CN105226285B - A kind of porous Si-C composite material and preparation method thereof - Google Patents
A kind of porous Si-C composite material and preparation method thereof Download PDFInfo
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- CN105226285B CN105226285B CN201410276413.2A CN201410276413A CN105226285B CN 105226285 B CN105226285 B CN 105226285B CN 201410276413 A CN201410276413 A CN 201410276413A CN 105226285 B CN105226285 B CN 105226285B
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Abstract
The invention provides a kind of porous Si-C composite material and preparation method thereof, specifically, described method includes step:(1) a silicon active metal alloy is provided;(2) reacted with the alloy with liquid phase pore creating material, to remove the active metal, obtain porous silicon nano material;(3) the porous silicon nano material is cleaned with hydrofluoric acid solution to remove silicon, obtains the porous silicon nano material handled through hydrofluoric acid clean;(4) by obtained nano silicon material and mixed with polymers and ball milling is carried out, obtains porous nano silicon/polymer uniform mixture;(5) nano-silicon/polymeric blends are calcined, obtains porous Si-C composite material.The method of the present invention can efficiently control the ratio of element silicon and carbon in Si-C composite material, when obtained material is as lithium ion battery anode active material, with good cyclical stability and coulombic efficiency.
Description
Technical field
The present invention relates to field of nanometer material technology, specifically, the invention provides a kind of porous silicon/carbon negative pole material and its system
Preparation Method, and its application in lithium ion battery.
Background technology
With developing rapidly for mobile electronic device, people propose higher requirement to the performance of electrochmical power source.Gao Gong
Rate lithium ion battery has the advantages that specific energy is big, monomer voltage is high, self discharge is small due to it, the weight researched and developed as countries in the world
Point and focus.Meanwhile, the problems such as lithium ion battery declines there is also security, cost height, cycle life.Therefore, how effectively
Improve the security of lithium ion battery, service life cycle, energy density and reduce its cost, as lithium ion battery technology
The key of development.Lithium ion battery negative material is as the key factor for improving the energy content of battery and cycle life, as research people
The focal point of member.At present, commercial li-ion battery material widely uses graphite and modified graphite, but its theoretical capacity is only
372mAh/g, volume and capacity ratio is 883mAh/cm3, it is impossible to the need for being applicable current development high-energy power lithium-ion battery.
Relative to the germanium for having higher capacity, tin, antimony negative material, the theoretical specific capacity of silicium cathode material is higher, reaches
4200mAh/g.Simultaneously as the relatively low production cost of silicon, and the most important thing studied as negative electrode of lithium ion battery.But
It is, on the one hand, Volume Changes are than larger (~300%) during removal lithium embedded for silicon materials, and structural stability is poor, is easily caused electricity
The powder of detached failure of pole material, causes the decay of silicium cathode material capacity serious.On the other hand, the electric conductivity of silicon is poor, influence
Its rate charge-discharge performance.Therefore, the change of silicium cathode volumetric expansion in battery charge and discharge process how is effectively suppressed
Cause inside lithium ion cell structural damage and how to be effectively improved the electric conductivity of silicon based anode material, so as to reach raising
The problem of silicon substrate lithium ion battery battery chemical cycle performance is this area urgent need to resolve.
In summary, this area still lacks one kind and conducted electricity very well, and being prepared available for lithium ion battery negative material has
The silicon nano material of high specific discharge capacity and the battery of charge and discharge cycles stability.
The content of the invention
Conducted electricity very well the invention provides one kind, being prepared available for lithium ion battery negative material has high reversible specific volume
The silicon nano material of the battery of amount and charge and discharge cycles stability.
The first aspect of the present invention includes step there is provided a kind of preparation method of porous silicon-carbon composite, methods described
Suddenly:
(1) one silicon-active metal alloy is provided;
(2) reacted with the alloy with liquid phase pore creating material, to remove the active metal, obtain porous silicon nanometer material
Material;
(3) the porous silicon nano material is cleaned with hydrofluoric acid solution to remove silicon, is obtained through at hydrofluoric acid clean
The porous silicon nano material of reason;
(4) by obtained nano silicon material and mixed with polymers and ball milling is carried out, obtains porous nano silicon/polymer uniform
Mixture;
(5) nano-silicon/polymeric blends are calcined, obtains 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;
Using 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 the alloy chip, the mass percent of described silicon is 1-99%, preferably
10-70%.
In another preference, methods described also includes:After the step (3) terminates, to described porous nano silicon/
Polymer uniform mixture is washed.
In another preference, described washing is to use deionized water and/or ethanol wash.
In another preference, the mass ratio of described hydrofluoric acid solution is 1%~30%.
In another preference, in the step (4), rotational speed of ball-mill is 300rpm~1500rpm, and Ball-milling Time is 8h
~120h, preferably 24-72h.
In another preference, in the step (5), the temperature range of the calcining is 600~1000 DEG C, preferably
It it is more preferably 700~850 DEG C for 650~900 DEG C.
In another preference, in the step (5), in the calcination process, described heating rate is with 1~10
DEG C/heating of min speed.
In another preference, in the step (5), the described reaction time is 0.1~24 hour, preferably 0.2
~12 hours, more preferably 0.2~5 hour.
In another preference, the porous silicon nano material handled through hydrofluoric acid clean is that component and pattern are more uniform
Porous silicon nanoparticles.
In another preference, in the step (5), in addition to:Described porous silicon-carbon composite electrode material is entered
Row post processing;It is preferred that described post processing includes:Washing, filtering, drying, or its combination.
In another preference, described " removing " refers to removal at least 95%, preferably at least 98%, more preferably at least
Active metal in the 99% alloy chip.
In another preference, described active metal is selected from the 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 can be with active metal reaction without molten with simple substance pasc reaction
Liquid;It is preferred that 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 the group:Hydrochloric acid, nitric acid, sulfuric acid, or its combination.
In another preference, described liquid phase pore creating material is the nothing that mass percent solution concentration is 0.5%~35%
Machine acid solution.
In another preference, described polymer is selected from the group:Polyacrylonitrile (PAN), polyvinylpyrrolidone
(PVP), the polymer (PAN-co-PMA) of 2- methyl acrylates and 2- acrylonitrile, or its combination.
In another preference, described step (5) is carried out under the atmosphere being selected from the group:Inert gas and/or reduction
Property gas or vacuum condition;
It is preferred that described inert gas is selected from the group:Inert gas:Nitrogen, helium, argon gas, neon, or its combination;
And/or
Described reducing gas is selected from the group:Hydrogen, carbon monoxide or its combination, or more any combination.
In another preference, described inert gas is a kind or at least two kinds of in nitrogen, helium, argon gas, neon
Combination;1 kind or at least two kinds of of combination preferably in nitrogen, helium, argon gas.
The second aspect of the present invention is there is provided a kind of porous silicon-carbon composite electrode material, and described electrode material is with such as
Prepared by the method described in first aspect present 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- of material gross weight
30wt%, preferably 2~25wt%, more preferably 4~25wt%.
In another preference, in the material, impurity content (i.e. the contents of other elements in addition to silicon, carbon)≤
1%, preferably≤0.5%, it is more preferably≤0.1%.
In another preference, described impurity is selected from the group:Al, Ti, K, V, Mn, Ni, Zr or its combination.
In another preference, also contain conductive metal in the material;It is preferred that described conductive metal is selected from
The following group:Cu, Ag, Zn, Fe, Al, or its combination.
In another preference, described electrode material has the one or more features being selected from the group:
Described electrode material is nano particle, and the particle diameter of the nano particle is 5nm-500nm;
The specific surface area of the electrode material is 10-500cm2/g;
In another preference, the charge specific capacity of described negative material is>800mAh/g, preferably>
1000mAh/g,>1100mAh/g, most preferably, the charge specific capacity of described negative material is 1200-1800mAh/g (10-
During 20 charge and discharge cycles).
In another preference, the specific discharge capacity of described negative material is>800mAh/g, preferably>
1000mAh/g,>1100mAh/g, most preferably, the specific discharge capacity of described negative material is 1200-1800mAh/g (10-
During 20 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 (for the second time or after the tenth charge and discharge cycles) of described negative material is >=93%, compared with
It is goodly >=95%, is more preferably >=97%.
In another preference, the coulombic efficiency E2 of second of charge and discharge cycles is imitated with the coulomb of first time charge and discharge cycles
The ratio between rate E1 is 1.05-1.5, preferably 1.1-1.4.
The third aspect of the present invention is there is provided a kind of GND, and described GND is to use such as second party of the present invention
Prepared by material described in face, or described GND contains material as described in respect of the second aspect of the invention.
In another preference, described GND also includes conductive agent and/or adhesive.
In another preference, described conductive agent is selected from the group:Acetylene black, SUPER P-Li, carbon fiber, coke, stone
Ink, carbonaceous mesophase spherules, hard carbon, or its combination;CNT, carbon nanocoils, Nano carbon balls, graphene are preferably chosen from, or
It is combined.
In another preference, described bonding agent is selected from the group:Kynoar (PVDF), Lithium polyacrylate (Li-
PAA), butadiene-styrene rubber (SBR) and sodium carboxymethylcellulose (CMC), or its combination.
In another preference, in the 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 gross weight meter of negative material.
In another preference, in the negative material, described silico-carbo combination electrode material, conductive agent, adhesive
The mass ratio of three is (80 ± 20):(20±10):(20±10).
Fourth aspect present invention is there is provided a kind of product, and described product is with material as described in respect of the second aspect of the invention
Expect what is prepared, or described product contains material as described in respect of the second aspect of the invention, or described product has such as the present invention
GND described in the third aspect.
In another preference, described battery is lithium ion battery.
In another preference, described product is battery, and described battery includes positive electrode, negative material, electricity
Liquid and barrier film are solved, and described negative material includes 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 the group:It is metal material, multiple
Condensation material, or its combination.
In another preference, described battery is non-aqueous battery.
In another preference, described barrier film is selected from the group:Ceramic porous membrane, perforated membrane, the glass of synthetic resin preparation
Glass fibre diaphragm.
In another preference, described positive electrode includes one or more reactive metal oxides and lived as positive pole
Property material, and described reactive metal oxides in also include the inactive metal element that is selected from the group:Manganese (Mn), iron (Fe),
Cobalt (Co), vanadium (V), nickel (Ni), chromium (Cr), or its combination;
It is preferred that described positive electrode active materials also include the component being selected from the 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 include being selected from down
The component of group:
LiMnO2,
LiMn2O4,
LiCoO2,
Li2CrO7,
LiNiO2,
LiFeO2,
LiNixCo1-XO2(0<x<1),
LiFePO4,
LiMnzNi1-ZO2(0<z<1;LiMn0.5Ni0.5O2),
LiMn0.33Co0.33Ni0.33O2,
LiMc0.5Mn1.5O4, wherein, Mc is divalent metal;
LiNixCoyMezO2, wherein Me represents one kind or several elements in Al, Mg, Ti, B, Ga, Si, 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 includes one or more electrolytic salts;And described electrolyte is included
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 includes at least one being replaced by one or more halogen atoms
Cyclic carbonate derivative;It is preferred that described organic solvent includes the amyl- 2- ketone of fluoro- 1, the 3- dioxanes of 4-.
In another preference, in charging process, the cation of described electrolytic salt can pass through electrolyte, from just
Pole material reaches negative material.
In another preference, in discharge process, the cation of described electrolytic salt can pass through electrolyte, from negative
Pole material reaches positive electrode.
It should be understood that within the scope of the present invention, above-mentioned each technical characteristic of the invention and have in below (eg embodiment)
It can be combined with each other between each technical characteristic of body description, so as to constitute new or preferred technical scheme.As space is limited, exist
This no longer tires out one by one states.
Brief description of the drawings
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 prepared porous silica material pictorial diagram in the embodiment of the present invention 1.
Fig. 4 is prepared porous silicon/carbon composite material pictorial diagram in the embodiment of the present invention 1.
Fig. 5 is the XRD of porous silicon/carbon material in the embodiment of the present invention 1.
Fig. 6 is the SEM figures of porous silicon/carbon material 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 of porous silicon negative material in the embodiment of the present invention 1 (under 50mA/g current densities
Test).
Fig. 9 is charge-discharge performance figure (the 500mA/g current densities of porous silicon negative material in the embodiment of the present invention 2
Lower test).
Figure 10 is the thermogravimetric collection of illustrative plates of porous silicon/carbon material in the embodiment of the present invention 1.
Figure 11 is with the high rate performance figure of porous silicon-carbon composite prepared by the embodiment of the present invention 1.
Embodiment
The present inventor's in-depth study by long-term, is prepared for a kind of porous silicon-carbon composite electrode material.With described
Battery prepared by material has higher theoretical specific capacity and preferable circulating battery stability, and is particularly suitable as lithium battery
Negative active core-shell material.Based on above-mentioned discovery, inventor completes the present invention.
Porous nano silico-carbo composite and its preparation
The present invention generates porous silicon grain using silicon-active metal alloy as raw material with inorganic acid reaction, adds conducting polymer
Thing, is sufficiently mixed the mixture that porous silicon/conducting polymer is obtained after ball milling, under inertia/reducing gas atmosphere or vacuum ring
In border, after being calcined, porous nano silicon materials are obtained.This porous silicon nano material can alleviate process of intercalation well
In silicium cathode volumetric expansion problem, on the premise of higher battery capacity is kept preferably improving silicon substrate lithium ion battery bears
The cyclical stability of pole material, can meet the requirement of high performance lithium ionic cell cathode material.
Specifically, preparation method of the invention includes step:
(1) one silicon-active metal alloy is provided;
(2) reacted with the alloy with liquid phase pore creating material, to remove the active metal, obtain porous silicon nanometer material
Material;
(3) the porous silicon nano material is cleaned with hydrofluoric acid solution to remove silicon, is obtained through at hydrofluoric acid clean
The porous silicon nano material of reason;
(4) by obtained nano silicon material and mixed with polymers and ball milling is carried out, obtains porous nano silicon/polymer uniform
Mixture;
(5) nano-silicon/polymeric blends are calcined, obtains porous silicon-carbon composite.
In another preference, (such as suspension, dispersion liquid form) is added above-mentioned polymer in a liquid-like manner.
In another preference, described silicon-active metal alloy is silicon-active metal alloy chip.Described silicon-work
Sprinkling metal alloy chip can be obtained by any means (prepared by such as commercially available or conventional method), in a kind of preferred feelings of the present invention
Under condition, described chip is prepared by the following method:
One silicon-active metal alloy pig is provided;
Using 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 the alloy chip, the mass percent of described silicon is 1-99%, preferably
10-70%.
In another preference, methods described also includes:After the step (3) terminates, to described porous nano silicon/
Polymer uniform mixture is washed.
In another preference, described washing is to use deionized water and/or ethanol wash.
In another preference, the mass ratio of described hydrofluoric acid solution is 1%~30%.
In another preference, in the step (4), rotational speed of ball-mill is 300rpm~1500rpm, and Ball-milling Time is 8h
~120h, preferably 24-72h.
In another preference, in the step (5), the temperature range of the calcining is 600~1000 DEG C, preferably
It it is more preferably 700~850 DEG C for 650~900 DEG C.
In another preference, in the step (5), in the calcination process, described heating rate is with 1~10
DEG C/heating of min speed.
In another preference, in the step (5), the described reaction time is 0.1~24 hour, preferably 0.2
~12 hours, more preferably 0.2~5 hour.
In another preference, the porous silicon nano material handled through hydrofluoric acid clean is that component and pattern are more uniform
Porous silicon nanoparticles.
In another preference, in the step (5), in addition to:Described porous silicon-carbon composite electrode material is entered
Row post processing;It is preferred that described post processing includes:Washing, filtering, drying, or its combination.
In another preference, described " removing " refers to removal at least 95%, preferably at least 98%, more preferably at least
Active metal in the 99% alloy chip.
Described active metal has no particular limits, can from it is any can with or not the solution of pasc reaction (i.e. liquid phase
Pore creating material) metal that is reacted.In a kind of preference of the present invention, described active metal is selected from the 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 arbitrarily can be with active metal reaction without the solution with simple substance pasc reaction;Compared with
Goodly, 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 the group:Hydrochloric acid, nitric acid, sulfuric acid, or its combination.
In another preference, described liquid phase pore creating material is the nothing that mass percent solution concentration is 0.5%~35%
Machine acid solution.
Polymer of the present invention is used to provide carbon source, and its species has no particular limits, and can select any containing C polymerizations
The polymer of thing, especially key containing CH and CN keys, preferred example includes (but being not limited to):Polyacrylonitrile (PAN), polyethylene pyrrole
The polymer (PAN-co-PMA) of pyrrolidone (PVP), 2- methyl acrylates and 2- acrylonitrile, or its combination.In the excellent of the present invention
Select in embodiment, described polymer is provided in the form of a solution.
Described step (5) is preferably entered under hypoxemia or oxygen-free environment, such as inert gas and/or reducibility gas atmosphere
OK, or under vacuum carry out.Available inert gas is selected from the group:Inert gas:Nitrogen, helium, argon gas, neon,
Or its combination;Available reducing gas is selected from the group:Hydrogen, carbon monoxide or its combination.Can also in two kinds of any of the above or
Described calcining step is carried out under the combination atmosphere of multiple gases.
In another preference, described inert gas is a kind or at least two kinds of in nitrogen, helium, argon gas, neon
Combination;1 kind or at least two kinds of of combination preferably in nitrogen, helium, argon gas.
The volume that this porous silico-carbo combination electrode material can be good at alleviating in silicium cathode material process of intercalation is swollen
Swollen problem, preferably improves the stable circulation of silicon substrate lithium ion battery negative material on the premise of higher battery capacity is kept
Property, the requirement of high performance lithium ionic cell cathode material can be met.
Cell negative electrode material
The silico-carbo combination electrode material of the present invention can be as negative active core-shell material, for preparing cell negative electrode material.
In another preference, described cell negative electrode material also includes conductive agent and/or adhesive.Wherein, it is described
Bonding agent is preferably selected from Kynoar (PVDF), Lithium polyacrylate (Li-PAA), butadiene-styrene rubber (SBR) and carboxymethyl cellulose
At least one of plain sodium (CMC).
In another preference, described conductive agent is selected from the group:Acetylene black, SUPER P-Li, carbon fiber, coke, stone
Ink, carbonaceous mesophase spherules, hard carbon, or its combination;CNT, carbon nanocoils, Nano carbon balls, graphene are preferably chosen from, or
It is combined.
In another preference, in the 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 gross weight meter of negative material.
In another preference, in the negative material, described negative active core-shell material, conductive agent, adhesive three
Mass ratio be (80 ± 20):(20±10):(20±10).
The negative material of the present invention is after multiple charge and discharge cycles, and coulombic efficiency and specific discharge capacity reach stabilization,
Show 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 apply to field of batteries.Wherein, it is a kind of preferred
The battery include positive electrode, negative material, electrolyte, barrier film, and described negative material and include as described herein
Porous silicon-carbon composite electrode material be used as negative active core-shell material.It is preferably applied to lithium battery.
Described negative material is by above-mentioned porous silicon/carbon compound cathode active material, conductive agent and adhesive composition.It is porous
The content of silico-carbo combination electrode material is 60~90wt%, and the content of conductive agent is 5~15%, the content of adhesive for 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 composites 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, such as Teflon septum, ceramics
Perforated membrane, fibreglass diaphragm etc..
In charging process, the cation of electrolytic salt can pass through electrolyte, and negative material is reached from positive electrode;
In discharge process, the cation of electrolytic salt passes through electrolyte, and positive electrode is reached from negative material.
Described electrolyte includes electrolytic salt solvent and dissolving in a solvent.It is described preferred solvents organic molten
Agent, including (but being not limited to):Methyl ethyl carbonate (Methyl Ethyl Carbonate), fluoro ethylene carbonate
(Fluoroethylene Carbonate), dimethyl carbonate (Dimethyl Carbonate), diethyl carbonate (Diethyl
Carbonate), ethylene carbonate (Ethylene Carbonate), propene carbonate (Propylene Carbonate), 1,
2- dimethoxy-ethanes, 1,3 dioxolanes, methyl phenyl ethers anisole, acetic acid esters, propionic ester, butyrate, diethyl ether, acetonitrile, propionitrile.It is another
Planting preferred organic solvent includes the cyclic carbonate derivative with halogen atom, can improve the cycle performance of electrode.Carbonic acid
Ester derivant includes amyl- 2- ketone of the fluoro- 1,3- dioxanes of 4- etc..
Described electrolytic salt includes cation, can such as use lithium salts.It is preferred that lithium salts include lithium hexafluoro phosphate, high chlorine
Sour lithium, lithium chloride, lithium bromide etc..
Electrolyte solvent can be used alone, and can also include two kinds or multi-solvents, and electrolytic salt can individually make
With can also include two kinds or a variety of lithium salts.
Described positive electrode has no particular limits, and may be referred to state of the art and is selected, or using this
The existing positive electrode in field.
Such as, when described battery is lithium battery, its positive electrode can include one or more kinds of lithium metal oxides,
Such as manganese (Mn), iron (Fe), cobalt (Co), vanadium (V), nickel (Ni), the oxide of chromium (Cr) metal.Described positive electrode active materials are also
One or more metal oxides and metal sulfide etc. can be included.Such as (including but is not limited to):LiMnO2, LiMn2O4,
LiCoO2, Li2CrO7,LiNiO2,LiFeO2,LiNixCo1-XO2(0<x<1),LiFePO4,LiMnzNi1-ZO2(0<x<1;
LiMn0.5Ni0.5O2),LiMn0.33Co0.33Ni0.33O2,LiMc0.5Mn1.5O4, wherein, Mc is a divalent metal;
LiNixCoyMezO2, wherein Me represents one kind or several elements in Al, Mg, Ti, B, Ga, Si, x>0;Y, z<1.In addition, institute
The positive electrode active materials stated may also comprise transition metal oxide, such as MnO2、V2O5;Transient metal sulfide, such as FeS2、MoS2、
TiS2.Wherein, lithium ion transition metal oxide has obtained more applications, including:LiMn2O4, LiCoO2,
LiNi0.8Co0.15Al0.05O2, LiFePO4And LiNi0.33Mn0.33Co0.33O2。
Main advantages of the present invention include:
(1) present invention successfully prepares porous silicon/carbon compound cathode active material.Compared with other existing negative materials, this
Material has higher theoretical specific capacity.
(2) porous silicon of the present invention/carbon compound cathode materials structure alleviates silicon in charge and discharge process because volume is swollen
Mechanical stress that is swollen and shrinking generation, eliminates bulk effect;
(3) lithium ion battery porous silicon of the present invention/new production technology of carbon compound cathode materials, with being produced into
The advantages of this cheap, technique is simple, large-scale production is easy;
(4) porous silicon/carbon compound cathode active material for preparing of the present invention can be successfully applied to lithium battery, show compared with
High capacity and preferable cyclical stability.
(5) method of the invention can better control over the consumption of carbon source compared with prior art, and obtained silico-carbo composite wood
In material, the mixing of element silicon and carbon evenly, therefore can prepare the high silico-carbo composite of cycle performance.
With reference to specific embodiment, the present invention is expanded on further.It should be understood that these embodiments are merely to illustrate the present invention
Rather than limitation the scope of the present invention.The experimental method of unreceipted actual conditions in the following example, generally according to conventional strip
Part, or according to the condition proposed by manufacturer.Unless otherwise indicated, otherwise percentage and number are calculated by weight.
Embodiment 1
Aluminium-silicon ingots (such as Fig. 1) is crushed first with the method for physical mechanical, the broken of 0.1mm~100mm is ground to form
After bits, by a diameter of 0.1mm~100mm alusil alloys chips of 20g (such as Fig. 2), 270ml 5% watery hydrochloric acid is slowly added into
Reacted in solution, magnetic agitation is uniform.After the mixed solution fully reacts completely, by mixed solution by filtering, spend
After the fully rinsing such as ionized water and ethanol, to remove AlCl3Obtain porous silicon nanoparticles;Porous silicon nanoparticles are added again
Enter the hydrofluoric acid solution cleaning to 5% mass ratio, removed after porous silicon nanoparticles surface or unnecessary silica, carried out
Filter, is fully rinsed, it is single that collection obtains composition, the more uniform porous nano silicon of pattern, such as Fig. 3 with deionized water and ethanol etc..
After porous nano silicon is mixed with polyacrylonitrile, ball milling (wet-milling), ball-grinding machine are carried out:German Lai Chi companies, type
Number:PM200, rotational speed of ball-mill 350rpm, the time is 24h, then argon gas (95%)/700 DEG C of (5%) hydrogen gas atmosphere (with
10 DEG C/min speed is warming up to 700 DEG C) under calcining obtain porous silicon-carbon composite electrode material within 180 minutes, as shown in Figure 4.
XRD structural analyses and sem analysis, test result such as Fig. 5 have been carried out to porous silicon nanoparticles prepared by embodiment 1
With shown in Fig. 6.From fig. 5, it can be seen that prepared porous silicon nanoparticles are the good crystalline silicon of crystallinity, main peak value exists
28.44 ° (111 face), 47.30 ° (220 face), 56.12 ° (311 face), 69.13 ° (400 face), 76.38 ° (331 face), without it
The appearance of his impurity peaks.It is high-purity nano polysilicon to prove prepared porous silicon nanoparticles.From fig. 6, it can be seen that institute
The Si materials of preparation are loose structure, and be can see from high power SEM figures, and porous nano silicon has uniformly coated one layer of carbon,
Electrode interior structural damage is caused so as to be conducive to alleviating Si volumetric expansions in charge and discharge process.
Thermogravimetric analysis is carried out to porous silicon nanoparticles prepared by embodiment 1, as a result shown, in silico-carbo composite
Carbon content is 23wt% or so the gross weight meter of composite (press), as shown in Figure 10.
By porous silicon-carbon composite electrode material, conductive carbon (Super-P) and sodium carboxymethylcellulose (CMC) according to 60:
20:20 mass ratio mixing in a solvent, stirs, obtains cathode size, prepare electrode, using lithium piece as negative pole, assembling
2032 button cells.Using lithium piece as negative pole, charge/discharge test is carried out under 50mA/g current conditions, the combination electrode material is measured
The first discharge specific capacity of material at room temperature is 1628.6mAh/g, and charge specific capacity is 1213.3mAh/g, first coulombic efficiency
Up to 74.5%, secondary specific discharge capacity is 1274.4mAh/g, and charge specific capacity is 1205.6mAh/g, coulombic efficiency
Up to 94.2%.The specific discharge capacity of the 4th time is 1293.6mAh/g, and charge specific capacity is 1233.8mAh/g, coulombic efficiency
Up to 95.4%, ascendant trend is presented, it is shown that preferable cyclical stability, as shown in Figure 7, Figure 8.
Embodiment 2
Aluminium-silicon ingots (such as Fig. 1) is crushed first with the method for physical mechanical, the broken of 0.1mm~100mm is ground to form
After bits, a diameter of 0.1mm~100mm alusil alloys chips of 50g are slowly added into 480ml 10% dilute hydrochloric acid solution
Reaction, magnetic agitation is uniform.After the mixed solution fully reacts completely, by mixed solution by filtering, deionized water is used
After the abundant rinsing such as ethanol, to remove AlCl3Obtain porous silicon nanoparticles;Porous silicon nanoparticles are added to again
The hydrofluoric acid solution cleaning of 5% mass ratio, has removed after porous silicon nanoparticles surface or unnecessary silica, has been filtered, used
Deionized water and ethanol etc. are fully rinsed, and it is single that collection obtains composition, the more uniform porous nano silicon of pattern.
After porous nano silicon is mixed with polyacrylonitrile, ball milling (wet-milling), ball-grinding machine are carried out:German Lai Chi companies, type
Number:PM200, rotational speed of ball-mill 450rpm, the time is 18h, then in vacuum environment 700 DEG C (be warming up to 10 DEG C/min speed
700 DEG C) under calcining obtain porous silicon-carbon composite electrode material within 120 minutes.
By porous silicon-carbon composite electrode material, conductive carbon (Super-P) and sodium carboxymethylcellulose (CMC) according to 60:
20:20 mass ratio mixing in a solvent, stirs, obtains cathode size, using lithium piece as negative pole, electrode is prepared, with lithium
Piece is negative pole, assembles 2032 button cells.Charge/discharge test is carried out under 50mA/g current conditions, the combination electrode material is measured
The first discharge specific capacity of material at room temperature is 1787.3mAh/g, and charge specific capacity is 1143.9mAh/g, first coulombic efficiency
Up to 64.0%, secondary specific discharge capacity is 1320.2mAh/g, and charge specific capacity is 1167.4mAh/g, coulombic efficiency
Up to 88.4%%.The specific discharge capacity of the 6th time is 1347.7mAh/g, and charge specific capacity is 1250.7mAh/g, coulomb effect
Rate may be up to 92.8%%, and the specific discharge capacity of the tenth time is 1394.7mAh/g, and charge specific capacity is 1308.7mAh/g, coulomb
Efficiency may be up to 93.8%%, and ascendant trend is presented, it is shown that preferable stability.Table one is obtained silicon-carbon composite cathode material
The chemical property of material.
The chemical property of the silicon-carbon cathode material of lithium ion battery is made in the embodiment 2 of table one
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 and stability under the conditions of high current charge-discharge
By porous silicon-carbon composite electrode material in embodiment 2, conductive carbon (Super-P) and sodium carboxymethylcellulose
(CMC) according to 60:20:20 mass ratio mixing in a solvent, stirs, obtains cathode size, prepare electrode, with lithium piece
For negative pole, 2032 button cells are assembled.Battery carries out charge/discharge cycle 2 times first under 50mA/g current conditions.From third time
Charge/discharge test is carried out under 500mA/g current conditions using high current, performance such as Fig. 9 institutes of 2032 button cells are measured
Show.
From fig. 9, it can be seen that battery is under 500mA/g current conditions after charge and discharge cycles 45 times, battery specific capacity energy
Enough stable in 950mAh/g, coulombic efficiency can be stablized more than 98.2%, under the conditions of high current (such as 500mA/g) discharge and recharge
Show higher specific capacity and preferable stability.
Embodiment 4:
Using porous silicon-carbon composite prepared by example 1 as electrode active material, it is tested in 2032 button cells
In cycle performance.Electrode material constitutes (mass percent):60% porous silicon-carbon composite electrode material, 20% conductive carbon
Black, 20%CMC:It is lithium metal to electrode.Electrolyte is 1mol/LiPF6FEC/EMC/DMC (volume ratio is 1:1:1) solution,
Barrier film is Cellgard2300 barrier films.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.Filled as can be seen from Figure 11 in different multiplying
Still it is 1140mAh/g under the conditions of discharge and recharge under 1000mA/g current densities after discharge cycles 25 times, and different multiplying condition
Lower performance is stable, shows the electrode material of the present invention and has good cyclical stability.
All documents referred in the present invention are all incorporated as reference in this application, independent just as each document
It is incorporated as with reference to such.In addition, it is to be understood that after the above-mentioned instruction content of the present invention has been read, those skilled in the art can
To be made various changes or modifications to the present invention, these equivalent form of values equally fall within the model that the application appended claims are limited
Enclose.
Claims (13)
1. a kind of preparation method of porous silicon-carbon composite, it is characterised in that including step:
(1) one silicon-active metal alloy is provided;
(2) reacted with the alloy with liquid phase pore creating material, to remove the active metal, obtain porous silicon nano material;
(3) the porous silicon nano material is cleaned with hydrofluoric acid solution to remove silicon, obtains what is handled through hydrofluoric acid clean
Porous silicon nano material;
(4) by obtained nano silicon material and mixed with polymers and ball milling is carried out, obtains porous nano silicon/polymer uniform mixing
Thing;
(5) nano-silicon/polymeric blends are calcined, obtains porous silicon-carbon composite;
Wherein, described silicon-active metal alloy is silicon-active metal alloy chip, and the size of described chip is
0.1mm~100mm.
2. the method as described in claim 1, it is characterised in that described active metal is selected from the group:Aluminium, iron, magnesium, zinc, calcium,
Lead, or its combination.
3. the method as described in claim 1, it is characterised in that described liquid phase pore creating material be can with active metal reaction without
With the solution of simple substance pasc reaction.
4. the method as described in claim 1, it is characterised in that described liquid phase pore creating material is inorganic acid.
5. the method as described in claim 1, it is characterised in that described liquid phase pore creating material is inorganic acid.
6. the method as described in claim 1, it is characterised in that described polymer is selected from the group:It is polyacrylonitrile (PAN), poly-
The polymer (PAN-co-PMA) of vinylpyrrolidone (PVP), 2- methyl acrylates and 2- acrylonitrile, or its combination.
7. the method as described in claim 1, it is characterised in that described step (5) is carried out under the atmosphere being selected from the group:It is lazy
Property gas and/or reducibility gas or vacuum condition.
8. method as claimed in claim 7, it is characterised in that described inert gas is selected from the group:Inert gas:Nitrogen,
Helium, argon gas, neon, or its combination;And/or
Described reducing gas is selected from the group:Hydrogen, carbon monoxide or its combination, or more any combination.
9. a kind of porous silicon-carbon composite electrode material, it is characterised in that described electrode material is to use claim 1-8 such as to appoint
Prepared by the method described in one.
10. material as claimed in claim 9, it is characterised in that described electrode material has one or many be selected from the group
Individual feature:
Described electrode material is nano particle, and the particle diameter of the nano particle is 5nm-500nm;
The specific surface area of the electrode material is 10-500cm2/g。
11. a kind of GND, it is characterised in that described GND is prepared with material as claimed in claim 9,
Or described GND contains material as claimed in claim 9.
12. a kind of product, it is characterised in that described product is prepared with material as claimed in claim 9, or described
Product contains material as claimed in claim 9, or described product has GND as claimed in claim 11.
13. product as claimed in claim 12, it is characterised in that described product is battery, and described battery is included just
Pole material, negative material, electrolyte and barrier film, and described negative material includes material as claimed in claim 12.
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CN107275590A (en) * | 2017-05-19 | 2017-10-20 | 浙江大学 | A kind of porous Si-C composite material and its preparation method and application |
CN107507972B (en) * | 2017-08-29 | 2020-11-20 | 北方奥钛纳米技术有限公司 | Preparation method of silicon-carbon negative electrode material, silicon-carbon negative electrode material and lithium ion battery |
CN108083282A (en) * | 2017-12-27 | 2018-05-29 | 洛阳联创锂能科技有限公司 | A kind of preparation method of three-dimensional porous silicon materials |
KR102264739B1 (en) | 2018-03-02 | 2021-06-15 | 주식회사 엘지에너지솔루션 | Negative electrode active material, preparing method of the same, negative electrode and lithium secondary battery including the same |
CN110289402B (en) * | 2019-06-10 | 2022-09-16 | 中国科学院合肥物质科学研究院 | Electrode material of crosslinked carbon-coated mesoporous silicon particles and preparation method thereof |
CN111009647B (en) * | 2019-12-10 | 2021-03-16 | 中南大学 | Lithium borosilicate alloy cathode active material of lithium secondary battery, cathode, preparation and application thereof |
CN111732092B (en) * | 2020-06-03 | 2021-09-07 | 广东工业大学 | Graphene/carbon nanotube/porous silicon composite material and preparation method and application thereof |
CN111928979B (en) * | 2020-07-22 | 2022-02-15 | 浙江理工大学 | Preparation method of high-sensitivity pressure sensor with hair follicle-like structure |
CN112430103B (en) * | 2020-11-19 | 2022-01-25 | 中国科学院金属研究所 | Photocuring 3D printing hierarchical pore ceramic material and preparation method thereof |
CN113793929B (en) * | 2021-09-16 | 2024-03-01 | 金川集团股份有限公司 | Porous Si/SiO x Preparation and application of composite material |
CN114864878A (en) * | 2022-04-13 | 2022-08-05 | 北京工业大学 | Preparation method of micron porous Si structure and lithium ion battery Si @ C electrode |
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