CN105742619A - Amorphous-form manganese oxide coated iron oxide lithium/sodium ion battery anode material and preparation method thereof - Google Patents
Amorphous-form manganese oxide coated iron oxide lithium/sodium ion battery anode material and preparation method thereof Download PDFInfo
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- CN105742619A CN105742619A CN201610113091.9A CN201610113091A CN105742619A CN 105742619 A CN105742619 A CN 105742619A CN 201610113091 A CN201610113091 A CN 201610113091A CN 105742619 A CN105742619 A CN 105742619A
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- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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- H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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Abstract
The invention discloses a preparation method of an amorphous-form manganese oxide coated iron oxide lithium/sodium ion battery anode material. The preparation method comprises the following steps of heating a mixture liquid of potassium permanganate and acid to 20-200 DEG C, dropwise adding an iron oxide solution which is uniformly dispersed in deionized water, carrying out heat preservation for 1-48 hours at 20-200 DEG C, and washing and centrifuging the product to a shell-core structured amorphous-form manganese oxide coated iron oxide composite material. The shell-core structured amorphous-form manganese oxide coated iron oxide lithium/sodium ion battery anode material prepared according to the preparation method has the advantages of high conductivity, stability in structure, high specific capacity and excellent cycle performance; and moreover, the amorphous-form manganese oxide coated iron oxide lithium/sodium ion battery anode material is rich in raw material and economic in cost, the preparation method is simple and controllable, and mass production can be achieved.
Description
Technical field
The invention belongs to field of energy source materials, be specifically related to a kind of new type lithium ion or sodium ion battery electrode material and preparation method thereof.
Background technology
Along with the fast development of global economy, energy and environment problem becomes increasingly conspicuous.Development of new green energy resource material becomes extremely urgent task, particularly in lithium ion/sodium ion battery electrode material aspect.Traditional negative material is the material with carbon elements such as graphite, due to the less (372mAhg of its specific capacity-1), it is difficult to meet current demand.In recent years, transition metal oxide is because of the high (~ 500-1000mAhg of its theoretical specific capacity-1), the feature such as energy density is big, abundant raw material, less costly and environmental friendliness, receive more and more attention, particularly iron oxides.Iron oxides currently as negative material is mainly Fe2O3And Fe3O4, theoretical specific capacity is 1007mAhg respectively-1And 928mAhg-1.Although iron oxides has plurality of advantages as electrode material, but the electrical conductivity of iron oxides is relatively low, charge and discharge process has bigger volumetric expansion, the change of structure occurs, solid electrolyte interface (SEI) film can not stable existence, thus causing capacity attenuation, cyclical stability to decline.At present, industry generally believes that it is the effective ways solving this problem of structural stability that iron oxides nano structural material carries out finishing, such as carbon-encapsulated iron oxide lithium ion battery negative material (typical domestic patent: application number 201410389784.1；Typical case document: Adv.Funct.Mater.2008,18,3941；Adv.EnergyMater.2015,5,1401123).Carbon coating layer improves the electronic conductivity of electrode material, also stabilizes SEI film simultaneously, improves the cycle performance of electrode material.But this material prepare temperature required higher (general 300-800 ° of C), it is difficult to realize large-scale production use.It addition, carbon does not store up lithium activity, specific capacity is low.Mn oxide also has higher theoretical specific capacity and relatively low running voltage as electrode material.Document (J.Mater.Chem.A, 2015,3,22066) is had to report MnO2It is compounded in Fe2O3As capacitor anode material, MnO behind surface2It is possible not only to be effective against change in volume, and the electric conductivity of material can be improved.But MnO in this material2There is crystal formation, therefore there is certain water of crystallization, and lithium/sodium-ion battery is had certain damaging effect by the existence of hydrone.
Summary of the invention
It is an object of the invention to, based on prior art Problems existing, it is provided that a kind of cost-effective unformed Mn oxide cladding iron oxides lithium/sodium ion battery electrode material and preparation method thereof.
The preparation method of unformed Mn oxide cladding iron oxides lithium/anode material of lithium-ion battery, comprises the following steps:
(1) by iron oxides disperse in deionized water, ultrasonic uniformly, obtain solution A；Described iron oxides concentration is 0.001-5M；A certain amount of potassium permanganate is dissolved in deionized water and obtains potassium permanganate solution, and add a certain amount of acid, obtain solution B；Described potassium permanganate solution concentration is 0.001-5M, potassium permanganate and H+Mol ratio is 0.01-10:1, and potassium permanganate solution is 1-100:1 with sour volume ratio；After solution B heating to 20-200 ° of C, in solution B, dropwise add solution A；Then under magnetic stirring mixed solution is incubated 1-48h at 20-200 ° of C；
(2) after natural cooling, then dry centrifugal to the product deionized water obtained in step (1) and ethanol purge and obtain brown ceramic powder for several times, be i.e. the unformed Mn oxide cladding silicon/iron oxide composite material of core-shell structure.
As preferably, the reaction vessel used in step (1) is the reaction vessel that sealing is good.
As preferably, described Mn oxide is the amorphous compound of manganese and oxygen.
Unformed Mn oxide cladding iron oxides lithium/anode material of lithium-ion battery is prepared according to said method.
Purposes according to unformed Mn oxide cladding iron oxides lithium/anode material of lithium-ion battery prepared by said method: unformed Mn oxide cladding silicon/iron oxide composite material or the mixture containing this material are used for making lithium/anode material of lithium-ion battery.
Lithium/sodium-ion battery negative pole: after adopting negative material described in claim 5 and binding agent, conductive agent to be mixed to form slurry in a solvent, even is coated onto on the collectors such as nickel foam, foam copper or copper sheet, dries and obtains lithium/sode cell negative pole after being pressed into sheet.
Lithium/sodium-ion battery: adopt above-mentioned negative pole, lithium or sodium as positive pole, and marginal barrier film and electrolyte composition lithium/sodium-ion battery.
Unformed Mn oxide cladding Mn oxide lithium/sodium ion battery electrode material of one of the present invention and preparation method thereof, specifically has the advantages that:
(1) preparation technology of the present invention is simple, with low cost, it may be achieved large-scale production is used.
(2) the unformed Mn oxide cladding silicon/iron oxide composite material appearance structure of core-shell structure prepared by the present invention is homogeneous, has good chemical property.
(3) the Mn oxide clad of the present invention not only increases the conductivity of material, and can resist iron oxides change in volume in charge and discharge process, improves the dynamic performance of electrode.
(4) Mn oxide of the present invention is unformed, is therefore absent from water of crystallization, will not lithium/sodium-ion battery be worked the mischief.
Accompanying drawing explanation
Below in conjunction with accompanying drawing, the specific embodiment of the present invention is described in further detail.
Fig. 1 is Fe2O3Unformed MnO with embodiment 1 preparation2Cladding Fe2O3The XRD figure of composite (heat time heating time is 8h).
Fig. 2 is Fe2O3300,000 times of scanning electron microscope (SEM) photographs.
Fig. 3 is the unformed MnO of embodiment 1 preparation2Cladding Fe2O3The scanning electron microscope (SEM) photograph of composite (heat time heating time is 8h).
MnO prepared by the prior art (J.Mater.Chem.A, 2015,3,22066) that Fig. 4 is closest to2Cladding Fe2O3The scanning electron microscope (SEM) photograph of composite.
Fig. 5 is the Fe of embodiment 1 preparation2O3With unformed MnO2Cladding Fe2O3The cycle performance figure of composite (heat time heating time is 8h).
Detailed description of the invention
The following is and be embodied as case based on technical solution of the present invention, the present invention can be more fully understood that by following example.It should be noted that the present invention is not limited solely to following example, it is also possible to have many deformation.Those skilled in the art, according to the principle of the invention, the insubstantial modifications of the form that the present invention is made and content aspect or change, broadly fall into the scope of protection of the invention.
Embodiment 1
Solution A: weigh 80mgFe2O3, it is dispersed in 25mL deionized water, after ultrasonic 30 minutes, obtains uniform dispersion liquid.Solution B: by 0.20gKMnO4It is dissolved in 25mL deionized water, is subsequently adding 0.8mL1MHCl, stir.After solution B heating to 95 ° of C, dropwise it is added thereto to solution A.Under magnetic stirring, mixed liquor is heated under 95 ° of C 2h.After natural cooling, by product deionized water and ethanol eccentric cleaning for several times, then dry under 80 ° of C, obtain brown unformed MnO2Cladding Fe2O3Composite.
Above-mentioned preparation method, heats mixed liquor 2h under 95 ° of C and extends to 5h, 8h, 14h or 23h, also can obtain brown unformed MnO2Cladding Fe2O3Composite.
With N-methyl-pyrrolidon (NMP) for solvent, by unformed MnO2Cladding Fe2O3Composite is mixed homogeneously with acetylene black and Kynoar (PVDF) 8:1:1 in mass ratio, even is coated in nickel foam, strikes out circular electrode sheet after vacuum drying, and metal lithium sheet is as positive pole, and electrolyte is 1MLiPF6/ DMC/EC (DMC and EC mol ratio is 1:1), barrier film is microporous polypropylene membrane Celgard2300, is assembled into simulated battery.
Simulated battery is carried out charge-discharge test, and when being 2h between when heated, electric current density is 50mAg-1, voltage range is 0.05-3.0V, and after 50 times circulate, specific capacity is 335mAhg-1；When being 5h between when heated, electric current density is 100mAg-1, voltage range is 0.05-3.0V, and after 50 times circulate, specific capacity is 619mAhg-1；When being 8h between when heated, electric current density is 100mAg-1, voltage range is 0.05-3.0V, and after 50 times circulate, specific capacity is 753mAhg-1；When being 14h between when heated, electric current density is 100mAg-1, voltage range is 0.05-3.0V, and after 50 times circulate, specific capacity is 758mAhg-1；When being 23h between when heated, electric current density is 100mAg-1, voltage range is 0.05-3.0V, and after 50 times circulate, specific capacity is 341mAhg-1。
Especially, when being 8h between when heated, as seen from Figure 1, MnO2Cladding Fe2O3The diffraction maximum position of composite and Fe2O3Diffraction maximum essentially identical, MnO is described2For unformed.From Fig. 2, Fig. 3 and Fig. 4, MnO2Fairly evenly it is coated on Fe2O3Surface.It addition, obtain the MnO of nucleocapsid structure compared to immediate prior art (J.Mater.Chem.A, 2015,3,22066) heats 24h at 160 ° of C2Cladding Fe2O3Composite, in the present embodiment, heat time heating time is shorter, and heating-up temperature is relatively low, and therefore cost is comparatively cheap.
Experimental result shows, when heat time heating time is about 8-14h, and MnO2At Fe2O3The ratio of upper growth is more uniform, is the time being comparatively suitable for；When time is shorter, MnO2Also in growth, Fe2O3On MnO2Seldom；When time is longer, such as 23h, Fe2O3On MnO2Decrease.
Experimental result shows, the XRD figure of 5h, 8h, 14h, 16h, the MnO obtained2It is all unformed.
Embodiment 2
Solution A: weigh 400mgFe2O3, it is dispersed in 25mL deionized water, after ultrasonic 30 minutes, obtains uniform dispersion liquid.Solution B: by 1.20gKMnO4It is dissolved in 25mL deionized water, is subsequently adding 10.0mL1MHCl, stir.After solution B heating to 140 ° of C, dropwise it is added thereto to solution A.Under magnetic stirring, mixed liquor is heated under 140 ° of C 8h.After natural cooling, by product deionized water and ethanol eccentric cleaning for several times, then dry under 80 ° of C, obtain brown unformed MnO2Cladding Fe2O3Composite.At H2(30%H2And 70%Ar) under atmosphere, will the MnO of preparation2Cladding Fe3O4Composite is at 350 ° of C calcination 5h.After being cooled to room temperature, it is centrifuged product cleaning, then dries and obtain unformed MnO2Cladding Fe3O4Composite.
With N-methyl-pyrrolidon (NMP) for solvent, by unformed MnO2Cladding Fe3O4Composite is mixed homogeneously with acetylene black and Kynoar (PVDF) 8:1:1 in mass ratio, even is coated in nickel foam, strikes out circular electrode sheet after vacuum drying, and metal lithium sheet is as positive pole, and electrolyte is 1MLiPF6/ DMC/EC (DMC and EC mol ratio is 1:1), barrier film is microporous polypropylene membrane Celgard2300, is assembled into simulated battery.Simulated battery is carried out charge-discharge test, and electric current density is 100mAg-1, voltage range is 0.05-3.0V, and after 50 times circulate, specific capacity is 494mAhg-1。
Embodiment 3
At H2(30%H2And 70%Ar) under atmosphere, by Fe2O3At 350 ° of C calcination 5h.After being cooled to room temperature, product is centrifuged cleaning, drying, obtains Fe3O4.Solution A: weigh 40mgFe3O4, it is dispersed in 25mL deionized water, after ultrasonic 30 minutes, obtains uniform dispersion liquid.Solution B: by 0.40gKMnO4It is dissolved in 25mL deionized water, is subsequently adding 0.5mL2MHCl, stir.After solution B heating to 95 ° of C, dropwise it is added thereto to solution A.Under magnetic stirring, mixed liquor is heated under 95 ° of C 8h.After natural cooling, by product deionized water and ethanol eccentric cleaning for several times, then dry under 80 ° of C, obtain brown unformed MnO2Cladding Fe3O4Composite.
With N-methyl-pyrrolidon (NMP) for solvent, by MnO2Cladding Fe3O4Composite is mixed homogeneously with acetylene black and Kynoar (PVDF) 8:1:1 in mass ratio, even is coated in nickel foam, strikes out circular electrode sheet after vacuum drying, and metal lithium sheet is as positive pole, and electrolyte is 1MLiPF6/ DMC/EC (DMC and EC mol ratio is 1:1), barrier film is microporous polypropylene membrane Celgard2300, is assembled into simulated battery.Simulated battery is carried out charge-discharge test, and electric current density is 100mAg-1, voltage range is 0.05-3.0V, and after 50 times circulate, specific capacity is 714mAhg-1。
Claims (7)
1. the preparation method of unformed Mn oxide cladding iron oxides lithium/anode material of lithium-ion battery, it is characterised in that comprise the following steps:
(1) by iron oxides disperse in deionized water, ultrasonic uniformly, obtain solution A；Described iron oxides concentration is 0.001-5M；A certain amount of potassium permanganate is dissolved in deionized water and obtains potassium permanganate solution, and add a certain amount of acid, obtain solution B；Described potassium permanganate solution concentration is 0.001-5M, potassium permanganate and H+Mol ratio is 0.01-10:1, and potassium permanganate solution is 1-100:1 with sour volume ratio；Solution B is heated after 20-200 DEG C, in solution B, dropwise adds solution A；Then under magnetic stirring mixed solution is incubated 1-48h at 20-200 DEG C；
(2) after natural cooling, then dry centrifugal to the product deionized water obtained in step (1) and ethanol purge and obtain brown ceramic powder for several times, be i.e. the unformed Mn oxide cladding silicon/iron oxide composite material of core-shell structure.
2. preparation method according to claim 1, it is characterised in that: the reaction vessel used in step (1) is the reaction vessel that sealing is good.
3. preparation method according to claim 1, it is characterised in that: described Mn oxide is the amorphous compound of manganese and oxygen.
4. method according to any one of claim 1-3 prepares unformed Mn oxide cladding iron oxides lithium/anode material of lithium-ion battery.
5. the purposes of unformed Mn oxide cladding iron oxides lithium/anode material of lithium-ion battery that prepared by method according to any one of claim 1-3, it is characterised in that: unformed Mn oxide cladding silicon/iron oxide composite material or the mixture containing this material are used for making lithium/anode material of lithium-ion battery.
6. lithium/sodium-ion battery negative pole, it is characterized in that: after adopting the negative material described in claim 5 to be mixed to form slurry in a solvent with binding agent, conductive agent, even it is coated onto on the collectors such as nickel foam, foam copper or copper sheet, dries and obtain lithium/sode cell negative pole after being pressed into sheet.
7. lithium/sodium-ion battery, it is characterised in that: adopting the negative pole described in claim 6, lithium or sodium are as positive pole, and marginal barrier film and electrolyte form lithium/sodium-ion battery.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113851616A (en) * | 2020-06-28 | 2021-12-28 | 宝山钢铁股份有限公司 | Method for coating manganese dioxide on lithium metal surface, negative electrode material and negative electrode |
| CN114229902A (en) * | 2021-12-20 | 2022-03-25 | 中原工学院 | Gamma/alpha heterogeneous-containing manganese sulfide and preparation method and application thereof |
| CN117334887A (en) * | 2023-12-01 | 2024-01-02 | 宜宾锂宝新材料有限公司 | Layered oxide composite positive electrode material, preparation method thereof and sodium battery |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104992850B (en) * | 2015-07-13 | 2017-07-28 | 同济大学 | A kind of Fe3O4/MnO2/ RGO materials and preparation method and application |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113851616A (en) * | 2020-06-28 | 2021-12-28 | 宝山钢铁股份有限公司 | Method for coating manganese dioxide on lithium metal surface, negative electrode material and negative electrode |
| CN114229902A (en) * | 2021-12-20 | 2022-03-25 | 中原工学院 | Gamma/alpha heterogeneous-containing manganese sulfide and preparation method and application thereof |
| CN114229902B (en) * | 2021-12-20 | 2023-09-15 | 中原工学院 | Manganese sulfide containing gamma/alpha heterogeneous junction and preparation method and application thereof |
| CN117334887A (en) * | 2023-12-01 | 2024-01-02 | 宜宾锂宝新材料有限公司 | Layered oxide composite positive electrode material, preparation method thereof and sodium battery |
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