CN109261981A - Bimetallic cobalt-based core-shell material and the preparation method and application thereof - Google Patents
Bimetallic cobalt-based core-shell material and the preparation method and application thereof Download PDFInfo
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- CN109261981A CN109261981A CN201810949570.3A CN201810949570A CN109261981A CN 109261981 A CN109261981 A CN 109261981A CN 201810949570 A CN201810949570 A CN 201810949570A CN 109261981 A CN109261981 A CN 109261981A
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- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
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- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
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Abstract
The present invention is a kind of bimetallic cobalt-based core-shell material and the preparation method and application thereof.The core of the material is magnetic metal Co, and shell is nonmagnetic metal Ag or Cu；Its pattern is threadiness or spherical shape, and fibre diameter is 1.3~36 μm, and spherical diameter is 1~7.3 μm；The atomic ratio of Co and Cu element is 0.25~21.6, Co and the atomic ratio of Ag element is 59.8~74.8；Saturation magnetization range is 62.2~159.9emug–1.The material is using metal replacement method in situ, and the Microwave Absorption Properties with wideband, high-selenium corn, wherein effective band width of the reflectivity less than or equal to -10dB is 5.1~7.76GHz；Bandwidth less than or equal to -20dB is 2.32~16.0GHz；Maximum reflection loss is -52.5~-19.7dB.Present invention process is simple, is easy to commercial introduction, and provided excellent material performance is good in fields application prospects such as catalysis, electrode material, microwave absorption, high density magnetic recording material, sensors.
Description
Technical field
The present invention relates to magnetic Nano complex technique fields, and in particular to a kind of letter for preparing bimetallic cobalt-based core-shell material
Easily, method controllably.
Background technique
Cobalt-based bimetallic material is widely used in high temperature self-lubricating composite, moves as important magnetic Nano metal material
Structural metallic material, magnetic recording material, catalyst, bio-sensing, the absorbing material etc. of power etching system high-temperature component.Commonly
Cobalt-based material has: CoNi alloy, Ni-Co-Al alloy, CoCr, CoCrTa, SmCo, Co-Cr-Al-Y etc..These materials are mainly
Alloy is seldom the bimetallic material of core-shell structure.The method for preparing cobalt-based material mainly has powder metallurgy, and (high-energy ball milling is mechanical
Alloying) method, sputtering method, laser melting and coating process, template, polyol reduction method, hydro-thermal method, microemulsion method collosol and gel
Method, chemical vapor infiltration, plasma Gas Evaporation Method etc..Currently, only a small amount of document and patent report cobalt-base alloys
The preparation of material.Chinese patent literature (CN201710520427.8) discloses a kind of cobalt-base alloys and its cobalt-base alloys system
Standby cladding layer.Chinese patent literature (CN201610075608.X) discloses a kind of cobalt alloy and cobalt oxide ore joint high pressure acid
The method of leaching.Chinese patent literature (CN108004515A) discloses a kind of preparation method of iron cobalt tantalum alloy-sputtering targets material, iron
Cobalt tantalum alloy-sputtering targets material and application.Chinese patent literature (CN106653264A) discloses the preparation of SmCo based composite magnetic material
Method and SmCo based composite magnetic material.Above-mentioned material uses powder metallurgy, sputtering method, laser melting and coating process or template
Method etc., there are many and diverse multistep, energy consumption is high for high temperature, have the shortcomings that special requirement to equipment, the period is long, condition is harsh.Therefore it opens
Send out easy, controllable template-free method becomes the new direction that researcher is studied.
In order to overcome the problems, such as that the above method exists, the present invention in, using low-temperature in-site metal replacement method preparation Co/Ag and
The bis- golden core-shell materials of Co/Cu.The ruler of the controllable particle such as the feed ratio of reaction temperature, reaction time, cobalt and copper or silver metal salt
Very little and composition.This method preparation process is simple and easy, reproducible, is not necessarily to special installation, green high-efficient, reaction temperature is low, institute
Cheap and easy to get with raw material, preparation cost is low.The bis- golden core-shell materials of prepared Co/Ag and Co/Cu have strong ferromagnetic characteristic and
Excellent microwave absorbing property will have wide application in fields such as catalysis, magnetic recording material, biosensor, microwave absorptions
Prospect.
Summary of the invention
The technical problems to be solved by the present invention are: provide a kind of size, composition and the adjustable Co/Ag of electrostatic theory and
The preparation method of the bis- golden core-shell materials of Co/Cu.Preparation process of the present invention is simple and easy, reproducible, is not necessarily to special installation, cost
It is low, yield is high, be easy to industrial application popularization；The bis- golden core-shell materials of resulting Co/Ag and Co/Cu have stronger magnetic responsiveness energy
It, will be in fields such as catalysis, electrode material, microwave absorption, high density magnetic recording material, sensors with excellent Microwave Absorption Properties
It has broad application prospects.
The present invention solves its technical problem, and the following technical solution is employed:
Bimetallic cobalt-based core-shell material provided by the invention, core are magnetic metal Co, and shell is nonmagnetic metal Ag or Cu；
Its pattern is threadiness or spherical shape, and fibre diameter is 1.3~36 μm, and spherical diameter is 1~7.3 μm；The atom of Co and Cu element
Than being 59.8~74.8 for the atomic ratio of 0.25~21.6, Co and Ag element；Saturation magnetization range be 62.2~
159.9emu·g-1。
The bimetallic cobalt-based core-shell material, the Microwave Absorption Properties with wideband, high-selenium corn, wherein reflectivity is less than
Or the effective band width equal to -10dB is 5.1~7.76GHz；Frequency range less than or equal to -20dB is 2.32~
16.0GHz；Maximum reflection loss is -52.5~-19.7dB.
The present invention is using metal replacement method in situ, it may be assumed that using Co fiber or Co microballoon as template, directed agents and reducing agent,
Ag or Cu ion in Co fiber or Co microsphere surface difference in-situ reducing at corresponding metal simple-substance, obtain the Co/Ag or
Co/Cu core-shell material.
The preparation method of bimetallic cobalt-based core-shell material provided by the invention is a kind of using metal replacement method preparation in situ
Bimetallic cobalt-based core-shell material, specifically: the cobalt fiber of certain mass or cobalt microballoon are distributed to certain density silver nitrate
Or in the solution of soluble copper salt, in room temperature~60 DEG C, heating water bath is stirred to react 2~10min；Then deionized water magnetic separation is used
Washing repeatedly, most obtains the bimetallic cobalt-based core-shell material through low-temperature vacuum drying afterwards.
Mantoquita concentration is 4.2 × 10-3~4.2 × 10-1mol·L–1, silver nitrate concentration is 4.2 × 10-5~8.5 × 10- 5mol·L–1；The ratio between the amount of Co and copper solution substance be (2~200): 1, Co and the ratio between the amount of silver nitrate solution substance be (100
~200): 1.
The mantoquita is one of soluble nitrate, sulfate or acetate.
The cobalt fiber is prepared using induced by magnetic field solvent-thermal method, specifically: cobalt salt, surfactant are dissolved in pure second
In glycol, stirring 2h obtains lavender solution；Volumetric concentration is added dropwise again to be 85% hydrazine hydrate and stir 1h, acquired solution is added
Strong magnets (0.12T) is added into polytetrafluoroethyllining lining and inside on or below lining, is sealed in stainless steel kettle and 160
~200 DEG C of heat preservation 4h；It by gained precipitating magnetic separation separation, is washed with deionized for several times, obtains grey black through low-temperature vacuum drying
Cobalt fiber.
In the above method, the concentration of cobalt salt is 0.025~0.20molL–1；The ratio between cobalt salt and the amount of substance of hydrazine hydrate
For 1:10.
The cobalt microballoon is prepared using solvent-thermal method, specifically: in polytetrafluoroethyllining lining, sequentially adding 1,2-the third
Glycol, cobalt salt and hexa are heated to 120 DEG C and continue to stir 10min, NaOH is added into the solution being completely dissolved
Solid continues 0.5-1h of stirring to solution and becomes blackish green by rose, and solid is completely dissolved.Reaction kettle is closed again,
5~20h is kept the temperature in baking oven under the conditions of 170 DEG C.It by gained precipitating magnetic separation separation, is washed with deionized for several times, through cryogenic vacuum
It is dried to obtain the magnetic pulverulent solids of grey black.
In the above method, the concentration of cobalt salt is 0.08molL–1；The ratio between the amount of substance of cobalt salt and NaOH 1:6~1:48；
The ratio between the amount of substance of cobalt salt and hexa 10:7~10:28.
In the above method, cobalt salt is acetate or villaumite.
In the above method, surfactant is polyethylene glycol (PEG-10000) or cetyl trimethylammonium bromide.
In the above method, prepared magnetic cobalt-based nucleocapsid alloy material is in catalyst, electrode material, microwave absorption, height
Application in density magnetic recording material or sensor.
The present invention due to the adoption of the above technical solution, is allowed to compared with prior art, have the following advantages that and accumulate
Pole effect:
(1) this method provides the preparation side of a kind of size, composition and the adjustable bimetallic cobalt-based core-shell material of electrostatic theory
Method.
(2) this method green high-efficient, reaction temperature is low, and raw materials used cheap and easy to get, preparation cost is low；Gained fiber is longer
(1.3~36.0 μm).
(3) this method preparation process is simple and easy, reproducible, is not necessarily to special installation.
(4) application is wide: the bimetallic cobalt-based core-shell material of offer has strong magnetic response and excellent microwave absorbing property,
It will have broad application prospects in fields such as catalysis, electrode material, microwave absorption, high density magnetic recording material, sensors.
In short, reaction temperature of the present invention is low, preparation flow is simple, raw material is cheap and easy to get, at low cost, yield is high, is easy to work
Industry application.Provided bimetallic cobalt-based core-shell material has strong magnetic response and excellent microwave absorbing property, will be
The fields such as catalysis, electrode material, microwave absorption, high density magnetic recording material, sensor have broad application prospects.
Detailed description of the invention
Fig. 1~2,7~15,18~24,29,31,35,37,39~40,42 be embodiment 1 respectively, 2~10,11~17,
18,19,20,21,22,23 pictures observed under scanning electron microscope.
Fig. 3 is the XRD phase structure map of embodiment 1,21,22.
Figure 25 is the XRD phase structure map of embodiment 17,18.
Figure 32 is the XRD phase structure map of embodiment 19,20.
Fig. 5 is the electrostatic theory curve of embodiment 1,21,22.
Figure 16 is the electrostatic theory curve of embodiment 10.
Figure 27 is the electrostatic theory curve of embodiment 17~20.
Fig. 4 is the power spectrum of embodiment 1,21~22.
Figure 26 is the power spectrum of embodiment 17~18.
Figure 33 is the power spectrum of embodiment 19~20.
Fig. 6,17,28,30,34,36,38,41,43 be the 2D reflection line chart of embodiment 1,10,17~23 respectively.
Specific embodiment
The present invention uses low-temperature in-site liquid phase reduction, regulates and controls magnetic by changing feed ratio, concentration, temperature, raw material etc.
The size of property cobalt-based nucleocapsid alloy material, composition, magnetostatic and Microwave Absorption Properties.Resulting bimetallic magnetism cobalt-based nucleocapsid alloy
The characteristics such as the composition and electrostatic theory of material are adjustable, and microwave absorbing property is excellent.
Below with reference to examples and drawings, the invention will be further described, but is not limited solely to the following examples.
Embodiment 1:
By 0.7137g CoCl2·6H2O (0.05M) and 0.8g PVP is dissolved in the pure ethylene glycol of 60mL, and magnetic agitation 2h makes
It is sufficiently dissolved, and obtains lavender solution；It is that 85% hydrazine hydrate continues to stir 1h that 1.76mL volume fraction is slowly added dropwise again.By institute
It obtains solution to be added in polytetrafluoroethyllining lining and strong magnets (0.12T) is added below liner, be sealed in stainless steel kettle,
In 160 DEG C of heat preservation 4h.The sediment of obtained grey black is separated with magnetic separation finally, and is washed for several times with dehydrated alcohol, warp
40 DEG C of vacuum drying obtain product, and product is fibrous cobalt material.
Products therefrom is grey black fibrous solids, and object phase, the pattern observed under scanning electron microscope, object are mutually respectively such as
Shown in Fig. 1~3, it is seen then that product is fibre structure, having a size of 7~15 μm.Its power spectrum is as shown in figure 4, its electrostatic theory such as Fig. 5
It is shown, saturation magnetization 150.33emug-1.Reflection loss curve is as shown in fig. 6, absorption maximum at 5.04GHz
For -41.8dB, counter sample is with a thickness of 4.3mm；Effective band width of the reflectivity less than -10dB is 8.24GHz；2.48~
9.0GHz and 14.64~18GHz frequency range internal reflection rate are less than -20dB, bandwidth 9.88GHz.
Embodiment 2:
It is identical as 1 step of embodiment, but hydrothermal temperature is 200 DEG C.Products therefrom is greyish black color fibre, in scanning electricity
The pattern observed under mirror is as shown in fig. 7, fibre diameter is 7~13 μm.
Embodiment 3:
It is identical as 1 step of embodiment, but 0.3569g CoCl is added2·6H2O (0.025M) and 0.88mL volume fraction
For 85% hydrazine hydrate.Products therefrom is greyish black color fibre, and the appearance structure observed under scanning electron microscope is as shown in figure 8, fibre
Tieing up diameter is 3~7 μm.
Embodiment 4:
It is identical as 1 step of embodiment, but 2.8548g CoCl is added2·6H2O (0.2M) and 7.04mL volume fraction are
85% hydrazine hydrate.Products therefrom is greyish black color fibre, and the appearance structure observed under scanning electron microscope is as shown in figure 9, fiber
Diameter is 18~36 μm.
Embodiment 5:
It is identical as 1 step of embodiment, but 0.8g polyethylene glycol (PEG-10000) is added.Products therefrom is greyish black color fibre,
The appearance structure that it is observed under scanning electron microscope is as shown in Figure 10, and fibre diameter is 6~10 μm.
Embodiment 6:
It is identical as 1 step of embodiment, but 0.8mL cetyl trimethylammonium bromide is added.Products therefrom is that grey black is fine
Dimension, the appearance structure observed under scanning electron microscope is as shown in figure 11, and fibre diameter is 6~16 μm.
Embodiment 7:
It is identical as 1 step of embodiment, but 0.7473g Co (CH is added3COO)2·4H2O(0.05M).Products therefrom is ash
Black fiber, the appearance structure observed under scanning electron microscope is as shown in figure 12, and fibre diameter is 2~3 μm.
Embodiment 8:
It is identical as 1 step of embodiment, but strong magnets are added in above polytetrafluoroethyllining lining.Products therefrom is that grey black is fine
Dimension, the appearance structure observed under scanning electron microscope is as shown in figure 13, and fibre diameter is 1.3~1.7 μm.
Embodiment 9:
It is identical as 1 step of embodiment, but strong magnets (0.12T) all is added up and down in polytetrafluoroethylene (PTFE).Products therefrom is
Greyish black color fibre, the appearance structure observed under scanning electron microscope is as shown in figure 14, and fibre diameter is 7~13 μm.
Embodiment 10:
In polytetrafluoroethyllining lining, 1,2-propylene glycol of 60mL is added, sequentially adds six water chlorination of 1.142g while stirring
Cobalt (0.08M) and 1.001g hexa (0.12M) are heated to 120 DEG C and continue to stir 10min, to what is be completely dissolved
2.4g (1M) NaOH solid is added in solution, continues stirring 0.5h~1h to solution and blackish green is become by rose, and solid is complete
Fully dissolved.Reaction kettle is closed again, then heats 10h under the conditions of 170 DEG C in baking oven.After completion of the reaction, gained is precipitated into magnetic separation
It separates, be washed with deionized for several times, in a vacuum drying oven 40 DEG C of dry 12h, it is magnetic powdered solid to obtain grey black
Body, the pattern observed under scanning electron microscope are as shown in figure 15.Particle diameter is 1.7~2.7 μm.Its electrostatic theory such as Figure 16 institute
Show, saturation magnetization 152.04emug-1.Reflection loss curve is as shown in figure 17.Absorption maximum at 4.64GHz
For -40.7dB, counter sample is with a thickness of 4mm；Effective band width of the reflectivity less than -10dB is 6.2GHz；Reflectivity be less than-
The frequency range of 20dB is 2.9~10.0GHz.It is less than -20dB in 2.9~10.0GHz frequency range internal reflection rate, bandwidth is
7.1GHz。
Embodiment 11:
It is identical as 10 step of embodiment, but the hydro-thermal reaction time is 5h.The magnetic pulverulent solids of grey black are obtained,
The pattern observed under scanning electron microscope is as shown in figure 18.Particle diameter is 1.2~2.5 μm.
Embodiment 12:
It is identical as 10 step of embodiment, but the hydro-thermal reaction time is 20h.It is magnetic powdered solid to obtain grey black
Body, the pattern observed under scanning electron microscope are as shown in figure 19.Particle diameter is 4.6~7.3 μm.
Embodiment 13:
It is identical as 10 step of embodiment, but 1.2g NaOH (0.5M) is added.It is magnetic powdered solid to obtain grey black
Body, the pattern observed under scanning electron microscope are as shown in figure 20.Particle diameter is 1~1.5 μm.
Embodiment 14:
It is identical as 10 step of embodiment, but 9.6g NaOH (4M) is added.It is magnetic powdered solid to obtain grey black
Body, the pattern observed under scanning electron microscope are as shown in figure 21.Particle diameter is 3~4.6 μm.
Embodiment 15:
It is identical as 10 step of embodiment, but 0.5g hexa (0.06M) is added.It is magnetic to obtain grey black
Pulverulent solids, the pattern observed under scanning electron microscope are as shown in figure 22.Particle diameter is 1.2~2 μm.
Embodiment 16:
It is identical as 10 step of embodiment, but 2.002g hexa (0.24M) is added.Grey black is obtained to be magnetic
Pulverulent solids, the pattern observed under scanning electron microscope is as shown in figure 23.Particle diameter is 1.7~3.2 μm.
Embodiment 17:
0.5g embodiment 10 is prepared cobalt powder to be placed in 100mL beaker, washs its surface with 10mL 0.5mol/L dilute hydrochloric acid
Oxide until there is a little bubble to generate, then is distilled water washing 4~5 times with 50mL, is finally placed in 50mL distilled water.
Configuration concentration 0.0042M CuSO4Solution 10mL, the cobalt of above-mentioned washing is added in (800r/min) under electric stirring
In powder, stop stirring after 2min.Cobalt/copper product is isolated in magnetic separation, is washed with distilled water 4~5 times, in 40 DEG C of items of vacuum oven
Dry 12h, obtains dark violet red powder product under part.The pattern that observes under scanning electron microscope, component are as shown in Figure 24~25.
Particle diameter is 4.5~6.2 μm.Energy spectrum analysis Co:Cu=21.6 as shown in figure 26, electrostatic theory is as shown in figure 27, saturation
The intensity of magnetization is 154.73emug-1.Reflection loss curve is as indicated at 28.Absorption maximum at 16.8GHz is -19.7dB,
Counter sample is with a thickness of 1.7mm；Effective band width of the reflectivity less than -10dB is 5.28GHz.
Embodiment 18:
It is identical as 17 step of embodiment, but the CuSO that 10mL concentration is 0.042M is added in cobalt powder4In solution.In scanning electricity
The pattern that observes under mirror, component are as shown in Figure 29, Figure 25.Particle diameter is 3.2~3.7 μm.Energy spectrum analysis is as shown in figure 26
Co:Cu=1.5, electrostatic theory is as shown in figure 27, saturation magnetization 141.22emug-1.Reflection loss curve such as 30
Shown, the absorption maximum at 13.2GHz is -50.4dB, and counter sample is with a thickness of 1.7mm；Reflectivity is effective less than -10dB's
Bandwidth is 5.44GHz；It is less than -20dB, bandwidth 8.72GHz in 7.76~16.48GHz frequency range internal reflection rate.
Embodiment 19:
0.5g embodiment 10 is prepared cobalt powder to be placed in 100mL beaker, washs its surface with 10mL 0.5mol/L dilute hydrochloric acid
Oxide until there is a little bubble to generate, then is distilled water washing 4~5 times with 50mL, is finally placed in 50mL distilled water.Configuration
The AgNO of 0.1mol/L3Solution, 0.42mL AgNO is added in (800r/min) under electric stirring3(4.2×10-5M it) is washed in above-mentioned
In the cobalt powder washed, stop stirring after 2min.Cobalt/silver product is isolated in magnetic separation, is washed with distilled water 4~5 times, in vacuum oven
Dry 12h, obtains product under the conditions of 40 DEG C.In reaction, washing and drying, it is protected from light with aluminium-foil paper.
The pattern that observes under scanning electron microscope, component are as shown in Figure 31~32.Particle diameter is 1~2.5 μm.Power spectrum point
Co:Ag=74.8 as shown in figure 33 is analysed, electrostatic theory is as shown in figure 27, saturation magnetization 151.4emug-1.Reflection
Damage curve is as indicated 34.Absorption maximum at 15.28GHz is -45.3dB, and counter sample is with a thickness of 1.65mm；Reflectivity
Effective band width less than -10dB is 7.76GHz；It is less than -20dB, bandwidth in 8.8~17.68GHz frequency range internal reflection rate
For 8.88GHz.
Embodiment 20:
It is identical as 19 step of embodiment, but 0.85mL0.1mol/LAgNO is added3Solution (8.5 × 10-5M).In scanning electricity
The pattern that observes under mirror, component are as shown in Figure 35,32.Particle diameter is 1.5~2.3 μm.Energy spectrum analysis Co as shown in figure 33:
Ag=59.8, electrostatic theory is as shown in figure 27, saturation magnetization 150.5emug-1.Such as 36 institute of reflection loss curve
Show.Absorption maximum at 15.92GHz is -35dB, and counter sample is with a thickness of 1.6mm；Reflectivity is less than effective frequency of -10dB
Bandwidth is 7.36GHz；It is less than -20dB, bandwidth 9.2GHz in 7.6~16.8GHz frequency range internal reflection rate.
Embodiment 21:
It 0.5g embodiment 1 is prepared into cobalt fiber is dissolved in 20mL deionized water and stir 0.5h to evenly dispersed, it will
0.0845g copper acetate monohydrate (0.042M) is dissolved completely in after 10mL deionized water to be transferred in cobalt fiber solution and stir
Cobalt/copper product is isolated in 10min, magnetic separation, is washed with distilled water 4~5 times, and dry 12h, obtains under the conditions of 40 DEG C of vacuum oven
To fibrous product.The pattern that observes under scanning electron microscope, component are as shown in Figure 37,3.Fibre diameter is 5.7~8 μm.Energy
Spectrum analysis Co:Cu=1.2 as shown in Figure 4, electrostatic theory is as shown in figure 5, saturation magnetization is 159.9emug-1.Reflection
Damage curve is as shown at 38.Absorption maximum at 11.36GHz is -52.5dB, and counter sample is with a thickness of 2.6mm；Reflectivity is small
In -10dB effective band width be 6.24GHz；In 10.72~12.24 and 16.64~17.44GHz frequency range internal reflection rate
Less than -20dB, bandwidth 2.32GHz.
Embodiment 22:
It is identical as 21 step of embodiment, but 0.8455g copper acetate monohydrate (0.42M) is added.It sees under scanning electron microscope
The pattern that measures, component are as shown in Figure 39~40,3.Fibre diameter is 10.8~21.2 μm.Energy spectrum analysis Co:Cu as shown in Figure 4
=0.25, electrostatic theory is as shown in figure 5, saturation magnetization is 62.2emug-1.Reflection loss curve is as shown at 41.?
Absorption maximum at 16.24GHz is -36.6dB, and counter sample is with a thickness of 1.7mm；Reflectivity is wide less than the effective band of -10dB
For 5.1GHz；It is less than -20dB, bandwidth 5.4GHz in 12.5~17.9GHz frequency range internal reflection rate.
Embodiment 23:
It is identical as 21 step of embodiment, but 0.338g copper acetate monohydrate (0.169M) is added.It sees under scanning electron microscope
The pattern measured is as shown in figure 42.Fibre diameter is 8.7~13 μm.Saturation magnetization is 110.2emug-1.Reflection loss
Curve is as shown in 43.Absorption maximum at 10.56GHz is -46.03dB, and counter sample is with a thickness of 2.3mm；Reflectivity be less than-
The effective band width of 10dB is 7.28GHz；It is less than -20dB in 2.0~17.9GHz frequency range internal reflection rate, bandwidth is
16GHz。
Claims (10)
1. a kind of bimetallic cobalt-based core-shell material, it is characterized in that core is magnetic metal Co, shell is nonmagnetic metal Ag or Cu；Its shape
Looks are threadiness or spherical shape, and fibre diameter is 1.3~36.0 μm, and spherical diameter is 1.0~7.3 μm；The atom of Co and Cu element
Than being 59.8~74.8 for the atomic ratio of 0.25~21.6, Co and Ag element；Saturation magnetization range be 62.2~
159.9emu·g–1。
2. bimetallic cobalt-based core-shell material as described in claim 1, it is characterised in that the material have wideband, high-selenium corn it is micro-
Wave-absorbing property, wherein effective band width of the reflectivity less than or equal to -10dB is 5.1~7.76GHz；Less than or equal to -20dB
Frequency range be 2.32~16.0GHz；Maximum reflection loss is -52.5~-19.7dB.
3. bimetallic cobalt-based core-shell material as described in claim 1, it is characterised in that using metal replacement method in situ, it may be assumed that with
Co fiber or Co microballoon are template, directed agents and reducing agent, Ag or Cu ion is in situ respectively in Co fiber or Co microsphere surface
It is reduced into corresponding metal simple-substance, obtains Co/Ag the or Co/Cu core-shell material.
4. a kind of preparation method of bimetallic cobalt-based core-shell material, it is characterized in that a kind of using the double of metal replacement method preparation in situ
Metal cobalt-based core-shell material, specifically: the cobalt fiber of certain mass or cobalt microballoon being distributed to certain density silver nitrate or can
In the solution of dissolubility mantoquita, in room temperature~60 DEG C, heating water bath is stirred to react 2~10min；Then it is washed with deionized water magnetic separation
Repeatedly, bimetallic cobalt-based core-shell material most is obtained afterwards through low-temperature vacuum drying；Mantoquita concentration is 4.2 × 10-3~4.2 × 10- 1mol·L–1, silver nitrate concentration is 4.2 × 10-5~8.5 × 10-5mol·L–1；The ratio between amount of Co and copper solution substance for (2~
200): the ratio between 1, Co and the amount of silver nitrate solution substance are (100~200): 1.
5. the preparation method of cobalt-based nucleocapsid alloy material as claimed in claim 4, it is characterised in that the mantoquita is solvable
One of property nitrate, sulfate or acetate.
6. the preparation method of bimetallic cobalt-based core-shell material as claimed in claim 4, it is characterized in that using induced by magnetic field solvent
Thermal method prepares cobalt fiber, specifically: cobalt salt, surfactant being dissolved in pure ethylene glycol, stirring 2h obtains lavender solution；Again
Volumetric concentration is added dropwise to be 85% hydrazine hydrate and stir 1h, acquired solution is added in polytetrafluoroethyllining lining and in interior lining or
Strong magnets are added in lower section, are sealed in stainless steel kettle and in 160~200 DEG C of heat preservation 4h；By gained precipitating magnetic separation separation, spend
Ion water washing obtains grey black cobalt fiber for several times, through low-temperature vacuum drying；The concentration of cobalt salt is 0.025~0.20molL-
1；The ratio between amount of substance of cobalt salt and hydrazine hydrate is 1:10.
7. the preparation method of bimetallic cobalt-based core-shell material as claimed in claim 6, it is characterised in that surfactant is poly-
Ethylene glycol or cetyl trimethylammonium bromide.
8. the preparation method of bimetallic cobalt-based core-shell material as claimed in claim 4, it is characterised in that claim 6 or 7 institutes
It states in method, cobalt salt is acetate or villaumite.
9. the preparation method of bimetallic cobalt-based core-shell material as claimed in claim 4, it is characterized in that being prepared using solvent-thermal method
Cobalt microballoon, specifically: in polytetrafluoroethyllining lining, sequentially adding 1,2-propylene glycol, cobalt salt and hexa, be heated to
120 DEG C and continue stir 10min, into the solution being completely dissolved be added NaOH solid, continue 0.5-1h of stirring to solution by rose
Red becomes blackish green, and solid is completely dissolved；Reaction kettle is closed again, keeps the temperature 5~20h under the conditions of 170 DEG C in baking oven；It will
Gained precipitating magnetic separation separation is washed with deionized for several times, and it is magnetic powdered solid to obtain grey black through low-temperature vacuum drying
Body；The concentration of cobalt salt is 0.08molL–1, the ratio between amount of substance of cobalt salt and NaOH 1:6~1:48, cobalt salt and hexa-methylene four
The ratio between amount of substance of amine 10:7~10:28.
10. the cobalt-based nucleocapsid alloy material that in claim 4~9 prepared by any claim the method, in catalyst, electricity
Application in pole material, microwave absorption, high density magnetic recording material or sensor.
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