CN102790217B - 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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- CN102790217B CN102790217B CN201210261156.6A CN201210261156A CN102790217B CN 102790217 B CN102790217 B CN 102790217B CN 201210261156 A CN201210261156 A CN 201210261156A CN 102790217 B CN102790217 B CN 102790217B
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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 carbon coated ferriferrous oxide lithium ion battery cathode material and its preparation method, belong to electrode material of secondary lithium ion battery field.
Background technology
Lithium rechargeable battery has the features such as voltage is high, specific energy is high, 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) of industrial application is 372 mAh g at present
-1, and in Novel anode material the theoretical capacity scope of transition metal oxide at 500-1000 mAh g
-1, form the study hotspot into people far above the theoretical capacity of carbon negative pole material.Tri-iron tetroxide (Fe in transition metal oxide
3o
4) not only there are high theoretical capacity (924 mAh g
-1), also there is safe voltage high (0.9 V), conductivity is high, cost is low, ABUNDANT NATUREAL RESOURSES, the advantage such as nontoxic.But the cycle performance that active material causes compared with large change in volume and owing to reuniting in a large number in insert/de-lithium process is poor, has limited Fe
3o
4application aspect lithium ion battery.
In order to improve Fe
3o
4chemical property, people have adopted a lot of methods to carry out modification to it, for example, prepare the Fe of nanometer
3o
4, the coated nanometer Fe of carbon
3o
4and nano level Fe
3o
4/ C composite material etc.In lithium ion charge and discharge process, nano material, owing to having larger specific area, shorter the evolving path and diffusion rate faster, can absorb and store a large amount of lithium ions, is conducive to improve its chemical property; Carbon coating layer can stop active material that larger change in volume occurs in battery charge and discharge process, and avoids the reunion of active material; Carbon base body also has good conductivity, lithium permeability is high, and the feature such as stable electrochemical property.
At present, the coated Fe of carbon
3o
4the preparation method of nano composite material mainly contains hydro thermal method, thermal decomposition method etc.Compared with traditional hydro thermal method, pyrolysismethod cost is low, and preparation process is simple, is easy to realize suitability for industrialized production.After pyrolysismethod refers to metal oxide source is fully mixed with carbon source, pyrolysis charring in inert atmosphere, obtains the coated nano-metal-oxide granular materials of carbon base body through subsequent treatment.(the Journal of Materials Chemistry such as Taegyun Yoon; 21 (2011) 17325) reported and first adopted silicon template; after the gel of resorcinol and formaldehyde mixing is dried; foamy carbon is prepared in 800 DEG C of calcinings, then after foamy carbon and molysite are fully mixed under the protection of inert gas low temperature calcination form Fe
3o
4the composite material of/foamy carbon.Yudai Huang etc. (Electrochimica Acta, 56 (2011) 9233-9239) first utilize chemical precipitation method to prepare Fe
2o
3nano particle, then by Fe
2o
3the mixing presoma of nano particle/phenolic resins is 450 DEG C of calcining 2h under the protection of inert gas, obtain the coated Fe of carbon of nucleocapsid structure
3o
4nano particle.
Comprehensive above document is found, is all to adopt multistep processes in above-mentioned method for pyrolysis, first prepares Fe
2o
3/ Fe
3o
4the precursor of nano particle or carbon, then source of iron and the mixed precursor calcining of carbon source are made to the coated Fe of carbon
3o
4composite material, step complexity, time and effort consuming; And the Fe obtaining
3o
4nano particle diameter homogeneity is 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 in keeping height ratio capacity, and its preparation method process is simple.
Technical scheme of the present invention realizes by following steps, and a kind of carbon coated ferriferrous oxide lithium ion battery negative material, is characterized in that, this lithium ion battery negative material is the coated Fe of carbon with nucleocapsid structure
3o
4composite material, its particle diameter is between 1 ~ 100nm, and carbon coating layer thickness is 2.5nm ~ 10nm, and its mass content is 40 ~ 80%, core 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 in a kind of carbon source of glucose, sucrose, starch or citric acid and ferric nitrate is (200 ~ 0.1): 1, and taking the mass ratio of iron and NaCl as (0.01 ~ 0.1): 1, carbon source, ferric nitrate and NaCl are added in deionized water, and ultrasonic agitation is made homogeneous solution;
B. solution step a being made is put into vacuum drying chamber in 60 ~ 200 DEG C of vacuumizes of temperature, obtains mixture until dry;
C. mixture grind into powder step b being obtained, then powder is paved in Noah's ark, then Noah's ark is placed in to tube furnace flat-temperature zone and calcines, the first N taking flow as 10 ~ 400 ml/min
2, under He or Ar inert gas shielding, be warming up to 100 ~ 500 DEG C with the programming rate of 1 ~ 10 DEG C/min, insulation 0.5 ~ 4 h, decomposes carbon source; Then continue to pass into the N that flow is 10 ~ 400ml/min
2, He or Ar inert gas be warming up to 400 ~ 1000 DEG C with the programming rate of 1 ~ 10 DEG C/min, insulation 1 ~ 6h carries out carbonization, after reaction finishes at N
2, be cooled to room temperature under the protection of He or Ar inert gas atmosphere, obtain the coated Fe of carbon
3o
4the calcined product of nano particle and NaCl;
D. collecting the calcined product obtaining in step c, through porphyrize, till being washed to and thering is no NaCl in calcined product, is to dry at 60 ~ 120 DEG C in temperature, and obtaining particle diameter is the coated Fe of carbon of 1 ~ 100nm
3o
4lithium ion battery negative material.
The invention has the advantages that: adopt the NaCl of solubility as dispersant and carrier, after it is fully mixed with ferric nitrate and glucose, sucrose, starch or citric acid carbon source, insert in tube furnace and calcine under uniform temperature.The 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, not exclusively gets rid of it, forms this carbon coated ferriferrous oxide nano particle, but can form carbon-encapsulated iron nano particle in the time that the oxygen in raw material is got rid of completely.The carbon-coating degree of graphitization of this nano particle is high, and specific area is larger, is conducive to absorption and the storage of lithium ion in active material, and scattered between particle, output is larger.Prepared carbon is coated Fe
3o
4nano particle grain lithium ion battery entered charge-discharge test, it is 92mA/g that result is presented at 0.1C(current density) circulation 30 weeks after, specific discharge capacity can remain on 620 ~ 900mAh/g, be 920mA/g in 1C(current density) circulation 50 weeks after, specific discharge capacity still can remain on 600 ~ 760mAh/g, above data declaration this lithium ion battery negative material there is higher reversible capacity and good cyclical stability.
Brief description of the drawings
Fig. 1 is the coated Fe of carbon that in the present invention, embodiment mono-makes
3o
4the TEM figure of nano particle.
Fig. 2 is the coated Fe of carbon that in the present invention, embodiment mono-makes
3o
4the TEM of individual particle figure in nano particle.
Fig. 3 is the coated Fe of carbon that in the present invention, embodiment mono-makes
3o
4the TG of nano particle and DTA figure.
Fig. 4 is the coated Fe of carbon that in the present invention, embodiment bis-makes
3o
4the TG of nano particle and DTA figure.
Fig. 5 is the coated Fe of carbon that in the present invention, embodiment mono-, two makes
3o
4the XRD figure of nano particle.
Fig. 6 is the coated Fe of carbon that in the present invention, embodiment mono-makes
3o
4charging and discharging curve under the different multiplying of nano particle lithium ion battery.
Fig. 7 is the coated Fe of carbon that in the present invention, embodiment mono-makes
3o
4cyclic voltammetric (CV) curve chart of nano particle lithium ion battery.
Fig. 8 is the coated Fe of carbon that in the present invention, embodiment bis-makes
3o
4charging and discharging curve under the different multiplying of nano particle lithium ion battery.
Fig. 9 is the coated Fe of carbon that in the present invention, embodiment bis-makes
3o
4cyclic voltammetric (CV) curve chart of nano particle lithium ion battery.
Embodiment
Below in conjunction with specific embodiment, particular content of the present invention is described as follows:
Embodiment mono-:
Take 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, stirring and dissolving wiring solution-forming, and then the ultrasonic 15min of ultrasonic device taking power as 400W, mix.The solution mixing is put into 80 DEG C of vacuumizes of vacuum drying chamber, obtain mixture until dry.Milled mixtures, the mixed-powder of getting 6g is placed in Noah's ark, and Noah's ark is put into tube furnace, under the Ar inert gas shielding taking flow as 200ml/min, is warming up to 300 DEG C of temperature carries out carbon source decomposition with the programming rate of 10 DEG C/min, after insulation 2h; Then to continue to pass into flow be the Ar inert gas of 200ml/min and be warming up to 750 DEG C of temperature with the programming rate of 10 DEG C/min, and insulation 2h carries out carbonization, after reaction finishes, under Ar atmosphere protection, is cooled to room temperature, obtains calcined product.Collect calcined product, porphyrize till being washed to and thering is no NaCl in product, is dried at 80 DEG C, and obtaining particle diameter is the coated Fe of carbon of 1-100nm
3o
4nano particle, TEM schemes as shown in Figure 1, 2.By coated carbon Fe
3o
4nano particle is evenly coated on Copper Foil after mixing according to the mass ratio of 80:10:10 with PVDF binding agent, 1-METHYLPYRROLIDONE, is placed on 80 DEG C of vacuumize 4h in baking oven, then temperature is elevated to 120 DEG C of vacuumize 12h, be cooled to after room temperature, punching press, makes electrode slice; Using lithium metal as to electrode, electrolyte is 1 mol/LLiPF
6
/ EC+DMC+EMC, the Celgard 2300 type barrier films that barrier film adopts U.S. Celgard company to produce complete the assembling of battery in humidity is less than 4% glove box, make Li/ carbon coated ferriferrous oxide half-cell.The lithium ion battery making is carried out to charge-discharge test on the electric CT2001A cell tester of indigo plant, is 92mA/g in 1C(current density) circulation is after 30 weeks, and the specific discharge capacity of battery is 758mAhg
-1, being 184mA/g in 2C(current density) and circulation is after 100 weeks, and the specific discharge capacity of battery is 829mAhg
-1, being 460mA/g in 5C(current density) and circulation is after 50 weeks, and the specific discharge capacity of battery is 630mAhg
-1, its its charge-discharge test curve as shown in Figure 6.Then utilize the electrochemical workstation that model is CHI660D to carry out cyclic voltammetry to the battery making, 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 as shown in Figure 7.
Embodiment bis-:
The coated Fe of carbon in the present embodiment
3o
4the preparation process of nano particle and battery preparation process are identical with embodiment mono-step process, have just changed calcining heat: become 700 DEG C from 750 DEG C.The lithium ion battery making is carried out to charge-discharge test on the electric CT2001A cell tester of indigo plant, is 24.5mA/g in 1C(current density) circulation is after 30 weeks, and the specific discharge capacity of battery is 522mAhg
-1, being 49mA/g in 2C(current density) and circulation is after 100 weeks, and the specific discharge capacity of battery is 181mAhg
-1, being 122.5mA/g in 5C(current density) and circulation is after 50 weeks, and the specific discharge capacity of battery is 72mAhg
-1, its its charge-discharge test curve as shown in Figure 8.Then utilize the electrochemical workstation that model is CHI660D to carry out cyclic voltammetry to the battery making, 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 as shown in Figure 9.
Embodiment tri-:
Take 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, stirring and dissolving wiring solution-forming, and then the ultrasonic 15min of ultrasonic device taking power as 400W, mix.The solution mixing is put into 80 DEG C of vacuumizes of vacuum drying chamber, obtain mixture until dry.Milled mixtures, the mixed-powder of getting 6g is placed in Noah's ark, Noah's ark is put into tube furnace, first pass into the Ar inert gas deaeration of 400ml/min, again with the Ar inert gas of 400ml/min and be warming up to 400 DEG C of temperature with the programming rate of 10 DEG C/min and carry out carbon source decomposition, after insulation 1h; Then to continue to pass into flow be the Ar inert gas of 400ml/min and be warming up to 750 DEG C of temperature with the programming rate of 10 DEG C/min, and insulation 2h carries out carbonization, after reaction finishes, under Ar atmosphere protection, is cooled to room temperature, obtains calcined product.Collect calcined product, porphyrize till being washed to and thering is no NaCl in product, is dried at 60 DEG C, and obtaining particle diameter is the coated Fe of carbon of 1-100nm
3o
4nano particle.By coated carbon Fe
3o
4nano particle is evenly coated on Copper Foil after mixing according to the mass ratio of 80:10:10 with PVDF binding agent, 1-METHYLPYRROLIDONE, is placed on 80 DEG C of vacuumize 4h in baking oven, then temperature is elevated to 120 DEG C of vacuumize 12h, be cooled to after room temperature, punching press, makes electrode slice; Using lithium metal as to electrode, electrolyte is 1 mol/LLiPF
6/ EC+DMC+EMC, the Celgard 2300 type barrier films that barrier film adopts U.S. Celgard company to produce complete the assembling of battery in humidity is less than 4% glove box, make Li/ carbon coated ferriferrous oxide half-cell.。
Embodiment tetra-:
Take 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, stirring and dissolving wiring solution-forming, and then the ultrasonic 15min of ultrasonic device taking power as 400W, mix.The solution mixing is put into 100 DEG C of vacuumizes of vacuum drying chamber, obtain mixture until dry.Milled mixtures, the mixed-powder of getting 6g is placed in Noah's ark, Noah's ark is put into tube furnace, first pass into the He inert gas deaeration of 400ml/min, again with the Ar inert gas of 400ml/min and be warming up to 400 DEG C of temperature with the programming rate of 10 DEG C/min and carry out carbon source decomposition, after insulation 2h; Then to continue to pass into flow be the He inert gas of 400ml/min and be warming up to 800 DEG C of temperature with the programming rate of 10 DEG C/min, and insulation 4h carries out carbonization, after reaction finishes, under He atmosphere protection, is cooled to room temperature, obtains calcined product.Collect calcined product, porphyrize till being washed to and thering is no NaCl in product, is dried at 80 DEG C, and obtaining particle diameter is the coated Fe of carbon of 1-100nm
3o
4nano particle.By coated carbon Fe
3o
4nano particle is evenly coated on Copper Foil after mixing according to the mass ratio of 80:10:10 with PVDF binding agent, 1-METHYLPYRROLIDONE, is placed on 80 DEG C of vacuumize 4h in baking oven, then temperature is elevated to 120 DEG C of vacuumize 12h, be cooled to after room temperature, punching press, makes electrode slice; Using lithium metal as to electrode, electrolyte is 1 mol/LLiPF
6/ EC+DMC+EMC, the Celgard 2300 type barrier films that barrier film adopts U.S. Celgard company to produce complete the assembling of battery in humidity is less than 4% glove box, make Li/ carbon coated ferriferrous oxide half-cell.
Embodiment five:
Take 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, stirring and dissolving wiring solution-forming, and then the ultrasonic 15min of ultrasonic device taking power as 400W, mix.The solution mixing is put into 80 DEG C of vacuumizes of vacuum drying chamber, obtain mixture until dry.Milled mixtures, the mixed-powder of getting 6g is placed in Noah's ark, and Noah's ark is put into tube furnace, first passes into the N of 200ml/min
2inert gas deaeration, then with the Ar inert gas of 200ml/min and be warming up to 300 DEG C of temperature with the programming rate of 10 DEG C/min and carry out carbon source decomposition, after insulation 2h; Then continue to pass into the N that flow is 200ml/min
2inert gas is also warming up to 750 DEG C of temperature with the programming rate of 10 DEG C/min, insulation 2h carry out carbonization, reaction finish after at N
2under atmosphere protection, be cooled to room temperature, obtain calcined product.Collect calcined product, porphyrize till being washed to and thering is no NaCl in product, is dried at 80 DEG C, and obtaining particle diameter is the coated Fe of carbon of 1-100nm
3o
4nano particle.By coated carbon Fe
3o
4nano particle is evenly coated on Copper Foil after mixing according to the mass ratio of 80:10:10 with PVDF binding agent, 1-METHYLPYRROLIDONE, is placed on 80 DEG C of vacuumize 4h in baking oven, then temperature is elevated to 120 DEG C of vacuumize 12h, be cooled to after room temperature, punching press, makes electrode slice; Using lithium metal as to electrode, electrolyte is 1 mol/LLiPF
6/ EC+DMC+EMC, the Celgard 2300 type barrier films that barrier film adopts U.S. Celgard company to produce complete the assembling of battery in humidity is less than 4% glove box, make Li/ carbon coated ferriferrous oxide half-cell.
Claims (1)
1. a preparation method for carbon coated ferriferrous oxide lithium ion battery negative material, described lithium ion battery negative material is the coated Fe of carbon with nucleocapsid structure
3o
4composite material, its particle diameter is between 1 ~ 100nm, and carbon coating layer thickness is 2.5nm ~ 10nm, and its mass content is 40 ~ 80%, core Fe
3o
4mass content be 20% ~ 60%, it is characterized in that comprising following process:
The mol ratio of a. pressing iron in carbon in a kind of carbon source of glucose, sucrose, starch or citric acid and ferric nitrate is (200 ~ 0.1): 1, and taking the mass ratio of iron and NaCl as (0.01 ~ 0.1): 1, carbon source, ferric nitrate and NaCl are added in deionized water, and ultrasonic agitation is made homogeneous solution;
B. solution step a being made is put into vacuum drying chamber in 60 ~ 200 DEG C of vacuumizes of temperature, obtains mixture until dry;
C. mixture grind into powder step b being obtained, then powder is paved in Noah's ark, then Noah's ark is placed in to tube furnace flat-temperature zone and calcines, the first N taking flow as 10 ~ 400 ml/min
2, under He or Ar inert gas shielding, be warming up to 100 ~ 500 DEG C with the programming rate of 1 ~ 10 DEG C/min, insulation 0.5 ~ 4 h, decomposes carbon source; Then continue to pass into the N that flow is 10 ~ 400ml/min
2, He or Ar inert gas be warming up to 400 ~ 1000 DEG C with the programming rate of 1 ~ 10 DEG C/min, insulation 1 ~ 6h carries out carbonization, after reaction finishes at N
2, be cooled to room temperature under the protection of He or Ar inert gas atmosphere, obtain the coated Fe of carbon
3o
4the calcined product of nano particle and NaCl;
Collecting the calcined product obtaining in step c, through porphyrize, till being washed to and thering is no NaCl in calcined product, is to dry at 60 ~ 120 DEG C in temperature, and obtaining particle diameter is the coated Fe of carbon of 1 ~ 100nm
3o
4lithium ion battery negative material.
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| CN114023937A (en) * | 2021-11-02 | 2022-02-08 | 欣旺达电动汽车电池有限公司 | Fe3O4/Fe7S8@ C composite material, preparation method thereof, lithium ion battery cathode and lithium ion battery |
| CN114267831A (en) * | 2021-12-21 | 2022-04-01 | 吉林大学 | Lithium ion battery anode material with ferroferric oxide @ polymethyl methacrylate microcapsule structure and preparation method thereof |
| CN114275824A (en) * | 2022-01-18 | 2022-04-05 | 杭州幄肯新材料科技有限公司 | Porous carbon-coated ferroferric oxide nano-particles and solid-phase preparation method thereof |
| CN114639815A (en) * | 2022-04-08 | 2022-06-17 | 东莞市沃泰通新能源有限公司 | Preparation method of sodium ion battery negative electrode material, negative electrode sheet and sodium ion battery |
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| CN101728526B (en) * | 2009-12-09 | 2011-11-09 | 北京化工大学 | Lithium ion battery cathode material and preparation method thereof |
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