CN117985769A - Carbon-coated ferroferric oxide lithium ion battery negative electrode material and preparation method thereof - Google Patents
Carbon-coated ferroferric oxide lithium ion battery negative electrode material and preparation method thereof Download PDFInfo
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 19
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 239000007773 negative electrode material Substances 0.000 title abstract description 6
- CUPCBVUMRUSXIU-UHFFFAOYSA-N [Fe].OOO Chemical compound [Fe].OOO CUPCBVUMRUSXIU-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000010405 anode material Substances 0.000 claims abstract description 16
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910021519 iron(III) oxide-hydroxide Inorganic materials 0.000 claims abstract description 15
- 239000012298 atmosphere Substances 0.000 claims abstract description 11
- 229960003638 dopamine Drugs 0.000 claims abstract description 8
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 7
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 claims abstract description 6
- 229960004887 ferric hydroxide Drugs 0.000 claims abstract description 5
- 239000002105 nanoparticle Substances 0.000 claims abstract description 4
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 3
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 3
- 239000002245 particle Substances 0.000 claims abstract description 3
- 229920001690 polydopamine Polymers 0.000 claims abstract description 3
- 239000002243 precursor Substances 0.000 claims abstract description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 38
- 239000000047 product Substances 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 239000008367 deionised water Substances 0.000 claims description 16
- 229910021641 deionized water Inorganic materials 0.000 claims description 16
- 229910002588 FeOOH Inorganic materials 0.000 claims description 13
- 239000000843 powder Substances 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 239000002135 nanosheet Substances 0.000 claims description 7
- 229920002873 Polyethylenimine Polymers 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 claims description 5
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 5
- 229960001149 dopamine hydrochloride Drugs 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 229910052573 porcelain Inorganic materials 0.000 claims description 5
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 5
- 235000011152 sodium sulphate Nutrition 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 4
- OWMVSZAMULFTJU-UHFFFAOYSA-N bis-tris Chemical compound OCCN(CCO)C(CO)(CO)CO OWMVSZAMULFTJU-UHFFFAOYSA-N 0.000 claims description 3
- 239000010406 cathode material Substances 0.000 claims description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 3
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims description 2
- 238000003763 carbonization Methods 0.000 claims description 2
- 238000005119 centrifugation Methods 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- 238000006722 reduction reaction Methods 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 claims description 2
- 238000005245 sintering Methods 0.000 claims description 2
- 239000012265 solid product Substances 0.000 claims description 2
- 239000004094 surface-active agent Substances 0.000 claims description 2
- 230000002441 reversible effect Effects 0.000 abstract description 7
- 238000012360 testing method Methods 0.000 abstract description 7
- 238000004146 energy storage Methods 0.000 abstract description 2
- 239000011232 storage material Substances 0.000 abstract description 2
- 231100000956 nontoxicity Toxicity 0.000 abstract 1
- 239000002131 composite material Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 229910052744 lithium Inorganic materials 0.000 description 5
- 238000003917 TEM image Methods 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000013543 active substance Substances 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000010532 solid phase synthesis reaction Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002064 nanoplatelet Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000004729 solvothermal method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention belongs to the technical field of energy storage materials, and particularly relates to a carbon-coated ferroferric oxide lithium ion battery anode material and a preparation method thereof. The preparation method comprises the following steps: preparing precursor ferric hydroxide by adopting a hydrothermal method; modifying the iron oxyhydroxide with dopamine; and (3) placing polydopamine modified ferric hydroxide into a tube furnace to be calcined in an inert atmosphere to obtain carbon-coated metal oxide nano particles, wherein the particle size is 50-250nm, and the thickness is 4-7nm. The lithium ion button cell prepared by the negative electrode material has excellent performance in a charge-discharge test, and after the current density is 200mA g ‑1 and the cycle is 120 weeks, the specific discharge capacity can be kept at 1629mAh g ‑1; after the current density is 20A g ‑1 and the cycle is 3000 weeks, the specific discharge capacity can still be maintained at 623.6mAh g ‑1; the lithium ion battery anode material has higher reversible capacity and good cycle stability. The preparation method has the characteristics of simple operation, safety and no toxicity.
Description
Technical Field
The invention belongs to the technical field of energy storage materials, and particularly relates to a carbon-coated ferroferric oxide lithium ion battery anode material and a preparation method thereof.
Background
Lithium ion secondary batteries are favored because of their high voltage, high specific energy, wide operating temperature range, low self-discharge rate, no memory effect, and environmental friendliness. Currently, lithium ion batteries are widely used in portable devices such as mobile phones, notebook computers, video cameras, and the like, and are being widely used in the fields of electric vehicles, satellites, military, and the like in the future [1].
In the field of negative electrode materials for lithium batteries, carbon negative electrode materials commonly used in the traditional industry have a theoretical capacity of 372mAh g -1 [2]. However, the transition metal oxides in the novel anode materials have a higher theoretical capacity, far exceeding carbon anode materials. The ferroferric oxide (Fe 3O4) not only has high theoretical capacity (924 mAh g -1), but also has the advantages of higher safety voltage, good conductivity, low cost, abundant natural resources, environmental protection and the like [3]. However, the use of Fe 3O4 in lithium ion batteries is limited by its large volume change during insertion/removal of lithium and poor cycling performance due to agglomeration [4]. To further improve the electrochemical properties of Fe 3O4, researchers have employed a variety of modification methods including the preparation of nano-sized Fe 3O4, carbon coated Fe 3O4, and Fe 3O4/graphene composites, etc. [5-7]. Nanomaterials, particularly two-dimensional nanoplatelets, have a large specific surface area and a short diffusion path, contributing to improved electrochemical performance [8]. The carbon coating layer can effectively relieve the large volume change of the active substances in the charging and discharging process of the battery, and avoid the aggregation of the active substances. At present, the preparation method of the carbon-coated Fe 3O4 nano composite material mainly comprises a hydrothermal method, a solvothermal method, a ball milling method, a coprecipitation method, a high-temperature solid phase method and the like [9-3]. Compared with the traditional hydrothermal method, the high-temperature solid-phase method has the advantages of low cost, simple preparation process, high yield, easy realization of industrial production and the like.
[1]Kim T,Song W,Son D Y,et al.Lithium-ion batteries:outlook on present,future,and hybridized technologies[J].Journal of materials chemistry A,2019,7(7):2942-2964.
[2]Wang Y,Deng Y,Qu Q,et al.Ultrahigh-capacity organic anode with high-rate capability and long cycle life for lithium-ion batteries[J].ACS Energy Letters,2017,2(9):2140-2148.
[3]Liu M,Jin H,Uchaker E,et al.One-pot synthesis of in-situ carbon-coated Fe3O4as a long-life lithium-ion battery anode[J].Nanotechnology,2017,28(15):155603.
[4]Hsieh C T,Lin J Y,Mo C Y.Improved storage capacity and rate capability of Fe3O4–graphene anodes for lithium-ion batteries[J].Electrochimica Acta,2011,58:119-124.
[5]Behera S K.Facile synthesis and electrochemical properties of Fe3O4nanoparticles for Liion battery anode[J].Journal of Power Sources,2011,196(20):8669-8674.
[6]Yu Y,Zhu Y,Gong H,et al.Fe3O4nanoparticles embedded in carbon-framework as anode material for high performance lithium-ion batteries[J].Electrochimica acta,2012,83:53-58.
[7]Gu S,Zhu A.Graphene nanosheets loaded Fe3O4nanoparticles as a promising anode material for lithium ion batteries[J].Journal of Alloys and Compounds,2020,813:152160.
[8]Li Z,Zhao H,Wang J,et al.3D heterostructure Fe3O4/Ni/C nanoplate arrays on Ni foam as binder-free anode for high performance lithium-ion battery[J].Electrochimica Acta,2015,182:398-405.
[9]Li H,Wang J,Li Y,et al.Hierarchical sandwiched Fe3O4@C/Graphene composite as anode material for lithium-ion batteries[J].Journal of Electroanalytical Chemistry,2019,847:113240.
[10]Gu S,Zhu A.Graphene nanosheets loaded Fe3O4nanoparticles as a promising anode material for lithium ion batteries[J].Journal of Alloys and Compounds,2020,813:152160.
[11]Liu H,Luo S,Hu D,et al.Design and synthesis of carbon-coatedα-Fe2O3@Fe3O4heterostructured as anode materials for lithium ion batteries[J].Applied Surface Science,2019,495:143590.
[12]Ai Q,Yuan Z,Huang R,et al.One-pot co-precipitation synthesis of Fe3O4nanoparticles embedded in 3D carbonaceous matrix as anode for lithium ion batteries[J].Journal of Materials Science,2019,54(5):4212-4224.
[13]Chen X,Zhu X,Cao G,et al.Fe3O4-based anodes with high conductivity and fast ion diffusivity designed for high-energy lithium-ion batteries[J].Energy&Fuels,2020,35(2):1810-1819.
Disclosure of Invention
The invention aims to provide a carbon-coated ferroferric oxide lithium ion battery anode material and a preparation method thereof, which are used for solving the problems that the conductivity of the Fe 3O4 anode material is poor, the specific capacity of the battery is attenuated too fast in the charge-discharge cycle process and the like.
The preparation method of the carbon-coated ferroferric oxide lithium ion battery cathode material comprises the steps of preparing precursor ferric oxide hydroxide by adopting a hydrothermal method; modifying the iron oxyhydroxide with dopamine; placing polydopamine modified iron oxyhydroxide into a tube furnace for calcination in an inert atmosphere to obtain carbon-coated metal oxide nanoparticles, wherein the specific steps are as follows:
(1) Preparation of iron oxyhydroxide:
Using deionized water as a solvent, dissolving Fe salt in ionized water to serve as an Fe source, simultaneously adding sodium sulfate and polyethyleneimine to serve as a surfactant, performing hydrothermal reaction, centrifugally cleaning the obtained product, and drying in vacuum to obtain iron oxyhydroxide powder which is marked as FeOOH.
The specific operation flow is as follows: at room temperature (20-25 ℃), dissolving Fe salt and sodium sulfate in deionized water; gradually adding the polyethyleneimine into the Fe salt solution, and transferring the mixture into a reaction kettle after stirring for 20-60 minutes; heating to 130-155 ℃ for 8-24 hours. Centrifuging the product, washing with deionized water for many times, and finally vacuum drying at 20-80 ℃ for 4-16 hours to obtain brown ferric hydroxide powder;
(2) Preparation of Fe 3O4 @ C nanosheets:
Uniformly dispersing FeOOH in deionized water by using deionized water as a solvent; the product is obtained through dopamine coating and carbonization reduction reaction under inert atmosphere, namely Fe 3O4 @C nano-sheets;
The specific operation flow is as follows:
Uniformly dispersing FeOOH in deionized water at room temperature (20-25 ℃); adjusting the pH value of the solution to be 8.5 through Bis-Tris buffer solution, and then adding dopamine hydrochloride solution, wherein the mass ratio of dopamine hydrochloride to FeOOH is 1:1-1:5; continuously stirring for 18-24 hours; transferring the product into a centrifuge tube, and performing centrifugal cleaning for a plurality of times by using deionized water; transferring the product into a vacuum drying oven, and drying at 20-80deg.C for 10-16 hr to obtain brown powder, namely dopamine coated ferric hydroxide, denoted FeOOH@dopa; placing the FeOOH@dopa product into a porcelain boat, heating to 400-600 ℃ at a heating rate of 1-5 ℃/min under a reducing atmosphere, and sintering at constant temperature for 3-6 hours; after the mixture is naturally cooled, a black solid product is obtained and is marked as Fe 3O4 @C.
In the step (1), feCl 3、Fe(NO3)2 or a hydrate thereof is adopted as the Fe salt; feCl 3·6H2 O is preferably used. Sodium sulfate and polyethyleneimine are additives.
In the step (2), the reducing atmosphere is Ar or N 2, and the flow rate of the gas is controlled to be 50-150mL/min.
The Fe 3O4 @C prepared by the method has the particle size of 50-250nm and the thickness of 4-7nm; the catalyst has excellent cycle performance; fe 3O4 @C can realize high-capacity long-cycle under the current density of 20A g -1, and can be used as a negative electrode material of a lithium ion battery; the lithium ion battery cathode material further improves the cycle stability while maintaining high specific capacity.
Compared with the prior art, the invention has the following advantages:
(1) The Fe 3O4 ultrathin nano-sheet has a huge specific surface area and excellent charge transmission rate, so that the reaction interface between the electrode and the electrolyte is enlarged, and the charge transfer is promoted, and the conductivity and the charge-discharge performance of the battery are improved.
(2) Because carbon has excellent conductivity, the Fe 3O4/carbon lithium ion battery composite anode material can conveniently conduct carriers in the charge and discharge process, and can effectively relieve volume change, thereby maintaining structural stability.
(3) The preparation process is simple, the synthesis is convenient, the yield is high, the repeatability is good, and therefore, the method is very suitable for being used in practical lithium ion battery application, and the feasibility of realizing large-scale production is realized.
Drawings
FIG. 1 is an XRD pattern of the iron oxyhydroxide material obtained in example 1 of the present invention.
FIG. 2 is an SEM image of the iron oxyhydroxide material obtained in example 1 of the present invention.
FIG. 3 is a TEM image of the iron oxyhydroxide material obtained in example 1 of the present invention.
Fig. 4 is an XRD pattern of the ferroferric oxide material obtained in example 1 of the present invention.
Fig. 5 is an SEM image of the ferroferric oxide material obtained in example 1 of the present invention.
Fig. 6 is a TEM image of the ferroferric oxide material obtained in example 1 of the present invention.
Fig. 7 is a graph showing charge and discharge performance of the composite anode material of the Fe 3O4 @ C lithium ion battery obtained in example 1 of the present invention as an anode material of the lithium ion battery at a current density of 500 mg -1.
Fig. 8 is a graph showing charge and discharge performance of the composite anode material of the Fe 3O4 @ C lithium ion battery obtained in example 1 of the present invention as an anode material of the lithium ion battery at a current density of 20Ag -1.
Detailed Description
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention.
Example 1:
(1) Preparation of iron oxyhydroxide
3Mmol of FeCl 3·6H2 O and 3mmol of Na 2SO4 were dissolved in 75mL of deionized water at room temperature (25 ℃) and stirred for 10 minutes. Subsequently, 0.006mmol of polyethylenimine was added and stirring was continued for 30 minutes. The mixture was transferred to a reaction kettle, heated to 150 ℃ and reacted for 20 hours. The product after the reaction was separated by centrifugation and washed 3 times with deionized water, and then vacuum-dried at 60 ℃ for 12 hours, to finally obtain brown powder. Analysis by X-ray powder diffraction (XRD) showed that the resulting product was pure iron oxyhydroxide without any other impurity phase (see figure 1 for details). The iron oxyhydroxide is shown in the form of flakes in a Scanning Electron Microscope (SEM) image, with a length of between 50 and 250nm (see fig. 2 for details). The iron oxyhydroxide is further shown in the form of flakes in Transmission Electron Microscopy (TEM) images to a thickness of about 4.8nm (see figure 3 for details).
(2) Preparation of Fe 3O4 @ C nanosheets:
80mg of FeOOH was dispersed in 50ml of deionized water at room temperature (20-25 ℃). The pH of the solution was adjusted to 8.5 by Bis-Tris solution, then 25ml (2 mg/ml) of dopamine hydrochloride solution was added and stirring was continued for 48 hours. Transferring the product into a centrifuge tube, carrying out centrifugal cleaning for a plurality of times by using deionized water, transferring the final product into a vacuum drying oven, and drying at 60 ℃ for 12 hours to obtain gray black powder which is the dopamine coated iron oxyhydroxide. Then, the product is placed in a porcelain boat, heated to 500 ℃ under the argon atmosphere, kept for 4 hours, and cooled naturally to obtain black Fe 3O4 @C solid powder. XRD analysis showed the resulting product to be pure ferroferric oxide without any other impurity phases (as shown in figure 4). The ferroferric oxide is seen in SEM pictures to be flake-like, with a length of 50-250nm (as shown in FIG. 5). In the TEM image, it can be seen that the carbon-coated ferroferric oxide is flake-like and has a thickness of 5.1nm (as shown in FIG. 6).
(3) The Fe 3O4 @C lithium ion battery composite anode material prepared in the embodiment and a lithium sheet are assembled into a button cell. When constant current charge and discharge test is carried out at 25 ℃ and a current density of 200mA g -1 in a range of 0.01-3.0V, the reversible capacity is 1629mAh g -1 after 120 weeks of circulation. When constant current charge and discharge test is carried out at 25 ℃ and current density of 20A g -1 in the interval of 0.01-3.0V, the reversible capacity is 623.6mAh g -1 after 3000 weeks of circulation.
Example 2:
Polydopamine-modified iron oxyhydroxide was prepared in the same manner as in steps (1) and (2) of example 1. 100mg of dopamine-modified iron oxyhydroxide powder is put into a porcelain boat, heated to 400 ℃ and kept at a constant temperature for 4 hours under the Ar atmosphere. After the reaction was completed, the mixture was cooled to room temperature and the black product was taken out. Further, XRD pattern analysis shows that the result of preparing the Fe 3O4 @C composite material is similar to that of example 1.
The Fe 3O4 @C lithium ion battery composite anode material prepared in the embodiment and a lithium sheet are assembled into a button cell. When the constant current charge and discharge test is carried out at 25 ℃ and a current density of 200mA g -1 in a range of 0.01-3.0V, the reversible capacity is 1210mAh g -1 after 120 weeks of circulation. When the constant current charge and discharge test is carried out at 25 ℃ and a current density of 20A g-1 in a range of 0.01-3.0V, the reversible capacity is 546.3mAh g -1 after 3000 weeks of circulation.
Example 3:
Polydopamine-modified iron oxyhydroxide was prepared in the same manner as in steps (1) and (2) of example 1. 100mg of dopamine-modified iron oxyhydroxide powder is put into a porcelain boat, heated to 500 ℃ and kept at a constant temperature for 4 hours under the Ar atmosphere. After the reaction was completed, the mixture was cooled to room temperature and the black product was taken out. Further, XRD pattern analysis shows that the result of preparing the Fe 3O4 @C composite material is similar to that of example 1.
The Fe 3O4 @C lithium ion battery composite anode material prepared in the embodiment and a lithium sheet are assembled into a button cell. When constant current charge and discharge test is carried out at 25 ℃ and a current density of 200mA g -1 in a range of 0.01-3.0V, the reversible capacity is 1013mAh g -1 after 120 weeks of circulation. When constant current charge and discharge test is carried out at 25 ℃ and current density of 20A g -1 in the interval of 0.01-3.0V, the reversible capacity is 466.1mAh g -1 after 3000 weeks of circulation.
Claims (6)
1. The preparation method of the carbon-coated ferroferric oxide lithium ion battery cathode material is characterized in that a hydrothermal method is adopted to prepare precursor ferric oxide hydroxide; modifying the iron oxyhydroxide with dopamine; placing polydopamine modified iron oxyhydroxide into a tube furnace for calcination in an inert atmosphere to obtain carbon-coated metal oxide nanoparticles, wherein the specific steps are as follows:
(1) Preparation of iron oxyhydroxide:
Dissolving Fe salt in ionized water to serve as an Fe source, adding sodium sulfate and polyethyleneimine to serve as a surfactant at the same time, performing hydrothermal reaction, centrifugally cleaning the obtained product, and drying in vacuum to obtain ferric hydroxide powder which is marked as FeOOH;
(2) Preparation of Fe 3O4 @ C nanosheets:
Uniformly dispersing FeOOH in deionized water; and obtaining a product, namely the Fe 3O4 @C nano sheet, through dopamine coating and carbonization reduction reaction carried out in inert atmosphere.
2. The preparation method according to claim 1, wherein the specific operation flow in the step (1) is as follows: at room temperature, dissolving Fe salt and sodium sulfate in deionized water; gradually adding the polyethyleneimine into the Fe salt solution, and transferring the mixture into a reaction kettle after stirring for 20-60 minutes; heating to 130-155 ℃ for 8-24 hours; the product is subjected to centrifugation and repeated deionized water cleaning, and is dried in vacuum at 20-80 ℃ for 4-16 hours, so as to obtain brown iron oxyhydroxide powder.
3. The method according to claim 2, wherein the Fe salt in step (1) is FeCl 3、Fe(NO3)2 or a hydrate thereof.
4. The preparation method according to claim 1, wherein the specific operation flow of step (2) is as follows: uniformly dispersing FeOOH in deionized water at room temperature; adjusting the pH value of the solution to be 8.5 through Bis-Tris buffer solution, and then adding dopamine hydrochloride solution, wherein the mass ratio of dopamine hydrochloride to FeOOH is 1:1-1:5; continuously stirring for 18-24 hours; transferring the product into a centrifuge tube, and performing centrifugal cleaning for a plurality of times by using deionized water; transferring the product into a vacuum drying oven, and drying at 20-80deg.C for 10-16 hr to obtain brown powder, namely dopamine coated ferric hydroxide, denoted FeOOH@dopa; placing the FeOOH@dopa product into a porcelain boat, heating to 400-600 ℃ at a heating rate of 1-5 ℃/min under a reducing atmosphere, and sintering at constant temperature for 4-6 hours; and after the mixture is naturally cooled, obtaining a black solid product, namely Fe 3O4 @C.
5. The method according to claim 4, wherein the reducing atmosphere in the step (2) is Ar or N 2, and the flow rate of the controlled gas is 50-150mL/min.
6. The carbon-coated ferric oxide lithium ion battery anode material obtained by the preparation method of one of claims 1 to 5 is a nano sheet, the particle size is 50 to 250nm, and the thickness is 4 to 7nm.
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