CN104393245B - A kind of lithium ion battery preparation method of the nano silicon-based negative pole of loose structure - Google Patents
A kind of lithium ion battery preparation method of the nano silicon-based negative pole of loose structure Download PDFInfo
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- CN104393245B CN104393245B CN201410750512.XA CN201410750512A CN104393245B CN 104393245 B CN104393245 B CN 104393245B CN 201410750512 A CN201410750512 A CN 201410750512A CN 104393245 B CN104393245 B CN 104393245B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
A kind of lithium ion battery preparation method of the nano silicon-based negative pole of loose structure, is related to lithium ion battery.Nano-silicon, conductive agent, dispersant are placed in decentralized medium and are dispersed into electrophoresis liquid;Working electrode, electrode is connected with the both positive and negative polarity of power supply respectively, electrophoretic deposition is carried out after energization, the nano silicon-based negative pole of lithium ion battery loose structure is obtained after being dried under reduced pressure.The electrode of lithium ion battery negative can be used as with easy direct preparation, the synthesis of material and number of assembling steps are united two into one, enormously simplify production technology.The electrode prepared or need not on a small quantity use binding agent, can improve the energy density of lithium ion battery.The electrode of preparation is cellular nanometer silicon electrode.The nanoscale of loose structure and silicon grain is conducive to improving the cycle performance of electrode.
Description
Technical field
The present invention relates to lithium ion battery, more particularly, to a kind of lithium ion battery nano silicon-based negative pole of loose structure
Preparation method.
Background technology
Developing rapidly for mobile electronic device make it that the development of high performance chemical electric power source is maked rapid progress.Lithium ion battery is certainly
Secondary cell of new generation since the nineties in last century, with energy density it is big, have extended cycle life, operating voltage is high, memoryless
Effect, the advantages of self discharge is small, operating temperature range is wide, in mobile communication, mobile computing, electric automobile, Aero-Space, biology
The every field such as engineering in medicine are widely used.Lithium ion battery is main by negative pole, positive pole, electrolyte and barrier film group
Into.Study high performance negative material extremely important for the performance for improving lithium ion battery.
At present, the negative material of lithium ion battery mainly has following several:Graphitized carbon material, amorphous carbon material, nitrogen
Compound, silica-base material, tin-based material, novel alloy etc..Graphitized carbon material is the most commonly used negative material, but its specific volume
Amount only has 372mAh g-1.And can form Li under Li and Si alloying reactions, normal temperature15Si4, theoretical specific capacity is up to 3579mAh
g-1.So the energy density of lithium ion battery can be significantly improved as negative material using silica-base material.But silicon is being circulated throughout
Because volumetric expansion shrinks violent in journey, material efflorescence can be caused and lose and be coupled with the electrochemistry of conductive substrates, most led at last
Cause the rapid decay of capacity.By silicon materials nanosizing, porous can reduce STRESS VARIATION of the silicon during lithiumation, reduce material
The efflorescence of material, is conducive to improving the cycle performance of silicon-based anode.There are certain methods to prepare porous silicon or nanometer at present
Silicon, but effect has much room for improvement.
Silicon materials (porous silicon) with loose structure can significantly improve the cycle performance of silicon based anode material.Chen etc.
(Chen D.,Mei X,Ji G,et al.Reversible Lithium-ion Storage in Silver-treated
Nanoscale Hollow Porous Silicon Particles[J].Angew.Chem.Int.Ed.,2012,51(10):
2409-2413) with polystyrene as template, tetraethyl orthosilicate is silicon source, and cetyl trimethyl ammonium is pore-creating surface-active
Agent, synthesizes hollow porous SiO at room temperature2, high-temperature calcination removes removing template and surfactant, then uses under reducing atmosphere
Magnesium powder makees reducing agent, by SiO2Reduction, obtains hollow porous silicon.But this template complex process, time-consuming, wastage of material
Greatly, it is impossible to industrialized production.Jiang Zhiyu etc. in Chinese patent CN103165874A using silicon alloy powder as raw material, with inorganic acid
Reaction generation porous silicon particulate;After removing Surface Oxygen SiClx through the cleaning of HF acid solutions again, washing, drying obtains porous silica material.
This method needs to use the HF acid of severe corrosive, and the porous silicon for preparing is not nanoscale.
The porous silica material of above-mentioned synthesis is all fabricated to final lithium ion using the method for currently known coating substantially
GND.For example, porous silica material, conductive agent, binding agent and solvent are first mixed into slurry, then slurry is coated in collector
On, obtain lithium ion battery negative after drying.The use of one side binding agent adds extra to lithium ion battery negative
Weight, is unfavorable for improving the energy density of battery;On the other hand the method for coating does not ensure that porous silica material and conductive agent
Uniform dispersing contact so that cycle performance of battery is poor.
The content of the invention
It is an object of the invention to provide a kind of preparation method of lithium ion battery with the nano silicon-based negative pole of loose structure.
The present invention's comprises the following steps that:
1) nano-silicon, conductive agent, dispersant are placed in decentralized medium and are dispersed into electrophoresis liquid;
2) working electrode, electrode is connected with the both positive and negative polarity of power supply respectively, electrophoretic deposition, drying under reduced pressure are carried out after energization
After obtain the nano silicon-based negative pole of lithium ion battery loose structure.
In step 1) in, the nano-silicon can be crystal or amorphous state, and the diameter of nano-silicon can be 10~500nm;
The conductive agent can be carbon material, the carbon material may be selected from carbon black conductive agent, graphite agent, carbon nano rod and
At least one in graphene etc.;The carbon black conductive agent may be selected from acetylene black, Super P, Super S, 350G, carbon fiber
(VGCF), one kind in CNT (CNTs), Ketjen black etc., the Ketjen black may be selected from KetjenblackEC300J,
One kind in KetjenblackEC600JD, Carbon ECP, Carbon ECP600JD etc.;The graphite agent may be selected from
One kind in KS-6, KS-15, SFG-6, SFG-15 etc.;It is preferred that acetylene black;
The dispersant may be selected from citric acid, policapram, polyacrylamide, ethyoxyl sodium alkyl sulfate, α-alkenyl sulphur
At least one in sour sodium, lauryl sodium sulfate, ethyoxyl alkyl ammonium sulfate etc., preferably citric acid;
The decentralized medium may be selected from water system or organic system, and the organic system may be selected from acetone, ethanol, acetylacetone,2,4-pentanedione, ring
At least one in hexane, isopropanol, acetic acid, dichloromethane, methyl ethyl ketone, toluene etc., preferably acetone;The decentralized medium
As long as not reacted with nano-silicon;
The nano-silicon, conductive agent, the mass ratio of dispersant can be 1: (0.1~1): (0.5~5), preferably 1: 0.4:
1;On the basis of 1L decentralized media, the mass concentration of nano-silicon can be 0.1~10g/L, preferably 1g/L, the mass concentration of conductive agent
Can be 0.01~5g/L, preferably 0.4g/L, the mass concentration of dispersant can be 0.1~10g/L, preferably 1g/L;
It is described to disperse by the way of mechanical agitation, magnetic agitation or ultrasonic oscillation to disperse.
In step 2) in, the power supply can use D.C. regulated power supply or pulse square wave power supply;
When using D.C. regulated power supply, electrophoretic voltage can be 5~1000V, and electrophoresis time can be 1~120s;It is preferred that electricity
Swimming 50~300V of voltage, 5~30s of electrophoresis time.
When using pulse square wave power supply, pulse voltage can be 5~1000V, and pulse width can be 0.1~5s, pulse week
Phase can be 0.1~10s, and electrophoresis time can be 1~120s;Preferred pulse voltage is 50~400V, and pulse width is 0.5~2s,
Pulse period is 1~4s, and electrophoresis time is 5~60s.
The working electrode is not particularly limited, and can use conductive metal material working electrode or metal alloy conductive material
Working electrode;The metal may be selected from least one in Al, Fe, Co, Ni, Cu, Zn, Ag, Pt, Au etc., preferably copper current collector;
It is described that electrode is not particularly limited, can using in graphite, Al, Fe, Co, Ni, Cu, Zn, Ag, Pt, Au etc. extremely
Few one kind, preferably graphite or platinum;
The temperature being dried under reduced pressure can be 50~300 DEG C, preferably 80 DEG C.
The nano silicon-based negative pole of lithium ion battery loose structure prepared by the present invention is gone back in for preparing lithium ion battery
Including the required part such as positive pole, barrier film and nonaqueous electrolytic solution.When the lithium ion battery prepared using the present invention is received with loose structure
During rice silicon-based anode processing nonaqueous electrolytic solution secondary battery, as long as nano silicon-based negative with loose structure with the lithium ion battery
Other inscapes are not particularly limited by pole, can be used same with existing known nonaqueous electrolytic solution secondary battery
Inscape.
The positive electrode that usual lithium ion battery is used can be used in the present invention.The positive electrode active material that positive pole is related to
Matter, it is possible to use the reversibly compound of occlusion-releasing (embedded and deintercalation) lithium ion, for example, can enumerate that LixMO is used2
Or LiyM2O4The lithium-contained composite oxide of (in formula, M is transition metal) expression, the oxide of spinelle shape, the gold of layer structure
Belong to chalkogenide, olivine structural etc..
As its specific example, LiCoO can be enumerated2Deng lithium and cobalt oxides, LiMn2O4Deng lithium manganese oxide, LiNiO2Deng
Lithium nickel oxide, li-mn-ni compound oxide, lithium manganese nickel cobalt composite oxides;With LiMPO4Olives such as (M=Fe, Mn, Ni)
Material of stone-type crystalline texture etc..
Lithium-contained composite oxide especially with layer structure or spinelle shape structure is preferred, LiCoO2、
LiMn2O4、LiNiO2、LiNi1/2Mn1/2O2Deng the li-mn-ni compound oxide for representative, LiNil/3Mn1/3Co1/3O2、
LiNi0.6Mn0.2Co0.2O2Deng lithium manganese nickel cobalt composite oxides or LiNi 1-x-y-zCoxAlyMgzO for representative2(in formula, 0
In, in i 1,0, in i 1-x, 0, in i 1-x, 0, the lithium-contained composite oxide such as i 1-x-y-zC.In addition, above-mentioned is compound containing lithium
A part for constitution element in oxide, by Ge, Ti, Zr, Mg, Al, Mo, Sn etc. addition element replaced it is multiple containing lithium
Oxide etc. is closed also comprising wherein.These positive active materials, both can be used alone a kind, but also two or more is used in combination.
Positive pole for constituting nonaqueous electrolytic solution secondary battery, for example, being properly added charcoal in above-mentioned positive active material
The conductive auxiliary agents such as black, acetylene black, or the adhesive such as Kynoar, PEO etc., anode mixture is prepared, by it with aluminium
The current-collecting members such as paper tinsel are used as on the banding formed body of core after coating.But, the preparation method of positive pole is not limited only to
Example.
In the nonaqueous electrolytic solution secondary battery that the present invention is provided, relative to aqueous electrolyte, organic system electrolyte or
Solid electrolyte is preferred.Esters or ether organic solvent are can select as the solvent of organic system electrolyte.
Esters can enumerate vinyl carbonate (EC), propylene carbonate (PC), butylene carbonic ester (BC), 1,2- dimethylvinylsiloxy
Carbonic ester (1,2-BC), ethyl butyl carbonate (BEC), carbonic acid first butyl ester (BMC), dibutyl carbonate (DBC), diethyl carbonate
(DEC), dimethyl carbonate (DMC), chloro-ethylene carbonate (ClEC), trifluoromethyl ethylene carbonate (CF3- EC), carbonic acid two
N-propyl (DPC), diisopropyl carbonate (DIPC), methyl ethyl carbonate (EMC), ethyl propyl carbonic acid ester (EPC), ethylene isopropyl ester
(EIPC), methyl propyl carbonate (MPC), carbonic acid first isopropyl ester (MIPC) etc..
Ethers can enumerate dimethoxy-ethane (DME), diethoxyethane (DEE), tetrahydrofuran (THF), 2- methyl four
Hydrogen furans (MeTHF), diglycol ethylene dimethyl ether (DGM), contracting TRIGLYME (TGM), contracting tetraethyleneglycol dimethyl ether
(TEGM), 1,3- dioxolanes (1,3-DOL) etc..
In the nonaqueous electrolytic solution secondary battery that the present invention is provided, electrolyte can select one kind or two of above-mentioned organic solvent
The mixture of the above is planted as solvent.In addition, fluorinated ethylene carbonate (FEC) can be added in electrolyte as additive, add
Plus the addition of agent, it is, for example, that 0.5~10wt% is preferred to organic electrolyte total amount.
The supporting electrolyte of electrolyte can select inorganic electrolyte lithium salts or organic bath lithium salts.
As inorganic electrolyte lithium salts, LiClO can be enumerated4、LiPF6、LiBF4、LiAsF6、LiSbF6, LiBOB (double oxalic acid
Lithium borate), LiDFBO (LiODFB) etc..
As organic bath lithium salts, trifluoromethyl sulfonic acid lithium, two (trimethyl fluoride sulfonyl) imine lithiums, three can be enumerated
(trimethyl fluoride sulfonyl) lithium methide, two (catechol) borate lithiums and double-[1,2- tetra- (trifluoromethyl) ethylene dioxy abutment
(2-)-O-O '] lithium borate etc..
The supporting electrolyte of electrolyte can select one or more kinds of mixtures of above-mentioned electrolyte lithium salt.Electrolysis
Concentration of the matter lithium salts in organic electrolyte, for example, 0.3mol/L (mol/L) above is it is preferred that, more preferably 0.7mol/L
More than, preferably below 1.7mol/L, more preferably below 1.2mol/L.When the concentration of electrolyte lithium salt is too low, ion conductivity
Too small, when too high, worry fails to dissolve complete electrolytic salt precipitation.
In the nonaqueous electrolytic solution secondary battery that the present invention is provided, for the barrier film that positive pole and negative pole separate not to be made spy yet
Do not limit, can be using the various barrier films used in existing known nonaqueous electrolytic solution secondary battery.
Because the effect of barrier film is to separate the both positive and negative polarity active material of battery, it is to avoid positive and negative any electron stream of interpolar is direct
Pass through, it is to avoid battery short circuit;Ion stream by when resistance it is as small as possible, so mostly select apertured polymeric film.For example, adopting
With polyolefin resins such as polyethylene, polypropylene, or the pore that the polyester resin such as polybutylene terephthalate (PBT) is formed
Barrier film is preferred.In addition, these pore barrier films (pore film) can also be overlapped and used.Above-mentioned polymer microporous film is through material
The modified obtained film in surface, such as ceramic powder (aluminum oxide, silica) are coated in the composite ceramics barrier film on polyolefin
It can also use.
Thickness to barrier film is not particularly limited yet, but security and the aspect of high capacity two in view of battery, preferably
It is 5~30 thickness.In addition, the air permeability (s/100mL) of barrier film is not particularly limited yet, but preferably 10~1000 (s/100mL),
More preferably 50~800 (s/100mL), particularly preferably 90~700 (s/100mL).
The preparation method of the nonaqueous electrolytic solution secondary battery that the present invention is provided, for example, between aforementioned positive electrode and negative pole, folder
Firmly it is subject to overlapping after foregoing barrier film, electrode layered product is made, is wound and is made after electrode coiling body, is filled in packaging body,
The positive and negative electrode terminal of positive and negative electrode and packaging body is attached by lead body (lead wire) etc., then foregoing nonaqueous electrolytic solution is noted
After entering in packaging body, sealed package and be made.
As the packaging body of battery, the packaging body such as square, the cylindrical shape that can be made of metal, or by metal (aluminium
Deng) the layered product packaging body etc. that is formed of laminated film.
Further, the construction of the manufacture method of nonaqueous electrolytic solution secondary battery and battery, is not particularly limited, in packaging body
Set after positive pole, negative pole, barrier film and nonaqueous electrolytic solution, before battery is fully sealed, the opening formation process charged is set
It is preferred.
So, the moisture of the interior residual of gas or battery that the charging initial stage produces can remove to outside battery.
The method that electric pool gas is removed after above-mentioned open formation process is carried out, is not particularly limited, can use nature
Any one for removing or being removed in vacuum.In addition, before battery is fully sealed, also can be using the appropriate forming battery such as extruding.This
Nano-silicon, conductive agent, dispersant and decentralized medium mixing dispersion are formed electrophoresis liquid by invention, and nano-silicon and conductive agent are in electrophoresis liquid
In will take negative electrical charge, electrophoresis liquid is placed in reaction unit, nano-silicon and conductive agent will under electric field force effect after energization
The nanometer silicon electrode for possessing loose structure is deposited and is self-assembly of on the working electrode (s.
The present invention carries out assembling design using the method for electrophoretic deposition to nano-silicon, is successfully prepared for Porous Silicon Electrode.
The method or need not on a small quantity use binding agent, by the synthesis of material and the step of assembling process one, can possess with easy preparing
The nanometer silicon electrode of loose structure.Loose structure can alleviate the STRESS VARIATION that volumetric expansion of the silicon during lithiumation is shunk,
Reduce silicon powder;The silicon materials of nanoscale can accelerate the transmission speed of lithium ion, and this is all conducive to improving following for battery
Ring performance.
The present invention has following advantages compared with prior art:
1st, the electrode of lithium ion battery negative can be used as with easy direct preparation using the method, by the synthesis of material with
Number of assembling steps unites two into one, and enormously simplify production technology.
2nd, the electrode prepared using this method or need not use binding agent on a small quantity, can improve the energy of lithium ion battery
Density.
3rd, electrode prepared by the present invention is cellular nanometer silicon electrode.The nanoscale of loose structure and silicon grain is conducive to
Improve the cycle performance of electrode.
Brief description of the drawings
Fig. 1 is reaction unit schematic diagram.
Fig. 2 is the SEM figures of the nanometer silicon electrode for possessing loose structure in embodiment 1.
Fig. 3 is the EDX mapping figures of the nanometer silicon electrode for possessing loose structure in embodiment 1.
Fig. 4 is the electrochemistry cycle performance figure of the nanometer silicon electrode for possessing loose structure in embodiment 1.
Fig. 5 be embodiment 2 in possess loose structure nanometer silicon electrode electrochemistry cycle performance figure.
Fig. 6 is the electrochemistry cycle performance figure of the nanometer silicon electrode prepared in comparative example 1 using conventional application method.
Embodiment
The present invention provides a kind of preparation method for the silicon substrate lithium ion battery negative for possessing loose structure.Make in this way
Can save traditional electrode preparation coating operation, without or on a small quantity use binding agent, by synthesis and being assembled into one of material,
Easy prepares the nanometer silicon electrode for possessing loose structure.This nanometer silicon electrode can be directly used as the negative of lithium ion battery
Pole, and with excellent cycle performance.Technical scheme is done further below in conjunction with drawings and Examples
It is bright, but the present invention is not limited in these embodiments.In addition, for device used, not also being particularly limited.
Fig. 1 provides reaction unit of the invention.In Fig. 1, the negative pole of power supply 1 is connected with to electrode 3, the positive pole of power supply 1
It is connected with to electrode 4, mark 2 is electrophoresis liquid.
Embodiment 1:
Using 50mL acetone as decentralized medium, 0.05g nano-silicons, 0.05g citric acids, 0.02g acetylene blacks are added.Ultrasound point
Scattered 20min obtains electrophoresis liquid.
Pt pieces (30mm × 30mm × 0.2mm) connect the negative pole of power supply as to electrode;Copper Foil (20mm × 20mm ×
0.01mm) as working electrode, the positive pole of power supply is connected.Using DC voltage-stabilizing mode constant voltage 120V to electrophoresis liquid electrophoresis 5s
After take out Copper Foil, 80 DEG C are dried under reduced pressure 12h and obtain porous nano silicon electrode.
The pattern of porous silicon nano-electrode is analyzed using SEM (HITACHI S-4800), Fig. 2 is obtained.From figure
2 as can be seen that nano-silicon has been self-assembled into vesicular texture on electrode surface, and does not reunite.Further carry out EDX
Mapping tests to obtain Fig. 3.Nano-silicon and acetylene black are evenly distributed in Cu paper tinsels surface as can be seen from Figure 3, and acetylene black can fill
Work as conductive network, it is ensured that electrochemistry connection good between nano-silicon and copper foil of affluxion body.
Electrochemical property test:
Using porous nano silicon electrode obtained above as positive pole, lithium metal is used as negative pole, 1mol L-1LiPF6It is dissolved in
EC: DMC: EMC (1: 1: 1)+5%FEC is filling as barrier film, glass fiber filter paper as electrolyte, PP films as imbibition film
2016 button cells are assembled into the glove box of full argon gas.
2016 button cells are subjected to constant current charge-discharge test on the discharge and recharge instrument system of Xin Wei Instrument Ltd..Put
Electric blanking voltage is 0.02V, and charge cutoff voltage is 1.5V, and current density is 0.1C.Obtain Fig. 4.By the method system of embodiment one
Standby nano-silicon electrode cycle after 50 weeks reversible capacity be 2315mAh/g, capability retention is 69%.
Embodiment 2:
Preparation method is similar to embodiment 1, and simply electrophoresis time is changed into 15s.
The surface topography of electrode is similar to Example 1, but is due to nano-silicon and acetylene on the increase of electrophoresis time, Copper Foil
Black loading is by 0.25mg/cm2Increase to 0.46mg/cm2。
Electro-chemical test is identical with embodiment one, obtains Fig. 5.By nano-silicon electrode cycle 50 weeks prepared by the method for embodiment one
Reversible capacity is 2276mAh/g afterwards, and capability retention is 68%.
Comparative example 1:
The comparative example uses currently known painting method assemble nanometer silicon electrode.Binder Composition is containing 50% SBR+
CMC (mass ratio 1: the 1) hydrosol, nano-silicon: acetylene black: binding agent=1: 1: 1, it is mixed into slurry.Slurry is uniform
Be coated on Copper Foil, 80 DEG C of drying under reduced pressure 12h obtain the nanometer silicon electrode using painting method construction.
Electrochemical property test:
Nanometer silicon electrode using use painting method obtained above construction is as positive pole, and lithium metal is used as negative pole, 1mol
L-1LiPF6It is dissolved in EC: DMC: EMC (1: 1: 1)+5%FEC makees as electrolyte, PP films as barrier film, glass fiber filter paper
For imbibition film, 2016 button cells are assembled into the glove box full of argon gas.
2016 button cells are subjected to constant current charge-discharge test on the discharge and recharge instrument system of Xin Wei Instrument Ltd..Put
Electric blanking voltage is 0.02V, and charge cutoff voltage is 1.5V, and current density is 0.1C.Obtain Fig. 6.Prepared by one method of contrast
Nano-silicon electrode cycle after 50 weeks reversible capacity be 1793mAh/g, capability retention is 54%.
Comparative example 2:
The comparative example assembles graphite electrode using electrophoretic deposition method.Using 50mL acetone as decentralized medium, 0.2g is added
Powdered graphite (mean particle diameter is 5 μm), 0.04g acetylene blacks.Ultrasonic disperse 20min obtains electrophoresis liquid.
Pt pieces (30mm × 30mm × 0.2mm) connect the negative pole of power supply as to electrode;Copper Foil (20mm × 20mm ×
0.01mm) as working electrode, the positive pole of power supply is connected.Using DC voltage-stabilizing mode constant voltage 120V to electrophoresis liquid electrophoresis
Copper Foil is taken out after 120s, 80 DEG C are dried under reduced pressure 12h and obtain graphite electrode.
Electrochemical property test:
Using graphite electrode obtained above as positive pole, lithium metal is used as negative pole, 1mol L-1LiPF6It is dissolved in EC: DMC:
EMC (1: 1: 1)+5%FEC are as electrolyte, and PP films are as barrier film, and glass fiber filter paper is as imbibition film, full of argon gas
Glove box in be assembled into 2016 button cells.
2016 button cells are carried out into constant current charge-discharge test on the discharge and recharge instrument system of Xin Wei Instrument Ltd..Put
Electric blanking voltage is 0.02V, and charge cutoff voltage is 1.5V, and current density is 0.1C.By nanometer prepared by the method for comparative example two
Reversible capacity is 290mAh/g after silicon electrode is circulated 50 weeks, and capability retention is 95%.
The electrochemistry cycle performance of each embodiment of table 1 and comparative example
As can be seen that embodiment 1 and 2 possesses porous knot using what electrophoretic deposition method was assembled from the statistics of table 1
The nanometer silicon electrode of structure after 50 circle circulations reversible capacity and capability retention apparently higher than using known painting method group
The nanometer silicon electrode of dress.Although the graphite electrode capability retention of the use electrophoretic deposition assembling of comparative example 2 is higher, reversible appearance
Amount is far below Examples 1 and 2.Illustrate that the nanometer silicon electrode for possessing loose structure prepared using the present invention has excellent circulation
Performance and higher energy density.
Claims (12)
1. a kind of lithium ion battery preparation method of the nano silicon-based negative pole of loose structure, it is characterised in that its specific steps is such as
Under:
1) nano-silicon, conductive agent, dispersant are placed in and electrophoresis liquid is dispersed into decentralized medium;The nano-silicon is crystal or amorphous
State, a diameter of 10~500nm of nano-silicon;The nano-silicon, conductive agent, the mass ratio of dispersant are 1: (0.1~1): (0.5
~5);On the basis of 1L decentralized media, the mass concentration of nano-silicon is 0.1~10g/L, the mass concentration of conductive agent for 0.01~
5g/L, the mass concentration of dispersant is 0.1~10g/L;The conductive agent is carbon material, and the carbon material is selected from carbon black conductive
At least one in agent, graphite agent, carbon nano rod and Graphene;The carbon black conductive agent be selected from acetylene black, Super P,
One kind in Super S, 350G, carbon fiber, CNT, Ketjen black, the Ketjen black be selected from KetjenblackEC300J,
One kind in KetjenblackEC600JD, Carbon ECP, Carbon ECP600JD;The graphite agent be selected from KS-6,
One kind in KS-15, SFG-6, SFG-15;The dispersant is selected from citric acid, policapram, polyacrylamide, alkyl ethoxylate
At least one in base sodium sulphate, α-sodium olefin sulfonate, lauryl sodium sulfate, ethyoxyl alkyl ammonium sulfate;
2) working electrode, electrode is connected with the both positive and negative polarity of power supply respectively, electrophoretic deposition is carried out after energization, after drying under reduced pressure
To the lithium ion battery nano silicon-based negative pole of loose structure.
2. a kind of lithium ion battery as claimed in claim 1 preparation method of the nano silicon-based negative pole of loose structure, its feature exists
In the dispersant be citric acid.
3. a kind of lithium ion battery as claimed in claim 1 preparation method of the nano silicon-based negative pole of loose structure, its feature exists
In in step 1) in, the decentralized medium is selected from water system or organic system, and the organic system is selected from acetone, ethanol, acetylacetone,2,4-pentanedione, ring
At least one in hexane, isopropanol, acetic acid, dichloromethane, methyl ethyl ketone, toluene.
4. a kind of lithium ion battery as claimed in claim 3 preparation method of the nano silicon-based negative pole of loose structure, its feature exists
In the organic system be acetone.
5. a kind of lithium ion battery preparation method of the nano silicon-based negative pole of loose structure as claimed in claim 1, its feature exists
In in step 1) in, the nano-silicon, conductive agent, the mass ratio of dispersant are 1: 0.4: 1;On the basis of 1L decentralized media, receive
The mass concentration of rice silicon is 1g/L, and the mass concentration of conductive agent is 0.4g/L, and the mass concentration of dispersant is 1g/L.
6. a kind of lithium ion battery preparation method of the nano silicon-based negative pole of loose structure as claimed in claim 1, its feature exists
In in step 1) in, the dispersion is disperseed by the way of mechanical agitation, magnetic agitation or ultrasonic oscillation.
7. a kind of lithium ion battery as claimed in claim 1 preparation method of the nano silicon-based negative pole of loose structure, its feature exists
In in step 2) in, the power supply uses D.C. regulated power supply or pulse square wave power supply;
When using D.C. regulated power supply, electrophoretic voltage is 5~1000V, and electrophoresis time is 1~120s;
When using pulse square wave power supply when, pulse voltage be 5~1000V, pulse width be 0.1~5s, the pulse period be 0.1~
10s, electrophoresis time is 1~120s.
8. a kind of lithium ion battery preparation method of the nano silicon-based negative pole of loose structure as claimed in claim 7, its feature exists
In when using D.C. regulated power supply, electrophoretic voltage is 50~300V, and electrophoresis time is 5~30s;
When using pulse square wave power supply when, pulse voltage be 50~400V, pulse width be 0.5~2s, the pulse period be 1~
4s, electrophoresis time is 5~60s.
9. a kind of lithium ion battery as claimed in claim 1 preparation method of the nano silicon-based negative pole of loose structure, its feature exists
In in step 2) in, the working electrode uses conductive metal material working electrode or metal alloy conductive material working electrode;
At least one of the metal in Al, Fe, Co, Ni, Cu, Zn, Ag, Pt, Au;
At least one used to electrode in graphite, Al, Fe, Co, Ni, Cu, Zn, Ag, Pt, Au.
10. a kind of lithium ion battery preparation method of the nano silicon-based negative pole of loose structure as claimed in claim 9, its feature exists
In the metal be copper current collector;
It is described that graphite or platinum are used to electrode.
A kind of 11. lithium ion batteries as claimed in claim 1 preparation method of the nano silicon-based negative pole of loose structure, its feature exists
In in step 2) in, the temperature of the drying under reduced pressure is 50~300 DEG C.
12. a kind of lithium ion battery preparation method of the nano silicon-based negative pole of loose structure as claimed in claim 11, its feature
It is that the temperature being dried under reduced pressure is 80 DEG C.
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