Method for producing a graphene oxide-based compound for an air electrode of a metal-air battery and associated compound

Abstract

A method for producing a graphene oxide-based compound for an air electrode of a metal-air battery. A nitrogen and sulfur-based organic compound is added to an aqueous suspension of a graphene oxide. The water of the suspension is evaporated in order to obtain a powder. This powder is heated under an inert atmosphere in order to sublime the organic compound and stimulate the incorporation of nitrogen from the organic compound into the graphitic sites of the graphene oxide. The nitrogen and sulfur-doped graphene oxide is added to a second aqueous suspension comprising a cobalt nitrate-based compound. This second suspension is heated in order to form nanoparticles of cobalt oxide at the surface of at least one nitrogen and sulfur-doped graphene oxide sheet.

Claims

1. A method for producing a graphene oxide-based compound for an air electrode of a metal-air battery, the method comprising: preparing a first aqueous suspension of a graphene oxide in water; adding a nitrogen- and sulfur-based organic compound to the first aqueous suspension; evaporating the water from the first aqueous suspension so as to obtain a powder; heating the powder under an inert atmosphere so as to sublime the nitrogen- and sulfur-based organic compound and to stimulate the incorporation of nitrogen from the nitrogen- and sulfur-based organic compound into graphitic sites of the graphene oxide in order to obtain nitrogen- and sulfur-doped graphene oxide; adding the nitrogen- and sulfur-doped graphene oxide to a second aqueous suspension comprising a cobalt nitrate-based compound; heating the second aqueous suspension so as to form nanoparticles of cobalt oxide at a surface of at least one nitrogen- and sulfur-doped graphene oxide sheet, thus forming the graphene oxide-based compound for the air electrode of the metal-air battery, wherein the nitrogen- and sulfur-based organic compound is thiourea.

2. The method according to claim 1, wherein the powder is heated under the inert atmosphere to a temperature of between 700° C. and 1100° C.

3. The method according to claim 1, wherein the powder is progressively heated by increasing the temperature under the inert atmosphere at a rate of between 1° C. per minute and 20° C. per minute.

4. The method according to claim 1, wherein the second aqueous suspension is heated to a temperature of between 80° C. and 150° C.

5. The method according to claim 1, wherein the second aqueous suspension is heated in a microwave oven.

6. The method according to claim 1, wherein the method also comprises: incorporating the graphene oxide-based compound for the air electrode of the metal-air battery into a porous air electrode structure.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) The method disclosed herein will be better understood by reading the following description of some examples of embodiments presented for illustrative purposes, without limitation, and by observing the drawings below in which:

(2) FIG. 1 is a flowchart representing the steps of the method for producing a graphene oxide-based compound for an air electrode of a metal-air battery;

(3) FIG. 2 is a schematic representation of a sheet of nitrogen-doped graphene, integrated into the sheet so as to occupy different sites within the sheet: graphitic, pyrrolic and pyrinidic sites;

(4) FIG. 3 is a schematic representation of a sheet of graphene oxide identifying different possible configurations for binding oxygen to the carbon in the sheet;

(5) FIG. 4 is a schematic representation of a metal-air battery comprising an air electrode produced from the compound,

(6) FIG. 5 is an X-ray diffractogram of the cobalt oxide nanoparticles on the surface of sheets of nitrogen- and sulfur-doped reduced graphene oxide,

(7) FIG. 6 represents a histogram of the distances separating two nearest-neighbor cobalt oxide nanoparticles, showing a homogeneous distribution of cobalt oxide nanoparticles on the nitrogen- and sulfur-doped graphene oxide sheets,

(8) FIG. 7 is a graph showing the repeatability of the electrical behavior of an air electrode comprising the compound that is the object of the disclosure during cycling.

(9) For reasons of clarity, the dimensions of the different elements represented in these figures are not necessarily in proportion with their real dimensions. In the figures, identical references correspond to identical elements.

DETAILED DESCRIPTION

(10) The present disclosure proposes an original method for producing a compound usable for improving the lifetime, optimizing the structure and reducing the weight of air electrodes for metal-air batteries. In particular, when the compound from the method is incorporated into an air electrode for metal-air batteries, the air electrode displays an equivalent or even better electrical performance than that of electrodes using manganese oxide as a catalyst, but does not encounter the degradation problems observed in air electrodes from the prior art during cycling. The term “cycling” refers to the periodic charges and discharges that take place during operation of the metal-air battery.

(11) In addition, by integrating the compound of the present disclosure into an air electrode of a metal-air battery, using solid or gelled electrolytes in metal-air batteries becomes possible, thereby avoiding the maintenance requirements that appear when using liquid electrolytes. A solid or gelled electrolyte is particularly advantageous for application in portable systems.

(12) The compound presented below may also be used for other applications, particularly those in which an electrochemical resistance to alkaline pHs typically greater than 13 is sought.

(13) FIG. 1 schematically illustrates several steps of a method for producing a compound according to an embodiment.

(14) In a first step S1, a first aqueous solution 1 of a graphene oxide 10 is obtained. This step may be carried out by using a known graphene oxide synthesis technique, such as for example the “Hummers” method described in the document Hummers, William S.; Offeman, Richard E. (Mar. 20, 1958). “Preparation of Graphitic Oxide,” Journal of the American Chemical Society. 80 (6): 1339.

(15) This method enables a graphite oxide to be obtained that can then be exfoliated in an ultrasonic bath in order to prepare the graphene oxide used in step S1.

(16) The first aqueous solution 1 may typically contain water and several sheets of graphene oxide.

(17) In a second step S2, a nitrogen- and sulfur-based organic compound 2 is added to the aqueous suspension 1. This compound may, for example, be chosen from among thiourea or thiourea derivatives. The water of the first aqueous suspension is evaporated during mechanical stirring by heating in an oil bath in order to obtain a powder 5 comprising sheets of graphene oxide.

(18) During the following steps S3 and S4, the powder 5 is heated in an oven to temperatures of typically between 700° C. and 1100° C. under an inert atmosphere (for example, argon) for approximately 2 hours. This step enables the nitrogen and the sulfur of the nitrogen- and sulfur-based compound 2 to be inserted into the graphene oxide. The oven progressively rises in temperature to promote the incorporation of nitrogen preferentially into the graphitic sites of the graphene oxide.

(19) The obtained intermediate compound 20 based on nitrogen-21 and sulfur-31 doped graphene oxide is added to a second aqueous suspension 3 comprising a water/ethanol mixture in a 50/50 ratio in step S5. Cobalt oxide 4 or cobalt nitrate hexahydrate is added to the second aqueous suspension. Ammonium hydroxide may be added to the second aqueous suspension 3 which is then heated to a temperature of 100° C. for approximately 10 minutes so as to promote the growth of cobalt oxide nanoparticles 41 on a surface of at least one nitrogen- and sulfur-doped graphene oxide sheet, in step S6.

(20) According to a particularly advantageous embodiment, the second aqueous solution can be heated by microwave heating, while the prior art generally uses hydrothermal heating. Microwave heating appears to contribute to the formation of spherical cobalt oxide nanoparticles 41 having a size of between 2 nm and 5 nm, directly on the surface of a nitrogen- and sulfur-doped graphene oxide sheet, with a homogeneous distribution on this surface.

(21) The compound 30 thus obtained in step S7 comprises graphene oxide sheets comprising nitrogen heteroatoms 21, sulfur heteroatoms 31 and cobalt oxide nanoparticles 41 distributed in a substantially uniform manner on the surface of the sheets.

(22) The method according to an embodiment disclosure naturally leads to the formation of a compound 30 in which nitrogen 21 represents up to 4 atomic percent of a sheet of compound 30, and occupies different sites in the sheet. In particular, it has been observed that after steps S3 and S4, nitrogen 21 occupies between 15% and 50% of graphitic sites, between 25% and 35% of pyrrolic sites and between 30% and 40% of pyrinidic sites in compound 30. It should be noted that nitrogen 21 doping may lead to a distribution of nitrogen either on the edges of the graphene oxide sheet, or by replacing carbon atoms in the sheet itself.

(23) Sulfur 31 occupies up to 0.6% atomic percent of a sheet of compound 30, oxygen occupies approximately 1.4% atomic percent of a sheet of compound 30 and carbon occupies approximately 93.7% atomic percent.

(24) The sulfur atoms in compound 30 are present at 76% in the form of C—S—C or C—S—F groups and 24% in the form of C—SO.sub.n type groups.

(25) FIG. 2 schematically represents a two-dimensional plane of nitrogen-doped graphene 200. This figure illustrates an example of a graphitic site 201, an example of a pyrrolic site 202, an example of a pyrinidic site 203, a pyridinium 204 and a pyridine-N-oxide nitrogen 205.

(26) FIG. 3 schematically represents a sheet of graphene oxide 10 comprising carbon atoms 12, oxygen atoms 11 and hydrogen atoms 13. The oxygen can typically form three different chemical bonds in the graphene. A first bond type 101 consists of forming an epoxide group. A second bond type 102 consists of forming a hydroxyl group. A third bond type 103 consists of forming a carboxyl group.

(27) FIG. 4 schematically illustrates a metal-air battery 400 comprising a negative terminal 410, and at least one positive terminal 411. The battery comprises an electrolyte 403 separating a negative electrode 401 from at least one positive electrode 402. The positive electrode 402 is, in the case of the disclosure, an air electrode comprising the compound 30 described above in its structure.

Exemplary Embodiment

(28) First, the graphite oxide is synthesized according to Hummers' method mentioned above. This technique comprises the following steps:

(29) The precursor material is a commercial graphite powder (with grain sizes of less than 20 μm). The graphite powder (typically 3 g) is dispersed in a sulfuric acid solution (46 mL) with magnetic stirring for 10 min. Sodium nitrate (1.5 g) is added to the suspension. The mixture is mechanically stirred for 10 min. The entire process is carried out at 20° C. The suspension is then cooled using an ice bath. 9 g of potassium permanganate are then added to the suspension, while magnetic stirring is still maintained. The entire mixture is then brought to 35° C. for 30 min using oil bath heating. A quantity (for example 10 mL) of pure water is added to the mixture. The temperature of the oil bath is then brought up to 98° C. for 15 min. The mixture is then cooled using an ice bath. 420 mL of water, then 5 mL of hydrogen peroxide are then added to the reaction mixture. The suspension is magnetically stirred for 30 min.

(30) The material then undergoes a recovery and washing protocol. The suspension is centrifuged for 15 min at a radial centrifugal acceleration (RCA) of 2744 g and at a controlled temperature of 5° C. The supernatant is eliminated following the centrifugation step. The centrifugation residue is resuspended in a hydrochloric acid solution. The suspension is centrifuged again for 15 min at an RCA of 2744 g and at a controlled temperature of 5° C. This washing operation is repeated twice. The same washing operation is repeated 5 times by replacing the hydrochloric acid with pure water, but this time at a temperature of 20° C. Following the washing step, the solid is oven-dried (at a typical temperature of 40° C.) for 48 hr. The powder is then manually ground in a mortar.

(31) After implementing Hummers' technique described above, the graphene oxide sheets are doped with nitrogen, sulfur and cobalt oxide nanoparticles.

(32) The graphene oxide is first exfoliated by the application of ultrasound waves. An aqueous suspension (pure water, volume 200 mL) containing a concentration of 1 mg/mL of the solid previously obtained is first created. The suspension is placed in an ultrasonic bath (800 W) for 1 hr. To the initially prepared suspension, 8 mg/mL of thiourea are added. The suspension is then mechanically stirred for 30 min. The water is then evaporated during mechanical stirring by heating in an oil bath at 100° C. A thermal treatment of the powder thus obtained is then carried out at 700° C. in an argon atmosphere for 2 hr. The rise in temperature of the oven is 10° C./min. The oven is then cooled by inertia.

(33) The deposition of cobalt oxide nanoparticles (also known as Co-based nanostructured spinels) onto the surface of a nitrogen- and sulfur-doped graphene oxide sheet may be carried out by the method described below.

(34) The powder of reduced graphene oxide doped with sulfur and nitrogen atoms (N,S-RGO for “nitrogen, sulfur and reduced graphene oxide”), obtained following the synthesis steps described in the previous paragraph, is redispersed into a mixture of pure water/ethanol in a 50/50 ratio by volume, at a concentration of 1 mg of powder per milliliter of liquid. This suspension is magnetically stirred for 24 hr in order to ensure dispersion of the reduced and doped graphene oxide sheets in the water/ethanol mixture. The suspension is then placed in an ultrasonic bath for 1 hr, to ensure that the exfoliation of the material is maintained. Immediately following the application of ultrasound waves, 0.130 g of cobalt nitrate hexahydrate is added to 20 mL of the N,S-RGO suspension. The mixture, which has a pink supernatant after the addition of cobalt salt, is mechanically stirred for 10 minutes. 2.5 mL of an 11% ammonium hydroxide aqueous solution are then added to the suspension, while continuing to stir. The color of the supernatant turns green following the addition of ammonium hydroxide.

(35) The 20 mL of suspension are transferred into a 30 mL glass reactor for a single-mode microwave oven. The synthesis temperature is controlled by a temperature probe (for example, a ruby insertion probe). After the temperature rises in a few seconds until 100° C. is reached within the reaction medium, this temperature is kept constant for 10 minutes. The reactor is then cooled in the microwave oven by a flow of compressed air for several minutes.

(36) After this last synthesis step, which enabled the formation of cobalt oxide nanoparticles grafted to the surface of the N,S-RGO sheets, the material is obtained in the form of an unstable suspension that sediments in a few seconds. It then undergoes a recovery and washing protocol. The suspension is centrifuged at an RCA of 29220 g for 30 minutes. The supernatant is then eliminated. The black powder remaining on the wall of the tube is then resuspended in pure water. This washing operation is repeated until the pH of the supernatant reaches a value of between 7 and 7.5. Lastly, the solid is dried under vacuum at 45° C. for 12 hr and the recovered powder is manually ground in a mortar.

(37) The material is characterized by X-ray diffraction. The results of this characterization are indicated in FIG. 5, which represents an X-ray diffractogram of Co.sub.3O.sub.4 on the nitrogen- and sulfur-doped graphene oxide. The y-axis 501 represents the intensity of the signal detected by diffractometry, and the x-axis 502 represents the orientation angle of the X-ray beam, 2-theta. The reference peaks (indicated by lines 503) show a single Co.sub.3O.sub.4 crystalline phase as well as the presence of a small quantity of stacked RGO sheets, evidenced by a large peak 504 at approximately 31° (2-theta Lambda Co Kα). The morphology is characterized by transmission electron microscopy. The monocrystalline Co.sub.3O.sub.4 particles have a spherical shape and a diameter varying from between 2 and 5 nm. A distinctive feature of the material is the selective deposition of Co.sub.3O.sub.4 nanoparticles on the N,S-RGO sheets: The proportion of unsupported nanoparticles is very low, less than approximately 10% by number. Lastly, the loading rate is estimated to be 50% by mass (ratio of the mass of supported nanoparticles to the total mass of the material, considering that 90% of the particles are effectively deposited on the RGO) by thermogravimetric analysis.

(38) In addition, FIG. 6 shows that the nanoparticles are distributed in a substantially homogeneous manner on each nitrogen- and sulfur-doped graphene oxide sheet. Axis 601 of FIG. 6 represents the percentage of nanoparticles while axis 602 represents the distance in nanometers separating two nearest-neighbor cobalt oxide nanoparticles. In FIG. 6, it appears that 80% of the distances separating two nearest-neighbor cobalt oxide nanoparticles 41 are between 0.5 nm and 3 nm, and only 16% of the nanoparticles are aggregated.

(39) Characterization of the Compound Obtained

(40) Experiments have been carried out in view of verifying the electrical properties and the chemical stability of an air electrode obtained by incorporating the compound 30 described above. A test example is presented below.

(41) Electrochemical measurements to evaluate the catalytic properties of the material with respect to the dioxygen evolution and reduction reactions are carried out using a potentiostat. The measurements are conducted in an aqueous electrolysis medium composed of potassium hydroxide at the 1 mol/L concentration. The measurements are carried out in a 50-mL 3-electrode electrochemical cell. A saturated calomel reference electrode is used. A counter electrode composed of a glassy carbon plate is used. The electrolyte is previously saturated with oxygen for 30 min. The electrolyte (100 mL) is made by dissolving 6.4 g of potassium hydroxide pellets in pure water.

(42) To make the electrodes, an ink is first made. This ink is composed of 750 μL pure water, 250 μL isopropanol and 60 μL of a solution of 5% Nafion® by mass in a mixture of aliphatic alcohols and 5 mg of powder of the previously synthesized material. The electrochemical measurements are carried out under quasi-stationary conditions by using a rotating disk electrode. Measurements aiming to determine the activity of the material with respect to the dioxygen reduction reaction are carried out at rotation speeds of the rotating disk electrode of 400, 900, 1600 and 2500 rotations per minute in the potential range of between 1 and 0.25 V/HRE (HRE designating the hydrogen reference electrode) at a linear rate of variation of the potential of 5 mV/s. Measurements aiming to determine the activity of the material with respect to the dioxygen evolution reaction are carried out at a rotation speed of the rotating disk electrode of 1600 rotations per minute in the potential range of between 1 and 1.8 V/HRE at a linear rate of variation of the potential of 5 mV/s. Once the polarization curves are obtained, the reversibility condition is determined by calculating the difference in potential between the potential required to have a current density of 10 mA/cm.sup.2 during the dioxygen evolution reaction and the potential required to have a current density of −1 mA/cm.sup.2 during the reduction reaction. A reversibility condition of 0.78 V is obtained for the composite material comprising a carbon loading rate of 50%.

(43) An evaluation of the stability of the materials was subsequently carried out by means of an air electrode. This electrode comprises a Teflon body. The electrical connection is ensured by a gold wire. The conductive mechanical support used for depositing the catalyst is a nickel foam that was previously treated by immersion in a hydrochloric acid solution at 6 mol/L for 30 min. The foam is then washed and oven-dried at 80° C. A catalytic ink composed of 54 μL of a 60% aqueous PTFE solution, 2 mL of ethanol and 8 mg of catalytic powder is made.

(44) The ink is homogenized by using an ultrasonic bath at 800 W for 1 hr. The nickel foam is impregnated with the catalytic ink by immersion or dip coating. The mass of the deposited catalyst is verified by weighing. The stability of the catalytic material during cycling is then evaluated in an aqueous electrolysis medium containing an electrolyte consisting of potassium hydroxide at the 6 mol/L concentration. Electrochemical measurements by chronopotentiometry are carried out by using a potentiostat in a 50-mL 3-electrode electrochemical cell. A saturated silver chloride reference electrode is used. A counter electrode consisting of a glassy carbon plate is used. Current densities of −8 mA/cm.sup.2 and 10 mA/cm.sup.2 are respectively applied during the discharge and charge cycles. The charge and discharge cycles have respective durations of 8 and 12 hr and the total duration of the test is 214 hr.

(45) FIG. 7 illustrates the results of these cycling tests, carried out by alternately applying current densities of −8 mA/cm.sup.2 (for 12 hr) and 10 mA/cm.sup.2 (for 8 hr). Axis 701 designates the potential measured in relation to the Ag/AgCl/KCl couple (saturated) in Volts. Axis 702 designates the current density measured in mA/cm.sup.2 and axis 703 designates the time in hours. This figure shows that the air electrode comprising the compound 30 described above does not undergo degradations during cycling, and maintains the same electrical performance even after several charge/discharge cycles.

(46) A second test was carried out on electrodes containing the material that is the subject of the disclosure bound with PTFE only on a nickel grid. These electrodes were cycled at +30 mA/cm.sup.2 and −30 mA/cm.sup.2 in ambient air in a solution of 8 mol/L of KOH. No degradation was observed over 50 cycles.

(47) Measurements of the electrode carried out by in situ infrared to detect the presence of carbonate or of carbonyl groups show that there is no oxidation of the doped graphene oxide prepared by the disclosure, even at high oxygen evolution potentials (>1.65V vs HRE) over 3000 hr of operation.