CN102531066A - Spherical ferrate having hollow structure and preparation method thereof - Google Patents
Spherical ferrate having hollow structure and preparation method thereof Download PDFInfo
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- CN102531066A CN102531066A CN2011103448834A CN201110344883A CN102531066A CN 102531066 A CN102531066 A CN 102531066A CN 2011103448834 A CN2011103448834 A CN 2011103448834A CN 201110344883 A CN201110344883 A CN 201110344883A CN 102531066 A CN102531066 A CN 102531066A
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Abstract
The invention discloses spherical ferrate having a hollow structure and a preparation method thereof. The ferrate MFe2O4 is of a hollow-structured spherical particle formed by self-assembling of nanocrystals having a particle size of 10-50nm, wherein M is Co, Ni or Zn, the diameter of the particle is 0.1-1mu m, and the thickness of a shell layer is 30-200nm. The spherical ferrate can be used as a negative electrode material of a lithium ion battery.
Description
?
Technical field
The present invention relates to a kind of spherical iron hydrochlorate in the lithium ion battery field with hollow structure, and preparation method thereof.
Background technology
Under the background of global resource scarcity and environmental degradation, people have to accelerate the paces of new energy development, and the exploitation of cleaning energy storage device also receives the concern energetically of countries in the world.Wherein, Lithium ion battery has that high-voltage, heavy body, volume are little, light weight, memoryless function, have extended cycle life, advantage such as safety performance is good; Become the first-selected object that can fill the formula power supply again of current portable type electronic product; Having broad application prospects in fields such as electromobile, space technologies, is the energy storage device that present various countries endeavour to develop.Wustite MFe
2O
4, M=(Co, Ni, Zn etc.) is one of lithium ion battery of new generation anode candidate material the most likely, its Theoretical Mass specific storage is about 900 mAhg
-1About, far above specific discharge capacity (372 mAhg of present business-like graphite
-1).Yet wustite can produce bigger volume change in charge and discharge process, bring bigger stress, can produce " efflorescence " problem, and promptly active substance and flow collection sheet are peeled off, thereby its specific storage is descended rapidly, causes material property to worsen.A large amount of existing documents show that the preparation hollow structure material is one of effective ways that solve transition metal oxide " efflorescence " problem.But preparation at present has the wustite material of hollow structure still to have difficulties, and this has seriously restricted the improvement of wustite material property and the application on lithium ion battery thereof.Therefore seek the wustite that a kind of easy method preparation has hollow structure and seem particularly important.
Summary of the invention
The purpose of this invention is to provide a kind of spherical iron hydrochlorate MFe with hollow structure
2O
4And preparation method thereof, M=Co, Ni or Zn.
Spherical iron hydrochlorate with hollow structure provided by the present invention, MFe
2O
4, M=Co, Ni or Zn are formed by the nanocrystalline self-assembly of 10～50nm, and its particle diameter is 0.1～1 μ m, has breach hollow ball shape structure, and shell thickness is at 30 ~ 200nm.
This spherical iron hydrochlorate with hollow structure can prepare according to the method that comprises the steps:
(1) be that the ratio of 2:1 takes by weighing trivalent iron salt and divalent metal salt respectively according to Mol ratio; Under magnetic agitation, it is dissolved in the ethylene glycol solution, being made into iron concentration is that 0.05～1mol/L, divalent-metal ion concentration are the solution of 0.025～0.5mol/L;
(2) in the solution that step (1) obtains, slowly add additive, the concentration that makes additive is 0.1～1.5mol/L;
(3) solution of step (2) gained is packed in the 100mL polytetrafluoroethyllining lining, compactedness 50 ~ 80% is put into stainless steel hydro-thermal still with liner, puts into the time variable control baking oven afterwards and heat-treats, and thermal treatment obtains black precipitate after finishing;
(4) black precipitate that step (3) is obtained is used deionized water and absolute ethanol washing respectively for several times; In vacuum drying oven, carry out drying treatment; Obtain the spherical iron hydrochlorate with hollow structure of different-grain diameter at last, this wustite sample can be used as lithium ion battery negative material.
In the above-mentioned steps (1) the trivalent iron salt that uses be in iron(ic)chloride, iron nitrate, ferric sulfate, the ironic acetate one or more; Employed divalent metal salt is a cobalt salt, nickel salt or zinc salt, and wherein cobalt salt is one or more in NSC 51149, Xiao Suangu, rose vitriol, the cobaltous acetate; Nickel salt is one or more in nickelous chloride, nickelous nitrate, single nickel salt, the nickelous acetate; Zinc salt is one or more in zinc chloride, zinc nitrate, rose vitriol, the cobaltous acetate.
The additive of above-mentioned steps (2) is a polyoxyethylene glycol, oleic acid, oleyl amine, one or more in the urea.
Thermal treatment temp is 100 ℃～240 ℃ in the above-mentioned steps (3), and the reaction times is 6～72 hours.
Drying temperature in the above-mentioned steps (4) is 40～100 ℃, and be 4～24 hours time of drying.
The present invention utilizes the process characteristic of solvent thermal, and through optimizing processing parameter, adjustment reactant and solvent species obtain the spherical iron hydrochlorate (MFe with hollow structure
2O
4, M=Co, Ni, Zn) material.The method that the present invention's preparation has the spherical iron hydrochlorate of hollow structure is a bubble template assisted synthesizing method, and wherein additive plays following three effects: alkaline environment is made in (1), quickens the formation of wustite; (2) form bubble, for wustite provides the bubble template; (3) increase soltion viscosity, stabilise bubbles.
The spherical iron hydrochlorate that adopts the inventive method to prepare with hollow structure; The chemical ingredients homogeneous; And even particle distribution; Its special self-assembly hollow structure helps fully contacting of electrolytic solution and material, and the boring structure helps cushioning the stress that it causes owing to volume change, the electric property and the work-ing life of having improved the wustite negative material greatly in charge and discharge process simultaneously.Through the add-on of control additive, the conditioned reaction temperature and time can be controlled the grain diameter scope (0.1～1 μ m) of the spherical iron hydrochlorate with hollow structure of self-assembly.Technological process is simple, and preparation parameter is easy to control, and good reproducibility can synthesize in mass-producing, and the compound formation temperature is low in the building-up process, makes that the product size distribution is more even.
Spherical iron hydrochlorate (MFe with hollow structure of the present invention
2O
4, M=Co, Ni, Zn) material can be used as the negative material of lithium ion battery.
Description of drawings
The spherical ZnFe of Fig. 1 for having hollow structure among the embodiment 1
2O
4X-ray diffracting spectrum.
The spherical ZnFe of Fig. 2 for having hollow structure among the embodiment 1
2O
4The stereoscan photograph of whole pattern.
The spherical ZnFe of Fig. 3 for having hollow structure among the embodiment 1
2O
4The partial sweep electromicroscopic photograph.
The spherical ZnFe of Fig. 4 for having hollow structure among the embodiment 1
2O
4Charging and discharging curve.
Embodiment
Main implementation process of the present invention is:
(1) be starting raw material with trivalent iron salt and divalent metal salt; It is dissolved in the ethylene glycol solution, and Mol ratio 2:1, the iron concentration that is made into ferric ion and divalent-metal ion is that 0.05～1mol/L, divalent-metal ion concentration are the solution of 0.025 ~ 0.5mol/L;
(2) in the solution that obtains, slowly add additive, additive concentration is 0.1～1.5mol/L;
(3) will add behind the additive solution of gained packs in the 100mL polytetrafluoroethyllining lining; Compactedness is 50 ~ 80%; Liner is put into stainless steel hydro-thermal still, put into the temperature programmed control baking oven afterwards and heat-treat, controlled temperature is between 100 ℃～240 ℃; Successive reaction is 6～72 hours, and thermal treatment obtains black precipitate after finishing;
(4) black precipitate that obtains is used deionized water and absolute ethanol washing respectively for several times; Place vacuum drying oven; Drying is 4～24 hours under 40～100 ℃, obtains the spherical iron hydrochlorate with hollow structure of different-grain diameter at last, and this wustite sample can be used as lithium ion battery negative material.
Below further illustrate characteristics of the present invention through embodiment, but be not limited to embodiment.
Experimental technique among the following embodiment if no special instructions, is ordinary method.
Embodiment 1:
Get the iron(ic)chloride of 10mmol and the zinc chloride of 5mmol, join in the 80mL terepthaloyl moietie, dissolving obtains settled solution, under vigorous stirring, slowly dropwise adds the polyoxyethylene glycol of 2ml then, adds 90mmol urea at last, continues to stir 20min.The solution that obtains is poured in the polytetrafluoroethyllining lining that capacity is 100ml, and compactedness is 80%.Pack into after the sealing in the stainless steel cauldron, be placed in the baking oven in 200 ℃ of reaction 24h.After the question response still is reduced to room temperature, collect product, and product is used ethanol and distilled water centrifuge washing for several times, the product after will washing is at last put into vacuum drying oven, promptly gets the zinc ferrite powder in 60 ℃ of dry 12h.Its Fig. 1 is the X-ray diffracting spectrum of the self-assembly zinc ferrite hollow microsphere powder of embodiment preparation for this reason, can find out that from collection of illustrative plates its thing is the zinc ferrite of cubic spinel structure mutually.Fig. 2 and Fig. 3 be whole pattern and the photo of local pattern of powder under JEOL JSM-6700 type field emission scanning electron microscope for this reason; Can find out that this powder has breach hollow ball shape structure; Particles dispersed is better and big or small than homogeneous; Average particulate diameter is 350nm, and by nanocrystalline composition the about 30nm, shell thickness is about 80nm.It is even that this powder, conductive carbon black and sticker PVDF (pvdf) are pressed mass ratio 4:4:2 mixed grinding, adds an amount of solvent NMP (N-Methyl pyrrolidone) then, evenly is coated on the Copper Foil 100 after mixing well pulping
oVacuum drying obtains pole piece under the C.With metal lithium sheet is to the utmost point, 1molL
-1LiPF
6/ EC+DMC+EMC (volume ratio 1:1:1) is an electrolytic solution, and polypropylene material is a barrier film, in being full of the glove box of argon gas, is assembled into 2025 type button cells.Adopt LAND CT2001A battery test system, carry out charge-discharge test with the constant current density, the charging/discharging voltage scope is between 0.01～3V, and charging and discharging currents density is 2000mAg
-1Fig. 4 is the charge-discharge test curve that obtains, and as can be seen from the figure, this material shows excellent chemical property during as the negative pole of lithium ion battery, and its first discharge specific capacity is up to 1402 mAhg
-1, reversible specific capacity is 1046mAhg
-1, after discharging and recharging through 20 times, its specific storage remains 634 mAhg
-1
Embodiment 2:
With the iron(ic)chloride of 10mmol and the NSC 51149 of 5mmol is starting raw material, joins in the 80mL terepthaloyl moietie, and dissolving obtains settled solution, under vigorous stirring, slowly dropwise adds the PEG-600 of 2ml then, adds 90mmol urea at last, continues to stir 20min.The solution that obtains is poured in the polytetrafluoroethyllining lining that capacity is 100ml, and compactedness is 50%.Pack into after the sealing in the stainless steel cauldron, be placed in the baking oven in 200 ℃ of reaction 24h.After the question response still is reduced to room temperature, collect product, and product is used ethanol and distilled water centrifuge washing for several times, the product after will washing is at last put into vacuum drying oven, promptly gets the cobalt ferrite powder in 60 ℃ of dry 12h.X-ray diffracting spectrum is the result show, its thing is the cobalt ferrite of cubic spinel structure mutually.Scanning electron microscopic observation is the result show, this powder has breach hollow ball shape structure, particles dispersed better and size than homogeneous, average particulate diameter is 350nm, by nanocrystalline composition the about 30nm, shell thickness is about 80nm.It is even that this powder, conductive carbon black and sticker PVDF (pvdf) are pressed mass ratio 4:4:2 mixed grinding, adds an amount of solvent NMP (N-Methyl pyrrolidone) then, evenly is coated on the Copper Foil 100 after mixing well pulping
oVacuum drying obtains pole piece under the C.With metal lithium sheet is to the utmost point, 1molL
-1LiPF
6/ EC+DMC+EMC (volume ratio 1:1:1) is an electrolytic solution, and polypropylene material is a barrier film, in being full of the glove box of argon gas, is assembled into 2025 type button cells.Adopt LAND CT2001A battery test system, carry out charge-discharge test with the constant current density, between charging/discharging voltage scope 0.01～3V, charging and discharging currents density 2000mAg
-1Charge-discharge test is the result show, this material shows excellent chemical property during as the negative pole of lithium ion battery, and its first discharge specific capacity is up to 1339mAhg
-1, reversible specific capacity is 945 mAhg
-1, after discharging and recharging through 20 times, its specific storage remains 663 mAhg
-1
Embodiment 3:
With the iron nitrate of 4mmol and the nickelous nitrate of 2mmol is starting raw material, joins in the 80mL terepthaloyl moietie, and dissolving obtains settled solution, under vigorous stirring, slowly dropwise adds the PEG-600 of 2ml then, adds 8mmol urea at last, continues to stir 20min.The solution that obtains is poured in the polytetrafluoroethyllining lining that capacity is 100ml, and compactedness is 80%.Pack into after the sealing in the stainless steel cauldron, be placed in the baking oven in 240 ℃ of reaction 6h.After the question response still is reduced to room temperature, collect product, and product is used ethanol and distilled water centrifuge washing for several times, the product after will washing is at last put into vacuum drying oven, in 60 ℃ of dry 12h.Finally obtain self-assembly nickel ferrite based magnetic loaded hollow microsphere powder.X-ray diffracting spectrum is the result show, the nickel ferrite based magnetic loaded of its thing phase cubic spinel structure.Scanning electron microscopic observation is the result show, this powder has breach hollow ball shape structure, particles dispersed better and size than homogeneous, average particulate diameter is 100nm, grain-size is 10nm, shell thickness is about 30nm.It is even that this powder, conductive carbon black and sticker PVDF (pvdf) are pressed mass ratio 4:4:2 mixed grinding, adds an amount of solvent NMP (N-Methyl pyrrolidone) then, evenly is coated on the Copper Foil 100 after mixing well pulping
oVacuum drying obtains pole piece under the C.With metal lithium sheet is to the utmost point, 1molL
-1LiPF
6/ EC+DMC+EMC (volume ratio 1:1:1) is an electrolytic solution, and polypropylene material is a barrier film, in being full of the glove box of argon gas, is assembled into 2025 type button cells.Adopt LAND CT2001A battery test system, carry out charge-discharge test with the constant current density, between charging/discharging voltage scope 0.01～3V, charging and discharging currents density 2000mAg
-1The charge-discharge test result shows excellent chemical property when showing this material as the negative pole of lithium ion battery, its first discharge specific capacity is 1220 mAhg
-1, reversible specific capacity is 930 mAhg
-1, after discharging and recharging through 20 times, its specific storage remains 755mAhg
-1
Embodiment 4:
With the iron(ic)chloride of 80mmol and the NSC 51149 of 40mmol is starting raw material; Join in the 80mL terepthaloyl moietie, dissolving obtains settled solution, under vigorous stirring, slowly dropwise adds PEG-600 and the 2mL oleic acid of 2ml then; Add 120 mmol urea at last, continue to stir 20min.The solution that obtains is poured in the polytetrafluoroethyllining lining that capacity is 100ml, and compactedness is 70%.Pack into after the sealing in the stainless steel cauldron, be placed in the baking oven in 240 ℃ of reaction 36h.After the question response still is reduced to room temperature, collect product, and with product with ethanol and zero(ppm) water centrifuge washing several, the product after will washing is at last put into vacuum drying oven, promptly gets self-assembly CoFe in 60 ℃ of dry 12h
2O
4The hollow microsphere powder.X-ray diffracting spectrum is the result show, its thing is the cobalt ferrite of cubic spinel structure mutually.Scanning electron microscopic observation is the result show, this powder has the hollow ball shape structure, particles dispersed better and size than homogeneous, average particulate diameter is 1 μ m, grain-size is about 50nm, shell thickness is about 200nm.It is even that this powder, conductive carbon black and sticker PVDF (pvdf) are pressed mass ratio 4:4:2 mixed grinding, adds an amount of solvent NMP (N-Methyl pyrrolidone) then, evenly is coated on the Copper Foil 100 after mixing well pulping
oVacuum drying obtains pole piece under the C.With metal lithium sheet is to the utmost point, 1molL
-1LiPF
6/ EC+DMC+EMC (volume ratio 1:1:1) is an electrolytic solution, and polypropylene material is a barrier film, in being full of the glove box of argon gas, is assembled into 2025 type button cells.Adopt LAND CT2001A battery test system, carry out charge-discharge test with the constant current density, between charging/discharging voltage scope 0.01～3V, charging and discharging currents density 2000mAg
-1The charge-discharge test curve shows good electrochemical when showing this material as the negative pole of lithium ion battery, and its first discharge specific capacity is 1320 mAhg
-1, reversible specific capacity is 935 mAhg
-1, after discharging and recharging through 20 times, its specific storage remains 650mAhg
-1
Embodiment 5:
Ironic acetate and 20mmol zinc acetate with 40mmol are starting raw material; Join in the 80mL terepthaloyl moietie, dissolving obtains settled solution, under vigorous stirring, slowly dropwise adds the oleic acid of 2ml and the oleyl amine of 2mL then; Add 50mmol urea at last, continue to stir 20min.The solution that obtains is poured in the polytetrafluoroethyllining lining that capacity is 100ml, and compactedness is 50%.Pack into after the sealing in the stainless steel cauldron, be placed in the baking oven in 100 ℃ of reaction 72h.After the question response still is reduced to room temperature, collect product, and product is used ethanol and distilled water centrifuge washing for several times, the product after will washing is at last put into vacuum drying oven, in 60 ℃ of dry 12h.Finally obtain self-assembly zinc ferrite hollow microsphere powder.X-ray diffracting spectrum is the result show, the zinc ferrite of its thing phase cubic spinel structure.Scanning electron microscopic observation is the result show, this powder has the hollow ball shape structure, particles dispersed better and size than homogeneous, average particulate diameter is 450nm, grain-size is about 40nm, shell thickness is about 100nm.It is even that this powder, conductive carbon black and sticker PVDF (pvdf) are pressed mass ratio 4:4:2 mixed grinding, adds an amount of solvent NMP (N-Methyl pyrrolidone) then, evenly is coated on the Copper Foil 100 after mixing well pulping
oVacuum drying obtains pole piece under the C.With metal lithium sheet is to the utmost point, 1molL
-1LiPF
6/ EC+DMC+EMC (volume ratio 1:1:1) is an electrolytic solution, and polypropylene material is a barrier film, in being full of the glove box of argon gas, is assembled into 2025 type button cells.Adopt LAND CT2001A battery test system, carry out charge-discharge test with the constant current density, between charging/discharging voltage scope 0.01～3V, charging and discharging currents density 2000mAg
-1The charge-discharge test curve shows good electrochemical when showing this material as the negative pole of lithium ion battery, and its first discharge specific capacity is 1368 mAhg
-1, reversible specific capacity is 985 mAhg
-1, after discharging and recharging through 20 times, its specific storage remains 522mAhg
-1
Embodiment 6:
Ferric sulfate and 5mmol single nickel salt with 10mmol are starting raw material; Join in the 80mL terepthaloyl moietie, dissolving obtains settled solution, under vigorous stirring, slowly dropwise adds the oleic acid of 2ml and the oleyl amine of 1mL then; Add 120mmol urea at last, continue to stir 20min.The solution that obtains is poured in the polytetrafluoroethyllining lining that capacity is 100ml, and compactedness is 80%.Pack into after the sealing in the stainless steel cauldron, be placed in the baking oven in 140 ℃ of reaction 6h.After the question response still is reduced to room temperature, collect product, and with product with ethanol and zero(ppm) water centrifuge washing several, the product after will washing is at last put into vacuum drying oven, in 40 ℃ of dry 24h, finally obtains self-assembly nickel ferrite based magnetic loaded powder.X-ray diffracting spectrum is the result show, the nickel ferrite based magnetic loaded of its thing phase cubic spinel structure.Scanning electron microscopic observation is the result show, this powder has the hollow ball shape structure, particles dispersed better and size than homogeneous, average particulate diameter is 350nm, grain-size is about 30nm, shell thickness is about 80nm.It is even that this powder, conductive carbon black and sticker PVDF (pvdf) are pressed mass ratio 4:4:2 mixed grinding, adds an amount of solvent NMP (N-Methyl pyrrolidone) then, evenly is coated on the Copper Foil 100 after mixing well pulping
oVacuum drying obtains pole piece under the C.With metal lithium sheet is to the utmost point, 1molL
-1LiPF
6/ EC+DMC+EMC (volume ratio 1:1:1) is an electrolytic solution, and polypropylene material is a barrier film, in being full of the glove box of argon gas, is assembled into 2025 type button cells.Adopt LAND CT2001A battery test system, carry out charge-discharge test with the constant current density, between charging/discharging voltage scope 0.01～3V, charging and discharging currents density 2000 mAg
-1The charge-discharge test curve shows good electrochemical when showing this material as the negative pole of lithium ion battery, and its first discharge specific capacity is 1362mAhg
-1, reversible specific capacity is 940 mAhg
-1, after discharging and recharging through 200 times, its specific storage remains 585mAhg
-1
Claims (6)
1. spherical iron hydrochlorate with hollow structure, MFe
2O
4, M=Co, Ni or Zn are formed by the nanocrystalline self-assembly of 10～50nm, and its particle diameter is 0.1～1 μ m, has breach hollow ball shape structure, and shell thickness is at 30 ~ 200nm.
2. described preparation method with spherical iron hydrochlorate of hollow structure of claim 1 may further comprise the steps:
(1) ratio according to Mol ratio 2:1 takes by weighing trivalent iron salt and divalence M metal-salt respectively; Under magnetic agitation, it is dissolved in the ethylene glycol solution, being made into iron concentration is that 0.05～1mol/L, divalent-metal ion concentration are the solution of 0.025 ~ 0.5mol/L.;
(2) in the solution that step (1) obtains, slowly add additive, the concentration that makes additive is 0.1～1.5mol/L;
(3) solution of step (2) gained is packed in the 100mL polytetrafluoroethyllining lining, compactedness 50 ~ 80% is put into stainless steel hydro-thermal still with liner, puts into the temperature programmed control baking oven afterwards and heat-treats, and obtains black precipitate;
(4) black precipitate that step (3) is obtained is used deionized water and absolute ethanol washing respectively for several times; In vacuum drying oven, carry out drying treatment; Obtain the spherical iron hydrochlorate with hollow structure of different-grain diameter at last, this wustite sample can be used as lithium ion battery negative material.
3. the preparation method with spherical iron hydrochlorate of hollow structure according to claim 2 is characterized in that: in the step (1) the trivalent iron salt that uses be in iron(ic)chloride, iron nitrate, ferric sulfate, the ironic acetate one or more; Employed divalence M metal-salt is cobalt salt, nickel salt or zinc salt, and wherein cobalt salt is one or more in NSC 51149, Xiao Suangu, rose vitriol, the cobaltous acetate; Nickel salt is one or more in nickelous chloride, nickelous nitrate, single nickel salt, the nickelous acetate; Zinc salt is one or more in zinc chloride, zinc nitrate, rose vitriol, the cobaltous acetate.
4. the preparation method with spherical iron hydrochlorate of hollow structure according to claim 2 is characterized in that: the additive of step (2) is a polyoxyethylene glycol, oleic acid, oleyl amine, one or more in the urea.
5. the preparation method with spherical iron hydrochlorate of hollow structure according to claim 2 is characterized in that: thermal treatment temp is 100 ℃～240 ℃ in the step (3), and the reaction times is 6～72 hours.
6. the preparation method with spherical iron hydrochlorate of hollow structure according to claim 2 is characterized in that: the drying temperature in the step (4) is 40～100 ℃, and be 4～24 hours time of drying.
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| 袁进等: "纳米NiFe2O4磁性颗粒的制备及表征", 《中北大学学报（自然科学版）》 * |
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