5% to about 20% at a temperature of about 23°C.
However, Fox, which is directed to polymer electrolyte membranes for lithium batteries teaches that a 20 wt.% PBDT-ionic liquid composite exhibits a strain at break of approximately 1.1.%, which falls within the claimed range (p. 37; Fig.11). This strain at break is beneficial because it preserves the load-bearing network structure and provides resistance to plasticization (p.37).
It would have been prima facie obvious to one of ordinary skill, in the art as of the effective filing date, to modify Wang’s composite electrolyte with the strain at break characteristic taught by Fox to preserve the load-bearing network structure and provide resistance to plasticization of the electrolyte composite (p.37).
Claim 5 is rejected under 35 U.S.C. 103 as being unpatentable over Wang et al., (Highly Conductive and Thermally Stable Ion Gels with Tunable Anisotropy and Modulus, Advanced Materials, January 2016) (herein after referred to as Wang) in view of Schauser et al., (Lithium Dendrite Growth in Glassy and Rubbery Nanostructured Block Copolymer Electrolytes, Journal of Electrochemical Society, December 2014) (herein after referred to as Schauser) as evidenced by Wang et al., US 2020/0373578 A1 (herein after referred to as Wang-578).
Regarding claim 5, Wang differs from claim 5 because it is silent to the composite electrolyte having a shear storage modulus at 200°C that is at least 60% of a reference shear storage modulus measured for the otherwise same composite electrolyte except measured at a temperature of 25°C. But the composite electrolyte exhibits a high tunable modulus (0.03-3 GPa) while maintaining high ionic conductivity, and high thermal stability, recognizing that modulus is an important mechanical property of the electrolyte.
But Schauser, which is directed to polymer electrolytes for lithium batteries, teaches the storage modulus (G’) varies with temperature while maintaining mechanical integrity over a range of temperatures (p. A403; Fig. 6). Schauser also teaches that solid electrolytes with a high shear modulus suppress dendrite growth and improve mechanical properties (p. A398).
It would have been obvious to one of ordinary skill, in the art as of the effective filing date, to optimize the temperature dependent storage module of Wang’s composite electrolyte to have a shear storage modulus at 200°C that is at least 60% of a reference shear storage modulus measured for the otherwise same composite electrolyte except measured at a temperature of 25°C, because storage modulus is a result-effective variable that directly affects the mechanical performance of the electrolyte. One of ordinary skill in the art would have a reasonable expectation of success of obtaining the claimed shear storage modulus.
Claim 9 is rejected under 35 U.S.C. 103 as being unpatentable over Wang et al., (Highly Conductive and Thermally Stable Ion Gels with Tunable Anisotropy and Modulus, Advanced Materials, January 2016) (herein after referred to as Wang) as evidenced by Wang et al., US 2020/0373578 A1 (herein after referred to as Wang-578).
Regarding claim 9, Wang teaches that the ion gel exhibits high ionic conductivity up to 8 mS cm-1 (p.1). Wang also teaches ionic conductivities at 22°C for the disclosed ion gels (p.4; Fig. 3d). Wang further teaches that the observed ionic conductivities lie in the range of 1-8 mS cm-1 (p.5). The ionic conductivities of Wang overlap with the claimed “wherein the composite electrolyte has an ionic conductivity of about 1 x10-6 S/cm to about 1.5x10-2 S/cm when measured at 25°C” establishing a prima facie case of obviousness.
Conclusion
The prior art made of record and not relied upon is considered pertinent to applicant's disclosure. Yang et al., US 2013/0063092 A1; Wu et al., US 2018/0019471 A1; Archer et al., US 2022/0085455 A1; and Burdynska et al., US 2020/0115505 A1.
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/S.M.A./Examiner, Art Unit 1772
/T. BENNETT MCKENZIE/Primary Examiner, Art Unit 1776
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