CN102790217A - Carbon cladded ferriferrous oxide negative electrode material of lithium ion battery and preparation method thereof - Google Patents
Carbon cladded ferriferrous oxide negative electrode material of lithium ion battery and preparation method thereof Download PDFInfo
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- CN102790217A CN102790217A CN2012102611566A CN201210261156A CN102790217A CN 102790217 A CN102790217 A CN 102790217A CN 2012102611566 A CN2012102611566 A CN 2012102611566A CN 201210261156 A CN201210261156 A CN 201210261156A CN 102790217 A CN102790217 A CN 102790217A
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Abstract
The invention discloses a carbon cladded ferriferrous oxide negative electrode material of a lithium ion battery and a preparation method thereof. The negative electrode material is a carbon cladded Fe3O4 composite material and has a particle size in a range of 1 to 100 nm. The preparation method comprises the following steps: with NaCl used as a dispersing agent and a supporter, fully mixing NaCl with a metal oxide source and a solid carbon source; drying an obtained mixed solution under vacuum to obtain a mixture; placing the mixture into a tubular furnace for calcination in an inert atmosphere so as to obtain a calcined product; and rinsing and grinding the calcined product to obtain carbon cladded metal oxide nanometer particles. The method is safe and non-toxic and is simple to operate; during charging and discharging tests of a lithium ion button cell made of the carbon cladded ferriferrous oxide negative electrode material, discharge specific capacity can be maintained at 620 to 900 mAh/g after 30 cycles of charging and discharging at a current of 0.1C (with current density being 92 mA/g), and discharge specific capacity can be maintained at 600 to 760 mAh/g after 50 cycles of charging and discharging at a current of 1C (with current density being 920 mA/g); and the negative electrode material of the lithium ion battery has high reversible capacity and good cycling stability.
Description
Technical field
The present invention relates to the carbon coated ferriferrous oxide lithium ion battery cathode material and its preparation method, belong to the electrode material of secondary lithium ion battery field.
Background technology
Lithium rechargeable battery has that voltage height, specific energy are high, characteristics such as operating temperature range is wide, self-discharge rate is low, memory-less effect, non-environmental-pollution, compare with Ni-MH battery with NI-G have extended cycle life, security performance is good.Therefore lithium ion battery partly substitutes other power supplys at present, is applied in the portable sets such as mobile phone, notebook computer, video camera, camera, and also will be widely used in military fields such as electric automobile, satellite and space flight future.
Its theoretical capacity of carbon negative pole material (native graphite, Delanium) that industry is at present used is 372 mAh g
-1, and in the novel negative material theoretical capacity scope of transition metal oxide at 500-1000 mAh g
-1, form research focus into people far above the theoretical capacity of carbon negative pole material.Tri-iron tetroxide (Fe in transition metal oxide
3O
4) not only have high theoretical capacity (924 mAh g
-1), have also that safe voltage height (0.9 V), conductivity are high, cost is low, an ABUNDANT NATUREAL RESOURSES, advantage such as nontoxic.But change in volume that active material is bigger in insert/taking off the lithium process and the cycle performance that causes owing to reuniting in a large number are poor, have limited Fe
3O
4Application aspect lithium ion battery.
In order to improve Fe
3O
4Chemical property, people have adopted a lot of methods that it is carried out modification, for example prepare the Fe of nanometerization
3O
4, the nanometer Fe that coats of carbon
3O
4And nano level Fe
3O
4/ C composite material etc.In the lithium ion charge and discharge process, nano material can absorb and store a large amount of lithium ions owing to have bigger specific area, short the evolving path and diffusion rate faster, helps improving its chemical property; Carbon coating layer can stop active material that bigger change in volume takes place in battery charge and discharge process, and the reunion of avoiding active material; It is high that carbon base body also has good electrical conductivity, lithium permeability, and characteristics such as stable electrochemical property.
At present, carbon coats Fe
3O
4The preparation method of nano composite material mainly contains hydro thermal method, thermal decomposition method etc.Compare with traditional hydro thermal method, the pyrolysismethod cost is low, and the preparation process is simple, is easy to realize suitability for industrialized production.Pyrolysismethod is meant that with metal oxide source with after carbon source is fully mixed, pyrolysis charring in inert atmosphere obtains the nano-metal-oxide granular materials that carbon base body coats through subsequent treatment.(Journal of Materials Chemistry such as Taegyun Yoon; 21 (2011) 17325) reported first employing silicon template; After the gel oven dry with resorcinol and formaldehyde mixing; Foamy carbon is prepared in 800 ℃ of calcinings, again foamy carbon and molysite is fully mixed back low temperature calcination formation Fe under the protection of inert gas
3O
4The composite material of/foamy carbon.(Electrochimica Acta, 56 (2011) 9233-9239) such as Yudai Huang utilize chemical precipitation method to prepare Fe earlier
2O
3Nano particle is then with Fe
2O
3The mixing presoma of nano particle/phenolic resins is 450 ℃ of calcining 2h under the protection of inert gas, and the carbon that obtains nucleocapsid structure coats Fe
3O
4Nano particle.
Comprehensive above document is found, all is to adopt multistep processes in the above-mentioned method for pyrolysis, promptly at first prepares Fe
2O
3/ Fe
3O
4The precursor of nano particle or carbon makes carbon coating Fe with source of iron and the mixed precursor calcining of carbon source again
3O
4Composite material, complicated steps, time and effort consuming; And the Fe that is obtained
3O
4The nano particle diameter homogeneity is relatively poor, and output is still less.
Summary of the invention
The object of the present invention is to provide a kind of carbon coated ferriferrous oxide lithium ion battery cathode material and its preparation method.This lithium ion battery negative material improves its cyclical stability when keeping height ratio capacity, its preparation method process is simple.
Technical scheme of the present invention realizes that through following steps a kind of carbon coated ferriferrous oxide lithium ion battery negative material is characterized in that, this lithium ion battery negative material is that the carbon with nucleocapsid structure coats Fe
3O
4Composite material, its particle diameter are between 1 ~ 100nm, and carbon coating layer thickness is 2.5nm ~ 10nm, and its mass content is 40 ~ 80%, nuclear Fe
3O
4Mass content be 20% ~ 60%.
The preparation method of the carbon coated ferriferrous oxide lithium ion battery negative material of said structure is characterized in that comprising following process:
The mol ratio of a. pressing iron in carbon and the ferric nitrate in a kind of carbon source of glucose, sucrose, starch or citric acid is (200 ~ 0.1): 1; And be (0.01 ~ 0.1): 1 with the mass ratio of iron and NaCl; Carbon source, ferric nitrate and NaCl are added in the deionized water, and ultrasonic agitation is processed homogeneous solution;
B. the solution that step a is made is put into vacuum drying chamber in 60 ~ 200 ℃ of vacuumizes of temperature, obtains mixture until oven dry;
C. the mixture grind into powder that step b is obtained paves powder in Noah's ark again, places the tube furnace flat-temperature zone to calcine Noah's ark then, at first is the N of 10 ~ 400 ml/min with flow
2, under He or the Ar inert gas shielding, be warming up to 100 ~ 500 ℃ with the programming rate of 1 ~ 10 ℃/min, insulation 0.5 ~ 4 h decomposes carbon source; Continuing then to feed flow is the N of 10 ~ 400ml/min
2, He or Ar inert gas and be warming up to 400 ~ 1000 ℃ with the programming rate of 1 ~ 10 ℃/min, insulation 1 ~ 6h carries out carbonization, reaction finishes the back at N
2, the protection of He or Ar inert gas atmosphere is cooled to room temperature down, obtains carbon coating Fe
3O
4The calcined product of nano particle and NaCl;
D. collect the calcined product that obtains among the step c, through porphyrize, washing does not have to the calcined product till the NaCl, is 60 ~ 120 ℃ of oven dry down in temperature, and the carbon that obtains particle diameter and be 1 ~ 100nm coats Fe
3O
4Lithium ion battery negative material.
The invention has the advantages that: the NaCl that adopts solubility is as dispersant and carrier, and it with after ferric nitrate and glucose, sucrose, starch or citric acid carbon source are fully mixed, is inserted in the tube furnace and under uniform temperature, calcine.This method safety non-toxic, environmentally friendly, preparation process " one-step method ", simple to operate.The eliminating amount of the present invention's oxygen in calcination process control raw material makes its incomplete eliminating, forms this carbon coated ferriferrous oxide nano particle, but when the oxygen in the raw material is got rid of fully, then can form the carbon-encapsulated iron nano particle.The carbon-coating degree of graphitization of this nano particle is high, and specific area is bigger, helps absorption and the storage of lithium ion in active material, and scattered between the particle, output is bigger.Prepared carbon coats Fe
3O
4Nano particle grain lithium ion battery advanced charge-discharge test; The result is presented at 0.1C (current density is 92mA/g) after 30 weeks of circulation; Specific discharge capacity can remain on 620 ~ 900mAh/g; After 50 weeks of 1C (current density is 920mA/g) circulation, specific discharge capacity still can remain on 600 ~ 760mAh/g, above data declaration this lithium ion battery negative material have higher reversible capacity and good cyclical stability.
Description of drawings
Fig. 1 coats Fe for the carbon that embodiment one among the present invention makes
3O
4The TEM figure of nano particle.
Fig. 2 coats Fe for the carbon that embodiment one among the present invention makes
3O
4The TEM of individual particle figure in the nano particle.
Fig. 3 coats Fe for the carbon that embodiment one among the present invention makes
3O
4The TG of nano particle and DTA figure.
Fig. 4 coats Fe for the carbon that embodiment two among the present invention makes
3O
4The TG of nano particle and DTA figure.
Fig. 5 coats Fe for the carbon that embodiment one, two among the present invention makes
3O
4The XRD figure of nano particle.
Fig. 6 coats Fe for the carbon that embodiment one among the present invention makes
3O
4Charging and discharging curve under the different multiplying of nano particle lithium ion battery.
Fig. 7 coats Fe for the carbon that embodiment one among the present invention makes
3O
4The cyclic voltammetric of nano particle lithium ion battery (CV) curve chart.
Fig. 8 coats Fe for the carbon that embodiment two among the present invention makes
3O
4Charging and discharging curve under the different multiplying of nano particle lithium ion battery.
Fig. 9 coats Fe for the carbon that embodiment two among the present invention makes
3O
4The cyclic voltammetric of nano particle lithium ion battery (CV) curve chart.
Embodiment
Below in conjunction with specific embodiment particular content of the present invention is specified as follows:
Embodiment one:
Take by weighing 1.2g glucose, 0.808g ferric nitrate and 11.1gNaCl; Mixture is dissolved in the deionized water of 50ml, with the magnetic stirring apparatus of mixing speed 300r/min, the stirring and dissolving wiring solution-forming; And then be the ultrasonic 15min of ultrasonic device of 400W with power, mix.The solution that mixes is put into 80 ℃ of vacuumizes of vacuum drying chamber, obtain mixture until oven dry.Milled mixtures, the mixed-powder of getting 6g places Noah's ark, and Noah's ark is put into tube furnace, is under the Ar inert gas shielding of 200ml/min with the flow, is warming up to 300 ℃ of temperature with the programming rate of 10 ℃/min and carries out carbon source and decompose, behind the insulation 2h; Continue to feed flow then and be the Ar inert gas of 200ml/min and be warming up to 750 ℃ of temperature with the programming rate of 10 ℃/min, insulation 2h carries out carbonization, and reaction finishes the back and under the Ar atmosphere protection, is cooled to room temperature, obtains calcined product.Collect calcined product, porphyrize, washing does not have to the product till the NaCl, and 80 ℃ of oven dry down, the carbon that obtains particle diameter and be 1-100nm coats Fe
3O
4Nano particle, TEM schemes like Fig. 1, shown in 2.Carbon is coated Fe
3O
4Nano particle and PVDF binding agent, N-methyl pyrrolidone evenly are coated on the Copper Foil after mixing according to the mass ratio of 80:10:10, are placed on 80 ℃ of vacuumize 4h in the baking oven; Then temperature is elevated to 120 ℃ of vacuumize 12h; After being cooled to room temperature, electrode slice is processed in punching press; As to electrode, electrolyte is 1 mol/LLiPF with lithium metal
6
The Celgard 2300 type barrier films that/EC+DMC+EMC, barrier film adopt U.S. Celgard company to produce are accomplished the assembling of battery in less than 4% glove box in humidity, process Li/ carbon coated ferriferrous oxide half-cell.The lithium ion battery that makes is carried out charge-discharge test on the electric CT2001A cell tester of indigo plant, after 30 weeks of circulation, the specific discharge capacity of battery is 758mAhg at 1C (current density is 92mA/g)
-1, after 100 weeks of circulation, the specific discharge capacity of battery is 829mAhg at 2C (current density is 184mA/g)
-1, after 50 weeks of circulation, the specific discharge capacity of battery is 630mAhg at 5C (current density is 460mA/g)
-1, its its charge-discharge test curve is as shown in Figure 6.Utilize model for the electrochemical workstation of CHI660D the battery that makes to be carried out the cyclic voltammetric test then, the voltage range of scanning is 0.01-3V, and sweep speed is 0.005mV, and the scan period is 5 times, and its cyclic voltammetry curve is as shown in Figure 7.
Embodiment two:
Carbon coats Fe in the present embodiment
3O
4The preparation process of nano particle and cell preparation process are identical with embodiment one step process, have just changed calcining heat: become 700 ℃ by 750 ℃.The lithium ion battery that makes is carried out charge-discharge test on the electric CT2001A cell tester of indigo plant, after 30 weeks of circulation, the specific discharge capacity of battery is 522mAhg at 1C (current density is 24.5mA/g)
-1, after 100 weeks of circulation, the specific discharge capacity of battery is 181mAhg at 2C (current density is 49mA/g)
-1, after 50 weeks of circulation, the specific discharge capacity of battery is 72mAhg at 5C (current density is 122.5mA/g)
-1, its its charge-discharge test curve is as shown in Figure 8.Utilize model for the electrochemical workstation of CHI660D the battery that makes to be carried out the cyclic voltammetric test then, the voltage range of scanning is 0.01-3V, and sweep speed is 0.005mV, and the scan period is 5 times, and its cyclic voltammetry curve is as shown in Figure 9.
Embodiment three:
Take by weighing 5g sucrose, 0.808g ferric nitrate and 11.1gNaCl, mixture is dissolved in the deionized water of 50ml, with the magnetic stirring apparatus of mixing speed 300r/min, the stirring and dissolving wiring solution-forming, and then be the ultrasonic 15min of ultrasonic device of 400W with power, mix.The solution that mixes is put into 80 ℃ of vacuumizes of vacuum drying chamber, obtain mixture until oven dry.Milled mixtures; The mixed-powder of getting 6g places Noah's ark; Noah's ark is put into tube furnace; At first feed the Ar inert gas deaeration of 400ml/min, again with the Ar inert gas of 400ml/min and be warming up to 400 ℃ of temperature with the programming rate of 10 ℃/min and carry out carbon source and decompose, behind the insulation 1h; Continue to feed flow then and be the Ar inert gas of 400ml/min and be warming up to 750 ℃ of temperature with the programming rate of 10 ℃/min, insulation 2h carries out carbonization, and reaction finishes the back and under the Ar atmosphere protection, is cooled to room temperature, obtains calcined product.Collect calcined product, porphyrize, washing does not have to the product till the NaCl, and 60 ℃ of oven dry down, the carbon that obtains particle diameter and be 1-100nm coats Fe
3O
4Nano particle.Carbon is coated Fe
3O
4Nano particle and PVDF binding agent, N-methyl pyrrolidone evenly are coated on the Copper Foil after mixing according to the mass ratio of 80:10:10, are placed on 80 ℃ of vacuumize 4h in the baking oven; Then temperature is elevated to 120 ℃ of vacuumize 12h; After being cooled to room temperature, electrode slice is processed in punching press; As to electrode, electrolyte is 1 mol/LLiPF with lithium metal
6The Celgard 2300 type barrier films that/EC+DMC+EMC, barrier film adopt U.S. Celgard company to produce are accomplished the assembling of battery in less than 4% glove box in humidity, process Li/ carbon coated ferriferrous oxide half-cell.。
Embodiment four:
Take by weighing 10g starch, 0.808g ferric nitrate and 11.1gNaCl; Mixture is dissolved in the deionized water of 50ml, with the magnetic stirring apparatus of mixing speed 300r/min, the stirring and dissolving wiring solution-forming; And then be the ultrasonic 15min of ultrasonic device of 400W with power, mix.The solution that mixes is put into 100 ℃ of vacuumizes of vacuum drying chamber, obtain mixture until oven dry.Milled mixtures; The mixed-powder of getting 6g places Noah's ark; Noah's ark is put into tube furnace; At first feed the He inert gas deaeration of 400ml/min, again with the Ar inert gas of 400ml/min and be warming up to 400 ℃ of temperature with the programming rate of 10 ℃/min and carry out carbon source and decompose, behind the insulation 2h; Continue to feed flow then and be the He inert gas of 400ml/min and be warming up to 800 ℃ of temperature with the programming rate of 10 ℃/min, insulation 4h carries out carbonization, and reaction finishes the back and under the He atmosphere protection, is cooled to room temperature, obtains calcined product.Collect calcined product, porphyrize, washing does not have to the product till the NaCl, and 80 ℃ of oven dry down, the carbon that obtains particle diameter and be 1-100nm coats Fe
3O
4Nano particle.Carbon is coated Fe
3O
4Nano particle and PVDF binding agent, N-methyl pyrrolidone evenly are coated on the Copper Foil after mixing according to the mass ratio of 80:10:10, are placed on 80 ℃ of vacuumize 4h in the baking oven; Then temperature is elevated to 120 ℃ of vacuumize 12h; After being cooled to room temperature, electrode slice is processed in punching press; As to electrode, electrolyte is 1 mol/LLiPF with lithium metal
6The Celgard 2300 type barrier films that/EC+DMC+EMC, barrier film adopt U.S. Celgard company to produce are accomplished the assembling of battery in less than 4% glove box in humidity, process Li/ carbon coated ferriferrous oxide half-cell.
Embodiment five:
Take by weighing 5g citric acid, 0.808g ferric nitrate and 11.1gNaCl; Mixture is dissolved in the deionized water of 50ml, with the magnetic stirring apparatus of mixing speed 300r/min, the stirring and dissolving wiring solution-forming; And then be the ultrasonic 15min of ultrasonic device of 400W with power, mix.The solution that mixes is put into 80 ℃ of vacuumizes of vacuum drying chamber, obtain mixture until oven dry.Milled mixtures, the mixed-powder of getting 6g places Noah's ark, and Noah's ark is put into tube furnace, at first feeds the N of 200ml/min
2The inert gas deaeration is again with the Ar inert gas of 200ml/min and be warming up to 300 ℃ of temperature with the programming rate of 10 ℃/min and carry out carbon source and decompose, behind the insulation 2h; Continuing then to feed flow is the N of 200ml/min
2Inert gas also is warming up to 750 ℃ of temperature with the programming rate of 10 ℃/min, and insulation 2h carries out carbonization, and reaction finishes the back at N
2Be cooled to room temperature under the atmosphere protection, obtain calcined product.Collect calcined product, porphyrize, washing does not have to the product till the NaCl, and 80 ℃ of oven dry down, the carbon that obtains particle diameter and be 1-100nm coats Fe
3O
4Nano particle.Carbon is coated Fe
3O
4Nano particle and PVDF binding agent, N-methyl pyrrolidone evenly are coated on the Copper Foil after mixing according to the mass ratio of 80:10:10, are placed on 80 ℃ of vacuumize 4h in the baking oven; Then temperature is elevated to 120 ℃ of vacuumize 12h; After being cooled to room temperature, electrode slice is processed in punching press; As to electrode, electrolyte is 1 mol/LLiPF with lithium metal
6The Celgard 2300 type barrier films that/EC+DMC+EMC, barrier film adopt U.S. Celgard company to produce are accomplished the assembling of battery in less than 4% glove box in humidity, process Li/ carbon coated ferriferrous oxide half-cell.
Claims (2)
1. a carbon coated ferriferrous oxide lithium ion battery negative material is characterized in that, this lithium ion battery negative material is that the carbon with nucleocapsid structure coats Fe
3O
4Composite material, its particle diameter are between 1 ~ 100nm, and carbon coating layer thickness is 2.5nm ~ 10nm, and its mass content is 40 ~ 80%, nuclear Fe
3O
4Mass content be 20% ~ 60%.
2. preparation method by the described carbon coated ferriferrous oxide lithium ion battery negative material of claim 1 is characterized in that comprising following process:
The mol ratio of a. pressing iron in carbon and the ferric nitrate in a kind of carbon source of glucose, sucrose, starch or citric acid is (200 ~ 0.1): 1; And be (0.01 ~ 0.1): 1 with the mass ratio of iron and NaCl; Carbon source, ferric nitrate and NaCl are added in the deionized water, and ultrasonic agitation is processed homogeneous solution;
B. the solution that step a is made is put into vacuum drying chamber in 60 ~ 200 ℃ of vacuumizes of temperature, obtains mixture until oven dry;
C. the mixture grind into powder that step b is obtained paves powder in Noah's ark again, places the tube furnace flat-temperature zone to calcine Noah's ark then, at first is the N of 10 ~ 400 ml/min with flow
2, under He or the Ar inert gas shielding, be warming up to 100 ~ 500 ℃ with the programming rate of 1 ~ 10 ℃/min, insulation 0.5 ~ 4 h decomposes carbon source; Continuing then to feed flow is the N of 10 ~ 400ml/min
2, He or Ar inert gas and be warming up to 400 ~ 1000 ℃ with the programming rate of 1 ~ 10 ℃/min, insulation 1 ~ 6h carries out carbonization, reaction finishes the back at N
2, the protection of He or Ar inert gas atmosphere is cooled to room temperature down, obtains carbon coating Fe
3O
4The calcined product of nano particle and NaCl;
Collect the calcined product that obtains among the step c, through porphyrize, washing does not have to the calcined product till the NaCl, is 60 ~ 120 ℃ of oven dry down in temperature, and the carbon that obtains particle diameter and be 1 ~ 100nm coats Fe
3O
4Lithium ion battery negative material.
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