CN104617276B - Lithium rechargeable battery porous silicon/carbon compound cathode materials and preparation method thereof - Google Patents
Lithium rechargeable battery porous silicon/carbon compound cathode materials and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a kind of lithium rechargeable battery porous silicon/carbon compound cathode materials and preparation method thereof.The composite is made up of porous silicon, graphite-like carbon material and amorphous carbon material.It is of the invention first using pyrolytic carbon as reducing agent, SiO 2 powder containing alkali (soil) metal chloride is prepared into silico-aluminum with the step of alumina powder mixture one, again by it after acid corrosion, vacuum drying, it is mixed in again with graphite in organic polymer soln, solvent evaporated, porous silicon/carbon composite material is produced after high-temperature roasting under last inert atmosphere.By adjusting silica alumina ratio and granular size in silico-aluminum preparation process, the hole size in final porous silicon/carbon material and pore size distribution can be controlled.Porous silicon/carbon material of the present invention has first that coulombic efficiency is high, has extended cycle life, the high feature of capacity.In addition, the raw materials used cost of the present invention is low, environment-friendly, preparation method instrument equipment is simple, and technological process is short, is adapted to industrialized production.
Description
Technical field
The present invention relates to ion secondary battery cathode material lithium and its technology of preparing, particularly a kind of lithium rechargeable battery
Porous silicon/carbon compound cathode materials and preparation method thereof.
Background technology
Lithium ion battery is many because its capacity is high, self-discharge rate is low, has extended cycle life etc. as a kind of high-energy chemistry power supply
Advantage and obtain more and more extensive application in daily life.At present, the ion secondary battery cathode material lithium of commercialization is adopted
Mainly carbons material.However, such material is present, theoretical capacity is low, first all irreversible capacities are high, during overcharge
Security difference the problems such as, the requirement that makes it be difficult to meet high capacity power source.
Silicon as a kind of negative electrode of lithium ion battery candidate material, due to theoretical specific capacity it is high, with carbon material current potential phase
The advantages such as near and aboundresources and receive much concern.But limited the shortcomings of the life-span is shorter, expensive caused by volumetric expansion
The large-scale applications of silicon materials.Research shows, porous silica material due to abundant pore passage structure, can be formed electronics and
The huge network of ionic conduction, so as to significantly improve reversible capacity.Nevertheless, after silicon is prepared into loose structure, poorly conductive
With it is bigger than surface caused by the fast problem such as low with coulombic efficiency first of capacity attenuation substantially do not solve yet.Therefore, by itself and carbon
Composition of material, to reach while high power capacity is kept, significantly improve cycle life and the first purpose of coulombic efficiency.
The porous silicon preparation method reported in document has a lot, such as heat-treats Si oxide method, acid corrosion silicon-base alloy
Method etc..Wherein, the advantages that acid corrosion silicon-base alloy method has cost low, and technique is simply controllable and have more industrial prospect.Silicon
Based alloy includes silico-aluminum, Antaciron, Si-Mg alloy etc., and its preparation method is mostly nitrogen atomization method, mechanical alloying, true
Empty carbon heat disproportionation decomposition method etc..Nitrogen atomization method and vacuum carbon heat disproportionation decomposition method are higher to instrument requirements, mechanical alloying
Need to use silica flour and other metal-powders, add cost.Therefore, a kind of silicon-base alloy new preparation process is developed to compel in eyebrow
Eyelash.
Chinese patent CN103103353A discloses a kind of method that silico-aluminum is prepared from diaspore type bauxite.
This method is using diaspore type bauxite as raw material, first using graphite as reducing agent, vacuum carbothermal reduction SiO2Afterwards, nothing is recycled
Water aluminium chloride makees chlorinating agent, and aluminium chloride generates with aluminum oxide (in the presence of carbon) under high temperature has volatile low price calorize
Compound, aluminium (AlCl) is decomposed into metallic aluminium and trivalent aluminum compound at low temperature, so as to form silico-aluminum.Should
Temperature is higher needed for method, and energy consumption is big, and experimentation is longer, is not easy to industrialized production.
Chinese patent CN1442916A discloses a kind of silicon aluminium alloy/carbon composite material used for lithium ion battery negative electrode and its system
Preparation Method.This method uses two-step sintering method, first passes through silica flour and aluminium powder mechanical ball mill-high-temperature calcination preparing silico-aluminum,
Then organic polymer is cracked again, graphite powder adds the silico-aluminum of preparation after being added thereto, slurry is formed, finally close
Temperature reaction is made in envelope system.Al addition in the material, the capacity of composite is reduced, causes capacity relatively low, and by
It is poor in cyclical stability, it is impossible to meet the requirement of commercialization high capacity power source.
Chinese patent CN103165874A discloses a kind of lithium ion battery porous silicon negative material and preparation method and use
On the way.This method is using silicon-base alloy powder as raw material, and porous silicon particulate is generated with inorganic acid reaction；Clean and remove through HF solution again
After Surface Oxygen SiClx, washing, drying obtains porous silica material.Although the material capacity is higher, coulombic efficiency is relatively low first
(60% or so), and HF solution has been used in preparation process, cause the pollution of environment.
Chinese patent CN103337612A discloses a kind of nano-structure porous silicon/carbon composite and preparation method thereof.The party
Method is that silicon aluminum carbon ternary material is placed in hydrochloric acid solution, sulfuric acid solution or sodium hydroxide solution to be corroded, and forms sponge
Shape porous silicon/carbon material.This method does not provide the preparation method of silicon aluminum carbon ternary material, and the material first coulombic efficiency compared with
It is low, poor circulation.
Chinese patent CN102157731A discloses a kind of silicon-carbon composite cathode material of lithium ion battery and preparation method thereof.
This method first prepares porous silicon matrix using magnesiothermic reduction mesoporous silicon oxide, then carries out carbon coating, obtains silicon-carbon composite cathode
Material.Mesoporous silicon oxide used in this method and magnesium powder cost are high, are unfavorable for industrialized production.
Chinese patent CN102969489A discloses a kind of Si-C composite material and preparation method thereof.This method is with active
Property be more than silicon and metal oxide obtained by metal (such as lithium, sodium, potassium, magnesium) the reduction silica of silicon, through acid corrosion, hydro-thermal bag
After covering carbon, Si-C composite material is obtained.Metal used is the very strong metal of activity in this method, and its simple substance cost is high, danger
It is dangerous big, therefore it is unfavorable for industrialized production.
The content of the invention
It is an object of the present invention to provide a kind of porous silicon/carbon compound cathode materials of lithium rechargeable battery and its preparation side
Method.The present invention will contain the SiO 2 powder and oxygen of alkali (soil) metal chloride using organic polymer pyrolytic carbon as reducing agent
Change the step of aluminium powder mixture one and prepare silico-aluminum, then by it after acid corrosion, vacuum drying, then be mixed in graphite amorphous
In carbon matrix precursor solution, solvent evaporated, porous silicon/carbon composite material is produced after high-temperature roasting under last inert atmosphere.Pass through silicon
Silica alumina ratio and granular size are adjusted in aluminium alloy preparation process, controls the hole size in final porous silicon/carbon material and pore size distribution.
Porous silicon/carbon material of the present invention has first that coulombic efficiency is high, has extended cycle life, the high feature of capacity.
Lithium rechargeable battery porous silicon/carbon compound cathode materials provided by the invention be with organic polymer pyrolytic carbon also
Silico-aluminum prepared by former SiO 2 powder and alumina powder mixture is raw material, and porous silicon is formed through acid corrosion, then
It is combined with graphite-like carbon material and amorphous carbon material presoma.Sial mass ratio is 3-25: 75-97 in silico-aluminum；
Porous silicon, graphite-like carbon material, the mass ratio of amorphous carbon material presoma are 1: 1-3: 5-15.Concrete technology is：Will oxidation
After aluminium powder, SiO 2 powder and organic polymer pyrolytic carbon carbon source powder ball milling mixing, with alkali (soil) metal chloride one
Rise and be placed in boron nitride crucible, room temperature is naturally cooled to after being reduced in inert atmosphere at 760-820 DEG C, you can obtain sial conjunction
Gold；Silico-aluminum is added into graphite and amorphous carbon presoma after acid corrosion again, is calcined under 550-950 DEG C of inert atmosphere, from
Room temperature so is cooled to, grinds and produces.
Described organic polymer pyrolytic carbon is by polyvinyl chloride, polyacrylonitrile, pitch, phenolic resin, polyvinyl alcohol
A kind of pyrolysis gained.
Described graphite-like carbon material and amorphous carbon material presoma, graphite are native graphite, before amorphous carbon material
Drive body is one kind in sucrose, phenolic resin, pitch.
A kind of preparation method of the porous silicon-carbon composite cathode material of lithium rechargeable battery provided by the invention, is specifically included
Following steps：
1) press and measure organic polymer carbon source powder, SiO 2 powder and alumina powder on planetary ball mill
Ball milling mixing is carried out, obtains once mixture.
2) once mixture and alkali metal or alkaline earth metal chloride are placed in boron nitride crucible, high temperature under inert atmosphere
Roasting, product washs through deionized water, filters, be dried in vacuo after obtain silico-aluminum.
3) it is silicon aluminium alloy powder is porous with being obtained after excessive acid corrosion 3-8h, suction filtration, 55-70 DEG C of vacuum drying 20-24h
Silicon.
4) porous silicon and graphite are added in the solution of amorphous carbon presoma, stirring, 100W ultrasonic disperses 5-
Porous silicon/carbon complex presoma is obtained after 30min, solvent evaporated in vacuo.
5) by the high-temperature roasting under an inert atmosphere of above-mentioned presoma, after natural cooling, grinding sieving；Finally granular size is
1-70 μm, specific surface area 100-700cm2/ g material.
Described organic polymer carbon source powder, SiO 2 powder and alumina powder mass ratio is 10: 0.1-0.7:
1.8-2.4；Ball milling condition is rotating speed 200-400rpm, Ball-milling Time 5-20h, ratio of grinding media to material 5-10: 1；
Described alkali metal or alkaline earth metal chloride are NaCl, KCl, CaCl2In one or more；It is described once
The mass ratio of mixture and alkali (soil) metal chloride is 1: 1-10.
Described carbon reducing condition is Ar gas or N2760-820 DEG C is warming up to 5-10 DEG C/min under gas shielded, is incubated 1-
5h。
In described silicon aluminium alloy powder silicone content be 3%-25%, granular size be 1-70 μm；Acid used is hydrochloric acid, sulphur
One kind in acid, phosphoric acid, its mass percent concentration is 5%-35%；
Described porous silicon, graphite, the mass ratio of amorphous carbon presoma are 1: 1-3: 5-15, before solvent regards amorphous carbon
It is one kind in water, ethanol, hexamethylene depending on driving body species；
Described roasting condition is：Ar gas or N2550-950 DEG C is warming up to 5-20 DEG C/min under gas shielded, is incubated 0.5-
7h。
Porous silicon/carbon compound cathode materials of lithium rechargeable battery of the present invention are with organic polymer carbon source powder
End, SiO 2 powder, alumina powder, graphite-like carbon material and amorphous carbon material precursor are raw material, overcome existing skill
The defects of art, silico-aluminum controllable preparation and the synthesis of porous silicon carbon material are realized, and solve existing silico-aluminum and prepare
The problems such as complex process, high cost, while also reached raising head by porous silicon/carbon material prepared by raw material of silico-aluminum
Effect, improve capacity and extend the purpose of cycle life.Porous silicon/carbon composite material provided by the invention is by porous silicon and carbon material
Composition, wherein porous silicon is formed by acid corrosion silico-aluminum, and silico-aluminum is by carbon thermal reduction one-step synthesis.In a step
Alkali (soil) metal chloride added in synthesizing Si-Al alloy process, serves the effect of solvent and catalyst.The present invention is prominent
It is that material therefor cost is low to go out advantage, and raw material is environment-friendly, and preparation process is easily operated, process conditions are convenient and easy, is fitted
Together in scale industrial production.
Brief description of the drawings
Fig. 1 is the X-ray diffractogram (XRD) of silico-aluminum prepared by the embodiment of the present invention 1.
Fig. 2 is the scanning electron microscope (SEM) photograph (SEM) of porous silicon/carbon composite material prepared by the embodiment of the present invention 1.
Fig. 3 is the X-ray diffractogram (XRD) of porous silicon/carbon composite material prepared by the embodiment of the present invention 1.
Fig. 4 is the electrochemistry cyclic curve and efficiency for charge-discharge of porous silicon/carbon composite material prepared by the embodiment of the present invention 1
Curve.
Embodiment
The present invention is further illustrated with reference to embodiments, they are not construed as limiting the scope of the invention.
Here involved experimental method and equipment are also particularly pointed out in embodiment unless otherwise specified, is conventional method or according to system
The condition for making manufacturers instruction suggestion is implemented, and involved reagent is commercially available without specified otherwise.
Embodiment 1：
Prepare silico-aluminum：
1) by polyacrylonitrile powder that mass ratio is 10: 0.7: 1.8, SiO 2 powder, alumina powder is planetary
Ball milling mixing is carried out on ball mill, obtains once mixture.Ball milling condition is：200rpm, ball milling 5h, ratio of grinding media to material 5: 1.
2) by mass ratio be 1: 1 once mixture, NaCl be placed in boron nitride crucible, N2With 5 DEG C/min under gas shielded
Be warming up to 820 DEG C, be incubated 2h, product washs through deionized water, filters, be dried in vacuo after obtain silico-aluminum.
Fig. 1 is the X-ray diffractogram (XRD) of the silico-aluminum of above-mentioned preparation.It can be seen that except silicon, aluminium two-phase
Do not find that other are mutually present outside.
The preparation of porous silicon/carbon compound cathode materials：
1) mass percent for the alusil alloy excess that be 25% by the silicone content of above-mentioned preparation, granular size is 35 μm
Concentration is to obtain porous silicon after 5% hydrochloric acid solution corrodes 3h, suction filtration, 55 DEG C of vacuum drying 20h.
2) porous silicon for measuring ratio and graphite are added in aqueous sucrose solution, porous silicon, graphite, the mass ratio of sucrose are
1: 3: 5, porous silicon/carbon complex presoma is obtained after stirring, 100W ultrasonic disperses 5min, solvent evaporated in vacuo.
3) presoma is calcined in tube furnace high temperature, roasting condition is that 10 DEG C/min of Ar atmosphere is warming up to 900 DEG C of insulations
4h, after naturally cold, grinding sieve produce final granular size be 35 μm, specific surface area 100cm2/ g material.
Fig. 2 is the SEM figures of the porous silicon of above-mentioned preparation.It can be seen that after hcl corrosion, form porous
Silicon, porous silicon are spongelike structure, and inside has electronics and the connected network of ionic conduction.
Fig. 3 is the X-ray diffractogram (XRD) of porous silicon/carbon composite material.Deposited it can be seen that finding no aluminium
Silicon and carbon two-phase are being comprised only in the material.
Using the porous silicon/carbon composite material of above-mentioned preparation as active electrode material, it is tested in 2032 type button cells
Cycle performance.Electrode material forms：Active material：Conductive agent：PVdF mass ratio is 70: 20: 10；It is metal to electrode
Lithium piece；Electrolyte is 1mol/L LiPF6EC/DMC (volume ratio 1: 1) solution；Barrier film is Cellgard2400 barrier films.Fig. 4
For the electrochemistry cyclic curve and coulombic efficiency curve of the composite electrode of above-mentioned preparation.It will be apparent from this figure that first
Discharge capacity is 1103.5mAh/g, charging capacity 893.3mAh/g, and coulombic efficiency is 80.9% first.After circulating 50 weeks, electricity
Pole reversible capacity is 820.7mAh/g.The above results show, the presence of Porous Silicon structures so that the material is ensureing high power capacity
Meanwhile also maintain good cyclical stability.
Embodiment 2：
Prepare silico-aluminum：
1) by polyvinyl chloride powder that mass ratio is 10: 0.1: 2.4, SiO 2 powder, alumina powder is planetary
Ball milling mixing is carried out on ball mill, obtains once mixture.Ball milling condition is：300rpm, ball milling 20h, ratio of grinding media to material 10: 1.
2) by once mixture of the mass ratio for 1: 4: 2: 4, KCl, NaCl, CaCl2It is placed in boron nitride crucible, Ar gas is protected
Be warming up to 760 DEG C with 5 DEG C/min under shield, be incubated 5h, product washs through deionized water, filters, be dried in vacuo after obtain silico-aluminum.
The X-ray diffractogram (XRD) of the silico-aluminum of above-mentioned preparation is similar with Fig. 1 in embodiment.It can be seen that
Do not find that other are mutually present in addition to silicon, aluminium two-phase.
Prepare porous silicon/carbon compound cathode materials：
1) quality hundred for the alusil alloy powder excess that be 3% by the silicone content of above-mentioned preparation, granular size is 70 μm
It is to obtain porous silicon after 35% sulfuric acid solution corrodes 8h, suction filtration, 70 DEG C of vacuum drying 24h to divide specific concentration.
2) porous silicon and graphite are added in the cyclohexane solution of pitch, porous silicon, graphite, the mass ratio of pitch are 1:
1: 15, porous silicon/carbon complex presoma is obtained after stirring, 100W ultrasonic disperses 5min, solvent evaporated in vacuo.
3) presoma is calcined in tube furnace high temperature, roasting condition is that Ar atmosphere is warming up to 950 DEG C with 20 DEG C/min, is protected
Warm 0.5h, after natural cooling, grinding sieve produce granular size be 70 μm, specific surface area 700cm2/ g material.
The SEM figures of porous silicon prepared by above-mentioned condition are similar with Fig. 2 in embodiment 1.It can be seen that through sour
After erosion, porous silicon is formd, porous silicon is spongelike structure, and inside has electronics and the connected network of ionic conduction.It is final more
X-ray diffractogram (XRD) figure of hole silicon/carbon composite is also similar with Fig. 3 in embodiment 1.It can be seen that do not find
With the presence of aluminium, silicon and carbon two-phase are comprised only in the material.
Using the composite of above-mentioned preparation as electrode active material, the cyclicity in 2032 type button cells is equally tested
Energy.Its electrode material composition is same as Example 1, and electrochemistry cyclic curve shape is also similar to Fig. 4 in embodiment 1.The electricity
Discharge capacity is 1082.8mAh/g, charging capacity 877.1mAh/g first for pole, and coulombic efficiency is 81.0% first, circulation 50
Zhou Hou, electrode reversible capacity are 804.8mAh/g.The result shows that the composite electrode has high power capacity and excellent circulation
Stability.
Embodiment 3：
The preparation of silico-aluminum：
1) by Phenolic resin powder that mass ratio is 10: 0.5: 2, SiO 2 powder, alumina powder is in planetary ball
Ball milling mixing is carried out on grinding machine, obtains once mixture.Ball milling condition is：350rpm, ball milling 10h, ratio of grinding media to material 8: 1.
2) by mass ratio be 1: 5: 4 once mixture, NaCl, KCl be placed in boron nitride crucible, N2With 10 under gas shielded
DEG C/min is warming up to 800 DEG C, is incubated 1h, product washs through deionized water, filters, be dried in vacuo after obtain silico-aluminum.
The X-ray diffractogram (XRD) of the silico-aluminum of above-mentioned preparation is similar with Fig. 1 in embodiment.It can be seen that
Do not find that other are mutually present in addition to silicon, aluminium two-phase.
The preparation of porous silicon/carbon compound cathode materials：
1) quality hundred for the alusil alloy powder excess that be 18% by the silicone content of above-mentioned preparation, granular size is 1 μm
It is to obtain porous silicon after 5% hydrochloric acid solution corrodes 3h, suction filtration, 65 DEG C of vacuum drying 22h to divide specific concentration.
2) porous silicon and graphite are added in the ethanol solution of phenolic resin, porous silicon, graphite, the quality of phenolic resin
Than for 1: 1: 5, porous silicon/carbon complex presoma is obtained after stirring, 100W ultrasonic disperses 20min, solvent evaporated in vacuo.
3) presoma is calcined in tube furnace high temperature, roasting condition is that Ar atmosphere is warming up to 550 DEG C of insulations with 5 DEG C/min
7h, after natural cooling, grinding sieve produce granular size be 1 μm, specific surface area 600cm2/ g material.
The SEM figures of porous silicon prepared by above-mentioned condition are similar with Fig. 2 in embodiment 1.It can be seen that through hydrochloric acid
After corrosion, porous silicon is formd, porous silicon is spongelike structure, and inside has electronics and the connected network of ionic conduction.Finally
X-ray diffractogram (XRD) figure of porous silicon/carbon composite material is also similar with Fig. 3 in embodiment 1.It can be seen that do not send out
Existing aluminium is present, and silicon and carbon two-phase are comprised only in the material.
Using the composite of above-mentioned preparation as electrode active material, the cyclicity in 2032 type button cells is equally tested
Energy.Its electrode material composition is same as Example 1, and electrochemistry cyclic curve shape is also similar to Fig. 4 in embodiment 1.The electricity
Discharge capacity is 1018.4mAh/g first for pole, and charging capacity is that coulombic efficiency is 82.3% to 838.1mAh/g first, is circulated 50 weeks
Afterwards, electrode reversible capacity is 813.2mAh/g.The result shows that the composite electrode has high power capacity and excellent circulation steady
It is qualitative.
Embodiment 4：
The preparation of silico-aluminum：
1) by asphalt powder that mass ratio is 10: 0.6: 1.9, SiO 2 powder, alumina powder is in planetary type ball-milling
Ball milling mixing is carried out on machine, obtains once mixture.Ball milling condition is：300rpm, ball milling 5h, ratio of grinding media to material 10: 1.
2) by once mixture of the mass ratio for 1: 10, CaCl2Be placed in boron nitride crucible, under Ar gas shieldeds with 10 DEG C/
Min is warming up to 790 DEG C, is incubated 4h, product washs through deionized water, filters, be dried in vacuo after obtain silico-aluminum.
The X-ray diffractogram (XRD) of the silico-aluminum of above-mentioned preparation is similar with Fig. 1 in embodiment.It can be seen that
Do not find that other are mutually present in addition to silicon, aluminium two-phase.
The preparation of porous silicon/carbon compound cathode materials：
1) quality hundred for the alusil alloy powder excess that be 22% by the silicone content of above-mentioned preparation, granular size is 55 μm
It is to obtain porous silicon after 30% phosphoric acid solution corrodes 8h, suction filtration, 70 DEG C of vacuum drying 20h to divide specific concentration.
2) porous silicon and graphite are added in the hexamethylene of pitch, porous silicon, graphite, the mass ratio of pitch are 1: 3:
15, porous silicon/carbon complex presoma is obtained after stirring, 100W ultrasonic disperses 8min, solvent evaporated in vacuo.
3) presoma is calcined in tube furnace high temperature, roasting condition is that Ar atmosphere is warming up to 550 DEG C of insulations with 5 DEG C/min
7h, after naturally cold, grinding sieve produce granular size be 55 μm, specific surface area 220cm2/ g material.
The SEM figures of porous silicon prepared by above-mentioned condition are similar with Fig. 2 in embodiment 1.It can be seen that through hydrochloric acid
After corrosion, porous silicon is formd, porous silicon is spongelike structure, and inside has electronics and the connected network of ionic conduction.Finally
X-ray diffractogram (XRD) figure of porous silicon/carbon composite material is also similar with Fig. 3 in embodiment 1.It can be seen that do not send out
Existing aluminium is present, and silicon and carbon two-phase are comprised only in the material.
Using the composite of above-mentioned preparation as electrode active material, the cyclicity in 2032 type button cells is equally tested
Energy.Its electrode material composition is same as Example 1, and electrochemistry cyclic curve shape is also similar to Fig. 4 in embodiment 1.The electricity
Discharge capacity is 1027.6mAh/g first for pole, and charging capacity is that coulombic efficiency is 80.8% to 830.3mAh/g first, is circulated 50 weeks
Afterwards, electrode reversible capacity is 813.2mAh/g.The result shows that the composite electrode has high power capacity and excellent circulation steady
It is qualitative.
Embodiment 5：
The preparation of silico-aluminum：
1) by Phenolic resin powder that mass ratio is 10: 0.7: 1.9, SiO 2 powder, alumina powder is planetary
Ball milling mixing is carried out on ball mill, obtains once mixture.Ball milling condition is：300rpm, ball milling 17h, ratio of grinding media to material 10: 1.
2) by once mixture of the mass ratio for 1: 6: 3, CaCl2, KCl be placed in boron nitride crucible, under Ar gas shieldeds with
10 DEG C/min is warming up to 760 DEG C, is incubated 5h, product washs through deionized water, filters, be dried in vacuo after obtain silico-aluminum.
The X-ray diffractogram (XRD) of the silico-aluminum of above-mentioned preparation is similar with Fig. 1 in embodiment.It can be seen that
Do not find that other are mutually present in addition to silicon, aluminium two-phase.
The preparation of porous silicon/carbon compound cathode materials：
1) mass percent for the alusil alloy excess that be 24% by the silicone content of above-mentioned preparation, granular size is 60 μm
Concentration is to obtain porous silicon after 25% hydrochloric acid solution corrodes 8h, suction filtration, 55 DEG C of vacuum drying 24h.
2) porous silicon and graphite are added in the aqueous solution of sucrose, porous silicon powder, graphite, the mass ratio of sucrose are 1:
2: 10, porous silicon/carbon complex presoma is obtained after stirring, 100W ultrasonic disperses 30min, solvent evaporated in vacuo.
3) presoma is calcined in tube furnace high temperature, roasting condition N2Atmosphere is warming up to 850 DEG C of guarantors with 20 DEG C/min
Warm 6h, after natural cooling, grinding sieve produce granular size be 60 μm, specific surface area 340cm2/ g material.
The SEM figures of porous silicon prepared by above-mentioned condition are similar with Fig. 2 in embodiment 1.It can be seen that through hydrochloric acid
After corrosion, porous silicon is formd, porous silicon is spongelike structure, and inside has electronics and the connected network of ionic conduction.Finally
X-ray diffractogram (XRD) figure of porous silicon/carbon composite material is also similar with Fig. 3 in embodiment 1.It can be seen that do not send out
Existing aluminium is present, and silicon and carbon two-phase are comprised only in the material.
Using the composite of above-mentioned preparation as electrode active material, the cyclicity in 2032 type button cells is equally tested
Energy.Its electrode material composition is same as Example 1, and electrochemistry cyclic curve shape is also similar to Fig. 4 in embodiment 1.The electricity
Discharge capacity is 1058.1mAh/g first for pole, and charging capacity is that coulombic efficiency is 83.1% to 879.3mAh/g first, is circulated 50 weeks
Afterwards, electrode reversible capacity is 805.5mAh/g.The result shows that the composite electrode has high power capacity and excellent circulation steady
It is qualitative.
Embodiment 6：
Prepare silico-aluminum：
1) by pva powder that mass ratio is 10: 0.5: 2.1, SiO 2 powder, alumina powder is planetary
Ball milling mixing is carried out on ball mill, obtains once mixture.Ball milling condition is：200rpm, ball milling 15h, ratio of grinding media to material 5: 1.
2) by mass ratio be 1: 3: 5 once mixture, NaCl, KCl be placed in boron nitride crucible, with 6 under Ar gas shieldeds
DEG C/min is warming up to 800 DEG C, is incubated 4h, product washs through deionized water, filters, be dried in vacuo after obtain silico-aluminum.
The X-ray diffractogram (XRD) of the silico-aluminum of above-mentioned preparation is similar with Fig. 1 in embodiment.It can be seen that
Do not find that other are mutually present in addition to silicon, aluminium two-phase.
The preparation of porous silicon/carbon compound cathode materials：
1) quality hundred for the alusil alloy powder excess that be 7% by the silicone content of above-mentioned preparation, granular size is 15 μm
It is to obtain porous silicon after 15% sulfuric acid solution corrodes 3h, suction filtration, 70 DEG C of vacuum drying 24h to divide specific concentration.
2) porous silicon and graphite are added in the ethanol solution of phenolic resin, porous silicon powder, graphite, phenolic resin
Mass ratio is 1: 1: 12, and porous silicon/carbon complex forerunner is obtained after stirring, 100W ultrasonic disperses 30min, solvent evaporated in vacuo
Body.
3) presoma is calcined in tube furnace high temperature, roasting condition N2Atmosphere is warming up to 550 DEG C of guarantors with 10 DEG C/min
Warm 4h, after natural cooling, grinding sieve produce granular size be 15 μm, specific surface area 100m2/ g material.
The SEM figures of porous silicon prepared by above-mentioned condition are similar with Fig. 2 in embodiment 1.It can be seen that through hydrochloric acid
After corrosion, porous silicon is formd, porous silicon is spongelike structure, and inside has electronics and the connected network of ionic conduction.Finally
X-ray diffractogram (XRD) figure of porous silicon/carbon composite material is also similar with Fig. 3 in embodiment 1.It can be seen that do not send out
Existing aluminium is present, and silicon and carbon two-phase are comprised only in the material.
Using the composite of above-mentioned preparation as electrode active material, the cyclicity in 2032 type button cells is equally tested
Energy.Its electrode material composition is same as Example 1, and electrochemistry cyclic curve shape is also similar to Fig. 4 in embodiment 1.The electricity
Discharge capacity is 1068.4mAh/g first for pole, and charging capacity is that coulombic efficiency is 81.7% to 872.9mAh/g first, is circulated 50 weeks
Afterwards, electrode reversible capacity is 813.2mAh/g.The result shows that the composite electrode has high power capacity and excellent circulation steady
It is qualitative.
Comparative example 1：
1) micron silicon and graphite are added in the aqueous solution of sucrose, silicon, graphite, the mass ratio of sucrose are 1: 2: 12, are stirred
Mix, silicon-carbon compound precursor is obtained after ultrasonic disperse, solvent evaporated in vacuo.
2) presoma is calcined in tube furnace high temperature, roasting condition is that Ar atmosphere is warming up to 650 DEG C of guarantors with 10 DEG C/min
Warm 4h, after natural cooling, grinding sieve produce granular size be 10 μm, specific surface area 26m2/ g product.
Using the composite of above-mentioned preparation as electrode active material, the cyclicity in 2032 type button cells is equally tested
Energy.Its electrode material composition is same as Example 1, and electrochemistry cyclic curve shape is also similar to Fig. 4 in embodiment 1.But should
Discharge capacity is 1045.5mAh/g to electrode first, and charging capacity is that coulombic efficiency is 71.3% to 745.9mAh/g first, circulation 50
Zhou Hou, electrode reversible capacity are 595.7mAh/g.The result shows, substitutes common micro silicon using porous silicon, can substantially carry
The cycle performance of high material, so as to more added with application prospect.
Described above is only the preferred embodiment of the present invention.It should be pointed out that the ordinary skill people for the art
For member, under the premise without departing from the principles of the invention, some improvements and modifications can also be made, these improvements and modifications also should
It is considered as protection scope of the present invention.
Claims (2)
1. a kind of preparation method of the porous silicon-carbon composite cathode material of lithium rechargeable battery, it is characterised in that pass through following step
Suddenly：
(1) silico-aluminum is prepared：
1) by polyvinyl chloride powder that mass ratio is 10: 0.1: 2.4, SiO 2 powder, alumina powder is in planetary type ball-milling
Ball milling mixing is carried out on machine, obtains once mixture；Ball milling condition is：300rpm, ball milling 20h, ratio of grinding media to material 10: 1；
2) by once mixture of the mass ratio for 1: 4: 2: 4, KCl, NaCl, CaCl2It is placed in boron nitride crucible, under Ar gas shieldeds
Be warming up to 760 DEG C with 5 DEG C/min, be incubated 5h, product washs through deionized water, filters, be dried in vacuo after obtain silico-aluminum；
(2) porous silicon/carbon compound cathode materials are prepared：
1) mass percent for the alusil alloy powder excess that be 3% by the silicone content of above-mentioned preparation, granular size is 70 μm
Concentration is to obtain porous silicon after 35% sulfuric acid solution corrodes 8h, suction filtration, 70 DEG C of vacuum drying 24h；
2) porous silicon and graphite are added in the cyclohexane solution of pitch, porous silicon, graphite, the mass ratio of pitch are 1: 1:
15, porous silicon/carbon complex presoma is obtained after stirring, 100W ultrasonic disperses 5min, solvent evaporated in vacuo；
3) presoma is calcined in tube furnace high temperature, roasting condition is that Ar atmosphere is warming up to 950 DEG C with 20 DEG C/min, insulation
0.5h, after natural cooling, grinding sieve produce granular size be 70 μm, specific surface area 700cm2/ g material.
2. the preparation method described in claim 1 obtains 2032 type button cell made of composite.
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| CN115832272B (en) * | 2023-02-24 | 2023-06-13 | 江苏正力新能电池技术有限公司 | Carbon-coated silicon anode material and preparation method and application thereof |
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