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Patent

Hybrid Anodes for Energy Storage Devices

This invention relates to a hybrid design of connected carbon-metal electrode for advanced Na and Li batteries. The invention covers the following: 1. A hybrid electrode made of connected carbon and metal electrode for Li and Na battery applications. The carbon can be intercalation carbon, high surface area carbon, or hard carbon. The carbon and the metal can be connected as speparate electrodes, or carbon coating on metal, or as mixed carbon-metal electrodes. 2. Li-S battery in which the anode is made of connected carbon-Li electrode. 3. Li-ion battery in which the anode is made of connected carbon-Li electrode. 4. Li-ion battery in which the anode is made of carbon-Si electrode. 5. Li-ion battery in which the anode is made of Carbon-metal electrode, and cathode is made of LiFePO4, LiMnPO4, mixed metal oxides, and mixed composites of the active materials, conductors and binders, or any combination of the cathdoe and anode materials. 6. Na-ion battery in which the anode is made of connected carbon-Na electrode. 7. Na-ion battery with carbon-Na anode, and any combination of the cathdoe and anode materials. 8. Li-air battery in which the anode is made of connected carbon-Li electrodes. 9. Other metal air battery in which the anode is made of connected carbon-metal electrodes. 10. Hybride capacitor-battery devices using connected active metal, active carbon as one of the electrode materials.

Patent

HYDROFLUOROCARBON (HFC)-BASED SAFE ELECTROLYTE FOR SECONDARY BATTERIES (iEdison No. 0685901-22-0118)

The present application relates to the technical field of secondary batteries and, specifically, relates to an electrolyte and lithium-related secondary batteries containing the electrolyte. The electrolyte of the present application comprises a lithium salt, organic solvent A and organic solvent B. The solvent A is hydrofluorocarbon (HFC) compounds and the chemical formula is CxHyFz, where x is from 4 to 10, Z:Y ratio is from 2:1 to 10:1. The solvent B is the common component used in state-of-art electrolyte in lithium-related battery technologies, like carbonates, esters or ethers. The molar ratio of the solvent A in the electrolyte ranges from 8 mol% to 80 mol%. The battery of the present application has high flash point, non-flammable and high capacity retention rate.

Patent

DIRECT RECYCLING AND CONVERTING CATHODE MATERIALS INTO HIGH-PERFORMANCE SINGLE CRYSTAL CATHODE MATERIALS (iEdison No. 0685901-22-0122)

A cost-effective approach is disclosed in this invention to converting recycled LiNixMnyCozO2 (referred to as NMC hereafter, x+y+z=1), regardless of the stoichiometry of Ni,Mn,Co and morphologies of different NMC used in various batteries, into high performance single crystal Ni-rich NMC such as LiNi0.8Mn0.1Co0.1O2 with simple heating process with Li2O (background IP: Cost effective synthesis of oxide materials for lithium ion batteries, US20220112094A1). The reported approach significantly simplifies the synthesis process of NMC by using recycled cathode materials which not only reduces manufacturing cost but supports a stable domestic supply chain. In addition, the different NMC cathodes recycled from various batteries are directly converted into single crystal Ni-rich NMC which is critical for large-scale deployment of Ni-rich NMC for current and future Li-based battery technologies. This invention is well aligned with the recent DOE FOA (DE-FOA-0002680) which focuses on battery recycling. Expedient filing of this invention will enable PNNL engagement with industry.

Patent

HIERARCHAL FRAMEWORK FOR INTEGRATING DISTRIBUTED ENERGY RESOURCES INTO DISTRIBUTION SYSTEMS

This paper focuses on developing a novel multi-layer market-based framework for effective coordination and control of a large number of distributed energy resources in distribution systems in order to more reliably manage the future U.S. electric power grid under the high penetration of renewable generation. The proposed framework provides a systematic view of the overall structure of the future distribution systems along with the underlying information flow, functional organization, and operational procedures. It is characterized by the features of being open, flexible and interoperable with the potential to support dynamic system configuration. Under the proposed framework, the energy consumption of various DERs is coordinated and controlled using market-based approaches in a hierarchical way. The real-time Volt/VAR control is simultaneously considered to complement the real power control in order to keep nodal voltages stable within acceptable ranges during real time. In addition, computational challenges associated with the proposed framework are also discussed with recommended practices.

Patent

SINGLE-REACTOR CONVERSION OF ETHANOL TO 1-/2-BUTENES

This invention relates to the single step conversion of ethanol (either aqueous or neat) to 1- and 2-butenes. 1-Butene itself a commodity chemical can be converted into polybutene, its main application is as a comonomer in the production of certain kinds of polyethylene, such as linear low-density polyethylene (LLDPE). 1-Butene has also been used as a precursor to polypropylene resins, butylene oxide, and butanone. Mixtures of 1-butene and 2-butene, as produced by the methods disclosed in this invention, can be oligomerized into gasoline, jet, and diesel fuels and/or into valuable fuel additives and lubricants. Currently, producing 1- and 2-butene from ethanol is performed by first dehydrating ethanol into ethylene and then ethylene can be dimerized into 1- and 2-butene in a second step. Here we disclose the methods for producing 1- and 2-butene mixtures directly from ethanol using specially tailored polyfunctional catalysts comprising metal component with relatively weak hydrogenation ability (e.g., Ag) with mildly acidic support materials (e.g., ZrO2 supported on SiO2). In previous work, including the filing of a separate patent, we demonstrated such catalytic materials to be active for converting ethanol into 1,3-butadiene in one reactor. In this disclosure we report these catalysts to be active and selective for converting ethanol to 1- and 2-butenes in one single reactor under mild reducing conditions (e.g., under H2, T = 325 degrees C, P = 7 bar). Furthermore, parameters such as H2 concentration, H2O concentration, space velocity and pressure were demonstrated to have significant effect on conversion, selectivity, and stability. H2-addition to the feed favors the formation of 1- and 2-butene at the expense of butadiene (see Table 1 in Slide 2 of the attached PPT file). For example, for a 4Ag/4ZrO2/SiO2 catalyst operating at 325 degrees C, P = 7 bar, WHSV= 0.23 hr-1, incremental addition of H2 to the feed gas from 0% to 100% (carrier gas content) leads to a decrease of conversion from 99 to 85% accompanied by an increase of the 1- and 2-butene combined selectivity from ~ 16 to 51%. Meanwhile the ethylene selectivity increases from ~ 8.6 to 26% while the butadiene selectivity decreases from 63.7% to 0%. Thus, in general 1- and 2-butene is formed at the expense of 1,3-butadiene when H2 content is added to the feed. We also demonstrated how catalytic stability is enhanced when H2 is added to N2 as the carrier gas for the process (see Slide 9 in the attached PPT summary). Thus, the addition of H2 (to the ethanol feed) not only alters the product distribution favoring a butene product slate but it also significantly suppresses coking resulting in enhanced catalytic stability. We also note that while H2 addition to the feed may add cost to the overall process, hydrogen is usually needed anyhow for fuels production as the final olefin product after oligomerization needs to be hydrotreated. Thus, the added hydrogen can be used in the latter hydrotreatment step and unconverted hydrogen can be recycled to the front end of the process. We further investigated process parameters that affect catalytic performance. For example, higher contact time favors the formation of 1- and 2-butenes (see Table 2 in Slide 3 of the attached PPT file). As shown in Table 2 decreasing the space velocity from 14.6 to 0.23 hr-1 while operating under H2 gas leads to an increase of the conversion from ~ 11 to 85% and an increase of both 1- and 2-butenes and ethylene selectivities from ~13 to 51% and ~15 to 26%, respectively. Meanwhile, both acetaldehyde and butyraldehyde selectivities decrease whereas butadiene selectivity remains negligible. This suggests that the mechanism for butene formation involves the conversion of acetaldehyde to crotyl alcohol, isomerization of crotyl alcohol to butyraldehyde, and butenes formation from butyraldehyde deoxygenation. The effect of operating pressure was also investigated and it was found that higher pressure favors the formation of butenes at the expense of butadiene (see Table 3 in Slide 4 in the attached PPT file). For example, increasing the pressure from atmospheric to 14 bar while operating under H2 gas leads to an increase of the conversion from 52 to 83% and an increase of the C4+ olefins selectivity from 8.1 to 44% while the selectivity toward butadiene and ethylene decreases from 43 to 0% and 22 to 7%, respectively. Addition of water to the feed also leads to a decrease of the conversion, from 94.0%, with 100 % ethanol as a feedstock, and to 76%, with 35% ethanol in H2O as a feedstock (see Table 4 in Slide 5 in the PPT file). The butenes selectivity is only slightly affected by the presence of water since it decreases from 58% to 55%. However, this demonstrates that diluted feeds of ethanol can be used as feedstock and separation of water and ethanol is not required prior to conversion. The product from the ethanol conversion contains primarily butenes and ethylene olefins mixed with H2. Thus, for purpose of producing fuels from the olefin precursors we also demonstrated feasibility for oligomerization by co-feeding ethylene and/or H2 with butene mixtures over zeolite catalysts. Oligomerization of butenes in the presence of H2 was found to be feasible (see Slide 6 in the attached file). Adding H2 to the feed leads to about 20% lower C8+ olefins production. Oligomerization of butenes + ethylene mixture was also investigated to determine the effect of ethylene on the oligomerization of butenes (see Slide 7 in the attached PPT file). Adding ethylene to the feed was also demonstrated to lead to higher paraffins/olefins ratio due to hydrogenation activity but does not affect the production of C8+ olefins since the same quantity of product was obtained w and w/o ethylene addition to the feed. Oligomerization of butenes in the presence of H2 and ethylene was also examined (see Slide 8 in the attached PPT file). The ratio paraffins/olefins is equal to about 0.4 in the presence of H2 + ethylene as opposed to < 0.5 without H 2 + ethylene indicating a significant hydrogenation activity. The quantity of C 8 + olefins produced is about 10% higher in the presence of H 2 and ethylene and is likely due to ethylene oligomerization to C 8 + product occurring in the meantime as butenes oligomerization. Thus, we demonstrate that oligomerization of 1-butene is feasible in the presence of H 2 and/or ethylene co-feed. We also note that in separate experiments (not shown) we show the product distribution for 2-butene oligomerization to be very similar to that of 1-butene. Thus, a feed containing mixtures and 1- and 2-butene would produce a similar product distribution.

Patent

Forward-looking transactive pricing schemes for use in a market-based resource allocation system

Disclosed herein are representative embodiments of methods, apparatus, and systems for distributing a resource (such as electricity) using a resource allocation system. One of the disclosed embodiments is a method for generating a bid value for purchasing electricity in a market-based resource allocation system. In this embodiment, a desired performance value indicative of a user's desired performance level for an electrical device is received. Price information from an electricity futures market is received. A bid value for purchasing electricity from a local resource allocation market sufficient to operate the electrical device at the desired performance level is computed. In this embodiment, the computing is performed based at least in part on the desired performance value and based at least in part on the price information from the electricity futures market.

Patent

Deoxygenation of fatty acids for preparation of hydrocarbons

Embodiments of methods for making renewable diesel by deoxygenating (decarboxylating/decarbonylating/dehydrating) fatty acids to produce hydrocarbons are disclosed. Fatty acids are exposed to a catalyst selected from a) Pt and MO3 on ZrO2 (M is W, Mo, or a combination thereof), or b) Pt/Ge or Pt/Sn on carbon, and the catalyst decarboxylates at least 10% of the fatty acids. In particular embodiments, the catalyst consists essentially of 0.7 wt % Pt and 12 wt % WO3, relative to a mass of catalyst, or the catalyst consists essentially of a) 5 wt % Pt and b) 0.5 wt % Ge or 0.5 wt % Sn, relative to a mass of catalyst. Deoxygenation is performed without added hydrogen and at less than 100 psi. Disclosed embodiments of the catalysts deoxygenate at least 10% of fatty acids in a fatty acid feed, and remain capable of deoxygenating fatty acids for at least 200 minutes to more than 350 hours.).

Patent

DISTRIBUTED HIERARCHICAL CONTROL ARCHITECTURE FOR INTEGRATING SMART GRID ASSETS DURING NORMAL AND DISRUPTED OPERATIONS

Disclosed herein are representative embodiments of methods, apparatus, and systems for facilitating operation and control of a resource distribution system (such as a power grid). Among the disclosed embodiments is a distributed hierarchical control architecture (DHCA) that enables smart grid assets to effectively contribute to grid operations in a controllable manner, while helping to ensure system stability and equitably rewarding their contribution. Embodiments of the disclosed architecture can help unify the dispatch of these resources to provide both market-based and balancing services.

Patent

CONTROL FOR ENERGY RESOURCES IN A MICROGRID

This concept uses a slider setting for microgrid operations that allows a user to select between "more efficient" and "more resilient". This is similar to the slider setting concept for transactive control, except that they are influencing different technical values. As the slider is set to more efficient, the dispatch and droop values of the generators are adjusted to increase the operating efficiency of the system. This is achieved by moving the operating points of the generators to their most efficient points while still meeting the current load. As the slider is set to more resilient, the dispatch and droop values of the generators are adjusted to minimize the frequency deviation from an expected increase in load or loss of generation. The value of the slider setting could be set by a human operator, or determined as part of a more complex control system. For example, the slider value could be determined as the output of a neural network that is optimization the operation of multiple networked microgrids. In its current state the work is using a modified version of the IEEE-123 node test system with 2 diesel generators and 1 PV inverter. As the slider setting is varied the control system determines the set points for both diesel generators and the PV inverter. The values for each generator include their power outputs and their current droop values for controls. The result is that the single slider setting determines multiple set points on multiple generators. The method is scalable, but the optimization becomes computationally burdensome with large number of generators. This should not be an issue with most operational microgrids.

Patent

COORDINATED VOLTAGE CONTROL AND REACTIVE POWER REGULATION BETWEEN TREANSMISSION AND DISTRIBUTION SYSTEMS (iEdison No. 0685901-18-0021, reporting done by North Carolina State University, 0578204-19-0014)

The invention is a new approach for coordinating volt-var control (VVC) between sub-transmission and distribution systems through optimal reactive power dispatch of distributed energy resources (DERs) that are aggregated as virtual power plants (VPPs). At the sub-transmission level, shunt devices and the reactive power provided by the VPPs are coordinated and optimised using VVC algorithm with weighted sum of multiple objects that include minimising voltage deviations from desirable levels at load buses, minimising loses, minimising solar curtailment, minimising demand response (DR) usage and minimising mechanical switching of shunt elements. The algorithm runs every five minutes and is solved using the AC optimal power flow technique. At the distribution level, each VPP runs a distribution VVC algorithm to dispatch reactive power from DERs. The goal of the VPP reactive power control is to meet sub-transmission service requirements while satisfying all the constraints at distribution side. Each VPP updates its reactive power capability every five minutes to allow the sub-transmission controller to formulate the optimisation problem for the next dispatch interval. The proposed tool is simulated on a Duke Energy Carolina system to demonstrate the capability of providing voltage support by dispatching reactive power of DERs as a VPP.

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