CN104201365B - A kind of preparation method of lithium ion battery hollow ferro manganese composite oxides material - Google Patents

A kind of preparation method of lithium ion battery hollow ferro manganese composite oxides material Download PDF

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CN104201365B
CN104201365B CN201410353445.8A CN201410353445A CN104201365B CN 104201365 B CN104201365 B CN 104201365B CN 201410353445 A CN201410353445 A CN 201410353445A CN 104201365 B CN104201365 B CN 104201365B
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composite oxides
manganese composite
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ion battery
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CN104201365A (en
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沈小平
严媛
杜飞虎
季振源
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Jiangsu University
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • 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 belongs to field of nano material preparation, be specifically related to the preparation method of a kind of lithium ion battery hollow ferro manganese composite oxides material.Have main steps that and the potassium ferricyanide is dissolved in the water, add surfactant, by the aqueous solution of solution Yu manganous salt, stirring reaction 13 h at 30 80 DEG C, by precipitation and centrifugal separation, it is dried after washing with water, obtains precursor Mn3[Fe(CN)6]2；By precursor Mn3[Fe(CN)6]2Calcine 25 h at 400 700 DEG C, obtain the ferro manganese composite oxides hollow nanostructures material of grain shape rule.Owing to the hollow structure of this material can provide a cushion space for embedding and removing, reduce material change in volume during charge and discharge cycles, therefore this material demonstrates storage lithium performance and the cyclical stability of excellence, is expected to be applied to the negative material of lithium ion battery.The invention provides a kind of new method preparing ferro manganese composite oxides hollow nanostructures material, preparation technology is simple, and the response time is short, and controllability is good, and production cost is low, it is easy to industrializing implementation.

Description

A kind of preparation method of lithium ion battery hollow ferro manganese composite oxides material
Technical field
The invention belongs to field of nano material preparation, particularly to a kind of lithium ion battery hollow ferro manganese composite oxides The preparation method of material.
Background technology
The demand of the energy is increased sharply by the fast development of global economy, due to non-renewable moneys such as coal, oil, natural gass The ecological deterioration problem day by day reducing and thus bringing in source, the development and utilization of new cleaning fuel has become facing mankind Urgent task.Lithium ion battery because having that voltage is high, energy density is big, safety good, light weight, self discharge be little, the circulation longevity Life length, memory-less effect, the advantage such as pollution-free, receive greatly paying close attention to of people.Lithium ion battery negative material is mostly at present Being with material with carbon elements such as graphite, but research shows, there is bigger capacitance loss and high-rate charge-discharge capability difference etc. and lacks in material with carbon element Point.Carbon anode is easily formed passivating film in organic bath, causes the irreversible loss of initial capacity, and the electrode electricity of material with carbon element Position is close with lithium metal, when the battery is overcharged, carbon electrodes easy precipitating metal lithium, form dendrite and cause short circuit.Therefore, Find the most more reliable Novel cathode material for lithium ion battery and become an important research direction.
In recent years, metal-oxide is (such as Mn2O3, Fe2O3, SnO2, TiO2) bear as the lithium ion battery that a class is novel Pole material has caused the biggest concern.It is good that metal-oxide has storage lithium performance, and abundant raw material is nontoxic, low cost Etc. advantage.Wherein, Mn2O3As lithium ion battery negative material, there are higher theoretical specific capacity (1018 mA h g-1) and relatively Low running voltage (average discharge volt 0.5 V, charging voltage 1.2 V), but its shortcoming poor, capacity attenuation that is cycle performance Hurry up.Fe2O3There is higher storage lithium performance (theoretical specific capacity 1007 mA h g-1), but its running voltage is of a relatively high (average Discharge voltage 1.0 V, charging voltage 1.9 V).In order to overcome independent Mn2O3And Fe2O3The deficiency of electrode material, the present invention closes Become ferro manganese composite oxides material, it is desirable to utilize Mn2O3And Fe2O3At the synergism of different charging/discharging voltages, improve its storage Lithium capacity and cycle performance.
Substantial amounts of research shows, its lithium electrical property is had a very big impact by the structure of nano material.Receiving of hollow structure The cushion space that rice material can react as active material and lithium due to its internal voids, can reduce electrode material and exist Change in volume in cyclic process, thus improve the cycle performance of electrode material, therefore hollow structure material is at lithium ion battery Aspect has good application prospect.Synthesis at present has the nano material of hollow structure and mainly uses sacrifice template, bag Include hard template method and soft template method.But, sacrifice template is relatively costly and synthesis step is complicated, meanwhile, the most very Rare to loose structure.People have repaid and have tried to utilize some new synthesis mechanisms to prepare the nanometer material with hollow structure recently Material, wherein uses coordination polymer to prepare metal oxide materials as precursor and has many advantages: first, coordination polymer Can preferably keep original pattern after calcining and loose structure can be produced.Secondly, compared with complicated template, before calcining The method of body is simple and low cost.Finally, by selecting suitable coordination polymer precursor, bimetallic can be synthesized even Polymetallic metal composite oxide.The present invention utilizes coordination polymer precursor method first, has prepared and has had regular shape The porous iron manganese composite oxide material of looks and hollow structure.It is used as lithium ion battery negative material, shows higher ratio Capacity (912 mA h g-1) and the cycle performance of excellence.
Summary of the invention
The present invention already allows for produced problem in prior art, it is therefore intended that provide a kind of lithium ion battery hollow The preparation method of ferro manganese composite oxides material, adopts the following technical scheme that
(1) preparation of solution a: be dissolved in deionized water by the potassium ferricyanide, adds a certain amount of surfactant；
(2) preparation of solution b: manganous salt is dissolved in deionized water；
(3) synthesis of presoma: joined by solution b in solution a, forms mixed solution, stirs 1-3 at 30-80 DEG C h；By gained precipitation and centrifugal separation, it is dried after being washed with deionized, obtains grain shape rule, the precursor of uniform particle sizes Mn3[Fe(CN)6]2；
(4) by precursor Mn3[Fe(CN)6]2Calcine, obtain ferro manganese composite oxides hollow nanostructures material.
Surfactant described in step (1) is sodium lauryl sulphate, 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；The concentration of manganous salt in described solution b It 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 the material of the potassium ferricyanide；
Calcining heat described in step (4) is 400-700 DEG C, and calcination time is 2-5 h.
The invention has the beneficial effects as follows to provide and a kind of prepare the brand-new of ferro manganese composite oxides hollow nanostructures material Method, preparation is simple, and the response time is short, and controllability is good, and production cost is low, it is easy to industrializing implementation.This material has There is the storage lithium performance of excellence, be expected to be used for the negative material of lithium ion battery.
Accompanying drawing explanation
Fig. 1 is the X-ray diffraction of the ferro manganese composite oxides hollow nanostructures material of the embodiment of the present invention 1 preparation (XRD) collection of illustrative plates；
Fig. 2 is the scanning electron microscope (SEM) of the ferro manganese composite oxides hollow nanostructures material of the embodiment of the present invention 1 preparation Photo；
Fig. 3 is the transmission electron microscope (TEM) of the ferro manganese composite oxides hollow nanostructures material of the embodiment of the present invention 1 preparation Photo；
Fig. 4 is that the ferro manganese composite oxides hollow nanostructures material of the embodiment of the present invention 1 preparation is used as lithium ion battery Negative material is 200 mA g in electric current density-1Cycle performance figure.
Detailed description of the invention
The present embodiment is implemented under premised on technical solution of the present invention, gives detailed embodiment, but this Invention is not limited to these embodiments.
Embodiment 1:
The 0.8 mmol potassium ferricyanide is dissolved in 20 ml deionized waters, adds 30 mmol sodium lauryl sulphates, stir Mix dissolving.1.2 mmol Manganese perchlorates are dissolved in 20 ml deionized waters, this solution are joined the above-mentioned potassium ferricyanide molten In liquid, mixture is stirred at 30 DEG C reaction 1 h.After stirring terminates, by precipitation and centrifugal separation, after being washed with deionized It is dried, obtains precursor Mn3[Fe(CN)6]2.By precursor Mn3[Fe(CN)6]2At 550 DEG C, calcine 2 h, finally produced Thing.From the XRD figure of Fig. 1 product, sample is ferro manganese composite oxides.Fig. 2 is the SEM figure of product, as we can see from the figure The pattern rule of ferro manganese composite oxides granule, size is uniform, and average-size is at about 500 nm.Fig. 3 is the TEM figure of product, It can be seen that ferro manganese composite oxides granule has hollow nanostructures, size about 500 nm, shell thickness is about It is 100 nm.Fig. 4 is the cycle performance that ferro manganese composite oxides hollow nanostructures material is used as lithium ion battery negative material Figure, shows that the material that we synthesize has higher specific capacity and cycle performance, is 200 mA g in electric current density-1Under hold first Amount is 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 sodium lauryl sulphates, stir Mix dissolving.1.8 mmol Manganese perchlorates are dissolved in 20 ml deionized waters, this solution are joined the above-mentioned potassium ferricyanide molten In liquid, mixed liquor stirs 1 h at 30 DEG C.After stirring terminates, centrifugation, it is dried after precipitate with deionized water washing, obtains Precursor Mn3[Fe(CN)6]2.By precursor Mn3[Fe(CN)6]2At 550 DEG C, calcine 2 h, obtain that there is hollow nano junction The ferro manganese composite oxides of structure.
Embodiment 3:
The 0.8 mmol potassium ferricyanide is dissolved in 20 ml deionized waters, adds 50 mmol sodium lauryl sulphates, stir Mix dissolving.1.2 mmol Manganese perchlorates are dissolved in 20 ml deionized waters, this solution are joined the above-mentioned potassium ferricyanide molten In liquid, mixed liquor stirs 1 h at 30 DEG C.After stirring terminates, centrifugation, it is dried after precipitate with deionized water washing, obtains Precursor Mn3[Fe(CN)6]2.By precursor Mn3[Fe(CN)6]2At 550 DEG C, calcine 2 h, obtain that there is hollow nano junction The ferro manganese composite oxides of structure.
Embodiment 4:
The 0.8 mmol potassium ferricyanide is dissolved in 20 ml deionized waters, adds 60 mmol sodium lauryl sulphates, stir Mix dissolving.1.2 mmol Manganese perchlorates are dissolved in 20 ml deionized waters, this solution are joined the above-mentioned potassium ferricyanide molten In liquid, mixed liquor stirs 1 h at 30 DEG C.After stirring terminates, centrifugation, it is dried after precipitate with deionized water washing, obtains Precursor Mn3[Fe(CN)6]2.By precursor Mn3[Fe(CN)6]2At 550 DEG C, calcine 2 h, obtain that there is hollow nano junction The ferro manganese composite oxides of structure.
Embodiment 5:
The 0.8 mmol potassium ferricyanide is dissolved in 20 ml deionized waters, adds 80 mmol sodium lauryl sulphates, stir Mix dissolving.1.2 mmol Manganese perchlorates are dissolved in 20 ml deionized waters, this solution are joined the above-mentioned potassium ferricyanide molten In liquid, mixed liquor stirs 1 h at 30 DEG C.After stirring terminates, centrifugation, it is dried after precipitate with deionized water washing, obtains Precursor Mn3[Fe(CN)6]2.By precursor Mn3[Fe(CN)6]2At 550 DEG C, calcine 2 h, obtain that there is hollow nano junction The ferro manganese composite oxides of structure.
Embodiment 6:
The 0.8 mmol potassium ferricyanide is dissolved in 20 ml deionized waters, adds 30 mmol sodium lauryl sulphates, stir Mix dissolving.1.2 mmol Manganese perchlorates are dissolved in 20 ml deionized waters, this solution are joined the above-mentioned potassium ferricyanide molten In liquid, mixed liquor stirs 1 h at 50 DEG C.After stirring terminates, centrifugation, it is dried after precipitate with deionized water washing, obtains Precursor Mn3[Fe(CN)6]2.By precursor Mn3[Fe(CN)6]2At 550 DEG C, calcine 2 h, obtain that there is hollow nano junction The ferro manganese composite oxides of structure.
Embodiment 7:
The 0.8 mmol potassium ferricyanide is dissolved in 20 ml deionized waters, adds 30 mmol sodium lauryl sulphates, stir Mix dissolving.1.2 mmol Manganese perchlorates are dissolved in 20 ml deionized waters, this solution are joined the above-mentioned potassium ferricyanide molten In liquid, mixed liquor stirs 1 h at 80 DEG C.After stirring terminates, centrifugation, it is dried after precipitate with deionized water washing, obtains Precursor Mn3[Fe(CN)6]2.By precursor Mn3[Fe(CN)6]2At 550 DEG C, calcine 2 h, obtain that there is hollow nano junction The ferro manganese composite oxides of structure.
Embodiment 8:
The 0.8 mmol potassium ferricyanide is dissolved in 20 ml deionized waters, adds 30 mmol sodium lauryl sulphates, stir Mix dissolving.1.2 mmol Manganese perchlorates are dissolved in 20 ml deionized waters, this solution are joined the above-mentioned potassium ferricyanide molten In liquid, mixed liquor stirs 2 h at 30 DEG C.After stirring terminates, centrifugation, it is dried after precipitate with deionized water washing, obtains Precursor Mn3[Fe(CN)6]2.By precursor Mn3[Fe(CN)6]2At 550 DEG C, calcine 2 h, obtain that there is hollow nano junction The ferro manganese composite oxides of structure.
Embodiment 9:
The 0.8 mmol potassium ferricyanide is dissolved in 20 ml deionized waters, adds 30 mmol sodium lauryl sulphates, stir Mix dissolving.1.2 mmol Manganese perchlorates are dissolved in 20 ml deionized waters, this solution are joined the above-mentioned potassium ferricyanide molten In liquid, mixed liquor stirs 3 h at 30 DEG C.After stirring terminates, centrifugation, it is dried after precipitate with deionized water washing, obtains Precursor Mn3[Fe(CN)6]2.By precursor Mn3[Fe(CN)6]2At 550 DEG C, calcine 2 h, obtain that there is hollow nano junction The ferro manganese composite oxides of structure.
Embodiment 10:
The 0.8 mmol potassium ferricyanide is dissolved in 20 ml deionized waters, adds 30 mmol sodium lauryl sulphates, stir Mix dissolving.1.2 mmol Manganese perchlorates are dissolved in 20 ml deionized waters, this solution are joined the above-mentioned potassium ferricyanide molten In liquid, mixed liquor stirs 1 h at 30 DEG C.After stirring terminates, centrifugation, it is dried after precipitate with deionized water washing, obtains Precursor Mn3[Fe(CN)6]2.By precursor Mn3[Fe(CN)6]2At 550 DEG C, calcine 3 h, obtain that there is hollow nano junction The ferro manganese composite oxides of structure.
Embodiment 11:
The 0.8 mmol potassium ferricyanide is dissolved in 20 ml deionized waters, adds 30 mmol sodium lauryl sulphates, stir Mix dissolving.1.2 mmol Manganese perchlorates are dissolved in 20 ml deionized waters, this solution are joined the above-mentioned potassium ferricyanide molten In liquid, mixed liquor stirs 1 h at 30 DEG C.After stirring terminates, centrifugation, it is dried after precipitate with deionized water washing, obtains Precursor Mn3[Fe(CN)6]2.By precursor Mn3[Fe(CN)6]2At 550 DEG C, calcine 5 h, obtain that there is hollow nano junction The ferro manganese composite oxides of structure.
Embodiment 12:
The 0.8 mmol potassium ferricyanide is dissolved in 20 ml deionized waters, adds 30 mmol sodium lauryl sulphates, stir Mix dissolving.1.2 mmol Manganese perchlorates are dissolved in 20 ml deionized waters, this solution are joined the above-mentioned potassium ferricyanide molten In liquid, mixed liquor stirs 1 h at 30 DEG C.After stirring terminates, centrifugation, it is dried after precipitate with deionized water washing, obtains Precursor Mn3[Fe(CN)6]2.By precursor Mn3[Fe(CN)6]2At 400 DEG C, calcine 2 h, obtain that there is hollow nano junction The ferro manganese composite oxides of structure.
Embodiment 13:
The 0.8 mmol potassium ferricyanide is dissolved in 20 ml deionized waters, adds 30 mmol sodium lauryl sulphates, stir Mix dissolving.1.2 mmol Manganese perchlorates are dissolved in 20 ml deionized waters, this solution are joined the above-mentioned potassium ferricyanide molten In liquid, mixed liquor stirs 1 h at 30 DEG C.After stirring terminates, centrifugation, it is dried after precipitate with deionized water washing, obtains Precursor Mn3[Fe(CN)6]2.By precursor Mn3[Fe(CN)6]2At 450 DEG C, calcine 2 h, obtain that there is hollow nano junction The ferro manganese composite oxides of structure.
Embodiment 14:
The 0.8 mmol potassium ferricyanide is dissolved in 20 ml deionized waters, adds 30 mmol sodium lauryl sulphates, stir Mix dissolving.1.2 mmol Manganese perchlorates are dissolved in 20 ml deionized waters, this solution are joined the above-mentioned potassium ferricyanide molten In liquid, mixed liquor stirs 1 h at 30 DEG C.After stirring terminates, centrifugation, it is dried after precipitate with deionized water washing, obtains Precursor Mn3[Fe(CN)6]2.By precursor Mn3[Fe(CN)6]2At 650 DEG C, calcine 2 h, obtain that there is hollow nano junction The ferro manganese composite oxides of structure.
Embodiment 15:
The 0.8 mmol potassium ferricyanide is dissolved in 20 ml deionized waters, adds 30 mmol sodium lauryl sulphates, stir Mix dissolving.1.2 mmol Manganese perchlorates are dissolved in 20 ml deionized waters, this solution are joined the above-mentioned potassium ferricyanide molten In liquid, mixed liquor stirs 1 h at 30 DEG C.After stirring terminates, centrifugation, it is dried after precipitate with deionized water washing, obtains Precursor Mn3[Fe(CN)6]2.By precursor Mn3[Fe(CN)6]2At 700 DEG C, calcine 2 h, obtain that there is hollow nano junction The ferro manganese composite oxides of structure.
Embodiment 16:
The 0.8 mmol potassium ferricyanide is dissolved in 20 ml deionized waters, adds 30 mmol sodium lauryl sulphates, stir Mix dissolving.1.2 mmol manganese chlorides are dissolved in 20 ml deionized waters, this solution is joined above-mentioned potassium ferricyanide solution In, mixed liquor stirs 1 h at 30 DEG C.After stirring terminates, centrifugation, it is dried, before obtaining after precipitate with deionized water washing Body Mn3[Fe(CN)6]2.By precursor Mn3[Fe(CN)6]2At 550 DEG C, calcine 2 h, obtain that there is hollow nanostructures Ferro manganese composite oxides.
Embodiment 17:
The 1.2 mmol potassium ferricyanides are dissolved in 20 ml deionized waters, add 30 mmol sodium lauryl sulphates, stir Mix dissolving.1.8 mmol manganese chlorides are dissolved in 20 ml deionized waters, this solution is joined above-mentioned potassium ferricyanide solution In, mixed liquor stirs 1 h at 30 DEG C.After stirring terminates, centrifugation, it is dried, before obtaining after precipitate with deionized water washing Body Mn3[Fe(CN)6]2.By precursor Mn3[Fe(CN)6]2At 550 DEG C, calcine 2 h, obtain that there is hollow nanostructures Ferro manganese composite oxides.

Claims (5)

1. the lithium ion battery preparation method of hollow ferro manganese composite oxides material, it is characterised in that: include walking as follows Rapid:
(1) preparation of solution a: be dissolved in deionized water by the potassium ferricyanide, adds a certain amount of surfactant sodium dodecyl base Sodium sulfate；
(2) preparation of solution b: manganous salt is dissolved in deionized water；
(3) synthesis of presoma: joined by solution b in solution a, forms mixed solution, stirs 1-3h at 30-80 DEG C；Will Gained precipitation and centrifugal separation, is dried after being washed with deionized, and obtains grain shape rule, the precursor Mn of uniform particle sizes3[Fe (CN)6]2；
(4) by precursor Mn3[Fe(CN)6]2Calcine, obtain ferro manganese composite oxides hollow nanostructures material.
The preparation method of a kind of lithium ion battery hollow ferro manganese composite oxides material, it is special Levying and be: in step (1), in described solution a, the concentration of surfactant is 1.5～4mol/L.
The preparation method of a kind of lithium ion battery hollow ferro manganese composite oxides material, it is special Levying and be: in step (2), described manganous salt is Manganese perchlorate or manganese chloride；The concentration of manganous salt in described solution b It is 0.06～0.09mol/L.
The preparation method of a kind of lithium ion battery hollow ferro manganese composite oxides material, it is special Levying and be: in step (3), in described mixed solution, manganous salt is 3:2 with the ratio of the amount of the material of the potassium ferricyanide.
The preparation method of a kind of lithium ion battery hollow ferro manganese composite oxides material, it is special Levying and be: in step (4), described calcining heat is 400-700 DEG C, calcination time is 2-5h.
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