CN111244451B - Magnesium ion battery negative electrode material, magnesium ion battery and preparation method thereof - Google Patents
Magnesium ion battery negative electrode material, magnesium ion battery and preparation method thereof Download PDFInfo
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- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 title claims abstract description 79
- 229910001425 magnesium ion Inorganic materials 0.000 title claims abstract description 79
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000007773 negative electrode material Substances 0.000 title claims abstract description 21
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 93
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 81
- 239000003792 electrolyte Substances 0.000 claims abstract description 68
- 229910009523 YCl3 Inorganic materials 0.000 claims abstract description 25
- 230000007547 defect Effects 0.000 claims abstract description 21
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims abstract description 20
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000010406 cathode material Substances 0.000 claims abstract description 12
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 5
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 13
- 239000006185 dispersion Substances 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 9
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 9
- PCMOZDDGXKIOLL-UHFFFAOYSA-K yttrium chloride Chemical compound [Cl-].[Cl-].[Cl-].[Y+3] PCMOZDDGXKIOLL-UHFFFAOYSA-K 0.000 claims description 9
- 239000002608 ionic liquid Substances 0.000 claims description 8
- -1 N-butylpyridinium bistrifluoromethylsulfonic acid Chemical compound 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 6
- 238000001237 Raman spectrum Methods 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims 2
- 230000001351 cycling effect Effects 0.000 abstract description 10
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium chloride Substances Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 abstract description 6
- 230000010287 polarization Effects 0.000 abstract description 2
- 239000002000 Electrolyte additive Substances 0.000 abstract 1
- 239000011777 magnesium Substances 0.000 description 16
- 238000006722 reduction reaction Methods 0.000 description 13
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 9
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 7
- 239000003365 glass fiber Substances 0.000 description 6
- 229910052749 magnesium Inorganic materials 0.000 description 5
- 238000009830 intercalation Methods 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 230000002687 intercalation Effects 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000002161 passivation Methods 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- 229910019436 Mg(PF6)2 Inorganic materials 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000005486 organic electrolyte Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910014033 C-OH Inorganic materials 0.000 description 1
- 229910014570 C—OH Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910017916 MgMn Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- IWCVDCOJSPWGRW-UHFFFAOYSA-M magnesium;benzene;chloride Chemical compound [Mg+2].[Cl-].C1=CC=[C-]C=C1 IWCVDCOJSPWGRW-UHFFFAOYSA-M 0.000 description 1
- WYPTZCBYSQFOQS-UHFFFAOYSA-N magnesium;bis(trimethylsilyl)azanide Chemical compound [Mg+2].C[Si](C)(C)[N-][Si](C)(C)C.C[Si](C)(C)[N-][Si](C)(C)C WYPTZCBYSQFOQS-UHFFFAOYSA-N 0.000 description 1
- SCEZYJKGDJPHQO-UHFFFAOYSA-M magnesium;methanidylbenzene;chloride Chemical compound [Mg+2].[Cl-].[CH2-]C1=CC=CC=C1 SCEZYJKGDJPHQO-UHFFFAOYSA-M 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000007614 solvation Methods 0.000 description 1
- 230000007847 structural defect Effects 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
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- 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
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
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Abstract
The invention discloses a magnesium ion battery cathode material which is defect-rich reduced graphene oxide obtained by reducing graphene oxide with a reducing agent hydrazine hydrate. The invention also discloses a magnesium ion battery and a preparation method thereof, and the magnesium ion battery comprises a positive electrode, a negative electrode, a diaphragm and electrolyte, wherein the negative electrode comprises a current collector and reduced graphene oxide attached to the current collector, and the electrolyte is MgCl2‑YCl3And (3) an electrolyte. In the magnesium ion battery of the present invention, YCl is used3As electrolyte additive to replace common AlCl3Can avoid Al3+With Mg2+The problem of co-deposition, lowering the polarization electrode potential; on the other hand, by adopting the reduced graphene oxide as a negative electrode material, the defect-rich reduced graphene oxide can adsorb more magnesium ions and MgCl2‑YCl3The base electrolyte has good matching property, and the magnesium ion battery assembled by matching the base electrolyte and the electrolyte has excellent electrochemical cycling stability and rate capability.
Description
Technical Field
The invention belongs to the technical field of secondary batteries, and particularly relates to a magnesium ion battery cathode material and a preparation method thereof, and also relates to a magnesium ion battery and a preparation method thereof.
Background
With the annual shortage of global fossil resources and the increased environmental pollution caused by the use of the fossil resources, the demand of people for green energy is increased. Electrochemical energy storage systems, especially rechargeable batteries, are becoming increasingly important. As is well known, a Lithium Ion Battery (LIB) has been widely used in portable electronic products and electric vehicles. However, the challenges of lithium raw material resource shortage, maldistribution, high cost, etc. limit the large-scale sustainable application of LIB.
The rechargeable magnesium ion battery has low cost, safe operation and theoretical volume capacity (3832mAh cm)-3) The lithium ion battery has the advantages of high grade, is widely concerned, and can be used as a substitute of the lithium ion battery. However, since the positive and negative electrodes and the electrolyte develop slowly, mayRechargeable magnesium ion batteries are still in the initial stage of research and development. To date, many researchers have focused on the development of electrolytes and positive electrodes, with fewer solutions being proposed for negative electrodes of magnesium ion batteries. At present, in Mg (TFSI)2、Mg(PF6)2、Mg(HMDS)2In the organic electrolyte system, the commonly used magnesium metal negative electrode forms a 'passivation layer' at the interface, and the formation of the passivation layer prevents the reversible plating/stripping of magnesium ions, and directly influences the cycle life and the performance of the rechargeable magnesium ion battery.
In order to solve the problem of "passivation layer" of the magnesium metal/electrolyte interface, researchers have studied various strategies for using metal or alloy type negative electrode materials such as tin (Sn), bismuth (Bi), antimony (Sb), indium (In), and lead (Pb). However, these metal or alloy type negative electrode materials have serious problems of volume expansion and pulverization during alloying/dealloying with magnesium, which are very disadvantageous in cycle stability of a battery and in battery life. Some researchers have tried graphite or high temperature pyrolytic graphite (HOPG) as a negative electrode material of a magnesium ion battery, but it was found that the intercalation of magnesium ions into graphite in the existing electrolytes is irreversible, and even though the intercalation of magnesium ions into HOPG in some electrolytes is electrochemically reversible, due to the high charge density of magnesium ions, the intercalation of magnesium ions into HOPG is very easy to occur with the solvation of surrounding solvent molecules to cause the co-intercalation of solvent and magnesium ions, resulting in poor overall capacity and short cycle life of the battery. Graphene, as a unique two-dimensional carbon material, has excellent electronic conductivity, chemical stability and large specific surface area, and shows excellent performance in an energy storage system, but the graphene is only rarely reported to be directly used as a magnesium ion battery cathode material. Manually prepared graphene inevitably has various structural defects based on the limitations of various preparation methods, and the defects affect the physical and chemical properties of the graphene, but high-quality graphene is often complex in preparation method, low in yield and high in cost.
In the electrolyte method, Mg (TFSI) is generally used2、Mg(PF6)2、Mg(HMDS)2When the organic electrolyte system decomposes on the magnesium metal surface, the magnesium ions are blockedTo solve the problems, it is proposed to use an inorganic electrolyte MgCl in a magnesium ion battery2-AlCl3But due to the electrode potential of Al (Al)(vs.SHE)-1.66V) reduction electrode potential (Mg) compared to Mg(vs.SHE)-2.37V) is high, Al and Mg co-deposit during the magnesium deposition process, affecting the overall electrochemical performance of the cell.
Disclosure of Invention
In view of the defects in the prior art, the invention provides a magnesium ion battery cathode material, a corresponding magnesium battery and a preparation method thereof, wherein the cathode material has good matching property with electrolyte, and the magnesium ion battery assembled by matching has excellent electrochemical cycling stability and rate capability.
In order to realize the purpose of the invention, the invention adopts the following technical scheme:
the magnesium ion battery negative electrode material is reduced graphene oxide rich in defects, wherein the reduced graphene oxide rich in defects is obtained by reducing graphene oxide with a reducing agent hydrazine hydrate, and the intensity ratio of a D peak to a G peak of a Raman spectrum of the reduced graphene oxide rich in defects is 1-1.5.
The preparation method of the magnesium ion battery anode material comprises the following steps:
s11, preparing graphene oxide by adopting an improved Hummers method;
s12, preparing the prepared graphene oxide into a solution with the concentration of 0.2-0.6 mg/mL, adding hydrazine hydrate, stirring and mixing, reducing at the temperature of 80-100 ℃ for 20 min-1 h to prepare reduced graphene oxide, and using the reduced graphene oxide as a magnesium ion battery cathode material.
Another aspect of the present invention is to provide a magnesium ion battery, comprising a positive electrode, a negative electrode, a separator and an electrolyte, wherein the negative electrode comprises a current collector and the negative electrode material attached to the current collector, and the electrolyte is MgCl2-YCl3And (3) an electrolyte.
Wherein the current collector is carbon paper or carbon film.
The electrolyte also comprises N-butylpyridine bistrifluoromethylsulfonic acid ionic liquid and diethylene glycol dimethyl ether.
Wherein, in the electrolyte, MgCl2And YCl3In a molar ratio of 1: 2.
The preparation method of the magnesium ion battery comprises the following steps:
preparation of negative electrode: adding the dispersion liquid of the magnesium ion battery negative electrode material onto a current collector and drying to prepare a negative electrode;
preparing an electrolyte: adding magnesium chloride and yttrium trichloride into N-butylpyridinium bistrifluoromethylsulfonic acid ionic liquid, adding diethylene glycol dimethyl ether to coordinate with magnesium ions, and preparing the product based on MgCl2-YCl3An electrolyte;
providing a positive electrode and a separator, and assembling the positive electrode, the negative electrode, the separator and the electrolyte to obtain the magnesium-ion battery.
Specifically, the preparation of the negative electrode comprises the following steps:
s11, preparing graphene oxide by adopting an improved Hummers method;
s12, preparing the prepared graphene oxide into a solution with the concentration of 0.2-0.6 mg/mL, adding hydrazine hydrate, stirring and mixing, and reducing at the temperature of 80-100 ℃ for 20 min-1 h to prepare reduced graphene oxide; the mass ratio of the graphene oxide to the hydrazine hydrate is 10: 8-10: 10;
s13, dissolving the reduced graphene oxide in absolute ethyl alcohol to obtain a dispersion liquid;
and S14, providing a current collector, dripping the dispersion liquid on the current collector and drying to prepare and obtain a negative electrode.
Specifically, the preparation of the electrolyte comprises the following steps:
s21, adding magnesium chloride and yttrium trichloride into N-butylpyridinebis-trifluoromethanesulfonic acid ionic liquid, heating and stirring at 120-160 ℃ for 12-24 h, and cooling to form a first solution;
s22, adding diethylene glycol dimethyl ether into the first solution to coordinate with magnesium ions to prepare and obtain the MgCl-based catalyst2-YCl3An electrolyte of the solution.
Wherein, in the step S21, the molar ratio of the magnesium chloride to the yttrium trichloride is 1: 2.
In the magnesium ion battery provided by the embodiment of the invention, the defect-rich reduced graphene oxide obtained by reducing graphene oxide with hydrazine hydrate serving as the negative electrode material of the magnesium ion battery, the negative electrode material and MgCl2-YCl3The base electrolyte has good matching performance, so that the magnesium ion battery obtained by assembling comprises the following components: in one aspect, MgCl2-YCl3The electrolyte can avoid the conventional AlCl-containing AlCl of the magnesium ion battery3Al in electrolyte3+With Mg2+The problem of co-deposition, lowering the polarization electrode potential; on the other hand, reduced graphene oxide is used as a negative electrode material, a large number of defect sites in the reduced graphene oxide rich in defects can adsorb more magnesium ions, and the electrode structure can keep stable in structure in the electrochemical cycle process; therefore, the magnesium ion battery assembled by matching the two has excellent electrochemical cycling stability and rate capability. In addition, the low-cost high-activity defect-rich graphene is used for magnesium ion battery cathode materials and corresponding magnesium ion batteries, and the defect is changed into 'waste' into valuable.
Drawings
Fig. 1 is a scanning electron micrograph of graphene oxide before and after reduction in example 1 of the present invention;
FIG. 2 is a graph comparing infrared spectra of graphene oxide before and after reduction in example 1 of the present invention;
FIG. 3 is a graph comparing the X-ray diffraction patterns of graphene oxide before and after reduction in example 1 of the present invention;
FIG. 4 is a comparison graph of Raman spectra of graphene oxide before and after reduction in example 1 of the present invention;
FIG. 5 shows a sample cell 1 at 175mA g in example 3 of the present invention-1A charge-discharge curve diagram under the current density of (a);
FIG. 6 shows a first set of samples at 175 of a battery according to example 3 of the present inventionmA g-1A battery cycle test chart at a current density of (a);
FIG. 7 shows a sample of a second group of cells at 105mA g in example 3 of the present invention-1A battery cycle test chart at the current density of (a);
FIG. 8 is a graph of cell cycling at different current densities for a second set of cell samples according to example 3 of the present invention;
FIG. 9 shows a sample of a second group of cells at 350mA g in example 3 of the present invention-1Current density of (a).
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, embodiments of the present invention are described in detail below with reference to the accompanying drawings. Examples of these preferred embodiments are illustrated in the accompanying drawings. The embodiments of the invention shown in the drawings and described in accordance with the drawings are exemplary only, and the invention is not limited to these embodiments.
It should be noted that, in order to avoid obscuring the present invention with unnecessary details, only the structures and/or processing steps closely related to the scheme according to the present invention are shown in the drawings, and other details not so relevant to the present invention are omitted.
The embodiment of the invention firstly provides a magnesium ion battery cathode material, wherein the magnesium ion battery cathode material is reduced graphene oxide which is obtained by reducing graphene oxide by a reducing agent hydrazine hydrate and is rich in defects; the defect-rich in the present invention refers to the intensity ratio (I) of the D peak to the G peak in the raman spectrum of reduced graphene oxideD/IG) Is in the range of 1 to 1.5. The preparation method comprises the following steps:
s11, preparing graphene oxide by adopting an improved Hummers method;
s12, preparing the prepared graphene oxide into a solution with the concentration of 0.2-0.6 mg/mL, adding hydrazine hydrate, stirring and mixing, reducing at the temperature of 80-100 ℃ for 20 min-1 h to prepare reduced graphene oxide, and using the reduced graphene oxide as a magnesium ion battery cathode material.
In the step S12, the mass ratio of the graphene oxide to the hydrazine hydrate is preferably 10:8 to 10: 10.
The embodiment of the invention firstly provides a magnesium ion battery, which comprises a positive electrode, a negative electrode, a diaphragm and electrolyte, wherein the negative electrode comprises a current collector and a negative electrode material (namely, reduced graphene oxide in the above embodiment) attached to the current collector, and the electrolyte is MgCl2-YCl3And (3) an electrolyte.
Specifically, the preparation of the negative electrode comprises the following steps:
reduced graphene oxide was prepared with reference to the above steps S11 and S12.
S13, dissolving the reduced graphene oxide in absolute ethyl alcohol to obtain a dispersion liquid.
And S14, providing a current collector, dripping the dispersion liquid on the current collector and drying to prepare and obtain a negative electrode. The current collector is carbon paper or a carbon film.
Specifically, the preparation of the electrolyte comprises the following steps:
s21, adding magnesium chloride and yttrium trichloride into N-butylpyridinium bistrifluoromethylsulfonic acid ionic liquid, heating and stirring at 120-160 ℃ for 12-24 h, and cooling to form a first solution. In the step, the molar ratio of magnesium chloride to yttrium trichloride is 1: 2.
S22, adding diethylene glycol dimethyl ether into the first solution to coordinate with magnesium ions to prepare and obtain the MgCl-based catalyst2-YCl3An electrolyte of the solution.
The preparation method of the magnesium ion battery comprises the following steps: the negative electrode obtained by the above preparation and MgCl2-YCl3And assembling the electrolyte, the positive electrode and the diaphragm to prepare the magnesium ion battery. The positive electrode can be any magnesium-containing positive electrode material which is used in a magnesium ion battery and is known in the prior art, wherein the positive electrode material is MgMn for example2O4,Mg2Fe0.25MnO4,MgNi1/2Co1/10Mn1/5O2Etc.; the separator can be any one of the separators which are known in the prior art and applied to the magnesium-ion battery, such as a glass fiber membrane.
Example 1: negative electrode material and preparation of negative electrode
(1) Firstly, preparing Graphene Oxide (GO) by adopting an improved Hummers method.
(2) And then preparing the prepared Graphene Oxide (GO) into a 0.5mg/mL solution, adding hydrazine hydrate, stirring and mixing, and then reducing at a high temperature.
(3) And after the reduction reaction is finished, performing suction filtration and washing by using deionized water until the reaction is neutral, and drying in an oven to obtain the high-activity defect-rich reduced graphene oxide (rGO).
(4) And dissolving the reduced graphene oxide in absolute ethyl alcohol to obtain a dispersion liquid, dripping the dispersion liquid on the current collector and drying to prepare the negative electrode.
In the embodiment, three reduced graphene oxide samples rGO-1, rGO-2 and rGO-3 are prepared and obtained by adjusting the mass ratio of hydrazine hydrate to graphene oxide added in the step (2) and the reduction reaction time. Wherein,
rGO-1: the mass ratio of hydrazine hydrate to graphene oxide is 10: and 8, the temperature of the reduction reaction is 100 ℃, and the reaction time is 20 min.
rGO-2: the mass ratio of hydrazine hydrate to graphene oxide is 10: and 8, the temperature of the reduction reaction is 90 ℃, and the reaction time is 1 h.
rGO-3: the mass ratio of hydrazine hydrate to graphene oxide is 10:10, the temperature of the reduction reaction is 80 ℃, and the reaction time is 1 h.
FIG. 1 shows scanning electron micrographs of graphene oxide GO and reduced graphene oxide samples rGO-1, rGO-2 and rGO-3 in this example. As can be seen from fig. 1, the reduced samples (rGO-1, rGO-2 and rGO-3) become rough in surface, more wrinkled and exposed edges, and are reduced graphene oxide rich in defects, compared to the sample before reduction (GO); wherein when the mass ratio of hydrazine hydrate to graphene oxide is 10: 8. when the reduction time is 1h, the exposed edge of the reduced graphene oxide sample rGO-2 is the most, and the defect is the most.
FIG. 2 shows a comparison graph of IR spectra of graphene oxide GO and reduced graphene oxide rGO (specifically sample rGO-2) in this example, wherein 1728cm-1Corresponding to C ═ O, 1262cm-1Corresponding to C-OH, 1065cm-1Corresponding to C-O, it can be seen from FIG. 2 that the oxygen-containing functional groups of the reduced sample substantially disappeared.
Fig. 3 shows the X-ray diffraction contrast of graphene oxide GO and reduced graphene oxide rGO (specifically sample rGO-2) in this example, and it can be seen from the diffraction peak positions that the interlayer distance of the reduced sample is significantly reduced due to the reduction of the oxygen-containing functional groups.
FIG. 4 shows a comparison of Raman spectra of graphene oxide GO and reduced graphene oxide rGO (specifically sample rGO-2) in this example, from ID/IGThe numerical value can be seen, and the defect degree of the reduced sample is higher.
In this example, two kinds of electrodes were prepared with reference to the above step (4): one method is to select a reduced graphene oxide sample rGO-2 as a negative electrode material, drop the dispersion liquid of the reduced graphene oxide sample rGO-2 onto carbon paper and dry the carbon paper to prepare and obtain a negative electrode, which is hereinafter referred to as negative electrode rGO. And another electrode is used for comparison, graphene oxide GO is selected as a negative electrode material, the dispersion liquid of the graphene oxide GO is dripped on carbon paper and dried, and a negative electrode is prepared and obtained and is marked as the negative electrode GO hereinafter.
Example 2: preparation of the electrolyte
(1) 19mg of magnesium chloride (MgCl)2) And 78mg of yttrium trichloride (YCl)3) Adding the mixture into 0.8mL of N-butylpyridinium bistrifluoromethylsulfonic acid ionic liquid, heating and stirring the mixture for 24h at 160 ℃, and then cooling the mixture to room temperature to form a first solution.
(2) Adding 1.5mL of diethylene glycol dimethyl ether into the first solution to coordinate with magnesium ions to prepare the MgCl-based catalyst2-YCl3Electrolyte of solution, hereinafter denoted as MgCl2-YCl3And (3) an electrolyte.
In comparison, two other electrolytes commonly used in magnesium ion batteries were also prepared in this example:
the first method comprises the following steps: 0.533g of aluminum trichloride (AlCl)3) The resulting solution was slowly added to 6mL of Tetrahydrofuran (THF), stirred to dissolve, and then 4mL of a benzylmagnesium chloride solution (2M PhMgCl in THF) was slowly added dropwise to the solution, and stirred at room temperature for 24 hours to prepare a PhMgCl-THF solution, hereinafter referred to as PhMgCl-THF electrolyte.
And the second method comprises the following steps: 517.6mg of magnesium bis (hexamethyldisilazide) (Mg (HMDS))2) Stirring with 3mL of diethylene glycol dimethyl ether at 140 ℃ for 1h, cooling the solution to room temperature, and adding 400mg of AlCl in small amount for many times3Stirring overnight at 90 ℃ to obtain Mg (HMDS)2-AlCl3Solution, hereinafter referred to as Mg (HMDS)2-AlCl3And (3) an electrolyte.
Example 3: electrochemical testing of magnesium ion batteries
In the present example, the negative electrode and the electrolyte prepared above were assembled to form a magnesium-ion half cell, and the electrochemical performance test was performed.
Specifically, the negative electrode prepared in example 1 was used as a working electrode, the electrolyte prepared in example 2 was used as an electrolyte, a glass fiber membrane was used as a separator, magnesium metal was used as a counter electrode, and a 2025 type battery case was used to assemble a button cell sample for electrochemical performance testing.
Battery sample 1: the working electrode adopts the electrode rGO prepared in example 1, and the electrolyte adopts MgCl prepared in example 22-YCl3Electrolyte, counter electrode is magnesium metal, and the diaphragm is made of glass fiber film.
Battery sample 2: the working electrode adopts the electrode rGO prepared in the embodiment 1, the electrolyte adopts the PhMgCl-THF electrolyte prepared in the embodiment 2, the counter electrode is magnesium metal, and the diaphragm adopts a glass fiber membrane.
Battery sample 3: working electrode employed was electrode rGO prepared in example 1 and electrolyte Mg (HMDS) prepared in example 22-AlCl3Electrolyte, counter electrode is magnesium metal, and the diaphragm is made of glass fiber film.
Battery sample 4: working electrode prepared according to example 1Electrode GO obtained, electrolyte MgCl obtained using the preparation of example 22-YCl3Electrolyte, counter electrode is magnesium metal, and the diaphragm is a glass fiber film.
FIG. 5 shows cell sample 1 at 175mA g-1A charge-discharge curve diagram at a current density of (a). It can be seen from the charge-discharge curve of fig. 5 that the discharge voltage plateau of the electrode rGO is below 0.5V, and the voltage plateau is low, and is a good negative electrode material of a magnesium ion battery. Meanwhile, the charging and discharging curves with different cycle numbers have better overlapping performance, which shows that the cycling stability of the electrode rGO is good.
FIG. 6 shows that the first set of cell samples ( cell samples 1, 2 and 3) was at 175mA g-1Current density of (a). As can be seen from FIG. 6, the electrodes rGO and MgCl provided by the present invention2-YCl3The battery assembled by matching the electrolyte has higher specific capacity and better cycling stability.
FIG. 7 shows the second set of cell samples (cell samples 1 and 4) at 105mA g-1Current density of (a). As can be seen from FIG. 7, the electrodes rGO and MgCl provided by the present invention2-YCl3The specific capacity of the battery assembled by matching the electrolyte is higher.
FIG. 8 is a graph of cell cycling for a second set of cell samples (cell samples 1 and 4) at different current densities, where the numbers on the curve correspond to the current densities in mA g-1. As can be seen from FIG. 8, the electrodes rGO and MgCl provided by the present invention2-YCl3The battery assembled by matching the electrolyte has higher specific capacity and better cycling stability.
FIG. 9 shows the second set of cell samples (cell samples 1 and 4) at 350mA g-1Current density of (a). As can be seen from FIG. 9, the electrodes rGO and MgCl provided by the present invention2-YCl3The battery assembled by matching the electrolyte has higher specific capacity, better cycling stability and longer cycle life.
As can be understood from the above FIGS. 6 to 9, in the present invention, the electrodes rGO and MgCl2-YCl3The base electrolyte has good matching performance, and the assembled magnesium ion battery is 105mA g-1The capacity of the capacitor reaches 277mAh g under the current density-1(ii) a At 350mA g-1Has a capacity of 242mAh g at a current density of-1And the capacity is still unchanged after 600 times of charging and discharging, and the high cycle stability is achieved; and has excellent rate capability of 35mA g-1Under the condition, the capacity is as high as 334mAh g-1Even if the current density is increased to 1050mA g-1The battery capacity still has 228mAh g-1Of the battery.
In summary, in the embodiments of the present invention, the defect-rich reduced graphene oxide obtained by reducing graphene oxide with a reducing agent hydrazine hydrate is used as a negative electrode material of a magnesium ion battery, and MgCl2-YCl3The base electrolyte has good matching property, and the magnesium ion battery assembled by matching the base electrolyte and the electrolyte has excellent electrochemical cycling stability and rate capability.
The foregoing is directed to embodiments of the present application and it is noted that numerous modifications and adaptations may be made by those skilled in the art without departing from the principles of the present application and are intended to be within the scope of the present application.
Claims (8)
1. The magnesium ion battery comprises a positive electrode, a negative electrode, a diaphragm and electrolyte, and is characterized in that the negative electrode comprises a current collector and a magnesium ion battery negative electrode material attached to the current collector, and the electrolyte is MgCl2-YCl3An electrolyte;
the magnesium ion battery cathode material is reduced by graphene oxide through a reducing agent hydrazine hydrate to obtain defect-rich reduced graphene oxide, and the intensity ratio of a D peak to a G peak of a Raman spectrum of the defect-rich reduced graphene oxide is 1-1.5;
the preparation method of the magnesium ion battery negative electrode material comprises the following steps:
s11, preparing graphene oxide by adopting an improved Hummers method;
s12, preparing the prepared graphene oxide into a solution with the concentration of 0.2-0.6 mg/mL, adding hydrazine hydrate, stirring, mixing, reducing at 80-100 ℃ for 20 min-1 h to obtain reduced graphene oxide, and using the reduced graphene oxide as a magnesium ion battery cathode material.
2. The magnesium-ion battery of claim 1, wherein the current collector is a carbon paper or a carbon film.
3. The magnesium-ion battery of claim 1, wherein the electrolyte further comprises N-butylpyridinium bistrifluoromethylsulfonic acid ionic liquid and diethylene glycol dimethyl ether.
4. The magnesium-ion battery of claim 3, wherein in the electrolyte, MgCl is present2And YCl3In a molar ratio of 1: 2.
5. A method of making a magnesium-ion battery according to any of claims 1-4, comprising:
preparation of negative electrode: adding the dispersion liquid of the magnesium ion battery negative electrode material onto a current collector and drying to prepare a negative electrode;
preparing an electrolyte: adding magnesium chloride and yttrium trichloride into N-butylpyridinium bistrifluoromethylsulfonic acid ionic liquid, adding diethylene glycol dimethyl ether to coordinate with magnesium ions, and preparing the product based on MgCl2-YCl3An electrolyte;
providing a positive electrode and a separator, and assembling the positive electrode, the negative electrode, the separator and the electrolyte to obtain the magnesium-ion battery.
6. The method of manufacturing a magnesium-ion battery according to claim 5, wherein the preparation of the negative electrode comprises the steps of:
s11, preparing graphene oxide by adopting an improved Hummers method;
s12, preparing the prepared graphene oxide into a solution with the concentration of 0.2-0.6 mg/mL, adding hydrazine hydrate, stirring and mixing, and reducing at the temperature of 80-100 ℃ for 20 min-1 h to prepare reduced graphene oxide; the mass ratio of the graphene oxide to the hydrazine hydrate is 10: 8-10: 10;
s13, dissolving the reduced graphene oxide in absolute ethyl alcohol to obtain a dispersion liquid;
and S14, providing a current collector, dripping the dispersion liquid on the current collector and drying to prepare and obtain a negative electrode.
7. The method for preparing a magnesium-ion battery according to claim 5, wherein the preparation of the electrolyte comprises the steps of:
s21, adding magnesium chloride and yttrium trichloride into N-butylpyridine bis-trifluoromethylsulfonic acid ionic liquid, heating and stirring at 120-160 ℃ for 12-24 h, and cooling to form a first solution;
s22, adding diethylene glycol dimethyl ether into the first solution to coordinate with magnesium ions to prepare and obtain the MgCl-based catalyst2-YCl3An electrolyte of the solution.
8. The method of claim 7, wherein in step S21, the molar ratio of magnesium chloride to yttrium trichloride is 1: 2.
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