CN110380032A - A kind of preparation method of transition metal oxide/carbon nano-fiber negative electrode material - Google Patents
A kind of preparation method of transition metal oxide/carbon nano-fiber negative electrode material Download PDFInfo
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Abstract
The invention discloses a kind of transition metal oxide/carbon nano-fiber negative electrode material preparation methods.The following steps are included: NaClO is added and adjusts between pH to 7.5~12, the oxidation reaction under NaOH Titration Conditions adds thereafter NaBH by being added in deionized water and stirring evenly without the biomass macromolecule of crosslinkable functionality, TEMPO, NaBr4Reduction, washing；Deionized water dispersion is added in well-oxygenated product, obtains nanofiber dispersion liquid I；Or deionized water is added in the biomass macromolecule with crosslinkable functionality and disperses to obtain nanofiber dispersion liquid II；The aqueous solution of soluble transition metal salt is added in a kind of above-mentioned nanofiber dispersion liquid, 12~72h is stood, then takes out hydrogel, after organic solvent is replaced, be dried to obtain aeroge；It is placed in tube furnace, under inert gas conditions 500~2000 DEG C of carbonizations, by carbothermic reduction reaction, obtains TMOs/C composite aerogel.
Description
Technical field
The invention belongs to technical field of composite materials, and in particular to a kind of transition metal oxide/carbon nano-fiber cathode
The preparation method of material.
Background technique
With the gradual depletion of fossil energy, energy storage becomes 21 century highly important research field.Numerous
Energy storage device in, lithium ion battery is had received widespread attention with its safety and stability.Since traditional graphite material is managed
By lower (the 372mA hg of specific capacity-1), it is extremely urgent to develop new negative electrode material.Transition metal oxide has theoretical specific volume
Measure height (926mA hg-1), rich reserves, it is cheap the advantages that, therefore receive the favor of Many researchers.However, transition
Metal oxide is easy to produce Volumetric expansion and agglomeration during deintercalate lithium ions, and its electric conductivity compared with
It is low, cause cyclical stability and high rate performance poor, limits the use in negative electrode of lithium ion battery.It is negative in order to alleviate these
Face is rung, and researchers generally use nanosizing or transition metal oxide is improved four oxygen with the compound method of carbon-based material
Change cyclical stability of the three-iron in lithium ion battery.
108428877 A of CN uses Fe3+It is lazy using ironic citrate chelate as presoma with the mode of ironic citrate complexing
High temperature cabonization has obtained Fe under property atmosphere3O4/ C composite negative pole material.It to be formed preferably since this kind of carbon-based material cannot overlap
Porous network structure, so affect further increasing for negative electrode material specific capacity.
104157832 A of CN, as biological template and carbon matrix precursor, is reacted using natural kawo fiber using micro- test tube
Method, in hollow tubular fiber wall loading Fe3O4Quantum dot prepares lithium ion battery negative material.Although this kind of method preparation
Preferable network structure is gone out, but natural kawo fiber is relatively large in diameter, Specific surface area can not be formed, limit composite wood
Material specific capacity further increases.
Summary of the invention
It is an object of that present invention to provide a kind of novel porous filamentous nanocarbon load TMOs nanoparticle negative electrode materials
Preparation method, gained TMOs/C aeroge have superelevation specific capacity and good cyclical stability.
In order to achieve the above objectives, as follows using technical solution:
A kind of preparation method of transition metal oxide/carbon nano-fiber negative electrode material, comprising the following steps:
1) it will be added in deionized water and stir without the biomass macromolecule of crosslinkable functionality, TEMPO, NaBr
It is even, NaClO is then added and adjusts between pH to 7.5~12, the oxidation reaction under NaOH Titration Conditions adds thereafter NaBH4
Reaction residual matter, is washed after the reaction was completed；Deionized water dispersion is added in well-oxygenated product, obtains nanofiber dispersion liquid
Ⅰ；
Or the biomass macromolecule with crosslinkable functionality is directly added into deionized water dispersion, obtain nanofiber point
Dispersion liquid II；
2) aqueous solution of soluble transition metal salt is added in a kind of above-mentioned nanofiber dispersion liquid, standing 12~
72h then takes out hydrogel, after organic solvent is replaced, is placed in drying in freeze drier or supercritical dryer, obtains
Aeroge；
3) gained aeroge is placed in tube furnace, under inert gas conditions 500~2000 DEG C of carbonizations, also by carbon heat
Original reaction, obtains TMOs/C composite aerogel.
According to the above scheme, TEMPO in step 1, without the biomass macromolecule of crosslinkable functionality, NaBr, NaClO,
NaBH4Mass ratio is 1:(5~100): (5~100): (5~100): (5~100).
According to the above scheme, dispersing mode is mechanical stirring, high-pressure homogeneous processing, ultrasonic cell disintegration instrument, ball milling in step 1
One of processing, high speed water shock treatment etc. are a variety of.
It according to the above scheme, is that chitin, wood pulp, cotton are short without the biomass macromolecule of crosslinkable functionality in step 1
Suede, stalk fibre, flaxen fiber, bagasse, reed, nut case fibre, any one in citrus fruit fibres；It is described to have cross-linking official
Can the biomass macromolecule of group be sodium alginate, xanthan gum, any one in pectin.
According to the above scheme, step 1 gained nanofiber dispersion liquid concentration is between 0.1~1.5wt%, wherein nanofiber
Length is in 200nm~5 μm, and diameter is between 1nm~30nm.
According to the above scheme, soluble transition metal salt is cobalt chloride, iron chloride, manganese chloride, cobalt nitrate, nitric acid in step 2
One of transition metal ions salt such as iron, manganese nitrate.
According to the above scheme, the concentration of soluble transition metal saline solution is between 1mM~1M in step 2, with Nanowire
The mass ratio of dispersion liquid is tieed up in 1:(1~100) between.
According to the above scheme, organic solvent is methanol, ethyl alcohol, the tert-butyl alcohol, any one or mixing in acetone in step 2,
The volume ratio of hydrogel and organic solvent is in 1:(1~100) between.
According to the above scheme, the temperature of carbothermic reduction reaction is 500~2000 DEG C in step 3, and soaking time is 0.5~10h.
The present invention is using biomass macromolecule surface with functional groups and nanometer fibrous special knots such as a large amount of carboxyls
Structure, by ionomer plastic, then high temperature pyrolysis, design form a kind of unique porous carbon fiber load TMOs nanoparticle
The aerogel structure of son greatly improves the specific capacity of material while keeping cyclical stability.
The beneficial effects of the present invention are:
The preferred surface of the present invention has carboxylate functionality and draw ratio is biggish cellulose nano-fibrous, utilizes iron ion
Crosslinking, acquisition hole enriches and the tridimensional network of high-specific surface area can be obtained by high temperature pyrolysis and carbothermic reduction reaction
Fe is loaded to porous filamentous nanocarbon3O4Nano particle structure.The structure can not only alleviate Fe3O4Nanoparticle is in removal lithium embedded
The Volumetric expansion and agglomeration occurred during ion improves the cyclical stability of negative electrode material, and is lithium ion
Transmission with electronics provides more channels, improves the mobility of lithium ion and electronics, so that material has the reversible of superelevation
Specific capacity.
The ionic cross-linking that the present invention uses is easy to operate, is easy to control, and the preparation for TMOs/C composite material provides
A kind of thinking.
Detailed description of the invention
Fig. 1: Fe prepared by example 13O4The electrochemistry cycle performance figure of/C aerogel composite.
Specific embodiment
Following embodiment further illustrates technical solution of the present invention, but not as limiting the scope of the invention.
Embodiment 1
A kind of transition metal oxide/carbon nanofiber aerogel composite preparation method, its step are as follows:
1) it prepares OCNF dispersion liquid: taking the cotton linters cellulose of dry weight 3g, 0.03g TEMPO, 0.03g NaBr addition is gone
In ionized water, magnetic agitation dissolution.Thereafter 3g NaClO is added, under 0.1M NaOH Titration Conditions, maintaining pH is 8.5, reaction
It filters, and is washed with deionized to neutrality after 4h, deionized water dispersion is added after dry, simultaneously ultrasound obtains mechanical stirring
The OCNF dispersion liquid of 1.0wt%.
2) OCNF-Fe is prepared3+Aeroge: it takes the above-mentioned OCNF dispersion liquid of 10ml to pour into small beaker, the Fe of 0.1M is added
(NO3)3Solution crosslinking obtains OCNF-Fe3+Hydrogel.It is freeze-dried at -50 DEG C after being replaced 3 times with the tert-butyl alcohol of 100ml,
Obtain OCNF-Fe3+Aeroge.
3) Fe is prepared3O4/ C aeroge: by above-mentioned OCNF-Fe3+Aeroge is placed in tube furnace, under 650 DEG C, Ar atmosphere
4h is kept the temperature, Fe is obtained3O4/ C composite aerogel.
Nano-cellulose after carbonization, which mutually overlaps, forms hole network structure abundant, Fe3O4Nanoparticle can uniformly divide
Cloth is wound in tridimensional network by carbon nano-fiber.This structure not only increases active material and electrolyte
Contact area is conducive to the mobility for improving lithium ion and electronics；And utilize the elasticity and package of carbon-based material, it is suppressed that
Fe3O4The Volumetric expansion and agglomeration of nanoparticle.
By Fe3O4/ C composite and PVDF, acetylene black are added NMP according to the ratio of 8:1:1 and are mixed into slurry, uniformly apply
It overlaying on copper foil, is washed into electrode slice with sheet-punching machine after drying, be to electrode with lithium piece, 2400 film of Celgard is diaphragm,
LiPF6/ DMC+DEC+EC (volume ratio 1:1:1) is electrolyte, assembles button half-cell, using blue electricity CT2001A test macro,
In 1Ag-1Current density under carry out charge and discharge cycles test.As shown in Figure 1, the button cell specific capacity reaches 1290mAh g-1,
Cyclical stability increases simultaneously, and cycle-index is up to 200 times.
Embodiment 2
A kind of transition metal oxide/carbon nanofiber aerogel composite preparation method, its step are as follows:
1) it prepares OCNF dispersion liquid: taking the chitin of dry weight 3g, deionized water is added in 0.03g TEMPO, 0.03g NaBr
In, magnetic agitation dissolution.Thereafter 3g NaClO is added, under 0.15M NaOH Titration Conditions, maintaining pH is 8.5, after reacting 4h
It filters, and is washed with deionized to neutrality, deionized water dispersion is added after dry, simultaneously ultrasound obtains 1.0wt% to mechanical stirring
OCNF dispersion liquid.
2) OCNF-Fe is prepared3+Aeroge: it takes the above-mentioned OCNF dispersion liquid of 10ml to pour into small beaker, the Fe of 0.1M is added
(NO3)3Solution crosslinking obtains OCNF-Fe3+Hydrogel.It is freeze-dried at -50 DEG C after being replaced 3 times with the tert-butyl alcohol of 100ml,
Obtain OCNF-Fe3+Aeroge.
3) Fe is prepared3O4/ C aeroge: by above-mentioned OCNF-Fe3+Aeroge is placed in tube furnace, under 650 DEG C, Ar atmosphere
4h is kept the temperature, Fe is obtained3O4/ C composite aerogel.
According to assembled battery described in example 1 and tested.Its cyclical stability is similar to example 1,1A g-1Electric current is close
Under degree, after 200 circulations, reversible specific capacity still has 1000mA h g-1。
Embodiment 3
A kind of transition metal oxide/carbon nanofiber aerogel composite preparation method, its step are as follows:
1) it prepares OCNF dispersion liquid: taking the stalk fibre of dry weight 3g, deionization is added in 0.03g TEMPO, 0.03g NaBr
In water, magnetic agitation dissolution.Thereafter 3g NaClO is added, under 0.2M NaOH Titration Conditions, maintaining pH is 8.5, after reacting 4h
It filters, and is washed with deionized to neutrality, deionized water dispersion is added after dry, simultaneously ultrasound obtains 1.0wt% to mechanical stirring
OCNF dispersion liquid.
2) OCNF-Fe is prepared3+Aeroge: it takes the above-mentioned OCNF dispersion liquid of 10ml to pour into small beaker, the Fe of 0.1M is added
(NO3)3Solution crosslinking obtains OCNF-Fe3+Hydrogel.It is freeze-dried at -50 DEG C after being replaced 3 times with the tert-butyl alcohol of 100ml,
Obtain OCNF-Fe3+Aeroge.
3) Fe is prepared3O4/ C aeroge: by above-mentioned OCNF-Fe3+Aeroge is placed in tube furnace, under 650 DEG C, Ar atmosphere
4h is kept the temperature, Fe is obtained3O4/ C composite aerogel.
According to assembled battery described in example 1 and tested.Its cyclical stability is similar to example 1,1A g-1Electric current is close
Under degree, after 200 circulations, reversible specific capacity still has 800mA h g-1。
Embodiment 4
A kind of transition metal oxide/carbon nanofiber aerogel composite preparation method, its step are as follows:
1) it prepares OCNF dispersion liquid: taking the bagasse of dry weight 3g, deionized water is added in 0.03g TEMPO, 0.03g NaBr
In, magnetic agitation dissolution.Thereafter 3g NaClO is added, under 0.1M NaOH Titration Conditions, maintaining pH is 8.5, is taken out after reacting 4h
Filter, and be washed with deionized to neutrality, deionized water dispersion is added after dry, simultaneously ultrasound obtains 1.0wt%'s to mechanical stirring
OCNF dispersion liquid.
2) OCNF-Fe is prepared3+Aeroge: it takes the above-mentioned OCNF dispersion liquid of 10ml to pour into small beaker, the Fe of 0.1M is added
(NO3)3Solution crosslinking obtains OCNF-Fe3+Hydrogel.It is freeze-dried at -50 DEG C after being replaced 3 times with the tert-butyl alcohol of 100ml,
Obtain OCNF-Fe3+Aeroge.
3) Fe is prepared3O4/ C aeroge: by above-mentioned OCNF-Fe3+Aeroge is placed in tube furnace, under 950 DEG C, Ar atmosphere
4h is kept the temperature, Fe is obtained3O4/ C composite aerogel.
According to assembled battery described in example 1 and tested.Its cyclical stability is similar to example 1,1A g-1Electric current is close
Under degree, after 200 circulations, reversible specific capacity still has 900mA h g-1。
Embodiment 5
A kind of transition metal oxide/carbon nanofiber aerogel composite preparation method, its step are as follows:
1) prepare OCNF dispersion liquid: taking the nut case fibre of dry weight 3g, 0.03g TEMPO, 0.03g NaBr addition go from
In sub- water, magnetic agitation dissolution.Thereafter 3g NaClO is added, under 0.1M NaOH Titration Conditions, maintaining pH is 8.5, reacts 4h
After filter, and be washed with deionized to neutrality, be added deionized water dispersion after dry, mechanical stirring and ultrasound obtains
The OCNF dispersion liquid of 1.0wt%.
2) OCNF-Fe is prepared3+Aeroge: it takes the above-mentioned OCNF dispersion liquid of 10ml to pour into small beaker, the Fe of 0.1M is added
(NO3)3Solution crosslinking obtains OCNF-Fe3+Hydrogel.It is freeze-dried at -50 DEG C after being replaced 3 times with the tert-butyl alcohol of 100ml,
Obtain OCNF-Fe3+Aeroge.
3) Fe is prepared3O4/ C aeroge: by above-mentioned OCNF-Fe3+Aeroge is placed in tube furnace, in 1250 DEG C, Ar atmosphere
Lower heat preservation 4h, obtains Fe3O4/ C composite aerogel.
According to assembled battery described in example 1 and tested.Its cyclical stability is similar to example 1,1A g-1Electric current is close
Under degree, after 200 circulations, reversible specific capacity still has 1000mA h g-1。
Embodiment 6
A kind of transition metal oxide/carbon nanofiber aerogel composite preparation method, its step are as follows:
1) it prepares OCNF dispersion liquid: taking the citrus fruit fibres of dry weight 3g, deionization is added in 0.03g TEMPO, 0.03g NaBr
In water, magnetic agitation dissolution.Thereafter 3g NaClO is added, under 0.1M NaOH Titration Conditions, maintaining pH is 8.5, after reacting 4h
It filters, and is washed with deionized to neutrality, deionized water dispersion is added after dry, simultaneously ultrasound obtains 1.0wt% to mechanical stirring
OCNF dispersion liquid.
2) OCNF-Co is prepared3+Aeroge: it takes the above-mentioned OCNF dispersion liquid of 10ml to pour into small beaker, the Co of 0.1M is added
(NO3)3Solution crosslinking obtains OCNF-Co3+Hydrogel.It is freeze-dried at -50 DEG C after being replaced 3 times with the tert-butyl alcohol of 100ml,
Obtain OCNF-Co3+Aeroge.
3) Co is prepared3O4/ C aeroge: by above-mentioned OCNF-Co3+Aeroge is placed in tube furnace, under 650 DEG C, Ar atmosphere
4h is kept the temperature, Co is obtained3O4/ C composite aerogel.
According to assembled battery described in example 1 and tested.Its cyclical stability is similar to example 1,1A g-1Electric current is close
Under degree, after 200 circulations, reversible specific capacity still has 1100mA h g-1。
Embodiment 7
A kind of transition metal oxide/carbon nanofiber aerogel composite preparation method, its step are as follows:
1) it prepares OCS dispersion liquid: taking the chitin of dry weight 3g, deionized water is added in 0.03g TEMPO, 0.03g NaBr
In, magnetic agitation dissolution.Thereafter 3g NaClO is added, under 0.1M NaOH Titration Conditions, maintaining pH is 8.5, is taken out after reacting 4h
Filter, and be washed with deionized to neutrality, deionized water dispersion is added after dry, simultaneously ultrasound obtains 1.0wt%'s to mechanical stirring
OCS dispersion liquid.
2) OCS-Fe is prepared3+Aeroge: it takes the above-mentioned OCS dispersion liquid of 10ml to pour into small beaker, the Fe of 0.1M is added
(NO3)3Solution crosslinking obtains OSC-Fe3+Hydrogel.It is freeze-dried, obtains at -50 DEG C after being replaced 3 times with the tert-butyl alcohol of 100ml
OCS-Fe3+Aeroge.
3) Fe is prepared3O4/ C aeroge: by above-mentioned OCS-Fe3+Aeroge is placed in tube furnace, under 650 DEG C, Ar atmosphere
4h is kept the temperature, Fe is obtained3O4/ C composite aerogel.
According to assembled battery described in example 1 and tested.Its cyclical stability is similar to example 1,1A g-1Electric current is close
Under degree, after 200 circulations, reversible specific capacity still has 1200mA h g-1。
Embodiment 8
A kind of transition metal oxide/carbon nanofiber aerogel composite preparation method, its step are as follows:
1) it prepares SA dispersion liquid: taking 0.5g sodium alginate to be dissolved in deionized water, obtain 2.0wt%SA dispersion liquid.
2) SA-Fe is prepared3+Aeroge: it takes the above-mentioned SA dispersion liquid of 10ml to pour into small beaker, the Fe (NO of 0.1M is added3)3
Solution crosslinking obtains SA-Fe3+Hydrogel.It is freeze-dried at -50 DEG C after being replaced 3 times with the tert-butyl alcohol of 100ml, obtains SA-Fe3+
Aeroge.
3) Fe is prepared3O4/ C aeroge: by above-mentioned SA-Fe3+Aeroge is placed in tube furnace, is protected under 650 DEG C, Ar atmosphere
Warm 4h, obtains Fe3O4/ C composite aerogel.
According to assembled battery described in example 1 and tested.Its cyclical stability is similar to example 1,1A g-1Electric current is close
Under degree, after 200 circulations, reversible specific capacity still has 1200mA h g-1。
Embodiment 9
A kind of transition metal oxide/carbon nanofiber aerogel composite preparation method, its step are as follows:
1) it prepares XTG dispersion liquid: taking 0.5g xanthan gum to be dissolved in deionized water, obtain 2.0wt%XTG dispersion liquid.
2) XTG-Fe is prepared3+Aeroge: it takes the above-mentioned XTG dispersion liquid of 10ml to pour into small beaker, the Fe of 0.1M is added
(NO3)3Solution crosslinking obtains XTG-Fe3+Hydrogel.It is freeze-dried, obtains at -50 DEG C after being replaced 3 times with the tert-butyl alcohol of 100ml
XTG-Fe3+Aeroge.
3) Fe is prepared3O4/ C aeroge: by above-mentioned XTG-Fe3+Aeroge is placed in tube furnace, under 650 DEG C, Ar atmosphere
4h is kept the temperature, Fe is obtained3O4/ C composite aerogel.
According to assembled battery described in example 1 and tested.Its cyclical stability is similar to example 1,1A g-1Electric current is close
Under degree, after 200 circulations, reversible specific capacity still has 1200mA h g-1。
Claims (9)
1. a kind of transition metal oxide/carbon nano-fiber negative electrode material preparation method, it is characterised in that the following steps are included:
1) it will be added in deionized water and stir evenly without the biomass macromolecule of crosslinkable functionality, TEMPO, NaBr, so
NaClO is added afterwards to adjust between pH to 7.5~12, the oxidation reaction under NaOH Titration Conditions adds thereafter NaBH4It reacts more
Excess matter, is washed after the reaction was completed；Deionized water dispersion is added in well-oxygenated product, obtains nanofiber dispersion liquid I；
Or the biomass macromolecule with crosslinkable functionality is directly added into deionized water dispersion, obtain nanofiber dispersion liquid
Ⅱ；
2) aqueous solution of soluble transition metal salt is added in a kind of above-mentioned nanofiber dispersion liquid, stands 12~72h, with
After take out hydrogel, after organic solvent is replaced, be placed in freeze drier or supercritical dryer dry, obtain airsetting
Glue；
3) gained aeroge is placed in tube furnace, 500~2000 DEG C of carbonizations, anti-by carbon thermal reduction under inert gas conditions
It answers, obtains TMOs/C composite aerogel.
2. transition metal oxide as described in claim 1/carbon nano-fiber negative electrode material preparation method, it is characterised in that step
TEMPO, biomass macromolecule, NaBr, NaClO, NaBH without crosslinkable functionality in rapid 14Mass ratio be 1:(5~
100): (5~100): (5~100): (5~100).
3. transition metal oxide as described in claim 1/carbon nano-fiber negative electrode material preparation method, it is characterised in that step
Dispersing mode is mechanical stirring, high-pressure homogeneous processing, ultrasonic cell disintegration instrument, ball-milling treatment, high speed water shock treatment etc. in rapid 1
One of or it is a variety of.
4. transition metal oxide as described in claim 1/carbon nano-fiber negative electrode material preparation method, it is characterised in that step
It without the biomass macromolecule of crosslinkable functionality is chitin in rapid 1, wood pulp, cotton linter, stalk fibre, flaxen fiber, sweet
Bagasse, reed, nut case fibre, any one in citrus fruit fibres；The biomass macromolecule with crosslinkable functionality is
Sodium alginate, xanthan gum, any one in pectin.
5. transition metal oxide as described in claim 1/carbon nano-fiber negative electrode material preparation method, it is characterised in that step
Rapid 1 gained nanofiber dispersion liquid concentration is between 0.1~1.5wt%, and wherein nanofiber length is in 200nm~5 μm, diameter
Between 1nm~30nm.
6. transition metal oxide as described in claim 1/carbon nano-fiber negative electrode material preparation method, it is characterised in that step
In rapid 2 soluble transition metal salt be the transition metal such as cobalt chloride, iron chloride, manganese chloride, cobalt nitrate, ferric nitrate, manganese nitrate from
One of alite.
7. transition metal oxide as described in claim 1/carbon nano-fiber negative electrode material preparation method, it is characterised in that step
The concentration of soluble transition metal saline solution is between 1mM~1M in rapid 2, and the mass ratio with nanofiber dispersion liquid is in 1:(1
~100) between.
8. transition metal oxide as described in claim 1/carbon nano-fiber negative electrode material preparation method, it is characterised in that step
Organic solvent is methanol, ethyl alcohol, the tert-butyl alcohol, any one or mixing in acetone, the volume of hydrogel and organic solvent in rapid 2
Than in 1:(1~100) between.
9. transition metal oxide as described in claim 1/carbon nano-fiber negative electrode material preparation method, it is characterised in that step
The temperature of carbothermic reduction reaction is 500~2000 DEG C in rapid 3, and soaking time is 0.5~10h.
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