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 Interpretation
The following is a quotation of 35 U.S.C. 112(f):
(f) Element in Claim for a Combination. – An element in a claim for a combination may be expressed as a means or step for performing a specified function without the recital of structure, material, or acts in support thereof, and such claim shall be construed to cover the corresponding structure, material, or acts described in the specification and equivalents thereof.
The following is a quotation of pre-AIA 35 U.S.C. 112, sixth paragraph:
An element in a claim for a combination may be expressed as a means or step for performing a specified function without the recital of structure, material, or acts in support thereof, and such claim shall be construed to cover the corresponding structure, material, or acts described in the specification and equivalents thereof.
The claims in this application are given their broadest reasonable interpretation using the plain meaning of the claim language in light of the specification as it would be understood by one of ordinary skill in the art. The broadest reasonable interpretation of a claim element (also commonly referred to as a claim limitation) is limited by the description in the specification when 35 U.S.C. 112(f) or pre-AIA 35 U.S.C. 112, sixth paragraph, is invoked.
As explained in MPEP § 2181, subsection I, claim limitations that meet the following three-prong test will be interpreted under 35 U.S.C. 112(f) or pre-AIA 35 U.S.C. 112, sixth paragraph:
(A) the claim limitation uses the term “means” or “step” or a term used as a substitute for “means” that is a generic placeholder (also called a nonce term or a non-structural term having no specific structural meaning) for performing the claimed function;
(B) the term “means” or “step” or the generic placeholder is modified by functional language, typically, but not always linked by the transition word “for” (e.g., “means for”) or another linking word or phrase, such as “configured to” or “so that”; and
(C) the term “means” or “step” or the generic placeholder is not modified by sufficient structure, material, or acts for performing the claimed function.
Use of the word “means” (or “step”) in a claim with functional language creates a rebuttable presumption that the claim limitation is to be treated in accordance with 35 U.S.C. 112(f) or pre-AIA 35 U.S.C. 112, sixth paragraph. The presumption that the claim limitation is interpreted under 35 U.S.C. 112(f) or pre-AIA 35 U.S.C. 112, sixth paragraph, is rebutted when the claim limitation recites sufficient structure, material, or acts to entirely perform the recited function.
Absence of the word “means” (or “step”) in a claim creates a rebuttable presumption that the claim limitation is not to be treated in accordance with 35 U.S.C. 112(f) or pre-AIA 35 U.S.C. 112, sixth paragraph. The presumption that the claim limitation is not interpreted under 35 U.S.C. 112(f) or pre-AIA 35 U.S.C. 112, sixth paragraph, is rebutted when the claim limitation recites function without reciting sufficient structure, material or acts to entirely perform the recited function.
Claim limitations in this application that use the word “means” (or “step”) are being interpreted under 35 U.S.C. 112(f) or pre-AIA 35 U.S.C. 112, sixth paragraph, except as otherwise indicated in an Office action. Conversely, claim limitations in this application that do not use the word “means” (or “step”) are not being interpreted under 35 U.S.C. 112(f) or pre-AIA 35 U.S.C. 112, sixth paragraph, except as otherwise indicated in an Office action.
This application includes one or more claim limitations that do not use the word “means,” but are nonetheless being interpreted under 35 U.S.C. 112(f) or pre-AIA 35 U.S.C. 112, sixth paragraph, because the claim limitation(s) uses a generic placeholder that is coupled with functional language without reciting sufficient structure to perform the recited function and the generic placeholder is not preceded by a structural modifier. Such claim limitation(s) is/are:
“separation unit that treats…with an ultrasonic wave” in claim 14. The specification discloses in paragraph 0036 that the corresponding structure can include “The separation unit 60 includes an ultrasonic device 20 and a pipe 62 through which water that serves as a treatment liquid 32 is fed to a treatment container 22 included in the ultrasonic device 20. The pipe 62 is provided with a valve 62a, which is arranged to select whether the treatment liquid 32 is fed to the treatment container 22 and adjust the rate at which the treatment liquid 32 is fed” and in paragraph 0037 that “The ultrasonic device 20 includes a treatment container 22 that accommodates the treatment target electrode 50 and the treatment liquid 32, a vibrator 28 arranged to come into contact with the treatment container 22, and an oscillator 30 that feeds an electrical signal to the vibrator 28 to cause the oscillation of the vibrator 28.”
Because this/these claim limitation(s) is/are being interpreted under 35 U.S.C. 112(f) or pre-AIA 35 U.S.C. 112, sixth paragraph, it/they is/are being interpreted to cover the corresponding structure described in the specification as performing the claimed function, and equivalents thereof.
If applicant does not intend to have this/these limitation(s) interpreted under 35 U.S.C. 112(f) or pre-AIA 35 U.S.C. 112, sixth paragraph, applicant may: (1) amend the claim limitation(s) to avoid it/them being interpreted under 35 U.S.C. 112(f) or pre-AIA 35 U.S.C. 112, sixth paragraph (e.g., by reciting sufficient structure to perform the claimed function); or (2) present a sufficient showing that the claim limitation(s) recite(s) sufficient structure to perform the claimed function so as to avoid it/them being interpreted under 35 U.S.C. 112(f) or pre-AIA 35 U.S.C. 112, sixth paragraph.
The term “controller that controls the separation unit” is not being interpreted under 35 U.S.C. 112(f) or pre-AIA 35 U.S.C. 112, sixth paragraph because the term “controller” is generally known in the arts to be a CPU or Microprocessor as well as associated structures. See also paragraph 0042 of applicant’s specification, which specifically recites that “The controller 15 is a microprocessor composed primarily of a CPU and includes, in addition to the CPU, a memory, an input/output port, and the like”.
Because this/these claim limitation(s) is/are not being interpreted under 35 U.S.C. 112(f) or pre-AIA 35 U.S.C. 112, sixth paragraph, it/they is/are not being interpreted to cover only the corresponding structure, material, or acts described in the specification as performing the claimed function, and equivalents thereof.
If applicant intends to have this/these limitation(s) interpreted under 35 U.S.C. 112(f) or pre-AIA 35 U.S.C. 112, sixth paragraph, applicant may: (1) amend the claim limitation(s) to remove the structure, materials, or acts that performs the claimed function; or (2) present a sufficient showing that the claim limitation(s) does/do not recite sufficient structure, materials, or acts to perform the claimed function.
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 1-13 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 the limitation "is treated with an ultrasonic wave in water while a frequency of the ultrasonic wave is swept" in lines 3-4. It is unclear if applicant is reciting a positive step of treating in water or sweeping the frequency or alternatively if the separation step is using the results of a prior steps.
As a general comment, the claims appear to be a literal translation of foreign language claims, and are not in conventional US format.
Claims 2-13 are rejected based on their dependency from claim 1.
Claim 8 recites the limitation "the current collector component" in line 2 and "the electrode mixture component " in lines 3-4. There is insufficient antecedent basis for this limitation in the claim. These elements are not recited in claim 1 and it is unclear if these elements have implicit antecedent basis to either “a current collector” and “an electrode mixture” as recited in claim 1. The examiner suggests using “a current collector component” and “an electrode mixture component”.
Claim 10 recites the limitation "continuous mode" in line 2. There is insufficient antecedent basis for this limitation in the claim. This is the first recitation of any continuous mode, and the examiner suggests amending the claim to recite “a continuous mode”.
Claim 11 recites the limitation "an electrode" in line 3 and "the electrode" in line 3. There is insufficient antecedent basis for this limitation in the claim. Parent claim 1 has already recited “a treatment target electrode” and “an electrode mixture”, and it is unclear how “an electrode” relates to this previous recitation. As previously noted, the claims appear to be a literal translation of foreign language claims, and are not in conventional US format.
Claim 13 recites the limitation "the current collector component" in line 13. There is insufficient antecedent basis for this limitation in the claim. These elements are not recited in claim 1 and it is unclear if these elements have implicit antecedent basis to either “a current collector” as recited in claim 1. The examiner suggests using “a current collector component” and “an electrode mixture component”.
Claim Rejections - 35 USC § 103
In the event the determination of the status of the application as subject to AIA 35 U.S.C. 102 and 103 (or as subject to pre-AIA 35 U.S.C. 102 and 103) is incorrect, any correction of the statutory basis (i.e., changing from AIA to pre-AIA ) for the rejection will not be considered a new ground of rejection if the prior art relied upon, and the rationale supporting the rejection, would be the same under either status.
The following is a quotation of 35 U.S.C. 103 which forms the basis for all obviousness rejections set forth in this Office action:
A patent for a claimed invention may not be obtained, notwithstanding that the claimed invention is not identically disclosed as set forth in section 102, if the differences between the claimed invention and the prior art are such that the claimed invention as a whole would have been obvious before the effective filing date of the claimed invention to a person having ordinary skill in the art to which the claimed invention pertains. Patentability shall not be negated by the manner in which the invention was made.
The factual inquiries for establishing a background for determining obviousness under 35 U.S.C. 103 are summarized as follows:
1. Determining the scope and contents of the prior art.
2. Ascertaining the differences between the prior art and the claims at issue.
3. Resolving the level of ordinary skill in the pertinent art.
4. Considering objective evidence present in the application indicating obviousness or nonobviousness.
This application currently names joint inventors. In considering patentability of the claims the examiner presumes that the subject matter of the various claims was commonly owned as of the effective filing date of the claimed invention(s) absent any evidence to the contrary. Applicant is advised of the obligation under 37 CFR 1.56 to point out the inventor and effective filing dates of each claim that was not commonly owned as of the effective filing date of the later invention in order for the examiner to consider the applicability of 35 U.S.C. 102(b)(2)(C) for any potential 35 U.S.C. 102(a)(2) prior art against the later invention.
Claim(s) 1-11 and 13-14 is/are rejected under 35 U.S.C. 103 as being unpatentable over Aldous (WO2012152402 A1) in view of Sato (JP 2006205138 A) and/or Hiroi (JP 2013204049 A).
As to claim 1, Aldous discloses a separation method comprising a separation step in which a treatment target electrode that includes a current collector and an electrode mixture disposed on the current collector is treated with an ultrasonic wave in water (“Water may therefore be used as the liquid 130”), in order to separate the current collector and the electrode mixture from each other.
See page 3, lines 29-35, disclosing:
According to a first aspect of the invention, there is provided a method for delaminating an electrode material of an electrode sheet from a current collector (e.g. a metal foil) of the electrode sheet. The method comprises: positioning the electrode sheet in a sonicating bath, and at least partially within a target area of a sonotrode; and ultrasonically treating the electrode sheet with an ultrasound power of greater than or equal to 1 kW, using the sonotrode.
See also page 11, lines 4-22, disclosing:
The ultrasound treatment is performed in a liquid 130 within a tank 120 (an ultrasound bath). As the electrode material 304, 306 is generally less dense than the liquid, whereas the foil 301 is more dense, the components may therefore automatically move apart due to their differing densities once delaminated, with the delaminated electrode material floating to the top.
The methods and apparatuses described herein may therefore enable foils 302 and active materials 304, 306 to be easily physically separated (delaminated, breaking the bond between the different components) and optionally also automatically physically segregated (by density, providing two distinct output streams).
Optionally, a mixture of shredded anodes and shredded cathodes, or a mixed stream of intact anodes and cathodes may be used - however, if anodes and cathodes are mixed, the active electrode materials (often referred to as black mass) differ, and the different active materials may then have to be separated in an additional step.
The ultrasound used is of high enough power to induce cavitation. Vacuum bubbles formed by cavitation implode on hitting a surface of the object 300 to be delaminated, and the shockwave generated by the imploding bubble causes material to break off. The components may then separate based on their density, with the foil 302 remaining on a substrate, whilst the detached binder and the electrode material 304, 306 floats to a surface of the liquid. As this is a physical separation process, any suitable liquid can be used as the ultrasound medium - chemical separation processes may be used in addition, but are not required. Water may therefore be used as the liquid 130.
See also Figures 1, 2, and 3, below:
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308
430
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302
394
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226
414
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Aldous, however, does not disclose that the current collector is treated with an ultrasonic wave in water while a frequency of the ultrasonic wave is swept.
However, both Sato and Hirio disclose that disclose a method wherein material that is treated with an ultrasonic wave in water while a frequency of the ultrasonic wave is swept.
Sato teaches that “if the ultrasonic cleaning is performed while changing the frequency between 50 kHz and 300 kHz, the cleaning effect is enhanced”. See the translation, disclosing:
In ultrasonic cleaning, the frequency of ultrasonic waves oscillated by the ultrasonic oscillator 115 can be determined as appropriate. For example, cleaning is performed at a frequency of 300 kHz. For example, if the ultrasonic cleaning is performed while changing the frequency between 50 kHz and 300 kHz, the cleaning effect is enhanced. The washing time is also appropriately determined depending on the amount of glass cullet to be washed.
An ultrasonic oscillator 115 is provided on the bottom surface of the first cleaning tank 101, and the glass cullet (240 g) of the waste fluorescent tube is adhered to the glass cullet by ultrasonic cleaning for about 3 minutes while changing between 50 kHz and 300 kHz. Mercury and fluorescent powder are almost peeled off (separated and removed).
Hirio teaches that “in order to enhance the cleaning effect, ultrasonic waves with different frequencies may be generated alternately” See especially Hirio, disclosing:
The cleaning tank 21 is installed on the ultrasonic transducer 24. The oscillation frequency of the ultrasonic vibrator 24 varies depending on the amount of the glass substrate 22 with reduced ITO to be put into the cleaning tank 21 and the amount of the cleaning liquid 23, but is not particularly defined, but is 20 to 20 as a frequency at which the cavitation effect is efficiently generated. 200 kHz is more preferable. Further, in order to enhance the cleaning effect, ultrasonic waves with different frequencies may be generated alternately. In the first embodiment, the ultrasonic transducer 24 is installed outside the cleaning tank 21, but may be installed in the cleaning tank 21.
Therefore, it would have been obvious to one of ordinary skill in the art at the time of the filing of the invention to have utilized a step wherein that the current collector is treated with an ultrasonic wave in water while a frequency of the ultrasonic wave is swept because Sato discloses that if the ultrasonic cleaning is performed while changing the frequency between 50 kHz and 300 kHz, the cleaning effect is enhanced and because Hirio discloses in order to enhance the cleaning effect, ultrasonic waves with different frequencies may be generated alternately.
As to claim 2, Aldous discloses wherein, in the separation step, the treatment target electrode including the electrode mixture including at least one selected from an organic binder (such as a carboxymethyl cellulose binder, polysaccharide, or polypeptide) and an aqueous binder is treated with the ultrasonic wave. See page 1, lines 20-26, disclosing:
Lithium ion battery (LiB) electrodes are generally fabricated by coating a carbon-based powder on a copper foil for the anode, and a metal oxide compound powder on aluminium foil for the cathode. These powder materials are held together using binders - often polymers such as polyvinylidene fluoride (PVDF) - and compacted together tightly through a calendaring process, so that the coating cannot be easily separated from the metal foil. Early versions of lithium ion batteries use polyvinylidene fluoride, PVDF, as the binder whereas more recent batteries generally use a mixture of carboxymethyl cellulose and styrene butadiene rubber, CMC-SBR.
See also page 13, lines 1-5, disclosing:
The liquid in which the delamination occurs (i.e. the liquid selected to fill the tank 120) may be selected depending on the binder in some embodiments. For example, if the binder is CMC/SBR (carboxymethyl cellulose / styrene butadiene rubber), water or an aqueous solution, optionally with a neutral pH, may be used. If PVDF is the binder, a mineral acid or base solution may be used in the tank 120 to increase the rate at which delamination occurs.
See also page 17, lines 1-10, disclosing:
In the examples being described, the electrode sheet 300 is an electrode from a lithium ion battery - either a carbon-coated 304, 306 metal foil 302 for the anode, or a layered metal oxide coated 304, 306 metal foil 302 for the cathode. The electrode material, or active material, is therefore carbon for the anode and a metal oxide for the cathode. A binder is used to bind the active material into a layer 304, 306, and to the foil 302. In various examples, the binder may be PVDF (polyvinylidene fluoride), CMC-PS (carboxymethyl cellulose-polystyrene), or the like, and/or a condensation or addition polymer. Optionally the binder could be a natural polymer such as a polysaccharide or polypeptide. The ultrasound treatment may aid the separation of the active electrode material from the binder as well as from the foil current collector 302. In alternative examples, any suitable electrode sheet 300 may be used.
As to claim 3, Aldous as applied to claim 1 does not disclose wherein treated with an ultrasonic wave in water while a frequency of the ultrasonic wave is swept and thus does not disclose further as in claim 3 that in the separation step, the sweeping is performed with a center being a fundamental frequency of 80 kHz or more and 200 kHz or less.
However, both Sato and Hirio disclose that a frequency of the ultrasonic wave is swept and also that in the separation step, the sweeping is performed with a center being a fundamental frequency of 80 kHz or more and 200 kHz or less..
Sato teaches that “if the ultrasonic cleaning is performed while changing the frequency between 50 kHz and 300 kHz, the cleaning effect is enhanced”. See the translation, disclosing:
In ultrasonic cleaning, the frequency of ultrasonic waves oscillated by the ultrasonic oscillator 115 can be determined as appropriate. For example, cleaning is performed at a frequency of 300 kHz. For example, if the ultrasonic cleaning is performed while changing the frequency between 50 kHz and 300 kHz, the cleaning effect is enhanced. The washing time is also appropriately determined depending on the amount of glass cullet to be washed.
An ultrasonic oscillator 115 is provided on the bottom surface of the first cleaning tank 101, and the glass cullet (240 g) of the waste fluorescent tube is adhered to the glass cullet by ultrasonic cleaning for about 3 minutes while changing between 50 kHz and 300 kHz. Mercury and fluorescent powder are almost peeled off (separated and removed).
Hirio teaches that “in order to enhance the cleaning effect, ultrasonic waves with different frequencies may be generated alternately” and also that 20 and 200 kHz are preferable ranges. See especially Hirio, disclosing:
The cleaning tank 21 is installed on the ultrasonic transducer 24. The oscillation frequency of the ultrasonic vibrator 24 varies depending on the amount of the glass substrate 22 with reduced ITO to be put into the cleaning tank 21 and the amount of the cleaning liquid 23, but is not particularly defined, but is 20 to 20 as a frequency at which the cavitation effect is efficiently generated. 200 kHz is more preferable. Further, in order to enhance the cleaning effect, ultrasonic waves with different frequencies may be generated alternately. In the first embodiment, the ultrasonic transducer 24 is installed outside the cleaning tank 21, but may be installed in the cleaning tank 21.
Therefore, it would have been obvious to one of ordinary skill in the art at the time of the filing of the invention to have utilized that in the separation step, the sweeping is performed with a center being a fundamental frequency of 80 kHz or more and 200 kHz or less because Sato discloses that if the ultrasonic cleaning is performed while changing the frequency between 50 kHz and 300 kHz, the cleaning effect is enhanced and because Hirio discloses in order to enhance the cleaning effect, ultrasonic waves with different frequencies may be generated alternately.
As to claim 4, Aldous, Sato and Hirio as applied to claim 1 above does not disclose or make obvious wherein, in the separation step, the sweeping is performed at a sweep width of within ±3 kHz with a center being a fundamental frequency.
However, Sato teaches in the translation (see excerpt above) that “if the ultrasonic cleaning is performed while changing the frequency between 50 kHz and 300 kHz, the cleaning effect is enhanced”. Similarly, Hirio teaches in the translation (see excerpt above) that “in order to enhance the cleaning effect, ultrasonic waves with different frequencies may be generated alternately” and also that 20 and 200 kHz are preferable values.
Additionally, optimization within prior art conditions or through routine experimentation is often obvious. MPEP 2144.05 II A. In this case, both Sato and Hirio disclose that changing the frequency during ultrasonic cleaning can enhance the cleaning effect.
Therefore, it would have been obvious to one of ordinary skill in the art at the time of the filing of the invention to have utilized wherein, in the separation step, the sweeping is performed at a sweep width of within ±3 kHz with a center being a fundamental frequency as an optimization within prior art conditions or through routine experimentation under MPEP 2144.05 II A in order to enhance the cleaning effect.
As to claim 5, Aldous, Sato and Hirio as applied to claim 1 above does not disclose or make obvious wherein, in the separation step, the sweeping is performed at a sweep rate of 500 sweep cycles/sec or more.
However, Sato teaches in the translation (see excerpt above) that “if the ultrasonic cleaning is performed while changing the frequency between 50 kHz and 300 kHz, the cleaning effect is enhanced”. Similarly, Hirio teaches in the translation (see excerpt above) that “in order to enhance the cleaning effect, ultrasonic waves with different frequencies may be generated alternately” and also that 20 and 200 kHz are preferable values.
Additionally, optimization within prior art conditions or through routine experimentation is often obvious. MPEP 2144.05 II A. In this case, both Sato and Hirio disclose that changing the frequency during ultrasonic cleaning can enhance the cleaning effect.
Therefore, it would have been obvious to one of ordinary skill in the art at the time of the filing of the invention to have utilized wherein, in the separation step, the sweeping is performed at a sweep rate of 500 sweep cycles/sec or more as an optimization within prior art conditions or through routine experimentation under MPEP 2144.05 II A in order to enhance the cleaning effect.
As to claim 6, Aldous disclose wherein, in the separation step, the ultrasonic treatment is performed for 10 minutes or less. See page 13, lines 12-15, disclosing:
The physical separation is relatively rapid, as compared to chemical separation techniques, allowing a shorter treatment time than the 30 minutes to 3 hours generally needed for prior approaches. For example, a treatment time of less than five minutes, and optionally less than a minute, or even less than a second, may be sufficient.
As to claim 7, Aldous does not disclose wherein, in the separation step, when an area of a contact portion between the current collector and the electrode mixture is defined as A and an output of the ultrasonic wave is defined as B, the ultrasonic treatment is performed such that an output density represented by B/A is 10 W/cm2 or less.
However, Aldous does disclose that the ultrasonic treatment is performed such that an output density represented by B/A is 50 W/cm2 or more (page 4, line 4). Additionally, Aldous does suggest and/or discuss using low power ultrasound disclosed in Aldous prior art discussion as a contrast to high power ultrasound. Aldous teaches on page 4, lines 16-25 that:
The use of high-powered ultrasound (which may be defined by an ultrasound power of at least 1 kW and/or by a sonotrode front face power density of at least 50 W/cm.sup.2) causes cavitation to occur at or near the interface between the active electrode material and the current collector foil, when the electrode sheet is in the target area. The implosion of bubbles formed by cavitation induces shock waves, prising apart the phase boundary mechanically. This physical separation process may allow delamination of the electrode material to occur in less than 5 seconds. By contrast, the relatively slow segregation of material with low power ultrasound as reported in papers cited above demonstrates that a different process is responsible for the separation - the slower separation reported previously is caused by foils abrading with each other and/or with a support, rather than through cavitation - cavitation is only observed at a much higher ultrasound power.
Additionally, optimization within prior art conditions or through routine experimentation is often obvious. MPEP 2144.05 II A.
Therefore, it would have been obvious to one of ordinary skill in the art at the time of the filing of the invention to have utilized wherein, in the separation step, when an area of a contact portion between the current collector and the electrode mixture is defined as A and an output of the ultrasonic wave is defined as B, the ultrasonic treatment is performed such that an output density represented by B/A is 10 W/cm2 or less as an optimization within prior art conditions or through routine experimentation under MPEP 2144.05 II A in order to enhance the cleaning effect.
As to claim 8, Aldous does not disclose wherein a proportion of the current collector component included in the electrode mixture separated in the separation step is less than 0.1% and a proportion of the electrode mixture component included in the current collector separated in the separation step is less than 0.2%.
However, Aldous does disclose that “Near-complete delamination was therefore achieved” with “”via the embodiments of Aldous. See page 26, line 6 to 29, disclosing:
Case Study 1 : delamination of LiB anode
A lithium ion battery (LiB) from a car battery was dissembled, and separated into anode and cathode “leaves’Vsheets 300. The anode sheets 300 were delaminated to separate active material from current collector file using techniques as described herein, with the following process conditions:
• The bath solution was chosen to be deionized water with 0.05 M citric acid;
• The sonicator 110 was operated at a power of 2200 W in a “continuous welding” mode;
• The gap between the sonotrode front face and the sample tray /support underneath was set to be 3 mm, such that the spacing between the sonotrode front face and the surface to be delaminated was less than 3 mm;
• The anode sheet 300 was fed through the target area at a speed of 3 cm/s;
• The sonotrode front face of the sonotrode 112 used is rectangular in shape, with dimensions of 15 mm x 210 mm.
The LiB anode leaf sheet 300 (shown in Figure 15(a)) has a size of 20 cm x 23 cm, with carbon powder (electrode active material) coated on both sides of a 15 pm thick copper foil (current collector). The carbon powder is bound by PVDF polymer (binder), the thickness of the coating is 70 pm. The anode sheets 300 were then fed, one by one, into the gap underneath the sonotrode 112 at a speed of 3 cm/s. The delaminated copper foil (Figure 15(b)) was then removed from the bath 120 on the other side of the sonotrode 112; the carbon coating is pulverised and left behind in the solution, so separating the layers.
Figure 15 shows (a) the anode sheet before delamination, showing the grey-black colour of the active material; and (b) the anode sheet after delamination, showing the copper-colour of the current collector foil, with only a few flecks of the active material remaining. Near-complete delamination was therefore achieved
Additionally, the percentage of electrode mixture and collector components remaining after separation is a result effective variable of the process, with lower proportions being a desirable result that indicates higher material separation and thus recycling. As noted above, optimization within prior art conditions or through routine experimentation is often obvious. MPEP 2144.05 II A.
Therefore, it would have been obvious to one of ordinary skill in the art at the time of the filing of the invention to have optimized to achieve a result of wherein a proportion of the current collector component included in the electrode mixture separated in the separation step is less than 0.1% and a proportion of the electrode mixture component included in the current collector separated in the separation step is less than 0.2% as an optimization within prior art conditions or through routine experimentation under MPEP 2144.05 II A in order to enhance the cleaning effect.
As to claim 9, Aldous discloses wherein, in the separation step, the ultrasonic treatment is performed in an unheated environment (compare Aldous, disclosing that “The method 1200 may be performed at room temperature”, with applicant’s own specification, paragraph 0024, which recites “Tn the separation step, the ultrasonic treatment is preferably performed in an unheated environment. The temperature at which the ultrasonic treatment is performed in the separation step may be, for example, 0°C or more and 30°C or less and may be 15°C or more and 25°C or less.”).
See page 25, line to page 21, line 1, disclosing:
The method 1200 of the embodiment being described is a continuous process - the electrode sheet 300, or a sequence of electrode sheets 300, are continuously moved through the sonicating bath 120 and delaminated as they pass the sonotrode 112. Removing the delaminated electrode material 304a from the surface of the liquid 130 may also be performed in parallel - either continually or at intervals. In alternative embodiments, the method 1200 may be performed as a batch process - for example treating a single electrode sheet 300 or a set number of electrode sheets 300, removing the foil 302, and then sieving the liquid 130 to separate out the electrode material 304, 306.
The method 1200 may be performed at room temperature.
As to claim 10, Aldous discloses wherein the ultrasonic treatment is performed in a batch (“as a batch process”) or continuous mode (“a continuous flow process”, “in a continuous process”). See page 23, lines 32, disclosing:
In particular, in various embodiments, the sonotrode 112 and electrode sheet 300 are arranged such that a sonic wave capable of bringing about an almost instantaneous breaking of the adhesive bond between the current collector and the binder of a laminated composite material is generated in the target area. To achieve this, the laminated material 300 is arranged to pass at a distance of less than 2 cm from the sonotrode in the embodiments described herein. This rapid treatment enables the delamination of laminated material to occur in a continuous flow process, on whole electrodes 300, rather than requiring a batch process which significantly increases the space-time-yield of a process.
See also page 25, lines 29-35, disclosing:
The method 1200 of the embodiment being described is a continuous process - the electrode sheet 300, or a sequence of electrode sheets 300, are continuously moved through the sonicating bath 120 and delaminated as they pass the sonotrode 112. Removing the delaminated electrode material 304a from the surface of the liquid 130 may also be performed in parallel - either continually or at intervals. In alternative embodiments, the method 1200 may be performed as a batch process - for example treating a single electrode sheet 300 or a set number of electrode sheets 300, removing the foil 302, and then sieving the liquid 130 to separate out the electrode material 304, 306. The method 1200 may be performed at room temperature.
As to claim 11, Aldous discloses further comprising: an extraction step in which an electrode is extracted from an energy storage device, wherein, in the separation step, the electrode extracted in the extraction step is used as the treatment target electrode and treated with the ultrasonic wave without being shredded (“The approach may be used with shredded electrode foils or with intact electrode foils.”).
See page 10, line 38 to page 11, line 3, disclosing:
The various embodiments described herein use mechanical abrasion caused by ultrasonically- induced cavitation to bring about rapid delamination of electrode foils 302 from the active material 304, 306 of the electrode 300. Anode and cathode materials may each be separated by passing the respective electrode sheet 300 under a high-power ultrasonic horn (sonotrode 112). The approach may be used with shredded electrode foils or with intact electrode foils.
See page 23, lines 10-16, disclosing:
In some embodiments, the electrode sheet 300 is not chemically treated, nor smelted, after being separated from a battery and before positioning in the sonicating bath 120. An intact electrode 300, or one or more strips 302 of a cut or shredded electrode, may therefore be used. Optionally, no pre treatment may be performed, or the sheet 300 or strips 302 may simply be washed, e.g. with water. The skilled person will appreciate that, at present, battery electrodes are often shredded to form ribbons as part of the recycling process, for example reducing the width, WE (e.g. from 20-30 cm to 0.5-1 cm), whilst keeping the length, L.sub.E (e.g. of 20-30 cm).
As to claim 13, Aldous discloses wherein the separation step is conducted such that one or more selected from (1) to (6) below are satisfied:
(1) in the separation step, a pH of the water used for the ultrasonic treatment is 11. 5 or less (See the page 22, lines 11-12, disclosing “In various embodiments, the liquid 130 has a pH in the range from 1 to 13, and optionally in the range from 4 to 10.” See also claim 12, disclosing “12. The method of any preceding claim, comprising at least partially filling the sonicating bath with water, or an aqueous solution, prior to the ultrasonic treatment, the liquid preferably having a pH in the range from 1 to 13 .”),
(2) in the separation step, a concentration of an alkali metal component in the water used for the ultrasonic treatment is 37.5 mg/L or less,
(3) in the separation step, an amount of the current collector dissolved in the water per weight of the current collector is 1.1% or less,
(4) in the separation step, an amount of waiting time during which the treatment target electrode that has not been subjected to the ultrasonic treatment is held in the water is 30 minutes or less,
(5) in the separation step, a proportion of the current collector component in the separated electrode mixture is 0.18% by weight or less, and
(6) in the separation step, a rejection rate at which the electrode mixture is removed from the current collector is 90% or more.
Additionally, with respect to (2) through (4), Aldous discloses some of the variables, although not the specific values. Aldous discloses as to (2) a solution of “a 0.1 M NaOH solution (Figure 10), the alkali solution”, as to (3) that “water has the advantages of being cheap, relatively safe to work with, and unlikely to dissolve any significant quantity of the desired output materials (at least on the timescale of the treatment)”, as to (4) that “If the tank 120 is left undisturbed for a sufficient time period, light particles (e.g. carbon) may separate from heavy particles (e.g. metal oxide), and these may be collected from different layers within the liquid 130 in the tank 120.” Thus, Aldous discloses that these are variables that can be relevant to recycling.
Additionally, as to (5) and (6) the proportion of the current collector component in the separated electrode mixture, and the rejection rate are all relevant variable to achieve efficient recycling. As noted above, optimization within prior art conditions or through routine experimentation is often obvious. MPEP 2144.05 II A.
Therefore, it would have been obvious to one of ordinary skill in the art at the time of the filing of the invention to have also utilized wherein the separation step is conducted such that one or more selected from (1) to (6) below are satisfied such as (2) in the separation step, a concentration of an alkali metal component in the water used for the ultrasonic treatment is 37.5 mg/L or less, (3) in the separation step, an amount of the current collector dissolved in the water per weight of the current collector is 1.1% or less, (4) in the separation step, an amount of waiting time during which the treatment target electrode that has not been subjected to the ultrasonic treatment is held in the water is 30 minutes or less, (5) in the separation step, a proportion of the current collector component in the separated electrode mixture is 0.18% by weight or less, and (6) in the separation step, a rejection rate at which the electrode mixture is removed from the current collector is 90% or more as result effective variables that improve the recycling yields
As to claim 14, Aldous discloses a separation device comprising: a separation unit (see Figures 1, 2, 3, disclosing liquid 130 within a tank 120) that treats a treatment target electrode including a current collector and an electrode mixture disposed on the current collector with an ultrasonic wave in water (“water may therefore be used as the liquid 130”) to separate the current collector and the electrode mixture from each other; and a controller that controls the separation unit such that the ultrasonic treatment (via sonicator 110) is performed (“suitable physical support, electrical components, and controls to enable the sonotrode 112 to function as desired.”).
See page 3, lines 29-35, disclosing:
According to a first aspect of the invention, there is provided a method for delaminating an electrode material of an electrode sheet from a current collector (e.g. a metal foil) of the electrode sheet. The method comprises: positioning the electrode sheet in a sonicating bath, and at least partially within a target area of a sonotrode; and ultrasonically treating the electrode sheet with an ultrasound power of greater than or equal to 1 kW, using the sonotrode.
See also page 11, lines 4-22, disclosing:
The ultrasound treatment is performed in a liquid 130 within a tank 120 (an ultrasound bath). As the electrode material 304, 306 is generally less dense than the liquid, whereas the foil 301 is more dense, the components may therefore automatically move apart due to their differing densities once delaminated, with the delaminated electrode material floating to the top.
The methods and apparatuses described herein may therefore enable foils 302 and active materials 304, 306 to be easily physically separated (delaminated, breaking the bond between the different components) and optionally also automatically physically segregated (by density, providing two distinct output streams).
Optionally, a mixture of shredded anodes and shredded cathodes, or a mixed stream of intact anodes and cathodes may be used - however, if anodes and cathodes are mixed, the active electrode materials (often referred to as black mass) differ, and the different active materials may then have to be separated in an additional step.
The ultrasound used is of high enough power to induce cavitation. Vacuum bubbles formed by cavitation implode on hitting a surface of the object 300 to be delaminated, and the shockwave generated by the imploding bubble causes material to break off. The components may then separate based on their density, with the foil 302 remaining on a substrate, whilst the detached binder and the electrode material 304, 306 floats to a surface of the liquid. As this is a physical separation process, any suitable liquid can be used as the ultrasound medium - chemical separation processes may be used in addition, but are not required. Water may therefore be used as the liquid 130.
See page 14, lines 13-21, disclosing:
The converter, booster 114 and sonotrode 112 are connected as a stack 112, 114 in the embodiment shown in Figure 2. The sonicator stack 112, 114 is mounted on a frame 116. The frame 116 is mounted on a base plate 118. In the embodiment shown, the frame 116 lies outside of the tank 120 and holds the sonotrode 112 such that it extends downwards into the tank 120. In alternative embodiments, the mounting arrangement of the sonicator 110 may be different, and/or no booster and/or converter 114 may be present. The sonicator 110 of various embodiments includes a sonotrode 112 capable of generating ultrasound at the required power / with the required power density and any suitable physical support, electrical components, and controls to enable the sonotrode 112 to function as desired.
See also Figures 1, 2, and 3, below:
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308
430
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302
394
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226
414
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However, Aldous does not disclose that the controller that controls the separation unit such that the ultrasonic treatment is performed while a frequency of the ultrasonic wave is swept.
However, both Sato and Hirio disclose that disclose a method wherein material that is treated with an ultrasonic wave in water while a frequency of the ultrasonic wave is swept.
Sato teaches that “if the ultrasonic cleaning is performed while changing the frequency between 50 kHz and 300 kHz, the cleaning effect is enhanced”. See the translation, disclosing:
In ultrasonic cleaning, the frequency of ultrasonic waves oscillated by the ultrasonic oscillator 115 can be determined as appropriate. For example, cleaning is performed at a frequency of 300 kHz. For example, if the ultrasonic cleaning is performed while changing the frequency between 50 kHz and 300 kHz, the cleaning effect is enhanced. The washing time is also appropriately determined depending on the amount of glass cullet to be washed.
An ultrasonic oscillator 115 is provided on the bottom surface of the first cleaning tank 101, and the glass cullet (240 g) of the waste fluorescent tube is adhered to the glass cullet by ultrasonic cleaning for about 3 minutes while changing between 50 kHz and 300 kHz. Mercury and fluorescent powder are almost peeled off (separated and removed).
Hirio teaches that “in order to enhance the cleaning effect, ultrasonic waves with different frequencies may be generated alternately” See especially Hirio, disclosing:
The cleaning tank 21 is installed on the ultrasonic transducer 24. The oscillation frequency of the ultrasonic vibrator 24 varies depending on the amount of the glass substrate 22 with reduced ITO to be put into the cleaning tank 21 and the amount of the cleaning liquid 23, but is not particularly defined, but is 20 to 20 as a frequency at which the cavitation effect is efficiently generated. 200 kHz is more preferable. Further, in order to enhance the cleaning effect, ultrasonic waves with different frequencies may be generated alternately. In the first embodiment, the ultrasonic transducer 24 is installed outside the cleaning tank 21, but may be installed in the cleaning tank 21.
Therefore, it would have been obvious to one of ordinary skill in the art at the time of the filing of the invention to have utilized a controller that controls the separation unit such that the ultrasonic treatment is performed while a frequency of the ultrasonic wave is swept because Sato discloses that if the ultrasonic cleaning is performed while changing the frequency between 50 kHz and 300 kHz, the cleaning effect is enhanced and because Hirio discloses in order to enhance the cleaning effect, ultrasonic waves with different frequencies may be generated alternately.
Claim(s) 12 is/are rejected under 35 U.S.C. 103 as being unpatentable over Aldous (WO2012152402 A1) in view of Sato (JP 2006205138 A) and/or Hiroi (JP 2013204049 A) as applied to claims 1-11 and 13-14 above, and further in view of Ho (US 20180013181 A1).
As to claim 12, Aldous, Sato and Hiroi do not disclose the method further comprising at least one selected from a current collector treatment step in which the current collector separated in the separation step is rinsed and subsequently dried and a mixture treatment step in which the electrode mixture is separated from mixture-containing water and subsequently dried, the mixture-containing water including the electrode mixture separated in the separation step.
However, Ho discloses and makes obvious the method further comprising at least one selected from a current collector treatment step in which the current collector separated in the separation step is rinsed and subsequently dried and a mixture treatment step in which the electrode mixture is separated from mixture-containing water and subsequently dried, the mixture-containing water including the electrode mixture separated in the separation step. Ho teaches immersing in deionized water (a rinse step), an ultrasonic agitation step, and a final oven dry step.
See paragraph 0130, 0137, disclosing:
Recycling of Batteries
[0130] Used lithium-ion batteries (˜20 kg) were fully discharged by soaking in 6% NaCl solution for 12 hours. After discharging, the lithium-ion batteries were chopped into pieces by a water jet cutting machine (YCWJ-3038-L2015-1D, YC Industry Co., Ltd., Jiangsu, China). The pieces of the chopped lithium-ion batteries, having an average length from about 0.5 inches to about 1.0 inches were immersed into deionized water (25 L) at 20° C. to form a heterogeneous mixture. The mixture was agitated by an ultrasonic probe (NP2500; obtained from Guangzhou Newpower Ultrasonic Electronic Equipment Co., Ltd., China) with an input power of 200 W for 2 hours at 20° C. The cathode material was detached from the aluminum foil, while the anode material fell off the copper foil. After ultrasonic processing, the structural part, copper foil and aluminum foil were removed by passing through a sieve having a mesh width of 4 mm to give a suspension comprising water and electrode materials. After removal of the structural part, copper foil and aluminum foil, the suspension was filtered to obtain the electrode materials. The recovered electrode materials were dried in an oven for 5 hours at 80° C. under atmospheric pressure and obtained in a yield of 63%.
…
Recycling of Batteries
[0137] Used lithium-ion batteries (0.5 kg) were fully discharged by soaking in 4% NaCl solution for 12 hours. After discharging, the lithium-ion batteries were chopped into pieces by a battery cutting machine (Kaidi Machinery, Zhengzhou, China). The pieces of the chopped lithium-ion batteries, having an average length from about 1 inches to about 1.5 inches were immersed into deionized water (10 L) at room temperature to form a heterogeneous mixture. The mixture was agitated ultrasonically at room temperature for 0.5 hour. The cathode material was detached from the aluminum foil, while the anode material fell off the copper foil. After stirring, the structural part, copper foil and aluminum foil were removed by passing through a sieve having a mesh width of 2 mm to give a suspension comprising water and electrode materials. After removal of the structural part, copper foil and aluminum foil, the suspension was filtered to obtain the electrode materials. The recovered electrode materials were dried in an oven for 5 hours at 80° C. under atmospheric pressure and obtained in a yield of 93%.
Therefore, it would have been obvious to one of ordinary skill in the art at the time of the filing of the invention to have utilized further comprising at least one selected from a current collector treatment step in which the current collector separated in the separation step is rinsed and subsequently dried and a mixture treatment step in which the electrode mixture is separated from mixture-containing water and subsequently dried, the mixture-containing water including the electrode mixture separated in the separation step as disclosed in Ho in order to recover the electrode materials.
Conclusion
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/GEORGE R KOCH/Primary Examiner, Art Unit 1745
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