Transition metal oxide particles and method of producing the same

Abstract

This application relates to oxide particles, preferably transition metal oxide particles, made via the application of a voltage across an electrolyte solution. The electrolyte solution includes a transition metal salt dissolved in water, and preferably also includes a compound for increasing the electrical conductivity of the electrolyte. The particles made by the processes disclosed herein, can have sizes in the micrometer or nanometer ranges. The oxide particles can have a variety of uses, including for charge storage devices. As an example, manganese oxide particles, and methods for making the same, are disclosed for a variety of uses including lithium ion batteries.

Claims

1. A method for making metal oxide particles, comprising the steps of: mixing with water, together or separately, a) a transition metal salt, and b) a soluble conductivity enhancing compound so as to form an electrolyte solution, the electrolyte solution being provided between electrodes; and applying potentiostatic pulse electrolysis to the solution so as to cause the formation of metal oxide particles at the first or second electrode, wherein the metal oxide particles become separated from the first or second electrode back into the electrolytic solution, wherein the oxide particles are disposed on the surface of the electrode for less than 1 second; and separating the metal oxide particles from the electrolytic solution.

2. The method of claim 1, wherein the metal oxide formed is selected from ZnO, In.sub.2O.sub.3, RuO.sub.2, IrO.sub.2, CrO.sub.2, MnO.sub.2 and ReO.sub.3.

3. The method of claim 1, wherein the metal oxide formed is a metal oxide of one or more of the metals selected from Ce, Zr, Zn, Co, Fe, Mg, Gd, Ti, Sn, Ru, Mn, Cr and Cu.

4. The method of claim 1, wherein the first and second electrodes are an anode and cathode, and wherein the metal oxide particles are formed on the anode and decouple from the anode so as to become free nanoparticulates in the electrolytic solution.

5. The method of claim 1, wherein the metal oxide particles formed are manganese oxide particles.

6. The method of claim 1, wherein the potentiostatic pulse electrolysis comprises a series of voltage pulses applied between the electrodes.

7. The method of claim 1, further comprising applying ultrasound to the electrolytic solution during potentiostatic pulse electrolysis.

8. The method of claim 4, wherein the anode is an array and comprises a plurality of electrodes.

9. The method of claim 1, wherein the potentiostatic pulse electrolysis comprises a series of voltage pulses having a pulse width of less than 1 second.

10. The method of claim 1, further comprising the step of separating the metal oxide particles from the electrolyte solution by filtering wherein, prior to said filtering, all of the metal oxide formed are particles in solution.

11. The method of claim 10, wherein substantially all the metal oxide formed at the electrode separates as particles into the electrolyte with no metal oxide remaining adhered to the electrode.

12. The method of claim 1, wherein the electrolyte has a pH of from 1 to 2 and an electrical conductivity of from 5 to 15 mS/cm.

13. The method of claim 1, wherein the formed metal oxide is further coated with silver, copper, nickel, titanium, silver oxide, copper oxide, titanium oxide, graphene, graphite, carbon nano tube, gold, platinum or palladium.

14. The method of claim 1, further comprising forming crystalline metal oxide particles.

15. The method of claim 1, wherein the potentiostatic pulse electrolysis comprises a series of voltage pulses provided between the electrodes, including forward and reverse voltage pulses.

16. The method of claim 1, wherein the step of separating the metal oxide particles from the electrolytic solution comprises allowing the particles to settle out of the electrolytic solution over a period of time, followed by removal of the electrolytic solution, and washing and drying of the remaining particles.

17. The method of claim 1, wherein the metal oxide particles separated from the electrolytic solution have an average diameter of less than 10 microns.

18. The method of claim 1, wherein the particle separation is caused by a delay between pulses.

Description

BRIEF DESCRIPTION OF DRAWINGS

(1) FIG. 1 is an SEM image of MnO.sub.2 particles obtained in Example 1;

(2) FIGS. 2A and 2B show an SEM image and an EDS plot, respectively, of MnO.sub.2 particles obtained in Example 2;

(3) FIGS. 3A and 3B show an SEM image and an EDS plot, respectively, of MnO.sub.2 particles obtained in Example 3;

(4) FIG. 4 depicts the XRD result of the MnO.sub.2 particles obtained in Example 4; and

(5) FIG. 5 shows in a schematic fashion a synthesis device which can be used in the present technology.

DESCRIPTION OF EMBODIMENTS

(6) Disclosed herein are methods and apparatus for making particles, such as microparticles, nanoparticles, etc.

(7) The processes in their various variations include first forming an aqueous electrolyte, disposing the electrolyte between electrodes, followed by performing electrolysis by applying a potential across the electrodes so as to form the desired particles. In preferred examples, the electrolyte is an aqueous solution formed by mixing water with a metal salt and a conductivity enhancing compound, followed by applying a voltage across the electrodes and through the electrolyte, which is preferably as a series of voltage pulses. The voltage pulses can be a series of on and off voltages, a series of high and low voltages, a series of forward and reverse voltage pulses, or a combination thereof.

(8) In one example for making oxide particles, an electrolyte solution is formed from a transition metal salt. Preferably a soluble conductivity enhancing compound is also provided to increase the conductivity of the electrolytic solution. Both the transition metal salt and the soluble conductivity enhancing compound can be added to water, or the transition metal salt can be added to a first source of water, and separately the soluble conductivity enhancing compound can be added to another source of water, and then both solutions combined together to form the electrolyte solution.

(9) The transition metal salt can be any desired transition metal compound that is soluble for the process. The transition metal can be a late transition metal, or an early transition metal. The transition metal is preferably a transition metal from columns 4 to 12 of the periodic table. The transition metal can be any suitable transition metal, though preferably selected from rows 4 to 6 of the periodic table. In one example, the transition metal is selected from row 4 of the periodic table, such as Ti, V, Cr, Mn, Fe, Co, Ni, Cu or Zn. The transition metal could also be selected from row 5 of the periodic table, such as, but not limited to Zr, Nb, Mo, Tc, Ru or Rh. The transition metal salt can be for example a compound that is a nitrate, sulphate, carbonate, phosphate or halogen salt.

(10) The soluble conductivity enhancing compound is a compound that is soluble in the electrolytic process for making the oxide particles. As an example, the conductivity enhancing compound is an acid, such as sulphuric acid, nitric acid, a chlorine containing acid, phosphoric acid or carbonic acid. The conductivity enhancing compound can be a halogen containing salt or acid.

(11) In a preferred example, the conductivity enhancing compound is a polar covalent compound, such as HCl, HBr, HI or H.sub.2SO.sub.4. In one example, the transition metal salt and the conductivity enhancing salt are both nitrates or both sulphates. In another example, the transition metal salt comprises a nitrate, sulphate, carbonate, phosphate or halogen group, and the conductivity enhancing salt comprises a nitrate, sulphate, carbonate, phosphate or halogen group that is different from the nitrate, sulphate, carbonate, phosphate or halogen group of the transition metal salt. Preferably the transition metal salt comprises a nitrate, sulphate, carbonate, phosphate or halogen group, and the conductivity enhancing salt comprises a nitrate, sulphate, carbonate, phosphate or halogen group that is the same as the nitrate, sulphate, carbonate, phosphate or halogen group of the transition metal salt.

(12) If desired, additional compounds or additives can be added to the electrolyte solution. Such compounds may be organic solvents, functional organic compounds, surfactants or polymers that impart in a beneficial way to the electrolysis process. More detailed examples of these classes of compounds can be alcohols, ketones, esters, organic acids, organic sulphur containing compounds, various anionic, cationic or non-polar surfactants, as well as functional polymers. The organic solvent can be acetic acid, glycolic acid, oxalic acid, decanoic acid or octanoic acid, among others. The functional polymers may be, but not limited to, copolymers of ethylene and propylene oxide, polyvinyl alcohols and polyvinylpyrrolidone

(13) The particle formed can have a diameter of 1 micron or greater on average (e.g. from 1 to 50 microns, or e.g. from 1 to 10 microns), however the methods are preferably used to form oxide nanoparticles having a diameter (or maximum dimension) of less than 1 micron.

(14) In one embodiment, the particles have an average diameter (or maximum dimension) of from 0.01 to 0.90 microns, and preferably from 0.025 to 0.85, e.g. 0.1 to 0.75 microns, and are substantially round (or spherical).

(15) Another embodiment comprises forming particles having the shapes of elongated rods, thin flakes or petals. Said particles have average largest dimensions in the above mentioned ranges.

(16) Nanoparticles having an average diameter, or maximum dimension, of less than 0.6 microns, e.g. less than 0.5 microns or even less than 0.3 microns, can be made according to the methods herein.

(17) In preferred examples, due to substantial uniformity of the sizes of the particles formed, for a particular average dimension in a range as above, substantially all of the particles formed will have dimensions in such range.

(18) The yield of formed metal oxide particles to the solution can be greater than 40%, preferably greater than 50%, including yields of 65% or more (up to 100%, or more commonly 99%).

(19) The pH of the electrolyte during the particle formation is preferably acidic, e.g. a pH of less than 7, such as a pH of from 1 to 6. A pH in the lower part of this range, such as from 1 to 4, or from 1 to 2.5, e.g. from 1 to 2, can be desirable. The temperature of the electrolyte during particle formation can be selected from a variety of temperatures, such as an electrolyte solution heated to a temperature of from 50 C. to 90 C. during particle formation, or from 60 C. to 80 C. during particle formation. However temperatures both lower and higher than these ranges, including less than 50 C., such as at ambient temperature or lower, can be used.

(20) In one example, the conductivity enhancing compound is a polar covalent compound, such as HCl, HBr, HI, HNO.sub.3 or H.sub.2SO.sub.4. It is also possible to use an alkali metal salt for the conductivity enhancing compound, or an alkaline earth metal salt. In such a case the alkali metal could be K or Na, or the alkaline earth metal could be Mg or Ca. Such a salt could also have an ion (anion) selected from NO.sub.3, SO.sub.4, PO.sub.4, BO.sub.3, CLO.sub.4, (COOH).sub.2 and halogen groups.

(21) The potentiostatic pulse electrolysis may include a series of voltage pulses provided from a power source, where the voltages are applied between an anode and cathode. The voltage pulses can include both forward and reverse pulses.

(22) In one example, only one or more forward pulses are provided across the electrodes, without any reverse pulses. However in a preferred example, both one or more forward pulses and one or more reverse voltages are provided.

(23) In one example, a plurality of forward pulses is followed by a plurality of reverse pulses.

(24) In another example, a plurality of forward pulses is followed by a single reverse pulse.

(25) In a third example, a single forward voltage pulse is followed by a plurality of reverse pulses.

(26) In a preferred example, a plurality of both forward and reverse pulses is provided, where each forward pulse is followed by a reverse pulse.

(27) In one example, a forward voltage pulse has a voltage, and optionally a reverse pulse, of 0.5 to 5 V/cm.sup.2 and a current of from 0.01 to 5 A/cm.sup.2. The forward voltage pulse is preferably followed by a reverse pulse having a voltage of from 0.01 to 5 A/cm.sup.2.

(28) In another example, a forward voltage pulse has any desired voltage, such as a voltage pulse of from 0.25 to 25 V/cm.sup.2, and preferably from 2 to 15 V/cm.sup.2, and a current of from 0.01 to 5 A/cm.sup.2, preferably from 0.1 to 5 A/cm.sup.2. This forward voltage pulse is followed by a reverse pulse having a voltage of from of from 0.25 to 25 V/cm.sup.2, and preferably from 2 to 15 V/cm.sup.2, and a current of from 0.1 to 5 A/cm.sup.2, preferably from 0.1 to 5 A/cm.sup.2, but of opposite polarity from the forward pulse.

(29) The forward and reverse pulses can be of the same magnitude, or the reverse pulse can be higher or lower than the forward pulse. In a number of examples, the reverse pulse is of lesser magnitude than the forward pulse, such as from 15% to 85% of the magnitude of the forward pulse. Also the length of time of the forward pulses need not be of the same duration throughout the electrolysis, nor do the reverse pulses need to be maintained at the same duration throughout the electrolysis, The forward pulses can be of shorter time duration at an earlier time in the electrolysis process than at a later time (or vice versa). Likewise the reverse pulses can be of shorter time duration at an earlier time in the electrolysis process than at a later time (or vice versa). In addition, the forward pulses and reverse pulses can have the same pulse duration or time width, or the reverse pulses can have a pulse duration different than the pulse duration of the forward pulses (either greater or less than the forward pulses) and this relation or ratio can change during the electrolysis process.

(30) Additionally, there may be a pulse delay between the pulses when no current is being applied in to the electrolytic cell. Such delays may be useful to permit the detachment of growing particles from the anode or cathode, respectively. The pulse delay can be shorter or longer that the forward or reverse pulses. Preferably, the pulse delays should be short to maximize the production yield of the process.

(31) Though the oxide particles can be formed at either the cathode or anode, in a preferred process the particles are formed at the anode, which can be any suitable electrode design including an ultramicroelectrode. The anode can be stainless steel, aluminium or lead anode, or an anode of any other suitable material such as copper or platinum. An ultrasonic or megasonic pulsator may optionally be provided, such as set forth in FIG. 1, in order to provide ultrasound to the electrolyte. The ultrasonic device can provide sound pressure waves with a frequency of from 20 kilohertz to 200 megahertz.

(32) The potentiostatic pulse electrolysis as a production method for oxide particles permits control of the particle crystallinity obtained. Using the method described, it is possible to obtain, for example, a manganese oxide nano sized material which contains to a significant degrees and phase. The crystallinity and the phase morphology can further be controlled by adjusting the parameters of the process.

(33) Thus, the present method provides for predominantly crystalline nanoparticles of metal oxides, such as manganese oxide, having and phases. Such particles may have particle sizes in the range of less than 1 micron, in particular 0.01 to 0.90 microns, and preferably from 0.025 to 0.85, e.g. 0.1 to 0.75 microns. The size is expressed as the average diameter or average maximum size of the particles (). A typical XRD spectrum for the particles is shown in FIG. 4.

(34) By contrast, simple chemical reduction of MnSO.sub.4 with KMnO.sub.4 leads to a predominately amorphous material containing some crystalline -phase.

(35) Thus, it can be estimated that the present technology provides crystalline metal oxide particles having a higher degree of crystallinity than particles formed by conventional technology. On an average, the non-crystalline portion of the present particles is less than 50% of the mass, in particular less than 40%, for example less than 30%, advantageously less than 20% or even less than 10% of the mass of the particles.

(36) Preferably the oxide particles are formed at the anode and separate from the anode back into solution after a short period of time. In one example, the oxide particles are disposed on the surface of the anode for less than 1 second, preferably less than 0.5 seconds, and more preferably less than 0.1 seconds. In other examples, the oxide particles separate from the anode within milliseconds of formation, such as within 0.01 to 100 milliseconds, e.g. from 1 to 100 milliseconds or even for periods of time such as from 0.01 to 1 milliseconds. Depending on the length of time of the voltage pulse widths, the oxide particles can be at the surface of the anode for from 1 to 100 pulse time widths, e.g. from 1 to 10 pulse time widths. Preferably all the metal oxide formed at the electrode separates as particles into the electrolyte with substantially no metal oxide remaining adhered to the electrode.

(37) The oxide particles formed can be metalloid oxide particles, though preferably are transition metal oxide particles such as oxide particles of Ce, Zr, Zn, Co, Fe, Mg, Gd, Ti, Sn, Ru, Mn, Cr or Cu. Other oxide particle examples include ZnO, In.sub.2O.sub.3, RuO.sub.2, IrO.sub.2, CrO.sub.2, MnO.sub.2 and ReO.sub.3. Oxides of post transition metals are also examples herein, though oxides of transition metals are preferred examples, with transition metals from columns 3 to 12 and in rows 4 to 6 of the periodic table of elements are preferred (particularly columns 5 to 12 and row 4 of the periodic table).

(38) After formation of the particles, the particles can be separated from the electrolyte solution, such as with a suitable filter or by allowing the particles to separate out over a period of time by gravitational forces, centrifugation, etc. Furthermore separating the formed free flowing particles from the electrolyte may comprise an additional hydrocyclone or decanting centrifuge separation step either in batch or continuous mode.

(39) After removing the remaining electrolyte solution from the formed particles, the particles can be washed with e.g. deionized water and dried. The particles can then be formulated as a slurry, ink or paste with one or more suitable carriers. Examples of this carrier are water and various organic solvents having 1-10 carbon atoms and one or more functional moiety. Examples of such are alcohol, ether, ketone, halogen, ester, alkane, double bond or aromaticity in the molecule. The carrier solvent molecule may bear one or more of the functional groups.

(40) The final formulation may further consist of more than one carrier solvent i.e. consist of a mixture of chemicals beneficial for a particular application. In addition, the final composition may include various surfactants, polymers or organic acids which permit the particles to perform as expected in their application.

(41) A charge storage device is a further embodiment, wherein a housing comprises a first electrode, a second electrode, and wherein one of the electrodes comprises a material made from the oxide particles disclosed herein. The oxide particles used for making the electrode material in the charge storage device can have a size of from 1 to 10 microns in diameter (or maximum dimension). However, as greater surface area is beneficial for the oxide particles at the electrode in the charge storage device, the particles preferably have an average diameter or maximum dimension of less than 1 micron, such as less than 800 nm, e.g. from 0.2 to 0.7 microns.

(42) In a further example, the particles have an average diameter (or maximum dimension) of from 50 to 850 nm, e.g. from 100 to 700 nm. Preferably the particles are substantially round, rather than elongated rods or flakes.

(43) The charge storage device can be a lithium ion battery that can be rechargeable (or not). It could also be another type of battery such as an alkaline battery. Between the anode and cathode of the charge storage device is an electrolyte comprising a lithium salt and a solvent. The solvent can be an organic solvent such as ethylene carbonate, propylene carbonate, dimethyl carbonate, ethyl methyl carbonate and/or diethyl carbonate.

(44) The anode in the charge storage device can be made of carbon, such as a graphite anode. The cathode in the charge storage device can be a spinel cathode, and can comprise for example a lithium manganese oxide spinel (LiMn.sub.2O.sub.4) made from the manganese oxide particles disclosed herein. Alternatively the oxide particles disclosed herein could be cobalt oxide particles for making a lithium cobalt oxide cathode, or oxide particles for making a lithium nickel manganese cobalt oxide electrode (e.g. a NMC spinel), or oxide particles for making a lithium nickel cobalt aluminium electrode. Preferably the formed electrode has a capacity of at least 175 mAh g.sup.1, preferably at least 200 mAh g.sup.1, and more preferably at least 250 mAh g.sup.1.

(45) Preferably the oxide is substantially free of metallic impurities. The lithium salt in the electrolyte can be LiPF, LiBF, LiClO or other suitable salt. If the charge storage device is a rechargeable lithium battery, the lithium in the electrolyte can be an intercalated lithium compound. A suitable lithium salt in the battery electrolyte, such as lithium triflate, lithium hexafluorophosphate, lithium perchlorate, lithium tetrafluoroborate, or lithium hexafluoroarsenate monohydrate, or other suitable lithium salt, can be used.

(46) The charge storage device may be equipped with a voltage regulator or temperature sensor as desired. The charge storage device can be a rechargeable lithium ion battery in an electric vehicle, or in a portable electronic device such as a cellular phone or smartphone, laptop, netbook, ebook reader, iPad or Android tablet, etc.

(47) The metal oxide particles can be also coated with additional material layers such as graphite, graphene, another metal oxide (e.g., titanium dioxide) or with metal layer such as silver, nickel, copper or their oxides or gold, platinum and palladium.

(48) The metal oxide may be blended or compounded in various ratios to polymer resins such as siloxanes, acrylates, epoxies, urethanes but not limited to these. Metal oxide containing resin may then be extruded or coated to function as electromagnetic absorber or antibacterial surface. For the antibacterial surface application it is also beneficial that the resin material is porous or partially porous.

(49) Embodiments are further illustrated by the following non-limiting examples.

EXAMPLES

Comparative Example 1

(50) An electrolyte based on MnSO.sub.4.H.sub.2O (0.43 g, 2.5 mmol) and sulphuric acid (0.25 g, 2.6 mmol) in 249.32 g deionized water was prepared in a 300 ml beaker. Two stainless steel plates (width 50 mm, thickness 1 mm) were immersed in the electrolyte to a depth of 50 mm. The stainless steel plates were connected to a potentiostat and a pulsed current was applied for synthesis of MnO.sub.2 particles. The forward pulse voltage and current were 14.97V and 0.67 A, while the same for the reverse 9.97V and 0.88 A. No formation of particles or films or either electrode was observed. Comparative example 2. The experiment in comparative example 1 was repeated by replacing the stainless steel anode with an aluminum sheet of equivalent size (width 50 mm, thickness 1 mm, immersed to 50 mm). The forward pulse voltage and current were 14.96V and 0.08 A, while the same for the reverse 9.97V and 0.67 A. No formation of particles or films or either electrode was observed.

Example 1

(51) The experiment in comparative example 1 was repeated by replacing the stainless steel anode with a lead sheet of approximately equivalent size (width 50 mm, thickness 1 mm, immersed to 50 mm). The forward pulse voltage and current were 14.96V and 0.59 A, while the same for the reverse 9.97V and 0.93 A. The synthesis was carried out for 5 min and the initially clear and colorless solution obtained a dark color due to the formation of solid particles in the solution. The particles settled to the bottom of the vessel they were stored in two days. The clear electrolyte was decanted from the particles and then the particles were re-dispersed into deionized water, allowed to settle, collected and dried. SEM images confirmed that submicron particles were obtained.

Example 2

(52) The experiment in Example 1 was repeated using an electrolyte based on MnSO.sub.4.H.sub.2O (1.29 g, 7.6 mmol) and sulphuric acid (0.75 g, 7.7 mmol) in 247.96 g deionized water. The forward pulse voltage and current were 9.98V and 0.84 A, while the same for the reverse 4.98V and 1.01 A. The synthesis was carried out for 7 min and the initially clear and colorless solution obtained a dark color due to the formation of solid particles in the solution. The particles settled to the bottom of the vessel they were stored in two days. The clear electrolyte was decanted from the particles and then the particles were re-dispersed into deionized water, allowed to settle, collected and dried. According to SEM images the particles were sub-micron sized.

Example 3

(53) The experiment in Example 1 was repeated using an electrolyte based on MnSO.sub.4.H.sub.2O (1.29 g, 7.6 mmol) and sulphuric acid (0.75 g, 7.7 mmol) in 247.96 g deionized water. The forward pulse voltage and current were 6.98V and 1.01 A, while the same for the reverse 1.98V and 1.18 A. The synthesis was carried out for 15 min and the particles were collected as previously. According to the SEM images (cf. FIG. 3) the particles were sub-micron sized.

Example 4

(54) The experiment in Example 2 was repeated using electrodes of size 256 cm.sup.2. The forward pulse voltage and current were 11.983V and 8.03 A, while the same for the reverse 8.96V and 9.83 A. The synthesis was carried out for 2 hours and the particles were collected as previously. According to SEM images the particles were sub-micron sized showing that the process is scalable. XRD of the materials confirmed that the material was crystalline (FIG. 4)

Example 5

(55) The experiment in Example 2 was repeated using an electrolyte based on MnSO.sub.4.H.sub.2O (2.6 g, 15.2 mmol) and sulphuric acid (1.5 g, 15.4 mmol) in 245.9 g deionized water. The forward pulse voltage and current were 4.69V and 1.01 A, while the same for the reverse 2.48V and 2.11 A. The initially clear and colorless solution obtained a dark color which turned clear after 1 h. A solid precipitate was found at the bottom of the electrolytic cell have particles with larger size than in Example 2.

Example 6

(56) The experiment in Example 5 was repeated using a forward pulse voltage and current were 9.49V and 3.13 A, while the same for the reverse 12.47V and 6.52 A. The initially clear and colorless solution very rapidly obtained a dark color. According to SEM images the particles were sub-micron sized showing that the process can be accelerated by increase of current.

Example 7

(57) The MnO.sub.2 nanoparticles of the Example 1 were coated with silver by mixing the powder with silver nitrate in ethanol and stirring the solution vigorously for 4 hours at room temperature. The silver coated particles were separated and dried. The silver coated MnO.sub.2 powder was then calcinated at elevated temperature. Alternatively MnO.sub.2 particles can be treated first with SnCl.sub.2 or SnCl.sub.2/PdCl.sub.2 treatment sequence prior silver nitrate treatment process.

REFERENCE SIGNS LIST

(58) 101=cathode, 102=anode 103=optional ultrasonic pulsator 104=potentiostat 105=electrolyte

CITATION LIST

Patent Literature

(59) D1 US2013199673 D2 CN 102243373 D3 US2012093680 D4 WO0027754