CN103296262A - Electrode composite material and preparation method of the same - Google Patents
Electrode composite material and preparation method of the same Download PDFInfo
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- CN103296262A CN103296262A CN2013100496483A CN201310049648A CN103296262A CN 103296262 A CN103296262 A CN 103296262A CN 2013100496483 A CN2013100496483 A CN 2013100496483A CN 201310049648 A CN201310049648 A CN 201310049648A CN 103296262 A CN103296262 A CN 103296262A
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Abstract
The invention relates to an electrode composite material and a preparation method of the same. The electrode composite material comprises silicon and silver, which covers the surface of the silicon. The electrode composite material obtained by the preparation method disclosed in the invention can well bear the cathode volume change without generating powdering phenomenon in a charge-discharge process. The nano-structured silver coating the silicon surface further enhances the conductivity of the electrode composite material, thus improving the electrochemical performance of the electrode composite material. In addition, the preparation method of the electrode composite material is simple, and is easy to control, thus having industrialized application prospects.
Description
Technical field
The present invention relates to a kind of electrode composite material, relate in particular to a kind of electrode composite material that contains silicon and silver.
The invention still further relates to a kind of preparation method of electrode composite material.
Background technology
Human extensive utilization to new forms of energy causes the demand of big capacity secondary battery is increased sharply, as: Aero-Space, medicine equipment, handheld electronic product, electric automobile field all require to have big weight ratio capacity and or the battery of volume and capacity ratio.The requirement in market has partly been satisfied in the development of lithium-ion electric pool technology, but never stops for the demand of high-capacity battery more.Lithium ion battery adopts graphitic carbon as the theoretical specific capacity of negative pole 372mAhg only to be arranged
-1
Therefore, people are devoted to study the negative material with higher lithium storage content always and replace lithium ion battery carbon back negative material.From the energy capacity angle, the elemental silicon weight ratio capacity is 3500mAhg
-1, volume and capacity ratio is 8500AhL
-1And far above other metals, nonmetallic materials.Yet, because the silicon electronic conductivity is lower, can generate the Li of multi phase state simultaneously during battery charge at negative pole
xSi
yProduct, as: Li
12S
I7, Li
7Si
3, Li
13Si
4, Li
21Si
5Make the negative pole volume change, the negative material build-up of pressure is given in the variation of negative pole volume, cause the particle efflorescence of material reactant and come off from negative current collector, have a strong impact on the cycle performance of battery, also the silicon materials of Zu Aiing are as the application of lithium ion battery negative material.Therefore, many researchs launch around the structural stability of the efflorescence that alleviates the negative pole silicon materials and raising silicon materials.
A kind of negative pole by the vapor-liquid-solid method preparation is provided among the WO2010129910A2, negative pole comprises negative current collector and the silicon nanowires that is formed on the negative pole currect collecting surface vertically, silicon nanowires is attached to the negative pole currect collecting surface, does not therefore need extra conductive agent and binding agent.Because the silicon nanowires size is less, can bear in the charge and discharge process change in volume and can efflorescence, negative pole presents better electrochemical performance.But still have some drawbacks in this invention: the gaseous reagent that relates in the vapor-liquid-solid method is also very expensive simultaneously to the human body danger close, needs Precious Metals-Gold to come catalysis in the process of negative current collector formation silicon nanowires.
Summary of the invention
The preparation method who the invention provides that a kind of chemical property is good, processing technology is simple, is 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 the described silicon, and described preparation method comprises the steps:
Reaction raw materials is inserted in the reaction vessel, described reaction raw materials comprises fluosilicate and as the metal of reducing agent, or magnesium metal and silicon dioxide, inserts electrode in described reaction vessel, described electrode comprises positive pole and negative pole, applies voltage between described positive pole and negative pole; Heating and stir described reaction raw materials under the protective gas atmosphere, continue described reaction raw materials to the first temperature of heating after, the insulation scheduled time, cooling obtains reduzate, with described reduzate washing and dry, obtains described silicon; Described silicon is handled the described electrode composite material of acquisition by silver mirror reaction.
Preferably, the voltage range that is applied between described positive pole and the negative pole is 2-12V.
Preferably, described just very silicon chip or graphite, described negative pole are silicon chip.
Preferably, described first temperature range is 140-200 ℃.
Preferably, to account for the scope of the percentage by weight of described electrode composite material be 70-95% to described silicon.
Preferably, the weight ratio scope 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 mechanical coarse processing 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 in the aqueous solution that contains silver nitrate, the scope that makes described pH value of aqueous solution is 8-10, add described silicon, 5% formaldehyde, stir after 0.5-3 hour, the filtering reaction product, the product oven dry with after filtering obtains described electrode composite material.
The present invention also provides a kind of electrode composite material, and described electrode composite material comprises silicon and silver, and described silicon exists with particle form, and particle size range is the 1-20 micron, and described silver is coated on the surface of described silicon.
The present invention also provides a kind of negative pole, comprises aforesaid electrode composite material.
The present invention also provides a kind of battery, comprises positive pole, negative pole, electrolyte and collector, and described electrolyte is located between described positive pole and the negative pole, and described negative pole comprises aforesaid electrode composite material.
A kind of electrode composite material provided by the invention, comprise silicon and silver, silicon has higher purity, in addition, further the silver of clad nano structure makes the electric conductivity of electrode composite material be improved on the surface of silicon, and the present invention also provides the method for preparing the kind electrode composite material, preparation method's technology is simple, condition is controlled easily, and the electrode composite material of preparation gained has good electrochemical, and manufacturing process possesses industrial prospect.
Description of drawings
The invention will be further described below in conjunction with drawings and embodiments.
Fig. 1 is the silicon of the three-dimensional structure of porous in the middle of containing among the present invention and the structural representation of the electrode composite material of silver;
Fig. 2 is the partial enlarged drawing shown in a among Fig. 1;
Fig. 3 is the X ray diffracting spectrum of the polysilicon that makes of embodiment 1-1.
Wherein:
1. electrode composite material 2. silver medals 3. silicon
Embodiment
A kind of electrode composite material that is applied in the electrochemical appliance, electrochemical appliance includes but are not limited to battery.Use the battery of this kind electrode composite material, can be applied to such as fields such as portable electron device, electric tool, electric automobiles.
Electrode composite material comprises silicon and silver, and silver is coated on the silicon, and silicon exists with particle form, and the size range of silicon grain is the 1-20 micron, and average particle size particle size is 5 μ m.In electrode composite material 1, silicon 3 shared weight percentage ranges are 70%-95%.
In order further to optimize the performance of silicon, can the silicon grain that obtain be handled by physics or chemical means, make it have loose structure, the processing means include but are not limited to coarse, the chemical corrosion of machinery.Silicon after the processing has the three-dimensional structure of middle porous, and the range of aperture size of silicon is 10nm-10 μ m, and the average-size in aperture is 200nm.
Silver is coated on the surface of silicon by silver mirror reaction with the form of particle and/or film, and the size of silver-colored particle can be nanoscale, and concrete scope is 5-500nm, and preferred, 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 maximum length, width or the height etc. of particle.Because the particle size of silver is little, flocking together to form film, and final silver is coated on the silicon with the form of film.
See also illustrated in figures 1 and 2ly, electrode composite material 1 comprises silicon 3 and silver 2, and silicon 3 has the three-dimensional structure of middle porous, and silver-colored 2 have nano-scale, and the silver 2 of nano-scale is coated on the surface of silicon 3.
Electrode composite material 1 among 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 middle porous, when electrode composite material 1 is applied in the battery, silicon 3 can better bear the change in volume when discharging and recharging, thereby guarantees that battery has stable cycle performance; On the other hand, surface at silicon 3 coats the silver 2 with nanostructure, silver 2 is coated on the surface of silicon 3 with particulate form or granuloplastic film, silver 2 has excellent electric conductivity, therefore, contain the electrode composite material 1 with silver-colored 2 silicon 3 that coat and obtain very big improvement than the electrode composite material that contains silicon merely at electric conductivity.The present invention improves the electrode composite material 1 that contains silicon 3 from form and two aspects of electric conductivity, and electrode composite material has excellent chemical property.
The present invention has also disclosed the preparation method of electrode composite material, comprises the steps:
Reaction raw materials is inserted in the reaction vessel, and reaction raw materials comprises fluosilicate and as the metal of reducing agent, or magnesium metal and silicon dioxide, inserts electrode in reaction vessel, and electrode comprises positive pole and negative pole, applies voltage between positive pole and negative pole; Heating and stirring reaction raw material under the protective gas atmosphere, after continuing to heat reaction raw materials to the first temperature, the insulation scheduled time, cooling obtains reduzate, with reduzate washing and drying, obtains silicon; Silicon is handled the acquisition electrode composite material by silver mirror reaction.
In a concrete execution mode, reaction raw materials comprises fluosilicate and as the metal of reducing agent.
The purity of fluosilicate is 98%-100%, fluosilicate as one of reaction raw materials needs to handle through super-dry before inserting reaction vessel, mainly be to remove the water that may exist in the fluosilicate, when containing low amounts of water in the fluosilicate, can react with metal, thereby produce unnecessary accessory substance, the temperature range of dry fluosilicate is 100-140 ℃, drying time, scope was 1-12 hour, and dry run can be to finish in vacuum drying chamber.Preferably, it is pure that the purity grade of fluosilicate is at least analysis, to avoid introducing other impurity in reaction system.Fluosilicate is the fluosilicate of IA family metallic element, and fluosilicate can be selected from solid prodan or anhydrous potassium fluosilicate.
Metal as reducing agent is used for the reduction fluosilicate, and metal is IA family 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 the fluosilicate is identical with metal as reducing agent.When the metallic element in the fluosilicate when identical as the metal of reducing agent, reduction reaction carry out more thoroughly and accessory substance few, be conducive to the purification of polysilicon.In addition, when metal is potassium, when reacting with prodan, the relative metal of temperature that reduction reaction takes place is sodium, low, therefore low to the requirement of consersion unit when fluosilicate is prodan, 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 with respect to metal, so that the intact fluosilicate of the unreacted in the water dissolving and reducing product in the follow-up purification process, reach the purpose of purified silicon, and when fluosilicate is too much, the required water amount is also many in the purification process, therefore, preferred, the part by weight of the metal of fluosilicate and reducing agent is 3:1.In embodiment, fluosilicate contains the solid prodan, and metal contains sodium metal, and the reaction principle that specifically prepares silicon is: 4Na+Na
2SiF
6=Si+6NaF.
In order further to optimize the performance of the silicon that makes by fluosilicate and metal, can the silicon grain that obtain be handled by physics or chemical means, make it have loose structure, the processing means include but are not limited to coarse, the chemical corrosion of machinery, and the silicon after the processing has the three-dimensional structure of middle porous.
In another concrete execution mode, reaction raw materials comprises magnesium metal and silicon dioxide.
Concrete, with SiO 2 powder ground and mixed in agate mortar of magnesium powder and porous, then the Dark grey colour mixture mixture that obtains is inserted reaction vessel, magnesium-reduced silicon dioxide obtains the silicon of porous.
After reaction raw materials is inserted reaction vessel, in reaction vessel, insert electrode, electrode comprises positive pole and negative pole, the voltage range that is applied between positive pole and the negative pole is 2-12V.Positive pole can be silicon chip or graphite flake, and negative pole can be silicon chip.Specifically be applied to the voltage difference between positive pole and the negative pole, the temperature that reduction reaction takes place is different, and in an embodiment, reaction raw materials is prodan and sodium metal, the voltage that is applied between positive pole and the negative pole is 3.4V, and reduction reaction can take place under 170 ℃; In another embodiment, the voltage that is applied between positive pole and the negative pole is 3.7V, and reduction reaction can take place under 160 ℃.
Preparation method of polycrystalline silicon provided by the invention, added direct voltage at reaction raw materials, namely in reaction system, provide energy, added electric work, according to the Gibbs free energy law, burst into reversible work to system, opened up a kind of new reaction path, reduction reaction activation energy reaction activity when not switching on is low during energising, reduced reaction and carried out required temperature fully, it is milder that reduction reaction is carried out, and optimized the process conditions of preparation polysilicon, requirement to consersion unit simultaneously reduces, and makes that the application of this preparation method in industrialization is more feasible.
The present invention reaches the purpose that electric energy is provided to reaction system by insert electrode in reaction vessel, thereby optimizes the condition that reduction reaction takes place, and any improvement based on this purpose of those skilled in the art all belongs within the scope of protection of present invention.
In the reduction reaction process, fully contact in order to make reaction raw materials, reduction reaction is more complete, need stir reaction raw materials, example, can in reaction vessel, add stirring-head, the concrete form of stirring-head is not limit, and can be mechanical agitation head or magnetic agitation head.
The reaction raw materials fluosilicate with as the metal of reducing agent; or magnesium metal and silicon dioxide generation reduction reaction need carry out under the protective gas atmosphere; to avoid air that reaction is impacted; and produce unnecessary addition product; protective gas does not react with reducing metal, is selected from a kind of in nitrogen, the argon gas.
Under the protective gas atmosphere; reaction raw materials is heated; after air drains in the question response container; stir and lasting heating reaction raw materials to the first temperature; the scope of first temperature is 140-200 ℃; after temperature reaches first temperature; the insulation scheduled time; purpose is to make reduction reaction continue to take place a period of time, and scheduled time scope is 0.5-4 hour, in embodiment; when reaction raw materials is sodium metal and prodan; voltage is 3V, remains in 165 ℃ of oil baths, and reduction reaction can be carried out fully.Preparation method provided by the invention owing to provide electric work to the reduction reaction system, therefore makes reduction reaction can take place smoothly under lower temperature, thereby makes required polysilicon, has optimized the technology of preparation polysilicon.
Because reduzate not only contains silicon, therefore, in order to obtain highly purified silicon, need further do purification processes to reduzate, be about to reduzate and wash.
Concrete, reduzate is used pure water, acid elution successively, filter the back drying, obtain having high-purity polycrystalline.In purification process, preferred, the purity grade of acid is that electronics is pure, is selected from hydrofluoric acid, hydrochloric acid, at least a in the sulfuric acid.The concrete selection as iron, calcium, magnesium, aluminium etc., but can not cause the elemental silicon oxidation, thereby obtain high-purity silicon according to being that acid can be removed by the impurity of metallic reducing under the normal temperature.Acid can be single acid, also can be the mixing of several acid, and mixed acid has stronger acidity with respect to single acid, and is better to the dissolubility of impurity.
Because silicon at middle high temperature surface oxidation takes place easily, temperature was unsuitable too high when therefore drying was handled silicon.Concrete, can be with the silicon of purifying 20 ~ 50 ℃ of following vacuum drying treatment, when dry vacuum degree at least less than 0.5 Pascal, or employing freeze drying, baking temperature is less than 25 ℃, with the minimizing silicon surface oxidation.
In concrete execution mode, the step of silver mirror reaction is: add ammoniacal liquor in the aqueous solution that contains silver nitrate, the scope that makes pH value of aqueous solution is 8-10, add silicon, 5% formaldehyde, stir after 0.5-3 hour, the filtering reaction product, the product oven dry with after filtering obtains electrode composite material.
Electrode composite material preparation method provided by the invention, added voltage at reaction raw materials, reduced the required temperature of reaction raw materials generation reduction reaction, not only avoided the high temperature energy consumption, but also having reduced requirement to reaction vessel, preparation method's industrial applications prospect of the electrode composite material that the present invention discloses is more objective.
Be in the execution mode of feedstock production electrode composite material at one with prodan and sodium metal, reaction raw materials prodan and sodium metal are weighed, insert to send out and answer in the container, in reaction vessel, add top electrode and stirring-head, electrode comprises positive pole and negative pole, graphite just very, negative pole is silicon chip, feed nitrogen in the container getting rid of air wherein to sending out to answer, heating reaction raw materials to 100 ℃ starts stirring-head, continue heating reaction raw materials to 160 ℃ subsequently, be incubated 2 hours and carry out reduction reaction, obtain reduzate, cooling.Because reduzate not only contains silicon, therefore need carry out purification processes to reduzate, concrete purification step is: adopt pure water washing reduzate for several times, vacuum filtration, the product that obtains behind the suction filtration is washed for several times by pure other hydrochloric acid of level of electronics, the oven dry of the product after the washing is namely got silicon.
Be in the execution mode of feedstock production electrode composite material at one with magnesium metal and porous silica, SiO 2 powder ground and mixed in mortar with magnesium powder and porous, insert to send out and answer in the container, in reaction vessel, add top electrode and stirring-head, electrode comprises positive pole and negative pole, silicon chip just very, negative pole is silicon chip, feed nitrogen in the container getting rid of air wherein to sending out to answer, heating reaction raw materials to 160 ℃ is incubated 2 hours and carries out reduction reaction, obtain reduzate, cooling successively with HCl and the HF washing of 1M, washs and obtains at 80 ℃ of following vacuumize 10h the silicon of porous with reduzate at last again by ethanol.
Thereby the silicon that obtains is further handled the silver that coating has nanostructure by silver mirror reaction.In the execution mode of the silver of concrete clad nano structure, silver nitrate is dissolved in the pure water of 200mL, the pH value that adds several ammoniacal liquor regulator solutions is 9.6, add silicon, 5% formaldehyde, vigorous stirring is the filtering reaction product after 2 hours, and the product after will filtering obtains containing the electrode composite material of silicon and silver 60 ℃ of following vacuumizes 12 hours.
The electrode composite material that contains silicon and silver by preparation method's acquisition provided by the invention, further, has loose structure by chemical corrosion or the coarse silicon that makes of machinery, 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, because the silver of electronics good conductor is coated on the surface of silicon and the surface in hole, make electronic energy pass to silicon fast, carry out electrochemical reaction, therefore reduce the interface impedance of electrode composite material, improved the chemical property of electrode composite material.In addition, electrode composite material has loose structure, when charge and discharge process brings the change in volume of electrode composite material, can have and well play cushioning effect, make electrode composite material can not subside or efflorescence, improve the cycle life of electrode composite material.The preparation method of electrode composite material is simple simultaneously, and control possesses the industrialization potentiality easily.
Electrode composite material by preparation method of the present invention makes can be used as negative material, further, can prepare the battery that negative pole contains this negative material.
Negative pole comprises negative material and negative current collector, and negative material contains the electrode composite material that comprises silicon and silver.In the execution mode of concrete preparation negative pole, with negative material, conductive agent, binding agent mixes according to a certain percentage, adds dispersant, makes cathode size after fully mixing.Dispersant includes but not limited to organic solvent, and organic solvent comprises N-methyl pyrrolidone, ethanol or acetone.By any suitable mode, as the scraper coating technique, modes such as spin coating are coated on the negative current collector and drying uniformly, obtain negative pole with cathode size.Wherein, in negative material, conductive agent and binding agent, the shared weight percentage ranges of negative material is 70%-90%, and in embodiment, the content of negative material is 70%.
Conductive agent is selected from one or more in conducting polymer, active carbon, Graphene, carbon black, carbon fiber, metallic fiber, metal dust and the sheet metal.In more excellent execution mode, conductive agent comprises section's qin carbon black (KB).
Binding agent is selected from polyethylene oxide, polypropylene oxide, a kind of or above-mentioned mixture of polymers and derivative in polyacrylonitrile, polyimides, polyester, polyethers, fluorinated polymer, polyvinylidene base polyethylene glycol, polyethyleneglycol diacrylate, the polyethylene glycol dimethacrylate.
The material of negative current collector includes but are not limited to a kind of in nickel foam, aluminium foil, Copper Foil, the stainless steel foil.In 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 be reversible deviates from-embedded ion or functional group.Preferably, lithium ion, sodium ion or magnesium ion can be reversible deviate from-embed to positive electrode active materials.
Positive electrode active materials of the present invention is that lithium ion is deviate from-when embedding compound, can be selected for use 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, can deviate from-embed composite and sodium ion composite NaVPO
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 have similar functions, can deviate from-compound of embedded ion or functional group can be as the anodal positive electrode active materials of battery of the present invention.
Preferred, positive electrode active materials comprises the sulfenyl material, and the sulfenyl material accounts for the 70-90% of positive electrode active materials total weight.The sulfenyl material is selected from elementary sulfur, Li
2S
n, organic sulfur compound and carbon sulphur polymer (C
2S
v)
mIn at least a, wherein, n 〉=1,2.5≤v≤50, m 〉=2.
In order to guarantee in charge and discharge process, there is the lithium ion that to deviate from-embed between the positive pole of battery and the negative pole, when the positive electrode of selecting and negative material do not contain the ion that can deviate from-embed or functional group simultaneously, need embed the ion that to deviate from-embed or the processing of functional group's lithium to positive pole and/or negative pole.Concrete embedded mode is not limit, and comprises that chemical reaction embeds or electrochemical reaction embeds.
Electrolyte comprises electrolyte lithium salt and organic solvent at least.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)
3And LiN (C
2F
5SO
2)
2In at least a.Affiliated technical field 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), diethyl carbonic ether (DEC), propylene carbonate (PC), 1,3-dioxolane (DIOX), ether, glyme, lactone, sulfone, sulfolane or above mixture; Organic solvent can be polymer also, as polyacrylonitrile; Also can comprise gel, as gelatin polymer (PEGMEMA1100-BMI).If adopt this electrolyte of gel, because itself is a kind of soft material, certain deformation can take place, too big variation can not take place in therefore corresponding cell production process.Certainly, also can adopt solid polymer electrolyte, for example Li
2S-P
2S
5Glass-ceramic, or P (EO)
20Li (CF
3SO
2)
2N-10wt.% γ-LiAlO
2
When electrolyte is liquid state, the preparation battery also needs to use barrier film, barrier film is arranged between positive pole and the negative pole, can be the non-conducting of a kind of solid or insulating properties material, positive pole and negative pole separated and make both mutually insulateds, thereby prevent internal short-circuit of battery, and barrier film can allow ion to transmit between positive pole and negative pole.Barrier film can be selected from but be not limited to a kind of in glass fibre, polyester, polyethylene, polypropylene, the polytetrafluoroethylene.
The form of battery includes but are not limited to the compressing tablet structure in the field of batteries, also comprises common button cell, cylindrical battery or board-like battery.
Although technical scheme of the present invention has been done detailed elaboration and for example above; for a person skilled in the art; on the basis that does not break away from essence of the present invention, above-described embodiment is modified and/or flexible or adopt similar replacement scheme, also in protection scope of the present invention.
The present invention is further described below by execution mode.
Embodiment 1-1
According to weight ratio 3:1 weighing reaction raw materials prodan and sodium metal, reaction raw materials is inserted in three mouthfuls of clean vials, feed N
2Get rid of the air in the bottle, in bottle, add electrode and stirring-head, electrode comprises positive pole and negative pole, anodal and negative pole is all silicon chip, and the direct voltage that is attached between positive pole and the negative pole is 3.7V, heats reaction raw materials to 100 ℃ and starts stirring, continue 160 ℃ of heating reaction raw materials to the first temperature subsequently, be incubated 2 hours, stop to stir, be cooled to room temperature.Change the reduzate of gained over to clean beaker that pure water is housed, washing and vacuum filtration with pure water washing 3 times, are used electronics pure hydrochloric acid further washing and vacuum filtration, at last 60 ℃ of following vacuumizes 12 hours with the product behind the suction filtration again.
Weighing silver nitrate 0.078g dissolves in the 200mL pure water, and adding several ammoniacal liquor regulator solution PH is 9.6, adds the synthetic silica flour of 0.24g then, dropwise add 5% formaldehyde 0.4mL, stir after 2 hours and filter, with the product oven dry that obtains after filtering, obtain containing the electrode composite material of silicon and silver.
Fig. 3 is the X ray diffracting spectrum of the polysilicon that makes of embodiment 1-1.Finally analyze the purity of demonstration silicon 99.9999% by ICP-Mass.
Embodiment 1-2
In embodiment 1-2, the electrode auxiliary voltage is 3.4V, and the first corresponding temperature is 170 ℃, and all the other preparation methods are with embodiment 1-1.
Embodiment 1-3
In embodiment 1-3, the electrode auxiliary voltage is 3V, and the first corresponding temperature is 165 ℃, and all the other preparation methods are with embodiment 1-1.
Embodiment 1-4
In embodiment 1-4, the electrode auxiliary voltage is 2V, and the first corresponding temperature is 200 ℃, and all the other preparation methods are with embodiment 1-1.
Embodiment 1-5
In embodiment 1-5, the electrode auxiliary voltage is 12V, and the first corresponding temperature is 140 ℃, and all the other preparation methods are with embodiment 1-1.
Changed the auxiliary voltage of electrode among the embodiment 1-2 to 1-5, correspondence changes first temperature simultaneously, and reduction reaction all can take place, and finally makes the electrode composite material that tool silver coats silicon.
Embodiment 2-1
Electrode composite material, binding agent PVDF, conductive agent AC are mixed with 7:1:2, add solvent NMP and stirred 12 hours, be coated on the nickel foam, vacuumize was cooled to room temperature after 4 hours in the time of 120 ℃, was cut into the disk of diameter 14mm subsequently, obtained negative pole.Be anodal with the lithium metal, porous polypropylene is barrier film, 1mol/LLiPF
6EC, DMC and the mixed solution of DEC (volume ratio 1:1:1) be electrolyte, in being full of the glove box of argon gas, be assembled into the CR2032 button cell.
Claims (9)
1. the preparation method of an electrode composite material, described electrode composite material comprises silicon and silver, described silver is coated on the described silicon, it is characterized in that: described preparation method comprises the steps:
Reaction raw materials is inserted in the reaction vessel, described reaction raw materials comprises fluosilicate and as the metal of reducing agent, or magnesium metal and silicon dioxide, inserts electrode in described reaction vessel, described electrode comprises positive pole and negative pole, applies voltage between described positive pole and negative pole; Heating and stir described reaction raw materials under the protective gas atmosphere, continue described reaction raw materials to the first temperature of heating after, the insulation scheduled time, cooling obtains reduzate, with described reduzate washing and dry, obtains described silicon;
Described silicon is handled the described electrode composite material of acquisition by silver mirror reaction.
2. preparation method according to claim 1, it is characterized in that: the voltage range that is applied between described positive pole and the negative pole is 2-12V.
3. preparation method according to claim 1, it is characterized in that: described just very silicon chip or graphite, described negative pole are silicon chip.
4. preparation method according to claim 1, it is characterized in that: described first temperature range is 140-200 ℃.
5. preparation method according to claim 1, it is characterized in that: described fluosilicate is selected from potassium fluosilicate or prodan.
6. preparation method according to claim 1, it is characterized in that: described metal is selected from potassium or sodium.
7. preparation method according to claim 1 is characterized in that: described silicon is carried out chemical corrosion or mechanical coarse processing acquisition loose structure.
8. preparation method according to claim 1, it is characterized in that: the step of described silver mirror reaction is: add ammoniacal liquor in the aqueous solution that contains silver nitrate, the scope that makes described pH value of aqueous solution is 8-10, add described silicon, 5% formaldehyde, stir after 0.5-3 hour, the filtering reaction product, the product oven dry with after filtering obtains described electrode composite material.
9. electrode composite material, it is characterized in that: described electrode composite material comprises silicon and silver, and described silicon exists with particle form, and particle size range is the 1-20 micron, and described silver is coated on the surface of described silicon.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310049648.3A CN103296262B (en) | 2012-02-23 | 2013-02-17 | The preparation method of electrode composite material and electrode composite material |
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210042359 | 2012-02-23 | ||
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| CN105206818A (en) * | 2015-10-22 | 2015-12-30 | 中国科学院宁波材料技术与工程研究所 | Preparation method and application of silicon/metal nano composite material |
| CN106943669A (en) * | 2017-02-21 | 2017-07-14 | 鑑道生命科技有限公司 | A kind of nano-Ag particles silicone body Surface Mount plate electrode and preparation method thereof |
| CN110931727A (en) * | 2019-10-25 | 2020-03-27 | 合肥国轩高科动力能源有限公司 | Preparation method of conductive polymer-coated silicon-based negative electrode material |
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| CN105206818A (en) * | 2015-10-22 | 2015-12-30 | 中国科学院宁波材料技术与工程研究所 | Preparation method and application of silicon/metal nano composite material |
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| CN106943669A (en) * | 2017-02-21 | 2017-07-14 | 鑑道生命科技有限公司 | A kind of nano-Ag particles silicone body Surface Mount plate electrode and preparation method thereof |
| CN110931727A (en) * | 2019-10-25 | 2020-03-27 | 合肥国轩高科动力能源有限公司 | Preparation method of conductive polymer-coated silicon-based negative electrode material |
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