CN109473663A - A kind of anode material of lithium-ion battery and preparation method thereof of redox graphene load antimony - Google Patents
A kind of anode material of lithium-ion battery and preparation method thereof of redox graphene load antimony Download PDFInfo
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- 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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/134—Electrodes based on metals, Si 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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a kind of anode material of lithium-ion batteries and preparation method thereof of redox graphene load antimony, are related to electrochemical energy storage technical field.The present invention is using antimony trichloride, ammonium hydroxide, crystalline flake graphite as raw material, graphene oxide is prepared using chemical oxidization method and stripping method, it improves liquid phase synthesizing method and loads antimony precursors particle in graphene oxide layer, the anode material of lithium-ion battery for obtaining redox graphene load antimony is handled eventually by thermal reduction.The anode material of lithium-ion battery of redox graphene load antimony of the present invention has excellent circulating ratio performance；In 2A g‑1High current density under circulation 100 circle after, Sb-rGO is still able to maintain 140mAh g‑1Above capacity, and coulombic efficiency maintains 97% or more；Addition surfactant and reducing agent are not needed in preparation method provided by the invention, method is simple, and cost is relatively low, is suitble to large scale preparation.
Description
Technical field
The present invention relates to electrochemical energy storage technical fields, relate generally to a kind of sodium ion of redox graphene load antimony
Cell negative electrode material and preparation method thereof.
Background technique
Caused by increasingly exhausted and fossil energy transition application with fossil energies such as petroleum, coal, natural gases
Environmental problem is increasingly sharpened, and the fast-developing demand to renewable and clean energy resource of science and technology and economic construction is extremely urgent.
Energy storage technology, especially to electric energy storage technology, the energy crisis of solution the problem of in be particularly important.Recyclable charge and discharge
Electric lithium ion has the energy density and power density higher than traditional chemical battery, and has slow self-discharge rate, high
The excellent properties such as operating voltage.However lithium resource is unevenly distributed, reserves are limited, and fancy price improves lithium ion battery
Production cost, thus the large-scale application of limiting lithium ion cell.Sodium and lithium have similar physical property and chemical property, and
And sodium resource reserve is abundant, it is cheap, therefore sodium-ion battery is expected to substitute lithium ion battery in extensive energy storage field.
Although sodium-ion battery has many advantages, such as low production cost, environmentally protective.But due to sodium ionHalf
Diameter is greater than lithium ion radiusSodium ion is caused to be not easy to be embedded in electrode material and deviate from, so that workable
Positive and negative pole material is very limited, especially the negative electrode material with excellent electrochemical storage sodium performance.In the research of negative electrode material,
Extensive concern of the antimony sill due to causing researcher with outstanding theoretical storage sodium capacity, is a kind of with application prospect
Anode material of lithium-ion battery.
However during sodium ion deintercalation huge bulk effect can occur for antimony Sb, so that being sent out in charge and discharge process
Feculaization and broken, cause the decaying of battery capacity and the reduction of efficiency, the strong influence practical application of this kind of material.For
Alleviate the volume change of material and caused by performance degradation, people are compound by Sb and carbon-based material progress, utilize carbon-based material
The features such as low volume change rate, high conductivity and high structural stability, solves problem above.Graphene (Graphene
Nanosheets, GNS) there is natural two-dimensional structure, there is excellent conductivity, high specific surface area and excellent power
Performance is learned, is the carrier of ideal electroactive material.The method of common production graphene mainly has mechanical stripping method, extension raw
Regular way, vapour deposition process, chemical synthesis and chemical stripping method, wherein chemical stripping method is due to easy to operate, production cost
The advantages that cheap and suitable large area produces and be concerned, be the method for most industrial production potential at present.Chemical method is raw
The graphene that output is come usually has loaded a small amount of oxygen-containing group, and the graphene produced is also referred to as redox graphene
(Reduced Graphene Oxide, rGO).Although rGO its performance compared with GNS is declined, but still is had good
Mechanical property and physical property can be widely used in industry research and development and industrialized production.Oxygen reduction used by reporting at present
The method that graphite alkene loads antimony is mainly ball-milling method and liquid phase method.The material particle size of ball-milling method preparation is uneven, Yi Fa
It is raw to reunite, the features such as discharge capacity is low, and high rate performance is poor is caused, the advantage of carbon-based material can not be played.Conventional liquid phase method needs
Surfactant and reducing agent are added, the loss of active material is easily caused during cleaning material, drops material capacity
It is low, and preparation section is complicated, greatly limits its mass production.
Therefore, develop that a kind of preparation method is simple, low cost, high efficiency, environmental-friendly redox graphene load
The sodium ion negative electrode material of antimony is of great significance.
Summary of the invention
To overcome volume change during de-/embedding sodium of sodium-ion battery antimony base negative electrode material in the prior art, repeatedly charge and discharge
Electric rear electrode material is easy dusting, leads to battery capacity decaying, poor circulation, and the present invention provides a kind of reduction-oxidation
The anode material of lithium-ion battery and preparation method thereof of graphene-supported antimony, the method is with antimony trichloride, ammonium hydroxide, crystalline flake graphite
For raw material, graphene oxide is prepared using chemical oxidization method and stripping method, improves liquid phase synthesizing method in graphene oxide layer
Antimony precursors particle is loaded, the sodium-ion battery cathode material for obtaining redox graphene load antimony is handled eventually by thermal reduction
Material.
The preparation method of the anode material of lithium-ion battery of the redox graphene load antimony, specific preparation step
It is rapid as follows:
Step 1: graphene oxide preparation: 4:3 in mass ratio weighs a certain amount of crystalline flake graphite and NaNO3In beaker,
It is slowly added to 200~300ml concentrated sulfuric acid (mass percent concentration 98%), magnetic agitation is to uniform；In magnetic agitation condition
Under be slowly added to 30~40g potassium permanganate, and continue stirring 96 hours, obtain dark gum matter；Into dark gum matter
700ml~800ml deionized water and 40~70ml hydrogen peroxide (mass percent concentration 30% of hydrogen peroxide) are sequentially added, is stirred
To uniform, acquisition yellow solution；By the high revolving speed centrifugation of gained yellow solution, high revolving speed centrifugation is repeated, and be washed to supernatant and be
It is neutral；Deionized water is added in high speed centrifugation product again to stir evenly, ultrasonic treatment is placed on centrifuge, and the slow-speed of revolution is centrifuged,
Collect upper layer taupe brown thick liquid；Above-mentioned slow-speed of revolution centrifugal process is repeated, the upper layer taupe brown being repeatedly collected by centrifugation is glued
Thick liquid is poured into bag filter, and dialysis obtains graphene oxide solution after two weeks；Graphene oxide solution is rotated to dense
It is thick, it can get graphene oxide after freeze-drying；Wherein crystalline flake graphite dosage is between 8~10g.
Step 2: it takes a certain amount of antimony trichloride to be configured to antimony trichloride ethanol solution, is obtained after 0.5~1h of ultrasound colourless
Clear solution；Step 1 is taken to prepare graphene oxide obtains dark brown in ethyl alcohol oxidation stone after 1~2h of ultrasound dispersion simultaneously
Black alkene ethanol solution；A small amount of ammonium hydroxide (mass percent concentration 25%) is added drop-wise to graphene oxide ethanol solution (dark brown
Solution) in, 2~3h of magnetic agitation；Under the conditions of magnetic agitation, with syringe by the antimony trichloride ethanol solution of above-mentioned achromaticity and clarification
It is slowly dropped in the dark brown solution containing ammonium hydroxide, and continues 9~12h of stirring, obtain precursor solution；By precursor solution from
Sediment after the heart is dried at 60 DEG C~80 DEG C obtains taupe presoma solid.
Step 3: above-mentioned taupe presoma solid is placed in tube furnace, 8~10 DEG C/min of heating rate, air-flow 50
~80sccm is heat-treated 2~4 hours acquisition redox graphenes under reducing atmosphere at 550~600 DEG C and loads antimony
Anode material of lithium-ion battery.
The concentration of the graphene oxide ethanol solution is 1mg/ml, and graphene oxide ethanol solution and ammonium hydroxide volume ratio are used
Amount is 200:1~250:1；Graphene oxide and antimony trichloride mass ratio are between 1:4~1:8；Antimony trichloride ethanol solution is dense
Degree is preferably between 0.0006~0.001mol/L.
In the present invention, high revolving speed centrifugation described in step 1 refers to that centrifuge speed is 5000rpm~6000rpm, centrifugation
Time is 5~10min.
In the present invention, the centrifugation of the slow-speed of revolution described in step 1 refers to that centrifuge speed is 2000rpm~3000rpm, centrifugation
Time is 5~10min.
In the present invention, freeze-drying described in step 1, temperature is -50 DEG C, pressure 20Mpa, and the time is for 24 hours.
In the present invention, precursor solution centrifugation refers to that centrifuge speed is 8000rpm~9000rpm, centrifugation in step 2
Time is centrifuged under the conditions of being 5~10min.
In the present invention, syringe described in step 2, which is slowly added dropwise, to be referred to: it is molten to draw achromaticity and clarification with 1mL range syringe
After liquid, syringe is connected into extension tube, after being vented and checking bubble-free, is fixed on syringe pump fixing bolt, syringe pump is started, with
Colorless cleared solution is added dropwise in flow velocity 0.1mL/min.It repeats the above steps if colorless cleared solution usage amount is more than 1mL.
In the present invention, reducing atmosphere described in step 3 refers to the mixed atmosphere of hydrogen and argon gas composition, preferably hydrogen
The mixed atmosphere formed with argon gas with 5:95 volume ratio.
Electrode using the negative electrode material as sodium-ion battery, the results show that in 100mA g-1Under current density,
Specific capacity is able to maintain in 359~502mAh.g after 10 circle of circulation-1；(the 2A g under high current density-1) circulation 100 times, Sb-
RGO negative electrode material electrode specific capacity can be stablized in 147.1~195.6mAh.g-1, show excellent cyclical stability, coulomb
Efficiency is greater than 97%.
The present invention has the advantages that
1. the anode material of lithium-ion battery of redox graphene load antimony of the present invention has excellent circulating ratio
Energy.In 2A g-1High current density under circulation 100 circle after, Sb-rGO is still able to maintain 200mAh g-1Capacity, and coulomb imitate
Rate maintains 97% or more.
2. preparation method provided by the present invention prepares the anode material of lithium-ion battery of redox graphene load antimony,
Its preparation process does not need addition surfactant and reducing agent, and method is simple, and cost is relatively low, is suitble to large scale preparation.
Detailed description of the invention
Fig. 1 is X-ray diffraction (XRD) map of Sb-rGO negative electrode material in embodiment 1；
Fig. 2 is surface sweeping Electronic Speculum (SEM) photo of Sb-rGO negative electrode material in embodiment 1；
Fig. 3 is transmission electron microscope (TEM) photo of Sb-rGO negative electrode material in embodiment 1, and illustration is selective electron diffraction
(SEAD) photo；
Fig. 4 is Sb-rGO negative electrode material (0.1A g under different current densities in embodiment 1-1, 0.2A g-1, 0.5A g-1, 1Ag-1, 2.5Ag-1, 5Ag-1, 10Ag-1) charging and discharging capacity performance map；
Fig. 5 is Sb-rGO negative electrode material in embodiment 1 in 2Ag-1The lower 100 cycle charge discharges electric circle number specific capacity of current density
Performance map.
Specific embodiment
With reference to the accompanying drawings and examples to a kind of sodium ion electricity of redox graphene load antimony provided by the invention
Pond negative electrode material and preparation method thereof is described in detail.
Embodiment 1
Redox graphene loads the preparation method of the anode material of lithium-ion battery of antimony:
Step 1: graphene oxide preparation.
Step 101. weighs 10g crystalline flake graphite and 7.5g NaNO3In beaker, it is slowly added to the 300ml concentrated sulfuric acid
(98%), magnetic agitation is to uniform；It is slowly added to 40g potassium permanganate under the conditions of magnetic agitation, and continues stirring 96 hours, obtains
Obtain dark gum matter.
Step 102. sequentially adds 800ml deionized water and 60ml hydrogen peroxide (30%) into dark gum matter, stirring
To uniform, acquisition yellow solution；By gained yellow solution under the conditions of 6000rpm, centrifugation time 5min high speed centrifugation, obtain height
Revolving speed is centrifuged product；It is further preferred that the high revolving speed centrifugal process repeats 3~5 times, and it is washed to after supernatant is neutral
Take high revolving speed centrifugation product.
High revolving speed centrifugation product is added deionized water again and stirred evenly by step 103., and ultrasonic treatment 10min is placed on
Centrifuge, slow-speed of revolution centrifugation, revolving speed 2000rpm are centrifuged 5min, collect upper layer taupe brown thick liquid；
Step 104. repeats the above steps 103 slow-speed of revolution centrifugal process 3~5 times, and the upper layer being repeatedly collected by centrifugation is glued
Thick liquid is poured into bag filter, and dialysis obtains graphene oxide solution after two weeks；Graphene oxide solution is rotated to dense
It is thick, it can get graphene oxide after freeze-drying.The freeze-drying, temperature are -50 DEG C, pressure 20Mpa, and the time is
24h.The temperature of the revolving is lower than 40 DEG C.
Step 2: the antimony trichloride of 2g is weighed in vial, 10ml ethyl alcohol is added dropwise, obtaining 10ml concentration after ultrasonic 0.5h is
The antimony trichloride ethanol solution of 0.8M achromaticity and clarification；Take the graphene oxide of the preparation of 20mg above-mentioned steps one in ethyl alcohol simultaneously,
Ultrasonic disperse 1h obtains 20ml graphene oxide ethanol solution；
The ammonium hydroxide (ammonia spirit for preparing percentage 25%) of 0.1ml is added drop-wise in graphene oxide ethanol solution, magnetic
Power stirs 3h；Under the conditions of magnetic agitation, 0.76ml colorless cleared solution is extracted with 1ml syringe, syringe is connected into extension tube,
It after being vented and checking bubble-free, is fixed on syringe pump fixing bolt, starts syringe pump, be added dropwise with flow velocity 0.1mL/min colourless clear
Clear solution, and continue to stir 12h, obtain black gray expandable precursor solution；By black gray expandable precursor solution under the conditions of 8000rpm from
The sediment obtained after heart 5min dry 12h at 80 DEG C obtains taupe presoma solid powder；
Step 3: above-mentioned taupe presoma solid powder is placed in tube furnace, 10 DEG C/min of heating rate, air-flow 50
~80sccm is heat-treated under the mixing reducing atmosphere that hydrogen and argon gas are formed with 5:95 volume ratio 2 small at 550 DEG C
When, obtain the anode material of lithium-ion battery of redox graphene load antimony.
Learnt as shown in Figure 1: through XRD analysis, step 3 preparation product be high crystallinity graphite alkene load antimony sodium from
Sub- cell negative electrode material.Diffraction maximum point at 23.6 °, 25.1 °, 28.7 °, 39.8 °, 42 °, 46.8 °, 48.4 °, 51.6 °
It does not correspond to antimony Sb (003), (101), (012), (104), (015), (006), (202) crystal face, all bright and sharp diffraction maximums
It is corresponding with the hexagonal structure antimony that PDF number is 85-1324.Fig. 2 is the SEM photograph for the product that step 3 obtains, it can be seen that also
Former graphene oxide is in almost transparent film, and antimony particle uniform load is in redox graphene surfaces externally and internally, and partial size is 80
Between~500nm.Fig. 3 is the TEM photo of the negative electrode material of step 3 preparation, and illustration is SEAD (electronic diffraction) picture,
SEAD diffraction fringe and the structure of Sb correspond, it was demonstrated that Sb particle exists, and large stretch of redox graphene area load is big
Measure antimony particle.
Sodium-ion battery electrode is prepared using the anode material of lithium-ion battery of the redox graphene load antimony
And test its performance:
The preparation of electrode is using the anode material of lithium-ion battery of above-mentioned redox graphene load antimony as active matter
Matter is mixed by weight 7:2:1 as electrode material with conductive agent (conductive black) and binder (sodium carboxymethylcellulose)；With
As solvent muddy is made in electrode material by deionized water, is coated on the rough surface of the round copper foil of the cleaning that diameter is 1.2cm
On, obtain electrode slice；Then electrode slice is placed in a vacuum drying oven, sodium ion electricity can be obtained in 80 DEG C of vacuum drying 15h
Pond electrode.The present invention tests battery and uses CR2032 type button cell, and using sodium sheet metal as to electrode, concentration of electrolyte is
1M, solute are sodium perchlorate (NaClO4), solvent is the propene carbonate (PC) and ethylene carbonate (EC) that volume ratio is 1:1.
It is 0.2C, 0.4C, 1C, 2C, 5C, 10C, 20C, 100 cyclic charging and discharging test current densities that high rate performance, which tests current density,
For 4C, wherein 1C is equal to 500mA/g, and test voltage range is 0.01~0.3V.
Fig. 4 is Sb-rGO negative electrode material electrode charging and discharging capacity performance map under different current densities, in 100mAg-1's
Under current density after 10 circle of circulation, negative electrode material electrode specific capacity can be stablized in 416mAh.g-1, in different current charging and dischargings
Under, coulombic efficiency remains to be maintained at 97% or more.Fig. 5 is Sb-rGO negative electrode material electrode in 2Ag-1It follows for current density lower 100 times
Ring charge and discharge electrograph.In 2Ag-1Under high current density, the specific capacity of prepared by the method Sb-rGO negative electrode material electrode can
Stablize in 171mAh.g-1, cycle performance is excellent.
Embodiment 2
Redox graphene loads antimony cathode material preparation method:
Step 1: with embodiment 1.
Step 2: the antimony trichloride of 2g is weighed in vial, 10ml ethyl alcohol is added dropwise, obtaining 10ml concentration after ultrasonic 0.5h is
The antimony trichloride ethanol solution of 0.8M achromaticity and clarification；The graphene oxide ultrasound 1h dispersion prepared in 30mg step 1 is measured simultaneously
In 40ml ethanol solution, dark brown solution is obtained；The ammonium hydroxide (25%) of 0.18ml is added drop-wise to graphene oxide ethanol solution
In, magnetic agitation 3h；Under the conditions of magnetic agitation, 0.85ml colorless cleared solution is extracted with 1ml syringe, syringe connection is prolonged
Long tube after being vented and checking bubble-free, is fixed on syringe pump fixing bolt, starts syringe pump, and nothing is added dropwise with flow velocity 0.1mL/min
Color clear solution, and continue to stir 12h, obtain black gray expandable solution；After black gray expandable solution is centrifuged 8min under the conditions of 8500rpm
The sediment of acquisition dry 10h at 80 DEG C obtains grey-brown powder；
Step 3: above-mentioned grey-brown powder is placed in tube furnace, heating rate 10 DEG C/min, 50~80sccm of air-flow,
2 hours are heat-treated under the mixing reducing atmosphere that hydrogen and argon gas are formed with 5:95 volume ratio at 550 DEG C, are restored
Graphene oxide-loaded antimony negative electrode material.
The anode material of lithium-ion battery of prepared redox graphene load antimony, is abbreviated as Sb-rGO cathode material
Material, large stretch of redox graphene area load antimony particle bear the load antimony of redox graphene prepared by step 3
Pole material is mixed by weight 7:2:1 as electrode material with conductive agent (conductive black) and binder (sodium carboxymethylcellulose)
Material, it is that 1.2cm is cleaned on round copper foil that electrode material, which is prepared into muddy, using deionized water as solvent and is coated in diameter
Electrode slice is obtained, is then placed electrode slice in a vacuum drying oven, sodium-ion battery can be obtained in 80 DEG C of vacuum drying 15h.
The present invention tests battery and uses CR2032 type button cell, and using sodium sheet metal as to electrode, concentration of electrolyte 1M, solute is
Sodium perchlorate (NaClO4), solvent is the propene carbonate (PC) and ethylene carbonate (EC) that volume ratio is 1:1.High rate performance is surveyed
It is 4C that examination current density, which is 0.2C, 0.4C, 1C, 2C, 5C, 10C, 20C, 100 cyclic charging and discharging test current densities, wherein 1C
Equal to 500mA/g, test voltage range is 0.01~0.3V.
In 100mAg-1Under current density, material electrodes first discharge specific capacity is up to 810mAh.g-1, compare after recycling 10 circles
Capacity is able to maintain in 410mAh.g-1, show excellent storage sodium capacity.(the 2Ag under high current density-1) circulation 100 times,
Sb-RGO negative electrode material electrode specific capacity can be stablized in 165.6mAh.g-1, show excellent cyclical stability, coulombic efficiency
Greater than 97%.
Embodiment 3:
Step 1: graphene oxide preparation:
Crystalline flake graphite 8g, in mass ratio 4:3 is taken to weigh NaNO3, the two is mixed in beaker, and is slowly added into beaker
The 200ml concentrated sulfuric acid (mass percent concentration 98%), magnetic agitation is to uniform；
It is slowly added to 30g potassium permanganate under the conditions of magnetic agitation, and continues stirring 96 hours, obtains dark gum
Matter；800ml deionized water and the 70ml hydrogen peroxide (mass percent concentration of hydrogen peroxide are sequentially added into dark gum matter
30%) it, is stirred until homogeneous, obtains yellow solution；
By the high revolving speed centrifugation of gained yellow solution, and supernatant is washed to as neutrality；High speed centrifugation product is added again
Deionized water stirs evenly, and ultrasonic treatment is placed on centrifuge, and upper layer taupe brown thick liquid is collected in slow-speed of revolution centrifugation；It repeats
Above-mentioned slow-speed of revolution centrifugal process pours into the upper layer taupe brown thick liquid being repeatedly collected by centrifugation in bag filter, dialyses two weeks
Graphene oxide solution is obtained afterwards；Graphene oxide solution is rotated to thick, available graphite oxide after freeze-drying
Alkene.
The high revolving speed centrifugal rotational speed is 5000rpmrpm, centrifugation time 10min.
The slow-speed of revolution centrifugal rotational speed is 2000rpm, centrifugation time 5min.
The freeze-drying, temperature are -50 DEG C, pressure 20Mpa, and the time is for 24 hours.
Step 2: it takes antimony trichloride to be configured to antimony trichloride ethanol solution, obtains colorless cleared solution after ultrasonic 0.5h；
Step 1 is taken to prepare graphene oxide obtains dark brown in ethyl alcohol graphene oxide after ultrasound 1h dispersion simultaneously
Ethanol solution；A small amount of ammonium hydroxide (mass percent concentration 25%) is added drop-wise to graphene oxide ethanol solution (dark brown solution)
In, magnetic agitation 2h；The concentration of the graphene oxide ethanol solution is 1mg/ml, graphene oxide ethanol solution and ammonium hydroxide body
Product is 200:1 than dosage；Graphene oxide and antimony trichloride mass ratio are 1:4.
Under the conditions of magnetic agitation, the antimony trichloride ethanol solution of above-mentioned achromaticity and clarification is slowly dropped to containing ammonia with syringe
In the dark brown solution of water, and continue 9~12h of stirring, obtains precursor solution；Sediment after precursor solution is centrifuged in
It is dry at 60 DEG C~80 DEG C to obtain taupe presoma solid.
Wherein, precursor solution centrifugation refers to that centrifuge speed is 8000rpm, and centrifugation time is centrifuged under the conditions of being 5min.
Step 3: above-mentioned taupe presoma solid is placed in tube furnace, heating rate 8 DEG C/min, air-flow 50sccm,
The sodium-ion battery cathode of 4 hours acquisition redox graphene load antimony is heat-treated under reducing atmosphere at 600 DEG C
Material.
Negative electrode material prepared by above-mentioned steps, including graphene oxide and antimony particle, redox graphene is in intimate
Transparent film, antimony particle uniform load is in the surfaces externally and internally on redox graphene surface, and partial size is between 80~500nm.
As a result electrode using the negative electrode material as sodium-ion battery, electrode preparation and performance test conditions are shown with embodiment 1
Show, in 100mAg-1Under current density, material electrodes first discharge specific capacity is 742mAh.g-1, specific capacity energy after circulation 10 is enclosed
Enough it is maintained at 359mAh.g-1(the 2Ag under high current density-1) circulation 100 times, Sb-RGO negative electrode material electrode specific capacity can
Stablize in 147.1mAhg-1, excellent cyclical stability is shown, coulombic efficiency is greater than 97%.
Embodiment 4:
Step 1: graphene oxide preparation:
Crystalline flake graphite 10g, in mass ratio 4:3 is taken to weigh NaNO3, the two is mixed in beaker, and is slowly added into beaker
Enter the 300ml concentrated sulfuric acid (mass percent concentration 98%), magnetic agitation is to uniform；
It is slowly added to 40g potassium permanganate under the conditions of magnetic agitation, and continues stirring 96 hours, obtains dark gum
Matter；700ml deionized water and the 40ml hydrogen peroxide (mass percent concentration of hydrogen peroxide are sequentially added into dark gum matter
30%) it, is stirred until homogeneous, obtains yellow solution；
By the high revolving speed centrifugation of gained yellow solution, high revolving speed centrifugation is repeated, and be washed to supernatant as neutrality；Will high speed from
Deionized water is added again and stirs evenly for heart product, and ultrasonic treatment is placed on centrifuge, and upper layer taupe brown is collected in slow-speed of revolution centrifugation
Thick liquid；Above-mentioned slow-speed of revolution centrifugal process is repeated, the upper layer taupe brown thick liquid being repeatedly collected by centrifugation is poured into dialysis
In bag, dialysis obtains graphene oxide solution after two weeks；Graphene oxide solution is rotated to thick, it can after freeze-drying
Obtain graphene oxide.
The high revolving speed centrifugal rotational speed is 6000rpm, centrifugation time 5min.
The slow-speed of revolution centrifugal rotational speed is 3000rpm, centrifugation time 10min.
The freeze-drying, temperature are -50 DEG C, pressure 20Mpa, and the time is for 24 hours.
Step 2: it takes a certain amount of antimony trichloride to be configured to antimony trichloride ethanol solution, obtains achromaticity and clarification after ultrasonic 1h
Solution；
Step 1 is taken to prepare graphene oxide obtains dark brown in ethyl alcohol graphene oxide after ultrasound 2h dispersion simultaneously
Ethanol solution；A small amount of ammonium hydroxide (mass percent concentration 25%) is added drop-wise to graphene oxide ethanol solution (dark brown solution)
In, magnetic agitation 3h；The concentration of the graphene oxide ethanol solution is 1mg/ml, graphene oxide ethanol solution and ammonium hydroxide body
Product is 250:1 than dosage；Graphene oxide and antimony trichloride mass ratio are 1:8.
Under the conditions of magnetic agitation, the antimony trichloride ethanol solution of above-mentioned achromaticity and clarification is slowly dropped to containing ammonia with syringe
In the dark brown solution of water, and continue 9~12h of stirring, obtains precursor solution；Sediment after precursor solution is centrifuged in
It is dry at 60 DEG C~80 DEG C to obtain taupe presoma solid.
Affiliated precursor solution centrifugation refers to that centrifuge speed is 9000rpm, centrifugation time be 10min under the conditions of from
The heart.
Step 3: above-mentioned taupe presoma solid is placed in tube furnace, 10 DEG C/min of heating rate, air-flow
80sccm is heat-treated the sodium ion electricity of 2 hours acquisition redox graphene load antimony at 550 DEG C under reducing atmosphere
Pond negative electrode material.
The negative electrode material, including graphene oxide and antimony particle, redox graphene is in almost transparent thin
Film, antimony particle uniform load is in the surfaces externally and internally on redox graphene surface, and partial size is between 80~500nm.
Electrode using the negative electrode material as sodium-ion battery, electrode preparation and the same embodiment of performance test conditions
1, discharge capacity is up to 773mAhg to negative electrode material electrode for the first time-1, in 100mAg-1Under current density, reversible capacity can be steady
It is scheduled on 502mAh g-1, (the 2Ag under high current density-1) circulation 100 times, Sb-RGO negative electrode material electrode specific capacity can be stablized
In 195.6mAhg-1, excellent cyclical stability is shown, coulombic efficiency is greater than 98%.
Claims (8)
1. a kind of preparation method of the anode material of lithium-ion battery of redox graphene load antimony, which is characterized in that including
Following steps:
Step 1: graphene oxide preparation:
4:3 in mass ratio weighs a certain amount of crystalline flake graphite and NaNO3In beaker, it is slowly added to 200~300ml concentrated sulfuric acid, magnetic
Power is stirred until homogeneous；It is slowly added to 30~40g potassium permanganate under the conditions of magnetic agitation, and continues stirring 96 hours, obtains black
Color colloid substance；Wherein crystalline flake graphite dosage is between 8~10g；
700ml~800ml deionized water and 40~70ml hydrogen peroxide are sequentially added into dark gum matter, are stirred until homogeneous,
Obtain yellow solution；By the high revolving speed centrifugation of gained yellow solution, high revolving speed centrifugation is repeated, and be washed to supernatant as neutrality；It will
Deionized water is added again and stirs evenly for high speed centrifugation product, and ultrasonic treatment is placed on centrifuge, and upper layer is collected in slow-speed of revolution centrifugation
Taupe brown thick liquid；Above-mentioned slow-speed of revolution centrifugal process is repeated, the upper layer taupe brown thick liquid being repeatedly collected by centrifugation is fallen
Enter in bag filter, dialysis obtains graphene oxide solution after two weeks；Graphene oxide solution is rotated to thick, freezing is dry
Graphene oxide is obtained after dry；
Step 2: it takes antimony trichloride to be configured to antimony trichloride ethanol solution, obtains colorless cleared solution after 0.5~1h of ultrasound；Together
When take step 1 prepare graphene oxide in ethyl alcohol 1~2h of ultrasound dispersion after obtain dark brown graphene oxide ethyl alcohol it is molten
Liquid；Ammonium hydroxide is added drop-wise in graphene oxide ethanol solution, 2~3h of magnetic agitation；It, will be upper with syringe under the conditions of magnetic agitation
The antimony trichloride ethanol solution for stating achromaticity and clarification is slowly dropped in the dark brown solution containing ammonium hydroxide, and continues 9~12h of stirring,
Obtain precursor solution；Sediment after precursor solution is centrifuged is dried acquisition taupe presoma at 60 DEG C~80 DEG C and is consolidated
Body；
Step 3: above-mentioned taupe presoma solid is placed in tube furnace, 8~10 DEG C/min of heating rate, and air-flow 50~
80sccm is heat-treated 2~4 hours at 550~600 DEG C under reducing atmosphere, obtains redox graphene and loads antimony
Anode material of lithium-ion battery.
2. a kind of preparation side of the anode material of lithium-ion battery of redox graphene load antimony according to claim 1
Method, it is characterised in that: in step 2, the graphene oxide ethanol solution and ammonium hydroxide volume ratio dosage are 200:1~250:1；
Graphene oxide and antimony trichloride dosage mass ratio are between 1:4~1:8；Antimony trichloride ethanol solution concentration be 0.0006~
Between 0.001mol/L；The concentration of graphene oxide ethanol solution is 1mg/ml.
3. a kind of preparation side of the anode material of lithium-ion battery of redox graphene load antimony according to claim 1
Method, it is characterised in that: high revolving speed centrifugation described in step 1 refers to that centrifuge speed is 5000rpm~6000rpm, centrifugation time
To be centrifuged under the conditions of 5~10min；The centrifugation of the slow-speed of revolution described in step 1 refers to that centrifuge speed is 2000rpm~3000rpm,
Centrifugation time is centrifuged under the conditions of being 5~10min；In step 2 precursor solution centrifugation refer to centrifuge speed be 8000rpm~
9000rpm, centrifugation time are centrifuged under the conditions of being 5~10min.
4. a kind of preparation side of the anode material of lithium-ion battery of redox graphene load antimony according to claim 1
Method, it is characterised in that: freeze-drying described in step 1, temperature are -50 DEG C, pressure 20Mpa, and the time is for 24 hours.
5. a kind of preparation side of the anode material of lithium-ion battery of redox graphene load antimony according to claim 1
Method, it is characterised in that: in step 2, the antimony trichloride ethanol solution of above-mentioned achromaticity and clarification is slowly dropped to containing ammonia with syringe
In the dark brown solution of water, specific operation process are as follows: after drawing colorless cleared solution with 1mL range syringe, syringe is connected
Extension tube is connect, after being vented and checking bubble-free, is fixed on syringe pump fixing bolt, starts syringe pump, with flow velocity 0.1mL/min drop
Add colorless cleared solution；It repeats the above steps if colorless cleared solution usage amount is more than 1mL.
6. a kind of preparation side of the anode material of lithium-ion battery of redox graphene load antimony according to claim 1
Method, it is characterised in that: reducing atmosphere described in step 3 refers to the mixed atmosphere of hydrogen and argon gas composition, hydrogen and argon gas with
The mixing of 5:95 volume ratio.
7. a kind of anode material of lithium-ion battery of redox graphene load antimony, it is characterised in that: the negative electrode material, also
Former graphene oxide is in almost transparent film, and antimony particle uniform load is in redox graphene surfaces externally and internally, and partial size is 80
Between~500nm.
8. the anode material of lithium-ion battery of application redox graphene as claimed in claim 7 load antimony prepares sodium ion electricity
Pond electrode, it is characterised in that:
Using the anode material of lithium-ion battery of redox graphene load antimony as active material, pressed with conductive agent and binder
Weight ratio 7:2:1 mixing is used as electrode material；Muddy is made in electrode material using deionized water as solvent, is coated on copper foil
On, obtain electrode slice；Then electrode slice is placed in a vacuum drying oven, 80 DEG C of vacuum drying 15h, obtains sodium-ion battery electricity
Pole.
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