CN104201365A - Preparation method of hollow ferrum-manganese composite oxide material used for lithium ion battery - Google Patents
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- CN104201365A CN104201365A CN201410353445.8A CN201410353445A CN104201365A CN 104201365 A CN104201365 A CN 104201365A CN 201410353445 A CN201410353445 A CN 201410353445A CN 104201365 A CN104201365 A CN 104201365A
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Abstract
The invention belongs to the field of preparation of nano materials and particularly relates to a preparation method of a hollow ferrum-manganese composite oxide material used for a lithium ion battery. The method includes following main steps: dissolving potassium ferricyanide in water with addition of a surfactant to obtain a solution; mixing the solution with an aqueous solution of a divalent manganate; performing a reaction with stirring for 1-3 h at 30-80 DEG C; performing centrifugal separation to a precipitate; washing the precipitate through water and drying the precipitate to obtain a precursor Mn3[Fe(CN)6]2; calcining the precursor Mn3[Fe(CN)6]2 at 400-700 DEG C for 2-5 h to obtain the hollow ferrum-manganese composite oxide nano material which is regular in particle shapes. Because of a hollow structure of the material, a buffering space can be provided for lithium embedding and lithium removing and a volume change during a charging-discharging circulation process of the material can be reduced, so that the material is excellent in a lithium-storage performance and circulation stability and is expected to be applied in an anode material of the lithium ion battery. The invention provides the preparation method of the hollow ferrum-manganese composite oxide material used for the lithium ion battery. The preparation method is simple, is short in reaction time, is good in controllability, is low in production cost and is easy to apply industrially.
Description
Technical field
The invention belongs to field of nano material preparation, particularly the preparation method of hollow ferro manganese composite oxides material for a kind of lithium ion battery.
Background technology
The fast development of global economy increases sharply to the demand of the energy, due to the ecological deterioration problem that day by day reduces and bring thus of the non-renewable resources such as coal, oil, natural gas, the development and utilization of new cleaning fuel has become the urgent task of facing mankind.Because having, voltage is high, energy density is large, fail safe is good, quality is light, self discharge is little for lithium ion battery, have extended cycle life, memory-less effect, the advantage such as pollution-free, has received people's very big concern.The shortcomings such as lithium ion battery negative material is mostly with material with carbon elements such as graphite at present, shows but study, and the capacitance loss that material with carbon element existence is larger and high-rate charge-discharge capability are poor.Carbon negative pole easily forms passivating film in organic bath, cause the irreversible loss of initial capacity, and the electrode potential of material with carbon element is close with lithium metal, in the time of battery overcharge, and the easy precipitating metal lithium of carbon electrodes, formation dendrite and cause short circuit.Therefore, find better more reliable Novel cathode material for lithium ion battery and become an important research direction.
In recent years, metal oxide is (as Mn
2o
3, Fe
2o
3, SnO
2, TiO
2) cause very large concern as the novel lithium ion battery negative material of a class.It is good that metal oxide has storage lithium performance, and abundant raw material is nontoxic, the advantages such as low cost.Wherein, Mn
2o
3there are higher theoretical specific capacity (1018 mA h g as lithium ion battery negative material
-1) and lower operating voltage (average discharge volt 0.5 V, charging voltage 1.2 V), but that its shortcoming is cycle performance is poor, capacity attenuation is fast.Fe
2o
3there are higher storage lithium performance (theoretical specific capacity 1007 mA h g
-1), but its operating voltage relatively high (average discharge volt 1.0 V, charging voltage 1.9 V).In order to overcome independent Mn
2o
3and Fe
2o
3the deficiency of electrode material, the present invention has synthesized ferro manganese composite oxides material, wishes to utilize Mn
2o
3and Fe
2o
3in the synergy of different charging/discharging voltages, improve its storage lithium capacity and cycle performance.
A large amount of researchs show, the structure of nano material has a great impact its lithium electrical property tool.The nano material of hollow structure is because its internal voids can be served as a cushion space of active material and lithium reaction, can reduce the change in volume of electrode material in cyclic process, thereby the cycle performance that improves electrode material, therefore hollow structure material has good application prospect aspect lithium ion battery.The synthetic nano material with hollow structure is mainly to adopt to sacrifice template at present, comprises hard template method and soft template method.But sacrifice template cost is higher and synthesis step is complicated, meanwhile, is difficult in this way obtain loose structure.People have repaid and have tried to utilize some new synthesis mechanisms to prepare the nano material with hollow structure recently, wherein use Coordination Polymer to prepare metal oxide materials as precursor and there are many advantages: first, after Coordination Polymer calcining, can keep preferably original pattern and can produce loose structure.Secondly,, compared with complicated template, the method for calcining precursor is simple and cost is low.Finally, by selecting suitable Coordination Polymer precursor, can synthesize the even polymetallic composite metal oxide of bimetallic.The present invention utilizes Coordination Polymer precursor method first, has prepared the porous iron manganese composite oxide material with regular morphology and hollow structure.It,, as lithium ion battery negative material, shows higher specific capacity (912 mA h g
-1) and excellent cycle performance.
Summary of the invention
The present invention has considered the problem occurring in prior art, and object is to provide the preparation method of a kind of lithium ion battery hollow ferro manganese composite oxides material, adopts following technical scheme:
(1) preparation of solution a: the potassium ferricyanide is dissolved in deionized water, adds a certain amount of surfactant;
(2) preparation of solution b: manganous salt is dissolved in deionized water;
(3) presoma is synthetic: solution b is joined in solution a, form mixed solution, stir 1-3 h at 30-80 DEG C; By gained precipitation and centrifugal separation, with dry after deionized water washing, obtain grain shape rule, the uniform precursor Mn of particle diameter
3[Fe (CN)
6]
2;
(4) by precursor Mn
3[Fe (CN)
6]
2calcine, obtain ferro manganese composite oxides hollow nanostructures material.
The described surfactant of step (1) is lauryl sodium sulfate, and in described solution a, the concentration of surfactant is 1.5 ~ 4mol/L;
Manganous salt described in step (2) is Manganese perchlorate or manganese chloride; In described solution b, the concentration of manganous salt is 0.06 ~ 0.09 mol/L;
In mixed solution described in step (3), manganous salt is 3: 2 with the ratio of the amount of substance of the potassium ferricyanide;
The described calcining heat of step (4) is 400-700 DEG C, and calcination time is 2-5 h.
The invention has the beneficial effects as follows a kind of completely new approach of preparing ferro manganese composite oxides hollow nanostructures material is provided, preparation is simple, and the reaction time is short, and controllability is good, and production cost is low, is easy to industrializing implementation.This material has excellent storage lithium performance, is expected to the negative material for lithium ion battery.
Brief description of the drawings
Fig. 1 is X-ray diffraction (XRD) collection of illustrative plates of the ferro manganese composite oxides hollow nanostructures material prepared of the embodiment of the present invention 1;
Fig. 2 is ESEM (SEM) photo of the ferro manganese composite oxides hollow nanostructures material prepared of the embodiment of the present invention 1;
Fig. 3 is transmission electron microscope (TEM) photo of the ferro manganese composite oxides hollow nanostructures material prepared of the embodiment of the present invention 1;
Fig. 4 is that ferro manganese composite oxides hollow nanostructures material prepared by the embodiment of the present invention 1 is 200 mA g as lithium ion battery negative material in current density
-1cycle performance figure.
Embodiment
The present embodiment is implemented under taking technical solution of the present invention as prerequisite, has provided detailed execution mode, but the invention is not restricted to these embodiment.
Embodiment 1:
The 0.8 mmol potassium ferricyanide is dissolved in 20 ml deionized waters, adds 30 mmol lauryl sodium sulfate, stirring and dissolving.1.2 mmol Manganese perchlorates are dissolved in 20 ml deionized waters, this solution is joined in above-mentioned potassium ferricyanide solution, by mixture stirring reaction 1 h at 30 DEG C.After stirring finishes, by precipitation and centrifugal separation, with dry after deionized water washing, obtain precursor Mn
3[Fe (CN)
6]
2.By precursor Mn
3[Fe (CN)
6]
2at 550 DEG C, calcine 2 h, obtain end product.From the XRD figure of Fig. 1 product, sample is ferro manganese composite oxides.Fig. 2 is the SEM figure of product, the pattern rule of ferro manganese composite oxides particle as we can see from the figure, and evenly, average-size is in 500 nm left and right for size.Fig. 3 is the TEM figure of product, and as can be seen from the figure, ferro manganese composite oxides particle has hollow nanostructures, about 500 nm of size, and shell thickness is approximately 100 nm.Fig. 4 is the cycle performance figure of ferro manganese composite oxides hollow nanostructures material as lithium ion battery negative material, shows that we have higher specific capacity and cycle performance by synthetic material, is 200 mA g in current density
-1under first capacity be 912 mA h g
-1, after 50 circle circulations, capacity is up to 969 mA h g
-1.
Embodiment 2:
The 1.2 mmol potassium ferricyanides are dissolved in 20 ml deionized waters, add 30 mmol lauryl sodium sulfate, stirring and dissolving.1.8 mmol Manganese perchlorates are dissolved in 20 ml deionized waters, this solution is joined in above-mentioned potassium ferricyanide solution, mixed liquor stirs 1 h at 30 DEG C.After stirring finishes, centrifugation, dry after precipitate with deionized water washing, obtain precursor Mn
3[Fe (CN)
6]
2.By precursor Mn
3[Fe (CN)
6]
2at 550 DEG C, calcine 2 h, obtain having the ferro manganese composite oxides of hollow nanostructures.
Embodiment 3:
The 0.8 mmol potassium ferricyanide is dissolved in 20 ml deionized waters, adds 50 mmol lauryl sodium sulfate, stirring and dissolving.1.2 mmol Manganese perchlorates are dissolved in 20 ml deionized waters, this solution is joined in above-mentioned potassium ferricyanide solution, mixed liquor stirs 1 h at 30 DEG C.After stirring finishes, centrifugation, dry after precipitate with deionized water washing, obtain precursor Mn
3[Fe (CN)
6]
2.By precursor Mn
3[Fe (CN)
6]
2at 550 DEG C, calcine 2 h, obtain having the ferro manganese composite oxides of hollow nanostructures.
Embodiment 4:
The 0.8 mmol potassium ferricyanide is dissolved in 20 ml deionized waters, adds 60 mmol lauryl sodium sulfate, stirring and dissolving.1.2 mmol Manganese perchlorates are dissolved in 20 ml deionized waters, this solution is joined in above-mentioned potassium ferricyanide solution, mixed liquor stirs 1 h at 30 DEG C.After stirring finishes, centrifugation, dry after precipitate with deionized water washing, obtain precursor Mn
3[Fe (CN)
6]
2.By precursor Mn
3[Fe (CN)
6]
2at 550 DEG C, calcine 2 h, obtain having the ferro manganese composite oxides of hollow nanostructures.
Embodiment 5:
The 0.8 mmol potassium ferricyanide is dissolved in 20 ml deionized waters, adds 80 mmol lauryl sodium sulfate, stirring and dissolving.1.2 mmol Manganese perchlorates are dissolved in 20 ml deionized waters, this solution is joined in above-mentioned potassium ferricyanide solution, mixed liquor stirs 1 h at 30 DEG C.After stirring finishes, centrifugation, dry after precipitate with deionized water washing, obtain precursor Mn
3[Fe (CN)
6]
2.By precursor Mn
3[Fe (CN)
6]
2at 550 DEG C, calcine 2 h, obtain having the ferro manganese composite oxides of hollow nanostructures.
Embodiment 6:
The 0.8 mmol potassium ferricyanide is dissolved in 20 ml deionized waters, adds 30 mmol lauryl sodium sulfate, stirring and dissolving.1.2 mmol Manganese perchlorates are dissolved in 20 ml deionized waters, this solution is joined in above-mentioned potassium ferricyanide solution, mixed liquor stirs 1 h at 50 DEG C.After stirring finishes, centrifugation, dry after precipitate with deionized water washing, obtain precursor Mn
3[Fe (CN)
6]
2.By precursor Mn
3[Fe (CN)
6]
2at 550 DEG C, calcine 2 h, obtain having the ferro manganese composite oxides of hollow nanostructures.
Embodiment 7:
The 0.8 mmol potassium ferricyanide is dissolved in 20 ml deionized waters, adds 30 mmol lauryl sodium sulfate, stirring and dissolving.1.2 mmol Manganese perchlorates are dissolved in 20 ml deionized waters, this solution is joined in above-mentioned potassium ferricyanide solution, mixed liquor stirs 1 h at 80 DEG C.After stirring finishes, centrifugation, dry after precipitate with deionized water washing, obtain precursor Mn
3[Fe (CN)
6]
2.By precursor Mn
3[Fe (CN)
6]
2at 550 DEG C, calcine 2 h, obtain having the ferro manganese composite oxides of hollow nanostructures.
Embodiment 8:
The 0.8 mmol potassium ferricyanide is dissolved in 20 ml deionized waters, adds 30 mmol lauryl sodium sulfate, stirring and dissolving.1.2 mmol Manganese perchlorates are dissolved in 20 ml deionized waters, this solution is joined in above-mentioned potassium ferricyanide solution, mixed liquor stirs 2 h at 30 DEG C.After stirring finishes, centrifugation, dry after precipitate with deionized water washing, obtain precursor Mn
3[Fe (CN)
6]
2.By precursor Mn
3[Fe (CN)
6]
2at 550 DEG C, calcine 2 h, obtain having the ferro manganese composite oxides of hollow nanostructures.
Embodiment 9:
The 0.8 mmol potassium ferricyanide is dissolved in 20 ml deionized waters, adds 30 mmol lauryl sodium sulfate, stirring and dissolving.1.2 mmol Manganese perchlorates are dissolved in 20 ml deionized waters, this solution is joined in above-mentioned potassium ferricyanide solution, mixed liquor stirs 3 h at 30 DEG C.After stirring finishes, centrifugation, dry after precipitate with deionized water washing, obtain precursor Mn
3[Fe (CN)
6]
2.By precursor Mn
3[Fe (CN)
6]
2at 550 DEG C, calcine 2 h, obtain having the ferro manganese composite oxides of hollow nanostructures.
Embodiment 10:
The 0.8 mmol potassium ferricyanide is dissolved in 20 ml deionized waters, adds 30 mmol lauryl sodium sulfate, stirring and dissolving.1.2 mmol Manganese perchlorates are dissolved in 20 ml deionized waters, this solution is joined in above-mentioned potassium ferricyanide solution, mixed liquor stirs 1 h at 30 DEG C.After stirring finishes, centrifugation, dry after precipitate with deionized water washing, obtain precursor Mn
3[Fe (CN)
6]
2.By precursor Mn
3[Fe (CN)
6]
2at 550 DEG C, calcine 3 h, obtain having the ferro manganese composite oxides of hollow nanostructures.
Embodiment 11:
The 0.8 mmol potassium ferricyanide is dissolved in 20 ml deionized waters, adds 30 mmol lauryl sodium sulfate, stirring and dissolving.1.2 mmol Manganese perchlorates are dissolved in 20 ml deionized waters, this solution is joined in above-mentioned potassium ferricyanide solution, mixed liquor stirs 1 h at 30 DEG C.After stirring finishes, centrifugation, dry after precipitate with deionized water washing, obtain precursor Mn
3[Fe (CN)
6]
2.By precursor Mn
3[Fe (CN)
6]
2at 550 DEG C, calcine 5 h, obtain having the ferro manganese composite oxides of hollow nanostructures.
Embodiment 12:
The 0.8 mmol potassium ferricyanide is dissolved in 20 ml deionized waters, adds 30 mmol lauryl sodium sulfate, stirring and dissolving.1.2 mmol Manganese perchlorates are dissolved in 20 ml deionized waters, this solution is joined in above-mentioned potassium ferricyanide solution, mixed liquor stirs 1 h at 30 DEG C.After stirring finishes, centrifugation, dry after precipitate with deionized water washing, obtain precursor Mn
3[Fe (CN)
6]
2.By precursor Mn
3[Fe (CN)
6]
2at 400 DEG C, calcine 2 h, obtain having the ferro manganese composite oxides of hollow nanostructures.
Embodiment 13:
The 0.8 mmol potassium ferricyanide is dissolved in 20 ml deionized waters, adds 30 mmol lauryl sodium sulfate, stirring and dissolving.1.2 mmol Manganese perchlorates are dissolved in 20 ml deionized waters, this solution is joined in above-mentioned potassium ferricyanide solution, mixed liquor stirs 1 h at 30 DEG C.After stirring finishes, centrifugation, dry after precipitate with deionized water washing, obtain precursor Mn
3[Fe (CN)
6]
2.By precursor Mn
3[Fe (CN)
6]
2at 450 DEG C, calcine 2 h, obtain having the ferro manganese composite oxides of hollow nanostructures.
Embodiment 14:
The 0.8 mmol potassium ferricyanide is dissolved in 20 ml deionized waters, adds 30 mmol lauryl sodium sulfate, stirring and dissolving.1.2 mmol Manganese perchlorates are dissolved in 20 ml deionized waters, this solution is joined in above-mentioned potassium ferricyanide solution, mixed liquor stirs 1 h at 30 DEG C.After stirring finishes, centrifugation, dry after precipitate with deionized water washing, obtain precursor Mn
3[Fe (CN)
6]
2.By precursor Mn
3[Fe (CN)
6]
2at 650 DEG C, calcine 2 h, obtain having the ferro manganese composite oxides of hollow nanostructures.
Embodiment 15:
The 0.8 mmol potassium ferricyanide is dissolved in 20 ml deionized waters, adds 30 mmol lauryl sodium sulfate, stirring and dissolving.1.2 mmol Manganese perchlorates are dissolved in 20 ml deionized waters, this solution is joined in above-mentioned potassium ferricyanide solution, mixed liquor stirs 1 h at 30 DEG C.After stirring finishes, centrifugation, dry after precipitate with deionized water washing, obtain precursor Mn
3[Fe (CN)
6]
2.By precursor Mn
3[Fe (CN)
6]
2at 700 DEG C, calcine 2 h, obtain having the ferro manganese composite oxides of hollow nanostructures.
Embodiment 16:
The 0.8 mmol potassium ferricyanide is dissolved in 20 ml deionized waters, adds 30 mmol lauryl sodium sulfate, stirring and dissolving.1.2 mmol manganese chlorides are dissolved in 20 ml deionized waters, this solution is joined in above-mentioned potassium ferricyanide solution, mixed liquor stirs 1 h at 30 DEG C.After stirring finishes, centrifugation, dry after precipitate with deionized water washing, obtain precursor Mn
3[Fe (CN)
6]
2.By precursor Mn
3[Fe (CN)
6]
2at 550 DEG C, calcine 2 h, obtain having the ferro manganese composite oxides of hollow nanostructures.
Embodiment 17:
The 1.2 mmol potassium ferricyanides are dissolved in 20 ml deionized waters, add 30 mmol lauryl sodium sulfate, stirring and dissolving.1.8 mmol manganese chlorides are dissolved in 20 ml deionized waters, this solution is joined in above-mentioned potassium ferricyanide solution, mixed liquor stirs 1 h at 30 DEG C.After stirring finishes, centrifugation, dry after precipitate with deionized water washing, obtain precursor Mn
3[Fe (CN)
6]
2.By precursor Mn
3[Fe (CN)
6]
2at 550 DEG C, calcine 2 h, obtain having the ferro manganese composite oxides of hollow nanostructures.
Claims (5)
1. a preparation method for hollow ferro manganese composite oxides material for lithium ion battery, is characterized in that: comprise the steps:
(1) preparation of solution a: the potassium ferricyanide is dissolved in deionized water, adds a certain amount of surfactant;
(2) preparation of solution b: manganous salt is dissolved in deionized water;
(3) presoma is synthetic: solution b is joined in solution a, form mixed solution, under 30-80 ° of C, stir 1-3 h; By gained precipitation and centrifugal separation, with dry after deionized water washing, obtain grain shape rule, the uniform precursor Mn of particle diameter
3[Fe (CN)
6]
2;
(4) by precursor Mn
3[Fe (CN)
6]
2calcine, obtain ferro manganese composite oxides hollow nanostructures material.
2. the preparation method of hollow ferro manganese composite oxides material for a kind of lithium ion battery according to claim 1, it is characterized in that: in step (1), described surfactant is lauryl sodium sulfate, and in described solution a, the concentration of surfactant is 1.5 ~ 4mol/L.
3. the preparation method of hollow ferro manganese composite oxides material for a kind of lithium ion battery according to claim 1, is characterized in that: in step (2), described manganous salt is Manganese perchlorate or manganese chloride; In described solution b, the concentration of manganous salt is 0.06 ~ 0.09 mol/L.
4. the preparation method of hollow ferro manganese composite oxides material for a kind of lithium ion battery according to claim 1, is characterized in that: in step (3), in described mixed solution, manganous salt is 3: 2 with the ratio of the amount of substance of the potassium ferricyanide.
5. the preparation method of hollow ferro manganese composite oxides material for a kind of lithium ion battery according to claim 1, is characterized in that: in step (4), described calcining heat is 400-700 ° of C, and calcination time is 2-5 h.
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| CN105869907A (en) * | 2016-05-06 | 2016-08-17 | 同济大学 | Preparation method of carbon-nitrogen-codoped NiFe2O4-Ni nanocomposite material with cubic structure |
| CN105869907B (en) * | 2016-05-06 | 2018-07-24 | 同济大学 | A kind of nitrogen co-doped NiFe of carbon2O4The preparation method of/Ni nano cubic structural composite materials |
| CN110342585A (en) * | 2019-07-12 | 2019-10-18 | 大连恒超锂业科技有限公司 | Four sides hollow out CoFe2O4Nano material and its preparation method and application |
| CN112694104A (en) * | 2020-12-29 | 2021-04-23 | 华中科技大学 | Prussian blue analogue, preparation method thereof, negative electrode material and application |
| CN112694104B (en) * | 2020-12-29 | 2022-11-01 | 华中科技大学 | Prussian blue analogue, preparation method thereof, negative electrode material and application |
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