CN102163711B - Method for preparing lithium ion battery negative material by utilizing mesoporous carbon supported nano particles - Google Patents
Method for preparing lithium ion battery negative material by utilizing mesoporous carbon supported nano particles Download PDFInfo
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- CN102163711B CN102163711B CN2011100580342A CN201110058034A CN102163711B CN 102163711 B CN102163711 B CN 102163711B CN 2011100580342 A CN2011100580342 A CN 2011100580342A CN 201110058034 A CN201110058034 A CN 201110058034A CN 102163711 B CN102163711 B CN 102163711B
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Abstract
The invention provides a method for preparing a lithium ion battery negative material by utilizing mesoporous carbon supported nano particles, belonging to the technical field of lithium ion batteries. The method comprises the following steps: adding an activated substance precursor in an oxidized mesoporous carbon substrate and then dissolving in a polar solvent for preparation so as to obtain a colloidal solution; carrying out high temperature calcination so as to obtain the lithium ion battery negative material. In the method, the mesoporous carbon substrate is used as a carrier, the colloidal solution of the nano particles is evenly dispersed in the pore path of the substrate by utilizing an ultrasonic technique, the nano particles with uniform particle sizes are generated in situ in the mesoporous pore path through sintering at a certain temperature, and the mesoporous pore path can be used for effectively inhibiting the volume variation of activated particles in the carbon-removal process of lithium ions, thereby improving the cycle property of the lithium ion battery.
Description
Technical field
What the present invention relates to is a kind of method of technical field of lithium ion, specifically is a kind of method that adopts the mesoporous carbon load nano particle to prepare lithium ion battery negative material.
Background technology
Along with people to the rapid growth of energy demand and the worsening shortages of traditional petroleum-based energy, the novel green battery more and more is subjected to people's attention, the focus that lithium ion battery is big with its operating voltage height, specific energy, have extended cycle life, self-discharge rate is low, memory-less effect and advantage such as environmentally friendly become research.Wherein the capacity of electrode material and cycle performance are the key factors of weighing lithium ion battery, the social negative material of widely used lithium ion battery mainly is graphitized carbon material at present, because the theoretical capacity of graphitized carbon material is relatively low, satisfies demands of social development so demand seeking the more superior electrode material of performance urgently.
In nearest research, multiple negative material is developed, and wherein a lot of materials have been obtained breakthrough at aspect of performance.These materials mainly comprise metal alloy, metal oxide, metal sulfide, hud typed composite material and nonmetallic composite etc.The capacity of novel negative material usually can be more a lot of greatly than traditional material with carbon element; but it is generally relatively poor aspect cyclicity; because new material itself generally crystallite district and amorphous area can occur; in the embedding of lithium ion and deviating from; storage lithium mechanism no longer is the equally single intercalation mechanism of image-stone China ink material with carbon element; but multiple mechanism coexistence, as molecule storage lithium mechanism, micropore storage lithium mechanism etc.In this case; electrode material lithium ion embed and the process of deviating from; usually bigger volumetric expansion and contraction can appear; sometimes cubical expansivity is up to percent hundreds of, and this huge change in volume is in the cyclic process of battery, and it is broken to cause battery material to take place; break away from pole piece; thereby make the battery electrode inactivation, whole lithium battery life termination can cause internal short-circuit of battery in severe case and explosion hazard is arranged.
At present, in order to improve the cycle performance of battery, people adopt following method more:
(1) with material nanoization and filming, expand to reduce absolute volume, reduce internal resistance thereby simultaneously lithium ion migration path in taking off the embedding process is shortened;
(2) introduce some inertia body dispersion or coating active material, thereby effectively alleviate volumetric expansion and the mechanical stress that active material produces in charge and discharge process;
(3) thus preparing compound that some has special construction improves cyclical stability.
These methods have suppressed the change in volume of electrode material to a certain extent well, but because idiographic flow and operation are loaded down with trivial details, and cost is higher, and its industrialized condition is left to be desired.
Find through the retrieval to prior art, Carbon 49 (2011) 89-95, A film of porous carbon nanofibers that contain Sn/SnOx nanoparticles in the pores and its electrochemical performance as an anode material for lithium ion batteries (preparation of the particle-filled porous carbon nano-fiber material of tin/tin oxide nano and the research of chemical property thereof) has introduced the composite material of a kind of porous carbon nanofiber and tin ash, but because the pore-size distribution of carbon nano-fiber is uncontrollable, and the electrostatic spinning process that adopts is had relatively high expectations to equipment, its practical application will be subjected to bigger restriction, and the interaction force of tin ash and carbon nano-fiber a little less than, in cyclic process, cause the disengaging of tin ash particle and carbon nano-fiber easily, make the battery inactivation.
Summary of the invention
The present invention is directed to the prior art above shortcomings, a kind of method that adopts the mesoporous carbon load nano particle to prepare lithium ion battery negative material is provided, with the mesoporous carbon basis material as carrier, utilize ultrasonic technique that the colloidal solution of nano particle is dispersed in the duct of matrix, sintering by uniform temperature, original position grows into the nano particle of uniform particle diameter in mesopore orbit, mesoporous duct is in the variation that can effectively suppress the active particle volume in the embedding process of taking off of lithium ion, thus the cycle performance of raising lithium ion battery.
The present invention is achieved by the following technical solutions, and the present invention is dissolved in to dispose in the polar solvent by the mesoporous carbon matrix adding active material presoma that oxidation processes is crossed and obtains colloidal solution, obtains lithium ion battery negative material after high-temperature calcination.
Described oxidation processes refers to: the mesoporous carbon matrix is added in the strong acid solution, and stirring is 2-6 hour under 50-100 degree centigrade of oil bath condition, treats that reflection finishes the back and filters also dry.
Described strong acid solution is sulfuric acid solution or salpeter solution or its mixing of 0.5-3mol/L.
The aperture of described mesoporous carbon matrix is the 10-60 nanometer.
Described polar solvent is the aqueous solution of water or alcohol.
Described dissolving refers to: the mesoporous carbon matrix after the oxidation processes is slowly added under stirring environment in the colloidal solution, after ultrasonic dispersion treatment 2-6 hour, filter also dry.
Described high-temperature calcination refers to: calcining is 2-4 hour under protective atmosphere, and calcining heat is 400-600 degree centigrade.
Described active material presoma is: corresponding villaumite, nitrate, sulfate or the oxalates of a kind of or its combination in stannous chloride, ferric nitrate, lead chloride, zinc chloride, titanium chloride, nickel nitrate or the cobalt chloride.
Tin ash negative material and the metal lithium sheet of the present invention preparation are assembled into lithium ion battery, discharge and recharge with the current density of 500mA/g, and reversible specific capacity and shows stable cycle performance after 300 charge and discharge cycles about 200mA/g.This method equipment is simple, and raw material is easy to get, and can realize suitability for industrialized production.
Description of drawings
Fig. 1 is the X-ray diffractogram of the mesoporous carbon load tin ash that obtains of embodiment 1.
Fig. 2 is the transmission electron microscope figure of the mesoporous carbon load tin ash that obtains of embodiment 1.
Fig. 3 is that the mesoporous carbon load tin ash that obtains of embodiment 1 is as the circulation discharge curve of negative material.
Embodiment
Below embodiments of the invention are elaborated, present embodiment is being to implement under the prerequisite with the technical solution of the present invention, provided detailed execution mode and concrete operating process, but protection scope of the present invention is not limited to following embodiment.
Embodiment 1
(1) get 1 mesoporous carbon of gram aperture about 20 nanometers and add in the sulfuric acid solution of 1mol/L, under 50 degrees centigrade of oil bath conditions, magnetic agitation 6 hours is filtered with sand core funnel then, and washing is to neutral, 80 degrees centigrade of following vacuumize 24 hours.
(2) preparation tin oxide colloid: get 1 gram stannous chloride and add in 10 milliliters of absolute ethyl alcohols, magnetic agitation 5 minutes is dissolved stannous chloride fully, dropwise drips deionized water in solution then, till occurring having the blue colloid of gloss.
(3) get 0.5 mesoporous carbon that restrains acidifying and add gradually in the above-mentioned colloidal solution, the limit edged stirs, and magnetic agitation is after 10 minutes; ultrasonic processing 4 hours; sand core funnel filters, and 80 degrees centigrade of vacuumizes were taken out after 24 hours; put into tube furnace; in nitrogen protection, be warming up to 400 ℃ with 5 ℃/min, be incubated 4 hours; naturally cooling obtains composite material.
The structure of the composite material that (4) prepares, by X-ray diffraction, N
2Analysis means of testing such as absorption/desorption isothermal adsorption curve characterize.Fig. 1 is the X-ray diffractogram of the mesoporous carbon load tin ash that obtains of embodiment one, and by mainly containing tin ash in the negative material as can be known among the figure, and the particle diameter of tin ash particle is about 10 nanometers.Fig. 2 is the transmission electron micrograph of the mesoporous carbon load tin ash that obtains of embodiment one, can be clearly seen that from figure the tin ash particle is evenly distributed in the carbon hole.
(5) performance test: get 0.2 restrain mesoporous carbon load tin ash, add 0.04 gram carbon black conductive agent and 0.03 and restrain the polyvinylidene fluoride bonding agent that is dissolved in nitrogen-nitrogen-dimethyl pyrrolidone solution, be mixed into uniform slurry, slurry be coated in make negative plate on the Copper Foil.In being full of the glove box of argon gas, be anodal with the metal lithium sheet, be assembled into button cell.In the voltage range of 0.25-2V, under the room temperature, carry out the charge and discharge cycles test with the electric current of 500mA/g.Fig. 3 be the mesoporous carbon load tin ash that obtains of embodiment one as the circulation discharge curve of negative material, as can be seen from the figure, because the restriction of mesopore orbit, after 300 circulations, material still has the reversible capacity of 150mA/g.
Embodiment 2
(1) get 1 mesoporous carbon of gram aperture about 10 nanometers and add in the sulfuric acid solution of 3mol/L, under 100 degrees centigrade of oil bath conditions, magnetic agitation 4 hours is filtered with sand core funnel then, and washing is to neutral, 50 degrees centigrade of following vacuumize 24 hours.
(2) preparation iron nitrate solution: the ferric nitrate of 1 gram is dissolved in in 100 ml waters, and mixing is configured to iron nitrate solution.
(3) get 0.5 mesoporous carbon that restrains acidifying and add gradually in the above-mentioned colloidal solution, the limit edged stirs, and magnetic agitation is after 20 minutes; ultrasonic processing 6 hours; sand core funnel filters, and 60 degrees centigrade of vacuumizes were taken out after 24 hours; put into tube furnace; in nitrogen protection, be warming up to 500 ℃ with 5 ℃/min, be incubated 2 hours; naturally cooling obtains the lithium ion anode material.
The structure of the composite material that (4) prepares, by XRD, analysis means of testing such as N2 absorption/desorption isothermal adsorption curve characterize.The particle diameter of di-iron trioxide particle is about 5 nanometers.The di-iron trioxide particle is evenly distributed in the carbon hole.
(5) performance test: get 0.2 restrain mesoporous carbon load di-iron trioxide, add 0.04 gram carbon black conductive agent and 0.03 and restrain the polyvinylidene fluoride bonding agent that is dissolved in nitrogen-nitrogen dimethyl pyrrolidone solution, be mixed into uniform slurry, slurry be coated in make negative plate on the Copper Foil.In being full of the glove box of argon gas, be anodal with the metal lithium sheet, be assembled into button cell.In the voltage range of 0.25-2V, under the room temperature, carry out the charge and discharge cycles test with the electric current of 500mA/g.This battery still has later the capacity of 120mA/g for 100 times in circulation.
Embodiment 3
(1) get 1 mesoporous carbon of gram aperture about 60 nanometers and add in the sulfuric acid solution of 0.5mol/L, under 100 degrees centigrade of oil bath conditions, magnetic agitation 2 hours is filtered with sand core funnel then, and washing is to neutral, 80 degrees centigrade of following vacuumize 24 hours.
(2) preparation cobalt oxide colloid: get 1 gram cobalt nitrate and add 20 ml waters, magnetic agitation 5 minutes is dissolved cobalt nitrate fully.
(3) get 0.5 mesoporous carbon that restrains acidifying and add gradually in the above-mentioned colloidal solution, the limit edged stirs, and magnetic agitation is after 30 minutes; ultrasonic processing 2 hours; sand core funnel filters, and 80 degrees centigrade of vacuumizes were taken out after 24 hours; put into tube furnace; in nitrogen protection, be warming up to 600 ℃ with 5 ℃/min, be incubated 3 hours; naturally cooling obtains composite material.
The structure of the composite material that (4) prepares, by XRD, analysis means of testing such as N2 absorption/desorption isothermal adsorption curve characterize.And the particle diameter of cobalt oxide particle is about the 40-50 nanometer.
(5) performance test: get 0.2 restrain mesoporous carbon load cobalt oxide, add 0.04 gram carbon black conductive agent and 0.03 and restrain the polyvinylidene fluoride bonding agent that is dissolved in nitrogen-nitrogen dimethyl pyrrolidone solution, be mixed into uniform slurry, slurry be coated in make negative plate on the Copper Foil.In being full of the glove box of argon gas, be anodal with the metal lithium sheet, be assembled into button cell.In the voltage range of 0.25-2V, under the room temperature, carry out the charge and discharge cycles test with the electric current of 500mA/g.This battery shows excellent cycle performance at the capacity that circulation still keeps later about 250mA/g for 100 times.
Embodiment 4
(1) get 1 mesoporous carbon of gram aperture about 40 nanometers and add in the sulfuric acid solution of 2.5mol/L, under 100 degrees centigrade of oil bath conditions, magnetic agitation 2 hours is filtered with sand core funnel then, and washing is to neutral, 80 degrees centigrade of following vacuumize 24 hours.
(2) preparing titanium dioxide colloid: under the condition of ice-water bath, pure and mild titanium tetrachloride is mixed, its volume ratio is 44: 10, and stirs.
(3) get 0.5 mesoporous carbon that restrains acidifying and add gradually in the above-mentioned colloidal solution, the limit edged stirs, and magnetic agitation is after 30 minutes; ultrasonic processing 2 hours; sand core funnel filters, and 80 degrees centigrade of vacuumizes were taken out after 24 hours; put into tube furnace; in nitrogen protection, be warming up to 600 ℃ with 5 ℃/min, be incubated 3 hours; naturally cooling obtains composite material.
The structure of the composite material that (4) prepares, by XRD, analysis means of testing such as N2 absorption/desorption isothermal adsorption curve characterize.And the particle diameter of TiO 2 particles is about the 20-30 nanometer.
(5) performance test: get 0.2 restrain the mesoporous carbon carried titanium dioxide, add 0.04 gram carbon black conductive agent and 0.03 and restrain the polyvinylidene fluoride bonding agent that is dissolved in nitrogen-nitrogen dimethyl pyrrolidone solution, be mixed into uniform slurry, slurry be coated in make negative plate on the Copper Foil.In being full of the glove box of argon gas, be anodal with the metal lithium sheet, be assembled into button cell.In the voltage range of 0.25-2V, under the room temperature, carry out the charge and discharge cycles test with the electric current of 500mA/g.This battery is after circulation 100 times, and reversible capacity is approximately about 100mA/g, shows excellent cycle performance.
Claims (2)
1. method that adopts the mesoporous carbon load nano particle to prepare lithium ion battery negative material, it is characterized in that, by being that the mesoporous carbon matrix of 10-60 nanometer adds in the sulfuric acid solution and/or salpeter solution of 0.5-3mol/L with the aperture, stirred 2-6 hour under 50-100 degree centigrade of oil bath condition, question response finishes the back and filters also dry; A kind of or its combination in stannous chloride, ferric nitrate, lead chloride, zinc chloride, titanium chloride, nickel nitrate or the cobalt chloride is dissolved in the aqueous solution of water or alcohol; again the mesoporous carbon matrix after the oxidation processes is being stirred slowly adding under the environment; after ultrasonic dispersion treatment 2-6 hour; filter and drying, under protective atmosphere, obtain lithium ion battery negative material with 400-600 degree centigrade of calcining after 2-4 hour.
2. a lithium ion battery negative material is characterized in that, prepares according to the described method of claim 1.
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| CN102386382A (en) * | 2011-11-03 | 2012-03-21 | 大连理工大学 | CMK-5 type mesoporous carbon-nano inorganic substance composite material, preparation method and application thereof |
| JP5758859B2 (en) * | 2012-08-21 | 2015-08-05 | トヨタ自動車株式会社 | Electrode body and battery including the electrode body |
| CN103219510B (en) * | 2013-03-21 | 2015-06-17 | 华中科技大学 | Lithium battery negative electrode material preparation method and its product |
| CN104733704A (en) * | 2013-12-19 | 2015-06-24 | 北汽福田汽车股份有限公司 | Membrane material and preparation method thereof, cathode material of lithium ion battery and preparation method thereof |
| CN105322161A (en) * | 2014-07-28 | 2016-02-10 | 中国科学院大连化学物理研究所 | Carbon-supported lithium vanadate and preparation method and application thereof |
| CN106159222A (en) * | 2015-04-28 | 2016-11-23 | 江南大学 | The lithium ion battery preparation method of Co/CMK-3 composite Nano negative material |
| CN106935861B (en) * | 2017-03-23 | 2019-09-27 | 中南大学 | A kind of sodium-ion battery carbon negative pole material and preparation method thereof |
| CN109119606A (en) * | 2018-08-02 | 2019-01-01 | 天能电池集团有限公司 | A kind of preparation method and application of nanometer of lead deposit hierarchical porous structure carbon composite |
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