CN107611425A - A kind of fusiform zinc ferrite/carbon lithium ion cell nano composite negative pole material and preparation method and application - Google Patents
A kind of fusiform zinc ferrite/carbon lithium ion cell nano composite negative pole material and preparation method and application Download PDFInfo
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Abstract
The invention discloses a kind of fusiform zinc ferrite/carbon lithium ion cell nano composite negative pole material and preparation method and application, the composite negative pole material is fusiform structure, it is made up of the compound zinc ferrite two level nano particle of carbon skeleton, wherein ferrous acid Zn content is the 60 90% of zinc ferrite/carbon lithium ion cell nano composite negative pole material quality.The material preparation method is：With organic metal framework as linking agent and carbon source, water-filling thermal response is mixed into metal salt, centrifuge washing obtains fusiform zinc ferrite/carbon lithium ion cell nano composite negative pole material by annealing reaction again after drying acquisition precursor；Fusiform structure zinc ferrite/carbon lithium ion cell nano composite negative pole material Stability Analysis of Structures of the present invention, electric conductivity is good, has excellent cyclical stability and high rate performance as lithium ion battery negative material；This method is simple to operate, easy to control, and cost is cheap, environment-friendly, can be applicable industrial-scale production, realizes the practical application of lithium ion battery.
Description
Technical field
The invention belongs to electrochemical field, and in particular to a kind of fusiform zinc ferrite/carbon lithium ion cell nano composite negative pole
Material and preparation method and application.
Background technology
As current social is to the growing of energy demand, increasingly serious energy crisis and environmental problem are result in,
So as to excite continuous research of the people for new energy and energy storage and switch technology.The success of 20 end of the century Sonies
Start the sight that commercialized lithium ion battery attracts vast majority of people, with it in terms of energy stores and conversion unique advantage
Now also apply in the various electronics such as computer, mobile phone.But with the further development of electric automobile and energy storage technology,
Higher requirement is proposed to lithium ion battery, it is desirable to the high rate performance kept while realizing high-energy-density and circulation
Stability and more light safe, environment-friendly., can be by important component from the composition of lithium ion battery
The research of electrode material improves this present situation.
Main body of the negative material as storage lithium, it is the important part of lithium ion battery, commercialized graphite cathode is only
There are 372 mAh g-1It is such a than relatively low theoretical specific capacity, far from reaching future development requirement.It is and excellent currently having
In the negative material of gesture, the transition metal oxide of nano-scale（TMOs）The notice of people is attracted significantly, has on the one hand received
The particulate matter of meter ruler cun has larger specific surface area, there is provided more reactivity sites, while shorten for lithium ion transport
Response path, another aspect transition metal oxide typically has higher theoretical specific capacity, especially with double oxo transition metals
The theoretical specific capacity of compound is higher.
The double transition metal oxides of iron-based as promising lithium cell cathode material for, it has the relative double gold of cobalt-based
Belong to oxide（MFe2O4, M=Ni, Mn, Zn, Co）It is lower toxicity, more cheap and more environment-friendly, and and can ensures there is one simultaneously
Individual high theoretical specific capacity.Among this, ZnFe2O4Highlighted again from the double transition metal of other iron-baseds, because the mistake of storage lithium
Conversion reaction, also Zn are not only existed in journey2+With Li+The alloy reaction of generation, specific volume is added so as to improve storage lithium ability
Amount.But similar to other transition metal oxides, ZnFe2O4Or there can be the i.e. low capacity of big capacity attenuation to keep
The Volume Changes of material in rate and charge and discharge process, cause material to have relatively low cyclical stability and invertibity.For above-mentioned
Some defects, researchers are made that very big effort to be improved one after another, for example, Won etc. by spray drying process 450
The ZnFe of core/hollow/shell is synthesized under the conditions of DEG C2O4, the material structure obtained under different synthesis temperatures is different, electrification
Learning performance also can be otherwise varied, and 200 circle circulations, the ZnFe of core/hollow/shell are undergone under the C of current density 0.52O4Discharge capacity
For 862 mAh g-1, the solid ZnFe that is obtained far above 350 DEG C2O4With 400 DEG C of obtained core shell structure ZnFe2O4（J. M.
Won, S. H. Choi, et al. Electrochemical properties of yolk-shell structured
ZnFe(2)O(4) powders prepared by a simple spray drying process as anode
material for lithium-ion battery[J]. Scientific reports, 2014, 4: 5857.）；Xing
The mutually octahedra ZnFe of monocrystalline is successfully prepared Deng using low-temperature hydrothermal reaction method2O4, from scanning electron microscope (SEM) photograph it can be seen that this octahedral
The external well-balanced surface of shape is smooth, and size is 100-350 nm, and electrochemical property test shows octahedra ZnFe2O4In 0.06C electric currents
Discharge capacity is 1350 mAh g first under density-1, it is 910 mAh g to have circulated the specific capacity after 80 times-1, equally in height
It is tested under current density 1C, the discharge capacity of the circle of circulation 300 still there are 730 mAh g-1, shown one and preferably followed
High power capacity performance under ring stability and high magnification（P. F. Teh, Y. Sharma, et al. Nanoweb anodes
composed of one-dimensional, high aspect ratio, size tunable electrospun
ZnFe2O4 nanofibers for lithium ion batteries[J]. J. Mater. Chem., 2011, 21,
14999–15008.）.
The present invention prepares fusiform zinc ferrite/carbon lithium ion battery using organic metal framework method combination hydrothermal reaction process
Nano composite material, up to now, also reported without the synthetic method of correlation, it is also no to utilize dependency structure composite
It is made as the report of lithium ion battery negative material.
The content of the invention
Low for commercial Li-ion battery graphite cathode material theoretical capacity traditional at present, transition metal oxide is born
The defects of pole material conductivity is poor, and its special capacity fade is too fast in battery charging and discharging cyclic process, the present invention propose a kind of fusiform
Zinc ferrite/carbon lithium ion cell nano composite negative pole material and preparation method and application, can improve negative electrode of lithium ion battery material
The structural stability and chemical property of material, improve cyclical stability and high rate performance of the material in charge and discharge process.In addition,
Zinc ferrite provided by the invention/carbon preparation method is simple, process is easily-controllable, cost is cheap and environment-friendly, can promote scale
Metaplasia produces lithium ion battery negative material, suitable for industrial applications.
The present invention is achieved through the following technical solutions.
A kind of preparation method of fusiform zinc ferrite/carbon lithium ion cell nano composite negative pole material, comprises the following steps：
（1）Fumaric acid is dissolved in dimethylformamide, stirred and evenly mixed, obtains dispersion liquid；
（2）To step（1）Ferrous metal salt and zinc metal salt are added in gained dispersion liquid, stirs, obtains mixed liquor；
（3）By step（2）Gained mixed liquor is transferred in hydrothermal reaction kettle, is put into hydro-thermal reaction in electric heating constant-temperature blowing drying box,
Room temperature is subsequently cooled to, is dried after centrifuge washing；
（4）By step（3）The powder obtained after drying is put into porcelain boat, places into tube furnace, in a nitrogen atmosphere annealing reaction,
Fusiform zinc ferrite/carbon lithium ion cell nano composite negative pole material is obtained after room temperature is dropped to.
Preferably, step（1）The usage amount of the fumaric acid is 4-32 mmol.
Preferably, step（1）The time stirred and evenly mixed is 2-4 hours.
Preferably, step（2）Mol ratio of the addition control of described ferrous metal salt and zinc metal salt in Fe and Zn
For 1.5~3：0.75~1.5, more preferably 2：1.
Preferably, step（2）Described ferrous metal salt is one kind in ferric nitrate and ferric trichloride；Described zinc metal
Salt is one kind in zinc nitrate and zinc acetate.
Preferably, step（2）The time to stir is 2-5 hours.
Preferably, step（3）The volume of the hydrothermal reaction kettle is 50 mL.
Preferably, step（3）The drying is 60-80 DEG C of drying of baking oven.
Preferably, step（3）The temperature of the hydro-thermal reaction is 100~150 DEG C, more preferably 100 DEG C；It is described
The time of hydro-thermal reaction is 10-12 hours.
Preferably, step（3）The centrifuge washing refers to first be washed 2-3 times with absolute ethyl alcohol, then with dimethyl formyl
Amine washs 1-2 times, is finally washed 2-3 times using absolute ethyl alcohol.
Preferably, step（4）The temperature of the annealing reaction is 500 ~ 600 DEG C, and the time is 1-2 hours.
A kind of fusiform structure zinc ferrite as made from the process described above/carbon lithium ion cell nano composite negative pole material
Material, it is again compound by carbon skeleton for the i.e. similar jujube core of fusiform structure, pointed at both ends, middle thick polyhedral structure, this fusiform structure
Two level nanometer zinc ferrite particle is formed, and the content of zinc ferrite is 60-90 wt% in the nano composite anode material.
Preferably, the particle diameter of zinc ferrite two level nano particle is 200 ~ 900 nm in the nano composite anode material.
A kind of above-described fusiform zinc ferrite/carbon lithium ion cell nano composite negative pole material is preparing lithium ion battery
In application.
Compared with prior art, the present invention has following features：
1）Because carbon material has good electric conductivity and skeleton function therein so that fusiform zinc ferrite/carbon lithium of the present invention from
Sub- cell nano composite negative pole material overcomes the problem of simple zinc ferrite metal conductive oxide difference in charge and discharge process,
Promote the quick transmission of carrier and effectively alleviate the stabilization of the Volume Changes of wherein metal material so as to holding structure.
2）Due to the effect of organic metal framework fumaric acid so that material has the unique texture of a fusiform, and
One hundreds of nanometers of size is maintained, improves the contact area between electrolyte and particulate matter and shortening well
The diffusion path of lithium ion, so as to realizing an ideal battery performance.
3）The preparation method is simple to operate, process is easily-controllable, cost is cheap and environment-friendly, can promote lithium ion battery
The practical application of negative material, realize that industrially scalable metaplasia is produced.
Brief description of the drawings
Fig. 1 is the SEM of gained fusiform zinc ferrite/carbon lithium ion cell nano composite negative pole material in the embodiment of the present invention 1
Figure.
Fig. 2 is the TEM of gained fusiform zinc ferrite/carbon lithium ion cell nano composite negative pole material in the embodiment of the present invention 1
Figure.
Fig. 3 is the XRD of gained fusiform zinc ferrite/carbon lithium ion cell nano composite negative pole material in the embodiment of the present invention 1
Figure.
Fig. 4 is the Raman of gained fusiform zinc ferrite/carbon lithium ion cell nano composite negative pole material in the embodiment of the present invention 1
Spectrogram.
Fig. 5 is fusiform zinc ferrite/carbon nano-composite material obtained by the embodiment of the present invention 1 as negative electrode of lithium ion battery material
Material is assembled into the constant current charge-discharge performance map of battery.
Fig. 6 is fusiform zinc ferrite/carbon nano-composite material obtained by the embodiment of the present invention 1 as negative electrode of lithium ion battery material
Material is assembled into the high rate performance figure of battery.
Embodiment
Further explanation is done to the present invention with reference to embodiment and accompanying drawing.The following example is merely to illustrate this hair
It is bright, but it is not used to limit the practical range of invention.
Embodiment 1
（1）Weigh 1.8571 g fumaric acid（C4H4O4, 99.0 %）It is added to 20 mL dimethylformamide（HCON
(CH3)2, AR）In, after magnetic agitation under 750 rpm speed mixes 2 hours, obtain transparent dispersion liquid.0.4040 is weighed again
G ferric nitrates (Fe (NO3)3·9H2O, 98.5 %) and 0.1487 g zinc nitrates（Zn(NO3)2·6H2O, 99.0 %）It is added to above-mentioned
Dispersion liquid in, stirred 3 hours under the speed for being equally 750 rpm, 50 mL water heating kettle sealing steel shell be transferred to after well mixed
In, 12 h of reaction are carried out at a temperature of 100 DEG C in electric heating constant-temperature blowing drying box.After room temperature is cooled to, by hydro-thermal reaction
Product separation of solid and liquid, after first washing 2 times with absolute ethyl alcohol for gained solid, then with dimethylformamide wash 1 time, again finally
Washed 2 times with absolute ethyl alcohol, above washing process is to centrifuge 2 min under 8000 rpm rotating speeds by centrifuge come real entirely
Existing, washing acquisition thing is put into thermostatic drying chamber 12 h are dried at 60 DEG C, obtain dry presoma solid powder；
（2）Precursor powder is uniformly placed in 30*60 mm porcelain boat, the flat-temperature zone of tube furnace is then placed in, is first passed through
50 min nitrogen excludes the air in pipe furnace, afterwards with 2 DEG C of min under same nitrogen atmosphere-1Heating rate risen
Temperature, 1h is incubated after being warming up to 500 DEG C, finally with 3 DEG C of min-1Speed cool to 400 DEG C of relief tube furnace Temperature falls to room
Temperature, the nitrogen flow in this whole process all maintain 10 mL min-1；It is 75.2 wt% to have finally given ferrous acid Zn content
Fusiform zinc ferrite/carbon lithium ion cell nano composite negative pole material.
Fig. 1 is the SEM figures of zinc ferrite/carbon nano-composite material obtained by the present embodiment.More than passing through as we know from the figure
The composite obtained after process has fusiform structure, keeps dispersed and size distribution well uniform between particle, size
For 300 ~ 450 nm.
Fig. 2 is the TEM figures of fusiform zinc ferrite/carbon nano-composite material obtained by the present embodiment.It can be seen in the figure that this
There is the presence of carbon component in fusiform zinc ferrite/carbon nano-composite material obtained by embodiment, and served in whole particle
The effect of structural framing is maintained, 10 ~ 20 nm of two level zinc ferrite particle is contained in centre.
Fig. 3 is the XRD of fusiform zinc ferrite/carbon nano-composite material obtained by the present embodiment.By each diffraction maximum in figure
Contrast PDF cards obtain the zinc ferrite of exactly cubic structure, the appearance without any miscellaneous peak.But obvious carbon is not found out yet
Diffraction maximum, this is probably to cause to be detected because carbon content is relatively low.
Fig. 4 is the Raman spectrogram of fusiform zinc ferrite/carbon nano-composite material obtained by the present embodiment.In figure 100 ~
1000 cm-1In the range of several big characteristic peaks, the exactly model of vibration of ferrous acid zinc material；1200~1600 cm-1In the range of it is several
The presence of big characteristic peak confirms that material is to learn that zinc ferrite/carbon is received containing carbon component, and after the two peak intensity is contrasted
Carbon material in nano composite material has certain degree of graphitization.
（3）By step（2）Obtained fusiform zinc ferrite/carbon lithium ion cell nano composite negative pole material is as active material
Material, acetylene black is conductive agent, and Kynoar is binding agent, and according to active material：Conductive agent：Binding agent=7：2：1 quality
Than inserting in 5 mL cillin bottle, the N-methyl pyrrolidones that 0.5 mL is then added dropwise stirs pulp after 4 h, and slurry is uniform
It is applied on copper foil, is then put into 120 DEG C of thermostatic drying chamber and dries 12 h, gone out after being dried to constant weight using sheet-punching machine as 14
Mm sequin is working electrode, and sequin is put into the glove box full of argon gas in the case of guarantee is anhydrous, purchase
Lithium piece is used as to electrode and reference electrode, and the type barrier films of Celgard 2400 used, electrolyte is 1 mol L-1LiPF6With carbon
Vinyl acetate（EC）, dimethyl carbonate（DMC）（EC：DMC=1：2, ν/ν）Mixed liquor, model is finally assembled into glove box
CR2025 button cell, the glove box in whole process must keep oxygen and water vapour content to be respectively less than 1 ppm.Thus make
Obtain the lithium ion battery of fusiform zinc ferrite/carbon lithium ion cell nano composite negative pole material.
Fig. 5 is the discharge and recharge of fusiform zinc ferrite/carbon lithium ion cell nano composite negative pole material obtained by the present embodiment
Cycle performance figure.At 25 DEG C, with 1000 mA g-1Current density charge and discharge cycles test is carried out between 0.01-3.0 V,
Its electric discharge and charge specific capacity first is respectively 1162.3 mAh g-1With 771.6 mAh g-1, the battery since enclosing the 70th
Circulation tends towards stability, and maintains 650 mAh g-1The higher reversible specific capacity in left and right one.
Fig. 6 is the forthright again of fusiform zinc ferrite/carbon lithium ion cell nano composite negative pole material obtained by the present embodiment
Can figure.Fusiform zinc ferrite/carbon lithium ion cell nano is compound under 0.2,0.4,0.8,1.6,3.2 C these current densities
Specific capacity corresponding to negative material is respectively 883,752,669,582,496 mAh g-1；Even under 6.4 higher C multiplying powers,
Material still maintains 389 mAh g-1Reversible specific capacity.And when the current ratio of circulation has returned to 0.2 C, the capacity of storage
It has been returned to 915 mAh g-1Left and right, and with circulation the number of turns increase capacity also gradually it is increased, illustrate fusiform iron
Sour zinc/carbon lithium ion cell nano composite negative pole material has preferable high rate performance and cyclical stability.
Embodiment 2
（1）Weigh 1.8571 g fumaric acid（C4H4O4, 99.0 %）It is added to 20 mL dimethylformamide（HCON
(CH3)2, AR）In, after stirring and evenly mixing 3 hours under 750 rpm speed, obtain, transparent dispersion liquid.0.8080 g is weighed again
Ferric nitrate (Fe (NO3)3·9H2O, 98.5 %) and 0.2974 g zinc nitrates（Zn(NO3)2·6H2O, 99.0 %）It is added to above-mentioned
Dispersion liquid in, stirred 3 hours under the speed for being equally 750 rpm, 50 mL water heating kettle sealing steel shell be transferred to after well mixed
In, 10 h of reaction are carried out at a temperature of 100 DEG C in electric heating constant-temperature blowing drying box.After room temperature is cooled to, by hydro-thermal reaction
Product separation of solid and liquid, after first washing 2 times with absolute ethyl alcohol for gained solid, then with dimethylformamide wash 1 time, again finally
Washed 2 times with absolute ethyl alcohol, above washing process is to centrifuge 2 min under 8000 rpm rotating speeds by centrifuge come real entirely
Existing, washing acquisition thing is put into thermostatic drying chamber 12 h are dried at 60 DEG C, obtain dry presoma solid powder；
（2）Precursor powder is uniformly placed in 30*60 mm porcelain boat, the flat-temperature zone of tube furnace is then placed in, is first passed through
50 min nitrogen excludes the air in pipe furnace, afterwards with 2 DEG C of min under same nitrogen atmosphere-1Heating rate carry out
Heating, is incubated 1 h, finally with 3 DEG C of min after being warming up to 600 DEG C-1Speed cool to 400 DEG C of relief tube furnaces and drop naturally
Temperature arrives room temperature, and the nitrogen flow in whole process all maintains 10 mLmin-1；The shuttle that ferrous acid Zn content is 68% is finally given
Shape zinc ferrite/carbon lithium ion cell nano composite negative pole material.
（3）By step（2）Obtained fusiform zinc ferrite/carbon lithium ion cell nano composite negative pole material is as active material
Material, acetylene black is conductive agent, and Kynoar is binding agent, and according to active material：Conductive agent：Binding agent=7：2：1 quality
Than inserting in 5 mL cillin bottle, the N-methyl pyrrolidones that 0.75 mL is then added dropwise stirs pulp after 4 h, and slurry is equal
It is even to be applied on copper foil, be then put into 120 DEG C of thermostatic drying chamber and dry 12 h, be dried to after constant weight using sheet-punching machine go out for
14 mm sequin is working electrode, and sequin is put into the glove box full of argon gas in the case of guarantee is anhydrous, bought
Lithium piece be used as to electrode and reference electrode, the type barrier films of Celgard 2400 used, electrolyte is 1 mol L-1LiPF6With
Ethylene carbonate（EC）, dimethyl carbonate（DMC）（EC：DMC=1：2, ν/ν）Mixed liquor, the last assembled formation in glove box
Number CR2025 button cell, the glove box in whole process must keep oxygen and water vapour content to be respectively less than 1 ppm.Thus
The lithium ion battery of fusiform zinc ferrite/carbon lithium ion cell nano composite negative pole material assembling is made.
Fusiform zinc ferrite/carbon lithium ion cell nano composite negative pole material that ferrous acid Zn content is 68 wt% is finally given
Material.
The composite obtained after above procedure has fusiform structure, keeps good dispersed and big between particle
Small to be evenly distributed, size is 450 ~ 600 nm.The fusiform ferrous acid under 0.2,0.4,0.8,1.6,3.2 C these current densities
Zinc/specific capacity corresponding to carbon lithium ion cell nano composite negative pole material is respectively 847,743,637,569,473 mAh g-1；
Even under 6.4 higher C multiplying powers, material still maintains 363 mAh g-1Reversible specific capacity.And when the current ratio of circulation
When having returned to 0.2 C, the capacity of storage has been returned to 839 mAh g-1Left and right, and as the increase capacity of the number of turns of circulation also exists
Gradually it is increased, illustrate fusiform zinc ferrite/carbon lithium ion cell nano composite negative pole material have preferable high rate performance and
Cyclical stability.
Embodiment 3
（1）Weigh 3.7142 g fumaric acid（C4H4O4, 99.0 %）It is added to 40 mL dimethylformamide（HCON
(CH3)2, AR）In, after stirring and evenly mixing 2 hours under 750 rpm speed, obtain, transparent dispersion liquid.0.8080 g is weighed again
Ferric nitrate (Fe (NO3)3·9H2O, 98.5 %) and 0.2974 g zinc nitrates（Zn(NO3)2·6H2O, 99.0 %）It is added to above-mentioned
Dispersion liquid in, stirred 3 hours under the speed for being equally 750 rpm, 50 mL water heating kettle sealing steel shell be transferred to after well mixed
In, 12 h of reaction are carried out at a temperature of 150 DEG C in electric heating constant-temperature blowing drying box.After room temperature is cooled to, by hydro-thermal reaction
Product separation of solid and liquid, after first washing 3 times with absolute ethyl alcohol for gained solid, then with dimethylformamide wash 2 times, again finally
Washed 3 times with absolute ethyl alcohol, above washing process is to centrifuge 2 min under 8000 rpm rotating speeds by centrifuge come real entirely
Existing, washing acquisition thing is put into thermostatic drying chamber 12 h are dried at 60 DEG C, obtain dry presoma solid powder；
（2）Precursor powder is uniformly placed in 30*60 mm porcelain boat, the flat-temperature zone of tube furnace is then placed in, is first passed through
50 min nitrogen excludes the air in pipe furnace, afterwards with 2 DEG C of min under same nitrogen atmosphere-1Heating rate carry out
Heating, is incubated 1 h, finally with 3 DEG C of min after being warming up to 550 DEG C-1Speed cool to 400 DEG C of relief tube furnaces and drop naturally
Temperature arrives room temperature, and the nitrogen flow in whole process all maintains 10 mL min-1；It is 75.2 % to have finally given ferrous acid Zn content
Fusiform zinc ferrite/carbon lithium ion cell nano composite negative pole material.
（3）By step（2）Obtained fusiform zinc ferrite/carbon lithium ion cell nano composite negative pole material is as active material
Material, acetylene black is conductive agent, and Kynoar is binding agent, and according to active material：Conductive agent：Binding agent=7：2：1 quality
Than inserting in 5 mL cillin bottle, the N-methyl pyrrolidones that 0.9 mL is then added dropwise stirs pulp after 4 h, and slurry is uniform
It is applied on copper foil, is then put into 120 DEG C of thermostatic drying chamber and dries 12 h, gone out after being dried to constant weight using sheet-punching machine as 14
Mm sequin is working electrode, and sequin is put into the glove box full of argon gas in the case of guarantee is anhydrous, purchase
Lithium piece is used as to electrode and reference electrode, and the type barrier films of Celgard 2400 used, electrolyte is 1 mol L-1LiPF6With carbon
Vinyl acetate（EC）, dimethyl carbonate（DMC）（EC：DMC=1：2, ν/ν）Mixed liquor, model is finally assembled into glove box
CR2025 button cell, the glove box in whole process must keep oxygen and water vapour content to be respectively less than 1 ppm.Thus make
Obtain the lithium ion battery of fusiform zinc ferrite/carbon lithium ion cell nano composite negative pole material assembling.
Fusiform zinc ferrite/carbon lithium ion cell nano composite negative pole material that ferrous acid Zn content is 75.2 wt% is finally given
Material.
The composite obtained after above procedure has fusiform structure, keeps good dispersed and big between particle
Small to be evenly distributed, size is 250 ~ 400 nm.The fusiform ferrous acid under 0.2,0.4,0.8,1.6,3.2 C these current densities
Zinc/specific capacity corresponding to carbon lithium ion cell nano composite negative pole material is respectively 891,767,672,593,506 mAh g-1；
Even under 6.4 higher C multiplying powers, material still maintains 397 mAh g-1Reversible specific capacity.And when the current ratio of circulation
When having returned to 0.2 C, the capacity of storage has been returned to 887 mAh g-1Left and right, and as the increase capacity of the number of turns of circulation also exists
Gradually it is increased, illustrate fusiform zinc ferrite/carbon lithium ion cell nano composite negative pole material have preferable high rate performance and
Cyclical stability.
Embodiment 4
（1）Weigh 3.7142 g fumaric acid（C4H4O4, 99.0 %）It is added to 40 mL dimethylformamide（HCON
(CH3)2, AR）In, after stirring and evenly mixing 2 hours under 750 rpm speed, obtain, transparent dispersion liquid.0.2702 g is weighed again
Ferric trichloride (FeCl3·6H2O, AR) and 0.1096 g zinc acetates（Zn(Ac)2·2H2O, 97.0 %）It is added to above-mentioned point
In dispersion liquid, stir 3 hours under the speed for being equally 750 rpm, be transferred to after well mixed in 50 mL water heating kettle sealing steel shell,
Carry out reacting 11 h at a temperature of 125 DEG C in electric heating constant-temperature blowing drying box.After room temperature is cooled to, hydro-thermal reaction is produced
Thing separation of solid and liquid, after first washing 2 times with absolute ethyl alcohol for gained solid, then washed 1 time with dimethylformamide, finally used again
Absolute ethyl alcohol washs 2 times, and above washing process is to centrifuge 2 min under 8000 rpm rotating speeds to realize by centrifuge entirely
, washing acquisition thing is put into thermostatic drying chamber 12 h are dried at 60 DEG C, obtain dry presoma solid powder；
（2）Precursor powder is uniformly placed in 30*60 mm porcelain boat, the flat-temperature zone of tube furnace is then placed in, is first passed through
50 min nitrogen excludes the air in pipe furnace, afterwards with 2 DEG C of min under same nitrogen atmosphere-1Heating rate carry out
Heating, is incubated 1 h after being warming up to 500 DEG C, then to 1 h is incubated after 600 DEG C, finally with 3 DEG C of min-1Speed cool to 400
To room temperature, the nitrogen flow in this whole process all maintains 10 mL min for DEG C relief tube furnace Temperature fall-1；Final
Fusiform zinc ferrite/carbon lithium ion cell nano composite negative pole material that ferrous acid Zn content is 60 % is arrived.
（3）By step（2）Obtained fusiform zinc ferrite/carbon lithium ion cell nano composite negative pole material is as active material
Material, acetylene black is conductive agent, and Kynoar is binding agent, and according to active material：Conductive agent：Binding agent=7：2：1 quality
Than inserting in 5 mL cillin bottle, the N-methyl pyrrolidones that 1 mL is then added dropwise stirs pulp after 4 h, and slurry is uniformly applied
12 h are dried in the thermostatic drying chamber on copper foil, being then put into 120 DEG C, are gone out after being dried to constant weight using sheet-punching machine as 14 mm
Sequin be working electrode, ensure it is anhydrous in the case of sequin is put into the glove box full of argon gas, the lithium of purchase
Piece is used as to electrode and reference electrode, and the type barrier films of Celgard 2400 used, electrolyte is 1 mol L-1LiPF6With carbonic acid
Vinyl acetate（EC）, dimethyl carbonate（DMC）（EC：DMC=1：2, ν/ν）Mixed liquor, model is finally assembled into glove box
CR2025 button cell, the glove box during this must keep oxygen and water vapour content to be respectively less than 1 ppm.Thus make
Obtain the lithium ion battery of fusiform zinc ferrite/carbon lithium ion cell nano composite negative pole material assembling.
Fusiform zinc ferrite/carbon lithium ion cell nano composite negative pole material that ferrous acid Zn content is 60 wt% is finally given
Material.
The composite obtained after above procedure has fusiform structure, keeps good dispersed and big between particle
Small to be evenly distributed, size is 200 ~ 350 nm.The fusiform ferrous acid under 0.2,0.4,0.8,1.6,3.2 C these current densities
Zinc/specific capacity corresponding to carbon lithium ion cell nano composite negative pole material is respectively 989,819,709,562,456 mAh g-1；
Even under 6.4 higher C multiplying powers, material still maintains 357 mAh g-1Reversible specific capacity.And when the current ratio of circulation
When having returned to 0.2 C, the capacity of storage has been returned to 995 mAh g-1Left and right, and as the increase capacity of the number of turns of circulation also exists
Gradually it is increased, illustrate fusiform zinc ferrite/carbon lithium ion cell nano composite negative pole material have preferable high rate performance and
Cyclical stability.
Embodiment 5
（1）Weigh 0.4643 g fumaric acid（C4H4O4, 99.0 %）It is added to 5 mL dimethylformamide（HCON(CH3)2,
AR）In, after magnetic agitation under 750 rpm speed mixes 2 hours, obtain transparent dispersion liquid.0.4040 g nitric acid is weighed again
Iron (Fe (NO3)3·9H2O, 98.5 %) and 0.1487 g zinc nitrates（Zn(NO3)2·6H2O, 99.0 %）It is added to above-mentioned point
In dispersion liquid, stir 3 hours under the speed for being equally 750 rpm, be transferred to after well mixed in 50 mL water heating kettle sealing steel shell,
Carry out reacting 11 h at a temperature of 150 DEG C in electric heating constant-temperature blowing drying box.After room temperature is cooled to, hydro-thermal reaction is produced
Thing separation of solid and liquid, after first washing 2 times with absolute ethyl alcohol for gained solid, then washed 1 time with dimethylformamide, finally used again
Absolute ethyl alcohol washs 3 times, and above washing process is to centrifuge 2 min under 8000 rpm rotating speeds to realize by centrifuge entirely
, washing acquisition thing is put into thermostatic drying chamber 12 h are dried at 60 DEG C, obtain dry presoma solid powder；
（2）Precursor powder is uniformly placed in 30*60 mm porcelain boat, the flat-temperature zone of tube furnace is then placed in, is first passed through
50 min nitrogen excludes the air in pipe furnace, afterwards with 2 DEG C of min under same nitrogen atmosphere-1Heating rate risen
Temperature, 1h is incubated after being warming up to 600 DEG C, finally with 3 DEG C of min-1Speed cool to 400 DEG C of relief tube furnace Temperature falls to room
Temperature, the nitrogen flow in this whole process all maintain 10 mL min-1；
（3）By step（2）Obtained fusiform zinc ferrite/carbon lithium ion cell nano composite negative pole material is as active material, second
Acetylene black is conductive agent, and Kynoar is binding agent, and according to active material：Conductive agent：Binding agent=7：2：1 mass ratio is put
In the cillin bottle for entering 5 mL, the N-methyl pyrrolidones that 1 mL is then added dropwise stirs pulp after 4 h, and slurry is uniformly applied into copper
On paper tinsel, then it is put into 120 DEG C of thermostatic drying chamber and dries 12 h, gone out after being dried to constant weight using sheet-punching machine as the small of 14 mm
Disk is working electrode, and sequin is put into the glove box full of argon gas in the case of guarantee is anhydrous, and the lithium piece of purchase is made
For to electrode and reference electrode, the type barrier films of Celgard 2400 used, electrolyte is 1 mol L-1LiPF6With ethylene carbonate
Ester（EC）, dimethyl carbonate（DMC）（EC：DMC=1：2, ν/ν）Mixed liquor, model CR2025 is finally assembled into glove box
Button cell, the glove box during this must keep oxygen and water vapour content to be respectively less than 1 ppm.Thus fusiform is made
The lithium ion battery of zinc ferrite/carbon lithium ion cell nano composite negative pole material assembling.
Fusiform zinc ferrite/carbon lithium ion cell nano composite negative pole material that ferrous acid Zn content is 90 wt% is finally given
Material.
The composite obtained after above procedure has fusiform structure, keeps good dispersed and big between particle
Small to be evenly distributed, size is 700 ~ 900 nm.The fusiform ferrous acid under 0.2,0.4,0.8,1.6,3.2 C these current densities
Zinc/specific capacity corresponding to carbon lithium ion cell nano composite negative pole material is respectively 799,739,657,469,397 mAh g-1；
Even under 6.4 higher C multiplying powers, material still maintains 301 mAh g-1Reversible specific capacity.And when the current ratio of circulation
When having returned to 0.2 C, the capacity of storage has been returned to 800 mAh g-1Left and right, and as the increase capacity of the number of turns of circulation also exists
Gradually it is increased, illustrate fusiform zinc ferrite/carbon lithium ion cell nano composite negative pole material have preferable high rate performance and
Cyclical stability.
Claims (10)
- A kind of 1. preparation method of fusiform zinc ferrite/carbon lithium ion cell nano composite negative pole material, it is characterised in that including with Lower step：（1）Fumaric acid is dissolved in dimethylformamide, stirred and evenly mixed, obtains dispersion liquid；（2）To step（1）Ferrous metal salt and zinc metal salt are added in gained dispersion liquid, stirs, obtains mixed liquor；（3）By step（2）Gained mixed liquor is transferred in hydrothermal reaction kettle, is put into hydro-thermal reaction in electric heating constant-temperature blowing drying box, Room temperature is subsequently cooled to, is dried after centrifuge washing；（4）By step（3）The powder obtained after drying is put into porcelain boat, places into tube furnace, in a nitrogen atmosphere annealing reaction, Fusiform zinc ferrite/carbon lithium ion cell nano composite negative pole material is obtained after room temperature is dropped to.
- 2. preparation method according to claim 1, it is characterised in that step（1）The usage amount of the fumaric acid is 4-32 mmol。
- 3. preparation method according to claim 1, it is characterised in that step（2）Described ferrous metal salt and zinc metal salt Addition control the mol ratio in Fe and Zn to be（1.5~3）：（0.75~1.5）.
- 4. preparation method according to claim 1, it is characterised in that step（2）Described ferrous metal salt be ferric nitrate and One kind in ferric trichloride；Described zinc metal salt is one kind in zinc nitrate and zinc acetate.
- 5. preparation method according to claim 1, it is characterised in that step（3）The temperature of the hydro-thermal reaction is 100 ~150 DEG C, the time is 10-12 hours.
- 6. preparation method according to claim 1, it is characterised in that step（3）The centrifuge washing refers to first with anhydrous Ethanol washs 2-3 times, then is washed 1-2 times with dimethylformamide, is finally washed 2-3 times using absolute ethyl alcohol.
- 7. preparation method according to claim 1, it is characterised in that step（4）The temperature of the annealing reaction be 500 ~ 600 DEG C, the time is 1-2 hours.
- A kind of 8. fusiform structure zinc ferrite/carbon lithium ion cell nano as made from the method described in claim any one of 1-7 Composite negative pole material, it is characterised in that the content of zinc ferrite is 60-90 wt% in the nano composite anode material.
- 9. a kind of fusiform structure zinc ferrite/carbon lithium ion cell nano composite negative pole material according to claim 8, its It is characterised by, the particle diameter of zinc ferrite two level nano particle is 200 ~ 900 nm in the nano composite anode material.
- 10. a kind of fusiform zinc ferrite/carbon lithium ion cell nano composite negative pole material described in claim 9 is preparing lithium ion Application in battery.
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