CN108682828B - Preparation method of nitrogen-doped carbon-coated positive electrode material - Google Patents
Preparation method of nitrogen-doped carbon-coated positive electrode material Download PDFInfo
- Publication number
- CN108682828B CN108682828B CN201810592131.1A CN201810592131A CN108682828B CN 108682828 B CN108682828 B CN 108682828B CN 201810592131 A CN201810592131 A CN 201810592131A CN 108682828 B CN108682828 B CN 108682828B
- Authority
- CN
- China
- Prior art keywords
- nitrogen
- doped carbon
- organic acid
- modified graphene
- coated
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 165
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 87
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 26
- 150000007524 organic acids Chemical class 0.000 claims abstract description 53
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 41
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000000463 material Substances 0.000 claims abstract description 40
- 239000010405 anode material Substances 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 22
- 238000010438 heat treatment Methods 0.000 claims abstract description 21
- 238000000227 grinding Methods 0.000 claims abstract description 19
- 238000001035 drying Methods 0.000 claims abstract description 18
- 238000011065 in-situ storage Methods 0.000 claims abstract description 17
- 238000010000 carbonizing Methods 0.000 claims abstract description 15
- 238000007873 sieving Methods 0.000 claims abstract description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000011258 core-shell material Substances 0.000 claims abstract description 12
- 239000011248 coating agent Substances 0.000 claims abstract description 9
- 238000000576 coating method Methods 0.000 claims abstract description 9
- 239000002904 solvent Substances 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 6
- 239000010410 layer Substances 0.000 claims description 55
- 239000012792 core layer Substances 0.000 claims description 23
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 22
- 239000010406 cathode material Substances 0.000 claims description 19
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 18
- 125000000524 functional group Chemical group 0.000 claims description 12
- 229910021389 graphene Inorganic materials 0.000 claims description 10
- 229910052786 argon Inorganic materials 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
- 239000002002 slurry Substances 0.000 claims description 7
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052744 lithium Inorganic materials 0.000 claims description 3
- FRMOHNDAXZZWQI-UHFFFAOYSA-N lithium manganese(2+) nickel(2+) oxygen(2-) Chemical compound [O-2].[Mn+2].[Ni+2].[Li+] FRMOHNDAXZZWQI-UHFFFAOYSA-N 0.000 claims description 3
- DVATZODUVBMYHN-UHFFFAOYSA-K lithium;iron(2+);manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[Fe+2].[O-]P([O-])([O-])=O DVATZODUVBMYHN-UHFFFAOYSA-K 0.000 claims description 3
- ILXAVRFGLBYNEJ-UHFFFAOYSA-K lithium;manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[O-]P([O-])([O-])=O ILXAVRFGLBYNEJ-UHFFFAOYSA-K 0.000 claims description 3
- UUNNUENETDBNPB-HKBOAZHASA-N (2s)-2-[[(2s,3r)-3-amino-2-hydroxy-4-(4-phenylmethoxyphenyl)butanoyl]amino]-4-methylpentanoic acid Chemical compound C1=CC(C[C@@H](N)[C@H](O)C(=O)N[C@@H](CC(C)C)C(O)=O)=CC=C1OCC1=CC=CC=C1 UUNNUENETDBNPB-HKBOAZHASA-N 0.000 claims description 2
- SYBYTAAJFKOIEJ-UHFFFAOYSA-N 3-Methylbutan-2-one Chemical compound CC(C)C(C)=O SYBYTAAJFKOIEJ-UHFFFAOYSA-N 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 239000001569 carbon dioxide Substances 0.000 claims description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 150000002894 organic compounds Chemical class 0.000 claims 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 6
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 6
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 5
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 21
- 238000003756 stirring Methods 0.000 description 20
- 239000000843 powder Substances 0.000 description 16
- 150000002148 esters Chemical class 0.000 description 9
- 229910002804 graphite Inorganic materials 0.000 description 9
- 239000010439 graphite Substances 0.000 description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 9
- 125000003277 amino group Chemical group 0.000 description 8
- 238000003763 carbonization Methods 0.000 description 8
- 238000012216 screening Methods 0.000 description 8
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 229910000473 manganese(VI) oxide Inorganic materials 0.000 description 4
- 229910000668 LiMnPO4 Inorganic materials 0.000 description 3
- 229910002099 LiNi0.5Mn1.5O4 Inorganic materials 0.000 description 3
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 3
- 229910015177 Ni1/3Co1/3Mn1/3 Inorganic materials 0.000 description 3
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 description 3
- 229920001940 conductive polymer Polymers 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- -1 nickel-cobalt-aluminum Chemical compound 0.000 description 3
- 229910052493 LiFePO4 Inorganic materials 0.000 description 2
- 229910015645 LiMn Inorganic materials 0.000 description 2
- 229910015855 LiMn0.7Fe0.3PO4 Inorganic materials 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910013191 LiMO2 Inorganic materials 0.000 description 1
- 229910014985 LiMnxFe1-xPO4 Inorganic materials 0.000 description 1
- 229910014982 LiMnxFe1−xPO4 Inorganic materials 0.000 description 1
- 229910013716 LiNi Inorganic materials 0.000 description 1
- 229910014333 LiNi1-x-yCoxMyO2 Inorganic materials 0.000 description 1
- 229910014832 LiNi1−x−yCoxMyO2 Inorganic materials 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 229910000572 Lithium Nickel Cobalt Manganese Oxide (NCM) Inorganic materials 0.000 description 1
- 229910016771 Ni0.5Mn0.5 Inorganic materials 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- FBDMTTNVIIVBKI-UHFFFAOYSA-N [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] Chemical compound [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] FBDMTTNVIIVBKI-UHFFFAOYSA-N 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000012982 microporous membrane Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
-
- 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
- H01M4/36—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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Composite Materials (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention belongs to the technical field of lithium ion batteries, and relates to a preparation method of a nitrogen-doped carbon-coated lithium ion battery anode material, which comprises the following steps: the preparation method comprises the steps of taking melamine as a nitrogen source, organic acid as a carbon source and modified graphene as a conductive bridge, uniformly mixing the melamine, the organic acid and the modified graphene in a solvent, then adding a positive electrode material, uniformly mixing, and drying; grinding and sieving the mixed dry material, transferring the material to a rotary furnace, introducing inert atmosphere, heating to 100-500 ℃, and coating the functional structure component generated in situ after the melamine reacts with the organic acid and the modified graphene on the surface of the positive electrode material; and then continuously heating and carbonizing to obtain the nitrogen-doped carbon-coated anode material with the core-shell structure. Compared with the prior art, the anode material is coated by in-situ nitrogen-doped carbon to obtain the uniformly coated anode material, and the material has the advantages of good conductivity, obvious improvement on cycle performance and good rate capability. And the method is simple, low in cost and very suitable for large-scale production and application.
Description
Technical Field
The invention belongs to the technical field of new energy lithium ion battery materials, and mainly relates to a preparation method of a nitrogen-doped carbon-coated positive electrode material.
Background
The lithium ion battery is gradually expanded from the initial 3C field to the electric automobile field due to the characteristics of high energy density, long cycle life, environmental protection and the like. The wide application prospect of the positive electrode material is restricted due to poor conductivity and poor cyclicity. Conventionally, for example, CN104900869A discloses a preparation method of a carbon-coated nickel-cobalt-aluminum ternary cathode material, which adopts a common organic carbon source for coating and has poor conductivity. CN104466135A discloses a method for coating a nickel cobalt lithium manganate positive electrode material with a conductive polymer, which is to directly add a conductive polymer, and then calcine the conductive polymer to obtain a carbon coating layer, but the coating layer is not uniform due to the technical defects of the process.
In view of the above, the present invention aims to provide a method for preparing a nitrogen-doped carbon-coated positive electrode material, in which an in-situ nitrogen-doped carbon-coated positive electrode material is adopted, so as to obtain a nitrogen-doped carbon-coated positive electrode material with uniform coating, and the material has the advantages of improved conductivity, obviously improved cycle performance, and good rate capability. And the method is simple, low in cost and very suitable for large-scale production and application.
Disclosure of Invention
The invention aims to: aiming at the defects of the prior art, the preparation method of the nitrogen-doped carbon-coated anode material is provided, the in-situ nitrogen-doped carbon-coated anode material is adopted, so that the nitrogen-doped carbon-coated anode material with uniform coating is obtained, the conductivity of the material is improved, the cycle performance is obviously improved, and the rate capability is good. And the method is simple, low in cost and very suitable for large-scale production and application.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a nitrogen-doped carbon-coated anode material at least comprises the following steps:
step one, melamine with high nitrogen content is used as a nitrogen source, organic acid is used as a carbon source, modified graphene is used as a conductive bridge, the melamine and the organic acid are uniformly mixed in a solvent, then an anode material is added, and the mixture is uniformly mixed to obtain wet slurry, and the wet slurry is dried;
and step two, grinding and sieving the dried material mixed in the step one, then transferring the material to a rotary furnace, introducing inert atmosphere, heating to 100-500 ℃, preserving heat for 0.1-5 h, reacting amino of melamine with organic acid and carboxyl in modified graphene respectively to generate a functional structure component containing C-N bonds, and generating esters from the carboxyl of the organic acid and hydroxyl in the modified graphene, wherein the functional structure component is coated on the surface of the anode material. And then, continuously heating to 500-1000 ℃, carbonizing the functional structure components for 0.5-24 h, removing oxygen and hydrogen in the functional structure, cooling, scattering and sieving to obtain the nitrogen-doped carbon-coated anode material with uniform coating.
As an improvement of the preparation method of the nitrogen-doped carbon-coated anode material, the nitrogen-doped carbon-coated anode material obtained in the step two has a core-shell structure, the shell layer is a nitrogen-doped carbon layer, the core layer is an anode material, and the nitrogen-doped carbon layer is obtained by carbonizing a functional structure component generated in situ after the reaction of melamine, organic acid and modified graphene. The thickness of the shell layer is 5 nm-100 nm, the conductivity is good, and the functional structural components are uniformly coated on the surface of the anode material.
As an improvement of the preparation method of the nitrogen-doped carbon-coated cathode material, the mass of the shell layer is 0.5-5% of that of the core layer.
As an improvement of the preparation method of the nitrogen-doped carbon-coated cathode material, the modified graphene in the step one is the graphene grafted with-OOH and-OH functional groups, and the modified graphene can react with organic acid and melamine.
As an improvement of the preparation method of the nitrogen-doped carbon-coated cathode material, the organic acid in the step one is an organic matter containing-COOH, so that the organic acid can react with melamine and modified graphene under heating to generate functional structural components. And the number of-COOH functional groups is 1 to 5, and the number of carbon atoms is 2 to 20. Preferably, the organic acid is at least one of citric acid, stearic acid and oxalic acid.
As an improvement of the preparation method of the nitrogen-doped carbon-coated cathode material, the solvent in the step one is at least one of water, ethanol, acetone, isopropanol, n-butanol, tetrahydrofuran and methyl butanone. The solid content of the wet slurry is 10-50%.
As an improvement of the preparation method of the nitrogen-doped carbon-coated cathode material, in the first step, the cathode is at least one of a ternary material, a lithium-rich material, lithium nickel manganese oxide, lithium iron phosphate, lithium manganese phosphate and lithium manganese iron phosphate, and D50 is 8-18 micrometers.
Preferably, the molecular formula of the ternary material is LiNi1-x-yCoxMyO2Wherein M ═ Mn, Al; x + y<0.6。
Preferably, the molecular general formula of the lithium-rich material is xLi2MnO3.(1-x)LiMO2Where M is Co, Ni0.5Mn0.5,Cr,Ni1/3Co1/3Mn1/3。
Preferably, the molecular general formula of the lithium nickel manganese oxide material is LiNi0.5Mn1.5O4。
Preferably, the molecular formula of the lithium manganate is LiMn2O4。
Preferably, the general molecular formula of the lithium iron phosphate material is LiFePO4。
Preferably, the molecular general formula of the lithium manganese phosphate material is LiMnPO4。
Preferably, the molecular general formula of the lithium iron manganese phosphate material is LiMnxFe1-xPO4(0.6≤x≤1)。
As an improvement of the preparation method of the nitrogen-doped carbon-coated cathode material, the drying temperature in the step one is 60-200 ℃.
As an improvement of the preparation method of the nitrogen-doped carbon-coated cathode material, in the first step, the mass ratio of the organic acid, the modified graphene, the melamine and the cathode material is (5-10): (0.1-1): (5-10): 100.
as an improvement of the preparation method of the nitrogen-doped carbon-coated anode material, the rotating speed of the rotary furnace in the second step is 0.1 rpm-1000 rpm; the inert atmosphere comprises at least one of helium, nitrogen, argon and carbon dioxide.
Compared with the prior art, the material prepared by the invention has a core-shell structure, the shell layer is a nitrogen-doped carbon layer, the core layer is an anode material, and the nitrogen-doped carbon layer is obtained by carbonizing functional structure components generated in situ after melamine reacts with organic acid and modified graphene. The shell layer obtained by carbonizing the N-C functional component generated by the in-situ reaction of the melamine, the organic acid and the modified graphene has the advantages of good conductivity and good spreadability on the surface of the anode material, so that the material provided by the invention has excellent cycle performance and rate capability, and can better meet the requirements of power lithium ion batteries. In addition, the method has simple process and convenient operation, and is suitable for large-scale production and preparation.
Detailed Description
Example 1
The embodiment provides a preparation method of a nitrogen-doped carbon-coated positive electrode material, which at least comprises the following steps:
firstly, 150g of melamine, 200g of citric acid as organic acid, 0.5g of modified graphene powder and 2000g of ethanol as a solvent are weighed and mixed uniformly on a small stirrer, then 1000g D50-15 mu m lithium iron phosphate is weighed and poured into a stirring tank, and after the uniform stirring, the mixture is transferred and placed into an oven at 80 ℃ for drying. Wherein, the modified graphene is the graphene grafted with-OOH, -OH functional groups.
And step two, drying, grinding, sieving with a 325-mesh sieve, transferring the powder into a cavity of a rotary furnace, introducing N2 for protection at the rotating speed of 800rpm, heating to 300 ℃, preserving heat for 3 hours, reacting amino groups of melamine with organic acid and carboxyl groups in the modified graphene respectively to generate functional structural components containing C-N bonds, generating esters from the carboxyl groups of the organic acid and the hydroxyl groups in the modified graphene, and then continuously heating to 800 ℃ for carbonization for 4 hours. And after the sample is cooled, taking out the sample, grinding, and screening by a 325-mesh screen to obtain the porous nitrogen-doped carbon-coated graphite modified material.
The nitrogen-doped carbon-coated anode material obtained in the step two has a core-shell structure, the core layer is lithium iron phosphate, the shell layer is a porous nitrogen-doped carbon layer, and the porous nitrogen-doped carbon layer is obtained by carbonizing functional structure components generated in situ after melamine reacts with organic acid and modified graphene. The mass of the shell layer is 0.7 percent of the mass of the core layer, and the thickness of the shell layer is 5 nm-100 nm.
Example 2
The embodiment provides a preparation method of a nitrogen-doped carbon-coated positive electrode material, which at least comprises the following steps:
firstly, 250g of melamine, 250g of citric acid as organic acid, 8g of modified graphene powder and 2000g of ethanol as a solvent are weighed and mixed uniformly on a small stirrer, then 1000g D50-8 μm NCM (lithium nickel cobalt manganese oxide) is weighed and poured into a stirring tank, and after uniform stirring, the mixture is transferred and dried in an oven at 100 ℃. Wherein, the modified graphene is the graphene grafted with-OOH, -OH functional groups.
And step two, drying, grinding, sieving with a 325-mesh sieve, transferring the powder into a cavity of a rotary furnace, introducing argon at the rotation speed of 600rpm, heating to 400 ℃, keeping the temperature for 4 hours, reacting amino groups of melamine with organic acid and carboxyl groups in the modified graphene respectively to generate functional structure components containing C-N bonds, and generating esters by the carboxyl groups of the organic acid and the hydroxyl groups in the modified graphene, and then continuously heating to 900 ℃ for carbonization for 5 hours. And after the sample is cooled, taking out the sample, grinding, and screening by a 325-mesh screen to obtain the porous nitrogen-doped carbon-coated graphite modified material.
The nitrogen-doped carbon-coated positive electrode material obtained in the second step has a core-shell structure, wherein the core layer is NCM (nickel cobalt lithium manganate), the shell layer is a porous nitrogen-doped carbon layer, and the porous nitrogen-doped carbon layer is obtained by carbonizing functional structure components generated in situ after the reaction of melamine, organic acid and modified graphene. The mass of the shell layer is 3.2 percent of that of the core layer, and the thickness of the shell layer is 5 nm-100 nm.
Example 3
The embodiment provides a preparation method of a nitrogen-doped carbon-coated positive electrode material, which at least comprises the following steps:
firstly, 200g of melamine, 180g of stearic acid as an organic acid, 4g of modified graphene powder and 1500g of isopropanol as a solvent are weighed and mixed uniformly on a small stirrer, then 1000g D50-12 μm NCM (nickel cobalt manganese aluminum lithium) is weighed and poured into a stirring tank, and after the uniform stirring, the mixture is transferred and dried in an oven at 150 ℃. Wherein, the modified graphene is the graphene grafted with-OOH, -OH functional groups.
And step two, grinding after drying, sieving with a 325-mesh sieve, transferring the powder into a cavity of a rotary furnace, introducing argon for protection at the rotating speed of 500rpm, heating to 200 ℃, preserving the heat for 2 hours, and reacting amino groups of melamine with organic acid and carboxyl groups in the modified graphene respectively to generate functional structure components containing C-N bonds, wherein the carboxyl groups of the organic acid and the hydroxyl groups in the modified graphene generate esters. Then the temperature is continuously increased to 700 ℃ for carbonization for 6 h. And after the sample is cooled, taking out the sample, grinding, and screening by a 325-mesh screen to obtain the porous nitrogen-doped carbon-coated graphite modified material.
The nitrogen-doped carbon-coated ink material obtained in the second step has a core-shell structure, wherein the core layer is NCM (nickel cobalt lithium manganate), the shell layer is a porous nitrogen-doped carbon layer, and the porous nitrogen-doped carbon layer is obtained by carbonizing functional structure components generated in situ after the reaction of melamine, organic acid and modified graphene. The mass of the shell layer is 1.4 percent of that of the core layer, and the thickness of the shell layer is 5 nm-100 nm.
Example 4
The embodiment provides a preparation method of a nitrogen-doped carbon-coated positive electrode material, which at least comprises the following steps:
firstly, 120g of melamine, 220g of oxalic acid as organic acid, 7g of modified graphene powder and 2500g of isopropanol as solvent are weighed and mixed uniformly on a small stirrer, and then 1000g D50-16 mu m 0.3Li is weighed2MnO3·0.7Li Ni1/3Co1/3Mn1/3O2Pouring into a stirring tank, uniformly stirring, transferring and drying in a 120 ℃ oven. Wherein, the modified graphene is the graphene grafted with-OOH, -OH functional groups.
And step two, drying, grinding, sieving with a 325-mesh sieve, transferring the powder into a cavity of a rotary furnace, introducing argon at the rotation speed of 300rpm, heating to 250 ℃, keeping the temperature for 2.5 hours, reacting amino groups of melamine with organic acid and carboxyl groups in the modified graphene respectively to generate functional structural components containing C-N bonds, and generating esters from the carboxyl groups of the organic acid and the hydroxyl groups in the modified graphene, and then continuously heating to 750 ℃ for carbonization for 10 hours. And after the sample is cooled, taking out the sample, grinding, and screening by a 325-mesh screen to obtain the porous nitrogen-doped carbon-coated graphite modified material.
The nitrogen-doped carbon-coated positive electrode material obtained in the step two has a core-shell structure, and the core layer is 0.3Li2MnO3·0.7LiNi1/3Co1/3Mn1/3O2The shell layer is a porous nitrogen-doped carbon layer, and the porous nitrogen-doped carbon layer is obtained by carbonizing functional structure components generated in situ after melamine reacts with organic acid and modified graphene. The mass of the shell layer is 2.6 percent of that of the core layer, and the thickness of the shell layer is 5 nm-100 nm.
Example 5
The embodiment provides a preparation method of a nitrogen-doped carbon-coated positive electrode material, which at least comprises the following steps:
firstly, 280g of melamine, 110g of citric acid as organic acid and 8g of modified graphene powder are weighed and put into a stirring tank, the materials are uniformly mixed on a small stirrer, and then 1000g D50-15 μm LiNi is weighed0.5Mn1.5O4Pouring into a stirring tank, stirring uniformly, transferring and drying in an oven at 130 ℃. Wherein, the modified graphene is the graphene grafted with-OOH, -OH functional groups.
And step two, grinding after drying, sieving with a 325-mesh sieve, transferring the powder into a cavity of a rotary furnace, introducing N2 for protection at the rotation speed of 750rpm, heating to 350 ℃, preserving heat for 3.5h, and reacting amino groups of melamine with organic acid and carboxyl groups in the modified graphene respectively to generate functional structure components containing C-N bonds, wherein the carboxyl groups of the organic acid and the hydroxyl groups in the modified graphene generate esters. Then the temperature is continuously increased to 850 ℃ for carbonization for 12 h. And after the sample is cooled, taking out the sample, grinding, and screening by a 325-mesh screen to obtain the porous nitrogen-doped carbon-coated graphite modified material.
The nitrogen-doped carbon-coated positive electrode material obtained in the step two has a core-shell structure, and the core layer is LiNi0.5Mn1.5O4The shell layer is a porous nitrogen-doped carbon layerThe doped carbon layer is obtained by carbonizing functional structural components generated in situ after the reaction of melamine, organic acid and modified graphene. The mass of the shell layer is 2.4 percent of that of the core layer, and the thickness of the shell layer is 5 nm-100 nm.
Example 6
The embodiment provides a preparation method of a nitrogen-doped carbon-coated positive electrode material, which at least comprises the following steps:
firstly, 260g of melamine, 130g of citric acid as organic acid and 5.5g of modified graphene powder are weighed and placed in a stirring tank, the materials are uniformly mixed on a small stirrer, and then 1000g D50-35 mu m LiMn is weighed2O4Pouring into a stirring tank, uniformly stirring, transferring and drying in a 140 ℃ oven. Wherein, the modified graphene is the graphene grafted with-OOH, -OH functional groups.
And step two, drying, grinding, sieving with a 325-mesh sieve, transferring the powder into a cavity of a rotary furnace, introducing argon at the rotation speed of 550rpm, heating to 150 ℃, keeping the temperature for 1.5h, reacting amino groups of melamine with organic acid and carboxyl groups in the modified graphene respectively to generate functional structural components containing C-N bonds, and generating esters from the carboxyl groups of the organic acid and the hydroxyl groups in the modified graphene, and then continuously heating to 650 ℃ for carbonization for 20 h. And after the sample is cooled, taking out the sample, grinding, and screening by a 325-mesh screen to obtain the porous nitrogen-doped carbon-coated graphite modified material.
The nitrogen-doped carbon-coated positive electrode material obtained in the second step has a core-shell structure, the core layer is LiMn2O4, the shell layer is a porous nitrogen-doped carbon layer, and the porous nitrogen-doped carbon layer is obtained by carbonizing functional structure components generated in situ after melamine reacts with organic acid and modified graphene. The mass of the shell layer is 2.1 percent of that of the core layer, and the thickness of the shell layer is 5 nm-100 nm.
Example 7
The embodiment provides a preparation method of a nitrogen-doped carbon-coated positive electrode material, which at least comprises the following steps:
firstly, 160g of melamine, 230g of citric acid as organic acid and 4.5g of modified graphene powder are weighed and placed in a stirring tank, uniformly mixed on a small stirrer,then 1000g D50 ═ 8 μm LiMnPO was weighed4Pouring into a stirring tank, uniformly stirring, transferring and drying in a 180 ℃ oven. Wherein, the modified graphene is the graphene grafted with-OOH, -OH functional groups.
And step two, drying, grinding, sieving with a 325-mesh sieve, transferring the powder into a cavity of a rotary furnace, introducing argon for protection at the rotating speed of 650rpm, heating to 210 ℃, keeping the temperature for 1.8h, reacting amino groups of melamine with organic acid and carboxyl groups in the modified graphene respectively to generate functional structural components containing C-N bonds, and generating esters from the carboxyl groups of the organic acid and the hydroxyl groups in the modified graphene, and then continuously heating to 720 ℃ for carbonization for 18 h. And after the sample is cooled, taking out the sample, grinding, and screening by a 325-mesh screen to obtain the porous nitrogen-doped carbon-coated graphite modified material.
The nitrogen-doped carbon-coated positive electrode material obtained in the step two has a core-shell structure, and the core layer is LiMnPO4The shell layer is a porous nitrogen-doped carbon layer, and the porous nitrogen-doped carbon layer is obtained by carbonizing functional structure components generated in situ after melamine reacts with organic acid and modified graphene. The mass of the shell layer is 2.6 percent of that of the core layer, and the thickness of the shell layer is 5 nm-100 nm.
Example 8
The embodiment provides a preparation method of a nitrogen-doped carbon-coated positive electrode material, which at least comprises the following steps:
firstly, 155g of melamine, 205g of citric acid as organic acid and 2.5g of modified graphene powder are weighed and placed in a stirring tank, the materials are uniformly mixed on a small stirrer, and then 1000g D50-15 mu m LiMn is weighed0.7Fe0.3PO4Pouring into a stirring tank, uniformly stirring, transferring and drying in a 160 ℃ oven. Wherein, the modified graphene is the graphene grafted with-OOH, -OH functional groups.
And step two, drying, grinding, sieving with a 325-mesh sieve, transferring the powder into a cavity of a rotary furnace, introducing argon for protection at the rotation speed of 750rpm, heating to 230 ℃, keeping the temperature for 1.6h, reacting amino groups of melamine with organic acid and carboxyl groups in the modified graphene respectively to generate functional structure components containing C-N bonds, and generating esters by the carboxyl groups of the organic acid and the hydroxyl groups in the modified graphene, and then continuously heating to 780 ℃ for carbonization for 14 h. And after the sample is cooled, taking out the sample, grinding, and screening by a 325-mesh screen to obtain the porous nitrogen-doped carbon-coated graphite modified material.
The nitrogen-doped carbon-coated positive electrode material obtained in the step two has a core-shell structure, and the core layer is LiMn0.7Fe0.3PO4The shell layer is a porous nitrogen-doped carbon layer, and the porous nitrogen-doped carbon layer is obtained by carbonizing functional structure components generated in situ after melamine reacts with organic acid and modified graphene. The mass of the shell layer is 1.6 percent of that of the core layer, and the thickness of the shell layer is 5 nm-100 nm.
Comparative example 1
The NCM622 is commercially available, the shell layer is carbon, the core layer is graphite, the mass of the shell layer is 0.5% of that of the core layer, and the thickness of the shell layer is 5-100 nm.
Electrochemical cycling performance was tested using the following method: the materials prepared in examples 1-8 and the material provided in comparative example 1 were taken and mixed as follows: a positive electrode material: SP PVDF 94: mixing the raw materials in a mass ratio of 5:2.5:3.0, adding a proper amount of NMP (N-methyl pyrrolidone) serving as a dispersing agent, mixing the mixture into slurry, coating the slurry on an aluminum foil, and preparing a positive plate through vacuum drying and rolling; the negative electrode adopts a metal Li sheet and uses 1mol/L LiPF6The three-component mixed solvent is an electrolyte mixed according to EC, DMC and EMC which are 1: 1(v/v), a polypropylene microporous membrane is used as a diaphragm, and the CR2016 type button cell is assembled in an inert gas glove box system filled with argon. The charge and discharge test of the button cell is carried out on a Neware cell test system of Shenzhen Newway Limited company under the conditions of normal temperature, constant current charge and discharge of 0.1C and LiMn2O4、LiNi0.5Mn1.5O4The charging and discharging voltage is limited to 3.0-4.9V; NCM, 0.3Li2MnO3·0.7Li Ni1/3Co1/ 3Mn1/3O2The discharge voltage is limited to 3.0-4.2V; LiMnPO4，LiFePO4，LiMn0.7Fe0.3PO4The charging and discharging voltage is limited to 2.75-3.6V.
The samples prepared in each example and comparative example were assembled into button cells, respectively, and then subjected to electrical property tests, wherein the first charge-discharge gram capacity and the first coulombic efficiency are shown in table 1.
Table 1: results of electrical performance testing of button cells comprising the materials prepared using the methods of examples 1-8 and the material provided in comparative example 1.
Table 2: results of electrical performance testing of button cells using the material provided in example 2, comparative example 1.
From tables 1 and 2, it can be seen that: the material prepared by the method has excellent cycle performance and rate capability, and can better meet the requirements of power lithium ion batteries. In addition, the method has simple process and convenient operation, and is suitable for large-scale production and preparation.
Appropriate changes and modifications to the embodiments described above will become apparent to those skilled in the art from the disclosure and teachings of the foregoing description. Therefore, the present invention is not limited to the specific embodiments disclosed and described above, and some modifications and variations of the present invention should fall within the scope of the claims of the present invention. Furthermore, although specific terms are employed herein, they are used in a generic and descriptive sense only and not for purposes of limitation.
Claims (9)
1. The preparation method of the nitrogen-doped carbon-coated cathode material is characterized by at least comprising the following steps of:
the method comprises the following steps of firstly, taking melamine as a nitrogen source, organic acid as a carbon source and modified graphene as a conductive bridge, uniformly mixing the melamine, the organic acid and the modified graphene in a solvent, then adding an anode material, uniformly mixing to obtain wet slurry, and drying;
step two, grinding and sieving the dried material mixed in the step one, transferring the material to a rotary furnace, introducing inert atmosphere, heating to 100-500 ℃, preserving heat for 0.1-5 h, reacting melamine with organic acid and modified graphene to generate a functional structure component in situ, and uniformly coating the functional structure component on the surface of the anode material; then, continuously heating to 500-1000 ℃, carbonizing for 0.5-24 h, cooling, scattering and sieving to obtain a nitrogen-doped carbon-coated positive electrode material with uniform coating;
the nitrogen-doped carbon-coated anode material obtained in the step two has a core-shell structure, the shell layer is a nitrogen-doped carbon layer, the core layer is an anode material, and the nitrogen-doped carbon layer is obtained by carbonizing a functional structure component generated in situ after the reaction of melamine, organic acid and modified graphene.
2. The method for preparing the nitrogen-doped carbon-coated cathode material as claimed in claim 1, wherein the mass of the shell layer is 0.5-5% of the mass of the core layer.
3. The method according to claim 1, wherein the modified graphene obtained in the first step is a graphene grafted with-OOH, -OH functional groups.
4. The method for preparing the nitrogen-doped carbon-coated cathode material according to claim 1, wherein the organic acid in the step one is an organic compound containing-COOH, the number of-COOH functional groups is 1 to 5, and the number of carbon atoms is 2 to 20.
5. The method for preparing the nitrogen-doped carbon-coated cathode material according to claim 1, wherein the solvent in the first step is at least one of water, ethanol, acetone, isopropanol, n-butanol, tetrahydrofuran and methyl butanone, and the solid content of the wet slurry is 10-50%.
6. The method for preparing the nitrogen-doped carbon-coated cathode material according to claim 1, wherein the cathode material in the first step is at least one of a ternary material, a lithium-rich material, lithium nickel manganese oxide, lithium iron phosphate, lithium manganese phosphate and lithium manganese iron phosphate, and D50 is 8-18 micrometers.
7. The method for preparing the nitrogen-doped carbon-coated cathode material as claimed in claim 1, wherein the drying temperature in the first step is 60-200 ℃.
8. The method for preparing the nitrogen-doped carbon-coated cathode material according to claim 1, wherein in the first step, the mass ratio of the organic acid to the modified graphene to the melamine to the cathode material is as follows: (5-10): (0.1-1): (5-10): 100.
9. the method for preparing the nitrogen-doped carbon-coated cathode material according to claim 1, wherein the rotation speed of the rotary furnace in the second step is 0.1rpm to 1000 rpm; the inert atmosphere comprises at least one of helium, nitrogen, argon and carbon dioxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810592131.1A CN108682828B (en) | 2018-06-11 | 2018-06-11 | Preparation method of nitrogen-doped carbon-coated positive electrode material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810592131.1A CN108682828B (en) | 2018-06-11 | 2018-06-11 | Preparation method of nitrogen-doped carbon-coated positive electrode material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108682828A CN108682828A (en) | 2018-10-19 |
| CN108682828B true CN108682828B (en) | 2020-10-23 |
Family
ID=63810663
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810592131.1A Active CN108682828B (en) | 2018-06-11 | 2018-06-11 | Preparation method of nitrogen-doped carbon-coated positive electrode material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108682828B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110098394B (en) * | 2019-04-28 | 2022-05-17 | 格林美(湖北)新能源材料有限公司 | Nitrogen and boron codoped carbon quantum dot coated nickel-cobalt lithium aluminate positive electrode material and preparation method thereof |
| CN110444747B (en) * | 2019-07-29 | 2023-03-21 | 盐城工学院 | High-performance carbon-coated metal phosphate nano material and preparation method and application thereof |
| KR102553635B1 (en) * | 2022-09-27 | 2023-07-10 | 주식회사 케이켐비즈 | Positive electrode active material, positive electrode and secondary battery comprising the same |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104282896A (en) * | 2014-09-18 | 2015-01-14 | 东莞市翔丰华电池材料有限公司 | Nitrogen-doped carbon-coated graphite negative electrode material and preparation method thereof |
| CN108063221A (en) * | 2017-05-11 | 2018-05-22 | 华为技术有限公司 | Prepare method, negative material, cathode pole piece and the lithium ion battery of negative material |
| CN108075128A (en) * | 2018-01-06 | 2018-05-25 | 福州大学 | A kind of N doping carbon coating cobalt nickel sulfide/graphene combination electrode material |
| CN108091863A (en) * | 2017-12-18 | 2018-05-29 | 江苏双登富朗特新能源有限公司 | Graphene is modified lithium-rich manganese-based anode material and preparation method thereof |
| CN108091833A (en) * | 2017-11-14 | 2018-05-29 | 山东丰元化学股份有限公司 | A kind of high compacted density composite ferric lithium phosphate material and preparation method thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103626158B (en) * | 2012-08-23 | 2016-04-06 | 中国科学院宁波材料技术与工程研究所 | The preparation method of nitrogen-doped graphene and application thereof |
| WO2015015386A1 (en) * | 2013-08-01 | 2015-02-05 | Basf Se | Two-dimensional graphene-based porous polymer and the preparation thereof |
| CN105762362B (en) * | 2016-05-23 | 2018-12-11 | 四川大学 | Carbon coated ferriferrous oxide/nitrogen-doped graphene composite material and its application and preparation |
-
2018
- 2018-06-11 CN CN201810592131.1A patent/CN108682828B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104282896A (en) * | 2014-09-18 | 2015-01-14 | 东莞市翔丰华电池材料有限公司 | Nitrogen-doped carbon-coated graphite negative electrode material and preparation method thereof |
| CN108063221A (en) * | 2017-05-11 | 2018-05-22 | 华为技术有限公司 | Prepare method, negative material, cathode pole piece and the lithium ion battery of negative material |
| CN108091833A (en) * | 2017-11-14 | 2018-05-29 | 山东丰元化学股份有限公司 | A kind of high compacted density composite ferric lithium phosphate material and preparation method thereof |
| CN108091863A (en) * | 2017-12-18 | 2018-05-29 | 江苏双登富朗特新能源有限公司 | Graphene is modified lithium-rich manganese-based anode material and preparation method thereof |
| CN108075128A (en) * | 2018-01-06 | 2018-05-25 | 福州大学 | A kind of N doping carbon coating cobalt nickel sulfide/graphene combination electrode material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108682828A (en) | 2018-10-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108565446B (en) | Preparation method of porous nitrogen-doped carbon-coated graphite material | |
| CN111029543B (en) | Negative electrode material, and electrochemical device and electronic device comprising same | |
| CN108807896B (en) | Preparation method of nitrogen-doped carbon-coated silicon-carbon composite material | |
| CN111900501A (en) | Lithium supplement additive and preparation method and application thereof | |
| CN112928246B (en) | Composite material, preparation method and application thereof | |
| CN112751075A (en) | Lithium ion battery and preparation method thereof | |
| CN108682828B (en) | Preparation method of nitrogen-doped carbon-coated positive electrode material | |
| CN111048775A (en) | In-situ sodium doping modification method for improving lithium storage performance of ternary cathode material | |
| CN113889594A (en) | Preparation method of boron-doped lithium lanthanum zirconate-coated graphite composite material | |
| JP2011249293A (en) | Lithium transition metal compound and its manufacturing method, and lithium ion battery | |
| CN115332532A (en) | Hard carbon material and preparation method thereof | |
| CN114300671B (en) | Graphite composite negative electrode material and preparation method and application thereof | |
| CN117766742B (en) | Porous silicon-carbon composite material, preparation method thereof and application thereof in secondary battery | |
| CN116014104A (en) | Lithium-rich nickel positive electrode material, preparation method thereof, positive electrode sheet and secondary battery | |
| CN114162879B (en) | Micron-sized lithium ion battery anode material and preparation method thereof | |
| CN114447321A (en) | Positive electrode material, positive plate comprising same and battery | |
| CN117219777A (en) | Lithium supplementing agent, preparation method thereof, positive electrode plate and secondary battery | |
| CN116706050A (en) | Medium-low nickel monocrystal ternary positive electrode material, preparation method thereof and battery | |
| CN109216692B (en) | Modified ternary cathode material, preparation method thereof and lithium ion battery | |
| CN107256966B (en) | Lithium ion battery positive pole piece and preparation method thereof | |
| Sun et al. | Preparation of CeO2-coated Li1. 2Mn0. 54Co0. 13Ni0. 13O2 as cathode materials for Lithium Ion Batteries | |
| CN114171739B (en) | Electrochemical device and electronic device | |
| CN113233440A (en) | Modified preparation method of hard carbon negative electrode material with high first efficiency and long cycle life | |
| CN114242982B (en) | Graphene-coated two-dimensional metal compound electrode material and preparation method and application thereof | |
| CN110165178B (en) | Lithium battery positive electrode material, preparation method thereof and lithium battery containing positive electrode material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CP01 | Change in the name or title of a patent holder |
Address after: 518055 Guangdong city of Shenzhen province Nanshan District Xili of Tsinghua Patentee after: Tsinghua Shenzhen International Graduate School Patentee after: HUBEI RT ADVANCED MATERIALS Co.,Ltd. Address before: 518055 Guangdong city of Shenzhen province Nanshan District Xili of Tsinghua Patentee before: GRADUATE SCHOOL AT SHENZHEN, TSINGHUA University Patentee before: HUBEI RT ADVANCED MATERIALS Co.,Ltd. |
|
| CP01 | Change in the name or title of a patent holder | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20220118 Address after: Second floor, building a, Tsinghua campus, Shenzhen University Town, Xili street, Nanshan District, Shenzhen City, Guangdong Province Patentee after: Tsinghua Shenzhen International Graduate School Address before: 518055 Guangdong city of Shenzhen province Nanshan District Xili of Tsinghua Patentee before: Tsinghua Shenzhen International Graduate School Patentee before: HUBEI RT ADVANCED MATERIALS Co.,Ltd. |
|
| TR01 | Transfer of patent right |