CN109786709A - A kind of ferroferric oxide/carbon composite negative electrode material and its preparation method and application - Google Patents
A kind of ferroferric oxide/carbon composite negative electrode material and its preparation method and application Download PDFInfo
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- CN109786709A CN109786709A CN201910062863.4A CN201910062863A CN109786709A CN 109786709 A CN109786709 A CN 109786709A CN 201910062863 A CN201910062863 A CN 201910062863A CN 109786709 A CN109786709 A CN 109786709A
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Abstract
The present invention provides a kind of ferroferric oxide/carbon composite negative electrode materials and its preparation method and application.Negative electrode material provided by the invention includes Fe3O4Particle and carbon-coating, the carbon-coating coat Fe3O4Particle and connecting is integrally formed, the Fe3O4/ C composite negative pole material is porous material.The preparation method includes: 1) to mix carbon containing reducer solution with source of iron, obtains reaction mixture；2) template microsphere is impregnated in step (1) described reaction mixture, separation of solid and liquid takes solid, obtains precursors；3) calcining step (2) precursors under protective atmosphere, obtain the Fe3O4/ C composite negative pole material.Negative electrode material of the invention has high charging and discharging capacity, cyclical stability and good electric conductivity, is suitable for sodium ions to potassium ions battery.Preparation method process of the invention is simple, and synthesis condition is relatively mild, and repeatability is high, low in cost.
Description
Technical field
The invention belongs to battery technology field, it is related to a kind of electrode material more particularly to a kind of ferroferric oxide/carbon is compound
Negative electrode material and its preparation method and application.
Background technique
Lithium ion battery has that energy density is high, have extended cycle life, discharge voltage is high, environmental-friendly and memory-less effect etc.
Advantage has been widely applied to electronic product, electric car, in smart grid.However, the rare of lithium resource limits lithium ion
The large-scale application of battery.On the other hand, cheap due to the rich reserves of sodium and potassium, and there is physics similar with lithium
Chemical property, therefore, sodium ions to potassium ions battery have been ground both at home and abroad as the novel secondary energy system of substitution lithium ion battery
The extensive concern for the person of studying carefully.
Traditional secondary battery graphite cathode material is used for sodium-ion battery, and capacity is about 20mAh/g.And kalium ion battery
Negative electrode material research be concentrated mainly on graphite, but its theoretical capacity is only 279mAh/g.For graphite, metal oxygen
Compound is widely studied due to having the weight ratio capacity and volume and capacity ratio higher than carbon material.However, metal aoxidizes
Object easily causes big volume change and low electronic conductivity during ion is embedded in, and causes capacity attenuation serious.
Therefore, it is extremely urgent to find a kind of high performance sodium ions to potassium ions cell negative electrode material.
CN107507978A discloses a kind of sodium-ion battery FeS2/Fe3O4/ C negative electrode material and preparation method thereof, the party
Method includes: to take source of iron solution and lignin sulfonic acid sodium solution to mix according to molar ratio 1:1~5 of Fe:S, obtains solution A；Solution A
Brownish black sediment is obtained after hydro-thermal process；Drying precipitate is fully ground to obtain composite material precursor；Before composite material
Body is driven under protective gas atmosphere, FeS can be obtained in calcination processing2/Fe3O4/ C composite.But program preparation process is numerous
Trivial, raw material is complicated, at high cost, and its specific capacity is still to be improved.
CN102208641A discloses a kind of one-step synthesis method hollow ball structure Fe3O4/ C lithium ion battery negative material
Method.This method mainly comprises the steps that step 1, by molysite, mineralizer, solvent, and surfactant and additive mixing are equal
Even, wherein molysite: the molar ratio of mineralizer is 1:5 to 1:15；Step 2, by step 1 gained mixture in 30-50 DEG C of thermostatted water
Bath lower stirring 0.5-5 hours, form uniform solution；The resulting solution of step 2 is transferred to 50mL polytetrafluoroethylene (PTFE) by step 3
In reaction kettle, reacted 6-96 hours at 180-220 DEG C；The resulting product of step 3 is centrifugated and uses distilled water by step 4
And dehydrated alcohol respectively washs 2-5 times, is dried in vacuo 9-12 hours at 80-110 DEG C, obtains product Fe3O4/C；Step 5, by institute
Obtained Fe 3O 4/C product uses XRD, SEM and TEM (HTEM) to characterize respectively, in 200 DEG C of solvent thermal reactions, 48 hours samples
Product carry out chemical property analysis.But this method preparation negative electrode material be lithium ion battery negative material, be not suitable for sodium/
Kalium ion battery.And this method complex steps, it is unfavorable for industrialized production.
CN103208625B discloses a kind of preparation method of ferroferric-oxide-bahigh-performance high-performance negative electrode material for lithium ion battery, the party
Case is the following steps are included: (1) configures solution: selection molysite is source of iron, weighs certain mass, is dissolved in a certain amount of solvent, stirs
It mixes and is formed uniformly clear solution, wherein in 0.02~1mol/100ml, this solution is labeled as solution A for the concentration control of molysite；Choosing
It is precipitating reagent with sodium salt, weighs required quality, be dissolved in a certain amount of solvent, adds a certain amount of dispersing agent and magnetic force stirs
It mixes, forms homogeneous transparent solution, wherein in 0.02~1mol/100ml, this solution is labeled as solution B for the concentration control of sodium salt；
(2) solution B is added dropwise in solution A, and be stirred continuously, until mixed solution is in yellowish-brown uniform solution；(3) it weighs certain
The carbonaceous host material of amount is added in mixed solution described in step (2) and continues stirring a period of time, then surpasses to suspension
Sound disperses 0.5~2h；(4) suspension formed in appropriate step (3) is poured into the water heating kettle with polytetrafluoroethyllining lining,
12~72h is reacted under certain temperature in insulating box, obtains powder granule, the certain temperature refers to the temperature of insulating box
It is 120~220 DEG C；(5) powder granule obtained in step (4) is separated, and with deionized water and ethanol washing, then will
Powder dries 5~12h under certain temperature in a vacuum drying oven, obtains loose porous Fe3O4/ C composite.But the party
Method process is complicated, long flow path, and the negative electrode material prepared is lithium ion battery negative material, is not suitable for sodium ions to potassium ions electricity
Pond.
Therefore, send out a kind of with high theoretical capacity, high electric conductivity, at low cost, ABUNDANT NATUREAL RESOURSES and nontoxic
Sodium ions to potassium ions cell negative electrode material is of great significance for this field.
Summary of the invention
Aiming at the above shortcomings existing in the prior art, it is multiple that the purpose of the present invention is to provide a kind of ferroferric oxide/carbons
Close negative electrode material and its preparation method and application.Ferroferric oxide/carbon (Fe provided by the invention3O4/ C) composite negative pole material tool
Have that specific capacity is big, cyclical stability is high, good conductivity, the low advantage of resistivity.
To achieve this purpose, the present invention adopts the following technical scheme:
In a first aspect, the present invention provides a kind of Fe3O4/ C composite negative pole material, the Fe3O4/ C composite negative pole material includes
Fe3O4Particle and carbon-coating, the carbon-coating coat Fe3O4Particle and connecting is integrally formed, the Fe3O4/ C composite negative pole
Material is porous material.
Fe provided by the invention3O4/ C composite negative pole material is because have porous structure, and Fe therein3O4Particle
By carbon-coating cladding and carbon-coating plays the role of bridging agent, by Fe3O4Particle is connected as an entirety.Such uniqueness
Structure makes Fe provided by the invention3O4/ C composite negative pole material is especially suitable for sodium ions to potassium ions battery.
It is used as currently preferred technical solution below, but not as the limitation to technical solution provided by the invention, leads to
Following preferred technical solution is crossed, can preferably reach and realize technical purpose and beneficial effect of the invention.
As currently preferred technical solution, the Fe3O4/ C composite negative pole material is three-dimensional ordered polyporous material.Three
Orderly structure is tieed up, charge and ion fast transferring can be made, alleviates volume expansion caused by cyclic process to a certain extent
Problem, can allow Fe provided by the invention3O4/ C composite negative pole material has more good chemical property, is more applicable for
Sodium ions to potassium ions battery.
Preferably, the Fe3O4/ C composite negative pole material includes macropore and mesoporous, and the aperture of the macropore is 50-100nm,
Such as 50nm, 60nm, 70nm, 80nm, 90nm or 100nm etc., it is not limited to cited numerical value, in the numberical range its
His unlisted numerical value is equally applicable, the mesoporous aperture be 5-15nm, such as 5nm, 8nm, 10nm, 12nm or 15nm etc.,
It is not limited to cited numerical value, other interior unlisted numerical value of the numberical range are equally applicable.
Preferably, the Fe3O4The porosity of/C composite negative pole material be 20%-70%, such as 20%, 30%, 40%,
50%, 60% or 70% etc., it is not limited to cited numerical value, other interior unlisted numerical value of the numberical range are equally suitable
With.
Preferably, the Fe3O4In/C composite negative pole material, the ratio between the pore volume of macropore and mesoporous pore volume are 2:1-
4:1.In the present invention, if the ratio between the pore volume of macropore and mesoporous pore volume are excessive, it is excessive to will lead to specific surface area, electricity occurs
Irreversible side reaction between pole material and electrolyte；If the ratio between the pore volume of macropore and mesoporous pore volume are too small, can lead
It causes specific surface area too small, is unfavorable for the quick diffusion of ion.
Preferably, the Fe3O4The specific surface area of/C composite negative pole material is 80-120m2g-1, such as 80m2g-1、
90m2g-1、100m2g-1、110m2g-1Or 120m2g-1Deng it is not limited to cited numerical value, in the numberical range, other are not
The numerical value enumerated is equally applicable.
Second aspect, the present invention provide a kind of Fe as described in relation to the first aspect3O4The preparation method of/C composite negative pole material, institute
State method the following steps are included:
(1) carbon containing reducer solution is mixed with source of iron, obtains reaction mixture；
(2) template microsphere is impregnated in step (1) described reaction mixture, separation of solid and liquid takes solid, obtains reaction precursor
Body；
(3) calcining step (2) precursors under protective atmosphere, obtain the Fe3O4/ C composite negative pole material
Material.
In preparation method provided by the invention, carbon containing reducer also serves as carbon source and reducing agent, by the leaching to template microsphere
Bubble obtains presoma, then this presoma is heat-treated, and finally obtains the Fe of 3-D ordered multiporous structure3O4/ C composite negative pole
Material, containing micropore and macropore, and even aperture distribution, be conducive to the transmission of ion and electronics.Preparation provided by the invention
In method, carbon containing reducer generates gas and makes negative electrode material product formation porous structure after being calcined.
Preparation method process provided by the invention is simple, and synthesis condition is relatively mild, and repeatability is high, low in cost.
As currently preferred technical solution, in step (1) the carbon containing reducer solution, carbon containing reducer is anti-bad
Hematic acid.
Preferably, the solvent in step (1) the carbon containing reducer solution is the mixed solvent of ethylene glycol and methanol.Using
This mixed solvent is to more effectively solve the problems, such as that metallic is reunited.
Preferably, the in the mixed solvent of the ethylene glycol and methanol, the ethylene glycol of addition and the volume ratio 3:1.5- of methanol
3:2.5, such as 3:1.5,3:1.7,3:2,3:2.3 or 3:2.5 etc., it is not limited to cited numerical value, the numberical range
Other interior unlisted numerical value are equally applicable, preferably 3:2.
As currently preferred technical solution, in step (1), the source of iron includes ferric nitrate.In the present invention, the nitre
Sour iron further includes the hydrate (Fe (NO of ferric nitrate without including pure ferric nitrate3)3·9H2O)。
Preferably, in step (1), the mixed method is to be stirred.
Preferably, in step (1), the mixed time is 1-3h, such as 1h, 1.5h, 2h, 2.5h or 3h etc., but simultaneously
It is not limited only to cited numerical value, other unlisted numerical value are equally applicable in the numberical range.
Preferably, in step (1) described reaction mixture, the concentration of source of iron is 0.5-3mol/L, such as 0.5mol/L,
1mol/L, 1.5mol/L, 2mol/L, 2.5mol/L or 3mol/L etc., it is not limited to cited numerical value, the numberical range
Other interior unlisted numerical value are equally applicable.
Preferably, in step (1) described reaction mixture, the molar ratio of source of iron and carbon containing reducer is 2:1-13:1, example
Such as 2:1,3:1,4:1,5:1,6:1,7:1,8:1,9:1,10:1,11:1,12:1 or 13:1, it is not limited to cited
Numerical value, other interior unlisted numerical value of the numberical range are equally applicable.
As the present invention preferably technical solution, in step (2), the time of the immersion is 8-15h, such as 8h, 9h,
10h, 11h, 12h, 13h, 14h or 15h etc., it is not limited to cited numerical value, other are unlisted in the numberical range
Numerical value is equally applicable.
Preferably, in step (2), the template microsphere is polystyrene (PS) microballoon.Using polystyrene microsphere conduct
Template can be removed in calcining, macropore be formed on negative electrode material product, but because negative electrode material has when calcining
A degree of contraction, and because of the limitation of characterizing method (scanning electron microscopic observation), the macropore diameter actually observed is small
In the diameter of template microsphere.
In the present invention, the polystyrene microsphere is preferably the good monodisperse polystyrene microsphere of self assembly.
Preferably, in step (2), the partial size of the template microsphere is 250-325nm, for example, 250nm, 260nm, 270nm,
280nm, 290nm, 300nm, 310nm, 320nm or 325nm etc., it is not limited to cited numerical value, in the numberical range
Other unlisted numerical value are equally applicable.If template microsphere partial size is excessive, it is excessive to will lead to specific surface area, electrode material occurs
The irreversible side reaction between electrolyte；If template microsphere partial size is too small, it is too small to will lead to specific surface area, is unfavorable for ion
Quick diffusion.
Preferably, in step (2), the mass ratio of the template microsphere and source of iron is 1:1-1:6, for example, 1:1,1:2,1:3,
1:4,1:5 or 1:6 etc., it is not limited to cited numerical value, other interior unlisted numerical value of the numberical range are equally applicable.
Preferably, in step (2), the method for the separation of solid and liquid includes vacuum filtration.
It preferably, further include that the solid obtained to separation of solid and liquid is dried in step (2).The specific item of the drying
Part can be selected according to the actual situation, such as can be carried out in 50 DEG C of air dry oven.
As currently preferred technical solution, step (3) described protective atmosphere includes nitrogen atmosphere and/or argon gas gas
Atmosphere.
Preferably, step (3) further include: after calcining, obtained product is cooled to 20-30 DEG C, that is, is cooled to room temperature.
As the present invention preferably technical solution, step (3) calcining is that two steps are calcined, and the temperature of second step calcining is high
In the temperature of first step calcining.In the present invention, it is preferred to use the calcining of two steps is to keep reaction more abundant, and template microsphere removes more dry
Only.If only carrying out one-step calcination, it will lead to and react insufficient, template microsphere removal is incomplete.
Preferably, the temperature of first step calcining is 250-350 DEG C, for example, 250 DEG C, 260 DEG C, 270 DEG C, 280 DEG C,
290 DEG C, 300 DEG C, 310 DEG C, 320 DEG C, 330 DEG C, 340 DEG C or 350 DEG C etc., it is not limited to cited numerical value, the numerical value
Other unlisted numerical value are equally applicable in range, and preferably 300 DEG C.
Preferably, the time of first step calcining is 3-5h, such as 3h, 3.5h, 4h, 4.5h or 5h etc., but simultaneously not only
It is limited to cited numerical value, other unlisted numerical value are equally applicable in the numberical range.
Preferably, the heating rate of first step calcining is 0.5-2 DEG C/min, for example, 0.5 DEG C/min, 1 DEG C/min,
1.5 DEG C/min or 2 DEG C/min etc., it is not limited to cited numerical value, other interior unlisted numerical value of the numberical range are same
Sample is applicable in.
Preferably, the temperature of second step calcining is 450-550 DEG C, for example, 450 DEG C, 460 DEG C, 470 DEG C, 480 DEG C,
490 DEG C, 500 DEG C, 510 DEG C, 520 DEG C, 530 DEG C, 540 DEG C or 550 DEG C etc., it is not limited to cited numerical value, the numerical value
Other unlisted numerical value are equally applicable in range, and preferably 500 DEG C.
Preferably, the time of second step calcining is 3-5h, such as 3h, 3.5h, 4h, 4.5h or 5h etc., but simultaneously not only
It is limited to cited numerical value, other unlisted numerical value are equally applicable in the numberical range.
Preferably, the heating rate of second step calcining is 0.5-2 DEG C/min, for example, 0.5 DEG C/min, 1 DEG C/min,
1.5 DEG C/min or 2 DEG C/min etc., it is not limited to cited numerical value, other interior unlisted numerical value of the numberical range are same
Sample is applicable in.
As the further preferred technical solution of preparation method of the present invention, the described method comprises the following steps:
(1) ascorbic acid solution and ferric nitrate are stirred 1-3h, obtain reaction mixture；
Wherein, the concentration of source of iron is 0.5-3mol/L, and the molar ratio of source of iron and carbon containing reducer is 2:1-13:1, described anti-
Solvent in bad hematic acid solution is the mixed solvent being made of the ethylene glycol and methanol of volume ratio 3:2；
(2) polystyrene microsphere 8-15h is impregnated in step (1) described reaction mixture, vacuum filtration takes solid, to institute
It states solid to be dried, obtains precursors；
Wherein, the partial size of the polystyrene microsphere is 250-325nm, the mass ratio of the polystyrene microsphere and source of iron
For 1:1-1:6；
(3) two step calcinings are carried out to step (2) precursors under protective atmosphere, the first step is calcined with 0.5-
Heat preservation calcining 3-5h, second step are calcined with the liter of 0.5-2 DEG C/min after temperature is risen to 300 DEG C by the heating rate of 2 DEG C/min
Heat preservation calcining 3-5h, is cooled to 20-30 DEG C later, obtains the Fe after temperature is risen to 500 DEG C by warm speed3O4/ C Compound Negative
Pole material.
The third aspect, the present invention provide a kind of Fe as described in relation to the first aspect3O4The purposes of/C composite negative pole material, it is described
Fe3O4/ C composite negative pole material is used for sodium-ion battery or kalium ion battery.
Compared with prior art, the invention has the following advantages:
(1) Fe provided by the invention3O4/ C composite negative pole material unique structure shows high charging and discharging capacity, circulation
Stability and good electric conductivity, especially suitable for sodium-ion battery or kalium ion battery.Fe provided by the invention3O4/ C is multiple
Negative electrode material is closed for its initial charge specific capacity of sodium-ion battery up to 361.1mAh/g, conductivity is up to 5.0 × 10-4S/m,
50 primary current density are the capacity retention ratio after the charge and discharge cycles of 50mA/g up to 88%；Fe provided by the invention3O4/ C is compound
Negative electrode material is for its initial charge specific capacity of kalium ion battery up to 294.9mAh/g, and conductivity is up to 4.0 × 10-4S/m, 50
Primary current density is the capacity retention ratio after the charge and discharge cycles of 50mA/g up to 84%；
(2) preparation method provided by the invention is easy to operate, at low cost, and yield is big, and repeatability is high, and product structure is easy control
System.
Detailed description of the invention
Fig. 1 is Fe prepared by embodiment 13O4The SEM scanning figure of/C composite negative pole material；
Fig. 2 is the Fe of embodiment 13O4/ C composite negative pole material and comparative example 1 prepare Fe3O4The XRD diffraction of negative electrode material
Figure；
Fig. 3 is Fe prepared by embodiment 13O4/ C composite negative pole material and comparative example 1 prepare Fe3O4Negative electrode material is as sodium
Cell negative electrode material is in the cycle performance figure that current density is 50mA/g.
Specific embodiment
In order to better illustrate the present invention, it is easy to understand technical solution of the present invention, below further specifically to the present invention
It is bright.But following embodiments is only simple example of the invention, does not represent or limit the scope of the present invention, this
Invention protection scope is subject to claims.
The following are typical but non-limiting embodiments of the invention:
Embodiment 1
The present embodiment prepares Fe with the following method3O4/ C composite negative pole material:
(1) it weighs 0.33 gram of ascorbic acid and is added in the mixed solution of 3ml ethylene glycol and 2ml methanol composition, stirring
To obtaining clear ascorbic acid solution；By 3.03 grams of Fe (NO3)3·9H2O is added in ascorbic acid solution, continues to stir
1.5h obtains reaction mixture；
In the reaction mixture, the concentration of ferric nitrate is 1.5mol/L, and the molar ratio of ferric nitrate and ascorbic acid is 4:
1。
(2) the good Monodisperse Polystyrene Microspheres (partial size 250-325nm) of 1 gram of self assembly are impregnated in the above solution, is impregnated
Time is 10h, and rear vacuum filtration obtains presoma, is placed in 50 DEG C of air dry oven and dries for 24 hours；
Wherein, PS microballoon and Fe (NO3)3·9H2The mass ratio of O is about 1:3.
(3) presoma after above-mentioned drying is placed in tube furnace, two step calcinings is carried out under an argon atmosphere, first with 1
DEG C/heating rate of min is warming up to 300 DEG C of heat preservations calcining 3h, 500 DEG C of heat preservations are then warming up to the heating rate of 1 DEG C/min
5h is calcined, after being cooled to 25 DEG C, obtains the Fe3O4/ C composite sodium ions to potassium ions cell negative electrode material.
To the sample of the present embodiment, surface structure characterization is carried out using scanning electron microscope (SEM), using full-automatic more
Function gas absorption instrument carries out Pore Characterization, and result is as follows.
Fe manufactured in the present embodiment3O4/ C composite negative pole material includes Fe3O4Particle and carbon-coating, the carbon-coating coat Fe3O4
Particle and connecting is integrally formed, the Fe3O4/ C composite negative pole material is three-dimensional ordered polyporous material, includes macropore
With it is mesoporous, the aperture of the macropore is 50-80nm, and the mesoporous aperture is 5-12nm；The Fe3O4/ C composite negative pole material
Porosity be 60%；The Fe3O4In/C composite negative pole material, the ratio between the pore volume of macropore and mesoporous pore volume are 4:1,
The Fe3O4The specific surface area of/C composite negative pole material is 120m2g-1。
Other embodiments also carry out structural characterization according to above-mentioned structured testing method.
Fe manufactured in the present embodiment3O4The electrochemical property test of/C composite negative pole material the results are shown in Table 1 and table 2.
Fig. 1 is Fe made from the present embodiment3O4The scanning electron microscopy of/C composite sodium ions to potassium ions cell negative electrode material
Mirror (SEM) scanning figure.As can be seen from Fig., the Fe by being decomposed thermally to form3O4/ C be apparent porous structure, containing it is mesoporous with
Macropore, and integrally show 3-D ordered multiporous structure.
Embodiment 2
The present embodiment prepares Fe with the following method3O4/ C composite negative pole material:
(1) it weighs 0.1887 gram of ascorbic acid and is added in the mixed solution of 3ml ethylene glycol and 2ml methanol composition, stir
It mixes to obtaining clear ascorbic acid solution；(2) by 3.03 grams of Fe (NO3)3·9H2O is added in ascorbic acid solution, is continued
2h is stirred, reaction mixture is obtained；
In the reaction mixture, the concentration of ferric nitrate is 1.5mol/L, and the molar ratio of ferric nitrate and ascorbic acid is 7:
1。
(2) the good Monodisperse Polystyrene Microspheres (partial size 250-325nm) of 1 gram of self assembly are impregnated in the above solution, is impregnated
Time is 12h, and rear vacuum filtration obtains presoma, is placed in 50 DEG C of air dry oven dry 30h；
Wherein, PS microballoon and Fe (NO3)3·9H2The mass ratio of O is about 1:3.
(3) presoma after above-mentioned drying is placed in tube furnace, carries out two step calcinings in a nitrogen atmosphere, first with
The heating rate of 0.5 DEG C/min is warming up to 300 DEG C of heat preservation calcining 3h, is then warming up to 500 DEG C with the heating rate of 0.5 DEG C/min
Heat preservation calcining 3h, after being cooled to 20 DEG C, obtains the Fe3O4/ C composite sodium ions to potassium ions cell negative electrode material.
Fe manufactured in the present embodiment3O4/ C composite negative pole material includes Fe3O4Particle and carbon-coating, the carbon-coating coat Fe3O4
Particle and connecting is integrally formed, the Fe3O4/ C composite negative pole material is three-dimensional ordered polyporous material, includes macropore
With it is mesoporous, the aperture of the macropore is 50-70nm, and the mesoporous aperture is 5-8nm；The Fe3O4/ C composite negative pole material
Porosity is 50%；The Fe3O4In/C composite negative pole material, the ratio between the pore volume of macropore and mesoporous pore volume are 2:1, institute
State Fe3O4The specific surface area of/C composite negative pole material is 98m2g-1。
Fe manufactured in the present embodiment3O4The electrochemical property test of/C composite negative pole material the results are shown in Table 1 and table 2.
Embodiment 3
The present embodiment prepares Fe with the following method3O4/ C composite negative pole material:
(1) it weighs 0.132 gram of ascorbic acid and is added in the mixed solution of 3ml ethylene glycol and 2ml methanol composition, stirring
To obtaining clear ascorbic acid solution；By 3.03 grams of Fe (NO3)3·9H2O is added in ascorbic acid solution, continues to stir
3h obtains reaction mixture；
In the reaction mixture, the concentration of ferric nitrate is 1.5mol/L, and the molar ratio of ferric nitrate and ascorbic acid is 10:
1。
(2) the good Monodisperse Polystyrene Microspheres (partial size 250-325nm) of 0.5 gram of self assembly are impregnated into leaching in the above solution
The bubble time is 15h, and rear vacuum filtration obtains presoma, is placed in 50 DEG C of air dry oven dry 20h；
Wherein, PS microballoon and Fe (NO3)3·9H2The mass ratio of O is about 1:6.
(3) presoma after above-mentioned drying is placed in tube furnace, carries out two step calcinings in a nitrogen atmosphere, first with
The heating rate of 1.5 DEG C/min is warming up to 300 DEG C of heat preservation calcining 4h, is then warming up to 500 DEG C with the heating rate of 1.5 DEG C/min
Heat preservation calcining 5h, after being cooled to 30 DEG C, obtains the Fe3O4/ C composite sodium ions to potassium ions cell negative electrode material.
Fe manufactured in the present embodiment3O4/ C composite negative pole material includes Fe3O4Particle and carbon-coating, the carbon-coating coat Fe3O4
Particle and connecting is integrally formed, the Fe3O4/ C composite negative pole material is three-dimensional ordered polyporous material, includes macropore
With it is mesoporous, the aperture of the macropore is 70-100nm, and the mesoporous aperture is 6-11nm；The Fe3O4/ C composite negative pole material
Porosity be 20%；The Fe3O4In/C composite negative pole material, the ratio between the pore volume of macropore and mesoporous pore volume are 3:1,
The Fe3O4The specific surface area of/C composite negative pole material is 89m2g-1。
Fe manufactured in the present embodiment3O4The electrochemical property test of/C composite negative pole material the results are shown in Table 1 and table 2.
Embodiment 4
The present embodiment prepares Fe with the following method3O4/ C composite negative pole material:
(1) it weighs 0.1016 gram of ascorbic acid and is added in the mixed solution of 3ml ethylene glycol and 2ml methanol composition, stir
Mix to obtain clarification ascorbic acid solution；By 3.03 grams of Fe (NO3)3·9H2O is added in ascorbic acid solution, continues to stir
1h obtains reaction mixture；
In the reaction mixture, the concentration of ferric nitrate is 1.5mol/L, and the molar ratio of ferric nitrate and ascorbic acid is 13:
1。
(2) the good Monodisperse Polystyrene Microspheres (partial size 250-325nm) of 0.8 gram of self assembly are impregnated into leaching in the above solution
The bubble time is 8h, and rear vacuum filtration obtains presoma, is placed in 50 DEG C of air dry oven dry 36h；
Wherein, PS microballoon and Fe (NO3)3·9H2The mass ratio of O is about 1:3.8.
(3) presoma after above-mentioned drying is placed in tube furnace, carries out two step calcinings under an argon atmosphere, first with
The heating rate of 0.5 DEG C/min is warming up to 300 DEG C of heat preservation calcining 3h, is then warming up to 500 DEG C with the heating rate of 0.5 DEG C/min
Heat preservation calcining 5h, after being cooled to 25 DEG C, obtains the Fe3O4/ C composite sodium ions to potassium ions cell negative electrode material.
Fe manufactured in the present embodiment3O4/ C composite negative pole material includes Fe3O4Particle and carbon-coating, the carbon-coating coat Fe3O4
Particle and connecting is integrally formed, the Fe3O4/ C composite negative pole material is three-dimensional ordered polyporous material, includes macropore
With it is mesoporous, the aperture of the macropore is 60-90nm, and the mesoporous aperture is 8-12nm；The Fe3O4/ C composite negative pole material
Porosity be 30%；The Fe3O4In/C composite negative pole material, the ratio between the pore volume of macropore and mesoporous pore volume are 3.5:
1, the Fe3O4The specific surface area of/C composite negative pole material is 87m2g-1。
Fe manufactured in the present embodiment3O4The electrochemical property test of/C composite negative pole material the results are shown in Table 1 and table 2.
Embodiment 5
The present embodiment prepares Fe with the following method3O4/ C composite negative pole material:
(1) it weighs 0.66 gram of ascorbic acid and is added in the mixed solution of 3ml ethylene glycol and 2ml methanol composition, stirring
To obtain clarification ascorbic acid solution；By 6.06 grams of Fe (NO3)3·9H2O is added in ascorbic acid solution, continues to stir 1h,
Obtain reaction mixture；
In the reaction mixture, the concentration of ferric nitrate is 3mol/L, and the molar ratio of ferric nitrate and ascorbic acid is 4:1.
(2) the good Monodisperse Polystyrene Microspheres (partial size 250-325nm) of 1.5 grams of self assemblies are impregnated into leaching in the above solution
The bubble time is 10h, and rear vacuum filtration obtains presoma, is placed in 50 DEG C of air dry oven dry 25h；
Wherein, PS microballoon and Fe (NO3)3·9H2The mass ratio of O is about 1:4.
(3) presoma after above-mentioned drying is placed in tube furnace, two step calcinings is carried out under an argon atmosphere, first with 1
DEG C/heating rate of min is warming up to 300 DEG C of heat preservations calcining 3h, 500 DEG C of heat preservations are then warming up to the heating rate of 1 DEG C/min
3h is calcined, after being cooled to 25 DEG C, obtains the Fe3O4/ C composite sodium ions to potassium ions cell negative electrode material.
Fe manufactured in the present embodiment3O4/ C composite negative pole material includes Fe3O4Particle and carbon-coating, the carbon-coating coat Fe3O4
Particle and connecting is integrally formed, the Fe3O4/ C composite negative pole material is three-dimensional ordered polyporous material, includes macropore
With it is mesoporous, the aperture of the macropore is 70-100nm, and the mesoporous aperture is 7-12nm；The Fe3O4/ C composite negative pole material
Porosity be 70%；The Fe3O4In/C composite negative pole material, the ratio between the pore volume of macropore and mesoporous pore volume are 2.1:
1, the Fe3O4The specific surface area of/C composite negative pole material is 80m2g-1。
Fe manufactured in the present embodiment3O4The electrochemical property test of/C composite negative pole material the results are shown in Table 1 and table 2.
Embodiment 6
The present embodiment prepares Fe with the following method3O4/ C composite negative pole material:
(1) it weighs 0.22 gram of ascorbic acid and is added in the mixed solution of 3ml ethylene glycol and 2ml methanol composition, stirring
To obtaining ascorbic acid solution；By 1.01 grams of Fe (NO3)3·9H2O is added in ascorbic acid solution, is continued stirring 1.5h and is obtained
Reaction mixture；
In the reaction mixture, the concentration of ferric nitrate is 0.5mol/L, and the molar ratio of ferric nitrate and ascorbic acid is 2:
1。
(3) the good Monodisperse Polystyrene Microspheres (partial size 250-325nm) of 1 gram of self assembly are impregnated in the above solution, is impregnated
Time is 11h, and rear vacuum filtration obtains presoma, is placed in 50 DEG C of air dry oven and dries for 24 hours；
Wherein, PS microballoon and Fe (NO3)3·9H2The mass ratio of O is about 1:1.
(4) presoma after above-mentioned drying is placed in tube furnace, two steps is carried out under the mixed atmosphere of nitrogen and argon gas
Calcining is warming up to 300 DEG C of heat preservation calcining 4h first with the heating rate of 1.5 DEG C/min, then with the heating rate of 1.5 DEG C/min
500 DEG C of heat preservation calcining 5h are warming up to, after being cooled to 25 DEG C, obtain the Fe3O4/ C composite sodium ions to potassium ions battery cathode material
Material.
Fe manufactured in the present embodiment3O4/ C composite negative pole material includes Fe3O4Particle and carbon-coating, the carbon-coating coat Fe3O4
Particle and connecting is integrally formed, the Fe3O4/ C composite negative pole material is three-dimensional ordered polyporous material, includes macropore
With it is mesoporous, the aperture of the macropore is 50-90nm, and the mesoporous aperture is 5-9nm；The Fe3O4/ C composite negative pole material
Porosity is 40%；The Fe3O4In/C composite negative pole material, the ratio between the pore volume of macropore and mesoporous pore volume are 3.2:1,
The Fe3O4The specific surface area of/C composite negative pole material is 90m2g-1。
Fe manufactured in the present embodiment3O4The electrochemical property test of/C composite negative pole material the results are shown in Table 1 and table 2.
Embodiment 7
The present embodiment prepares Fe with the following method3O4/ C composite negative pole material:
(1) it weighs 0.22 gram of ascorbic acid and is added in the mixed solution of 3ml ethylene glycol and 2ml methanol composition, stirring
To obtain clarification ascorbic acid solution；By 2.02 grams of Fe (NO3)3·9H2O is added in ascorbic acid solution, continues to stir
2.5h obtains reaction mixture；
In the reaction mixture, the concentration of ferric nitrate is 1mol/L, and the molar ratio of ferric nitrate and ascorbic acid is 4:1.
(2) the good Monodisperse Polystyrene Microspheres (partial size 250-325nm) of 1.5 grams of self assemblies are impregnated into leaching in the above solution
The bubble time is 10h, and rear vacuum filtration obtains presoma, is placed in 50 DEG C of air dry oven dry 28h；
Wherein, PS microballoon and Fe (NO3)3·9H2The mass ratio of O is about 1:35.
(3) presoma after above-mentioned drying is placed in tube furnace, two steps is carried out under the mixed atmosphere of nitrogen and argon gas
Calcining is warming up to 300 DEG C of heat preservation calcining 3h first with the heating rate of 0.5 DEG C/min, then with the heating rate of 0.5 DEG C/min
500 DEG C of heat preservation calcining 4h are warming up to, after being cooled to 25 DEG C, obtain the Fe3O4/ C composite sodium ions to potassium ions battery cathode material
Material.
Fe manufactured in the present embodiment3O4/ C composite negative pole material includes Fe3O4Particle and carbon-coating, the carbon-coating coat Fe3O4
Particle and connecting is integrally formed, the Fe3O4/ C composite negative pole material is three-dimensional ordered polyporous material, includes macropore
With it is mesoporous, the aperture of the macropore is 60-85nm, and the mesoporous aperture is 11-15nm；The Fe3O4/ C composite negative pole material
Porosity be 60%；The Fe3O4In/C composite negative pole material, the ratio between the pore volume of macropore and mesoporous pore volume are 3.5:
1, the Fe3O4The specific surface area of/C composite negative pole material is 97m2g-1。
Fe manufactured in the present embodiment3O4The electrochemical property test of/C composite negative pole material the results are shown in Table 1 and table 2.
Embodiment 8
The Fe of the present embodiment3O4Referring to embodiment 1, difference is /C composite negative pole material preparation method:
In step (1), ascorbic acid is added in the mixed solution of 3ml ethylene glycol and 1.5ml methanol composition.
In step (2), soaking time 15h.
In step (3), 250 DEG C of heat preservation calcining 5h are warming up to the heating rate of 2 DEG C/min first, then with 2 DEG C/min
Heating rate be warming up to 450 DEG C of heat preservations calcining 5h.
Fe manufactured in the present embodiment3O4/ C composite negative pole material includes Fe3O4Particle and carbon-coating, the carbon-coating coat Fe3O4
Particle and connecting is integrally formed, the Fe3O4/ C composite negative pole material is three-dimensional ordered polyporous material, includes macropore
With it is mesoporous, the aperture of the macropore is 70-100nm, and the mesoporous aperture is 8-11nm；The Fe3O4/ C composite negative pole material
Porosity be 60%；The Fe3O4In/C composite negative pole material, the ratio between the pore volume of macropore and mesoporous pore volume are 3.7:
1, the Fe3O4The specific surface area of/C composite negative pole material is 98m2g-1。
Fe manufactured in the present embodiment3O4The electrochemical property test of/C composite negative pole material the results are shown in Table 1 and table 2.
Embodiment 9
The Fe of the present embodiment3O4Referring to embodiment 1, difference is /C composite negative pole material preparation method:
In step (1), ascorbic acid is added in the mixed solution of 3ml ethylene glycol and 2.5ml methanol composition.
In step (3), it is warming up to 350 DEG C of heat preservation calcinings first, then heats to 550 DEG C of heat preservation calcinings
Fe manufactured in the present embodiment3O4/ C composite negative pole material includes Fe3O4Particle and carbon-coating, the carbon-coating coat Fe3O4
Particle and connecting is integrally formed, the Fe3O4/ C composite negative pole material is three-dimensional ordered polyporous material, includes macropore
With it is mesoporous, the aperture of the macropore is 80-100nm, and the mesoporous aperture is 10nm；The Fe3O4/ C composite negative pole material
Porosity is 50%；The Fe3O4In/C composite negative pole material, the ratio between the pore volume of macropore and mesoporous pore volume are 4:1, institute
State Fe3O4The specific surface area of/C composite negative pole material is 100m2g-1。
Fe manufactured in the present embodiment3O4The electrochemical property test of/C composite negative pole material the results are shown in Table 1 and table 2.
Comparative example 1
This comparative example is prepared as follows Fe3O4Negative electrode material:
(1) 3.03 grams of Fe (NO are weighed3)3·9H2O is simultaneously added in the mixed solution of 3ml ethylene glycol and 2ml methanol composition,
1.5h is stirred, reaction mixture is obtained；
In the reaction mixture, the concentration of ferric nitrate is 1.5mol/L.
(2) the good Monodisperse Polystyrene Microspheres of 1 gram of self assembly (partial size is identical as the PS microballoon in embodiment 1) are immersed in above-mentioned
In solution, soaking time 10h, rear vacuum filtration obtains presoma, is placed in 50 DEG C of air dry oven and dries for 24 hours；
(3) presoma after above-mentioned drying is placed in tube furnace, two step calcinings is carried out under an argon atmosphere, first with 1
DEG C/heating rate of min is warming up to 300 DEG C of heat preservations calcining 3h, 500 DEG C of heat preservations are then warming up to the heating rate of 1 DEG C/min
Calcining 5h obtains Fe after being cooled to 25 DEG C3O4Powder.
The Fe of this comparative example preparation3O4The electrochemical property test of cathode the results are shown in Table 1 and table 2.
Fig. 2 is the Fe of embodiment 13O4/ C composite negative pole material (is denoted as Fe in figure3O4/ C) and the preparation of comparative example 1 Fe3O4It is negative
Pole material (is denoted as Fe in figure3O4) XRD diffraction pattern.As shown, Fe prepared by embodiment 13O4Prepared by/C and comparative example 1
Fe3O4Each diffraction maximum of material is and Fe3O4The diffraction maximum of standard card (JCPDS No.88-0315) is all corresponding, and
Do not occur impurity peaks, shows its purity with higher.On the other hand, due to Fe in the product of embodiment 13O4Surface packet
The carbon-coating covered is amorphous carbon, therefore does not have apparent XRD diffraction maximum in the product.
Fig. 3 is Fe prepared by embodiment 13O4/ C composite negative pole material and comparative example 1 prepare Fe3O4Negative electrode material is as sodium
Cell negative electrode material (is prepared into the specific method of sodium-ion battery referring to electrification in the cycle performance figure that current density is 50mA/g
Learn performance test methods part).From this figure, it can be seen that Fe prepared by embodiment 13O4/ C composite negative pole material is in current density
Fine for the cyclical stability of 50mA/g, after continuous charge and discharge 50 times, charging and discharging capacity stills remain in 300mAh/g
Left and right, and Fe prepared by comparative example 13O4The specific discharge capacity of particle is only left 80mAh/g or so after continuous charge and discharge 50 times.
Electrochemical property test method:
Using four probe resistance rate tester testing conductivities.
Negative electrode material prepared by each embodiment and comparative example is fabricated to sodium-ion battery or kalium ion battery carries out specific volume
Amount and cycle performance performance test.
The method for being fabricated to sodium and kalium ion battery are as follows: weigh the resulting three-dimensional porous Fe of 0.24g3O4/ C powder, 0.03g
Acetylene black conductor be added agate mortar in, grind 20 minutes, add the N- methylpyrrole dissolved with the 5% of PVDF binder
Alkanone solution 0.6g continues grinding 10 minutes, is then applied on copper foil and prepares Fe3O4/ C electrode slice.By the electrode slice of preparation in true
Dried 8 hours at 120 DEG C in empty drying box, after in argon gas glove box assemble sodium/potassium battery, Fe3O4/ C electrode slice is work electricity
Pole, for sode cell, metallic sodium is to electrode, and glass fibre is diaphragm.The electrolyte solute that sode cell uses is NaClO4, molten
Agent is (EC/DEC 1:1 (W/W), 5%FEC), solution concentration 1mol/L.For potassium battery, metallic potassium is to electrode, glass
Fiber is diaphragm.The electrolyte solute that potassium battery uses is KPF6, solvent is (EC/DEC1:1 (W/W)), and solution concentration is
0.8mol/L。
It is carried out between 0.01-3.0V at 25 DEG C with the current density of 50mA/g using the blue electric battery test system in Wuhan
Charge and discharge cycles test specific capacity and cycle performance.Electrochemical property test the results are shown in Table 1 and table 2.
Table 1 is prepared into the test result of sodium-ion battery
Table 2 is prepared into the test result of kalium ion battery
Based on the above embodiments with comparative example it is found that Fe provided by the invention3O4/ C composite negative pole material unique structure, than
Surface area is big, and has high charging and discharging capacity, cyclical stability and good electric conductivity, especially suitable for sodium ion
Battery or kalium ion battery.Comparative example does not use the solution of the present invention, because that carbon containing reducer is not added in preparation process,
Fe3O4On do not coat carbon-coating, product is also not three-dimensional ordered polyporous material, thus its properties of product is not as good as embodiment 1.
The Applicant declares that the present invention is explained by the above embodiments detailed process equipment and process flow of the invention,
But the present invention is not limited to the above detailed process equipment and process flow, that is, it is above-mentioned detailed not mean that the present invention must rely on
Process equipment and process flow could be implemented.It should be clear to those skilled in the art, any improvement in the present invention,
Addition, selection of concrete mode of equivalence replacement and auxiliary element to each raw material of product of the present invention etc., all fall within of the invention
Within protection scope and the open scope.
Claims (10)
1. a kind of Fe3O4/ C composite negative pole material, which is characterized in that the Fe3O4/ C composite negative pole material includes Fe3O4Particle and
Carbon-coating, the carbon-coating coat Fe3O4Particle and connecting is integrally formed, the Fe3O4/ C composite negative pole material is porous
Material.
2. Fe according to claim 13O4/ C composite negative pole material, which is characterized in that the Fe3O4/ C composite negative pole material is
Three-dimensional ordered polyporous material；
Preferably, the Fe3O4/ C composite negative pole material includes macropore and mesoporous, and the aperture of the macropore is 50-100nm, described
Mesoporous aperture is 5-15nm；
Preferably, the Fe3O4The porosity of/C composite negative pole material is 20%-70%；
Preferably, the Fe3O4In/C composite negative pole material, the ratio between the pore volume of macropore and mesoporous pore volume are 2:1-4:1；
Preferably, the Fe3O4The specific surface area of/C composite negative pole material is 80-120m2g-1。
3. a kind of Fe as claimed in claim 1 or 23O4The preparation method of/C composite negative pole material, which is characterized in that the method
The following steps are included:
(1) carbon containing reducer solution is mixed with source of iron, obtains reaction mixture；
(2) template microsphere is impregnated in step (1) described reaction mixture, separation of solid and liquid takes solid, obtains precursors；
(3) calcining step (2) precursors under protective atmosphere, obtain the Fe3O4/ C composite negative pole material.
4. preparation method according to claim 3, which is characterized in that carbon containing in step (1) the carbon containing reducer solution
Reducing agent is ascorbic acid；
Preferably, the solvent in step (1) the carbon containing reducer solution is the mixed solvent of ethylene glycol and methanol；
Preferably, the in the mixed solvent of the ethylene glycol and methanol, the ethylene glycol of addition and the volume ratio 3:1.5-3 of methanol:
2.5, preferably 3:2.
5. preparation method according to claim 3 or 4, which is characterized in that in step (1), the source of iron includes ferric nitrate；
Preferably, in step (1), the mixed method is to be stirred；
Preferably, in step (1), the mixed time is 1-3h；
Preferably, in step (1) described reaction mixture, the concentration of source of iron is 0.5-3mol/L；
Preferably, in step (1) described reaction mixture, the molar ratio of source of iron and carbon containing reducer is 2:1-13:1.
6. according to the described in any item preparation methods of claim 3-5, which is characterized in that in step (2), the time of the immersion
For 8-15h；
Preferably, in step (2), the template microsphere is polystyrene microsphere；
Preferably, in step (2), the partial size of the template microsphere is 250-325nm；
Preferably, in step (2), the mass ratio of the template microsphere and source of iron is 1:1-1:6；
Preferably, in step (2), the method for the separation of solid and liquid includes vacuum filtration；
It preferably, further include that the solid obtained to separation of solid and liquid is dried in step (2).
7. according to the described in any item preparation methods of claim 3-6, which is characterized in that step (3) the protective atmosphere packet
Include nitrogen atmosphere and/or argon atmosphere；
Preferably, step (3) further include: after calcining, obtained product is cooled to 20-30 DEG C.
8. according to the described in any item preparation methods of claim 3-7, which is characterized in that step (3) calcining is that two steps are forged
It burns, the temperature of second step calcining is higher than the temperature of first step calcining；
Preferably, the temperature of the first step calcining is 250-350 DEG C, preferably 300 DEG C；
Preferably, the time of the first step calcining is 3-5h；
Preferably, the heating rate of the first step calcining is 0.5-2 DEG C/min；
Preferably, the temperature of the second step calcining is 450-550 DEG C, preferably 500 DEG C；
Preferably, the time of the second step calcining is 3-5h；
Preferably, the heating rate of the second step calcining is 0.5-2 DEG C/min.
9. according to the described in any item preparation methods of claim 3-8, which is characterized in that the described method comprises the following steps:
(1) ascorbic acid solution and ferric nitrate are stirred 1-3h, obtain reaction mixture；
Wherein, the concentration of source of iron is 0.5-3mol/L, and the molar ratio of source of iron and carbon containing reducer is 2:1-13:1, the Vitamin C
Solvent in acid solution is the mixed solvent being made of the ethylene glycol and methanol of volume ratio 3:2；
(2) polystyrene microsphere 8-15h is impregnated in step (1) described reaction mixture, vacuum filtration takes solid, to described solid
Body is dried, and obtains precursors；
Wherein, the partial size of the polystyrene microsphere is 250-325nm, and the mass ratio of the polystyrene microsphere and source of iron is 1:
1-1:6；
(3) under protective atmosphere to step (2) precursors carry out two step calcinings, the first step calcining with 0.5-2 DEG C/
Heat preservation calcining 3-5h after temperature is risen to 300 DEG C by the heating rate of min, the heating speed that second step is calcined with 0.5-2 DEG C/min
Heat preservation calcining 3-5h, is cooled to 20-30 DEG C later, obtains the Fe after temperature is risen to 500 DEG C by degree3O4/ C composite negative pole material
Material.
10. a kind of Fe as claimed in claim 1 or 23O4The purposes of/C composite negative pole material, which is characterized in that the Fe3O4/ C is multiple
It closes negative electrode material and is used for sodium-ion battery or kalium ion battery.
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