CN103872327B - Preparation method and negative pole and the lithium ion battery of anode material for lithium battery - Google Patents
Preparation method and negative pole and the lithium ion battery of anode material for lithium battery Download PDFInfo
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Abstract
The preparation method and negative pole and the lithium ion battery that the present invention relates to lithium battery anode material, belong to lithium cell cathode material field. The invention provides a kind of preparation method of negative electrode for lithium ion battery composite, it is taking siloxanes and condensation polymer monomer as reaction raw materials, make solvent with alcohol and distilled water mixed solution, surfactant is template, alkali lye is catalyst, under room temperature, obtains lithium ion battery composite by self assembly, Co-sol-gel and heat treatment; Wherein, the mass ratio of siloxanes and condensation polymer monomer is 1 ︰ 9-5 ︰ 1, and the volume ratio of alcohol and distilled water is 1 ︰ 15-6 ︰ 1; Described condensation polymer monomer comprises formaldehyde and the 3rd monomer, wherein, the 3rd monomer be can with the monomer of formaldehyde generation polycondensation reaction, the mass ratio of formaldehyde and the 3rd monomer is 2-1.1 ︰ 1. Method simple possible of the present invention, suitability for industrialized is produced; And utilize the standby material of this legal system to have desirable structure and pattern, capacity is high, cycle performance is excellent.
Description
Technical field
The present invention relates to the preparation method of a kind of lithium battery negative electrode for lithium ion battery composite and negative pole and lithium fromSub-battery, belongs to lithium ion battery negative material preparing technical field.
Background technology
Compared with other energy-storage batteries, lithium ion battery has that open-circuit voltage is high, energy density is large, long service life, nothingThe advantages such as memory effect, have been widely used as the power supply of portable electric appts, and to electric automobile, electric tool and storageThe field development such as energy peak load stations. At present, the obstacle that restriction lithium ion battery is applied on large-capacity high-power equipment is its appearanceAmount and energy density can not meet the requirement of these equipment. Due to the power density of lithium ion battery and energy density all mainly byElectrode material determine, development safety, cost is low, capacity is high and the electrode material of stable cycle performance is the pass addressing the above problemKey.
At present, commercial li-ion cell negative electrode material is carbon-based material, the low (372mAhg of theoretical capacity-1), the sky of improvementBetween very little, the Novel anode material that searching can substitute material with carbon element is an important directions of electrode material research and development. ?In the negative material of research, silicon is because there being the highest theoretical capacity (4200mAhg-1) and satisfied doff lithium electromotive force and being considered toThe ideal candidates negative material of a new generation's lithium ion battery.
But the subject matter of restriction silicon electrode practical application is that silicon enormousness in cyclic process changes the electricity causingElectrode structure unstability, thus show the cycle performance of extreme difference. Up to now, having carried out a large amount of work solves and siliconThe problem that bulk effect is relevant. For example build nano silicon particles, silicon nanowires, nano-tube, porous silicon and they and otherCompound etc. between inertia or low volumes of materials. Study and show, the nanometer of silicon and Composite are to solve silicon bulk effectEffective way. But, how to build high performance nanometer silicon composite material but by simple synthetic route in practiceIt is a huge challenge. For example, nano-silicon has been widely used as the presoma of silicon based composite material, but in building-up processBut two insoluble practical difficulties have been run into. The one, require in theory the particle diameter of nano-silicon as far as possible little, and get over granuleThe silicon in footpath means larger specific surface energy, and this can make the dispersion of nano-silicon more difficult. The nano-silicon aggregate not disperseing very easilyCause the local failure of electrode structure, thereby have a strong impact on the improvement of electrode cycle performance. Secondly, nano-silicon is mainly by gasMutually prepared by deposition or the mode of sputter, and the high and difficult a large amount of production of cost, has a strong impact on the application of its corresponding composite.
In recent years, Si oxide does presoma and prepares nano silicon-based composite and caused great interest. SilicaThing has comprised SiO and the SiO that stoichiometric proportion is integer2And stoichiometric proportion is not the SiO of integerx(0 < x < 2). Storage lithium holdsAmount generally reduces with the increase of silicone atom ratio, but cycle performance improves. Si oxide in cyclic process first firstBe reduced to nano-silicon by lithium and be evenly dispersed in the lithia and lithium metasilicate medium of formation both volumes to silicon afterwardsChange and have better cushioning effect, therefore Si oxide electrode has conventionally has more excellent than the combination electrode of directly preparing with nano-siliconDifferent cycle performance. But the electron conduction of Si oxide electrode is poor, stock utilization is not high, how to reduce Si oxideParticle diameter and to improve its electric conductivity be to improve the key of such electrode electro Chemical performance. In silicon oxide compound, only has at present SiOAnd SiO2Commercialization, but bulk SiO2Do not store up lithium activity, therefore research mainly concentrates on SiO. Due to business SiO beHigh-temperature process Si and SiO under vacuum condition2Obtain, not only cost is high, and last product cut size is conventionally all at tensMicron, therefore in the time being used as initiation material and preparing electrode material, although ball milling is widely adopted to reduce its particle diameter,Ball milling is difficult to be reduced to less nanoscale, and particle diameter wider distribution, usually contains large SiO in the material of preparationParticle. Contemporaneous heterotopic facies synthetic method is difficult to make SiO uniform particles to be dispersed in conductive matrices. Therefore utilize business SiO to prepareAlthough electrode material has high specific capacity, cycle performance is still undesirable, and the cycle performance that great majority have kept arrives between 50Between 100 circulations, only have only a few bibliographical information can reach 200 circulations, clearly this also has very long from practical applicationDistance. Recently, there is the partial oxidation of a few studies nano-silicon to prepare the SiO of non-metering ratiox, this method cost is too high,And experiment poor reproducibility. The SiO of non-metering ratio is done presoma and can obtain by chemical reaction in recent findings with siloxanesx，But in bibliographical information, still adopt two-step method, first prepared nanometer SiOx, and then coated, this method is in preparation processNot only program complexity, and the nanometer SiOx that need to prepare the first step disperses, due to the dispersion skill of a large amount of nano materialsArt does not still solve at present, and this method is not suitable for suitability for industrialized production. In addition, for the material that has volumetric expansion and poorly conductive, the composition structure of material, particle size, pattern has conclusive impact to its chemical property, and so far there are no has spyThe SiOx composite wood of different structure and pattern
Summary of the invention
The present invention is directed to above-mentioned defect, the invention provides the preparation method of a kind of lithium battery anode material, the partyMethod simple possible does not relate to the dispersion of any sensitive experiment condition and nano material, suitable industry in the preparation process of materialChange and produce; And utilize the standby material of this legal system to have desirable structure and pattern, capacity is high, cycle performance is excellent.
First technical problem that the present invention will solve has been to provide the preparation side of above-mentioned lithium battery anode materialMethod, it,, taking siloxanes and condensation polymer monomer as reaction raw materials, makes solvent with alcohol and distilled water mixed solution, and surfactant is mouldPlate, alkali lye is catalyst, under room temperature, obtains lithium ion battery composite wood by self assembly, Co-sol-gel and heat treatmentMaterial; Wherein, the mass ratio of siloxanes and condensation polymer monomer is 1 ︰ 9-5 ︰ 1, and the volume ratio of alcohol and distilled water is 1 ︰ 15-6 ︰ 1, described inCondensation polymer monomer comprises formaldehyde and the 3rd monomer, wherein, the 3rd monomer be can with the monomer of formaldehyde generation polycondensation reaction, formaldehyde andThe mass ratio of the 3rd monomer is 2-1.1 ︰ 1.
Described siloxanes general formula is: RnSi(ORˊ)4-n, wherein R, R ˊ are alkyl, 0≤n≤2.
Preferably, described siloxanes general formula is: RnSi(ORˊ)4-n, wherein R is-C2H5、-C2H4、-CH2C6H6, R ˊ is-C2H5，0≤n≤2。
Preferred, described siloxanes is (C2H5O)3SiC2H5、(C2H5O)4Si、(C2H5O)3SiC2H4Or (C2H5O)3SiCH2C6H6。
Preferably, described the 3rd monomer be in phenol, catechol, resorcinol, phloroglucin or melamine extremelyFew a kind of.
Described alcohol is at least one in methyl alcohol, ethanol, propyl alcohol, butanols, isobutanol or amylalcohol.
Described surfactant is in cetyl ammonium bromide, polyoxyethylene polyoxypropylene copolymer (F123) or P127At least one.
In the present invention, all alkali lye all can be used as catalyst and uses, and is preferably at least one in ammoniacal liquor, amino acid or NaOHKind; More preferably ammoniacal liquor.
Preferably, the volume ratio of described alcohol and distilled water is 5 ︰ 2-6 ︰ 1; Preferred, the volume of described alcohol and distilled waterThan being 5 ︰ 2 and 6 ︰ 1.
Described self assembly is that first siloxanes, condensation polymer monomer are assembled altogether, then urged by electrostatic interaction in templatePolymerization reaction take place under the effect of agent, polymerisation adopts and refluxes or hydro-thermal reaction.
Preferably, preparation method's concrete steps of the above-mentioned composite of the present invention are:
A, alcohol and distilled water are stirred mixed, wherein, the volume ratio of alcohol and distilled water is: 1 ︰ 15-6 ︰ 1;
B, add alkali lye and the 3rd monomer, stirring reaction 0.2-1h;
C, add surfactant, stir 0.2-1h and obtain mixed solution;
D, in above-mentioned mixed solution, add successively formalin and siloxanes, the mass ratio of siloxanes and condensation polymer monomerBe 1 ︰ 9-5 ︰ 1, then at room temperature stir 10-48h, then the 5-48h that refluxes at 50-100 DEG C forms pink or brown sinkingForm sediment;
E, precipitation through centrifugation or filter after at 50-90 DEG C vacuum drying 3-12h, then at 800-1200 DEG C heatProcess 1-5h, naturally cool to room temperature.
Preferably, in above-mentioned steps a, the volume ratio of alcohol and distilled water is 5 ︰ 2-6 ︰ 1.
Preferably, in described a step, the volume ratio of alcohol and distilled water is 1 ︰ 15-4 ︰ 3.
Preferably, described in above-mentioned c step, the concentration of alkali lye is 0.2-5wt%.
Preferably, in above-mentioned c step, the concentration of surfactant is 0.5-2%.
Preferably, in described d step, the mass ratio of siloxanes and condensation polymer monomer is 1 ︰ 9-4.3 ︰ 1.
Preferably, in described e step, heat treatment is carried out under inert gas shielding, more preferably under argon gas stream protection, entersOK.
Preferably, in described e step, heat treatment is heat-treated in tube furnace.
Preferably, in described e step, at 1000 DEG C, heat-treat.
Preferably, in described e step, heating rate is 2-10K/min, and gas flow rate is 20-100mLmin-1; Gas velocityRate can affect the composition of product, and the accessory substance of the too little cracking of air-flow can not be discharged rapidly, and air-flow too conference causes waste or handleSample blows and flies up; The rate of heat addition can affect pattern, pore structure and the degree of crystallinity of material.
Second technical problem that the present invention will solve is to provide a kind of negative pole for lithium rechargeable battery, described negativeThe utmost point comprises collector and load on the negative material on this collector, and wherein, described negative material contains lithium provided by the inventionIon battery composite.
The 3rd technical problem that the present invention will solve has been to provide a kind of lithium ion battery, and this battery comprises pole piece and electricitySeparate liquid, described pole piece comprises positive pole, negative pole and the membrane layer between positive pole and negative pole, and wherein, described negative pole is the present inventionThe negative pole providing.
Preferably, the carrier of paper tinsel, net, porous body, foams or corpus fibrosum material that described collector is various conductions, exampleAs Copper Foil, nickel screen, nickel foam and carbon felt.
Preferably, the solute of electrolyte is 1molL-1LiPF6; Solvent is that volume ratio is the ethylene carbonate of 1:1:1(EC) ethylene carbonate (EC) and carbonic acid diformazan that, dimethyl carbonate (DMC) and methyl ethyl carbonate (EMC) or volume ratio are 1:1Ester (DMC); Film for additive is 1-5% vinylene carbonate (VC) and 2-10% fluorinated ethylene carbonate (FEC) or both is mixedAnd thing.
The inventive method has following beneficial effect:
It is dispersed that first passage self assembly of the present invention and sol-gal process have been realized the height of SiOx in carbon medium, materialMaterial has the nano composite structure of porous, and the SiOx/C that has obtained different-shape by simple change solvent composition is compoundMaterial, has improved the stability of electrode structure and has reduced electrolyte and the path of lithium ion diffusion, thereby significantly improvedThe chemical property of electrode. In the time being used as the electrode material of lithium ion battery, this composite can be stood in long-term cyclic processThe tension force that middle silicon Volume Changes causes, has high capacity and very excellent cycle performance. And method of the present invention simply canOK, suitability for industrialized is produced.
Brief description of the drawings
Fig. 1 is the SEM figure of embodiment 1 gained SiOx/C composite.
Fig. 2 is embodiment 1 gained SiOxThe TEM figure of/C composite.
Fig. 3 is embodiment 1 gained SiOx/ C composite is 50mAg in current density-1Charging and discharging curve.
Fig. 4 is embodiment 1 gained SiOx/ C composite is at 50mAg-1Cycle performance.
Fig. 5 is embodiment 1 gained SiOxThe high rate performance of/C composite.
Fig. 6 is embodiment 2 gained SiOxThe SEM figure of/C composite.
Fig. 7 is embodiment 2 gained SiOxThe SEM enlarged drawing of/C composite.
Fig. 8 is embodiment 2 gained SiOx/ C composite is at 50mAg-1Cycle performance.
Fig. 9 is embodiment 2 gained SiOxThe high rate performance of/C composite.
Figure 10 is the SEM figure of embodiment 3 gained SiOx/C composites.
Figure 11 is the cycle performances of embodiment 3 gained SiOx/C materials at 50mAg-1.
Figure 12 is that embodiment 4 gained SiOx/C composites are 50mAg in current density-1Cycle performance.
Figure 13 is the SEM figure that embodiment 5 prepares composite.
Figure 14 is embodiment gained SiOx/ C composite is 50mAg in current density-1Cycle performance.
Figure 15 is comparative example 1 gained SiOxComposite is at 100mAg-1Cycle performance.
Detailed description of the invention
The present invention is prepared as particle diameter evenly by electrode material and has the nanoporous composite of special appearance and structure,Be conducive to improve the stability of electrode structure and reduce electrolyte and lithium ion the evolving path, thereby significantly improving electrodeChemical property. For the present invention, alkylsiloxane, formaldehyde and the 3rd monomer (monomer that can react with formaldehyde) are for initial formerMaterial, surfactant is template, alkali is catalyst, at room temperature obtains tool by self assembly, Co-sol-gel and heat treatmentThere is the SiO of different-shape and structurex/ C(1 < x < 2) nano composite material, to improve SiOxThe electric conductivity of (1 < x < 2) and shortening lithiumThe diffusion path of ion in material and overcome SiOxThe destruction of Volume Changes to electrode structure.
Below in conjunction with embodiment, the specific embodiment of the present invention is further described, therefore the present invention is not limitAmong described scope of embodiments.
In following embodiment, characterize the composition of material with elemental analyser and XPS; Characterize material with SEM and TEMPattern.
In following embodiment, electrochemical property test is specific as follows: in the glove box that is filled with high-purity argon, with electrode materialFor working electrode, lithium sheet is to electrode, is assembled into the test of 2032 button cells as electrode material chemical property. Wherein,Working electrode is by 75% active material, 10% acetylene black and 15% sodium alginate composition, and film adopts traditional the tape casting, for carryingThe cementitiousness of high silicon mosanom, electrode slice is application of vacuum 6-10h at 100-115 DEG C. Electrolyte solute is 1MLiPF6, moltenAgent is dimethyl carbonate (DMC), diethyl carbonate (DEC) and the ethylene carbonate (EC) of volume ratio 1:1:1, and additive is 2-5%Ethylene carbonate (VC) and 2-10% fluorinated ethylene carbonate (FEC). Be lithium sheet to electrode. The electrochemical property test adoptingTechnology is constant current charge-discharge, and current density is from 50mAg-1-600mAg-1, charging/discharging voltage scope is 0-3V.
Embodiment 1
The ratio of 6:1 measures distilled water and the absolute ethyl alcohol of aequum by volume, then add successively 0.2mL ammoniacal liquor and0.2g resorcinol at room temperature stirs 0.5h, then adds 0.2g cetyl ammonium bromide (CTAB) continuation stirring 0.5h to form whiteLook emulsion. In above-mentioned mixed solution, add successively 0.28mL formalin and 1mL ethyl triethoxysilane (EtSi(OEt)3), at room temperature stir the 24h that refluxes after 24h and form pink or brown precipitation at 80 DEG C, after filtering and at 70 DEG CLower vacuum drying 8h then, under argon gas stream protection, processes 3h for 1000 DEG C in tube furnace, naturally cools to room temperature, and speed heats upRate is 10K/min, and gas flow rate is 100mLmin-1。
Fig. 1 and Fig. 2 are respectively the SiO of preparationxThe SEM of/C composite and TEM, as can be seen from the figure, this material isNano bar-shape, the external diameter of rod is between 50-150nm, and rod is to be linked together by the carbon of cracking by some nanometer beads. FromSiOxThe content of the bright carbon of/C composite element analytical table is approximately 43.7%, and according to XPS and energy spectrum analysis, x value is approximately1.51。
Fig. 3 is SiOx/ C compound bar is 50mAg in current density-1Charging and discharging curve. On first discharge curve, largeRespectively there is a short flat gradient and all disappear in second circulation about 1.2V and 0.85V left and right. Research shows, the former is rightShould be decomposed to form in electrolysis additive fluorinated ethylene carbonate (FEC) process of solid liquid interface (SEI) film, and the latter is mainly rightShould form in the reduction decomposition of electrolyte ethylene carbonate (EC) and additive VC the process of SEI film. Length in 0.5V left and right is obliqueSlope forms the process of nano-silicon and silicate and lithia corresponding to lithium reduction SiO. The discharge capacity first of this material and fillingCapacitance is respectively 1331mAhg-1And 981mAhg-1, low coulomb efficiency is mainly by the decomposition of electrolyte and lithium reduction siliconOxide causes. In second circulation, discharge capacity and charging capacity are respectively 888mAhg-1And 847mAhg-1, coulombEfficiency is greatly improved.
Fig. 4 is SiOx/ C compound bar is 50mAg in current density-1Cycle performance, as can be seen from the figure, more than tenAfter individual circulation, capacity reaches stable, 690mAhg-1Stable discharging capacity can be obtained, and do not decline in circulation subsequentlySubtract, coulomb efficiency also maintains 99.0-100%.
Fig. 5 is SiOx/ C compound bar is at 50-600mAg-1High rate performance under current density, as can be seen from Figure, this materialMaterial has good multiplying power stability, even at 600mAg-1Under, this material has also showed about 390mAhg-1Discharge capacity,When electric current is returned to 50mAg-1After, the discharge capacity of material is replied completely, shows that the electrode structure of material is not damaged.
Embodiment 2
The ratio of 5:2 measures distilled water and the absolute ethyl alcohol of aequum by volume, then add successively 0.2mL ammoniacal liquor and0.2g resorcinol at room temperature stirs 0.5h, then adds 0.2gCTAB continuation stirring 0.5h to form white emulsion. Above-mentionedIn mixed solution, add successively 0.28mL formalin and 1mLEtSi (OEt)3, at room temperature stir after 24h at 80 DEG C next timeStream 24h forms pink or brown precipitation, vacuum drying 8h after filtering and at 70 DEG C, and then under argon gas stream protection,In tube furnace, process 3h for 1000 DEG C, naturally cool to subsequently room temperature, heating rate is 10Kmin-1, gas flow rate is100mLmin-1。
Fig. 6 and Fig. 7 are respectively the SEM of composite under different amplification of preparation, as can be seen from the figure, and this materialMaterial is spherical, and the radius of ball is between 300-500 nanometer, and whole large ball is again to be piled up and form at the bead of tens nanometers by particle diameter,And adjacent bead links together by carbon. SiOxThe elementary analysis of/C composite balls shows that the content of carbon is approximately 39.4%.
Fig. 8 is SiOx/ C composite balls is 50mAg in current density-1Cycle performance, as can be seen from the figure, more than tenAfter individual circulation, capacity reaches stable, approximately 635mAhg-1Reversible capacity can be obtained, and do not decline in circulation subsequentlySubtract, coulomb efficiency maintains 99.0-100%.
Fig. 9 is SiOx/ C compound bar is at 100-600mAg-1The high rate performance circulating under current density, as can be seen from Figure,This material has good multiplying power stability, even at 600mAg-1Under, this material has also showed about 354mAhg-1Electric dischargeCapacity, when electric current is returned to 100mAg-1After, the discharge capacity of material is replied completely, shows that the electrode structure of material is quite steadyFixed.
Embodiment 3:
The ratio of 4:3 measures distilled water and the absolute ethyl alcohol of aequum by volume, then add successively 0.2mL ammoniacal liquor and0.2g resorcinol at room temperature stirs 0.5h, then adds 0.2gCTAB continuation stirring 0.5h to form white emulsion. Above-mentionedIn mixed solution, add successively 0.28mL formalin and 1mLEtSi (OEt)3, at room temperature stir after 24h at 80 DEG C next timeStream 24h forms pink or brown precipitation, vacuum drying 8h after filtering and at 70 DEG C, and then under argon gas stream protection,In tube furnace, process 3h for 1000 DEG C, naturally cool to room temperature, heating rate is 10Kmin-1, and gas flow rate is 100mLmin-1。
Figure 10 is the SEM for preparing composite, and as can be seen from the figure, this composite, except part spheroid, also wrapsContain part irregular geometry. SiOxThe compound irregular ball elementary analysis of/C shows that the content of carbon is approximately 41.2%.
Figure 11 is SiOxThe compound irregular ball of/C is 50mAg in current density-1Cycle performance, as can be seen from the figure,After about 20 circulations, capacity reaches stable, and stable discharging capacity is approximately 525mAhg-1, coulomb efficiency maintains99.0-100%. Relatively can find out with embodiment 1 and embodiment 2, along with the change of ethanol content in solvent, the SiO of preparationx/CThe storage lithium performance of the pattern of composite and material also changes thereupon, and ethanol content is higher, and it is large that material particle size becomes, and capacity is lower.
Embodiment 4:
The ratio of 1:15 measures distilled water and the absolute ethyl alcohol of aequum by volume, then adds successively 0.2mL ammoniacal liquorAt room temperature stir 0.5h with 7.7g catechol, then add 0.2gCTAB continuation stirring 0.5h to form white emulsion. UpperState and in mixed solution, add successively 10.8mL formalin and 1mLEtSi (OEt)3, at room temperature stir after 24h at 80 DEG CBackflow 24h forms pink or brown precipitation, vacuum drying 8h after filtering and at 70 DEG C, and then under argon gas stream protection,In tube furnace, process 3h for 1000 DEG C, naturally cool to room temperature, heating rate is 10Kmin-1, gas flow rate is 100mLmin-1。
This composite is irregular how much blocks (not providing). Elementary analysis shows that the content of carbon is approximately 90.7%.
Figure 12 is SiOxThe compound irregular ball of/C is 50mAg in current density-1Cycle performance, as can be seen from the figure,After several circulations, capacity reaches stable, the about 360mAhg of stable discharging capacity-1, coulomb efficiency maintains 99.0-100%.
Embodiment 5:
The ratio of 3:1 measures distilled water and the absolute ethyl alcohol of aequum by volume, then add successively 0.2mL ammoniacal liquor and0.20g melamine at room temperature stirs 0.5h, then adds 0.2gCTAB continuation stirring 0.5h to form white emulsion. UpperState and in mixed solution, add successively 0.5mL formalin and 1mL (C2H5O)3SiCH2C6H6, at room temperature stir after 24h at 80 DEG CLower backflow 24h form pink or brown precipitation, filter after and at 70 DEG C vacuum drying 8h, then protect in argon gas streamUnder, in tube furnace, process 3h for 1000 DEG C, naturally cool to room temperature, heating rate is 10Kmin-1, gas flow rate is 100mLmin-1。
Figure 13 is the SEM for preparing composite, and as can be seen from the figure, this composite is regular geometric body. SiOx/CCompound irregular ball elementary analysis shows that the content of carbon is approximately 38.6%.
Figure 14 is SiOxThe compound irregular ball of/C is 50mAg in current density-1Cycle performance, as can be seen from the figure,After about 20 circulations, capacity reaches stable, and stable discharging capacity is approximately 642mAhg-1, coulomb efficiency maintains99.0-100%。
Known by above-described embodiment: the forming SiO of solventxThe pattern of/C composite and particle diameter have strong impact,With the increase of alcohol content, SiOx/ C composite is from nanometer rods, nanometer rule ball, and the irregular ball of nanometer changes, and particle diameter increases graduallyGreatly, but relatively little on carbon content impact. Lithium storage content is with SiOx/ C composite nanorod is the highest, is secondly regular SiOx/ C receivesRice composite balls, the poorest is the irregular ball of nanometer.
Comparative example 1:
The ratio of 6:1 measures distilled water and the absolute ethyl alcohol of aequum by volume, then adds under 0.2mL ammoniacal liquor room temperatureStir 0.5h, then add 0.2gCTAB to continue to stir 0.5h. In above-mentioned mixed solution, add successively 1mLEtSi (OEt)3，At room temperature stir the 24h that refluxes after 24h and form white precipitate at 80 DEG C, vacuum drying 8h after filtering and at 70 DEG C, thenUnder argon gas stream protection, in tube furnace, process 3h for 1000 DEG C, naturally cool to subsequently room temperature, heating rate is 10K/min, gasRate of flow of fluid is 100mLmin-1。
Gained composite out-of-shape, particle diameter distributes wide, and from hundreds of nanometers to several microns, phosphorus content is approximately7%。
Figure 15 is the SiO of preparationxThe cycle performance of composite, due to SiOxPoorly conductive and also there is volumetric expansionProblem, after several circulations, discharge capacity quickly falls to 400mAhg-1Below, and can not stablize.
Compared with embodiment 1, in comparative example 1, do not add formaldehyde and resorcinol, therefore in polymerizate, just there is no phenolUrea formaldehyde high polymer, simultaneously in polymerization process, electronegative siloxanes is hydrolyzed little molecule and has there is no novolak resin precursor bodyCompetition, can be assembled in positively charged template in a large number, does not have the obstruct of carbon easily to reunite in sintering process.
Comparative example 2:
The ratio of 5:2 measures distilled water and the absolute ethyl alcohol of aequum by volume, then adds under 0.2mL ammoniacal liquor room temperatureStir 0.5h, then add 0.2gCTAB to continue to stir 0.5h. In above-mentioned mixed solution, add successively 1mLEtSi (OEt)3，At room temperature stir the 24h that refluxes after 24h and form white precipitate at 80 DEG C, vacuum drying 8h after filtering and at 70 DEG C, thenUnder argon gas stream protection, in tube furnace, process 3h for 1000 DEG C, naturally cool to subsequently room temperature, heating rate is 10K/min, gasRate of flow of fluid is 100mLmin-1. Change SiO prepared by ethanol contentxChemical property and comparison example 1 there is no obvious districtNot, do not provide corresponding figure at this.
Table 1 raw material and proportioning thereof
Table 2 composite property table
Claims (11)
1. the preparation method of anode material for lithium battery, is characterized in that, it is taking siloxanes and condensation polymer monomer as reactionRaw material, makes solvent with alcohol and distilled water mixed solution, and surfactant is template, and alkali lye is catalyst, under room temperature, passes through from groupDress, Co-sol-gel and heat treatment obtain lithium ion battery composite; Wherein, described condensation polymer monomer comprises formaldehydeWith the 3rd monomer, wherein, the 3rd monomer be can with the monomer of formaldehyde generation polycondensation reaction, the mass ratio of formaldehyde and the 3rd monomer is1.1-2︰1；
Described preparation method comprises the following steps:
A, alcohol and distilled water are stirred mixed, wherein, the volume ratio of alcohol and distilled water is: 1 ︰ 15-6 ︰ 1;
B, add alkali lye and the 3rd monomer, stirring reaction 0.2-1h;
C, add surfactant, stir 0.2-1h and obtain mixed solution;
D, in above-mentioned mixed solution, add successively formalin and siloxanes, the mass ratio of siloxanes and condensation polymer monomer is 1 ︰9-5 ︰ 1, then at room temperature stirs 10-48h, then the 5-48h that refluxes at 50-100 DEG C forms pink or brown precipitation;
E, precipitation vacuum drying 3-12h, then heat treatment at 800-1200 DEG C at 50-90 DEG C after centrifugation or filtration1-5h, naturally cools to room temperature.
2. the preparation method of anode material for lithium battery according to claim 1, is characterized in that described siloxanesGeneral formula is: RnSi(ORˊ)4-n, wherein R, R ˊ are alkyl, 0≤n≤2.
3. the preparation method of anode material for lithium battery according to claim 2, is characterized in that described siloxanesFor (C2H5O)3SiC2H5、(C2H5O)4Si、(C2H5O)3SiC2H4Or (C2H5O)3SiCH2C6H6。
4. the preparation method of anode material for lithium battery according to claim 1 and 2, is characterized in that, described theThree monomers are at least one in phenol, catechol, resorcinol, phloroglucin or melamine.
5. the preparation method with anode material according to the lithium battery described in claim 1-3 any one, is characterized in that instituteStating alcohol is at least one in methyl alcohol, ethanol, propyl alcohol, butanols, isobutanol or amylalcohol; Described surfactant is cetyl bromineChange at least one in ammonium, F123 or P127; Described alkali lye is at least one in ammoniacal liquor, amino acid or NaOH.
6. the preparation method of anode material for lithium battery according to claim 4, is characterized in that, described alcohol is firstAt least one in alcohol, ethanol, propyl alcohol, butanols, isobutanol or amylalcohol; Described surfactant be cetyl ammonium bromide,At least one in F123 or P127; Described alkali lye is at least one in ammoniacal liquor, amino acid or NaOH.
7. the preparation method with anode material according to the lithium battery described in claim 1-3 any one, is characterized in that instituteState self assembly and be siloxanes, condensation polymer monomer first in template by electrostatic interaction assemble altogether, then in the effect of catalystLower polymerization reaction take place.
8. the preparation method with anode material according to the lithium battery described in claim 1-3 any one, is characterized in that instituteStating the volume ratio of alcohol and distilled water in a step is 1 ︰ 15-4 ︰ 3; Described in described b step, the concentration of alkali lye is 0.2-5wt%; InstituteStating the mass ratio of siloxanes and condensation polymer monomer in d step is 1 ︰ 9-4.3 ︰ 1.
9. the preparation method with anode material according to the lithium battery described in claim 1-3 any one, is characterized in that instituteState in e step, heating rate is 2-10K/min, and gas flow rate is 20-100mLmin-1。
10. for a negative pole for lithium rechargeable battery, described negative pole comprises collector and loads on bearing on this collectorUtmost point material, is characterized in that, described negative material contains answering that the preparation method that adopts described in claim 1-9 any one makesCondensation material.
11. 1 kinds of lithium ion batteries, this battery comprises pole piece and electrolyte, described pole piece comprises positive pole, negative pole and is positioned at positive poleAnd membrane layer between negative pole, wherein, described negative pole is negative pole claimed in claim 10.
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| CN111900396A (en) * | 2020-07-07 | 2020-11-06 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of carbon-coated silicon monoxide nanorod |
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| WO2012036354A1 (en) * | 2010-09-13 | 2012-03-22 | Yeil Electronics Co., Ltd. | SiO-C COMPOSITE POWDER FOR LITHIUM SECONDARY BATTERIES AND PREPARATION METHOD THEREOF |
| CN103236520A (en) * | 2013-04-24 | 2013-08-07 | 北京科技大学 | Preparation method of lithium ion battery silicon oxide/carbon composite negative pole material |
| CN103682359A (en) * | 2012-08-29 | 2014-03-26 | 苏州宝时得电动工具有限公司 | Negative electrode material, preparation method of material, negative electrode, and battery comprising negative electrode |
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| CN103682359A (en) * | 2012-08-29 | 2014-03-26 | 苏州宝时得电动工具有限公司 | Negative electrode material, preparation method of material, negative electrode, and battery comprising negative electrode |
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