CN105024055A - Lithium-ion battery porous nanometer silicon-carbon composite negative electrode material and preparation method thereof - Google Patents
Lithium-ion battery porous nanometer silicon-carbon composite negative electrode material and preparation method thereof Download PDFInfo
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Abstract
The present invention provides a lithium-ion battery porous nanometer silicon-carbon composite negative electrode material and a preparation method thereof. Specifically the method comprises: (1) providing a silicon-active metal alloy block; (2) carrying out a reaction of the alloy block and a liquid-phase pore forming agent to remove the active metal from the alloy block so as to obtain a porous silicon nanometer material; (3) washing the porous silicon nanometer particles with hydrofluoric acid to remove the silicon oxide so as to obtain the porous silicon nanometer material washed with the hydrofluoric acid; and (4) in an inert gas, in the presence of a carbon source, calcining the porous silicon nanometer material washed with the hydrofluoric acid to obtain the porous silicon-carbon composite electrode material. The porous silicon material prepared through the method of the present invention has the nanometer porous structure and the small and uniform silicon nanoparticle size, can be adopted as the lithium-ion battery negative electrode material, and shows the high discharge capacity and the high charge-discharge cycling stability.
Description
Technical field
The present invention relates to lithium ion battery negative material field, particularly, the present invention relates to a kind of porous nano silicon materials with height ratio capacity and good circulation performance that can be used as lithium ion battery negative material, and preparation method thereof.
Background technology
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 electrokinetic cell can not be suitable for.In recent years, development of new li-ion electrode materials is subject to the extensive concern of whole world scientific and technical personnel, and particularly research and development have high-energy-density, the negative material of good circulation life-span and simple preparation technology becomes one of focus of lithium ion cell electrode research.Silicon, germanium, the negative materials such as tin replace the negative material of carbon-based material as lithium ion battery because its higher theoretical capacity (being respectively ca.4200, ca.1600, ca.990mAh/g) is expected to become.But make a general survey of silicon, germanium, the negative material Problems existing such as tin, be mainly reflected in the following aspects: (1) silicon, germanium, there is larger change in volume in the negative materials such as tin, its volumetric expansion of silicium cathode material that wherein theoretical specific capacity is the highest is up to 300% in electrochemistry cyclic process, cause the rapid decay of lithium ion battery electrochemistry cycle performance own to degenerate, have a strong impact on the useful life of lithium ion battery; (2) due to the unsteadiness of silicium cathode material structure in battery charging and discharging cyclic process, along with Li
+embedding and deviate to cause the breaking of active electrode material, efflorescence, come off, new electrode surface layer can be formed, consume lithium, and then create larger irreversible capacity loss, therefore the problem in useful life based on the silica-based cathode material lithium ion battery of micron order of routine becomes the bottleneck restricting its technical development, also counteracts that the commercialization process of silicon based anode material simultaneously; (3) conductivity due to silicon itself is poor, have impact on the carrying out of the high rate charge-discharge process of lithium ion battery.
Relative to germanium and tin, the theoretical capacity of silicon is higher, reaches 4212mAh/g, simultaneously due to the production cost that negative pole silicon is relatively low, and becomes the most important thing of lithium ion battery negative research.Therefore, how effectively suppress silicium cathode change of volume 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 specific discharge 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 block is provided;
(2) carry out reacting to remove the active metal in described alloy block with described alloy block and liquid phase pore creating material, obtain porous silicon nano material;
(3) porous silicon nano material described in hydrofluoric acid clean is used to remove silica, to obtain the porous silicon nano material through hydrofluoric acid clean process;
(4) in inert gas, under carbon source exists, the described porous silicon nano material through hydrofluoric acid clean process is calcined, obtains porous silicon-carbon composite.
In another preference, in described alloy block, the mass percent of described silicon is 1-99%, is preferably 10-80%.
In another preference, the mass ratio of described hydrofluoric acid solution is 1% ~ 30%.
In another preference, in described step (4), the temperature range of described calcining is 300 ~ 1900 DEG C, is preferably 400 ~ 1700 DEG C, is more preferably 600 ~ 1500 DEG C.
In another preference, in described step (4), 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 (4), 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 homogeneous porous silicon nanoparticles of component and pattern; Preferably, content≤2% of described silica in the porous silicon nano material of hydrofluoric acid clean process, preferably≤1%, more preferably≤0.5%.
In another preference, in described step (4), 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 block 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 block is alusil alloy block.
In another preference, the size of described alusil alloy block is 0.1mm ~ 60mm.
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 carbon source is carbonaceous gas, is preferably selected from lower group: methane, ethane, propane, ethene, propylene, acetylene, propine, or its combination.
In another preference, described carbon source is the combination of in methane, ethane, propane, ethene, propylene, acetylene, propine a kind or at least 2 kinds.
In another preference, described inert gas is selected from lower group: nitrogen, helium, argon gas, neon, or its combination.
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 2-30wt% of material total weight, preferably 3 ~ 20wt%.
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, 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-300nm;
The specific area of described electrode material is 10-500cm
2/ g;
In another preference, the specific discharge capacity of described negative material is >900mAh/g, is preferably >1000mAh/g, >1100mAh/g, best, the specific discharge capacity of described negative material is 1200-1600mAh/g.
In another preference, the coulombic efficiency (after second time charge and discharge cycles) of described negative material is >=92%, and being preferably >=95%, is more preferably >=97%.
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, SUPER P-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 ± 10): (10 ± 2): (10 ± 2).
A fourth aspect of the 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 the scanning electron microscopic picture of embodiment 1 porous silicon-carbon compound cathode materials.
Fig. 2 is embodiment 1 porous silicon-carbon compound cathode materials pictorial diagram.
Fig. 3 is the X-ray diffractogram of embodiment 1 porous silicon-carbon compound cathode materials.
Fig. 4 is the charging and discharging curve figure of embodiment 1 porous silicon-carbon compound cathode materials.
Fig. 5 is the charging and discharging curve figure of embodiment 2 porous silicons-carbon compound cathode materials and coulombic efficiency figure (▲ be coulombic efficiency curve).
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.
Term
As used herein, term " carbon is coated " or " carbon compound " are used interchangeably, and all refer to that the porous silica material through pore-creating is calcined under carbon source exists, thus form the process of silico-carbo composite material.
Porous nano silico-carbo composite material and preparation thereof
The invention provides a kind of preparation method of porous silicon-carbon composite, described method for raw material with aluminium-active metal alloy block, is reacted with liquid phase pore creating material and is generated porous silicon particle; Again behind hydrofluoric acid solution cleaning removing surface or unnecessary silica, carry out that carbon is coated obtains porous silicon-carbon composite.The material of method gained of the present invention is used as lithium ion battery negative, has higher specific discharge capacity and stable charge/discharge.
Particularly, described method comprises step:
(1) one silicon-active metal alloy block is provided;
(2) carry out reacting to remove the active metal in described alloy block with described alloy block and liquid phase pore creating material, obtain porous silicon nano material;
(3) porous silicon nano material described in hydrofluoric acid clean is used to remove silica, to obtain the porous silicon nano material through hydrofluoric acid clean process;
(4) in inert gas, under carbon source exists, the described porous silicon nano material through hydrofluoric acid clean process is calcined, obtains porous silicon-carbon composite.
In another preference, in described alloy block, the mass percent of described silicon is 1-99%, is preferably 10-80%.
The concentration of described hydrofluoric acid solution has no particular limits, and preferably, described hydrofluoric acid solution is weak solution, and more preferably, the mass ratio of described hydrofluoric acid solution is 1% ~ 30%.
In another preference, in described carbon encapsulation steps (i.e. step (4)), the temperature range of described calcining is 300 ~ 1900 DEG C, is preferably 400 ~ 1700 DEG C, is more preferably 600 ~ 1500 DEG C.
In the coated process of described carbon, the temperature of calcining needs slowly to raise; In another preference, in described step (4), 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 (4), 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 homogeneous porous silicon nanoparticles of component and pattern.
In described carbon encapsulation steps (i.e. step (4)), preferably 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.
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 block is alusil alloy block.The size of described alusil alloy block is not particularly limited, and preferably, the diameter of described silicon-aluminum block is 0.1mm ~ 60mm.
Described liquid phase pore creating material can be arbitrary, can react with active metal and the solution that do 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.
Described carbon source can be carbonaceous gas, as the hydro carbons of gaseous state.Preferably, described carbon source is selected from lower group: methane, ethane, propane, ethene, propylene, acetylene, propine, or its combination.In another preference, described carbon source is the combination of in methane, ethane, propane, ethene, propylene, acetylene, propine a kind or at least 2 kinds.
Described inert gas can be any gas not carrying out reacting with carbon source or silicon, as (but being not limited to) is selected from the gas of lower group: nitrogen, helium, argon gas, neon, or its combination.
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, SUPER P-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 ± 10): (10 ± 2): (10 ± 2).
Negative material of the present invention is after repeatedly charge and discharge cycles, coulombic efficiency and specific discharge capacity reach stable, especially, after more than 2 times charge and discharge cycles, coulombic efficiency and specific discharge capacity reach peak (being greater than first time charge and discharge cycles).In a preferred example, described battery is after 2-10 discharge and recharge, and charging and discharging capacity and coulombic efficiency reach the highest.
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 80:10:10.
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 (Methyl Ethyl Carbonate), dimethyl carbonate (Dimethyl Carbonate), diethyl carbonate (Diethyl Carbonate), ethylene carbonate (Ethylene Carbonate), propene carbonate (Propylene Carbonate), 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 existing other materials, 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.
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.
Universal method charge-discharge performance is tested
In following examples, the test condition of charge-discharge property test and cycle performance test is:
Specific capacity is pressed 4000mAh/g and is calculated, rate of charge is that 0.1C is (namely by theoretical calculation of capacity, discharge and recharge respectively needs 10 hours) or 0.05C (namely by theoretical calculation of capacity, discharge and recharge respectively needs 20 hours), charging/discharging voltage scope is 0.01V ~ 1.5V.
The instrument used in embodiment is respectively:
XRD: adopt German Brooker company/Bruker AXS; Model: D8Advance;
SEM: adopt HIT; Model: S ~ 4800;
Embodiment 1
Be 0.1mm ~ 60mm alusil alloy block (about containing the silicon of 20%) by 25g diameter, join in the dilute hydrochloric acid solution of 5% of 300ml 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 uniform porous nano silicon of pattern, as Fig. 1.
Then under argon gas (80%)/(20%) acetylene gas atmosphere 400 DEG C (being warming up to 400 DEG C with the speed of 5 DEG C/min), calcining obtains porous silicon-carbon composite electrode material, as Fig. 2 in 20 minutes.
Carried out XRD structural analysis to porous nano silicon prepared by embodiment 1, test result as shown in Figure 3.As can be seen from Figure 3, 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 polycrystalline silicon.
By porous silicon-carbon composite electrode material, conductive carbon (Super-P) and Lithium polyacrylate (Li-PAA) mix in a solvent according to the mass ratio of 80:10:10, stir, obtain cathode size, with lithium sheet for negative pole, 0.1C multiplying power carries out charge/discharge test, recording this combination electrode material first discharge specific capacity is at room temperature 1479.4mAh/g, charge specific capacity is 1137.3mAh/g, coulombic efficiency can up to 76.9% first, secondary specific discharge capacity is 1707.8mAh/g, charge specific capacity is 1558.9mAh/g, coulombic efficiency can up to 91.3%.The specific discharge capacity of third time is 1675.5mAh/g, and charge specific capacity is 1575.4mAh/g, and coulombic efficiency up to 94.0%, can present ascendant trend, shows good cyclical stability, as shown in Figure 4.
Embodiment 2
Be 0.1mm ~ 60mm alusil alloy block (about containing the silicon of 30%) by 35g diameter, join in the dilute hydrochloric acid solution of 5% of 400ml 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, obtain 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 uniform porous silicon nanoparticles of pattern.Then under argon gas (80%)/(20%) acetylene gas atmosphere 690 DEG C (being warming up to 690 DEG C with the speed of 10 DEG C/min), calcining obtains porous silicon/carbon composite electrode material in 10 minutes.By porous silicon-carbon composite electrode material, conductive carbon (Super-P) and sodium carboxymethylcellulose (CMC) according to 70: 20: 10 mass ratio mixing in a solvent, stir, obtain cathode size, with lithium sheet for negative pole, 0.05C multiplying power carries out charge/discharge test, recording this combination electrode material first discharge specific capacity is at room temperature 1466.1mAh/g, charge specific capacity is 898.1mAh/g, coulombic efficiency can up to 61.3% first, secondary specific discharge capacity is 1175.1mAh/g, charge specific capacity is 1034.8mAh/g, coulombic efficiency can up to 88.1%.The specific discharge capacity of third time is 1114.8mAh/g, and charge specific capacity is 1038.9mAh/g, and coulombic efficiency up to 93.2%, can present ascendant trend, shows good stability.Table one is the chemical property of obtained silicon-carbon cathode material, and Fig. 5 is charging and discharging curve figure and the coulombic efficiency figure of embodiment 2 porous silicons-carbon compound cathode materials.
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 | 898.1 | 1466.1 | 61.3% |
| 2 | 1034.8 | 1175.1 | 88.1% |
| 3 | 1038.9 | 1114.8 | 93.2% |
| 4 | 1041.9 | 1100.0 | 94.7% |
| 5 | 1032.8 | 1082.0 | 95.4% |
| 6 | 1039.8 | 1082.0 | 96.1% |
| 7 | 1039.3 | 1081.6 | 96.1% |
| 8 | 1021.4 | 1056.3 | 96.7% |
| 9 | 1015.2 | 1045.0 | 97.2% |
| 10 | 1001.5 | 1029.1 | 97.3% |
| 11 | 1013.1 | 1038.9 | 97.5% |
| 12 | 1017.1 | 1046.1 | 97.2% |
| 13 | 998.8 | 1024.8 | 97.5% |
| 14 | 1005.0 | 1034.1 | 97.2% |
| 15 | 993.6 | 1024.4 | 97.0% |
Embodiment 3
Be 0.1mm ~ 60mm alusil alloy block (about containing the silicon of 50%) by 30g diameter, join in the dilute hydrochloric acid solution of 10% of 300ml and fully 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, obtain porous silicon nanoparticles; Again porous silicon nanoparticles is joined the hydrofluoric acid solution cleaning of 10% 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 uniform porous silicon nanoparticles of pattern.Then under argon gas (80%)/(20%) ethylene gas atmosphere 800 DEG C (being warming up to 800 DEG C with the speed of 5 DEG C/min), calcining obtains porous silicon/carbon composite electrode material in 30 minutes.With lithium sheet for negative pole, 0.05C multiplying power carries out charge/discharge test, recording this combination electrode material first discharge specific capacity is at room temperature 1428.3mAh/g, charge specific capacity is 1305.4mAh/g, coulombic efficiency can up to 91.4% first, secondary specific discharge capacity is 1722.0mAh/g, and the specific discharge capacity of third time is 1539.0mAh/g, and the coulombic efficiency of second time and third time can up to 95-97%.After 50 charge and discharge cycles, coulombic efficiency still can up to more than 97%, and after second time charge and discharge cycles, specific discharge capacity is platform-like, and this represents that embedding/de-lithium ability of electrode material reaches stable state gradually after charge and discharge cycles several times.The negative material made of material of the present invention has good cyclical stability after repeatedly charge and discharge cycles.
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 block is provided;
(2) carry out reacting to remove the active metal in described alloy block with described alloy block and liquid phase pore creating material, obtain porous silicon nano material;
(3) porous silicon nano material described in hydrofluoric acid clean is used to remove silica, to obtain the porous silicon nano material through hydrofluoric acid clean process;
(4) in inert gas, under carbon source exists, the described porous silicon nano material through hydrofluoric acid clean process is calcined, obtains 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, is characterized in that, described carbon source is carbonaceous gas, is preferably selected from lower group: methane, ethane, propane, ethene, propylene, acetylene, propine, or its combination.
5. the method for claim 1, is characterized in that, described inert gas is selected from lower group: nitrogen, helium, argon gas, neon, or its combination.
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 preferably, the particle diameter of described nano particle is 5nm-300nm;
The specific area of described electrode material is 10-500cm
2/ g;
The specific discharge capacity of described negative material is >900mAh/g, be preferably >1000mAh/g, >1100mAh/g, best, the specific discharge capacity of described negative material is 1200-1600mAh/g;
The coulombic efficiency (after second time charge and discharge cycles) of described negative material is >=92%, and being preferably >=95%, is more preferably >=97%.
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 pole, negative pole, electrolyte and barrier film, and described negative material comprises material as claimed in claim 6, or described negative pole is battery cathode according to claim 8.
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| CN108640118A (en) * | 2018-04-25 | 2018-10-12 | 山东大学 | A kind of preparation method of high-purity porous silicon |
| CN110350181A (en) * | 2019-07-16 | 2019-10-18 | 昆明理工大学 | A kind of preparation method of lithium ion cell nano porous silicon negative electrode material |
| CN112768663A (en) * | 2021-01-26 | 2021-05-07 | 惠州锂威新能源科技有限公司 | Nano porous silicon/carbon negative electrode material, preparation method thereof and lithium ion battery |
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| CN108640118A (en) * | 2018-04-25 | 2018-10-12 | 山东大学 | A kind of preparation method of high-purity porous silicon |
| CN110350181A (en) * | 2019-07-16 | 2019-10-18 | 昆明理工大学 | A kind of preparation method of lithium ion cell nano porous silicon negative electrode material |
| CN112768663A (en) * | 2021-01-26 | 2021-05-07 | 惠州锂威新能源科技有限公司 | Nano porous silicon/carbon negative electrode material, preparation method thereof and lithium ion battery |
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