Jellyfish-derived graphene structure, methods of preparing same and uses thereof
By using laser-irradiated jellyfish biomass to create a 3D porous graphene structure integrated with silicon nanoparticles, the method addresses the limitations of current lithium-ion battery anodes, achieving improved performance and sustainability.
Patent Information
- Application Number
- PCT/IL2024/050917
- Authority / Receiving Office
- WO · WO
- Patent Type
- Applications
- Current Assignee / Owner
- Priority Date
- 2023-09-11
- Filing Date
- 2024-09-11
- Publication Date
- 2025-03-20
AI Technical Summary
Current lithium-ion batteries face challenges with graphite anodes due to limited theoretical gravimetric capacity, high cost, and supply shortages, while silicon anodes suffer from severe volume changes leading to performance degradation.
A method of preparing a 3D porous graphene structure using jellyfish biomass as a carbonaceous material, combined with silicon nanoparticles, through laser irradiation to form a conductive composite suitable for use as electrodes in lithium-ion batteries.
The jellyfish-derived graphene structure enhances the cyclic stability, capacity retention, and rate performance of lithium-ion batteries, offering a sustainable and cost-effective alternative to traditional anode materials.
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Figure IL2024050917_20032025_PF_FP_ABST
Abstract
Description
[0001] JELLYFISH-DERIVED GRAPHENE STRUCTURE, METHODS OF PREPARING SAME AND USES THEREOF
[0002] RELATED APPLICATION / S
[0003] This application claims the benefit of priority of U.S. Provisional Patent Application Nos. 63 / 537,648 and 63 / 537,645 filed on September 11, 2023, the contents of which are incorporated herein by reference in their entirety.
[0004] This application also relates to co-filed PCT International Patent Application having Attorney’s Docket No. 101007 and entitled “GRAPHENE-SILICON COMPOSITE STRUCTURES, METHODS OF PREPARING SAME AND USES THEREOF”, which claims priority from U.S. Provisional Patent Application Nos. 63 / 537,648 and 63 / 537,645 filed on September 11, 2023.
[0005] FIELD AND BACKGROUND OF THE INVENTION
[0006] The present invention, in some embodiments thereof, relates to material science, and more particularly, but not exclusively, to jellyfish-derived graphene structures, to methods of preparing same and to uses thereof, for example, as electrodes in alkali metal ion batteries.
[0007] Increasing technological demands, rising inflation, and global ecological crises of the modern era pose challenges that require extensive research dedicated to improving energy-storage technology using high-performance, economically viable, and sustainable materials.
[0008] Lithium-ion batteries (LIBs) have emerged as the primary choice for powering a wide range of applications since their commercialization in 1991. These batteries operate by moving lithium ions between the anode and cathode during charging and discharging cycles. During charging, lithium ions are extracted from the cathode and intercalated into the anode in a process known as lithiation. Upon discharge, the reverse process, delithiation, occurs as lithium ions migrate back to the cathode, releasing energy that powers the device. A critical aspect of this operation is the formation of the solid electrolyte interphase (SEI), a passivation layer that forms on the anode surface from the decomposition products of the electrolyte. The SEI selectively allows lithium ions to pass through while blocking electrons, thereby preventing further electrolyte decomposition and ensuring the stability of electrochemical reactions. The quality of the SEI is essential for maintaining the battery's cyclability, rate capacity, and safety, making it a key factor in determining the overall performance, energy density, and cycle life of lithium-ion batteries.
[0009] Presently, lithium-ion batteries (LIBs) are widely regarded as the leading field in energy- storage technology due to their relatively long life cycle and high energy density.
[0010] The typical anode in lithium-ion batteries is made of graphite, owing to its stability and low intercalation potential. However, graphite has a theoretical gravimetric capacity of only 372 mAh / g, which is not sufficient to meet the growing demand for higher-energy-density devices. Moreover, the cost of graphite is relatively high (from $2,000 to $5,000 per ton), which can significantly increase the cost of manufacturing. Additionally, the high demand for graphite in other industries, such as the steel industry, can cause supply shortages and price fluctuations, stirring further instabilities. Thus, global motivation has been fueled to explore alternatives for carbon as an anode material which does not suffer from the same shortcomings [a review by Claro et al. Appl. Phys. Rev. 9, 041305 (2022)].
[0011] Silicon has emerged as a highly promising anode material due to several advantages over carbon as an anode material for Lithium-ion batteries. Silicon has a higher theoretical specific capacity than carbon (>3579 mAh / g), which means that it can store significantly more lithium ions per gram of material. This enables higher energy densities and longer run times for the batteries. Further, silicon is extremely abundant and relatively inexpensive, making it an attractive alternative to other high- capacity anode materials.
[0012] However, some detrimental limitations have hindered the integration and commercialization of silicon anodes: silicon anodes undergo severe volume changes, which can reach about 400 %, during the delithiation and lithiation processes that occur during operation of the Lithium-ion battery, which result in the pulverization of the active material, low coulombic efficiencies, uncontrolled growth of the solid electrolyte interface (SEI), and the loss of contact between the components and the current collector. See, for example, Chen et al. [Adv Mater. (2022) 34(21), 2200894], teaching graphite carbon-containing composite silicon nanodots (NDs) / MOF anode for lithium-ion batteries. Obrovac and Christensen [Electrochem. Solid-State Lett. 7, (2004)] teach the structural changes in silicon electrochemically lithiated and de-lithiated at room temperature, and show that crystalline silicon becomes amorphous during lithium insertion, and that highly lithiated amorphous silicon suddenly crystallizes at 50 mV to form a lithium silicide phase (containing, e.g., Li 15S 14 )- They also demonstrate that cycling silicon anodes above 50 mV avoids the formation of crystallized phases completely, resulting in better cycling performance. For commercial lithium ion batteries, most electrode syntheses employed today are energy- intensive, multiple-steps, complex, and additives-heavy. Some non-environmentally remediating silicon-carbon composites were previously used in lithium-ion batteries. The sustainability of the carbon sources and their electrochemical performances are summarized in Table 1 herein.
[0013] Table 1
[0014] *1-11 refer to the following background art documents: (1) Shin et al. ACS Sustain. Chem. Eng. 8, 14150-14158 (2020); (2) Parekh et al. Advanced Energy Materials 1902799, 1-12 (2020); (3) Chen et al. Adv Mater. 34(21), 2200894 (2022) (4) Wang et al. Energy Storage Mater. 24, 312-318 (2020); (5) Wang et al. Carbon N. Y. 192, 277-284 (2022); (6) Pei et al. Carbon N Y 203, 436-444
[0015] (2023) (7) Liu et al. ACS Appl. Mater. Interfaces (2022); (8) Liu et al. Energy Storage Mater. 19, 299- 305 (2019); (9) Wang et al. Small 20, (2024); (10) Kim et al. Carbon N Y210, (2023); and (11) Zhang et al. Small 19, (2023).
[0016] Current methods for conversion of bio-materials to conductive carbon for functional applications make extensive use of energy-intensive methods for inducing carbonization. Employment of such methods are fundamentally counter-productive to the overarching objective of developing a fully sustainable approach to energy-storage applications, spanning from the origin of the carbonaceous material to the ultimate stages of product refinement. Carbonaceous matrices, including graphene, graphene nanosheets (GNs), and reduced graphene oxide (rGO), have been pursued as additives in silicon-based composite anodes of Lithium- ion batteries. These materials possess desirable chemical and physical properties, such as excellent mechanical flexibility, chemical stability, and electronic conductivity, which ultimately have shown partial success in overcoming the inherent challenges of Si-based anodes in Lithium-ion batteries [Minami et al. Nano Sei. 3, 1192-1200 (2022)].
[0017] Popular approaches to form these carbonaceous matrices rely on techniques such as chemical vapor deposition (CVD), mechanical peeling of bulk graphite, and reduction of graphene oxide. However, these methodologies are limited by insufficient suitability for bulk production, and by the extreme conditions (e.g., very high operating temperatures) and hazardous chemicals involved in the lengthy preparation processes [a review by Duo et al. Electrochem. Energy Rev. 2, 149-198 (2019); a review by Shen et al. J. Energy Chem. 2018, 27, 1067-1090].
[0018] Laser irradiation can induce transformation of polyimide substrates to free-standing graphene in what is called Laser-Induced Graphene (LIG). Under ambient conditions, typically using a pulsed or continuous UV or CO2 laser of varying wavelengths (400 nm-10.6 μm), a highly disordered graphene -based substance can be created from different carbonaceous sources such as polyimide, PEEK22, and phenolic resins [Lin et al. Nat. Commun. 2014, 5, 5714; Stanford et al. ACS Appl Mater Interfaces. 2020, 12(9), 10902-10907; Zhang et al. Carbon, 2018, 127, 287-296; a review by Guo et al. Nanomaterials 2022, 72(14), 2336; a review by Scardaci, V. Appl. Sci. 2021, 11, 6304; Le et al. Adv. Funct. Mater. 2205158, 1-39 (2022)]. Carbon-containing molecules of such structures can be rearranged into the coveted hexagonal lattice by the high temperature and pressure conditions caused by localized laser irradiation, while excess material inherent to the precursor is released as gaseous by- products. This results in a highly porous network of interconnected LIG-domains [a review by Alhajji et al. Energy Technol. 2021, 9, 1-15].
[0019] Minami et al. teach the formation of Si@C and SiC@C core-shell nanoparticles, which can be used as anode materials for lithium ion batteries, via pulsed laser irradiation-induced propagation of a tablet comprising a mixture of graphite and waste Si powders.
[0020] Jellyfish biomass should be overwhelmingly abundant for the foreseeable future, with a study conducted across multiple marine ecosystems concluding that in a majority of the world jellyfish populations are rapidly increasing due to anthropogenic causes. Rising ocean temperatures caused by global climate change along with a plethora of human activities such as overfishing and cultural eutrophication have induced large-scale ecosystem changes that were directly linked to increasing jellyfish reproduction rates and life cycles.
[0021] This global jellyfish “invasion” is also having severe direct ecological impacts, with surging populations of jellyfish species causing massive disruptions in natural food webs and fluctuations in aquatic species populations globally, with several studies estimating that millions of tons of jellyfish are overtaking native fish populations in Namibia and the Barents Sea alone. Economic consequences caused by unmitigated jellyfish population growth are no less ubiquitous. For example, several studies have concluded that jellyfish overtaking fish populations and clogging nets has resulted in extraordinary revenue losses for fisheries, estimated at over 1 billion USD in countries like Turkey, Iran and Korea.
[0022] Coastal tourism economies have also been severely affected, with several estimates of millions of dollars in revenue loss due to negative publicity related to jellyfish. The city of Cannes removed almost 11 million tons of jellyfish from its beaches and spent close to 50,000 USD on floaters and netting to make two of its most popular beaches jellyfish-free areas the size of Olympic swimming pools. Additionally, jellyfish frequently clogging seawater intakes of power and desalination plants have led to increased maintenance costs and temporary shutdowns.
[0023] Jellyfish population increases and their consequences have created an incredible economic and ecological incentive for finding widespread use of jellyfish biomass in commercial applications, hoping that the “trash” of the present becomes the treasure of the future. A global jellyfish biomass of approximately half a billion tons of carbon (0.46 PgC) is estimated, with an overwhelming majority readily available as an untapped sustainable resource [Wright et al. Biogeosciences 18, 1291-1320 (2021)]. This estimate surpasses by far the global estimated reserves of graphite without any of the added geopolitical issues associated today with graphite production.
[0024] Presently, the global market for raw jellyfish is mostly attributed to the Asian food industry, accounting for several hundred thousand metric tons harvested annually with a small market size of about 100 million USD. Alternative uses for jellyfish biomass as a sustainable resource in biotechnological and biomedical applications have been explored; however, these studies were relegated to relatively small potential markets with minimal impact on the global issues that jellyfish population growth has created.
[0025] Additional background art includes Daffan et al. ChemRxiv, 1 (2024); Daffan et al. Journal of Energy Chemistry, 97, 553-565 (2024); Kothuru et al. Carbon Energy, 6(7), e507 (2024); and Daffan et al. Advanced Energy Materials, 2401832 (2024). SUMMARY OF THE INVENTION
[0026] According to an aspect of some embodiments of the present invention there is provided a method of preparing an electrochemically active component, the method comprising depositing a mixture that comprises a carbonaceous material and an electrochemically active material on a conductive substrate, to thereby to thereby obtain the conductive substrate having the mixture deposited on at least a portion of a surface thereof; and exposing the conductive substrate having the mixture deposited thereon to laser irradiation, to thereby form a 3D porous structure deposited onto the at least a portion of the surface of the conductive substrate, the 3D porous structure comprising a 3D porous graphene matrix having the electrochemically active material dispersed and / or entrapped and / or embedded therewithin, wherein the carbonaceous material comprises a jellyfish biomass.
[0027] According to some of any of the embodiments described herein, the jellyfish biomass is prepared by homogenizing a jellyfish or a part thereof.
[0028] According to some of any of the embodiments described herein, the mixture further comprises a carrier.
[0029] According to some of any of the embodiments described herein, the mixture comprises a paste, a powder or particles of the jellyfish biomass dispersed in or mixed with the carrier.
[0030] According to some of any of the embodiments described herein, the electrochemically active material is in a form of particles.
[0031] According to some of any of the embodiments described herein, the particles have an average diameter in a range of from 1 to 300 nm, or from 1 to 200 nm.
[0032] According to some of any of the embodiments described herein, the electrochemically active material comprises silicon.
[0033] According to some of any of the embodiments described herein, a weight ratio of the carbonaceous material and the electrochemically active material ranges from 10: 1 to 1: 10, or from 10:1 to 1: 1.
[0034] According to some of any of the embodiments described herein, the carbonaceous material further comprises at least one additional carbonaceous material (e.g., which capable of forming graphene when exposed to laser irradiation).
[0035] According to some of any of the embodiments described herein, the mixture further comprises a flame retardant. According to some of any of the embodiments described herein, an amount of the flame retardant is up to 10 %, or ranges from 0.1 to 10, %, by weight of the total weight of the mixture.
[0036] According to some of any of the embodiments described herein, the flame retardant is or comprises boric acid.
[0037] According to some of any of the embodiments described herein, the depositing is effected by spin coating.
[0038] According to some of any of the embodiments described herein, the exposing is of at least one layer of the mixture, and wherein a thickness of the layer is no more than 10 micrometers or ranges from 2 to 10, micrometers.
[0039] According to some of any of the embodiments described herein, the exposing comprises laser rastering.
[0040] According to some of any of the embodiments described herein, the exposing comprises irradiating the deposited mixture with a continuous visible laser irradiation (e.g., 450 nm).
[0041] According to some of any of the embodiments described herein, a spot size diameter of the laser irradiation is in a range of from 5 to 20, or is about 10, μm.
[0042] According to some of any of the embodiments described herein, a speed of the laser irradiation is in a range of from 1 to 40, or is about 20, mm / s.
[0043] According to some of any of the embodiments described herein, a hatch spacing of the laser irradiation is in a range of from 0.01 to 0.5, or is about 0.1, mm.
[0044] According to some of any of the embodiments described herein, the laser irradiation has a power in a range of from 2.0 to 3.5, or is about 2.8, W.
[0045] According to some of any of the embodiments described herein, the conductive substrate is a current collector.
[0046] According to some of any of the embodiments described herein, the substrate comprises stainless steel.
[0047] According to some of any of the embodiments described herein, the conductive substrate comprises copper (e.g., is a current collector is a form of a copper foil).
[0048] According to some of any of the embodiments described herein, the conductive substrate having the porous structure deposited therein forms or comprises an electrode.
[0049] According to some of any of the embodiments described herein, the electrochemically active component is or comprises an electrode. According to some of any of the embodiments described herein, the electrode is usable as an anode in a lithium-ion battery.
[0050] According to an aspect of some embodiments of the present invention there is provided an electrochemically active component obtained by the method as described herein in any of the respective embodiments and any combination thereof.
[0051] According to an aspect of some embodiments of the present invention there is provided an electrochemically active component comprising a 3D porous structure which comprises a 3D porous graphene matrix having the electrochemically active material dispersed and / or entrapped and / or embedded therewithin, wherein the graphene matrix is formed of a carbonaceous material that comprises a jellyfish biomass.
[0052] According to some of any of the embodiments described herein, the 3D porous graphene matrix is in a form of a continuous porous matrix (e.g., a continuous film).
[0053] According to some of any of the embodiments described herein, the 3D porous graphene matrix features at least one of: an average pore diameter in a range of from 2 to 20, or about 7, micrometers; and an overall porosity of at least 30, or at least 40, or at least 45, or about 49, %.
[0054] According to some of any of the embodiments described herein, an amount of the electrochemically active material in the 3D porous structure ranges from 10 to 90, or from 15 to 70, % by weight of the total weight of the 3D porous structure.
[0055] According to some of any of the embodiments described herein, an amount of carbon in the 3D porous structure ranges from 10 to 70, or from 30 to 60, % by weight of the total weight of the 3D porous structure.
[0056] According to some of any of the embodiments described herein, an amount of oxygen in the 3D porous structure is at least 1 or at least 5 or ranges from 1 to 50, or from 5 to 20, % by weight of the total weight of the 3D porous structure.
[0057] According to some of any of the embodiments described herein, an amount of nitrogen in the 3D porous structure is at least 0.1 or at least 0.5 or ranges from 0.1 to 50, or from 0.5 to 5, or from 0.8 to 2, % by weight of the total weight of the 3D porous structure.
[0058] According to some of any of the embodiments described herein, an amount of boron in the 3D porous structure is at least 0.01 or at least 0.1 or ranges from 0.01 to 30, or from 0.1 to 10, % by weight of the total weight of the 3D porous structure. According to some of any of the embodiments described herein, the 3D porous structure is characterized by one or more of: an amount of oxygen relative to a total amount of oxygen and carbon in the 3D porous structure (% weight of oxygen / % weight of oxygen + % weight of carbon) is at least 5, or at least 10, or at least 15, or ranges from 5 to 40, or from 10 to 30; and / or an atomic amount of oxygen relative to a total atomic amount of oxygen and carbon in the JF- derived (e.g., 3D porous) structure (graphene matrix) (% atomic of oxygen / % atomic of oxygen + % atomic of carbon) is at least 5, or at least 10, or ranges from 5 to 40, or from 10 to 25; and / or an amount of oxygen relative to a total amount of oxygen, nitrogen and carbon in the 3D porous structure (% weight of oxygen / % weight of oxygen + % weight of carbon + % weight of nitrogen) is at least 5, or at least 10, or at least 12, or ranges from 5 to 40, or from 12 to 30, %; and / or an atomic amount of oxygen relative to a total atomic amount of oxygen, nitrogen and carbon in the 3D porous structure (% atomic of oxygen / % atomic of oxygen + % atomic of carbon + % atomic of nitrogen) is at least 5, or at least 10, or ranges from 5 to 40, or from 10 to 30, or from 10 to 25, %; and / or an amount of nitrogen relative to a total amount of nitrogen and carbon in the 3D porous structure (% weight of nitrogen / % weight of nitrogen + % weight of carbon) is at least 0.5 or at least 1 or ranges from 0.5 to 20, or from 1 to 15, or from 2 to 10, or from 2 to 5, %; and / or an atomic amount of nitrogen relative to a total atomic amount of nitrogen and carbon in the 3D porous structure (% atomic of nitrogen / % atomic of nitrogen + % atomic of carbon) is at least 0.1, or at least 0.5, or at least 1, or ranges from 0.1 to 20, or from 0.5 to 15, or from 1 to 10, or from 1 to 5, %; and / or an amount of nitrogen relative to a total amount of oxygen, nitrogen and carbon in the 3D porous structure (% weight of nitrogen / % weight of oxygen + % weight of carbon + % weight of nitrogen) is at least 0.1, or at least 0.5, or at least 1, or ranges from 0.1 to 20, or from 0.5 to 15, or from 1 to 10, or from 1 to 5, %; and / or an atomic amount of nitrogen relative to a total atomic amount of oxygen, nitrogen and carbon in the 3D porous structure (% atomic of nitrogen / % atomic of oxygen + % atomic of carbon + % atomic of nitrogen) is at least 0.1, or at least 0.5, or at least 1, or ranges from 0.1 to 20, or from 0.5 to 15, or from 1 to 10, or from 1 to 5, %; and / or an amount of boron relative to the a amount of boron and carbon in the 3D porous structure (graphene matrix) (% weight of boron / % weight of boron + % weight of carbon) is at least 0.01, or ranges from 0.01 to 0.1, %; and / or an atomic amount of boron relative to a total atomic amount of boron and carbon in the 3D porous structure (% atomic of boron / % atomic of boron + % atomic of carbon) is at least 0.01, or ranges from 0.01 to 0.1, %.
[0059] According to some of any of the embodiments described herein, the electrochemically active component further comprises a conductive substrate, wherein the 3D porous structure is deposited onto at least a portion of a surface of the conductive substrate.
[0060] According to some of any of the embodiments described herein, the electrochemically active component is or comprised an electrode.
[0061] According to some of any of the embodiments described herein, the conductive substrate is a current collector.
[0062] According to an aspect of some embodiments of the present invention there is provided an electrochemical system comprising the electrochemically active component as described herein in any of the respective embodiments and any combination thereof.
[0063] According to some of any of the embodiments described herein, the electrochemical system is or forms a part of an alkali metal ion battery.
[0064] According to some of any of the embodiments described herein, the electrochemical system further comprises an alkali metal ion cathode.
[0065] According to some of any of the embodiments described herein, the alkali metal ion cathode is a lithium ion cathode selected from NMC (lithium nickel manganese cobalt oxide, i.e., LiNixMnyCozO2) cathodes; lithium cobalt oxide (LiCoO2) cathodes; NCA (lithium nickel cobalt aluminum oxide, i.e., LiNiCoAlO2) cathodes; LMO (lithium manganese oxide, i.e., LiMn2O2) cathodes; LFP (lithium iron phosphate, i.e., LiFePO2) cathodes; and lithium / sulfur cathodes.
[0066] According to some of any of the embodiments described herein, the lithium ion cathode is a lithium iron phosphate cathode.
[0067] According to some of any of the embodiments described herein, the electrochemical system further comprises an electrolyte.
[0068] According to some of any of the embodiments described herein, the electrolyte is or comprises
[0069] LiPF6. According to some of any of the embodiments described herein, the electrochemical system is characterized by a cyclic stability of at least 500, or at least 1000, and up to 10,000, cycles.
[0070] According to some of any of the embodiments described herein, the electrochemical system is characterized by an areal capacity in a range of at least 1.2, or at least 1.3, and up to 10.0, mAh / cm2.
[0071] According to some of any of the embodiments described herein, the electrochemical system is characterized by a gravimetric capacity of at least 1800, or at least 2000, and up to 10,000, mAh / g.
[0072] According to some of any of the embodiments described herein, the electrochemical system is characterized by a Coulombic efficiency of at least 95, or at least 99, and up to 100, %.
[0073] According to some of any of the embodiments described herein, the electrochemical system is characterized by a C-rate of at least C / 20, or at least C / 12, and up to 10C.
[0074] According to some of any of the embodiments described herein, the electrochemical system is characterized by a capacity retention of at least 40, or at least 50, and up to 100, %, after 1000 cycles.
[0075] According to an aspect of some embodiments of the present invention there is provided a method of preparing a graphene matrix (e.g., a 3D porous graphene matrix), the method comprising exposing a mixture that comprises a carbonaceous material to laser irradiation, to thereby form the graphene matrix, wherein the carbonaceous material comprises a jellyfish biomass, as described herein in any of the respective embodiments.
[0076] According to an aspect of some embodiments of the present invention there is provided a graphene matrix obtained by the method as described herein.
[0077] According to an aspect of some embodiments of the present invention there is provided a jellyfish-derived graphene matrix as described herein in any of the respective embodiments and any combination thereof.
[0078] According to some of any of the embodiments described herein, the jellyfish-derived graphene matrix is characterized by one or more of: an atomic amount of oxygen of at least 5, or at least 10, or ranges from 5 to 40, or from 10 to 30, or from 10 to 25, %, including any intermediate values and subranges therebetween; and / or an atomic amount of nitrogen of at least 0.1, or at least 0.5, or at least 1, or ranges from 0.1 to 20, or from 0.5 to 15, or from 1 to 10, or from 1 to 5, %, including any intermediate values and subranges therebetween; and / or an amount of oxygen of at least 5, or at least 10, or at least 12, or ranges from 5 to 40, or from 12 to 30, % by weight of the total weight of the jellyfish-derived graphene matrix, including any intermediate values and subranges therebetween; and / or an amount of nitrogen of at least 0.1, or at least 0.5, or at least 1, or ranges from 0.1 to 20, or from 0.5 to 15, or from 1 to 10, or from 1 to 5, % by weight of the total weight of the jellyfish-derived graphene matrix, including any intermediate values and subranges therebetween; and / or an amount of boron relative to a total amount of boron and carbon in the JF-derived (e.g., 3D porous) structure (graphene matrix) (% weight of boron / % weight of boron + % weight of carbon) is at least 0.01, or ranges from 0.01 to 1, or from 0.01 to 0.1, %, including any intermediate values and subranges therebetween; and / or an atomic amount of boron relative to a total atomic amount of boron and carbon in the JF- derived (e.g., 3D porous) structure (graphene matrix) (% atomic of boron / % atomic of boron + % atomic of carbon) is at least 0.01, or ranges from 0.01 to 1, or from 0.01 to 0.1, %, including any intermediate values and subranges therebetween; and / or an amount of boron relative to a total amount of boron, oxygen, nitrogen and carbon in the JF- derived (e.g., 3D porous) structure (graphene matrix) (% weight of boron / % weight of boron + % weight of oxygen + % weight of carbon + % weight of nitrogen) is at least 0.01, or ranges from 0.01 to 1, or from 0.01 to 0.1, %, including any intermediate values and subranges therebetween; and / or an atomic amount of boron relative to a total atomic amount of boron, oxygen, nitrogen and carbon in the JF-derived (e.g., 3D porous) structure (graphene matrix) (% atomic of boron / % atomic of boron + % atomic of oxygen + % atomic of carbon + % atomic of nitrogen) is at least 0.01, or ranges from 0.01 to 1, or from 0.01 to 0.1, %, including any intermediate values and subranges therebetween.
[0079] Unless otherwise defined, all technical and / or scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the invention pertains. Although methods and materials similar or equivalent to those described herein can be used in the practice or testing of embodiments of the invention, exemplary methods and / or materials are described below. In case of conflict, the patent specification, including definitions, will control. In addition, the materials, methods, and examples are illustrative only and are not intended to be necessarily limiting.
[0080] Implementation of the method and / or system of embodiments of the invention can involve performing or completing selected tasks manually, automatically, or a combination thereof. Moreover, according to actual instrumentation and equipment of embodiments of the method and / or system of the invention, several selected tasks could be implemented by hardware, by software or by firmware or by a combination thereof using an operating system.
[0081] For example, hardware for performing selected tasks according to embodiments of the invention could be implemented as a chip or a circuit. As software, selected tasks according to embodiments of the invention could be implemented as a plurality of software instructions being executed by a computer using any suitable operating system. In an exemplary embodiment of the invention, one or more tasks according to exemplary embodiments of method and / or system as described herein are performed by a data processor, such as a computing platform for executing a plurality of instructions. Optionally, the data processor includes a volatile memory for storing instructions and / or data and / or a non-volatile storage, for example, a magnetic hard-disk and / or removable media, for storing instructions and / or data. Optionally, a network connection is provided as well. A display and / or a user input device such as a keyboard or mouse are optionally provided as well.
[0082] BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWING(S)
[0083] Some embodiments of the invention are herein described, by way of example only, with reference to the accompanying drawings. With specific reference now to the drawings in detail, it is stressed that the particulars shown are by way of example and for purposes of illustrative discussion of embodiments of the invention. In this regard, the description taken with the drawings makes apparent to those skilled in the art how embodiments of the invention may be practiced.
[0084] In the drawings:
[0085] FIG. 1A is a schematic illustration of an exemplary method of forming a 3D porous structure deposited onto a conductive substrate from raw jellyfish biomass according to some embodiments of the present invention.
[0086] FIG. IB is a schematic presentation of the lithiation of a 3D porous carbon-silicon composite network, showing an effective mechanical buffering during standard silicon-lithium alloying. FIG. 1C presents the components of an exemplary CR2032 coin cell battery with which a jellyfish-derived composite material of some of the present embodiments, deposited on a current collector, is assembled.
[0087] FIG. ID presents a Raman spectrum of the jellyfish biomass pre-lasing, showing high fluorescence intensity at 514 nm, indicative of the proteinaceous jellyfish biomass.
[0088] FIG. IE presents a HRTEM image of the jellyfish-derived composite structure, following laser irradiation.
[0089] FIG. IF presents a confocal fluorescence microscope image depicting the high fluorescence of the jellyfish biomass pre-lasing, indicative of the proteinaceous jellyfish biomass.
[0090] FIG. 1G presents dark-field confocal microscope imaging depicting the freeze-dried jellyfish biomass pre-lasing. FIGs. 2A-B present representative HRSEM images of the surface (FIG. 2B) and cross-section (FIG. 2A) of a jellyfish-derived composite structure according to some of the present embodiments, after laser rastering.
[0091] FIG. 2C presents representative HRSEM images of a jellyfish-derived mixture according to some embodiments of the present invention, before (left) and after (right) laser writing.
[0092] FIG. 2D presents representative HRSEM images of a jellyfish-derived mixture according to some embodiments of the present invention, before laser rastering (left) and within a macropore which was formed following laser rastering (right).
[0093] FIG. 2E presents a FIB / HRSEM cross-sectional image of the exemplary jellyfish-derived mixture according to some embodiments of the present invention, after laser writing.
[0094] FIG. 2F presents an HRSEM image of the surface of the exemplary jellyfish-derived 3D porous structure obtained after laser rastering.
[0095] FIGs. 2G-H present a binary (black and white; threshold 125) HRSEM image (FIG. 2G) and ImageJ particle analysis software image (FIG. 2H) based on the HRSEM image displayed in FIG. 2F of the exemplary jellyfish-derived 3D porous structure according to some embodiments of the present invention, obtained after laser rastering.
[0096] FIG. 21 presents a histogram of pore size diameter distribution calculated based on the data of FIG. 2H.
[0097] FIG. 3A presents a TEM bright-field image of an exemplary JF / SiNP composite structure.
[0098] FIG. 3B presents a bright-field STEM image of an exemplary JF / SiNP composite structure (left) and the corresponding carbon and silicon EDS mapping (right).
[0099] FIG. 3C presents HAADAF-STEM images of an exemplary JF / SiNP composite structure (left) and the corresponding full EDS mappings (center and right).
[0100] FIG. 3D presents EDS spectra of an exemplary JF / SiNP composite structure, at varying JF:SiNP ratios (10:1.5, 10:3.0, 10:4.5, as indicated).
[0101] FIG. 4A presents a selected-area electron diffraction (SAED) pattern of a cluster of crystalline SiNPs in the composite structure; scale bar is 10 nm. The inset presents an image of the selected-area aperture; scale bar is 400 nm.
[0102] FIG. 4B presents a bright-field TEM image of a single-crystalline SiNP within the jellyfish- derived 3D porous graphene matrix (left) and HRTEM imaging of the SiNP depicting the (111) lattice plane spacing (right). FIGs. 4C-D present Raman spectra depicting preservation of pristine crystalline SiNPs (FIG. 4C) and Raman spectrum of the jellyfish-derived 3D porous graphene matrix (FIG. 4D).
[0103] FIGs. 4E-F present HRSEM image (FIG. 4E) and a scatter plot showing EIS analysis (FIG. 4F) of the surface of an exemplary JF / SiNP composite structure that underwent laser irradiation without the addition of boric acid.
[0104] FIG. 4G presents HRSEM images of JF / SiNP composite structures following lasing at different lasing parameters: varying lasing speed (from 60 mm / s to 20 mm / s, as indicated) and multiplicity of lasing passes (1 pass or 2 passes, as indicated).
[0105] FIG. 4H presents a BET adsorption isotherm of the exemplary JF / SiNP composite post-lasing.
[0106] FIG. 41 presents an XPS survey of the exemplary JF / SiNP composite post-lasing.
[0107] FIGs. 4J-L present high-resolution XPS spectra of the Si 2p orbital of the exemplary JF / SiNP composite post-lasing (FIG. 4J) and of the C is orbital of the JF / SiNP composite pre-lasing (FIG. 4K) and post-lasing (FIG. 4L).
[0108] FIG. 4M presents a schematic representation of the laser-induced graphitization of the jellyfish biomass, showing the formation of gaseous byproducts, breaking of C-O, C-N and C-H bonds, and the role of boric acid as a flame retardant according to some embodiments of the present invention.
[0109] FIG. 4N presents XPS depth profile analysis of the C is spectrum of an exemplary JF / SiNP composite structure, showing the reduction in oxygen content in the bulk.
[0110] FIG. 5 A presents a Cyclic Voltammetry (CV) curve of an electrochemical cell containing an exemplary JF / SiNP-based electrode cycled at a scan rate of 0.02 mV / s between 0.05 and 1 V vs. Li / Li+.
[0111] FIG. 5B presents EIS analysis of an exemplary electrochemical cell containing an exemplary 2-layer JF / SiNP-based electrode depicting the impedance of various battery components at different cycling stages, before the lasing process and without the presence of boric acid as a flame retardant according to some of the present embodiments.
[0112] FIG. 5C presents comparative plots showing galvanostatic cycling of an exemplary electrochemical cell containing an exemplary 2-layer JF / SiNP-based electrode over 1170 cycles, cycled in a half cell configuration at 500 mA / g.
[0113] FIG. 5D presents comparative CV curves showing differential capacity analysis of the galvanostatic cycling depicted in FIG. 5C over different cycling stages.
[0114] FIG. 5E presents comparative plots showing voltage profiles of the cell cycled in FIG. 5C between 0.05 and 1 V vs. Li / Li+. FIG. 5F presents comparative plots showing rate performance of an exemplary electrochemical cell containing an exemplary 2-layer JF / SiNP-based electrode at different current densities (50-1600 mA / g, as indicated).
[0115] FIG. 5G presents comparative plot showing a JF / SiNP-based electrode according to some of the present embodiments, cycled in a half cell configuration with a copper foil (15 μm) current collector instead of stainless steel.
[0116] FIG. 5H presents plots showing a voltage profile of an exemplary JF / SiNP-based electrode with additional spin coated layers (6) and a mass loading of 1 mg / cm2, cycled at C / 20 with stable reversible capacity of approximately 1.2 mAh / cm2.
[0117] FIG. 51 presents plots showing galvanostatic cycling of an exemplary electrochemical cell containing a 5-layer JF / SiNP-based electrode for 50 cycles at rates of 100 mA / g and 800 mA / g.
[0118] FIG. 5J presents plots showing galvanostatic cycling performance of a full cell configuration containing a JF / SiNP-based anode and a lithium iron phosphate (LiFePO4 ;LFP) cathode, cycled between 2.2 and 4 V at a rate of C / 12.
[0119] FIG. 5K presents equivalent cell used for EIS analysis, results from which are presented in FIG. 5B. The bulk resistance of the cell is designated as RBUik and is equal to the intercept of the first semicircle with the x-axis at high frequencies. The charge transfer resistance at the electrode- electrolyte interface and the constant-phase element of the double layer is represented by RCT and CPEdi, respectively. Impedance that arises due to diffusion limitations at low frequencies is known as the Warburg impedance and is proportional to the 45-degree linear slope observed in the Nyquist plot.
[0120] FIGs. 5L-M present cyclic voltammetry data of an electrochemical cell containing the exemplary JF / SiNP-based electrode at varying scan rates (FIG. 5L) and a linear fitting of the current at a fixed potential (FIG. 5M) based on the analysis in FIG. 5L and in accordance with the Randles- Sevcik equation. The diffusion coefficient can be accordingly extracted from the slope of the linear fit of FIG. 5M.
[0121] FIG. 5N presents FIB / SEM cross-sectional imaging of high-loading JF / SiNP 3D porous structure with three additional spin-coated layers.
[0122] FIGs. 5O-P are plots showing a voltage profile (cycling performance) of exemplary JF / SiNP- based electrode with additional spin coated layers (two layers (FIG. 50) and three layers (FIG. 5P)) and a mass loadings of 1 mg / cm2(FIG. 50) and 2 mg / cm2(FIG. 5P), cycled at C / 20 with stable reversible capacity of approximately 1.2 mAh / cm2(FIG. 50) and 2.1 mAh / cm2(FIG. 5P). FIG. 6A presents HAADAF-STEM images showing SiNPs encapsulated within the JF / SiNP 3D porous structure after 1170 cycles (left) and EDS mapping of the corresponding image (right).
[0123] FIG. 6B presents a selected-area electron diffraction pattern of the SiNPs depicted in FIG. 6A.
[0124] FIG. 6C presents a bright-field TEM image of an amorphous SiNP within the 3D porous graphene matrix.
[0125] FIG. 7 depicts an exemplary electrochemical cell according to some embodiments of the invention, comprising an electrochemically active component according to some embodiments of the invention.
[0126] DESCRIPTION OF SPECIFIC EMBODIMENTS OF THE INVENTION
[0127] The present invention, in some embodiments thereof, relates to material science, and more particularly, but not exclusively, to jellyfish-derived graphene structures, to methods of preparing same and to uses thereof, for example, as electrodes.
[0128] Before explaining at least one embodiment of the invention in detail, it is to be understood that the invention is not necessarily limited in its application to the details set forth in the following description or exemplified by the Examples. The invention is capable of other embodiments or of being practiced or carried out in various ways.
[0129] Before explaining at least one embodiment of the invention in detail, it is to be understood that the invention is not necessarily limited in its application to the details of construction and the arrangement of the components and / or methods set forth in the following description and / or illustrated in the drawings and / or the Examples. The invention is capable of other embodiments or of being practiced or carried out in various ways.
[0130] The escalating impacts of global climate change and resource scarcities demand a redefinition of sustainable energy-storage systems, emphasizing the need to assess the full environmental impact of renewable resources. The present inventors have conceived exploiting the rapid increase in jellyfish populations due to climate change and human activities causing significant ecological and economic disruptions, by utilizing overabundant jellyfish biomass as a carbonaceous material that can be integrated, for example, in energy-storage systems that are both financially beneficial and environmentally remediating. This approach aligns with a comprehensive view of sustainability, requiring eco-friendly solutions throughout the entire lifecycle, from material sourcing to battery production, without compromising performance. The present inventors have utilized laser irradiation to induce a photochemical and / or photothermal reaction in the jellyfish biomass as a proteinaceous carbon source or carbon precursor material (being referred to herein as a carbonaceous material) that transforms into a three-dimensional graphene structure with controllable properties such as porosity and conductivity using different lasing parameters.
[0131] The present inventors have pursued the production of an additive-free conductive 3D porous composite structure which is usable in, e.g., alkali metal ion batteries such as Lithium-ion batteries (LIBs), through the integration of an electrochemically active material or substance, like silicon, embedded into the jellyfish (JF)-derived 3D porous structure. The present inventors have demonstrated the first everjellyfish-based lithium-ion battery. These jellyfish-based batteries exhibit remarkable cyclic stability of over a thousand cycles with high capacity retention, surpassing that of graphite anodes for all cycles, along with excellent areal capacity and rate capabilities.
[0132] As demonstrated in the Examples section that follows, the present inventors have designed and successfully transformed a mixture that comprises substantially unprocessed jellyfish biomass and silicon nanoparticles (SiNPs) into a conductive 3D porous carbon network that encapsulates the nanoparticles and thus forms a composite structure. Based on this newly developed composite structure, the present inventors have successfully prepared an electrode (anode) which has be integrated into electrochemical cells and systems such as a 2032 coin-cell lithium ion batteries (LIB).
[0133] Without being bound to any particular theory, it is assumed that the conductive carbon matrix improves contact between the electrolyte, current collector, and electrochemically active component while its porosity acts as a buffer to reduce the impact of silicon volume expansion on mechanical stability.
[0134] Lithium-based electrochemical systems comprising an exemplary JE-derived composite structure as an electrode displayed remarkable performances, such as an outstanding cyclic stability (>1000 cycles), excellent capacity retention (>50 % retention after 1000 cycles), exceptional coulombic efficiency (>99 %), superb reversible gravimetric capacity (>2000 mAh / g), high areal capacity capabilities (>1.2 mAh / cm2), and high rate performance capability (>1.6 A / g), paving a new path to future sustainable energy production. This fully sustainable synthesis therefore uses an environmentally remediating and economically feasible carbonaceous material that is virtually unprocessed, can be devoid of binders or conductive additives, and can employ solely water-based solvents at low-energy consumption and room-temperature conditions. Given that current electrode syntheses for commercial lithium-ion batteries are often energy- intensive, complex, and reliant on multiple additives, embodiments of the present invention introduce a novel methodology that utilizes low-energy laser irradiation of jellyfish biomass, optionally embedded with electrochemically active agents, to create additive-free 3D composite anodes. Incorporating jellyfish biomass into the rapidly growing energy storage (e.g., lithium-ion battery) market, expected to reach about 50 billion USD by 2024, could incentivize global regulation of jellyfish populations while reducing battery production costs and environmental pollution.
[0135] The electrodes disclosed herein meet the necessary performance prerequisites for integration into next-generation lithium-ion batteries, along with opening the door to extensive research and integration into a variety of energy-storage systems. Equally significant is the potential that widespread utilization of jellyfish biomass has for environmental remediation and restoration of imperiled marine ecosystems. This approach represents an unparalleled paradigm for sustainability compared to use of traditional "sustainable" materials that, at best, have negligible environmental benefits. Implementation of three-dimensional porous conductive carbon composites from virtually unprocessed raw jellyfish biomass embedded with different electrochemically active agents for use in energy-storage systems holds immense potential for widespread applications. Future applications of this technique have the potential to enable the production of batteries suitable for a wide array of uses by means of four-dimensional control, with three dimensions related to the anode architecture and an additional dimension controlling the lasing parameters. The resulting batteries can display diverse characteristics, such as varying sizes, degrees of porosity, and compositions. This proposed new technique, from material sourcing to battery production, prioritizes high-performance values while maintaining simplicity, redefining the complete overall package of sustainability for next-generation lithium-ion batteries.
[0136] Electrodes as disclosed herein differ from currently practiced silicon-carbon composite electrodes by their favorable electrochemical performance, their unique structural properties, the carbonaceous material used for preparing same, and the method of preparing same.
[0137] In the currently practiced methodologies, the selection of a carbonaceous material for commercial use is made while balancing the need for high-performance and cost-effectiveness with its potential negative impact on the environment and society.
[0138] Commonly used petroleum-based, coal-based, biomass-based, and synthetic carbonaceous materials [Shen et al. (2018) supra-, Duo et al. (2019) supra} all have their own unique properties and characteristics that make them suitable for preparing silicon-carbon composites therefrom (for use in electrochemical applications), but they also have various environmental, social, and economic trade- offs that must be considered. Petroleum-based, coal-based, and synthetic precursors are inherently costly, unsustainable, and environmentally harmful due to the finite nature of their origin, and also require significant investment in source extraction processes, thus consuming large amounts of energy, and generating substantial greenhouse gas emissions. Additionally, the refinement of these precursors for battery applications requires further energy intensive processes, such as high-temperature carbonization and purification, which can lead to additional environmental impacts and costs.
[0139] Biomass-based precursors, while allegedly renewable, can nevertheless be resource-intensive and environmentally damaging if the biomass is not obtained and handled sustainably. For example, the industrial use of lignocellulosic biomass resources might necessitate significant inputs of agricultural land, water, and fertilizers, which can cause soil erosion, water pollution, deforestation, and greenhouse gas emissions. Furthermore, the majority of typical natural precursors typically require significant energy and resource use during extraction and processing.
[0140] Synthetic precursors, such as polyacrylonitrile (PAN) or phenolic resins, offer high purity and consistent chemical and physical properties, which can result in improved performance and reliability of the resulting composite structures. However, synthesized precursors typically require complex chemical reactions and high-temperature processing. The production of PAN, for example, involves the use of fossil fuel-based chemicals and solvents, which can generate hazardous by-products and contribute to greenhouse gas emissions.
[0141] Overall, the selection of a carbonaceous material for battery production should consider not only its suitability and performance for the application, but also its environmental and economic impacts throughout its production and supply chain [Mori R. RSC Sustain. 2 (2023); Zhang et al. Electrochem. Commun. 138, 107283 (2022)].
[0142] As previously explained, and in unison with the exhibited electrochemical analysis, carbonaceous materials derived from protein-rich jellyfish biomass satisfy these criteria entirely. Due to the anticipated proliferation of jellyfish populations and their associated adverse consequences, jellyfish biomass represents a readily available, cost-effective, and truly sustainable carbonaceous material that requires minimal processing and refinement. Moreover, unlike the examples listed above, the widespread implementation of jellyfish biomass in energy-storage systems could yield numerous positive ecological, economic, and social outcomes, including environmental remediation of devastated marine ecosystems, reduction of disruptions and maintenance expenses for fisheries and power plants, and the mitigation of the detrimental effects of jellyfish on civilians at public beaches. In conjunction with the environmental concerns related to prevalent carbonaceous materials, the procedures utilized for manufacturing contemporary silicon-carbon composite anodes can also prove to be both energetically demanding and ecologically harming. Conventional synthesis techniques typically involve high-temperature procedures, often surpassing 1000 °C, including chemical vapor deposition, atomic layer deposition, carbonization, and spray pyrolysis [Dong et al. Ionics (Kiel). 28, 3057-3077 (2022)]. These methods give rise to considerable emissions of greenhouse gases and other pollutants, and their associated equipment and energy expenditures render them problematic for large-scale production. Alternately, employed methods such as high-energy ball milling and electrospinning are impractical as well due to their limited production volume and scale- up capability [Bitew et al. Sustain. Energy Fuels 6, 1014-1050 (2022); Xiao et al. J. Solid State Electrochem. 26, 1125-1136 (2022)].
[0143] Low-power laser writing techniques, on the other hand, are inherently cost-effective, eco- friendly, and highly scalable. One of the primary reasons for this is their lower energy consumption and low maintenance requirements, which not only reduces the carbon footprint but also minimizes operating costs. Laser writing also offers the flexibility of using multiple lasing heads simultaneously and sharp increases of scanning speeds, resulting in higher throughput rates, enhancing productivity and efficiency [Le et al. (2022) supra]. Laser pyrolysis was previously used to create silicon carbon composites, however they typically involved the use of common unsustainable carbonaceous materials such as graphite or acetylene [Sourice et al. ACS Appl. Mater. Interfaces, 7, 12, 6637-6644 (2015); Minami et al. Nano Sei. 3, 1192-1200 (2022)]. Additionally, the synthesis only created base particles, compared to direct laser writing of whole anodes.
[0144] The proposed one-step laser writing technique for JF-derived graphene matrices eliminates any need for high-temperature and vacuum environments by operating at room temperature in open air, thus reducing energy consumption and operating costs while providing greater flexibility in design and production.
[0145] A comparative study showcasing the electrochemical performance of the exemplary JF / SiNP anodes according to some of the present embodiments in comparison with other reported silicon- carbon composites (presented in Table 1 of the Background section) for lithium-ion batteries is summarized in Table A herein. Table A
[0146] As depicted in Table 1 (see, Background section), the currently practiced carbonaceous materials were graphitized using high-temperature energy-intensive syntheses. When comparing gravimetric capacities (cycled at < 500 mA / g), areal capacities (not reported at all in the background art documents), maximum reported cycle life, and capacity loss per cycle (even compared to cells run for much fewer cycles), it is clear that the extensive use of unsustainable expensive carbonaceous materials and complex energy-intensive syntheses, as described in Table 1, do not necessarily yield enhanced performances.
[0147] Embodiments of the present invention relate to a method of forming a graphene matrix or graphene structure from jellyfish (JF) biomass, to graphene matrices obtained thereby, to utilizing this methodology for forming jellyfish-derived 3D porous composite structures that further comprise an electrochemically active component such as silicon, and to uses of such composite structures as electrodes in electrochemical systems, for example, in energy storage devices such alkali metal ion batteries (e.g., LIBs).
[0148] According to an aspect of some embodiments of the present invention there is provided a method of preparing a 3D porous structure that comprises a 3D porous graphene matrix. According to some of any of the embodiments described herein, the method is effected by exposing a mixture that comprises a carbonaceous material to laser irradiation, to thereby form the 3D porous structure. According to the present embodiments, the carbonaceous material comprises a jellyfish biomass.
[0149] As used herein and in the art (see, e.g., Scardini, 2021, supra), the term “graphene” describes a single layer of carbon atoms arranged in a two-dimensional honeycomb lattice. As graphene is characterized by favorable electrical conductivity, mechanical strength, and thermal properties, it is useful, e.g., in enhancing the performance of anodes in, e.g., lithium-ion batteries. When using laser irradiation for its preparation, graphene is typically obtained via one of two ways: by reducing graphene oxide (GO) deposited onto a surface, resulting in what is commonly referred to as “laser- reduced graphene” (LRG), or by transforming carbonaceous materials (as those are described herein), which are non-graphitic, into graphene (also referred to as “laser-induced graphene”, or by its abbreviation, LIG).
[0150] As used herein, the phrase “non-graphitic materials” describes carbonaceous materials that do not possess the layered, hexagonal 3D lattice structure characteristic of graphite.
[0151] As the formation of the 3D porous graphene matrix as described herein in any of the respective embodiments is induced by laser irradiation as described herein, in some of any of the embodiments described herein, the 3D porous graphene matrix comprises laser-induced graphene (LIG).
[0152] Herein throughout, the phrases “3D porous graphene matrix”, “3D graphene matrix”, “conductive 3D porous carbon network”, “3D porous conductive carbon structure”, “macroporous structure”, “porous carbon matrix”, “conductive carbon matrix”, “carbon matrix”, “porous network”, and “conductive three-dimensional porous matrix”, are used interchangeably, and all describe a network of graphene carbon-based structure having a three-dimensional architecture.
[0153] According to some of any of the embodiments described herein, the laser-induced graphene is obtained by exposing a carbonaceous material to laser irradiation as described herein in any of the respective embodiments.
[0154] Herein throughout, the phrases “carbonaceous material”, “carbon source” and “carbon precursor” are used interchangeably, and describe an organic material (that inherently comprises carbon atoms), preferably a carbon-enriched organic material, which is capable of transforming to graphene when exposed to suitable conditions.
[0155] According to some of any of the embodiments described herein, the carbonaceous material is an organic material that inherently comprises carbon atoms, and which is capable of forming graphene when exposed to laser irradiation.
[0156] According to some of any of the embodiments described herein, the carbonaceous material is selected capable of transforming to graphene following the exposure to the laser irradiation. Such materials are typically carbon-rich materials and include, for example, polymerizable and / or crosslinkable materials, including polymeric and non-polymeric synthetic materials, and natural substances.
[0157] According to the present embodiments, the carbonaceous material is or comprises a jellyfish biomass. As used herein, the term “jellyfish” (also abbreviated herein to “JF”) encompasses jellyfish from the families Scyphozoa (true jellyfish) and Cubozoa (box jellyfish). Jellyfish from other families (e.g., Hydrozoa, Staurozoa) are also contemplated.
[0158] Non-limiting examples of jellyfish species include Aurelia aurita (moon jellyfish), Chrysaora hysoscella (compass jellyfish), Cyanea capillata (lion's mane jellyfish), Pelagia noctiluca (mauve stinger), Rhizostoma pulmo (barrel jellyfish), Cotylorhiza tuberculata (fried egg jellyfish), Chrysaora fuscescens (Pacific sea nettle), Cassiopea andromeda (upside-down jellyfish), Stomolophus meleagris (cannonball jellyfish), Phyllorhiza punctata (Australian spotted jellyfish), Nemopilema nomurai (Nomura's jellyfish), Desmonema glaciale (Antarctic jellyfish), Chironex fleckeri (sea wasp), Carukia barnesi (Irukandji jellyfish), Chiropsalmus quadrigatus (four-handed box jellyfish), Malo kingi (Irukandji jellyfish), Carybdea marsupialis (middling jellyfish), Drymonema dalmatinum (pink meanie), Atolla wyvillei (coronate jellyfish), Tamoya haplonema (four-hand jellyfish), Craspedacusta sowerbyi (freshwater jellyfish), Rhopilema nomadica (nomad jellyfish), Aequorea forskalea (many- ribbed jellyfish), Olindias phosphorica (flower hat jellyfish), and Pelagia benovici.
[0159] Non-limiting examples of jellyfish species which are commonly found in the Mediterranean Sea include Rhopilema nomadica (nomad jellyfish), Pelagia noctiluca (mauve stinger), Rhizostoma pulmo (Barrel jellyfish), Aurelia aurita (moon jellyfish), Cotylorhiza tuberculata (fried egg jellyfish), Phyllorhiza punctata (Australian spotted jellyfish), Chrysaora hysoscella (compass jellyfish), Aequorea forskalea (many-ribbed jellyfish), Olindias phosphorica (flower hat jellyfish), and Pelagia benovici.
[0160] As used herein, the phrase “jellyfish biomass” (also being referred to herein as “JF biomass”) describes a substance (typically a mixture of materials or substances) that is derived from at least a part of a jellyfish. The JF biomass can be unprocessed, such that it is used as is (as found in its natural environment), or can be minimally processed (also referred to herein as “substantially unprocessed), such that it has undergone mild processing such as milling, grounding, drying and / or homogenization, or can be processed, for example, by undergoing extractions and / or other chemical processes that may involve chemical reagents and / or reactions.
[0161] According to some of any of the embodiments described herein, the jellyfish biomass is minimally processed, as described herein.
[0162] According to some of any of the embodiments described herein, the jellyfish biomass is of the whole jellyfish or of a portion of the jellyfish. The jellyfish biomass can comprise, for example, the bell, the tentacles, the oral arms, the manubrium, the gonads, the mouth, the rophalia, and any combination thereof.
[0163] According to some of any of the embodiments described herein, the jellyfish biomass comprises or consists of the bell of the jellyfish.
[0164] The bell of a jellyfish includes mostly water and collagen and other structural proteins, as well as muscle cells, nerve cells and sensor organs.
[0165] According to some of any of the embodiments described herein, the method comprises, prior to exposing the carbonaceous material that comprises the JF biomass to laser irradiation, processing the JF biomass (e.g., the JF bell).
[0166] According to some of any of the embodiments described herein, the jellyfish biomass (e.g., a jellyfish bell) is a dried JF biomass, such that the processing the JF biomass comprises drying the JF biomass (e.g., the JF bell).
[0167] In some of any of the embodiments described herein, the jellyfish biomass is in a dry form at room temperature. In alternative embodiments, the jellyfish biomass is in a form of a liquid or a semi- solid (e.g., a gel) at room temperature.
[0168] Non-limiting examples of dry forms include powders, flakes, granules, and pellets.
[0169] According to some of any of the embodiments described herein, upon drying a jellyfish (e.g., as described herein in any of the respective embodiments) or a portion thereof (e.g., the bell of the jellyfish), a (dry) jellyfish biomass as described herein in any of the respective embodiments is obtained.
[0170] In some of any of the embodiments described herein, drying the jellyfish or the portion thereof is effected by freeze-drying. However, any other drying processes known in the art are contemplated. Preferably, the drying process is such that does not affect the proteinaceous nature (collagen-enriched) of the JF biomass. According to some embodiments, drying the JF biomass, and / or the entire processing of the JF biomass is performed at temperatures that do not exceed 30 °C, or do not exceed 25 °C.
[0171] According to some of any of the embodiments described herein, processing the JF biomass (e.g., a JF bell), comprises centrifuging the jellyfish biomass. In some embodiments, centrifuging the jellyfish biomass is performed in the presence of a solvent (e.g., a polar non-hazardous solvent such as ethanol). The formed precipitate (typically in a form of a paste) is then used. According to some of any of the embodiments described herein, processing the JF biomass is effected by centrifuging the jellyfish biomass as described herein, collecting the thus obtained precipitate (e.g., paste) and drying it as described herein.
[0172] According to some of any of the embodiments described herein, processing the JF biomass is effected by centrifuging the jellyfish biomass as described herein, and collecting the thus obtained precipitate (e.g., paste).
[0173] According to some of any of the embodiments described herein, processing the JF biomass comprises homogenizing the jellyfish or the portion thereof (e.g., the bell). Non-limiting examples homogenizing procedures include pounding (e.g., by a mortar), triturating, mixing, grinding, blending, mashing, emulsifying, and any combination thereof. In exemplary embodiments, homogenizing the jellyfish or the portion thereof is effected by pounding and / or triturating and mixing.
[0174] According to some of any of the embodiments described herein, processing the JF biomass (e.g., a JF bell) is effected by homogenizing the JF portion, as described herein, centrifuging the homogenized biomass as described herein, and collecting the precipitate (e.g., paste) formed in the centrifugation. Optionally, the thus formed precipitate is dried, as described herein.
[0175] According to some of any of the embodiments described herein, a mixture that comprises a carbonaceous material that comprises a JF biomass comprises a processed JF biomass, which is a form of a paste (obtained by centrifugation as described herein) or in a dry form, as described herein.
[0176] According to some of any of the embodiments described herein, the mixture further comprises a liquid or semi-solid carrier (e.g., an aqueous carrier, e.g., water, ethanol, or a gel).
[0177] According to some of any of the embodiments described herein, the carrier is an aqueous carrier, for example, water.
[0178] According to some of any of the embodiments described herein, the mixture comprises a powder or particles of the dried jellyfish biomass dispersed in or mixed with the carrier. Alternatively, in some embodiments, the mixture comprises a paste as described herein, mixed with the carrier.
[0179] According to some of any of the embodiments described herein, when the JF biomass is mixed with a carrier, a concentration of the (e.g., processed) jellyfish biomass in the mixture is in a range of from 1 to 95, or from 10 to 90% by weight of the total weight of the mixture, including any intermediate values and subranges therebetween.
[0180] According to some of any of the embodiments described herein, the carbonaceous material in the mixture further comprises at least one additional carbonaceous material (e.g., which is capable of forming graphene when exposed to laser irradiation). Exemplary (additional) carbonaceous materials usable in the context of these embodiments include, but are not limited to, graphite, graphite oxide, graphene oxide, polyimides (PI), silicon polyethers such a PDMS, polyetherimides (PEI), polycarbonates (PC), poly( ether ketones) (PEEK), poly(alkylenes glycols), sulfonate poly(ether ketones) (SPEEK), poly(methyl methacrylates) (PMMA), polyacrylonitriles (PAN)), polypyrroles, aromatic (e.g., phenolic) resins, cellulose, cellulose derivatives (e.g., carboxymethyl cellulose (CMC)), MOFs, hemicelluloses, lignin, chitosan, sucrose, wheat starch, and any combination thereof.
[0181] An additional carbonaceous material can be derived from a natural source or be a natural biomass, for example, wood and wheat, or from a carbon-enriched food substance such as bread and potatoes. An additional carbonaceous material can comprise saccharides and / or polysaccharides (e.g., sucrose, chitosan) or can be a biomass enriched with saccharides and / or polysaccharides (e.g., crustaceans).
[0182] An additional carbonaceous material can alternatively be or comprise carbon-enriched polymeric or non-polymeric synthetic material, such as, for example, aromatic resins, for example, phenolic resins. A phenolic resin is typically partially polymerized (e.g., it comprises oligomeric or short polymeric chains) and undergoes polymerization and / or cross-linking when subjected to suitable conditions, either alone or when mixed with a cross-linking agent.
[0183] Any additional carbonaceous material or a mixture of carbonaceous materials that is / are capable of transforming to graphene when subjected to laser irradiation is contemplated.
[0184] According to some of any of the embodiments described herein, the additional carbonaceous material (if present) is other than graphite or graphite oxide. According to some of any of the embodiments described herein, the carbonaceous material is devoid of graphite.
[0185] As used herein throughout, the phrase “devoid of’ describes an amount of a compound that is lower than 10 %, or lower than 5 %, or lower than 1 %, or lower than 0.5 %, or lower than 0.1 %, or even lower, such as 0 %, meaning the compound is substantially absent.
[0186] Without being bound to any particular theory, it is assumed that carbonaceous materials according to some embodiments described herein are transformed into a carbon-based matrix by the temperature and pressure conditions generated by laser irradiation, while excess material inherent to the precursor is released as gaseous by-products, thus resulting in a 3D porous structure.
[0187] According to some of any of the embodiments described herein, the carbonaceous material consists of a jellyfish biomass as described herein in any of the respective embodiments and any combination thereof. According to some of any of the embodiments described herein, the method is effected by preparing a mixture than comprises a JF biomass as described herein and optionally a carrier as described herein, whereby preparing the mixture is effected by mixing the JF biomass with the carrier and optionally homogenizing the mixture as described herein, or by processing the JF biomass as described herein in any of the respective embodiments, or by using any other protocol suitable for processing jellyfish, preferably while maintaining its protein (e.g., collagenj-enriched composition, and optionally mixing the processed JF biomass with a carrier as described herein.
[0188] According to some of any of the embodiments described herein, the mixture does not comprise additives (e.g., at least one of catalysts, conductive additives, binders (such as organic polymer binders), polymer additives, and metal oxides). According to some of any of the embodiments described herein, the method does not involve an addition of additives as described herein. In some embodiments, the 3D porous structure is devoid of additives (e.g., as those are defined herein) and / or decomposition products of the additives.
[0189] Non-limiting examples for binders include polyvinylidene fluoride (PVDF), carboxymethyl cellulose (CMC), and styrene -butadiene rubber (SBR).
[0190] Non-limiting examples for conductive additives include carbon black, carbon nanotubes (CNTs), and Super P®.
[0191] Non-limiting examples for polymer additives include polyethylene oxide (PEO) and polyacrylic acid (PAA).
[0192] Non-limiting examples for metal oxides include titanium oxide (TiO2), manganese dioxide (MnO2) or nickel oxide (NiO).
[0193] According to some of any of the embodiments described herein, the mixture further comprises a flame retardant.
[0194] As used herein, the phrase “flame retardant” describes a substance that is optionally added to prevent the start or slow the spread of fire (combustion) caused, e.g., due to laser irradiation.
[0195] Non-limiting examples of flame -retardants include boric acid, aluminum hydroxide, ammonium polyphosphate, antimony trioxide, halogenated compounds, and intumescent coatings. In exemplary embodiments, the flame retardant is or comprises boric acid.
[0196] According to some of any of the embodiments described herein, an amount of the flame retardant is at least 0.1 %, or at least 1 %, and up to 30, or up to 20, or up to 10, % by weight of the total weight of the mixture, including any intermediate values and subranges therebetween. In exemplary embodiments, an amount of the flame retardant is up to 10 % by weight of the total weight of the mixture.
[0197] According to some of any of the embodiments described herein, the method is effected by depositing a mixture comprising a carbonaceous material as described herein in any of the respective embodiments, which comprises or consists of a JF biomass as described herein in any of the respective embodiments on a substrate as described herein in any of the respective embodiments, and exposing the substrate to the laser irradiation (e.g., a laser irradiation that transforms the carbonaceous material to a 3D porous graphene (e.g., continuous) matrix as described herein).
[0198] According to some of any of the embodiments described herein, the method is effected by depositing at least one layer of the mixture as described herein in any of the respective embodiments onto the substrate, to thereby obtain the substrate having the at least one layer of the mixture deposited on at least a portion of a surface thereof, as described herein in any of the respective embodiments; and exposing the substrate having the at least one layer deposited thereon to laser irradiation, as described herein in any of the respective embodiments. The method is such that forms a 3D porous structure deposited onto the at least a portion of the surface of the substrate, as described herein in any of the respective embodiments.
[0199] According to some of any of the embodiments described herein, the mixture is deposited in the substrate so as to form a layer of the mixture onto at least portion of a surface of the substrate. Depositing the mixture onto the substrate can be effected by any technique suitable for depositing liquid or semi-solid (e.g., slurry) mixtures, including, for example, spin coating, dip coating, spray coating, doctor blading, electrophoretic deposition, drop casting, bar coating, slot-die coating, Langmuir-Blodgett deposition, inkjet printing, electrospinning, and smearing and / or applying by hand.
[0200] In exemplary embodiments, depositing is effected by spin coating.
[0201] As used herein and in the art, the phrase "spin coating" describes a method in which a mixture is deposited onto the center of a substrate, which is then rapidly spun at high speeds. The centrifugal force spreads the mixture evenly across the surface, forming a thin film as the solvent evaporates.
[0202] As used herein and in the art, the phrase "dip coating" describes a method in which a substrate is immersed in a mixture and then withdrawn at a controlled speed, allowing a thin film to form on the surface as the solvent evaporates.
[0203] As used herein and in the art, the phrase "spray coating" describes a method where a mixture is sprayed onto a surface using a spray nozzle, often followed by drying or curing to form a uniform coating. As used herein and in the art, the phrase "doctor blading" (also known as "tape casting") describes a method in which a mixture is spread over a surface using a blade or flat edge, creating a uniform thin film as the blade moves across the substrate.
[0204] As used herein and in the art, the phrase "electrophoretic deposition" (EPD) describes a method where charged particles in a mixture are deposited onto a conductive substrate by applying an electric field, causing the particles to migrate and form a coating on the surface.
[0205] As used herein and in the art, the phrase "drop casting" describes a method in which a mixture is dropped onto a surface and allowed to spread and dry naturally, forming a film as the solvent evaporates.
[0206] As used herein and in the art, the phrase "bar coating" (also known as "wire-wound rod coating") describes a method where a wire-wound rod (bar) is used to spread a uniform layer of a mixture across a surface as it is drawn over the substrate.
[0207] As used herein and in the art, the phrase "slot-die coating" describes a method in which a mixture is extruded through a narrow slot and deposited directly onto a moving substrate, providing precise control over the thickness of the coating.
[0208] As used herein and in the art, the phrase "Langmuir-Blodgett deposition" describes a method in which a monolayer or multilayer film is transferred from the surface of a liquid to a substrate by dipping the substrate through the liquid-air interface.
[0209] As used herein and in the art, the phrase "inkjet printing" describes a method in which a mixture is precisely deposited onto a surface using inkjet printing technology, allowing for patterning or selective area coverage.
[0210] As used herein and in the art, the phrase "electrospinning" describes a method in which a mixture is ejected from a needle under a high-voltage electric field, forming fibers that are collected on a substrate as a non-woven mat.
[0211] As used herein and in the art, the phrase "smearing and / or applying by hand" describes a manual method in which a mixture is spread over a surface by physically smearing or applying it by hand, which is useful, e.g., to ensure coverage on irregular surfaces or when precision tools are not required.
[0212] According to some of any of the embodiments described herein, the depositing is effected on a portion of the substrate, preferably of a surface of the substrate, for example, on at least 10 %, or at least 20 %, or at least 30 %, or at least 40 %, or at least 50 %, or at least 60, or at least 70, or at least 80, or at least 90, or substantially all (100 %) of the surface of the substrate. According to some of any of the embodiments described herein, the depositing is of one layer of the mixture. According to some of any of the embodiments described herein, the depositing is of two or more layers of the mixture.
[0213] According to some of any of the embodiments described herein, a number of layers and a thickness of each layer are selected such that a total thickness of the layer or two or more (e.g., a plurality of layers ranges from 1 to 1000, or from 10 to 1000, or from 100 to 1000, or from 500 to 1000, or from 1 to 500, or from 10 to 500, or from 100 to 500, or from 1 to 200, or from 1 to 150, or from 1 to 100, or from 1 to 50, or from 1 to 10, or from 50 to 200, or from 50 to 150, or from 100 to 200, or from 150 to 200, or from 1 to 100, or from 10 to 100, or from 50 to 100, micrometers, including any intermediate values and subranges therebetween. In exemplary embodiments, the total thickness of the two or more (plurality of) layers is at least 15, or at least 20, micrometers.
[0214] In some of any of the embodiments described herein, a thickness of one layer is in a range of from 1 to 30, or from 1 to 20, or from 1 to 15, or from 1 to 10, or 1 to 8, or from 1 to 5, or from 2 to 10, or from 2 to 8, or from 2 to 5, or from 3 to 10, or from 3 to 8, micrometers, including any intermediate values and subranges therebetween.
[0215] According to some of any of the embodiments described herein, the exposing is of at least one layer of the mixture, and a thickness of each layer is in a range of from 1 to 30, or from 1 to 20, or from 1 to 15, or from 1 to 10, or 1 to 8, or from 1 to 5, or from 2 to 10, or from 2 to 8, or from 2 to 5, or from 3 to 10, or from 3 to 8, micrometers, including any intermediate values and subranges therebetween.
[0216] According to some of any of the embodiments described herein, the layer thickness and parameters of the laser irradiation are selected such that at least 50, or at least 60, or at least 70, or at least 80, or at least 90, or at least 95, or at least 98, %, or all of the carbonaceous material comprising the JF biomass is converted to the 3D porous graphene matrix.
[0217] It is to be understood that a number and / or thickness of the one or more layers of the mixture can be manipulated as desired, per the selected deposition technique as described herein, per the parameters of the laser irradiation, and / or per the selected application, so as to control the conversion of the carbonaceous material comprising the JF biomass to the graphene matrix..
[0218] In some of any of the embodiments described herein, a thickness of the 3D porous structure is lower by at least 2, or at least 5, or at least 10, or at least 15, or at least 20, and up to 1000, % of the thickness of a mixture deposited onto the conductive substrate prior to exposing the conductive substrate to laser irradiation, including any intermediate values and subranges therebetween. According to some of any of the embodiments described herein, once the mixture is deposited, the method can optionally comprise heating the substrate having the mixture deposited thereon.
[0219] According to some of any of the embodiments described herein, if heating is effected, heating the substrate having the at least one layer deposited thereon is at a temperature of from 40, and up to 200, or up to 150, or up to 120, or up to 100, °C, for example, is in a range of from 40 to 200, or from 40 to 150, or from 40 to 120, or from 40 to 100, or from 50 to 150, or from 50 to 120, or from 50 to 100, °C, including any intermediate values and subranges therebetween. Such heating is also referred to herein as “soft baking”.
[0220] According to some of any of the embodiments described herein, heating is for a time period of at least 10 seconds, or at least 30 seconds, or at least 45 seconds, or at least or at least 1 minute, for example, is in a range of from 10 seconds to 1 hour, or from 10 second to 30 minutes, or from 10 seconds to 10 minutes, or from 10 seconds to 1 minute, or from 10 seconds to 30 seconds, including any intermediate values and subranges therebetween.
[0221] In some of any of the embodiments described herein, heating is at a temperature of up to 200, or up to 150, or up to 120, or up to 100, °C, including any intermediate values and subranges therebetween; and for a time period of at least 10 seconds, or at least 30 seconds, or at least 45 seconds, or at least 1 minute, and up to 10 hours, including any intermediate values and subranges therebetween.
[0222] According to some of any of the embodiments described herein, heating is performed subsequent to depositing each of the one or more layers.
[0223] In some embodiments, heating is performed at least twice, subsequent to depositing each of the two or more layers (i.e., the method comprises depositing a first layer of the mixture; performing a first heating of the substrate having the first layer deposited thereon; depositing a second layer of the mixture; performing a second heating of the substrate having the second layer deposited thereon; and so forth). In some such embodiments, each heating (e.g., the first heating and the second heating, and following heatings) is performed at the same temperature and / or time period. Alternatively, each heating (after depositing each layer) is performed at a different temperature and / or different time period. In some such embodiments, the second heating is a temperature lower than the temperature of the first heating. In some such embodiments, the second heating is at a temperature higher than the first heating. In some such embodiments, when three or more heatings are performed over three or more deposited layers, each heating is at a temperature lower that the preceding heating. Alternatively, each heating is at a temperature higher than a preceding heating. In exemplary embodiments, the first heating at a temperature of up to 100, or up to 75, or up to 50, or up to 40, °C, including any intermediate values and subranges therebetween; and the second heating is at a higher temperature; and following heatings, if further layers are deposited are at the same or higher temperatures than a preceding heating. In some such embodiments, the first heating is at a temperature of up to 50 °C, and the second heating is at a temperature in a range of from 50 to 200, or from 50 to 150, or from 50 to 120, or from 50 to 100, °C, including any intermediate values and subranges therebetween.
[0224] In alternative embodiments, heating is performed subsequent to depositing two or more layers of the mixture (i.e., the method comprises depositing two or more layers of the mixture, and performing a heating of the substrate after all layers have been deposited.
[0225] According to some of any of the embodiments described herein, the substrate can be made of any material that remains inert during the depositing, optional heating and laser irradiation, as described herein. The substrate can be made of organic or inorganic materials, for example, metal, metal alloy, plastic, glass, other polymeric materials, etc.
[0226] According to some of any of the embodiments described herein, the substrate is a conductive substrate which comprises one or more conductive materials, for example, one or more conductive or semi-conductor materials such as, for example, conductive or semi-conductive metals. In exemplary embodiments, the conductive substrate comprises one or more of stainless steel, copper, and aluminum. According to some of any of the embodiments described herein, the substrate is a conductive substrate made of materials that can later on be integrated in an electrochemical system.
[0227] According to some of any of the embodiments described herein, the conductive substrate is or can form a part of a component of an electrochemical system, such that when the 3D porous structure is formed on at least a portion thereof, the resulting structure can be integrated in an electrochemical system.
[0228] According to some embodiments, the conductive substrate is or forms a part of a current collector.
[0229] According to some embodiments, the substrate comprises stainless steel.
[0230] According to some embodiments, the conductive substrate comprises copper (e.g., is a current collector is a form of a copper foil).
[0231] According to some embodiments, the conductive substrate having the porous structure deposited therein forms or comprises an electrode. As used herein, the phrase “current collector” describes a conductive component in an electrochemical cell that facilitates the transfer of electric current between the external circuit and the active material within the cell, as described further hereinbelow.
[0232] In some of any of the embodiments described herein, once all layers have been deposited, the method proceeds to exposing the deposited mixture to laser irradiation. According to some of any of the embodiments described herein, exposing is subsequent to depositing the two or more layers.
[0233] It is to be understood that it does not matter how many layers and how and if some or all of the layers are heated, irradiation is applied to all layers altogether, unless otherwise indicated (e.g., when the 3D porous structure or the electrochemically active component comprising same as described hereinafter is prepared by additive manufacturing, as described herein in any of the respective embodiments).
[0234] As used herein and in the art, the term "lasing" describes the process by which a laser generates coherent light through the amplification of photons in a gain medium via stimulated emission.
[0235] As used herein and in the art, the phrase "laser writing" describes the process of using a laser beam to directly inscribe, engrave, or modify a material's surface according to a predefined pattern or design.
[0236] As used herein and in the art, the term "rastering" describes a laser processing technique where a laser or other imaging device scans back and forth over a surface in a systematic pattern, usually in parallel lines, to create or modify an image or material. Unlike laser writing, rastering is typically used when the entire area needs to be uniformly covered, rather than following a specific vector path or design outline.
[0237] Herein throughout, the term “laser irradiation” and grammatical diversions thereof, encompasses and used interchangeably with lasing, laser writing and laser rastering or simply rastering or irradiation.
[0238] According to some of any of the embodiments described herein, exposing the mixture to laser irradiation is effected by laser rastering. In some of any of the embodiments described herein, the rastering is performed in one or more scans (paths, passes) across the surface of the (e.g., conductive) substrate, for example, the rastering can be performed in 2, 3, 4, 5, 6, or even more, scans. The number of scans depends on the desired depth of modification on the conductive substrate (e.g., depends on the number of layers and / or thickness of the deposited mixture and / or the desired degree of transformation to graphene). In exemplary embodiments, the rastering is performed in two scans. According to some of any of the embodiments described herein, a number scans and a fluence are selected such that a full transformation is achieved.
[0239] According to some of any of the embodiments described herein, the laser irradiation is performed at any wavelength (i.e., from UV to NIR; from 10 nm to 1400 nm, including any intermediate values and subranges therebetween). According to some of any of the embodiments described herein, the laser irradiation is performed within a UV wavelength range (i.e., from 10 nm to 400 nm, including any intermediate values and subranges therebetween). According to some of any of the embodiments described herein, the laser irradiation is performed at NIR wavelength length (i.e., from 700 nm to 1400 nm, including any intermediate values and subranges therebetween). According to some of any of the embodiments described herein, the laser irradiation is performed at visible wavelength length (i.e., from 400 nm to 700 nm, including any intermediate values and subranges therebetween). According to some of any of the embodiments described herein, the laser irradiation is performed at a wavelength in a range of from 400 to 700 nm, or from 400 to 500 nm, including any intermediate values and subranges therebetween. In exemplary embodiments, the laser irradiation is performed at wavelength of about 450 nm.
[0240] According to some of any of the embodiments described herein, the laser irradiation is performed at a power level of at least 1.0 W, or at least 2.0 W, or at least 2.5 W, or at least 2.8 W, or at least 4.0 W, or at least 6.0 W, or at least 8.0 W, or at least 10.0 W, or at least 20.0 W, or even higher, e.g., 200 W, including any intermediate values and subranges therebetween. In exemplary embodiments, the laser irradiation is performed at a power level of about 2.8 W.
[0241] According to some of any of the embodiments described herein, the laser irradiation is performed for a time period of at least 1 second, or at least 5 seconds, or at least 10 seconds, or at least 30 seconds, or more, and up to 1 hour, for example, from 1 second to 30 second, or from 5 second to 30 seconds, including any intermediate values and subranges therebetween.
[0242] According to some of any of the embodiments described herein, the laser irradiation is performed at a fluence in a range of at least 3.5, or at least 4.0, or at least 4.4, and up to 50.0, J / cm2, including any intermediate values and subranges therebetween. In exemplary embodiments, the laser irradiation is performed at a fluence of 5.5, J / cm2.
[0243] Herein, the term "fluence" describes the energy per unit area delivered by a laser beam to a surface. The fluence determines the amount of energy applied to the mixture, which can affect the extent of physical or chemical changes induced by the laser irradiation. In some of any of the embodiments described herein, exposing comprises irradiating the deposited mixture with a continuous visible laser irradiation (e.g., 450 nm).
[0244] In some of any of the embodiments described herein, a spot size diameter of the laser irradiation is in a range of from 5 to 20, or is about 10, μm (micrometers), including any intermediate values and subranges therebetween.
[0245] In some of any of the embodiments described herein, a speed of the laser irradiation is in a range of from 1 to 40, or is about 20, mm / s, including any intermediate values and subranges therebetween. It is to be understood that
[0246] In some of any of the embodiments described herein, a hatch spacing of the laser irradiation is in a range of from 0.01 to 0.5, or is about 0.1, mm, including any intermediate values and subranges therebetween.
[0247] In some of any of the embodiments described herein, subsequent to exposing to laser irradiation as described herein, heating the substrate having the 3D porous structure deposited thereon is effected.
[0248] According to some of any of the embodiments described herein, heating is at a temperature of at least 100 °C, or at least 120 °C, or at least 150 °C, for example, in a range of from 100 °C to 250 °C, or from 100 °C to 200 °C, or is about 150 °C, including any intermediate values and subranges therebetween. Such heating is also referred to herein as “hard baking”.
[0249] According to some of any of the embodiments described herein, the heating (e.g., the hard baking) is for a time period of at least 1 minute, or at least 5 minutes, or at least 10 minutes, or at least 15 minutes, and up to 1 hour, including any intermediate values and subranges therebetween.
[0250] The method as described herein in any of the respective embodiments and any combination thereof, provides a 3D porous structure that comprises a 3D porous graphene matrix. According to some embodiments, the method provides a 3D porous structure deposited on a substrate as described herein.
[0251] A method as described herein is such that the carbonaceous material which comprises the JF biomass as described herein in any of the respective embodiments, forms a 3D porous structure upon exposure to laser irradiation as described herein in any of the respective embodiments. A method as described herein is such that the carbonaceous material which comprises the JF biomass as described herein in any of the respective embodiments, forms a laser-induced graphene.
[0252] The formed 3D porous graphene matrix and / or laser-induced graphene is a jellyfish-derived graphene matrix. According to an aspect of some embodiments of the present invention there is provided a jellyfish-derived graphene.
[0253] According to an aspect of some embodiments of the present invention there is provided a jellyfish-derived laser-induced graphene.
[0254] According to an aspect of some embodiments of the present invention there is provided a jellyfish-derived 3D porous graphene matrix.
[0255] According to an aspect of some embodiments of the present invention there is provided a jellyfish-derived 3D porous laser-induced graphene.
[0256] According to an aspect of some embodiments of the present invention, there is provided a 3D porous structure that comprises a 3D porous graphene matrix as described herein in any of the respective embodiments, and which is a JF-derived graphene matrix.
[0257] According to an aspect of some embodiments of the present invention, there is provided a 3D porous structure that comprises a 3D porous laser-induced graphene matrix as described herein in any of the respective embodiments, and which is a JF-derived laser-induced graphene matrix.
[0258] According to some of any of the embodiments described herein, the JF-derived 3D porous structure or laser-induced graphene is deposited in a substrate as described herein, and provided is a structure that comprises a substrate having deposited on at least a portion thereof the JF-derived graphene matrix and / or 3D porous structure.
[0259] According to some of any of the embodiments described herein, the JF-derived graphene matrix or JF-derived 3D porous graphene matrix (e.g., laser-induced) is obtainable or obtained by a method as described herein in any of the respective embodiments.
[0260] As used herein, the term "3D porous structure" describes a 3D continuous network, for example, in a form of a film, having a plurality of interconnected pores (holes, voids) therewithin.
[0261] According to the present embodiments, the 3D porous structure comprises a 3D graphene matrix, that is the graphene that is formed by laser irradiation (laser-induced graphene; LIG) is in a form of a 3D continuous network, for example, in a form of a film, having a plurality of interconnected pores (holes, voids) therewithin.
[0262] According to some of any of the embodiments described herein, the 3D graphene matrix is in a non-particulated form, that is, it is substantially devoid of graphene particles, but is rather is a form of a continuous 3D network (e.g., film).
[0263] According to some of any of the embodiments described herein, the 3D porous graphene matrix is in a form of a continuous porous matrix (e.g., a continuous film) or network. By the term “continuous” it is meant that the 3D porous graphene matrix is not fragmented or interrupted or particulates or granulated. Continuity of a matrix can be examined, e.g., via TEM analysis, as exemplified, e.g., in FIG. IE.
[0264] According to some of any of the embodiments described herein, the 3D porous graphene matrix features an overall porosity of at least 20, or at least 30, or at least 40, or at least 45, and up to 80, for example, is in a range of from 20 to 80, or from 20 to 70, or from 20 to 60, or from 20 to 50, or from 30 to 80, or from 40 to 80, or from 30 to 70, or from 40 to 70, or from 30 to 60, or from 40 to 60, or from 30 to 50, or from 40 to 50, %, including any intermediate values and subranges therebetween, when analyzing a binary SEM image with a threshold of 125. In exemplary embodiments, the 3D porous graphene matrix features an overall porosity of about 49 % when analyzing a binary SEM image with a threshold of 125.
[0265] Herein, the phrase “binary SEM image” refers to an image in which each pixel is represented by one of two colors, black or white, where black represents the background and white represents the foreground, or vice versa. The image is generated from a scanning electron microscope (SEM) image, and each pixel is converted to black or white based on a specified threshold value ranging from 0 to 255 (e.g., 125), where 0 represents black, 255 represents white, and values in between determine whether the pixel is converted to black or white depending on whether they fall below or above the threshold.
[0266] According to some of any of the embodiments described herein, the 3D porous graphene matrix features an average pore diameter in a range of from 2 to 20, or from 2 to 15, or from 2 to 10, or from 3.5 to 20, or from 3.5 to 15, or from 3.5 to 10, or from 5 to 20, or from 5 to 15, or from 5 to 10, micrometers, including any intermediate values and subranges therebetween. In exemplary embodiments, the 3D porous graphene matrix features an average pore diameter of about 7 micrometers.
[0267] According to some of any of the embodiments described herein, the 3D porous graphene matrix features at least one of: an average pore diameter in a range of from 2 to 20, or from 2 to 15, or from 2 to 10, or from 3.5 to 20, or from 3.5 to 15, or from 3.5 to 10, or from 5 to 20, or from 5 to 15, or from 5 to 10, or about 7, micrometers, including any intermediate values and subranges therebetween; and an overall porosity of the 3D porous structure is of at least 20, or at least 30, or at least 40, or at least 45, and up to 80, for example, in a range of from 20 to 80, or from 20 to 70, or from 20 to 60, or from 20 to 50, or from 30 to 80, or from 40 to 80, or from 30 to 70, or from 40 to 70, or from 30 to 60, or from 40 to 60, or from 30 to 50, or from 40 to 50, or is about 49, %, including any intermediate values and subranges therebetween, when analyzing a binary SEM image with a threshold of 125.
[0268] According to some of any of the embodiments described herein, an amount of carbon in the JF-derived (e.g., 3D porous) structure (graphene matrix) ranges from 10 to 10 to 70, or from 20 to 70, or from 30 to 70, or from 10 to 60, or from 20 to 60, or from 30 to 60, % by weight of the total weight of the JF-derived (e.g., 3D porous) structure (graphene matrix), including any intermediate values and subranges therebetween.
[0269] According to some of any of the embodiments described herein, an amount of carbon in the JF-derived (e.g., 3D porous) structure (graphene matrix) of at least 10, or at least 20, or at least 30, and up to 60, % by weight of the total weight of the JF-derived (e.g., 3D porous) structure (graphene matrix), including any intermediate values and subranges therebetween.
[0270] In some embodiments, an amount of carbon in the JF-derived (e.g., 3D porous) structure (graphene matrix) ranges from 40 to 100, or from 50 to 100, or from 60 to 100, or from 70 to 100, or from 80 to 100, or from 90 to 100, % by weight of the total weight of the JF-derived (e.g., 3D porous) structure (graphene matrix), including any intermediate values and subranges therebetween.
[0271] In some embodiments, an atomic amount of oxygen in the JF-derived (e.g., 3D porous) structure (graphene matrix) ranges from 1 to 30, or from 5 to 20, %, including any intermediate values and subranges therebetween.
[0272] In some embodiments, an amount of oxygen in the JF-derived (e.g., 3D porous) structure (graphene matrix) ranges from 1 to 30, or from 5 to 25, % by weight of the total weight of the JF- derived (e.g., 3D porous) structure (graphene matrix), including any intermediate values and subranges therebetween.
[0273] In some of any of the embodiments described herein, the relatively high oxygen content in the JF-derived (e.g., 3D porous) structure (graphene matrix) is indicative of the relatively high amount of oxidized species that are derived from the proteins in the protein -rich jellyfish biomass.
[0274] According to some of any of the embodiments described herein, an amount of nitrogen in the JF-derived (e.g., 3D porous) structure (graphene matrix) ranges from 0.1 to 50, or from 0.1 to 20, or from 0.1 to 10, or from 0.1 to 5, or from 0.1 to 3, or from 0.5 to 50, or from 0.1 to 20, or from 0.5 to 10, or from 0.5 to 5, or from 0.5 to 3, or from 1 to 50, or from 1 to 20, or from 1 to 10, or from 1 to 5, or from 1 to 3, % by weight of the total weight of the JF-derived (e.g., 3D porous) structure (graphene matrix), including any intermediate values and subranges therebetween. According to some of any of the embodiments described herein, an atomic amount of nitrogen in the JF-derived (e.g., 3D porous) structure (graphene matrix) ranges from 0.1 to 50, or from 0.1 to 20, or from 0.1 to 10, or from 0.1 to 5, or from 0.1 to 3, or from 0.5 to 50, or from 0.1 to 20, or from 0.5 to 10, or from 0.5 to 5, or from 0.5 to 3, or from 1 to 50, or from 1 to 20, or from 1 to 10, or from 1 to 5, or from 1 to 3, %, including any intermediate values and subranges therebetween.
[0275] In some of any of the embodiments described herein, the relatively high nitrogen content in the JF-derived (e.g., 3D porous) structure (graphene matrix) is indicative of the relatively high amount of species that are derived from the proteins in the protein-rich jellyfish biomass.
[0276] According to some of any of the embodiments described herein, an amount of oxygen relative to a total amount of oxygen and carbon in the JF-derived (e.g., 3D porous) structure (graphene matrix) (% weight of oxygen / % weight of oxygen + % weight of carbon) is at least 5, or at least 10, or at least 15, or ranges from 5 to 40, or from 10 to 30, %, including any intermediate values and subranges therebetween.
[0277] According to some of any of the embodiments described herein, an atomic amount of oxygen relative to a total atomic amount of oxygen and carbon in the JF-derived (e.g., 3D porous) structure (graphene matrix) (% atomic of oxygen / % atomic of oxygen + % atomic of carbon) is at least 5, or at least 10, or ranges from 5 to 40, or from 10 to 25, %, including any intermediate values and subranges therebetween.
[0278] According to some of any of the embodiments described herein, an amount of oxygen relative to a total amount of oxygen, nitrogen and carbon in the JF-derived (e.g., 3D porous) structure (graphene matrix) (% weight of oxygen / % weight of oxygen + % weight of carbon + % weight of nitrogen) is at least 5, or at least 10, or at least 12, or ranges from 5 to 40, or from 12 to 30, %, including any intermediate values and subranges therebetween.
[0279] According to some of any of the embodiments described herein, an atomic amount of oxygen relative to a total atomic amount of oxygen, nitrogen and carbon in the JF-derived (e.g., 3D porous) structure (graphene matrix) (% atomic of oxygen / % atomic of oxygen + % atomic of carbon + % atomic of nitrogen) is at least 5, or at least 10, or ranges from 5 to 40, or from 10 to 30, or from 10 to 25, %, including any intermediate values and subranges therebetween.
[0280] According to some of any of the embodiments described herein, an amount of nitrogen relative to a total amount of nitrogen and carbon in the JF-derived (e.g., 3D porous) structure (graphene matrix) (% weight of nitrogen / % weight of nitrogen + % weight of carbon) is at least 0.5 or at least 1 or ranges from 0.5 to 20, or from 1 to 15, or from 2 to 10, or from 2 to 5, %, including any intermediate values and subranges therebetween.
[0281] According to some of any of the embodiments described herein, an atomic amount of nitrogen relative to a total atomic amount of nitrogen and carbon in the JF-derived (e.g., 3D porous) structure (graphene matrix) (% atomic of nitrogen / % atomic of nitrogen + % atomic of carbon) is at least 0.1, or at least 0.5, or at least 1, or ranges from 0.1 to 20, or from 0.5 to 15, or from 1 to 10, or from 1 to 5, %, including any intermediate values and subranges therebetween.
[0282] According to some of any of the embodiments described herein, an amount of nitrogen relative to a total amount of oxygen, nitrogen and carbon in the JF-derived (e.g., 3D porous) structure (graphene matrix) (% weight of nitrogen / % weight of oxygen + % weight of carbon + % weight of nitrogen) is at least 0.1, or at least 0.5, or at least 1, or ranges from 0.1 to 20, or from 0.5 to 15, or from 1 to 10, or from 1 to 5, %, including any intermediate values and subranges therebetween.
[0283] According to some of any of the embodiments described herein, an atomic amount of nitrogen relative to a total atomic amount of oxygen, nitrogen and carbon in the JF-derived (e.g., 3D porous) structure (graphene matrix) (% atomic of nitrogen / % atomic of oxygen + % atomic of carbon + % atomic of nitrogen) is at least 0.1, or at least 0.5, or at least 1, or ranges from 0.1 to 20, or from 0.5 to 15, or from 1 to 10, or from 1 to 5, %, including any intermediate values and subranges therebetween.
[0284] According to some of any of the embodiments described herein, an amount of oxygen relative to a total amount of oxygen and carbon in the JF-derived (e.g., 3D porous) structure (graphene matrix) (% weight of oxygen / % weight of oxygen + % weight of carbon) is at least 5, or at least 10, or at least 15, or ranges from 5 to 40, or from 10 to 30, %, including any intermediate values and subranges therebetween; and an amount of nitrogen relative to a total amount of nitrogen and carbon in the JF- derived (e.g., 3D porous) structure (graphene matrix) (% weight of nitrogen / % weight of nitrogen + % weight of carbon) is at least 0.5 or at least 1 or ranges from 0.5 to 20, or from 1 to 15, or from 2 to 10, or from 2 to 5, %, including any intermediate values and subranges therebetween.
[0285] According to some of any of the embodiments described herein, an atomic amount of oxygen relative to a total atomic amount of oxygen and carbon in the JF-derived (e.g., 3D porous) structure (graphene matrix) (% atomic of oxygen / % atomic of oxygen + % atomic of carbon) is at least 5, or at least 10, or ranges from 5 to 40, or from 10 to 25, %, including any intermediate values and subranges therebetween; and an atomic amount of nitrogen relative to a total atomic amount of nitrogen and carbon in the JF-derived (e.g., 3D porous) structure (graphene matrix) (% atomic of nitrogen / % atomic of nitrogen + % atomic of carbon) is at least 0.1, or at least 0.5, or at least 1, or ranges from 0.1 to 20, or from 0.5 to 15, or from 1 to 10, or from 1 to 5, %, including any intermediate values and subranges therebetween.
[0286] According to some of any of the embodiments described herein, an amount of oxygen relative to a total amount of oxygen, nitrogen and carbon in the JF-derived (e.g., 3D porous) structure (graphene matrix) (% weight of oxygen / % weight of oxygen + % weight of carbon + % weight of nitrogen) is at least 5, or at least 10, or at least 12, or ranges from 5 to 40, or from 12 to 30, %, including any intermediate values and subranges therebetween; and an amount of nitrogen relative to a total amount of oxygen, nitrogen and carbon in the JF-derived (e.g., 3D porous) structure (graphene matrix) (% weight of nitrogen / % weight of oxygen + % weight of carbon + % weight of nitrogen) is at least 0.1, or at least 0.5, or at least 1, or ranges from 0.1 to 20, or from 0.5 to 15, or from 1 to 10, or from 1 to 5, %, including any intermediate values and subranges therebetween.
[0287] According to some of any of the embodiments described herein, an atomic amount of oxygen relative to a total atomic amount of oxygen, nitrogen and carbon in the JF-derived (e.g., 3D porous) structure (graphene matrix) (% atomic of oxygen / % atomic of oxygen + % atomic of carbon + % atomic of nitrogen) is at least 5, or at least 10, or ranges from 5 to 40, or from 10 to 30, or from 10 to 25, %, including any intermediate values and subranges therebetween; and an atomic amount of nitrogen relative to a total atomic amount of oxygen, nitrogen and carbon in the JF-derived (e.g., 3D porous) structure (graphene matrix) (% atomic of nitrogen / % atomic of oxygen + % atomic of carbon + % atomic of nitrogen) is at least 0.1, or at least 0.5, or at least 1, or ranges from 0.1 to 20, or from 0.5 to 15, or from 1 to 10, or from 1 to 5, %, including any intermediate values and subranges therebetween.
[0288] According to some of any of the embodiments described herein, the 3D porous structure is characterized by one or more of: an amount of oxygen of at least 1 or at least 5 or ranges from 1 to 50, or from 5 to 20, %, by weight of the total weight of the 3D porous structure; and / or an atomic amount of oxygen of at least 1 or at least 5 or ranges from 1 to 50, or from 5 to 20, %; and / or an amount of nitrogen of at least 0.1 or at least 0.5 or ranges from 0.1 to 50, or from 0.5 to 5, or from 0.8 to 2, %, by weight of the total weight of the 3D porous structure; and / or an atomic amount of nitrogen of at least 0.1 or at least 0.5 or ranges from 0.1 to 50, or from 0.5 to 5, or from 0.8 to 2, %; and / or an amount of oxygen relative to a total amount of oxygen and carbon (% weight of oxygen / % weight of oxygen + % weight of carbon) of at least 5, or at least 10, or at least 15, or ranges from 5 to 40, or from 10 to 30; and / or an atomic amount of oxygen relative to a total atomic amount of oxygen and carbon (graphene matrix) (% atomic of oxygen / % atomic of oxygen + % atomic of carbon) of at least 5, or at least 10, or ranges from 5 to 40, or from 10 to 25; and / or an amount of oxygen relative to a total amount of oxygen, nitrogen and carbon (% weight of oxygen / % weight of oxygen + % weight of carbon + % weight of nitrogen) of at least 5, or at least 10, or at least 12, or ranges from 5 to 40, or from 12 to 30, %; and / or an atomic amount of oxygen relative to a total atomic amount of oxygen, nitrogen and carbon (% atomic of oxygen / % atomic of oxygen + % atomic of carbon + % atomic of nitrogen) of at least 5, or at least 10, or ranges from 5 to 40, or from 10 to 30, or from 10 to 25, %; and / or an amount of nitrogen relative to a total amount of nitrogen and carbon (% weight of nitrogen / % weight of nitrogen + % weight of carbon) of at least 0.5 or at least 1 or ranges from 0.5 to 20, or from 1 to 15, or from 2 to 10, or from 2 to 5, %; and / or an atomic amount of nitrogen relative to a total atomic amount of nitrogen and carbon (% atomic of nitrogen / % atomic of nitrogen + % atomic of carbon) of at least 0.1, or at least 0.5, or at least 1, or ranges from 0.1 to 20, or from 0.5 to 15, or from 1 to 10, or from 1 to 5, %; and / or an amount of nitrogen relative to a total amount of oxygen, nitrogen and carbon (% weight of nitrogen / % weight of oxygen + % weight of carbon + % weight of nitrogen) of at least 0.1 , or at least 0.5, or at least 1, or ranges from 0.1 to 20, or from 0.5 to 15, or from 1 to 10, or from 1 to 5, %; and / or an atomic amount of nitrogen relative to a total atomic amount of oxygen, nitrogen and carbon (% atomic of nitrogen / % atomic of oxygen + % atomic of carbon + % atomic of nitrogen) of at least 0.1, or at least 0.5, or at least 1, or ranges from 0.1 to 20, or from 0.5 to 15, or from 1 to 10, or from 1 to 5, %.
[0289] When the mixture further comprises a flame retardant such as boric acid, an amount of boron relative to a total amount of boron and carbon in the JF-derived (e.g., 3D porous) structure (graphene matrix) (% weight of boron / % weight of boron + % weight of carbon) is at least 0.01, or ranges from 0.01 to 0.1, %, including any intermediate values and subranges therebetween.
[0290] When the mixture further comprises a flame retardant such as boric acid, an atomic amount of boron relative to a total atomic amount of boron and carbon in the JF-derived (e.g., 3D porous) structure (graphene matrix) (% atomic of boron / % atomic of boron + % atomic of carbon) is at least 0.01, or ranges from 0.01 to 0.1, %, including any intermediate values and subranges therebetween.
[0291] In some of any of the embodiments described herein, the JF-derived (e.g., 3D porous) structure (graphene matrix) is characterized by one or more, or two or more, or three or more, or all, of: an atomic amount of oxygen of at least 5, or at least 10, or ranges from 5 to 40, or from 10 to 30, or from 10 to 25, %, including any intermediate values and subranges therebetween; and / or an atomic amount of nitrogen of at least 0.1, or at least 0.5, or at least 1, or ranges from 0.1 to 20, or from 0.5 to 15, or from 1 to 10, or from 1 to 5, %, including any intermediate values and subranges therebetween; and / or an amount of oxygen of at least 5, or at least 10, or at least 12, or ranges from 5 to 40, or from 12 to 30, % by weight of the total weight of the jellyfish-derived structure, including any intermediate values and subranges therebetween; and / or an amount of nitrogen of at least 0.1, or at least 0.5, or at least 1, or ranges from 0.1 to 20, or from 0.5 to 15, or from 1 to 10, or from 1 to 5, % by weight jellyfish-derived structure, including any intermediate values and subranges therebetween; and / or an amount of boron relative to a total amount of boron and carbon in the JF-derived (e.g., 3D porous) structure (graphene matrix) (% weight of boron / % weight of boron + % weight of carbon) is at least 0.01, or ranges from 0.01 to 1, or from 0.01 to 0.1, %, including any intermediate values and subranges therebetween; and / or an atomic amount of boron relative to a total atomic amount of boron and carbon in the JF- derived (e.g., 3D porous) structure (graphene matrix) (% atomic of boron / % atomic of boron + % atomic of carbon) is at least 0.01, or ranges from 0.01 to 1, or from 0.01 to 0.1, %, including any intermediate values and subranges therebetween. an amount of boron relative to a total amount of boron, oxygen, nitrogen and carbon in the JF- derived (e.g., 3D porous) structure (graphene matrix) (% weight of boron / % weight of boron + % weight of oxygen + % weight of carbon + % weight of nitrogen) is at least 0.01, or ranges from 0.01 to 1, or from 0.01 to 0.1, %, including any intermediate values and subranges therebetween. an atomic amount of boron relative to a total atomic amount of boron, oxygen, nitrogen and carbon in the JF-derived (e.g., 3D porous) structure (graphene matrix) (% atomic of boron / % atomic of boron + % atomic of oxygen + % atomic of carbon + % atomic of nitrogen) is at least 0.01, or ranges from 0.01 to 1, or from 0.01 to 0.1, %, including any intermediate values and subranges therebetween. In some of any of the embodiments described herein, a thickness of the 3D porous graphene matrix is determined by a number of layers and a thickness of each layer as described herein.
[0292] According to some of any of the embodiments described herein, the 3D porous structure, by being formed by subjecting a carbonaceous material to laser irradiation, comprises a 3D porous matrix that comprises or consists of laser-induced graphene (LIG).
[0293] According to some of any of the embodiments described herein, a ratio of an intensity of D and G bands (ID / IG) of the 3D porous structure, as measured by Raman spectroscopy, is at least 0.75 and is up to 1.3, or up to 1.2, for example, is in a range of from 0.75 to 1.3, or from 0.75 to 1.2, or from 0.8 to 1.2, or from 0.9 to 1.2, or from 1.0 to 1.2, or from 1.1 to 1.2, including any intermediate values and subranges therebetween.
[0294] It should be understood that a ratio of an intensity of D and G bands (ID / IG) in a range according to some of these embodiments is indicative of a presence of graphene, and is thus indicative of a 3D graphene matrix as described herein.
[0295] In some of any of the embodiments described herein, the 3D porous structure is devoid of graphite.
[0296] In some of any of the embodiments described herein, the 3D porous structure is devoid of additives (e.g., at least one of catalysts, conductive additives, binders (such as organic polymer binders), polymer additives, dopants and functional groups, and metal oxides) and / or decomposition products of the additives.
[0297] Non-limiting examples for binders include polyvinylidene fluoride (PVDF), carboxymethyl cellulose (CMC), and styrene -butadiene rubber (SBR).
[0298] Non-limiting examples for conductive additives include carbon black, carbon nanotubes (CNTs), and Super P®.
[0299] Non-limiting examples for polymer additives include polyethylene oxide (PEG) and polyacrylic acid (PAA).
[0300] Non-limiting examples for dopants and functional groups include nitrogen (N)-doping and oxygen functional groups.
[0301] Non-limiting examples for metal oxides include titanium oxide (TiO2), manganese dioxide (MnO2) or nickel oxide (NiO).
[0302] According to some of the present embodiments, the 3D porous structure is or forms a part of an electrochemically active component. Herein the phrase “electrochemically active component” describes a component that can be integrated in an electrochemical system such as an electrochemical half-cell, cell or battery, as an active component that participates in the electrochemical reaction that occurs when the system operates. An electrochemically active component can be an electrode (e.g., an anode or a cathode), a portion of an electrode, or an electrode that is in electric communication with a current collector, for example, is deposited on a current collector.
[0303] According to some of any of the embodiments described herein, the electrochemically active component is such that can be integrated in an alkali ion battery such as a lithium ion battery (also abbreviated herein as LIB or referred to interchangeably as lithium battery), as described herein.
[0304] Herein, the phrase “alkali metal” encompasses lithium, sodium, potassium, rubidium and cesium and combinations thereof, and encompasses alkali metal atoms (e.g., metallic forms of alkali metals) and alkali metal cations. According to some embodiments, the alkali metal is lithium.
[0305] According to some of these embodiments, the method as described herein in any of the respective embodiments and any combination thereof, so as to provide an electrochemically active material or agent associated with the JF-derived graphene matrix.
[0306] According to some of any of the embodiments, the electrochemically active material or agent is physically associated with the JF-derived graphene matrix such that it is embedded / entrapped / dispersed within the graphene matrix as described herein in any of the respective embodiments.
[0307] Herein, the phrases “electrochemically active material”, “electrochemically active agent”, “active material” and “active agent” are used interchangeably and all describe a material (agent) that can participate in an electrochemical reaction, such that when it is present in an electrochemical system such as a battery as described herein, it participates in the electrochemical reaction that occurs when the system (e.g., battery) operates.
[0308] According to some of any of the embodiments described herein, the electrochemically active material is such that can participate in an electrochemical reaction that occurs when an alkali metal- based electrochemical system such as a battery as described herein operates. According to some of these embodiments, the electrochemically active material is such that is capable of reversibly releasing an alkali metal ion, for example, a lithium ion.
[0309] According to some of these embodiments, the electrochemically active material is such that can form a part of an anode in an alkali metal battery. The phrase “reversibly releasing” means that the material is capable of absorbing and / or interacting with the alkali metal (e.g., an alkali metal ion), e.g., by forming a chemical complex (e.g., an alloy) with the alkali metal, during charging, and is capable of releasing the alkali metal (e.g., alkali metal ion) during discharging.
[0310] When the alkali metal is lithium, the electrochemically active material is capable of reversibly undergoing lithiation during charging and delithiation during discharging.
[0311] According to some embodiments of the present invention, the electrochemically active material features a theoretical capacity, which is higher than that of graphene, for example, is higher by at least 50 %, or by at least 100 %, or by at least 200 %, or more, for example, up to 100,000 %, than the theoretical capacity of graphene with respect to lithium.
[0312] According to some of any of the embodiments described herein, electrochemically active material is in a form of particles. In some of any of the embodiments described herein, the electrochemically active material is in a form of a plurality of particles. The particles can be, for example, microparticles and / or nanoparticles.
[0313] According to some of any of the embodiments described herein, the electrochemically active material is in a form of a plurality of nanoparticles.
[0314] According to some of any of the embodiments described herein, the particles have an average diameter in a range of from 1 to 800, or from 1 to 600, or from 1 to 500, or from 1 to 300, nm, including any intermediate values and subranges therebetween. According to some of any of the embodiments described herein, the particles have an average diameter in a range of from 1 to 300, or from 10 to 300, or from 25 to 300, or from 50 to 300, or from 75 to 300, or from 1 to 200, or from 10 to 200, or from 25 to 200, or preferably from 50 to 200, or from 75 to 200, or from 10 to 250, or from or from 25 to 250, or from 50 to 250, or from 75 to 250, or from 1 to 175, or from 10 to 175, or from 25 to 175, or from 50 to 175, or from 75 to 175, or from 1 to 150, or from 10 to 150, or from 25 to 150, or from 50 to 150, or from 75 to 150, or from 1 to 125, or from 10 to 125, or from 25 to 125, or from 50 to 125, or from 75 to 125, including any intermediate values and subranges therebetween, or of up to 200 nm. In exemplary embodiments, the particles have an average diameter of about 100 nm.
[0315] According to some of any of the embodiments described herein, the electrochemically active material is or comprises silicon.
[0316] According to some of any of the embodiments described herein, the electrochemically active material is silicon. According to some of any of the embodiments described herein, electrochemically active material is or comprises a plurality of silicon particles, for example, a plurality of silicon nanoparticles.
[0317] According to some of any of the embodiments described herein, the electrochemically active material is or comprises silicon, and the particles are or comprise silicon nanoparticles.
[0318] In some of any of the embodiments described herein, the electrochemically active material dispersed and / or embedded and / or entrapped therewithin the graphene matrix is crystalline.
[0319] As used herein, the term “crystalline” describes a compound that has a well-defined, ordered atomic structure, characterized by a repeating pattern in three dimensions. This ordered structure gives rise to specific crystallographic orientations of planes, which are described by Miller indices. These indices represent particular planes within the crystal lattice, each with a unique arrangement of atoms. The degree to which these ordered planes are present in a material is referred to as its crystallinity, which can be determined through techniques like X-ray diffraction (XRD) or Selected Area Electron Diffraction (SAED).
[0320] In some of any of the embodiments described herein, a crystallographic orientation of plane of the electrochemically active material dispersed and / or embedded and / or entrapped therewithin the graphene matrix is similar to the a crystallographic orientation of plane of the electrochemically active material prior to the exposure of a mixture comprising it to laser irradiation (i.e., it retains its crystallographic orientations of planes upon exposure to laser irradiation). Crystallographic orientations of planes can be determined, e.g., via Selected Area Electron Diffraction (SAED) analysis, as exemplified, e.g., in FIG. 4A. In some of any of the embodiments described herein, a crystallographic orientations of planes within the electrochemically active material dispersed and / or embedded and / or entrapped therewithin the graphene matrix is (111), (220).
[0321] According to some of any of the embodiments described herein, the method of this aspect of the present embodiments is such that the mixture that comprises the carbonaceous material that comprises a JF biomass as described herein in any of the respective embodiments, further comprises the electrochemically active material as described herein in any of the respective embodiments and any combination thereof.
[0322] According to some of any of the embodiments described herein, the method of this aspect of the present embodiments is such that the mixture that comprises the carbonaceous material that comprises a JF biomass as described herein in any of the respective embodiments, further comprises silicon particles (e.g., nanoparticles) as described herein in any of the respective embodiments and any combination thereof. According to some of any of the embodiments described herein, an amount of the electrochemically active material as described herein in any of the respective embodiments in the mixture ranges from 1 to 90, or from 1 to 70, or from 1 to 50, or from 1 to 30, or from 1 to 20, or from 1 to 10, or from 1 to 5, or from 10 to 90, or from 20 to 90, or from 50 to 90, or from 70 to 90, or from 30 to 80, or from 50 to 80, or from 20 to 60, %, by total weight of the electrochemically active material and the carbonaceous material that comprises a JF biomass (as those are described herein in any of the respective embodiments) in the mixture, including any intermediate values and subranges therebetween.
[0323] According to some of any of the embodiments described herein, a weight ratio of the carbonaceous material that comprises a JF biomass as described herein in any of the respective embodiments and the electrochemically active material as described herein in any of the respective embodiments in the mixture ranges from 1000: 1 to 1: 1000, or from 1000: 1 to 1: 100, or from 1000: 1 to 1:10, or from 1000: 1 to 1: 1, or from 100: 1 to 1: 100, or from 100:1 to 1: 10, or from 100:1 to 1: 1, or from 10: 1 to 1:10, or from 10:1 to 1: 1, including any intermediate values and subranges therebetween. In exemplary embodiments, a weight ratio of the carbonaceous material and the electrochemically active material is in range of from 10: 1.5 to 10:4.5.
[0324] According to an aspect of some embodiments of the present invention there is provided a method of preparing an electrochemically active component. In some of any of the embodiments described herein, the method comprises depositing a mixture that comprises a carbonaceous material which comprises a JF biomass as described herein, and an electrochemically active material, as described herein, on a substrate, preferably a conductive substrate as described herein, to thereby to thereby obtain the (e.g., conductive) substrate having the mixture deposited on at least a portion of a surface thereof; and exposing the (e.g., conductive) substrate having the mixture deposited thereon to laser irradiation.
[0325] According to some of any of the embodiments described herein, a mixture that comprises a carbonaceous material as described in some of any of the present embodiments (e.g., jellyfish biomass, e.g., dry) and an electrochemically active material as described in some of any of the present embodiments (e.g., silicon; e.g., in a form of particles, e.g., nanoparticles) is deposited onto an electrically conductive substrate as described in some of any of the present embodiments. In some of any of the embodiments described herein, prior to the depositing, the mixture is homogenized.
[0326] According to some of any of the embodiments described herein, the method is effected by depositing a mixture of a carbonaceous material as described herein in any of the respective embodiments and an electrochemically active material as described herein in any of the respective embodiments on a substrate as described herein in any of the respective embodiments, and exposing the substrate to a laser irradiation (e.g., laser irradiation that transforms the carbonaceous material to a 3D porous graphene (e.g., continuous) matrix as described herein).
[0327] According to some of any of the embodiments described herein, the method is effected by depositing at least one layer of a mixture that comprises a carbonaceous material and an electrochemically active material as described herein in any of the respective embodiments onto a substrate such as a conductive substrate as described herein in any of the respective embodiments, to thereby obtain the conductive substrate having the at least one layer deposited on at least a portion of a surface thereof, as described herein in any of the respective embodiments; and exposing the conductive substrate having the at least one layer deposited thereon to laser irradiation, as described herein in any of the respective embodiments. The method is such that forms a 3D porous structure deposited onto the at least a portion of the surface of the (e.g., conductive) substrate, as described herein in any of the respective embodiments.
[0328] In some of any of the embodiments described herein, the mixture is devoid of additives (e.g., at least one of catalysts, conductive additives, binders (such as organic polymer binders), polymer additives, dopants and functional groups, and metal oxides), as those are described herein in any of the respective embodiments, and / or of decomposition products of the additives.
[0329] In some of any of the embodiments described herein, the electrochemically active material is dispersed in or mixed with a mixture that comprises a carbonaceous material that comprises a JF biomass comprises a processed JF biomass, which is a form of a paste (obtained by centrifugation as described herein) or in a dry form, as described herein.
[0330] According to some of any of the embodiments described herein, the mixture that comprises the electrochemically active material and the carbonaceous material that comprises a JF biomass further comprises a liquid or semi-solid carrier (e.g., an aqueous carrier, e.g., water, ethanol, or a gel).
[0331] According to some of any of the embodiments described herein, the carbonaceous material is in a form of a liquid or a semi-solid (e.g., a gel) at room temperature.
[0332] According to some of these embodiments, when the electrochemically active material is in a form of a plurality of particles, the mixture is in a form of a slurry that comprises the particles dispersed in the carbonaceous material.
[0333] According to some of any of the embodiments described herein, the mixture is devoid of graphite or is devoid of a graphitic substance or is devoid of graphite powder. According to some of any of the embodiments described herein, the mixture comprises a paste, a powder or particles of the jellyfish biomass dispersed in or mixed with the carrier.
[0334] According to some of any of the embodiments described herein, the mixture comprises an electrochemically active material as described herein and a powder or particles of the dried jellyfish biomass dispersed in or mixed with the carrier. Alternatively, in some embodiments, the mixture comprises an electrochemically active material as described herein and a paste as described herein, mixed with the carrier. One or more carbonaceous materials and one or more electrochemically active materials can be included in the mixture.
[0335] According to some of any of the embodiments described herein, the mixture further comprises a flame retardant (e.g., boric acid).
[0336] In some of any of the embodiments described herein, prior to depositing the mixture on a substrate, the mixture is subjected to homogenization (the mixture is homogenized). Non-limiting examples for homogenizing a mixture include mechanical stirring, ultra-sonication, high-shear mixing, and ball milling.
[0337] It is to be understood that a liquid or a semi-solid consistency of the mixture may facilitate depositing the mixture onto the conductive substrate, while subjecting the mixture to homogenization assures that the deposition is consistent and uniform.
[0338] According to some of any of the embodiments described herein, the depositing, the substrate, and the laser irradiation, are each independently as described herein in any of the respective embodiments and any combination thereof.
[0339] According to some of any of the embodiments described herein, upon laser irradiation, a thickness of the 3D porous structure is at least 5 %, or at least 10 %, or at least 15 %, or of about 20 %, lower than a thickness of the (deposited) JF biomass (i.e., pre-lasing). Without being bound to any particular theory, this is primarily attributed to the degassing of the JF biomass and the additional carbonaceous material (if present).
[0340] The method as described herein in any of the respective embodiments of this aspect and any combination thereof provides a 3D porous structure that comprises a JF-derived 3D porous graphene matrix and an electrochemically active material dispersed and / or entrapped and / or embedded therewithin.
[0341] The method as described herein in any of the respective embodiments of this aspect and any combination thereof is such that the carbonaceous materials and the electrochemically active material, as those are described herein in any of the respective embodiments, form a 3D porous structure upon exposure to laser irradiation as described herein in any of the respective embodiments.
[0342] In some of any of the embodiments described herein, the jellyfish-derived porous structure as described herein in any of the respective embodiments has an electrochemically active material as described herein in any of the respective embodiments (e.g., silicon particles) dispersed and / or embedded and / or entrapped therewithin.
[0343] According to some of any of the embodiments described herein, the electrochemically active material (e.g., silicon particles) is present or occupies in at least a portion of the pores within the 3D graphene matrix, such that it is dispersed and / or embedded and / or entrapped within the matrix.
[0344] According to some of any of the embodiments described herein, an amount of the electrochemically active material (e.g., silicon) in the 3D porous structure comprising same ranges from 10 to 90, or from 15 to 90, or from 10 to 80, or from 15 to 80, or from 10 to 70, or from 15 to 70, % by weight of the total weight of the 3D porous structure, including any intermediate values and subranges therebetween.
[0345] According to some of any of the embodiments described herein, an amount of the electrochemically active material (e.g., silicon) in the 3D porous structure comprising same of at least 10, or at least 15, and up to 80, % by weight of the total weight of the 3D porous structure, including any intermediate values and subranges therebetween.
[0346] According to some of any of the embodiments described herein, an atomic amount of the electrochemically active material (e.g., silicon) in the 3D porous structure comprising same ranges from 1 to 90, or from 5 to 90, or from 10 to 80, or from 10 to 60, or from 10 to 50, or from 10 to 45, %, including any intermediate values and subranges therebetween.
[0347] According to some of any of the embodiments described herein, an amount of carbon in the 3D porous structure that comprises the electrochemically active material ranges from 10 to 70, or from 20 to 70, or from 30 to 70, or from 10 to 60, or from 20 to 60, or from 30 to 60, % by weight of the total weight of the 3D porous structure, including any intermediate values and subranges therebetween.
[0348] According to some of any of the embodiments described herein, an amount of carbon in the 3D porous structure that comprises the electrochemically active material is of at least 10, or at least 20, or at least 30, and up to 60, % by weight of the total weight of the 3D porous structure, including any intermediate values and subranges therebetween.
[0349] According to some of any of the embodiments described herein, an atomic amount of carbon in the 3D porous structure that comprises the electrochemically active material is from 40 % and up to 70 %, or ranges from 10 to 90, or from 20 to 80, or from 30 to 70, or from 40 to 80, or from 50 to 70, %, including any intermediate values and subranges therebetween.
[0350] According to some of any of the embodiments described herein, a 3D porous structure that comprises a JF-derived graphene matrix and an electrochemically active component as described herein in any of the respective embodiments is also referred to herein as a composite structure or a composite 3D structure, and the like.
[0351] According to some of any of the embodiments described herein, the composite structure is characterized by a relative amount and / or atomic % of oxygen and nitrogen, as described herein in any of the respective embodiments that relate to JF-derived graphene matrix.
[0352] According to some of any of the embodiments described herein, an amount of oxygen in the composite structure (the 3D porous structure) is at least 1 or at least 5 or ranges from 1 to 50, or from 5 to 20, %, by weight of the total weight of the composite structure, including any intermediate values and subranges therebetween.
[0353] According to some of any of the embodiments described herein, an atomic amount of oxygen in the composite structure (the 3D porous structure) is at least 1 or at least 5 or ranges from 1 to 50, or from 5 to 20, %, including any intermediate values and subranges therebetween.
[0354] According to some of any of the embodiments described herein, an amount of nitrogen in the composite structure (in the 3D porous structure) is at least 0.1 or at least 0.5 or ranges from 0.1 to 50, or from 0.5 to 5, or from 0.8 to 2, %, by weight of the total weight of the composite structure, including any intermediate values and subranges therebetween.
[0355] According to some of any of the embodiments described herein, an atomic amount of nitrogen in the composite structure (the 3D porous structure) is at least 0.1 or at least 0.5 or ranges from 0.1 to 50, or from 0.5 to 5, or from 0.8 to 2, %, including any intermediate values and subranges therebetween.
[0356] When the mixture further comprises a flame retardant such as boric acid, an amount of boron in the composite structure (the 3D porous structure) is at least 0.01 or at least 0.1 or ranges from 0.01 to 30, or from 0.1 to 10, including any intermediate values and subranges therebetween.
[0357] In some of any of the embodiments described herein, the 3D porous structure is characterized by one or more, or by two or more, or by three or more, or all, of: an amount of oxygen of at least 1 or at least 5 or ranges from 1 to 50, or from 5 to 20, %, by weight of the total weight of the 3D porous structure; and / or an atomic amount of oxygen of at least 1 or at least 5 or ranges from 1 to 50, or from 5 to 20, %; and / or an amount of nitrogen of at least 0.1 or at least 0.5 or ranges from 0.1 to 50, or from 0.5 to 5, or from 0.8 to 2, %, by weight of the total weight of the 3D porous structure; and / or an atomic amount of nitrogen of at least 0.1 or at least 0.5 or ranges from 0.1 to 50, or from 0.5 to 5, or from 0.8 to 2, %.
[0358] According to some of any of the embodiments described herein, an amount of oxygen in the composite structure is at least 1 or at least 5 or ranges from 1 to 50, or from 5 to 20, %, by weight of the total weight of the composite structure, including any intermediate values and subranges therebetween; and / or
[0359] According to some of any of the embodiments described herein, an atomic amount of oxygen in the composite structure is at least 1 or at least 5 or ranges from 1 to 50, or from 5 to 20, %, including any intermediate values and subranges therebetween; and / or
[0360] According to some of any of the embodiments described herein, an amount of nitrogen in the composite structure is at least 0.1 or at least 0.5 or ranges from 0.1 to 50, or from 0.5 to 5, or from 0.8 to 2, %, by weight of the total weight of the composite structure, including any intermediate values and subranges therebetween; and / or
[0361] According to some of any of the embodiments described herein, an atomic amount of nitrogen in the composite structure is at least 0.1 or at least 0.5 or ranges from 0.1 to 50, or from 0.5 to 5, or from 0.8 to 2, %, including any intermediate values and subranges therebetween; and / or
[0362] When the mixture further comprises a flame retardant such as boric acid, an amount of boron in the composite structure is at least 0.01 or at least 0.1 or ranges from 0.01 to 30, or from 0.1 to 10, including any intermediate values and subranges therebetween.
[0363] According to some of any of the embodiments described herein, the method is practiced while using as a conductive substrate a component of an electrochemical system as described herein. According to some of any of the embodiments described herein, the conductive substrate is or forms a part of current collector as described herein, and the formed 3D porous structure forms an electrode deposited on the current collector.
[0364] According to some of any of the embodiments described herein, the electrode is usable as an electrode in an electrochemical system as described herein, for example, in an alkali metal ion battery.
[0365] According to some of any of the embodiments described herein, the electrode is usable as an anode in an alkali metal ion battery.
[0366] According to some of any of the embodiments described herein, the alkali metal ion battery is a lithium-ion battery. According to some of any of the embodiments described herein, the electrode is usable as an electrode in a lithium-ion battery.
[0367] According to some of any of the embodiments described herein, the electrode is usable as an anode in a lithium-ion battery.
[0368] According to some of any of the embodiments described herein, the method is effected at temperatures that do not exceed 200, or 250, °C, such that a temperature at which any of the steps of the method is performed ranges from room temperature (e.g., 15-25, or 20-25, °C) to 200 or 250 °C.
[0369] According to an aspect of some embodiments of the present invention there is provided an electrochemically active component as defined and described herein, which comprises a 3D porous structure (e.g., as described herein in any of the respective embodiments), which comprises a (e.g., continuous) JF-derived 3D porous graphene matrix (e.g., as described herein in any of the respective embodiments), having an electrochemically active material (e.g., as described herein in any of the respective embodiments) dispersed and / or embedded and / or entrapped therewithin.
[0370] According to an aspect of some embodiments of the present invention there is provided an electrochemically active component obtained by the method as described herein in any of the respective embodiments.
[0371] According to an aspect of some embodiments of the present invention there is provided an electrochemically active component comprising a 3D porous structure (a composite structure) which comprises a JF-derived 3D porous graphene matrix having the electrochemically active material dispersed and / or entrapped and / or embedded therewithin. In some such embodiments, the graphene matrix is formed of a carbonaceous material (e.g., as described herein in any of the respective embodiments) that comprises a jellyfish biomass (e.g., as described herein in any of the respective embodiments).
[0372] According to some of any of the embodiments described herein, the electrochemically active component comprises a conductive substrate, and the 3D porous structure (composite structure) is deposited onto at least a portion of a surface of the conductive substrate.
[0373] According to some of any of the embodiments described herein, the electrochemically active component is or comprises an electrode as described herein in any of the respective embodiments and in any combination thereof. In some of any of the embodiments described herein, the electrode is in an electric communication with a current collector. In exemplary embodiments, the electrode deposited on the current collector as described herein in any of the respective embodiments.
[0374] According to some of any of the embodiments described herein, the conductive substrate is a current collector, and the electrochemically active component is or comprises an electrode deposited on the current collector.
[0375] According to some of any of the embodiments described herein, the (e.g., continuous) JF- derived 3D porous graphene matrix is or comprises a laser-induced graphene.
[0376] According to some of any of the embodiments described herein, the laser-induced graphene is obtained by exposing a mixture comprising a carbonaceous material which comprises a JF biomass and particles of an electrochemically active material to a laser irradiation as described herein in any of the respective embodiments.
[0377] In some of the present embodiments, the phrases “three-dimensional porous conductive carbon composite”, “3D porous carbon composite structure”, “conductive 3D porous composite structure”, “3D porous conductive carbon-silicon composite”, “3D porous conductive carbon-silicon composite”, “a composite”, a “composite structure”, and variations thereof are used interchangeably to describe a 3D porous structure formed by a method according to some of the embodiments described herein.
[0378] According to an aspect of some embodiments of the present invention there is provided an electrochemical system comprising the electrochemically active component (composite structure) as described herein in any of the respective embodiments.
[0379] Herein throughout, the term "electrochemical system" describes any configuration that comprises at least one electrode, a power source, and a substance that undergoes redox (reduction- oxidation) reactions. An electrochemical system typically further comprises an electrolyte to facilitate ion movement between electrodes. The term "electrochemical system" encompasses various configurations, including but not limited to electrochemical half-cells, full cells, fuel cells, and batteries.
[0380] Electrochemical systems that comprise graphene can serve multiple functions, depending on their design and application. Non-limiting examples for possibly suitable applications of electrochemical systems that comprise graphene include electronics and semiconductors, energy storage, sensors, composites, thermal management, water filtration, and medical applications.
[0381] As used herein, the phrase “electronics and semiconductors” describes devices or materials that manipulate electric current for various functions, including computing, sensing, and power management. Non-limiting examples include transistors, transparent conductors, and flexible electronics.
[0382] As used herein, the phrase “energy storage” describes systems or devices that capture energy for use at a later time, typically by converting energy into a chemical or electrical form. Non-limiting examples include supercapacitors and batteries.
[0383] As used herein, the term “sensor” describes a device that detects or measures a physical property or chemical composition and converts this information into a signal that can be read or interpreted. Non-limiting examples include electrochemical sensors, chemical sensors, and biosensors.
[0384] As used herein, the term “composites” describes materials made from two or more different substances that, when combined, produce a material with enhanced properties. Non-limiting examples include structural materials and conductive inks.
[0385] As used herein, the phrase “thermal management” describes the control and dissipation of heat in electronic devices or systems to maintain optimal operating temperatures. Non-limiting examples include heat spreaders and thermal interface materials.
[0386] As used herein, the phrase “water filtration” describes processes or materials used to remove impurities or contaminants from water, making it suitable for specific uses. Non-limiting examples include graphene oxide membranes for desalination and water purification.
[0387] As used herein, the phrase “medical applications” describes the use of materials or devices in healthcare for diagnosis, treatment, or prevention of diseases. Non-limiting examples include drug delivery systems and tissue engineering scaffolds.
[0388] Electrochemical systems that comprise a graphene matrix that have the electrochemically active material dispersed and / or entrapped and / or embedded therewithin can serve multiple functions, depending on their design and application. Non-limiting examples for the possible application of electrochemical systems include energy storage devices (batteries), sensors, fuel cells, electrolyzers, electrosynthesis systems, photovoltaics, thermal management materials, flexible electronics, and structural composites.
[0389] As used herein, the phrase “energy storage device” describes a system or apparatus that stores electrical energy for later use, typically by converting and storing energy in a chemical form. Non- limiting examples include batteries (e.g., lithium-ion batteries), supercapacitors, and flywheels.
[0390] As used herein, the phrase “fuel cell” describes an electrochemical cell that converts the chemical energy of a fuel, such as hydrogen, directly into electricity through redox reactions, typically involving an oxidizing agent like oxygen. Non-limiting examples include proton exchange membrane (PEM) fuel cells, solid oxide fuel cells (SOFCs), and alkaline fuel cells.
[0391] As used herein, the term “electrolyzer” describes a device that uses electrical energy to drive a non-spontaneous chemical reaction. Non-limiting examples include proton exchange membrane (PEM) electrolyzers, alkaline electrolyzers, and solid oxide electrolyzers.
[0392] As used herein, the phrase “electrosynthesis system” describes an apparatus or system that uses electrical energy to drive chemical synthesis processes. Non-limiting examples include systems for electrochemical reduction of CO2, electrochemical polymerization, and electroorganic synthesis.
[0393] As used herein, the phrase “photovoltaics” describes technology that converts light into electricity using semiconductor materials. Non-limiting examples include solar cells and photovoltaic modules.
[0394] As used herein, the phrase “flexible electronics” describes electronic devices or components that are bendable or stretchable, allowing them to be used in non-rigid applications. Non-limiting examples include flexible batteries and supercapacitors.
[0395] As used herein, the phrase “structural composites” describes materials made by combining two or more distinct materials to create a product with enhanced mechanical, thermal, or electrical properties. Non-limiting examples include reinforced materials used, e.g., in aerospace and automotive industries.
[0396] A JF-derived 3D porous graphene matrix and silicon as an electrochemically active material are usable is electrochemical systems such as alkali metal ion batteries.
[0397] According to some of any of the embodiments described herein, the electrochemical system is or forming a part of an alkali metal ion battery.
[0398] As used herein and in the art, the phrase “an alkali metal ion battery” describes a type of rechargeable battery in which the ions of an alkali metal, such as lithium, sodium, or potassium, migrate between the anode and cathode during charging and discharging cycles. Non-limiting examples of alkali metal ion batteries include lithium-ion batteries (LIBs), sodium-ion batteries (SIBs), and potassium-ion batteries (KIBs).
[0399] According to some of these embodiments, the 3D porous structure as described herein is usable as an anode in the electrochemical system.
[0400] According to some of these embodiments, the electrochemical system further comprises lithium, in a form of metallic lithium or oxidized lithium (lithium ions). According to some of any of these embodiments described herein, the electrochemical system further comprises an alkali metal ion cathode.
[0401] As used herein and in the art, the phrase “alkali metal ion cathode” describes the electrode in an alkali metal ion battery that hosts the alkali metal ions during the discharge process and releases them during the charge process. Non-limiting examples of alkali metal ion cathodes include transition metal oxides (e.g., lithium cobalt oxide in lithium-ion batteries), poly-anionic compounds (e.g., sodium iron phosphate in sodium-ion batteries), Prussian blue analogs (e.g., potassium iron hexacyanoferrate in potassium-ion batteries), NMC (lithium nickel manganese cobalt oxide, i.e., LiNixMnyCozO2) cathodes; lithium cobalt oxide (LiCoO4) cathodes; NCA (lithium nickel cobalt aluminum oxide, i.e., LiNiCoAlO2) cathodes; LMO (lithium manganese oxide, i.e., LiM O2) cathodes; LFP (lithium iron phosphate, i.e., LiFePO2) cathodes; and lithium / sulfur cathodes.
[0402] According to some of any of the embodiments described herein, the electrochemical system further comprises a lithium-ion cathode.
[0403] Non-limiting examples of lithium-ion cathodes include NMC (lithium nickel manganese cobalt oxide, i.e., LiNixMnyCozO2) cathodes; lithium cobalt oxide (LiCoO2) cathodes; NCA (lithium nickel cobalt aluminum oxide, i.e., LiNiCoAlO4) cathodes; LMO (lithium manganese oxide, i.e., LiMmO4) cathodes; LFP (lithium iron phosphate, i.e., LiFePO4) cathodes; and lithium / sulfur cathodes. In exemplary embodiments, the lithium ion cathode is a lithium iron phosphate cathode.
[0404] It is expected that during the life of a patent maturing from this application many relevant cathodes will be developed and the scope of the terms “cathode” and “lithium ion cathode” are intended to include all such new technologies a priori.
[0405] According to some of any of the embodiments described herein, the electrochemical system further comprises an electrolyte.
[0406] As used herein and in the art, the term “electrolyte” describes a substance that facilitates the movement of ions between the anode and cathode during the charging and discharging cycles of the battery, enabling the flow of electric current within the system. The electrolyte can be solid, semi- solid or liquid, and can further comprise one or more additives in addition to a substance as described herein.
[0407] According to some of any of the embodiments described herein, the electrolyte is any electrolyte suitable for use in alkali metal ion batteries such as LIB.
[0408] Non-limiting examples of electrolytes suitable for lithium-ion batteries include solutions of lithium salts, such as LiPFe, in organic solvents like ethylene carbonate (EC) and diethyl carbonate (DEC), or solid-state electrolytes like lithium sulfide (Li2S). In exemplary embodiments, the electrolyte is or comprises LiPFe.
[0409] Non-limiting examples of electrolyte additives include fluoroethylene carbonate (FEC) in lithium-ion batteries include vinylene carbonate (VC), ethylene sulfate (DTD, EC-S), lithium difluoro(oxalato)borate (LiDFOB), lithium bis(oxalate)borate (LiBOB), propylene carbonate (PC), sulfur-based electrolyte additives (e.g., dimethyl sulfite, ethylene sulfite), and 1,3-propane sultone (PS).
[0410] In exemplary embodiments, the electrolyte additive is fluoroethylene carbonate (FEC). Any other additives suitable for use in alkali metal ion batteries are contemplated.
[0411] Without being bound to any particular theory, the presence of such electrolyte additives facilitates the formation of a stable solid electrolyte interphase (SEI) layer, improves electrochemical stability, reduces electrolyte decomposition, and / or enhances performance under various operating conditions.
[0412] According to some of any of the embodiments described herein, the electrochemical system (e.g., cell or battery) is characterized by a cyclic stability of at least 100, or at least 250, or at least 500, or at least 750, or at least 1000, and up to 10,000, cycles, for example, from 100 to 10,000, or from 500 to 10,000, or from 1000 to 10,000, or from 100 to 5000, or from 500 to 5000, or from 1000 to 5000, cycles, or from 100 to 2000, or from 500 to 2000, or from 1000 to 2000, cycles, including any intermediate values and subranges therebetween.
[0413] According to some of any of the embodiments described herein, the electrochemical system (e.g., cell or battery) is characterized by an areal capacity in a range of at least 1.0, or at least 1.2, or at least 1.3, and up to 10.0, mAh / cm2, including any intermediate values and subranges therebetween.
[0414] According to some of any of the embodiments described herein, the electrochemical system (e.g., cell or battery) is characterized by a gravimetric capacity of at least 1200, or at least 1500, or at least 1800, or at least 2000, and up to 10,000, mAh / g, including any intermediate values and subranges therebetween.
[0415] According to some of any of the embodiments described herein, the electrochemical system (e.g., cell or battery) is characterized by a Coulombic efficiency of at least 90, or at least 95, or at least 99, and up to 100, %, including any intermediate values and subranges therebetween.
[0416] According to some of any of the embodiments described herein, the electrochemical system (e.g., cell or battery) is characterized by a capacity retention of at least 40, or at least 50, and up to 100, for example, in a range of from 40 to 100, or from 50 to 100, % after 1000 cycles, including any intermediate values and subranges therebetween.
[0417] According to some of any of the embodiments described herein, the electrochemical system (e.g., cell or battery) is characterized by a C-rate of at least C / 20, or at least C / 12, and up to 10C, including any intermediate values and subranges therebetween.
[0418] As used herein and in the art, the term "C-rate" describes the rate at which a battery is charged or discharged relative to its nominal capacity. For example, at a 4C rate, a battery with a capacity of 1000 mAh would be discharged at 4000 mA, fully discharging in ¼ of an hour.
[0419] According to some of any of the embodiments described herein, the electrochemical system (e.g., cell or battery) is characterized at least by a cyclic stability of at least 100, or at least 250, or at least 500, or at least 750, or at least 1000, and up to 10,000, cycles, for example, from 100 to 10,000, or from 500 to 10,000, or from 1000 to 10,000, or from 100 to 5000, or from 500 to 5000, or from 1000 to 5000, cycles, or from 100 to 2000, or from 500 to 2000, or from 1000 to 2000, cycles, including any intermediate values and subranges therebetween; and by an areal capacity in a range of at least 1.0, or at least 1.2, or at least 1.3, and up to 10.0, mAh / cm2, including any intermediate values and subranges therebetween.
[0420] According to some of any of the embodiments described herein, the electrochemical system (e.g., cell or battery) is characterized at least by a cyclic stability of at least 100, or at least 250, or at least 500, or at least 750, or at least 1000, and up to 10,000, cycles, for example, from 100 to 10,000, or from 500 to 10,000, or from 1000 to 10,000, or from 100 to 5000, or from 500 to 5000, or from 1000 to 5000, cycles, or from 100 to 2000, or from 500 to 2000, or from 1000 to 2000, cycles, including any intermediate values and subranges therebetween; and by a gravimetric capacity of at least 1200, or at least 1500, or at least 1800, or at least 2000, and up to 10,000, mAh / g, including any intermediate values and subranges therebetween.
[0421] According to some of any of the embodiments described herein, the electrochemical system (e.g., cell or battery) is characterized at least by a cyclic stability of at least 100, or at least 250, or at least 500, or at least 750, or at least 1000, and up to 10,000, cycles, for example, from 100 to 10,000, or from 500 to 10,000, or from 1000 to 10,000, or from 100 to 5000, or from 500 to 5000, or from 1000 to 5000, cycles, or from 100 to 2000, or from 500 to 2000, or from 1000 to 2000, cycles, including any intermediate values and subranges therebetween; and by a Coulombic efficiency of at least 90, or at least 95, or at least 99, and up to 100, %, including any intermediate values and subranges therebetween. According to some of any of the embodiments described herein, the electrochemical system (e.g., cell or battery) is characterized at least by a cyclic stability of at least 100, or at least 250, or at least 500, or at least 750, or at least 1000, and up to 10,000, cycles, for example, from 100 to 10,000, or from 500 to 10,000, or from 1000 to 10,000, or from 100 to 5000, or from 500 to 5000, or from 1000 to 5000, cycles, or from 100 to 2000, or from 500 to 2000, or from 1000 to 2000, cycles, including any intermediate values and subranges therebetween; and by a capacity retention of at least 40, or at least 50, and up to 100, for example, in a range of from 40 to 100, or from 50 to 100, % after 1000 cycles, including any intermediate values and subranges therebetween.
[0422] According to some of any of the embodiments described herein, the electrochemical system (e.g., cell or battery) is characterized at least by a cyclic stability of at least 100, or at least 250, or at least 500, or at least 750, or at least 1000, and up to 10,000, cycles, for example, from 100 to 10,000, or from 500 to 10,000, or from 1000 to 10,000, or from 100 to 5000, or from 500 to 5000, or from 1000 to 5000, cycles, or from 100 to 2000, or from 500 to 2000, or from 1000 to 2000, cycles, including any intermediate values and subranges therebetween; and by a C-rate of at least C / 20, or at least C / 12, and up to 10C, including any intermediate values and subranges therebetween.
[0423] According to some of any of the embodiments described herein, the electrochemical system (e.g., cell or battery) is characterized at least by a gravimetric capacity of at least 1200, or at least 1500, or at least 1800, or at least 2000, and up to 10,000, mAh / g, including any intermediate values and subranges therebetween; and by a Coulombic efficiency of at least 90, or at least 95, or at least 99, and up to 100, %, including any intermediate values and subranges therebetween.
[0424] According to some of any of the embodiments described herein, the electrochemical system (e.g., cell or battery) is characterized at least by a gravimetric capacity of at least 1200, or at least 1500, or at least 1800, or at least 2000, and up to 10,000, mAh / g, including any intermediate values and subranges therebetween; and by a capacity retention of at least 40, or at least 50, and up to 100, for example, in a range of from 40 to 100, or from 50 to 100, % after 1000 cycles, including any intermediate values and subranges therebetween.
[0425] According to some of any of the embodiments described herein, the electrochemical system (e.g., cell or battery) is characterized at least by a gravimetric capacity of at least 1200, or at least 1500, or at least 1800, or at least 2000, and up to 10,000, mAh / g, including any intermediate values and subranges therebetween; and by a C-rate of at least C / 100, or at least C / 20, or at least C / 15, or at least C / 12, or at least C / 10, and up to 10C, including any intermediate values and subranges therebetween. According to some of any of the embodiments described herein, the electrochemical system (e.g., cell or battery) is characterized at least by an areal capacity in a range of at least 1.0, or at least
[0426] 1.2, or at least 1.3, and up to 10.0, mAh / cm2, including any intermediate values and subranges therebetween; and by a gravimetric capacity of at least 1200, or at least 1500, or at least 1800, or at least 2000, and up to 10,000, mAh / g, including any intermediate values and subranges therebetween.
[0427] According to some of any of the embodiments described herein, the electrochemical system (e.g., cell or battery) is characterized at least by a C-rate of at least C / 20, or at least C / 12, and up to 10C, including any intermediate values and subranges therebetween; and by a capacity retention of at least 40, or at least 50, and up to 100, for example, in a range of from 40 to 100, or from 50 to 100, % after 1000 cycles, including any intermediate values and subranges therebetween.
[0428] According to some of any of the embodiments described herein, the electrochemical system (e.g., cell or battery) is characterized at least by a Coulombic efficiency of at least 90, or at least 95, or at least 99, and up to 100, %, including any intermediate values and subranges therebetween; and by a capacity retention of at least 40, or at least 50, and up to 100, for example, in a range of from 40 to 100, or from 50 to 100, % after 1000 cycles, including any intermediate values and subranges therebetween.
[0429] According to some of any of the embodiments described herein, the electrochemical system (e.g., cell or battery) is characterized at least by an areal capacity in a range of at least 1.0, or at least
[0430] 1.2, or at least 1.3, and up to 10.0, mAh / cm2, including any intermediate values and subranges therebetween; and by a capacity retention of at least 40, or at least 50, and up to 100, for example, in a range of from 40 to 100, or from 50 to 100, % after 1000 cycles, including any intermediate values and subranges therebetween.
[0431] According to some of any of the embodiments described herein, the electrochemical system (e.g., cell or battery) is characterized at least by an areal capacity in a range of at least 1.0, or at least
[0432] 1.2, or at least 1.3, and up to 10.0, mAh / cm2, including any intermediate values and subranges therebetween; and by a C-rate of at least C / 20, or at least C / 12, and up to 10C, including any intermediate values and subranges therebetween.
[0433] According to some of any of the foregoing embodiments, the electrochemical system is or forms a part of an alkali ion metal battery such as LIB.
[0434] Without being bound by any particular theory, it is assumed that the advantageous, efficient and even superior performance of the electrochemical systems as described herein, is attributed to, or facilitated by, integrating a JF-derived 3D porous structure as described herein in any of the respective embodiments in the system.
[0435] According to some embodiments, the JF-derived 3D porous structure is such that enables an increase in the volume of the electrochemically active material (e.g., silicon) therewithin, repeated breakdown and reformation of the SEI layer, which otherwise consumes lithium ions and reduces the cyclic stability of the electrochemical cell, are reduced or prevented.
[0436] Alternatively, or in addition, the JF-derived 3D porous structure is such that enables a reduction in a mechanical stress that results from an increase in a volume of the electrochemically active component (e.g., the increase in silicon volume upon lithiation), by absorbing the strain by interconnected pores of the 3D porous structure, and thereby reduces or prevents the SEI layer from cracking or fracturing, which would otherwise necessitate repeated SEI reformation and result in lithium loss.
[0437] Alternatively, or in addition, the JF-derived 3D porous structure is such that enables a mass transport of the electrochemically active components which is higher than a mass transport of the electrochemically active material when used alone. Assessing the mass transport of electrodes can be effected using, e.g., EIS or CV.
[0438] Alternatively, or in addition, the JF-derived 3D porous structure is such that a wetting of the electrochemical system comprising same is higher than a wetting of an electrochemical cell comprising the electrochemically active material embodiments alone (in the absence of the JF-derived 3D porous graphene matrix). Assessing the wetting of an electrode by an electrolyte can be effected by immersing the electrode in the electrolyte and measuring the amount of electrolyte absorbed by the electrode material and weighing the electrode before and after immersion.
[0439] According to some of the present embodiments, the electrochemically active component as described herein forms a part of an electrochemical system which is an alkali metal ion battery such as LIB. According to some embodiments, the electrochemically active component as described herein forms an anode material in an electrochemical system which is an alkali metal ion battery such as LIB.
[0440] A schematic presentation of an exemplary assembly of an electrochemical cell 10 (also referred to herein interchangeably as a “full cell”), which is an alkali ion metal battery such as LIB according to some embodiments of the present invention is presented in FIG. 7.
[0441] Electrochemical cell 10 comprises a composite electrode 20 which comprises a JF-derived 3D porous structure (according to any of the embodiments described herein), which acts as an anode material. Electrochemical cell 10 further comprises a cathode 30, which may be or comprise any suitable cathode material known in the art (e.g., for a lithium ion cell; e.g., a cathode according to some of any of the embodiments described herein), as described herein in any of the respective embodiments. Electrode (anode) 20 (e.g., electrochemically active component as described herein in any of the respective embodiments) and / or cathode 30 (e.g., cathode as described herein in any of the respective embodiments) may optionally further comprise a conductive coating.
[0442] Electrochemical cell 10 further comprises an electrolyte 40, which may be a solid and / or liquid electrolyte (e.g., according to some of any of the embodiments described herein), between electrode (anode) 20 and cathode 30, and optionally in contact or in electric communication with electrode (anode) 20 and / or cathode 30.
[0443] Electrochemical cell 10 optionally further comprises current collector 22 (e.g., current collector as described herein in any of the respective embodiments) configured for electrically connecting anode 20 to an electrical device to be powered by electrochemical cell 10 and / or current collector 32 is configured for electrically connecting cathode 30 to an electrical device electrical circuit to be powered by electrochemical cell 10. Current collectors 22 and / or 32 (e.g., current collector as described herein in any of the respective embodiments) may optionally be configured for secure electrical contact with standard configurations (e.g., in commercial devices) for holding power sources such as batteries.
[0444] A plurality (not shown) of electrochemical cells 10 may optionally be configured in series (e.g., so as to obtain a voltage corresponding to the sum of the voltages of the individual cells), optionally encased within a single casing to form a battery.
[0445] An electrochemical cell according to the present embodiments can follow any of the designs known in the art, and can include one or more anodes and / or cathodes. Exemplary designs include, without limitation, rotating disk-ring electrodes, ultramicro-electrodes, or screen printed electrodes.
[0446] The configuration of the components of electrochemical cell 10 as presented in FIG. 7 are for illustrative purpose only and are not to be regarded as limiting in any way.
[0447] In some of any of the embodiments described herein, an energy density of a lithium ion battery is at least 150, or at least 200, or at least 250, or at least 275, or at least 300, or at least 325, or at least 350, and up to 3,500, Wh / kg (watt-hours per kg). In comparison, energy densities of commercial lithium ion batteries are typically in a range of from 150 to 250 Wh / kg.
[0448] In some of any of the embodiments described herein relating to a lithium ion battery, the lithium ion battery is rechargeable, i.e., designed and / or identified for re-use upon recharging the battery by application of a suitable electric potential. In some of any of the embodiments described herein relating to a lithium ion battery, the lithium ion battery is rechargeable, i.e., designed and / or identified for re-use upon recharging the battery by application of a suitable electric potential.
[0449] According to an aspect of some embodiments of the present invention there is provided a method of preparing an electrochemical system as described herein in any of the respective embodiments. According to some of these embodiments, the method is effected by preparing the electrochemically active component as described herein in any of the respective embodiments; and integrating the electrochemically active component at least with a complementary electrode and an electrolyte, thereby preparing the electrochemical cell. Integrating can be effected by assembling the electrochemically active component (e.g., a current collector having an anode material deposited thereon) with other components in the system, using methods well known in the art. See, e.g., FIG. 1C.
[0450] According to some of any of the embodiments described herein, preparing the electrochemically active component is effected by additive manufacturing (AM), which is also referred to herein and in the art as 3D-printing or 4D-printing.
[0451] According to some of any of the embodiments described herein, one or more of the electrochemically active component, the complementary electrode, the electrolyte, and the current collector, each is as described herein in any of the respective embodiments, are prepared by additive manufacturing.
[0452] In some embodiments, one or more of the electrochemically active component, the complementary electrode, the electrolyte, and the current collector, each is as described herein in any of the respective embodiments, is / are prepared by additive manufacturing independently, and is / are subsequently integrated to form the electrochemical system according to some of any of the embodiments described herein. In some such embodiments, each of the electrochemically active component, the complementary electrode, the electrolyte, and the current collector is prepared independently and the components are subsequently assembled to form the electrochemical system. In some of any of the embodiments described herein, each of the electrochemically active component and at least the complementary electrode and the electrolyte is prepared by additive manufacturing, and subsequently integrated to form the electrochemical system according to some of any of the embodiments described herein. Alternatively, one or more of the electrochemically active component, the complementary electrode, the electrolyte, and the current collector are prepared by AM altogether in a single pass. Additive manufacturing is process that is generally effected by sequentially forming a plurality of layers in a configured pattern corresponding to the shape of the object, thereby forming the object. In some AM methodologies, formation of each layer is effected by forming a layer of an uncured building material, and exposing the uncured building material to a curing condition to thereby form a hardened (cured) material.
[0453] Herein throughout, the phrase “building material” encompasses the phrases “uncured building material” or “uncured building material formulation” and collectively describes the materials that are used to sequentially form the layers, as described herein. This phrase encompasses uncured materials which form the final object, namely, one or more uncured modeling material formulation(s), and optionally also uncured materials used to form a support, namely uncured support material formulations. The building material can also include non-curable materials that do not undergo (or are not intended to undergo) any change during the process.
[0454] The building material is also referred to herein interchangeably as “printing medium”.
[0455] An uncured building material can comprise one or more modeling material formulations, and can be used in the AM such that different parts of the object are made upon hardening (e.g., curing) of different modeling formulations, and hence are made of different hardened (e.g., cured) modeling materials or different mixtures of hardened (e.g., cured) modeling materials.
[0456] The method of the present embodiments manufactures three-dimensional objects in a layerwise manner by forming a plurality of layers in a configured pattern corresponding to the shape of the object.
[0457] Each layer is formed by an additive manufacturing apparatus which scans a two-dimensional surface and patterns it. While scanning, the apparatus visits a plurality of target locations on the two- dimensional layer or surface, and decides, according to a pre-set algorithm, for each target location or a group of target locations, whether or not the target location or group of target locations is to be occupied by a building material, and which type of a building material is to be delivered thereto, or whether or not the building material is cured. The decision is made according to a computer image of the surface.
[0458] When the AM is by three-dimensional inkjet printing, an uncured building material, as defined herein, is dispensed from a dispensing head having a set of nozzles to deposit building material in layers on a supporting structure. The AM apparatus thus dispenses building material in target locations which are to be occupied and leaves other target locations void. The apparatus typically includes a plurality of dispensing heads, each of which can be configured to dispense a different building material (for example, different modeling material formulations, each containing a different curable material; or each containing a different concentration of a curable material, and / or different support material formulations). Thus, different target locations can be occupied by different building materials (e.g., a modeling formulation and / or a support formulation, as defined herein).
[0459] The final three-dimensional object is made of the hardened modeling material or a combination of hardened modeling materials or a combination of hardened modeling material / s and support material / s or modification thereof (e.g., following curing). All these operations are well-known to those skilled in the art of additive manufacturing (also known as solid freeform fabrication).
[0460] In some of any of the embodiments described herein, the current collector as described herein in any of the respective embodiments is prepared by AM in a configured pattern (e.g., by FFF as defined hereinbelow). In alternative embodiments, a pre-made is used as a conductive substrate as described herein.
[0461] In some of any of the embodiments described herein, at least one layer of the mixture (as described herein in any of the respective embodiments) are formed in a configured pattern on the current collector, and are exposed to laser irradiation.
[0462] In some of any of the embodiments described herein, the current collector as described herein in any of the respective embodiments is prepared by AM in a configured pattern, and at least one layer of the mixture (as described herein in any of the respective embodiments) is formed in a configured pattern on the current collector, and are exposed to laser irradiation.
[0463] In alternative embodiments, a pre-made current collector is used as a conductive substrate as described herein, and at least one layer of the mixture (as described herein in any of the respective embodiments) are formed in a configured pattern on the current collector, and are exposed to laser irradiation.
[0464] It is to be understood that upon performing AM-based methods an electrochemically active component (e.g., anode) is obtained, and can either be integrated in an electrochemical system, or AM of additional components can be sequentially performed.
[0465] In some of any of the embodiments described herein, an electrolyte material is prepared by AM, for example, by layerwise depositing the electrolyte material in a configured pattern. In alternative embodiments, a matrix that can thereafter be doped or soaked with the electrolyte is prepared by AM. In some of any of the embodiments described herein, a cathode and a (cathodic) current collector is / are prepared by AM in a configured pattern. In alternative embodiments, a cathode is prepared by AM in a configured pattern, and a pre-made (cathodic) current collector is used.
[0466] An exemplary AM process according to some embodiments of the present invention starts by receiving 3D printing data corresponding to the shape of the respective one or more components in a system as described herein. The data can be received, for example, from a host computer which transmits digital data pertaining to fabrication instructions based on computer object data, e.g., in a form of a Standard Tessellation Language (STL) or a StereoLithography Contour (SLC) format, Virtual Reality Modeling Language (VRML), Additive Manufacturing File (AMF) format, Drawing Exchange Format (DXF), Polygon File Format (PLY), Digital Imaging and Communications in Medicine (DICOM) or any other format suitable for Computer-Aided Design (CAD).
[0467] In some of any of the embodiments described herein, the building material (e.g., the printing medium) comprises modeling material formulation(s) (a mixture comprising a carbonaceous material which is or comprises a jellyfish biomass as described herein in any of the respective embodiments and an electrochemically active material as described herein in any of the respective embodiments) and optionally support material formulation(s), and all are selected to include materials or combination of materials that do not interfere with the electrochemical and / or structural features of the 3D porous structure.
[0468] In some embodiments, a printing system for effecting a printing process / method as described herein is configured so as to allow formation of the layers under conditions that do not significantly affect structural and / or functional properties of the formed 3D porous structure.
[0469] In some of any of the embodiments described herein, the additive manufacturing (e.g., printing) process and system are configured such that the process parameters (e.g., temperature, shear forces, shear strain rate) do not interfere with (do not substantially affect) the functional and / or structural features of the formed 3D porous structure.
[0470] In some of any of the embodiments described herein, the additive manufacturing process (the printing) is performed at a temperature in a range of from room temperature and up to 200, or up to 250, °C, including any intermediate values and subranges therebetween.
[0471] In some of any of the embodiments described herein, the above-indicated temperatures / temperature ranges are the temperatures at which the building material (e.g., at least a modeling material formulation that comprises a carbonaceous material which is or comprises a jellyfish biomass and an electrochemically active material as those are described herein) are dispensed, that is, a temperature of a dispensing head in the AM system and / or a temperature at which the modeling material formulation is maintained prior to passing in the dispensing head.
[0472] In some of any of the embodiments described herein, the additive manufacturing process (printing) is performed while applying a shear force that does adversely affect structural and / or electrochemical properties of the formed 3D porous structure). Applying the shear force can be effected by passing the building material (e.g., at least a modeling material formulation that comprises a carbonaceous material which is or comprises a jellyfish biomass and an electrochemically active material as those are described herein) through the dispensing head, and is to be regarded also as subjecting the building material to shear force.
[0473] The following describes exemplary AM printing methodologies that are usable in the context of embodiments of the present invention.
[0474] A printing method and a corresponding system can be any of the methods and systems known in the art for performing additive manufacturing, and exemplary such systems and methods are described hereinabove. A suitable method and system can be selected upon considering its printing capabilities, which include resolution, deposition speed, scalability, and ease-of-use.
[0475] Exemplary suitable printing systems usually contain a dispensing system (either equipped with temperature control module or at ambient temperature), and stage (a receiving medium), and a movement along the x, y and z axes directed by a CAD-CAM software. A curing source (e.g., a light or heat source) which applies a curing energy (e.g., by applying light or heat radiation) or a curing condition to the deposition area (the receiving medium) so as to promote curing of the formed layers and / or a humidifier, can also be included in the system. There are printers that use multiple dispensing heads to facilitate a serial dispensing of several materials.
[0476] Generally, printing can be effected using any of the known techniques for additive manufacturing. The following lists some exemplary additive manufacturing techniques, although any other technique is contemplated.
[0477] 3D Inkjet printing: 3D Inkjet printing is a common type of 3D printer for various applications. Inkjet printers use thermal or acoustic forces to eject drops of liquid onto a substrate, which can support or form part of the final construct. In this technique, controlled volumes of liquid are delivered to predefined locations, and a high-resolution printing with precise control of (1) ink drops position, and (2) ink volume, which is beneficial in cases of microstructure-printing or when small amounts of reactive agents or drugs are added, is received. Inkjet printers can be used with several types of ink. Furthermore, the printing is fast and can be applied onto culture plates. Extrusion printing: This technique uses continuous beads of material rather than liquid droplets. These beads of material are deposited in 2D, the stage (receiving medium) or extrusion head moves along the z axis, and the deposited layer serves as the basis for the next layer.
[0478] Stereolithography (SLA) and Digital Light Processing (DLP): SLA and DLP are additive manufacturing technologies in which an uncured building material in a bath is converted into hardened material(s), layer by layer, by selective curing using a light source while the uncured material is later separated / washed from the hardened material. SLA is widely used to create models, prototypes, patterns, and production parts for a range of industries including for printing.
[0479] Electrospinning: Electrospinning is a fiber production technique, which uses electric force to draw charged threads of polymer solutions, or polymer melts.
[0480] Eused Eilament Fabrication (FFF), also known as Fused Deposition Modeling (FDM) (a trademarked term): an additive manufacturing technique where a thermoplastic filament is melted and extruded layer by layer to create a three-dimensional object.
[0481] As used herein the term “about” refers to ± 10 % or ± 5 %.
[0482] The terms “comprises”, “comprising”, “includes”, “including”, “having” and their conjugates mean “including but not limited to”.
[0483] The term “consisting of’ means “including and limited to”.
[0484] The term “consisting essentially of’ means that the composition, method or structure may include additional ingredients, steps and / or parts, but only if the additional ingredients, steps and / or parts do not materially alter the basic and novel characteristics of the claimed composition, method or structure.
[0485] As used herein, the singular form “a”, “an” and “the” include plural references unless the context clearly dictates otherwise. For example, the term “a compound” or “at least one compound” may include a plurality of compounds, including mixtures thereof.
[0486] Throughout this application, various embodiments of this invention may be presented in a range format. It should be understood that the description in range format is merely for convenience and brevity and should not be construed as an inflexible limitation on the scope of the invention. Accordingly, the description of a range should be considered to have specifically disclosed all the possible subranges as well as individual numerical values within that range. For example, description of a range such as from 1 to 6 should be considered to have specifically disclosed subranges such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6 etc., as well as individual numbers within that range, for example, 1, 2, 3, 4, 5, and 6. This applies regardless of the breadth of the range.
[0487] Whenever a numerical range is indicated herein, it is meant to include any cited numeral (fractional or integral) within the indicated range. The phrases “ranging / ranges between” a first indicate number and a second indicate number and “ranging / ranges from” a first indicate number “to” a second indicate number are used herein interchangeably and are meant to include the first and second indicated numbers and all the fractional and integral numerals therebetween.
[0488] As used herein the term “method” refers to manners, means, techniques and procedures for accomplishing a given task including, but not limited to, those manners, means, techniques and procedures either known to, or readily developed from known manners, means, techniques and procedures by practitioners of the chemical, pharmacological, biological, biochemical and medical arts.
[0489] It is appreciated that certain features of the invention, which are, for clarity, described in the context of separate embodiments, may also be provided in combination in a single embodiment. Conversely, various features of the invention, which are, for brevity, described in the context of a single embodiment, may also be provided separately or in any suitable subcombination or as suitable in any other described embodiment of the invention. Certain features described in the context of various embodiments are not to be considered essential features of those embodiments, unless the embodiment is inoperative without those elements.
[0490] Various embodiments and aspects of the present invention as delineated hereinabove and as claimed in the claims section below find experimental support in the following examples.
[0491] EXAMPLES
[0492] Reference is now made to the following examples, which together with the above descriptions illustrate some embodiments of the invention in a non-limiting fashion.
[0493] MATERIALS AND METHODS
[0494] Jellyfish Biomass Preparation: Jellyfish biomass was prepared based on a previously published method [Nudelman et al. Adv. Fund. Mater. 29, 1902783 (2019)] from locally-collected jellyfish (Mediterranean Sea). In short, the upper “umbrella” (AKA, the bell) of the jellyfish was separated and homogenized (by mortar / trituration and mixing) into a white paste, diluted with ethanol, and centrifuged. The precipitate was then freeze-dried and grounded into a white powder in order to make an accurate assessment of the solid biomass content used in the preparation of the LIG (e.g., the anode synthesis).
[0495] It is noted that the freeze-drying process was performed for optimization purposes and is not an essential step, considering that the biomass is being re-hydrated directly thereafter (see, FIG. 1A).
[0496] LFP Cathode: The lithium iron phosphate (LiFePO4 ;LFP) cathode (Nanografi, 5 μm diameter) was prepared with a loading of 2 mg / cm2of active material, along with a PVDF binder (Nanografi) and conductive additive (Super Carbon P, Nanografi), ratio 90:5:5, respectively.
[0497] Material Characterization: High-resolution scanning electron microscopy (HRSEM) imaging was conducted using a Zeiss GeminiSEM 300 system. HRSEM imaging of materials containing jellyfish biomass were first coated with a 10 nm layer of gold nanoparticles using a PVD-20 Magnetron Sputtering system (Vinci). Transmission electron microscopy (TEM), scanning transmission electron microscopy (STEM) and energy-dispersive X-ray spectroscopy (EDS) analyses were conducted using a Themis Z G3 system (ThermoFisher®). Cross-sectional imaging and lamella preparation for TEM analysis were conducted using a Helios Nanolab 460FlLite Dual Beam Focused Ion Beam / Scanning Electron Microscope (FIB / SEM, ThermoFisher®). Raman spectroscopy measurements were conducted using an InVia Confocal Raman Microscope (Renishaw) at a wavelength of 514 nm. ImageJ software was to analyze and compute the porosity from the HRSEM imaging.
[0498] Electrochemical Measurements: Half-cells were assembled as CR2032 coin cells. The cells containing the dried anode (12 mm diameter) pre-deposited on a current collector, separator, lithium metal, 316L stainless steel spacer and a spring were assembled in a glovebox (<0.1 ppm O2). A schematic view of an assembled coin cell is presented in FIG. 1C. The separator used was a 2325 Celgard separator and the lithium metal discs (15 mm diameter, S4R, France). The electrolyte used in all experiments was 85 % LiPFe(45 pL, 1 M) in EC / DEC (1: 1) and 15 % fluoroethylene carbonate (FEC, Solvay-Fluor). The mass loading of the cells ranged from 0.15-1.5 mg / cm2, depending on the layer configuration.
[0499] The cells were kept at 30 °C throughout the experiments.
[0500] All electrochemical measurements were conducted using a Bio-Logic™ BCS battery cycler.
[0501] Potentiostatic electrical impedance spectroscopy (PEIS) measurements were conducted using a frequency range of 0.01 MHz to 1 Hz with an amplitude of 10 mV after delithiation.
[0502] Post-mortem analysis was conducted after delithiation. EXAMPLE 1
[0503] Synthesis and Structural Analysis
[0504] Although graphitic carbon anodes exhibit excellent stability and low irreversible capacity loss, their low theoretical capacity severely limits performance potential and uses in future technology. Furthermore, graphite has unsustainable production routes that are costly, energy intensive and extremely polluting. Accordingly, battery grade graphite is tremendously expensive, with costs ranging at 8,000-15,000 USD per ton.
[0505] This being the case, disclosed herein is the first use of raw jellyfish biomass as a cheap, sustainable, and eco-friendly carbon precursor that can be utilized, for example, to form silicon- graphene composite anodes.
[0506] In order to have industrial potential and be truly sustainable, the use of jellyfish biomass as a carbon precursor requires a cheap, scalable, low-energy and additive-free synthesis process that is ecologically and economically viable.
[0507] The present inventors have utilized laser irradiation to produce a 3D porous graphene matrix from a jellyfish biomass as a carbon precursor. In order to utilize the formed matrix as electrochemically active component in energy storage devices such as alkali metal batteries, the present inventors have utilized a mixture of the jellyfish biomass and silicon particles, as an exemplary electrochemically active component, so to form, via laser irradiation, Jellyfish (JF) / SiNP composite structures.
[0508] The composition of dry jellyfish organic biomass is similar across most species [Hubot et al. Journal of Plankton Research, 44, 337-344 (2022)] and predominantly contain a variety of proteins (about 80 %), mostly Type I and Type II collagen and Q-mucin glycoproteins, along with various lipids, carbohydrates, nucleic acids [Khong et al. Food Chem. 196, 953-960 (2016); Masuda et al. J. Nat. Prod. 70, 1089-1092 (2007); Kogovsek et al. Mar. Ecol. Prog. Ser. 510, 275-288 (2014)], and an estimated carbon contents of up to 41 % [Tinta et al. PLoS One 7, e39274 (2012); Tinta et al. Front. Microbiol. 11, 1-18 (2020)]. Given the substantial and partially heterocyclic carbon structures found in collagen and Q-mucin glycoproteins, as well as the wide variety of other biological materials present, the present inventors have considered utilizing these constituents for generating a conductive three-dimensional porous matrix via laser irradiation.
[0509] An exemplary Jellyfish (JF) / SiNP composite structure was prepared as schematically illustrated in FIG. 1A. Generally, dry jellyfish biomass is mixed with an electrochemically active material (e.g., in a form of particles), the mixture is optionally homogenized and then deposited by, for example, spin coating, onto an electrically conductive substrate. Laser irradiation is then employed to convert the deposited carbon-silicon mixture to a 3D porous conductive carbon-silicon composite.
[0510] The deposited 3D porous conductive carbon-silicon composite may serve as an anode, and can be deposited on a current collector as a substrate, such that the formed composite can be integrated into a lithium ion battery as exemplified in FIG. 1C.
[0511] As can be seen in FIG. IB, following lithiation, the 3D porous conductive carbon-silicon composite network expands with effective buffering during standard silicon-lithium alloying.
[0512] In an exemplary procedure, dry Jellyfish biomass was prepared as described under the Materials and Methods sections hereinabove. FIGs. 1F-G show fluorescence and optical microscopy images, respectively, of the jellyfish biomass. As FIG. IF shows high level of fluorescence, these indicate the existence of a protein-rich surface.
[0513] A slurry of the dry jellyfish biomass and silicon nanoparticles (Nanografi, average diameter 100 nm, crystalline) was prepared with a mass ratio of 10:3 in deionized (D.I.) water. No binders or conductive additives were used. The slurry was sonicated for 20 minutes and vortexed for 5 minutes to prevent agglomeration of the SiNPs and homogenize the slurry. Raman spectroscopy of the jellyfish-derived mixture was performed pre-lasing, and is presented in FIG. ID. These data suggest the presence of a variety of organic compounds, and may be attributed to vibrations in proteins side chains.
[0514] For thin-layer battery configurations, layers of the slurry were spin-coated onto a 316L stainless steel current collector (12 mm diameter, 0.5 mm thickness or battery-grade copper foil (15 μm thick, then punched into 12 mm disks) at 400 rpm for 10 seconds and then 2000 rpm for 40 seconds. The resulting layers were hot baked for 5 minutes at 50 °C for 15 minutes at 100 °C after each layer. The thin film was then treated with 20 pL of 5 wt / wt % of boric acid (> 99.5 %, Sigma- Aldrich®) in D.I. water and hot baked for additional 20 minutes at 100 °C.
[0515] The resulting layer(s) of dried film deposited on the current collector was laser-rastered with continuous visible laser irradiation (2.8 W, 450 nm wavelength, Zmorph Fab) using lasing parameters of 100 % power, a spot size diameter of 10 μm, a lasing speed of 20 mm / s, and a hatch spacing of 0.1 mm. The coated current collector was washed with D.I. water and dried in order to remove residual salts inherent from the biomass and boric acid.
[0516] The SiNPs displayed excellent adhesion to the freeze-dried jellyfish biomass, creating a homogenous slurry with minimal agglomeration of SiNPs. The JF / SiNP film was spin-coated directly onto a stainless steel current collector as an exemplary conductive substrate, resulting in the formation of a relatively uniform thin layer, with two layers measuring approximately 12 micrometers in thickness.
[0517] When subjected to continuous visible laser irradiation, the dried thin film underwent a significant alteration in both color and surface topography. Specifically, the color of the film was changed from brown to black, and its previously smooth and flat surface became visibly rough and porous. This transformation following the lasing process is evident by high-resolution scanning electron microscopy (HRSEM) imaging of the composite presented in FIG. 2C (left) in comparison with FIGs. 2A-B and 2C (right), which show that a relatively smooth surface was transformed to an immensely macroporous structure. A thickness reduction of around 20 % was observed, which is primarily attributable to the degassing of the biomass.
[0518] The thickness of the single-layer film composite cross-section was analyzed using a lamella extracted from the anode with a focused ion beam (FIB), where a thickness of approximately 5 micrometers can be observed in FIG. 2E.
[0519] Porosity measurements based on the HRSEM image in FIG. 2F are depicted in FIGs. 2G-I, and show an average pore diameter of approximately 7 microns and an overall porosity of 49 %.
[0520] Additional higher magnification HRSEM imaging are depicted in FIG. 2C (left) and FIG. 2C (right), before and after laser writing, respectively, providing a more detailed depiction of the substantial changes in surface topography and porosity, and the inner workings of the highly macroporous architecture.
[0521] FIG. 2D (left) presents agglomerates of SiNPs that are dispersed within the jellyfish biomass before the lasing process, with FIG. 2D (right) showing the SiNPs after the lasing process encased within a nanoporous network. As seen in FIG. 2D (right), further inspection of the macropores created by the lasing process reveals that it is comprised of smaller periodic nanoporous structures. Notably, the spherical SiNPs of approximately 100 nm in diameter are observed to be encapsulated within “veins” of varying sizes of the nanoporous structure, as further confirmed by additional structural analysis.
[0522] A lamella extracted from the exemplary composite after the lasing process (see, e.g., FIG. 2E) was thinned utilizing a focused-ion beam (FIB) and subjected to additional characterization using transmission electron microscopy (TEM) and scanning transmission electron microscopy (STEM). The results are depicted in FIGs. 3A-C.
[0523] TEM bright-field imaging of SiNPs embedded within the carbon matrix is depicted in FIG. 3A, showing a carbonaceous matrix surrounding the nanoparticles. Bright-field STEM analysis was performed, and a representative image is displayed in FIG. 3B. The data clearly shows a contrast of spherical nanoparticles within the porous network, with the corresponding energy-dispersive X-ray spectroscopy (EDS) mapping prominently displaying the homogeneous distribution of carbon and silicon throughout the structure. High-angle annular dark-field STEM (HAADAF-STEM) imaging at a higher magnification of the same area within the porous network is depicted in FIG. 3C.
[0524] The TEM / STEM and the corresponding EDS analyses reveal that the SiNPs are uniformly dispersed and encapsulated within the porous carbon network of the exemplary JF / SiNP composite, which indicates the complete entrapment of the SiNPs within the carbon matrix. The EDS spectrum of the exemplary composite at varying JF / SiNP weight ratios is presented in FIG. 3D and the respective mass / atomic percentages of the JF / SiNP composites are summarized herein in Table 2.
[0525] Table 2
[0526] As can be seen, EDS spectrum on FIG. 3D and Table 2 show a silicon content of approximately 46.9 % in the anode prepared using a 10:3.0 JF / SiNP ratio in the slurry. Table 2 further shows that the silicon content can be meticulously controlled through varying ratios of JF biomass to SiNPs in the initial blend, to provide silicon contents of 23.2, 46.9 and 61.4 wt.%.
[0527] Table 2 also shows the presence of oxygen in relatively high amounts. Nitrogen was also detected, as evident by FIG. 41, and its amount (both weight and atomic %) was identified to be in a range of from about 0.8 % to about 2 %, of the total weight of the composite structure, and in a range of from about 1.3 % to about 2.6 %, of the total weight of the JF-derived structure (the graphene matrix alone) (data not shown). The presence of oxygen and nitrogen is likely to arise from presence of various decomposition products of the proteinaceous (collagen-enriched) jellyfish biomass.
[0528] Structural analyses of the SiNPs and carbon matrix are presented in FIGs. 4A-E. To investigate the structural characteristics of the SiNPs after the lasing process, selected-area electron diffraction (SAED) was conducted and is displayed in FIG. 4A. The SAED pattern displays lattice plane spacing values corresponding to the (111) and (220) planes of pristine silicon, indicating the retention of the crystalline nature of the SiNPs throughout the lasing process [Yacoot et al. Meas. Sci. Technol. 31 (12), 121001 (2020)].
[0529] Moreover, high-resolution transmission electron microscopy (HRTEM) imaging of the SiNPs encased in a carbon shell, depicted in FIG. 4B, illustrates the crystal lattice spacing, which could be attributed to the (111) plane, with the conductive carbon shell surrounding it.
[0530] The specific surface area of the exemplary JF / SiNP composites was analyzed using Brunauer- Emmett-Teller (BET) theory, measured at a high value of 134.1 m2 / g. The adsorption isotherm is presented in FIG. 4H. This value is the same or higher in comparison with porous nano-silicon / carbon composites having similar silicon content [Zhao et al. J Colloid Interface Sci 664, 790-800 (2024); Yang et al. Chemical Engineering Journal 423, (2021); and a mini review by dos Reis et al. Electrochemistry Communications 153 (2023)], and is important for mechanical buffering of volume expansion during lithiation.
[0531] XPS survey of the JF / SiNP anode post-lasing is presented in FIG. 41, and indicates the presence of oxygen. High-resolution XPS analysis of the Si 2p orbital before and after the lasing process in FIG. 4J further corroborates the fact that the silicon active material was unaffected by the lasing process, depicting mostly elemental Si-Si bonding with some expected minor native oxide Si-0 bonds [Jensen et al. Surface Science Spectra 20, 36-42 (2013)].
[0532] The Raman spectrum shown in FIG. 4C provides further evidence that the silicon was not oxidized during the lasing process and its crystallinity was retained, with the spectrum depicting typical values of crystalline elemental silicon [Shabir et al. Silicon, 3, 173-176 (2011)]. The absence of any silicon-carbon peaks [Koyanagi et al. J. Raman Spectrosc. 49, 1686-1692 (2018)] also confirms the physical encapsulation of the particles as opposed to chemical bonding.
[0533] These results, in conjunction with the EDS analyses, which exhibited only uniform native oxides encasing the SiNPs, confirm the retention of crystalline elemental silicon throughout the lasing process. Preservation of the structural properties of the electrochemically active agent during the lasing process is of the upmost importance, as it suggests that despite the intense conditions and rapid kinetics that transformed the carbonaceous material left the silicon unaffected. Accordingly, it can be ascertained that the porous structure that is formed can be attributed to the carbonization and subsequent outgassing of the biomass, which in turn physically encapsulates the unaffected SiNPs within the as-forming matrix.
[0534] The Raman spectrum in FIG. 4D indicates formation of a graphene-like structure [Malard et al. Phys. Rep. 473, 51-87 (2009)], as the G (-1580 cm1) and D (-1340 cm1) bands are typically observed in the Raman spectrum of such structures. The G band arises from in-plane vibrations of sp2 hybridized carbon atoms in the crystal lattice, while the D band arises from out of plane vibrations in the lattice that are activated by structural defects such as vacancies, edges, and grain boundaries, and is used to study levels of structural disorder. As the characteristic graphene peaks are not visible in the Raman spectrum pre-lasing (FIG. ID), these data suggest that graphene is formed following lasing, e.g., is a laser-induced graphene (LIG).
[0535] Here, a relatively high ID / IG ratio (-1.15) is observed, which suggests increased disorder and defect density, indicating a less pristine lattice [Beams et al. J. Phys. Condens. Matter 27, (2015)]. This indicates a very short-terXm order that can be categorized as almost amorphous scattered domains of sp2 hybridized honeycomb-like fragments [Sheka et al. Nanomaterials, 10, 1-22 (2020); Moseenkov et al. Materials, 16 (3), 1112 (2023)]. Moreover, partial oxidation under an ambient atmosphere may contribute to the high ID / IG ratio [Torrisi et al. Vacuum 153, 122-131 (2018); Bruna et al. ACS Nano 8, 7432-7441 (2014)]. The displayed spectrum, indicating the formation of sp2hybridized carbon domains that are highly disordered and doped, are consistent with the erratic localized high temperatures and pressures resulting from rapid lasing under ambient conditions.
[0536] These findings indicate a correlation with the amorphous and nano-crystalline domains that were observed in HRTEM analysis (FIG. 4B).
[0537] Without being bound to any particular theory, it is assumed that during the lasing process, fast photochemical and photothermal reactions occur, creating high localized temperatures and pressures, breaking C-O, C=O and C-N bonds, and releasing minor gaseous by-products. This is schematically illustrated in FIG. 4M. The rapid kinetics and heat dissipation cause residual carbon atoms to recombine and form scattered domains of sp2hybridized graphene and amorphous carbon domains, while the high-pressure release of gaseous by-products transforms the structure into a highly macroporous network [Alhajji et al. (2021) supra; Le et al. (2022) supra].
[0538] The breaking of these bonds and subsequent sp2hybridization is evident in the pre-lasing and post-lasing high-resolution XPS analysis of the C Is orbitals shown in FIGs. 4K and 4L, respectively, where a substantial decrease in C-O, C-N, C=N and C=O bonds can be seen along with an increase in sp2C-C bonds [Al-Gaashani et al. Ceram Int 45, 14439-14448 (2019)]. This finding aligns with previous studies of LIG mechanisms that have found the standard gases formed when such bonds are broken are mostly attributed to H2O, H2, NH3, N2 and CO [Dong et al. Carbon N. Y. 104, 47-55 (2016)].
[0539] XPS depth profile analysis of the C Is spectrum was performed. The results, presented in FIG. 4N, show the decrease in C-O bond content in the bulk of the material, indicating that the larger amount of oxygen is present near the surface of the material due to oxygen-rich lasing environment.
[0540] In order to encourage pyrolysis and carbonization of the residual carbon over combustion and decomposition, the film was first treated with a catalytic amount of diluted boric acid that acts as a flame retardant under oxygen-rich ambient conditions and is washed out after the lasing process. The effect of adding boric acid as an exemplary flame retardant was studied, and the results are presented in FIGs. 4E-F. Without being bound to any particular theory, the boric acid is assumed to function as a heat sink and also aids the formation of glassy coating, improving in char formation, flame dilution, and the formation of less combustible gases [Dogan et al. Compos. Part B Eng. 222, 109088 (2021)]. This method successfully circumvents combustion by multiple lasing and encourages formation of 3D porous conductive carbon structures.
[0541] As can be seen in FIGs. 4E-F, SEM analysis (FIG. 4E) show that a non-porous structure is obtained, and electrochemical impedance spectroscopy (EIS) analysis (FIG. 4F) showing a decrease in conductivity when boric acid is not added to encourage pyrolysis during laser irradiation, indicating a high resistance of the resulting composite. These findings suggest that the addition of a flame retardant is recommended as it may affect the carbon-based structure.
[0542] The generation of a three-dimensional porous carbon matrix via laser irradiation may be influenced by the laser irradiation conditions, including lasing speeds, spot sizes, multiplicity of lasing passes, and laser powers, which can yield different fluence levels (J / cm2).
[0543] The heat capacity and thickness of the lasing substrate also serve important roles in the heat dissipation, affecting the resulting transformation. For battery applications, for example, achieving a full transformation throughout the electrode thickness is imperative in order to ensure optimal electrical contact. Attaining the optimal balance between these parameters is desirable, as different ratios may result in no reaction, combustion or decomposition of the precursor, material ablation, or partial depth of transformation [Vivaldi et al. ACS Appl. Mater. Interfaces 13, 30245-30260 (2021)].
[0544] HRSEM analyses of the optimization process under different laser fluences is presented in FIG. 4G. It can be seen that at high speeds (lower fluence) the transformation of the jellyfish biomass into a porous carbon structure is non-existent or is limited to a thin area of the surface, and accordingly the depth increases with an increase in the fluence. At slower speeds (larger fluence) the depth of transformation is larger. Multiplicity of lasing passes is also seen to be vital in achieving maximum transformation, with a second pass of the laser resulting in a complete transformation throughout the thickness of the anode.
[0545] These data demonstrate the importance of full penetration depth of the lasing process in order to avoid an insulating base layer between the conductive carbon electrode and the conductive substrate.
[0546] EXAMPLE 2
[0547] Electrochemical Analysis
[0548] The JF / SiNP composites were assembled into 2032 coin cells versus lithium metal (see, FIG.
[0549] 1C) and underwent electrochemical analysis to evaluate their suitability as anodic material for use in lithium-ion batteries. Cyclic voltammetry (CV) was conducted in order to assess the electrochemical activity retention of the SiNPs after laser processing along with characterizing the voltage window of the half- cells and is depicted in FIG. 5A. The CV was conducted within the voltage range of 0.05 V to 1 V vs. Li / Li+using a scan rate of 0.02 mV / s, ensuring lithiation in accordance with the known charge and discharge range of silicon-lithium alloying.
[0550] The resulting delithiation peaks observed at 0.49 V and 0.29 V, as well as the lithiation peaks at 0.21 V and 0.07 V, are sharp and definitive, matching the theoretical values and indicating that the electrochemical activity of the silicon was preserved after the lasing process [Liu et al. Phys. Chem. Chem. Phys. 20, 23480-23491 (2018)].
[0551] In order to assess the transformation of the JF biomass into conductive carbon, electrical impedance spectroscopy (EIS) was conducted on a 2-layered JF / SiNP cell over a frequency range of 0.01 MHz to 1 Hz after delithiation over different cycling stages and is displayed in the Nyquist plot in FIG. 5B. The equivalent circuit utilized for the impedance analysis is illustrated in FIG. 5K, and values of each component in the EIS plots depicted in FIG. 5B are summarized herein in Table 3.
[0552] Table 3
[0553] The diameter of the depressed semicircle represents the charge transfer resistance (Ret). The impedance values confirm the sharp increase in conductivity after the lasing process, which are comparable to reported values of silicon / graphene-based composites in lithium-ion batteries [Wu et al. Powder Technol. 311, 200-205 (2017); Liu et al. ACS Nano , 9 (2), 1198-1205 (2015); ELkhodary et al. Rare Met. 41, 368-377 (2022)] and are well above impedance values displayed by pristine SiNPs [Liu et al. Minerals, 8(5), 180 (2018)]. As anticipated, the EIS analysis shows that the initial impedance of the battery was lower prior to cycling, with subsequent cycles resulting in the development of the solid electrolyte interface (SEI) layer, leading to a small gradual increase in impedance. However, the overall impedance of the battery stabilized after a few cycles and remained relatively constant thereafter [Middlemiss et al. Energy Reports 6, 232-241 (2020); Zhang et al. Electrochim. Acta 51, 1636-1640 (2006)].
[0554] To further characterize the enhanced kinetics of the JF / SiNP composite, FIGs. 5L-M depict CVs conducted at several scan rates, used to determine the diffusion coefficient of lithium within the exemplary JF / SiNP composite, using the Randles-Sevcik equation [Leftheriotis, G. et al. Solid State Ion 178, 259-263 (2007)]:
[0555] Where ipis the current measured at a constant voltage over different scan rates (v), n is the number electrons transferred in the reaction, F is the Faraday constant, A is the surface area of the electrode, CLiis the Li concentration in the electrolyte, R is the gas constant, T is the operating temperature and DLiis the diffusion coefficient of lithium. The diffusion coefficient was measured to be 3.57 x 1011cm2 / s, several orders of magnitude above the approximate Li diffusion kinetics in Si (ranging from 1014to 1016cm2 / s) [Wang et al. J Power Sources 307, 77-85 (2016)] and in line with reported diffusion coefficients for silicon / carbon composites [Xia et al. J Alloys Compd 800, 50-57 (2019); Dimov et al. J Power Sources 114, 88-95 (2003)], showing a clear increase in lithium diffusion relative to pristine Si.
[0556] FIG. 5C displays galvanostatic cycling of a typical 2-layer JF / SiNP thin anode in a half-cell configuration performed at a constant current density of 500 mA / g (approximately C / 5) over 1170 cycles and in accordance with the characteristic voltage window observed in the voltammogram. The possible capacity contribution of the carbon or trace impurities found in the matrix such as sulfur or phosphorus was ruled out in this voltage range by cycling a control anode at the same current density without silicon, as is also depicted in FIG. 5C.
[0557] Additionally, differential capacity analysis of the same cell displayed in FIG. 5D over different cycling stages clearly shows that the only electrochemical activity occurring during cycling is that of silicon. The analysis clearly shows sole electrochemical activity of silicon during over 1000 cycles, with clear lithiation and delithiation peaks related to silicon-lithium alloying. The dQ / dV peaks observed at approximately 270-300 mV and 500 mV correspond to distinct phase transformations related to the delithiation of the lithium silicides. Two additional lithiation peaks are observed at about 100 mV and between 250-300 mV, which can be attributed to the gradual lithiation of large silicon clusters to lithium silicide.
[0558] The gravimetric capacity of the cell was calculated by measuring the dry mass fraction (about 30 %) of silicon added after each spin-coated layer before the lasing process. The initial gravimetric capacity was 1402 mAh / g, with the initial decrease in capacity observed in the first cycles being attributed primarily to the formation of the SEI passivation layer [Wang et al. npj Comput. Mater. 4, 15 (2018)]. Upon stabilization of the SEI, the battery exhibited excellent reversible capacity retention, as demonstrated by the voltage profiles of the cell depicted at different cycles in FIG. 5E. During the initial cycles, the battery displayed a high retention rate of reversible capacity, with 82 % retention between the 10thcycle and 100thfrom a starting reversible gravimetric capacity of about 1250 mAh / g. Notably, the capacity retention continued to improve with additional cycles, reaching an impressive retention rate of 98 % between the 400th and 500th cycle, indicating significant improvement in long- term battery durability and performance.
[0559] Overall, the battery demonstrated remarkable stability and capacity, exceeding the theoretical value of graphite anodes for all cycles, and retaining over 50 % of reversible capacity with 690 mAh / g after 1000 cycles.
[0560] The slow decay and high retention correlates to the high calculated coulombic efficiency, with an average of over 99 %. FIG. 5F depicts the rate performance of a typical 2-layer JF / SiNP cell. At a lower current density of 50 mA / g, the battery exhibits an excellent reversible gravimetric capacity of -2000 mAh / g. The decline in capacity over increasing current densities was gradual, resulting in less than a 50 % decrease in reversible capacity between moderate cycling at 50 mA / g and faster cycling at 800 mA / g. Even when cycled rapidly at a current density of 1600 mA / g, the cell still exhibits an excellent gravimetric capacity of 850 mAh / g. The high retention rate and gravimetric capacities following changes in current densities, with respect to the complete absence of conductive additives, highlights the immense potential of these results.
[0561] An additional electrode was similarly prepared by spin-coating on a different type of conductive substrate, 15 μm copper foil, and its galvanostatic cycling data is presented in FIG. 5G. As depicted in FIG. 5G, when cycling at the same current density, a similar stability, loading and gravimetric capacity for over 100 cycles are observed. These data indicate that the disclosed method and system are not limited to stainless steel-based current collectors. This proposed technique of a deposited layered material allows for high flexibility in battery design, giving complete control of the anode dimensions in accordance with the needs of the functional application. Accordingly, the anodes can range from ultra-thin films with low areal loading (but high volumetric loading), as depicted in the above analysis, which are useful for small devices such as wearable electronics, to loadings that are used in high-energy density commercial batteries of over 1 mg / cm2. As such, cycling performance from anodes with additional spin coated layers (6) are displayed in FIG. 5H. The anodes possess a mass loading of 1 mg / cm2cycled at C / 20 with stable reversible capacity of approximately 1.2 mAh / cm2.
[0562] FIG. 51 displays the galvanostatic cycling performance of a 5-layer JF / SiNP cell cycled at current densities of 100 mA / g and 800 mA / g for 50 cycles. The cell cycled at a slower rate displayed an impressive initial areal capacity of approximately 1.3 mAh / cm2at a thickness of only 42 micrometers, exhibiting industrial-level market targets while still remaining reasonably thin. Additionally, even when cycled at higher current densities of 800 mA / g, the thicker cell exhibited excellent stability and adequate areal capacity.
[0563] Cycling performance from anodes with two and three additional layers (1 mg / cm2and 2 mg / cm2, respectively) are displayed in FIGs. 50 and 5P, respectively, and show stable reversible areal capacities of 1.2 and 2 mAh / cm2, respectively. A FIB / SEM cross-sectional image of high-loading JF / SiNP 3D porous structure with three additional spin-coated layers is presented in FIG. 5N.
[0564] In an effort to examine the performance of an electrochemical system comprising a JF / SiNP composite anode according to some of the present embodiments, a full cell configuration comprising the exemplary JF / SiNP composite anode and a lithium iron phosphate (LiFePO4 ;LFP) cathode, which was prepared as described herein, was assembled and cycled between 2.2 and 4 V at a rate of C / 12. The galvanostatic cycling performances are presented in FIG. 5J, and indicate excellent cyclic stability.
[0565] The phenomenal electrochemical performance displayed by the exemplary JF / SiNP composite electrodes may be related to their unique structure, which is further investigated in the post-mortem analysis and the resulting data based on the JF / SiNP cell that ran for 1170 cycles (FIG. 5C) is presented in FIGs. 6A-C.
[0566] As can be observed in FIG. 6A, the now amorphous SiNPs [Obrovac and Christensen (2004) supra] is still completely encapsulated within the conductive carbon matrix after cycling, indicating that the mechanical integrity of the carbon matrix can sufficiently function as a buffer to mitigate the severe volume expansion of silicon during lithiation for many cycles, thus reducing the likelihood of loss of active material due to pulverization and cracking. The absence of such a buffer may also lead to fracturing of the SEI layer, resulting in recurrent formation and breakdown of unstable SEI layers. Accordingly, the EDS analysis of Fluoride (from the LiPF6in the electrolyte) also shown in FIG. 6A suggest a uniform dispersion of the SEI throughout the carbon matrix, contributing to the enhanced stability of JF / SiNP batteries and indicating that the wetting of the electrolyte was optimal [Harpak et al. Chem. Eng. J. 429, 132077 (2022)].
[0567] As indicated by the rate performance capabilities of the cells presented in FIG. 5F, the incorporation of silicon encapsulated in conductive carbon can augment electrode conductivity by facilitating an advantageous continuous pathway for electron transport. The anode material is also directly deposited on the current collector during the synthesis and prior to battery assembly, ensuring sufficient adhesion and optimal electrical contact. The same is true for the increase in porosity of the anode material as a result of the development of the 3D porous carbon polymorph architecture, with the increase in contact area between the encapsulated silicon and electrolyte enabling enhanced wetting and ion transport [Cohen et al. ACS Appl. Mater. Interfaces 14, 28911-28923 (2022)].
[0568] As evident by the structural analysis, the pristine SiNPs are completely encapsulated within the conductive carbon matrix. The encapsulated SiNPs are uniformly dispersed within the periodic nanoporous conductive carbon network that can sufficiently function as a buffer to mitigate the severe volume expansion of silicon during lithiation. The absence of such a buffer may lead to fracturing of the SEI layer, resulting in recurrent formation and breakdown of unstable SEI layers. This, in turn, leads to a decline in battery capacity and cyclic stability due to increased consumption of lithium ions.
[0569] Moreover, the carbon encapsulation improves the mechanical stability of the anode during volume expansion, reducing the likelihood of loss of active material due to pulverization and cracking. Furthermore, the incorporation of silicon encapsulated in conductive carbon within a larger conductive carbon network can augment electrode conductivity by facilitating an advantageous continuous pathway for electron transport. The anode material is also directly deposited on the current collector during the synthesis and prior to battery assembly, ensuring sufficient adhesion and optimal electrical contact. The same is true for the increase in surface area of the anode material as a result of the development of the 3D porous architecture, with the increase in contact area between the anode and electrolyte enabling enhanced wetting and ion transport [Cohen et al. (2022) supra} .
[0570] Through the mitigation of recurrent SEI layer breakdown and active material loss caused by pulverization, as well as the improvement of ion and electron conductivity, the stability and capacity of the batteries is significantly enhanced [Luo et al. J. Electrochem. Soc. 162, A2509-A2528 (2015)]. Consequently, due to the cumulative effect of these factors on JF / SiNP battery performance, use of conductive additives or binders can be eliminated, as corroborated by the electrochemical analysis.
[0571] Although the invention has been described in conjunction with specific embodiments thereof, it is evident that many alternatives, modifications and variations will be apparent to those skilled in the art. Accordingly, it is intended to embrace all such alternatives, modifications and variations that fall within the spirit and broad scope of the appended claims.
[0572] It is the intent of the applicant(s) that all publications, patents and patent applications referred to in this specification are to be incorporated in their entirety by reference into the specification, as if each individual publication, patent or patent application was specifically and individually noted when referenced that it is to be incorporated herein by reference. In addition, citation or identification of any reference in this application shall not be construed as an admission that such reference is available as prior art to the present invention. To the extent that section headings are used, they should not be construed as necessarily limiting. In addition, any priority document(s) of this application is / are hereby incorporated herein by reference in its / their entirety.
Claims
WHAT IS CLAIMED IS:
1. A method of preparing an electrochemically active component, the method comprising depositing a mixture that comprises a carbonaceous material and an electrochemically active material on a conductive substrate, to thereby to thereby obtain said conductive substrate having said mixture deposited on at least a portion of a surface thereof; and exposing the conductive substrate having said mixture deposited thereon to laser irradiation, to thereby form a 3D porous structure deposited onto said at least a portion of said surface of said conductive substrate, said 3D porous structure comprising a 3D porous graphene matrix having said electrochemically active material dispersed and / or entrapped and / or embedded therewithin, wherein said carbonaceous material comprises a jellyfish biomass.
2. The method of claim 1, wherein said jellyfish biomass is prepared by homogenizing a jellyfish or a part thereof.
3. The method of claim 1 or 2, wherein said mixture further comprises a carrier.
4. The method of claim 3, wherein said mixture comprises a paste, a powder or particles of said jellyfish biomass dispersed in or mixed with said carrier.
5. The method of any one of claims 1 to 4, wherein said electrochemically active material is in a form of particles.
6. The method of claim 5, wherein said particles have an average diameter in a range of from 1 to 300 nm, or from 1 to 200 nm.
7. The method of any one of claims 1 to 6, wherein said electrochemically active material comprises silicon.
8. The method of any one of claims 1 to 7, wherein a weight ratio of said carbonaceous material and said electrochemically active material ranges from 10: 1 to 1:10, or from 10:1 to 1: 1.
9. The method of any one of claims 1 to 8, wherein said mixture further comprises a flame retardant.
10. The method of claim 9, wherein an amount of said flame retardant is up to 10 %, or ranges from 0.1 to 10, %, by weight of the total weight of said mixture.
11. The method of claim 9 or 10, wherein said flame retardant is or comprises boric acid.
12. The method of any one of claims 1 to 11, wherein said depositing is effected by spin coating.
13. The method of any one of claims 1 to 12, wherein said exposing is of at least one layer of said mixture, and wherein a thickness of said layer ranges from 1 to 10, micrometers.
14. The method of any one of claims 1 to 13, wherein said exposing comprises laser rastering.
15. The method of any one of claims 1 to 14, wherein said exposing comprises irradiating said deposited mixture with a continuous visible laser irradiation.
16. The method of any one of claims 1 to 15, wherein said conductive substrate is a current collector.
17. The method of any one of claims 1 to 16, wherein said substrate comprises conductive metallic substance.
18. The method of claim 17, wherein said conductive metallic substance is selected from stainless steel, copper and aluminum.
19. The method of any one of claims 1 to 18, wherein said conductive substrate having said porous structure deposited therein forms or comprises an electrode.
20. The method of any one of claims 1 to 19, wherein the electrochemically active component is or comprises an electrode.
21. The method of claim 20, wherein said electrode is usable as an anode in a lithium-ion battery.
22. An electrochemically active component obtained by the method of any one of claims 1 to 21.
23. An electrochemically active component comprising a 3D porous structure which comprises a 3D porous graphene matrix having said electrochemically active material dispersed and / or entrapped and / or embedded therewithin, wherein said graphene matrix is formed of a carbonaceous material that comprises a jellyfish biomass.
24. The electrochemically active component of claim 22 or 23, wherein said 3D porous structure is characterized by one or more of: an amount of oxygen of at least 1 or at least 5 or ranges from 1 to 50, or from 5 to 20, %, by weight of the total weight of said 3D porous structure; and / or an atomic amount of oxygen of at least 1 or at least 5 or ranges from 1 to 50, or from 5 to 20, %; and / or an amount of nitrogen of at least 0.1 or at least 0.5 or ranges from 0.1 to 50, or from 0.5 to 5, or from 0.8 to 2, %, by weight of the total weight of said 3D porous structure; and / or an atomic amount of nitrogen of at least 0.1 or at least 0.5 or ranges from 0.1 to 50, or from 0.5 to 5, or from 0.8 to 2, %; and / or an amount of oxygen relative to a total amount of oxygen and carbon (% weight of oxygen / % weight of oxygen + % weight of carbon) of at least 5, or at least 10, or at least 15, or ranges from 5 to 40, or from 10 to 30; and / or an atomic amount of oxygen relative to a total atomic amount of oxygen and carbon (graphene matrix) (% atomic of oxygen / % atomic of oxygen + % atomic of carbon) of at least 5, or at least 10, or ranges from 5 to 40, or from 10 to 25; and / oran amount of oxygen relative to a total amount of oxygen, nitrogen and carbon (% weight of oxygen / % weight of oxygen + % weight of carbon + % weight of nitrogen) of at least 5, or at least 10, or at least 12, or ranges from 5 to 40, or from 12 to 30, %; and / or an atomic amount of oxygen relative to a total atomic amount of oxygen, nitrogen and carbon (% atomic of oxygen / % atomic of oxygen + % atomic of carbon + % atomic of nitrogen) of at least 5, or at least 10, or ranges from 5 to 40, or from 10 to 30, or from 10 to 25, %; and / or an amount of nitrogen relative to a total amount of nitrogen and carbon (% weight of nitrogen / % weight of nitrogen + % weight of carbon) of at least 0.5 or at least 1 or ranges from 0.5 to 20, or from 1 to 15, or from 2 to 10, or from 2 to 5, %; and / or an atomic amount of nitrogen relative to a total atomic amount of nitrogen and carbon (% atomic of nitrogen / % atomic of nitrogen + % atomic of carbon) of at least 0.1, or at least 0.5, or at least 1, or ranges from 0.1 to 20, or from 0.5 to 15, or from 1 to 10, or from 1 to 5, %; and / or an amount of nitrogen relative to a total amount of oxygen, nitrogen and carbon (% weight of nitrogen / % weight of oxygen + % weight of carbon + % weight of nitrogen) of at least 0.1, or at least 0.5, or at least 1, or ranges from 0.1 to 20, or from 0.5 to 15, or from 1 to 10, or from 1 to 5, %; and / or an atomic amount of nitrogen relative to a total atomic amount of oxygen, nitrogen and carbon (% atomic of nitrogen / % atomic of oxygen + % atomic of carbon + % atomic of nitrogen) of at least 0.1, or at least 0.5, or at least 1, or ranges from 0.1 to 20, or from 0.5 to 15, or from 1 to 10, or from 1 to 5, %.
25. The electrochemically active component of any one of claims 22 to 24, further comprising a conductive substrate, wherein said 3D porous structure is deposited onto at least a portion of a surface of said conductive substrate.
26. The electrochemically active component of any one of claims 22 to 25, being or comprising an electrode.
27. The electrochemically active component of any one of claims 22 to 26, wherein said conductive substrate is a current collector.
28. An electrochemical system comprising the electrochemically active component of any one of claims 22 to 27.
29. The electrochemical system of claim 28, being or forming a part of an alkali metal ion battery.
30. The electrochemical system of claim 28 or 29, further comprising an electrolyte.
31. A method of preparing a graphene matrix, the method comprising exposing a mixture that comprises a carbonaceous material to laser irradiation, to thereby form the graphene matrix, wherein said carbonaceous material comprises a jellyfish biomass.
32. A graphene matrix obtained by the method of claim 31.
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