CN104766953A - Preparation method of titanium dioxide/iron oxide composite anode material - Google Patents

Preparation method of titanium dioxide/iron oxide composite anode material Download PDF

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CN104766953A
CN104766953A CN201510149172.XA CN201510149172A CN104766953A CN 104766953 A CN104766953 A CN 104766953A CN 201510149172 A CN201510149172 A CN 201510149172A CN 104766953 A CN104766953 A CN 104766953A
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titanium dioxide
oxide composite
iron oxide
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negative pole
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CN104766953B (en
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郭兴忠
朱文均
王子晨
杨辉
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Zhejiang University ZJU
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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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • 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
    • 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
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Abstract

The invention discloses a preparation method of a titanium dioxide/iron oxide composite anode material. The preparation method sequentially comprises the following steps of (1) dissolving titanyl sulfate into deionized water, then, adding iron salt, and stirring until the iron salt is dissolved; (2) adding polyvinylpyrrolidone into the solution obtained in the step (1), and stirring until polyvinylpyrrolidone is completely dissolved; (3) dropwise adding methanamide into the solution obtained in the step (2) while fiercely stirring, and aging gel after stirring for 5-10 minutes; (4) drying the gel obtained in the step (3) under normal pressure at 50-70 DEG C for 22-26 hours to obtain a precursor product; and (5) heating the precursor product at the air atmosphere to 500-800 DEG C, keeping the temperature for 5-7 hours, and cooling to the room temperature to obtain the titanium dioxide/iron oxide composite anode material. The titanium dioxide/iron oxide composite anode material has relatively-high specific capacity and stable circulating performance.

Description

The preparation method of titanium dioxide/iron oxide composite negative pole material
Technical field
The invention belongs to lithium ion battery new energy Material Field, be specifically related to the preparation method of a kind of titanium dioxide/iron oxide composite negative pole material.
Background technology
Lithium ion battery is widely used in all kinds of Miniature Portable Units such as mobile phone, video camera and computer as a kind of novel green high-energy chemistry power supply, also has important application prospect in the field such as electric automobile, Aero-Space simultaneously.In recent years, be that the novel industrial technology of representative obtains and develops rapidly with electric automobile, meanwhile also higher performance requirement proposed to lithium ion battery.Negative material is part main in lithium ion battery, and current commercial Li-ion battery generally adopts graphite-based material as negative material, and its storage lithium specific capacity is less than 350mAh g usually -1, this lower specific capacity is more and more difficult to practical requirement.In addition, the intercalation potential of this graphite-based negative material is close with lithium metal, easily occurs Li dendrite, causes battery short circuit, thus occur safety problem in charge and discharge process.Therefore, Novel high-specific capacity flexible is researched and developed and the better negative material of fail safe is important all the more.
Titanic oxide material is considered to a kind of negative material of excellence, and the removal lithium embedded voltage platform of its anatase titanium dioxide, at about 1.75V, effectively avoids the generation of Li dendrite, improves the use safety of battery.Its titanyl forms octahedral structure in addition, and this structure change in volume in charge and discharge process is smaller, makes cycle performance more stable.But, although the theoretical specific capacity of titanium dioxide reaches 335mAh g -1, but in actual use generally the titanium dioxide of every mole only can realize the lithium of deintercalation 0.5 mole, specific capacity is about 168mAh g -1, lower specific capacity also limits its practical application largely.
In recent years, there is the transition metal oxide of higher theoretical specific capacity (as Fe 2o 3, Co 3o 4deng) receive increasing concern.As Fe 2o 3lithium storage content up to about 1008mAh g -1, close to 3 times of conventional graphite base cathode specific capacity.For this reason, by Fe 2o 3material and titanic oxide material carry out compound effectively can utilize Fe 2o 3height ratio capacity and the stable cycle performance of titanium dioxide, the composite material obtained has higher specific capacity and excellent cycle performance.
Current existing Fe 2o 3material and titanic oxide material carry out the preparation method of compound, mainly by hydro thermal method or chemical precipitation method synthesis wherein a kind of material (Fe 2o 3or titanium dioxide), and then carry out next step another material of load (titanium dioxide or Fe 2o 3), finally obtain Fe 2o 3with the composite material of titanium dioxide, this method step is loaded down with trivial details, and the cycle is long, and energy consumption is large, is unfavorable for large-scale production, yet there are no report one-step method Fe 2o 3material and composite titania material.
At present for Fe 2o 3with the composite material of titanium dioxide, the patent that yet there are no for lithium ion battery is reported.Application number be 200510023961.5 patent reported a kind of iron oxide sensitized lamellar titanium oxide visible light catalyst and preparation method.The people such as Lou (Yu L, Wang Z, Zhang L, et al.TiO 2nanotube arrays grafted with Fe 2o 3hollow nanorods asintegrated electrodes for lithium-ion batteries [J] .Journal of Materials Chemistry A, 2013,1 (1): 122-127.) first synthesize Fe by coprecipitation 2o 3hollow pipe, then carries out the Fe of carried titanium dioxide synthesis hollow at skin 2o 3/ composite titania material, it is in the charging/discharging voltage interval of 0.05 ~ 3.0V, and its first charge-discharge capacity is respectively 750mAhg -1with 600mAh g -1, at 100mA cm -250 its reversible capacities that circulate under current density are 395mAh g -1.The people such as Guo (Zhang, X.; Chen, H.X.; Xie, Y.P.; Guo, J.X., Ultralong life lithium-ion battery anode withsuperior high-rate capability and excellent cyclic stability from mesoporous Fe 2o 3@TiO 2core-shellnanorods.Journal Of Materials Chemistry A 2014,2 (11), 3912-3918.) first synthesize FeOOH/TiO in conjunction with hydro thermal method and chemical precipitation method 2presoma, then calcining obtains the Fe with nucleocapsid structure 2o 3/ TiO 2composite material, as lithium ion battery negative material, is that 0.01 ~ 3.0V carries out electrochemical property test in charging/discharging voltage interval, its first discharge capacity be 1223mAh g -1, initial charge capacity is 792mAh g -1.At 0.1A g -150 its reversible capacities that circulate under current density are 450mAh g -1.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of preparation method of titanium dioxide/iron oxide composite negative pole material of stable cycle performance.
In order to solve the problems of the technologies described above, the invention provides the preparation method of a kind of titanium dioxide/iron oxide composite negative pole material, it is characterized in that comprising the following steps successively:
1), 1.39 × 10 are taken -3~ 2.71 × 10 -3the titanyl sulfate of mol is dissolved in deionized water, then adds molysite, stirs until iron salt dissolved, obtains solution (for orange solution);
Titanium and Fe 3+mol ratio is 1.0 ~ 2.0:1;
2), to step 1) add 0.2 ~ 0.3 gram of polyvinylpyrrolidone in the solution of gained, be stirred to polyvinylpyrrolidone and dissolve completely;
3), with vigorous stirring, to step 2) in solution drip the formamide of (dropwising for about 0.5 ~ 1 minute) 0.5 ~ 1.0 milliliter, stir after 5 ~ 10 minutes, carry out aged gel 2 ~ 3 hours in 50 ~ 70 DEG C (being preferably 60 DEG C);
4), by step 3) gained gel dry 22 ~ 26 hours (being preferably 24 hours) under normal pressure 50 ~ 70 DEG C (being preferably 60 DEG C), obtain precursor product;
5), by step 4) precursor product of gained is warming up to 500 ~ 800 DEG C of insulations 5 ~ 7 hours in air atmosphere, and be cooled to room temperature, obtain titanium dioxide/iron oxide composite negative pole material.
Improvement as the preparation method of titanium dioxide of the present invention/iron oxide composite negative pole material: described step 1) in molysite be ferric nitrate, high iron chloride or ferric sulfate.
Further improvement as the preparation method of titanium dioxide of the present invention/iron oxide composite negative pole material: described step 1) in the mol ratio of deionized water and titanyl sulfate be 78 ~ 120:1 (being preferably 79 ~ 90:1).
Further improvement as the preparation method of titanium dioxide of the present invention/iron oxide composite negative pole material: described step 2) in polyvinylpyrrolidonemolecules molecules amount be 10000 ~ 130000.
Further improvement as the preparation method of titanium dioxide of the present invention/iron oxide composite negative pole material:
Described step 1) in, molysite is high iron chloride, titanium and Fe 3+mol ratio is 1 ~ 1.5:1 (being more preferred from 1 ~ 1.35:1);
Described step 2) in, the amount of polyvinylpyrrolidone is 0.25 ~ 0.3 gram;
Described step 5) in, in 600 DEG C of insulations 5 hours.
In the present invention, vigorous stirring refers to 800 ~ 1000 rev/min, and all the other rotating speeds stirred are 600 ~ 800 rev/min.
The present invention first adopts the precursor product xerogel of sol-gal process one-step synthesis titanium dioxide and ferric oxide composite material, after after heat treatment obtain titanium dioxide and iron oxide composite negative pole material.Preparation condition of the present invention is simply gentle, and equipment requirement is low, and process route is simple, is convenient to large-scale production.The titanium dioxide obtained/iron oxide composite negative pole material has higher specific capacity and stable cycle performance.Titanium dioxide of the present invention/iron oxide composite negative pole material has higher charge/discharge capacity and more stable cycle performance (at 0.1A g -150 its reversible capacities gram that circulate under current density remain 930mAh g -1).
The present invention adopts sol-gal process one-step synthesis Fe 2o 3with the presoma of composite titania material, by calcination processing fabricated in situ Fe 2o 3with the composite material of titanium dioxide, this preparation method is simple, and the cycle is short, cheap, is applicable to large-scale production.
Accompanying drawing explanation
Below in conjunction with accompanying drawing, the specific embodiment of the present invention is described in further detail:
Fig. 1 is the XRD figure of titanium dioxide/iron oxide composite negative pole material prepared by embodiment 1.
Fig. 2 is the XRD figure of titanium dioxide/iron oxide composite negative pole material prepared by embodiment 2.
Fig. 3 is 500 times of scanning electron microscopic picture of titanium dioxide/iron oxide composite negative pole material prepared by embodiment 3.
Fig. 4 is 3000 times of scanning electron microscopic picture of titanium dioxide/iron oxide composite negative pole material prepared by embodiment 5.
Fig. 5 be embodiment 1 prepare titanium dioxide/iron oxide composite negative pole material cycle performance figure.
Fig. 6 be embodiment 2 prepare titanium dioxide/iron oxide composite negative pole material cycle performance figure.
Fig. 7 be embodiment 3 prepare titanium dioxide/iron oxide composite negative pole material cycle performance figure.
Fig. 8 be embodiment 4 prepare titanium dioxide/iron oxide composite negative pole material cycle performance figure.
Fig. 9 be embodiment 5 prepare titanium dioxide/iron oxide composite negative pole material cycle performance figure.
Embodiment
The molecular weight of the polyvinylpyrrolidone used in following case is 10000-130000.Vigorous stirring refers to 800 ~ 1000 rev/min, and all the other rotating speeds stirred are 600 ~ 800 rev/min.
The preparation method of embodiment 1, a kind of titanium dioxide/iron oxide composite negative pole material, carries out following steps successively:
1) 0.36 gram (1.39 × 10, is taken -3mol) titanyl sulfate, is dissolved in 2 ml deionized water (0.11mol), after add 0.37 gram (1.37 × 10 -3mol) high iron chloride, stirs and forms orange-yellow solution;
2), to step 1) solution of gained adds 0.25 gram of polyvinylpyrrolidone and is stirred to it and dissolves completely;
3), under intense agitation, to step 2) slowly drip 0.5 milliliter of formamide (that is, about half a minute drips off) in gained solution, to stir after 5 minutes at 60 DEG C aged gel 3 hours;
4), by step 3) gained gel at normal pressure 60 DEG C dry 24 hours, obtain precursor product;
5), by the precursor product of gained be warming up to 600 DEG C of insulations 5 hours in air atmosphere, be cooled to room temperature, obtain titanium dioxide/iron oxide composite negative pole material (powder).
Experiment 1, be that 8:1:1 mixes by obtained titanium dioxide/ferric oxide composite material, acetylene black and PVDF (Kynoar) with mass ratio, be dispersed in NMP (1-METHYLPYRROLIDONE) (described NMP be the 20-39 of above-mentioned 3 weight sums doubly); Make slurry, evenly be coated on Copper Foil, circular electrode pole piece (coating layer thickness is 0.1-0.5mm) is stamped into after vacuum drying, be to electrode with metal lithium sheet, 1mol/L LiPF6/DMC+EC (volume ratio is 1:1) is electrolyte, Celgard2300 is barrier film, is assembled into button cell and carries out electro-chemical test, and its charging/discharging voltage scope is 0.01 ~ 3.0V.At 0.1A g -1its reversible capacity after 50 times that circulates still remains on 930mAh g -1, its first discharge capacity be 1215mAh g -1, charging capacity is 843mAh g -1.
The preparation method of embodiment 2, a kind of titanium dioxide/iron oxide composite negative pole material, carries out following steps successively:
1) 0.36 gram (1.39 × 10, is taken -3mol) titanyl sulfate, is dissolved in 2 milliliters of (0.11mol) deionized waters, after add 0.5 gram (1.85 × 10 -3mol) high iron chloride, stir formation orange solution;
2), to step 1) solution of gained adds 0.25 gram of polyvinylpyrrolidone and is stirred to it and dissolves completely,
3), under intense agitation, to step 2) slowly drip 0.5 milliliter of formamide (about half a minute drips off) in gained solution, stir and at 60 DEG C, carry out aged gel 3 hours after 5 minutes;
4), by step 3) gained gel at normal pressure 60 DEG C dry 24 hours, obtain precursor product;
5), by the precursor product of gained be warming up to 600 DEG C of insulations 5 hours in air atmosphere, be cooled to room temperature, obtain titanium dioxide/iron oxide composite negative pole material (powder).
Detected as experiment 1 by obtained titanium dioxide/ferric oxide composite material, its charging/discharging voltage scope is 0.01 ~ 3.0V.At 0.1A g -1its reversible capacity after 50 times that circulates still remains on 952mAh g -1, its first discharge capacity be 1421mAhg -1, charging capacity is 983mAh g -1.
The preparation method of embodiment 3, a kind of titanium dioxide/iron oxide composite negative pole material, carries out following steps successively:
1) 0.7 gram (2.71 × 10, is taken -3mol) titanyl sulfate, is dissolved in 4 milliliters of (0.22mol) deionized waters, after add 0.37 gram (1.37 × 10 -3mol) high iron chloride, stir formation orange solution;
2), to step 1) solution of gained adds 0.25 gram of polyvinylpyrrolidone and is stirred to it and dissolves completely;
3), under intense agitation to step 2) slowly drip 0.5 milliliter of formamide (about half a minute drips off) in gained solution, stir and at 60 DEG C, carry out aged gel 3 hours after 5 minutes;
4), by step 3) gained gel is dry at normal pressure 60 DEG C within 24 hours, obtains precursor product;
5), by the precursor product of gained be warming up to 600 DEG C of insulations 5 hours in air atmosphere, be cooled to room temperature, obtain titanium dioxide/iron oxide composite negative pole material powder.
Detected as experiment 1 by obtained titanium dioxide/ferric oxide composite material, its charging/discharging voltage scope is 0.01 ~ 3.0V.At 0.1A g -1its reversible capacity after 50 times that circulates still remains on 285mAh g -1, its first discharge capacity be 1291mAhg -1, charging capacity is 862mAh g -1.
The preparation method of embodiment 4, a kind of titanium dioxide/iron oxide composite negative pole material, carries out following steps successively:
1) 0.7 gram (2.71 × 10, is taken -3mol) titanyl sulfate, is dissolved in 4 milliliters of (0.22mol) deionized waters, after add 0.5 gram (1.85 × 10 -3mol) high iron chloride, stir formation orange solution;
2), to step 1) add 0.25 gram of polyvinylpyrrolidone in the solution of gained and be stirred to it and dissolve completely;
3), under intense agitation to step 2) slowly drip 0.5 milliliter of formamide (about half a minute drips off) in gained solution, stir and at 60 DEG C, carry out aged gel 3 hours after 5 minutes;
4), by step 3) gained gel is dry at normal pressure 60 DEG C within 24 hours, obtains precursor product;
5), by the precursor product of gained be warming up to 600 DEG C of insulations 5 hours in air atmosphere, be cooled to room temperature, obtain titanium dioxide/iron oxide composite negative pole material powder.
Detected as experiment 1 by obtained titanium dioxide/ferric oxide composite material, its charging/discharging voltage scope is 0.01 ~ 3.0V.At 0.1A g -1its reversible capacity after 50 times that circulates still remains on 589mAh g -1, its first discharge capacity be 1124mAhg -1, charging capacity is 867mAh g -1.
The preparation method of embodiment 5, a kind of titanium dioxide/iron oxide composite negative pole material, carries out following steps successively:
1) 0.36 gram (1.39 × 10, is taken -3mol) titanyl sulfate, is dissolved in 2 milliliters of (0.11mol) deionized waters, after add 0.37 gram (1.37 × 10 -3mol) high iron chloride, stir formation orange solution;
2), to step 1) solution of gained adds 0.2 gram of polyvinylpyrrolidone and is stirred to it and dissolves completely;
3), under intense agitation to step 2) slowly drip 0.5 milliliter of formamide (about half a minute drips off) in gained solution, stir and at 60 DEG C, carry out aged gel 3 hours after 5 minutes;
4), by step 3) gained gel at normal pressure 60 DEG C dry 24 hours, obtain precursor product;
5), by the precursor product of gained be warming up to 600 DEG C of insulations 5 hours in air atmosphere, be cooled to room temperature, obtain titanium dioxide/iron oxide composite negative pole material powder.
Detected as experiment 1 by obtained titanium dioxide/ferric oxide composite material, its charging/discharging voltage scope is 0.01 ~ 3.0V.At 0.1A g -1its reversible capacity after 50 times that circulates still remains on 731mAh g -1, its first discharge capacity be 1108mAhg -1, charging capacity is 845mAh g -1.
The preparation method of embodiment 6, a kind of titanium dioxide/iron oxide composite negative pole material, carries out following steps successively:
1) 0.36 gram (1.39 × 10, is taken -3mol) titanyl sulfate, is dissolved in 2 milliliters of (0.11mol) deionized waters, after add 0.37 gram (1.37 × 10 -3mol) high iron chloride, stir formation orange solution;
2), to step 1) add 0.25 gram of polyvinylpyrrolidone in the solution of gained and be stirred to it and dissolve completely;
3), under intense agitation to step 2) slowly drip 0.5 milliliter of formamide (about half a minute drips off) in gained solution, stir and at 60 DEG C, carry out aged gel 3 hours after 5 minutes;
4), by step 3) gained gel is dry at normal pressure 60 DEG C within 24 hours, obtains precursor product;
5), by the precursor product of gained be warming up to 800 DEG C of insulations 5 hours in air atmosphere, be cooled to room temperature, obtain titanium dioxide/iron oxide composite negative pole material powder.
Detected as experiment 1 by obtained titanium dioxide/ferric oxide composite material, its charging/discharging voltage scope is 0.01 ~ 3.0V.At 0.1A g -1its reversible capacity after 50 times that circulates still remains on 534mAh g -1, its first discharge capacity be 1084mAhg -1, charging capacity is 862mAh g -1.
The preparation method of embodiment 7, a kind of titanium dioxide/iron oxide composite negative pole material, carries out following steps successively:
1) 0.36 gram (1.39 × 10, is taken -3mol) titanyl sulfate, is dissolved in 2 milliliters of (0.11mol) deionized waters, after add 0.37 gram (1.37 × 10 -3mol) high iron chloride, stir formation orange solution;
2), to step 1) add 0.3 gram of polyvinylpyrrolidone in the solution of gained and be stirred to it and dissolve completely;
3), under intense agitation to step 2) slowly drip 0.5 milliliter of formamide (about half a minute drips off) in gained solution, stir and at 60 DEG C, carry out aged gel 3 hours after 5 minutes;
4), by step 3) gained gel at normal pressure 60 DEG C dry 24 hours, obtain precursor product;
5), by the precursor product of gained be warming up to 600 DEG C of insulations 5 hours in air atmosphere, be cooled to room temperature, obtain titanium dioxide/iron oxide composite negative pole material powder.
Detected as experiment 1 by obtained titanium dioxide/ferric oxide composite material, its charging/discharging voltage scope is 0.01 ~ 3.0V.At 0.1A g -1its reversible capacity after 50 times that circulates still remains on 647mAh g -1, its first discharge capacity be 1126mAhg -1, charging capacity is 883mAh g -1.
Finally, it is also to be noted that what enumerate above is only several specific embodiments of the present invention.Obviously, the invention is not restricted to above embodiment, many distortion can also be had.All distortion that those of ordinary skill in the art can directly derive from content disclosed by the invention or associate, all should think protection scope of the present invention.

Claims (5)

1. the preparation method of titanium dioxide/iron oxide composite negative pole material, is characterized in that comprising the following steps successively:
1), 1.39 × 10 are taken -3~ 2.71 × 10 -3the titanyl sulfate of mol is dissolved in deionized water, then adds molysite, stirs until iron salt dissolved, obtains solution;
Titanium and Fe 3+mol ratio is 1.0 ~ 2.0:1;
2), to step 1) add 0.2 ~ 0.3 gram of polyvinylpyrrolidone in the solution of gained, be stirred to polyvinylpyrrolidone and dissolve completely;
3), with vigorous stirring, to step 2) in solution drip the formamide of 0.5 ~ 1.0 milliliter, stir after 5 ~ 10 minutes, carry out aged gel 2 ~ 3 hours in 50 ~ 70 DEG C;
4), by step 3) gained gel at normal pressure 50 ~ 70 DEG C dry 22 ~ 26 hours, obtain precursor product;
5), by step 4) precursor product of gained is warming up to 500 ~ 800 DEG C of insulations 5 ~ 7 hours in air atmosphere, and be cooled to room temperature, obtain titanium dioxide/iron oxide composite negative pole material.
2. require the preparation method of described titanium dioxide/iron oxide composite negative pole material according to right 1, it is characterized in that: described step 1) in molysite be ferric nitrate, high iron chloride or ferric sulfate.
3. require the preparation method of described titanium dioxide/iron oxide composite negative pole material according to right 2, it is characterized in that: described step 1) in the mol ratio of deionized water and titanyl sulfate be 78 ~ 120:1.
4. require the preparation method of described titanium dioxide/iron oxide composite negative pole material according to right 3, it is characterized in that: described step 2) in polyvinylpyrrolidonemolecules molecules amount be 10000 ~ 130000.
5. require the preparation method of described titanium dioxide/iron oxide composite negative pole material according to right 4, it is characterized in that:
Described step 1) in, molysite is high iron chloride, titanium and Fe 3+mol ratio is 1 ~ 1.5:1;
Described step 2) in, the amount of polyvinylpyrrolidone is 0.25 ~ 0.3 gram;
Described step 5) in, in 600 DEG C of insulations 5 hours.
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CN108172780A (en) * 2017-12-07 2018-06-15 北京理工大学 A kind of alkali metal secondary battery negative electrode active material and preparation method thereof
CN108448082A (en) * 2018-03-07 2018-08-24 华南师范大学 Electrode material and its petal-shaped porous structure iron-based composite oxides and preparation method thereof
CN110176596A (en) * 2019-06-17 2019-08-27 启东启澳新材料科技发展有限公司 A method of improving lithium battery anode coating material chemical property
CN112290002A (en) * 2020-11-04 2021-01-29 齐鲁工业大学 Titanium dioxide hydroxyl ferric oxide cathode material of lithium ion battery and preparation method and application thereof
CN113793931A (en) * 2021-11-18 2021-12-14 河南电池研究院有限公司 Iron oxide negative electrode material for lithium ion battery and preparation method thereof

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