CN116895749A - Lithium battery anode material and preparation method thereof - Google Patents
Lithium battery anode material and preparation method thereof Download PDFInfo
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- CN116895749A CN116895749A CN202310873609.9A CN202310873609A CN116895749A CN 116895749 A CN116895749 A CN 116895749A CN 202310873609 A CN202310873609 A CN 202310873609A CN 116895749 A CN116895749 A CN 116895749A
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 31
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 239000010405 anode material Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims abstract description 64
- BWHDROKFUHTORW-UHFFFAOYSA-N tritert-butylphosphane Chemical compound CC(C)(C)P(C(C)(C)C)C(C)(C)C BWHDROKFUHTORW-UHFFFAOYSA-N 0.000 claims abstract description 50
- AUHZEENZYGFFBQ-UHFFFAOYSA-N 1,3,5-trimethylbenzene Chemical compound CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 claims abstract description 34
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims abstract description 30
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000002131 composite material Substances 0.000 claims abstract description 23
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000000243 solution Substances 0.000 claims abstract description 21
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 20
- 229940078552 o-xylene Drugs 0.000 claims abstract description 20
- 238000003756 stirring Methods 0.000 claims abstract description 20
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 15
- 229960003638 dopamine Drugs 0.000 claims abstract description 15
- 229920000570 polyether Polymers 0.000 claims abstract description 15
- CCIVUDMVXNBUCY-UHFFFAOYSA-N 4-bromo-n-phenylaniline Chemical compound C1=CC(Br)=CC=C1NC1=CC=CC=C1 CCIVUDMVXNBUCY-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000007983 Tris buffer Substances 0.000 claims abstract description 13
- 239000007864 aqueous solution Substances 0.000 claims abstract description 13
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims abstract description 13
- 239000007774 positive electrode material Substances 0.000 claims abstract description 13
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 claims abstract description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 7
- 239000002244 precipitate Substances 0.000 claims abstract description 7
- 238000010992 reflux Methods 0.000 claims abstract description 7
- 239000008367 deionised water Substances 0.000 claims description 18
- 229910021641 deionized water Inorganic materials 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 13
- 229940078494 nickel acetate Drugs 0.000 claims description 13
- 238000005406 washing Methods 0.000 claims description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 239000012043 crude product Substances 0.000 claims description 12
- 239000002243 precursor Substances 0.000 claims description 12
- 238000010926 purge Methods 0.000 claims description 12
- 238000009210 therapy by ultrasound Methods 0.000 claims description 12
- 239000012300 argon atmosphere Substances 0.000 claims description 7
- 238000001291 vacuum drying Methods 0.000 claims description 7
- 229910052786 argon Inorganic materials 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 238000004321 preservation Methods 0.000 claims description 6
- 238000007711 solidification Methods 0.000 claims description 6
- 230000008023 solidification Effects 0.000 claims description 6
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 6
- 239000003792 electrolyte Substances 0.000 abstract description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 238000000354 decomposition reaction Methods 0.000 abstract description 3
- 239000001301 oxygen Substances 0.000 abstract description 3
- 229910052760 oxygen Inorganic materials 0.000 abstract description 3
- 239000000047 product Substances 0.000 abstract description 3
- 230000001737 promoting effect Effects 0.000 abstract description 2
- 230000002349 favourable effect Effects 0.000 abstract 1
- 229920001690 polydopamine Polymers 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229920000767 polyaniline Polymers 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- ZOIKAOIYOCLPME-UHFFFAOYSA-N lithium iron(2+) borate Chemical compound B([O-])([O-])[O-].[Fe+2].[Li+] ZOIKAOIYOCLPME-UHFFFAOYSA-N 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- 229910000733 Li alloy Inorganic materials 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- GJEAMHAFPYZYDE-UHFFFAOYSA-N [C].[S] Chemical compound [C].[S] GJEAMHAFPYZYDE-UHFFFAOYSA-N 0.000 description 1
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 238000005808 aromatic amination reaction Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000001989 lithium alloy Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000011255 nonaqueous electrolyte Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229920005569 poly(vinylidene fluoride-co-hexafluoropropylene) Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
Classifications
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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
- H01M4/364—Composites as mixtures
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/0666—Polycondensates containing five-membered rings, condensed with other rings, with nitrogen atoms as the only ring hetero atoms
- C08G73/0672—Polycondensates containing five-membered rings, condensed with other rings, with nitrogen atoms as the only ring hetero atoms with only one nitrogen atom in the ring
-
- 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
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
-
- 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
- H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
- H01M4/602—Polymers
- H01M4/606—Polymers containing aromatic main chain polymers
-
- 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
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
-
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
Abstract
The invention discloses a lithium battery anode material and a preparation method thereof, comprising the following steps: s1, preparing a carrier; s2, adding polyether and 1,3, 5-trimethylbenzene into an ethanol aqueous solution, adding a Tris buffer solution, adding a carrier, stirring at a constant speed, adding dopamine, continuously stirring, reacting for 30 hours, centrifuging for 5 minutes, and collecting a precipitate to prepare a composite carrier; s3, adding the composite carrier into a three-neck flask, adding o-xylene, sequentially adding 4-bromodiphenylamine, sodium tert-butoxide and palladium acetate, then dropwise adding an o-xylene solution of tri-tert-butylphosphine, and carrying out reflux reaction for 12 hours to obtain a lithium battery anode material; the porous graphene is used as a carrier, and the special porous structure can promote the transportation of electrolyte and oxygen, is favorable for promoting the formation and decomposition of discharge products, and forms a multi-element composite positive electrode material.
Description
Technical Field
The invention relates to the field of lithium battery anode materials and a preparation method thereof.
Background
Lithium batteries are a type of batteries using a nonaqueous electrolyte solution with lithium metal or lithium alloy as a positive/negative electrode material; the existing lithium battery anode material mainly comprises ternary lithium iron phosphate, nickel cobalt manganese and the like, the theoretical specific capacity of the lithium iron phosphate is about 170mAh/g, the theoretical specific capacity of the lithium iron borate is about 220mAh/g and is larger than the theoretical specific capacity of the lithium iron phosphate, and the material can be used as a substitute material of the lithium iron phosphate, and has higher specific capacity, better conductivity and extremely small volume change rate; lithium iron borate is getting more and more attention as a novel lithium ion nano positive electrode material.
Graphene, as a conductive material, can well promote intercalation and deintercalation of ions, thus exhibiting good positive electrode material properties. Experimental results show that in the lithium ion battery, the energy storage property of the graphene material is better than that of the traditional carbon negative electrode material, so that the energy storage efficiency of the lithium ion battery is greatly improved, but how to improve the cycle performance and the rate performance is still a technical problem to be solved urgently.
Disclosure of Invention
In order to solve the technical problems, the invention provides a lithium battery anode material and a preparation method thereof.
The aim of the invention can be achieved by the following technical scheme:
a preparation method of a lithium battery anode material comprises the following steps:
s1, adding graphene oxide prepared by a Humemrs method into deionized water, performing ultrasonic dispersion for 1h, then adding a 15% nickel acetate aqueous solution by mass fraction, continuing ultrasonic treatment for 2h, pouring liquid nitrogen until solidification is achieved after ultrasonic treatment is finished to prepare a precursor, transferring the precursor into a tube furnace, heating to 900 ℃ at a heating rate of 5-10 ℃/min, performing heat preservation and calcination for 1h, then cooling to room temperature to prepare a carrier crude product, transferring the carrier crude product into a 10% hydrochloric acid aqueous solution by mass fraction for 5h, performing filtration, washing with deionized water for three times, and performing vacuum drying at 85 ℃ for 12h to prepare the carrier;
in the step S1, graphene oxide is used as a matrix, nickel acetate is used as an etchant, then the substrate is calcined, nickel-based substances react with graphene at high temperature, so that carbon atoms on the surface of the graphene are oxidized into carbon oxide gas to be removed, then metal nickel is removed through hydrochloric acid washing, and a carrier with different pore diameter structures is prepared, and the special porous structure can promote the transportation of electrolyte and oxygen and is beneficial to promoting the formation and decomposition of discharge products;
s2, adding polyether (F127) and 1,3, 5-trimethylbenzene into an ethanol water solution with the volume fraction of 50%, adding a Tris buffer with the pH value of 8.5, adding a carrier, stirring at a constant speed, adding dopamine, continuously stirring and reacting for 30 hours, centrifuging for 5 minutes at the rotating speed of 10000r/min, collecting precipitate, and alternately washing with absolute ethanol and acetone for three times respectively to obtain a composite carrier;
in the step S2, polyether (F127) is used as a surfactant and pore expansion agent 1,3, 5-trimethylbenzene to cooperatively form a template, then dopamine is self-assembled and polymerized on the template to form polydopamine, pi-pi accumulation action can be carried out on the polydopamine and 1,3, 5-trimethylbenzene to enter the inside of the template, finally the template is removed, a porous polydopamine structure can be formed on the surface of a carrier as far as possible, polydopamine is coated on the surface of the carrier, and the influence of the coating structure on holes of the carrier is reduced through the special porous structure of the polydopamine.
S3, adding the composite carrier into a three-neck flask, adding o-xylene, sequentially adding 4-bromodiphenylamine, sodium tert-butoxide and palladium acetate, purging under argon atmosphere, stirring at a high speed for 15min, then dropwise adding an o-xylene solution of tri-tert-butylphosphine, purging with argon for 10min, heating to 160 ℃, and carrying out reflux reaction for 12h to obtain a lithium battery anode material;
in the step S3, 4-bromodiphenylamine is used as a monomer, and an aromatic amination reaction is carried out under the action of a palladium catalyst, so that the polyaniline is prepared, and the specific capacity and the cycle stability of the lithium battery can be improved through the structure of the polyaniline in the structure.
Further: in the step S1, the dosage ratio of graphene oxide, nickel acetate and deionized water is controlled to be 150-200 mg:15-20 mg:100 mL.
Further: in the step S2, the weight ratio of polyether (F127), 1,3, 5-trimethylbenzene, tris buffer, carrier and dopamine is controlled to be 200 mg/20 mg/100-150 mg/50-60 mg.
Further: in the step S3, the dosage ratio of the composite carrier, the 4-bromodiphenylamine, the sodium t-butoxide, the palladium acetate, the o-xylene and the tri-t-butylphosphine is controlled to be 30-50 mg:10.24-10.28 mg:21 mg:0.4-0.5 mg:50 mL:0.4 mmol.
Further: the ortho-xylene solution of the tri-tert-butyl phosphine in the step S3 is prepared by mixing tri-tert-butyl phosphine and ortho-xylene according to the dosage ratio of 0.4mmol to 10 mL.
The lithium battery anode material is prepared by the preparation method.
The invention has the beneficial effects that:
according to the lithium battery anode material, porous graphene is used as a carrier, a special porous structure can promote transportation of electrolyte and oxygen, formation and decomposition of a discharge product are facilitated, polyether (F127) is used as a surfactant and pore expansion agent 1,3, 5-trimethylbenzene to cooperatively form a template, dopamine is self-assembled on the template to be polymerized into polydopamine, pi-pi stacking effect with 1,3, 5-trimethylbenzene can be carried out to enter the inside of the template, the template is removed, a porous polydopamine structure can be formed on the surface of the carrier as far as possible, polydopamine is coated on the surface of the carrier, the influence of the coating structure on holes of the carrier is reduced through the special porous structure, and finally polyaniline synthesized through adhesion characteristics of polydopamine is formed into the multi-element composite anode material, so that the anode material prepared by the method can endow higher specific capacity and cycle stability to the lithium battery.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
A preparation method of a lithium battery anode material comprises the following steps:
s1, adding graphene oxide prepared by a Humemrs method into deionized water, performing ultrasonic dispersion for 1h, then adding a 15% nickel acetate aqueous solution by mass fraction, continuing ultrasonic treatment for 2h, pouring liquid nitrogen until solidification is achieved after ultrasonic treatment is finished to prepare a precursor, transferring the precursor into a tube furnace, heating to 900 ℃ at a heating rate of 5 ℃/min, performing heat preservation and calcination for 1h, then cooling to room temperature to prepare a carrier crude product, transferring the carrier crude product into a 10% hydrochloric acid aqueous solution by mass fraction for 5h, filtering, washing with deionized water for three times, performing vacuum drying at 85 ℃ for 12h, and controlling the dosage ratio of the graphene oxide, the nickel acetate and the deionized water to be 150 mg:15 mg:100 mL;
s2, adding polyether (F127) and 1,3, 5-trimethylbenzene into an ethanol water solution with the volume fraction of 50%, then adding a Tris buffer with the pH value of 8.5, adding a carrier, stirring at a constant speed, adding dopamine, continuously stirring and reacting for 30 hours, centrifuging for 5 minutes at the rotating speed of 10000r/min, collecting precipitate, alternately washing with absolute ethanol and acetone for three times respectively to prepare a composite carrier, and controlling the weight ratio of the polyether (F127), the 1,3, 5-trimethylbenzene, the Tris buffer, the carrier and the dopamine to be 200 mg:200 mg:20 mg:100 mg:50 mg;
and S3, adding the composite carrier into a three-neck flask, adding o-xylene, sequentially adding 4-bromodiphenylamine, sodium tert-butoxide and palladium acetate, purging under argon atmosphere, stirring at a high speed for 15min, then dropwise adding an o-xylene solution of tri-tert-butylphosphine, purging with argon for 10min, heating to 160 ℃, and carrying out reflux reaction for 12h to obtain the lithium battery anode material, wherein the dosage ratio of the composite carrier to the 4-bromodiphenylamine to the sodium tert-butoxide to the palladium acetate to the o-xylene to the tri-tert-butylphosphine is controlled to be 30 mg:10.24 mg:21 mg:0.4 mg:50 mL:0.4 mmol.
The ortho-xylene solution of the tri-tert-butyl phosphine is prepared by mixing tri-tert-butyl phosphine and ortho-xylene according to the dosage ratio of 0.4mmol to 10 mL.
Example 2
A preparation method of a lithium battery anode material comprises the following steps:
s1, adding graphene oxide prepared by a Humemrs method into deionized water, performing ultrasonic dispersion for 1h, then adding a 15% nickel acetate aqueous solution by mass fraction, continuing ultrasonic treatment for 2h, pouring liquid nitrogen until solidification is achieved after ultrasonic treatment is finished to prepare a precursor, transferring the precursor into a tube furnace, heating to 900 ℃ at a heating rate of 10 ℃/min, performing heat preservation and calcination for 1h, then cooling to room temperature to prepare a carrier crude product, transferring the carrier crude product into a 10% hydrochloric acid aqueous solution by mass fraction for 5h, filtering, washing with deionized water for three times, performing vacuum drying at 85 ℃ for 12h, and controlling the dosage ratio of the graphene oxide, the nickel acetate and the deionized water to be 160 mg/16 mg/100 mL;
s2, adding polyether (F127) and 1,3, 5-trimethylbenzene into an ethanol water solution with the volume fraction of 50%, then adding a Tris buffer with the pH value of 8.5, adding a carrier, stirring at a constant speed, adding dopamine, continuously stirring and reacting for 30 hours, centrifuging for 5 minutes at the rotating speed of 10000r/min, collecting precipitate, alternately washing with absolute ethanol and acetone for three times respectively to prepare a composite carrier, and controlling the weight ratio of the polyether (F127), the 1,3, 5-trimethylbenzene, the Tris buffer, the carrier and the dopamine to be 200 mg/20 mg/120 mg/52 mg;
and S3, adding the composite carrier into a three-neck flask, adding o-xylene, sequentially adding 4-bromodiphenylamine, sodium tert-butoxide and palladium acetate, purging under argon atmosphere, stirring at a high speed for 15min, then dropwise adding an o-xylene solution of tri-tert-butylphosphine, purging with argon for 10min, heating to 160 ℃, and carrying out reflux reaction for 12h to obtain the lithium battery anode material, wherein the dosage ratio of the composite carrier to the 4-bromodiphenylamine to the sodium tert-butoxide to the palladium acetate to the o-xylene to the tri-tert-butylphosphine is controlled to be 35 mg:10.26 mg:21 mg:0.4 mg:50 mL:0.4 mmol.
The ortho-xylene solution of the tri-tert-butyl phosphine is prepared by mixing tri-tert-butyl phosphine and ortho-xylene according to the dosage ratio of 0.4mmol to 10 mL.
Example 3
A preparation method of a lithium battery anode material comprises the following steps:
s1, adding graphene oxide prepared by a Humemrs method into deionized water, performing ultrasonic dispersion for 1h, then adding a 15% nickel acetate aqueous solution by mass fraction, continuing ultrasonic treatment for 2h, pouring liquid nitrogen until solidification is achieved after ultrasonic treatment is finished to prepare a precursor, transferring the precursor into a tube furnace, heating to 900 ℃ at a heating rate of 5 ℃/min, performing heat preservation and calcination for 1h, then cooling to room temperature to prepare a carrier crude product, transferring the carrier crude product into a 10% hydrochloric acid aqueous solution by mass fraction for 5h, filtering, washing with deionized water for three times, performing vacuum drying at 85 ℃ for 12h, and controlling the dosage ratio of the graphene oxide, the nickel acetate and the deionized water to be 180 mg:18 mg:100 mL;
s2, adding polyether (F127) and 1,3, 5-trimethylbenzene into an ethanol water solution with the volume fraction of 50%, then adding a Tris buffer with the pH value of 8.5, adding a carrier, stirring at a constant speed, adding dopamine, continuously stirring and reacting for 30 hours, centrifuging for 5 minutes at the rotating speed of 10000r/min, collecting precipitate, alternately washing with absolute ethanol and acetone for three times respectively to prepare a composite carrier, and controlling the weight ratio of the polyether (F127), the 1,3, 5-trimethylbenzene, the Tris buffer, the carrier and the dopamine to be 200 mg:200 mg:20 mg:140 mg:58 mg;
and S3, adding the composite carrier into a three-neck flask, adding o-xylene, sequentially adding 4-bromodiphenylamine, sodium tert-butoxide and palladium acetate, purging under argon atmosphere, stirring at a high speed for 15min, then dropwise adding an o-xylene solution of tri-tert-butylphosphine, purging with argon for 10min, heating to 160 ℃, and carrying out reflux reaction for 12h to obtain the lithium battery anode material, wherein the dosage ratio of the composite carrier to the 4-bromodiphenylamine to the sodium tert-butoxide to the palladium acetate to the o-xylene to the tri-tert-butylphosphine is controlled to be 45 mg:10.28 mg:21 mg:0.5 mg:50 mL:0.4 mmol.
The ortho-xylene solution of the tri-tert-butyl phosphine is prepared by mixing tri-tert-butyl phosphine and ortho-xylene according to the dosage ratio of 0.4mmol to 10 mL.
Example 4
A preparation method of a lithium battery anode material comprises the following steps:
s1, adding graphene oxide prepared by a Humemrs method into deionized water, performing ultrasonic dispersion for 1h, then adding a 15% nickel acetate aqueous solution by mass fraction, continuing ultrasonic treatment for 2h, pouring liquid nitrogen until solidification is achieved after ultrasonic treatment is finished to prepare a precursor, transferring the precursor into a tube furnace, heating to 900 ℃ at a heating rate of 10 ℃/min, performing heat preservation and calcination for 1h, then cooling to room temperature to prepare a carrier crude product, transferring the carrier crude product into a 10% hydrochloric acid aqueous solution by mass fraction for 5h, filtering, washing with deionized water for three times, performing vacuum drying at 85 ℃ for 12h, and controlling the dosage ratio of the graphene oxide, the nickel acetate and the deionized water to be 200 mg:20 mg:100 mL;
s2, adding polyether (F127) and 1,3, 5-trimethylbenzene into an ethanol water solution with the volume fraction of 50%, then adding a Tris buffer with the pH value of 8.5, adding a carrier, stirring at a constant speed, adding dopamine, continuously stirring and reacting for 30 hours, centrifuging for 5 minutes at the rotating speed of 10000r/min, collecting precipitate, alternately washing with absolute ethanol and acetone for three times respectively to prepare a composite carrier, and controlling the weight ratio of the polyether (F127), the 1,3, 5-trimethylbenzene, the Tris buffer, the carrier and the dopamine to be 200 mg:200 mg:20 mg:150 mg:60 mg;
and S3, adding the composite carrier into a three-neck flask, adding o-xylene, sequentially adding 4-bromodiphenylamine, sodium tert-butoxide and palladium acetate, purging under argon atmosphere, stirring at a high speed for 15min, then dropwise adding an o-xylene solution of tri-tert-butylphosphine, purging with argon for 10min, heating to 160 ℃, and carrying out reflux reaction for 12h to obtain the lithium battery anode material, wherein the dosage ratio of the composite carrier to the 4-bromodiphenylamine to the sodium tert-butoxide to the palladium acetate to the o-xylene to the tri-tert-butylphosphine is controlled to be 50 mg:10.28 mg:21 mg:0.5 mg:50 mL:0.4 mmol.
The ortho-xylene solution of the tri-tert-butyl phosphine is prepared by mixing tri-tert-butyl phosphine and ortho-xylene according to the dosage ratio of 0.4mmol to 10 mL.
Comparative example 1
In this comparative example, graphene was used as a positive electrode material as compared with example 1.
Comparative example 2
The comparative example is a commercially available sulfur-carbon composite positive electrode material.
The positive electrode materials prepared in examples 1 to 4 and comparative examples 1 to 2, acetylene black and polyethylene oxide were uniformly coated on a current collector, and dried at 22℃for 20 hoursCut into 1X 1cm 2 Drying the electrode plate in a vacuum drying oven at 65 ℃ for 10 hours to prepare an anode plate, wherein a lithium plate is used as a cathode, a diaphragm is PVDF-HFP, and LiPF6/EC-DMC-EMC (1:1:1) with the molar concentration of 1mol/L is used as electrolyte; assembling a simulated battery in a glove box in an argon atmosphere, and testing the charge and discharge performance of the assembled battery sample at 25 ℃ with the charge and discharge current density of 0.6mA.cm 2 The test voltage ranges from 1.8 to 3.0V, and the results are shown in table 1 below:
TABLE 1
| Specific discharge capacity mAh/g | Specific capacity mAh/g after 120 times of circulation | |
| Example 1 | 1478 | 1215 |
| Example 2 | 1481 | 1220 |
| Example 3 | 1480 | 1218 |
| Example 4 | 1482 | 1223 |
| Comparative example 1 | 987 | 440 |
| Comparative example 2 | 1260 | 886 |
From table 1 above, it can be seen that the positive electrode materials prepared in examples 1 to 4 of the present invention can improve the specific capacity and cycle stability of the battery.
The foregoing is merely illustrative and explanatory of the principles of the invention, as various modifications and additions may be made to the specific embodiments described, or similar thereto, by those skilled in the art, without departing from the principles of the invention or beyond the scope of the appended claims.
Claims (6)
1. A preparation method of a lithium battery anode material is characterized by comprising the following steps: the method comprises the following steps:
s1, adding graphene oxide prepared by a Humemrs method into deionized water, performing ultrasonic dispersion for 1h, then adding a 15% nickel acetate aqueous solution by mass fraction, continuing ultrasonic treatment for 2h, pouring liquid nitrogen until solidification is achieved after ultrasonic treatment is finished to prepare a precursor, transferring the precursor into a tube furnace, heating to 900 ℃ at a heating rate of 5-10 ℃/min, performing heat preservation and calcination for 1h, then cooling to room temperature to prepare a carrier crude product, transferring the carrier crude product into a 10% hydrochloric acid aqueous solution by mass fraction for 5h, performing filtration, washing with deionized water for three times, and performing vacuum drying at 85 ℃ for 12h to prepare the carrier;
s2, adding polyether and 1,3, 5-trimethylbenzene into an ethanol water solution with the volume fraction of 50%, adding a Tris buffer with the pH value of 8.5, adding a carrier, stirring at a constant speed, adding dopamine, continuously stirring and reacting for 30 hours, centrifuging for 5 minutes at the rotating speed of 10000r/min, collecting precipitate, and alternately washing with absolute ethanol and acetone for three times respectively to obtain a composite carrier;
and S3, adding the composite carrier into a three-neck flask, adding o-xylene, sequentially adding 4-bromodiphenylamine, sodium tert-butoxide and palladium acetate, purging under an argon atmosphere, stirring at a high speed for 15min, then dropwise adding an o-xylene solution of tri-tert-butylphosphine, purging with argon for 10min, heating to 160 ℃, and carrying out reflux reaction for 12h to obtain the lithium battery anode material.
2. The method for preparing the positive electrode material of the lithium battery according to claim 1, wherein the method comprises the following steps: in the step S1, the dosage ratio of graphene oxide, nickel acetate and deionized water is controlled to be 150-200 mg:15-20 mg:100 mL.
3. The method for preparing the positive electrode material of the lithium battery according to claim 1, wherein the method comprises the following steps: in the step S2, the weight ratio of polyether, 1,3, 5-trimethylbenzene, tris buffer, carrier and dopamine is controlled to be 200 mg/20 mg/100-150 mg/50-60 mg.
4. The method for preparing the positive electrode material of the lithium battery according to claim 1, wherein the method comprises the following steps: in the step S3, the dosage ratio of the composite carrier, the 4-bromodiphenylamine, the sodium t-butoxide, the palladium acetate, the o-xylene and the tri-t-butylphosphine is controlled to be 30-50 mg:10.24-10.28 mg:21 mg:0.4-0.5 mg:50 mL:0.4 mmol.
5. The method for preparing the positive electrode material of the lithium battery according to claim 1, wherein the method comprises the following steps: the ortho-xylene solution of the tri-tert-butyl phosphine in the step S3 is prepared by mixing tri-tert-butyl phosphine and ortho-xylene according to the dosage ratio of 0.4mmol to 10 mL.
6. A lithium battery positive electrode material, characterized by being prepared by the preparation method of any one of claims 1 to 5.
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