Background technology
Electrokinetic cell is the heart of New-energy electric vehicle, it it is the key of New-energy electric vehicle industry development, but the energy density of the lithium ion battery being widely used on mobile electronic product at present, security performance, high rate performances etc. still can not meet people's instructions for use on electric automobile, becomes the bottleneck hindering electric automobile spread. Lithium ion battery is made up of positive and negative pole material, barrier film and electrolyte, and wherein electrode material is the core of battery, decides battery electrochemical storage lithium performance, and therefore the performance of negative electrode material directly affects the performance of lithium ion battery. Business-like lithium ion battery negative material currently mainly is based on graphite cathode material, its actual specific capacity is already close to the theoretical value of 372mAh/g, its relatively low theoretical capacity constrains the raising of the energy density of lithium ion battery, therefore researches and develops the negative material with height ratio capacity, excellent cyclical stability and safety further extremely urgent.
Silicon has the theoretical specific capacity of 4200mAh/g as lithium ion battery negative material, capacity far above graphite, as negative material can by a relatively large margin improve battery energy density, and the discharge platform of silicon is slightly above graphite cathode material, being not likely to produce analysis lithium, security performance is better than graphite, and additionally silicon capacity enriches, cheap, therefore it is the most promising current lithium ion battery negative material. But silicon also has obvious shortcoming as lithium ion battery negative material, if silicon is as semi-conducting material, himself electrical conductivity is relatively low; At charge and discharge process, along with the embedding of lithium ion with deviate from, silicon materials change in volume is relatively big, causes material efflorescence, comes off, and ultimately results in and collector departs from, and cyclical stability is poor.
The methods such as doping, nanorize are generally adopted to improve the chemical property of silica-base material in order to solve the problems referred to above. Publication number is that CN104332621A Chinese patent literature discloses a kind of method utilizing metallothermic reduction to prepare hollow nano silicon ball, utilize active metal reduction silica nanosphere, the content controlling active metal makes its reduction silica nanosphere surface, and kernel remains silicon dioxide, then utilize hydrochloric acid and Fluohydric acid. to remove metal-oxide and silicon dioxide, obtain hollow nano silicon ball. Publication number is that CN101179126B Chinese patent literature discloses and a kind of includes, for lithium secondary battery, the electrode material that silicon is main component, and this electrode material includes the atomic ratio relative to silicon of at least one element in boron, aluminum, gallium, antimony and phosphorus 1 �� 10- 5To 1 �� 10- 1Scope in dopant dose silicon is adulterated.These methods improve the chemical property of silica-base material to a certain extent, but these preparation methoies are more complicated, and relatively costly, not easily prepared by scale, and chemical property needs to be improved further.
Summary of the invention
In order to obtain the Si-C composite material with relatively excellent electrochemical performance, the present invention provides a kind of Si-C composite material, preparation method and application thereof.
The preparation method of a kind of Si-C composite material, comprises the following steps:
Step (1): carbon compound: mixed with graphite by silicon metal alloy compositions, then through two road pickling, prepares porous silicon carbon composite;
Step (2): carbon is coated with: the porous silicon carbon composite that step (1) prepares is mixed with organic carbon source, thermally treated prepared Si-C composite material.
The present invention, by silicon metal alloy compositions carries out two road acid corrosions, prepares porous silicon (porous silicon carbon composite), and by preparing Si-C composite material with carbon compound and carbon cladding. In Si-C composite material, the existence of carbon and micropore has cushioned the volumetric expansion of silicon effectively, enhances conduction and the chemical property of silicon. The inventive method technique is simple, abundant raw materials, cheap, is conducive to industry's enlarging production.
In step (1), being clayed into power by silicon metal alloy compositions first with ball-milling method, then prepare graphite/silicon metal alloy composite with graphite mixing, wherein, the rotating speed of ball milling is 300��1000 revs/min, Ball-milling Time 2��48 hours; The mixing quality of silicon metal alloy compositions and graphite is than for 0.2-5:1.
The present invention utilizes high-energy ball milling method to prepare graphite/silicon metal alloy composite (powder). Improve the mixed effect of raw material, be conducive to the acid corrosion of subsequent step simultaneously.
As preferably, in silicon metal alloy compositions, the content of silicon is 20��95wt%, and other compositions are one or more in chosen from Fe, aluminum, copper, chromium, nickel, stannum, manganese, calcium, magnesium, cobalt, titanium and germanium.
Above-mentioned metallic element can be compounded to form stable alloy or partially-alloyed compound with silicon, has good metal ductility, improves the processing characteristics of silicon metal alloy compositions.
The content of described silicon is the silicon percentage by weight relative to silicon metal alloy compositions. It is further preferred that in silicon metal alloy compositions, except silicon, other are ferrum and/or aluminum. Acid is good to the corrosive effect of this eka-silicon metal alloy compositions, is conducive to the porous silicon carbon composite that processability is good.
As preferably, the powder of the graphite/silicon metal alloy composite prepared by ball-milling method is inspected by random samples with 100 mesh standard sieves, and 100% passes through.
Silicon metal alloy mixes in described ratio with graphite, by ball-milling method, Si metal alloy, C is carried out compound, is introduced by material with carbon element in silicon metal alloy compositions. Graphite/silicon metal alloy the composite prepared, then through two road acid elutions, removes the metallic element in graphite/silicon metal alloy composite and Si oxide.
As preferably, the acid that first pickling adopts is one or more in sulphuric acid, nitric acid, hydrochloric acid, and molar concentration is 0.1��10mol/L. It is preferred that, in first pickling, adopt above-mentioned aqueous acid.
Graphite/silicon metal alloy composite is immersed in above-mentioned acid solution, and by stirring the touch opportunity improving acid and metal, as preferably, mixing time is 10-20h, filter subsequently and with deionized water wash repeatedly, dried, remove the metallic element in graphite/silicon metal alloy composite.
After first pickling, then carrying out second pickling, as preferably, the acid that second pickling adopts is Fluohydric acid., and mass percent is 1%��20%.
It is preferred that, the Fluohydric acid. that second pickling adopts is aqueous solution.
Second pickling mode is with reference to first pickling.
After second pickling, through the repeatedly washing of filtration, deionized water and ethanol, dry and obtain porous silicon carbon composite. Porous silicon carbon composite carries out the carbon cladding of step (2) again.
As preferably, in step (2), described organic carbon source is selected from one or more in glucose, sucrose, citric acid, DOPA amine salt, formaldehyde, phenolic resin, xylenol, polyacrylonitrile, polypyrrole, polyaniline and polythiophene.
In order to improve the organic carbon source covered effect to porous silicon carbon composite, above-mentioned organic carbon source can utilize water or other solvents dissolve; For improving effect and the efficiency of the filling porous Si-C composite material of organic carbon source further, as preferably, in step (2), porous silicon carbon composite mixes under malleation or negative pressure atmosphere with the solution of organic carbon source. Silicon/graphite/organic carbon source composite material is obtained through intensification solvent evaporated after mixing.
As preferably, in organic carbon source, the weight that adds of carbon is in silicon metal alloy compositions 0.05-0.5 times of silicon weight.
It is preferred that, in organic carbon source, the weight that adds of carbon is 0.1 times of silicon weight in silicon metal alloy compositions.
Silicon/graphite/organic carbon source composite material is placed in tube furnace, under the atmosphere of noble gas, carries out heat treatment, without there being oxygen in described noble gas, it is preferable that nitrogen, argon or helium.
As preferably, described heat treatment temperature is 400��1200 DEG C, and heat treatment time is 1��8 hour.
After heat treatment completes, utilize deionized water or absolute ethanol washing; Solid-liquid separation (as filtering or centrifugal); The solid collected, through vacuum drying, prepares described Si-C composite material. As preferably, vacuum drying temperature is 60��120 DEG C, and drying time is 2��12 hours.
As preferably, in the Si-C composite material of final preparation, the content of silicon is 5%��50wt%.
Present invention additionally comprises the Si-C composite material adopting above-mentioned preparation method to prepare.
Present invention additionally comprises the application adopting above-mentioned Si-C composite material as lithium ion battery negative material.
Adopting existing lithium ion battery negative electrode fabrication to prepare lithium ion battery negative electrode, described electrode material is made up of Si-C composite material (active material), conductive agent and binding agent. The conductive agent, the binding agent that adopt are existing conventional material. As, conductive carbon black (super-p), Kynoar (PVDF).
As, the Si-C composite material (active material) that the inventive method is prepared: conductive agent (conductive carbon black, super-p): binding agent (Kynoar, PVDF) by certain mass than mixing, add a certain amount of N-Methyl pyrrolidone (NMP) solvent, be uniformly mixed prepared slurry. Coating machine is utilized to be coated uniformly on Copper Foil by slurry, tabletting after vacuum drying, section, the dry i.e. prepared lithium ion battery negative electrode containing Si-C composite material of the present invention.
Present invention additionally comprises a kind of lithium ion battery, containing the Si-C composite material that said method prepares. Described Si-C composite material is prepared into electrode active material material (lithium ion battery negative electrode) by prior art, is assembled into lithium ion again through prior art.
The inventive method technique is simple, with low cost, can be mass-produced. The carbon silicon accounting of the Si-C composite material prepared is reasonable, aperture is reasonable, has and preferably bears the advantages such as volume adaptability to changes, the specific surface area degree of depth big, lithium ion deintercalation is little, ion the evolving path is short, reversible capacity is high, coulombic efficiency is high, have extended cycle life.
Embodiment 1:
1, the preparation of Si-C composite material
Utilizing planetary ball mill to be pulverized by the Antaciron that silicone content is 65% is little granule, and wherein, ball material mass ratio is about 5:1, and rotating speed is 400 revs/min, and Ball-milling Time obtains Antaciron powder after 4 hours. Weighing graphite 13g, silicone content is Antaciron 10g and the 20ml ethanol of 65%, utilizes ball mill within 8 hours, to obtain graphite/Antaciron composite with the rotating speed ball milling of 450 revs/min. Being placed in beaker by the graphite obtained/Antaciron composite, add the sulphuric acid that excessive molar concentration is 1mol/L, utilize magnetic stirrer to remove ferrous metal element in 24 hours at normal temperatures, product utilizes deionized water to clean 3 times; Then it is excessive in removing Si oxide, magnetic agitation 12 hours under room temperature in the hydrofluoric acid solution that mass fraction is 5% to be added by product, and product utilizes deionized water and Fluohydric acid. to be respectively washed 3 times to obtain porous silicon/graphite composite material. The aqueous solution (sucrose 5g) containing 5g sucrose is joined to the porous silicon/graphite composite material obtained, under room temperature, in subnormal ambient, magnetic agitation is beneficial in sucrose solution immersion porous silicon space for 3 hours, then at 90 DEG C, magnetic agitation to aqueous solution is all evaporated (mixture, silicon/graphite/organic carbon source composite material). Mixture is placed in tube furnace, in nitrogen environment, is heated to 700 DEG C with the heating rate of 5 DEG C/min, be incubated 4 hours, naturally cool to room temperature; Wash respectively 3 times with deionized water and ethanol again, dry at 100 DEG C in vacuum drying oven and obtain Si-C composite material in 5 hours.
2, the preparation of Si-C composite material negative pole
Sample will be prepared by Si-C composite material (active material): conductive agent (conductive carbon black, super-p): binding agent (Kynoar, the mass ratio mixing of PVDF)=8:1:1, add a certain amount of N-Methyl pyrrolidone (NMP) solvent, utilize magnetic agitation mix homogeneously. Utilize coating machine to be coated uniformly on Copper Foil by slurry, 100 DEG C of vacuum dryings 10 hours in vacuum drying oven, after through tabletting, section, dry, weighing etc. obtains pole piece, battery to be assembled.
3, the preparation of lithium ion battery and test
Dry pole piece is put into assembled battery in the glove box containing high-purity argon gas, and in the button cell of assembling, just extremely Si-C composite material, negative pole is lithium sheet, and barrier film is polypropylene screen, and electrolyte is containing the lithium hexafluoro phosphate (LiPF that lithium salts is 1mol/L6), solvent is volume ratio is the ethylene carbonate (EC) of 1:1:1: dimethyl carbonate (DMC): Ethyl methyl carbonate (EMC). Utilizing blue electrical testing system constant current that lithium ion battery is carried out charge-discharge test, voltage tester ranges for 0.01��1.5V.