CN105702945B - Liquid phase in-situ reducing-cold quenching preparation method and applications of composite negative pole material - Google Patents
Liquid phase in-situ reducing-cold quenching preparation method and applications of composite negative pole material Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/387—Tin or alloys based on tin
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- H—ELECTRICITY
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—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
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention discloses the liquid phase in-situ reducing cold quenching preparation methods of composite negative pole material, using graphite as raw material, graphite oxide is prepared using modified Hummers methods, by graphite oxide ultrasonic disperse in tin ion, in the solution of antimony ion and cobalt ions, pass through fabricated in situ technique, using titration reduction method, in-situ preparation SnSbCo alloys while graphite oxide is reduced into graphene by reducing agent, and liquid nitrogen is added and carries out cold quenching processing so that graphene securely wraps up Nanoalloy particle, argon gas protective condition, after calcining at a certain temperature, SnSbCo/ graphene composite negative poles are prepared.Compared with the existing technology, preparation method of the invention effectively improves material preparation efficiency and structural stability；The sodium-ion battery that material using the present invention assembles has high charge-discharge specific capacity, good high rate performance and cycle performance.
Description
Technical field
The present invention relates to field of new energy technologies more particularly to the liquid phase of composite negative pole material in-situ reducing-cold quenching to prepare
Method and its application.
Background technology
Currently, the storage and conversion of the energy have become the major issue for restricting world economy sustainable development.Lithium-ion electric
Since it has, high voltage, high-energy-density, self discharge be small and the advantages such as have extended cycle life in pond, is obtained in portable electrical power applications
Tremendous development.Be all I main group sodium ion and lithium ion property there are many similarity, although sodium-ion battery study into
It postpones slowly, but with the gradually development of accumulation power supply and electric vehicle, global lithium resource will be unable to effectively meet power lithium
The great demand of ion battery increases battery cost to will further raise price with lithium associated materials, it is final hinder it is new
The development of energy industry.On the contrary, sodium-ion battery because its raw material rich reserves (4~5 orders of magnitude higher than lithium), it is cheap,
The features such as friendly to environment green and be increasingly becoming research hotspot, be widely regarded as the ideal of next-generation energy storage and power battery
Selection.
The study found that with sodium ion metallic alloying react can occur for tri- kinds of metals of Pb, Sn, Sb.Since Pb belongs to heavy metal
Material, pollution is not widely studied greatly, and Na15Sn4、Na3Sb alloys can provide up to 847mAh/g, 660mAh/g's respectively
Theoretical specific capacity is the anode material of lithium-ion battery of potential high power capacity.The researchers such as Xiao report sodium-ion battery
SnSb/C negative materials, the charge and discharge cycles after 125 weeks under the current density of 55mA/g, specific capacity stablize in 525mAh/g and
Coulombic efficiency reach 97% (L.Xiao, Y.Cao, J.Xiao, et al.Chemical Communications, 2012,48:
3321-3323).The specific capacity that metal Sn electrodes are recycled in the first two is up to 460mAh/g, but to third cycle, specific capacity
163mAh/g can be decayed to.Equally there is quick special capacity fade in metal Sb electrodes, after 20 cycles, capacity rapidly from
342mAh/g decays to 100mAh/g or less.It can be seen that two kinds of electrodes all have Na very poor recyclability.Sn/C electrodes are passing through
After 13 cycles, specific capacity falls below the 20% of initial capacity, and Sb/C electrodes recycle all very stable, reversible specific volume at first 30
Amount is reduced to 397mAh/g from 494mAh/g, and capacity retention ratio reaches 80.4%, but after being recycled at 50, capacity is decayed rapidly
To 100mAh/g.The researchers such as Lin are prepared for sodium-ion battery Sn using surfactant auxiliary wet chemistry method0.9Cu0.1It is negative
Pole material, under the current density of 169mA/g, charge and discharge cycles after 100 weeks, stablize in 420mAh/g, capacity retention ratio by capacity
It is 97%, shows high circulation stability, and pure Sn negative materials is under the conditions of identical charge and discharge, nanoscale Sn and micron order
The capacity of Sn only remains 250mAh/g and 66mAh/g (Y.M.Lin, Paul R.Abel, A.Gupta, et al.ACS respectively
Appl.Mater.Interfaces,2013,5,8273-8277)。
In order to solve this problem, the researchers such as Yui propose incorporation Co, can make the electrochemistry of SnCo bianry alloys
It can be superior to simple substance Sn, same cycle 30 weeks, the capacity of SnCo is maintained at 300mAh/g or so, and simple substance Sn negative materials are basic
Loss of activity (Y.Yui, Y.Ono, M.Hayashi, et al.Journal of the Electrochemical Society,
2015,162:A3098-A3102).But the chemical property of the bianry alloy cannot still meet existing requirement.
Graphene is widely used in electricity because having due to surface area is big, conductivity is superior and good mechanical strength the characteristics of
The study on the modification of pole material.Possess height defect by the graphene that chemistry redox obtains, improve its conductivity instead,
For example graphite oxide (GO) is prepared using modified Hummers methods, recycle electronation removal oxygen-containing functional group to obtain oxygen reduction
Graphite alkene (rGO), because it has high conductivity (16000S m-1) and equally attract attention.It is similar with graphene, rGO performances
Go out high resiliency, high conductivity and start gradually to be applied to sodium-ion battery as base material.Nithya passes through chemical reduction method
It is prepared for Sb/rGO, is recycled 50 weeks under the current density of 131mA/g, capacity maintains 598mAh/g, and rGO makes material as substrate
Expect structure more firm (C.Nithya, S.Gopukumar.J.Mater.Chem.A., 2014,2:10516-10525).Thus,
It is necessary to sodium-ion battery carry out composite negative pole material further research, with improve the charging and discharging capacity of electrode material with
And improve its cycle performance.
Invention content
The present invention is to solve the deficiencies in the prior art, provides one kind with graphene (rGO) for base material, two
It introduces the third Elements C o on the basis of first alloy SnSb, prepares with high charge-discharge specific capacity, good high rate performance
SnSbCo/ graphene composite negative poles.
The purpose of the present invention is what is realized by following technical side：
Liquid phase in-situ reducing-cold quenching preparation method of composite negative pole material, includes the following steps：
(1) pink salt, antimonic salt and salt solubility are obtained into mixing salt solution in solvent；By graphite oxide ultrasonic disperse in
In mixing salt solution；
(2) reducing agent is dissolved in solvent, obtains reducing solution；Reducing solution is added dropwise to the salt-mixture of step (1)
In solution and continue to stir；After completion of dropwise addition, turbid solution is obtained, turbid solution is stirred to react in 50-80 DEG C；
(3) after the quick cold quenching of liquid nitrogen being added into the turbid solution of step (2), vacuum filtration is freeze-dried after repeatedly washing
Or vacuum drying, obtain SnSbCo/ graphene precursor powders；
(4) under inert gas shielding, precursor powder is warming up to constant temperature at 200-450 DEG C with certain heating rate and is forged
It burns, obtains SnSbCo/ graphene composite negative poles.
Compared with the existing technology, the present invention is preparing the same of graphene by fabricated in situ technique using titration reduction method
When formed nanometer SnSbCo multi-nary alloy particles, effectively improve material preparation efficiency；Liquid nitrogen rapid cooling is added, passes through cold quenching work
Skill makes flake graphite alkene firmly wrap up SnSbCo alloying pellets, effectively improves the structural stability of electrode material.
Further, in step (1) described mixing salt solution, a concentration of 0.01-0.5mol/L of pink salt, antimonic salt it is a concentration of
0.01-0.5mol/L, a concentration of 0.001-0.05mol/L of cobalt salt；Tin ion, antimony ion, cobalt ions molar ratio be 1:1:
0.1。
Further, the volume that liquid nitrogen is added in step (3) and the volume ratio of turbid solution in step (2) are 0.5:1-2:1.
Further, in the mixing salt solution that step (1) obtains, a concentration of 0.5-2mg/mL of graphite oxide.
Further, in step (2) reducing solution a concentration of 0.1-2mol/L；The reducing agent be hydrazine hydrate, ammonium hydroxide,
NaBH4With one kind in HI.
Further, power ultrasonic in step (1) is 100-200W；Rate of addition in step (2) is 1-3mL/min；
Mixing speed in step (2) is 200-1000r/min.
Further, the pink salt is stannous chloride or stannous acetate, and the antimonic salt is antimony chloride or antimony acetate, the cobalt salt
For cobalt chloride or cobalt acetate；Solvent described in step (1) and step (2) is any one or the two in deionized water, ethyl alcohol
Mixed solvent.
The present invention also provides a kind of preparation methods of sodium-ion battery, include the following steps：SnSbCo/ graphenes are answered
It is (50-80) that negative material, conductive black, binder, which are closed, according to mass ratio：(30-10)：(20-10) is coated in after mixing
On copper foil, vacuum drying is sliced after roll-in, obtains circular electric pole piece；By electrode slice, metallic sodium piece, electrolyte be assembled into sodium from
Sub- battery.The SnSbCo/ graphene composite negative poles are the SnSbCo/ graphite that the above-mentioned any means referred to are prepared
Alkene composite negative pole material.
Compared with the existing technology, the sodium-ion battery that material using the present invention assembles has high charge-discharge specific volume
Amount, good high rate performance and cycle performance.
Further, the binder is one kind in LA132, polyvinylidene fluoride or CMC binders；The coating thickness
It is 60-120 μm；The thickness of the roll-in is 35-90 μm.
The present invention also provides a kind of sodium-ion battery, including circular electric pole piece, metallic sodium piece and electrolyte, the circles
Electrode slice is (50-80) according to mass ratio by SnSbCo/ graphene composite negative poles, conductive black, binder：(30-10)：
(20-10) is coated on copper foil after mixing, and vacuum drying, slice obtains after roll-in, the SnSbCo/ graphenes Compound Negative
Pole material is the SnSbCo/ graphene composite negative poles that the above-mentioned any means referred to are prepared.
Compared with the existing technology, sodium-ion battery of the invention SnSbCo/ graphene composite negatives material using the present invention
Material so that sodium-ion battery has high charge-discharge specific capacity, good high rate performance and cycle performance.
In order to better understand and implement, the invention will now be described in detail with reference to the accompanying drawings.
Description of the drawings
Fig. 1 is the XRD spectrum for the SnSbCo/ graphene composite negative poles that embodiment 1 is prepared.
Fig. 2 is the SEM figures for the SnSbCo/ graphene composite negative poles that embodiment 1 is prepared.
Fig. 3 is the TEM figures for the SnSbCo/ graphene composite negative poles that embodiment 1 is prepared.
Fig. 4 is the XRD spectrum for the SnSbCo/ graphene composite negative poles that comparative example is prepared.
Fig. 5 is the SEM figures for the SnSbCo/ graphene composite negative poles that comparative example is prepared.
Fig. 6 is the TEM figures for the SnSbCo/ graphene composite negative poles that comparative example is prepared.
Fig. 7 is the constant current of the sodium-ion battery for the SnSbCo/ graphene composite negative poles assembling that embodiment 1 is prepared
Charge-discharge performance figure.
Fig. 8 is the sodium-ion battery for the SnSbCo/ graphene composite negative poles assembling that comparative example is prepared
Constant current charge-discharge performance map.
Specific implementation mode
Liquid phase in-situ reducing-cold quenching preparation method of composite negative pole material disclosed by the invention, includes the following steps：
(1) pink salt, antimonic salt and salt solubility are obtained into mixing salt solution in solvent；By graphite oxide ultrasonic disperse in
In mixing salt solution；
(2) reducing agent is dissolved in solvent, obtains reducing solution；Reducing solution is added dropwise to the salt-mixture of step (1)
In solution and continue to stir；After completion of dropwise addition, turbid solution is obtained, turbid solution is stirred to react 1-12h in 50-80 DEG C；
(3) after the quick cold quenching of liquid nitrogen being added into the turbid solution of step (2), vacuum filtration carries out vacuum after repeatedly washing
Dry or freeze-drying, obtains SnSbCo/ graphene precursor powders；
(4) under inert gas shielding, precursor powder is warming up to calcining at constant temperature at 200-450 DEG C with certain heating rate
2-6h obtains SnSbCo/ graphene composite negative poles.
Wherein, in the mixing salt solution of step (1), a concentration of 0.01-0.5mol/L of pink salt, antimonic salt it is a concentration of
0.01-0.5mol/L, a concentration of 0.001-0.05mol/L of cobalt salt；Tin ion, antimony ion, cobalt ions molar ratio be 1:1:
0.1；In the mixing salt solution that step (1) obtains, a concentration of 0.5-2mg/mL of graphite oxide.
Ultrasonic power is 100-200W in step (1).
Reducing agent described in step (2) is hydrazine hydrate, ammonium hydroxide, NaBH4With any one in HI；The reducing agent it is dense
Degree is 0.1-2mol/L.
Solvent described in step (1) and step (2) be deionized water, any one or two kinds of mixing in ethyl alcohol it is molten
Agent.
The volume of liquid nitrogen and the volume ratio of turbid solution in step (2) are 0.5 in step (3):1-2:1.
Vacuum drying temperature is 50-80 DEG C in step (3), time 10-24h.
Freeze-drying temperature is -45 DEG C, pressure 0.37Pa, time 40-70h in step (3).
Heating rate described in step (4) is 1-10 DEG C/min.
Embodiment 1
In the present embodiment, liquid phase in-situ reducing-cold quenching preparation method of composite negative pole material includes the following steps：
(1) SnCl of 0.001mol is weighed2, the SbCl of 0.001mol3, the CoCl of 0.0001mol2·6H2O and
0.0032mol C6H5Na3O7·2H2O, and be dissolved completely in the deionized water of 100mL, obtain mixing salt solution.By 0.1g oxygen
Graphite ultrasonic disperse is in mixing salt solution, wherein the ultrasonic power is 150W.
(2) the reducing agent NaBH of 0.1mol/L is adjusted with NaOH4Aqueous solution makes its pH >=12；By the 300mL's of pH >=12
The NaBH of 0.1mol/L4Aqueous solution is slowly added dropwise into the mixing salt solution in step (1) and continues to stir；After completion of dropwise addition,
Turbid solution is obtained, turbid solution is heated into 5h at 80 DEG C.Wherein NaBH4The rate of addition of aqueous solution is 2mL/min, mixing speed
For 800r/min.
(3) it is 0.5 according to the volume ratio of turbid solution in liquid nitrogen volume and step (2):1, add into the turbid solution of step (2)
After entering 200mL liquid nitrogen, vacuum filtration, and obtained sediment will be filtered successively with after deionized water, absolute ethyl alcohol repeatedly washing
It is freeze-dried, obtains SnSbCo/ graphene precursor powders；Then precursor powder is placed in tube furnace, in argon gas
Under protective condition, 300 DEG C of calcining at constant temperature 4h obtain SnSbCo/ graphene composite negative poles.Wherein, the condition of freeze-drying
For 0.37Pa and -45 DEG C, sublimation drying 40h；The heating rate of tube furnace is 2 DEG C/min.
Hydrazine hydrate, ammonium hydroxide or HI also can be selected in reducing agent described in step (2).
In the present embodiment, the preparation method of graphite oxide is as follows：By 2g natural flake graphites and 2g sodium nitrate be added to
It pre-cools into the concentrated sulfuric acid of 0 DEG C of 110mL, 15-30min is persistently stirred under condition of ice bath；Under condition of ice bath slowly
12g potassium permanganate is added, stirs 20-40min, is then continuously stirred at room temperature 48h；184mL deionized waters are slowly added to, are stirred
Mix 150min；The deionized water and 50mL hydrogenperoxide steam generators stirring 25min that 560mL temperature is 50-60 DEG C are added, with dilute salt
Freeze-drying obtains graphite oxide after sour repeatedly centrifuge washing.The method for preparing graphite oxide is not limited to this, other can make
The standby method for obtaining graphite oxide.
The present embodiment additionally provides a kind of sodium ion electricity prepared using the SnSbCo/ graphene composite negative poles
Pond.Specifically, by SnSbCo/ graphene composite negative poles, conductive black, binder according to mass ratio be 5:3:2 mixing are equal
After even, it is 100 μm of thin uniform layer that thickness is applied as on copper foil, and the dry 12h at 80 DEG C of vacuum is cut into circular electric after roll-in
Pole piece.By circular electric pole piece, the NaClO of metallic sodium piece, 1mol/L4/ EC/DEC electrolyte is assembled into sodium-ion battery.In this reality
It applies in example, the binder is CMC binders, and the thickness after the thin layer roll-in is 70 μm, the diameter of the circular electric pole piece
For 18mm.
When preparing sodium-ion battery, LA132 binders or polyvinylidene fluoride binder also can be selected in the binder.
Embodiment 2
In the present embodiment, liquid phase in-situ reducing-cold quenching preparation method of composite negative pole material includes the following steps：
(1) stannous acetate of 0.02mol, the antimony acetate of 0.02mol, the cobalt acetate and 0.032mol of 0.002mol are weighed
C6H5Na3O7·2H2O, and be dissolved completely in the deionized water of 100mL, obtain mixing salt solution.0.05g graphite oxides are surpassed
Sound is scattered in mixing salt solution, wherein the ultrasonic power is 100W.
(2) the reducing agent NaBH of 1mol/L is adjusted with NaOH4Aqueous solution makes its pH >=12；By the 300mL's of pH >=12
The NaBH of 1mol/L4Aqueous solution is slowly added dropwise into the mixing salt solution in step (1) and continues to stir；After completion of dropwise addition, obtain
To turbid solution, turbid solution is heated into 12h at 50 DEG C.Wherein NaBH4The rate of addition of aqueous solution is 1mL/min, mixing speed
For 200r/min.
(3) it is 1 according to the volume ratio of turbid solution in liquid nitrogen volume and step (2):1, it is added into the turbid solution of step (2)
After 400mL liquid nitrogen, vacuum filtration, and will filter obtained sediment repeatedly washed with deionized water, absolute ethyl alcohol successively it is laggard
Row vacuum drying, obtains SnSbCo/ graphene precursor powders；Then precursor powder is placed in tube furnace, is protected in argon gas
Under the conditions of shield, 450 DEG C of calcining at constant temperature 2h obtain SnSbCo/ graphene composite negative poles.Wherein, vacuum drying temperature is
50-80 DEG C, drying time 10-24h；The heating rate of tube furnace is 10 DEG C/min.
Hydrazine hydrate, ammonium hydroxide or HI also can be selected in reducing agent described in step (2).
The present embodiment additionally provides a kind of sodium ion electricity prepared using the SnSbCo/ graphene composite negative poles
Pond.Specifically, by SnSbCo/ graphene composite negative poles, conductive black, binder according to mass ratio be 8:1:1 mixing is equal
After even, it is 120 μm of thin uniform layer that thickness is applied as on copper foil, at 50 DEG C of vacuum it is dry for 24 hours, circular electric is cut into after roll-in
Pole piece.The NaClO4/EC/DEC electrolyte of circular electric pole piece, metallic sodium piece, 1mol/L are assembled into sodium-ion battery.In this reality
It applies in example, the binder is CMC binders, and the thickness after the thin layer roll-in is 35 μm, the diameter of the circular electric pole piece
For 18mm.
When preparing sodium-ion battery, LA132 binders or polyvinylidene fluoride binder also can be selected in the binder.
Embodiment 3
In the present embodiment, liquid phase in-situ reducing-cold quenching preparation method of composite negative pole material includes the following steps：
(1) SnCl of 0.05mol is weighed2, the SbCl of 0.05mol3, the CoCl of 0.005mol2·6H2O and 0.032mol
C6H5Na3O7·2H2O, and be dissolved completely in the deionized water of 100mL, obtain mixing salt solution.By 0.2g graphite oxide ultrasounds
It is scattered in mixing salt solution, wherein the ultrasonic power is 200W.
(2) the reducing agent NaBH of 2mol/L is adjusted with NaOH4Aqueous solution makes its pH >=12；By the 300mL's of pH >=12
The NaBH of 2mol/L4Aqueous solution is slowly added dropwise into the mixing salt solution in step (1) and continues to stir；After completion of dropwise addition, obtain
To turbid solution, turbid solution is heated into 1h at 80 DEG C.Wherein NaBH4The rate of addition of aqueous solution is 3mL/min, and mixing speed is
1000r/min。
(3) it is 2 according to the volume ratio of turbid solution in liquid nitrogen volume and step (2):1, it is added into the turbid solution of step (2)
After 800mL liquid nitrogen, vacuum filtration, and will filter obtained sediment repeatedly washed with deionized water, absolute ethyl alcohol successively it is laggard
Row freeze-drying, obtains SnSbCo/ graphene precursor powders；Then precursor powder is placed in tube furnace, is protected in argon gas
Under the conditions of shield, 200 DEG C of calcining at constant temperature 6h obtain SnSbCo/ graphene composite negative poles.Wherein, the condition of freeze-drying is
0.37Pa and -45 DEG C, sublimation drying 70h；The heating rate of tube furnace is 1 DEG C/min.
Hydrazine hydrate, ammonium hydroxide or HI also can be selected in reducing agent described in step (2).
The present embodiment additionally provides a kind of sodium ion electricity prepared using the SnSbCo/ graphene composite negative poles
Pond.Specifically, by SnSbCo/ graphene composite negative poles, conductive black, binder according to mass ratio be 6:2:2 mixing are equal
After even, it is 60 μm of thin uniform layer that thickness is applied as on copper foil, and the dry 20h at 60 DEG C of vacuum is cut into circular electric after roll-in
Pole piece.By circular electric pole piece, the NaClO of metallic sodium piece, 1mol/L4/ EC/DEC electrolyte is assembled into sodium-ion battery.In this reality
It applies in example, the binder is CMC binders, and the thickness after the thin layer roll-in is 90 μm, the diameter of the circular electric pole piece
For 18mm.
When preparing sodium-ion battery, LA132 binders or polyvinylidene fluoride binder also can be selected in the binder.
Comparative example
The preparation method of SnSbCo/ graphene negative materials, includes the following steps：
(1) SnCl of 0.001mol is weighed2, the SbCl of 0.001mol3, the CoCl of 0.0001mol2·6H2O and
0.032mol C6H5Na3O7·2H2O, and be dissolved completely in the deionized water of 100mL, obtain mixing salt solution.By 0.05g oxygen
Graphite ultrasonic disperse is in mixing salt solution, wherein the ultrasonic power is 100W.
(2) NaBH of 0.1mol/L is adjusted with NaOH4Aqueous solution makes its pH >=12；By the 0.1mol/L's of pH >=12
NaBH4Aqueous solution is slowly added dropwise into the mixing salt solution in step (1) and continues to stir；After completion of dropwise addition, by mixed solution
5h is heated at 80 DEG C.Wherein NaBH4The rate of addition of aqueous solution is 2mL/min, mixing speed 800r/min.
(3) mixed solution is filtered by vacuum, and suction filtration is obtained into sediment and is repeatedly washed with deionized water, absolute ethyl alcohol successively
It is dried in vacuo after washing, obtains SnSbCo/ graphene precursor powders；Then precursor powder is placed in tube furnace,
Under argon gas protective condition, 300 DEG C of calcining at constant temperature 4h obtain SnSbCo/ graphene negative materials.Wherein, the heating speed of tube furnace
Rate is 2 DEG C/min.
A kind of sodium-ion battery prepared by the SnSbCo/ graphene negative materials prepared using comparative example.Specifically,
By SnSbCo/ grapheme materials, conductive black, binder according to mass ratio be 5:3:2 after mixing, is applied as on copper foil
Thin uniform layer, dry 12h, is cut into circular electric pole piece at 80 DEG C of vacuum after roll-in.By circular electric pole piece, metallic sodium piece, 1mol/
The NaClO of L4/ EC/DEC electrolyte is assembled into sodium-ion battery.In the present embodiment, the binder is CMC binders, institute
It is 70 μm to state the thickness after thin layer roll-in, a diameter of 18mm of the circular electric pole piece.
Measure of merit compares
It please refers to Fig.1 and Fig. 4, is the SnSbCo/ graphene Compound Negatives prepared by embodiment 1 and comparative example respectively
The XRD spectrum of pole material.The XRD spectrum of SnSbCo/ graphene composite negative poles prepared by embodiment 1 is close to 23 ° of diffraction
There are the diffraction maximums of graphene for the position at angle, and at the same time there are Sn-Sb, Co-Sb and Co-Sn alloy phases.And comparative example
The diffraction maximum of graphite oxide, surface NaBH are not present in the XRD spectrum of the SnSbCo/ graphene negative materials of preparation4It can fill
Divide reduction-oxidation graphite.The position of the diffraction maximum of main alloy phase Sn-Sb in SnSbCo/ graphene composite negative poles with
JCPDS standard cards (33-0118) match, and exist simultaneously Co-Sb and Co-Sn alloy phases.
It is the SnSbCo/ graphenes prepared by embodiment 1 and comparative example respectively please refer to Fig. 2-3 and 5-6
The SEM and TEM of composite negative pole material scheme.It is found that SnSbCo/ graphene composite negatives prepared by embodiment 1 from Fig. 2 and Fig. 3
Graphene content in material is more, can be good at wrapping up alloying pellet, effectively reduces the reunion of alloying pellet.And from Fig. 5
With Fig. 6 it is found that in SnSbCo/ graphene composite negative poles prepared by comparative example, graphene content is few, alloying pellet
Agglomeration is serious, cannot be effectively embedded into graphene sheet layer.
Use the sodium-ion battery that the SnSbCo/ graphene composite negative poles prepared by embodiment 1 assemble for simulation electricity
Pond 1 uses the sodium-ion battery that the SnSbCo/ graphene composite negative poles prepared by comparative example assemble for simulated battery
2。
The simulated battery 1 being prepared and simulated battery 2 are subjected to constant current charge-discharge test respectively, test condition is：Electricity
Current density is 100mA/g；Voltage is 0-2.5V.Fig. 7 and Fig. 8 is the charge-discharge cycle of simulated battery 1 and simulated battery 2 respectively
It can figure.As shown in Figure 7, for simulated battery 1 under the current density of 100mA/g, first discharge specific capacity is 998mAh/g, cycle 30
Secondary specific capacity is positively retained at 600mAh/g, shows higher specific capacity and good cycle performance.And as shown in Figure 8, simulation
Battery 2 is under the current density of 100mA/g, first discharge specific capacity 677mAh/g, and specific capacity is reduced to after recycling 30 times
464mAh/g, capacity is relatively low and attenuation trend is apparent.
The main reason for charge-discharge performance of simulated battery 2 is than 1 difference of simulated battery is implemented for the comparison that simulated battery 2 uses
SnSbCo/ graphene composite negative poles prepared by example, graphene content is few, and alloying pellet agglomeration is serious, cannot be effective
Embedded graphene sheet layer.
The SnSbCo/ graphene composite negative poles prepared using embodiment 2 equally keep material internal steady because liquid nitrogen is added
Solidity increases, but since the content of graphite oxide is reduced compared with Example 1, its specific capacity is made to increase but cyclical stability
It is not good enough, but still it is better than the performance of material in comparative example.
Liquid nitrogen is largely added compared with Example 1 in the SnSbCo/ graphene composite negative poles prepared using embodiment 3
Cold quenching is carried out, further graphene is promoted to wrap up alloying pellet more securely, irreversible capacity can be effectively reduced, is made follow-up
Charge and discharge cycles specific capacity increases.
Compared with the existing technology, the present invention is preparing the same of graphene by fabricated in situ technique using titration reduction method
When formed nanometer SnSbCo multi-nary alloy particles, effectively improve material preparation efficiency.Liquid nitrogen rapid cooling is added, passes through cold quenching work
Skill makes flake graphite alkene firmly wrap up SnSbCo alloying pellets, effectively improves the structural stability of electrode material.System of the present invention
Graphene content in standby obtained SnSbCo/ graphene composite negative poles is more, can be good at wrapping up alloying pellet, have
Effect reduces the reunion of alloying pellet, and on the one hand the graphene of high conductivity can improve the electric conductivity of electrode material, another
The volume expansion that alloying pellet generates in charge and discharge process can be effectively relieved in aspect.Material using the present invention assembles to obtain
Sodium-ion battery have high charge-discharge specific capacity, good high rate performance and cycle performance.
The invention is not limited in the above embodiments, if the various changes or deformation to the present invention do not depart from the present invention
Spirit and scope, if these changes and deformation belong within the scope of the claim and equivalent technologies of the present invention, then this hair
It is bright to be also intended to comprising these changes and deformation.
Claims (8)
1. liquid phase in-situ reducing-cold quenching preparation method of composite negative pole material, it is characterised in that：Include the following steps：
(1) pink salt, antimonic salt and salt solubility are obtained into mixing salt solution in solvent；By graphite oxide ultrasonic disperse in mixing
In salting liquid；In the mixing salt solution, a concentration of 0.01-0.5mol/L of pink salt, a concentration of 0.01-0.5mol/ of antimonic salt
L, a concentration of 0.001-0.05mol/L of cobalt salt；Tin ion, antimony ion, cobalt ions molar ratio be 1:1:0.1；
(2) reducing agent is dissolved in solvent, obtains reducing solution；Reducing solution is added dropwise to the mixing salt solution of step (1)
In and continue to stir；After completion of dropwise addition, turbid solution is obtained, turbid solution is stirred to react in 50-80 DEG C；
(3) it after the quick cold quenching of liquid nitrogen being added into the turbid solution of step (2), is freeze-dried after vacuum filtration, multiple washing or true
Sky is dry, obtains SnSbCo/ graphene precursor powders；The volume ratio of the liquid nitrogen and turbid solution is 0.5:1-2:1；
(4) under inert gas shielding, precursor powder is warming up to calcining at constant temperature at 200-450 DEG C with certain heating rate, is obtained
To SnSbCo/ graphene composite negative poles.
2. liquid phase in-situ reducing-cold quenching preparation method of composite negative pole material according to claim 1, it is characterised in that：
In the mixing salt solution that step (1) obtains, a concentration of 0.5-2mg/mL of graphite oxide.
3. liquid phase in-situ reducing-cold quenching preparation method of composite negative pole material according to claim 2, it is characterised in that：
A concentration of 0.1-2mol/L of reducing solution in step (2)；The reducing agent is hydrazine hydrate, ammonium hydroxide, NaBH4With one in HI
Kind.
4. liquid phase in-situ reducing-cold quenching preparation method of composite negative pole material according to claim 2, it is characterised in that：
Ultrasonic power is 100-200W in step (1)；Rate of addition in step (2) is 1-3mL/min；Stirring in step (2)
Speed is 200-1000r/min.
5. liquid phase in-situ reducing-cold quenching preparation method of composite negative pole material according to claim 2, it is characterised in that：
The pink salt is stannous chloride or stannous acetate, and the antimonic salt is antimony chloride or antimony acetate, and the cobalt salt is cobalt chloride or acetic acid
Cobalt；
Solvent described in step (1) and step (2) is the solvent of any one or the two mixing in deionized water, ethyl alcohol.
6. a kind of preparation method of sodium-ion battery, it is characterised in that：Include the following steps：By SnSbCo/ graphene Compound Negatives
Pole material, conductive black, binder are (50-80) according to mass ratio：(30-10)：(20-10) is coated in copper foil after mixing
On, vacuum drying is sliced after roll-in, obtains circular electric pole piece；Electrode slice, metallic sodium piece, electrolyte are assembled into sodium ion electricity
Pond；The SnSbCo/ graphene composite negative poles are that preparation method described in any claim is prepared into claim 1-5
The SnSbCo/ graphene composite negative poles arrived.
7. the preparation method of sodium-ion battery according to claim 6, it is characterised in that：The binder is LA132, gathers
One kind in vinylidene fluoride or CMC binders；The coating thickness is 60-120 μm；The thickness of the roll-in is 35-90 μm.
8. a kind of sodium-ion battery, it is characterised in that：Including circular electric pole piece, metallic sodium piece and electrolyte, the circular electrode
Piece is (50-80) according to mass ratio by SnSbCo/ grapheme materials composite negative pole material, conductive black, binder：(30-10)：
(20-10) is coated on copper foil after mixing, and vacuum drying, slice obtains after roll-in, the SnSbCo/ graphenes Compound Negative
Pole material is the SnSbCo/ graphene composite negatives that preparation method is prepared described in any claim in claim 1-5
Material.
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| CN113346076B (en) * | 2021-05-14 | 2023-01-24 | 沁新集团(天津)新能源技术研究院有限公司 | Surface modified graphite negative electrode material of lithium ion battery and preparation method thereof |
| CN113881399B (en) * | 2021-09-27 | 2022-09-30 | 宁波金榜新能源有限公司 | Brake pad friction material for new energy automobile and preparation method thereof |
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| CN102231436A (en) * | 2011-05-20 | 2011-11-02 | 浙江大学 | Preparation method of Sn-Sb/grapheme nano-composite material |
| CN103762348A (en) * | 2014-01-25 | 2014-04-30 | 华南师范大学 | SnSbCu/MCMB/C core-shell structure serving as anode material of lithium ion battery and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102231436A (en) * | 2011-05-20 | 2011-11-02 | 浙江大学 | Preparation method of Sn-Sb/grapheme nano-composite material |
| CN103762348A (en) * | 2014-01-25 | 2014-04-30 | 华南师范大学 | SnSbCu/MCMB/C core-shell structure serving as anode material of lithium ion battery and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| Flake structured SnSbCo/MCMB/C composite as high performance anodes for lithium ion battery;Xiaoqiu Chen等;《Journal of Alloys and Compounds》;20150623;第646卷;第794-802页 * |
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