CN103928676A - Hollow nano cubic NiCo2O4 dual-metal oxide material and preparation method thereof - Google Patents

Hollow nano cubic NiCo2O4 dual-metal oxide material and preparation method thereof Download PDF

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CN103928676A
CN103928676A CN201410169966.8A CN201410169966A CN103928676A CN 103928676 A CN103928676 A CN 103928676A CN 201410169966 A CN201410169966 A CN 201410169966A CN 103928676 A CN103928676 A CN 103928676A
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template
preparation
nano cubic
hollow nano
nicl
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郭洪
刘丽香
王亚朋
杨项军
王世雄
陈景
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Yunnan University YNU
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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
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/523—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron for non-aqueous cells
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G51/00—Compounds of cobalt
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/04—Oxides; Hydroxides
    • 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
    • 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 hollow nano cubic NiCo2O4 dual-metal oxide material and a preparation method thereof, and belongs to a metallurgical powder material and preparation thereof. The material disclosed by the invention is in the structure of a hollow nano cross cube of which the diameter is 500nm, the highest reversible capacity is 1160mAh/g, the capacity is greater than or equal to 1060mAh/g after circulating 100 times, the specific capacity is kept at 84%, and the performance is stable. According to the preparation method, a polyvinyl pyrrolidone (PVP) solution dissolved into high-purity water and ethanol is taken as a solvent, NiC12.6H2O and CoC12.6H2O are taken as metal sources, and S2O3<2+> and a home-made Cu2O nano cubic template from selective erosion are utilized at proper temperature, thereby finally generating the NiCo2O4 dual-metal oxide with the hollow nano cubic structure. The hollow nano cubic NiCo2O4 dual-metal oxide material is simple in preparation technology, and low in cost, and has industrial prospect.

Description

Hollow nano cubic NiCo 2o 4bimetallic oxide material and preparation method
Technical field
The invention belongs to metallurgical powder and preparation method, particularly for bimetallic transition metal oxide material and the method for lithium ion battery negative.
Background technology
Energy saving environment protecting electric vehicle and hybrid electric vehicle are the developing direction of automobile industry, at present commercialization graphite cathode material can not meet the demand of high power capacity, highly secure lithium ion battery, and the important research direction of industry and academia is to develop that specific capacity is high, stable cycle performance, high charge-discharge magnification, cost are low, the reliable Novel cathode material for lithium ion battery of security performance.2000, J.M. Tarascon group study was found nano transition metal oxides Ni, Co, and Mo, Cu etc. have higher specific discharge capacity 700-900mAhg -1with good high rate performance, far above specific capacity 372 mAhg of current commercial graphite -1, especially volume and capacity ratio is up to 3500-4500 mAhmL -1(mean energy density 5 gmL -1); Meanwhile, its current potential, higher than lithium metal, can prevent the generation of Li dendrite, guarantees the fail safe of battery; Especially, there is variable chemical valence and various phase structure in this type oxide, can design and obtain pattern uniqueness, the different nano-micro structure of composition under different synthesis conditions; And this quasi-metal oxides draws materials extensively, cost is lower, for industrial scale, produces guarantee is provided.Wherein, the Co base oxide in 3d metal is owing to having higher theoretical capacity (Co 3o 4, 892 mAhg -1; CoO, 715 mAhg -1) be subject to extensive concern, restricting single Co base oxide development be that its volumetric expansion in charging process is more obvious.On the other hand, the existing electro-chemical activity part of ternary metal oxide, there is again skeleton part simultaneously, can effectively improve cycle performance and the high rate performance of lithium ion battery, therefore indicate that developing ternary Co Base Metal/mixed oxide multivariant oxide alloy is an important means that improves its cycle performance of battery.In pertinent literature, the CoSnO that Low seminar is synthetic 3@C and CoMn 2o 4cube composite negative pole material has stable circulation and high rate performance; The mesoporous NiCo of the synthetic classification such as Srinivasan 2o 4electrode material is at 100mAg -1under, the capacity that circulates after 60 times is still up to 939 mAhg -1; Cherian etc. have prepared the CoMoO being connected by thermal decomposition polymer precursor 4network, under 0.1C charging and discharging currents density, specific capacity is up to 990 mAhg -1, and keep stable performance in 50 charge and discharge cycles.These results show: multi-element transition metal oxides material not only may have higher first discharge specific capacity, in lithium ion battery field, there is potential application power, and lithium ion embeds in multicomponent alloy and to deviate from behavior significant to understanding theoretically.
In preparation technology, NiCo 2o 4the synthetic method of bimetallic oxide negative material relates generally to ball milling and heat treatment, and product particle scale is larger, poor as the cycle performance of lithium ion battery negative material.
Summary of the invention
First object of the present invention is to provide a kind of nano cubic NiCo 2o 4bimetallic oxide lithium ion battery negative material, this material granule is evenly tiny, and degree of crystallinity is high, and the lithium ion battery negative material specific capacity prepared with it is high, good cycling stability.
Meanwhile, the present invention proposes a kind of coordination erosion template that adopts and by Ni salt and Co salt, is prepared the method for above material, and not only preparation process is simple for the method, cost is low, and has the prospect of industrialized development.
For achieving the above object, the present invention realizes in the following manner, comprising:
(1) hollow nano cubic NiCo 2o 4bimetallic oxide lithium ion battery negative material
This material is that degree of crystallinity is high, the hollow nanometer cross cube of wall thickness 40-50 nm, diameter 500 nm.
The reversible capacity of described material is up to 1157 mAh/g, more than circulating and still remaining on 1060 mAh/g after 100 times.
(2) a kind of hollow nano cubic NiCo for preparing 2o 4the method of bimetallic oxide lithium ion battery negative material
Comprise the following steps:
With hollow nano cubic structure C u 2o is template, NiCl 26H 2o is Ni source, CoCl 26H 2o is Co source, and preparation is enough to make Ni, Co to be hydrolyzed to compound ion Ni source and the Co source of self aggregation around template, under the reaction temperature of suitable coordination erosion template, adds S 2o 3 2+to corrode template, the hydroxide presoma of the formwork structure that is maintained, then through high-temperature roasting, obtain material.
Described method is further:
(1) by raw material NiCl 26H 2o, CoCl 26H 2o and Na 2s 2o 3with high-purity water as solvent, be mixed with respectively 0.02 mM, the solution of 0.04 mM and 1 M;
(2) 1.65 g PVP are dissolved in to the high purity water of volume ratio 1:1 and alcohol mixeding liquid in totally 10 mL, then by 10 mg Cu 2o hollow nano cubic stay in place form adds in mixed solution, fully stirs;
(3) under 60 ℃ of reaction temperatures, by 2 mL NiCl 26H 2o, 2 mL CoCl 26H 2the O aqueous solution joins has Cu 2in the mixed solution of O template, stir, dropwise add 4 mL Na 2s 2o 3the aqueous solution, 5 ~ 30min is carried out in reaction, and the turbid solution obtaining is centrifugal, with high purity water washing for several times, air drying;
(4) step (3) product 450 ℃ of roasting 4 h under Ar gas, naturally cool to room temperature, obtain NiCo free from admixture phase, that have hollow nano cubic structure 2o 4bimetallic oxide.
As principle, the present invention adopts template to corrode strategy in conjunction with coordinating, with S 2o 3 2+by shell, to core, coordinate to corrode Cu 2o hollow nano cubic stay in place form, controls the Co of solution state, the hydrolysis rate of Ni salt forms Ni-Co compound ion, is attached to template surface, with solution environmental middle and high concentration OH -self aggregation forms precipitation, obtains the Ni-Co hydroxide presoma of hollow structure, and has certain change with its pattern of variation in reaction time.And then under Ar gas 450 ℃ of roasting 4 h, obtain the NiCo of 500 about nm, hollow nanometer cross cube structure 2o 4bimetallic oxide lithium ion battery negative material.
The distinguishing feature that the present invention has and progress are:
The present invention adopts template in conjunction with coordinate corroding strategy, generates the presoma that has kept formwork structure, then high temperature obtains the method for powder bimetallic oxide material, and its technical process is simple, and consuming time few, productive rate is high, and cost is low, has the prospect of industrialized development.
According to above preparation method's synthesized material except having hollow nanometer cross cube feature, also there is degree of crystallinity high, the features such as specific area is larger, thereby be conducive to lithium ion de-embedding in material, cushion the change in volume of material in removal lithium embedded process, improved the cyclical stability of material.
Evidence: the NiCo that the present invention prepares 2o 4bimetallic oxide cell negative electrode material specific capacity is high, stable cycle performance, and reversible capacity is up to 1157 mAh/g, and more than circulating and still remaining on 1060 mAh/g after 100 times, specific capacity remains on 84%.Thereby, the NiCo being proposed by the present invention 2o 4bimetallic oxide and preparation method have the development prospect of industrialization.
Accompanying drawing explanation
Fig. 1 is that the present invention coordinates to corrode the synthetic NiCo of template 2o 4bimetallic oxide is 60 ℃ of reaction temperatures, and SEM during reaction time 0 min schemes.
Fig. 2 is that the present invention coordinates to corrode the synthetic NiCo of template 2o 4bimetallic oxide is 60 ℃ of reaction temperatures, and SEM during reaction time 5 min schemes.
Fig. 3 is that the present invention coordinates to corrode the synthetic NiCo of template 2o 4bimetallic oxide is 60 ℃ of reaction temperatures, and SEM during reaction time 10 min schemes.
Fig. 4 is that the present invention coordinates to corrode the synthetic NiCo of template 2o 4bimetallic oxide is 60 ℃ of reaction temperatures, and SEM during reaction time 15 min schemes.
Fig. 5 is that the present invention coordinates to corrode the synthetic NiCo of template 2o 4bimetallic oxide is 60 ℃ of reaction temperatures, and SEM during reaction time 20 min schemes.
Fig. 6 is that the present invention coordinates to corrode the synthetic NiCo of template 2o 4bimetallic oxide is 60 ℃ of reaction temperatures, and SEM during reaction time 30 min schemes.
Fig. 7 is that the present invention coordinates to corrode the synthetic NiCo of template 2o 4the XRD figure of bimetallic oxide powder, 60 ℃ of reaction temperatures, reaction time 10 min.
Fig. 8 is that the present invention coordinates to corrode the synthetic NiCo of template 2o 4specific capacity-cycle-index curve of bimetallic oxide negative pole, 60 ℃ of reaction temperatures, the time is respectively 5 min, 10 min, 15 min, 20 min, 30 min.
Below in conjunction with embodiment, the present invention will be further described, and embodiment comprises but do not limit the scope that the present invention protects.
Embodiment
Embodiment 1:
With NiCl 26H 2o(purity >99.9%), CoCl 26H 2o(purity >99.9%) and Na 2s 2o 3(purity >99.9%), PVP K30(purity >99%) and ethanol (purity >99%) be initial feed, by raw material NiCl 26H 2o, CoCl 26H 2o and Na 2s 2o 3with high-purity water as solvent, be formulated as respectively 0.02 mM, the solution of 0.04 mM and 1 M.1.65 g PVP are dissolved in the high purity water of 1:1 volume ratio and the mixed solution of ethanol, then by homemade 10 mg Cu 2o powder template adds in mixed solution, fully stirs.Under 60 ℃ of reaction temperatures, by 2 mL NiCl 26H 2o, 2 mLCoCl 26H 2the O aqueous solution joins has Cu 2in the mixed solution of O template, stir, dropwise add 4 mL Na 2s 2o 3the aqueous solution, 5 min are carried out in reaction.The turbid solution obtaining is centrifugal, with high purity water washing for several times, air drying.The product obtaining is under Ar gas, and 450 ℃ of roasting 4 h, naturally cool to room temperature.As Fig. 2, the XRD material phase analysis result of gained sample shows, synthetic product is the NiCo with hollow nano cubic structure 2o 4bimetallic oxide, without the existence of any impurity phase.
The conductive agent acetylene black that synthetic material is added to 10 wt%, the binding agent PVDF of 10 wt% makes slurry, evenly be applied on copper platinum, after oven dry, block circular pole piece, form test cell with lithium metal, carry out constant current charge-discharge experiment, charging and discharging currents is 200mA/g, and charging/discharging voltage scope control is between 0.01-1.5V.The SnO of preparation 2the maximum reversible capacity of-C composite negative pole material is 1156 mAh/g, and the specific capacity circulating after 100 times is 1015 mAh/g, and capability retention is 87.8%.
Embodiment 2:
With NiCl 26H 2o(purity >99.9%), CoCl 26H 2o(purity >99.9%) and Na 2s 2o 3(purity >99.9%), PVP K 30(purity >99%) and ethanol (purity >99%) be initial feed, by raw material NiCl 26H 2o, CoCl 26H 2o and Na 2s 2o 3with high-purity water as solvent, be formulated as respectively 0.02 mM, the solution of 0.04 mM and 1 M.1.65 g PVP are dissolved in the high purity water of 1:1 volume ratio and the mixed solution of ethanol, then by homemade 10 mg Cu 2o powder template adds in mixed solution, fully stirs.Under 60 ℃ of reaction temperatures, by 2 mL NiCl 26H 2o, 2 mL CoCl 26H 2the O aqueous solution joins has Cu 2in the mixed solution of O template, stir, dropwise add 4 mL Na 2s 2o 3the aqueous solution, 10 min are carried out in reaction.The turbid solution obtaining is centrifugal, with high purity water washing for several times, air drying.The product obtaining is under Ar gas, and 450 ℃ of roasting 4 h, naturally cool to room temperature.As Fig. 2, the XRD material phase analysis result of gained sample shows, synthetic product is the NiCo with hollow nano cubic structure 2o 4bimetallic oxide, without the existence of any impurity phase.
The conductive agent acetylene black that synthetic material is added to 10 wt%, the binding agent PVDF of 10 wt% makes slurry, evenly be applied on copper platinum, after oven dry, block circular pole piece, form test cell with lithium metal, carry out constant current charge-discharge experiment, charging and discharging currents is 200mA/g, and charging/discharging voltage scope control is between 0.01-1.5V.The SnO of preparation 2the maximum reversible capacity of-C composite negative pole material is 1157 mAh/g, and the specific capacity circulating after 100 times is 1060 mAh/g, and capability retention is 95.60%.
Embodiment 3:
With NiCl 26H 2o(purity >99.9%), CoCl 26H 2o(purity >99.9%) and Na 2s 2o 3(purity >99.9%), PVP K 30(purity >99%) and ethanol (purity >99%) be initial feed, by raw material NiCl 26H 2o, CoCl 26H 2o and Na 2s 2o 3with high-purity water as solvent, be formulated as respectively 0.02 mM, the solution of 0.04 mM and 1 M.1.65 gPVP are dissolved in the high purity water of 1:1 volume ratio and the mixed solution of ethanol, then by homemade 10 mg Cu 2o powder template adds in mixed solution, fully stirs.Under 60 ℃ of reaction temperatures, by 2 mL NiCl 26H 2o, 2 mLCoCl 26H 2the O aqueous solution joins has Cu 2in the mixed solution of O template, stir, dropwise add 4 mL Na 2s 2o 3the aqueous solution, 15 min are carried out in reaction.The turbid solution obtaining is centrifugal, with high purity water washing for several times, air drying.The product obtaining is under Ar gas, and 450 ℃ of roasting 4 h, naturally cool to room temperature.As Fig. 2, the XRD material phase analysis result of gained sample shows, synthetic product is the NiCo with hollow nano cubic structure 2o 4bimetallic oxide, without the existence of any impurity phase.
The conductive agent acetylene black that synthetic material is added to 10 wt%, the binding agent PVDF of 10 wt% makes slurry, evenly be applied on copper platinum, after oven dry, block circular pole piece, form test cell with lithium metal, carry out constant current charge-discharge experiment, charging and discharging currents is 200mA/g, and charging/discharging voltage scope control is between 0.01-1.5V.The SnO of preparation 2the maximum reversible capacity of-C composite negative pole material is 1116 mAh/g, and the specific capacity circulating after 100 times is 1039 mAh/g, and capability retention is 93.1%.
Embodiment 4:
With NiCl 26H 2o(purity >99.9%), CoCl 26H 2o(purity >99.9%) and Na 2s 2o 3(purity >99.9%), PVP K 30(purity >99%) and ethanol (purity >99%) be initial feed, by raw material NiCl 26H 2o, CoCl 26H 2o and Na 2s 2o 3with high-purity water as solvent, be formulated as respectively 0.02 mM, the solution of 0.04 mM and 1 M.1.65 g PVP are dissolved in the high purity water of 1:1 volume ratio and the mixed solution of ethanol, then by homemade 10 mg Cu 2o powder template adds in mixed solution, fully stirs.Under 60 ℃ of reaction temperatures, by 2 mL NiCl 26H 2o, 2 mLCoCl 26H 2the O aqueous solution joins has Cu 2in the mixed solution of O template, stir, dropwise add 4 mL Na 2s 2o 3the aqueous solution, 20 min are carried out in reaction.The turbid solution obtaining is centrifugal, with high purity water washing for several times, air drying.The product obtaining is under Ar gas, and 450 ℃ of roasting 4 h, naturally cool to room temperature.As Fig. 2, the XRD material phase analysis result of gained sample shows, synthetic product is the NiCo with hollow nano cubic structure 2o 4bimetallic oxide, without the existence of any impurity phase.
The conductive agent acetylene black that synthetic material is added to 10 wt%, the binding agent PVDF of 10 wt% makes slurry, evenly be applied on copper platinum, after oven dry, block circular pole piece, form test cell with lithium metal, carry out constant current charge-discharge experiment, charging and discharging currents is 200mA/g, and charging/discharging voltage scope control is between 0.01-1.5V.The SnO of preparation 2the maximum reversible capacity of-C composite negative pole material is 1016 mAh/g, and the specific capacity circulating after 100 times is 657 mAh/g, and capability retention is 64.7%.
Embodiment 5:
With NiCl 26H 2o(purity >99.9%), CoCl 26H 2o(purity >99.9%) and Na 2s 2o 3(purity >99.9%), PVP K 30(purity >99%) and ethanol (purity >99%) be initial feed, by raw material NiCl 26H 2o, CoCl 26H 2o and Na 2s 2o 3with high-purity water as solvent, be formulated as respectively 0.02 mM, the solution of 0.04 mM and 1 M.1.65 gPVP are dissolved in the high purity water of 1:1 volume ratio and the mixed solution of ethanol, then by homemade 10 mg Cu 2o powder template adds in mixed solution, fully stirs.Under 60 ℃ of reaction temperatures, by 2 mL NiCl 26H 2o, 2 mLCoCl 26H 2the O aqueous solution joins has Cu 2in the mixed solution of O template, stir, dropwise add 4 mL Na 2s 2o 3the aqueous solution, 30 min are carried out in reaction.The turbid solution obtaining is centrifugal, with high purity water washing for several times, air drying.The product obtaining is under Ar gas, and 450 ℃ of roasting 4 h, naturally cool to room temperature.As Fig. 2, the XRD material phase analysis result of gained sample shows, synthetic product is the NiCo with hollow nano cubic structure 2o 4bimetallic oxide, without the existence of any impurity phase.
The conductive agent acetylene black that synthetic material is added to 10 wt%, the binding agent PVDF of 10 wt% makes slurry, evenly be applied on copper platinum, after oven dry, block circular pole piece, form test cell with lithium metal, carry out constant current charge-discharge experiment, charging and discharging currents is 200mA/g, and charging/discharging voltage scope control is between 0.01-1.5V.The SnO of preparation 2the maximum reversible capacity of-C composite negative pole material is 828 mAh/g, and the specific capacity circulating after 100 times is 156 mAh/g, and capability retention is 87.0%.

Claims (5)

1. hollow nano cubic NiCo 2o 4bimetallic oxide material, is characterized in that this material is that degree of crystallinity is high, the hollow nanometer cross cube of wall thickness 40-50 nm, diameter 500 nm.
2. lithium ion battery negative material according to claim 1, is characterized in that this material reversible capacity is up to 1157 mAh/g, more than circulating and still remaining on 1060 mAh/g after 100 times.
3. a method of preparing material as described in claim 1～2, comprises the following steps:
With nano cubic structure C u 2o is template, NiCl 26H 2o is Ni source, CoCl 26H 2o is Co source, and preparation is enough to make Ni, Co to be hydrolyzed to compound ion Ni source and the Co source of self aggregation around template, under the reaction temperature of suitable coordination erosion template, adds S 2o 3 2+to corrode template, the hydroxide presoma of the formwork structure that is maintained, then through high-temperature roasting, obtain material.
4. preparation method according to claim 3, is characterized in that:
(1) by raw material NiCl 26H 2o, CoCl 26H 2o and Na 2s 2o 3with high-purity water as solvent, be mixed with respectively 0.02 mM, the solution of 0.04 mM and 1 M;
(2) 1.65 g PVP are dissolved in to the high purity water of volume ratio 1:1 and alcohol mixeding liquid in totally 10 mL, then by 10 mg Cu 2o powder template adds in mixed solution, fully stirs;
(3) under 60 ℃ of reaction temperatures, by 2 mL NiCl 26H 2o, 2 mL CoCl 26H 2the O aqueous solution joins has Cu 2in the mixed solution of O template, stir, dropwise add 4 mL Na 2s 2o 3the aqueous solution, 5 ~ 30min is carried out in reaction, and the turbid solution obtaining is centrifugal, with high purity water washing for several times, air drying;
(4) step (3) product 450 ℃ of roasting 4 h under Ar gas, naturally cool to room temperature, obtain NiCo free from admixture phase, that have hollow nano cubic structure 2o 4bimetallic oxide.
5. according to the preparation method described in claim 3 or 4, its feature is further that 10 min are carried out in step (3) reaction.
CN201410169966.8A 2014-04-25 2014-04-25 Hollow nano cubic NiCo2O4 dual-metal oxide material and preparation method thereof Pending CN103928676A (en)

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