CN105006550A - Nanocrystalline iron oxide coating stereoplasm carbon microsphere composite material and preparing method and application thereof - Google Patents
Nanocrystalline iron oxide coating stereoplasm carbon microsphere composite material and preparing method and application thereof Download PDFInfo
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- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 title claims abstract description 148
- 239000004005 microsphere Substances 0.000 title claims abstract description 57
- 239000002131 composite material Substances 0.000 title claims abstract description 39
- 238000000034 method Methods 0.000 title claims abstract description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title abstract description 24
- 229910052799 carbon Inorganic materials 0.000 title abstract description 24
- 239000011248 coating agent Substances 0.000 title abstract description 9
- 238000000576 coating method Methods 0.000 title abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 239000008367 deionised water Substances 0.000 claims abstract description 15
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 15
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 9
- 239000004094 surface-active agent Substances 0.000 claims abstract description 9
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims abstract description 8
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims abstract description 8
- 229930006000 Sucrose Natural products 0.000 claims abstract description 8
- 239000008103 glucose Substances 0.000 claims abstract description 8
- 239000005720 sucrose Substances 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims abstract description 7
- 239000003513 alkali Substances 0.000 claims abstract description 5
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims abstract description 5
- 239000011258 core-shell material Substances 0.000 claims abstract description 5
- 238000001035 drying Methods 0.000 claims abstract description 3
- 229910021385 hard carbon Inorganic materials 0.000 claims description 67
- 239000002105 nanoparticle Substances 0.000 claims description 61
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 32
- 238000002360 preparation method Methods 0.000 claims description 26
- 239000000243 solution Substances 0.000 claims description 19
- 239000002245 particle Substances 0.000 claims description 14
- 238000013019 agitation Methods 0.000 claims description 12
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 8
- 229910052744 lithium Inorganic materials 0.000 claims description 8
- 238000000967 suction filtration Methods 0.000 claims description 8
- 150000002505 iron Chemical class 0.000 claims description 7
- 239000012266 salt solution Substances 0.000 claims description 7
- 230000002776 aggregation Effects 0.000 claims description 6
- 239000010406 cathode material Substances 0.000 claims description 6
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 claims description 6
- 238000004220 aggregation Methods 0.000 claims description 4
- 238000010792 warming Methods 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000001816 cooling Methods 0.000 abstract description 3
- 238000001914 filtration Methods 0.000 abstract 1
- 239000004615 ingredient Substances 0.000 abstract 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 abstract 1
- 239000000463 material Substances 0.000 description 16
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 239000003610 charcoal Substances 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 6
- 238000002389 environmental scanning electron microscopy Methods 0.000 description 6
- 238000009413 insulation Methods 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 229910000859 α-Fe Inorganic materials 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 230000007246 mechanism Effects 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 230000002427 irreversible effect Effects 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000007770 graphite material Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 239000002931 mesocarbon microbead Substances 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229960004887 ferric hydroxide Drugs 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 description 1
- YOBAEOGBNPPUQV-UHFFFAOYSA-N iron;trihydrate Chemical compound O.O.O.[Fe].[Fe] YOBAEOGBNPPUQV-UHFFFAOYSA-N 0.000 description 1
- 239000010977 jade Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 235000013759 synthetic iron oxide Nutrition 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000012546 transfer Methods 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
- H01M4/366—Composites as layered products
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- 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
-
- 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
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Composite Materials (AREA)
- Nanotechnology (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
Provided is a nanocrystalline iron oxide coating stereoplasm carbon microsphere composite material. The composite material is of a core-shell structure. A stereoplasm carbon microsphere serves as an inner core, nanocrystalline iron oxide serves as a coating shell, and the surface of the stereoplasm carbon microsphere is coated with the nanocrystalline iron oxide. A preparing method comprises the following steps that glucose and sucrose are dissolved in deionized water, reaction is carried out under a heating condition, cooling is carried out, repeated extracting and filtering are conducted, and drying is carried out; a product is placed into an inert atmosphere tube furnace again, the temperature is increased to reach above 900 DEG C, and high-heat treatment is carried out; an obtained product is mixed with a surface active agent and is added into the deionized water, a molysite solution is added, after full stirring is carried out, alkali liquor is added dropwise, hydrothermal reaction is carried out under the temperature ranging from 110 DEG C to 150 DEG C, and the nanocrystalline iron oxide coating stereoplasm carbon microsphere composite material is obtained. The product ingredients are simple, preparing is easy to carry out, the cost is low, the safety is achieved, the environment is protected, and the product performance is better.
Description
Technical field
The invention belongs to material with carbon element preparing technical field, particularly the preparation technology of cell negative electrode material nano-sized iron oxide load carbon microballoon and application.
Background technology
In the industrial application in modern times, lithium cell cathode material generally selects graphite material, due to the limitation that graphite material exists unsustainable property, the restriction of storage lithium mechanism causes limited and other aspect of performances of theoretical capacity, cause other material with carbon elements, such as hard carbon microballoon, MCMB become extremely potential lithium cell cathode material.Hard carbon microballoon is generally the unformed charcoal that biological material prepares, and its degree of crystallinity is lower and structure organization is unordered, complicated; And MCMB is a kind of graphitized carbon material be obtained by reacting from asphalt material, degree of crystallinity is high.Bi-material belongs to different Carbon Materials.Hard carbon microballoon has good spherical morphology, specific area is large, easily has good cyclical stability at area load nano-sized iron oxide.And the specific capacity of nano-sized iron oxide is large, but due to the reaction in electrochemical process irreversible, cause cycle performance not good.
At present, hard carbon ball does not also carry out suitability for industrialized production in a large number, and the method preparing now hard carbon ball is mainly hydro thermal method, in single hydro thermal method, the growth of charcoal ball mainly meets Lamer model, under certain experiment condition, polymerization reaction take place, form aromatic compound and compound sugar, along with time lengthening and reaction temperature raise, there is nucleation, this is the cross-linking reaction caused due to dehydration intermolecular between compound sugar, or in previous steps, have other macromolecular formation, and the core then formed is in the solution caused by isotropic growth.And the charcoal ball that method prepares thus is difficult to keep comparatively intact spherical morphology while further loaded with nano oxide, be also difficult to loaded with nano oxide equably, electrochemical properties has some limitations.
The oxide of iron due to its aboundresources, low price, do not have the features such as toxicity to be applied as lithium cell cathode material yet, in electrochemical reaction process, its mechanism may be due to alloy mechanism, primary irreversible capacity is large, and after repeatedly circulating, capacity attenuation is comparatively large, have impact on cyclical stability.
In recent years, rapidly, the theoretical capacity of material with carbon element is little, but cycle performance is better, and the oxide capacity of iron is comparatively large in C-base composte material development, but it is high that the crystal structure irreversible degree that subsides easily occurs in course of reaction.For adapting to the technical requirements such as lithium ion battery negative lithium storage content is large, conductance is high, good cycling stability, be necessary to be further improved existing preparation technology.
Summary of the invention
Technical problem to be solved by this invention is, overcome the deficiency and defect mentioned in above background technology, there is provided that a kind of composition is simple, preparation easily, safe green and the coated hard carbon microsphere composite of the better nano-sized iron oxide of properties of product, also correspondingly provide the preparation method of the coated hard carbon microsphere composite of simple, easy to operate, the low-cost nano-sized iron oxide of a kind of technique and the application as lithium cell cathode material, this application can improve the charge/discharge capacity of battery, and ensures cyclical stability.
For solving the problems of the technologies described above, the technical scheme that the present invention proposes is the coated hard carbon microsphere composite of a kind of nano-sized iron oxide, and this composite material is coreshell type structure, with hard carbon microballoon for kernel, using nano-sized iron oxide as coated housing, nano-sized iron oxide is coated on hard carbon microsphere surface.
The coated hard carbon microsphere composite of above-mentioned nano-sized iron oxide, preferred: the particle mean size of described hard carbon microballoon is at 2 μm ~ 5 μm, and the particle mean size of described nano-sized iron oxide is at 50 ~ 100nm.
The coated hard carbon microsphere composite of above-mentioned nano-sized iron oxide, preferred: described nano-sized iron oxide is coated on hard carbon microsphere surface by situ aggregation method.
The said goods scheme of the present invention is mainly based on following thinking: first, hard carbon micro-sphere material is a kind of novel carbon based negative electrodes material, the chemical property comparatively excellent due to himself and its spherical structure have larger specific area, condition is provided to the fabricated in situ of nano-sized iron oxide, nano-sized iron oxide is attached to possibility hard carbon microballoon matrix decreasing reunion, this makes this material have larger capacity and good cycle performance, and environmental friendliness and preparation cost cheap.
As a total technical conceive, the present invention also provides the preparation method of the coated hard carbon microsphere composite of a kind of above-mentioned nano-sized iron oxide, comprises the following steps:
(1) by glucose or sucrose dissolved in deionized water, fully stir and pour in reactor, fully react in a heated condition, after reaction, be cooled to room temperature, repeatedly suction filtration dry; The dominant mechanism of this step is that glucose or sucrose are dissolved in deionized water, forms oligomer, then by hydro-thermal reaction, oligomer is polymerized, then nucleation, balling-up;
(2) product that above-mentioned steps (1) obtains is placed in the tube furnace of inert atmosphere, is warming up to more than 900 DEG C and carries out high-temperature heat treatment; This step can stablize the charcoal spherical structure of above-mentioned formation, for next step complex iron oxide is prepared;
(3) add in deionized water after the product that above-mentioned steps (2) obtains being mixed with surfactant, ultrasonic agitation, add iron salt solutions gradually, after fully stirring, dropwise add alkali lye (preferred sodium hydroxide solution, also potassium hydroxide or ammoniacal liquor can be used), ultrasonic agitation, pours in reactor, at 110 DEG C ~ 150 DEG C, carry out hydro-thermal reaction, after reaction, suction filtration also dry process repeatedly, obtains the coated hard carbon microsphere composite of nano-sized iron oxide; This step assists synthetic iron oxide by utilizing surfactant, and controls its particle size, generates ferric hydroxide colloid after adding certain density alkali lye, then through hydro-thermal reaction, forms iron oxide.
In above-mentioned preparation method, preferably, in described step (1), glucose or the sucrose dissolved concentration after deionized water is 0.5mol/L ~ 1mol/L, reaction temperature after described heating is 160 DEG C ~ 180 DEG C, and the time of fully reaction is 4 ~ 6h.
In above-mentioned preparation method, preferably, in described step (2), it is 5 ~ 10 DEG C/s that heating rate controls, and heat treated temperature is 900 DEG C ~ 1100 DEG C, and the heat treated time is 4 ~ 6h.
In above-mentioned preparation method, preferably, in described step (3), described iron salt solutions is iron nitrate solution, and the concentration of described iron salt solutions is 0.5 ~ 1mol/L, and the consumption of iron salt solutions is depending on other raw materials, be generally about 20mL, the concentration of described sodium hydroxide solution is 0.5mol/L ~ 2mol/L, and the rate of addition of described sodium hydroxide solution is 4 ~ 10/10s, and consumption is preferably about 10mL).
In above-mentioned preparation method, preferably, in described step (3), softex kw selected by described surfactant, and the mass ratio when product that step (2) obtains mixes with surfactant is 1: 0.5 ~ 1: 1.
In above-mentioned preparation method, preferably, in described step (3), the temperature of hydro-thermal reaction is 110 DEG C ~ 150 DEG C, and the reaction time is 12h ~ 24h.
Above-mentioned preparation method of the present invention mainly adopts glucose or sucrose as the raw material preparing hard carbon microballoon, hard carbon microballoon is prepared, then further loaded with nano iron oxide and then obtain a kind of novel composite lithium ion battery negative material on this basis by two-step method.
As a total technical conceive, the present invention also provides the coated hard carbon microsphere composite of a kind of above-mentioned nano-sized iron oxide as the application of lithium cell cathode material.
Compared with prior art, the invention has the advantages that:
1. the present invention has prepared the coated hard carbon microsphere composite of the more excellent nano-sized iron oxide of a kind of performance, our electrochemistry experiment shows: adopt the lithium ion battery that the coated hard carbon microsphere composite of nano-sized iron oxide of the present invention is prepared into, compare battery prepared by single material, its cycle performance and capacity have had obvious lifting.
2. the raw materials that adopts of the present invention and preparation technology are on the basis keeping the advantages such as existing production craft step is simple, low cost of manufacture, also have the advantage of following uniqueness:
(1) by two step synthesis hard carbon microballoon, on the basis of water heat transfer charcoal ball, again under an inert gas high-temperature heat treatment is carried out to the material of first step synthesis, to stablize its pattern, improve the character of its colloid ball, reduce and reunite, ensure that in the process of synthesis of nano iron oxide, charcoal ball can not change its pattern and character;
(2) add surfactant in the process of synthesis of nano iron oxide in position simultaneously, enhance the active deposit position on charcoal ball surface, while the particle diameter controlling nano-sized iron oxide can uniform load on hard carbon microballoon;
(3) the present invention to prepare in hard carbon ball process without the need to carrying out the operations such as freeze drying, in building-up process, avoids the use of harmful substance, makes whole course of reaction clean environment firendly, have sustainability, and with low cost.
Accompanying drawing explanation
In order to be illustrated more clearly in the embodiment of the present invention or technical scheme of the prior art, be briefly described to the accompanying drawing used required in embodiment or description of the prior art below, apparently, accompanying drawing in the following describes is some embodiments of the present invention, for those of ordinary skill in the art, under the prerequisite not paying creative work, other accompanying drawing can also be obtained according to these accompanying drawings.
Fig. 1 is the preparation flow figure of the coated hard carbon microballoon of nano-sized iron oxide of the present invention.
Fig. 2 is the ESEM microphoto of carbon microspheres before and after nano-sized iron oxide particles coat in the embodiment of the present invention 1.Wherein, left figure be coated before ESEM microphoto, right figure be coated after ESEM microphoto.
Fig. 3 is the XRD figure of the coated hard carbon microsphere composite of nano-sized iron oxide in the embodiment of the present invention 1,2.
Fig. 4 is the embodiment of the present invention 1 coating product Fe
2o
3battery specific capacity-cycle-index performance test curve that front and back are made.
Fig. 5 is transmission electron microscope (TEM) figure of the coated hard carbon microsphere composite of product nano-sized iron oxide that the embodiment of the present invention 1 obtains.Wherein, a figure is low resolution TEM (embedded figure is shape appearance figure), and b figure is high-resolution TEM.
Fig. 6 is the ESEM microphoto of carbon microspheres before and after nano-sized iron oxide particles coat in the embodiment of the present invention 2.Wherein, left figure be coated before ESEM microphoto, right figure be coated after ESEM microphoto.
Fig. 7 is the embodiment of the present invention 2 coating product Fe
2o
3battery specific capacity-cycle-index performance test curve that front and back are made.
Embodiment
For the ease of understanding the present invention, hereafter will do to describe more comprehensively, meticulously to the present invention in conjunction with Figure of description and preferred embodiment, but protection scope of the present invention is not limited to following specific embodiment.
Unless otherwise defined, hereinafter used all technical terms are identical with the implication that those skilled in the art understand usually.The object of technical term used herein just in order to describe specific embodiment is not be intended to limit the scope of the invention.
Unless otherwise specified, the various raw material, reagent, instrument and equipment etc. used in the present invention are all bought by market and are obtained or prepare by existing method.
Embodiment 1:
The coated hard carbon microsphere composite of a kind of nano-sized iron oxide of the present invention, this composite material is coreshell type structure, and with hard carbon microballoon for kernel, using nano-sized iron oxide as coated housing, nano-sized iron oxide is coated on hard carbon microsphere surface.The particle mean size of the hard carbon microballoon of the present embodiment is at about 3 μm, and the particle mean size of nano-sized iron oxide is at 50nm.This nano-sized iron oxide is coated on hard carbon microsphere surface by situ aggregation method.
The above-mentioned coated hard carbon microsphere composite of nano-sized iron oxide of the present embodiment mainly adopts following steps to prepare (see Fig. 1):
1. the preparation of hard carbon microballoon:
The 1.1 sucrose solution 70ml getting 0.5mol/L, ultrasonic agitation 1h, the capacity of moving to is in the teflon-lined autoclave of 100ml, be placed in baking oven again and be heated to 180 DEG C of insulation 5h, room temperature is cooled to after reaction, colloidal solution deionized water and ethanol are replaced suction filtration 3 times repeatedly, dries 4h in 70 DEG C.
Product after above-mentioned oven dry to be positioned over and to be connected with in the tube furnace of nitrogen by 1.2, and with the ramp to 1000 DEG C of 5 DEG C/S, insulation 5h, takes out after being cooled to room temperature, then by it fully grinding obtain sample.
2. the preparation of the coated hard carbon microballoon of nano-sized iron oxide:
2.1 hard carbon microballoon products above-mentioned steps 1 prepared are got 0.2g and are added 30ml deionized water, then add 0.2g softex kw with the ratio of mass ratio 1:1, ultrasonic agitation 1h.
2.2 by the nine water iron nitrate solution 20ml of 0.5mol/L, and abundant stirring and dissolving, then adds in the mixed liquor of above-mentioned steps 2.1, ultrasonic agitation 1h gradually by iron nitrate solution.
2.3 by 1mol/L sodium hydroxide solution 10ml, instill in the mixture of step 2.2 with dropper with the speed of 5/10s again, the capacity that moved to by mixture after ultrasonic agitation 2h is in the teflon-lined autoclave of 100ml, it is positioned over baking oven, is warming up to 130 DEG C, insulation 18h, after naturally cooling, replace suction filtration 3 times through deionized water and ethanol, dry 4h in 70 DEG C, obtain the coated hard carbon microsphere composite of nano-sized iron oxide.
As shown in Figure 2, the not coated carbon microspheres shown in Fig. 2 and the present embodiment contrast through the scanning electron micrograph of the coated hard carbon microballoon of nano-sized iron oxide the electron scanning micrograph of the coated hard carbon microsphere composite of the product nano-sized iron oxide that above-mentioned the present embodiment obtains by we.As can be seen from Figure 2, not coated carbon microspheres smooth surface, spherical complete, size is at about 3 μm; And the product of the present invention after nano-sized iron oxide is coated still maintains perfect spherical morphology, and it is evenly coated, the result of the product contrast of coated front and back shows, carbon microspheres in product of the present invention is effectively coated by nano oxidized iron material, and the pattern of coated rear carbon microspheres keeps complete, iron oxide uniform particle sizes, without obvious agglomeration, covering amount is better.The XRD figure of the coated hard carbon microsphere composite of the product nano-sized iron oxide that the present embodiment obtains as shown in Figure 3.As seen from Figure 3, the product of the present embodiment after XRD test, product in (012), (104), (113), (024), (116), (214), (330), the crystal face such as (1010) and (220) can corresponding α-Fe
2o
32 θ=24.1 ° in standard diagram (JCPDS Card No.33-0664), 33.1 °, 35.6 °, 49.4 °, 54.0 °, 62.4 °, 63.9 °, 71.0 ° and 75 ° are angularly.
Fig. 5 is the transmission electron microscope picture of the coated hard carbon microsphere composite of product nano-sized iron oxide that the present embodiment obtains, as can be seen from Figure 5, covered effect and observe in SEM figure more consistent, obviously to see the area load obvious nanometer α of the lattice-Fe at agraphitic carbon amorphous substance under high-resolution-ration transmission electric-lens
2o
3, coating thickness is about 100nm, learns that (104) interplanar distance of iron oxide in this sample is through measurements and calculations
, in JADE, obtain (104) interplanar distance is
, this just can in conjunction with the test result of above-mentioned XRD, and the peak in (104) face is the most obvious by force, and in detail in this figure, the total amount in this face is also maximum.Determine α-Fe
2o
3successfully be coated on the surface of carbon microspheres, and its crystal formation is obvious, degree of crystallinity is fine.
The present embodiment coating product Fe
2o
3battery specific capacity-cycle-index performance test curve that front and back are made as shown in Figure 4, as seen from Figure 4, after the circulation of 30 times, the battery discharge specific capacity that the present embodiment material is made remains on 310.1mAh/g, the battery that not coated carbon microspheres is made then only has 204.5mAh/g, and this shows through nanometer α-Fe
2o
3after coated, battery specific capacity has had and has significantly improved, and cycle performance is also more stable.
Embodiment 2:
The coated hard carbon microsphere composite of a kind of nano-sized iron oxide of the present invention, this composite material is coreshell type structure, and with hard carbon microballoon for kernel, using nano-sized iron oxide as coated housing, nano-sized iron oxide is coated on hard carbon microsphere surface.The particle mean size of the hard carbon microballoon of the present embodiment about 2 μm, the particle mean size of nano-sized iron oxide is about 50nm.This nano-sized iron oxide is coated on hard carbon microsphere surface by situ aggregation method.
The above-mentioned coated hard carbon microsphere composite of nano-sized iron oxide of the present embodiment mainly adopts following steps to prepare (see Fig. 1):
1. the preparation of hard carbon microballoon:
The 1.1 glucose solution 70ml getting 0.5mol/L, ultrasonic agitation 1h, the capacity of moving to is in the teflon-lined autoclave of 100ml, be placed in baking oven again and be heated to 170 DEG C of insulation 4h, room temperature is cooled to after reaction, colloidal solution deionized water and ethanol are replaced suction filtration 3 times repeatedly, dries 4h in 70 DEG C.
Product after above-mentioned oven dry to be positioned over and to be connected with in the tube furnace of nitrogen by 1.2, and with the ramp to 900 DEG C of 5 DEG C/S, insulation 6h, takes out after being cooled to room temperature, then by it fully grinding obtain sample.
2. the preparation of the coated hard carbon microballoon of nano-sized iron oxide:
2.1 hard carbon microballoon products above-mentioned steps 1 prepared are got 0.2g and are added 30ml deionized water, then add 0.2g softex kw with the ratio of mass ratio 1:1, ultrasonic agitation 1h.
2.2 by the nine water iron nitrate solution 20ml of 0.5mol/L, and abundant stirring and dissolving, then adds in the mixed liquor of above-mentioned steps 2.1, ultrasonic agitation 1h gradually by iron nitrate solution.
2.3 by 1mol/L sodium hydroxide solution 10ml, instill in the mixture of step 2.2 with dropper with the speed of 5/10s again, the capacity that moved to by mixture after ultrasonic agitation 2h is in the teflon-lined autoclave of 100ml, it is positioned over baking oven, is warming up to 130 DEG C, insulation 18h, after naturally cooling, replace suction filtration 3 times through deionized water and ethanol, dry 4h in 70 DEG C, obtain the coated hard carbon microsphere composite of nano-sized iron oxide.
As shown in Figure 6, the not coated carbon microspheres shown in Fig. 6 and the present embodiment contrast through the scanning electron micrograph of the coated hard carbon microballoon of nano-sized iron oxide the electron scanning micrograph of the coated hard carbon microsphere composite of the product nano-sized iron oxide that above-mentioned the present embodiment obtains by we.As can be seen from Figure 6, not coated carbon microspheres smooth surface, spherical complete, size is at about 2 μm; And the product of the present invention after nano-sized iron oxide is coated still maintains perfect spherical morphology, and it is evenly coated, the result of the product contrast of coated front and back shows, carbon microspheres in product of the present invention is effectively coated by nano oxidized iron material, and the pattern of coated rear carbon microspheres keeps complete, iron oxide uniform particle sizes, without obvious agglomeration, covering amount is better.The XRD figure of the coated hard carbon microsphere composite of the product nano-sized iron oxide that the present embodiment obtains as shown in Figure 3.As seen from Figure 3, the product of the present embodiment after XRD test, product in (012), (104), (113), (024), (116), (214), (330), the crystal face such as (1010) and (220) can corresponding α-Fe
2o
32 θ=24.1 ° in standard diagram (JCPDS Card No.33-0664), 33.1 °, 35.6 °, 49.4 °, 54.0 °, 62.4 °, 63.9 °, 71.0 ° and 75 ° are angularly.
The present embodiment coating product Fe
2o
3battery specific capacity-cycle-index performance test curve that front and back are made as shown in Figure 7, as seen from Figure 7, after the circulation of 30 times, the battery discharge specific capacity that the present embodiment material is made remains on 219.3mAh/g, the battery that not coated carbon microspheres is made then only has 204.5mAh/g, and this shows through nanometer α-Fe
2o
3after coated, battery specific capacity has had certain raising, and cycle performance is also more stable.
Claims (10)
1. the coated hard carbon microsphere composite of nano-sized iron oxide, it is characterized in that: this composite material is coreshell type structure, with hard carbon microballoon for kernel, using nano-sized iron oxide as coated housing, nano-sized iron oxide is coated on hard carbon microsphere surface.
2. the coated hard carbon microsphere composite of nano-sized iron oxide according to claim 1, is characterized in that: the particle mean size of described hard carbon microballoon is at 2 μm ~ 5 μm, and the particle mean size of described nano-sized iron oxide is at 50 ~ 100nm.
3. the coated hard carbon microsphere composite of nano-sized iron oxide according to claim 1 and 2, is characterized in that: described nano-sized iron oxide is coated on hard carbon microsphere surface by situ aggregation method.
4. the preparation method of the coated hard carbon microsphere composite of nano-sized iron oxide according to any one of claims 1 to 3, comprises the following steps:
(1) by glucose or sucrose dissolved in deionized water, fully stir and pour in reactor, fully react in a heated condition, after reaction, be cooled to room temperature, repeatedly suction filtration dry;
(2) product that above-mentioned steps (1) obtains is placed in the tube furnace of inert atmosphere, is warming up to more than 900 DEG C and carries out high-temperature heat treatment;
(3) add in deionized water after the product that above-mentioned steps (2) obtains being mixed with surfactant, ultrasonic agitation, add iron salt solutions gradually, after fully stirring, dropwise add alkali lye, ultrasonic agitation, pour in reactor, at 110 DEG C ~ 150 DEG C, carry out hydro-thermal reaction, after reaction, suction filtration also dry process repeatedly, obtains the coated hard carbon microsphere composite of nano-sized iron oxide.
5. preparation method according to claim 4, it is characterized in that, in described step (1), glucose or the sucrose dissolved concentration after deionized water is 0.5mol/L ~ 1mol/L, reaction temperature after described heating is 160 DEG C ~ 180 DEG C, and the time of fully reaction is 4 ~ 6h.
6. the preparation method according to claim 4 or 5, is characterized in that, in described step (2), it is 5 ~ 10 DEG C/s that heating rate controls, and heat treated temperature is 900 DEG C ~ 1100 DEG C, and the heat treated time is 4 ~ 6h.
7. the preparation method according to claim 4 or 5, it is characterized in that, in described step (3), described iron salt solutions is iron nitrate solution, the concentration of described iron salt solutions is 0.5 ~ 1mol/L, described alkali lye is sodium hydroxide solution, and the concentration of sodium hydroxide solution is 0.5mol/L ~ 2mol/L, and the rate of addition of described sodium hydroxide solution is 4 ~ 10/10s.
8. the preparation method according to claim 4 or 5, it is characterized in that, in described step (3), softex kw selected by described surfactant, and the mass ratio when product that step (2) obtains mixes with surfactant is 1: 0.5 ~ 1: 1.
9. the preparation method according to claim 4 or 5, is characterized in that, in described step (3), the temperature of hydro-thermal reaction is 110 DEG C ~ 150 DEG C, and the reaction time is 12h ~ 24h.
10. the coated hard carbon microsphere composite of according to any one of claims 1 to 3 or that preparation method obtains any one of claim 4 ~ 9 nano-sized iron oxide is as the application of lithium cell cathode material.
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| CN110137465A (en) * | 2019-05-13 | 2019-08-16 | 江苏科技大学 | A kind of carbon@Fe2O3@carbosphere composite material and its application |
| CN110723754A (en) * | 2019-09-19 | 2020-01-24 | 桂林理工大学 | Using Fe (OH)3Preparation of alpha-Fe from colloid and sucrose2O3Method for preparing electrode material |
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| CN101302005A (en) * | 2008-05-22 | 2008-11-12 | 同济大学 | One-step synthesis method of surface loaded magnetic Fe2O3 nano-particle colloidal carbon ball |
| CN101817562A (en) * | 2009-09-05 | 2010-09-01 | 大连理工大学 | Method for preparing hollow spherical Alpha-Fe2O3 by carbon-sugar microsphere template method |
| CN103208625A (en) * | 2013-04-24 | 2013-07-17 | 北京科技大学 | Preparation method of ferroferric-oxide-based high-performance negative electrode material for lithium ion battery |
| CN104393284A (en) * | 2014-11-17 | 2015-03-04 | 天津大学 | Nickel oxide nano-particle loaded porous hard carbon sphere negative electrode material and preparation method thereof |
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| CN101302005A (en) * | 2008-05-22 | 2008-11-12 | 同济大学 | One-step synthesis method of surface loaded magnetic Fe2O3 nano-particle colloidal carbon ball |
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| CN110137465A (en) * | 2019-05-13 | 2019-08-16 | 江苏科技大学 | A kind of carbon@Fe2O3@carbosphere composite material and its application |
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| CN110723754A (en) * | 2019-09-19 | 2020-01-24 | 桂林理工大学 | Using Fe (OH)3Preparation of alpha-Fe from colloid and sucrose2O3Method for preparing electrode material |
| CN110723754B (en) * | 2019-09-19 | 2022-03-22 | 桂林理工大学 | Using Fe (OH)3Preparation of alpha-Fe from colloid and sucrose2O3Method for preparing electrode material |
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