The present application, filed on or after March 16, 2013, is being examined under the first inventor to file provisions of the AIA .
The following is a quotation of the first paragraph of 35 U.S.C. 112(a):
(a) IN GENERAL.—The specification shall contain a written description of the invention, and of the manner and process of making and using it, in such full, clear, concise, and exact terms as to enable any person skilled in the art to which it pertains, or with which it is most nearly connected, to make and use the same, and shall set forth the best mode contemplated by the inventor or joint inventor of carrying out the invention.
Claim 17 is rejected under 35 U.S.C. 112(a), as failing to comply with the enablement requirement. The claim(s) contains subject matter which was not described in the specification in such a way as to enable one skilled in the art to which it pertains, or with which it is most nearly connected, to make and/or use the invention. In order to determine compliance with the enablement requirement of 35 U.S.C. 112(a), the Federal Circuit developed a framework of factors in In re Wands, 858 F.2d 731, 737, 8 USPQ2d 1400, 1404 (Fed. Cir. 1988), referred to as the Wands factors to assess whether any necessary experimentation required by the specification is "reasonable" or is "undue." These factors include, but are not limited to:
(A) The breadth of the claims;
(B) The nature of the invention;
(C) The state of the prior art;
(D) The level of one of ordinary skill;
(E) The level of predictability in the art;
(F) The amount of direction provided by the inventor;
(G) The existence of working examples; and
(H) The quantity of experimentation needed to make or use the invention based on the content of the disclosure.
In the instant case, relative to the breadth of claims factor, claim 1 requires generating an optical signal and transmitting it through the optical fiber, detecting, using an infrared spectrometer, said transmitted optical signal at an output extremity of the optical fiber, recording the detected optical signal over time, locating, using fiber evanescent wave spectroscopy signature wavelengths for which the optical signal intensity is above a predetermined threshold. In this language the transmission of the optical fiber needs to be such that the fiber creates an evanescent wave. Claim 17 requires that the optical fiber has a cross-section that is star-shaped or a cross-section that is disk-shaped including a local section that is V-shaped. Thus the evanescent wave must be present in an optical fiber that has either of these cross-sections. With respect to the level of one of ordinary skill in the art, they would understand what it takes to cause or destroy an evanescent wave as the optical signal is transmitted through the optical fiber. With respect to the direction provided by the inventor or the presence of working examples, the star shaped cross-section and the disc shaped cross-section with a local V shape is only mentioned in conjunction with instant figure 7 as a way to increase the surface area. There are no examples with either of these shapes presented in the disclosure. With respect to the state of the prior art examiner points to the cited Oyama patent (US 5,233,679) in which an optical figure is used to diffuse light along its length through a light radiating surface (see at least the abstract). Where the body is an optical fiber (10), the light radiating surface is the circumferential surface (14) of the fiber (10). A plurality of striations (16), (44) are formed in the light radiating surface (14), (46) parallel to the axis (12), (42), which cause light entering the body (10), (40) along the axis (12), (42) to be radiated out of the body (10), (40) through the light radiating surface (14), (46) with substantially uniform intensity along the axis (12), (42). Column 2, lines 54-63 of Oyama teach that the invention overcomes the drawbacks of the prior art by forming striations in a light radiating or diffusing surface of an optical fiber or panel in such a manner that the intensity of light radiated out of the fiber or panel perpendicular to the longitudinal axis thereof is substantially uniform along the longitudinal axis. This is accomplished by forming the striations parallel to the longitudinal axis. The striations may be ridges or grooves having a circular, square, V-shaped, or other appropriate cross section. Column 5, lines 17-29 of Oyama describe striations in several of the figures. Particularly relevant to the instant disclosure is figure 4, showing an optical fiber 74 formed with striations in the form of grooves 76 having a V-shaped cross section. Since the figure shows groove s space along the entirety of the outer surface, the shape is also similar to the star cross section of instant figure 7c. The Oyama patent teaches that such structures diffuse/radiate light which one of ordinary skill in the art would recognize as being different from an evanescent wave as light (an optical signal) is transmitted through an optical fiber. The instant disclosure does not provide anything to show that the fibers having the cross=section require by claim 17 behave differently than taught by Oyama. Thus, Oyama provides evidence that instant claim 17 is not enabled.
Claims 7-9, 13 and 20 are rejected under 35 U.S.C. 112(b) or 35 U.S.C. 112 (pre-AIA ), second paragraph, as being indefinite for failing to particularly point out and distinctly claim the subject matter which the inventor or a joint inventor (or for applications subject to pre-AIA 35 U.S.C. 112, the applicant), regards as the invention. In claim 7, “the spectra database” does not have antecedent basis. With respect to claim 13, “comprising essentially” does not have a recognized scope in the same way “comprising” and “consisting essentially of” do. With respect to claim 20the coating thickness requirement is between 0 and 10 μm. It is not clear what applicant intends to claim. Does the range require some level of coating including a coating that is a partial coating such as a single atom or molecule from the electrode or is claim 20 attempting to claim that no coating needs to be present? For examination purposes examiner will treat the claim as covering any level of coating that would be associated with the fiber through contact with the electrode material during formation of the battery with an embedded optical fiber.
The following is a quotation of pre-AIA 35 U.S.C. 103(a) which forms the basis for all obviousness rejections set forth in this Office action:
(a) A patent may not be obtained though the invention is not identically disclosed or described as set forth in section 102, if the differences between the subject matter sought to be patented and the prior art are such that the subject matter as a whole would have been obvious at the time the invention was made to a person having ordinary skill in the art to which said subject matter 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 pre-AIA 35 U.S.C. 103(a) 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 under pre-AIA 35 U.S.C. 103(a), the examiner presumes that the subject matter of the various claims was commonly owned at the time any inventions covered therein were made absent any evidence to the contrary. Applicant is advised of the obligation under 37 CFR 1.56 to point out the inventor and invention dates of each claim that was not commonly owned at the time a later invention was made in order for the examiner to consider the applicability of pre-AIA 35 U.S.C. 103(c) and potential pre-AIA 35 U.S.C. 102(e), (f) or (g) prior art under pre-AIA 35 U.S.C. 103(a).
Claims 1-11 13-16 and 20 are rejected under pre-AIA 35 U.S.C. 103(a) as being unpatentable over Ghannoum (ACS Applied Materials & Interfaces 2017, herein after called Ghannoum ‘17) in view of Ellis (Journal of the Electrochemical Society 2018) or Vizintim (Nature Communications 2018) and further in view of Heo (Applied Optics 1991) or Bureau (Optical Engineering 2014). In the paper Ghannoum ’17 teaches the development, fabrication, and embedment of fiber-optic evanescent wave sensors (FOEWSs) to monitor the state of charge (SOC) and the state of health (SOH) of lithium-ion batteries (LIBs). Etching of FOEWSs is performed using a solution of 40 wt % ammonium fluoride (NH4F) and 49 wt % hydrofluoric acid (HF) (6:1), which is found to be superior to an etching solution containing just 49 wt % HF. FOEWSs were characterized using glycerol and found to have the highest sensitivity in a lithium-ion battery when they lose 92% of their transmittance in the presence of glycerol on their sensing region. The physical effect that the FOEWS has on the graphite anode was also investigated and found to be much more significant in Swagelok cells compared to that in in-house-fabricated pouch cells, mainly due to pressure variation. The FOEWS was found to be most sensitive to the changes in the LIB when it was completely embedded using a slurry of graphite anode material within a pouch cell. The optimized fabrication process of the embedded FOEWS demonstrates the potential of using such sensors commercially for real-time monitoring of the SOC and SOH of LIBs while in operation. With respect to claim 1, Ghannoum ‘17 teaches a method for operando characterization of the chemical composition of a battery cell, comprising: inserting at least one optical fiber through the battery cell (see at least figures 3 and 7 and the paragraph bridging pages 41285-41285), generating an optical signal and transmitting it through the optical fiber (850 nm, see at least the “Fiber-Optic Evanescent Wave Sensor Transmittance and Glycerol Testing” section on pages 41288-41289), detecting, said transmitted optical signal at an output extremity of the optical fiber, recording the detected optical signal over time (see at least figure 9). Ghannoum ‘17 does not teach that the optical fiber is made of chalcogenide glass, the detecting is using an infrared spectrometer or locating, using fiber evanescent wave spectroscopy, signature wavelengths for which the optical signal intensity is above a predetermined threshold, associating said located signature wavelengths to at least one predetermined chemical species.
In the paper Ellis introduced a method for determining unknown concentrations of major components in typical lithium-ion battery electrolytes. The method is quick, cheap, and accurate. Machine learning techniques are used to match features of the Fourier transform infrared (FTIR) spectrum of an unknown electrolyte to the same features of a database of FTIR spectra with known compositions. With this method, LiPF6 concentrations can be determined with similar accuracy and precision as an inductively coupled plasma optical emission spectrometry (ICP-OES) method. The ratios of organic carbonate solvent species can be determined with more rapidity than gas chromatography (GC). This FTIR method is faster and less expensive than GC and ICP-OES, and has the added benefit of being able to determine LiPF6 concentration and solvent fractions simultaneously. Application of this tool can facilitate electrolyte analysis of aged lithium-ion cells, and will help elucidate mechanisms for cell degradation. The paragraph bridging the left columns of page A256 teaches that a method of determining the concentration of LiPF6 and weight fractions of solvents in unknown electrolyte solutions, using attenuated total reflectance (ATR) Fourier transform infrared (FTIR) spectroscopy is presented in the paper. Until the time the paper was published, FTIR had only been used for qualitative electrolyte analysis, and for the determination of solvation structures. Quantitative analysis was achieved using a machine learning (ML) algorithm to match features in the FTIR spectra of unknown electrolyte solutions to those interpolated from a spectral database of known electrolyte solutions. The method is very fast. Once the spectral database and machine learning algorithm have been set up, there is no need for sample preparation, instrument calibration, or for data manipulation. The accuracy and precision of the method was first validated by determining the concentration of LiPF6 and weight fractions of solvents in known “unknown” solutions. Then the method was used to determine the LiPF6 concentration and weight fractions of solvents in the electrolyte extracted from aged lithium-ion cells. The results were found to be in good agreement with results from GC/MS and ICP-OES measured on the same electrolytes. This method is easy, fast and allows for systematic studies of liquid electrolytes in lithium-ion cells as they age. Page A256 teaches that FTIR spectra were collected using a Cary 630 FTIR equipped with a germanium crystal attenuated total reflectance (ATR) accessory. Sixteen scans were collected for each background and sample measurement, at a resolution of 4 cm-1, using MicroLab PC software. Fourier transforms were performed using HappGenzel apodization, Mertz phase correction, and a zero-fill factor of 2. All measurements were performed in a thermostatic room maintained at 12–14 °C to hinder evaporation of DMC. The paragraph bridging pages A256-A257 describes the machine learning software as FTIR/ML software was written in Mathematica 11.1.21 First, the raw FTIR spectra were normalized such that the total integrated area over the range 650–2000 cm-1 equaled one. Then, n selected features in the absorbance spectra (see Table I) of each of the 81 database samples were measured. For example, one such feature consists of the area of the normalized signal in a region centered around 839 cm cm-1 and with a half width of 25 cm cm-1. This procedure produced an n-component array of values, where each n-component array is associated with a database sample of known composition. Figure 1 shows ATR-FTIR spectra of electrolyte solutions with a range of LiPF6, EC, and DMC concentrations. The evolution of a spectral feature between about 1750 cm-1 and 1800 cm-1 was identified as strongly correlated with [LiPF6] in DMC solutions. Evolution of another spectral feature between about 1050 cm-1 and 1225 cm-1 was identified as correlated with [EC] in DMC solutions. The conclusion on page A261 teaches that a satisfactory proof of concept for this method was shown from the characterization of known “unknown” solutions, and from the relatively good agreement between FTIR and GC-MS/ICP-OES on electrolytes taken from cycled Li-ion cells. It was found that the concentration of LiPF6 was depleted by 10–20% in cells which had undergone 200 cycles at 55◦C. This amount of salt loss is large, and is likely a significant contributor to eventual cell failure. The speed, ease and cost advantages of the FTIR method will allow for analyses of the depletion of salt in aged lithium-ion cells and dramatic changes in solvent ratio. What is most important is that it is now possible to easily and quickly analyze the electrolytes from all cells in this laboratory at end of life or at specified points during life. Given that about 1300 Li-ion cells were tested each month in their laboratory, it is likely that the research will yield many interesting and important results, and will allow deeper insight into the failure mechanisms of lithium-ion cells. Future work in this subject will not only be focused on the application of the database and methods described here, but will also focus on expanding and improving the spectral database and machine learning algorithm. Efforts were underway to construct spectral libraries which include other common electrolyte co-solvents (diethyl carbonate, ethyl methyl carbonate, propylene carbonate, and others). Improvements in the machine learning algorithm may allow for the detection of transesterification reactions between the alkyl carbonates, which is another parasitic reaction that was thought to signal insufficient graphite passivation.
In the paper Vizintim described probing electrochemical reactions in organic cathode materials via in operando infrared spectroscopy. Organic materials are receiving an increasing amount of attention as electrode materials for future post lithium-ion batteries due to their versatility and sustainability. However, their electrochemical reaction mechanism has seldom been investigated. This is a direct consequence of a lack of straightforward and broadly available analytical techniques. Herein, a straightforward in operando attenuated total reflectance infrared spectroscopy method is developed that allows visualization of changes of all infrared active bands that occur as a consequence of reduction/oxidation processes. In operando infrared spectroscopy is applied to the analysis of three different organic polymer materials in lithium batteries. Moreover, this in operando method is further extended to investigation of redox reaction mechanism of poly (anthraquinonyl sulfide) in a magnesium battery, where a reduction of carbonyl bond was demonstrated as a mechanism of electrochemical activity. Conclusions done by the in operando results are complemented by synthesis of model compound and density functional theory calculation of infrared spectra. the first three paragraphs on page 2 of the paper teach that although Li-ion batteries are the most suitable mature battery technology for commercial applications, researchers are actively exploring the alternatives. Among these technologies metal–organic batteries are attracting increasing attention due to their versatility, low cost and sustainability. Unlike most inorganic materials, organic materials can be used with a variety of counter ions, which removes any possible concerns about Li supply out of the picture. Due to the electrochemical conversion reaction, they bypass the intercalation and solid-state diffusion limitations inside inorganic hosts and can achieve high rates without the need for nanosizing the materials. Use of organic cathode materials has already been successfully demonstrated for several battery systems. Although some of the organic cathode materials show stable and long-term cycling, the electrochemical mechanism in certain materials is still under debate. Most often electrochemical mechanism of organic materials is presumed only on predictions and analogies based on post-mortem measurements. The main reason is lack of analytical techniques that allow simultaneous electrochemical and spectroscopic characterization (i.e., in operando investigations) and rather fast degradation of ex situ samples coupled with troublesome handling, especially in their discharged state. As a result, the proposed electrochemical reaction mechanisms were rarely investigated, much less confirmed. Previously, the electrochemical reaction mechanism inside of organic battery cathodes had been investigated by X-ray diffraction, nuclear magnetic resonance (NMR), Raman and infrared (IR) spectroscopy. However, there are certain limitations to these techniques; X-ray diffraction is limited to crystalline samples and Raman spectroscopy is troublesome due to fluorescence and laser-induced sample damage. Both IR and NMR techniques were limited to the analysis of ex situ samples. In this context development of in operando techniques was needed for future progress of both metal–organic batteries and other types of batteries. In operando techniques help us improve our knowledge about mechanisms of battery operation and degradation and in future might allow real-time monitoring of the battery state of health. The paper demonstrates/shows in operando measurements based on attenuated total reflectance (ATR)-IR of the electrode composite inside a modified pouch cell on the established redox-active polymer, poly(anthraquinonyl sulfide) (PAQS), that has been used in several battery systems (Li, Na, Mg, K). Measurements were performed in Li and Mg battery systems. They employed subtractive normalization of the obtained IR spectra for visualization of the IR-active spectral changes caused by electrochemical cycling of the electrode. The reduction of the carbonyl bond in Li and Mg PAQS systems was confirmed. Good reversibility in both battery systems confirms the applicability of organic electrodes as low cost, versatile and sustainable cathode materials. In operando measurements were complemented by comparing IR spectra of a simple anthraquinone (AQ) and a synthesized lithium salt of 9,10-dihydroxy anthracene (Li2AQ). To confirm the applicability of the in operando ATR-IR method to other compounds, they extended the study to polyanthraquinone (PAQ) and polyaniline (PANI) electroactive compounds. Furthermore, interpretation of experimental ATR-IR spectra is supported by quantum mechanical calculation based on density functional theory (DFT), which allowed the assignment of bands. Figures 2c and 3a show ATR-IR spectra of the PAQS cathode during galvanostatic cycling (discharge and charge) in the region from 1800 to 1500 cm–1. Figure 3a identifies regions of the spectra associated with the following molecular features: C=O, -C=C- and -C=O-. Page 6 of the paper teaches that the system used an operando ATR-FTIR cell. On the same page, in the IR characterization paragraph, it is taught that the ATR-IR measurements were performed on a Bruker IFS-66/2 with a liquid nitrogen cooled mercury cadmium telluride (MCT) detector.
In the paper Heo described remote fiber-optic chemical sensing using evanescent-wave interactions in chalcogenide glass fibers. An infrared-transmitting chalcogenide fiber was used as an optical probe to analyze qualitatively and quantitatively various chemical substances in aqueous solutions. An unclad fiber with 380-µm diameter was combined with a Fourier transform infrared spectrometer to monitor the concentration of the analytes in solutions by measuring the changes in the absorbance of their fundamental vibration peaks. A linear relationship was observed between the absorption by the evanescent field and concentrations of various analytes. For this study low concentrations of acetone, ethyl alcohol, and sulfuric acid were detected in aqueous solutions. The minimum detection limit for these three chemical substances was 5, 3, and 2 vol. %, respectively, with a sensor length of 15 cm. It was also demonstrated that the same sensor design is capable of monitoring gaseous species such as dichlorodifluoromethane. The first three paragraphs of the paper teach that the use of optical fibers for remote monitoring of various chemical substances has received considerable interest over the decade prior to the paper. Optical methods can provide in situ, continuous, and real-time analyses of hostile and hazardous manufacturing processes in which the sampling is extremely important and difficult. Some of the potential applications include monitoring of environmental pollutants, detection of explosive and flammable gases in mines and other industrial sites, and the measurement of blood gases, pH, and a number of other parameters in the human body. Remote monitoring can also be cost effective with multiple sensing units being controlled by one central analytical instrument through proper multiplexing and switching. Traditionally, high-silica fiber optics have been used for remote spectroscopy because they are reliable and relatively inexpensive and the component technology for compatible sources, detectors, and couplers is advanced. For example one paper measured direct absorptions of the combination (n2 + 2n3 at 1.33 µm) and overtone (2n3 at 1.66 µm) bands from CH4 molecules using an InGaAsP light-emitting diode and a Ge detector. The lowest detection limit remotely measured at 1.33 µm with a 2-km-long low-loss silica fiber was ~2000 parts in 106, which is 4% of the lower explosion limit of CH4 in air. They further proved that the 2n3 band at 1.66 µm can provide an improved detection sensitivity as low as ~400 parts in 106, that is, 0.8% of the lower explosion limit. They also suggested that their sensor design consisting of a near-IR high-radiant light-emitting diode in combination with a low-loss silica fiber and a 50-cm sample cell is capable of measuring not only CH4 gas but a large number of petrochemical substances, such as C2H6, C3H8, and C4H10. The substitution of silica fibers with IR-transmitting fibers can offer a much broader wavelength region for remote spectroscopy. For instance, the transmission window of the silica fiber is limited only up to 3 µm to the IR side, whereas those of fluoride and chalcogenide glasses extend up to 7 and 12 µm, respectively. In addition, certain crystalline materials, such as alkali halides, can also exhibit low optical loss within the mid-IR region. The extended IR transparency provided by various glass and crystalline fibers offers a good opportunity to detect the strong fundamental vibration absorption instead of weaker overtone or combination absorption bands. Therefore a much improved sensitivity can be expected from the incorporation of IR fibers into the detection schemes of sensor design. The paragraph bridging pages 3944-3945 teaches that chalcogenide fibers were used in a prior paper to detect the presence of liquid 2-butanone as well as to monitor the curing reaction in composite materials, using the evanescent wave phenomenon. The first full paragraph on page 3945 teaches that in that study, fibers were also combined with the FTIR spectrometer, and the feasibility of using chalcogenide fibers to monitor the progressive changes of starting materials to the final products during the curing process was demonstrated. Figure 1 shows the experimental arrangement of the FTIR-chalcogenide fiber sensing system with its HgCdTe detector. This paper is aimed at demonstrating the capabilities of chalcogenide glass fibers as sensor materials for quantitative analysis of various liquids and gases. Chalcogenide glasses are unique amorphous materials that show high transparency in the 6-12-µm region. Therefore they are one of the most promising sensor materials for monitoring any chemical substances that exhibit their fundamental absorption in the mid-IR. Further, chalcogenide glasses, contrary to the other IR fibers, generally show good durability against water, various acids, and some solvents and, therefore, can be immersed directly into these solutions to record the evanescent-wave spectra without being damaged. The chemical substances selected for this study were acetone, ethyl alcohol, and sulfuric acid, which are important industrial chemicals known to pose certain environmental threats. All these substances have their fundamental vibrations located in the 6-12-µm wavelength region and, therefore, their concentration in water can be measured with high sensitivity using chalcogenide glass fibers. The paragraph bridging the columns of page 3945 teaches that infrared spectra of solutions and gas were recorded with a spectrometer having a KBr beam splitter (see figure 1). The FTIR has been modified to emit a 2.5-cm-diameter collimated external beam of IR radiation. An off-axis parabola was used to redirect the beam 90° and launch it into an unclad chalcogenide fiber. Unclad fiber was chosen over the plastic-clad fiber because the evanescent wave is generally observed by the plastic especially in the mid-IR region. The fibers used for this study had a 380-µm diameter with the composition of Ge27Se18Te55 (at. %). The fibers had an attenuation loss of 1-5 dB/m in the wavelength region of 5-11 µm. Each end of the fiber was mounted upon an XYZ micropositioner to permit accurate adjustments for maximum energy throughput. Three sample cells with 5-, 10-, and 15-cm path lengths were used to investigate the effect of sensor length on the detection sensitivity. The middle section of the continuous chalcogenide fiber was encapsulated by the glass sample cells. The output signal at the other end of the fiber was focused onto a 1-mm2 HgCdTe detector. All the optics were reflective rather than transmissive to eliminate possible absorption or dispersion commonly encountered in the transmission optics of IR systems. Figures 2-3, 5-6, 8 and 10 show various spectra recorded with the fibers. Figure 4, 7 and 9 show calibration curves based on the recorded spectra.
In the paper Bureau discusses/teaches chalcogenide optical fibers for mid-infrared sensing. Chalcogenide glasses are a matchless material as far as mid-infrared (IR) applications are concerned. They transmit light typically from 2 to 12 μm and even as far as 20 μm depending on their composition, and numerous glass compositions can be designed for optical fibers. One of the most promising applications of these fibers consists in implementing fiber evanescent wave spectroscopy, which enables detection of the mid-IR signature of most biomolecules. The principles of fiber evanescent wave spectroscopy are recalled together with the benefit of using selenide glass to carry out this spectroscopy. Then, two large-scale studies in recent years in medicine and food safety are exposed. To conclude, the future strategy is presented. It focuses on the development of rare earth-doped fibers used as mid-IR sources on one hand and tellurium-based glasses to shift the limit of detection toward longer wavelength on the other hand. The introduction section on page 1 teaches that the glass-forming ability of systems rich in chalcogen elements has been known for several decades but compared with oxide glasses, especially silicates, this class of vitreous materials is just emerging from its infancy. Emerging technologies related to thermal imaging, as well as infrared (IR) sensors, have nucleated new projects involving IR transmitting materials including chalcogenide glasses. The main attention paid to these materials relies on their large optical window extending in the mid-IR and covering usually the two atmospheric windows ranging from 3 to 5 and 8 to 12 μm. This situation leads to fundamental vibrational modes shifted far in the IR, and rendering these glasses interesting for the fabrication of thermal-imaging systems. This exceptional transparency, associated to suitable viscosity/temperature dependence, creates a good opportunity for the development of optical fibers. The most exciting application for this fiber consists in implementing fiber evanescent wave spectroscopy (FEWS). Indeed, the optical sensors operating in the mid-IR region, where the main IR signatures of molecules and biomolecules are located, play an important role in the development of analytical techniques giving in situ information on metabolic patterns. Chemical detection using chalcogenide glass fibers was initially reported in the late 1980s with the characterization of butanone. Chemical analyses were then performed on acetone, ethanol, and sulfuric acid using Ge-Te-Se fibers. A wider range of organic species, including carcinogens such as benzene, toluene, and trichloroethylene, were later detected. In parallel, AgCl/AgBr polycrystalline fibers have also been developed as sensors. They possess the required optical quality and transmit light up to 20 μm in the IR spectral domain. However, polycrystalline fibers are very sensitive to air contamination, losing their properties of transparency. Moreover, they are obtained by extrusion methods, which are costly and difficult to implement. Last, their sensitivity is lowered due to their large diameter of about 1 mm. During the decade prior to the paper, new chalcogenide glasses transparent from the visible to the far IR domains have been developed in order to fabricate some optical fibers for IR sensing. Thus, numerous works have been carried out in different domains of application such as detection of pollutants in waste water, monitoring of chemical processes, detection of bacterial contamination in food, monitoring of bacterial biofilm spreading, and metabolic imaging of tumorous tissues and human biological fluids such as serum, plasma, or human cells. The aim of the paper was to give an overview of the work that had been carried out, demonstrating the potential of chalcogenide glass fibers for implementing mid-IR FEWS experiments. Section 2 on pages 1-2 teach that the advantage of the FEWS is to perform remote, real-time analyses in situ. The principle of this IR spectroscopy is based on the fact that the light propagating in the optical fiber provides an evanescent wave at the interface between the fiber and the surrounding area. If a chemical or biological species is in direct physical contact with the fiber and has absorption bands in the IR spectral region, then the evanescent waves will be partially absorbed at each reflection, leading to a reduction of the fiber transmission which can then be measured. The FEWS method is quite simple to implement, since the measurement necessitates only a standard spectrometer equipped with special kits to focus the light and an MCT detector cooled by liquid nitrogen. The beam, produced by a blackbody source, is focused at the input of the fiber by two off-axis parabolic mirrors coated with gold. At the output of the fiber, the signal is again focused by two parabolic mirrors on the sensitive part of the MCT detector. The absorbance spectrum A is obtained by using an equation. The critical point is to fabricate the optical fibers transmitting light in the mid-IR, which contains the signature of most chemical and biological molecules through the fundamental vibration modes of their functional groups. A large range of glass formulations are available to obtain suitable optical fibers with large IR transparency ranges and low energy losses. Among chalcogens, selenium is a good glass former, providing very stable glasses quite easy to shape. In particular, the Te2As3Se5 glass composition (TAS glass) is an interesting compromise with a Tg = 137 °C, which enables implementing experiments at room temperature. This glass offers a large spectral window, typically ranging from 2 to 16 μm for a bulk with a thickness of 1 mm. Moreover, this glass composition exhibits an excellent resistance to devitrification, thus permitting it to be shaped into an optical fiber. The attenuation curve of the fiber is given in figure 1. The minimum of attenuation is less than 1 dB/m and is located between 6.5 and 9 μm. This value is far from the one obtained with silica glass fiber, but the light transmission is sufficient for short distance applications such as remote spectroscopy. Overall, the fiber spectral window encompasses the mid-infrared domain, since transparency is observed from 800 to 4000 cm−1 on FEWS spectra. Several examples of biomedical diagnosis and food safety were given. In the paragraph bridging pages 4-5 of the paper Bureau teaches that although the pathogens detected in the food safety examples have the same biochemical constituents, namely proteins, polysaccharides, phospholipids, and nucleic acids, the biochemical diversity within these biochemical classes from one strain to another were sufficient to provide distinct FT-IR spectra for each pathogen. The most useful FT-IR features for bacterial identification appear at wavenumbers around 1000 to 3000 cm−1 and correspond to the deformation, bending, stretching, and ring vibrations of various functional groups. Also, the statistical analyses were performed on the regions 1000 to 1800 cm−1 and 2800 to 3000 cm−1, providing the greatest contribution to the total variance in the FT-IR spectral data. Thus there is evidence that points to the use of an FT-IR spectrometer with the optical fibers.
With respect to claim 1, it would have been obvious to one of ordinary skill in the art at the time the application was filed to exchange/replace the optical fibers of Ghannoum ‘17 with the chalcogenide fibers of Heo or Bureau because of the ability to sense mid-infrared signals in a quantitative manner as taught by at least Heo, the advantages of sensing direct absorption signals in the mid-infrared range compared to overtone signals in the near-infrared range as taught by at least Heo, the ability to form robust fibers capable of detecting various compounds in the midinfrared region as taught by Heo and Bureau, the use of chalcogenide fibers to sense molecules through evanescence of the region surrounding the fiber as taught by Heo and Bureau, the ability to sense compounds that are recognized as important to the functioning of batteries in the mid-infrared region as taught by Ellis and Vizintin and the desire to sense compounds providing information relative to the state of batteries with an optical fiber through the evanescent signal as taught by Ghannoum ’17. It would have been obvious to one of ordinary skill in the art at the time the application was filed to use the infrared source and detection structure of Heo or Bureau in the Ghannoum ’17 method because of the ability to record spectra over a range of wavelengths required to detect/quantify compounds in the mid-infrared range as taught by at least Heo. With respect to claim 2, Ghannoum ’17 cycles the batteries while detecting the infrared signal. Ellis and Vizintin also cycle the batteries so that it would have been obvious to continue to perform that task with the modified Ghannoum ’17 method because of the reasons given above for claim 1 and because Ellis and Vizintin clearly show that there are mid-infrared detectable compounds for which the mid-infrared signal changes when cycling the battery that are relevant to the state of the battery. With respect to claim 3, Heo and Bureau show that spectra can be acquired with the chalcogenide fibers and Ellis and Vizintin show that infrared spectra related to battery status can be acquired from internal reflection devices in contact with the battery components so that claim 3 would have been obvious for the reasons given above for claim 1. With respect to claim 4 at least Heo and Vizintin show that the chalcogenide fibers can be used to quantitate components through their spectra so that claim 4 would have been obvious for the reasons given above for claim 1. With respect to claim 5, at least Ellis shows that the infrared spectral peaks can be associated with compounds within the battery that are relevant to the state of the battery so that claim 5 would have been obvious for the reasons given above for claim 1. With respect to claim 6, at least Heo shows that a calibration curve associating a quantity of at least one predetermined chemical species to the intensity of the optical signal for a particular wavelength, so that claim 6 would have been obvious for the reasons given above for claim 1. With respect to claims 7-9, at least the discussion of the machine learning aspect of Ellis shows a prior step of establishing a spectra database from spectra produced outside of the battery for quantitation purposes so that claims 7-9 would have been obvious for the reasons given above for claim 1. With respect to claims 10-11, figure 7 of Ghannoum ’17 shows the fiber embedded in the electrode (figure 7c) and inserted through the electrolyte (figure 7b). With respect to claim 13, at least Bureau teaches a chalcogenide optical fiber made from a material consisting essentially of a Te2As3Se5 glass composition (TAS glass), so that claim 13 would have been obvious for the reasons given above for claim 1. With respect to claim 14, Ghannoum ’17 teaches that the diameter of the optical fiber is between 100 and 400 μm (see paragraph bridging columns of page 41285, core of 105 μm). With respect to 15, both Heo and Bureau teach chalcogenide glass optical fibers that are transparent to electromagnetic radiation of wavenumber (wavelengths) between 2 and 12 μm, so that claim 15 would have been obvious for the reasons given above for claim 1. With respect to claim 16, figure 7c of Ghannoum ’17 shows the fiber embedded in the electrode which would constitute the optical fiber being covered with a coating made of the same material as an electrode of the battery cell. With respect to claim 20, as noted above the claim appears to include a scope that requires no coating or a coating so small that any inherent association of the electrode components with the optical fiber is within the claim scope so that the insertion of the Ghannoum ’17 optical fiber without a coating or the components(s) of the electrode associated therewith or coated thereon through the action resulting in the fiber being embedded in the electrode would meet the requirement of claim 20.
Claim 12 is rejected under pre-AIA 35 U.S.C. 103(a) as being unpatentable over Ghannoum ’17 in view of Ellis or Vizintim and Heo or Bureau as applied to claim 10 above, and further in view of Modrzynski (IEEE Sensors 2019). Ghannoum ’17 does not teach a first optical fiber embedded in an electrode of the battery cell and a second optical fiber inserted through the electrolyte of the battery cell.
In the paper Modrzynski teaches optical fiber measurements for cell state determination via simultaneous observation of both electrodes of a lithium-ion-battery. The integration of fiber optics is done using commercial electrodes set up in pouch configuration. This system extends the method, shown previously for the graphite anode. Lithium iron phosphate cathodes suffer from poor optical observability due to the addition of carbon black as conductive agent. Hence, carbon black is locally replaced by an electrochromic marker additive. Transmissions through integrated fibers were monitored during battery cycling and results show that the cell state of charge directly influences both transmission signals. Optical data can be utilized as a parameter independent of electrical measurements to estimate the state of charge. The first full paragraph on page 3 of the paper teaches that embedding a fiber into both electrodes will measurably interact with light that is transmitted through each fiber. Figure 2 shows the structure of the battery with embedded electrodes. The first full paragraph of the right column on page 3 of the paper teaches that to use the optical behavior of the cathode as a sensor, technical improvements are necessary. One aspect is the high cost of ITO. To mitigate this issue, the fiber can be coated with a thin layer of the LFP/ITO slurry before embedding it in the LFP/C slurry while maintaining the optical behavior. The second aspect is to avoid complex optical devices like a spectrometer. To this effect, a simple optical system based on multi-colored LEDs and a light sensor has been developed (see figure 5) that gave similar results. The final target is to use this optical system in combination with battery cell sensors based on an ultra-low power microcontroller. The conclusion on page 3 of the paper teaches that a new method was presented to determine the state of charge in a lithium ion battery pouch configuration via the simultaneous observation of the lithium iron phosphate and graphite electrodes with modified optical fibers. Indium tin oxide was used as electrochromic marker in the cathode material, which can be used to optically reveal the electrode state. The observed optical effects in anode and cathode correlate with the state of charge. In comparison, the fiber sensors in the two electrodes show a similar behavior as the transmission increases and decreases with the SOC. However, differences were also noted that indicate a different relaxation behavior. Because of cross-influences from pressure and temperature a simple calibration curve is not applicable. More sophisticated referencing using different wavelength and calibration methods during formation were under development for the sensor system. The results point toward novel optical battery cell state sensors, complementary to state-of-the-art electrical state estimation methods.
With respect to claim 12, it would have nee obvious to one of ordinary skill in the art at the time the application was filed to add a second optical fiber embedded in/inserted through a second component of the battery as taught by Modrzynski In the modified Ghannoum ’17 method because of the ability to simultaneously obtain complementary information regarding the state of the battery and/or its components as taught by Modrzynski.
Claims 18-19 and 21-22 are rejected under pre-AIA 35 U.S.C. 103(a) as being unpatentable over Ghannoum ’17 in view of Ellis or Vizintim and Heo or Bureau (all five documents as discussed above) and further in view of Klein (US 2017/0303830). With respect to claim 18, Ghannoum ’17 teaches a characterization device for identifying the chemical species within a battery cell, comprising: an optical fiber inserted through the battery cell (see at least figure 3), an electrical power source for charging and discharging the battery (see at least the paragraph bridging pages 41285-41286, batteries are cycled using an eight-channel battery analyzer), an optical signal generator generating, while cycling the battery, an optical signal through the optical fiber, a detector detecting the optical signal transmitted through the optical fiber at an output extremity of the optical fiber (see at least the paragraph bridging pages 41285-41286, the optical signal is recorded using a custom optical sensor interrogator with a narrow-band light-emitting diode concentrated at 850 nm connected to a computer). While the light emitting diode is in the near infrared and a computer would have some form of processor and memory, Ghannoum ’17 does not teach that the optical fiber is made of chalcogenide glass, that the optical signal generator is an infrared optical signal generator with wavelengths other than the narrow band around 850 nm, that the computer memory is used for recording the detected optical signal, or that the computer processor is used for locating signature wavelengths for which the optical signal intensity is above a predetermined threshold within the spectrum and associating said located signature wavelengths to at least one predetermined chemical species.
With respect to claim 18, it would have been obvious to one of ordinary skill in the art at the time the application was filed to exchange/replace the optical fibers of Ghannoum ‘17 with the chalcogenide fibers of Heo or Bureau because of the ability to sense mid-infrared signals in a quantitative manner as taught by at least Heo, the advantages of sensing direct absorption signals in the mid-infrared range compared to overtone signals in the near-infrared range as taught by at least Heo, the ability to form robust fibers capable of detecting various compounds in the midinfrared region as taught by Heo and Bureau, the use of chalcogenide fibers to sense molecules through evanescence of the region surrounding the fiber as taught by Heo and Bureau, the ability to sense compounds that are recognized as important to the functioning of batteries in the mid-infrared region as taught by Ellis and Vizintin and the desire to sense compounds providing information relative to the state of batteries with an optical fiber through the evanescent signal as taught by Ghannoum ’17. It would have been obvious to one of ordinary skill in the art at the time the application was filed to use the infrared source and detection structure of Heo or Bureau in the Ghannoum ’17 method because of the ability to record spectra over a range of wavelengths required to detect/quantify compounds in the mid-infrared range as taught by at least Heo and the showing that such spectra include peaks that can be associated with and used to detect compounds that are important to determining the state of a battery during charging and discharging the battery as taught by at least Ellis and Vizintin. With respect to claims 19 and 20, at least Heo (see at least figure 1 and the paragraph bridging the columns of page 3945), Bureau (see at least the paragraph bridging pages 4-5 of the paper), Vizintin (see at least the “ In operando ATR-FTIR cell” and “IR characterization” paragraphs on page 6 of the paper) and Ellis (see at least the title, abstract and “FTIR measurements” paragraph on page A256 of the paper) teach one or more of a Fourier transform infrared spectrometer for measurement of compounds using optical fibers or measuring compounds in a battery and a mercury cadmium telluride detector, so that modification of the system of Ghannoum ’17 by the teachings of these references would have show the obviousness of claims 19 and 21 for the reasons given above for claim 18.
With respect to a Fourier transform infrared spectrometer having memory and processor that would be used as required by claim 18, the Klein reference teaches systems, devices and methods for noninvasive analysis of tissue, by irradiating a surface of the tissue with infrared radiation such that an interaction of the radiation with a component of the tissue other than water in two spectral bands is substantially identical, measuring an intensity of the radiation that emerges from the tissue in each of the spectral bands, determining change in at least one of shape and intensity of signals received by the at least one radiation detector, calculating a relative absorption by the tissue of radiation in one of the first and second spectral bands relative to absorption by the tissue of radiation in the other of the first and second spectral bands, and determining concentration of a predetermined substance, in accordance with the calculated relative absorption and in accordance with determined change in the received signal. In particular figure 8 is a block diagram showing elements of a measurement unit. Paragraph [0209] describes figure 8 as a block diagram showing elements of a measurement unit. A measurement unit 300 (e.g., optical transmission and/or reflectance unit) may be used to measure signals of the body in order to determine concentration of predetermined substances (e.g., Propofol). The measurement unit 300 may include a central controller or processor 301 (e.g., such as controller 28 shown in figure 1A), at least one light source 302, and at least one light sensor 303. Paragraph [0210] teaches that the at least one light source 302 may be coupled to at least one optical element 306 (e.g., collimating lenses, filters, focusing lenses), and the at least one light sensor may be coupled to a spectrometer 307. Processor 301 may communicate (e.g., receive and/or send signals) with coupled elements (such as the light source and/or the light sensor) and analyze the received measurement data. Processor 301 may communicate (e.g., receive and/or send signals) with an external device using a communication module 308 (e.g., via Bluetooth). Paragraph [0211] teaches that measurements may be carried out with attenuated total reflection (ATR) spectroscopy using optical elements and/or sensors operated in the ATR regime in the range of 4000 cm-1 to 400 cm-1 (or 2.5 µm to 25 µm). In some embodiments, analysis of such measured data may be carried out with evanescent wave Fourier transform infrared (EW-FTIR) spectroscopy and/or FTIR-ATR spectroscopy. Paragraph [0212] teaches that as may be appreciated by someone with ordinary skill in the art, in the MIR range some fundamental molecular vibrations may occur as well as many of the first overtones and combinations thereof. The spectral bands in the MIR range tend to be sharp and may have high absorption. Since the bands are sharp, most small molecules may have distinctive spectral “fingerprints” that can be readily identified in mixtures (e.g., a mixture of Propofol and blood). Moreover, since individual peaks can often be associated with individual functional groups, it may be possible to detect changes in the spectrum of individual objects during the monitoring due to the corresponding specific reaction. Paragraph [0213] teaches that Fourier transform infrared (FTIR) spectroscopy is based on the interaction between the radiation and the sample, which absorbs the IR wavelengths causing transitions between vibrational energetic levels, and thus vibrational modes of different chemical bonds and/or molecules may be detected. Paragraph [0215] teaches that in some embodiments, the beam of radiation propagating in ATR may undergo total internal reflection at the interface of ATR-sample. Total internal reflection of the light at the interface between the two media of different refractive index (crystal-tissue) may therefore create an “evanescent wave” that penetrates into the medium of lower refractive index (or tissue). The intensity of evanescent waves may decay exponentially with distance from the interface at which they are formed. Such distance may be for example in the 1-25 µm range. Paragraph [0216] teaches that the evanescent wave may be attenuated in regions of the spectrum where the sample absorbs energy, and the attenuated energy may be passed back to the optical element. The radiation may then exit the optical element and impinge on a detector through optical waveguide and/or fiber. The detector may record the attenuated radiation, which may be transformed to generate a spectrum (e.g., an absorption spectra). Paragraph [0218] teaches that the sample under test may be placed in tight contact with the ATR element along the IR radiation pathway, between the source and the detector side. When the ATR element is in contact with the sample, the evanescent wave may be either partially or totally absorbed at specific absorption lines as determined by the biochemical composition of the sample. The total transmission through the ATR element and the sample may decrease at the absorption lines that correspond to molecular bonds in particular classes of bio-molecules. In some embodiments, a core silver halide fiber may be used as the ATR element, since the polycrystalline silver halide (e.g., AgClxBr1-x) fibers are useful for applications in the mid-IR. These fibers may have a wide transparency range (˜2-20 µm wavelength), they are non-toxic, flexible and may be insoluble in water. Paragraphs [0095]-[0097] describe a controller in communication with memory (and/or external processing device's memory). The memory may include one or more volatile or nonvolatile memory devices. The memory may be incorporated within reflection measurement unit, an external processing device, or elsewhere. The memory may be utilized to store, for example, programmed instructions for operation of the controller, data or parameters for use by the controller during operation, or results of operation of the controller. A controller and/or processor may communicate with a data storage device. The data storage device may include one or more fixed or removable nonvolatile data storage devices and may be incorporated within the reflection measurement unit, an external processing device, or elsewhere. For example, the data storage device may include a computer readable medium for storing program instructions for operation of processing unit of the controller or of an external processing device. The data storage device may be utilized to store data or parameters for use by the controller 28 during operation or results of operation of controller (e.g., detection of radiation). The data storage device may be used to store data that relates spectral absorption, transmission, or reflection characteristics of the tissue surface to one or more medical conditions. The data may be stored in the form of a database.
Based on Klein a typical Fourier transform infrared spectrometer would have included the memory and processor in a configuration that would allow the processor to function as required by claim 18
With respect to claim 22, page 10 lines 16-18 of the instant specification teach that a mercury-cadmium-telluride (MCT) detector cooled with liquid nitrogen has the spectral range required by claim 22. Thus the liquid nitrogen cooled mercury cadmium telluride (MCT) detector of the Vizintin reference should inherently meet the requirement of claim 22 so that modification of the system of Ghannoum '17 with the Fourier transform infrared spectrometer teaching of Vizintin in the "IR measurements" paragraph on page 6 of the paper would meet the requirements of claim 22 for the reasons given above for claim 18.
The prior art made of record and not relied upon is considered pertinent to applicant's disclosure. The additionally cited art is directed to various infrared detection devices, methods and the structures used to interface with and/or interrogate a sample.
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/ARLEN SODERQUIST/ Primary Examiner, Art Unit 1797
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