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 § 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, 4-5, 10, 13-14, and 16-17 are rejected under 35 U.S.C. 102(a)(1) as being anticipated by Zheng (Zheng, Q., Yamada, Y., Shang, R. et al. A cyclic phosphate-based battery electrolyte for high voltage and safe operation. Nat Energy 5, 291–298 (2020)).
Regarding claim 1, Zheng teaches:
A battery that cycles lithium ions (Zheng, abstract), the battery comprising:
a positive electrode comprising an electroactive material comprising a layered lithium transition metal oxide (Zheng teaches a layered lithium transition metal oxide as the cathode material; LiNi1/3Mn1/3Co1/3O2 (NMC) and LiNi0.5Mn1.5O4 (LNMO), pg. 292, column 1, paragraph 2, lines 13-16);
and an electrolyte infiltrating the positive electrode (Zheng teaches a positive electrode (LNMO/NMC) in contact with an electrolyte, featuring a TFEP solvent that forms a passivation layer on the current collector and a cathode electrolyte interphase (CEI) layer to prevent oxidation and dissolution, inherently requiring infiltration into the positive electrode structure; pg. 297, “Conclusions” paragraph, lines 12-21),
the electrolyte comprising: an organic solvent; a lithium salt in the organic solvent; and a fluorinated phosphate ester additive in the organic solvent (Zheng, TFEP represents the fluorinated phosphate ester additive in the organic solvent; pg. 292, column 2, paragraph 2, lines 1-3),
the fluorinated phosphate ester additive comprising at least one of: (i) a chemical compound comprising a phosphate group attached to two or three branched-chain fluorocarbon groups (Zheng, Fig. 1),
or (ii) a chemical compound comprising a cyclic phosphate group attached to a fluorocarbon group (Zheng, TFEP in Fig. 1).
Regarding claim 2, Zheng teaches all features of claim 1, and further teaches that the fluorinated phosphate ester additive comprises a fluorinated phosphate triester having the formula (1):
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where X1, X2, X3, X4, X5, and X6 are each individually a fluorocarbon group, R1, R2, R3, R4, R5, and R6 are each individually a fluorinated or unfluorinated bivalent hydrocarbon group, and Y1, Y2, and Y3 are each individually hydrogen (H) or fluorine (F) (Zheng, FTEP in Fig. 1).
Regarding claim 4, Zheng teaches all features of claim 1, and further teaches that the fluorinated phosphate ester additive comprises a fluorinated cyclic phosphate ester having the formula (2):
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where R1 is an unfluorinated bivalent hydrocarbon group, R2 is a fluorinated or unfluorinated bivalent hydrocarbon group, and X is a fluorocarbon group (Zheng, EP and TFEP in Fig. 1).
Regarding claim 5, Zheng teaches all features of claim 4, and further teaches that the fluorinated phosphate ester additive comprises 2-(2,2,2-trifluoroethoxy)-1,3,2-dioxaphospholane 2-oxide (Zheng, TFEP; pg. 292, column 1, paragraph 2, lines 1-6).
Regarding claim 10, Zheng teaches all features of claim 1, and further teaches that
the electroactive material of the positive electrode comprises a layered lithium nickel-rich transition metal oxide (Zheng teaches a layered lithium nickel-rich transition metal oxide as the cathode material; LiNi1/3Mn1/3Co1/3O2 (NMC) and LiNi0.5Mn1.5O4 (LNMO), pg. 292, column 1, paragraph 2, lines 13-16),
and wherein the organic solvent comprises a mixture of ethylene carbonate (EC) and dimethyl carbonate (DMC) (Zheng, Fig. 2).
Regarding claim 13, Zheng teaches:
A battery that cycles lithium ions (Zheng, abstract), the battery comprising:
a positive electrode comprising an electroactive material comprising a layered lithium transition metal oxide (Zheng teaches a layered lithium transition metal oxide as the cathode material; LiNi1/3Mn1/3Co1/3O2 (NMC) and LiNi0.5Mn1.5O4 (LNMO), pg. 292, column 1, paragraph 2, lines 13-16);
a negative electrode comprising an electroactive material comprising silicon oxide, lithiated silicon oxide, graphite, or a combination thereof (Zheng teaches graphite as the anode material, pg. 297, column 1, “Electrode preparation” paragraph, lines 6-8);
and an electrolyte infiltrating the positive electrode and the negative electrode, the electrolyte comprising (Zheng teaches a positive electrode and negative electrode in contact with an electrolyte featuring a TFEP solvent that (1) forms a stable SEI interface on the anode (graphite) which achieved stable cycling, and (2) forms a CEI layer on the cathode (LNMO/NMC) to prevent oxidation and dissolution, which inherently requires infiltration into both electrode structures; pg. 297, “Conclusions” paragraph):
an organic solvent comprising a cyclic carbonate and a linear carbonate (Zheng, EC and FEC in Fig 1; cyclic and linear carbonates in Table 1);
a lithium salt in the organic solvent (Zheng, LiFSI; pg. 292, column 2, paragraph 2, lines 1-3);
and a fluorinated phosphate ester additive in the organic solvent, the fluorinated phosphate ester additive comprising at least one of: (i) a chemical compound comprising a phosphate group attached to two or three branched-chain fluorocarbon groups (Zheng, Fig. 1),
or (ii) a chemical compound comprising a cyclic phosphate group attached to a fluorocarbon group (Zheng, TFEP in Fig. 1).
Regarding claim 14, Zheng teaches all features of claim 13, and further teaches that the fluorinated phosphate ester additive comprises a fluorinated phosphate triester having the formula (1):
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where X1, X2, X3, X4, X5, and X6 are each individually a fluorocarbon group, R1, R2, R3, R4, R5, and R6 are each individually a fluorinated or unfluorinated bivalent hydrocarbon group, and Y1, Y2, and Y3 are each individually hydrogen (H) or fluorine (F) (Zheng, FTEP in Fig. 1).
Regarding claim 16, Zheng teaches all features of claim 13, and further teaches that the fluorinated phosphate ester additive comprises a fluorinated cyclic phosphate ester having the formula (2):
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where R1 is an unfluorinated bivalent hydrocarbon group, R2 is a fluorinated or unfluorinated bivalent hydrocarbon group, and X is a fluorocarbon group (Zheng, EP and TFEP in Fig. 1).
Regarding claim 17, Zheng teaches all features of claim 16, and further teaches that the fluorinated phosphate ester additive comprises 2-(2,2,2-trifluoroethoxy)-1,3,2-dioxaphospholane 2-oxide (Zheng, TFEP; pg. 292, column 1, paragraph 2, lines 1-6).
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, 6-9, and 11-12 are rejected under 35 U.S.C. 103 as being unpatentable over Zheng as applied to claim 1 above, and further in view of Ji (US2020388882A1).
Regarding claim 3, Zheng teaches all features of claim 2 as described above, but does not disclose that the fluorinated phosphate ester additive comprises tris(1,1,1,3,3,3-hexafluoropropan-2-yl) phosphate, tris(1,1,1,5,5,5-hexafluoropentan-3-yl) phosphate, tris(1,1,1,2,3,3,3-heptafluoropropan-2-yl) phosphate, or a combination thereof.
Ji teaches a lithium-ion battery and an electrolyte comprising a fluorinated additive compound comprising tris(1,1,1,3,3,3-hexafluoropropan-2-yl) phosphate (Ji, specification, [0067], [0184]). Ji further teaches that including fluorinated electrolyte additives into electrolyte solutions enhances the thermal stability of the electrolyte and improves the overall electrochemical performance and safety of the battery due to their beneficial flame resistance and fire-retardant properties (Ji, specification, [0042]).
Therefore, it would have been obvious to someone of ordinary skill in the art before the effective filing date of the claimed invention to modify the electrolyte composition of Zheng to include a fluorinated electrolyte additive compound comprising tris(1,1,1,3,3,3-hexafluoropropan-2-yl) phosphate as taught by Ji, because such additives were known to improve lithium-ion battery performance in terms of flammability and safety. The modification would have involved the use of known electrolyte additives to perform the same function of improving the battery in a predictable manner.
Regarding claim 6, Zheng teaches all features of claim 1, but does not expressly disclose a battery wherein the fluorinated phosphate ester additive constitutes, by weight, greater than or equal to about 0.5% to less than or equal to about 2.5% of the electrolyte.
Ji teaches a lithium-ion battery and electrolyte comprising a fluorinated phosphate ester additive, wherein the fluorinated phosphate ester additive is present in a weight percent range that overlaps with the claimed range of the fluorinated phosphate ester additive constituting, by weight, greater than or equal to about 0.5% to less than or equal to about 2.5% of the electrolyte (Ji, specification, [0060]-[0062]).
Therefore, it would have been obvious to someone of ordinary skill in the art before the effective filing date of the claimed invention to include the fluorinated phosphate ester additive in the electrolyte composition of Zheng in an amount within the overlapping range as taught by Ji because Ji teaches that such weight percent amounts are suitable for lithium-ion battery electrolytes and provide the desired electrochemical performance.
Regarding claim 7, Zheng teaches all features of claim 1, and further teaches a lithium-ion battery and electrolyte wherein the electroactive material of the positive electrode comprises a layered lithium- and manganese-rich transition metal oxide (Zheng, pg. 292, column 1, paragraph 2), and wherein the organic solvent comprises fluoroethylene carbonate (FEC) (Zheng, Fig. 1). However, Zheng does not teach that the organic solvent comprises a mixture of both fluoroethylene carbonate (FEC) and diethyl carbonate (DEC).
Ji teaches a lithium-ion battery and electrolyte comprising an organic solvent wherein the organic solvent comprises a mixture of fluoroethylene carbonate (FEC) and diethyl carbonate (DEC) (Ji, specification, [0056]).
Therefore, it would have been obvious to someone of ordinary skill in the art before the effective filing date of the claimed invention to modify the organic solvent of Zheng to include diethyl carbonate (DEC) as taught by Ji (hereby referred to as “modified Zheng”), because Ji teaches that organic solvent mixtures of fluoroethylene carbonate (FEC) and diethyl carbonate (DEC) are suitable solvent systems for lithium-ion battery electrolytes. The combination of known solvent components in lithium-ion battery electrolytes would have yielded the predictable results of improved battery performance (Ji, specification, [0055]).
Regarding claim 8, modified Zheng teaches all features of claim 7, and further teaches that the electrolyte of the battery includes a lithium salt in the organic solvent that comprises lithium hexafluorophosphate (LiPF6) (Zheng, Fig. 2). However, Zheng does not expressly disclose a battery wherein the electrolyte further comprises lithium difluorophosphate (LiPO2F2).
Ji discloses a battery wherein the electrolyte comprises a lithium salt in the organic solvent comprising lithium hexafluorophosphate (LiPF6), and further discloses the electrolyte further comprising lithium difluorophosphate (LiPO2F2) (Ji, specification, [0061]-[0063]).
Therefore, it would have been obvious to someone of ordinary skill in the art before the effective filing date of the claimed invention to further modify the electrolyte of Zheng (as previously modified in view of Ji above) to further include lithium difluorophosphate (LiPO2F2) as taught by Ji because Ji teaches that such electrolyte compositions are suitable for use in lithium-ion battery electrolytes and provide improved battery performance (Ji, specification, [0055]). The use of known lithium salts in combination with each other within a similar lithium-ion battery electrolyte would have yielded predictable results in terms of battery performance.
Regarding claim 9, modified Zheng teaches all features of claim 8, which further includes lithium difluorophosphate (LiPO2F2) in the electrolyte, but does not expressly teach a lithium-ion battery electrolyte wherein:
the fluorinated phosphate ester additive constitutes, by weight, greater than or equal to about 0.5% to less than or equal to about 1.5% of the electrolyte,
and wherein the LiPO2F2 constitutes, by weight, greater than or equal to about 0.5% to less than or equal to about 1.5% of the electrolyte.
Ji discloses lithium difluorophosphate (LiPO2F2) as an electrolyte additive for lithium ion battery electrolytes and further discloses that electrolyte additives may be present in amounts ranging from about 0.2% to less than 10%, by weight, of the electrolyte, which includes values within the claimed range (Ji, specification, [0060]-[0063]).
Therefore, it would have been obvious to someone of ordinary skill in the art before the effective filing date of the claimed invention to include LiPO2F2 in the electrolyte of Zheng in an amount within the range as taught by Ji because Ji teaches that such electrolyte additives are suitable for use in lithium-ion battery electrolytes and provide improved battery performance (Ji, specification, [0055]), and that their use in such amounts as taught by Ji would have yielded predictable results in terms of battery performance.
Regarding claim 11, Zheng teaches all features of claim 10 as described above, and further teaches a lithium-ion battery and electrolyte comprising a lithium salt, where the lithium salt comprises lithium hexafluorophosphate (LiPF6); Zheng further teaches a battery wherein the electrolyte further comprises fluoroethylene carbonate (FEC). However, Zheng does not disclose a battery wherein:
the lithium salt comprises both lithium hexafluorophosphate (LiPF6) and lithium difluoro(oxalato)borate (LiDFOB), and
the electrolyte further comprises both fluoroethylene carbonate (FEC) and vinylene carbonate (VC).
Ji discloses lithium-ion battery and electrolyte comprising a lithium salt wherein:
the lithium salt comprises both lithium hexafluorophosphate (LiPF6) and lithium difluoro(oxalato)borate (LiDFOB) (Ji, specification, [0216]), and
the electrolyte further comprises both fluoroethylene carbonate (FEC) and vinylene carbonate (VC) (Ji, specification, [0058]-[0060]).
Therefore, it would have been obvious to someone of ordinary skill in the art before the effective filing date of the claimed invention to modify the electrolyte of Zheng to (1) include a lithium salt further comprising lithium difluoro(oxalato)borate (LiDFOB) and (2) include vinylene carbonate (VC) (hereby referred to as “modified Zheng”) as taught by Ji, because Ji teaches that such salts and organic solvent mixtures are suitable for lithium-ion battery electrolyte systems and provide improved battery performance (Ji, specification, [0055]). The combination of known salt and solvent components in lithium-ion battery electrolytes would have yielded predictable results in terms of battery performance.
Regarding claim 12, modified Zheng teaches all features of claim 11, but does not expressly teach that:
the fluorinated phosphate ester additive constitutes, by weight, greater than or equal to about 1.5% to less than or equal to about 2.5% of the electrolyte,
the LiDFOB constitutes, by weight, greater than or equal to about 0.5% to less than or equal to about 1.5% of the electrolyte,
the FEC constitutes, by weight, greater than or equal to about 1.5% to less than or equal to about 2.5% of the electrolyte,
and the VC constitutes, by weight, greater than or equal to about 0.5% to less than or equal to about 1.5% of the electrolyte.
Ji discloses a fluorinated phosphate ester, lithium difluoro(oxalato)borate (LiDFOB), fluoroethylene carbonate (FEC), and vinylene carbonate (VC) as electrolyte additives for lithium-ion battery electrolytes (Ji, specification, [0058]-[0063]). Ji further discloses that electrolyte additives may be present in amounts ranging from about 0.2% to less than 10%, by weight, of the electrolyte, which includes values within the claimed ranges (Ji, specification, [0060]-[0063]).
Therefore, it would have been obvious to someone of ordinary skill in the art before the effective filing date of the claimed invention to include a fluorinated phosphate ester, LiDFOB, FEC, and VC in the electrolyte of Zheng in an amount within the range as taught by Ji because Ji teaches that such electrolyte additives are suitable for use in lithium-ion battery electrolytes and provide improved battery performance (Ji, specification, [0055]), and that their use in such amounts as taught by Ji would have yielded predictable results in terms of battery performance.
Claims 15, and 18-20 are rejected under 35 U.S.C. 103 as being unpatentable over Zheng as applied to claim 13 above, and further in view of Ji (US2020388882A1).
Regarding claim 15, Zheng teaches all features of claim 14 as described above, but does not disclose that the fluorinated phosphate ester additive comprises tris(1,1,1,3,3,3-hexafluoropropan-2-yl) phosphate, tris(1,1,1,5,5,5-hexafluoropentan-3-yl) phosphate, tris(1,1,1,2,3,3,3-heptafluoropropan-2-yl) phosphate, or a combination thereof.
Ji teaches a lithium-ion battery comprising a fluorinated electrolyte additive compound comprising tris(1,1,1,3,3,3-hexafluoropropan-2-yl) phosphate (Ji, specification, [0067], [0184]). Ji further teaches that including fluorinated electrolyte additives into electrolyte solutions enhances the thermal stability of the electrolyte and improves the overall electrochemical performance and safety of the battery due to their beneficial flame resistance and fire-retardant properties (Ji, specification, [0042]).
Therefore, it would have been obvious to someone of ordinary skill in the art before the effective filing date of the claimed invention to modify the electrolyte composition of Zheng to include a fluorinated electrolyte additive compound comprising tris(1,1,1,3,3,3-hexafluoropropan-2-yl) phosphate as taught by Ji, because such additives were known to improve lithium-ion battery performance in terms of flammability and safety. The modification would have involved the use of known electrolyte additives to perform the same function of improving the battery in a predictable manner.
Regarding claim 18, Zheng teaches all features of claim 13, but does not expressly disclose a battery wherein the fluorinated phosphate ester additive constitutes, by weight, greater than or equal to about 0.5% to less than or equal to about 2.5% of the electrolyte.
Ji teaches a lithium-ion battery and electrolyte comprising a fluorinated phosphate ester additive in the organic solvent, wherein the fluorinated phosphate ester additive is present in a weight percent range that overlaps with the claimed range of the fluorinated phosphate ester additive constituting, by weight, greater than or equal to about 0.5% to less than or equal to about 2.5% of the electrolyte. (Ji, specification, [0060]-[0062]).
Therefore, it would have been obvious to someone of ordinary skill in the art before the effective filing date of the claimed invention to include the fluorinated phosphate ester additive in the electrolyte composition of Zheng in an amount within the overlapping range as taught by Ji because Ji teaches that such weight percent amounts are suitable for lithium-ion battery electrolytes and provide the desired electrochemical performance.
Regarding claim 19, Zheng teaches all features of claim 13 as described above, and further teaches that the electroactive material of the positive electrode comprises a layered lithium- and manganese-rich transition metal oxide (Zheng, pg. 292, column 1, paragraph 2). Zheng further discloses an electrolyte that includes an organic solvent comprising fluoroethylene carbonate (FEC) (Zheng, Fig. 1) and wherein the lithium salt comprises lithium hexafluorophosphate (LiPF6) (Zheng, Fig. 2). However, Zheng does not teach an electrolyte wherein:
the organic solvent comprises a mixture of both fluoroethylene carbonate (FEC) and diethyl carbonate (DEC),
the electrolyte further comprises lithium difluorophosphate (LiPO2F2),
and wherein the fluorinated phosphate ester additive constitutes, by weight, greater than or equal to about 0.5% to less than or equal to about 1.5% of the electrolyte,
and the LiPO2F2 constitutes, by weight, greater than or equal to about 0.5% to less than or equal to about 1.5% of the electrolyte.
Ji discloses fluoroethylene carbonate (FEC), diethyl carbonate (DEC), lithium difluorophosphate (LiPO2F2), and a fluorinated phosphate ester as electrolyte additives for lithium-ion battery electrolytes (Ji, specification, [0056], [0061]-[0063]). Ji further discloses that electrolyte additives may be present in amounts ranging from about 0.2% to less than 10%, by weight, of the electrolyte, which includes values within the claimed ranges (Ji, specification, [0060]-[0063]).
Therefore, it would have been obvious to someone of ordinary skill in the art before the effective filing date of the claimed invention to further include DEC in the organic solvent and LiPO2F2 within the electrolyte of Zheng in an amount within the range as taught by Ji because Ji teaches that such electrolyte additives are suitable for use in lithium-ion battery electrolytes and provide improved battery performance (Ji, specification, [0055]), and that their use in such amounts as taught by Ji would have yielded predictable results in terms of battery performance.
Regarding claim 20, Zheng teaches all features of claim 13, and further teaches that:
the electroactive material of the positive electrode comprises a layered lithium nickel-rich transition metal oxide (Zheng, pg. 292, column 1, paragraph 2),
the organic solvent comprises a mixture of ethylene carbonate (EC) and dimethyl carbonate (DMC) (Zheng, Fig. 2),
the lithium salt comprises lithium hexafluorophosphate (LiPF6) (Zheng, Fig. 2),
and the electrolyte further comprises fluoroethylene carbonate (FEC) (Zheng, Fig. 1).
However, Zheng does not teach an electrolyte wherein:
the lithium salt comprises both lithium hexafluorophosphate (LiPF6) and lithium difluoro(oxalato)borate (LiDFOB),
the electrolyte further comprises both fluoroethylene carbonate (FEC) and vinylene carbonate (VC),
and wherein the fluorinated phosphate ester additive constitutes, by weight, greater than or equal to about 1.5% to less than or equal to about 2.5% of the electrolyte,
the LiDFOB constitutes, by weight, greater than or equal to about 0.5% to less than or equal to about 1.5% of the electrolyte,
the FEC constitutes, by weight, greater than or equal to about 1.5% to less than or equal to about 2.5% of the electrolyte,
and the VC constitutes, by weight, greater than or equal to about 0.5% to less than or equal to about 1.5% of the electrolyte.
Ji discloses lithium-ion battery and electrolyte comprising:
a lithium salt comprising both lithium hexafluorophosphate (LiPF6) and lithium difluoro(oxalato)borate (LiDFOB) (Ji, specification, [0216]),
and the electrolyte further comprises both fluoroethylene carbonate (FEC) and vinylene carbonate (VC) (Ji, specification, [0058]-[0060]),
Ji further discloses that electrolyte additives may be present in amounts ranging from about 0.2% to less than 10%, by weight, of the electrolyte, which includes values within the claimed ranges (Ji, specification, [0060]-[0063]).
Therefore, it would have been obvious to someone of ordinary skill in the art before the effective filing date of the claimed invention to further include vinylene carbonate (VC) and LiPO2F2 in the electrolyte of Zheng in an amount within the range as taught by Ji because Ji teaches that such electrolyte additives are suitable for use in lithium-ion battery electrolytes and provide improved battery performance (Ji, specification, [0055]), and that their use in such amounts as taught by Ji would have yielded predictable results in terms of battery performance.
Conclusion
The prior art made of record and not relied upon is considered pertinent to applicant's disclosure:
Masahiro (JP2013157280A): appears to disclose a lithium-ion battery and electrolyte comprising fluorine-containing phosphate additives (Masahiro, claims).
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/A.R.O./Examiner, Art Unit 1789
/MARLA D MCCONNELL/Supervisory Patent Examiner, Art Unit 1789
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