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 .
Response to Amendment
The amendment filed 06/04/2026 has been entered. Support is found in the previous claims. Claims 1-9, 12-16, and 19 remain pending.
Response to Arguments
Applicant’s arguments, see Remarks at pages 12-14, filed 06/04/2026, with respect to the rejection(s) of claim(s) 1, 14, 19 and dependent claims under 35 USC 103 have been fully considered and are partially persuasive, in that the amended Markush group – namely of anions – differentiated from and overcomes the specific rejection of record (which relied on the specific cited portions of secondary reference Shen used in the 03/09/2026 Office action). However, upon further consideration, a new ground(s) of rejection is made in view of the amended claim limitations, and the Zhang primary reference is still applicable, along with other teachings of Shen as well as an additional teaching references (Chang and Park) cited below. As discussed in the 05/27/2026 interview of record, narrowing the claims necessitated further consideration of the cited references as well as further searching.
Claim Objections
Claim 9 is objected to because of the following informalities: “the anion is a first ionic” appears to be a typographical error, which likely intends to read “the anion is a first anion”. Appropriate correction is required; otherwise, a 35 USC 112 issue may be present.
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.
Claim(s) 1-10, 14, 16-17, and 19 is/are rejected under 35 U.S.C. 103 as being unpatentable over
Zhang et al. (US 20160240896 A1, as cited in the previous Office action) in view of Shen et al. (US 20210020986 A1, as cited in the previous Office action), Chang et al. (US 20190214672 A1, as cited in the previous Office action in a further 103), and (alternatively), in further view of Park et al. (US 20200168950 A1, newly cited).
Regarding claim 1, Zhang teaches an electrolyte (electrolyte [0039, 0061-0066]; e.g. 3 M to 6 M lithium bis(fluorosulfonyl)imide (LiFSI) in 1,2-dimethoxyethane (DME) per [0008, 0064]) for an anode-free electrochemical cell (an anode-free battery, [0022]; a highly stable electrolyte and a stable anode current collector allow for the practical application of the anode-free rechargeable battery per [0062]) that cycles lithium ions (cycling the rechargeable alkali metal battery where M may be Li, [0006]; the electrolyte has a Li+ concentration, [0008]; Li plated and stripped during cycling, [0015]; Li+ intercalation, [0041-0042]), the electrolyte comprising:
greater than or equal to about 20 wt.% to less than or equal to about 99.5 wt.% (“consists essentially of” option in [0063] – thus interpreted to read on falling within a range of greater than 50%, which obviates 20-99.5 wt.% per MPEP 2144.05 I) of a concentrated electrolyte (a lithium salt dissolved in a solvent as majority component, [0063]), having a lithium salt concentration (concentration of lithium salt in the electrolyte, [0064]; lithium salt such as lithium bis(fluorosulfonyl)imide (LiFSI), [0008, 0063-0064]) greater than or equal to about 2 M to less than or equal to about 6 M (e.g. 3 M to 6 M LiFSI in DME, [0008, 0064]; EXAMPLE: 4 M LiFSI-DME as the liquid electrolyte in [0083]); and
greater than or equal to about 0.5 wt.% to less than or equal to about 80 wt.% (ionic compounds of [0063] would be minor additives, thus interpreted to fall within a range of less than 50% of the composition which overlaps and obviates the claimed 0.5-50 wt.% per MPEP 2144.05 I) of an ionic [compound] (“consists essentially of” also means that the electrolyte may include other non-electrochemically active components … Typical additives that do not affect the battery performance may include nonmetal halide salts, such as ammonium chloride (NH4Cl) or tetraethylammonium chloride (Et4NCl); [0063]), wherein
the anode-free electrochemical cell (EXAMPLE: Cu|LiFePO4 Anode-free Li rechargeable cells, [0083]) comprises a positive electrode (positive electrode / cathode, [0057]; EXAMPLE: LiFePO4 coated on Al foil in [0083]) and a negative electrode current collector (an anode current collector and no anode, [0006]; Anode-free refers to an initial cell configuration in which an alkali metal or carbon-based anode is not present prior to an initial charge cycle of the battery, [0028]; EXAMPLE: copper (Cu) foil in [0083]) configured to receive a negative electroactive material and form a negative electrode after one or more formation cycles of the anode-free electrochemical cell (During a first charge cycle an alkali metal anode is formed in situ on the anode current collector as alkali metal cations are reduced and deposit on the anode current collector, [0028]; in anode-free configuration the electrolyte and/or cathode serves as the source of the anode material that is formed during the charging process, [0051]).
However, as cited above, although Zhang [0063] teaches the concentrated electrolyte of lithium salt dissolved in solvent as majority component and ionic compounds (such as ammonium chloride or tetraethylammonium chloride, cited above – where NH4+ or [N(CH2CH3)4]+ would be the cation and Cl- would be anion) as minor additives, these compounds are known in the art to be solids, such that Zhang fails to teach such additive being an ionic liquid. Further, Zhang fails to teach that the ionic liquid comprises a cation selected from the group consisting of:
1,2-dimethyl-3-butylimidazolium ([DMBim]), 1,3-diallylimidazolium ([Daim]+), 1-allyl-3- vinylimidazolium ([Avim]+), 1,3-dicyanomethyl-imidazolium ([BCNim]+), methyl-methylcarboxymethyl-pyrrolidinium ([MMMPyr]+), tetramethylammonium ([N1111]+), tetraethylammonium ([N2222]+), tributylmethylammonium ([N4441]+), diallyldimethylammonium ([DADMA]+),N-N-diethyl-N-methyl-N-(2-methoxyethyl)ammonium ([DEME]+),N,N-diethyl-N-(2-methacryloylethyl)-N-methylammonium ([DEMM]+),trimethylisobutyl-phosphonium ([P111i4]+), triisobutylmethylphosphonium ([P1i444]+), tributylmethylphosphonium ([P1444]+), diethylmethylisobutyl-phosphonium ([P1224]+), trihexdecylphosphonium ([P66610]+),trihexyltetradecylphosphonium ([P66614]+), and combinations thereof,
and an anion selected from the group consisting of:
hexafluoroarsenate, tetrafluoroborate, cyclo-difluoromethane-1,1-bis(sulfonyl)imide (DMSI), bis(fluoromalonato)boarate (BFMB), and combinations thereof.
Shen is analogous in the art of electrolyte for anode-free rechargeable battery (title) and teaches the electrolyte includes an ionic liquid and an electrolyte salt dispersed in the ionic liquid (abstract). Shen teaches in [0018] the incorporation of ionic liquid having low melting point, high ionic conductivity, solubility with many compounds, negligible volatility, flame retardancy, moderate viscosity, high polarity, etc. into the electrolytes can be used to improve the safety of the electrolytes because the introduction of the ionic liquid can prevent fire and explosion caused by the excessive rise of temperature in the battery, so as to improve the safety of the battery. Shen teaches in [0019] that the cations of the ionic liquid may be, for example, organic nitrogen cation (including exemplary ammonium cations, e.g. quaternary ammonium cation, as listed in Shen [0019]). Such “quaternary ammonium cation” is similar to the “tetraethylammonium” cation – i.e., [Et4N]+ – in the exemplary tetraethylammonium chloride additive of Zhang [0063] as cited above, which is also notably among the instantly claimed group of cations. Notably, Shen [0019] teaches toward “Non-limiting examples of suitable cations of the ionic liquid” which can include exemplary “N-N-diethyl-N-methyl-N-(2-methoxyethyl)ammonium”. This is an also example of a cation among the instantly claimed group.
Shen further teaches non-limiting examples of suitable anions of the ionic liquid include Cl−, bis(fluorosulfonyl)imide, and etc. (Shen [0020]). Such Cl− anion is similar to that of Zhang [0063] additive as cited above, and bis(fluorosulfonyl)imide correlates to the lithium “bis(fluorosulfonyl)imide” salt component cited above to Zhang, e.g. at Zhang [0008].
However, both Zhang and Shen fail to specifically teach toward the instantly-claimed group of anions (hexafluoroarsenate, tetrafluoroborate, cyclo-difluoromethane-1,1-bis(sulfonyl)imide (DMSI), bis(fluoromalonato)boarate (BFMB), and combinations thereof), although bis(fluorosulfonyl)imide as taught toward by both references as cited above is a related compound to the instantly claimed cyclo-difluoromethane-1,1-bis(sulfonyl)imide.
Chang is analogous in the art of anodeless lithium metal battery (title, abstract) and teaches liquid electrolytes which include an ionic liquid and/or a polymer ionic liquid ([0054-0059]). Chang teaches in [0055] non-limiting examples of the anions include tetrafluoroborate (BF4) (Chang [0055]), which is among the instantly claimed anion group. Chang at [0056] teaches that any suitable material that may be used as the ionic liquid in the art may be used; thus, non-limiting ion examples from Shen and Chang would be obvious to combine as both are taught a suitable within the prior art. Shen does teach BF4- in [0020] as a suitable anion for use in the ionic liquid; in view of Chang citation above, such reads on instantly claimed tetrafluoroborate.
Shen also teaches battery performance is generally affected by the cation, and that the cations have more significant influence on the viscosity of the electrolytes per [0019], and teaches that the anion of the ionic liquid plays a substantial role in the electrochemical stability and consequently wideness of the potential window per [0020]. Thus, Shen teaches that since ionic liquids are basically composed of ions (cations and anions as cited above) that may undergo almost unlimited structural variations because of the easy preparation of a large variety of their components ([0019]) such that various kinds of ionic liquids can be used in the ionic liquid electrolyte ([0021]).
It would have been obvious, at the time of filing, for a person having ordinary skill in the art to modify the electrolyte of the anode-free battery of Zhang to also include an ionic liquid with the motivation of achieving improved the safety of the electrolytes due to fire prevention properties of ionic liquid, as taught toward by Shen. Further, in view of the teachings of Shen and Chang that the cations and anions useable in the ionic liquid for electrolytes are not particularly limited, as well as in view of MPEP 2144.07 (since the selection of a known material based on its suitability for its intended use supports a prima facie obviousness determination), a person having ordinary skill in the art would have found it obvious to specifically select tetraethylammonium (from Zhang) or N-N-diethyl-N-methyl-N-(2-methoxyethyl)ammonium (from Shen) as a suitable cation of the ionic liquid, and select tetrafluoroborate (from Chang and Shen) as a suitable anion of the ionic liquid, and expect a functional ionic liquid for use in the electrolyte of the anode-free cell of modified Zhang.
Further regarding the limitations “greater than or equal to about 20 wt.% to less than or equal to about 99.5 wt.% of a concentrated electrolyte having a lithium salt” and “greater than or equal to about 0.5 wt.% to less than or equal to about 80 wt.% of an ionic liquid”, although Zhang [0063] is interpreted per the above explanation to obviate these limitations, Park is also cited herein to further obviate the numerical ranges. Park is analogous in the art of electrolytes including ionic liquid and teaches that the ionic liquid may be included in an amount of 50 parts by weight or less, particularly 0.1 part by weight to 50 parts by weight, and more particularly 1 part by weight to 30 parts by weight based on 100 parts by weight of the non-aqueous electrolyte solution injected ([0129]) because: when the amount of the ionic liquid is greater than 50 parts by weight based on a total weight of the non-aqueous electrolyte solution, since the movement of the lithium ions may be difficult due to high viscosity, a uniform lithium ion movement effect may not be provided, and thus, lithium dendrites may be formed on the surface of the lithium negative electrode ([0130]).
Therefore, in further view of Park, a person having ordinary skill in the art would have found it obvious to further modify Zhang to ensure the amount of ionic liquid was particularly 0.1 part by weight to 50 parts by weight based on 100 parts by weight of the non-aqueous electrolyte solution, which overlaps the claimed range “greater than or equal to about 0.5 wt.% to less than or equal to about 80 wt.% of an ionic liquid” (an obviates per MPEP 2144.05 I) as taught toward by Park in order to ensure desirable viscosity and uniform lithium ion movement to prevent lithium dendrite formation on the lithium negative electrode within Zhang.
Thus, the instant claim 1 is rendered obvious.
Regarding claim 2 and claim 3, modified Zhang teaches the limitations of claim 1 above and teaches the concentrated electrolyte comprises a lithium salt (Zhang [0063-0064]), wherein the lithium salt comprises lithium bis(fluorosulfonyl)imide (LiFSI) (4M LiFSI, Zhang [0008, 0064, 0083]).
Regarding claim 4 and claim 5, modified Zhang teaches the limitations of claim 1 above and teaches the concentrated electrolyte comprises a solvent (lithium salt dissolved in a solvent, Zhang [0063]), wherein the solvent comprises dimethoxyethane (DME) (in DME solvent, Zhang [0008, 0064, 0083]; see also Shen [0063] Example 6 having DME within the ionic liquid electrolyte, as applied to modified Zhang above).
Regarding claim 6, modified Zhang teaches the limitations of claim 1 above but fails to explicitly teach that the cation is a first cation and the ionic liquid further comprises a second cation selected from the group consisting of: 1-alkyl-3-methylimidazolium ([Cnmim]+), 1-allyl-3-methylimidazolium ([Amim]+), 1-vinyl-3-ethylimidazolium ([Veim]+), 1-cyanomethyl-3-methylimidazolium ([MCNim]+), 1-propyl-1-methylpiperidinium ([PP13]+), 1-butyl-1-methylpiperidinium ([PP14]+), 1-methyl-1-ethylpyrrolidinium ([Pyr12]+), 1-butyl-1-methylpyrrolidinium ([Pyr14]+), methyl-methylcarboxymethyl-pyrrolidinium ([MMMPyr]+), and combinations thereof.
However, as cited above, Shen does teach in [0019] that the cation examples are non-limiting and suitable examples include N-methyl-N-butyl-pyrrolidinium and 1-butyl-1-methylpyrrolidinium. which reads on the instantly claimed “1-butyl-1-methylpyrrolidinium ([Pyr14]+)”. Chang, as also cited above, also teaches various suitable cations and teaches the ionic liquid may include a cation comprising at least one of the listed non-limiting examples, and that a combination comprising at least one of the listed cations may be used (Chang [0055]).
Since Shen [0019] also teaches that the properties of the ionic liquid and battery performance are affected by the cation, a person having ordinary skill in the art would have found it obvious in further view of Chang to select a second cation (i.e., 1-butyl-1-methylpyrrolidinium taught by Shen) also for use in the ionic liquid and expect suitable resultant properties.
Thereby, claim 6 is obvious.
Regarding claim 7, modified Zhang teaches the limitations of claim 1 above but fails to explicitly teach that the cation is a first cation and the ionic liquid further comprises a second cation comprising 1-butyl-1methylpyrrolidinium ([Py14]+).
However, as cited above, Shen does teach in [0019] that the cation examples are non-limiting and suitable examples include N-methyl-N-butyl-pyrrolidinium and 1-butyl-1-methylpyrrolidinium. which reads on the instantly claimed “1-butyl-1-methylpyrrolidinium ([Pyr14]+)”. Chang, as also cited above, also teaches various suitable cations and teaches the ionic liquid may include a cation comprising at least one of the listed non-limiting examples, and that a combination comprising at least one of the listed cations may be used (Chang [0055]).
Since Shen [0019] also teaches that the properties of the ionic liquid and battery performance are affected by the cation, a person having ordinary skill in the art would have found it obvious in further view of Chang to select a second cation (i.e., 1-butyl-1-methylpyrrolidinium taught by Shen) also for use in the ionic liquid and expect suitable resultant properties.
Thereby, claim 7 is obvious.
Regarding claim 8, modified Zhang teaches the limitations of claim 1 above but fails to explicitly teach that the anion is a first anion and the ionic liquid further comprises a second anion selected from the group consisting of: bis(fluorosulfonyl)imide (FSI), bis(perfluoroethanesulfonyl)imide (BETI), bis(oxalate)borate (BOB), difluoro(oxalato)borate (DFOB), and combinations thereof.
However, as cited above, Shen does teach in [0020] that the anion examples are non-limiting and suitable examples include Bisperfluoroethylsulfonyl imide (BETI), bis(fluorosulfonyl)imide, and difluoro(oxalato)borate (DFOB). Chang, as also cited above, also teaches BETI for use alongside tetrafluoroborate, since a combination comprising at least one of the non-limiting examples of listed anions is suitable for use in the ionic liquid per Chang [0055]. Chang further teaches in [0053] the battery including both a first liquid electrolyte and a second liquid electrolyte, wherein compositions of the first liquid electrolyte and the second liquid electrolyte are different from each other and are independently selected (therefore amounting to first and second cations in the resultant electrolyte) in order to compensate for any electrochemical disadvantages of the anodeless lithium metal battery, such as high-voltage oxidation and electrolyte loss due to dendrite growth.
The selection of a known material based on its suitability for its intended use supports a prima facie obviousness determination (MPEP 2144.07), such that a person having ordinary skill in the art would have found it obvious to also select a second anion from the list of Shen in view of the teachings of Chang when modifying Zhang to include the ionic liquid.
Thus, claim 8 is obvious.
Regarding claim 9, modified Zhang teaches the limitations of claim 1 above but fails to explicitly teach that the anion is a first [anion] and the ionic liquid further comprises a second anion comprising bis(trifluoromethanesulfonyl)imide (TFSI) or difluoro(oxalato)borate (DFOB).
However, as cited above, Shen does teach in [0020] that the anion examples are non-limiting and suitable examples include bis(trifluoromethane)sulphonamide (TFSI-) and difluoro(oxalato)borate (DFOB). Chang, as also cited above, also teaches TFSI for use alongside tetrafluoroborate, since a combination comprising at least one of the non-limiting examples of listed anions is suitable for use in the ionic liquid per Chang [0055]. Chang further teaches in [0053] the battery including both a first liquid electrolyte and a second liquid electrolyte, wherein compositions of the first liquid electrolyte and the second liquid electrolyte are different from each other and are independently selected (therefore amounting to first and second anions in the resultant electrolyte) in order to compensate for any electrochemical disadvantages of the anodeless lithium metal battery, such as high-voltage oxidation and electrolyte loss due to dendrite growth.
The selection of a known material based on its suitability for its intended use supports a prima facie obviousness determination (MPEP 2144.07), such that a person having ordinary skill in the art would have found it obvious to also select a second anion from the list of Shen in view of the teachings of Chang when modifying Zhang to include the ionic liquid.
Thus, claim 9 is obvious.
Regarding claim 12, modified Zhang teaches electrolyte of claim 9 above, and wherein a molar ratio of the first anion to the second anion is greater than or equal to about 0.001:3 to less than or equal to about 3:0.001 (Example 1 in Chang [0106, 0108]: 3.5M first liquid electrolyte comprising FSI- anion, 0.4M second electrolyte comprising TFSI- anion – such that molar ratio of first:second anion = 3.5:0.4 = 1:0.114, which falls within the claimed range). When modifying the electrolyte in view of Chang to have two anions as cited above in the rejection of claim 9, it would have further been obvious to select a molar concentration of each as taught by Chang in order to achieve the desirable properties of Chang.
Regarding claim 13, modified Zhang teaches electrolyte of claim 1 above, but fails to explicitly teach that wherein the anion is a first anion and the ionic liquid further comprises a second anion comprising bis(trifluoromethanesulfonyl)imide (TFSI) and a third anion comprising difluoro(oxalato)borate (DFOB).
However, as cited above, Shen does teach in [0020] that the anion examples are non-limiting and suitable examples include bis(trifluoromethane)sulphonamide (TFSI-) and difluoro(oxalato)borate (DFOB). Chang, as also cited above, also teaches TFSI for use alongside tetrafluoroborate, and teaches that s combination comprising at least one of the non-limiting examples of listed anions is suitable for use in the ionic liquid per Chang [0055]. Chang further teaches in [0053] the battery multiple compositions of liquid electrolytes which are different from each other and are independently selected (reading on multiple different anions included in the electrolyte) in order to compensate for any electrochemical disadvantages of the anodeless lithium metal battery, such as high-voltage oxidation and electrolyte loss due to dendrite growth.
The selection of a known material based on its suitability for its intended use supports a prima facie obviousness determination (MPEP 2144.07), such that a person having ordinary skill in the art would have found it obvious when modifying Zhang to additionally select a second anion and a third anion from the list of Shen, for use in the ionic liquid alongside the first anion, in view of the teachings of Chang to arrive at an electrolyte that compensates for electrochemical disadvantages of the anodeless lithium metal battery.
Thus, claim 13 is obvious.
Regarding claim 14, Zhang teaches An anode-free electrochemical cell (an anode-free battery, [0022]; a highly stable electrolyte and a stable anode current collector allow for the practical application of the anode-free rechargeable battery per [0062]) that cycles lithium ions (cycling the rechargeable alkali metal battery where M may be Li, [0006]; the electrolyte has a Li+ concentration, [0008]; Li plated and stripped during cycling, [0015]; Li+ intercalation, [0041-0042]), the anode-free electrochemical cell (EXAMPLE: Cu|LiFePO4 Anode-free Li rechargeable cells, [0083]) comprising:
a positive electrode assembly comprising a positive current collector and a positive electroactive material layer (positive electrode / cathode on a conductive substrate- e.g., a cathode current collector, [0057]; EXAMPLE: LiFePO4 coated on Al foil in [0083]);
a negative current collector comprising a surface (an anode current collector and no anode, [0006]; Anode-free refers to an initial cell configuration in which an alkali metal or carbon-based anode is not present prior to an initial charge cycle of the battery, [0028]; the surface of the bare anode current collector, [0051]; EXAMPLE: copper (Cu) foil in [0083]) configured to receive a negative electroactive material after one or more formation cycles of the anode-free electrochemical cell, wherein the negative current collector together with the negative electroactive material forms a negative electrode after the one or more formation cycles (During a first charge cycle an alkali metal anode is formed in situ on the anode current collector as alkali metal cations are reduced and deposit on the anode current collector, [0028, 0051]); and
a separating layer (porous sheet or film, [0044]) disposed between the positive electroactive material layer and the surface of the negative current collector (separator placed between the anode and cathode, [0044]), the separating layer comprising an electrolyte (separator infused with electrolyte, [0050]; electrolyte of [0039, 0061-0066] - e.g. 3 M to 6 M lithium bis(fluorosulfonyl)imide (LiFSI) in 1,2-dimethoxyethane (DME) per [0008, 0064]) that comprises:
greater than or equal to about 20 wt.% to less than or equal to about 99.5 wt.% (“consists essentially of” option in [0063] – thus interpreted to read on falling within a range of greater than 50%, which obviates 20-99.5 wt.% per MPEP 2144.05 I) of a concentrated electrolyte (a lithium salt dissolved in a solvent as majority component, [0063]), having a lithium salt concentration (concentration of lithium salt in the electrolyte, [0064]; lithium salt such as lithium bis(fluorosulfonyl)imide (LiFSI), [0008, 0063-0064]) greater than or equal to about 2 M to less than or equal to about 6 M (e.g. 3 M to 6 M LiFSI in DME, [0008, 0064]; EXAMPLE: 4 M LiFSI-DME as the liquid electrolyte in [0083]); and
greater than or equal to about 0.5 wt.% to less than or equal to about 80 wt.% (ionic compounds of [0063] would be minor additives, thus interpreted to fall within a range of less than 50% of the composition which overlaps and obviates the claimed 0.5-50 wt.% per MPEP 2144.05 I) of an ionic [compound] (“consists essentially of” also means that the electrolyte may include other non-electrochemically active components … Typical additives that do not affect the battery performance may include nonmetal halide salts, such as ammonium chloride (NH4Cl) or tetraethylammonium chloride (Et4NCl); [0063]), wherein
the anode-free electrochemical cell (EXAMPLE: Cu|LiFePO4 Anode-free Li rechargeable cells, [0083]) comprises a positive electrode (positive electrode / cathode, [0057]; EXAMPLE: LiFePO4 coated on Al foil in [0083]) and a negative electrode current collector (an anode current collector and no anode, [0006]; Anode-free refers to an initial cell configuration in which an alkali metal or carbon-based anode is not present prior to an initial charge cycle of the battery, [0028]; EXAMPLE: copper (Cu) foil in [0083]) configured to receive a negative electroactive material and form a negative electrode after one or more formation cycles of the anode-free electrochemical cell (During a first charge cycle an alkali metal anode is formed in situ on the anode current collector as alkali metal cations are reduced and deposit on the anode current collector, [0028]; in anode-free configuration the electrolyte and/or cathode serves as the source of the anode material that is formed during the charging process, [0051]).
However, as cited above, although Zhang [0063] teaches the concentrated electrolyte of lithium salt dissolved in solvent as majority component and ionic compounds (such as ammonium chloride or tetraethylammonium chloride, cited above – where NH4+ or [N(CH2CH3)4]+ would be the cation and Cl- would be anion) as minor additives, these compounds are known in the art to be solids, such that Zhang fails to teach such additive being an ionic liquid. Further, Zhang fails to teach that the ionic liquid comprises a cation selected from the group consisting of:
1,2-dimethyl-3-butylimidazolium ([DMBim]), 1,3-diallylimidazolium ([Daim]+), 1-allyl-3- vinylimidazolium ([Avim]+), 1,3-dicyanomethyl-imidazolium ([BCNim]+), methyl-methylcarboxymethyl-pyrrolidinium ([MMMPyr]+), tetramethylammonium ([N1111]+), tetraethylammonium ([N2222]+), tributylmethylammonium ([N4441]+), diallyldimethylammonium ([DADMA]+),N-N-diethyl-N-methyl-N-(2-methoxyethyl)ammonium ([DEME]+),N,N-diethyl-N-(2-methacryloylethyl)-N-methylammonium ([DEMM]+),trimethylisobutyl-phosphonium ([P111i4]+), triisobutylmethylphosphonium ([P1i444]+), tributylmethylphosphonium ([P1444]+), diethylmethylisobutyl-phosphonium ([P1224]+), trihexdecylphosphonium ([P66610]+),trihexyltetradecylphosphonium ([P66614]+), and combinations thereof,
and an anion selected from the group consisting of:
hexafluoroarsenate, tetrafluoroborate, cyclo-difluoromethane-1,1-bis(sulfonyl)imide (DMSI), bis(fluoromalonato)boarate (BFMB), and combinations thereof.
Shen is analogous in the art of electrolyte for anode-free rechargeable battery (title) and teaches the electrolyte includes an ionic liquid and an electrolyte salt dispersed in the ionic liquid (abstract). Shen teaches in [0018] the incorporation of ionic liquid having low melting point, high ionic conductivity, solubility with many compounds, negligible volatility, flame retardancy, moderate viscosity, high polarity, etc. into the electrolytes can be used to improve the safety of the electrolytes because the introduction of the ionic liquid can prevent fire and explosion caused by the excessive rise of temperature in the battery, so as to improve the safety of the battery. Shen teaches in [0019] that the cations of the ionic liquid may be, for example, organic nitrogen cation (including exemplary ammonium cations, e.g. quaternary ammonium cation, as listed in Shen [0019]). Such “quaternary ammonium cation” is similar to the “tetraethylammonium” cation – i.e., [Et4N]+ – in the exemplary tetraethylammonium chloride additive of Zhang [0063] as cited above, which is also notably among the instantly claimed group of cations. Notably, Shen [0019] teaches toward “Non-limiting examples of suitable cations of the ionic liquid” which can include exemplary “N-N-diethyl-N-methyl-N-(2-methoxyethyl)ammonium”. This is an also example of a cation among the instantly claimed group.
Shen further teaches non-limiting examples of suitable anions of the ionic liquid include Cl−, bis(fluorosulfonyl)imide, and etc. (Shen [0020]). Such Cl− anion is similar to that of Zhang [0063] additive as cited above, and bis(fluorosulfonyl)imide correlates to the lithium “bis(fluorosulfonyl)imide” salt component cited above to Zhang, e.g. at Zhang [0008].
However, both Zhang and Shen fail to specifically teach toward the instantly-claimed group of anions (hexafluoroarsenate, tetrafluoroborate, cyclo-difluoromethane-1,1-bis(sulfonyl)imide (DMSI), bis(fluoromalonato)boarate (BFMB), and combinations thereof), although bis(fluorosulfonyl)imide as taught toward by both references as cited above is a related compound to the instantly claimed cyclo-difluoromethane-1,1-bis(sulfonyl)imide.
Chang is analogous in the art of anodeless lithium metal battery (title, abstract) and teaches liquid electrolytes which include an ionic liquid and/or a polymer ionic liquid ([0054-0059]). Chang teaches in [0055] non-limiting examples of the anions include tetrafluoroborate (BF4) (Chang [0055]), which is among the instantly claimed anion group. Chang at [0056] teaches that any suitable material that may be used as the ionic liquid in the art may be used; thus, non-limiting ion examples from Shen and Chang would be obvious to combine as both are taught a suitable within the prior art. Shen does teach BF4- in [0020] as a suitable anion for use in the ionic liquid; in view of Chang citation above, such reads on instantly claimed tetrafluoroborate.
Shen also teaches battery performance is generally affected by the cation, and that the cations have more significant influence on the viscosity of the electrolytes per [0019], and teaches that the anion of the ionic liquid plays a substantial role in the electrochemical stability and consequently wideness of the potential window per [0020]. Thus, Shen teaches that since ionic liquids are basically composed of ions (cations and anions as cited above) that may undergo almost unlimited structural variations because of the easy preparation of a large variety of their components ([0019]) such that various kinds of ionic liquids can be used in the ionic liquid electrolyte ([0021]).
It would have been obvious, at the time of filing, for a person having ordinary skill in the art to modify the electrolyte of the anode-free battery of Zhang to also include an ionic liquid with the motivation of achieving improved the safety of the electrolytes due to fire prevention properties of ionic liquid, as taught toward by Shen. Further, in view of the teachings of Shen and Chang that the cations and anions useable in the ionic liquid for electrolytes are not particularly limited, as well as in view of MPEP 2144.07 (since the selection of a known material based on its suitability for its intended use supports a prima facie obviousness determination), a person having ordinary skill in the art would have found it obvious to specifically select tetraethylammonium (from Zhang) or N-N-diethyl-N-methyl-N-(2-methoxyethyl)ammonium (from Shen) as a suitable cation of the ionic liquid, and select tetrafluoroborate (from Chang and Shen) as a suitable anion of the ionic liquid, and expect a functional ionic liquid for use in the electrolyte of the anode-free cell of modified Zhang.
Further regarding the limitations “greater than or equal to about 20 wt.% to less than or equal to about 99.5 wt.% of a concentrated electrolyte having a lithium salt” and “greater than or equal to about 0.5 wt.% to less than or equal to about 80 wt.% of an ionic liquid”, although Zhang [0063] is interpreted per the above explanation to obviate these limitations, Park is also cited herein to further obviate the numerical ranges. Park is analogous in the art of electrolytes including ionic liquid and teaches that the ionic liquid may be included in an amount of 50 parts by weight or less, particularly 0.1 part by weight to 50 parts by weight, and more particularly 1 part by weight to 30 parts by weight based on 100 parts by weight of the non-aqueous electrolyte solution injected ([0129]) because: when the amount of the ionic liquid is greater than 50 parts by weight based on a total weight of the non-aqueous electrolyte solution, since the movement of the lithium ions may be difficult due to high viscosity, a uniform lithium ion movement effect may not be provided, and thus, lithium dendrites may be formed on the surface of the lithium negative electrode ([0130]).
Therefore, in further view of Park, a person having ordinary skill in the art would have found it obvious to further modify Zhang to ensure the amount of ionic liquid was particularly 0.1 part by weight to 50 parts by weight based on 100 parts by weight of the non-aqueous electrolyte solution, which overlaps the claimed range “greater than or equal to about 0.5 wt.% to less than or equal to about 80 wt.% of an ionic liquid” (an obviates per MPEP 2144.05 I) as taught toward by Park in order to ensure desirable viscosity and uniform lithium ion movement to prevent lithium dendrite formation on the lithium negative electrode within Zhang.
Thus, the instant claim 14 is rendered obvious.
Regarding claim 15, modified Zhang teaches the anode-free electrochemical cell of claim 14 above and teaches at least one of the positive current collector and the negative current collector is in contact with the electrolyte (bare anode current collector, the electrolyte and/or cathode serves as the source of the anode material that is formed during the charging process, the anode current collector is when in physical contact with the electrolyte in an operating voltage window of the battery; Zhang [0051-0052]) but fails to teach the positive electroactive material layer also comprises the electrolyte.
Zhang does teach in [0057] that the cathode includes a conductive additive which is stable with the electrolyte within the operation voltage window of the battery. Shen also teaches in [0055] a cathode includes one or more of the electroactive material in electrical contact with the electrolyte.
Chang as cited above teaches in [0040] a cathode that a cathode active material layer, which is disposed on the cathode current collector may, include a cathode active material and a second liquid electrolyte. Chang [0077] teaches that ions may freely migrate in the first liquid electrolyte or the second liquid electrolyte, and ion conductivity may be improved.
Since Zhang and Shen teach the cathode materials being conductive of lithium ions and being stable against electrolyte, a person having ordinary skill in the art would have further found it obvious in view of the teaching of Chang to modify the battery of modified Zhang to include a second liquid electrolyte within the cathode active material layer on the cathode current collector as taught by Chang (thus reading on “the positive electroactive material layer also comprises the electrolyte”) in order to allow for free migration of ions therethrough, thus improving lithium ion conductivity in the cathode.
Thereby, claim 15 is rendered obvious.
Regarding claim 16, modified Zhang teaches the limitations of claim 14 above and teaches the concentrated electrolyte comprises a lithium salt (a lithium salt dissolved in a solvent, Zhang [0063]) selected from … lithium bis(fluorosulfonyl)imide (LiFSI) (4M LiFSI, Zhang [0008, 0064, 0083]), and
a solvent (a lithium salt dissolved in a solvent, Zhang [0063]) selected from … dimethoxyethane (DME) (in DME solvent, Zhang [0008, 0064, 0083]).
Regarding claim 19, Zhang teaches an electrolyte (electrolyte [0039, 0061-0066]; e.g. 3 M to 6 M lithium bis(fluorosulfonyl)imide (LiFSI) in 1,2-dimethoxyethane (DME) per [0008, 0064]) for an anode-free electrochemical cell (an anode-free battery, [0022]; a highly stable electrolyte and a stable anode current collector allow for the practical application of the anode-free rechargeable battery per [0062]) that cycles lithium ions (cycling the rechargeable alkali metal battery where M may be Li, [0006]; the electrolyte has a Li+ concentration, [0008]; Li plated and stripped during cycling, [0015]; Li+ intercalation, [0041-0042]), the electrolyte comprising:
greater than or equal to about 20 wt.% to less than or equal to about 99.5 wt.% (“consists essentially of” option in [0063] – thus interpreted to read on falling within a range of greater than 50%, which obviates 20-99.5 wt.% per MPEP 2144.05 I) of a concentrated electrolyte (a lithium salt dissolved in a solvent as majority component, [0063]), having a lithium salt concentration (concentration of lithium salt in the electrolyte, [0064]; lithium salt such as lithium bis(fluorosulfonyl)imide (LiFSI), [0008, 0063-0064]) greater than or equal to about 2 M to less than or equal to about 6 M (e.g. 3 M to 6 M LiFSI in DME, [0008, 0064]; EXAMPLE: 4 M LiFSI-DME as the liquid electrolyte in [0083]), wherein the concentrated electrolyte comprises:
a lithium salt (a lithium salt dissolved in a solvent, Zhang [0063]) selected from … lithium bis(fluorosulfonyl)imide (LiFSI) (e.g. 4M LiFSI, Zhang [0008, 0064, 0083]; see also Shen [0063] Example 6 having LiFSI as lithium salt within the ionic liquid electrolyte, as applied to modified Zhang below in the present rejection), and
a solvent (a lithium salt dissolved in a solvent. Zhang [0063]) selected from … dimethoxyethane (DME) (e.g. in DME solvent, Zhang [0008, 0064, 0083]; see also Shen [0063] Example 6 having DME within the ionic liquid electrolyte, as applied to modified Zhang below in the present rejection); and
greater than or equal to about 0.5 wt.% to less than or equal to about 80 wt.% (ionic compounds of [0063] would be minor additives, thus interpreted to fall within a range of less than 50% of the composition which overlaps and obviates the claimed 0.5-50 wt.% per MPEP 2144.05 I) of an ionic [compound] (“consists essentially of” also means that the electrolyte may include other non-electrochemically active components … Typical additives that do not affect the battery performance may include nonmetal halide salts, such as ammonium chloride (NH4Cl) or tetraethylammonium chloride (Et4NCl); [0063]).
However, as cited above, although Zhang [0063] teaches the concentrated electrolyte of lithium salt dissolved in solvent as majority component and ionic compounds (such as ammonium chloride or tetraethylammonium chloride, cited above – where NH4+ or [N(CH2CH3)4]+ would be the cation and Cl- would be anion) as minor additives, these compounds are known in the art to be solids, such that Zhang fails to teach such additive being an ionic liquid. Further, Zhang fails to teach that the ionic liquid comprises a cation selected from the group consisting of:
1,2-dimethyl-3-butylimidazolium ([DMBim]), 1,3-diallylimidazolium ([Daim]+), 1-allyl-3- vinylimidazolium ([Avim]+), 1,3-dicyanomethyl-imidazolium ([BCNim]+), methyl-methylcarboxymethyl-pyrrolidinium ([MMMPyr]+), tetramethylammonium ([N1111]+), tetraethylammonium ([N2222]+), tributylmethylammonium ([N4441]+), diallyldimethylammonium ([DADMA]+),N-N-diethyl-N-methyl-N-(2-methoxyethyl)ammonium ([DEME]+),N,N-diethyl-N-(2-methacryloylethyl)-N-methylammonium ([DEMM]+),trimethylisobutyl-phosphonium ([P111i4]+), triisobutylmethylphosphonium ([P1i444]+), tributylmethylphosphonium ([P1444]+), diethylmethylisobutyl-phosphonium ([P1224]+), trihexdecylphosphonium ([P66610]+),trihexyltetradecylphosphonium ([P66614]+), and combinations thereof,
and an anion selected from the group consisting of:
hexafluoroarsenate, tetrafluoroborate, cyclo-difluoromethane-1,1-bis(sulfonyl)imide (DMSI), bis(fluoromalonato)boarate (BFMB), and combinations thereof.
Shen is analogous in the art of electrolyte for anode-free rechargeable battery (title) and teaches the electrolyte includes an ionic liquid and an electrolyte salt dispersed in the ionic liquid (abstract). Shen teaches in [0018] the incorporation of ionic liquid having low melting point, high ionic conductivity, solubility with many compounds, negligible volatility, flame retardancy, moderate viscosity, high polarity, etc. into the electrolytes can be used to improve the safety of the electrolytes because the introduction of the ionic liquid can prevent fire and explosion caused by the excessive rise of temperature in the battery, so as to improve the safety of the battery. Shen teaches in [0019] that the cations of the ionic liquid may be, for example, organic nitrogen cation (including exemplary ammonium cations, e.g. quaternary ammonium cation, as listed in Shen [0019]). Such “quaternary ammonium cation” is similar to the “tetraethylammonium” cation – i.e., [Et4N]+ – in the exemplary tetraethylammonium chloride additive of Zhang [0063] as cited above, which is also notably among the instantly claimed group of cations. Notably, Shen [0019] teaches toward “Non-limiting examples of suitable cations of the ionic liquid” which can include exemplary “N-N-diethyl-N-methyl-N-(2-methoxyethyl)ammonium”. This is an also example of a cation among the instantly claimed group.
Shen further teaches non-limiting examples of suitable anions of the ionic liquid include Cl−, bis(fluorosulfonyl)imide, and etc. (Shen [0020]). Such Cl− anion is similar to that of Zhang [0063] additive as cited above, and bis(fluorosulfonyl)imide correlates to the lithium “bis(fluorosulfonyl)imide” salt component cited above to Zhang, e.g. at Zhang [0008].
However, both Zhang and Shen fail to specifically teach toward the instantly-claimed group of anions (hexafluoroarsenate, tetrafluoroborate, cyclo-difluoromethane-1,1-bis(sulfonyl)imide (DMSI), bis(fluoromalonato)boarate (BFMB), and combinations thereof), although bis(fluorosulfonyl)imide as taught toward by both references as cited above is a related compound to the instantly claimed cyclo-difluoromethane-1,1-bis(sulfonyl)imide.
Chang is analogous in the art of anodeless lithium metal battery (title, abstract) and teaches liquid electrolytes which include an ionic liquid and/or a polymer ionic liquid ([0054-0059]). Chang teaches in [0055] non-limiting examples of the anions include tetrafluoroborate (BF4) (Chang [0055]), which is among the instantly claimed anion group. Chang at [0056] teaches that any suitable material that may be used as the ionic liquid in the art may be used; thus, non-limiting ion examples from Shen and Chang would be obvious to combine as both are taught a suitable within the prior art. Shen does teach BF4- in [0020] as a suitable anion for use in the ionic liquid; in view of Chang citation above, such reads on instantly claimed tetrafluoroborate.
Shen also teaches battery performance is generally affected by the cation, and that the cations have more significant influence on the viscosity of the electrolytes per [0019], and teaches that the anion of the ionic liquid plays a substantial role in the electrochemical stability and consequently wideness of the potential window per [0020]. Thus, Shen teaches that since ionic liquids are basically composed of ions (cations and anions as cited above) that may undergo almost unlimited structural variations because of the easy preparation of a large variety of their components ([0019]) such that various kinds of ionic liquids can be used in the ionic liquid electrolyte ([0021]).
It would have been obvious, at the time of filing, for a person having ordinary skill in the art to modify the electrolyte of the anode-free battery of Zhang to also include an ionic liquid with the motivation of achieving improved the safety of the electrolytes due to fire prevention properties of ionic liquid, as taught toward by Shen. Further, in view of the teachings of Shen and Chang that the cations and anions useable in the ionic liquid for electrolytes are not particularly limited, as well as in view of MPEP 2144.07 (since the selection of a known material based on its suitability for its intended use supports a prima facie obviousness determination), a person having ordinary skill in the art would have found it obvious to specifically select tetraethylammonium (from Zhang) or N-N-diethyl-N-methyl-N-(2-methoxyethyl)ammonium (from Shen) as a suitable cation of the ionic liquid, and select tetrafluoroborate (from Chang and Shen) as a suitable anion of the ionic liquid, and expect a functional ionic liquid for use in the electrolyte of the anode-free cell of modified Zhang.
Further regarding the limitations “greater than or equal to about 20 wt.% to less than or equal to about 99.5 wt.% of a concentrated electrolyte having a lithium salt” and “greater than or equal to about 0.5 wt.% to less than or equal to about 80 wt.% of an ionic liquid”, although Zhang [0063] is interpreted per the above explanation to obviate these limitations, Park is also cited herein to further obviate the numerical ranges. Park is analogous in the art of electrolytes including ionic liquid and teaches that the ionic liquid may be included in an amount of 50 parts by weight or less, particularly 0.1 part by weight to 50 parts by weight, and more particularly 1 part by weight to 30 parts by weight based on 100 parts by weight of the non-aqueous electrolyte solution injected ([0129]) because: when the amount of the ionic liquid is greater than 50 parts by weight based on a total weight of the non-aqueous electrolyte solution, since the movement of the lithium ions may be difficult due to high viscosity, a uniform lithium ion movement effect may not be provided, and thus, lithium dendrites may be formed on the surface of the lithium negative electrode ([0130]).
Therefore, in further view of Park, a person having ordinary skill in the art would have found it obvious to further modify Zhang to ensure the amount of ionic liquid was particularly 0.1 part by weight to 50 parts by weight based on 100 parts by weight of the non-aqueous electrolyte solution, which overlaps the claimed range “greater than or equal to about 0.5 wt.% to less than or equal to about 80 wt.% of an ionic liquid” (an obviates per MPEP 2144.05 I) as taught toward by Park in order to ensure desirable viscosity and uniform lithium ion movement to prevent lithium dendrite formation on the lithium negative electrode within Zhang.
Thus, the instant claim 19 is rendered obvious.
Conclusion
Applicant's amendment necessitated the new ground(s) of rejection presented in this Office action. Accordingly, THIS ACTION IS MADE FINAL. See MPEP § 706.07(a). Applicant is reminded of the extension of time policy as set forth in 37 CFR 1.136(a).
A shortened statutory period for reply to this final action is set to expire THREE MONTHS from the mailing date of this action. In the event a first reply is filed within TWO MONTHS of the mailing date of this final action and the advisory action is not mailed until after the end of the THREE-MONTH shortened statutory period, then the shortened statutory period will expire on the date the advisory action is mailed, and any nonprovisional extension fee (37 CFR 1.17(a)) pursuant to 37 CFR 1.136(a) will be calculated from the mailing date of the advisory action. In no event, however, will the statutory period for reply expire later than SIX MONTHS from the mailing date of this final action.
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/JESSIE WALLS-MURRAY/ Primary Examiner, Art Unit 1728
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