CN103066262B - Preparation method of anode material of Mn0.5-xCuxZn0.5 Fe2O4 lithium ion battery - Google Patents
Preparation method of anode material of Mn0.5-xCuxZn0.5 Fe2O4 lithium ion battery Download PDFInfo
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- CN103066262B CN103066262B CN201310008834.2A CN201310008834A CN103066262B CN 103066262 B CN103066262 B CN 103066262B CN 201310008834 A CN201310008834 A CN 201310008834A CN 103066262 B CN103066262 B CN 103066262B
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- lithium ion
- anode material
- ion battery
- sulfate
- copper sheet
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a preparation method of an anode material of a Mn0.5-xCuxZn0.5 Fe2O4 lithium ion battery. The method comprises the following steps of: 1) weighing manganese sulfate, zinc sulfate, ferrous sulfate and copper sulfate; 2) dissolving sulfate in deionized water, and stirring to prepare mixed liquor; 3) dropwise adding ammonium bicarbonate liquor to the mixed liquor and continuously stirring; 4) inserting a copper sheet into the mixed liquor and carrying out hydrothermal reaction for 15-30hours at 150-200 DEG C; and 5) washing and drying to obtain the anode material of the Mn0.5-xCuxZn0.5 Fe2O4 lithium ion battery. The anode material of the Mn0.5-xCuxZn0.5 Fe2O4 lithium ion battery prepared by the invention has very high embedding amount of lithium ions and good embedding-removing reversibility, so that not only is the actual capacity of the battery improved, but also the recycling service life is greatly prolonged.
Description
Technical field
The present invention relates to a kind of preparation method of lithium ion battery anode material, particularly a kind of Mn
0.5-xcu
xzn
0.5fe
2o
4the preparation method of lithium ion battery anode material.
Background technology
Since Gaston Plante in 1859 proposes lead-sour cells concepts, the secondary cell that chemical power source circle is being explored new high-energy-density always, had extended cycle life.Sony Corporation of Japan took the lead in succeeding in developing and realized commercial lithium ion battery nineteen ninety, illustrate wide application prospect and potential great economic benefit in many-sides such as portable electric appts, electric automobile, space technology, national defense industry, become rapidly the study hotspot widely paid close attention in recent years.
One of key of exploitation lithium ion battery finds suitable anode material, makes battery have sufficiently high lithium embedded quantity and good lithium deintercalation invertibity, to ensure the high voltage of battery, Large Copacity and long circulation life.Material with carbon element is applied because having higher specific capacity in commercial Li-ion batteries, and shows good electrochemical behavior, but still there is the low defect of theoretical capacity.Since P. Poizot etc. reports with other transition metal oxides as FeO, CoO, MoO, Cu
2since the chemical property as lithium rechargeable battery anode material such as O, other transition metal oxides and ferrite such as ZnFe
2o
4, CoFe
2o
4deng the focus also becoming research gradually, and these material lists reveal higher specific discharge capacity.But the application of lithium ion battery success, key is the preparation of the anode material reversibly embedding deintercalate lithium ions.
Summary of the invention
In view of this, the invention provides a kind of Mn
0.5-xcu
xzn
0.5fe
2o
4the preparation method of lithium ion battery anode material, the Mn of preparation
0.5-xcu
xzn
0.5fe
2o
4lithium ion battery anode material can realize the high power capacity discharge and recharge of battery, and has extended cycle life.
Mn of the present invention
0.5-xcu
xzn
0.5fe
2o
4the preparation method of lithium ion battery anode material, comprises the following steps:
1) manganese sulfate, zinc sulfate, ferrous sulfate and copper sulphate is taken according to following atomic percent: Mn
0.5-xcu
xzn
0.5fe
2o
4, wherein
x=0.1 ~ 0.4;
2) sulfate that step 1) takes is dissolved in deionized water, stirs and be made into mixed solution;
3) toward step 2) dropwise add ammonium bicarbonate soln in the mixed solution that is made into, and constantly stir;
4) be inserted into by copper sheet in the mixed solution that step 3) obtains, hydro-thermal reaction 15 ~ 30 hours at 150 ~ 200 DEG C, obtaining growth has Mn
0.5-xcu
xzn
0.5fe
2o
4the copper sheet of nano particle;
5) drying steps 4 is rinsed) growth that obtains has Mn
0.5-xcu
xzn
0.5fe
2o
4the copper sheet of nano particle, obtains Mn
0.5-xcu
xzn
0.5fe
2o
4lithium ion battery anode material.
Further, in described step 4), first remove the oxide layer on copper sheet surface with watery hydrochloric acid cleaning, then copper sheet is inserted in mixed solution that step 3) obtains.
Further, in described step 4), hydrothermal temperature is 180 DEG C, and the reaction time is 24 hours.
Beneficial effect of the present invention is: the present invention utilizes the method for hydro-thermal reaction directly on copper sheet, to grow Mn
0.5-xcu
xzn
0.5fe
2o
4nano particle, Mn
0.5-xcu
xzn
0.5fe
2o
4good with copper sheet tack, do not need to add binding agent again, and surface defines a large amount of Micro porosities, thus advantageously in embedded quantity and the good deintercalation invertibity of lithium ion, therefore it can be used as lithium ion battery anode material, not only can improve the actual capacity of battery, and service life cycle can be extended widely; Mn prepared by the present invention
0.5-xcu
xzn
0.5fe
2o
4lithium ion battery anode material can realize long-life, the high power capacity of battery, can be used in the desirable lithium ion battery of various electronic device.
Accompanying drawing explanation
In order to make the object, technical solutions and advantages of the present invention clearly, below in conjunction with accompanying drawing, the present invention is described in further detail, wherein:
Fig. 1 is the Mn that embodiment 1 and embodiment 2 prepare
0.5-xcu
xzn
0.5fe
2o
4the XRD figure of lithium ion battery anode material;
Fig. 2 is the Mn that embodiment 1 and embodiment 2 prepare
0.5-xcu
xzn
0.5fe
2o
4the SEM plane of lithium ion battery anode material and sectional view;
Fig. 3 is the CV curve of two button lithium ion batteries of embodiment 1 and embodiment 2;
Fig. 4 is first three charge and discharge cycles curve of two button lithium ion batteries of embodiment 1 and embodiment 2;
Fig. 5 is the capacity of two button lithium ion batteries under different discharge-rate---the cycle-index curve of embodiment 1 and embodiment 2;
Fig. 6 is the capacity of two button lithium ion batteries under same discharge-rate---the cycle-index curve of embodiment 1 and embodiment 2;
Fig. 7 is the impedance curve of two button lithium ion batteries before discharge and recharge and after discharge and recharge of embodiment 1 and embodiment 2.
Embodiment
Hereinafter with reference to accompanying drawing, the preferred embodiments of the present invention are described in detail.
embodiment 1
The Mn of embodiment 1
0.5-xcu
xzn
0.5fe
2o
4the preparation method of lithium ion battery anode material, comprises the following steps:
1) manganese sulfate, zinc sulfate, ferrous sulfate and copper sulphate is taken according to following atomic percent: Mn
0.5-xcu
xzn
0.5fe
2o
4, wherein
x=0.1;
2) sulfate that step 1) takes is dissolved in deionized water, stirs and be made into mixed solution;
3) toward step 2) dropwise add ammonium bicarbonate soln in the mixed solution that is made into, and constantly stir;
4) first remove the oxide layer on copper sheet surface with watery hydrochloric acid cleaning, then be inserted into by copper sheet in mixed solution that step 3) obtains, hydro-thermal reaction 24 hours at 180 DEG C, obtaining growth has Mn
0.5-xcu
xzn
0.5fe
2o
4the copper sheet of nano particle;
5) drying steps 4 is rinsed) growth that obtains has Mn
0.5-xcu
xzn
0.5fe
2o
4the copper sheet of nano particle, obtains Mn
0.5-xcu
xzn
0.5fe
2o
4lithium ion battery anode material.
embodiment 2
The Mn of embodiment 2
0.5-xcu
xzn
0.5fe
2o
4the preparation method of lithium ion battery anode material, comprises the following steps:
1) manganese sulfate, zinc sulfate, ferrous sulfate and copper sulphate is taken according to following atomic percent: Mn
0.5-xcu
xzn
0.5fe
2o
4, wherein
x=0.2;
2) sulfate that step 1) takes is dissolved in deionized water, stirs and be made into mixed solution;
3) toward step 2) dropwise add ammonium bicarbonate soln in the mixed solution that is made into, and constantly stir;
4) first remove the oxide layer on copper sheet surface with watery hydrochloric acid cleaning, then be inserted into by copper sheet in mixed solution that step 3) obtains, hydro-thermal reaction 24 hours at 180 DEG C, obtaining growth has Mn
0.5-xcu
xzn
0.5fe
2o
4the copper sheet of nano particle;
5) drying steps 4 is rinsed) growth that obtains has Mn
0.5-xcu
xzn
0.5fe
2o
4the copper sheet of nano particle, obtains Mn
0.5-xcu
xzn
0.5fe
2o
4lithium ion battery anode material.
Fig. 1 is the Mn that embodiment 1 and embodiment 2 prepare
0.5-xcu
xzn
0.5fe
2o
4the XRD figure of lithium ion battery anode material, as shown in Figure 1, as can be seen from XRD figure, embodiment 1 and the Mn prepared by embodiment 2
0.5-xcu
xzn
0.5fe
2o
4nano particle well-crystallized, and without any dephasign.
Fig. 2 is the Mn that embodiment 1 and embodiment 2 prepare
0.5-xcu
xzn
0.5fe
2o
4the SEM plane of lithium ion battery anode material and sectional view, as shown in Figure 2, Fig. 2 (a) and (b) Mn prepared by embodiment 1
0.5-xcu
xzn
0.5fe
2o
4the plane graph of nano particle, Fig. 2 (c) and (d) Mn prepared by embodiment 2
0.5-xcu
xzn
0.5fe
2o
4the plane graph of nano particle, Fig. 2 (e) and (f) are its sectional view.As can be seen from Figure 2, prepared in embodiment 1 Mn
0.5-xcu
xzn
0.5fe
2o
4nanoparticle Size is even; Mn prepared in embodiment 2
0.5-xcu
xzn
0.5fe
2o
4nanoparticle Size is uneven, but the hole that surface is formed is relatively large.Sectional view can find out the Mn of preparation
0.5-xcu
xzn
0.5fe
2o
4the thickness of nanoparticle layers is approximately 500 nm.
Respectively by Mn that embodiment 1 and embodiment 2 prepare
0.5-xcu
xzn
0.5fe
2o
4lithium ion battery anode material is as work electrode, and lithium sheet, as to electrode, is prepared into two button lithium ion batteries.
Fig. 3 is the CV curve of two button lithium ion batteries, as shown in Figure 3, as can be seen from CV curve, and embodiment 1 and the Mn prepared by embodiment 2
0.5-xcu
xzn
0.5fe
2o
4nano particle has good redox characteristic.
Fig. 4 is first three charge and discharge cycles curve of two button lithium ion batteries, as shown in Figure 4, can obviously find out, embodiment 1 and the Mn prepared by embodiment 2
0.5-xcu
xzn
0.5fe
2o
4the discharge platform of nano particle is all at about 1.0 V.
Fig. 5 is the capacity of two button lithium ion batteries under different discharge-rate---cycle-index curve, as shown in Figure 5, can find out, embodiment 1 and the Mn prepared by embodiment 2
0.5-xcu
xzn
0.5fe
2o
4nano particle is under different discharging current, and its capacity is all very stable, and the capacity of embodiment 1 is corresponding larger.
Fig. 6 is the capacity of two button lithium ion batteries under same discharge-rate---cycle-index curve, as shown in Figure 6, can find out, the capacity of two button lithium ion batteries all can increase with the increase of cycle-index, but comparatively speaking, the battery performance of embodiment 2 preparation is more outstanding.
Fig. 7 is the impedance curves of two button lithium ion batteries before discharge and recharge and after discharge and recharge, as shown in Figure 7, can find out, along with the increase of discharge and recharge number of times, its impedance all can increase, but comparatively speaking, the battery impedance implemented prepared by 2 increases must be slow.
Can be proved by above-mentioned experiment, embodiment 1 and embodiment 2 directly grow Mn by the method for hydro-thermal reaction on copper sheet
0.5-xcu
xzn
0.5fe
2o
4nano particle, and surface defines a large amount of Micro porosities, thus advantageously in embedded quantity and the good deintercalation invertibity of lithium ion, it can be used as lithium ion battery anode material, improve the actual capacity of battery, extend the service life cycle of battery.
In the present invention, Mn
0.5-xcu
xzn
0.5fe
2o
4in
xcan be 0.1 ~ 0.4; Hydrothermal temperature can be 150 ~ 200 DEG C, preferably 180 DEG C, and the reaction time can be 15 ~ 30 hours, preferably 24 hours.
What finally illustrate is, above embodiment is only in order to illustrate technical scheme of the present invention and unrestricted, although by referring to the preferred embodiments of the present invention, invention has been described, but those of ordinary skill in the art is to be understood that, various change can be made to it in the form and details, and not depart from the spirit and scope of the present invention that appended claims limits.
Claims (3)
1. a Mn
0.5-xcu
xzn
0.5fe
2o
4the preparation method of lithium ion battery anode material, is characterized in that: comprise the following steps:
1) manganese sulfate, zinc sulfate, ferrous sulfate and copper sulphate is taken according to following atomic percent: Mn
0.5-xcu
xzn
0.5fe
2o
4, wherein
x=0.1 ~ 0.4;
2) sulfate that step 1) takes is dissolved in deionized water, stirs and be made into mixed solution;
3) toward step 2) dropwise add ammonium bicarbonate soln in the mixed solution that is made into, and constantly stir;
4) be inserted into by copper sheet in the mixed solution that step 3) obtains, hydro-thermal reaction 15 ~ 30 hours at 150 ~ 200 DEG C, obtaining growth has Mn
0.5-xcu
xzn
0.5fe
2o
4the copper sheet of nano particle;
5) drying steps 4 is rinsed) growth that obtains has Mn
0.5-xcu
xzn
0.5fe
2o
4the copper sheet of nano particle, obtains Mn
0.5-xcu
xzn
0.5fe
2o
4lithium ion battery anode material.
2. Mn according to claim 1
0.5-xcu
xzn
0.5fe
2o
4the preparation method of lithium ion battery anode material, is characterized in that: in described step 4), first removes the oxide layer on copper sheet surface with watery hydrochloric acid cleaning, then is inserted into by copper sheet in mixed solution that step 3) obtains.
3. Mn according to claim 1
0.5-xcu
xzn
0.5fe
2o
4the preparation method of lithium ion battery anode material, is characterized in that: in described step 4), and hydrothermal temperature is 180 DEG C, and the reaction time is 24 hours.
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