CN107204422A - A kind of preparation method of carbon/nickel ferrite based magnetic loaded nanometer composite fiber material - Google Patents
A kind of preparation method of carbon/nickel ferrite based magnetic loaded nanometer composite fiber material Download PDFInfo
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- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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Abstract
The invention discloses a kind of carbon/nickel ferrite based magnetic loaded nanometer composite fiber material, it is, using materials with hide glue fibril as template, materials with hide glue fibril template to be coated as metal oxide precursor using molysite, nickel salt, then is made by high-temperature calcination.The material source that the present invention is selected is extensive, with low cost, and preparation process is succinct, environmentally friendly, low to equipment degree of dependence, is a kind of effective way for preparing carbon/nickel ferrite based magnetic loaded nanometer composite fiber material.
Description
Technical field
The invention belongs to lithium ion battery electrode material and its preparing technical field, and in particular to one kind utilizes template legal system
The universal method of standby oxidate nano composite fibre negative material.
Background technology
Negative material is the important composition of lithium ion battery.Conventional graphite negative material have good stability in use and
Security performance.However, the theoretical energy density of graphite cathode only 372 mAh g-1（F. Wu, R. Huang, D. Mu, et
al., New Synthesis of a Foamlike Fe3O4/C Composite via a Self-Expanding Pr℃
ess and Its Electr℃hemical Performance as Anode Material for Lithium-Ion
Batteries [J]. ACS Applied Materials &Interfaces, 2014, 6, 19254-19264.）, it is impossible to
Meet demand of the people to high-performance lithium battery.In recent years, transition metal oxide negative material is because its energy density is big, cost
Low and environment-friendly the features such as, receives the concern of vast researcher.Wherein, nickel ferrite based magnetic loaded bimetallic oxide is because its is high
Mass energy density（915 mAh g-1）Become the study hotspot of novel anode material（Y. Ding, Y. Yang, H.
Shao, One-Pot Synthesis of NiFe2O4/C Composite as An Anode Material for
Lithium-Ion Batteries [J]. Journal of Power Sources, 2013, 244, 610-613.）.So
And, bulk effect change of the nickel ferrite based magnetic loaded in charge-discharge can cause caving in for material structure, cause active material powder, follow
Ring stability is poor（C. T. Cherian, J. Sundaramurthy, M. V. Reddy, et al.,
Morphologically Robust NiFe2O4Nano bers as High Capacity Li-Ion Battery Anode
Material [J], ACS Applied Materials &Interfaces, 2013, 5, 9957-9963.）；Meanwhile, iron
Reversible discharge capacity is low under the conditions of the relatively low electrical conductivity of sour nickel itself has also had a strong impact on its high rate performance, high current（P.
Preetham, S. Mohapatra, S. V. Nair, et al., Ultrafast Pyro-Synthesis of
NiFe2O4 Nanoparticles Within A Full Carbon Network as A High-Rate and Cycle-
Stable Anode Material for Lithium Ion Batteries [J], RSC advances, 2016, 6,
38064-38070.）.At present, the chemical property of nickel ferrite based magnetic loaded is mainly improved using following two methods：One is to be prepared into nanometer
Polarizing electrode material（J. Wang, G. Yang, L. Wang, et al., Synthesis of One-Dimensional
NiFe2O4 Nanostructures: Tunable Morphology and High-Performance Anode
Materials for Li-ion Batteries [J], Journal of Materials Chemistry A, 2016,
4, 8620-8629.）, i.e., by nickel ferrite based magnetic loaded be prepared into nanoscale electrode material come effectively suppress the structure that bulk effect is caused
Cave in, improve cycle performance；Meanwhile, nanosizing can shorten ion transmission range, improve the contact area of electrode and electrolyte, by force
Change high rate performance；Two be to carry out carbon material coating decoration（E. K. Heidari, B. Zhang, M. H. Sohi, et
al., Sandwich-Structure Graphene-NiFe2O4-Carbon Nan℃omposite Anodes with
Exceptional Electr℃hemical Performance for Li Ion Batteries [J], Journal of Materials Chemistry A, 2014, 2, 8314-8322.）, by by nickel ferrite based magnetic loaded and the higher carbon material of electrical conductivity
It is combined to improve the electrical conductivity of electrode material, so as to optimize mass transfer dynamicses and then obtain good high rate performance.
At present, nickel ferrite based magnetic loaded nano-electrode material mainly passes through hydro-thermal method（G. Huang, F. Zhang, L. Zhang,
et al., Hierarchical NiFe2O4/Fe2O3 Nanotubus Derived from Mental Organic
Frameworks for Superior Lithium Ion Battery Anodes [J], Journal of Materials Chemistry A, 2014, 2, 8048-8053. ）, sol-gal process（C. Vidal-Abarca, P. Lavela, J.
L. Tirado, The Origin of Capacity Fading in NiFe2O4 Conversion Electrodes for
Lithium Ion Batteries Unfolded by Fe Mossbauer Spectroscopy [J], Journal of Physical Chemistry C, 2010, 12828-12832.）Prepared etc. technology.However, there is technique in above-mentioned technology of preparing
The problems such as complicated, equipment requirement is high, manufacturing cost is high.In addition, nano-electrode material is also deposited when carrying out carbon material coating decoration
The problems such as carbon material cladding inequality and carbon coating layer thickness are difficult to regulation and control.For these reasons, reported nickel ferrite based magnetic loaded is received
Rice electrode material is still needed to be further improved in terms of cyclical stability and high rate capability.To solve the above problems, needing badly
Research and develop the technology of preparing of simple, the with low cost preparation high-performance nickel ferrite based magnetic loaded nano-electrode material of technique.
The content of the invention
In order to solve the above problems, the present invention is used as metal oxide using materials with hide glue fibril as template by the use of molysite, nickel salt
Presoma is coated to materials with hide glue fibril template, then can prepare carbon/nickel ferrite based magnetic loaded nano-composite fiber by high-temperature calcination.Should
Nano-composite fiber completely remains the nanofibrous structures of collagenous fibres, as lithium ion battery negative material in use, tool
There is excellent cyclical stability and high rate capability, be to prepare the preferable negative material of high performance lithium ion battery of new generation.
Its concrete technical scheme is：A kind of preparation method of carbon/nickel ferrite based magnetic loaded nanometer composite fiber material, it is characterised in that：
This method comprises the following steps：
（1）Collagenous fibres and deionized water are stirred and pH value of solution are adjusted to 1.5-2.5, Fe is then added3+Presoma is molten
Alkaline solution is slowly added dropwise after liquid, reaction 2-6 h, system pH is risen to 3.0-6.0 in 4 h, then by system reaction temperature
Rise to 25-60 DEG C and react 4-12 h, fully washing, filtering after reaction terminates obtains loading Fe3+Collagenous fibres（Fe3+-
CF）；
（2）By the collagenous fibres of above-mentioned load iron ion（Fe3+-CF）It is well mixed with deionized water, adds Ni2+Presoma is molten
Alkaline solution is slowly added dropwise after liquid, reaction 2-6 h, system pH is risen to 5.0-7.5 in 4 h.Then by reaction system liter
Temperature is to 25-60 DEG C and reacts 4-12 h, and fully washing, filtering after reaction terminates obtains loading Fe after drying3+And Ni2+Collagen
Fiber（Fe3+-Ni2+-CF）；
（3）Under vacuum conditions, by Fe3+-Ni2+- CF is with 1-20 DEG C/min heating rate from room temperature is to 300 DEG C and protects
Warm 1-3 h, 500-700 DEG C is then warming up in air atmosphere and 2-6 h are kept, carbon/nickel ferrite based magnetic loaded nano-composite fiber is produced
Material.
Further, the collagenous fibres are that routinely process hides pretreating process removes fiber for livestock animals skin or leftover pieces
Collagenous fibres or commodity collagenous fibres purchased in market that length is 0.1-5.0 mm are ground into after interstitial.
Further, the Fe3+Precursor solution is any one in ferric sulfate, ferric nitrate or iron chloride and deionization
The concentration that water is configured to is 0.2mol/L-0.6mol/L solution.
Further, the Ni2+Precursor solution is any one in nickel sulfate, nickel nitrate or nickel chloride and deionization
The concentration that water is configured to is 0.2 mol/L-0.4 mol/L solution.
Further, the alkaline solution is sodium acid carbonate, sodium carbonate or ammoniacal liquor.
Further, carbon/nickel ferrite based magnetic loaded nanometer composite fiber material can be carried out using the A/g-2.0 A/g of high current density 0.3
Initial activation processing, effectively lifts its cyclical stability and high rate performance.
The activation current density that preceding 10 discharge and recharges are used in the initial activation processing is 0.5 A/g-1.0 A/g.
Count by weight ratio, the step（1）In preferably 50 parts of collagenous fibres, deionized water prioritizing selection 100-
300 parts, Fe3+Preferably 50 parts of precursor solution, is slowly added dropwise the time preferred 1-3 h that alkaline solution lifts pH, alkali is slowly added dropwise
Property the solution elevating preferred 3.5-4.5 of pH scopes, reaction time preferred 6-12 h after heating.
Count by weight ratio, the step（2）In preferably 50 parts of collagenous fibres, deionized water prioritizing selection 100-
300 parts, Ni2+Preferably 50 parts of precursor solution, is slowly added dropwise the time preferred 1-3 h that alkaline solution lifts pH, alkali is slowly added dropwise
Property the solution elevating preferred 6.5-7.5 of pH scopes, reaction time preferred 6-8 h after heating.
The step（3）In preferred 5-10 DEG C/min of calcining heating rate, be warming up to 300 DEG C and keep 1-2 h, then
It is warming up to 500-700 DEG C and keeps 2-4 h.
The present invention compared with prior art, has the following advantages that：
1. the collagenous fibres that the present invention is used are the supramolecular aggregations being self-assembly of by tropocollagen molecule, its own contains greatly
Amount-COOH ,-OH ,-NH2、-CONH2With-CONH- isoreactivity groups, a variety of chemical reactions can be carried out, contribute to presoma ion
Absorption.
2. the distinctive three-dimensional structure of collagenous fibres, effectively inhibits bulk effect during charge-discharge, without artificial again
Structural texture, not only reduces process, reduces preparation cost, it is thus also avoided that the problems such as man-made structures are uneven.
3. the present invention will obtain completely multiple using the method for high-temperature calcination after the collagenous fibres calcining of loaded metal ion
The nanometer composite fiber material of glue fibrillation pattern.Collagenous fibres template is converted into carbon by high-temperature calcination, is on the one hand lifted
The electrical conductivity of fibrous material, makes electrode have good chemical property, another aspect carbon material carries for reactive nanoparticles
Carrier is supplied, it is therefore prevented that the agglomeration in electrochemical reaction process, has helped to lift the cyclical stability of electrode material.
4. the material source that the present invention is selected is extensive, with low cost, preparation process is succinct, environmental protection, to equipment degree of dependence
It is low, it is a kind of effective way for preparing carbon/nickel ferrite based magnetic loaded nanometer composite fiber material.
5. the present invention carries out initial activation processing using high current can be obviously improved carbon/nickel ferrite based magnetic loaded nano-composite fiber material
The cyclical stability and high rate performance of material.
Brief description of the drawings
Fig. 1 is the X-ray diffraction energy spectrum analysis of carbon/nickel ferrite based magnetic loaded nano-composite fiber obtained by the present invention（XRD）Figure.By Fig. 1
Understand, 220,311,400,422,511,440 grade lattice diffraction locations the material can be formed with qualitative analysis after high-temperature calcination
NiFe2O4。
Fig. 2 is the Raman spectrogram of carbon/nickel ferrite based magnetic loaded nano-composite fiber, D bands and G bands in Fig. 2, through high-temperature calcination
Afterwards, there is graphited carbon in the composite.
Fig. 3 is the SEM of carbon/nickel ferrite based magnetic loaded nano-composite fiber（SEM）Shape appearance figure.From the figure 3, it may be seen that carbon/iron
Sour nickel nano-composite fiber replicates the structural integrity of collagenous fibres.
Fig. 4 is the transmission electron microscope of carbon/nickel ferrite based magnetic loaded nano-composite fiber（TEM）Shape appearance figure, as shown in Figure 4, ferrous acid
Nickel reactive nanoparticles are evenly coated at outside carbon material.
Fig. 5 is the circulation charge-discharge performance test of carbon/nickel ferrite based magnetic loaded nano-composite fiber as obtained by the embodiment of the present invention 1
Figure.
Fig. 6 is the multiplying power charge-discharge performance test of carbon/nickel ferrite based magnetic loaded nano-composite fiber as obtained by the embodiment of the present invention 2
Figure.
Fig. 7 is the circulation charge-discharge performance test of carbon/nickel ferrite based magnetic loaded nano-composite fiber as obtained by the embodiment of the present invention 4
Figure.
Fig. 8 is the circulation charge-discharge performance test of carbon/nickel ferrite based magnetic loaded nano-composite fiber as obtained by the embodiment of the present invention 5
Figure.
Fig. 9 be as obtained by the embodiment of the present invention 6 carbon/nickel ferrite based magnetic loaded nano-composite fiber under 0.5 A/g current density
Circulation charge-discharge performance test figure after activation.
Figure 10 be as obtained by the embodiment of the present invention 6 carbon/nickel ferrite based magnetic loaded nano-composite fiber under 1.0 A/g current density
Circulation charge-discharge performance test figure after activation.
Embodiment
The present invention is specifically described below by embodiment.It is necessarily pointed out that, the present embodiment is only used
Further illustrated in the present invention, it is impossible to be interpreted as to protection scope of the present invention.Those skilled in the art is according to above-mentioned
Some nonessential improvement and adjustment that the content of the invention is done, are also considered as within the scope of the present invention.
What deserves to be explained is：1）The number of material used is parts by weight in embodiment.2）Carbon/ferrous acid in following examples
Nickel nanometer composite fiber material is assembled into fastening lithium ionic cell to test its charge-discharge performance.Specific assembly method
It is carbon/nickel ferrite based magnetic loaded nano-composite fiber, the conductive electrode that will be prepared in embodiment（CNT）And binding agent（Polyvinylidene fluoride
Alkene）It is 7 in mass ratio:2:1 ratio is well mixed and is coated on copper foil substrate, is subsequently placed in vacuum drying chamber and dries,
Test electrode is made.Electrode slice after drying, CR2032 type both positive and negative polarities battery case, lithium piece, barrier film, electrolyte are placed in filled with argon
Assembled package in the glove box of gas.The electrode slice of active material is wherein scribbled as the positive pole of the test battery, lithium piece is as negative
Pole, barrier film selects polypropylene porous film, 1.0 mol/L LiPF6（Solvent EC:DMC:EMC volume ratios are 1:1:1）It is used as electrolysis
Liquid.Stand after 12 h, in charge-discharge tester（New prestige Neware CT-3008）Upper test charge-discharge performance.
As shown in Figure 1,220,311,400,422,511,440 grade lattice diffraction locations, the material can be existed with qualitative analysis
NiFe is formd after high-temperature calcination2O4.In Fig. 2, after high-temperature calcination, there is graphite in D bands and G bands in the composite
The carbon of change.From the figure 3, it may be seen that carbon/nickel ferrite based magnetic loaded nano-composite fiber replicates the structural integrity of collagenous fibres.As shown in Figure 4,
Nickel ferrite based magnetic loaded reactive nanoparticles are evenly coated at outside carbon material.
Embodiment 1
5 parts of collagenous fibres and 200 parts of deionized waters are stirred and solution system pH to 2.0 is adjusted.Add 50 part 0.4
mol/L Fe3+Alkaline solution is slowly added dropwise after precursor solution, 2 h of reaction, system pH is risen to 4.0 in 4 h.Regulation reaction
System temperature rises to 40 DEG C and reacts 9 h, fully washing, filtering after reaction terminates, and obtains loading Fe3+Collagenous fibres（Fe3 +-CF）.
By above-mentioned Fe3+- CF is well mixed with 200 parts of deionized waters.Add 50 part of 0.3 mol/L Ni2+Presoma is molten
Alkaline solution is slowly added dropwise after liquid, 2 h of reaction, system pH is promoted to 7.0 in 4 h, then by system temperature and 45 are risen to
DEG C and react 6 h.Fully washing, filtering after reaction terminates, obtains loading Fe after drying3+And Ni2+Collagenous fibres（Fe3+-Ni2 +-CF）.
Under vacuum conditions, by Fe3+-Ni2+- CF is with 5 DEG C/min heating rate from room temperature is to 300 DEG C and protects
1 h of temperature, 600 DEG C are then warming up under air atmosphere and 3 h are incubated, you can carbon/nickel ferrite based magnetic loaded nano-composite fiber material is obtained
Material.
The carbon of gained/nickel ferrite based magnetic loaded nano-composite fiber is assembled into battery, the test loop on charge-discharge tester
Can, its performance is as shown in Figure 5.
Embodiment 2
5 parts of collagenous fibres and 250 parts of deionized waters are stirred and solution ph are adjusted to 2.5.Add 50 part of 0.4 mol/
L Fe3+Alkaline solution is slowly added dropwise after precursor solution, 2 h of reaction, system pH is risen to 3.5, then by system temperature liter
To 45 DEG C and react 12 h.Fully washing, filtering after reaction terminates, obtains loading Fe3+Collagenous fibres（Fe3+-CF）.
By Fe3+- CF is well mixed with 250 parts of deionized waters, adds 50 part of 0.4 mol/L Ni2+Precursor solution, reaction
Alkaline solution is slowly added dropwise after 2 h, system pH is risen to 7.0 in 4 h, temperature of reaction system is then risen to 45 DEG C and anti-
Answer 6 h.Fully washing, filtering after reaction terminates, obtains loading Fe after drying3+And Ni2+Collagenous fibres（Fe3+-Ni2+-CF）.
Under vacuum conditions, by Fe3+-Ni2+- CF with 8 DEG C/min heating rate from room temperature to 300 DEG C and be incubated 1
H, 600 DEG C are then warming up under air atmosphere and 3 h are incubated, you can carbon/nickel ferrite based magnetic loaded nano-composite fiber is obtained.
The carbon of gained/nickel ferrite based magnetic loaded nano-composite fiber is assembled into battery, tests forthright again on charge-discharge tester
Can, its performance is as shown in Figure 6.
Embodiment 3
5 parts of collagenous fibres are stirred with 100 parts of deionized waters, regulation solution ph to 1.8.Add 50 part of 0.2 mol/L
Fe3+Alkaline solution is slowly added dropwise after precursor solution, 2 h of reaction, system pH is risen to 3.8 in 4 h.Then regulation reaction
System temperature is to 35 DEG C and reacts 6 h, and fully washing, filtering after reaction terminates obtains loading Fe3+Collagenous fibres（Fe3+-
CF）.
By Fe3+- CF is well mixed with 150 parts of deionized waters, adds 50 part of 0.3 mol/L Ni2+Precursor solution, reaction
Alkaline solution is slowly added dropwise after 2 h, system pH is risen to 6.0 in 4 h, then temperature of reaction system is to 50 DEG C and reacts for regulation
12 h.Fully washing, filtering after reaction terminates, obtains loading Fe after drying3+And Ni2+Collagenous fibres（Fe3+-Ni2+-CF）.
Under vacuum conditions, by Fe3+-Ni2+- CF is with 10 DEG C/min heating rate from room temperature is to 300 DEG C and protects
3 h of temperature, 700 DEG C are then warming up under air atmosphere and 3 h are incubated, you can carbon/nickel ferrite based magnetic loaded nano-composite fiber is obtained.
The carbon of gained/nickel ferrite based magnetic loaded nano-composite fiber negative material is assembled into battery, tested on charge-discharge test instrument
Cycle performance, its performance is as shown in Figure 7.
Embodiment 5
5 parts of collagenous fibres are stirred with 350 parts of deionized waters, regulation solution ph to 2.5.Add 50 part of 0.6 mol/
LFe3+Alkaline solution is slowly added dropwise after precursor solution, 2 h of reaction, system pH is risen to 3.5 in 4 h, then by system temperature
Degree is warming up to 50 DEG C and reacts 9 h.Fully washing, filtering after reaction terminates, obtains loading Fe3+Collagenous fibres（Fe3+-CF）.
By Fe3+- CF is well mixed with 400 parts of deionized waters, adds 50 part of 0.4 mol/LNi2+Ion precursor solution,
Alkaline solution is slowly added dropwise after reacting 2 h, system pH is risen to 6.0 in 4 h, temperature of reaction system is then warming up to 50 DEG C
And react 12 h.Fully washing, filtering after reaction terminates, obtains loading Fe after drying3+And Ni2+Collagenous fibres（Fe3+-Ni2+-
CF）.
Under vacuum conditions, by Fe3+-Ni2+- CF is with 15 DEG C/min heating rate from room temperature is to 300 DEG C and protects
1 h of temperature, is then warming up to 500 DEG C and is incubated 3 h, you can obtain carbon/nickel ferrite based magnetic loaded nano-composite fiber in air atmosphere.
The carbon of gained/nickel ferrite based magnetic loaded nano-composite fiber is assembled into battery, the test loop performance on charge-discharge test instrument,
Its performance is as shown in Figure 8.
Embodiment 6
5 parts of collagenous fibres are stirred with 200 parts of deionized waters, regulation solution ph to 2.2.Add 50 part of 0.4 mol/
LFe3+Alkaline solution is slowly added dropwise after precursor solution, 3 h of reaction, system pH is risen to 4.0 in 2 h, then by system temperature
Degree is warming up to 40 DEG C and reacts 12 h.Fully washing, filtering after reaction terminates, obtains loading Fe3+Collagenous fibres（Fe3+-
CF）.
By Fe3+- CF is well mixed with 200 parts of deionized waters, adds 50 part of 0.4 mol/LNi2+Ion precursor solution,
Alkaline solution is slowly added dropwise after reacting 2 h, system pH is risen to 6.5 in 2 h, temperature of reaction system is then warming up to 40
DEG C and react 6 h.Fully washing, filtering after reaction terminates, obtains loading Fe after drying3+And Ni2+Collagenous fibres（Fe3+-Ni2 +-CF）.
Under vacuum conditions, by Fe3+-Ni2+- CF is with 5 DEG C/min heating rate from room temperature is to 300 DEG C and is incubated
1 h, is then warming up to 600 DEG C and is incubated 3 h, you can obtain carbon/nickel ferrite based magnetic loaded nano-composite fiber in air atmosphere.
Gained carbon/nickel ferrite based magnetic loaded nano-composite fiber is assembled into battery, in 0.5 A g-1Current density under circulation 10 enclose
Test result afterwards is as shown in Figure 9.
Gained carbon/nickel ferrite based magnetic loaded nano-composite fiber is assembled into battery, in 1.0 A g-1Current density under circulation 10 enclose
Test result afterwards is as shown in Figure 10.
Claims (9)
1. a kind of carbon/nickel ferrite based magnetic loaded nanometer composite fiber material, its be using materials with hide glue fibril as template, by the use of molysite, nickel salt as
Metal oxide precursor is coated to materials with hide glue fibril template, then is made by high-temperature calcination.
2. a kind of preparation method of carbon/nickel ferrite based magnetic loaded nanometer composite fiber material, it is characterised in that：This method comprises the following steps：
（1）Collagenous fibres and deionized water are stirred and pH value of solution are adjusted to 1.5-2.5, Fe is then added3+Presoma is molten
Alkaline solution is slowly added dropwise after liquid, reaction 2-6 h, system pH is risen to 3.0-6.0 in 4 h, then by system reaction temperature
Rise to 25-60 DEG C and react 4-12 h, fully washing, filtering after reaction terminates obtains loading Fe3+Collagenous fibres（Fe3+-
CF）；
（2）By the collagenous fibres of above-mentioned load iron ion（Fe3+-CF）It is well mixed with deionized water, adds Ni2+Presoma is molten
Alkaline solution is slowly added dropwise after liquid, reaction 2-6 h, system pH is risen to 5.0-7.5 in 4 h；Then by reaction system liter
Temperature is to 25-60 DEG C and reacts 4-12 h, and fully washing, filtering after reaction terminates obtains loading Fe after drying3+And Ni2+Collagen
Fiber（Fe3+-Ni2+-CF）；
（3）Under vacuum conditions, by Fe3+-Ni2+- CF is with 1-20 DEG C/min heating rate from room temperature is to 300 DEG C and is incubated
1-3 h, 500-700 DEG C is then warming up in air atmosphere and 2-6 h are kept, and produces carbon/nickel ferrite based magnetic loaded nano-composite fiber material
Material.
3. the preparation method according to claim 2, it is characterised in that：The collagenous fibres are livestock animals skin or corner
Routinely process hides pretreating process removes the collagenous fibres or purchased in market for being ground into that length is 0.1-5.0 mm after interfibrillar substance to material
Commodity collagenous fibres.
4. the preparation method according to claim 2, it is characterised in that：The Fe3+Precursor solution is ferric sulfate, nitric acid
The solution that any one concentration being configured to deionized water in iron or iron chloride is 0.2mol/L-0.6mol/L.
5. the preparation method according to claim 2, it is characterised in that：The Ni2+Precursor solution is nickel sulfate, nitric acid
The solution that any one concentration being configured to deionized water in nickel or nickel chloride is 0.2 mol/L-0.4 mol/L.
6. the preparation method according to claim 2, it is characterised in that：The alkaline solution is sodium acid carbonate, sodium carbonate
Or ammoniacal liquor.
7. a kind of carbon/nickel ferrite based magnetic loaded nanometer composite fiber material as obtained by claim 2-6 any one methods describeds.
8. the initial activation processing method of carbon/nickel ferrite based magnetic loaded nanometer composite fiber material pair as described in claim 1 or 7：Using 0.3
A/g-2.0 A/g high current density carries out initial activation processing.
9. processing method according to claim 8, it is characterised in that：Preceding 10 discharge and recharges are used in initial activation processing
Activation current density is 0.5 A/g-1.0 A/g.
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