WO2017172044A2 - Composite de noir de carbone pyrolytique et procédé de production dudit composite - Google Patents

Composite de noir de carbone pyrolytique et procédé de production dudit composite Download PDF

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WO2017172044A2
WO2017172044A2 PCT/US2017/016541 US2017016541W WO2017172044A2 WO 2017172044 A2 WO2017172044 A2 WO 2017172044A2 US 2017016541 W US2017016541 W US 2017016541W WO 2017172044 A2 WO2017172044 A2 WO 2017172044A2
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carbon black
battery
carbon
temperature
conducted
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PCT/US2017/016541
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WO2017172044A3 (fr
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Amit K. Naskar
Mariappan Parans Paranthaman
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Ut-Battelle, Llc
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Priority claimed from US15/056,184 external-priority patent/US10320000B2/en
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Publication of WO2017172044A2 publication Critical patent/WO2017172044A2/fr
Publication of WO2017172044A3 publication Critical patent/WO2017172044A3/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/44—Carbon
    • C09C1/48—Carbon black
    • C09C1/482—Preparation from used rubber products, e.g. tyres
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/44—Carbon
    • C09C1/48—Carbon black
    • C09C1/487—Separation; Recovery
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • H01G11/34—Carbon-based characterised by carbonisation or activation of carbon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • H01G11/44—Raw materials therefor, e.g. resins or coal
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/85—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by XPS, EDX or EDAX data
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/12—Surface area
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/14—Pore volume
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/16—Pore diameter
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/16—Pore diameter
    • C01P2006/17—Pore diameter distribution
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • H01G11/38—Carbon pastes or blends; Binders or additives therein
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • This invention relates generally to producing materials containing carbon particles, and more specifically to the production of materials containing carbon particles for battery electrodes.
  • the tire rubber formulation contains significant quantities of carbon black that is used as reinforcing fillers and abrasive resistance for rubber matrices.
  • a tire consists of natural rubber, synthetic polyisoprene, butadiene rubber, styrene- butadiene rubber, carbon black and a fractional amount of additives.
  • High structure carbon black made of clusters of -10 - 100 nm size fundamental particles are used in tire rubber formulations to enhance mechanical properties of the product.
  • the regular direct pyrolysis process results in the production of about 30-40 wt. % carbon black, depending on the pyrolysis conditions. Rubber particles do not exist as a single fundamental particle; rather they are fused together during production of black to make aggregates of various structures. Such structures are retained in vulcanized rubber products such as pneumatic tires that contain dispersed phases of carbon black in rubber matrix.
  • the waste tire rubber is usually cryogenically pulverized into small micron- sized rubber particles. Cut rubber pieces are also ground in ambient conditions to get powder buffing. Those powdered tire rubbers are usually used as fillers in various low-cost rubber or plastic products. Isolation of the carbon black from tire formulations was tried but such products are not necessarily good reinforcing fillers for a new rubber formulation. Utilization of tire rubber materials for value-added applications would be very attractive not only for the recovery of materials but also to control global pollution.
  • SIBs sodium-ion batteries
  • LIBs lithium-ion batteries
  • a method of recovering carbon black comprises the steps of providing a carbonaceous source material containing carbon black, contacting the carbonaceous source material with a sulfonation bath to produce a sulfonated material, and pyrolyzing the sulfonated material to produce a carbon black containing product comprising a glassy carbon matrix phase having carbon black dispersed therein.
  • the sulfonation bath can be an oleum bath.
  • the sulfonation bath can comprise a sulfonation agent such as chlorosulfonic acid in 1 ,2 dichloroethane solution.
  • the sulfonation bath can comprise between 0.1 - 65 wt. % SO3.
  • the sulfonation bath can comprise 2 - 30 wt. % SO3.
  • the sulfonation bath can have a temperature of between -20 °C to 200 °C.
  • the pyrolysis step can be conducted at a temperature that is greater than 200 °C.
  • the pyrolysis step can be conducted at a temperature that is greater than 400 °C.
  • the pyrolysis step can be conducted at a temperature that is greater than 1000 °C.
  • the pyrolysis step can be conducted at a temperature that is between 200-1000 °C.
  • the duration of the pyrolysis step can be from 1 minute to 48 hours.
  • the method can further comprising the step of reducing the carbonaceous source material to a powder prior to contacting the carbonaceous source material with the oleum bath.
  • the powder or crumb rubber pieces can have an average maximum dimension of less than 100 nm to 1 0 cm.
  • the carbonaceous source material can comprise carbon reinforced composites.
  • the carbon reinforcing agent can be at least one selected from the group consisting of carbon black, carbon particles, nanoparticles, mesoparticles and fibers. Mesoparticles are in the range of 100 nm to few microns in size with a pore diameter of 7-20 nm and high surface area.
  • the carbonaceous source material can be a waste material, for example, particularly recyclable material.
  • the waste material can be rubber tires, for example.
  • the average pore size of the carbon black product can be less than 8 nm.
  • the average pore size of the carbon black product can be between 2 and 1 20 nm.
  • the isolated carbon can be further surface activated and the density of average pore size of the carbon black product between 1 and 20 nm can be increased.
  • the carbon black containing product can have a specific surface area of less than 3000 m 2 /g.
  • the carbon black containing product can have a specific surface area of less than 2000 m 2 /g, or less than 1000 m 2 /g.
  • the carbon black containing product can have a specific surface area of less than 1 00 m 2 /g.
  • the carbon black containing product can have a specific surface area of less than 10 m 2 /g.
  • the pyrolyzing step can occur after the contacting step.
  • the pyrolyzing step can occur before the contacting step.
  • a method of making a battery electrode comprising carbon black can include the steps of providing a carbonaceous source material containing carbon black, contacting the carbonaceous source material with an oleum bath to produce a sulfonated material, pyrolyzing the sulfonated material to produce a carbon black product comprising a glassy carbon matrix phase having carbon black dispersed therein, and forming a battery electrode from the carbon black containing product.
  • the battery electrode can be an anode.
  • the battery can be a lithium ion or a sodium ion battery.
  • the battery electrode can be two active electrodes.
  • the battery can be a supercapacitor.
  • a method of recovering carbon black includes the step of providing a carbonaceous source material containing carbon black.
  • the carbonaceous source material is contacted with a sulfonation bath to produce a sulfonated material.
  • the sulfonated material is pyrolyzed at a temperature of from 1 1 00 to 1490 °C to produce a layered carbon black containing product comprising a glassy carbon matrix phase having carbon black dispersed therein.
  • the layered carbon black containing product has an interlayer spacing of from 4 to 5 angstroms (0.4 to 0.5 nm).
  • a method of making a battery electrode comprising carbon black can include the step of providing a carbonaceous source material containing carbon black, contacting the carbonaceous source material with an oleum bath to produce a sulfonated material, and pyrolyzing the sulfonated material at a temperature of from 1 1 00 to 1490 °C to produce a layered carbon black product comprising a glassy carbon matrix phase having carbon black dispersed therein.
  • the layered carbon black containing product can have an interlayer spacing of from 4 to 5 angstroms (0.4 to 0.5 nm).
  • a battery electrode can then be formed from the carbon black containing product.
  • a battery can include an anode comprising layered carbon black containing product obtained by providing a carbonaceous source material containing carbon black, contacting the carbonaceous source material with an oleum bath to produce a sulfonated material, pyrolyzing the sulfonated material at a temperature of from 1 1 00 to 1490 °C to produce the layered carbon black product comprising a glassy carbon matrix phase having carbon black dispersed therein.
  • the layered carbon black containing product having an interlayer spacing of from 4 to 5 angstroms (0.4-0.5 nm).
  • a cathode is provided and an electrolyte is disposed between the anode and the cathode.
  • Figure 1 is a schematic diagram of a method for recovering carbon black in modified form from recycled tire rubber.
  • Figure 2 is thermogravimetric analysis (TGA) thermograms of precursors for Sample # 1 (control tire rubber) and Sample # 2 (sulfonated tire rubber).
  • Figure 3A is cumulative pore volume data based on BET adsorption- desorption data analysis of carbons from Sample # 1 (control tire rubber-derived carbon) and Sample # 2 (carbon from sulfonated tire rubber powder).
  • Figure 3B is differential pore volume in both carbons (in magnified scale) at smaller pore widths.
  • Figure 4 is cycling performance of the control tire rubber-derived carbon (Sample # 1 ) anode at 0.1 C.
  • Figure 5 is the 1 st and 2nd charge-discharge curves of the control tire rubber (Sample #1 ) -derived carbon anode at 0.1 C.
  • Figure 6 is rate performance of the control tire rubber (Sample #1 ) -derived carbon anode.
  • Figure 7 is cycling performance of the sulfonated tire rubber (Sample #2)- derived carbon anode at 0.1 C.
  • Figure 8 is 1 st and 2nd charge-discharge curves of the sulfonated tire rubber (Sample #2) -derived carbon anode at 0.1 C.
  • Figure 9 is the rate performance of the half-cell made from sulfonated tire rubber (Sample #2) -derived carbon.
  • Figures 10A, 1 0B, and 10C are TEM images of control tire rubber (Sample #1 ) - derived carbon.
  • Figure 1 0D is a Selected Area Electron Diffraction pattern.
  • Figures 1 1 A and 1 1 B are TEM images of sulfonated rubber tire (Sample #2) - derived carbon.
  • Figure 1 1 C is a Selected Area Electron Diffraction pattern.
  • Figure 12A is X-ray diffraction patterns and Figure 1 2B Raman spectra of tire- derived carbons obtained by pyrolyzing at different temperatures.
  • Figures 13A and 13B are X-ray photoemission spectroscopy (XPS) of sulfonated tire rubber-derived carbons.
  • Figure 1 3A shows C1 s scans and
  • Figure 13B shows S2p scans.
  • the insert in Figure 13A shows the expanded binding energy plots.
  • Figures 14A, 14B, 14C and 14D demonstrate cycling performances of (14A) TC1 1 00, (14B) TC1400, and (14C) TC1600, and (14D) a comparison of discharge and charge curves of all the carbons.
  • Figure 15 is a comparison of the discharge and charge curves of TC1 600 at 25th, 50th, 75th, and 100th cycles.
  • Figure 16 is the long-cycle stability test of TC1 100 at a current density of 20 mA g "1 .
  • a method of recovering carbon black as shown in Figure 1 includes the step of providing a carbonaceous source material containing carbon black.
  • the carbonaceous source material is soaked in a sulfonation bath to produce a sulfonated material.
  • the sulfonated material is pyrolyzed to produce a carbon black containing product comprising a glassy carbon matrix phase having carbon black dispersed therein.
  • the sulfonation bath can comprise any reactant composition capable of sulfonating rubber. It is also capable of sulfonating vulcanized particulate rubbers containing carbon black or carbon particles or carbon fiber or carbon nanomaterials.
  • the sulfonation bath can be an oleum bath.
  • the oleum bath can comprise up to 65 wt. % SO3 in concentrated sulfuric acid. Very high SO3 content in oleum bath causes solidification of reactant mix and therefore, may not be useful for processing.
  • the sulfonation bath can be a sulfuric acid (H2SO 4 ) solution. The concentration of sulfuric acid in the oleum bath can be between 1 0 and 100 wt. %.
  • the sulfonation bath can comprise other sulfonation agents such as chlorosulfonic acid in 1 ,2 dichloroethane solution, organic solvents (such as 1 ,2 dicholoroethane) containing SO3 gas, or equimolar mixture of acetic anhydride concentrated sulfuric acid that yields acetyl sulfate.
  • Acetyl sulfate assists in electrophilic sulfonation of aromatic ring in styrene containing rubbers but SOs can aid free radical sulfonation of aliphatic segments.
  • the sulfonation bath can comprise a liquid, a gas, or a liquid and a gas.
  • the sulfonation bath can comprise between 0.1 -65 wt. % SO3 in liquid medium that can be concentrated sulfuric acid or organic solvents.
  • the sulfonation bath can comprise any minimum percentage and maximum percentage within this range, such as 5-20, 2-18, 2-30, or 0.1 -2 wt. % S0 3 .
  • the sulfonation bath can have a temperature of between -20 to 200 °C.
  • the pyrolysis step can be conducted at a temperature that is greater than 400 °C.
  • the pyrolysis step can be conducted at a temperature that is greater than 1000 °C.
  • the pyrolysis step can be conducted at a temperature that is between 200-1000 °C.
  • the duration of the pyrolysis step can be from 1 minute to 12 hours or more.
  • the conditions of the pyrolysis step such as temperature and duration can be selected depending on process conditions including the particular carbonaceous source material that is being pyrolyzed.
  • the pyrolysis step of high carbon content hydrocarbon polymer composites can also be maintained at the desulfonation temperature range when sulfur containing volatiles comes out of the material leaving unsaturated hydrocarbon with high carbon content.
  • the carbon content in pyrolyzed carbon materials can be higher than 80 wt.
  • the method can include the steps of reducing the carbonaceous source material to a powder prior to contacting the carbonaceous source material with the oleum bath.
  • the powder can be formed by any suitable method such as grinding, milling, cutting, and cryogenic pulverization.
  • the powder so formed can have an average maximum dimension of less than 1 00 nm to 10 cm.
  • crumb rubber with a size of less than 10 cm wide can also be used without grinding.
  • Metal particles such as Ni, stainless steel, Iron, and oxides such as ZnO, S1O2 and others present along with carbonaceous source material may also dissolve in the oleum bath and yield carbon powder with no metals and/or oxides or up to ppm levels of metals.
  • the presence of Ca comes from caolin or talc filler in rubber compounds and can form insoluble sulfates by reaction with sulfonating agents such as, for example, sulfuric acid.
  • sulfonating agents such as, for example, sulfuric acid.
  • the tire rubbers can be washed with aqueous hydrochloric acid, nitric acid, or an acidic salt (for example ammonium chloride) solution prior to sulfonation.
  • the carbonaceous source material can be any suitable carbon black containing source material.
  • One such source material comprises carbon black loaded plastics, scrap electronic casing containing carbon black loaded plastics that serve as electromagnetic shielding material, polymeric carbon nanocomposites containing carbon particles, and carbon fiber reinforced composites.
  • the carbonaceous source material can be a waste material, such as scrap vulcanized rubber tires or recycled vulcanized rubbers from other sources.
  • the product of the invention is a carbon black containing product comprising a glassy carbon matrix phase having carbon black dispersed therein.
  • the carbon black containing carbonaceous product is porous with a multi-modal pore size distribution with some pore width r, where 8 nm ⁇ r > 120 nm and some pore width less than 8 nm but greater than 2 nm.
  • the average pore size of the carbon black containing product can be between 2 and 120 nm.
  • the carbon black containing product can have a Brunauer-Emmett-Teller (BET) specific surface area of less than 1000 m 2 /g depending on the continuity of carbon matrix.
  • the specific surface area in composite can be less than 1 00 m 2 /g.
  • the BET specific surface area in the carbon particle containing carbon matrix products can further be modified by deploying a surface activation process.
  • Surface activation process is well known in art that produces activated carbon.
  • Activated carbon can be synthesized from pyrolyzed carbon residues by activating it in steam or CO2 at elevated temperature ranging from 200 to 1000 °C that results partially burnt out carbon residue with higher porosity.
  • the added porosity by surface activation is usually microporosity with pore widths less than 50 nm.
  • Activation of carbon can also be achieved by treating it with alkali followed by heat treatment in the presence of water vapors.
  • a battery electrode can be formed from the carbon black containing product. This electrode can be an anode for lithium-ion or sodium-ion batteries.
  • a method of making a battery electrode comprising carbon black can include the steps of providing a carbonaceous source material containing carbon black, contacting the carbonaceous source material with a sulfonation bath to produce a sulfonated material, pyrolyzing the sulfonated material to produce a carbon black containing product comprising a glassy carbon matrix phase having carbon black dispersed therein; and forming a battery electrode from the carbon black containing product.
  • the electrode can be an anode.
  • the battery can be formed by suitable techniques.
  • the battery can be a lithium (Li) ion battery, and/or a sodium (Na) ion battery.
  • Carbon black was recovered from powdered tire rubber by two methods: (1 ) simple pyrolysis of powder rubber at 1000 °C (nitrogen atmosphere) that yields 30- 40% carbon (control rubber tire-derived carbon, Sample # 1 ) and (2) digestion of rubber powders in a hot oleum bath (18 - 24% SO3) to yield sulfonated rubber powder that was then filtered, washed and compressed to make a solid cake followed by pyrolysis in an inert atmosphere (sulfonated rubber tire-derived carbon, Sample # 2).
  • Sample 2 produced a carbon monolith with a little higher yield (2 - 5 % increase in carbon yield compared to the control rubber powder; Sample 1 ) whereas Sample 1 produced fluffy (low bulk density) powder of carbon black.
  • the isolated carbon material (from either sample) was used to test their electrochemical performance as an active anode material in Li-ion battery.
  • Carbon black was also isolated from ground tire rubber by conventional pyrolysis (400 - 1000 °C in inert atmosphere) followed by treatment of the char with oleum bath and subsequent heat treatment of washed/dried charred residue in inert environment.
  • the oleum bath can have a concentration of 0.1 - 30 wt. % SO3. Since the material was charred before treatment in sulfonation bath it does not require very high temperature treatment in second carbonization step.
  • the second heat treatment can be above 200 °C; however, higher temperature gives higher rigidity or graphitic order in the derived carbon.
  • Tire rubber powder of 80 - 120 ⁇ size range consisting of polymer mixture of natural rubber, butadiene rubber, and styrene-butadiene rubber (45 %), carbon black (33 %), inorganic filler and vulcanization activator (10 %) and residual extractable and volatile materials with specific gravity of 1 .15 g/cc was used for the pyrolytic recovery of carbon black.
  • the powder rubber sample was heated in a tubular furnace under nitrogen atmosphere at 1000 °C. The temperature of the furnace was raised from room temperature to 1000 °C by heating it at 10°C/min and when it reached at 1000 °C it was held at that temperature for 15 minutes. The furnace was cooled to room temperature and the carbon residue was collected. The sample is termed as control carbon (Sample #1 ). The carbon black yield was 33%.
  • Tire rubber powder of 80-1 20 ⁇ size range consisting of polymer mixture of natural rubber, butadiene rubber, and styrene-butadiene rubber (45 %), carbon black (33 %), inorganic filler and vulcanization activator (10 %) and residual extractable and volatile materials with specific gravity of 1 .15 g/cc was used for a chemical pretreatment prior to pyrolysis.
  • the tire rubber powder was treated with fuming sulfuric acid containing 20 wt. % free SO3 gas at 70 °C for 12 h.
  • the tire rubber slurry was filtered on a Buchner funnel with sintered glass disc (fritted glass funnel) using an aspirator followed by washing with distilled water.
  • the washed sulfonated tire rubber cake was then dried at 80 °C for 1 h followed by pyrolysis in tubular furnace under nitrogen atmosphere at 1000 °C.
  • the furnace temperature was reached to 1000 °C by heating the furnace from room temperature at 1 0 °C/min and allowing a soak time of 15 minute at 1000°C.
  • the furnace was allowed to cool to room temperature and the environment was maintained under nitrogen before the sample was taken out.
  • Tire rubber powder of 80-1 20 ⁇ size range consisting of polymer mixture of natural rubber, butadiene rubber, and styrene-butadiene rubber (45 %), carbon black (33 %), inorganic filler and vulcanization activator (10 %) and residual extractable and volatile materials with specific gravity of 1 .15 g/cc was used for a chemical pretreatment prior to pyrolysis.
  • the tire rubber powder was treated with fuming sulfuric acid containing 20 wt. % free SO3 gas at 70 °C for 12 h.
  • the tire rubber slurry was filtered on a Buchner funnel with sintered glass disc (fritted glass funnel) using an aspirator followed by washing with distilled water.
  • the washed sulfonated tire rubber cake was then pressed between Teflon sheets under a hot plate inside a compression mold at 1 10°C to get rid of moisture and to obtain a thick (2 mm) molded sheet followed by pyrolysis in tubular furnace under nitrogen atmosphere at 1000 °C.
  • the furnace temperature reached 1000 °C by heating the furnace from room temperature at 10 °C/min and allowing a soak time of 15 minutes at 1000°C.
  • the furnace was allowed to cool to room temperature and the environment was maintained under nitrogen before the monolith carbon sample was taken out.
  • the sample is termed as sulfonated tire-rubber-derived carbon (Sample #2).
  • the yield of carbon based on as received material (non-sulfonated rubber) was 38 %.
  • Example 4 The tire rubber of 0.5 mm size consisting of polymer mixture of natural rubber, butadiene rubber, and styrene-butadiene rubber (42%), carbon black (33 %), inorganic filler and vulcanization activator (1 1 %) and residual extractable and volatile materials with specific gravity of 1 .14 g/cc was used for a chemical pretreatment prior to pyrolysis.
  • the tire rubber was treated with fuming sulfuric acid containing 30 wt. % free SO3 gas at 40 °C for 48 h.
  • the tire rubber slurry was filtered on a fritted glass funnel using an aspirator followed by washing with distilled water.
  • the washed sulfonated tire rubber cake was then dried at 80 °C for 1 h followed by pyrolysis in tubular furnace under nitrogen atmosphere at 600 °C.
  • the furnace temperature reached 600 °C by heating the furnace from room temperature at 1 0 °C/min and allowing a soak time of 60 minutes at 600 °C.
  • the furnace was allowed to cool to room temperature and the environment was maintained under nitrogen before the sample was taken out.
  • the yield of carbon based on as received material (non-sulfonated rubber) was 40 %.
  • Tire rubber powder of 80 - 120 ⁇ size range consisting of polymer mixture of natural rubber, butadiene rubber, and styrene-butadiene rubber (45 %), carbon black (33 %), inorganic filler and vulcanization activator (10 %) and residual extractable and volatile materials with specific gravity of 1 .15 g/cc was used for a chemical pretreatment prior to pyrolysis.
  • the tire rubber powder was treated with concentrated sulfuric acid (98 % H 2 S0 4 ) at 100 °C for 24 h.
  • the tire rubber slurry was filtered on a fritted glass funnel using an aspirator followed by washing with distilled water.
  • Washed sulfonated tire rubber cake was then dried at 80 °C for 1 h followed by pyrolysis in tubular furnace under nitrogen atmosphere at 600 °C.
  • the furnace temperature reached 600 °C by heating the furnace from room temperature at 10 °C/min and allowing a soak time of 60 minute at 600°C.
  • the furnace was allowed to cool to room temperature and the environment was maintained under nitrogen before the sample was taken out.
  • the yield of carbon based on as received material (non-sulfonated rubber) was 37 %.
  • Carbon black was isolated from ground tire rubber by conventional pyrolysis at 600 °C in inert atmosphere.
  • the isolated porous carbon or the char was treated in oleum bath at 70 °C for 12 h; the oleum had 20 wt. % SO3 in concentrated sulfuric acid.
  • the slurry of carbonaceous mass was washed, dried, and subsequent heat treated in inert environment (N2) at 1 000 °C. The heating of furnace was conducted at 1 2 °C /min from room temperature to 1000 °C and maintained 1000 °C for 15 minutes before it was cooled to room temperature.
  • pyrolysis can also be done in Argon or other inert atmosphere such as Helium instead of nitrogen atmosphere.
  • the TGA data of the Samples 1 -2 are shown in Figure 2.
  • the first weight loss in sample 2 around 150 °C is the desulfonation step that shifts the pyrolysis temperature of rubber to slightly higher temperature.
  • the relative char yield in desulfonated material, compared to control tire rubber (Sample #1 ), is slightly higher.
  • the coin half cells were assembled in an argon-filled glove box using recycled carbon (Samples # 1 and # 2), as the working electrode and metallic lithium foil as the counter electrode.
  • the anode was prepared by casting slurry of 80% active recycled carbon material, 5 wt.% super conducting carbon, and 15 wt.% polyvinylidene difluoride (PVDF) binder in n-methyl-2-pyrrolidone (NMP) solvent on copper foil.
  • PVDF polyvinylidene difluoride
  • NMP n-methyl-2-pyrrolidone
  • PVDF polyvinylidene difluoride
  • NMP n-methyl-2- pyrrolidone
  • the electrolyte for Li-ion batteries consisted of a solution of 1 M LiPF6 in ethylene carbonate (EC)/dimethyl carbonate (DMC)/diethyl carbonate (DEC) (1 :1 :1 by volume). Galvanostatic charge/ discharge cycling between the voltages of 0 - 3.0 V was performed at room temperature under different rates using an Arbin potentiostat/galvanostat multichannel system.
  • Example #1 or 2 The use of active super carbon in the electrode slurry composition can be minimized and finally eliminated if the isolated carbons (Sample #1 or 2) are activated by conventional method for activated carbon synthesis, followed by high temperature treatment at temperature T, where 3000 °C ⁇ T > 1000 °C, that increases electrical conductivity significantly. Steam or CO2 activation increases porosity and active surface area in the produced or recovered carbon materials.
  • Figure 4 shows the cycling performance of the control tire rubber (Sample #1 )-derived carbon at 0.1 C or C/10 (where 1 C corresponds to one charge- discharge cycle in an hour).
  • Figure 5 shows the galvanostatic discharge/charge curves of the same anodes (control tire rubber-derived carbon) between 0 and 3 V at a rate of 0.1 C.
  • Sample # 1 -derived carbon exhibited an initial capacity of -900 mAh/g at the first discharge, but the reversible capacity of only -500 mAh/g was attained, which led to much lower initial coulombic efficiency of 45%. Then the capacity decreased to ⁇ 200 mAh/g and the coulombic efficiency increased slowly to 99% after 45 cycles.
  • Figure 6 shows the rate performance of the control tire rubber (Sample # 1 )-derived carbon anodes. It clearly shows a rate performance with -1 00 mAh/g at 1 C, only -40 mAh/g at 5 C, which are much lower than the sulfonated tire rubber (Sample #2)-derived carbon.
  • Figure 7 shows the cycling performance of the half-cell made from sulfonated tire rubber-derived carbon (Sample # 2) materials.
  • a half-cell made by use of Sample # 2 exhibited a reversible capacity of - 400 mAh/g after 100 cycles with coulombic efficiency of almost 1 00%. This result is comparable to the theoretical capacity of 362 mAh/g for commercial carbon anodes.
  • Figure 8 shows the galvanostatic discharge/charge curves of the anodes made from sulfonated tire rubber-derived carbon between 0 and 3 V at a rate of 0.1 C. During the first discharge, the voltage pseudoplateau near 0 V contributes to a large irreversible capacity.
  • the first discharge capacity is around 500 mAh/g, and a reversible charge capacity around 400 mAh/g, leading to an irreversible capacity of 100 mAh/g.
  • both second discharge capacity and reversible charge capacity is around 400 mAh/g.
  • the reversible capacity was maintained to 100 cycles.
  • Figure 9 shows the rate performance of the sulfonated tire rubber-derived carbon (Sample # 2) anodes. It clearly shows a good rate performance with -270 mAh/g at 1 C, 1 60 mAh/g at 5 C, and over 50 mAh/g at 10 C. Results obtained from Sample # 1 were compared with Sample # 2. Based on these results, electrochemical performances of carbon from Sample # 2 are much better than those from Sample # 1 .
  • Sample # 1 ( Figure 1 0) has the morphology of spherical nanoparticles with an irregular cluster shape. Selected Area Electron Diffraction pattern indicates the presence of completely amorphous carbon materials.
  • Sample # 2-derived carbon ( Figure 1 1 ) has the morphology of 1 D (one dimensional) nanostructure. It formed a monolith hard carbon and when that was ground it formed fibriler or oriented structure. Selected Area Electron Diffraction pattern indicates the presence of both crystalline and amorphous carbon materials.
  • the activation can also be done by treating sulfonated precursor to a high temperature where desulfonating gases cause surface activation.
  • Sulfuric acid treated graphites particles are conventionally used to make exfoliated graphene oxide material [Hummers WS; Offeman RE. J. Am. Chem. Soc. 1985, 80(6), 1 339].
  • a method of recovering carbon black includes the step of providing a carbonaceous source material containing carbon black.
  • the carbonaceous source material is contacted with a sulfonation bath to produce a sulfonated material.
  • the sulfonated material is pyrolyzed at a temperature of from 1 1 00 to 1490 °C to produce a layered carbon black containing product comprising a glassy carbon matrix phase having carbon black dispersed therein.
  • the layered carbon black containing product has an interlayer spacing of from 4 to 5 angstroms (0.4 - 0.5 nm).
  • the sulfonation bath can be an oleum bath.
  • the sulfonation bath can include a sulfonation agent which can be chlorosulfonic acid in 1 ,2 dichloroethane solution.
  • the sulfonation bath can include between 0.1 - 65 wt.% SO3.
  • the sulfonation bath can include 2 - 30 wt. % SO3.
  • the sulfonation bath can have a temperature of between -20 °C to 200 °C.
  • the pyrolysis step can be conducted at any suitable temperature or range of temperatures from 1 100 °C to 1490°C.
  • the pyrolysis step can be conducted at a temperature that is greater than 1 200 °C.
  • the pyrolysis step can be conducted at a temperature that is greater than 1 300 °C.
  • the pyrolysis step can be conducted at a temperature from 1200-1400 °C.
  • the pyrolysis step can be conducted at a temperature from 1250-1350 °C.
  • the pyrolysis step is conducted at a temperature from 1 100-1400 °C.
  • the pyrolysis step can be from 1 minute to 12 hours.
  • the method can further include the steps of reducing the carbonaceous source material to a powder or shredded tire pieces prior to contacting the carbonaceous source material with the oleum bath.
  • the powder and/or crumb rubber pieces can have an average maximum dimension of less than 1 00 nm to 10 cm.
  • the carbonaceous source material can include carbon reinforced composites.
  • the carbon reinforcing agent can be least one selected from the group consisting of carbon black, carbon particles, nanoparticles, mesoparticles and fibers.
  • the carbonaceous source material can be a waste material.
  • the waste material can be rubber tires.
  • the average pore size of the carbon black product can be less than 8 nm.
  • the average pore size of the carbon black product can be between 2 and 1 20 nm.
  • the isolated carbon can be further surface activated and the density of average pore size of the carbon black product between 1 and 20 nm is increased.
  • the carbon black containing product can have a specific surface area of less than 2000 m 2 /g.
  • the carbon black containing product can have a specific surface area of less than 1000 m 2 /g.
  • the carbon black containing product can have a specific surface area of less than 1 00 m 2 /g.
  • the pyrolyzing step can occur after the contacting step.
  • the pyrolyzing step can occur before the contacting step.
  • a method of making a battery electrode comprising carbon black can include the step of providing a carbonaceous source material containing carbon black, contacting the carbonaceous source material with an oleum bath to produce a sulfonated material, and pyrolyzing the sulfonated material at a temperature of from 1 1 00 to 1490 °C to produce a layered carbon black product comprising a glassy carbon matrix phase having carbon black dispersed therein.
  • the layered carbon black containing product can have an interlayer spacing of from 4 to 5 angstroms (0.4 - 0.5 nm).
  • a battery electrode can then be formed from the carbon black containing product.
  • the battery electrode can be an anode.
  • the battery can be a lithium ion battery or a sodium ion battery.
  • the battery can have any suitable construction.
  • a battery can include an anode comprising layered carbon black containing product obtained by providing a carbonaceous source material containing carbon black, contacting the carbonaceous source material with an oleum bath to produce a sulfonated material, pyrolyzing the sulfonated material at a temperature of from 1 1 00 to 1490 °C to produce the layered carbon black product comprising a glassy carbon matrix phase having carbon black dispersed therein.
  • the layered carbon black containing product having an interlayer spacing of from 4 to 5 angstroms (0.4 - 0.5 nm).
  • a cathode is provided and an electrolyte is disposed between the anode and the cathode.
  • the layered carbon black containing product can have a surface atomic composition that is greater than 92% carbon.
  • Pulverized tire rubber powder in the size range of 80-120 ⁇ was obtained from Lehigh Technologies, Inc., Georgia.
  • the tire rubber powders were soaked in a concentrated sulfuric acid bath (kept at 1 10 Q C for overnight) to yield the sulfonated tire rubber that was then washed and filtered off.
  • the washed sulfonated tire rubber was then pyrolyzed at 1 1 00 Q C, 1400 °C, and 1 600 Q C, respectively, in a tube furnace under flowing nitrogen gas, and they are hereafter designated as TC1 100, TC1400, and TC1600.
  • Raman spectra were collected with a Horiba LabRam HR using an excitation wavelength of 473nm, a 600 gr/mm grating and an 800 mm monochromator.
  • a Zeiss Merlin VP scanning electron microscope (SEM) operated at 3kV was used to characterize the surface morphologies of the samples. Interlayer distances of the carbons were determined by a Hitachi HD- 2300A scanning transmission electron microscope (STEM) with a field emission source operated at 200 kV in bright-field imaging mode at a 2.1 A resolution. XPS data were collected with a Thermo-Fisher K-alpha XPS with a monochromatic Al- Kaipha, a 1486.6 eV source, 400 ⁇ spot, and an argon ion flood gun.
  • Electrochemical properties were characterized with half cells against a sodium-metal electrode.
  • the working electrode was prepared by spreading the mixed slurry consisting of the active material, conductive carbon C45 and PVDF binder in N-methyl-2-pyrrolidone (NMP) solvent at a weight ratio of 80:10:10. The resulting slurry was then cast onto a copper foil current collector and transferred to a vacuum oven for drying at 120 °C overnight. The typical loading amount of active material was 2 to 2.5 mg cm "2 .
  • the electrolyte was a solution of 1 M NaCI0 4 in ethylene carbonate (EC) and diethyl carbonate (DEC) (1 :1 in vol).
  • Coin cells consisting of the tire-derived carbon electrode, glass fiber, a sodium metal counter electrode and electrolyte were assembled in an Ar-filled glove box.
  • Galvanostatic charge/discharge was carried out on a Land CT2001 battery test system (Wuhan, China) over a voltage range of 0 - 3 V at current density of 20 mA g "1 at room temperature.
  • the sodiated electrodes were disassembled in an Ar-filled glovebox and placed in an air-sensitive sample holder for further characterizations.
  • the ex situ XRD analysis was performed on a Rigaku Miniflex600 diffractometer with Cu Ka radiation.
  • XRD collected on bulk materials indicate that the tire-derived carbons pyrolyzed at different temperatures are mainly composed of poorly crystalline carbonaceous material.
  • the broad peak near 2 ⁇ ⁇ 26.6° suggests lack of significant order in the bulk of the carbon materials and this peak is related to the (002) plane.
  • the R value for TC1 100, TC1400, and TC1600 are 1 .58, 2.27 and 2.67, respectively.
  • R is defined as the peak height divided by the background height at the position of the peak.
  • the value of R can be used to estimate the fraction of graphene sheets, which increases as the proportion of the graphene layers with parallel neighbors increases.
  • TC1 600 shows the largest graphene fraction by the comparing three R values.
  • Raman spectra obtained on tailored carbons are shown in Figure 12B.
  • the ID/IG ratio for TC1 1 00, TC1400, and TC16000 increases from 0.85 to 0.96 to 0.99. Such a trend has also been reported for hard carbon material obtained from other precursors.
  • the ID/IG ratio changes differently in a three-stage model of increasing disorder.
  • the G peak is due to the bond stretching of all pairs of sp2 atoms in both rings and chains.
  • the D peak is due to the breathing modes of sp2 atoms in the rings.
  • the ratio of ID/IG is proportional to the number of aromatic rings.
  • the increased relationship in the ID/IG ratio and G band position for the tire-derived carbons shows that more sp2 amorphous carbon turns into nanocrystalline graphite at higher temperatures. This tendency can also be concluded and confirmed by the R values.
  • the BET surface areas for TC1 100, TC1400, and TC1600 are determined to be 189, 21 0 and 148 m 2 g "1 , respectively.
  • the pore volume distribution shows a relatively wide pore size distribution with prominent microporosity with a pore width of less than 2 nm and a noticeable volume fraction of pore widths in the range of 6 - 8 nm.
  • the dominant microporosity could be attributed to the fact that the sulfuric acid pretreated tire powder produces SO2 and steam which yields activated tire-derived carbon.
  • the SEM images of different temperature treated tire-derived carbons exhibit similar surface porosity properties.
  • SEM images of TC1400 show a large number of macro- and meso-pores are visible on the sample surface.
  • STEM high resolution scanning transmission electron microscopy
  • the interlayer distances for crystalline areas were determined to be 4.7 A, 4.5 A, and 4.0 A for TC1 100, TC1400 and TC1600, respectively. These values are larger than the required distance (0.37 nm) for sodium intercalation and follow the general trend that the carbon interlayer distance decreases with increasing pyrolysis temperatures.
  • SAED selected area electron diffraction
  • X-ray photoemission spectroscopy (XPS) data on the tire-derived carbons are shown in Figure 13.
  • the C1 s spectrum in Figure 1 3A for the samples shows a sharp peck at 284.8 eV, which is due to the sp 2 configuration.
  • the small peak at around 291 eV could be related to the presence of aromatic rings in the materials and as shown in the inset that its relative intensity increases with the pyrolysis temperatures. This result also confirms the conclusion by Raman spectra that more aromatic rings are present in the higher temperature samples.
  • Figure 13B shows the S2p scans of the samples. The doublets at about
  • 164 eV are related to the thiol group and the peak at 169 eV is due to the sulfate group. It is shown that as the temperature increases, sulfate groups are removed from the samples.
  • the XPS elemental analysis for the samples is shown in Table 1 .
  • the impurities of Si and Fe could be due to the additives or impurities present in the tire powders. It is clear that the purity improves as the pyrolysis temperature increases since more functional groups are eliminated at higher temperatures.
  • FIG. 14 A-C show the cycling stability of the three samples tested under a current density of 20 mA g "1 .
  • TC1 100 provides an initial capacity of 520 mAh g "1 for discharge and 250 mAh g "1 during charge, which corresponds to only 48% coulombic efficiency for the first cycle in Figure 14A.
  • the large irreversible capacity loss could be associated with the high surface area of the carbon material and the reduction of carbon surface functional groups followed by electrolyte decomposition and formation of solid electrolyte interphase (SEI). Surface coating techniques could be used in the future to reduce the surface area and to improve the efficiency.
  • SEI solid electrolyte interphase
  • the cycling results for TC1400 and TC1600 in Figure 14B and Figure 14C show improvements in first cycle efficiency and capacity.
  • TC1400 exhibits 57% first cycle efficiency and a capacity of 185 mAh g "1 after 100 cycles whereas TC1600 shows further enhancement of the first cycle efficiency to 66% and a capacity of 203 mAh g "1 at 1 00th cycle.
  • the improved cycling performance may be related to the reduced number of surface functional groups and also reduced amount of defects in the carbon after the higher temperature treatment.
  • Figure 14D presents the electrochemical voltage profiles when sodium is intercalated and deintercalated from the various tire-derived carbons. It can be seen that the TC1 100 voltage profile mostly consists of the sloping region during cycling. However, both the TC1400 and TC1 600 charge and discharge curves can be divided into two regions, a sloping voltage region extending down to 0.2 V and a large portion of the plateau region. Similar voltage profiles of other high temperature treated carbon materials for sodium-ion batteries have also been reported previously. The observed charge capacity of the plateau region for TC1400 is 1 65 mAh g "1 , which is approximately 65% of the whole capacity.
  • the plateau capacity increases to 197 mAh g "1 , accounting for 71 % of the total capacity.
  • the disordered graphene layers are randomly distributed and can be modeled like a "house of cards".
  • the sloping region of the potential profile corresponds to the insertion of sodium between the turbostratically disordered graphene layers and the low-potential plateau region can be attributed to the insertion of the metal into the nanopores between randomly stacked layers through a process analogous to adsorption.
  • TC1 100 shows a capacity of 1 56 mAh g "1 after 500 cycles at a current density of 20 mA g "1 .
  • the invention provides for the use of solid-waste-tire-derived carbons as anodes for sodium-ion batteries.
  • the pyrolysis temperature is increased from 1 1 00 to 1600°C, the capacity of the plateau below 0.2 V increases dramatically and this could help increase the full cell energy density.
  • the 1600°C treated carbon shows a capacity of 203 mAh g "1 after 100 cycles.
  • These tire-derived carbons demonstrate a low-cost, easily scalable option with good electrochemical capacity and stability for sodium-ion battery anodes.
  • This invention can be embodied in other forms without departing from the spirit or essential attributes thereof. Reference should be made to the following claims to determine the scope of the invention.

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Abstract

La présente invention concerne un procédé de récupération de noir de carbone comprenant l'étape consistant à obtenir un matériau source carboné contenant du noir de carbone. Le matériau source carboné est mis en contact avec un bain de sulfonation pour produire un matériau sulfoné. Le matériau sulfoné est pyrolysé pour produire un produit contenant du noir de carbone constitué d'une phase matrice vitreuse carbonée dans laquelle du noir de carbone est dispersé. La pyrolyse peut être menée à une température de 1100 °C à 1490 °C. La présente invention concerne également un procédé de fabrication d'une électrode de batterie et une batterie lithium-ion ou sodium-ion.
PCT/US2017/016541 2016-02-29 2017-02-03 Composite de noir de carbone pyrolytique et procédé de production dudit composite WO2017172044A2 (fr)

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