Background technology
Power battery is the heart of New-energy electric vehicle, is the key that New-energy electric vehicle industry development, however mesh
The energy density of the preceding lithium ion battery being widely used on mobile electronic product, security performance, high rate performance etc. are still
Requirement of the people on electric vehicle cannot be met, become the bottleneck that electric vehicle is hindered to be widely applied.Lithium-ion electric
Pond is made of positive and negative pole material, diaphragm and electrolyte, and wherein electrode material is the core of battery, decides battery electrochemical
Lithium performance is stored up, therefore the performance of negative electrode material directly affects the performance of lithium ion battery.It is main commercialized at present
Lithium ion battery negative material based on graphite cathode material, actual specific capacity already close to 372mAh/g theoretical value,
Relatively low theoretical capacity constrains the raising of the energy density of lithium ion battery, thus further research and development with height ratio capacity, excellent
Different cyclical stability and the negative material of safety are extremely urgent.
Silicon has the theoretical specific capacity of 4200mAh/g as lithium ion battery negative material, far above the capacity of graphite, makees
The energy density of raising battery that can be by a relatively large margin for negative material, and the discharge platform of silicon is slightly above graphite cathode material
Material is not likely to produce analysis lithium, and security performance is better than graphite, and in addition silicon capacity enriches, cheap, therefore is most promising at present
Lithium ion battery negative material.But silicon also has the shortcomings that apparent as lithium ion battery negative material, if silicon is as semiconductor
Material, its own conductivity are relatively low;In charge and discharge process, with the insertion and abjection of lithium ion, silicon materials volume change is larger,
Lead to material dusting, come off, eventually lead to and be detached from collector, cyclical stability is poor.
The chemical property of silica-base material is improved the methods of generally use doping, nanosizing to solve the above-mentioned problems.It is public
The number of opening discloses a kind of method that hollow Nano silicon ball is prepared using metallothermic reduction for CN104332621A Chinese patent literatures,
Silica nanosphere is restored using active metal, controlling the content of active metal makes it only restore silica nanosphere table
Face, and kernel is still silica, then using hydrochloric acid and hydrofluoric acid removal metal oxide and silica, is obtained hollow
Nano silicon spheres.Publication No. CN101179126B Chinese patent literatures disclose it is a kind of for lithium secondary battery include silicon based on
The electrode material of ingredient is wanted, which includes atomic ratio of at least one of boron, aluminium, gallium, the antimony and phosphorus element relative to silicon
1 × 10- 5To 1 × 10- 1In the range of dopant dose silicon is doped.These methods improve silicon substrate to a certain extent
The chemical property of material, however these preparation methods are more complicated, cost is higher, is not easy scale preparation, and chemical property
Need to be further improved.
Invention content
In order to obtain the Si-C composite material having compared with excellent electrochemical performance, the present invention provides a kind of silicon-carbon composite wood
Material, preparation method and applications.
A kind of preparation method of Si-C composite material, includes the following steps:
Step (1):Carbon is compound:Silicon metal alloy compositions with graphite are mixed, using two pickling, porous silicon-carbon is made
Composite material;
Step (2):Carbon coating:Porous Si-C composite material made from step (1) is mixed with organic carbon source, it is thermally treated
Si-C composite material is made.
Porous silicon (porous silicon-carbon composite wood is made by carrying out two acid corrosions to silicon metal alloy compositions in the present invention
Material), and by compound and carbon coating prepares Si-C composite material with carbon.In Si-C composite material, carbon and micropore there are effective
Ground has buffered the volume expansion of silicon, enhances the conduction and chemical property of silicon.The method of the present invention is simple for process, and raw material are rich
It is rich, cheap, be conducive to industry's enlarging production.
In step (1), silicon metal alloy compositions are clayed into power first with ball-milling method, are then mixed to prepare stone with graphite
Ink/silicon metal alloy composite material, wherein, the rotating speed of ball milling is 300~1000 revs/min, Ball-milling Time 2~48 hours;Silicon gold
The mixing quality ratio for belonging to alloy material and graphite is 0.2-5:1.
The present invention prepares graphite/silicon metal alloy composite material (powder) using high-energy ball milling method.Improve the mixing of raw material
Effect, while be conducive to the acid corrosion of subsequent step.
Preferably, in silicon metal alloy compositions, the content of silicon is 20~95wt%, other compositions be selected from iron, aluminium,
It is one or more in copper, chromium, nickel, tin, manganese, calcium, magnesium, cobalt, titanium and germanium.
Above-mentioned metallic element can be compounded to form stable alloy or partially-alloyed compound with silicon, have good metal
Ductility improves the processing performance of silicon metal alloy compositions.
The content of the silicon is silicon relative to the weight percent of silicon metal alloy compositions.It is further preferred that silicon is golden
Belong in alloy material, in addition to silicon, other are iron and/or aluminium.Acid is good to the corrosive effect of the eka-silicon metal alloy compositions, favorably
In the good porous Si-C composite material of processability.
Preferably, it is taken out by 100 mesh standard sieves of powder of graphite made from ball-milling method/silicon metal alloy composite material
Inspection, 100% passes through.
Silicon metal alloy and graphite are mixed in the ratio, by ball-milling method that Si metal alloys, C progress is compound, by carbon
Material is introduced into silicon metal alloy compositions.Graphite obtained/silicon metal alloy composite material removes stone using two acid elutions
Metallic element and Si oxide in ink/silicon metal alloy composite material.
Preferably, acid is one or more, the molar concentration in sulfuric acid, nitric acid, hydrochloric acid used by first of pickling
For 0.1~10mol/L.Further preferably, in first of pickling, using the aqueous solution of above-mentioned acid.
Graphite/silicon metal alloy composite material is immersed in above-mentioned acid solution, and is passed through stirring and improved sour and metal connect
It has a sudden inspiration meeting, preferably, mixing time is 10-20h, then filters and be washed with deionized repeatedly, be dried, remove stone
Metallic element in ink/silicon metal alloy composite material.
After first of pickling, then second pickling is carried out, preferably, acid is hydrofluoric acid used by second pickling,
Mass percent is 1%~20%.
Further preferably, the hydrofluoric acid that second pickling uses is aqueous solution.
Second pickling mode refers to first of pickling.
After second pickling, the multiple washing of filtered, deionized water and alcohol is dried to obtain porous silicon-carbon composite wood
Material.Porous Si-C composite material carries out the carbon coating of step (2) again.
Preferably, in step (2), the organic carbon source is selected from glucose, sucrose, citric acid, DOPA amine salt, first
It is one or more in aldehyde, phenolic resin, xylenol, polyacrylonitrile, polypyrrole, polyaniline and polythiophene.
In order to improve covered effect of the organic carbon source to porous Si-C composite material, can by above-mentioned organic carbon source using water or
Other solvents are dissolved;The effect and efficiency of porous Si-C composite material are filled to further improve organic carbon source, as excellent
It selects, in step (2), porous Si-C composite material is mixed with the solution of organic carbon source under positive pressure or negative pressure atmosphere.After mixing
Through heating up, solvent evaporated obtains silicon/graphite/organic carbon source mixing material.
Preferably, 0.05-0.5 times adding weight and being silicon weight in silicon metal alloy compositions of carbon in organic carbon source.
Further preferably, 0.1 times adding weight and being silicon weight in silicon metal alloy compositions of carbon in organic carbon source.
Silicon/graphite/organic carbon source mixing material is placed in tube furnace, hot place is carried out under the atmosphere of inert gas
It manages, oxygen, preferably nitrogen, argon gas or helium is not contained in the inert gas.
Preferably, the heat treatment temperature is 400~1200 DEG C, heat treatment time is 1~8 hour.
After the completion of heat treatment, washed using deionized water or absolute ethyl alcohol;Separation of solid and liquid (is such as filtered or is centrifuged);It collects
Solid is vacuum dried, and the Si-C composite material is made.Preferably, vacuum drying temperature is 60~120 DEG C, drying time
It is 2~12 hours.
Preferably, the content of silicon is 5%~50wt% in the Si-C composite material finally prepared.
The invention also includes using Si-C composite material made from above-mentioned preparation method.
The invention also includes using application of the above-mentioned Si-C composite material as lithium ion battery negative material.
Negative electrode of lithium ion battery electrode, the electrode material are prepared using existing negative electrode of lithium ion battery electrode fabrication
Material is made of Si-C composite material (active material), conductive agent and binding agent.The conductive agent that uses, binding agent for it is existing often
Advise material.Such as, conductive carbon black (super-p), Kynoar (PVDF).
Such as, the Si-C composite material (active material) the method for the present invention being prepared:Conductive agent (conductive carbon black,
super-p):Binding agent (Kynoar, PVDF), than mixing, adds a certain amount of N-Methyl pyrrolidone by certain mass
(NMP) solvent is uniformly mixed obtained slurry.Slurry is coated uniformly on copper foil using coating machine, is pressed after vacuum drying
Piece, slice, drying obtain the negative electrode of lithium ion battery electrode containing Si-C composite material of the present invention.
The invention also includes a kind of lithium ion battery, the Si-C composite material being prepared containing the above method.By described in
Si-C composite material by prior art preparation into electrode activity thing material (negative electrode of lithium ion battery electrode), then by existing
Technology is assembled into lithium ion.
The method of the present invention is simple for process, of low cost, can be mass-produced.The carbon silicon accounting of Si-C composite material obtained
Rationally, aperture is reasonable, has and preferably bears that volume adaptability to changes, large specific surface area, the depth of lithium ion deintercalation be small, ion expands
Dissipate that path is short, reversible capacity is high, coulombic efficiency is high, the advantages that having extended cycle life.
Embodiment 1:
1st, the preparation of Si-C composite material
It is little particle to be crushed the Antaciron that silicone content is 65% using planetary ball mill, wherein, ball material mass ratio
About 5:1, rotating speed is 400 revs/min, and Ball-milling Time obtains Antaciron powder after 4 hours.Graphite 13g is weighed, silicone content is
65% Antaciron 10g and 20ml alcohol obtains graphite/silicon in 8 hours using ball mill with 450 revs/min of rotating speed ball milling
Ferroalloy composite material.Obtained graphite/Antaciron composite material is placed in beaker, adding in excessive molar concentration is
The sulfuric acid of 1mol/L, at normal temperatures using the removal ferrous metal element of magnetic stirrer 24 hours, reaction product using go from
Sub- water cleans 3 times;Then by product addition excess containing Si oxide is removed in the hydrofluoric acid solution that mass fraction is 5%, often
The lower magnetic agitation of temperature 12 hours, reaction product are respectively washed that obtain porous silicon/graphite 3 times compound using deionized water and hydrofluoric acid
Material.The aqueous solution (sucrose 5g) of the sucrose containing 5g is added to obtained porous silicon/graphite composite material, in negative pressure ring under room temperature
Magnetic agitation 3 hours is immersed in porous silicon gap in favor of sucrose solution in border, then at 90 DEG C magnetic agitation to aqueous solution
All it is evaporated (mixture, silicon/graphite/organic carbon source mixing material).Mixture is placed in tube furnace, in nitrogen environment with
The heating rate of 5 DEG C/min is heated to 700 DEG C, keeps the temperature 4 hours, naturally cools to room temperature;Distinguished again with deionized water and alcohol
Washing 3 times obtains Si-C composite material in dry 5 hours at 100 DEG C in vacuum drying oven.
2nd, the preparation of Si-C composite material cathode
Sample will be prepared by Si-C composite material (active material):Conductive agent (conductive carbon black, super-p):
Binding agent (Kynoar, PVDF)=8:1:1 mass ratio mixing, it is molten to add a certain amount of N-Methyl pyrrolidone (NMP)
Agent is uniformly mixed using magnetic agitation.Slurry is coated uniformly on copper foil using coating machine, in vacuum drying oven 100 DEG C it is true
Dry 10 hours of sky, after by tabletting, be sliced, it is dry, weigh etc. and to obtain pole piece, battery to be assembled.
3rd, the preparation and test of lithium ion battery
Dry pole piece is put into assembled battery in the glove box containing high-purity argon gas, in the button cell of assembling, just extremely
Si-C composite material, cathode are lithium piece, and diaphragm is polypropylene screen, electrolyte for be 1mol/L containing lithium salts lithium hexafluoro phosphate
(LiPF6), solvent is that volume ratio is 1:1:1 ethylene carbonate (EC):Dimethyl carbonate (DMC):Methyl ethyl carbonate (EMC).
Charge-discharge test, voltage tester ranging from 0.01~1.5V are carried out to lithium ion battery using blue electrical measurement test system constant current.