CN103400980A - Iron sesquioxide/nickel oxide core-shell nanorod array film as well as preparation method and application thereof - Google Patents

Iron sesquioxide/nickel oxide core-shell nanorod array film as well as preparation method and application thereof Download PDF

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CN103400980A
CN103400980A CN2013103258190A CN201310325819A CN103400980A CN 103400980 A CN103400980 A CN 103400980A CN 2013103258190 A CN2013103258190 A CN 2013103258190A CN 201310325819 A CN201310325819 A CN 201310325819A CN 103400980 A CN103400980 A CN 103400980A
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nickel oxide
iron trioxide
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array film
nano rod
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熊琴琴
涂江平
***
谷长栋
夏新辉
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Zhejiang University ZJU
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Abstract

The invention discloses an iron sesquioxide/nickel oxide core-shell nanorod array film as well as a preparation method and an application thereof. The preparation method comprises the following steps of: mixing soluble iron salt and sodium sulfate with water, so as to obtain a precursor solution; putting a clean substrate into a reaction kettle, adding the precursor solution into the reaction kettle, reacting for 4-24 hours at 110 to 160 DEG C, and carrying out thermal treatment for 1-5 hours at 400 to 500 DEG C, so as to obtain the substrate grown with an iron sesquioxide nanorod array; and mixing nickel sulfate, potassium peroxydisulfate and ammonia with water, putting the substrate grown with an iron sesquioxide nanorod array into a nickel oxide reaction solution to react, and carrying out thermal treatment for 1-3 hours at 300 to 400 DEG C after the reaction, so as to obtain the iron sesquioxide/nickel oxide core-shell nanorod array film. The preparation method disclosed by the invention is relatively low in manufacture cost and is liable to industrialize; the film has a shape of the core-shell nanorod array growing on the substrate; and the negative pole of a prepared lithium ion battery has the advantages of high discharge capacity, stable cycle performance, excellent rate capability and the like.

Description

Di-iron trioxide/nickel oxide core-shell nano rod array film and its preparation method and application
Technical field
The invention belongs to the lithium ion battery negative material field, be specifically related to a kind of di-iron trioxide/nickel oxide core-shell nano rod array film and its preparation method and application.
Background technology
With traditional secondary cell, compare, the favor that lithium ion battery has that platform voltage is high, energy density is large, self discharge is little, memory-less effect, advantages of environment protection are subject to industry-by-industry, just progressively move towards the application of electric bicycle, electric automobile and military project aspect from the application of mobile phone, notebook computer, portable electronics.
At present, the 3d transition metal oxide, as one of the most promising lithium ion battery negative material, is studied widely.Because it has than the capacity of high 2～3 times of graphite electrode, the change in volume less than alloy electrode in charge and discharge process, be expected to realize that lithium ion battery is in many-sided application such as electric automobile, military affairs.In transition metal oxide, di-iron trioxide and nickel oxide, have the advantages such as high theoretical capacity, asepsis environment-protecting, storage be abundant, cheap, attracted increasing concern.But still there is following shortcoming:
One, poorly conductive is poor, in electrochemical reaction process, larger polarization can occur, and has hindered that electronics fast and effeciently transmits and the diffusion of lithium ion in material;
Two, change in volume is large in the conversion reaction process, and produce certain internal stress, in constantly circulating, make material efflorescence gradually, not only with collector, lose and electrically contact, and make the nano metal particles reunion form bulky grain, reduce the contact interface of active material and electrolyte and lose electro-chemical activity, caused the loss of irreversible capacity, poor chemical property, thus limited practical application widely.
In order to address these problems, carried out a lot of research, comprise the nanostructure that preparation is different, as nano particle, porous ball, nanometer rods, nano wire, nanobelt etc.; Compound with various material with carbon elements, as compound as transition metal oxide and Graphene, CNT (carbon nano-tube), amorphous carbon; Prepare thin-film material etc., but still do not reach the requirement of practical application.
Summary of the invention
In order in the discharge capacity improving lithium ion battery negative material, to maintain again cycle performance preferably, a kind of effective method for designing is assembled into two kinds of active cathode material a 3D nano compound film electrode exactly, form and good electrically contact, reduce nonactive interface, remain the discharge capacity that the characteristics such as Stability Analysis of Structures improve material, can keep cyclical stability preferably again simultaneously.
The invention provides a kind of di-iron trioxide/nickel oxide core-shell nano rod array film and its preparation method and application, this preparation method has built two kinds of transition metal oxide nuclear shell nano-rod film structures, preparation technology controls conveniently, manufacturing cost is lower, can large tracts of land production, be easy to realize industrialization.Di-iron trioxide/nickel oxide core-shell nano rod array film is usingd the di-iron trioxide nanometer stick array as nuclear structure, nickel oxide layer is coated on nanorod surfaces as shell, have the core-shell nanometer rod array pattern of growing in substrate, the lithium ion battery negative of preparation has high discharge capacity, stable cycle performance and the excellent advantages such as high rate performance.
The preparation method of a kind of di-iron trioxide/nickel oxide core-shell nano rod array film comprises the following steps:
1) soluble ferric iron salt, sodium sulphate and water are mixed, obtain precursor solution;
2) substrate of cleaning is put into to reactor, and the precursor solution in step 1) is joined in reactor, in 110 ℃～160 ℃ the reaction 4h～24h, then under the protection of protective gas in 400 ℃～500 ℃ heat treatment 1h～5h, obtaining growing has the substrate of di-iron trioxide nanometer stick array;
3) nickelous sulfate, potassium persulfate, ammonia and water are mixed; obtain the nickel oxide reactant liquor; by step 2) in growth have the substrate of di-iron trioxide nanometer stick array to put into the nickel oxide reactant liquor to react; after reaction under the protection of protective gas in 300 ℃～400 ℃ heat treatment 1h～3h, obtain di-iron trioxide/nickel oxide core-shell nano rod array film.
In step 1), precursor solution is as the raw material of di-iron trioxide nanometer stick array, and as preferably, described soluble ferric iron salt is FeCl 36H 2O, FeCl 3Or Fe (NO 3) 3Deng.Above-mentioned soluble ferric iron salt, as source of iron, is conducive to the formation of di-iron trioxide nanometer stick array.
Soluble ferric iron salt in precursor solution and sodium sulfate concentration have a certain impact to the formation of di-iron trioxide nanometer stick array, as preferably, the concentration of the soluble ferric iron salt in described precursor solution is 0.005～0.065mol/L, the concentration of the sodium sulphate in described precursor solution is 0.01～0.08mol/L, more is conducive to the formation of di-iron trioxide nanometer stick array.
Step 2) in, in order to be conducive at the superficial growth di-iron trioxide nanometer stick array of substrate and to prevent that other impurity are to exerting an influence that finally prepd di-iron trioxide nanometer stick array and nickel oxide layer coat, before in substrate, preparing the di-iron trioxide nanometer stick array, it need to be cleaned up, as preferably, the preparation of clean substrate comprises: first substrate is used respectively to acetone, deionized water and ethanol supersound washing, then oven dry.Above-mentioned steps is better to the clean effect of substrate, on the surface of substrate, contains hardly forming the impurity that di-iron trioxide/nickel oxide core-shell nano rod array film exerts an influence.
In reactor; in precursor solution, each raw material components is in 110 ℃～160 ℃ reaction 4h～24h; the di-iron trioxide nanometer stick array namely starts to grow on the surface of substrate; and under the protection of protective gas in 400 ℃～500 ℃ heat treatment 1h～5h; its pattern is done to further processing; make di-iron trioxide nanometer stick array after heat treatment more easily coat nickel oxide layer, finally obtain having the di-iron trioxide of specific morphology/nickel oxide core-shell nano rod array film, better performances.
Step 2) and 3), protective gas is nitrogen or inert gas, and inert gas can be selected argon gas etc., step 2) and 3) in selected protective gas can be identical or not identical.
In step 3), the nickel oxide reactant liquor is as the raw material of the nickel oxide layer that coats on the di-iron trioxide nanometer stick array, and in the nickel oxide reactant liquor, the concentration of each raw material all has a certain impact to nickel oxide layer.As preferably, in described nickel oxide reactant liquor, the concentration of nickelous sulfate is 0.1～2mol/L, in described nickel oxide reactant liquor, the concentration of potassium persulfate is 0.01～0.5mol/L, in described nickel oxide reactant liquor, the concentration of ammonia is 0.5～3mol/L, all the other are water, the nickel oxide reactant liquor of above-mentioned concentration has specific character, as specific amount ratio, specific pH etc., is very beneficial for coating nickel oxide layer on the di-iron trioxide nanometer stick array.
As preferably, the condition of described reaction is: at 10 ℃～40 ℃ reaction 1～60min, above-mentioned reaction condition is conducive to coat nickel oxide layer on the di-iron trioxide nanometer stick array.
After reaction under the protection of protective gas in 300 ℃～400 ℃ heat treatment 1h～3h; help the formation of pattern; make the di-iron trioxide that obtains/nickel oxide core-shell nano rod array film have the core-shell nanometer rod array pattern of growing in substrate; using the di-iron trioxide nanometer stick array as nuclear structure; nickel oxide layer is coated on nanorod surfaces as shell, makes it possess excellent performance.
As preferably, the preparation method of described di-iron trioxide/nickel oxide core-shell nano rod array film comprises the following steps:
1) by FeCl 36H 2O, Na 2SO 4With water, mix, obtain precursor solution, wherein, the FeCl in precursor solution 36H 2The concentration of O is 0.042mol/L, the Na in precursor solution 2SO 4Concentration be 0.048mol/L;
2) substrate of cleaning is put into to reactor, and the precursor solution in step 1) is joined in reactor, in 120 ℃ the reaction 6h, then under the protection of protective gas in 450 ℃ of heat treatment 3h, obtaining growing has the substrate of di-iron trioxide nanometer stick array;
3) nickelous sulfate, potassium persulfate, ammonia and water are mixed, obtain the nickel oxide reactant liquor, in the nickel oxide reactant liquor, the concentration of nickelous sulfate is 0.5mol/L, and in the nickel oxide reactant liquor, the concentration of potassium persulfate is 0.1mol/L, and in the nickel oxide reactant liquor, the concentration of ammonia is 1.45mol/L;
By step 2) in growth have the substrate of di-iron trioxide nanometer stick array put into the nickel oxide reactant liquor in 25 ℃ the reaction 8min; after reaction under the protection of protective gas in 350 ℃ of heat treatment 1.5h, obtain di-iron trioxide/nickel oxide core-shell nano rod array film.
Di-iron trioxide prepared by above-mentioned condition/nickel oxide core-shell nano rod array film is during as lithium ion battery negative, after being assembled into lithium ion battery, under current density 200mA/g, more than di-iron trioxide/nickel oxide core-shell nano rod array film discharge capacity maintains 1000mAh/g after 50 circulations, and high rate performance is outstanding, in current density, reach under 2000mA/g more than discharge capacity reaches 750mAh/g, have high discharge capacity, good cycle performance and excellent high rate performance.
Di-iron trioxide prepared by described preparation method/nickel oxide core-shell nano rod array film, its thickness is 200～1000nm.
Described di-iron trioxide/nickel oxide core-shell nano rod array film is suitable for preparing lithium ion battery negative very much, described substrate is a kind of in carbon cloth, Copper Foil, titanium sheet and nickel foam etc., after in substrate, preparing di-iron trioxide/nickel oxide core-shell nano rod array film, after section, namely can be used as lithium ion battery negative, have that reversible capacity is high, cycle performance is stable and excellent high-rate charge-discharge capability.
A kind of lithium ion battery negative comprises the following steps:
The substrate that is prepared with di-iron trioxide/nickel oxide core-shell nano rod array film is placed in to vacuum drying oven in 90 ℃ of dry 12h, through the section after directly as lithium ion battery negative.
Lithium ion battery negative and metal lithium sheet are assembled into to lithium ion battery.It is barrier film that lithium ion battery adopts microporous polypropylene membrane (Cellgard2300), usings the diethyl carbonate (DEC) of volume ratio 7:3 and ethylene carbonate (EC) as solvent, by LiPF 6Be dissolved in solvent, make electrolyte, LiPF in electrolyte 6Concentration be 1mol/L.The lithium ion battery assembling process completes in the dry glove box of water volume content lower than 0.1ppm.The lithium ion battery that assembles carries out the constant current charge-discharge test after placing 12h, and charging/discharging voltage is 0.01V～3V, and Reversible lithium insertion capacity, charge-discharge performance and the high magnification characteristic of lithium ion battery negative measured in circulation in 25 ± 2 ℃ of environment.
Compared with prior art, the present invention has following advantage:
The preparation method of di-iron trioxide of the present invention/nickel oxide core-shell nano rod array film takes hydro-thermal and chemical bath deposition two-step synthetic method, at the regularly arranged di-iron trioxide of the upper preparation of various substrates (as carbon cloth, Copper Foil, titanium sheet and nickel foam etc.)/nickel oxide core-shell nano rod array film, using the di-iron trioxide nanometer stick array as nuclear structure, and the nickel oxide lamella is coated on nanorod surfaces as shell.And this preparation technology is simple, and the core-shell nanometer rod diameter of movement and the pattern that form film can conveniently be controlled, and manufacturing cost is lower, is easy to realize large tracts of land production, possesses wide application prospect.
In the present invention, be prepared with the substrate of di-iron trioxide/nickel oxide core-shell nano rod array film directly as lithium ion battery negative, the electrode that obtains with the single oxide material, compare have higher discharge capacity, stable cycle performance and the excellent advantages such as high rate performance, not only can be used for lithium ion battery material, can also be for Sensitive Apparatus, photocatalysis and energy conversion field.
The accompanying drawing explanation
Fig. 1 is scanning electron microscopy (SEM) photo on embodiment 1 gained di-iron trioxide/nickel oxide core-shell nano rod array film surface;
Fig. 2 is transmission electron microscope (TEM) photo of embodiment 1 gained di-iron trioxide/nickel oxide core-shell nano rod array film;
Fig. 3 is the high rate performance test of substrate during as lithium ion battery negative that is prepared with di-iron trioxide/nickel oxide core-shell nano rod array film in embodiment 1.
Embodiment
Below in conjunction with embodiment and accompanying drawing, describe the present invention in detail, but the present invention is not limited to this.
Embodiment 1:
1) (physics and chemistry (Hong Kong) Co., Ltd, W0S1002) as substrate, with acetone, deionized water and the ultrasonic 30min of ethanol difference, obtain clean carbon cloth by carbon cloth after oven dry to select carbon cloth;
2) by 0.8g FeCl 36H 2O, 0.479g Na 2SO 4Be dissolved in the 70mL deionized water for stirring, obtain precursor solution, wherein, the FeCl in precursor solution 36H 2The concentration of O is 0.042mol/L, the Na in precursor solution 2SO 4Concentration be 0.048mol/L;
3) carbon cloth of cleaning is put in the reactor polytetrafluoroethylliner liner, and by step 2) in precursor solution pour in reactor, in 120 ℃ of reaction 6h, after reaction completes, reactor is taken out, cooling in air;
Again in tube furnace under argon shield in 450 ℃ of heat treatment 3h, obtaining growing has the substrate of di-iron trioxide nanometer stick array;
4) by 26.285g NiSO 46H 2O is dissolved in 100mL deionized water, 5.4gK 2S 2O 8Be dissolved in the 80mL deionized water, rear mixing stirs, adding 20mL ammonia mass percent is 27% ammoniacal liquor again, obtain the nickel oxide reactant liquor, in the nickel oxide reactant liquor, the concentration of nickelous sulfate is 0.5mol/L, in the nickel oxide reactant liquor, the concentration of potassium persulfate is 0.1mol/L, and in the nickel oxide reactant liquor, the concentration of ammonia is 1.45mol/L, and all the other are water;
Having the substrate of di-iron trioxide nanometer stick array to put into the nickel oxide reactant liquor growth in step 3) reacts; at 25 ℃ of reaction 8min; after reaction, with deionized water and ethanol, clean; vacuumize; then 350 ℃ of heat treatment 1.5h under argon shield in tube furnace, obtain di-iron trioxide/nickel oxide core-shell nano rod array film.
Film obtained above is carried out to constituent analysis and structure and performance characterization, measure it and be di-iron trioxide/nickel oxide core-shell nano rod array film, concrete outcome is as follows:
As can be known from X-ray diffraction analysis, di-iron trioxide prepared by the present embodiment/nickel oxide core-shell nano rod array film is by NiO (JCPDF card no.44-1159) and Fe 2O 3(JCPDF card no.33-0664) forms, and crystal property is good.Utilize SEM to observe the film of preparation, as shown in Figure 1, the di-iron trioxide of preparation/nickel oxide core-shell nano rod array film, take the di-iron trioxide nanometer rods as nuclear structure for photo, the nickel oxide thin slice that is coated on nanometer rods is shell, and the thickness of shell is in the 100nm left and right.The nickel oxide lamella of deposition evenly is coated on the nanometer rods top layer, and connects well between the nickel oxide lamella, forms a netted nucleocapsid array structure of 3D, is conducive to remain the stable of structure.Di-iron trioxide prepared by the transmission tem observation/nickel oxide core-shell nano rod array film, as shown in Figure 2, can clearly observe nucleocapsid structure.
The carbon cloth that is prepared with di-iron trioxide/nickel oxide core-shell nano rod array film, directly as electrode material, is placed in to vacuum drying oven in 90 ℃ of dry 12h, and lithium ion battery negative is made in section.The lithium ion battery negative of preparation and metal lithium sheet are assembled into to lithium ion battery.It is barrier film that lithium ion battery adopts microporous polypropylene membrane (Cellgard2300), usings the diethyl carbonate (DEC) of volume ratio 7:3 and ethylene carbonate (EC) as solvent, by LiPF 6Be dissolved in solvent, make electrolyte, LiPF in electrolyte 6Concentration be 1mol/L.The lithium ion battery assembling process in water volume content namely assembles environment lower than 0.1ppm(water volume content lower than 0.1ppm) dry glove box in complete.The lithium ion battery that assembles carries out constant current charge-discharge test and electrochemical impedance test after placing 12h, charging/discharging voltage is 0.01V～3V, Reversible lithium insertion capacity, charge-discharge performance and the high magnification characteristic of lithium ion battery negative measured in circulation in 25 ± 2 ℃ of environment, and the carbon cloth that will be prepared with the carbon cloth of di-iron trioxide nanometer rods and be prepared with nickel oxide layer as a comparison case, and result as shown in Figure 3.
After being assembled into lithium ion battery, under current density 200mA/g, di-iron trioxide/nickel oxide core-shell nano rod array film discharge capacity maintains 1047.2mAh/g after 50 circulations, and high rate performance is outstanding, in current density, reaches discharge capacity under 2000mA/g and reaches 783.3mAh/g.When as can be seen here, the above-mentioned di-iron trioxide that makes/nickel oxide core-shell nano rod array film is as lithium ion battery negative, have high discharge capacity, good cycle performance and excellent high rate performance.
Embodiment 2:
1) (physics and chemistry (Hong Kong) Co., Ltd, W0S1002) as substrate, with acetone, deionized water and the ultrasonic 30min of ethanol difference, obtain clean carbon cloth by carbon cloth after oven dry to select carbon cloth;
2) by 1.2g FeCl 36H 2O, 0.479g Na 2SO 4Be dissolved in the 70mL deionized water for stirring, obtain precursor solution, wherein, the FeCl in precursor solution 36H 2The concentration of O is 0.063mol/L, the Na in precursor solution 2SO 4Concentration be 0.048mol/L;
3) carbon cloth of cleaning is put in the reactor polytetrafluoroethylliner liner, and by step 2) in precursor solution pour in reactor, in 120 ℃ of reaction 6h, after reaction completes, reactor is taken out, cooling in air;
Again in tube furnace under argon shield in 450 ℃ of heat treatment 3h, obtaining growing has the substrate of di-iron trioxide nanometer stick array;
4) by 26.285g NiSO 46H 2O is dissolved in 100mL deionized water, 5.4gK 2S 2O 8Be dissolved in the 80mL deionized water, rear mixing stirs, adding 20mL ammonia mass percent is 27% ammoniacal liquor again, obtain the nickel oxide reactant liquor, in the nickel oxide reactant liquor, the concentration of nickelous sulfate is 0.5mol/L, in the nickel oxide reactant liquor, the concentration of potassium persulfate is 0.1mol/L, and in the nickel oxide reactant liquor, the concentration of ammonia is 1.45mol/L, and all the other are water;
Having the substrate of di-iron trioxide nanometer stick array to put into the nickel oxide reactant liquor growth in step 3) reacts; at 25 ℃ of reaction 8min; after reaction, with deionized water and ethanol, clean; vacuumize; then 350 ℃ of heat treatment 1.5h under argon shield in tube furnace, obtain di-iron trioxide/nickel oxide core-shell nano rod array film.
Film obtained above is carried out to constituent analysis and structure and performance characterization, measure it and be di-iron trioxide/nickel oxide core-shell nano rod array film, concrete outcome is as follows:
As can be known from X-ray diffraction analysis, di-iron trioxide prepared by the present embodiment/nickel oxide core-shell nano rod array film is by NiO (JCPDF card No.44-1159) and Fe 2O 3(JCPDF card No.33-0664) forms, and crystal property is good.Utilize SEM to observe the film of preparation, core-shell nanometer rod is basically perpendicular to substrate grown, and take the di-iron trioxide nanometer rods as nuclear structure, the nickel oxide thin slice that is coated on the di-iron trioxide nanometer rods is shell.When adding 1.2g FeCl 36H 2O, the nickel oxide lamella of deposition not only is coated on the nanometer rods top layer, and is deposited in the gap of nanometer rods, has destroyed to a certain extent the netted nucleocapsid array structure of good 3D.
The carbon cloth that is prepared with di-iron trioxide/nickel oxide core-shell nano rod array film, directly as electrode material, is placed in to vacuum drying oven in 90 ℃ of dry 12h, and lithium ion battery negative is made in section.The lithium ion battery negative of preparation and metal lithium sheet are assembled into to lithium ion battery.It is barrier film that lithium ion battery adopts microporous polypropylene membrane (Cellgard2300), usings the diethyl carbonate (DEC) of volume ratio 7:3 and ethylene carbonate (EC) as solvent, by LiPF 6Be dissolved in solvent, make electrolyte, LiPF in electrolyte 6Concentration be 1mol/L.The lithium ion battery assembling process in water volume content namely assembles environment lower than 0.1ppm(water volume content lower than 0.1ppm) dry glove box in complete.The lithium ion battery that assembles carries out constant current charge-discharge test and electrochemical impedance test after placing 12h, charging/discharging voltage is 0.01V～3V, Reversible lithium insertion capacity, charge-discharge performance and the high magnification characteristic of lithium ion battery negative measured in circulation in 25 ± 2 ℃ of environment, and result is as shown in table 1.
After being assembled into lithium ion battery, under current density 200mA/g, after 50 circulations, adding di-iron trioxide/nickel oxide core-shell nano rod array film discharge capacity and maintain 782.7mAh/g.Under current density reached 2000mA/g, discharge capacity reached 521.3mAh/g.When as can be seen here, prepared di-iron trioxide/nickel oxide core-shell nano rod array film is as lithium ion battery negative, have higher discharge capacity, good cycle performance and high rate performance.
Embodiment 3:
1) (physics and chemistry (Hong Kong) Co., Ltd, W0S1002) as substrate, with acetone, deionized water and the ultrasonic 30min of ethanol difference, obtain clean carbon cloth by carbon cloth after oven dry to select carbon cloth;
2) by 0.8g FeCl 36H 2O, 0.479g Na 2SO 4Be dissolved in the 70mL deionized water for stirring, obtain precursor solution, wherein, the FeCl in precursor solution 36H 2The concentration of O is 0.042mol/L, the Na in precursor solution 2SO 4Concentration be 0.048mol/L;
3) carbon cloth of cleaning is put in the reactor polytetrafluoroethylliner liner, and by step 2) in precursor solution pour in reactor, in 120 ℃ of reaction 6h, after reaction completes, reactor is taken out, cooling in air;
Again in tube furnace under argon shield in 450 ℃ of heat treatment 3h, obtaining growing has the substrate of di-iron trioxide nanometer stick array;
4) by 26.285g NiSO 46H 2O is dissolved in 100mL deionized water, 5.4gK 2S 2O 8Be dissolved in the 80mL deionized water, rear mixing stirs, adding 20mL ammonia mass percent is 27% ammoniacal liquor again, obtain the nickel oxide reactant liquor, in the nickel oxide reactant liquor, the concentration of nickelous sulfate is 0.5mol/L, in the nickel oxide reactant liquor, the concentration of potassium persulfate is 0.1mol/L, and in the nickel oxide reactant liquor, the concentration of ammonia is 1.45mol/L, and all the other are water;
Having the substrate of di-iron trioxide nanometer stick array to put into the nickel oxide reactant liquor growth in step 3) reacts; at 25 ℃ of reaction 15min; after reaction, with deionized water and ethanol, clean; vacuumize; then 350 ℃ of heat treatment 1.5h under argon shield in tube furnace, obtain di-iron trioxide/nickel oxide core-shell nano rod array film.
Film obtained above is carried out to constituent analysis and structure and performance characterization, measure it and be di-iron trioxide/nickel oxide core-shell nano rod array film, concrete outcome is as follows:
As can be known from X-ray diffraction analysis, di-iron trioxide prepared by the present embodiment/nickel oxide core-shell nano rod array film is by NiO (JCPDF card no.44-1159) and Fe 2O 3(JCPDF card no.33-0664) forms, and crystal property is good.Utilize SEM to observe the film of preparation, core-shell nanometer rod is basically perpendicular to substrate and vertically grows, and take the di-iron trioxide nanometer rods as nuclear structure, the nickel oxide thin slice that is coated on the di-iron trioxide nanometer rods is shell.When sedimentation time was 15min, the nickel oxide lamella of deposition not only was coated on the nanometer rods top layer, and is deposited in the gap of nanometer rods, had reduced the netted space of 3D.
The carbon cloth that is prepared with di-iron trioxide/nickel oxide core-shell nano rod array film, directly as electrode material, is placed in to vacuum drying oven in 90 ℃ of dry 12h, and lithium ion battery negative is made in section.The lithium ion battery negative of preparation and metal lithium sheet are assembled into to lithium ion battery.It is barrier film that lithium ion battery adopts microporous polypropylene membrane (Cellgard2300), usings the diethyl carbonate (DEC) of volume ratio 7:3 and ethylene carbonate (EC) as solvent, by LiPF 6Be dissolved in solvent, make electrolyte, LiPF in electrolyte 6Concentration be 1mol/L.The lithium ion battery assembling process in water volume content namely assembles environment lower than 0.1ppm(water volume content lower than 0.1ppm) dry glove box in complete.The lithium ion battery that assembles carries out constant current charge-discharge test and electrochemical impedance test after placing 12h, charging/discharging voltage is 0.01V～3V, and Reversible lithium insertion capacity, charge-discharge performance and the high magnification characteristic of lithium ion battery negative measured in circulation in 25 ± 2 ℃ of environment.
After being assembled into lithium ion battery, under current density 200mA/g, di-iron trioxide/nickel oxide core-shell nano rod array film discharge capacity maintains 712.7mAh/g after 50 circulations.In current density, reach discharge capacity under 2000mA/g and reach 509.2mAh/g.The discharge capacity that when as can be seen here, prepared di-iron trioxide/nickel oxide core-shell nano rod array film was as lithium ion battery negative, tool was relatively high, good cycle performance and excellent high rate performance.
The carbon cloth that is prepared with di-iron trioxide/nickel oxide core-shell nano rod array film in embodiment 1～3 is prepared into lithium ion battery negative, be assembled into lithium ion battery after its maximum discharge capacity under the current density that do not coexist as shown in table 1.
Table 1
Figure BDA00003587944500101

Claims (10)

1. the preparation method of di-iron trioxide/nickel oxide core-shell nano rod array film, is characterized in that, comprises the following steps:
1) soluble ferric iron salt, sodium sulphate and water are mixed, obtain precursor solution;
2) substrate of cleaning is put into to reactor, and the precursor solution in step 1) is joined in reactor, in 110 ℃～160 ℃ the reaction 4h～24h, then under the protection of protective gas in 400 ℃～500 ℃ heat treatment 1h～5h, obtaining growing has the substrate of di-iron trioxide nanometer stick array;
3) nickelous sulfate, potassium persulfate, ammonia and water are mixed; obtain the nickel oxide reactant liquor; by step 2) in growth have the substrate of di-iron trioxide nanometer stick array to put into the nickel oxide reactant liquor to react; after reaction under the protection of protective gas in 300 ℃～400 ℃ heat treatment 1h～3h, obtain di-iron trioxide/nickel oxide core-shell nano rod array film.
2. the preparation method of di-iron trioxide according to claim 1/nickel oxide core-shell nano rod array film, is characterized in that, in step 1), described soluble ferric iron salt is FeCl 36H 2O, FeCl 3Or Fe (NO 3) 3.
3. the preparation method of di-iron trioxide according to claim 1/nickel oxide core-shell nano rod array film, it is characterized in that, in step 1), the concentration of the soluble ferric iron salt in described precursor solution is 0.005～0.065mol/L, and the concentration of the sodium sulphate in described precursor solution is 0.01～0.08mol/L.
4. the preparation method of di-iron trioxide according to claim 1/nickel oxide core-shell nano rod array film, it is characterized in that, step 2) in, the preparation of clean substrate comprises: first substrate is used respectively to acetone, deionized water and ethanol supersound washing, then oven dry.
5. the preparation method of di-iron trioxide according to claim 1/nickel oxide core-shell nano rod array film, it is characterized in that, in step 3), in described nickel oxide reactant liquor, the concentration of nickelous sulfate is 0.1～2mol/L, in described nickel oxide reactant liquor, the concentration of potassium persulfate is 0.01～0.5mol/L, and in described nickel oxide reactant liquor, the concentration of ammonia is 0.5～3mol/L.
6. the preparation method of di-iron trioxide according to claim 1/nickel oxide core-shell nano rod array film, is characterized in that, in step 3), the condition of described reaction is: at 10 ℃～40 ℃ reaction 1～60min.
7. the preparation method of di-iron trioxide according to claim 1/nickel oxide core-shell nano rod array film, is characterized in that, comprises the following steps:
1) by FeCl 36H 2O, Na 2SO 4With water, mix, obtain precursor solution, wherein, the FeCl in precursor solution 36H 2The concentration of O is 0.042mol/L, the Na in precursor solution 2SO 4Concentration be 0.048mol/L;
2) substrate of cleaning is put into to reactor, and the precursor solution in step 1) is joined in reactor, in 120 ℃ the reaction 6h, then under the protection of protective gas in 450 ℃ of heat treatment 3h, obtaining growing has the substrate of di-iron trioxide nanometer stick array;
3) nickelous sulfate, potassium persulfate, ammonia and water are mixed, obtain the nickel oxide reactant liquor, in the nickel oxide reactant liquor, the concentration of nickelous sulfate is 0.5mol/L, and in the nickel oxide reactant liquor, the concentration of potassium persulfate is 0.1mol/L, and in the nickel oxide reactant liquor, the concentration of ammonia is 1.45mol/L;
By step 2) in growth have the substrate of di-iron trioxide nanometer stick array put into the nickel oxide reactant liquor in 25 ℃ the reaction 8min; after reaction under the protection of protective gas in 350 ℃ of heat treatment 1.5h, obtain di-iron trioxide/nickel oxide core-shell nano rod array film.
8. the di-iron trioxide for preparing of the described preparation method of according to claim 1～7 any one/nickel oxide core-shell nano rod array film.
9. di-iron trioxide according to claim 8/nickel oxide core-shell nano rod array film, is characterized in that, thickness is 200～1000nm.
10. according to claim 8 or claim 9 the di-iron trioxide/application of nickel oxide core-shell nano rod array film in preparing lithium ion battery negative.
CN2013103258190A 2013-07-30 2013-07-30 Iron sesquioxide/nickel oxide core-shell nanorod array film as well as preparation method and application thereof Pending CN103400980A (en)

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