CN110589897B - Method for preparing carbon-loaded Fe-Ti-O negative electrode material by taking metal organic framework as precursor - Google Patents
Method for preparing carbon-loaded Fe-Ti-O negative electrode material by taking metal organic framework as precursor Download PDFInfo
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- 229910003077 Ti−O Inorganic materials 0.000 title claims abstract description 35
- 239000007773 negative electrode material Substances 0.000 title claims abstract description 24
- 238000000034 method Methods 0.000 title claims abstract description 21
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 14
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 12
- 239000002243 precursor Substances 0.000 title claims abstract description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 15
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 12
- 239000013086 titanium-based metal-organic framework Substances 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 11
- 239000002904 solvent Substances 0.000 claims abstract description 10
- 238000000227 grinding Methods 0.000 claims abstract description 9
- 229910052742 iron Inorganic materials 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 239000004570 mortar (masonry) Substances 0.000 claims abstract description 7
- 238000001816 cooling Methods 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims abstract description 5
- 229910052573 porcelain Inorganic materials 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 8
- 239000010405 anode material Substances 0.000 claims description 7
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 7
- 239000010406 cathode material Substances 0.000 claims description 6
- 239000011812 mixed powder Substances 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910005451 FeTiO3 Inorganic materials 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical group Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 claims description 2
- YPJCVYYCWSFGRM-UHFFFAOYSA-H iron(3+);tricarbonate Chemical compound [Fe+3].[Fe+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O YPJCVYYCWSFGRM-UHFFFAOYSA-H 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 8
- 239000011363 dried mixture Substances 0.000 abstract 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 8
- 239000006230 acetylene black Substances 0.000 description 8
- 229910052744 lithium Inorganic materials 0.000 description 8
- 239000002033 PVDF binder Substances 0.000 description 6
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 5
- 239000011230 binding agent Substances 0.000 description 4
- 239000006258 conductive agent Substances 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 239000002131 composite material Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- 229910001290 LiPF6 Inorganic materials 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000000024 high-resolution transmission electron micrograph Methods 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 229910017135 Fe—O Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- YDZQQRWRVYGNER-UHFFFAOYSA-N iron;titanium;trihydrate Chemical compound O.O.O.[Ti].[Fe] YDZQQRWRVYGNER-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 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
- C01G49/08—Ferroso-ferric oxide [Fe3O4]
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- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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Abstract
A method for preparing a carbon-loaded Fe-Ti-O negative electrode material by taking a metal organic framework as a precursor belongs to the technical field of batteries. Mixing Ti-MOF and an iron source according to a certain proportion, dissolving the mixture in a solvent, and stirring at a certain temperature to uniformly mix the mixture until the solvent volatilizes; and (3) putting the dried mixture into a mortar for grinding, then putting the ground mixture into an atmosphere furnace for high-temperature treatment, and cooling to room temperature to obtain the carbon-loaded Fe-Ti-O negative electrode material. The Fe-Ti-O @ C material synthesized by the method has good electrochemical performance and high specific capacity; for the lithium ion battery, especially under high-rate charge and discharge, after 200 cycles, the capacity can also be maintained at 455mAh g‑1Good cyclability is exhibited.
Description
Technical Field
The invention belongs to the technical field of batteries, in particular to FeTiO3A method for preparing a cathode material by taking a metal organic framework as a precursor of a lithium ion battery.
Background
The lithium ion battery, as a representative of modern high-performance batteries, has the advantages of high specific energy, light weight, environmental protection and the like. Therefore, it is widely used for hybrid electric vehicles and portable electronic devices. Anode materials are an important component of lithium ion batteries and are the primary supplier of capacity. However, the theoretical capacity of graphite of the negative electrode material of the commercial lithium ion battery is only 372mAh g-1This is a major obstacle to its use. Therefore, promising anode substitutes with high specific capacity and cycle life were sought.
Metal Organic Frameworks (MOFs) and their derivatives have attracted a wide range of interest due to the high porosity, multifunctional structure and controllable chemical composition [1 ]]MOFs offer great possibilities for electrode materials for rechargeable batteries. For example,yu et al reported the synthesis of CoS using a ZIF-67 hollow prism2Nanometer bubble hollow prism [2 ]]Muhammad et al inspired by the local structure of CoZn-ZIF synthesized ZnCoS @ Co9S8NC polyhedron at 2000mA g-1Still providing 1095mAh g after 400 cycles at high current density-1Reversible capacity of [3 ]]。
Transition metal oxides have received a great deal of attention because of their high theoretical specific capacity, among which anatase TiO2The negative electrode material has stable structure because the volume change is only 3-4% in the charging and discharging process, but the low theoretical capacity is only 168-335 mAh g-1Thus, its application is limited. With TiO2Electrode comparison, Fe3O4The electrode has high theoretical specific capacity (930mAh g-1) In the aspects of earth abundance and environmental friendliness, Ti-based and Fe-based transition metal oxides have good development prospects. In view of TiO2And Fe3O4Can develop a new anode material by combining them. In this study, we developed a new composite negative electrode material, a carbon-supported Fe-Ti-O composite material, for use in lithium ion battery negative electrode materials. Li et al have recently reported a carbon-coated Ti-Fe-O composite for use in lithium ion batteries containing ilmenite, FeTiO3、Fe3O4、TiO2Particles at 500mA g-1After 500 cycles of circulation, 321.7mAh g can be maintained-1Capacity of (2) shows excellent cycle stability [4]This shows that the addition of carbon is effective in improving FeTiO3Electrochemical performance of
As the metal organic framework is used as the material synthesized by the precursor, a series of advantages are provided, so that in the work, the Fe-Ti-O nano particles loaded with carbon obtain high initial reversible capacity and cycle performance through the negative electrode material prepared by using the metal organic framework as the precursor, so that the Fe-Ti-O nano particles have more advantages and can be used as the anode material of the lithium ion battery.
Reference documents:
[1]R.Zhao,Z.Liang,R.Zou,Q.Xu,Metal-Organic Frameworks for Batteries,Joule,2(2018)2235-2259.
[2]L.Yu,J.F.Yang,X.W.Lou,Formation of CoS2 Nanobubble Hollow Prisms for Highly Reversible Lithium Storage,Angewandte Chemie International Edition,55(2016)13422-13426.
[3]M.K.Aslam,S.S.A.Shah,S.Li,C.Chen,Kinetically controlled synthesis of MOF nanostructures:single-holed hollow core–shell ZnCoS@Co9S8/NC for ultra-high performance lithium-ion batteries,Journal of Materials Chemistry A,6(2018)14083-14090.
[4]T.Li,X.Bai,N.Lun,Y.-X.Qi,Y.Tian,Y.-J.Bai,Nitrogen-doped carbon-coated Ti–Fe–O nanocomposites with enhanced reversible capacity and rate capability for high-performance lithium-ion batteries,RSC Advances,6(2016)65266-65274.
disclosure of Invention
The invention aims to prepare a lithium ion battery cathode material Fe-Ti-O @ C (wherein Fe-Ti-O represents FeTiO) with excellent electrochemical performance by adopting a simple experimental method3And Fe3O4The ratio of the two substances is not limited), the technical scheme of the invention is as follows.
A method for preparing a carbon-loaded Fe-Ti-O negative electrode material by taking a metal organic framework as a precursor is characterized by comprising the following steps of:
(1) mixing an iron source and Ti-MOF according to a certain proportion, dissolving in a solvent, heating and stirring until the solvent is volatilized;
(2) putting the mixed powder into a mortar for grinding to obtain powder;
(3) and placing the ground mixed powder into a porcelain boat, placing the porcelain boat into an atmosphere furnace, performing high-temperature treatment, and cooling to room temperature to obtain the Fe-Ti-O @ C negative electrode material.
The iron source is selected from ferric trichloride, ferric acetate, ferric carbonate, ferric nitrate, etc.;
the mass ratio of the Ti-MOF to the iron source is 1 (2-12);
the solvent is water, ethanol, etc.
The Ti-MOF is selected from MIL-125.
The high temperature treatment in the step (3)The conditions are as follows: n is a radical of2Or Ar and other inert atmosphere, raising the temperature to 600-800 ℃ at the speed of 5 ℃/min, and calcining the mixture powder for 5h in the constant-temperature process.
The cathode material obtained by the invention is used for the cathode material of the lithium ion battery.
The invention has the following advantages:
(1) the Fe-Ti-O @ C material provided by the invention is simple in preparation method, low in raw material price and harmless to the environment.
(2) The Fe-Ti-O @ C material synthesized by the method has good electrochemical performance and high specific capacity; particularly, under high-rate charge and discharge, the specific capacity can be kept high after about 200 cycles. Therefore, the invention successfully synthesizes the lithium ion battery cathode material with good electrochemical performance, and has great development potential and application prospect.
Drawings
FIG. 1 is an XRD graph, a is an XRD graph of a Ti-MOF material in example 1, and b is an XRD graph of a synthesized Fe-Ti-O @ C material in example 1; as can be seen from FIG. 1, FeTiO is present in XRD3And Fe3O4Characteristic peak of diffraction of (1). From the XRD pattern, the peak intensity of the resulting sample was high, indicating that the synthesized Fe-Ti-O @ C had high crystallinity.
FIG. 2 is an HRTEM image of Fe-Ti-O @ C (1:2.85) synthesized in example 1, from which it can be seen that Fe-Ti-O and C form a clad structure and a C shell is outside of Fe-Ti-O, and further demonstration that this method synthesizes an in-situ carbon clad is provided by the HRTEM image.
FIG. 3 is a graph showing the discharge specific capacity during charge and discharge in example 1, in which the lithium secondary battery prepared according to the present invention has a high discharge specific capacity, and (a) shows Fe-Ti-O @ C (1:2.85) at a current density of 200mA g-1The charge-discharge diagram of the previous three cycles under the conditions of (1); (b) shown is the current density at 2000mA g at high magnification-1The high specific capacity is kept after 200 cycles of discharge cycle diagram under the condition of (1), which shows that the Fe-Ti-O @ C battery prepared by the invention has excellent electrochemical performance.
FIG. 4 example 2 shows rate capability of lithium secondary battery prepared by the present invention during charging and dischargingHas good rate capability, and FIG. 4 shows that Fe-Ti-O @ C (1:3.8) has a current density of 100-2000mA g-1Discharge rate of 2000mA g at high rate current density-1Under the condition (1), the average capacity is 398mAh g-1This shows that the rate performance of the Fe-Ti-O @ C battery prepared by the invention is good.
Detailed Description
The present invention will be further described with reference to specific examples and comparative examples, but the present invention is not limited to the following examples.
Example 1:
(1) mixing Ti-MOF (MIL-125) with FeCl3·6H2Mixing O according to a certain proportion, dissolving in 100ml deionized water, stirring at 100 ℃ until the solvent is volatilized.
(2) The mixture was put in a mortar for grinding, and ground into powder.
(3) And placing the ground mixed powder into a porcelain boat, placing the porcelain boat into an atmosphere furnace, performing high-temperature treatment, and cooling to room temperature to obtain the Fe-Ti-O @ C negative electrode material.
The following is a detailed description of the above preparation:
Ti-MOF and FeCl in step one of the invention3·6H2The mass ratio of O is 1: 2.85.
The high-temperature treatment conditions in the third step are as follows: and (5) heating to 600 ℃ at the speed of 5 ℃/min in the Ar atmosphere, keeping the temperature constant, and calcining the mixture powder for 5 hours in the process of keeping the temperature constant.
The method comprises the steps of taking the Fe-Ti-O @ C material prepared in example 1 as a negative electrode material, PVDF as a binder and acetylene black as a conductive agent, weighing a certain amount of the negative electrode material and the acetylene black according to a certain proportion (the mass ratio of an active substance to the conductive agent to the binder is 8:1:1), pouring the negative electrode material and the acetylene black into a mortar, uniformly grinding the negative electrode material and the acetylene black, adding a certain amount of 10% PVDF, continuously grinding the PVDF to obtain uniform viscous black slurry, and uniformly coating the slurry on copper foil paper to prepare the electrode plate. Assembling lithium batteries in a vacuum glove box, and assembling according to the sequence of a negative electrode shell, a lithium sheet, a diaphragm, a positive electrode, a steel sheet, a spring sheet and a positive electrode shell (5-6 drops of electrolyte is dropped before the positive electrode sheet is placed, and the electrolyte is 1mol/L LiPF6Then, the assembled lithium battery is respectively subjected to discharge test under the conditions of (a) normal temperature of 25 ℃ and 200mA/g, and the reversible specific capacity of the first loop can reach 583mAh g-1. (b) 2000mA g at 25 ℃ and normal temperature-1The discharge test is carried out under the condition, after the circulation is carried out for 200 circles, the capacity can also be maintained at 455mAh g-1The good cyclability was exhibited, and the results are shown in FIG. 3.
Example 2:
(1) mixing Ti-MOF (MIL-125) with FeCl3·6H2Mixing O according to a certain proportion, dissolving in 100ml deionized water, stirring at 100 ℃ until the solvent is volatilized.
(2) The mixture was put in a mortar for grinding, and ground into powder.
(3) And placing the ground mixed powder into a porcelain boat, placing the porcelain boat into an atmosphere furnace, performing high-temperature treatment, and cooling to room temperature to obtain the Fe-Ti-O @ C negative electrode material.
The following is a detailed description of the above preparation:
Ti-MOF and FeCl in the first step3·6H2The mass ratio of O is 1: 3.8.
The high-temperature treatment conditions in the third step are as follows: and (5) heating to 600 ℃ at the speed of 5 ℃/min in the Ar atmosphere, keeping the temperature constant, and calcining the mixture powder for 5 hours in the process of keeping the temperature constant.
The electrode plate is prepared by taking the Fe-Ti-O @ C material prepared in the example 2 as a negative electrode material, PVDF as a binder and acetylene black as a conductive agent, weighing a certain amount of the negative electrode material and the acetylene black according to a certain proportion (active substance: conductive agent: binder: 8:1:1), pouring the negative electrode material and the acetylene black into a mortar, uniformly grinding the negative electrode material and the acetylene black, adding a certain amount of 10% PVDF, continuously grinding the PVDF to obtain uniform viscous black slurry, and uniformly coating the slurry on copper foil paper. Assembling lithium batteries in a vacuum glove box, and assembling according to the sequence of a negative electrode shell, a lithium sheet, a diaphragm, a positive electrode, a steel sheet, a spring sheet and a positive electrode shell (5-6 drops of electrolyte is dropped before the positive electrode sheet is placed, and the electrolyte is 1mol L-1LiPF6Then the assembled lithium battery is processed at normal temperature of 25 ℃ and at the temperature of 100-2000mA g-1Rate performance test under the condition of high rate 2000mA g-1At a discharge rate of (2), average capacity of398mAh g-1The results are shown in FIG. 4.
Claims (6)
1. A method for preparing a carbon-loaded Fe-Ti-O cathode material by taking a metal organic framework as a precursor is characterized in that Fe-Ti-O represents FeTiO3And Fe3O4The method comprises the following steps:
(1) mixing an iron source and Ti-MOF according to a certain proportion, dissolving in a solvent, heating and stirring until the solvent is volatilized;
(2) putting the mixed powder into a mortar for grinding to obtain powder;
(3) placing the ground mixed powder into a porcelain boat, placing the porcelain boat into an atmosphere furnace, performing high-temperature treatment, and cooling to room temperature to obtain a Fe-Ti-O @ C negative electrode material;
the mass ratio of the Ti-MOF to the iron source is 1 (2-12); the high-temperature treatment conditions in the step (3) are as follows: n is a radical of2Or Ar inert atmosphere, raising the temperature to 600-800 ℃ at the speed of 5 ℃/min, and calcining the mixture powder for 5h in the constant-temperature process.
2. The method for preparing the carbon-supported Fe-Ti-O negative electrode material by using the metal organic framework as the precursor according to claim 1, wherein the iron source is selected from ferric trichloride, ferric acetate, ferric carbonate and ferric nitrate.
3. The method for preparing the carbon-supported Fe-Ti-O negative electrode material by using the metal organic framework as the precursor according to claim 1, wherein the solvent is one or more of water and ethanol.
4. The method for preparing a carbon-supported Fe-Ti-O anode material by using a metal organic framework as a precursor according to claim 1, wherein the Ti-MOF is selected from MIL-125.
5. A carbon-supported Fe-Ti-O anode material prepared according to the method of any one of claims 1 to 4.
6. Use of the carbon-supported Fe-Ti-O anode material prepared according to the method of any one of claims 1 to 4 as an anode material for lithium ion batteries.
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