CN112467118B - Graphite composite material, preparation method thereof and lithium battery cathode - Google Patents
Graphite composite material, preparation method thereof and lithium battery cathode Download PDFInfo
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- CN112467118B CN112467118B CN202011383819.2A CN202011383819A CN112467118B CN 112467118 B CN112467118 B CN 112467118B CN 202011383819 A CN202011383819 A CN 202011383819A CN 112467118 B CN112467118 B CN 112467118B
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 125
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 91
- 239000010439 graphite Substances 0.000 title claims abstract description 91
- 239000002131 composite material Substances 0.000 title claims abstract description 74
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000006258 conductive agent Substances 0.000 claims abstract description 39
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 33
- 239000007784 solid electrolyte Substances 0.000 claims abstract description 32
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 12
- 239000002243 precursor Substances 0.000 claims description 27
- 239000003792 electrolyte Substances 0.000 claims description 26
- 239000002904 solvent Substances 0.000 claims description 23
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 16
- 239000000654 additive Substances 0.000 claims description 16
- 230000000996 additive effect Effects 0.000 claims description 16
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- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 15
- 238000010000 carbonizing Methods 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 9
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 238000003763 carbonization Methods 0.000 claims description 9
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 229910021389 graphene Inorganic materials 0.000 claims description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 239000011149 active material Substances 0.000 claims description 6
- 239000002041 carbon nanotube Substances 0.000 claims description 6
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 6
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 claims description 6
- FVXHSJCDRRWIRE-UHFFFAOYSA-H P(=O)([O-])([O-])[O-].[Ge+2].[Al+3].[Li+].P(=O)([O-])([O-])[O-] Chemical compound P(=O)([O-])([O-])[O-].[Ge+2].[Al+3].[Li+].P(=O)([O-])([O-])[O-] FVXHSJCDRRWIRE-UHFFFAOYSA-H 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 4
- 239000002033 PVDF binder Substances 0.000 claims description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 4
- CVJYOKLQNGVTIS-UHFFFAOYSA-K aluminum;lithium;titanium(4+);phosphate Chemical compound [Li+].[Al+3].[Ti+4].[O-]P([O-])([O-])=O CVJYOKLQNGVTIS-UHFFFAOYSA-K 0.000 claims description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 3
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 3
- WVDJDYHWHDLSAZ-UHFFFAOYSA-N [O].[Ti].[La].[Li] Chemical compound [O].[Ti].[La].[Li] WVDJDYHWHDLSAZ-UHFFFAOYSA-N 0.000 claims description 3
- XRNHBMJMFUBOID-UHFFFAOYSA-N [O].[Zr].[La].[Li] Chemical compound [O].[Zr].[La].[Li] XRNHBMJMFUBOID-UHFFFAOYSA-N 0.000 claims description 3
- 239000011230 binding agent Substances 0.000 claims description 3
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- 239000008096 xylene Substances 0.000 claims description 3
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 2
- 239000004917 carbon fiber Substances 0.000 claims description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims 1
- 229920002125 Sokalan® Polymers 0.000 claims 1
- 239000001768 carboxy methyl cellulose Substances 0.000 claims 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims 1
- 239000004584 polyacrylic acid Substances 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 19
- 230000005540 biological transmission Effects 0.000 abstract description 6
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- 238000000227 grinding Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- -1 Polyethylene Polymers 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
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- 238000000576 coating method Methods 0.000 description 3
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- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910001290 LiPF6 Inorganic materials 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- NRJJZXGPUXHHTC-UHFFFAOYSA-N [Li+].[O--].[O--].[O--].[O--].[Zr+4].[La+3] Chemical compound [Li+].[O--].[O--].[O--].[O--].[Zr+4].[La+3] NRJJZXGPUXHHTC-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000002134 carbon nanofiber Substances 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- CEMTZIYRXLSOGI-UHFFFAOYSA-N lithium lanthanum(3+) oxygen(2-) titanium(4+) Chemical compound [Li+].[O--].[O--].[O--].[O--].[Ti+4].[La+3] CEMTZIYRXLSOGI-UHFFFAOYSA-N 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical group O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910001228 Li[Ni1/3Co1/3Mn1/3]O2 (NCM 111) Inorganic materials 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
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- 230000005611 electricity Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 229910021385 hard carbon Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
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Images
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Composite Materials (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The application relates to the field of battery materials, in particular to a graphite composite material, a preparation method thereof and a lithium battery cathode. The graphite composite material comprises: an inner core comprising graphite; and an outer shell, the outer shell being wrapped around the inner core, the outer shell comprising a pre-lithiated solid electrolyte, a conductive agent, and carbon. The solid electrolyte can improve the lithium ion transmission rate of the material, and the conductive agent can effectively solve the problem of poor electron conductivity of the solid electrolyte, so that the electron conductivity of the graphite composite material is improved; the solid electrolyte can cause lithium ion loss in the charging and discharging process, the pre-lithiation solid electrolyte can effectively avoid the problem, and in addition, the shell of the graphite composite material has the effect of an artificial SEI film. The application provides a graphite composite can effectively improve the first efficiency and the lithium ion conductivity of promotion material.
Description
Technical Field
The application relates to the field of battery materials, in particular to a graphite composite material, a preparation method thereof and a lithium battery cathode.
Background
The lithium ion battery generally uses graphite as a negative electrode, the theoretical specific capacity of the graphite is 372mAh/g, and the application requirements of the lithium ion power battery such as high capacity, high power, safety and stability cannot be met; at present, the multiplying power of the graphite material is improved mainly by coating soft carbon or hard carbon on the surface of graphite to improve the multiplying power and the safety performance of the material. However, the coating layer of this method is limited to increase the transmission rate and diffusion rate of lithium ions.
Disclosure of Invention
An object of the embodiments of the present application is to provide a graphite composite material, a preparation method thereof, and a lithium battery negative electrode, which aim to solve the problem of low transmission rate of existing graphite lithium ions.
A first aspect of the present application provides a graphite composite material comprising:
an inner core comprising graphite; and
and the shell is coated outside the inner core and comprises a pre-lithiated solid electrolyte, a conductive agent and carbon.
The solid electrolyte can improve the lithium ion transmission rate of the material, and the conductive agent can effectively solve the problem of poor electron conductivity of the solid electrolyte, so that the electron conductivity of the graphite composite material is improved; the solid electrolyte can cause lithium ion loss in the charging and discharging process, the pre-lithiation solid electrolyte can effectively avoid the problem, and in addition, the shell of the graphite composite material has the effect of an artificial SEI film. The application provides a graphite composite can effectively improve the first efficiency and the lithium ion conductivity of promotion material.
In some embodiments of the first aspect of the present application, the pre-lithiated solid electrolyte is selected from at least one of pre-lithiated lithium lanthanum zirconium oxygen, pre-lithiated lithium lanthanum titanium oxygen, pre-lithiated titanium aluminum lithium phosphate, and pre-lithiated germanium aluminum lithium phosphate;
optionally, the conductive agent is selected from at least one of conductive carbon black, carbon nanotubes, graphene, porous carbon, and conductive carbon fibers.
In some embodiments of the first aspect of the present application, the graphite composite material has a particle size of 10 to 18 μm.
In some embodiments of the first aspect of the present application, the mass ratio of the pre-lithiated solid electrolyte, the conductive agent, and the carbon is (10-30): (1-5): (1-5).
In a second aspect, the present application provides a method for preparing the graphite composite material, including:
mixing electrolyte, conductive agent, additive, graphite and solvent to obtain mixed solution, drying the mixed solution to remove the solvent, and then carbonizing and crushing to obtain a precursor;
and (3) contacting and pressurizing the precursor with lithium, adding the lithium battery electrolyte, and keeping the pressurized state for 12-72 h to obtain the graphite composite material.
In some embodiments of the second aspect of the present application, in the step of drying and carbonizing the mixed solution, the carbonizing temperature is 700 ℃ to 1000 ℃ and the carbonizing time is 24h to 72 h.
In some embodiments of the second aspect of the present application, the mass ratio of the electrolyte, the conductive agent, the additive and the solvent is (10-30): 1-5): 500.
in some embodiments of the second aspect of the present application, the mass ratio of the sum of the mass of the electrolyte, the conductive agent, the additive, and the solvent to the mass of the graphite is 100 (100 to 300).
In some embodiments of the second aspect of the present application, the solvent comprises at least one of N, N-dimethylformamide, N-dimethylacetamide, N-methyl-2-pyrrolidone, acetone, butanone, ethanol, propanol, isopropanol, butanol, toluene, xylene, methyl ethyl ketone, dimethyl sulfoxide, tetrahydrofuran, dioxane, acetonitrile, ethyl acetate, methyl formate, chloroform, dimethyl carbonate, and diethyl carbonate.
A third aspect of the present application provides a negative electrode for a lithium battery, the negative electrode for a lithium battery including a current collector and an active material disposed on the current collector; the active material comprises a graphite composite material as provided in the first aspect of the present application.
The lithium battery cathode provided by the embodiment of the application has all the advantages of the graphite composite material, and the first efficiency and the lithium ion conductivity of the material can be effectively improved.
Drawings
To more clearly illustrate the technical solutions of the embodiments of the present application, the drawings needed in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present application and therefore should not be considered as limiting the scope, and those skilled in the art can also obtain other related drawings based on the drawings without inventive efforts.
Fig. 1 shows an SEM image of the graphite composite material prepared in example 1.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present application clearer, the technical solutions of the embodiments of the present application will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The graphite composite material, the method for preparing the same, and the negative electrode for a lithium battery according to the examples of the present application will be specifically described below.
A graphite composite material comprises an inner core and an outer shell, wherein the outer shell is coated outside the inner core, and the inner core comprises graphite; the housing includes a pre-lithiated solid electrolyte, a conductive agent, and carbon.
Illustratively, the pre-lithiated solid electrolyte is selected from at least one of pre-lithiated lithium lanthanum zirconium oxide, pre-lithiated lithium lanthanum titanium oxide, pre-lithiated titanium aluminum lithium phosphate, and pre-lithiated germanium aluminum lithium phosphate.
Illustratively, the conductive agent is selected from at least one of carbon nanotubes, graphene, porous carbon, and vapor grown carbon fiber.
In some embodiments of the present application, the mass ratio of the pre-lithiated solid electrolyte, the conductive agent and the carbon is (10-30): (1-5): 1-5). For example, the mass ratio of the prelithiated solid electrolyte, the conductive agent, and the carbon may be 10: 1:1, 12: 2:1, 20: 5:1, 30: 5:2, 30: 1:5, 30: 5:5, and so on.
In some embodiments of the present application, the mass ratio of the sum of the mass of the electrolyte, the conductive agent, and the carbon to the solvent is (1-5): 100. the mass ratio of the sum of the mass of the electrolyte, the conductive agent, the carbon and the solvent to the mass of the graphite is 100 (100-300).
As an example, the mass ratio of graphite to shell may be 100: (0.5 to 5);
in some embodiments of the present application, the particle size of the graphite composite material is 10 to 18 μm. For example, the particle size of the graphite composite material may be 10 μm, 11 μm, 13 μm, 15 μm, 17 μm, or 18 μm, or the like.
In the examples of the present application, the pre-lithiated solid electrolyte, the conductive agent, and carbon are dispersed in carbon to constitute the outer shell; for example, at least a portion of the conductive agent is dispersed in at least a portion of the pre-lithiated solid electrolyte, the conductive agent is uniformly dispersed between the pre-lithiated solid electrolyte, and at least a portion of the pre-lithiated solid electrolyte and/or at least a portion of the conductive agent is in contact with the core.
The graphite composite material provided by the embodiment of the application has at least the following advantages:
the pre-lithiation solid electrolyte is used for carrying out surface coating modification on the graphite material, the solid electrolyte can improve the lithium ion transmission rate of the material, and the conductive agent can effectively solve the problem of poor electronic conductivity of the solid electrolyte, so that the electronic conductivity of the graphite composite material is improved; solid-state electrolyte can lead to the lithium ion loss at the charge-discharge in-process, and the lithiation solid-state electrolyte can effectively avoid this problem in advance, and the shell that carbon, lithiation solid-state electrolyte in advance, conductive agent constitute has the effect of artifical SEI membrane, and this rete has certain elasticity simultaneously, can restrain graphite composite's volume expansion to a certain extent, to sum up, the graphite composite that this application provided can effectively improve the first efficiency and the lithium ion conductivity of promotion material.
The application also provides a preparation method of the graphite composite material, which mainly comprises the following steps:
mixing electrolyte, conductive agent, additive, graphite and solvent to obtain a mixed solution, drying the mixed solution, carbonizing, and crushing to obtain a precursor.
And (3) contacting and pressurizing the precursor with lithium, adding the lithium battery electrolyte, and keeping the pressurized state for 12-72 h to obtain the graphite composite material.
Furthermore, in the process of preparing the precursor, the mass ratio of the electrolyte, the conductive agent and the additive can be (10-30): (1-5): 1-5); the mass ratio of the electrolyte to the graphite may be (0.4-4): 100.
the electrolyte is at least one of lithium lanthanum zirconium oxygen, lithium lanthanum titanium oxygen, lithium titanium aluminum phosphate and lithium germanium aluminum phosphate.
The main function of the solvent is to fully mix the electrolyte, the conductive agent and the additive, and the solvent can be volatilized and removed in the drying process. And the solvent does not react with the additive.
In some embodiments, the solvent comprises at least one of N, N dimethylformamide, N dimethylacetamide, N-methyl-2-pyrrolidone, acetone, butanone, ethanol, propanol, isopropanol, butanol, toluene, xylene, methyl ethyl ketone, dimethyl sulfoxide, tetrahydrofuran, dioxane, acetonitrile, ethyl acetate, methyl formate, chloroform, dimethyl carbonate, and diethyl carbonate.
As mentioned above, the additive is a binder, and at least one of polyvinylidene fluoride and polyethylene oxide can be selected. The conductive agent is selected from at least one of carbon nanotubes, graphene, porous carbon and vapor grown carbon fibers.
In some embodiments of the present application, in the step of mixing the electrolyte, the conductive agent, the additive, the graphite, and the solvent to obtain the mixed solution, the electrolyte, the conductive agent, the additive, and the solvent may be first mixed uniformly, and then mixed with the graphite to obtain the mixed solution, so that uniformity of the material may be increased.
And drying the mixed solution, carbonizing and crushing to obtain a precursor. In the carbonization process, the additive is carbonized, and in some embodiments, the mixed solution is dried by adopting a spray drying mode; it is understood that in other embodiments of the present application, other drying methods may be used, such as freeze drying.
In some embodiments, the carbonization conditions are as follows: the carbonization temperature is 700-1000 ℃, and the carbonization time is 24-72 h. For example, the carbonization temperature is 700 ℃, 740 ℃, 810 ℃, 870 ℃, 890 ℃, 900 ℃, 910 ℃, 940 ℃, 950 ℃, 990 ℃ or 1000 ℃ or the like; the carbonization time may be 24h, 30h, 37h, 43h, 57h, 67h, 70h, 72h, and the like.
And after the precursor is prepared, pre-lithiating the precursor, enabling the precursor to be in contact with lithium and pressurizing, adding a lithium battery electrolyte, and keeping the pressurizing state for 12-72 hours to obtain the graphite composite material.
In other words, the precursor and lithium are pressed together, and then the lithium battery electrolyte is added, so that the precursor and lithium are in a pressed state and are kept for 12-72 hours, and the graphite composite material is obtained. For example, the precursor is pressed on a lithium sheet, an electrolyte is dripped into the lithium sheet, and the lithium sheet is kept still for 12-72 hours under the action of pressure to obtain the graphite composite material.
The preparation method of the graphite composite material provided by the embodiment of the application is simple in process, the graphite composite material can be obtained, and the prepared graphite composite material can effectively improve the first efficiency of the material and the lithium ion conductivity.
The application also provides a lithium battery cathode, which comprises a current collector and an active material arranged on the current collector; the active material includes the graphite composite material described above.
The features and properties of the present application are described in further detail below with reference to examples.
Example 1
The embodiment provides a graphite composite material which is mainly prepared by the following steps:
1) 20g of lithium lanthanum zirconium oxide, 3g of carbon nanotubes, 3g of polyvinylidene fluoride and 858ml of N, N-dimethylformamide were mixed to prepare a precursor mixture.
2) Mixing 100g of precursor mixed solution and 200g of artificial graphite, spray-drying, grinding, carbonizing at 800 ℃ for 48h, and grinding to obtain a precursor;
3) and pressing 20g of the precursor on a lithium sheet by adopting the pressure of 2T, dropwise adding 100ml of electrolyte, and standing for 48 hours under the action of the pressure to obtain the graphite composite material.
The graphite composite material prepared in example 1 was subjected to SEM test, and fig. 1 shows an SEM image of the graphite composite material prepared in example 1; as can be seen from FIG. 1, the graphite composite material is granular, has a particle size of 10-20 μm, and has uniform and reasonable size distribution.
Example 2
The embodiment provides a graphite composite material which is mainly prepared by the following steps:
1) mixing 10g of lithium lanthanum titanium oxide, 1g of graphene conductive agent, 1g of polyethylene oxide and 1000ml of N, N-dimethylacetamide to prepare a precursor mixed solution;
2) mixing 100g of precursor mixed solution and 100g of artificial graphite, spray-drying, grinding, carbonizing at 700 ℃ for 72 hours, and grinding to obtain a precursor;
3) pressing 20g of the precursor on a lithium sheet by adopting the pressure of 2T, dropwise adding 100ml of electrolyte, and standing for 12h to obtain the graphite composite material.
Example 3
The embodiment provides a graphite composite material which is mainly prepared by the following steps:
1) 30g of lithium aluminum germanium phosphate, 5g of porous carbon, 5g of polyethylene oxide and 800ml of chloroform were mixed to prepare a precursor mixture.
2) And mixing 100g of precursor mixed solution and 300g of artificial graphite, spray-drying, crushing, carbonizing at 1000 ℃ for 24 hours, and crushing to obtain the precursor.
3) And pressing 20g of the precursor on a lithium sheet by adopting the pressure of 2T, dropwise adding 100ml of electrolyte, and carrying out 12h to obtain the graphite composite material.
Comparative example 1
The present comparative example provides a graphite composite material, prepared mainly by the steps of:
mixing 5g of carbon nano tube, 5g of polyvinylidene fluoride and 500ml of N, N-dimethylformamide solvent to prepare a precursor mixed solution, then uniformly mixing 200g of artificial graphite, spray-drying, crushing, carbonizing at 800 ℃ for 48h, and crushing to obtain the graphite composite material.
Test example 1
The graphite composites provided in examples 1-3 and comparative example 1 were assembled into button cells, respectively, and labeled: the button cell assembled from the graphite composite material of example 1 was labeled a1, the button cell assembled from the graphite composite material of example 2 was labeled a2, the button cell assembled from the graphite composite material of example 3 was labeled A3, and the button cell assembled from the graphite composite material of comparative example 1 was labeled B1.
The preparation method of the button cell comprises the following steps: and adding a binder, a conductive agent and a solvent into the graphite composite material, stirring and mixing uniformly for pulping, coating the obtained slurry on a copper foil, drying and rolling to obtain the button cell. The adhesive is LA132 adhesive, the conductive agent is SP, and the solvent is secondary distilled water; and the weight ratio of the graphite composite material, the conductive agent SP, the LA132 adhesive and the secondary distilled water is as follows: 95:1:4:220.
The simulated battery assembly is carried out in a glove box filled with argon by taking a metal lithium sheet as a counter electrode, taking a composite film of Polyethylene (PE), polypropylene (PP) and polyethylene propylene (PEP) as a diaphragm and taking LiPF6/EC + DEC (1:1) as electrolyte. Button cells A1, A2, A3 and B1 were respectively mounted on a Wuhan blue electricity CT2001A type battery tester, and charged at a rate of 0.1C, with a charge-discharge voltage range of 0.005V to 2.0V, and the measured first discharge capacity and first discharge efficiency were as shown in Table 1.
TABLE 1 Studies of the Properties of the graphite composites of examples 1-3 and comparative example 1
As can be seen from Table 1, the discharge capacities of the composite anode materials prepared in examples 1 to 3 were significantly higher than that of comparative example 1; the reason is that the surface of the graphite material is coated with the pre-lithiated solid electrolyte material with high lithium ion conductivity, so that the irreversible loss of the material is reduced, and the ion conductivity of the material is improved, thereby improving the first efficiency of the material; meanwhile, the electron conductivity of the material is improved by the conductive agents such as graphene and the like, so that the multiplying power performance of the material is improved.
Test example 2
The graphite composite materials provided in examples 1-3 and comparative example 1 were used as negative electrode materials, ternary material (LiNi1/3Co1/3Mn1/3O2) was used as a positive electrode, LiPF6 (solvent EC + DEC, volume ratio 1:1, concentration 1.3mol/L) was used as an electrolyte, and celegard2400 was used as a separator to prepare a 2Ah pouch battery.
Rate capability test
The charging and discharging voltage range is 2.8-4.2V, charging is carried out at 1.0C, 3.0C and 5.0C under the condition of 25 +/-3.0 ℃, and discharging is carried out at 1.0C; the constant current ratio and temperature of the battery were tested in different charging modes and the results are shown in table 2.
TABLE 2 Rate Properties of examples 1-3 and comparative example 1
As can be seen from table 2, the rate charging performance of the pouch batteries prepared from the graphite composite materials of examples 1 to 3 is significantly better than that of comparative example 1, and the charging time is shorter, which indicates that the graphite composite material of the present application has good quick charging performance. The battery needs lithium ion migration in the charging process, the surface of the graphite composite material of the embodiment contains a solid electrolyte with more lithium ions, convenience is provided for lithium ion insertion, the multiplying power performance of the battery is improved, meanwhile, the electronic conductivity of the graphene is improved, and the temperature rise of the graphene is reduced.
Cycle performance test
The following experiment was performed on the pouch batteries manufactured from the graphite composite materials of examples 1 to 3 and comparative example 1: the capacity retention rate was measured by sequentially performing 10, 300, and 500 cycles of charge and discharge with a charge and discharge current of 2C/2C and a voltage range of 2.8-4.2V, and the results are shown in Table 3.
TABLE 3 cyclability of the lithium ion batteries of examples 1-3 and comparative example 1
As can be seen from Table 3, the cycle performance of the lithium ion batteries prepared by using the graphite composite negative electrode materials obtained in examples 1-3 is obviously superior to that of the comparative examples at each stage. The fact that the solid electrolyte and the conductive agent are coated on the surface of the graphite proves that the transmission rate of lithium ions can be improved, and the cycle performance of the lithium ion battery is improved.
The above description is only a preferred embodiment of the present application and is not intended to limit the present application, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, improvement and the like made within the spirit and principle of the present application shall be included in the protection scope of the present application.
Claims (10)
1. A graphite composite material for a negative electrode of a lithium ion battery, the graphite composite material comprising:
an inner core comprising graphite; and
an outer shell encasing the inner core, the outer shell comprising a pre-lithiated solid electrolyte, a conductive agent, and carbon;
the pre-lithiated solid electrolyte is selected from at least one of pre-lithiated lithium lanthanum zirconium oxygen, pre-lithiated lithium lanthanum titanium oxygen, pre-lithiated titanium aluminum lithium phosphate and pre-lithiated germanium aluminum lithium phosphate.
2. The graphite composite material for a negative electrode of a lithium ion battery according to claim 1, wherein the conductive agent is at least one selected from the group consisting of conductive carbon black, carbon nanotubes, graphene, porous carbon, and conductive carbon fibers.
3. The graphite composite material for a negative electrode of a lithium ion battery according to claim 1, wherein the particle size of the graphite composite material is 10 to 18 μm.
4. The graphite composite material for the negative electrode of a lithium ion battery according to claim 1, wherein the mass ratio of the pre-lithiated solid electrolyte, the conductive agent and the carbon is (10-30): 1-5.
5. The method for preparing the graphite composite material for the negative electrode of the lithium ion battery according to any one of claims 1 to 4, characterized by comprising:
mixing a solid electrolyte, a conductive agent, an additive, graphite and a solvent to obtain a mixed solution, drying the mixed solution to remove the solvent, and then carbonizing and crushing to obtain a precursor;
and (3) contacting and pressurizing the precursor with lithium, adding lithium battery electrolyte, and keeping the pressurized state for 12-72 h to obtain the graphite composite material.
6. The method for producing a graphite composite material for a negative electrode of a lithium ion battery according to claim 5,
the carbonization conditions are as follows: the carbonization temperature is 700-1000 ℃, and the carbonization time is 24-72 h.
7. The preparation method of the graphite composite material for the negative electrode of the lithium ion battery as claimed in claim 5 or 6, wherein the mass ratio of the solid electrolyte, the conductive agent, the additive and the solvent is (10-30): 1-5): 500.
8. the method for producing a graphite composite material for a negative electrode of a lithium ion battery according to claim 5 or 6, wherein the mass ratio of the sum of the mass of the solid electrolyte, the conductive agent, the additive, and the solvent to the mass of the graphite is 100 (100 to 300).
9. The method for preparing a graphite composite material for a negative electrode of a lithium ion battery according to claim 5 or 6, wherein the solvent includes at least one of N, N-dimethylformamide, N-dimethylacetamide, N-methyl-2-pyrrolidone, acetone, methyl ethyl ketone, ethanol, propanol, isopropanol, butanol, toluene, xylene, methyl ethyl ketone, dimethyl sulfoxide, tetrahydrofuran, dioxane, acetonitrile, ethyl acetate, methyl formate, chloroform, dimethyl carbonate, and diethyl carbonate;
the additive is a binder;
the additive is at least one selected from polyvinylidene fluoride, polyethylene oxide, carboxymethyl cellulose and polyacrylic acid.
10. A negative electrode for a lithium battery, comprising a current collector and an active material disposed on the current collector; the active material comprises the graphite composite material for a negative electrode of a lithium ion battery according to any one of claims 1 to 4.
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| CN113555539A (en) * | 2021-07-15 | 2021-10-26 | 洛阳月星新能源科技有限公司 | A high-energy-density fast-charging graphite composite negative electrode material and preparation method thereof, and lithium ion battery |
| CN114122358A (en) * | 2021-11-10 | 2022-03-01 | 云南中晟新材料有限责任公司 | Quick-filling graphite composite material and preparation method thereof |
| CN114142011B (en) * | 2021-11-29 | 2023-06-16 | 蜂巢能源科技有限公司 | Hard carbon composite material and preparation method and application thereof |
| CN114497508A (en) * | 2022-01-29 | 2022-05-13 | 辽宁中宏能源新材料股份有限公司 | Power type artificial graphite composite material and preparation method thereof |
| CN114665082A (en) * | 2022-05-17 | 2022-06-24 | 湖南镕锂新材料科技有限公司 | Negative electrode material and preparation method and application thereof |
| CN115050932B (en) * | 2022-05-25 | 2024-08-09 | 贝特瑞新材料集团股份有限公司 | Composite negative electrode material, preparation method thereof and lithium ion battery |
| CN115117434B (en) * | 2022-07-22 | 2025-02-21 | 欣旺达电子股份有限公司 | Composite material and preparation method thereof, solid-state battery and electrical equipment |
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