CN103296262B - The preparation method of electrode composite material and electrode composite material - Google Patents
The preparation method of electrode composite material and electrode composite material Download PDFInfo
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- CN103296262B CN103296262B CN201310049648.3A CN201310049648A CN103296262B CN 103296262 B CN103296262 B CN 103296262B CN 201310049648 A CN201310049648 A CN 201310049648A CN 103296262 B CN103296262 B CN 103296262B
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Abstract
The present invention relates to the preparation method of a kind of electrode composite material and electrode composite material, described electrode composite material comprises silicon and silver, described silver is coated on the surface of described silicon, the electrode composite material that the preparation method disclosed by the present invention is obtained, in charge and discharge process, can be good at bearing the change of negative electrode volume and powder phenomenon-tion can not be produced, be coated on the silver with nanostructure of silicon face, further increase the conductivity of electrode composite material, the chemical property of electrode composite material is improved.In addition, the preparation method of electrode composite material is simple, and easily control, preparation method possesses industrial applications prospect.
Description
Technical field
The present invention relates to a kind of electrode composite material, particularly relate to a kind of containing silicon and silver-colored electrode composite material.
The invention still further relates to a kind of preparation method of electrode composite material.
Background technology
The mankind, to the extensive utilization of new forms of energy, cause increasing sharply to the demand of Large Copacity secondary cell, as: Aero-Space, medicine equipment, handheld electric products, electric automobile field all require to have large weight ratio capacity and or the battery of volume and capacity ratio.The development part of lithium ion battery technology meets the requirement in market, but never stops for the demand of more high-capacity battery.Lithium ion battery adopts graphitic carbon only to have 372mAhg as the theoretical specific capacity of negative pole
-1.
Therefore, people be devoted to study always there is higher lithium storage content negative material to replace lithium ion battery carbon back negative material.From energy capacity angle, elemental silicon weight ratio capacity is 3500mAhg
-1, volume and capacity ratio is 8500AhL
-1and far above other metals, nonmetallic materials.But, because silicon electronic conductivity is lower, the Li of multi phase state during battery charging simultaneously, can be generated at negative pole
xsi
yproduct, as: Li
12s
i7, Li
7si
3, Li
13si
4, Li
21si
5negative electrode volume is changed, the change of negative electrode volume is to negative material build-up of pressure, cause material reactant granule atomization and come off from negative current collector, having a strong impact on the cycle performance of battery, the silicon materials also hindered are as the application of lithium ion battery negative material.Therefore, much research is around alleviating the efflorescence of negative pole silicon materials and improving the structural stability expansion of silicon materials.
A kind of negative pole prepared by vapor-liquid-solid method is provided in WO2010129910A2, negative pole comprises negative current collector and is formed in the silicon nanowires of negative pole currect collecting surface vertically, silicon nanowires is attached to negative pole currect collecting surface, does not therefore need extra conductive agent and binding agent.Because silicon nanowires size is less, can bear change in volume in charge and discharge process and can not efflorescence, negative pole presents good chemical property.But, still there are some drawbacks in this invention: the gaseous reagent related in vapor-liquid-solid method is simultaneously also very expensive to human body danger close, negative current collector is formed in the process of silicon nanowires and needs Precious Metals-Gold to carry out catalysis.
Summary of the invention
The preparation method the invention provides that a kind of chemical property is good, processing technology is simple, being easy to the electrode composite material of industrialization.
The invention provides a kind of preparation method of electrode composite material, described electrode composite material comprises silicon and silver, and described silver is coated on described silicon, and described preparation method comprises the steps:
Reaction raw materials is inserted in reaction vessel, described reaction raw materials comprises fluosilicate and the metal as reducing agent, or magnesium metal and silicon dioxide, electrode insertion in described reaction vessel, described electrode comprises positive pole and negative pole, between described positive pole and negative pole, apply voltage; Heat under protective gas atmosphere and stir described reaction raw materials, after reaction raw materials to the first temperature described in continuous heating, the insulation scheduled time, cooling obtains reduzate, by also dry for described reduzate washing, obtains described silicon; Described silicon is obtained described electrode composite material by silver mirror reaction process.
Preferably, the voltage range be applied between described positive pole and negative pole is 2-12V.
Preferably, described just very silicon chip or graphite, described negative pole is silicon chip.
Preferably, described first temperature range is 140-200 DEG C.
Preferably, described silicon accounts for the scope of the percentage by weight of described electrode composite material is 70-95%.
Preferably, the weight ratio of described silicate and metal is 2.8:1 to 4:1.
Preferably, described fluosilicate is selected from potassium fluosilicate or prodan.
Preferably, described metal is selected from potassium or sodium.
Preferably, described silicon is carried out chemical corrosion or machinery coarse process acquisition loose structure.
Preferably, described drying is vacuumize or freeze drying.
Preferably, described protective gas is selected from argon gas or nitrogen.
Preferably, the step of described silver mirror reaction is: add ammoniacal liquor to containing in the aqueous solution of silver nitrate, the scope of the pH value of the described aqueous solution is made to be 8-10, add described silicon, 5% formaldehyde, stir after 0.5-3 hour, filter product, the product after filtering is dried, obtains described electrode composite material.
Present invention also offers a kind of electrode composite material, described electrode composite material comprises silicon and silver, and described silicon exists in granular form, and particle size range is 1-20 micron, and described silver is coated on the surface of described silicon.
Present invention also offers a kind of negative pole, comprise electrode composite material as above.
Present invention also offers a kind of battery, comprise positive pole, negative pole, electrolyte and collector, described electrolyte is located between described positive pole and negative pole, and described negative pole comprises electrode composite material as above.
A kind of electrode composite material provided by the invention, comprise silicon and silver, silicon has higher purity, in addition, on the surface of silicon, the silver of further clad nano structure makes the electric conductivity of electrode composite material be improved, and present invention also offers the method preparing this electrode composite material, preparation method's technique is simple, condition easily controls, and the electrode composite material preparing gained has good chemical property, and manufacturing process possesses industrial prospect.
Accompanying drawing explanation
Below in conjunction with drawings and embodiments, the invention will be further described.
Fig. 1 is the structural representation of the silicon of the three-dimensional structure containing intermediate porous in the present invention and the electrode composite material of silver;
Fig. 2 is the partial enlarged drawing in Fig. 1 shown in a;
Fig. 3 is the X ray diffracting spectrum of the polysilicon that embodiment 1-1 obtains.
Wherein:
1. electrode composite material 2. silver medal 3. silicon
Embodiment
Be applied to the electrode composite material in electrochemical appliance, electrochemical appliance includes but are not limited to battery.Apply the battery of this kind of electrode composite material, the fields such as such as portable electron device, electric tool, electric automobile can be applied to.
Electrode composite material comprises silicon and silver, and silver is coated on silicon, and silicon exists in granular form, and the size range of silicon grain is 1-20 micron, and average particle size particle size is 5 μm.In electrode composite material 1, the weight percentage ranges shared by silicon 3 is 70%-95%.
In order to optimize the performance of silicon further, can be processed by the silicon grain of acquisition, make it have loose structure by physics or chemical means, process means include but are not limited to coarse, the chemical corrosion of machinery.Silicon after process has the three-dimensional structure of intermediate porous, and the range of aperture size of silicon is 10nm-10 μm, and the average-size in aperture is 200nm.
Silver is coated on the surface of silicon with the form of particle and/or film by silver mirror reaction, the size of Argent grain can be nanoscale, and concrete scope is 5-500nm, and preferably, the granularity average-size of silicon grain is 50nm.Silicon grain can be the silicon ball of nano-scale, also can be the silicon grain of the nano-scale of other shape.Here the particle mean size of indication, includes but are not limited to the average diameter of particle, and for erose particle, the size of particle can refer to the maximum length of particle, width or height etc.Because the particle size of silver is little, flock together and can form film, final silver is coated on silicon in membrane form.
See also shown in Fig. 1 and Fig. 2, electrode composite material 1 comprises silicon 3 and silver 2, and silicon 3 has the three-dimensional structure of intermediate porous, and silver 2 has nano-scale, and the silver 2 of nano-scale is coated on the surface of silicon 3.
Electrode composite material 1 in the present invention, comprises silicon 3 and silver 2.On the one hand, can can optimize silicon 3 by physics or chemical means, make it have coarse surface or the three-dimensional structure of intermediate porous, when electrode composite material 1 is applied in the battery, silicon 3 better can bear change in volume during discharge and recharge, thus ensures that battery has stable cycle performance; On the other hand, the Surface coating of silicon 3 has the silver 2 of nanostructure, silver 2 is coated on the surface of silicon 3 with particulate form or granuloplastic film, silver 2 has excellent electric conductivity, therefore, be very significantly improved on electric conductivity than the simple electrode composite material containing silicon containing the electrode composite material 1 with the coated silicon 3 of silver 2.The present invention improves the electrode composite material 1 containing silicon 3 from form and electric conductivity two aspects, and electrode composite material has excellent chemical property.
Present invention further teaches the preparation method of electrode composite material, comprise the steps:
Inserted by reaction raw materials in reaction vessel, reaction raw materials comprises fluosilicate and the metal as reducing agent, or magnesium metal and silicon dioxide, electrode insertion in reaction vessel, and electrode comprises positive pole and negative pole, applies voltage between a positive electrode and a negative electrode; Heating also stirring reaction raw material under protective gas atmosphere, after continuous heating reaction raw materials to the first temperature, the insulation scheduled time, cooling obtains reduzate, is washed and drying by reduzate, obtains silicon; Silicon is obtained electrode composite material by silver mirror reaction process.
In a concrete execution mode, reaction raw materials comprises fluosilicate and the metal as reducing agent.
The purity of fluosilicate is 98%-100%, fluosilicate as one of reaction raw materials needs through super-dry process before inserting reaction vessel, mainly remove the water that may exist in fluosilicate, when containing a small amount of water in fluosilicate, can react with metal, thus produce unnecessary accessory substance, the temperature range of dry fluosilicate is 100-140 DEG C, drying time, scope was 1-12 hour, and dry run can be complete in vacuum drying chamber.Preferably, the purity grade of fluosilicate be at least analyze pure, to avoid the impurity introducing other in reaction system.Fluosilicate is the fluosilicate of IA race metallic element, and fluosilicate can be selected from solid prodan or anhydrous potassium fluosilicate.
As the metal of reducing agent for reducing fluosilicate, metal is IA race metallic element, is selected from sodium metal or metallic potassium.Preferably, the purity grade of metal is at least chemical pure.Preferred, the metallic element in fluosilicate is same with the Metal Phase as reducing agent.When the metallic element in fluosilicate and the Metal Phase as reducing agent while, reduction reaction is carried out more thoroughly and accessory substance is few, is conducive to the purification of polysilicon.In addition, when metal is potassium, when reacting with prodan, the temperature opposing metallic that reduction reaction occurs is sodium, low, therefore low to the requirement of consersion unit when being prodan of fluosilicate, but sodium metal is compared potassium and had cost advantage.
The scope of the weight ratio of fluosilicate and metal is 2.8:1 to 4:1.Fluosilicate is excessive a little relative to metal, so that with the fluosilicate that the unreacted in water-soluble solution reduzate is complete in subsequent purification process, reach the object of purified silicon, and when fluosilicate is too much, in purification process, required water amount is also many, therefore, preferably, the part by weight of the metal of fluosilicate and reducing agent is 3:1.In a specific embodiment, fluosilicate contains solid prodan, and metal contains sodium metal, and the reaction principle specifically preparing silicon is: 4Na+Na
2siF
6=Si+6NaF.
In order to optimize the performance of the silicon obtained by fluosilicate and metal further, by physics or chemical means, the silicon grain of acquisition can be processed, make it have loose structure, process means include but are not limited to coarse, the chemical corrosion of machinery, and the silicon after process has the three-dimensional structure of intermediate porous.
In another particular embodiment of the invention, reaction raw materials comprises magnesium metal and silicon dioxide.
Concrete, by SiO 2 powder ground and mixed in agate mortar of magnesium powder and porous, then the Dark grey colour mixture mixture obtained is inserted reaction vessel, magnesium-reduced silicon dioxide obtains the silicon of porous.
After reaction raw materials inserts reaction vessel, electrode insertion in reaction vessel, electrode comprises positive pole and negative pole, and the voltage range applied between a positive electrode and a negative electrode is 2-12V.Positive pole can be silicon chip or graphite flake, and negative pole can be silicon chip.Concrete applying voltage is between a positive electrode and a negative electrode different, the temperature that reduction reaction occurs is different, and in an embodiment, reaction raw materials is prodan and sodium metal, the voltage applied between a positive electrode and a negative electrode is 3.4V, and reduction reaction can occur at 170 DEG C; In another embodiment, the voltage applied between a positive electrode and a negative electrode is 3.7V, and reduction reaction can occur at 160 DEG C.
The preparation method of polysilicon provided by the invention, reaction raw materials addition of direct voltage, namely in reaction system, energy is provided, addition of electric work, according to Gibbs free energy law, burst into reversible work to system, open a kind of new reaction path, during energising, activation energy is lower than reaction activity when not being energized, reduce reaction and carry out completely required temperature, reduction reaction is carried out milder, optimize the process conditions preparing polysilicon, the requirement of consersion unit is reduced simultaneously, make the application of this preparation method in industrialization more feasible.
The present invention, by electrode insertion in reaction vessel, reaches the object providing electric energy to reaction system, thus optimizes the condition of reduction reaction generation, and any improvement based on this object of those skilled in the art all belongs within the scope of protection of present invention.
In reduction reaction process, in order to make reaction raw materials fully contact, reduction reaction is more complete, need to stir reaction raw materials, example, stirring-head can be added in reaction vessel, the concrete form of stirring-head is not limit, and can be mechanical agitation head or magnetic agitation head.
Reaction raw materials fluosilicate and the metal as reducing agent; or magnesium metal and silicon dioxide generation reduction reaction need be carried out under protective gas atmosphere; to avoid air, reaction is impacted; and produce unnecessary addition product; protective gas does not react with reducing metal, is selected from the one in nitrogen, argon gas.
Under protective gas atmosphere; reaction raw materials is heated; after in question response container, air drains; stir and continuous heating reaction raw materials to the first temperature; the scope of the first temperature is 140-200 DEG C; after temperature reaches the first temperature; the insulation scheduled time; object makes reduction reaction continue a period of time occurs, and scheduled time scope is 0.5-4 hour, in a specific embodiment; when reaction raw materials be sodium metal and prodan time; voltage is 3V, and remain in 165 DEG C of oil baths, reduction reaction can be carried out completely.Preparation method provided by the invention, owing to providing electric work to reduction reaction system, therefore makes reduction reaction can occur smoothly at a lower temperature, thus obtained required polysilicon, optimize the technique preparing polysilicon.
Because reduzate is not only containing silicon, therefore, in order to obtain highly purified silicon, needs to do purification processes further to reduzate, washing by reduzate.
Concrete, reduzate is used pure water, acid elution successively, dry after filtering, obtain that there is highly purified polysilicon.In purification process, preferably, the purity grade of acid is electronic pure, is selected from hydrofluoric acid, hydrochloric acid, at least one in sulfuric acid.Concrete selection gist is that under normal temperature, acid can be removed by the impurity of metallic reducing, as iron, calcium, magnesium, aluminium etc., but elemental silicon can not be caused to be oxidized, thus obtain high-purity silicon.Acid can be single acid, and also can be the mixing of several acid, mixed acid has stronger acidity relative to single acid, better to the dissolubility of impurity.
Because silicon easily surface oxidation occurs at middle high temperature, therefore during dry process silicon, temperature is unsuitable too high.Concrete, can by purified silicon vacuum drying treatment at 20 ~ 50 DEG C, time dry, vacuum degree is at least less than 0.5 Pascal, or adopts freeze drying, and baking temperature is less than 25 DEG C, to reduce silicon surface oxidation.
In a particular embodiment, the step of silver mirror reaction is: add ammoniacal liquor to containing in the aqueous solution of silver nitrate, the scope of the pH value of the aqueous solution is made to be 8-10, add silicon, 5% formaldehyde, stir after 0.5-3 hour, filter product, the product after filtering is dried, obtains electrode composite material.
Electrode composite material preparation method provided by the invention, reaction raw materials addition of voltage, reduce the temperature needed for reaction raw materials generation reduction reaction, not only avoid high temperature energy consumption, but also the requirement reduced reaction vessel, preparation method's industrial applications prospect of the electrode composite material that the present invention discloses is more objective.
One with prodan and sodium metal for raw material is prepared in the execution mode of electrode composite material, reaction raw materials prodan and sodium metal are weighed, inserting to send out answers in container, top electrode and stirring-head is added in reaction vessel, electrode comprises positive pole and negative pole, just very graphite, negative pole is silicon chip, pass into nitrogen to get rid of air wherein to sending out to answer in container, heating reaction raw materials to 100 DEG C, starts stirring-head, continue heating reaction raw materials subsequently to 160 DEG C, be incubated and carry out reduction reaction in 2 hours, obtain reduzate, cooling.Because reduzate is not only containing silicon, therefore need to carry out purification processes to reduzate, concrete purification step is: adopt pure water reduzate for several times, vacuum filtration, the product obtained after suction filtration is washed for several times by the hydrochloric acid of electronic pure rank, the product after washing is dried and obtained silicon.
One with magnesium metal and porous silica for raw material is prepared in the execution mode of electrode composite material, by SiO 2 powder ground and mixed in mortar of magnesium powder and porous, inserting to send out answers in container, top electrode and stirring-head is added in reaction vessel, electrode comprises positive pole and negative pole, just very silicon chip, negative pole is silicon chip, nitrogen is passed into get rid of air wherein to sending out to answer in container, heating reaction raw materials to 160 DEG C, be incubated and carry out reduction reaction in 2 hours, obtain reduzate, cooling, reduzate is washed with HCl and HF of 1M successively, last to be washed by ethanol again and vacuumize 10h obtains the silicon of porous at 80 DEG C.
By the silicon obtained further by silver mirror reaction process thus the coated silver with nanostructure.In the execution mode of the silver of concrete clad nano structure, silver nitrate is dissolved in the pure water of 200mL, adding several ammoniacal liquor regulates the pH value of solution to be 9.6, add silicon, the formaldehyde of 5%, vigorous stirring filtered product after 2 hours, and by the product vacuumize 12 hours at 60 DEG C after filtering, obtained containing silicon and silver-colored electrode composite material.
By the electrode composite material containing silicon and silver that preparation method provided by the invention obtains, further, by chemical corrosion or the coarse silicon that makes of machinery, there is loose structure, the argent of nanostructure is coated on the surface of silicon with particulate form or granuloplastic film, silicon is in battery charge and discharge process, silver due to electronics good conductor is coated on the surface of silicon and the surface in hole, electronic energy is made to pass to silicon fast, carry out electrochemical reaction, because this reducing the interface impedance of electrode composite material, improve the chemical property of electrode composite material.In addition, electrode composite material has loose structure, can have when charge and discharge process brings the change in volume of electrode composite material and well play cushioning effect, electrode composite material can not be subsided or efflorescence, improve the cycle life of electrode composite material.The preparation method of electrode composite material is simple simultaneously, easily controls, possesses industrialization potential.
By the electrode composite material that preparation method of the present invention obtains, can negative material be used as, further, the battery that negative pole contains this negative material can be prepared.
Negative pole comprises negative material and negative current collector, and negative material contains the electrode composite material comprising silicon and silver.Specifically preparing in the execution mode of negative pole, by negative material, conductive agent, binding agent mixes according to a certain percentage, adds dispersant, fully obtained cathode size after mixing.Dispersant includes but not limited to organic solvent, and organic solvent comprises 1-METHYLPYRROLIDONE, ethanol or acetone.By cathode size by any suitable mode, as scraper for coating technology, the modes such as spin coating, are coated on negative current collector also dry uniformly, obtain negative pole.Wherein, in negative material, conductive agent and binding agent, the weight percentage ranges shared by negative material is 70%-90%, and in a specific embodiment, the content of negative material is 70%.
Conductive agent be selected from conducting polymer, active carbon, Graphene, carbon black, carbon fiber, metallic fiber, metal dust and sheet metal one or more.In preferably execution mode, conductive agent comprises section's qin carbon black (KB).
Binding agent is selected from polyethylene oxide, polypropylene oxide, the mixture of a kind of or above-mentioned polymer in polyacrylonitrile, polyimides, polyester, polyethers, fluorinated polymer, polyvinylidene base polyethylene glycol, polyethyleneglycol diacrylate, glycol dimethacrylates and derivative.
The material of negative current collector includes but are not limited to the one in nickel foam, aluminium foil, Copper Foil, stainless steel foil.In a preferred embodiment, negative current collector is nickel foam.
The positive pole of battery comprises positive electrode and plus plate current-collecting body, and positive electrode comprises positive electrode active materials, conductive agent and binding agent.
Positive electrode active materials participates in electrochemical reaction, and can reversible deviate from-embedded ion or functional group.Preferably, lithium ion, sodium ion or magnesium ion can deviate from-embedded to positive electrode active materials reversiblely.
Positive electrode active materials of the present invention be lithium ion deviate from-inlaid scheme time, can select as LiMn
2o
4, LiFePO
4, LiCoO
2, LiM
xpO
4, LiM
xsiO
ycompounds such as (wherein M are a kind of variable valency metal).In addition, the compound N aVPO of sodium ion can be deviate from-embed
4f, can deviate from-embed the compound Mg M of magnesium ion
xo
y(wherein M is a kind of metal, 0.5<x<3,2<y<6) and there is similar functions, can deviate from-compound of embedded ion or functional group can as the positive pole positive electrode active materials of battery of the present invention.
Preferred, positive electrode active materials comprises sulfenyl material, and sulfenyl material accounts for the 70-90% of positive electrode active materials total weight.Sulfenyl material is selected from elementary sulfur, Li
2s
n, organic sulfur compound and carbon-sulfur polymer (C
2s
v)
min at least one, wherein, n>=1,2.5≤v≤50, m>=2.
In order to ensure in charge and discharge process, the lithium ion can deviate from-embed is there is between the positive pole of battery and negative pole, when the positive electrode selected and negative material be not simultaneously containing the ion can deviate from-embed or functional group, the process carrying out ion or the functional group's lithium embedding can deviate from-embed is needed to positive pole and/or negative pole.Concrete embedded mode is not limit, and comprises chemical reaction and embeds or electrochemical reaction embedding.
Electrolyte at least comprises electrolyte lithium salt and organic solvent.Electrolyte comprises anodolyte and catholyte.
Lithium salts can include but are not limited to LiPF
6, LiBF
4, LiClO
4, Li (CF
3sO
2)
2, LiCF
3sO
2, LiC (CF
3sO
2)
3with LiN (C
2f
5sO
2)
2in at least one.Art is known, and the lithium salts of debita spissitudo can effectively increase electrolytical ionic conductivity.
Organic solvent can be common organic aqueous solution, as dimethoxy-ethane (DME), ethene carbonic ether (EC), dimethyl carbonate (DMC), carbovinate fat (DEC), propylene carbonate (PC), 1,3-dioxolane (DIOX), ether, glyme, lactone, sulfone, sulfolane or more mixture; Organic solvent can be also polymer, as polyacrylonitrile; Also gel can be comprised, as gelatin polymer (PEGMEMA1100-BMI).If adopt this electrolyte of gel, because itself is a kind of soft material, certain distortion can occur, therefore can not there is too large change in the manufacture craft of corresponding battery.Certainly, also solid polymer electrolyte can be adopted, such as Li
2s-P
2s
5glass-ceramic, or P (EO)
20li (CF
3sO
2)
2n-10wt.% γ-LiAlO
2.
When electrolyte is liquid, prepare battery also to need to use barrier film, barrier film is arranged between positive pole and negative pole, can be the non-conducting of a kind of solid or Ins. ulative material, positive pole and negative pole are separated and makes both mutually insulateds, thus prevent internal short-circuit of battery, and barrier film can allow ion to transmit between a positive electrode and a negative electrode.Barrier film can be selected from but be not limited to the one in glass fibre, polyester, polyethylene, polypropylene, polytetrafluoroethylene.
The form of battery includes but are not limited to the tabletting structure in field of batteries, also comprises common button cell, cylindrical battery or plate-type battery.
Although done detailed elaboration and citing to technical scheme of the present invention above; for a person skilled in the art; on the basis not departing from essence of the present invention, above-described embodiment to be modified and/or flexible or adopt similar replacement scheme, also in protection scope of the present invention.
Below by execution mode, the present invention is further described.
Embodiment 1-1
Weigh reaction raw materials prodan and sodium metal according to weight ratio 3:1, reaction raw materials is inserted in three mouthfuls of clean vials, pass into N
2get rid of the air in bottle, electrode and stirring-head is added in bottle, electrode comprises positive pole and negative pole, positive pole and negative pole are all silicon chip, and additional direct voltage is between a positive electrode and a negative electrode 3.7V, and heating reaction raw materials to 100 DEG C also starts stirring, continue heating reaction raw materials to the first temperature 160 DEG C subsequently, be incubated 2 hours, stop stirring, be cooled to room temperature.The reduzate of gained is proceeded to the clean beaker that pure water is housed, washing vacuum filtration, by the pure water 3 times of the product after suction filtration, then wash also vacuum filtration further with electronics pure hydrochloric acid, finally vacuumize 12 hours at 60 DEG C.
Weigh silver nitrate 0.078g to dissolve in 200mL pure water, add several ammoniacal liquor and regulate solution PH to be 9.6, then add the silica flour of 0.24g synthesis, dropwise add 5% formaldehyde 0.4mL, stir after 2 hours and filter, the product obtained after filtration is dried, obtain the electrode composite material containing silicon and silver.
Fig. 3 is the X ray diffracting spectrum of the polysilicon that embodiment 1-1 obtains.The purity of display silicon is analyzed 99.9999% eventually through ICP-Mass.
Embodiment 1-2
In embodiment 1-2, electrode auxiliary voltage is 3.4V, and the first corresponding temperature is 170 DEG C, and all the other preparation methods are with embodiment 1-1.
Embodiment 1-3
In embodiment 1-3, electrode auxiliary voltage is 3V, and the first corresponding temperature is 165 DEG C, and all the other preparation methods are with embodiment 1-1.
Embodiment 1-4
In embodiment 1-4, electrode auxiliary voltage is 2V, and the first corresponding temperature is 200 DEG C, and all the other preparation methods are with embodiment 1-1.
Embodiment 1-5
In embodiment 1-5, electrode auxiliary voltage is 12V, and the first corresponding temperature is 140 DEG C, and all the other preparation methods are with embodiment 1-1.
Change the auxiliary voltage of electrode in embodiment 1-2 to 1-5, simultaneously corresponding change the first temperature, reduction reaction all can occur, and the electrode composite material of final obtained tool silver coated Si.
Embodiment 2-1
Electrode composite material, binding agent PVDF, conductive agent AC are mixed with 7:1:2, add solvent NMP and stir 12 hours, be coated in nickel foam, 120 DEG C time, vacuumize was cooled to room temperature after 4 hours, was cut into the disk of diameter 14mm subsequently, obtained negative pole.Take lithium metal as positive pole, porous polypropylene is barrier film, 1mol/LLiPF
6the mixed solution of EC, DMC and DEC (volume ratio 1:1:1) be electrolyte, in the glove box being full of argon gas, be assembled into CR2032 button cell.
Claims (6)
1. a preparation method for electrode composite material, described electrode composite material comprises silicon and silver, and described silver is coated on described silicon, it is characterized in that: described preparation method comprises the steps:
Reaction raw materials is inserted in reaction vessel, described reaction raw materials comprises fluosilicate and the metal as reducing agent, or magnesium metal and silicon dioxide, electrode insertion in described reaction vessel, described electrode comprises positive pole and negative pole, between described positive pole and negative pole, apply voltage, the voltage range be applied between described positive pole and negative pole is 2-12V; Heat under protective gas atmosphere and stir described reaction raw materials, after reaction raw materials to the first temperature described in continuous heating, the insulation scheduled time, cooling obtains reduzate, by also dry for described reduzate washing, obtains described silicon; Described first temperature range is 140-200 DEG C;
Described silicon is obtained described electrode composite material by silver mirror reaction process.
2. preparation method according to claim 1, is characterized in that: described just very silicon chip or graphite, and described negative pole is silicon chip.
3. preparation method according to claim 1, is characterized in that: described fluosilicate is selected from potassium fluosilicate or prodan.
4. preparation method according to claim 1, is characterized in that: described metal is selected from potassium or sodium.
5. preparation method according to claim 1, is characterized in that: described silicon is carried out chemical corrosion or machinery coarse process acquisition loose structure.
6. preparation method according to claim 1, it is characterized in that: the step of described silver mirror reaction is: add ammoniacal liquor to containing in the aqueous solution of silver nitrate, the scope of the pH value of the described aqueous solution is made to be 8-10, add described silicon, 5% formaldehyde, stir after 0.5-3 hour, filter product, the product after filtering is dried, obtains described electrode composite material.
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| US4597948A (en) * | 1982-12-27 | 1986-07-01 | Sri International | Apparatus for obtaining silicon from fluosilicic acid |
| US4642228A (en) * | 1985-07-24 | 1987-02-10 | Angel Sanjurjo | Fluxing system for reactors for production of silicon |
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| Novel Three-Dimensional Mesoporous Silicon for High Power Lithium-Ion Battery Anode Material;Haiping Jia等;《Advanced Energy Materials》;20111006;第1卷(第6期);第1036～1039页 * |
| Reversible Storage of Lithium in Silver-Coated Three-Dimensional Macroporous Silicon;Yan Yu等;《Advanced Materials》;20100330;第22卷(第20期);第2247～2250页 * |
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