WO2013130018A1 - A transition metal nitride/carbon composite and a method for producing said composite - Google Patents

A transition metal nitride/carbon composite and a method for producing said composite Download PDF

Info

Publication number
WO2013130018A1
WO2013130018A1 PCT/SG2013/000087 SG2013000087W WO2013130018A1 WO 2013130018 A1 WO2013130018 A1 WO 2013130018A1 SG 2013000087 W SG2013000087 W SG 2013000087W WO 2013130018 A1 WO2013130018 A1 WO 2013130018A1
Authority
WO
WIPO (PCT)
Prior art keywords
transition metal
metal nitride
carbon composite
composite
graphene
Prior art date
Application number
PCT/SG2013/000087
Other languages
French (fr)
Inventor
Linfei LAI
Zexiang Shen
Jianyi Lin
Original Assignee
Nanyang Technological University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nanyang Technological University filed Critical Nanyang Technological University
Priority to SG11201406009RA priority Critical patent/SG11201406009RA/en
Publication of WO2013130018A1 publication Critical patent/WO2013130018A1/en

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
    • C04B35/52—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbon, e.g. graphite
    • 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
    • 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
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/38—Non-oxide ceramic constituents or additives
    • C04B2235/3852—Nitrides, e.g. oxynitrides, carbonitrides, oxycarbonitrides, lithium nitride, magnesium nitride
    • 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
    • H01M12/00—Hybrid cells; Manufacture thereof
    • H01M12/04—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type
    • H01M12/06—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type with one metallic and one gaseous electrode
    • 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

  • the present invention relates to a transition metal nitride/carbon composite and a method for producing the aforementioned composite.
  • Li-ion batteries lithium-ion batteries, particularly in relation to improving the volumetric and gravimetric capacity of the anode of the batteries.
  • the anode of batteries is typically made from graphite, which has a gravimetric capacity of 372 mAh/g.
  • Lithinated transition metal nitrides have been found to provide high gravimetric capacities, such as, for example, 900 mAh/g for Li 2 . 6 Coo.4N.
  • lithinated transition metal nitrides are suitable for use as anodes of batteries.
  • the method includes heating at least one transition metal ion precursor and at least one organic amine under reflux in an alcohol solvent, the heating being for obtaining at least one transition metal chelate; and loading the at least one transition metal chelate onto a graphene oxide layer to form the transition metal nitride/carbon composite.
  • the method may further include annealing the transition metal nitride/carbon composite at a predetermined temperature under inert gas conditions, the predetermined temperature being between 550°C and 1050°C.
  • the method may also further include reduction of graphene oxide via chemical exfoliation of graphite.
  • the method may also further include washing the transition metal nitride/carbon composite in diluted acid, de-ionised water and ethanol to remove excessive iron oxide, the diluted acid being 1 M of sulphuric acid.
  • the transition metal nitride may be a salt of, for example, iron (Fe), cobalt (Co), zinc (Zn), nickel (Ni) and the like.
  • the at least one organic amine may be ethylene di-amine, and the alcohol solvent is either ethanol or methanol.
  • the graphene oxide is decorated with oxygen containing functional groups, the oxygen containing groups being, for example, carboxylic acids, phenols, lactones, carboxylic anhydrates, ketones, ethers, pyrones, quinines and so forth.
  • oxygen containing groups being, for example, carboxylic acids, phenols, lactones, carboxylic anhydrates, ketones, ethers, pyrones, quinines and so forth.
  • transition metal nitride/carbon composite as produced using the aforementioned method.
  • the transition metal nitride/carbon composite can be used in applications such as, for example, an anode in a Li-ion battery, a fuel cell catalyst, and a lithium-air battery cathode.
  • a gravimetric capacity of the composite is advantageously higher than a gravimetric capacity of graphite when the composite is used as the anode.
  • the gravimetric capacity of the composite advantageously increases during repeated charging cycles when the composite is used as the anode.
  • Figure 1 shows a schematic diagram for the production of transition metal nitride/carbon composite.
  • Figure 2 shows a process flow for the production of transition metal nitride/carbon composite.
  • Figure 3 shows cyclic voltammetry curves of a FeN-graphene composite electrode (90% graphene) for three cycles at a scan rate of 0.1 mV/s.
  • Figure 4 shows charge/discharge profiles of a FeN-graphene composite electrode (90% graphene) between 0.02V and 1.5V at a current density of 0.05 A/g.
  • Figure 5 shows charge/discharge profiles of a FeN-graphene composite electrode (90% graphene) between 0.02V and 1.5V at a current density of 0.1 A/g.
  • Figure 6 shows charge/discharge profiles of a FeCoN-graphene composite electrode (90% graphene) between 0.02V and 1.5V at a current density of 0.05 A/g.
  • Figure 7 shows charge/discharge profiles of a FeCoN-graphene composite electrode (90% graphene) between 0.02V and 1.5V at a current density of 0.1 A g.
  • Figure 8 shows field-emission scanning electron microscopy (FESEM) images of a FeN- graphene composite.
  • Figure 9 shows transmission electron microscopy (TEM) of FeN-graphene composite post- annealing.
  • Figure 10 shows a N1s x-ray photoelectron spectroscopy (XPS) spectrum of FeN-graphene composite.
  • Figure 11 shows the first three charge/discharge profiles of a FeN-graphene composite electrode (90% graphene) at a current density of 100 mA/g.
  • Figure 12 shows capacity retention and coulombic efficiency profiles of a FeN-graphene composite electrode (90% graphene) at a current density of 50 mA/g for 50 cycles.
  • Figure 13 shows electrochemical capacity comparison curves of reduced graphene oxide (rG-O), N modified rG-0 (N-rG-O) and FeN-graphene at a current density of 100 mA/g.
  • Figure 14 shows capacity retention profiles of CoN-graphene and NiN-graphene at a current density of 50 mA/g for 80 cycles
  • the present invention relates to a transition metal nitride/carbon composite which demonstrates favourable characteristics for use as an anode in Li-ion batteries, amongst other applications.
  • the favourable characteristics include low cost of production, ease of scalability for the production process, high reversible capacity, and desirable cycle behavior.
  • a method to produce the composite is also provided. Details relating to how the aforementioned advantages are brought about will be provided in the following description.
  • FIG. 1 and 2 there is provided a schematic diagram and a process flow respectively for a method 20 for the production of a transition metal nitride/carbon composite.
  • Graphene and some functionalized carbons can be effectively loaded with transition metal nitrides in order to form a transition metal nitride/carbon composite.
  • Figure 1 shows the functionalization of carboxyl groups 18, adsorption of transition metal chelates 16, and annealing 14 after the adsorption stage 16. Greater detail of the method 20 is provided in Figure 2.
  • Graphene can be obtained from treating graphene oxide (22) using the reduction of graphene oxide via chemical exfoliation of graphite (24).
  • the graphene oxide itself is decorated with oxygen containing functional groups, such as, carboxylic acids, phenols, lactones, carboxylic anhydrates, ketones, ethers, pyrones, or quinines.
  • the functional groups provide abundant adsorption sites for transition metal chelates.
  • the transition metal nitride is a salt of, for example, iron (Fe), cobalt (Co), zinc (Zn), nickel (Ni) and the like.
  • At least one transition metal nitride is heated together with at least one organic amine (for example, ethylene di-amine) under reflux in an alcohol solvent (for example, ethanol, methanol and the like) (26), the heating being to obtain at least one transition metal chelate, and the at least one transition metal chelate is then loaded onto the graphene oxide layer (28).
  • organic amine for example, ethylene di-amine
  • alcohol solvent for example, ethanol, methanol and the like
  • transition metal ions coordinate with organic amine and forms transition metal chelate.
  • the transition metal chelate/graphene oxide composite is then annealed under inert gas conditions (30) at a temperature range of 550°C to 1050°C.
  • the composite may be washed in diluted acid like for example, 1 M of sulphuric acid (H 2 S0 4 ) , de-ionised water and ethanol to remove excessive iron oxide.
  • FESEM field-emission scanning electron microscopy
  • Figure 8(b) shows FeN-graphene composite at 850°C, where FeN with size of approximately 10 to 20 nm is uniformly distributed onto graphene layers of G-O.
  • Figure 9(a) shows transmission electron microscopy (TEM) images of FeN-graphene with FeN nanoparticles intercalated between the graphene layers.
  • Figure 9(b) shows uniform size distribution.
  • Figure 9(c) shows an enlarged view of a portion of Figure 9(b).
  • Figure 9(c) shows FeN with lattice spacing of 0.21 ⁇ 0.05 nm coated with graphitic shells with 5 to 7 layers of carbon.
  • XPS x-ray photoemission spectroscopy
  • the FeN-graphene composite was assembled into a model cell as the anode and LiCI0 4 solution was used as the electrolyte in the model cell.
  • the properties being demonstrated include capacity and cyclic behavior.
  • cyclic voltammetry curves (CV) of the FeN-graphene composite for three cycles at a scan rate (current density) of 0.1 mV/s. It should be appreciated that the 2 nd and 3 rd cycle curves of the FeN 2 -graphene composite are consistently shaped, indicating predictable cycle behavior and that reversible electrochemical reactions between lithium ions and the FeN-graphene composite occurred after the 1 st cycle.
  • FIGS. 4 and 5 there is shown charge/discharge profiles of a FeN-graphene composite electrode (90% graphene) between 0.02V and 1.5V at a current density of 0.05 A/g and 0.1 A/g respectively.
  • reversible charging/discharging capacity of 630 ( ⁇ 10) mAh/g is maintained for about 25 cycles at a current density of 0.05 A/g.
  • reversible charging/discharging capacity of around 500 ( ⁇ 20) mAh/g is maintained for about 120 cycles at a current density of 0.1 A/g.
  • the FeN-graphene composite electrode (90% graphene) has very high reversible capacity.
  • the charge/discharge profiles of both FeN-graphene composite electrode (90% graphene) and FeCoN-graphene composite electrode (90% graphene) are similar.
  • a reversible charging capacity of 500 - 600 mAh/g is demonstrated by the FeCoN-graphene composite electrode (90% graphene) for both current densities bf 0.05 A/g and 0.1 A/g.
  • the capacity does not decrease with an increase in the number of cycles and the capacity actually increases with the number of cycles.
  • Figures 11 to 13 show electrochemical characterisations of a half cell composed of FeN- graphene and Li. The specific capacities are calculated based on the mass of FeN-graphene composite including binder and carbon black.
  • FIG. 11 there is shown charge/discharge profiles of a FeN-graphene composite electrode (90% graphene) between 0.02V and 3V at a current density of 0.1 A/g.
  • the third cycle curve shows slight differences compared with the second cycle curve, indicating the electrochemical reversibility of FeN-graphene occurs after the first cycle.
  • the reversible capacity of N doped graphene (5% NH 3 in Ar at 850°C for 1h) is larger than that of reduced graphene, but still lower than that of FeN- graphene.
  • the elemental composition of the catalysts was analyzed on an inductively coupled plasma-optical emission spectrometer (ICP-OES).
  • the weight ratio of FeN is found to be 10 ⁇ 2% in FeN-graphene composite. Therefore, the addition of FeN with weight ratio of only 10% could increase the capacity of graphene by at least 200 mAh/g or 50%.
  • the FeN-graphene composite electrode (90% graphene) has very high reversible capacity.
  • the method 20 is a process which is easily scalable, and as such, large scale production of the transition metal nitride/carbon composite is possible. Compared with magnetron sputtering as mentioned in the background, chemical methods are much cheaper and easily up-scaled.
  • the transition metal nitride/carbon composite which results from the method 20 can be used to replace graphite as the anode material in a Li-ion battery, whereby there is no necessity to modify existing battery production processes. Moreover, the higher gravimetric capacity of the transition metal nitride/carbon composite and the no-degradation behavior over repeated charging cycles of the transition metal nitride/carbon composite anode clearly brings about several advantages compared to use of graphite anodes. In addition, the transition metal nitride/carbon composite also has advantageous properties which enables it to be used as, for example, a fuel cell catalyst, and a lithium-air battery cathode.

Abstract

There is provided a method for producing a transition metal nitride/carbon composite. The method includes heating at least one transition metal ion precursor and at least one organic amine under reflux in an alcohol solvent, the heating being for obtaining at least one transition metal chelate; and loading the at least one transition metal chelate onto a graphene oxide layer to form the transition metal nitride/carbon composite. Applications of the composite are also provided.

Description

A TRANSITION METAL NITRIDE/CARBON COMPOSITE AND A METHOD FOR PRODUCING SAID COMPOSITE
FIELD OF INVENTION
The present invention relates to a transition metal nitride/carbon composite and a method for producing the aforementioned composite.
BACKGROUND
An increasing amount of emphasis and attention is placed on clean energy and renewable energy sources in this age of enhanced environmental awareness. Batteries are viewed as an important component of clean energy, particularly when used to power vehicles which typically rely on the burning of polluting fossil fuels. Existing electric vehicles generally face issues relating to the batteries used to power the vehicles, and resolving these issues will lead to better reliability and more widespread acceptance of electric vehicles.
Improvements are continually sought to enhance the energy densities and usage life of batteries. Extensive research has been carried out in these areas for lithium-ion (Li-ion) batteries, particularly in relation to improving the volumetric and gravimetric capacity of the anode of the batteries.
The anode of batteries is typically made from graphite, which has a gravimetric capacity of 372 mAh/g. Lithinated transition metal nitrides have been found to provide high gravimetric capacities, such as, for example, 900 mAh/g for Li2.6Coo.4N. As such, lithinated transition metal nitrides are suitable for use as anodes of batteries.
Even though the preparation and application of transition metal nitrides using magnetron sputtering is commonly employed with nitrogen gas being the metal nitridation source, the inert nature of N2 leads to high costs and as such, the use of magnetron sputtering is not suitable for large-scale applications.
As such, the cost to produce lithinated transition metal nitrides using conventional methods is high, and the batteries which utilize pure lithinated transition metal nitrides as anodes suffer from issues like, for example, low reversible capacity and poor cycling behavior. SUMMARY
There is provided a method for producing a transition metal nitride/carbon composite. The method includes heating at least one transition metal ion precursor and at least one organic amine under reflux in an alcohol solvent, the heating being for obtaining at least one transition metal chelate; and loading the at least one transition metal chelate onto a graphene oxide layer to form the transition metal nitride/carbon composite.
The method may further include annealing the transition metal nitride/carbon composite at a predetermined temperature under inert gas conditions, the predetermined temperature being between 550°C and 1050°C. The method may also further include reduction of graphene oxide via chemical exfoliation of graphite. The method may also further include washing the transition metal nitride/carbon composite in diluted acid, de-ionised water and ethanol to remove excessive iron oxide, the diluted acid being 1 M of sulphuric acid. The transition metal nitride may be a salt of, for example, iron (Fe), cobalt (Co), zinc (Zn), nickel (Ni) and the like. The at least one organic amine may be ethylene di-amine, and the alcohol solvent is either ethanol or methanol.
Preferably, the graphene oxide is decorated with oxygen containing functional groups, the oxygen containing groups being, for example, carboxylic acids, phenols, lactones, carboxylic anhydrates, ketones, ethers, pyrones, quinines and so forth.
There is also provided a transition metal nitride/carbon composite as produced using the aforementioned method. The transition metal nitride/carbon composite can be used in applications such as, for example, an anode in a Li-ion battery, a fuel cell catalyst, and a lithium-air battery cathode. A gravimetric capacity of the composite is advantageously higher than a gravimetric capacity of graphite when the composite is used as the anode. In addition, the gravimetric capacity of the composite advantageously increases during repeated charging cycles when the composite is used as the anode.
There is provided a Li-ion battery using the aforementioned transition metal nitride/carbon composite as an anode in the battery. There is also provided a lithium-air battery using the aforementioned transition metal nitride/carbon composite as a cathode in the battery. Finally, there is provided a fuel cell using the aforementioned transition metal nitride/carbon composite as a cathode in the fuel cell. DESCRIPTION OF FIGURES
In order that the present invention may be fully understood and readily put into practical effect, there shall now be described by way of non-limitative example only preferred embodiments of the present invention, the description being with reference to the accompanying illustrative figures.
Figure 1 shows a schematic diagram for the production of transition metal nitride/carbon composite.
Figure 2 shows a process flow for the production of transition metal nitride/carbon composite. Figure 3 shows cyclic voltammetry curves of a FeN-graphene composite electrode (90% graphene) for three cycles at a scan rate of 0.1 mV/s.
Figure 4 shows charge/discharge profiles of a FeN-graphene composite electrode (90% graphene) between 0.02V and 1.5V at a current density of 0.05 A/g.
Figure 5 shows charge/discharge profiles of a FeN-graphene composite electrode (90% graphene) between 0.02V and 1.5V at a current density of 0.1 A/g.
Figure 6 shows charge/discharge profiles of a FeCoN-graphene composite electrode (90% graphene) between 0.02V and 1.5V at a current density of 0.05 A/g.
Figure 7 shows charge/discharge profiles of a FeCoN-graphene composite electrode (90% graphene) between 0.02V and 1.5V at a current density of 0.1 A g.
Figure 8 shows field-emission scanning electron microscopy (FESEM) images of a FeN- graphene composite.
Figure 9 shows transmission electron microscopy (TEM) of FeN-graphene composite post- annealing.
Figure 10 shows a N1s x-ray photoelectron spectroscopy (XPS) spectrum of FeN-graphene composite.
Figure 11 shows the first three charge/discharge profiles of a FeN-graphene composite electrode (90% graphene) at a current density of 100 mA/g.
Figure 12 shows capacity retention and coulombic efficiency profiles of a FeN-graphene composite electrode (90% graphene) at a current density of 50 mA/g for 50 cycles.
Figure 13 shows electrochemical capacity comparison curves of reduced graphene oxide (rG-O), N modified rG-0 (N-rG-O) and FeN-graphene at a current density of 100 mA/g.
Figure 14 shows capacity retention profiles of CoN-graphene and NiN-graphene at a current density of 50 mA/g for 80 cycles
DESCRIPTION OF PREFERRED EMBODIMENTS The present invention relates to a transition metal nitride/carbon composite which demonstrates favourable characteristics for use as an anode in Li-ion batteries, amongst other applications. The favourable characteristics include low cost of production, ease of scalability for the production process, high reversible capacity, and desirable cycle behavior. In addition, a method to produce the composite is also provided. Details relating to how the aforementioned advantages are brought about will be provided in the following description.
Referring to Figures 1 and 2, there is provided a schematic diagram and a process flow respectively for a method 20 for the production of a transition metal nitride/carbon composite. Graphene and some functionalized carbons can be effectively loaded with transition metal nitrides in order to form a transition metal nitride/carbon composite.
Figure 1 shows the functionalization of carboxyl groups 18, adsorption of transition metal chelates 16, and annealing 14 after the adsorption stage 16. Greater detail of the method 20 is provided in Figure 2.
Graphene can be obtained from treating graphene oxide (22) using the reduction of graphene oxide via chemical exfoliation of graphite (24). The graphene oxide itself is decorated with oxygen containing functional groups, such as, carboxylic acids, phenols, lactones, carboxylic anhydrates, ketones, ethers, pyrones, or quinines. The functional groups provide abundant adsorption sites for transition metal chelates. The transition metal nitride is a salt of, for example, iron (Fe), cobalt (Co), zinc (Zn), nickel (Ni) and the like.
Subsequently, at least one transition metal nitride is heated together with at least one organic amine (for example, ethylene di-amine) under reflux in an alcohol solvent (for example, ethanol, methanol and the like) (26), the heating being to obtain at least one transition metal chelate, and the at least one transition metal chelate is then loaded onto the graphene oxide layer (28). It should be appreciated that transition metal ions coordinate with organic amine and forms transition metal chelate. Next, the transition metal chelate/graphene oxide composite is then annealed under inert gas conditions (30) at a temperature range of 550°C to 1050°C. After annealing, the composite may be washed in diluted acid like for example, 1 M of sulphuric acid (H2S04) , de-ionised water and ethanol to remove excessive iron oxide. Referring to Figure 8(a), field-emission scanning electron microscopy (FESEM) shows graphene oxide with platelets in crumpled conformations. Figure 8(b) shows FeN-graphene composite at 850°C, where FeN with size of approximately 10 to 20 nm is uniformly distributed onto graphene layers of G-O. Figure 9(a) shows transmission electron microscopy (TEM) images of FeN-graphene with FeN nanoparticles intercalated between the graphene layers. Figure 9(b) shows uniform size distribution. Figure 9(c) shows an enlarged view of a portion of Figure 9(b). Figure 9(c) shows FeN with lattice spacing of 0.21 ± 0.05 nm coated with graphitic shells with 5 to 7 layers of carbon. Referring to Figure 10, a survey scan of the FeN-graphene composite using x-ray photoemission spectroscopy (XPS) also confirms the presence of Fe-N bond with binding energy of approximately 398.4 eV.
In order to demonstrate the properties of the FeN-graphene composite, the FeN-graphene composite was assembled into a model cell as the anode and LiCI04 solution was used as the electrolyte in the model cell. The properties being demonstrated include capacity and cyclic behavior.
Referring to Figure 3, there is shown cyclic voltammetry curves (CV) of the FeN-graphene composite for three cycles at a scan rate (current density) of 0.1 mV/s. It should be appreciated that the 2nd and 3rd cycle curves of the FeN2-graphene composite are consistently shaped, indicating predictable cycle behavior and that reversible electrochemical reactions between lithium ions and the FeN-graphene composite occurred after the 1st cycle.
Referring to Figures 4 and 5, there is shown charge/discharge profiles of a FeN-graphene composite electrode (90% graphene) between 0.02V and 1.5V at a current density of 0.05 A/g and 0.1 A/g respectively. Referring to Figure 4, it can be observed that reversible charging/discharging capacity of 630 (± 10) mAh/g is maintained for about 25 cycles at a current density of 0.05 A/g. Referring to Figure 5, it can be observed that reversible charging/discharging capacity of around 500 (± 20) mAh/g is maintained for about 120 cycles at a current density of 0.1 A/g. Thus, it is clearly demonstrated that the FeN-graphene composite electrode (90% graphene) has very high reversible capacity.
Referring to Figures 6 and 7, there is shown charge/discharge profiles of a FeCoN-graphene composite electrode (90% graphene) between 0.02V and 1.5V at a current density of 0.05 A/g and 0.1 A/g respectively. Firstly, the charge/discharge profiles of both FeN-graphene composite electrode (90% graphene) and FeCoN-graphene composite electrode (90% graphene) are similar. Furthermore, it should be appreciated that a reversible charging capacity of 500 - 600 mAh/g is demonstrated by the FeCoN-graphene composite electrode (90% graphene) for both current densities bf 0.05 A/g and 0.1 A/g. In addition, it should be noted that the capacity does not decrease with an increase in the number of cycles and the capacity actually increases with the number of cycles.
Figures 11 to 13 show electrochemical characterisations of a half cell composed of FeN- graphene and Li. The specific capacities are calculated based on the mass of FeN-graphene composite including binder and carbon black.
Referring to Figure 11 , there is shown charge/discharge profiles of a FeN-graphene composite electrode (90% graphene) between 0.02V and 3V at a current density of 0.1 A/g. The third cycle curve shows slight differences compared with the second cycle curve, indicating the electrochemical reversibility of FeN-graphene occurs after the first cycle.
Referring to Figure 12, it can be observed that reversible charging/discharging capacity of approximately 650 (± 20) mAh/g is maintained for about 25 cycles at a current density of 0.05 A/g.
With reference to Figure 13, for rG-0 material, the capacity retention after 100 cycles was only about 278 mAh/g and the irreversible capacity loss for rG-0 during cycling was 959 mAh/g. Reduced graphene (rG-O) by thermal annealing of graphite oxide (850°C in Ar gas environment) has large amount of defects at edge sites and internal/basal plane (vacancies etc.) which can react with electrolyte irreversibly and further induce capacity loss and cycle degradation. Heteroatoms doping, especially N, is effective for Li-ion battery capacity and cycling improvement. However, the reversible capacity of N doped graphene (5% NH3 in Ar at 850°C for 1h) is larger than that of reduced graphene, but still lower than that of FeN- graphene. The elemental composition of the catalysts was analyzed on an inductively coupled plasma-optical emission spectrometer (ICP-OES). The weight ratio of FeN is found to be 10±2% in FeN-graphene composite. Therefore, the addition of FeN with weight ratio of only 10% could increase the capacity of graphene by at least 200 mAh/g or 50%. Thus, it is clearly demonstrated that the FeN-graphene composite electrode (90% graphene) has very high reversible capacity.
With reference to Figure 14, there is shown cycling stability of NiN-graphene, and CoN- graphene. At current density of 50 mA/g, the capacity retention of NiN/N-rG-O, and CoN/N- rG-0 are 710 and 600 mAh/g respectively. Furthermore, it should be appreciated that a reversible charging capacity of 500 - 700 mAh/g is demonstrated by the MeN-graphene composite electrode (90% graphene) for both current densities of. 0.05 A/g and 0.1 A/g. In addition, it should be noted that the capacity does not decrease with an increase in the number of cycles and the capacity actually increases with the number of cycles.
It should be appreciated that the method 20 is a process which is easily scalable, and as such, large scale production of the transition metal nitride/carbon composite is possible. Compared with magnetron sputtering as mentioned in the background, chemical methods are much cheaper and easily up-scaled.
The transition metal nitride/carbon composite which results from the method 20 can be used to replace graphite as the anode material in a Li-ion battery, whereby there is no necessity to modify existing battery production processes. Moreover, the higher gravimetric capacity of the transition metal nitride/carbon composite and the no-degradation behavior over repeated charging cycles of the transition metal nitride/carbon composite anode clearly brings about several advantages compared to use of graphite anodes. In addition, the transition metal nitride/carbon composite also has advantageous properties which enables it to be used as, for example, a fuel cell catalyst, and a lithium-air battery cathode.
Whilst there has been described in the foregoing description preferred embodiments of the present invention, it will be understood by those skilled in the technology concerned that many variations or modifications in details of design or construction may be made without departing from the present invention.

Claims

1. A method for producing a transition metal nitride/carbon composite, the method including:
heating at least one transition metal ion precursor and at least one organic amine under reflux in an alcohol solvent, the heating being for obtaining at least one transition metal chelate; and
loading the at least one transition metal chelate onto a graphene oxide layer to form the transition metal nitride/carbon composite.
2. The method as claimed in claim 1 , further including annealing the transition metal nitride/carbon composite at a predetermined temperature under inert gas conditions, the predetermined temperature being between 550°C and 1050°C.
3. The method as claimed in either claim 1 or 2, wherein the transition metal nitride is selected from a salt of a group consisting of: iron (Fe), cobalt (Co), zinc (Zn), and nickel (Ni).
4. The method as claimed in any one of claims 1 to 3, further including reduction of graphene oxide via chemical exfoliation of graphite.
5. ' The method as claimed in any one of claims 1 to 4, wherein the graphene oxide is decorated with oxygen containing functional groups, the oxygen containing groups being selecting from a group consisting of: carboxylic acids, phenols, lactones, carboxylic anhydrates, ketones, ethers, pyrones, and quinines.
6. The method as claimed in any one of claims 1 to 5, further including washing the transition metal nitride/carbon composite in diluted acid, de-ionised water and ethanol to remove excessive iron oxide, the diluted acid being 1 M of sulphuric acid.
7. The method as claimed in any one of claims 1 to 6, wherein the at least one organic amine is ethylene di-amine, and wherein the alcohol solvent is either ethanol or methanol.
8. A transition metal nitride/carbon composite as produced using the method as claimed in any one of claims 1 to 7.
9. The transition metal nitride/carbon composite as claimed in claim 8 being used in applications selected from a group consisting of: an anode in a Li-ion battery, a fuel cell catalyst, and a lithium-air battery cathode.
10. The transition metal nitride/carbon composite as claimed in claim 9, wherein a gravimetric capacity of the composite is higher than a gravimetric capacity of graphite when the composite is used as the anode.
11. The transition metal nitride/carbon composite as claimed in claim 9, wherein the gravimetric capacity of the composite increases during repeated charging cycles when the composite is used as the anode.
12. A Li-ion battery using the transition metal nitride/carbon composite as claimed in claim 8, the transition metal nitride/carbon composite being used as an anode in the battery.
13. A lithium-air battery using the transition metal nitride/carbon composite as claimed in claim 8, the transition metal nitride/carbon composite being used as a cathode in the battery.
14. A fuel cell using the transition metal nitride/carbon composite as claimed in claim 8, the transition metal nitride/carbon composite being used as a cathode in the fuel cell.
PCT/SG2013/000087 2012-03-02 2013-03-04 A transition metal nitride/carbon composite and a method for producing said composite WO2013130018A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
SG11201406009RA SG11201406009RA (en) 2012-03-02 2013-03-04 A transition metal nitride/carbon composite and a method for producing said composite

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US201261606029P 2012-03-02 2012-03-02
US61/606,029 2012-03-02

Publications (1)

Publication Number Publication Date
WO2013130018A1 true WO2013130018A1 (en) 2013-09-06

Family

ID=49083077

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/SG2013/000087 WO2013130018A1 (en) 2012-03-02 2013-03-04 A transition metal nitride/carbon composite and a method for producing said composite

Country Status (2)

Country Link
SG (1) SG11201406009RA (en)
WO (1) WO2013130018A1 (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104174437A (en) * 2014-09-10 2014-12-03 天津工业大学 Graphene/C60/g-C3N4 heterojunction composite film and preparation method thereof
DE102014225350A1 (en) * 2014-12-10 2016-06-16 Bayerische Motoren Werke Aktiengesellschaft Electrode active material for a lithium-containing energy storage
CN110416552A (en) * 2019-07-05 2019-11-05 江苏科技大学 A kind of micro-nano structure phosphide/oxide/graphene composite material preparation method and applications

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090130502A1 (en) * 2006-02-17 2009-05-21 Monsanto Technology Llc Transition metal-containing catalysts and processes for their preparation and use as fuel cell catalysts
US7745047B2 (en) * 2007-11-05 2010-06-29 Nanotek Instruments, Inc. Nano graphene platelet-base composite anode compositions for lithium ion batteries

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090130502A1 (en) * 2006-02-17 2009-05-21 Monsanto Technology Llc Transition metal-containing catalysts and processes for their preparation and use as fuel cell catalysts
US7745047B2 (en) * 2007-11-05 2010-06-29 Nanotek Instruments, Inc. Nano graphene platelet-base composite anode compositions for lithium ion batteries

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
CAMELIA MATEI GHIMBEU. ET AL.: "Vanadium nitride/carbon nanotube nanocomposites as electrodes for supercapacitors", J. MATER. CHEM., vol. 21, 2011, pages 13268 - 13275 *
HYE RYUNG BYON ET AL.: "Graphene-based non-noble-metal catalysts for oxygen reduction reaction in acid", CHEM. MATER., vol. 23, no. 15, 2011, pages 3421 - 3428, XP002736284, DOI: doi:10.1021/cm2000649 *
WEN Z ET AL.: "Metal nitride/graphene nanohybrids: General synthesis and multifunctional titanium nitride/graphene electrocatalyst", ADV MATER, vol. 23, 2011, pages 5445 - 5450, XP055083484, DOI: doi:10.1002/adma.201102772 *
YUE Y. ET AL.: "In situ synthesis of a graphene/titanium nitride hybrid material with highly improved performance for lithium storage", J. MATER. CHEM., vol. 22, 31 January 2012 (2012-01-31), pages 4938 - 4943 *
ZHANG K. ET AL.: "A hybrid material of vanadium nitride and nitrogen-doped graphene for lithium storage", J. MATER. CHEM., vol. 21, 2011, pages 11916 - 11922 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104174437A (en) * 2014-09-10 2014-12-03 天津工业大学 Graphene/C60/g-C3N4 heterojunction composite film and preparation method thereof
DE102014225350A1 (en) * 2014-12-10 2016-06-16 Bayerische Motoren Werke Aktiengesellschaft Electrode active material for a lithium-containing energy storage
CN110416552A (en) * 2019-07-05 2019-11-05 江苏科技大学 A kind of micro-nano structure phosphide/oxide/graphene composite material preparation method and applications
CN110416552B (en) * 2019-07-05 2022-05-31 江苏科技大学 Preparation method and application of phosphide/oxide/graphene composite material with micro-nano structure

Also Published As

Publication number Publication date
SG11201406009RA (en) 2014-11-27

Similar Documents

Publication Publication Date Title
Zhang et al. Ultra-high mass-loading cathode for aqueous zinc-ion battery based on graphene-wrapped aluminum vanadate nanobelts
Liu et al. Rational design of nitrogen doped hierarchical porous carbon for optimized zinc-ion hybrid supercapacitors
He et al. N, P co-doped carbon microsphere as superior electrocatalyst for VO2+/VO2+ redox reaction
Guo et al. Growth of highly nitrogen-doped amorphous carbon for lithium-ion battery anode
CN108598390B (en) Preparation method of positive electrode material for lithium-sulfur battery and lithium-sulfur battery
Hou et al. An electrochemical study of Sb/acetylene black composite as anode for sodium-ion batteries
Puthusseri et al. Improving the energy density of Li-ion capacitors using polymer-derived porous carbons as cathode
Gong et al. Preparation of carbon-coated MgFe2O4 with excellent cycling and rate performance
Wang et al. Dual function flower-like CoP/C nanosheets: high stability lithium-ion anode and excellent hydrogen evolution reaction catalyst
Xiao et al. Constructing yolk-shell MnO@ C nanodiscs through a carbothermal reduction process for highly stable lithium storage
Qiu et al. Nitrogen-doped mesoporous carbon as an anode material for high performance potassium-ion batteries
JP2016500895A (en) Highly dispersible graphene composition and method for producing the same, and electrode for lithium ion secondary battery including highly dispersible graphene composition
KR102389113B1 (en) Method of Synthesizing Carbon-Based Lithium Ion Battery Anode from Carbon Dioxide and Carbon-Based Lithium Ion Battery Anode Prepared Thereby
Chen et al. Cactus-like iron diphosphide@ carbon nanotubes composites as advanced anode materials for lithium-ion batteries
Han et al. A film coating assembled by tubular nitrogen-doped carbon fibers as an efficient membrane spacer to suppress the shuttle effect for long-life lithium–sulfur batteries
CN112151779B (en) Binary anode composite material and preparation method and application thereof
Narayanasamy et al. Nanohybrid engineering of the vertically confined marigold structure of rGO-VSe2 as an advanced cathode material for aqueous zinc-ion battery
Feng et al. Designing hierarchical MnO/polypyrrole heterostructures to couple polysulfides adsorption and electrocatalysis in lithium-sulfur batteries
Palmieri et al. High performance bi-metallic manganese cobalt oxide/carbon nanotube Li-ion battery anodes
CN102157727B (en) Preparation method for nano MnO of negative electrode material of lithium ion battery
Patel et al. Superior cycling stability of saturated graphitic carbon nitride in hydrogel reduced graphene oxide anode for Sodium-ion battery
CN109950503B (en) CoMoOxPreparation method of/carbon/sulfur composite nano material, lithium ion battery cathode and lithium ion half battery
Ranjith et al. Defect and interface engineering of MXene-tagged N, F-doped carbon-CoSe2 heterostructure for superior hydrogen evolution reactions and supercapacitors
Xu et al. The effect of NiO as graphitization catalyst on the structure and electrochemical performance of LiFePO4/C cathode materials
Wang et al. Uniform AlF3 thin layer to improve rate capability of LiNi1/3Co1/3 Mn1/3O2 material for Li-ion batteries

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 13754833

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 13754833

Country of ref document: EP

Kind code of ref document: A1