CN111285408A - Method for preparing iron oxide negative electrode material of lithium ion power battery - Google Patents
Method for preparing iron oxide negative electrode material of lithium ion power battery Download PDFInfo
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- CN111285408A CN111285408A CN202010096787.1A CN202010096787A CN111285408A CN 111285408 A CN111285408 A CN 111285408A CN 202010096787 A CN202010096787 A CN 202010096787A CN 111285408 A CN111285408 A CN 111285408A
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- electrode material
- lithium ion
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- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 238000000034 method Methods 0.000 title claims abstract description 21
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 16
- 239000007773 negative electrode material Substances 0.000 title claims description 19
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 24
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000012279 sodium borohydride Substances 0.000 claims abstract description 11
- 229910000033 sodium borohydride Inorganic materials 0.000 claims abstract description 11
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000012300 argon atmosphere Substances 0.000 claims abstract description 7
- 239000010406 cathode material Substances 0.000 claims abstract description 5
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims abstract 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 14
- 238000001354 calcination Methods 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- 239000012153 distilled water Substances 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 239000010453 quartz Substances 0.000 claims description 7
- 238000000227 grinding Methods 0.000 claims description 5
- 239000004570 mortar (masonry) Substances 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims 1
- 238000002360 preparation method Methods 0.000 abstract description 8
- 239000002131 composite material Substances 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 5
- 239000007772 electrode material Substances 0.000 abstract description 4
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 abstract description 4
- 239000002243 precursor Substances 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 4
- 238000003980 solgel method Methods 0.000 abstract description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 2
- 239000001301 oxygen Substances 0.000 abstract description 2
- 229910052760 oxygen Inorganic materials 0.000 abstract description 2
- 239000002738 chelating agent Substances 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 abstract 1
- 238000011056 performance test Methods 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 5
- 229910052744 lithium Inorganic materials 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 239000000956 alloy Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 239000000499 gel Substances 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- -1 polypropylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 235000010413 sodium alginate Nutrition 0.000 description 1
- 239000000661 sodium alginate Substances 0.000 description 1
- 229940005550 sodium alginate Drugs 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 239000011240 wet gel Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/02—Oxides; Hydroxides
- C01G49/06—Ferric oxide [Fe2O3]
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
- C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
-
- 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
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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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/523—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron for non-aqueous cells
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C01P2006/40—Electric properties
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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Abstract
The invention discloses a method for preparing an iron oxide cathode material for a lithium ion power battery, and relates to the technical field of preparation of electrode materials of lithium ion batteries; the method is based on a sol-gel method, adopts the precursor raw materials of nano iron oxide, glycol, butyl titanate and other materials, and adopts proper temperature, time and component control to realize the long cycle life and high specific capacity of the iron oxide cathode; the reactions involved are: (1) fe is prepared by taking nano iron oxide as a template, butyl titanate as a precursor and citric acid as a chelating agent2O3@TiO2，TiO2Can be used as a buffer material in the electrode to inhibit the volume expansion of the ferric oxide; (2) the strong reducibility of sodium borohydride is utilized to reduce the composite material under the argon atmosphere to increase oxygen vacancy and increase the conductivity of the material. The invention has simple raw materials and easy realization of the process, and the obtained electrode material keeps high capacity level in long circulation.
Description
Technical Field
The invention relates to the technical field of preparation of lithium ion battery electrode materials, in particular to a method for preparing an iron oxide negative electrode material of a lithium ion power battery.
Background
With continuous innovation and development of science and technology, the novel energy overcomes the advantages of environmental friendliness, no pollution, low price, easy obtainment and the like to overcome the traditional chemical energy which is easy to cause pollution. The green water mountain is the Jinshan Yinshan, and the development of new energy sources is a great trend and is the central importance of energy development. Lithium batteries are popular among new energy sources, are widely used in small electric energy devices such as watches, mobile phones, and digital cameras, and are also indispensable for transportation networks such as electric vehicles, ships, electric bicycles, and airplanes.
The negative electrode material of lithium battery is one of the key factors determining the electrochemical performance of lithium battery in lithium battery. Lithium ion battery negative electrode materials are generally classified into three categories: (1) carbon materials such as natural graphite, graphene, carbon fiber, and the like; (2) oxide materials such as iron oxide, ferroferric oxide, and silica; (3) alloy materials such as magnesium-based alloys, aluminum-based alloys, silicon-based alloys, and the like. Graphene, which has been commercialized at present, has low theoretical capacity (372mAh g)-1) Iron oxide relies on a high theoretical capacity (1007mAh x g) and cannot meet the growing high energy demand-1) Can be distinguished. Fe2O3Has the advantages of natural abundance, high conductivity, low cost and high performance, but the initial coulombic efficiency is low and the capacity cycle is rapidly declined due to the large volume expansion and low conductivity during the charge and discharge processes.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a method for preparing the iron oxide cathode material of the lithium ion power battery, the raw materials are simple, the process is easy to realize, the obtained electrode material keeps high capacity level in long circulation, and a possible path is provided for commercialization of the iron oxide cathode.
In order to achieve the purpose, the invention is realized by the following technical scheme:
a method for preparing an iron oxide negative electrode material of a lithium ion power battery comprises the following steps:
(1) mixing nano Fe2O3Adding into a mixed solution of distilled water and ethylene glycol, dripping butyl titanate, mixing and placing in a crucible; stirring at room temperature, adding citric acid after completely dissolving, stirring, adding dropwise concentrated ammonia water after completely dissolving to adjust pH to 6, and stirring at 100 deg.C for 2.5-3.5 h; stopping stirring after sol appears, and placing the mixture in an oven at 100 ℃ for drying overnight; after drying, placing the mixture in a muffle furnace at 490-535 ℃ for calcining for 2.5-4h, wherein the heating rate is 0.8-1.3 ℃/min;
(2) adding sodium borohydride into the product obtained in the step (1), grinding and mixing the product in an agate mortar, transferring the mixture into a quartz boat, calcining the quartz boat in a tubular furnace in an argon atmosphere at the temperature of 340-; washing with distilled water after calcination for 3 times, and drying to obtain the cathode material Fe2O3@TiO2。
Preferably, in the step (1), Fe2O3The adding amount of the citric acid is 3.2g, the adding amount of the distilled water is 30mL, the adding amount of the ethylene glycol is 30mL, and the adding amount of the citric acid is 10 g; the addition amount of butyl titanate is 0.25-1.8 ml. Further preferably, the addition amount of the butyl titanate is 0.358ml to 1.201 ml.
Preferably, in the step (2), the amount of sodium borohydride added is 0.03-0.15 g. Further preferably, the amount of sodium borohydride added is 0.03158-0.1057 g.
Preferably, in the step (1), after drying, the mixture is placed in a muffle furnace at 500 ℃ for calcining for 3 hours, and the heating rate of the muffle furnace is 1 ℃/min.
Preferably, in the step (2), the mixture is placed in a tube furnace and calcined for 1 hour under the argon atmosphere, the temperature is 350 ℃, and the heating rate is 2 ℃/min.
Compared with the prior art, the invention has the following technical effects:
(1) the method provided by the invention is based on a sol-gel method and atmosphere protection calcination, and the adopted raw materials are common chemicals such as commercial micron-sized iron oxide, butyl titanate, ethylene glycol and the like, and are easy to obtain and low in cost.
(2) Preparation of negative electrode Material Fe2O3@TiO2In the process, sodium borohydride is used as a reducing agent to reduce the composite material, so that the surface oxygen vacancy is increased, and the improvement of the material performance is obviously facilitated.
(3) Negative electrode material Fe in the invention2O3@TiO2The core-shell structure formed by coating iron oxide with titanium dioxide effectively inhibits the volume expansion of the iron oxide; the iron oxide cathode material has high capacity and high stability.
(4) No acid washing, no toxicity, no pungent smell and other organic solvent and gas are involved and exhausted during synthesis, and this is favorable to environment protection in industrial production.
Drawings
FIG. 1 is a scanning electron micrograph of commercially pure iron oxide used in example 1 of the present invention.
FIG. 2 shows Fe obtained in example 1 of the present invention2O3@0.2TiO2Scanning electron micrograph (c).
FIG. 3 shows Fe obtained in examples 1 to 3 of the present invention2O3@TiO2Battery cycle life map of (a).
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1:
1)Fe2O3@0.2TiO2preparation of
Weigh 3.2g of nano Fe2O3The mixture was placed in a crucible, 30mL of distilled water and 30mL of ethylene glycol were added, and 0.756mL of butyl titanate was added dropwise to the crucible. And (3) placing the crucible on a magnetic stirrer, stirring at room temperature, weighing 10g of citric acid after complete dissolution, adding into the mixed solution, continuing stirring for 30min, and dropwise adding concentrated ammonia water to adjust the pH value of the solution to 6 after complete dissolution. Then heated to 100 ℃ and stirred for 3h at 100 ℃. Stirring was stopped after sol formation to give a brown wet gel which was immediately dried in an oven at 100 ℃ overnight. Drying to obtain brown dry gel, calcining the dry gel in a muffle furnace at 500 ℃ for 3h at the heating rate of 1 ℃/min, and then cooling to room temperature at the cooling rate of 5 ℃/min to obtain Fe2O3@0.2TiO2A composite material.
2)Fe2O3@0.2TiO2By reduction of
0.06656g of sodium borohydride is weighed and placed in an agate mortar, the sample obtained in the step 1) is added for grinding and mixing, the grinding time is 30 hours, the operation is carried out in a glass room, and the water content is about 20%. Transferring the mixture into a quartz boat, calcining the quartz boat in a tube furnace under the argon atmosphere for 1 hour at the temperature of 350 ℃ and the heating rate of 2 ℃/min, and then cooling the quartz boat to room temperature at the cooling rate of 5 ℃/min. The black sample is obtained after calcination, and is placed in a long-neck funnel and washed and filtered for 3 times by distilled water. Filtering, drying at 45 ℃ to obtain reduced sample Fe2O3@0.2TiO2。
The scanning electron micrograph of the commercially pure iron oxide used in this example is shown in FIG. 1. As can be seen from FIG. 1, commercially pure iron oxide is irregular in shape and has a particle size of substantially between 0.7 and 0.8 um. This example, step 2) preparation of Fe2O3@0.2TiO2The scanning electron micrograph of (a) is shown in FIG. 2. As can be seen from FIG. 2, the iron oxide is coated by a sol-gel process to form a bulk TiO2The small particles are densely gathered on the outer layer of the ferric oxide to coat the ferric oxide, so that the problem of cycle life attenuation caused by the volume expansion of the silicon material can be effectively inhibited.
3) Preparation of electrode slice
The prepared composite material Fe2O3@0.2TiO2And (2) as a battery negative electrode active material, fully and uniformly grinding the active material by using an agate mortar for 20min, and mixing the active material with a conductive agent acetylene black and a water-based binder (2% sodium alginate solution) according to a mass ratio of 8: 1:1, fully mixing the raw materials by taking ultrapure water as a solvent and absolute ethyl alcohol as an auxiliary solvent, and then preparing slurry with proper viscosity; coating the prepared slurry on the current collector on the copper foil evenly by using a full-automatic coating machine; putting the coated electrode into a 60 ℃ oven, drying at 60 ℃ for 6h, taking out, tabletting the electrode by using a powder tabletting machine, and keeping the gage pressure of 10MPa to ensure that the prepared composite negative electrode material, acetylene black and a binder can be coated on a clean copper foil in a smooth manner; the compacted pole pieces are processed into the electrode plates by a sheet punching machine, and the electrode plates are dried in a vacuum oven at 120 ℃ for 12 hours before use. And weighing after the completion, putting the sample into a sample bag, and transferring the sample bag into a glove box under an argon atmosphere for later use.
4) Half cell assembly
A battery is assembled in a glove box filled with argon, a diaphragm is a polypropylene film, electrolyte is LiPF6+ EC/DMC/EMC (volume ratio is 1:1:1) with concentration of 1mol/L, a metal lithium sheet is used as a negative electrode, and the battery is assembled into a button battery with the model number of CR 2025.
5) Half cell test
The half cell needs to be kept stand for 24h before testing.
The device used by the invention is a NEWARE-BTS-5V/10mA battery test system, the voltage test range is 0.01-2.5V, and the current density of the cycle life is 100 mA/g. The current density of the rate performance test is 25, 50, 100, 200, 400, 800, 400, 200, 100, 50 and 25 mA/g. The results of the performance tests are shown in table 1 and fig. 3.
Example 2:
precursor powder preparation and tableting were the same as in example 1 except that: step 2) titanium additionThe amount of butyl acetate was 0.358ml, and 0.03158g of sodium borohydride was used for the reduction. Preparing to obtain a sample Fe2O3@0.1TiO2. The performance test method is the same as example 1, and the performance test results are shown in table 1 and fig. 3.
Example 3:
precursor powder preparation and tableting were the same as in example 1 except that: 1.201ml of butyl titanate is added in the step 2), and 0.1057g of sodium borohydride is used for reduction. Preparing to obtain a sample Fe2O3@0.3TiO2. The performance test method is the same as example 1, and the performance test results are shown in table 1 and fig. 3.
TABLE 1 electrochemical Performance test
As can be seen from fig. 3 of the present invention, the cycle life performance of the battery is greatly improved after the iron oxide is coated by the sol-gel method. After 100 circles of circulation under the current of 100mA, the specific discharge capacity can be kept to be 457.536mAh/g, and only 35.431mAh/g of pure ferric oxide is remained.
The above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (7)
1. A method for preparing an iron oxide negative electrode material of a lithium ion power battery is characterized by comprising the following steps:
(1) mixing nano Fe2O3Adding into mixed solution of distilled water and glycol, dripping titanic acidMixing butyl esters and placing the mixture in a crucible; stirring at room temperature, adding citric acid after completely dissolving, stirring, adding dropwise concentrated ammonia water after completely dissolving to adjust pH to 6, and stirring at 100 deg.C for 2.5-3.5 h; stopping stirring after sol appears, and placing the mixture in an oven at 100 ℃ for drying overnight; after drying, placing the mixture in a muffle furnace at 490-535 ℃ for calcining for 2.5-4h, wherein the heating rate is 0.8-1.3 ℃/min;
(2) adding sodium borohydride into the product obtained in the step (1), grinding and mixing the product in an agate mortar, transferring the mixture into a quartz boat, calcining the quartz boat in a tubular furnace in an argon atmosphere at the temperature of 340-; washing with distilled water after calcination for 3 times, and drying to obtain the cathode material Fe2O3@TiO2。
2. The method for preparing the iron oxide negative electrode material for the lithium ion power battery according to claim 1, wherein in the step (1), Fe2O3The adding amount of the citric acid is 3.2g, the adding amount of the distilled water is 30mL, the adding amount of the ethylene glycol is 30mL, and the adding amount of the citric acid is 10 g; the addition amount of butyl titanate is 0.25-1.8 ml.
3. The method of preparing an iron oxide negative electrode material for a lithium ion power battery as claimed in claim 2, wherein the added amount of the butyl titanate is 0.358ml to 1.702 ml.
4. The method for preparing an iron oxide negative electrode material for a lithium ion power battery according to claim 2, wherein in the step (2), the amount of sodium borohydride added is 0.03-0.15 g.
5. The method for preparing the iron oxide negative electrode material for the lithium ion power battery as claimed in claim 4, wherein the addition amount of the sodium borohydride is 0.03158-0.1057 g.
6. The method for preparing the iron oxide negative electrode material for the lithium ion power battery according to claim 1, wherein in the step (1), the dried iron oxide negative electrode material is placed in a muffle furnace at 500 ℃ for calcination for 3h, and the heating rate of the muffle furnace is 1 ℃/min.
7. The method for preparing the iron oxide negative electrode material for the lithium ion power battery according to claim 1, wherein in the step (2), the iron oxide negative electrode material is calcined in a tube furnace under an argon atmosphere at a temperature of 350 ℃ and a heating rate of 2 ℃/min for 1 hour.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113546625A (en) * | 2021-04-02 | 2021-10-26 | 中国科学院城市环境研究所 | Electrostatic spinning defective TiO2/Fe3O4Composite nanofiber material and preparation method thereof |
| CN113793931A (en) * | 2021-11-18 | 2021-12-14 | 河南电池研究院有限公司 | Iron oxide negative electrode material for lithium ion battery and preparation method thereof |
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| CN103618069A (en) * | 2013-11-28 | 2014-03-05 | 扬州大学 | Preparation method of lithium titanate-coated ferric oxide anode material of lithium ion battery |
| CN110176596A (en) * | 2019-06-17 | 2019-08-27 | 启东启澳新材料科技发展有限公司 | A method of improving lithium battery anode coating material chemical property |
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| CN103618069A (en) * | 2013-11-28 | 2014-03-05 | 扬州大学 | Preparation method of lithium titanate-coated ferric oxide anode material of lithium ion battery |
| CN110176596A (en) * | 2019-06-17 | 2019-08-27 | 启东启澳新材料科技发展有限公司 | A method of improving lithium battery anode coating material chemical property |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113546625A (en) * | 2021-04-02 | 2021-10-26 | 中国科学院城市环境研究所 | Electrostatic spinning defective TiO2/Fe3O4Composite nanofiber material and preparation method thereof |
| CN113546625B (en) * | 2021-04-02 | 2024-04-16 | 中国科学院城市环境研究所 | Electrostatic spinning defect TiO 2 /Fe 3 O 4 Composite nanofiber material and preparation method thereof |
| CN113793931A (en) * | 2021-11-18 | 2021-12-14 | 河南电池研究院有限公司 | Iron oxide negative electrode material for lithium ion battery and preparation method thereof |
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