CN106935814A - For the ferrous disulfide/graphene oxide composite material and preparation method of sodium-ion battery negative pole - Google Patents
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- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
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- 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
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Abstract
The invention provides a kind of ferrous disulfide/graphene oxide composite material and preparation method for sodium-ion battery negative pole, add graphene oxide into ethylene glycol and N, in the mixed liquor of N dimethylformamides, ultrasound obtains the finely dispersed mixed liquor of graphene oxide；Reacted to after ferrous sulfate, sublimed sulfur and urea are added in the mixed liquor and being sufficiently stirred for, being transferred in hydrothermal reaction kettle；Centrifugation sediment, with deionized water and ethanol wash, then vacuum drying obtains ferrous disulfide/graphene oxide composite material.Graphene oxide is dispersed between curing iron ball in the ferrous disulfide/graphene oxide composite material, forms graphene oxide communicating passage, wherein straight footpath≤3 μm of graphene oxide.Graphene oxide communicating passage can improve the electric conductivity of material in the composite, and volumetric expansion of the simultaneous buffering ferrous disulfide in charge and discharge process greatly improves cyclical stability of the ferrous disulfide material as sodium ion negative pole.
Description
Technical field
The invention belongs to inorganic nano material synthesis field.In particular, for the curing of sodium-ion battery negative pole
Iron/graphene oxide composite material and preparation method；It is related to prepare anode material of lithium-ion battery with hydro-thermal method.
Background technology
With developing rapidly for modern industry and communications, tellurian energy resources gradually become exhausted, therefore newly
The appearance tool of the energy is of great significance.Lithium ion battery has that energy density is high, discharge voltage is high, self discharge is small, nothing
The advantages of memory effect, small environmental pollution, the fields such as electronic product, electric motor car and military affairs are had been widely used at present.
But, with electric automobile, the real arrival in intelligent grid epoch, the lithium resource in the whole world will be unable to effectively meet lithium ion power
The great demand of battery, so as to will further raise the price with lithium associated materials, increases battery cost, finally hinders new energy
The development of industry.Therefore, the related energy storage technology for developing other cheap alternative lithium ion batteries is very crucial.
Sodium and lithium belong to same main group, and the amount of storage with similar chemical property, and sodium is 4-5 quantity of lithium
Level, therefore the price of sodium will be significantly lower than lithium, therefore can effectively alleviate the energy and price problem with sodium substitution lithium.But due to sodium from
The radius of son is larger so that insertion and abjection of the sodium ion in positive and negative pole material are relatively difficult.Therefore, find and improve suitable
Sodium ion is embedded in and the material of abjection is particularly important.What is had now been found that is suitable as the main of anode material of lithium-ion battery
Have：Metal oxide (tin oxide, iron oxide and titanium oxide etc.), metal (tin and antimony etc.), sulfide (molybdenum bisuphide, artificial gold
With iron sulfide etc.), non-metal simple-substance (mainly elemental phosphorous), sodium titanate and carbon etc..Ferrous disulfide wherein in sulfide is simultaneously
With commercial advantage and theoretical capacity high (the 847mA h g such as cheap, pollution-free, energy reserve is abundant-1) electrochemistry it is excellent
Gesture, has broad application prospects in sodium-ion battery field.But at present to ferrous disulfide as anode material of lithium-ion battery
Research and few, this mainly due to ferrous disulfide as semiconducting electrical conductivity it is poor, in charge and discharge process because converting
The problems such as reacting and make its volumetric expansion (increase about 280%) and cause the efflorescence of material, causes it as sodium-ion battery
Negative pole stability in cyclic process is poor.The method for solving the problem at present is mainly optimization blanking voltage and reduces ferrous disulfide
Particle size, the volumetric expansion that ferrous disulfide is produced in charge and discharge process is alleviated using these methods really, improves two sulphur
Change stable circulation problem of the iron as sodium-ion battery negative pole, but can not simultaneously improve ferrous disulfide using these methods and make
It is the electric conductivity of sodium-ion battery negative pole.By ferrous disulfide and carbon material it is compound prepare ferrous disulfide/carbon composite can be same
The electric conductivity of Shi Gaishan ferrous disulfide materials and alleviate its bulk effect, be successfully applied to lithium ion battery positive and negative electrode.But
Be because ferrous disulfide is easily decomposed in air (600~700 DEG C), therefore can not be using conventional glucose, sucrose thermal decomposition (700
More than DEG C) method bag carbon.Preparing the common method that ferrous disulfide/carbon composite is applied at present has two kinds, and one kind is first
Porous carbon is coated in iron particle, then sulphur is vaporized through porous carbon by high temperature and reacted to prepare the two of carbon coating with iron
Vulcanization iron composite material, but the requirement of this method complex process, reaction condition is high, is unfavorable for commercially producing；Another kind is
Ferrous disulfide pelletizing in hydro-thermal method, but the ferrous disulfide/carbon composite prepared in this way is got together by carbon
Material is coated, and is unfavorable for the abundant infiltration of ion and the volumetric expansion of alleviation ferrous disulfide.Therefore, using process is simple, reaction
It is required that low method prepares the finely dispersed ferrous disulfide/carbon composite of ferrous disulfide, it is to prepare high-performance sodium ion electricity
One of effective measures of pond negative material.
The content of the invention
The purpose of the present invention be by prepared using the step of hydro-thermal method one can be used for the ferrous disulfide of sodium-ion battery negative pole/
Graphene oxide composite material.Graphene oxide is dispersed between curing iron ball in the composite, forms graphene oxide
Communicating passage, wherein ferrous disulfide Zhi Jing≤3 μm.The graphene oxide communicating passage can improve the electric conductivity of material, promote two
Iron sulfide it is dispersed, while the volumetric expansion that ferrous disulfide is produced in charge and discharge process can also be buffered, so that significantly
Improve cyclical stability of the ferrous disulfide material as sodium-ion battery negative pole.
The present invention provides a kind of use hydro-thermal method one-step synthesis and can be used for the ferrous disulfide/oxidation stone of sodium-ion battery negative pole
Black alkene composite and its method.
Technical scheme is as follows：
For the preparation method of the ferrous disulfide/graphene oxide composite material of sodium-ion battery negative pole；Step is as follows：
1) during adds graphene oxide into the mixed solution of ethylene glycol and DMF, ultrasonic 4-8h makes
Obtain the dispersed mixed liquor of graphene oxide；
2) ferrous sulfate is added to step 1 by) it is obtained in the dispersed mixed liquor of graphene oxide, with 200-400r/
After min stirrings 10-30min, sublimed sulfur and urea are added, it is ensured that the mass ratio of ferrous sulfate and sublimed sulfur is 1.5:1, continue with
200-400r/min stirs 0.5-1h, and the mixed liquor containing graphene oxide, molysite and sulphur is obtained；
3) is by step 2) the obtained mixed liquor containing graphene oxide, molysite and sulphur source carries out hydro-thermal；
4) hydrothermal product is gone the removal of impurity by using deionized water and ethanol cyclic washing, and ferrous disulfide/oxygen is obtained after drying
Graphite alkene composite.
The step 1) ethylene glycol and N,N-dimethylformamide volume ratio are 1 in mixed solution:1-2:1；
The step 1) graphene oxide concentration is 0.5-2.8g/L in mixed liquor.
The step 2) in the mass ratio of ferrous sulfate and graphene oxide be 1:0.05-1:0.4.
The step 2) in sublimed sulfur and urea mass ratio be 1:1.5-1:2.
The step 3) in hydrothermal condition it is preferred：170-190 DEG C of hydro-thermal soaking time is 12-48h, is then naturally cooled to
Room temperature.
The step 4) with deionized water and ethanol washing times preferably 6-10 times；
The step 4) preferably drying temperature condition be to be vacuum dried 10-12h at 60-110 DEG C.
Application of the ferrous disulfide/graphene oxide composite material as negative material in sodium-ion battery, is embodied as follows：
Obtained material and conductive black and PVDF (Kynoar) and NMP (1-METHYLPYRROLIDONE) are fully mixed
Conjunction forms uniform pastel, is coated on Copper Foil matrix as test electrode, using metallic sodium as to electrode assembling into button
Battery, its electrolyte is 1M NaSO3CF3/ DIG (diethylene glycol dimethyl ether).
The present invention prepares ferrous disulfide/graphene oxide composite material, and graphene oxide is dispersed in two in the composite
Between vulcanization iron ball, graphene oxide communicating passage, wherein straight footpath≤3 μm of ferrous disulfide are formed.
Ferrous disulfide/graphene oxide composite material of the invention is used as anode material of lithium-ion battery.
Effect of the invention is can to prepare to can be used for the ferrous disulfide/graphene oxide composite wood of sodium-ion battery negative pole
Material, graphene oxide is dispersed between curing iron ball in the composite, graphene oxide communicating passage is formed, wherein two sulphur
Change iron Zhi Jing≤3 μm.Due to there is graphene oxide communicating passage in the composite, the conduction of negative material is remarkably improved
Property, promote the dispersed of ferrous disulfide, while the Volume Changes of negative pole during sodium ion insertion abjection can also be buffered, have
Beneficial to the cycle performance for improving sodium-ion battery, in 1A g-1Current density under test its performance, its specific volume afterwards of circulation 50 times
Amount is up to 355.9mA h g-1More than, coulombic efficiency does sodium-ion battery and bears close to 100%, higher than the ferrous disulfide of current research
Capacity (the 1A g of pole material-1Current density under circulate 50 capacity be maintained at 200mA h g-1, coulombic efficiency is about 100%).
Brief description of the drawings
Fig. 1 is the X-ray diffractogram of ferrous disulfide/graphene oxide composite material prepared by embodiment 1, illustrates prepared
Product be made up of ferrous disulfide/graphene oxide, wherein ferrous disulfide has excellent crystallinity.
Fig. 2 is the scanning electron microscopic picture of ferrous disulfide/graphene oxide composite material prepared by embodiment 2, illustrates made
Graphene oxide is dispersed between curing iron ball in standby product, forms graphene oxide communicating passage, wherein ferrous disulfide
Zhi Jing≤3 μm.
Fig. 3 is ferrous disulfide/graphene oxide composite material prepared by embodiment 3 as anode material of lithium-ion battery group
The charge and discharge cycles stability figure tested after battery is dressed up, as illustrated, battery is 1A g in current density-1Under discharge first
Specific capacity is 560.6mAh g-1, first coulombic efficiency be up to 95.5%, the reversible discharge specific capacity of battery is after the circle of circulation 50
355.9mAh g-1, coulombic efficiency is close to 100%, and battery capacity does not almost decay, and shows good stable circulation
Property.
Specific embodiment
The method of the embodiment of the present invention, is described by preferred embodiment, and person skilled substantially can be not
Depart from and methods and techniques described herein route is modified or reconfigured in present invention, spirit and scope, come real
Now final technology of preparing.In particular, all similar replacements and change for a person skilled in the art
It is it will be apparent that they are considered as being included in spirit of the invention, scope and content.
1) during adds graphene oxide into the mixed solution of ethylene glycol and DMF, it is ensured that mixing is molten
Ethylene glycol and N,N-dimethylformamide volume ratio are 1 in liquid:1-2:1, it is 0.5-2.8g/L to add graphene oxide concentration, is surpassed
Sound 4-8h, is obtained the dispersed mixed liquor of graphene oxide；
2) ferrous sulfate is added to step 1 by) obtained in the dispersed mixed liquor of graphene oxide, it is ensured that sulfuric acid
Ferrous is 1 with graphene oxide mass ratio:0.05-1:0.4,200-400r/min stirring 10-30min after, add sublimed sulfur and
Urea, it is ensured that the mass ratio of ferrous sulfate and sublimed sulfur is 1.5:1, the mass ratio of sublimed sulfur and urea is 1:1.5-1:2, continue
0.5-1h is stirred with 200-400r/min, the mixed liquor containing graphene oxide, molysite and sulphur is obtained；
3) is by step 2) in hydro-thermal under the conditions of obtained 170-190 DEG C of the mixed liquor containing graphene oxide, molysite and sulphur source
Insulation 12-48h；
4) hydrothermal product is gone the removal of impurity for 6-10 times by using deionized water and ethanol cyclic washing, and 60-110 DEG C of vacuum is done
Ferrous disulfide/graphene oxide composite material is obtained after dry 10-12h.
Application of the ferrous disulfide/graphene oxide composite material as negative material in sodium-ion battery, is embodied as follows：
Obtained material and conductive black and PVDF (Kynoar) and NMP (1-METHYLPYRROLIDONE) are fully mixed
Conjunction forms uniform pastel, is coated on Copper Foil matrix as test electrode, using metallic sodium as to electrode assembling into button
Battery, its electrolyte is 1M NaSO3CF3/ DIG (diethylene glycol dimethyl ether).
Embodiment 1：
1) be added to for 0.3g graphene oxides mixed containing 400ml ethylene glycol and 200ml N,N-dimethylformamides by
Close in solution, ultrasonic 4h obtains the dispersed mixed liquor of graphene oxide, and graphene oxide concentration is in the mixed liquor
0.5g/L；
2) 6g ferrous sulfate is added to step 1 by) obtained in the dispersed mixed liquor of graphene oxide, with 200r/
After min stirrings 10min, 4g sublimed sulfurs and 6g urea are added, continue to stir 1h with 200r/min, be obtained and contain graphene oxide, iron
The mixed liquor of salt and sulphur；
3) is by step 2) 170 DEG C of hydro-thermals insulation 48h of the obtained mixed liquor containing graphene oxide, molysite and sulphur；
4) hydrothermal product is gone the removal of impurity for 6 times by using deionized water and ethanol cyclic washing, after 110 DEG C of vacuum drying 12h
Obtain ferrous disulfide/graphene oxide composite material.
Application of the ferrous disulfide/graphene oxide composite material as negative material in sodium-ion battery, is embodied as follows：
Obtained material and conductive black and PVDF (Kynoar) and NMP (1-METHYLPYRROLIDONE) are fully mixed
Conjunction forms uniform pastel, is coated on Copper Foil matrix as test electrode, using metallic sodium as to electrode assembling into button
Battery, its electrolyte is 1M NaSO3CF3/ DIG (diethylene glycol dimethyl ether).The current density for testing discharge and recharge is 1A g-1。
As shown in figure 1, the product for preparing is made up of ferrous disulfide/graphene oxide, wherein ferrous disulfide has excellent
Crystallinity.
Embodiment 2：
1) 1g graphene oxides are added to the mixing containing 400ml ethylene glycol and 400ml N,N-dimethylformamides
In solution, ultrasonic 6h obtains the dispersed mixed liquor of graphene oxide, and graphene oxide concentration is 1.25g/ in the mixed liquor
L；
2) 5g ferrous sulfate is added to step 1 by) obtained in the dispersed mixed liquor of graphene oxide, with 300r/
After min stirrings 20min, 3.33g sublimed sulfurs and 6.66g urea are added, continue to stir 0.5h with 300r/min, oxygen-containing fossil is obtained
The mixed liquor of black alkene, molysite and sulphur；
3) is by step 2) 190 DEG C of hydro-thermals insulation 24h of the obtained mixed liquor containing graphene oxide, molysite and sulphur；
4) hydrothermal product is gone the removal of impurity for 8 times by using deionized water and ethanol cyclic washing, after 100 DEG C of vacuum drying 10h
Obtain ferrous disulfide/graphene oxide composite material.
Application of the ferrous disulfide/graphene oxide composite material as negative material in sodium-ion battery, is embodied as follows：
Obtained material and conductive black and PVDF (Kynoar) and NMP (1-METHYLPYRROLIDONE) are fully mixed
Conjunction forms uniform pastel, is coated on Copper Foil matrix as test electrode, using metallic sodium as to electrode assembling into button
Battery, its electrolyte is 1M NaSO3CF3/ DIG (diethylene glycol dimethyl ether).The current density for testing discharge and recharge is 1A g-1。
As shown in Fig. 2 the product for preparing is that graphene oxide is dispersed between curing iron ball in product, oxidation stone is formed
Black alkene communicating passage, wherein ferrous disulfide Zhi Jing≤3 μm.
Embodiment 3：
1) be added to for 1.4g graphene oxides mixed containing 300ml ethylene glycol and 200ml N,N-dimethylformamides by
Close in solution, ultrasonic 1h obtains the finely dispersed mixed liquor of graphene oxide, and graphene oxide concentration is in the mixed liquor
2.8g/L；
2) 3.5g ferrous sulfate is added to step 1 by) obtained in the finely dispersed mixed liquor of graphene oxide, with
After 400r/min stirrings 30min, 2.33g sublimed sulfurs and 4.19g urea are added, continue to stir 1h with 400r/min, be obtained oxygen-containing
The mixed liquor of graphite alkene, molysite and sulphur；
3) is by step 2) 180 DEG C of hydro-thermals insulation 12h of the obtained mixed liquor containing graphene oxide, molysite and sulphur；
4) hydrothermal product is gone the removal of impurity for 8 times by using deionized water and ethanol cyclic washing, after 60 DEG C of vacuum drying 12h
Obtain ferrous disulfide/graphene oxide composite material.
Application of the ferrous disulfide/graphene oxide composite material as negative material in sodium-ion battery, is embodied as follows：
Obtained material and conductive black and PVDF (Kynoar) and NMP (1-METHYLPYRROLIDONE) are fully mixed
Conjunction forms uniform pastel, is coated on Copper Foil matrix as test electrode, using metallic sodium as to electrode assembling into button
Battery, its electrolyte is 1M NaSO3CF3/ DIG (diethylene glycol dimethyl ether).The current density for testing discharge and recharge is 1A g-1。
As shown in figure 3, negative material of the ferrous disulfide/graphene oxide composite material as sodium-ion battery, electricity is obtained
Pond is 1A g in current density-1Lower first discharge specific capacity is 560.6mAh g-1, first coulombic efficiency be up to 95.5%, circulation
The reversible discharge specific capacity of battery is 355.9mAh g after 50 circles-1, coulombic efficiency is close to 100%, and battery capacity does not almost have
There is decay, show good cyclical stability.
To sum up the accompanying drawing of embodiment can also clearly find out that the product prepared by the present invention is born to can be used for sodium-ion battery
Ferrous disulfide/the graphene oxide composite material of pole, graphene oxide is dispersed between curing iron ball in the composite, shape
Into graphene oxide communicating passage, wherein ferrous disulfide Zhi Jing≤3 μm.The graphene oxide communicating passage improves the conduction of material
Property, promote the dispersed of ferrous disulfide, while further suppress ferrous disulfide volumetric expansion in charge and discharge process, it is combined this
Material as sodium-ion battery negative material when with good chemical property.
Claims (10)
1. a kind of ferrous disulfide/graphene oxide composite material for sodium-ion battery negative pole, it is characterized in that：In composite
Graphene oxide is dispersed between curing iron ball, forms graphene oxide communicating passage, wherein straight footpath≤3 μm of ferrous disulfide.
2. the preparation method of the ferrous disulfide/graphene oxide composite material for sodium-ion battery negative pole of claim 1, its
It is characterized in step as follows：
1) during adds graphene oxide into the mixed liquor of ethylene glycol and DMF, ultrasonic 4-8h is obtained oxidation
The scattered mixed liquor of graphene uniform；
2) ferrous sulfate is added to step 1 by) obtained in the dispersed mixed liquor of graphene oxide, with 200-400r/
After min stirrings 10-30min, sublimed sulfur and urea are added, the wherein mass ratio of ferrous sulfate and sublimed sulfur is 1.5:1, continue with
200-400r/min stirs 0.5-1h, and the mixed liquor containing graphene oxide, molysite and sulphur is obtained；
3) is by step 2) mixed liquor containing graphene oxide, molysite and sulphur is obtained carries out hydro-thermal；
4) hydrothermal product is gone the removal of impurity by using deionized water and ethanol cyclic washing, is obtained with ferrous disulfide/oxygen after drying
Graphite alkene composite.
3. method as claimed in claim 2, it is characterized in that the step 1) in ethylene glycol and N, N- dimethyl in mixed solution
Formamide volume ratio is 1:1-2:1.
4. method as claimed in claim 2, it is characterized in that step 1) in graphene oxide concentration be 0.5-2.8g/L.
5. method as claimed in claim 2, it is characterized in that the step 2) ferrous sulfate and graphene oxide mass ratio
It is 1:0.2-1:1.
6. method as claimed in claim 2, it is characterized in that the step 2) in the mass ratio of sublimed sulfur and urea be 1:1.5-
1:2。
7. method as claimed in claim 2, it is characterized in that the step 3) hydrothermal condition：170-190 DEG C of hydro-thermal soaking time
It is 12-48h, then naturally cools to room temperature.
8. method as claimed in claim 2, it is characterized in that the step 4) with deionized water and ethanol washing times 6-10 times.
9. method as claimed in claim 2, it is characterized in that the step 4) drying condition is：It is vacuum dried at 60-110 DEG C
10-12h。
10. ferrous disulfide/the graphene oxide composite material of claim 1 is applied as negative material in sodium-ion battery.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108417808A (en) * | 2018-03-21 | 2018-08-17 | 南京工业大学 | A kind of carbon fiber-silicon-graphene oxide composite material and preparation method thereof |
| CN108735991A (en) * | 2018-05-07 | 2018-11-02 | 北京科技大学 | A kind of kalium ion battery negative material and preparation method and electrolyte |
| CN111162261A (en) * | 2020-01-14 | 2020-05-15 | 广东工业大学 | Iron disulfide/graphene oxide/nitrogen-doped multi-walled carbon nanotube composite material and preparation method and application thereof |
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| CN102760877A (en) * | 2012-07-23 | 2012-10-31 | 浙江大学 | Transition metal sulfide/graphene composite material, and preparation method and application thereof |
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- 2017-02-27 CN CN201710108194.0A patent/CN106935814A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102760877A (en) * | 2012-07-23 | 2012-10-31 | 浙江大学 | Transition metal sulfide/graphene composite material, and preparation method and application thereof |
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| ZHE HU等: "Pyrite FeS2 for high-rate and long-life rechargeable sodium batteries", 《ENERGY＆ENVIRONMENTAL SCIENCE》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108417808A (en) * | 2018-03-21 | 2018-08-17 | 南京工业大学 | A kind of carbon fiber-silicon-graphene oxide composite material and preparation method thereof |
| CN108735991A (en) * | 2018-05-07 | 2018-11-02 | 北京科技大学 | A kind of kalium ion battery negative material and preparation method and electrolyte |
| CN108735991B (en) * | 2018-05-07 | 2021-03-05 | 北京科技大学 | Negative electrode material for potassium ion battery, preparation method and electrolyte |
| CN111162261A (en) * | 2020-01-14 | 2020-05-15 | 广东工业大学 | Iron disulfide/graphene oxide/nitrogen-doped multi-walled carbon nanotube composite material and preparation method and application thereof |
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