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WO2017045573A1 - Poudres de carbone activé pour systèmes hybrides de supercondensateur-batterie - Google Patents

Poudres de carbone activé pour systèmes hybrides de supercondensateur-batterie Download PDF

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Publication number
WO2017045573A1
WO2017045573A1 PCT/CN2016/098708 CN2016098708W WO2017045573A1 WO 2017045573 A1 WO2017045573 A1 WO 2017045573A1 CN 2016098708 W CN2016098708 W CN 2016098708W WO 2017045573 A1 WO2017045573 A1 WO 2017045573A1
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Prior art keywords
positive electrode
activated carbon
ranging
nitrogen
powder
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Inventor
Bing Li
Fang DAI
Mei Cai
Cunman Zhang
Qiangfeng Xiao
Scott W. Jorgensen
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GM Global Technology Operations LLC
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GM Global Technology Operations LLC
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Priority to CN201680053263.6A priority Critical patent/CN108352253A/zh
Priority to DE112016004175.6T priority patent/DE112016004175T5/de
Publication of WO2017045573A1 publication Critical patent/WO2017045573A1/fr
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    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/30—Active carbon
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/30—Active carbon
    • C01B32/312—Preparation
    • C01B32/318—Preparation characterised by the starting materials
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/30—Active carbon
    • C01B32/312—Preparation
    • C01B32/318—Preparation characterised by the starting materials
    • C01B32/324—Preparation characterised by the starting materials from waste materials, e.g. tyres or spent sulfite pulp liquor
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/30—Active carbon
    • C01B32/312—Preparation
    • C01B32/336—Preparation characterised by gaseous activating agents
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/30—Active carbon
    • C01B32/312—Preparation
    • C01B32/342—Preparation characterised by non-gaseous activating agents
    • 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
    • H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
    • 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
    • H01G11/38—Carbon pastes or blends; Binders or additives therein
    • 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
    • H01G11/04—Hybrid capacitors
    • 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
    • Y02E60/13—Energy storage using capacitors

Definitions

  • Advanced energy storage systems are in demand to satisfy requirements of fast-growing electrical vehicle (EV) applications.
  • EV electrical vehicle
  • supercapacitors and lithium-ion batteries are currently recognized as two promising systems.
  • Supercapacitors are often used in power-based applications, as they deliver a high power density (as high as 10 kW/kg) with a low energy density (less than 10 Wh/kg) .
  • lithium-ion batteries are often used as energy-based systems, as they can deliver high energy densities (100-200 Wh/kg) .
  • Activated carbon powders for hybrid supercapacitor-battery systems may be formed from a corncob or an egg white.
  • a corncob is dried and ground to form a precursor powder.
  • the precursor powder is heat treated under an inert gas flow until a predetermined temperature is reached. While the predetermined temperature is maintained, the inert gas flow is replaced with an ammonia gas (NH 3 ) flow. With this method, a nitrogen-doped activated carbon powder is formed.
  • an egg white is diluted with water to form a protein solution.
  • An alcohol is added to the protein solution to precipitate proteins out of the protein solution.
  • the precipitated proteins are filtered and exposed to a heat treatment to form a carbonized egg white.
  • the carbonized egg white is mixed with an alkali hydroxide base to form a mixture.
  • the mixture is exposed to an activation temperature to form the activated carbon powder.
  • Fig. 1 is a schematic view of a method for forming a nitrogen-doped activated carbon
  • Fig. 2 is a schematic view of a hybrid supercapacitor-battery system
  • Fig. 3A is a scanning electron microscopy (SEM) image of nitrogen-doped activated carbon formed at 400°C;
  • Figs. 3B-3D are transmission electron microscopy (TEM) images of nitrogen-doped activated carbon formed at 0°C (NAC-0) , 400°C (NAC-400) , and 600°C (NAC-600) , respectively;
  • TEM transmission electron microscopy
  • Fig. 4A depicts the X-ray photoelectron spectroscopy (XPS) spectra for carbon, oxygen, and nitrogen of NAC-400, where the coordinates are intensity (arbitrary units, a. u. (Y axis) ) versus binding energy (B.E. ) (eV, X axis) ;
  • XPS X-ray photoelectron spectroscopy
  • Fig. 4B depicts the Raman spectra for all of the NACs formed in Example 1 (i.e., NAC-0, NAC-400, and NAC-600) , where the coordinates are intensity (arbitrary units, a.u. (Y axis) ) versus wavenumber (cm -1 , X axis) ;
  • Fig. 4C depicts nitrogen adsorption isotherms at 77K for all of the NACs formed in Example 1, where the coordinates are quantity absorbed (cm 3 g -1 , Y axis) versus relative pressure (P P 0 -1 , X axis) ;
  • Fig. 4D depicts the calculated pore-size distribution of all of the NACs formed in Example 1, where the coordinates are differential pore volume (cm 3 g -1 , Y axis) versus pore width (nm, X axis) ;
  • Figs. 5A and 5B are the X-ray photoelectron spectroscopy (XPS) spectra of NAC-0, where the coordinates are intensity (arbitrary units, a. u. (Y axis) ) versus binding energy (eV, X axis) ;
  • XPS X-ray photoelectron spectroscopy
  • Figs. 5C and 5D are the X-ray photoelectron spectroscopy (XPS) spectra of NAC-600, where the coordinates are intensity (arbitrary units, a.u. (Y axis) ) versus binding energy (eV, X axis) ;
  • XPS X-ray photoelectron spectroscopy
  • Fig. 6A is a graph depicting the cycling performance, specifically the specific capacity (mAh/g, left Y axis) and Coulombic efficiency (%, right Y axis) versus cycle number (#, X axis) , of half cells formed with each of the NACs of Example 1;
  • Fig. 6B is a graph depicting the cyclic voltammetry (CV) profiles (at a scan rate of 5 mV/s) for the half cells formed with each of the NACs of Example 1, where the coordinates are current (mA, Y axis) versus voltage (V, X axis) ;
  • Fig. 6C is a graph depicting the rate performance, specifically discharge capacity (mAh/g, left Y axis) versus cycle number (#, X axis) , for the half cells formed with each of the NACs of Example 1;
  • Fig. 6D is a graph depicting the voltage profiles (at different current densities) for the half cells formed with NAC-400, where the coordinates are potential vs. Li + /Li (V, Y axis) versus specific capacity (mAh/g, X axis) ;
  • Fig. 7 is the electrochemical impedance spectroscopy of the NACs of Example 1, where the coordinates are imaginary impedance-Im (Z) or-Z im (Ohm, Y axis) versus real impedance Re (Z) or Z re (Ohm, X axis) ;
  • Fig. 8A is a graph depicting the cyclic voltammetry (CV) profiles (at different scan rates) for a hybrid supercapacitor-battery full cell formed with NAC-400 and Si/C, where the coordinates are current (mA, Y axis) versus voltage (V, X axis) ;
  • Fig. 8B is a graph depicting the voltage profiles (at different current densities) for the hybrid supercapacitor-battery full cell formed with NAC-400 and Si/C, where the coordinates are voltage (V, Y axis) versus time (seconds, X-axis) ;
  • Fig. 8C is a graph depicting the long cycling performance, specifically specific capacity (mAh/g, left Y axis) and Coulombic efficiency (%, right Y axis) versus cycle number (#, X axis) , of the hybrid supercapacitor-battery full cell formed with NAC-400 and Si/C at 0.4 A/g (specific capacity is normalized to NAC-400) ;
  • Fig. 8D is a Ragone plot of the hybrid supercapacitor-battery full cell formed with NAC-400 and Si/C, where the coordinates are energy density (Wh/kg, Y axis) versus power density (W/kg, X axis) ;
  • Fig. 9 is a graph depicting the long cycling performance, specifically specific capacity (mAh/g, Y axis) versus cycle number (#, X axis) , of the hybrid supercapacitor-battery full cell formed with NAC-400 and Si/C using a narrow voltage window of 2.0 V to 4.0 V;
  • Figs. 10A-10D are SEM images of activated carbon formed from egg whites at 700°C(eAC-700) , 800°C (eAC-800) , 900°C (eAC-900) , and 1000°C (eAC-1000) , respectively;
  • Figs. 11A-11D are TEM images of the activated carbon formed from egg whites at 700°C (eAC-700) , 800°C (eAC-800) , 900°C (eAC-900) , and 1000°C (eAC-1000) , respectively;
  • Fig. 12A depicts the Raman spectra for all of the eACs formed in Example 2 (i.e., eAC-700, eAC-800, eAC-900, and eAC-1000) , where the coordinates are intensity (arbitrary units, a. u. (Y axis) ) versus wavenumber (cm -1 , X axis) ;
  • Fig. 12B depicts the X-ray photoelectron spectroscopy (XPS) spectra for all of the eACs formed in Example 2, where the coordinates are intensity (arbitrary units, a. u. (Y axis) ) versus binding energy (eV, X axis) ;
  • XPS X-ray photoelectron spectroscopy
  • Fig. 12C depicts nitrogen adsorption isotherms at 77K for all of the eACs formed in Example 2, where the coordinates are quantity absorbed (cm 3 g -1 , Y axis) versus relative pressure (P P 0 -1 , X axis) ;
  • Fig. 12D depicts the calculated pore-size distribution for all of the eACs formed in Example 2, where the coordinates are differential pore volume (cm 3 g -1 , Y axis) versus pore width (nm, X axis) ;
  • Figs. 13A, 13B, and 13C are graphs respectively depicting: (A) the cyclic voltammetry (CV) profiles (at a scan rate of 5 mV/s) for the half cells formed with each of the eACs of Example 2, where the coordinates are current (mA, Y axis) versus voltage (V, X axis) , (B) the impedance spectra of the half cells formed with each of the eACs of Example 2, where the coordinates are imaginary impedance-Im (Z) or-Z im (Ohm, Y axis) versus real impedance Re (Z) or Z re (Ohm, X axis) , and (C) the cycling performance, specifically specific capacity (mAh/g, Y axis) versus cycle number (#, X axis) , of half cells formed with each of the eACs of Example 2;
  • CV cyclic voltammetry
  • Figs. 14A-14D are graphs respectively depicting the rate performance of the eACs of Example 2 at current densities ranging from 0.4 A/g to 12.8 A/g, where the coordinates are potential vs. Li + /Li (V, Y axis) versus specific capacity (mAh/g, X axis) ;
  • Figs. 15A and 15B are graphs respectively depicting: (A) a Ragone plot of the hybrid supercapacitor-battery full cell formed with eAC-900 and Si/C in comparison with energy densities at maximum power densities of other work, where the coordinates are energy density (Wh/kg, Y axis) versus power density (W/kg, X axis) , and (B) the cycling performance of the hybrid supercapacitor-battery full cells formed with the eACs of Example 2 and Si/C, where the coordinates are capacity normalized to eAC (mAh/g, Y axis) versus cycle number (#, X axis) ;
  • Figs. 16A-16D are graphs respectively depicting the voltage profiles from galvanostatic charge/discharge at different current densities for hybrid supercapacitor-battery full cells formed with the eACs of Example 2 and Si/C, where the coordinates are potential vs. Li + /Li (V, Y axis) versus time (seconds, X axis) ; and
  • Fig. 17 is a graph depicting the cycling performance of the hybrid supercapacitor-battery full cells formed with eAC-900 of Example 2 and Si/C with a voltage window from 2.0 V to 4.0 V, where the coordinates are capacity (mAh/g, Y axis) versus cycle number (#, X axis) .
  • the systems disclosed herein are hybrid supercapacitor-battery systems (e.g., lithium-ion capacitors) , which integrate the high power density of supercapacitors with the high energy density of lithium-ion batteries.
  • activated carbon based materials may be used as supercapacitor type positive electrode materials
  • silicon-carbon composites may be used as lithium-ion battery type negative electrode materials.
  • the hybrid supercapacitor-battery system is considered asymmetrical, in part because the active materials of the positive electrode and negative electrode are different types, and because the supercapacitor type positive electrode material operates via sorption of ions, and the lithium-ion battery type negative electrode material operates via ion insertion/intercalation.
  • the activated carbon based materials disclosed herein are formed from low cost, agricultural carbon precursors and are formedby non-toxic preparation processes.
  • the agricultural carbon precursors are corncobs or egg whites.
  • the non-toxic preparation processes disclosed herein enable the resulting activated carbon based materials to have a narrow pore size distribution, which contributes to the materials delivering a relatively high specific capacity.
  • the example of the method utilizing corncob precursors is a one-step process that forms nitrogen-doped activated carbon.
  • Nitrogen-doping may increase the specific capacitance due, in part, to the faradaic reaction of the nitrogen-containing functional groups and the improved wettability of the activated carbon pore walls. Nitrogen doping may also increase the conductivity of the activated carbon materials.
  • the one-step process that forms nitrogen-doped activated carbon begins with a dried and ground corncob precursor.
  • the corncob (s) may be dried at a temperature ranging from about 60°C to about 200°C for a time ranging from about 1 hour to about 24 hours. In an example, the corncob (s) may be dried at about 120°C for about 12 hours.
  • the dried corncob (s) may be ground using any suitable grinder, and grinding may be performed until a precursorpowder is obtained.
  • the precursorpowder may be mixed with a base (e.g., an alkali hydroxide base, such as potassium hydroxide (KOH) , sodium hydroxide (NaOH) , or lithium hydroxide (LiOH) ) to form a mixture.
  • a base e.g., an alkali hydroxide base, such as potassium hydroxide (KOH) , sodium hydroxide (NaOH) , or lithium hydroxide (LiOH)
  • the mass ratio of precursorpowder to base is 3: 1.
  • the one-step process involves heat treating the precursor powder (which may be part of a mixture with the base) under an inert gas flow (e.g., argon gas (Ar) , nitrogen gas N 2 , etc. ) until a predetermined temperature is reached, and while maintaining the predetermined temperature, replacing the inert gas flow with an ammonia gas (NH 3 ) flow.
  • an inert gas flow e.g., argon gas (Ar
  • This process forms the nitrogen-doped activated carbon powder from the precursor powder.
  • the heat treatment may take place in any suitable oven, furnace, etc., such as a tubular furnace.
  • the predetermined temperature ranges from about 400°C to about 1500°C. In an example, the predetermined temperature ranges from about 400°Cto about 800°C.
  • the NH 3 flow may be continued for a time ranging from about 30 minutes to about 10 hours.
  • Fig. 1 is a schematic illustration of the reaction that takes place between the corncob particles 18 and the ammonia gas (NH 3 ) 20 during the heat treatment in a high temperature (i.e., 400°C to 800°C) tubular furnace 22 to form nitrogen-doped microporous carbon 26.
  • a high temperature i.e., 400°C to 800°C
  • the nitrogen-doped activated carbon powder formed from corncob precursors according to the method disclosed herein has a micro-to meso-pore size distribution.
  • the nitrogen-doped activated carbon powder formed from corncob precursors according to the method disclosed herein also has a nitrogen content ranging from about 1 wt%to about 10 wt%. In an example, the nitrogen content ranges from about 2 wt%to about 4 wt%.
  • the example of the method utilizing egg white precursors is a biomass transfer process that forms activated carbon powder.
  • the egg whites may be diluted with water at a ratio of egg whites: water ranging from about 1: 1 to about 1: 10.
  • the egg whites are diluted with water at a ratio of 1: 4 to form a transparent protein solution.
  • An alcohol such as methanol, ethanol, isopropanol, etc. is poured into the protein solution to precipitate the proteins.
  • the precipitated egg white proteins are then filtered out and carbonized in a tubular furnace under a flow of inert gas (e.g., Ar) .
  • inert gas e.g., Ar
  • Carbonization may take place by ramping the temperature of the tubular furnace up to a temperature ranging from about 400°C to about 700°C over a time period ranging from about 1 hour to about 5 hours at a suitable heating rate.
  • the temperature of the tubular furnace is ramped up to 650°C over two hours at a heating rate of 5°C min -1 .
  • a carbonized egg white is formed.
  • the carbonized egg white is mixed with an alkali hydroxide base, such as potassium hydroxide (KOH) , sodium hydroxide (NaOH) , or lithium hydroxide (LiOH) , to form a mixture, and the mixture is exposed to an activation temperature to form the activated carbon powder.
  • the mass ratio of the alkali hydroxide base to the carbonized egg white in the mixture ranges from about 1: 1 to about 6: 1. In an example, the mass ratio of KOH to carbonized egg white is 3: 1.
  • the activation temperature may range from about 700°C to about 1000°C. Exposure to the activation temperature may take place for about 3 hours under an inert gas flow (e.g., Ar) .
  • the activated carbon powder may be washed with an acid (e.g., with HCl, HNO 3 , HBr, H 2 SO 4 , or H 2 SO 3 overnight) to remove the impurities, and then may be rinsed (e.g., 3, 4, or more times) with deionized (DI) water before use. Three rinses may be suitable depending upon the relative volume of wash to powder and the length of the wash.
  • an acid e.g., with HCl, HNO 3 , HBr, H 2 SO 4 , or H 2 SO 3 overnight
  • DI deionized
  • the activated carbon powder formed from egg white precursors according to the method disclosed herein has a micro-to meso-pore size distribution.
  • Either the nitrogen-doped activated carbon powder or the activated carbon powder formed via the methods disclosed herein may be used to form a positive electrode.
  • the nitrogen-doped activated carbon powder or the activated carbon powder is mixed with a polymer binder and a conductive filler.
  • the polymer binder structurally holds the nitrogen-doped activated carbon powder or the activated carbon powder and the conductive filler together.
  • suitable polymer binders include polyvinylidene fluoride (PVdF) , polyethylene oxide (PEO) , an ethylene propylene diene monomer (EPDM) rubber, carboxymethyl cellulose (CMC) , styrene-butadiene rubber (SBR) , styrene-butadiene rubber carboxymethyl cellulose (SBR-CMC) , polyacrylic acid (PAA) , cross-linked polyacrylic acid-polyethylenimine, polyimide, or any other suitable binder material.
  • the still other suitable binders include polyvinyl alcohol (PVA) , sodium alginate, or other water-soluble binders.
  • the conductive filler may be a conductive carbon material.
  • the conductive carbon may be a high surface area carbon, such as acetylene black or another carbon material (e.g., Super P) .
  • Other examples of suitable conductive fillers include porous carbon (e.g., AX-21) graphene, graphite, carbon nanotubes, and/or carbon nanofibers.
  • the conductive filler ensures electron conduction between the positive-side current collector and the nitrogen-doped activated carbon powder or the activated carbon powder in the positive electrode.
  • the nitrogen-doped activated carbon powder or the activated carbon powder may be present in the mixture in an amount ranging from greater than 0 wt%up to 99 wt% (based on the total solid wt%of the dispersion/mixture) .
  • Each of the conductive filler and the binder may be present in an amount ranging from 0 wt%to about 99 wt%.
  • the mixture may include from about 50 wt%to about 95 wt% (based on total solid wt%of the dispersion/mixture) of the nitrogen-doped activated carbon powder or the activated carbon powder, from about 5 wt%to about 20 wt% (based on total solid wt%of the dispersion/mixture) of the conductive filler, and from about 5 wt%to about 20 wt% (based on total solid wt%of the dispersion/mixture) of the binder. All of these components may be manually mixed by dry-grinding.
  • the ground components are combined with water or organic solvent (depending on the binder used) to form a dispersion/slurry.
  • the solvent is a polar aprotic solvent.
  • suitable polar aprotic solvents include dimethylacetamide (DMAc) , N-methyl-2-pyrrolidone (NMP) , dimethylformamide (DMF) , dimethylsulfoxide (DMSO) , or another Lewis base, or combinations thereof.
  • DMAc dimethylacetamide
  • NMP N-methyl-2-pyrrolidone
  • DMF dimethylformamide
  • DMSO dimethylsulfoxide
  • the solvent may be water.
  • the dispersion may be mixed by milling. Milling aids in transforming the dispersion into a coatable slurry. Low-shear milling or high-shear milling may be used to mix the dispersion.
  • the dispersion milling time ranges from about 10 minutes to about 20 hours depending on the milling shear rate. In an example, a rotator mixer is used for about 20 minutes at about 2000 rpm to mill the dispersion.
  • the support is a positive-side current collector.
  • the positive-side current collector may be formed from aluminum, or any other appropriate electrically conductive material known to skilled artisans.
  • the support that is selected should be capable of collecting and moving free electrons to and from an external circuit connected thereto.
  • the slurry may be deposited using any suitable technique.
  • the slurry may be cast on the surface of the support, or may be spread on the surface of the support, or may be coated on the surface of the support using a slot die coater.
  • the deposited slurry may be exposed to a drying process in order to remove any remaining solvent and/or water. Drying may be accomplished using any suitable technique. For example, the drying is conducted at ambient conditions (i.e., at room temperature, about 18°C to 22°C, and 1 atmosphere) . Drying may be performed at an elevated temperature ranging from about 60°C to about 150°C. In some examples, vacuum may also be used to accelerate the drying process. As one example of the drying process, the deposited slurry may be exposed to vacuum at about 120°C for about 12 to 24 hours.
  • the drying process results in the formation of the positive electrode.
  • the thickness of the dried slurry i.e., positive electrode
  • the thickness of the dried slurry ranges from about 5 ⁇ m to about 200 ⁇ m.
  • the thickness of the dried slurry ranges from about 10 ⁇ m to about 100 ⁇ m.
  • the water and/or organic solvent (s) is/are removed, and thus the resulting positive electrode includes from about 50 wt%to about 95 wt% (based on total wt%of the positive electrode) of the nitrogen-doped activated carbon powder or the activated carbon powder, from about 5 wt%up to 20 wt% (based on total wt%of the positive electrode) of the conductive filler, and from about 5 wt%up to 20 wt% (based on total wt%of the positive electrode) of the binder.
  • the hybrid supercapacitor-battery system 10 shown in Fig. 2 includes the positive electrode 12 formed with the nitrogen-doped activated carbon powder (formed from corncobs) or the activated carbon powder (formed from egg whites) disclosed herein.
  • the hybrid supercapacitor-battery system 10 also includes a negative electrode 14 formed of a silicon-carbon composite (including from about 5 wt%to about 30 wt%carbon) , a silicon film, or a lithium foil.
  • the silicon-carbon composite (including about 10 wt%carbon) or the silicon film may be combined with a conductive filler and/or a polymer binder, and may be formed in a similar manner to the process described for the positive electrode 12.
  • the negative electrode 14 may include from about 50 wt%to about 95 wt% (based on total wt%of the negative electrode) of the silicon-carbon composite or the silicon film, from about 5 wt%up to 20 wt% (based on total wt%of the negative electrode) of the conductive filler, and from about 5 wt%up to 20 wt% (based on total wt%of the negative electrode) of the binder.
  • These negative electrodes 14 may be formed on a copper, or other suitable, current collector. These types of negative electrodes may also be pre-lithiated using any suitable technique.
  • any suitable separator 16 may be positioned between the positive and negative electrodes 12, 14.
  • the separator 16 is a polypropylene (PP) membrane having a thickness of about 25 ⁇ m.
  • the separator 16 may be other polyolefin membranes, such as polyethylene (PE) , a blend of PE and PP, or multi-layered structure of porous films of PE and/or PP.
  • the polyolefin may be a homopolymer (derived from a single monomer constituent) or a heteropolymer (derived from more than one monomer constituent) , and may be either linear or branched.
  • the polyolefin may assume any copolymer chain arrangement, including those of a block copolymer or a random copolymer. The same holds true if the polyolefin is a heteropolymer derived from more than two monomer constituents.
  • the separator 16 may be formed from another polymer chosen from polyethylene terephthalate (PET) , polyvinylidene fluoride (PVdF) , polyamides (Nylons) , polyurethanes, polycarbonates, polyesters, polyetheretherketones (PEEK) , polyethersulfones (PES) , polyimides (PI) , polyamide-imides, polyethers, polyoxymethylene (e.g., acetal) , polybutylene terephthalate, polyethylenenaphthenate, polybutene, acrylonitrile-butadiene styrene copolymers (ABS) , polystyrene copolymers, polymethylmethacrylate (PMMA) , polyvinyl chloride (PVC) , polysiloxane polymers (such as polydimethylsiloxane (PDMS) ) , polybenzimidazole (PBI)
  • PET poly
  • the separator 16 may contain a single layer or a multi-layer laminate fabricated from either a dry or wet process.
  • a single layer of the polyolefin and/or other listed polymer may constitute the entirety of the porous separator 16.
  • multiple discrete layers of similar or dissimilar polyolefins and/or polymers may be assembled into the porous separator 16.
  • a discrete layer of one or more of the polymers may be coated on a discrete layer of the polyolefin to form the porous separator 16.
  • porous separator 16 may further be included in the porous separator 16 as a fibrous layer to help provide the porous separator 16 with appropriate structural and porosity characteristics.
  • suitable porous separators 16 include those that have a ceramic layer attached thereto, and those that have ceramic filler in the polymer matrix (i.e., an organic-inorganic composite matrix) .
  • the electrolyte solution may be a non-aqueous liquid electrolyte solution that includes a lithium salt dissolved in an organic solvent or a mixture of organic solvents.
  • lithium salts may be dissolved in a variety of organic solvents, such as cyclic carbonates (ethylene carbonate (EC) , propylene carbonate (PC) , butylene carbonate, fluoroethylene carbonate (FEC) ) , linear carbonates (dimethyl carbonate (DMC) , diethyl carbonate (DEC) , ethylmethyl carbonate (EMC) ) , aliphatic carboxylic esters (methyl formate, methyl acetate, methyl propionate) , ⁇ -lactones ( ⁇ -butyrolactone, ⁇ -valerolactone) , chain structure ethers (1, 2-dimethoxyethane, 1-2-diethoxyethane, ethoxymethoxyethane, tetraglyme) , cyclic ethers (tetrahydrofuran, 2-methyltetrahydrofuran, 1, 3-dioxolane) , and mixtures thereof.
  • organic solvents such as
  • the hybrid supercapacitor-battery system 10 has an initial specific capacity ranging from about 120 mAh/g to about 130 mAh/g. In another example, the hybrid supercapacitor-battery system 10 has a capacity retention of at least 75%after 5000 cycles. In still another example, the hybrid supercapacitor-battery system 10 has an energy density ranging from about 140 Wh/kg to about 260 Wh/kg. In still another example, the hybrid supercapacitor-battery system 10 has a power density ranging from about 860 W/kg to about 30130 W/kg.
  • Scanning electron microscopy SEM, FEI SIRION 200/INCA, OXFORD
  • TEM transmission electron microscopy
  • Elemental analysis Elementar, vario EL III
  • XPS X-ray photoelectron spectroscopy
  • UlVAC-PHI PHI UlVAC-PHI PHI 5000 VersaProbe
  • Nitrogen sorption isotherms and textural properties of all samples were determined at -196°C using nitrogen in a conventional volumetric technique by a Micromeritics ASAP 2020 sorptometer over a wide relative pressure range from about 10 -6 to 0.995.
  • the surface area was calculated using the Brunauer–Emmett–Teller (BET) equation based on adsorption data in the partial pressure (P/P 0 ) ranging from 0.02 to 0.25 and the total pore volume was determined from the amount of nitrogen adsorbed at a relative pressure of 0.98.
  • Pore size distributions were calculated by using the Density Functional Theory (DFT) Plus Software (provided by Micromeritics Instrument Corporation) , which is based on calculated adsorption isotherms for pores of different sizes. All of the samples were degassed at 300°C for 10 hours (600 minutes) prior to the measurements.
  • DFT Density Functional Theory
  • NAC nitrogen-doped activated carbons
  • Example 2 eAC electrodes and Si/C electrodes were used as working electrodes and Li metal as the reference electrode.
  • the NAC and eAC electrodes were prepared by mixing 80 wt. %active material (NAC or eAC) , 10 wt. %Super-P carbon black and 10 wt. %Na-Alginate binder in de-ionized water to form a homogeneous slurry, which was then coated on aluminum foil.
  • the Si/C electrode was prepared by mixing 70 wt. %active material (Si/C) , 15 wt. %Super-P carbon black and 15 wt. %Na-Alginate binder to form a homogeneous slurry, which was then coated on copper foil.
  • the mass loadings of the active materials in the cathodes and anodes were about 4 mg/cm2 and 2 mg/cm2, respectively.
  • 1.2 M LiPF 6 dissolved in a mixture of ethylene carbonate, diethyl carbonate and dimethyl carbonate (EC: DEC: DMC 1: 1: 1 by vol. ) and 10 wt%fluoroethylene carbonate (FEC) electrolyte was employed as the electrolyte.
  • Hybrid supercapacitor-battery full cells were also assembled in coin cells. These cells included pre-cycled Si/C anodes and either NAC cathode (Example 1) or eAC cathode (example 2) in the same electrolyte (as the half cells) .
  • the optimized mass ratio of cathode and anode was 2: 1. All the electrochemical tests were carried out at room temperature.
  • the voltage range of the Si/C electrode was 0.01 V-1.5 V.
  • the NAC and eAC electrodes and the hybrid supercapacitor-battery full cells were measured at the same voltage range of2.0 V-4.5 V.
  • the energy density and power density were calculated based on the total mass of active materials on both the anode and cathode.
  • Cyclic voltammetry (CV, 2 V to 4.5 V, scan rate ranging from 5 to 20 mV s -1 ) and electrochemical impedance spectroscopy (EIS, frequency ranging from 0.1 Hz to 100,000 Hz with potential amplitude of 10 mV) were performed on a VMP3 (bio-logic) electrochemical workstation.
  • E (Wh kg -1 ) energy density
  • I the constant current density (A g -1 )
  • V the voltage
  • t 1 , t 2 the start time and end time in the discharge process, respectively.
  • Corncobs were utilized as the precursor for nitrogen-doped activated carbon (NAC) preparation.
  • the corncobs were pre-dried at 120°C for 12 hours.
  • the corncobs were ground and sieved into powders with typical size of more than 880 ⁇ m.
  • the powders were mixed with KOH in a 3: 1 mass ratio.
  • the mixture was then transferred to ceramic boats and heated to desired temperature (0°C, 400°C, and 600°C) under N 2 flow of 1.5 L/min in a horizontal quartz tube furnace.
  • the N 2 was then switched to NH 3 gas with a flowrate of 1.5 L/min.
  • the powder mixture was heated for a desired time.
  • the NH 3 was switched back to N 2 while activation was completed and the temperature was reduced to room temperature.
  • the three as-prepared products were denoted as NAC-x (NH3 Activated Carbon) , where x is activation temperature (NAC-0, NAC-400, NAC-600) , and were used for
  • Nanosized Si powder was purchase from MTI. Carbon coating was accomplished by thermal decomposition of acetylene at 700°C.
  • the bulkparticle of NAC-400 was micron-sized ranging from 5 ⁇ m to 30 ⁇ m, as shown in Fig. 3A. There were no observable macro-sized pores or large meso-sized pores (i.e., meso pores having a size greater than (>) 30 ⁇ m, e.g., from 30 ⁇ m to 50 ⁇ m) based on the TEM images of all of the NACs shown in Figs. 3B-3D.
  • the nitrogen content of all of the samples was determined by elemental analysis. The results indicate that as the heat treatment temperature increases, the nitrogen content increases from 2.97 wt%for NAC-400 to 3.98 wt%for NAC-600. The oxygen content was also determined. NAC-400 had an oxygen content of 9.8 wt%, while NAC-600 had an oxygen content of 9.05 wt%.
  • NAC-400 X-rayphotoelectron spectroscopy
  • Fig. 4A Typical C1s, O1s and N1s of the synthesized carbon (NAC-400) are shown in Fig. 4A.
  • NAC-0 and NAC-600 showed similar C and O signals in XPS spectra (see Figs. 5A through 5D) .
  • the C1s peak is dominated by C-C bond (diamond and graphite type) at 248.8 eV.
  • Fig. 4B illustrates the Raman spectra for all of the NACs.
  • the G band ( ⁇ 1600 cm -1 ) is a characteristic feature of the graphitic layers and corresponds to the tangential vibration of the carbon atoms
  • D band ( ⁇ 1350 cm -1 ) corresponds to disordered carbon or defective graphitic structures.
  • the intensity ratio of I G and I D depends on the graphitization degree.
  • the Raman spectra showed intensive G bands for all of the samples, suggesting partial graphication of all activated carbon materials. With higher heat treatment temperature, much more graphication is obtained for NAC materials, as shown in Table 1.
  • the pore structure of the NACs was analyzed by N 2 -sorption at 77K.
  • the isotherm plots in Fig. 4C clearly show type I isotherm curves with well-defined plateaus, suggesting a microporous nature of the NACs.
  • the pore size distributions were calculated by Density Functional Theory (DFT) method and are shown in Fig. 4D. All samples had pore distribution peaks between0.5 nm and 5 nm, which suggests the formation of both micropores and small mesopores. As the heat treatment temperature increases, the pore size distribution peaks at the mesopore range become broader, suggesting formation of slightly larger size mesopores.
  • DFT Density Functional Theory
  • All NACs showed similar high BET specific surface area (S BET in Table 1) of2759, 2859 and2787 m 2 g -1 for NAC-0, NAC-400 and NAC-600, respectively.
  • the electrochemical performance of the NACs was evaluated using a half cell in a coin format cell (as described above) .
  • Fig. 6A shows the cycling performance of all NAC materials at current density of0.4 A/g.
  • Both NAC-0 and NAC-400 exhibited high initial specific capacity of 129 mAh/g (185 F/g) and 127 mAh/g (182 F/g) , respectively.
  • the NAC-600 had a lower initial capacity of 110 mAh/g.
  • all NAC materials showed good cycling stability and Coulombic efficiency (CE) .
  • the coin cell formed with NAC-400 showed the best capacity retention of about 86% (110 mAh/g) after 500 cycles among all samples.
  • the cycling CE was above 99.2%after initial cycles.
  • cyclic voltammetry (CV) profiles of the coin cells with the various NACs maintain quasi-rectangular shape at 5 mV/s scan rate, indicating the capacitive behavior of all samples.
  • Fig. 6C shows the performance of the coin cells formed with the various NAC materials under various current densities. The difference in specific capacities of all samples becomes more and more distinct with increased current density. At low current densities of0.4 A/g, all three NACs showed similar specific capacity above 110 mAh/g. However, at elevated current density of0.8 A/g and 1.6 A/g, the specific capacity of NAC-600 dropped significantly lower than the other two materials.
  • the NAC-400 provided a capacity of73.7 mAh/g, which was 15%and 33%higher than those of NAC-0 (63.8 mAh/g) and NAC-600 (55.3 mAh/g) .
  • the electrochemical performance of the NAC materials was considered depending on the N-doping of the materials. Both the specific capacity and cycling stability were improved by increasing the N amount from 0 wt%of NAC-0 to 2.97 wt%of NAC-400. However, when the N-doping further increased to 3.98 wt%for NAC-600, the electrochemical performance-including reversible capacity, capacity retention, and rate performance-become worse compared with those results for NAC-400.
  • the much increased oxidized pyridinic N found in NAC-600 is considered as one key factors resulting in capacity drop, due to the positive charge on N which will affect the ion adsorption.
  • a slightly reduced BET surface area of NAC-600 may also affect the specific capacity drop.
  • the N-doping of NACs also helps improve the conductivity, as supported by electrochemical impedance spectroscopy (EIS) (Fig. 7) .
  • EIS electrochemical impedance spectroscopy
  • the diameter of the kinetic loop corresponds to charge transfer resistance of the NAC-400, which has a strong impact on the specific capacity, was much smaller than that of the NAC-0.
  • a hybrid supercapacitor-battery full cell was assembled using NAC-400 as the cathode/positive electrode and Si/C as the anode/negative electrode, as described above.
  • the CV profile of the hybrid supercapacitor-battery full cell showed a gradual deviation from the ideal rectangular shape with increasing scan rate, which is due to the overlapping effects of two different energy-storage mechanisms (Fig. 8A) .
  • This observation is consistent with the voltage profile of the hybrid supercapacitor-battery full cell using a galvanostatic charge/discharge method, which showed little deviation from the linear slop (Fig. 8B) .
  • the hybrid supercapacitor-battery full cell showed good cycling stability of77%capacity retention in 5000 cycles at a high current density of1.6 A/g (Fig. 8C) .
  • the Coulombic efficiency of the full cell is relative high, with an average of99.8%.
  • the Ragone plot power density vs.
  • the energy density, material level) of the hybrid supercapacitor-battery full cell is shown in Fig. 8D.
  • the energy density and power density were calculated based on the total mass of active materials on both the cathode and the anode.
  • the hybrid supercapacitor-battery full cell showed a high energy density of230 Wh/kg at 1747 W/kg, which remained at 141 Wh/kg even when the power density improved to 30127 W/kg. This performance is among the best reported hybrid type of supercapacitors.
  • Example 1 the N-doped activated carbons were synthesized from corncobs via a one-step method.
  • the obtained NACs showed excellent electrochemical performance with specific capacity up to 129 mAh/g and capacity retention of86%in 5000 cycles.
  • the N-doping of the NACs was found to help improve the performance.
  • the hybrid-type supercapacitor was further assembled and evaluated utilizing NACs and Si/C nanocomposite. With the optimized N/P ratio, the hybrid system showed high energy densities of230-141 Wh/kg at power densities from 1747 to 30127 W/kg, which are among the highest of reported hybrid-type systems. Good long cycling stability was also obtained with a capacity retention of77%after 5000 cycles for the hybrid-type supercapacitor.
  • Egg white (50 mL) was diluted with 200 mL water to form a transparent protein solution. Isopropanol (250 mL) was poured into the protein solution to precipitate the proteins. The precipitated egg white was then filtered out and carbonized in a tubular furnace (650°C for2 h, heating rate: 5°C min -1 ) under Ar. The carbonized egg white, mixed with KOH (KOH and carbonized egg white mass ratio: 3: 1) , was further activated at 700-1000°C for3 hours under Ar and named eAC-n, where n indicates the activated temperature (eAC-700, eAC-800, eAC-900, eAC-1000) . The obtained carbon powder was washed with HCl (6 M) overnight to remove the impurities and rinsed4 times with DI water before use.
  • Nanosized Si power purchased from Aldrich was used. Carbon coated porous Si was obtained by thermal decomposition of acetylene gas at 700°C in a quartz furnace. The C content was around 10 wt%of the Si/C nanocomposite.
  • Figs. 10A-10D and 11A-11D respectively show SEM and TEM images of eAC-700, eAC-800, eAC-900, and eAC-1000.
  • SEM images of Figs. 10A-10D the eACs were all micro-sized chunks with irregular edges.
  • the TEM images of Figs. 11A-11D there was not obvious large mesopores or macropores in any of the eAC materials.
  • the G band ( ⁇ 1600 cm -1 ) is a characteristic feature of the graphitic layers and corresponds to the tangential vibration of the carbon atoms
  • D band ( ⁇ 1350 cm -1 ) corresponds to disordered carbon or defective graphitic structures.
  • the intensity ratio of I G and I D depends on the graphitization degree. As shown in Fig. 12A and Table 3, with elevated process temperature, the I G /I D ratio increased from 0.39 for eAC-700 to 0.53 for eAC-900. When the process temperature reached 1000°C, the I G /I D increased sharply to 3.39, suggesting it is mostly graphitized.
  • Fig. 12B shows the O1s region from X-ray photoelectron spectroscopy (XPS) of all eAC samples.
  • the existence of the carboxylic groups can further improve the wettability of the carbon surface and reduce the charge transfer resistance, which are beneficial to the improvement of the electrochemical performance of eACs.
  • the N 2 -sorption isotherms and pore size distributions of all samples are schematically shown in Figs. 12C and 12D.
  • the isotherm of samples eAC-700, eAC-800, eAC-900 and eAC-1000 belongs to typical type I according to the IUPAC classification, which suggests their microporous structure. More detailed information about the microstructure characteristic is shown in Table 2.
  • Table 2 More detailed information about the microstructure characteristic is shown in Table 2.
  • eAC-1000 showed the lowest BET specific surface area of2268 m 2 /g
  • the sample eAC-900 showed the highest BET surface area of3250 m 2 /g.
  • eAC samples showed pore distribution in the micropore range (0.5 nm–2 nm) , as shown in DFT pore analysis in Fig. 12D. As the process temperature increased, small-sized mesopores appeared in the structure in a range of2 nm–10 nm, while the pore size distribution peaks also shifted toward larger pore size area.
  • the pore structure of eAC is considered to be suitable for Li-ion capacitor as the micropores between 0.8 and 1.4 nm are fully accessible to PF 6 - anions of electrolyte.
  • CV cyclic voltammetry
  • galvanostatic charge/discharge process The electrochemical performance of the eACs was evaluated by half cell configuration using both cyclic voltammetry (CV) and galvanostatic charge/discharge process.
  • CV diagrams in Fig. 13A show quasi-rectangular shapes at scan rate of5 mV/s, which indicated the capacitive behavior.
  • Figs. 14A-14D show the rate performance of eACs at the current densities of0.4-12.8 A/g. It can be seen that the specific capacity of eAC-900 changed from 128 to 39 mAh/g at 0.4-12.8 A/g (see Fig. 14C) .
  • the linear galvanostatic charge/discharge profiles of all eACs suggests their capacitive behavior with the adsorption/desorption of ions on the electrode surface.
  • the eAC-900 delivered the best initial discharge capacity of128 mAh/g at 0.4 A/g among all eACs (comparing Fig. 14C with Figs. 14A, 14B, and 14D) , which is also higher than previously published results for various activated carbons in the same voltage range.
  • the excellent rate performance of eAC-900 is possibly due to the existence of the carboxylic groups which can further improve the wettability of the carbon surface and reduce the charge transfer resistance, as proven by electrochemical impedance spectroscopy (EIS) in Fig. 13B.
  • EIS electrochemical impedance spectroscopy
  • the diameter of the kinetic loop corresponds to charge transfer resistance of the eAC-900, which has a strong impact on the discharge performance, and was much smaller than that of other samples.
  • Fig. 13C it can be seen that the eAC-900 showed the best cycling stability in all the samples.
  • the capacity ofeAC-900 obtained 110 mAh/g, with ⁇ 92%capacity retention after 1000 cycles at 0.4 A/g, while eAC-700 only delivered 90 mAh/g after 1000 cycles, retaining only 75%of its initial capacity.
  • eAC-1000 provided excellent capacity retention of95%in 1000 cycles, the reversible capacity is relatively low comparing with other eAC samples.
  • Figs. 16A-16D show the voltage profiles from galvanostatic charge/discharge at different current densities. The voltage curves show little deviation from the linear slope of an ideal supercapacitor, especially at low current densities, indicating that the hybrid supercapacitor-battery full cells exhibited charge/discharge performance of a combination with a supercapacitor and a battery.
  • the Ragone plot (power density vs. energy density) of the hybrid supercapacitor-battery full cells is presented in Fig. 15A and Table 4.
  • the energy density and power density were calculated based on the total mass of active materials on both the cathode and the anode. It can be seen that the hybrid supercapacitor-battery full cell exhibits a high material level energy density of258 Wh/kg at 867 W/kg, while remains at 147 Wh/kg with an elevated power density of29893 W/kg. Furthermore, compared with the performance of other reported hybrid supercapacitors, such as, LTO//AC system, MnO//AC system, Fe 3 O 4 /G//3DGraphene system, and B-Si/SiO 2 /C//AC system, the Si/C//eAC LIC system achieved the highest energy-to-power ratio, which is summarized in Fig. 15A.
  • Fig. 15B shows the cycling performance of the hybrid supercapacitor-battery full cells at a high current density of 1.6 A/g.
  • the hybrid supercapacitor-battery full cells showed an excellent cycling stability with the capacity retention of79%after 5000 cycles.
  • the influence of voltage window on the performance and cycling stability of the hybrid supercapacitor-battery full cell was also studied. When the cut-off voltage was down to 4.0 V from 4.5 V, the cycling performance was much improved with a capacity retention of86%after 5000 cycles (Fig. 17) . However, as shown in Fig.
  • Example 2 novel activated carbons were synthesized through a simple biomass transfer process from egg white.
  • the electrochemical performance of the obtained eAC materials showed specific capacity as high as 128 mAh/g, with good capacity retention.
  • the hybrid supercapacitor-battery full cells exhibited material level energy densities of257-147 Wh/kg at power densities from 867 to 29893 W/kg, which are the highest energy-to-power ratio among all reported hybrid-type supercapacitors.
  • this device can achieve a long cycle life, with 79%capacity retention after 5000 cycles.
  • ranges provided herein include the stated range and any value or sub-range within the stated range.
  • a range of from about 50 wt%to about 95 wt% should be interpreted to include not only the explicitly recited limits of from about 50 wt%to about 95 wt%, but also to include individual values, such as 70 wt%, 82.5 wt%, etc., and sub-ranges, such as from about 60 wt%to about 85 wt%, etc.
  • “about” is utilized to describe a value, this is meant to encompass minor variations (up to+/-10%) from the stated value.

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Abstract

La présente invention concerne des poudres de carbone activé pour systèmes hybrides de supercondensateur-batterie pouvant être formées à partir d'un épi de maïs ou d'un blanc d'œuf. Selon un exemple d'un procédé de fabrication d'un exemple de la poudre de carbone activé, un épi de maïs est séché et broyé pour former une poudre précurseur. La poudre précurseur est soumise à un traitement thermique sous un flux de gaz inerte jusqu'à ce qu'une température prédéterminée soit atteinte. Tandis que la température prédéterminée est maintenue, le flux de gaz inerte est remplacé par un flux d'ammoniac gazeux (NH3). Grâce à ce procédé, une poudre de carbone activé dopé à l'azote est formée.
PCT/CN2016/098708 2015-09-15 2016-09-12 Poudres de carbone activé pour systèmes hybrides de supercondensateur-batterie Ceased WO2017045573A1 (fr)

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