CN110416495A - A kind of CNF- metallic compound absolute electrode material and its preparation method and application - Google Patents
A kind of CNF- metallic compound absolute electrode material and its preparation method and application Download PDFInfo
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Abstract
The invention belongs to field of lithium ion battery, a kind of CNF- metallic compound absolute electrode material and its preparation method and application is disclosed.By dissolving metal salts in dimethylformamide, adds polyacrylonitrile powder and be uniformly mixed, obtain blend spinning liquid;By carrying out spinning under high voltage electrostatic field, polyacrylonitrile-metal salt compound nonwoven cloth is obtained;It is soaked in the methanol solution of organic ligand again, using the metal ion of dissolution and the strong coordination of organic ligand, is formed uniformly one layer of organic metal framework material on polyacrylonitrile fibre surface, obtains polyacrylonitrile-metal salt@organic metal framework;It places it in tube furnace again, pre-oxidizes polyacrylonitrile at 280 DEG C, then the high temperature cabonization under hydrogen/argon gas mixed atmosphere, finally aoxidized, vulcanized or selenization again, obtain the CNF- metallic compound absolute electrode material of sheet.It is cut into electrode slice, is directly used in lithium ion battery as cathode.
Description
Technical field
The invention belongs to field of lithium ion battery, in particular to a kind of CNF- metallic compound absolute electrode material and its system
Preparation Method and application.
Background technique
Lithium ion battery receives significant attention in recent years as the energy storage device with superior prospect.Meanwhile with new energy
The fast development of source automobile and intelligent portable equipment, mentions the energy storage device with higher reversible capacity and long circulation life
Urgent demand is gone out.However, commercial graphite electrode has lower theoretical capacity (372mAhg at present-1), far below big rule
Mould energy applies required specification.Metallic compound sill is a kind of very promising active material, is constantly subjected to researcher
Extensive concern.Such as Co3O4Material can theoretically provide the capacity of up to conventional commercial graphite electrode three times.But
Since there are biggish volume change, metal oxygens/sulphur/selenides base electrode in poorly conductive itself and charge-discharge process
In practical applications by very big obstruction.
Summary of the invention
In order to overcome shortcoming and deficiency existing in the prior art, the primary purpose of the present invention is that providing a kind of CNF- gold
Belong to the preparation method of compound absolute electrode material.
It is independent another object of the present invention is to provide a kind of CNF- metallic compound that above-mentioned preparation method is prepared
Electrode material;The active material has superior high rate performance and long circulating stability energy.
A further object of the present invention is to provide a kind of applications of above-mentioned CNF- metallic compound absolute electrode material.
The object of the invention is achieved through the following technical solutions:
A kind of preparation method of CNF- metallic compound absolute electrode material, comprising the following steps: by metal salt and poly- third
Alkene nitrile blend spinning obtains non-woven fabrics, then is soaked in the methanol solution of organic ligand, one layer of organic metal of in-situ preparation
Frame (MOF);Polyacrylonitrile is pre-oxidized at 280 DEG C it, be carbonized under the mixed atmosphere of hydrogen and argon gas, most again
It aoxidized, vulcanized or selenizing obtains pellet electrode material, as CNF- metallic compound absolute electrode material again afterwards.
The preparation method of above-mentioned CNF- metallic compound absolute electrode material a kind of specifically includes the following steps:
(1) under magnetic agitation by dissolving metal salts in dimethylformamide, after being completely dissolved be added polyacrylonitrile powder,
Stirring makes to be uniformly mixed, and obtains spinning solution;
(2) by spinning solution in 10ml syringe, using 20G stainless steel syringe needle, spinning parameter is set, carries out spinning;
60 DEG C of drying in an oven are removed after spinning, obtain polyacrylonitrile-metal salt non-woven fabrics;
(3) organic ligand is dissolved in methanol, polyacrylonitrile-metal salt non-woven fabrics obtained by step (2) is soaked in it
In, one layer of organic metal framework MOF is formed in fiber surface, is dried at 60 DEG C in an oven after taking-up, obtains polyacrylonitrile-gold
Belong to salt@MOF non-woven fabrics.
(4) polyacrylonitrile-metal salt@MOF non-woven fabrics is placed in ceramic boat, heats up in tube furnace, first makes poly- third
Alkene nitrile-metal salt@MOF non-woven fabrics pre-oxidizes in air at 280 DEG C, is then carbonized, obtains in hydrogen-argon-mixed body high temperature
CNF- metal fiber cloth is finally aoxidized at 300 DEG C, is vulcanized or selenization, makes the metal in carbon nano-fiber
Grain becomes metallic compound;It is cooled to room temperature, obtains CNF- metallic compound absolute electrode material.
Metal salt described in step (1) is ferric nitrate, ferric sulfate, nickel nitrate, nickel sulfate, cobalt nitrate, cobalt acetate, sulfuric acid
One or more of cobalt, zinc nitrate, zinc acetate, zinc sulfate;The mass ratio of the polyacrylonitrile and metal salt is 1:1~1:3,
The solid content of polyacrylonitrile is between 8%~16% in the spinning solution.
Spinning parameter described in step (2) are as follows: spinning spacing 16cm~22mm, spinning voltage 12kV~18kV, injection
Device fltting speed 0.3ml/h~1ml/h receives mode as aluminium foil reception.
Organic ligand described in step (3) is trimesic acid, terephthalic acid (TPA), methylimidazole, one in benzimidazole
Kind or more;The solution concentration that the organic ligand is dissolved in methanol formation is 0.05mol/L~0.15mol/L;The immersion
Time is 4h~for 24 hours.
Hydrogen-argon-mixed body described in step (4) includes the H of percentage by volume 5%2With the Ar of percentage by volume 95%;Institute
The heating rate stated is 2 DEG C/min~5 DEG C/min.
The temperature of high temperature cabonization described in step (4) is between 550 DEG C~900 DEG C;The time of the pre-oxidation is 2
~6h;The time of the high temperature cabonization is 2~4h;The time of the oxidation, vulcanization or selenization is 1~3h.
Oxidation described in step (4) is directly to carry out in air, and the sulphur source used that vulcanizes is thiocarbamide, the selenium
Changing the selenium source used is selenium powder.
A kind of CNF- metallic compound absolute electrode material being prepared according to above-mentioned preparation method.
Application of the above-mentioned CNF- metallic compound absolute electrode material in lithium ion battery negative material, the application
It is by CNF- metallic compound absolute electrode material cutting into battery pole piece size, is applied to lithium ion battery directly as cathode
On.
Compared with prior art, the present invention has the following advantages and beneficial effects:
(1) CNF- metallic compound absolute electrode material prepared by the present invention, by mixing metal salt and polyacrylonitrile
Electrostatic spinning, being then immersed in the methanol solution of organic ligand makes fiber surface coat one layer of organic metal framework material, then
Make at 280 DEG C polyacrylonitrile fibre pre-oxidize and high temperature and hydrogen-argon-mixed atmosphere under carbonization and 300 DEG C at oxygen/sulphur/selenium
Change, obtains CNF- metallic compound fiber cloth.So as to so that metal oxygen/sulphur/selenides particle size reduction to nanometer ruler
Degree, and it is uniformly embedded into it among carbon nano-fiber derived from polyacrylonitrile;Due to the cladding of carbon material, can delay well
The volume expansion that occurs in charge and discharge process of solution metal oxide particle, thus improve battery long circulation life and
High rate performance.It is needed with traditional negative electrode active material and PVDF, conductive black is configured to slurry re-coating on copper foil, drying,
Then it is cut into pole piece difference, CNF- metal oxygen/sulphur/selenizing fiber cloth obtained can be cut into pole piece size by the present invention,
It is directly used as the cathode of lithium ion battery, is used as a kind of absolute electrode.Therefore the present invention have good development prospect and
Application market, so this CNF- metallic compound absolute electrode material and preparation method thereof is of great significance.
(2) CNF- metal oxygen/sulphur/selenides electrode material prepared by the present invention have fiber cloth-like structure, fiber it
Between connection of taking for electronics provide transportation route, effectively raise the efficiency of transmission of electronics or ion, be large current discharge with reducing
When capacity attenuation, fiber surface thin carbon layer as derived from MOF can be further improved stability of material and electric conductivity, makes material
High rate performance and cycle performance to being obviously improved.
(3) present invention has preparation process simple, and equipment is easy to operate, and production cost is low, environment friendly and pollution-free, nonhazardous etc.
Feature, reaction temperature and time are easier to control, it is easy to accomplish industrialized production.
Detailed description of the invention
Fig. 1 is material SEM photograph prepared by embodiment 1, is followed successively by metal salt from left to right, from top to bottom and polymer is mixed
Spin fiber, the blend fibre with MOF and final electrode material.
Fig. 2 is material SEM photograph prepared by embodiment 2, is followed successively by metal salt from left to right, from top to bottom and polymer is mixed
Spin fiber, the blend fibre with MOF and final electrode material.
Fig. 3 is material SEM photograph prepared by embodiment 3, is followed successively by metal salt from left to right, from top to bottom and polymer is mixed
Spin fiber, the blend fibre with MOF and final electrode material.
Fig. 4 is the high rate performance test chart of material prepared by embodiment 1.
Fig. 5 is the cycle performance test chart and high rate performance test chart of material prepared by embodiment 2, wherein (a) is circulation
Performance test figure (b) is high rate performance test chart.
Fig. 6 is the cycle performance test chart of material prepared by embodiment 3.
Fig. 7 is the photo of material prepared by embodiment 3.
Specific embodiment
Below with reference to embodiment, the present invention is described in further detail, and embodiments of the present invention are not limited thereto.
Embodiment 1:
(1) by 1g cobalt acetate (Co (Ac) under magnetic agitation2·4H2) and 2g nickel nitrate (Ni (NO O3)2·6H2O it) is dissolved in
In 15g dimethylformamide (DMF), 2.2g polyacrylonitrile (PAN) powder is added after being completely dissolved, stirring for 24 hours, obtains polypropylene
The uniform blend spinning liquid that nitrile solid content is 11%.
(2) by blend spinning liquid in 10ml syringe, using the stainless steel syringe needle of 20G, spinning parameter is set: being promoted
Speed 1ml/h, voltage 14kV, spinning distance 20cm, are received using aluminium foil;60 DEG C of drying in an oven are removed after spinning,
Obtain PAN- metal salt non-woven fabrics, as metal salt and polyblend fibre.
(3) 4g terephthalic acid (TPA) is dissolved in and forms the solution that concentration is 0.15mol/L in 300ml methanol, by step (2)
Obtained PAN- metal salt non-woven fabrics is soaked in wherein for 24 hours, due to the coordination of cobalt ions, nickel ion and terephthalic acid (TPA),
One layer of MOF can be formed in fiber surface, be dried at 60 DEG C in an oven after taking-up, obtain PAN- metal salt@MOF non-woven fabrics,
As with the blend fibre of MOF.
(4) the PAN- metal salt@MOF non-woven fabrics that step (3) obtains is placed in ceramic boat, according to 5 in tube furnace
DEG C/heating rate of min rises to 280 DEG C, 6h is kept the temperature, PAN is pre-oxidized in air, increases the stabilization of polymer fiber
Property, make it that still there is certain toughness in the carbonized.Then with same heating rate, in hydrogen-argon-mixed body (H25%/Ar
95%) it is carbonized at 900 DEG C in, keeps the temperature 2h.Finally 300 DEG C of thermal oxides in air keep the temperature 2h, are cooled to room temperature and obtain final electricity
Pole material, as CNF- metal oxide (CNF-Co3O4/ ZnO) fiber cloth material.
The SEM photograph of metal salt and polyblend fibre, the blend fibre with MOF and final electrode material is as schemed
Shown in 1.
CNF- metal-oxide fiber cloth material obtained is cut into battery pole piece size, directly as independent negative
Pole uses lithium piece as anode, using 2400 diaphragm of Celgard, assembles lithium ion battery using 2032 formula button cell structures,
Carry out charge-discharge test.
As shown in figure 4, the electrode material is in 0.1,0.2,0.5,1,2 and 4Ag-1Initial discharge capacity be 935,523,
466,396,373 and 285mAh g-1, coulombic efficiency can achieve 98%, it is meant that the composite material has splendid electrification
Learn invertibity.
Embodiment 2:
(1) by 2.3g cobalt acetate (Co (Ac) under magnetic agitation2·4H2) and 1g zinc acetate (Zn (Ac) O2·2H2O it) dissolves
In 30g dimethylformamide (DMF), 3.3g polyacrylonitrile (PAN) powder is added after being completely dissolved, is stirred in 60 DEG C of oil baths
For 24 hours, the uniform blend spinning liquid that polyacrylonitrile solid content is 9% is obtained.
(2) by blend spinning liquid in 10ml syringe, using the stainless steel syringe needle of 20G, spinning parameter is set: being promoted
Speed 0.6ml/h, voltage 15kV, spinning distance 20cm, are received using aluminium foil.60 DEG C of bakings in an oven are removed after spinning
It is dry, obtain PAN- metal salt non-woven fabrics, as metal salt and polyblend fibre.
(3) 3g methylimidazole is dissolved in and forms the solution that concentration is 0.05mol/L in 100ml methanol, by step (2)
Obtained PAN- metal salt non-woven fabrics is soaked in wherein 4h, can due to the coordination of cobalt ions, zinc ion and methylimidazole
To form one layer of MOF in fiber surface, is dried at 60 DEG C in an oven after taking-up, obtain PAN- metal salt@MOF non-woven fabrics, i.e.,
For the blend fibre with MOF.
(4) the PAN- metal salt@MOF non-woven fabrics that step (3) obtains is placed in ceramic boat, according to 5 in tube furnace
DEG C/heating rate of min rises to 280 DEG C, 2h is kept the temperature, PAN is pre-oxidized in air, increases the stabilization of polymer fiber
Property, make it that still there is certain toughness in the carbonized.Then with 2 DEG C/min heating rate, in hydrogen-argon-mixed body (H25%/
Ar 95%) in be carbonized at 800 DEG C, keep the temperature 3h.Finally in N2In 300 DEG C vulcanized with thiocarbamide, keep the temperature 1h, be cooled to room temperature
Obtain final electrode material, as CNF- metal sulfide (CNF-Co3S4/ ZnS) fiber cloth material.
The SEM photograph of metal salt and polyblend fibre, the blend fibre with MOF and final electrode material is as schemed
Shown in 2.
By CNF- metal sulfide (CNF-Co obtained3S4/ ZnS) fiber cloth material is cut into battery pole piece size, directly
As independent cathode, lithium piece is used to be assembled as anode using 2400 diaphragm of Celgard using 2032 formula button cell structures
Lithium ion battery carries out charge-discharge test.
As shown in figure 5, using 1Ag-1Current density to composite material carry out cycle performance charge-discharge test, composite material
After 600 charge and discharge cycles capacity remain at 307mAhg-1High discharge capacity, illustrate that the composite material has
High capacity and stability.
As shown in figure 5, the electrode material is in 0.1,0.2,0.5,1,2 and 4Ag-1Initial discharge capacity be 1021,
592,489,386,298 and 183mAh g-1, coulombic efficiency can achieve 98%, it is meant that the composite material has splendid
Electrochemical reversibility.
Embodiment 3:
(1) by 2g cobalt acetate (Co (Ac) under magnetic agitation2·4H2O it) is dissolved in 15g dimethylformamide (DMF), it is complete
3g polyacrylonitrile (PAN) powder is added after fully dissolved, is stirred for 24 hours in 60 DEG C of oil baths, obtaining polyacrylonitrile solid content is 15%
Uniform blend spinning liquid.
(2) by blend spinning liquid in 10ml syringe, using the stainless steel syringe needle of 20G, spinning parameter is set: being promoted
Speed 0.3ml/h, voltage 13kV, spinning distance 22cm, are received using aluminium foil.60 DEG C of bakings in an oven are removed after spinning
It is dry, obtain PAN- metal salt non-woven fabrics, as metal salt and polyblend fibre.
(3) 10g methylimidazole is dissolved in and forms the solution that concentration is 0.1mol/L in 200ml methanol, by step (2)
Obtained PAN- metal salt non-woven fabrics is soaked in wherein for 24 hours, can be in fibre due to the coordination of cobalt ions and methylimidazole
Dimension table face forms one layer of MOF, dries at 60 DEG C in an oven after taking-up, obtains PAN- metal salt@MOF non-woven fabrics, as with
The blend fibre of MOF.
(4) the PAN- metal salt@MOF non-woven fabrics that step (3) obtains is placed in ceramic boat, according to 5 in tube furnace
DEG C/heating rate of min rises to 280 DEG C, 2h is kept the temperature, PAN is pre-oxidized in air, increases the stabilization of polymer fiber
Property, make it that still there is certain toughness in the carbonized.Then with the heating rate of 3 DEG C/min, in hydrogen-argon-mixed body (H2
5%/Ar 95%) in be carbonized at 550 DEG C, keep the temperature 3h.Finally in N2In 300 DEG C mixed with selenium powder carry out selenizing, keep the temperature 3h, it is cold
But it arrives room temperature and obtains final electrode material, as CNF- metal selenide (CNF-CoSe) fiber cloth material, photo figure such as Fig. 7 institute
Show.
The SEM photograph of metal salt and polyblend fibre, the blend fibre with MOF and final electrode material is as schemed
Shown in 3.
CNF- metal selenide (CNF-CoSe) fiber cloth material obtained is cut into battery pole piece size, directly as
Independent cathode uses lithium piece as anode, using 2400 diaphragm of Celgard, using 2032 formula button cell structures assembling lithium from
Sub- battery carries out charge-discharge test.
As shown in fig. 6, the electrode material is in 0.1,0.2,0.5,1,2 and 4Ag-1Initial discharge capacity be 1202,
754,647,550,439 and 256mAh g-1, coulombic efficiency can achieve 98%, it is meant that the composite material has splendid
Electrochemical reversibility.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention,
It should be equivalent substitute mode, be included within the scope of the present invention.
Claims (10)
1. a kind of preparation method of CNF- metallic compound absolute electrode material, it is characterised in that the following steps are included: by metal
Salt and polyacrylonitrile blend spinning obtain non-woven fabrics, then are soaked in the methanol solution of organic ligand, one layer of in-situ preparation
Organic metal framework (MOF);Pre-oxidize polyacrylonitrile at 280 DEG C it again, in the mixed atmosphere of hydrogen and argon gas
Lower carbonization is finally aoxidized again, is vulcanized or selenizing obtains pellet electrode material, as CNF- metallic compound absolute electrode
Material.
2. a kind of preparation method of CNF- metallic compound absolute electrode material according to claim 1, it is characterised in that
Specifically includes the following steps:
(1) under magnetic agitation by dissolving metal salts in dimethylformamide, after being completely dissolved be added polyacrylonitrile powder, stirring
Make to be uniformly mixed, obtains spinning solution;
(2) by spinning solution in 10ml syringe, using 20G stainless steel syringe needle, spinning parameter is set, carries out spinning;Spinning
After remove in an oven 60 DEG C drying, obtain polyacrylonitrile-metal salt non-woven fabrics;
(3) organic ligand is dissolved in methanol, polyacrylonitrile-metal salt non-woven fabrics obtained by step (2) is soaked in wherein, In
Fiber surface forms one layer of organic metal framework MOF, dries at 60 DEG C in an oven after taking-up, obtains polyacrylonitrile-metal salt@
MOF non-woven fabrics.
(4) polyacrylonitrile-metal salt@MOF non-woven fabrics is placed in ceramic boat, heats up in tube furnace, first makes polyacrylonitrile-
Metal salt@MOF non-woven fabrics pre-oxidizes in air at 280 DEG C, is then carbonized in hydrogen-argon-mixed body high temperature, obtains CNF- gold
Belong to fiber cloth, is finally aoxidized, vulcanized or selenization at 300 DEG C, become the metallic particles in carbon nano-fiber
Metallic compound;It is cooled to room temperature, obtains CNF- metallic compound absolute electrode material.
3. preparation method according to claim 2, it is characterised in that: metal salt described in step (1) is ferric nitrate, sulfuric acid
One or more of iron, nickel nitrate, nickel sulfate, cobalt nitrate, cobalt acetate, cobaltous sulfate, zinc nitrate, zinc acetate, zinc sulfate;Described
The mass ratio of polyacrylonitrile and metal salt is 1:1~1:3, in the spinning solution solid content of polyacrylonitrile be 8%~16% it
Between.
4. preparation method according to claim 2, it is characterised in that: spinning parameter described in step (2) are as follows: between spinning
Away from 16cm~22mm, spinning voltage 12kV~18kV, syringe fltting speed 0.3ml/h~1ml/h, reception mode connects for aluminium foil
It receives.
5. preparation method according to claim 2, it is characterised in that: organic ligand described in step (3) be trimesic acid,
One or more of terephthalic acid (TPA), methylimidazole, benzimidazole;The solution that the organic ligand is dissolved in methanol formation is dense
Degree is 0.05mol/L~0.15mol/L;The soaking time is 4h~for 24 hours.
6. preparation method according to claim 2, it is characterised in that: hydrogen-argon-mixed body described in step (4) includes body
The H of product percentage 5%2With the Ar of percentage by volume 95%;The heating rate is 2 DEG C/min~5 DEG C/min.
7. preparation method according to claim 2, it is characterised in that: the temperature of high temperature cabonization described in step (4) is
Between 550 DEG C~900 DEG C;The time of the pre-oxidation is 2~6h;The time of the high temperature cabonization is 2~4h;The oxygen
The time of change, vulcanization or selenization is 1~3h.
8. preparation method according to claim 2, it is characterised in that: oxidation described in step (4) is directly in air
Middle progress, the sulphur source used that vulcanizes is thiocarbamide, and the selenium source that the selenizing uses is selenium powder.
9. a kind of CNF- metallic compound absolute electrode material that preparation method according to claim 1 or 2 is prepared.
10. CNF- metallic compound absolute electrode material according to claim 9 is in lithium ion battery negative material
Using, it is characterised in that: the application is by CNF- metallic compound absolute electrode material cutting into battery pole piece size, directly
It is applied on lithium ion battery as cathode.
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