CN112624204A - Method for preparing lithium ion battery anode material based on Bayer process red mud photoreduction - Google Patents
Method for preparing lithium ion battery anode material based on Bayer process red mud photoreduction Download PDFInfo
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- 238000004131 Bayer process Methods 0.000 title claims abstract description 52
- 238000000034 method Methods 0.000 title claims abstract description 27
- 238000007540 photo-reduction reaction Methods 0.000 title claims abstract description 25
- 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
- 239000010405 anode material Substances 0.000 title claims description 15
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 50
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 25
- 238000007885 magnetic separation Methods 0.000 claims abstract description 10
- 239000010406 cathode material Substances 0.000 claims abstract description 6
- 239000002270 dispersing agent Substances 0.000 claims abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 34
- 239000000463 material Substances 0.000 claims description 26
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 24
- 150000001875 compounds Chemical class 0.000 claims description 20
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 238000001291 vacuum drying Methods 0.000 claims description 11
- 238000000227 grinding Methods 0.000 claims description 10
- 238000003760 magnetic stirring Methods 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
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- 238000010438 heat treatment Methods 0.000 claims description 9
- ULQISTXYYBZJSJ-UHFFFAOYSA-N 12-hydroxyoctadecanoic acid Chemical compound CCCCCCC(O)CCCCCCCCCCC(O)=O ULQISTXYYBZJSJ-UHFFFAOYSA-N 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 8
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 7
- 238000005286 illumination Methods 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 239000011521 glass Substances 0.000 claims description 5
- 229910052724 xenon Inorganic materials 0.000 claims description 5
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 5
- 229940114072 12-hydroxystearic acid Drugs 0.000 claims description 4
- 229920002367 Polyisobutene Polymers 0.000 claims description 3
- BFSVOASYOCHEOV-UHFFFAOYSA-N 2-diethylaminoethanol Chemical compound CCN(CC)CCO BFSVOASYOCHEOV-UHFFFAOYSA-N 0.000 claims description 2
- DXYUWQFEDOQSQY-UHFFFAOYSA-N n'-octadecylpropane-1,3-diamine Chemical compound CCCCCCCCCCCCCCCCCCNCCCN DXYUWQFEDOQSQY-UHFFFAOYSA-N 0.000 claims description 2
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052744 lithium Inorganic materials 0.000 abstract description 2
- 238000003860 storage Methods 0.000 abstract description 2
- 239000002131 composite material Substances 0.000 abstract 1
- 238000006460 hydrolysis reaction Methods 0.000 abstract 1
- 238000011065 in-situ storage Methods 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 15
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 10
- 229910052742 iron Inorganic materials 0.000 description 6
- 239000007772 electrode material Substances 0.000 description 5
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- 239000002028 Biomass Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
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- 238000006722 reduction reaction Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
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- 239000011889 copper foil Substances 0.000 description 1
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- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000000157 electrochemical-induced impedance spectroscopy Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
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- 229910001385 heavy metal Inorganic materials 0.000 description 1
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- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000002360 preparation method 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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- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
- C01G23/08—Drying; Calcining ; After treatment of titanium oxide
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
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Abstract
The invention discloses a method for preparing a lithium ion battery cathode material based on Bayer process red mud photoreduction, which comprises the steps of taking Bayer process red mud as a raw material, uniformly dispersing P25 type titanium dioxide in the Bayer process red mud through a hyper-dispersant, further extracting ferroferric oxide through microwave treatment, photoreduction reaction and a magnetic separation method, and then carrying out low-temperature hydrolysis reaction on in-situ composite titanium dioxide to obtain the lithium ion battery cathode material which has excellent lithium storage capacity.
Description
Technical Field
The invention relates to the technical field of red mud resource utilization and lithium ion batteries, in particular to a method for preparing a lithium ion battery anode material by red mud photoreduction based on a Bayer process.
Background
The red mud is a solid waste residue discharged when alumina is extracted in the aluminum industry, also contains various oxides and other heavy metal ions, is called red mud because the red mud contains a large amount of iron oxide which is red, and can be subdivided into Bayer process red mud, sintering process red mud and combination process red mud according to the treatment of different preparation processes. The natural ecological environment and the life of people are seriously influenced by the mass stockpiling of the red mud. At present, a plurality of laws issued by the nation prohibit a large amount of solid wastes such as red mud from being accumulated, and a conference research and development solution is held for a plurality of times, so that the technical direction of comprehensive utilization of the solid wastes is determined, and the industrial economic cycle, green and high-quality development is promoted. Although red mud is a waste which causes pollution to the environment, it contains some high-value metal elements and is a valuable resource. In recent years, the proportion of bayer process red mud in the total amount of red mud in China is increasing, and because bayer process red mud is red mud with high iron content, the recovery of iron resources from bayer process red mud is still the main research direction in China. Researchers show that various materials are extracted from Bayer process red mud, and diversified development is provided for recycling of the red mud. However, in the process of reducing iron oxide in red mud, reducing is generally adopted, and then magnetic separation is carried out to obtain iron ore concentrate for blast furnace ironmaking, so that the application of magnetic ferroferric oxide is usually ignored. For example: CN107385197 discloses a resource utilization method of red mud, which comprises the steps of adding a reduction transforming agent to carry out an alkalization thermal reduction reaction transformation product to obtain iron ore concentrate; CN107311479B discloses a method for synchronously improving the activity of inorganic components by reducing iron oxide in red mud with biomass, which utilizes the biomass to calcine and reduce the Bayer process red mud to obtain iron ore concentrate.
Disclosure of Invention
The invention mainly aims to solve the problems and provides a method for preparing a lithium ion battery cathode material by red mud photoreduction based on a Bayer process, which is applied to the lithium ion battery cathode material, and the technical scheme adopted by the invention is as follows:
(1) crushing the Bayer process red mud in a crusher, crushing the crushed Bayer process red mud in a ball mill, grinding the crushed Bayer process red mud into fine powder, adding deionized water and P25 type titanium dioxide, ultrasonically vibrating for 10 to 30min, then adding a hyper-dispersant, ultrasonically vibrating for 10 to 30min, and then carrying out microwave heating to prepare the Bayer process red mud/P25 compound;
(2) washing the Bayer process red mud/P25 compound prepared in the step (1) by using ethanol and deionized water respectively to remove surface organic matters, mixing the compound with 50-200mL of ethanol after vacuum drying, introducing nitrogen for 5-20min, transferring the compound into a three-neck flask sealed by a glass plug, continuously introducing nitrogen, carrying out illumination under magnetic stirring, and carrying out washing, magnetic separation and vacuum drying after the reaction is finished to obtain magnetic ferroferric oxide;
(3) and (3) mixing the ferroferric oxide prepared in the step (2) with ethanol, stirring for 5-10min, then adding titanium tetrachloride under magnetic stirring, quickly stirring for 5-30min, transferring to a 40 ℃ drying oven for drying, and grinding to obtain the ferroferric oxide/titanium dioxide material.
Preferably, the bayer process red mud of step (1) is a high-iron red mud, wherein the content of ferric oxide is 25.6-28.2%.
Preferably, the fine powder in the step (1) is 0.1-0.02 mm.
Preferably, the hyperdispersant in the step (1) is one or more of diethylethanolamine, octadecylaminopropylamine, 12-hydroxystearic acid and terminal polyisobutene.
Preferably, the mass-to-volume ratio of the Bayer process red mud, the deionized water, the P25 type titanium dioxide and the hyperdispersant in the step (1) is (2-5) g, (100-300) mL, (2-5) g, (0.1-0.5) g.
Preferably, the microwave heating in step (1) is heating at 350-.
Preferably, the nitrogen in the step (2) is introduced at a flow rate of 2-3 bubbles per second under 0.4 MPa.
Preferably, the light irradiation in the step (2) is a xenon lamp with an ultraviolet filter for carrying out the photoreduction reaction for 10-24 h.
Preferably, the magnetic separation in the step (2) is to extract ferroferric oxide accounting for 12.1-19.6% of the red mud in the Bayer process.
Preferably, the mass-to-volume ratio of the ferroferric oxide, the ethanol and the titanium tetrachloride in the step (3) is (0.1-1) g of (50-100) mL of (2-5) mL of titanium tetrachloride.
Compared with the prior art, the technical scheme of the invention has the following beneficial effects:
(1) the method utilizes the characteristic of high iron content of Bayer process red mud, adopts high dispersant and high photocatalytic activity P25 for compounding, further excites electrons through a green photoreduction method, reduces the material, and further extracts ferroferric oxide.
(2) The red mud photoreduction-based ferroferric oxide/titanium dioxide lithium ion battery cathode material prepared by the method has good electrochemical performance, and benefits from the synergistic effect of titanium dioxide and ferroferric oxide, and the ferroferric oxide increases the conductivity of the material, thereby being beneficial to the rapid transmission of electrons.
Drawings
FIG. 1 is an X-ray diffraction pattern of the material prepared in example 3.
Fig. 2 is a graph of cycle performance of lithium ion batteries of the materials prepared in example 3 and comparative example 2.
FIG. 3 is a graph showing electrochemical impedance curves of the materials prepared in example 3 and comparative example 2.
Detailed Description
To further clarify the disclosure, features and advantages of the present invention, reference will now be made to the following examples and to the accompanying drawings.
Example 1
A method for preparing a lithium ion battery anode material based on Bayer process red mud photoreduction specifically comprises the following steps:
(1) crushing 5g of Bayer process red mud in a crusher, crushing the crushed material in a ball mill, grinding the crushed material into fine powder, adding 250mL of deionized water and 5g P25 type titanium dioxide, carrying out ultrasonic oscillation for 10min, adding 0.4g of 12-hydroxystearic acid, carrying out ultrasonic oscillation for 20min, and then carrying out microwave heating for 1h at 400W to prepare a Bayer process red mud/P25 compound;
(2) washing the Bayer process red mud/P25 compound prepared in the step (1) by using ethanol and deionized water respectively to remove surface organic matters, mixing the compound with 200mL of ethanol after vacuum drying, introducing nitrogen for 10min, transferring the compound into a three-neck flask sealed by a glass plug, continuously introducing nitrogen, performing illumination for 20h by using a xenon lamp with an ultraviolet filter under magnetic stirring, and performing washing, magnetic separation and vacuum drying after the reaction is finished to obtain magnetic ferroferric oxide;
(3) and (3) mixing 1g of ferroferric oxide prepared in the step (2) with 100mL of ethanol, stirring for 5min, then adding 4mL of titanium tetrachloride under magnetic stirring, quickly stirring for 15min, transferring to an oven at 40 ℃ for drying, and grinding to obtain the ferroferric oxide/titanium dioxide material.
Example 2
A method for preparing a lithium ion battery anode material based on Bayer process red mud photoreduction specifically comprises the following steps:
(1) crushing 5g of Bayer process red mud in a crusher, crushing the crushed material in a ball mill, grinding the crushed material into fine powder, adding 250mL of deionized water and 5g P25 type titanium dioxide, carrying out ultrasonic oscillation for 10min, adding 0.3g of 12-hydroxystearic acid, carrying out ultrasonic oscillation for 20min, and then carrying out microwave heating for 1h at 500W to prepare a Bayer process red mud/P25 compound;
(2) washing the Bayer process red mud/P25 compound prepared in the step (1) by using ethanol and deionized water respectively to remove surface organic matters, mixing the compound with 200mL of ethanol after vacuum drying, introducing 15min of nitrogen, transferring the compound into a three-neck flask sealed by a glass plug, continuously introducing nitrogen, performing 24-hour illumination by using a xenon lamp with an ultraviolet filter under magnetic stirring, and performing washing, magnetic separation and vacuum drying after the reaction is finished to obtain magnetic ferroferric oxide;
(3) and (3) mixing 0.75g of ferroferric oxide prepared in the step (2) with 100mL of ethanol, stirring for 5min, then adding 3mL of titanium tetrachloride under magnetic stirring, quickly stirring for 15min, transferring to an oven at 40 ℃ for drying, and grinding and finely crushing to obtain the ferroferric oxide/titanium dioxide material.
Example 3
A method for preparing a lithium ion battery anode material based on Bayer process red mud photoreduction specifically comprises the following steps:
(1) crushing 5g of Bayer process red mud in a crusher, crushing the crushed red mud in a ball mill, grinding the crushed red mud into fine powder, adding 250mL of deionized water and 5g P25 type titanium dioxide, ultrasonically vibrating for 10min, adding 0.5g of end group polyisobutene, ultrasonically vibrating for 20min, and then heating the mixture for 1h under 400W to prepare a Bayer process red mud/P25 compound;
(2) washing the Bayer process red mud/P25 compound prepared in the step (1) by using ethanol and deionized water respectively to remove surface organic matters, mixing the compound with 200mL of ethanol after vacuum drying, introducing nitrogen for 10min, transferring the compound into a three-neck flask sealed by a glass plug, continuously introducing nitrogen, performing illumination for 24h by using a xenon lamp with an ultraviolet filter under magnetic stirring, and performing washing, magnetic separation and vacuum drying after the reaction is finished to obtain magnetic ferroferric oxide;
(3) and (3) mixing 0.75g of ferroferric oxide prepared in the step (2) with 100mL of ethanol, stirring for 5min, then adding 4mL of titanium tetrachloride under magnetic stirring, quickly stirring for 15min, transferring to an oven at 40 ℃ for drying, and grinding and finely crushing to obtain the ferroferric oxide/titanium dioxide material.
The ferroferric oxide/titanium dioxide material prepared in the embodiment 3 of the invention is subjected to X-ray diffraction characterization test, battery cycle performance test and electrochemical impedance test to further analyze the physical and chemical properties of the material.
Comparative example 1
The difference between the comparative example 1 and the example 3 is that the P25 type titanium dioxide and the hyperdispersant are not added during the extraction of the ferroferric oxide.
When the material is subjected to magnetic separation after the photoreduction reaction, only 3.8 percent of magnetic substances can be extracted, and the photoreduction is incomplete because the P25 type titanium dioxide and the hyperdispersant are not added.
Comparative example 2
Comparative example 2 of the present invention differs from example 3 in that no magnetite is added.
The electrochemical performance test scheme is as follows:
(1) assembling the battery: the electrode material prepared by the embodiment is weighed with the super conductive carbon and the polyvinylidene fluoride according to the mass ratio of 7:2:1, dissolved in N-methyl pyrrolidone, ground into uniform slurry, coated on copper foil, dried at low temperature, placed in a vacuum drying oven for drying for 6 hours, and finally cut into wafers by a slicing machine. The cells were assembled in a glove box under argon and then tested for electrochemical performance using a blue cell tester and an electrochemical workstation.
(2) And (3) testing charge and discharge cycles: placing the battery in a battery channel of a blue battery tester, setting the theoretical specific capacity of the material to be 376mAh/g, setting the voltage test interval to be 1-3V, carrying out charge-discharge test at the current density of 168mA/g, and circulating 150 times in total to finish the experiment. After the test is finished, the data information of the battery cycle times and the specific capacity can be obtained from the blue battery system, and then the data can be further plotted and analyzed, as shown in fig. 2.
(3) Electrochemical impedance spectroscopy test: the cell was placed in the cell holder of an Auto Lab electrochemical workstation, the voltage test interval was set to 1-3V, 80 data points were selected, and the test was performed at a scan rate of 0.5 mV/s. After the test is completed, the data can be further plotted and analyzed, as shown in fig. 3.
FIG. 1 is an X-ray diffraction pattern of the material prepared in example 3, which was measured using an X-ray diffractometer of the Japanese XRD-7000S/L type, with a scanning range of 5-70 DEG and a scanning speed of 10 DEG per minute. The diffraction peak of titanium dioxide can be obviously observed from the XRD pattern in the figure, and can be matched with the standard PDF card (21-1272) of the titanium dioxide, and two strong diffraction peaks are also found at 36.6 and 65.1, and can be correspondingly matched with the (311) crystal face and the (440) crystal face of ferroferric oxide, which further indicates that the ferroferric oxide is successfully extracted from the material and the titanium dioxide is successfully compounded.
Fig. 2 is a graph of cycle performance of lithium ion batteries of the materials prepared in example 3 and comparative example 2. The electrode materials prepared in the embodiment 3 and the comparative example 2 of the invention have large fluctuation of specific capacity value in the first 5-cycle charge and discharge test, and the specific capacity of the electrode materials gradually tends to be stable after 5-cycle test, because the electrode materials are in an activation stage at the initial stage of the battery test. It can be observed from the graph that after the battery is stabilized, the specific discharge capacities of example 3 and comparative example 2 are 252mAh/g and 132mAh/g in turn when the 5 th cycle of charge and discharge test is carried out; the specific discharge capacity in the 150 th cycle of charge-discharge test is 186mAh/g and 101mAh/g in sequence, and the capacity loss is 26.2 percent and 23.5 percent in sequence. This shows that the ferroferric oxide/titanium dioxide material prepared in example 3 of the present invention has excellent lithium storage capacity, and the capacity loss rate after 150 cycles is 26.2%, and still has a high specific capacity value.
Fig. 3 is a graph showing electrochemical impedance curves of the materials prepared in example 3 and comparative example 2, which consists of a semicircle and a diagonal line, wherein the diameter of the semicircle represents the impedance generated by the electrochemical reaction occurring between the electrolyte and the electrode material. It can be clearly observed from the figure that example 3 has a smaller impedance value, because the ferroferric oxide has good electron conductivity, and the ferroferric oxide and the titanium dioxide are successfully compounded into the material to increase the conductivity, thereby accelerating the electron transmission, and the reason that the ferroferric oxide/titanium dioxide material has better performance is also laterally illustrated.
While the foregoing is directed to the preferred embodiment of the present invention, other and further embodiments of the invention may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow. Such modifications and variations are considered to be within the scope of the invention.
Claims (10)
1. A method for preparing a lithium ion battery cathode material based on Bayer process red mud photoreduction is characterized by comprising the following steps:
(1) crushing the Bayer process red mud in a crusher, crushing the crushed Bayer process red mud in a ball mill, grinding the crushed Bayer process red mud into fine powder, adding deionized water and P25 type titanium dioxide, ultrasonically vibrating for 10 to 30min, then adding a hyper-dispersant, ultrasonically vibrating for 10 to 30min, and then carrying out microwave heating to prepare the Bayer process red mud/P25 compound;
(2) washing the Bayer process red mud/P25 compound prepared in the step (1) by using ethanol and deionized water respectively to remove surface organic matters, mixing the compound with 50-200mL of ethanol after vacuum drying, introducing nitrogen for 5-20min, transferring the compound into a three-neck flask sealed by a glass plug, continuously introducing nitrogen, carrying out illumination under magnetic stirring, and carrying out washing, magnetic separation and vacuum drying after the reaction is finished to obtain magnetic ferroferric oxide;
(3) and (3) mixing the ferroferric oxide prepared in the step (2) with ethanol, stirring for 5-10min, then adding titanium tetrachloride under magnetic stirring, quickly stirring for 5-30min, transferring to a 40 ℃ drying oven for drying, and grinding to obtain the ferroferric oxide/titanium dioxide material.
2. The method for preparing the lithium ion battery anode material based on Bayer process red mud photoreduction according to claim 1, wherein the Bayer process red mud in the step (1) is high-iron red mud, and the content of ferric oxide is 25.6-28.2%.
3. The method for preparing the lithium ion battery anode material based on Bayer process red mud photoreduction according to claim 1, wherein the fine powder in the step (1) is 0.1-0.02 mm.
4. The method for preparing the lithium ion battery anode material based on Bayer process red mud photoreduction according to claim 1, wherein the hyperdispersant in the step (1) is one or more of diethylethanolamine, octadecylaminopropylamine, 12-hydroxystearic acid and terminal group polyisobutene.
5. The method for preparing the lithium ion battery anode material based on Bayer process red mud photoreduction according to claim 1, wherein the mass-to-volume ratio of the Bayer process red mud to deionized water, the P25 type titanium dioxide and the hyperdispersant in the step (1) is (2-5) g, (100) -300 mL, (2-5) g and (0.1-0.5) g.
6. The method for preparing the lithium ion battery anode material based on Bayer process red mud photoreduction according to claim 1, wherein the microwave heating in the step (1) is heating at 350-600W for 0.5-2 h.
7. The method for preparing the lithium ion battery anode material by the Bayer process red mud photoreduction according to claim 1, wherein the nitrogen in the step (2) is introduced at a flow rate of 2-3 bubbles per second under 0.4 MPa.
8. The method for preparing the lithium ion battery anode material based on Bayer process red mud photoreduction according to claim 1, wherein the illumination in the step (2) is a photoreduction reaction carried out for 10-24h by a xenon lamp with an ultraviolet filter.
9. The method for preparing the lithium ion battery anode material based on Bayer process red mud photoreduction according to claim 1, wherein the magnetic separation in the step (2) is that the extracted ferroferric oxide accounts for 12.1-19.6% of the Bayer process red mud.
10. The method for preparing the lithium ion battery anode material based on Bayer process red mud photoreduction according to claim 1, wherein the mass-to-volume ratio of the ferroferric oxide, the ethanol and the titanium tetrachloride in the step (3) is (0.1-1) g, (50-100) mL and (2-5) mL.
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