CN104393245A - Preparation method of nano silicon based negative electrode with porous structure for lithium ion battery - Google Patents

Preparation method of nano silicon based negative electrode with porous structure for lithium ion battery Download PDF

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CN104393245A
CN104393245A CN201410750512.XA CN201410750512A CN104393245A CN 104393245 A CN104393245 A CN 104393245A CN 201410750512 A CN201410750512 A CN 201410750512A CN 104393245 A CN104393245 A CN 104393245A
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nano
lithium ion
silicon
ion battery
electrode
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CN104393245B (en
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赵金保
杨阳
陈丁琼
李雪
刘波
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Xiamen University
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Xiamen University
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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
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention discloses a preparation method of a nano-silicon based negative electrode with a porous structure for a lithium ion battery, and relates to a lithium ion battery. The preparation method comprises the following steps of placing nano silicon, a conductive agent and a dispersion agent into a dispersion medium, and dispersing into an electrophoresis solution; connecting a working electrode and a counter electrode with positive and negative electrodes of a power supply respectively, electrifying, then carrying out electrophoretic deposition, and carrying out pressure-reduction drying so as to obtain the nano-silicon based negative electrode with the porous structure for the lithium ion battery. The electrode for the negative electrode of the lithium ion battery can be prepared directly, simply and conveniently; the synthesis and assembling steps of the material are combined into one, so that the production technology is simplified greatly. The prepared electrode does not use a binder or uses less binder, so that the energy density of the lithium ion battery can be improved; the prepared electrode is a porous nano-silicon electrode; the porous structure and the nanoscale of the silicon particles are conductive to improving the cyclic performance of the electrode.

Description

The preparation method of the nano silicon-based negative pole of a kind of lithium ion battery loose structure
Technical field
The present invention relates to lithium ion battery, especially relate to the preparation method of the nano silicon-based negative pole of a kind of lithium ion battery loose structure.
Background technology
The develop rapidly of mobile electronic device makes the development of high performance chemical electric power source make rapid progress.Lithium ion battery has been the secondary cell of new generation since the nineties in last century, have energy density large, have extended cycle life, the advantage such as operating voltage is high, memory-less effect, self discharge is little, operating temperature range is wide, be widely used in every field such as mobile communication, mobile computing, electric automobile, Aero-Space, biomedical engineerings.Lithium ion battery forms primarily of negative pole, positive pole, electrolyte and barrier film.Study high performance negative material extremely important for the performance improving lithium ion battery.
At present, the negative material of lithium ion battery mainly contains following several: graphitized carbon material, amorphous carbon material, nitride, silica-base material, tin-based material, novel alloy etc.Graphitized carbon material is the negative material commonly used the most, but its specific capacity only has 372mAh g -1.And Li and Si alloying reaction, can Li be formed under normal temperature 15si 4, theoretical specific capacity is up to 3579mAh g -1.So the energy density of lithium ion battery can be significantly improved using silica-base material as negative material.But silicon because volumetric expansion is shunk violent, can cause material efflorescence and lose and connect with the electrochemistry of conductive substrates, causing the rapid decay of capacity the most at last in cyclic process.By silicon materials nanometer, porous can reduce the STRESS VARIATION of silicon in lithiumation process, reduces the efflorescence of material, is conducive to the cycle performance improving silicon-based anode.Had certain methods can prepare porous silicon or nano-silicon at present, but effect all have much room for improvement.
The silicon materials (porous silicon) with loose structure significantly can improve the cycle performance of silicon based anode material.(the Chen D. such as Chen, Mei X, Ji G, et al.Reversible Lithium-ion Storage in Silver-treatedNanoscale Hollow Porous Silicon Particles [J] .Angew.Chem.Int.Ed., 2012,51 (10): 2409-2413) take polystyrene as template, tetraethoxysilane is silicon source, cetyl trimethyl ammonium is pore-creating surfactant, at room temperature synthesizes the SiO of hollow porous 2, template and surfactant are removed in high-temperature calcination, then make reducing agent, by SiO with magnesium powder under reducing atmosphere 2reduction, obtains hollow porous silicon.But this template complex process, length consuming time, wastage of material is large, cannot suitability for industrialized production.Jiang Zhiyu etc. are raw material with silicon alloy powder in Chinese patent CN103165874A, generate porous silicon particulate with inorganic acid reaction; Again after HF acid solution cleaning removing Surface Oxygen SiClx, washing, dries and obtains porous silica material.This method needs the HF acid using severe corrosive, and the porous silicon of preparation is not nanoscale.
The porous silica material of above-mentioned synthesis substantially all adopts the method for current known coating to be made into final lithium ion battery negative.Such as, porous silica material, conductive agent, binding agent and solvent are first mixed into slurry, then by slurry coating on a current collector, obtain lithium ion battery negative after drying.The use of binding agent adds extra weight to lithium ion battery negative on the one hand, is unfavorable for the energy density improving battery; The method of coating can not ensure porous silica material and the uniform dispersing contact of conductive agent on the other hand, makes cycle performance of battery poor.
Summary of the invention
The object of this invention is to provide the preparation method of the nano silicon-based negative pole of a kind of lithium ion battery loose structure.
Concrete steps of the present invention are as follows:
1) nano-silicon, conductive agent, dispersant are placed in decentralized medium and are dispersed into electrophoresis liquid;
2) work electrode, electrode is connected with the both positive and negative polarity of power supply respectively, carry out electrophoretic deposition after energising, after drying under reduced pressure, obtain the nano silicon-based negative pole of lithium ion battery loose structure.
In step 1) in, described nano-silicon can be crystal or amorphous state, and the diameter of nano-silicon can be 10 ~ 500nm;
Described conductive agent can be material with carbon element, and described material with carbon element can be selected from least one in carbon black conductive agent, graphite agent, carbon nano rod and Graphene etc.; Described carbon black conductive agent can be selected from the one in acetylene black, Super P, Super S, 350G, carbon fiber (VGCF), carbon nano-tube (CNTs), Ketjen black etc., and described Ketjen black can be selected from the one in KetjenblackEC300J, KetjenblackEC600JD, Carbon ECP, Carbon ECP600JD etc.; Described graphite agent can be selected from the one in KS-6, KS-15, SFG-6, SFG-15 etc.; Preferred acetylene black;
Described dispersant can be selected from least one in citric acid, policapram, polyacrylamide, ethyoxyl sodium alkyl sulfate, α-sodium olefin sulfonate, lauryl sodium sulfate, ethyoxyl alkyl ammonium sulfate etc., is preferably citric acid;
Described decentralized medium can be selected from water system or organic system, and described organic system can be selected from least one in acetone, ethanol, acetylacetone,2,4-pentanedione, cyclohexane, isopropyl alcohol, acetic acid, carrene, methyl ethyl ketone, toluene etc., preferred acetone; Described decentralized medium only otherwise react with nano-silicon;
The mass ratio of described nano-silicon, conductive agent, dispersant can be 1: (0.1 ~ 1): (0.5 ~ 5), is preferably 1: 0.4: 1; With 1L decentralized medium for benchmark, the mass concentration of nano-silicon can be 0.1 ~ 10g/L, preferred 1g/L, and the mass concentration of conductive agent can be 0.01 ~ 5g/L, preferred 0.4g/L, and the mass concentration of dispersant can be 0.1 ~ 10g/L, preferred 1g/L;
Described dispersion can adopt the mode of mechanical agitation, magnetic agitation or ultrasonic oscillation to disperse.
In step 2) in, described power supply can adopt D.C. regulated power supply or pulse square wave power supply;
When adopting D.C. regulated power supply, electrophoretic voltage can be 5 ~ 1000V, and electrophoresis time can be 1 ~ 120s; Preferred electrophoretic voltage 50 ~ 300V, electrophoresis time 5 ~ 30s.
When adopting pulse square wave power supply, pulse voltage can be 5 ~ 1000V, and pulse duration can be 0.1 ~ 5s, and the pulse period can be 0.1 ~ 10s, and electrophoresis time can be 1 ~ 120s; Preferred pulse voltage is 50 ~ 400V, and pulse duration is 0.5 ~ 2s, and the pulse period is 1 ~ 4s, and electrophoresis time is 5 ~ 60s.
Described work electrode is not particularly limited, and can adopt conductive metal material work electrode or metal alloy electric conducting material work electrode; Described metal can be selected from least one in Al, Fe, Co, Ni, Cu, Zn, Ag, Pt, Au etc., preferably copper collector;
Described electrode to be not particularly limited, at least one in graphite, Al, Fe, Co, Ni, Cu, Zn, Ag, Pt, Au etc. can be adopted, preferred graphite or platinum;
The temperature of described drying 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, for the preparation of in lithium ion battery, also comprises the required parts such as positive pole, barrier film and nonaqueous electrolytic solution.When the lithium ion battery loose structure adopting the present invention to prepare nano silicon-based negative pole processing nonaqueous electrolytic solution secondary battery, as long as have the nano silicon-based negative pole of described lithium ion battery loose structure, other inscapes are not particularly limited, the inscape same with existing known nonaqueous electrolytic solution secondary battery can be adopted.
The positive electrode that usual lithium ion battery uses can use in the present invention.The positive active material that positive pole relates to, can use the compound of reversibly occlusion-releasing (Infix and desfix) lithium ion, such as, can enumerate and use LixMO 2or LiyM 2o 4lithium-contained composite oxide, the oxide of spinelle shape, the metal chalcogenide, olivine structural etc. of layer structure that (in formula, M is transition metal) represents.
As its object lesson, LiCoO can be enumerated 2deng lithium and cobalt oxides, LiMn 2o 4deng lithium manganese oxide, LiNiO 2deng lithium nickel oxide, li-mn-ni compound oxide, lithium manganese nickel cobalt composite oxides; There is LiMPO 4material of olivine-type crystalline textures such as (M=Fe, Mn, Ni) etc.
The lithium-contained composite oxide particularly adopting layer structure or spinelle shape structure is preferred, LiCoO 2, LiMn 2o 4, LiNiO 2, LiNi 1/2mn 1/2o 2deng li-mn-ni compound oxide, LiNi for representative l/3mn 1/3co 1/3o 2, LiNi 0.6mn 0.2co 0.2o 2deng being the lithium manganese nickel cobalt composite oxides of representative or LiNi 1-x-y-zCoxAlyMgzO 2(in formula, in 0, in i 1,0, in i 1-x, 0, in i 1-x, 0, the lithium-contained composite oxides such as i 1-x-y-zC.In addition, a part for the constitution element in above-mentioned lithium-contained composite oxide, by Ge, Ti, Zr, Mg, lithium-contained composite oxide etc. that the Addition ofelements of Al, Mo, Sn etc. replaces also comprises wherein.These positive active materials, both can be used alone a kind, but also two or more are also used.
For forming the positive pole of nonaqueous electrolytic solution secondary battery, such as, the conductive auxiliary agent such as carbon black, acetylene black is suitably added in above-mentioned positive active material, or the adhesive such as Kynoar, poly(ethylene oxide) etc., preparation anode mixture, uses after it being coated with on the banded formed body using current-collecting members such as aluminium foils as core.But the manufacture method of positive pole is not limited only to example.
In nonaqueous electrolytic solution secondary battery provided by the invention, relative to aqueous electrolyte, organic system electrolyte or solid electrolyte are preferred.Solvent as organic system electrolyte can select ester class or ether organic solvent.
Ester class 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 (CF 3-EC), carbonic acid di-n-propyl ester (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), oxolane (THF), 2-methyltetrahydrofuran (MeTHF), diglycol ethylene dimethyl ether (DGM), contracting TRIGLYME (TGM), contracting tetraethyleneglycol dimethyl ether (TEGM), 1,3-dioxolane (1,3-DOL) etc.
In nonaqueous electrolytic solution secondary battery provided by the invention, optional one or more the mixture with above-mentioned organic solvent of electrolyte is as solvent.In addition, fluorinated ethylene carbonate (FEC) can add in electrolyte as additive, the addition of additive, be such as 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 enumerated 4, LiPF 6, LiBF 4, LiAsF 6, LiSbF 6, LiBOB (di-oxalate lithium borate), LiDFBO (LiODFB) etc.
As organic bath lithium salts, trifluoromethyl sulfonic acid lithium can be enumerated, two (trimethyl fluoride sulfonyl) imine lithium, three (trimethyl fluoride sulfonyl) lithium methide, two (catechol) borate lithium and two-[1,2-tetra-(trifluoromethyl) ethylene dioxy abutment (2-)-O-O '] lithium borate etc.
The supporting electrolyte of electrolyte can select one or more mixture of above-mentioned electrolyte lithium salt.The concentration of electrolyte lithium salt in organic electrolyte, such as, more than 0.3mol/L (mol/L) is preferred, more preferably more than 0.7mol/L, preferred below 1.7mol/L, more preferably below 1.2mol/L.When the concentration of electrolyte lithium salt is too low, ionic conduction is spent little, time too high, worries that failing to dissolve electrolytic salt completely separates out.
In nonaqueous electrolytic solution secondary battery provided by the invention, be not particularly limited for the barrier film that positive pole and negative pole are separated yet, the various barrier films adopted in existing known nonaqueous electrolytic solution secondary battery can be adopted.
Effect due to barrier film is separated by the both positive and negative polarity active material of battery, avoids any electron stream between both positive and negative polarity directly to pass through, avoid battery short circuit; When ion current passes through, resistance is little as far as possible, so mostly select apertured polymeric film.Such as, adopt the polyolefin resin such as polyethylene, polypropylene, or the pore barrier film that the polyester resin such as polybutylene terephthalate (PBT) is formed is preferred.In addition, these pore barrier films (pore film) also can overlappingly use.The film that above-mentioned polymer microporous film obtains after material surface modifying, the composite ceramics barrier film be coated on polyolefin as ceramic powder (aluminium oxide, silica etc.) also can use.
The thickness of barrier film is not particularly limited yet, but considers fail safe and high capacity two aspect of battery, be preferably 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 nonaqueous electrolytic solution secondary battery provided by the invention, such as, between aforementioned positive electrode and negative pole, to clamp after aforementioned barrier film in addition overlapping, make electrode layer laminate, reeled after making electrode coiling body, be filled in packaging body, the positive and negative electrode terminal of positive and negative electrode and packaging body is connected by lead body (lead wire) etc., then after aforementioned nonaqueous electrolytic solution is injected packaging body, sealed package and making.
As the packaging body of battery, the packaging bodies such as metal square, cylindrical shape can be adopted, or the layered product packaging body etc. formed by metal (aluminium etc.) laminated film.
Further, the manufacture method of nonaqueous electrolytic solution secondary battery and the structure of battery, be not particularly limited, and arrange positive pole, negative pole, barrier film and nonaqueous electrolytic solution in packaging body after, before battery seals completely, it is preferred for arranging the open formation process carrying out charging.
Like this, in the gas that produces of charging initial stage or battery, residual moisture can be removed to outside battery.
After carrying out above-mentioned open formation process, remove the method for electric pool gas, be not particularly limited, any one that nature removes or vacuum removes can be adopted.In addition, before battery seals completely, also can adopt the suitable forming battery such as extruding.Nano-silicon, conductive agent, dispersant and decentralized medium mixing dispersion is formed electrophoresis liquid by the present invention, nano-silicon and conductive agent will bring negative electrical charge in electrophoresis liquid, electrophoresis liquid is placed in reaction unit, and after energising, nano-silicon and conductive agent will deposit also self assembly on the working electrode (s and form the nano-silicon electrode possessing loose structure under electric field force effect.
The present invention adopts the method for electrophoretic deposition to carry out assembling design to nano-silicon, has successfully prepared Porous Silicon Electrode.The method without the need to or use binding agent on a small quantity, by the synthesis of material and assembling process one step, can be easy prepare the nano-silicon electrode possessing loose structure.Loose structure can alleviate the STRESS VARIATION that the volumetric expansion of silicon in lithiumation process is shunk, and reduces silicon powder; The silicon materials of nanoscale can accelerate the transmission speed of lithium ion, and this is all conducive to the cycle performance improving battery.
The present invention compared with prior art has following advantages:
1, the direct preparation that use the method can be easy is used as the electrode of lithium ion battery negative, the synthesis of material and number of assembling steps is united two into one, enormously simplify production technology.
2, use the electrode prepared of the method without the need to or use binding agent on a small quantity, the energy density of lithium ion battery can be improved.
3, the electrode that prepared by the present invention is cellular nano-silicon electrode.The nanoscale of loose structure and silicon grain is conducive to the cycle performance improving electrode.
Accompanying drawing explanation
Fig. 1 is reaction unit schematic diagram.
Fig. 2 is the SEM figure of the nano-silicon electrode possessing loose structure in embodiment 1.
Fig. 3 is that the EDX mapping of the nano-silicon electrode possessing loose structure in embodiment 1 schemes.
Fig. 4 is the electrochemistry cycle performance figure of the nano-silicon electrode possessing loose structure in embodiment 1.
Fig. 5 is the electrochemistry cycle performance figure of the nano-silicon electrode possessing loose structure in embodiment 2.
Fig. 6 is the electrochemistry cycle performance figure of the nano-silicon electrode adopting conventional application method to prepare in comparative example 1.
Embodiment
The invention provides a kind of preparation method possessing the silica-based lithium ion battery negative of loose structure.Make can to save in this way coating operation prepared by traditional electrode, without the need to or use binding agent on a small quantity, by the synthesis of material and being assembled into one, easy preparing possesses the nano-silicon electrode of loose structure.This nano-silicon electrode directly can be used as the negative pole of lithium ion battery, and has excellent cycle performance.Below in conjunction with drawings and Examples, technical scheme of the present invention is described further, but the present invention is not limited in these embodiments.In addition, for device used, be not particularly limited yet.
Fig. 1 provides reaction unit of the present invention.In FIG, the negative pole of power supply 1 is connected with to electrode 3, and the positive pole of power supply 1 is connected with to electrode 4, and mark 2 is electrophoresis liquid.
Embodiment 1:
Using 50mL acetone as decentralized medium, add 0.05g nano-silicon, 0.05g citric acid, 0.02g acetylene black.Ultrasonic disperse 20min obtains electrophoresis liquid.
Pt sheet (30mm × 30mm × 0.2mm), as to electrode, connects the negative pole of power supply; Copper Foil (20mm × 20mm × 0.01mm), as work electrode, connects the positive pole of power supply.Adopt DC voltage-stabilizing mode constant voltage 120V to take out Copper Foil to after electrophoresis liquid electrophoresis 5s, 80 DEG C of drying under reduced pressure 12h obtain porous nano silicon electrode.
Use scanning electron microscopy (HITACHI S-4800) to analyze the pattern of porous silicon nano-electrode, obtain Fig. 2.As can be seen from Figure 2, on electrode surface, nano-silicon is self-assembled into vesicular texture, and does not reunite.Carry out EDX mapping further and test to obtain Fig. 3.Nano-silicon and acetylene black are dispersed in Cu paper tinsel surface uniformly as can be seen from Figure 3, and acetylene black can serve as conductive network, ensure that nano-silicon is connected with electrochemistry good between copper foil of affluxion body.
Electrochemical property test:
Using porous nano silicon electrode obtained above as positive pole, lithium metal as negative pole, 1mol L -1liPF 6be dissolved in EC: DMC: EMC (1: 1: 1)+5%FEC as electrolyte, PP film is as barrier film, and glass fiber filter paper, as imbibition film, is assembled into 2016 button cells in the glove box being full of argon gas.
2016 button cells are carried out constant current charge-discharge test on the discharge and recharge instrument system of Xin Wei Instrument Ltd..Discharge cut-off voltage is 0.02V, and charge cutoff voltage is 1.5V, and current density is 0.1C.Obtain Fig. 4.The nano-silicon electrode cycle prepared by embodiment one method 50 weeks rear reversible capacities are 2315mAh/g, and capability retention is 69%.
Embodiment 2:
Preparation method is similar to embodiment 1, and just electrophoresis time becomes 15s.
The surface topography of electrode is similar to Example 1, but due to the increase of electrophoresis time, on Copper Foil, the loading of nano-silicon and acetylene black is by 0.25mg/cm 2increase to 0.46mg/cm 2.
Electro-chemical test is identical with embodiment one, obtains Fig. 5.The nano-silicon electrode cycle prepared by embodiment one method 50 weeks rear reversible capacities are 2276mAh/g, and capability retention is 68%.
Comparative example 1:
This comparative example adopts current known painting method assemble nanometer silicon electrode.Binder Composition is the hydrosol of the SBR+CMC (mass ratio 1: 1) containing 50%, and nano-silicon: acetylene black: binding agent=1: 1: 1, mixes form slurry.Slurry is coated on Copper Foil uniformly, and 80 DEG C of drying under reduced pressure 12h obtain the nano-silicon electrode adopting painting method structure.
Electrochemical property test:
Using the nano-silicon electrode of employing painting method obtained above structure as positive pole, lithium metal as negative pole, 1mol L -1liPF 6be dissolved in EC: DMC: EMC (1: 1: 1)+5%FEC as electrolyte, PP film is as barrier film, and glass fiber filter paper, as imbibition film, is assembled into 2016 button cells in the glove box being full of argon gas.
2016 button cells are carried out constant current charge-discharge test on the discharge and recharge instrument system of Xin Wei Instrument Ltd..Discharge cut-off voltage is 0.02V, and charge cutoff voltage is 1.5V, and current density is 0.1C.Obtain Fig. 6.The nano-silicon electrode cycle prepared by contrast one method 50 weeks rear reversible capacities are 1793mAh/g, and capability retention is 54%.
Comparative example 2:
This comparative example adopts electrophoretic deposition method assembling graphite electrode.Using 50mL acetone as decentralized medium, add 0.2g powdered graphite (mean particle diameter is 5 μm), 0.04g acetylene black.Ultrasonic disperse 20min obtains electrophoresis liquid.
Pt sheet (30mm × 30mm × 0.2mm), as to electrode, connects the negative pole of power supply; Copper Foil (20mm × 20mm × 0.01mm), as work electrode, connects the positive pole of power supply.Adopt DC voltage-stabilizing mode constant voltage 120V to take out Copper Foil to after electrophoresis liquid electrophoresis 120s, 80 DEG C of drying under reduced pressure 12h obtain graphite electrode.
Electrochemical property test:
Using graphite electrode obtained above as positive pole, lithium metal as negative pole, 1mol L -1liPF 6be dissolved in EC: DMC: EMC (1: 1: 1)+5%FEC as electrolyte, PP film is as barrier film, and glass fiber filter paper, as imbibition film, is assembled into 2016 button cells in the glove box being full of argon gas.
2016 button cells are carried out constant current charge-discharge test on the discharge and recharge instrument system of Xin Wei Instrument Ltd..Discharge cut-off voltage is 0.02V, and charge cutoff voltage is 1.5V, and current density is 0.1C.The nano-silicon electrode cycle prepared by comparative example two method 50 weeks rear reversible capacities are 290mAh/g, and capability retention is 95%.
The electrochemistry cycle performance of each embodiment of table 1 and comparative example
As can be seen from the statistics of table 1, the nano-silicon electrode the possessing loose structure nano-silicon electrode that reversible capacity and capability retention are assembled apparently higher than the known painting method of employing after 50 circle circulations of embodiment 1 and 2 employing electrophoretic deposition method assembling.Although the graphite electrode capability retention of the employing electrophoretic deposition assembling of comparative example 2 is higher, reversible capacity is far below embodiment 1 and 2.Illustrate that the nano-silicon electrode possessing loose structure adopting the present invention to prepare has excellent cycle performance and higher energy density.

Claims (10)

1. a preparation method for the nano silicon-based negative pole of lithium ion battery loose structure, is characterized in that its concrete steps are as follows:
1) nano-silicon, conductive agent, dispersant are placed in decentralized medium and are dispersed into electrophoresis liquid;
2) work electrode, electrode is connected with the both positive and negative polarity of power supply respectively, carry out electrophoretic deposition after energising, after drying under reduced pressure, obtain the nano silicon-based negative pole of lithium ion battery loose structure.
2. the preparation method of the nano silicon-based negative pole of a kind of lithium ion battery loose structure as claimed in claim 1, is characterized in that in step 1) in, described nano-silicon is crystal or amorphous state, and the diameter of nano-silicon is 10 ~ 500nm.
3. the preparation method of the nano silicon-based negative pole of a kind of lithium ion battery loose structure as claimed in claim 1, it is characterized in that in step 1) in, described conductive agent is material with carbon element, and described material with carbon element is selected from least one in carbon black conductive agent, graphite agent, carbon nano rod and Graphene; Described carbon black conductive agent can be selected from the one in acetylene black, Super P, Super S, 350G, carbon fiber, carbon nano-tube, Ketjen black, and described Ketjen black can be selected from the one in KetjenblackEC300J, KetjenblackEC600JD, Carbon ECP, Carbon ECP600JD; Described graphite agent can be selected from the one in KS-6, KS-15, SFG-6, SFG-15; Preferred acetylene black.
4. the preparation method of the nano silicon-based negative pole of a kind of lithium ion battery loose structure as claimed in claim 1, it is characterized in that in step 1) in, described dispersant is selected from least one in citric acid, policapram, polyacrylamide, ethyoxyl sodium alkyl sulfate, α-sodium olefin sulfonate, lauryl sodium sulfate, ethyoxyl alkyl ammonium sulfate, is preferably citric acid.
5. the preparation method of the nano silicon-based negative pole of a kind of lithium ion battery loose structure as claimed in claim 1, it is characterized in that in step 1) in, described decentralized medium is selected from water system or organic system, described organic system can be selected from least one in acetone, ethanol, acetylacetone,2,4-pentanedione, cyclohexane, isopropyl alcohol, acetic acid, carrene, methyl ethyl ketone, toluene, preferred acetone.
6. the preparation method of the nano silicon-based negative pole of a kind of lithium ion battery loose structure as claimed in claim 1, it is characterized in that in step 1) in, the mass ratio of described nano-silicon, conductive agent, dispersant is 1: (0.1 ~ 1): (0.5 ~ 5), is preferably 1: 0.4: 1; With 1L decentralized medium for benchmark, the mass concentration of nano-silicon can be 0.1 ~ 10g/L, preferred 1g/L, and the mass concentration of conductive agent can be 0.01 ~ 5g/L, preferred 0.4g/L, and the mass concentration of dispersant can be 0.1 ~ 10g/L, preferred 1g/L.
7. the preparation method of the nano silicon-based negative pole of a kind of lithium ion battery loose structure as claimed in claim 1, is characterized in that in step 1) in, described dispersion adopts the mode of mechanical agitation, magnetic agitation or ultrasonic oscillation to disperse.
8. the preparation method of the nano silicon-based negative pole of a kind of lithium ion battery loose structure as claimed in claim 1, is characterized in that in step 2) in, described power acquisition D.C. regulated power supply or pulse square wave power supply;
When adopting D.C. regulated power supply, electrophoretic voltage can be 5 ~ 1000V, and electrophoresis time can be 1 ~ 120s; Preferred electrophoretic voltage 50 ~ 300V, electrophoresis time 5 ~ 30s;
When adopting pulse square wave power supply, pulse voltage can be 5 ~ 1000V, and pulse duration can be 0.1 ~ 5s, and the pulse period can be 0.1 ~ 10s, and electrophoresis time can be 1 ~ 120s; Preferred pulse voltage is 50 ~ 400V, and pulse duration is 0.5 ~ 2s, and the pulse period is 1 ~ 4s, and electrophoresis time is 5 ~ 60s.
9. the preparation method of the nano silicon-based negative pole of a kind of lithium ion battery loose structure as claimed in claim 1, is characterized in that in step 2) in, described work electrode adopts conductive metal material work electrode or metal alloy electric conducting material work electrode; Described metal can be selected from least one in Al, Fe, Co, Ni, Cu, Zn, Ag, Pt, Au, preferably copper collector;
Described electrode to be not particularly limited, at least one in graphite, Al, Fe, Co, Ni, Cu, Zn, Ag, Pt, Au can be adopted, preferred graphite or platinum.
10. the preparation method of the nano silicon-based negative pole of a kind of lithium ion battery loose structure as claimed in claim 1, is characterized in that in step 2) in, the temperature of described drying under reduced pressure is 50 ~ 300 DEG C, preferably 80 DEG C.
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CN105161694A (en) * 2015-06-12 2015-12-16 南通彩都新能源科技有限公司 Preparation method for silicon-carbon-graphene composite negative electrode for lithium ion battery
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WO2020138313A1 (en) * 2018-12-26 2020-07-02 昭和電工株式会社 Composite particle for negative electrode of lithium ion secondary battery

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