CN105226285A - A kind of porous silicon carbon composite and preparation method thereof - Google Patents
A kind of porous silicon carbon composite and preparation method thereof Download PDFInfo
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- CN105226285A CN105226285A CN201410276413.2A CN201410276413A CN105226285A CN 105226285 A CN105226285 A CN 105226285A CN 201410276413 A CN201410276413 A CN 201410276413A CN 105226285 A CN105226285 A CN 105226285A
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Abstract
The invention provides a kind of porous silicon carbon composite and preparation method thereof, particularly, described method comprises step: (1) provides one silicon-active metal alloy; (2) react with described alloy and liquid phase pore creating material, to remove described active metal, obtain porous silicon nano material; (3) clean described porous silicon nano material to remove silica with hydrofluoric acid solution, obtain the porous silicon nano material through hydrofluoric acid clean process; (4) nano silicon material obtained and polymer mixed are carried out ball milling, obtain porous nano silicon/polymer uniform mixture; (5) nano-silicon/polymeric blends is calcined, obtain porous silicon-carbon composite.Method of the present invention can control the ratio of element silicon and carbon in Si-C composite material effectively, when obtained material is as lithium ion battery anode active material, has good cyclical stability and coulombic efficiency.
Description
Technical field
The present invention relates to field of nanometer material technology, particularly, the invention provides a kind of porous silicon/carbon negative pole material and preparation method thereof, and the application in lithium ion battery.
Background technology
Along with the develop rapidly of mobile electronic device, the performance of people to chemical power source is had higher requirement.High power lithium ion cell has due to it advantage that specific energy is large, monomer voltage is high, self discharge is little, becomes emphasis and the focus of countries in the world research and development.Meanwhile, lithium ion battery also have that fail safe, cost are high, degradation problem under cycle life.Therefore, how effectively to improve the fail safe of lithium ion battery, service life cycle, energy density and reduce its cost, becoming the key of lithium ion battery technology development.Lithium ion battery negative material, as the key factor improving the energy content of battery and cycle life, becomes the focal point of researcher.At present, commercial li-ion battery material widely uses graphite and modified graphite, but its theoretical capacity is only 372mAh/g, and volume and capacity ratio is 883mAh/cm
3, the needs of current development high-energy power lithium-ion battery can not be suitable for.
Relative to the germanium, tin, the antimony negative material that have higher capacity, the theoretical specific capacity of silicium cathode material is higher, reaches 4200mAh/g.Meanwhile, due to the production cost that silicon is relatively low, and become the most important thing of lithium ion battery negative research.But on the one hand, silicon materials change in volume in removal lithium embedded process larger (~ 300%), structural stability is poor, easily causes the powder of detached of electrode material to lose efficacy, and causes silicium cathode material capacity to decay serious.On the other hand, the conductivity of silicon is poor, have impact on its rate charge-discharge performance.Therefore, how effectively suppress silicium cathode change of volumetric expansion in battery charge and discharge process to cause inside lithium ion cell structural damage and how effectively to improve the conductivity of silicon based anode material, thus reach that to improve silica-based lithium ion battery battery chemical cycle performance be the problem that this area needs solution badly.
In sum, this area still lacks one and conducts electricity very well, and can be used for the silicon nano material that lithium ion battery negative material preparation has the battery of high specific discharge capacity and charge and discharge cycles stability.
Summary of the invention
The invention provides one to conduct electricity very well, can be used for the silicon nano material that lithium ion battery negative material preparation has the battery of high reversible specific capacity and charge and discharge cycles stability.
A first aspect of the present invention, provide a kind of preparation method of porous silicon-carbon composite, described method comprises step:
(1) one silicon-active metal alloy is provided;
(2) react with described alloy and liquid phase pore creating material, to remove described active metal, obtain porous silicon nano material;
(3) clean described porous silicon nano material to remove silica with hydrofluoric acid solution, obtain the porous silicon nano material through hydrofluoric acid clean process;
(4) nano silicon material obtained and polymer mixed are carried out ball milling, obtain porous nano silicon/polymer uniform mixture;
(5) nano-silicon/polymeric blends is calcined, obtain porous silicon-carbon composite.
In another preference, described silicon-active metal alloy is silicon-active metal alloy chip.
In another preference, described silicon-active metal alloy chip is prepared by the following method:
One silicon-active metal alloy pig is provided;
Utilize mechanical means by silicon-active metal alloy pig fragmentation, grind to form chip.
In another preference, the size of described chip is 0.1mm ~ 100mm.
In another preference, in described alloy chip, the mass percent of described silicon is 1-99%, is preferably 10-70%.
In another preference, described method also comprises: after described step (3) terminates, and washs described porous nano silicon/polymer uniform mixture.
In another preference, described washing is for using deionized water and/or ethanol wash.
In another preference, the mass ratio of described hydrofluoric acid solution is 1% ~ 30%.
In another preference, in described step (4), rotational speed of ball-mill is 300rpm ~ 1500rpm, and Ball-milling Time is 8h ~ 120h, is preferably 24-72h.
In another preference, in described step (5), the temperature range of described calcining is 600 ~ 1000 DEG C, is preferably 650 ~ 900 DEG C, is more preferably 700 ~ 850 DEG C.
In another preference, in described step (5), in described calcination process, described heating rate is heat up with the speed of 1 ~ 10 DEG C/min.
In another preference, in described step (5), the described reaction time is 0.1 ~ 24 hour, and being preferably 0.2 ~ 12 hour, is more preferably 0.2 ~ 5 hour.
In another preference, the described porous silicon nano material through hydrofluoric acid clean process is the more homogeneous porous silicon nanoparticles of component and pattern.
In another preference, in described step (5), also comprise: reprocessing is carried out to described porous silicon-carbon composite electrode material; Preferably, described reprocessing comprises: washing, filtration, oven dry, or its combination.
In another preference, described " removing " refers to remove at least 95%, preferably at least 98%, more preferably at least 99% described alloy chip in active metal.
In another preference, described active metal is selected from lower group: aluminium, iron, magnesium, zinc, calcium, lead, or its combination.
In another preference, described alloy is alusil alloy.
In another preference, described liquid phase pore creating material is the solution that can react with active metal and not react with elemental silicon; Preferably, described liquid phase pore creating material is inorganic acid; More preferably, described liquid phase pore creating material is inorganic acid.
In another preference, described liquid phase pore creating material is selected from lower group: hydrochloric acid, nitric acid, sulfuric acid, or its combination.
In another preference, described liquid phase pore creating material to be mass percent solution concentration be 0.5% ~ 35% inorganic acid solution.
In another preference, described polymer is selected from lower group: the polymer (PAN-co-PMA) of polyacrylonitrile (PAN), polyvinylpyrrolidone (PVP), 2-methyl acrylate and 2-acrylonitrile, or its combination.
In another preference, described step (5) is carried out being selected under the atmosphere of lower group: inert gas and/or reducibility gas or vacuum condition;
Preferably, described inert gas is selected from lower group: inert gas: nitrogen, helium, argon gas, neon, or its combination; And/or
Described reducing gas is selected from lower group: hydrogen, carbon monoxide or its combination, or more combination in any.
In another preference, described inert gas is the combination of in nitrogen, helium, argon gas, neon a kind or at least 2 kinds; 1 kind preferably in nitrogen, helium, argon gas or the combination of at least 2 kinds.
A second aspect of the present invention, provides a kind of porous silicon-carbon composite electrode material, and described electrode material prepares by method as described in the first aspect of the invention.
In another preference, described electrode material is lithium ion battery electrode material.
In another preference, in the material, the mass ratio of described carbon is the 1-30wt% of material total weight, preferably 2 ~ 25wt%, more preferably 4 ~ 25wt%.
In another preference, in the material, the impurity content content of other elements (namely outside silica removal, carbon)≤1%, being preferably≤0.5%, is more preferably≤0.1%.
In another preference, described impurity is selected from lower group: Al, Ti, K, V, Mn, Ni, Zr or its combination.
In another preference, also containing conductive metal in described material; Preferably, described conductive metal is selected from lower group: Cu, Ag, Zn, Fe, Al, or its combination.
In another preference, described electrode material has the one or more features being selected from lower group:
Described electrode material is nano particle, and the particle diameter of described nano particle is 5nm-500nm;
The specific area of described electrode material is 10-500cm
2/ g;
In another preference, the charge specific capacity of described negative material is >800mAh/g, be preferably >1000mAh/g, >1100mAh/g, best, the charge specific capacity of described negative material is 1200-1800mAh/g (during the 10-20 time charge and discharge cycles).
In another preference, the specific discharge capacity of described negative material is >800mAh/g, be preferably >1000mAh/g, >1100mAh/g, best, the specific discharge capacity of described negative material is 1200-1800mAh/g (during the 10-20 time charge and discharge cycles).
In another preference, the coulombic efficiency of described negative material first time charge and discharge cycles is 60%-90%.In another preference, the coulombic efficiency of described negative material (second time or the tenth charge and discharge cycles after) is >=93%, and being preferably >=95%, is more preferably >=97%.
In another preference, the coulombic efficiency E2 of second time charge and discharge cycles is 1.05-1.5 with the ratio of coulombic efficiency E1 of first time charge and discharge cycles, is preferably 1.1-1.4.
A third aspect of the present invention, provides a kind of battery cathode, and described battery cathode prepares with material as described in respect of the second aspect of the invention, or described battery cathode contains material as described in respect of the second aspect of the invention.
In another preference, described battery cathode also comprises conductive agent and/or adhesive.
In another preference, described conductive agent is selected from lower group: acetylene black, SUPERP-Li, carbon fiber, coke, graphite, carbonaceous mesophase spherules, hard carbon, or its combination; Preferably be selected from carbon nano-tube, carbon nanocoils, Nano carbon balls, Graphene, or its combination.
In another preference, described bonding agent is selected from lower group: Kynoar (PVDF), Lithium polyacrylate (Li-PAA), butadiene-styrene rubber (SBR) and sodium carboxymethylcellulose (CMC), or its combination.
In another preference, in described negative material, the content of described silico-carbo combination electrode material is 60-90wt%;
The content of described conductive agent is 5-15wt%;
The content of described adhesive is 5-25wt%, with the total weight of negative material.
In another preference, in described negative material, described silico-carbo combination electrode material, conductive agent, the mass ratio of adhesive three is (80 ± 20): (20 ± 10): (20 ± 10).
Fourth aspect present invention, provide a kind of goods, described goods prepare with material as described in respect of the second aspect of the invention, or described goods contain material as described in respect of the second aspect of the invention, or described goods have the battery cathode as described in third aspect present invention.
In another preference, described battery is lithium ion battery.
In another preference, described goods are batteries, and described battery positive electrode, negative material, electrolyte and barrier film, and described negative material comprises material as described in respect of the second aspect of the invention.
In another preference, described battery is lithium battery.
In another preference, described battery also has shell; And described shell is selected from lower group: metal material, composite material, or its combination.
In another preference, described battery is non-aqueous battery.
In another preference, described barrier film is selected from lower group: perforated membrane, fibreglass diaphragm prepared by ceramic porous membrane, synthetic resin.
In another preference, described positive electrode comprises one or more reactive metal oxides as positive electrode active materials, and in described reactive metal oxides, also comprise the inactive metal element being selected from lower group: manganese (Mn), iron (Fe), cobalt (Co), vanadium (V), nickel (Ni), chromium (Cr), or its combination;
Preferably, described positive electrode active materials also comprises the component being selected from lower group: the metal oxide of inactive metal, metal sulfide, transition metal oxide, transient metal sulfide, or its combination.
In another preference, described active metal is lithium.
In another preference, when described battery is lithium battery, described positive electrode active materials also comprises the component being selected from lower group:
LiMnO
2，
LiMn
2O
4，
LiCoO
2，
Li
2CrO
7，
LiNiO
2，
LiFeO
2，
LiNi
xCo
1-XO
2(0<x<1)，
LiFePO
4，
LiMn
zNi
1-ZO
2(0<z<1；LiMn
0.5Ni
0.5O
2)，
LiMn
0.33Co
0.33Ni
0.33O
2，
LiMc
0.5mn
1.5o
4, wherein, Mc is divalent metal;
LiNi
xco
yme
zo
2, wherein Me represents one in Al, Mg, Ti, B, Ga, Si or several element, x>0; Y<1, z<1,
Transition metal oxide,
Transient metal sulfide,
Or its combination.
In another preference, described transition metal oxide is lithium ion transition metal oxide.
In another preference, described electrolyte comprises one or more electrolytic salts; And described electrolyte comprises one or more organic solvents.
In another preference, when described battery is lithium battery, described electrolytic salt is lithium salts.
In another preference, described organic solvent comprises the cyclic carbonate derivative that at least one is replaced by one or more halogen atom; Preferably, described organic solvent comprises fluoro-1, the 3-dioxane penta-2-ketone of 4-.
In another preference, in charging process, the cation of described electrolytic salt can pass electrolyte, arrives negative material from positive electrode.
In another preference, in discharge process, the cation of described electrolytic salt can pass electrolyte, arrives positive electrode from negative material.
Should be understood that within the scope of the present invention, above-mentioned each technical characteristic of the present invention and can combining mutually between specifically described each technical characteristic in below (eg embodiment), thus form new or preferred technical scheme.As space is limited, tiredly no longer one by one to state at this.
Accompanying drawing explanation
Fig. 1 is aluminium-silicon ingots pictorial diagram in the present invention.
Fig. 2 is alusil alloy chip pictorial diagram in the embodiment of the present invention 1.
Fig. 3 is porous silica material pictorial diagram prepared in the embodiment of the present invention 1.
Fig. 4 is porous silicon/carbon composite material pictorial diagram prepared in the embodiment of the present invention 1.
Fig. 5 is the XRD figure of porous silicon/material with carbon element in the embodiment of the present invention 1.
Fig. 6 is the SEM figure of porous silicon/material with carbon element in the embodiment of the present invention 1.
Fig. 7 is the first charge-discharge figure of porous silicon negative material in the embodiment of the present invention 1.
Fig. 8 is the charge-discharge performance figure (testing under 50mA/g current density) of porous silicon negative material in the embodiment of the present invention 1.
Fig. 9 is the charge-discharge performance figure (testing under 500mA/g current density) of porous silicon negative material in the embodiment of the present invention 2.
Figure 10 is the thermogravimetric collection of illustrative plates of porous silicon/material with carbon element in the embodiment of the present invention 1.
Figure 11 is with the high rate performance figure of the porous silicon-carbon composite prepared by the embodiment of the present invention 1.
Embodiment
The present inventor, through long-term and deep research, has prepared a kind of porous silicon-carbon composite electrode material.With battery prepared by described material, there is higher theoretical specific capacity and good circulating battery stability, and be particularly suitable as the negative active core-shell material of lithium battery.Based on above-mentioned discovery, inventor completes the present invention.
Porous nano silico-carbo composite material and preparation thereof
The present invention with silicon-active metal alloy for raw material, porous silicon particle is generated with inorganic acid reaction, add conducting polymer, the mixture of porous silicon/conducting polymer is obtained after abundant mixing and ball milling, under inertia/reducing gas atmosphere or in vacuum environment, after calcining, obtain porous nano silicon materials.The silicon nano material of this porous can alleviate the silicium cathode volumetric expansion problem in embedding lithium process well, under the prerequisite keeping higher battery capacity, improve the cyclical stability of silica-based lithium ion battery negative material preferably, the requirement of high performance lithium ionic cell cathode material can be met.
Particularly, preparation method of the present invention comprises step:
(1) one silicon-active metal alloy is provided;
(2) react with described alloy and liquid phase pore creating material, to remove described active metal, obtain porous silicon nano material;
(3) clean described porous silicon nano material to remove silica with hydrofluoric acid solution, obtain the porous silicon nano material through hydrofluoric acid clean process;
(4) nano silicon material obtained and polymer mixed are carried out ball milling, obtain porous nano silicon/polymer uniform mixture;
(5) nano-silicon/polymeric blends is calcined, obtain porous silicon-carbon composite.
In another preference, above-mentioned polymer in a liquid-like manner (as the form such as suspension-turbid liquid, dispersion liquid) adds.
In another preference, described silicon-active metal alloy is silicon-active metal alloy chip.Described silicon-active metal alloy chip can pass through any means (as commercially available or conventional method preparation) and obtain, and under a kind of preferable case of the present invention, described chip is prepared by the following method:
One silicon-active metal alloy pig is provided;
Utilize mechanical means by silicon-active metal alloy pig fragmentation, grind to form chip.
In another preference, the size of described chip is 0.1mm ~ 100mm.
In another preference, in described alloy chip, the mass percent of described silicon is 1-99%, is preferably 10-70%.
In another preference, described method also comprises: after described step (3) terminates, and washs described porous nano silicon/polymer uniform mixture.
In another preference, described washing is for using deionized water and/or ethanol wash.
In another preference, the mass ratio of described hydrofluoric acid solution is 1% ~ 30%.
In another preference, in described step (4), rotational speed of ball-mill is 300rpm ~ 1500rpm, and Ball-milling Time is 8h ~ 120h, is preferably 24-72h.
In another preference, in described step (5), the temperature range of described calcining is 600 ~ 1000 DEG C, is preferably 650 ~ 900 DEG C, is more preferably 700 ~ 850 DEG C.
In another preference, in described step (5), in described calcination process, described heating rate is heat up with the speed of 1 ~ 10 DEG C/min.
In another preference, in described step (5), the described reaction time is 0.1 ~ 24 hour, and being preferably 0.2 ~ 12 hour, is more preferably 0.2 ~ 5 hour.
In another preference, the described porous silicon nano material through hydrofluoric acid clean process is the more homogeneous porous silicon nanoparticles of component and pattern.
In another preference, in described step (5), also comprise: reprocessing is carried out to described porous silicon-carbon composite electrode material; Preferably, described reprocessing comprises: washing, filtration, oven dry, or its combination.
In another preference, described " removing " refers to remove at least 95%, preferably at least 98%, more preferably at least 99% described alloy chip in active metal.
Described active metal has no particular limits, and whether can select arbitrarily can with the metal or not carrying out the solution (i.e. liquid phase pore creating material) of pasc reaction reacting.In a kind of preference of the present invention, described active metal is selected from lower group: aluminium, iron, magnesium, zinc, calcium, lead or its combination.In another preference, described alloy is alusil alloy.
Described liquid phase pore creating material can be the solution that can react with active metal arbitrarily and not react with elemental silicon; Preferably, described liquid phase pore creating material is inorganic acid; More preferably, described liquid phase pore creating material is inorganic acid.
In another preference, described liquid phase pore creating material is selected from lower group: hydrochloric acid, nitric acid, sulfuric acid, or its combination.
In another preference, described liquid phase pore creating material to be mass percent solution concentration be 0.5% ~ 35% inorganic acid solution.
Polymer of the present invention is used for providing carbon source, its kind has no particular limits, can select any containing C polymer, especially the polymer of CH key and CN key is contained, preferred example comprises (but being not limited to): the polymer (PAN-co-PMA) of polyacrylonitrile (PAN), polyvinylpyrrolidone (PVP), 2-methyl acrylate and 2-acrylonitrile, or its combination.In a preferred embodiment of the invention, described polymer provides in the form of a solution.
Described step (5), preferably at hypoxemia or oxygen-free environment, as carried out under inert gas and/or reducibility gas atmosphere, or is carried out under vacuum.Available inert gas is selected from lower group: inert gas: nitrogen, helium, argon gas, neon, or its combination; Available reducing gas is selected from lower group: hydrogen, carbon monoxide or its combination.Also described calcining step can be carried out under the combination atmosphere of above two or more gases arbitrarily.
In another preference, described inert gas is the combination of in nitrogen, helium, argon gas, neon a kind or at least 2 kinds; 1 kind preferably in nitrogen, helium, argon gas or the combination of at least 2 kinds.
The silico-carbo combination electrode material of this porous can be good at alleviating the volumetric expansion problem in the embedding lithium process of silicium cathode material, under the prerequisite keeping higher battery capacity, improve the cyclical stability of silica-based lithium ion battery negative material preferably, the requirement of high performance lithium ionic cell cathode material can be met.
Cell negative electrode material
Silico-carbo combination electrode material of the present invention can as negative active core-shell material, for the preparation of cell negative electrode material.
In another preference, described cell negative electrode material also comprises conductive agent and/or adhesive.Wherein, described bonding agent is preferably selected from least one in Kynoar (PVDF), Lithium polyacrylate (Li-PAA), butadiene-styrene rubber (SBR) and sodium carboxymethylcellulose (CMC).
In another preference, described conductive agent is selected from lower group: acetylene black, SUPERP-Li, carbon fiber, coke, graphite, carbonaceous mesophase spherules, hard carbon, or its combination; Preferably be selected from carbon nano-tube, carbon nanocoils, Nano carbon balls, Graphene, or its combination.
In another preference, in described negative material, the content of described silicon/carbon compound cathode active material is 60-90wt%;
The content of described conductive agent is 5-15wt%;
The content of described adhesive is 5-25wt%, with the total weight of negative material.
In another preference, in described negative material, described negative active core-shell material, conductive agent, the mass ratio of adhesive three is (80 ± 20): (20 ± 10): (20 ± 10).
Negative material of the present invention is after repeatedly charge and discharge cycles, and coulombic efficiency and specific discharge capacity reach stable, shows higher reversible specific capacity and coulombic efficiency (after stable >=98% or higher).
Battery containing porous silicon-carbon compound cathode active material
Porous silicon prepared by the present invention-carbon compound cathode active material can be applied to field of batteries.Wherein, a kind of preferred described battery positive electrode, negative material, electrolyte, barrier film, and described negative material comprises porous silicon-carbon composite electrode material as described in the present invention as negative active core-shell material.Preferably be applied to lithium battery.
Described negative material is by above-mentioned porous silicon/carbon compound cathode active material, and conductive agent and adhesive form.The content of porous silicon-carbon composite electrode material is 60 ~ 90wt%, and the content of conductive agent is 5 ~ 15%, and the content of adhesive is 5 ~ 25wt%.In another preference, porous silicon-carbon composite electrode material, conductive agent, the ratio of adhesive is 60:20:20.
In another preference, described battery also has shell.Described shell is not particularly limited, and can be metal material or other composite materials etc.
In another preference, described battery is preferably non-aqueous battery.
The barrier film of described battery can be the existing battery diaphragm in any this area, as Teflon septum, ceramic porous membrane, fibreglass diaphragm etc.
In charging process, the cation of electrolytic salt can pass electrolyte, arrives negative material from positive electrode; In discharge process, the cation of electrolytic salt, through electrolyte, arrives positive electrode from negative material.
The electrolytic salt that described electrolyte comprises solvent and dissolves in a solvent.Described preferred solvents ground is organic solvent, comprise (but being not limited to): methyl ethyl carbonate (MethylEthylCarbonate), fluoro ethylene carbonate (FluoroethyleneCarbonate), dimethyl carbonate (DimethylCarbonate), diethyl carbonate (DiethylCarbonate), ethylene carbonate (EthyleneCarbonate), propene carbonate (PropyleneCarbonate), 1, 2-dimethoxy-ethane, 1, 3 dioxolanes, methyl phenyl ethers anisole, acetic acid esters, propionic ester, butyrate, diethyl ether, acetonitrile, propionitrile.Another kind of preferred organic solvent comprises the cyclic carbonate derivative with halogen atom, can improve the cycle performance of electrode.Carbonic acid ester derivative comprises fluoro-1, the 3-dioxane penta-2-ketone of 4-etc.
Described electrolytic salt comprises cation, as used lithium salts.Preferred lithium salts comprises lithium hexafluoro phosphate, lithium perchlorate, lithium chloride, lithium bromide etc.
Electrolyte solvent can be used alone, and also can comprise two kinds or multi-solvents, electrolytic salt can be used alone, and also can comprise two kinds or multiple lithium salts.
Described positive electrode has no particular limits, and can select with reference to state of the art, or adopts the existing positive electrode in this area.
As, when described battery is lithium battery, its positive electrode can comprise one or more lithium metal oxides, as the oxide of the metals such as manganese (Mn), iron (Fe), cobalt (Co), vanadium (V), nickel (Ni), chromium (Cr).Described positive electrode active materials can also comprise one or more metal oxide and metal sulfides etc.As (including, but are not limited to): LiMnO
2, LiMn
2o
4, LiCoO
2, Li
2crO
7, LiNiO
2, LiFeO
2, LiNi
xco
1-Xo
2(0<x<1), LiFePO
4, LiMn
zni
1-Zo
2(0<x<1; LiMn
0.5ni
0.5o
2), LiMn
0.33co
0.33ni
0.33o
2, LiMc
0.5mn
1.5o
4, wherein, Mc is a divalent metal; LiNi
xco
yme
zo
2, wherein Me represents one in Al, Mg, Ti, B, Ga, Si or several element, x>0; Y, z<1.In addition, described positive electrode active materials also can comprise transition metal oxide, as MnO
2, V
2o
5; Transient metal sulfide, as FeS
2, MoS
2, TiS
2.Wherein, lithium ion transition metal oxide obtains more application, comprising: LiMn
2o
4, LiCoO
2, LiNi
0.8co
0.15al
0.05o
2, LiFePO
4and LiNi
0.33mn
0.33co
0.33o
2.
Major advantage of the present invention comprises:
(1) the present invention successfully prepares porous silicon/carbon compound cathode active material.Compared with other negative materials existing, this material has higher theoretical specific capacity.
(2) porous silicon of the present invention/carbon compound cathode materials structure alleviates silicon because of volumetric expansion and the mechanical stress of shrinking generation in charge and discharge process, elimination bulk effect;
(3) production technology that lithium ion battery porous silicon/carbon compound cathode materials of the present invention is novel, has the advantages such as low production cost, technique is simple, large-scale production is easy;
(4) porous silicon/carbon compound cathode active material that prepared by the present invention can be successfully applied to lithium battery, shows higher capacity and good cyclical stability.
(5) method of the present invention can control the consumption of carbon source better compared with prior art, and in the silico-carbo composite material obtained, element silicon and carbon mix evenly, therefore can prepare the silico-carbo composite material that cycle performance is high.
Below in conjunction with specific embodiment, set forth the present invention further.Should be understood that these embodiments are only not used in for illustration of the present invention to limit the scope of the invention.The experimental technique of unreceipted actual conditions in the following example, usually conveniently condition, or according to the condition that manufacturer advises.Unless otherwise indicated, otherwise percentage and number calculate by weight.
Embodiment 1
First the method for physical mechanical is utilized to be pulverized by aluminium-silicon ingots (as Fig. 1), after grinding to form the chip of 0.1mm ~ 100mm, it is 0.1mm ~ 100mm alusil alloy chip (as Fig. 2) by 20g diameter, slowly join in the dilute hydrochloric acid solution of 5% of 270ml and react, magnetic agitation is even.After treating that this mixed solution fully reacts completely, by mixed solution through filtering, after deionized water and ethanol etc. fully rinsing, to remove AlCl
3obtain porous silicon nanoparticles; Again porous silicon nanoparticles is joined the hydrofluoric acid solution cleaning of 5% mass ratio, after having removed porous silicon nanoparticles surface or unnecessary silica, filter, with the fully rinsing such as deionized water and ethanol, it is single that collection obtains composition, and the more uniform porous nano silicon of pattern, as Fig. 3.
After porous nano silicon is mixed with polyacrylonitrile, carry out ball milling (wet-milling), ball-grinding machine: German Lai Chi company, model: PM200, rotational speed of ball-mill 350rpm, time is 24h, and then under argon gas (95%)/(5%) hydrogen gas atmosphere 700 DEG C (being warming up to 700 DEG C with the speed of 10 DEG C/min), calcining obtains porous silicon-carbon composite electrode material in 180 minutes, as shown in Figure 4.
Carried out XRD structural analysis and sem analysis to porous silicon nanoparticles prepared by embodiment 1, test result as shown in Figure 5 and Figure 6.As can be seen from Figure 5, prepared porous silicon nanoparticles is the good crystalline silicon of crystallinity, main peak value is in 28.44 ° (111 faces), 47.30 ° (220 face), 56.12 ° (311 face), 69.13 ° (400 face), 76.38 ° (331 face), does not have the appearance of other impurity peaks.Porous silicon nanoparticles prepared by proof is high-purity nano polysilicon.As can be seen from Figure 6, prepared Si material is loose structure, and can see from high power SEM figure, porous nano silicon is coated uniformly one deck carbon, thus is conducive to alleviating Si volumetric expansion in charge and discharge process and causes electrode interior structural damage.
To embodiment 1 prepare porous silicon nanoparticles carry out thermogravimetric analysis, result show, the carbon content in silico-carbo composite material in about 23wt% (total weight by composite material), as shown in Figure 10.
Porous silicon-carbon composite electrode material, conductive carbon (Super-P) and sodium carboxymethylcellulose (CMC) mass ratio according to 60:20:20 is mixed in a solvent, stir, obtain cathode size, prepare electrode, with lithium sheet for negative pole, assemble 2032 button cells.With lithium sheet for negative pole, charge/discharge test is carried out under 50mA/g current condition, recording this combination electrode material first discharge specific capacity is at room temperature 1628.6mAh/g, charge specific capacity is 1213.3mAh/g, coulombic efficiency can up to 74.5% first, secondary specific discharge capacity is 1274.4mAh/g, and charge specific capacity is 1205.6mAh/g, and coulombic efficiency can up to 94.2%.The specific discharge capacity of the 4th time is 1293.6mAh/g, and charge specific capacity is 1233.8mAh/g, and coulombic efficiency up to 95.4%, can present ascendant trend, shows good cyclical stability, as shown in Figure 7, Figure 8.
Embodiment 2
First the method for physical mechanical is utilized to be pulverized by aluminium-silicon ingots (as Fig. 1), after grinding to form the chip of 0.1mm ~ 100mm, be 0.1mm ~ 100mm alusil alloy chip by 50g diameter, slowly join in the dilute hydrochloric acid solution of 10% of 480ml and react, magnetic agitation is even.After treating that this mixed solution fully reacts completely, by mixed solution through filtering, after deionized water and ethanol etc. fully rinsing, to remove AlCl
3obtain porous silicon nanoparticles; Again porous silicon nanoparticles is joined the hydrofluoric acid solution cleaning of 5% mass ratio, after having removed porous silicon nanoparticles surface or unnecessary silica, filter, with the fully rinsing such as deionized water and ethanol, it is single that collection obtains composition, the more uniform porous nano silicon of pattern.
After porous nano silicon is mixed with polyacrylonitrile, carry out ball milling (wet-milling), ball-grinding machine: German Lai Chi company, model: PM200, rotational speed of ball-mill 450rpm, time is 18h, and then under vacuum environment 700 DEG C (being warming up to 700 DEG C with the speed of 10 DEG C/min), calcining obtains porous silicon-carbon composite electrode material in 120 minutes.
Porous silicon-carbon composite electrode material, conductive carbon (Super-P) and sodium carboxymethylcellulose (CMC) mass ratio according to 60:20:20 is mixed in a solvent, stir, obtain cathode size, with lithium sheet for negative pole, prepare electrode, with lithium sheet for negative pole, assemble 2032 button cells.Charge/discharge test is carried out under 50mA/g current condition, recording this combination electrode material first discharge specific capacity is at room temperature 1787.3mAh/g, charge specific capacity is 1143.9mAh/g, coulombic efficiency can up to 64.0% first, secondary specific discharge capacity is 1320.2mAh/g, charge specific capacity is 1167.4mAh/g, and coulombic efficiency can up to 88.4%%.The specific discharge capacity of the 6th time is 1347.7mAh/g, charge specific capacity is 1250.7mAh/g, coulombic efficiency can up to 92.8%%, the specific discharge capacity of the tenth time is 1394.7mAh/g, charge specific capacity is 1308.7mAh/g, coulombic efficiency up to 93.8%%, can present ascendant trend, shows good stability.Table one is the chemical property of obtained silicon-carbon composite cathode material.
Table one embodiment 2 obtains the chemical property of the silicon-carbon cathode material of lithium ion battery
| Cycle-index | Charge specific capacity (mAh/g) | Specific discharge capacity (mAh/g) | Coulombic efficiency |
| 1 | 1143.9 | 1787.3 | 64.0％ |
| 2 | 1167.4 | 1320.2 | 88.4％ |
| 3 | 1196.5 | 1336.9 | 89.5％ |
| 4 | 1213.9 | 1337.0 | 90.8％ |
| 5 | 1236.4 | 1345.8 | 91.9％ |
| 6 | 1250.7 | 1347.7 | 92.8％ |
| 7 | 1282.4 | 1380.0 | 92.9％ |
| 8 | 1298.8 | 1399.3 | 92.8％ |
| 9 | 1301.3 | 1390.6 | 93.6％ |
| 10 | 1308.7 | 1394.7 | 93.8％ |
Embodiment 3
Specific capacity under high current charge-discharge condition and stability
Porous silicon-carbon composite electrode material in embodiment 2, conductive carbon (Super-P) and sodium carboxymethylcellulose (CMC) mass ratio according to 60:20:20 is mixed in a solvent, stir, obtain cathode size, prepare electrode, with lithium sheet for negative pole, assemble 2032 button cells.First battery carries out charge/discharge cycle 2 times under 50mA/g current condition.Adopt big current namely under 500mA/g current condition, to carry out charge/discharge test from third time, record the performance of 2032 button cells as shown in Figure 9.
As can be seen from Figure 9, battery is under 500mA/g current condition after charge and discharge cycles 45 times, battery specific capacity can be stabilized in 950mAh/g, coulombic efficiency can be stabilized in more than 98.2%, under big current (as 500mA/g) discharge and recharge condition, show higher specific capacity and good stability.
Embodiment 4:
Using the porous silicon-carbon composite prepared by example 1 as electrode active material, test its cycle performance in 2032 button cells.Electrode material composition (mass percent) is: 60% porous silicon-carbon composite electrode material, 20% conductive carbon black, 20%CMC: be lithium metal to electrode.Electrolyte is 1mol/LiPF
6fEC/EMC/DMC (volume ratio is 1:1:1) solution, barrier film is Cellgard2300 barrier film.Charging/discharging voltage scope is 0.001 ~ 1.5V, and charging and discharging currents density is respectively 50mA/g, 100mA/g, 200mA/g, 500mA/g, 1000mA/g.
Figure 11 is the cycle performance curve of porous silicon-carbon composite electrode material.Be still 1140mAh/g under discharge and recharge condition under different multiplying charge and discharge cycles 25 later 1000mA/g current densities as can be seen from Figure 11, and stable performance under different multiplying condition, show that electrode material of the present invention has good cyclical stability.
The all documents mentioned in the present invention are quoted as a reference all in this application, are just quoted separately as a reference as each section of document.In addition should be understood that those skilled in the art can make various changes or modifications the present invention, and these equivalent form of values fall within the application's appended claims limited range equally after having read above-mentioned instruction content of the present invention.
Claims (10)
1. a preparation method for porous silicon-carbon composite, is characterized in that, comprises step:
(1) one silicon-active metal alloy is provided;
(2) react with described alloy and liquid phase pore creating material, to remove described active metal, obtain porous silicon nano material;
(3) clean described porous silicon nano material to remove silica with hydrofluoric acid solution, obtain the porous silicon nano material through hydrofluoric acid clean process;
(4) nano silicon material obtained and polymer mixed are carried out ball milling, obtain porous nano silicon/polymer uniform mixture;
(5) nano-silicon/polymeric blends is calcined, obtain porous silicon-carbon composite.
2. the method for claim 1, is characterized in that, described active metal is selected from lower group: aluminium, iron, magnesium, zinc, calcium, lead, or its combination.
3. the method for claim 1, is characterized in that, described liquid phase pore creating material is the solution that can react with active metal and not react with elemental silicon; Preferably, described liquid phase pore creating material is inorganic acid; More preferably, described liquid phase pore creating material is inorganic acid.
4. the method for claim 1, it is characterized in that, described polymer is selected from lower group: the polymer (PAN-co-PMA) of polyacrylonitrile (PAN), polyvinylpyrrolidone (PVP), 2-methyl acrylate and 2-acrylonitrile, or its combination.
5. the method for claim 1, is characterized in that, described step (5) is carried out being selected under the atmosphere of lower group: inert gas and/or reducibility gas or vacuum condition;
Preferably, described inert gas is selected from lower group: inert gas: nitrogen, helium, argon gas, neon, or its combination; And/or
Described reducing gas is selected from lower group: hydrogen, carbon monoxide or its combination, or more combination in any.
6. porous silicon-carbon composite electrode material, is characterized in that, described electrode material prepares by the method as described in as arbitrary in claim 1-5.
7. material as claimed in claim 6, it is characterized in that, described electrode material has the one or more features being selected from lower group:
Described electrode material is nano particle, and the particle diameter of described nano particle is 5nm-500nm;
The specific area of described electrode material is 10-500cm
2/ g.
8. a battery cathode, is characterized in that, prepared by described battery cathode material as claimed in claim 6, or described battery cathode is containing, for example material according to claim 6.
9. goods, is characterized in that, prepared by described goods material as claimed in claim 6, or described goods are containing, for example material according to claim 6, or described goods have battery cathode as claimed in claim 8.
10. goods as claimed in claim 9, it is characterized in that, described goods are batteries, and described battery positive electrode, negative material, electrolyte and barrier film, and described negative material comprises material as claimed in claim 6.
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