CN106252638A - A kind of silicon/oxide composite negative pole material with Lithium metasilicate boundary layer and preparation method - Google Patents

A kind of silicon/oxide composite negative pole material with Lithium metasilicate boundary layer and preparation method Download PDF

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CN106252638A
CN106252638A CN201610887984.9A CN201610887984A CN106252638A CN 106252638 A CN106252638 A CN 106252638A CN 201610887984 A CN201610887984 A CN 201610887984A CN 106252638 A CN106252638 A CN 106252638A
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silicon
oxide
lithium
alcohol
boundary layer
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CN106252638B (en
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文钟晟
杜路路
王冠琴
李嵩
孙俊才
季世军
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Dalian Maritime University
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Dalian Maritime University
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/386—Silicon or alloys based on silicon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention provides a kind of silicon/oxide composite negative pole material with Lithium metasilicate boundary layer and preparation, belong to field of lithium ion battery.Described silicon/the oxide composite negative pole material with Lithium metasilicate boundary layer, including silicon active center, oxide matrix and the Lithium metasilicate boundary layer between silicon active center and oxide matrix.The present invention uses the method that chemical precipitation combines with high temperature solid state reaction; utilize the high absorption property absorption excess lithium ion of precipitation product; make its silicon oxide with silicon face trace in high temperature solid state reaction; one layer of Lithium metasilicate boundary layer it is formed in situ between silicon active center and oxide matrix; provide not only the continuous passage of lithium ion transport; and can be as the reactivity being effectively protected between reduction active center, interface and oxide matrix; therefore, there is good electrochemistry cycle performance.The technical process that invention relates to is very simple, adopts the composite being prepared from this way and has the interface compatibility of excellence.

Description

A kind of silicon/oxide composite negative pole material with Lithium metasilicate boundary layer and preparation Method
Technical field
The present invention relates to a kind of lithium ion battery negative material, preparation method and application, belong to field of lithium ion battery.Tool Say body, relate to a kind of can be used as lithium ion battery negative have height ratio capacity, high cycle life silicon/oxide be combined Material and its preparation method and application.
Background technology
Relative to other secondary chemical sources of electric energy systems, lithium ion battery has high-energy-density, long-life and to environment The characteristic such as pollution-free, and be widely used in mobile terminal and transport the energy supplyystem of instrument.For current lithium-ion electric For the carbon negative pole material that pond is widely used, due to process technology and the high speed development of mounting technology, by battery assemble ability Promote and improve further the method for its reversible electrochemical energy storage efficiency and reached bottleneck.Current lithium ion battery is needed badly Develop new electrode material system, so that its performance obtains substantial breakthrough.
In alloy type known today and semiconductor type negative material, silicon is owing to having the theoretical appearance of up to 4200mAh/g Measure and become the study hotspot of high-capacity cathode material.But owing to silicon there will be serious volume during electrochemistry removal lithium embedded Expansion makes its electrochemistry cycle performance drastically deteriorate.Therefore, at present the research emphasis of silicon is used various modified methods, improve silicon Cycle performance.
In numerous modified methods, relatively conventional is the material conduct using and having relatively low volumetric expansion Matrix material, by compound method, by silicon mosaic in these matrix materials, to alleviate the embedding due to lithium ion and abjection The change in volume caused.Matrix material plays a part buffer mechanism stress.Relatively conventional matrix material is carbons material, bag Include graphite, Polymer-pyrolysis carbon, CNT, carbon nano-fiber etc..But for silicon, although graphite negative electrodes material There is more preferable mechanical property, lower cubical expansivity (only 9%, far below the 400% of silicon), but owing to absolute volume is swollen Swollen still exist, therefore, the building method of this kind of composite, it is possible to alleviate the bulk effect of silicon to a certain extent, but silicon The long-term electrochemical cycle stability of class material is not significantly improved.And, in following cycle, along with circular response Proceeding, matrix material and silicon active center are due to the mismatch of volumetric expansion, and its interface cohesion therebetween also will be subject to Heavy damage, causes the decay of electrochemistry cycle performance.
Another effective ways of silicium cathode material modification are, the nanorize of silicon.The nanorize of silicon, including nano silicon particles, Silicon nanowires, nano-tube, silicon wafer must etc. preparation, by improve silicon materials itself mechanical property with reach alleviation volume swollen Swollen problem.Preparing silicon nanowires is to overcome its volumetric expansion, improves the effective ways of its electrochemistry cycle performance. (C.K.Chani,H.Peng,G.Liu,K.Mcilwrath,X.F.Zhang,R.A.Huggins,；Y.Cui,Nature Nanotech., 2008,3,31-35.).These method for making Nano, are not only effectively increased the mechanical property of silicon active material itself Can, also substantially increase the specific surface area of silicon, reduce the relative volume expansion rate of silicon.Therefore, the nanorize of silicon is the most Through becoming the universal method of silicon active material.
Surface modification is also one of method of modifying of silicon materials.Silicon, during serious volumetric expansion, can cause its table The instability in face, fresh active surface is constantly exposed in electrolyte, makes side reaction aggravation therebetween, thus produces The most thick and heavy solid electrolyte film (SEI film), and the electrolyte that this layer of SEI film is lost also is to cause in all previous cyclic process One of reason of low coulombic efficiency.At present the most general method be silicon materials surface deposition or one layer of carbon thin layer of parcel or other Compound layer, with the interface of stable electrolyte Yu electrode, thus improves the electrochemistry cycle performance of material.Additionally, by bonding The change of agent, it is also possible to effectively alleviate the destructive consequence that bulk effect is brought.
Up to the present, the rarest research relates to the method connected by interface, the silicon with transition zone that structure is unique Base negative material is to improve the Electrochemical Lithiation/Delithiation of silicon class negative material.
Summary of the invention
For influence factors such as the volumetric expansion mismatch of silicon in solution prior art with matrix material, the surface instabilities of silicon Easily causing the problem that silicon active center separates with matrix material in follow-up cyclic process, the present invention provides one to have silicon Silicon/the oxide composite negative pole material of acid lithium boundary layer and preparation method.
The present invention uses following technological means:
A kind of silicon/oxide composite negative pole material with Lithium metasilicate boundary layer, including silicon active center and oxide-base Body, and the Lithium metasilicate boundary layer between silicon active center and oxide matrix.Of the present invention have Lithium metasilicate circle Silicon/the oxide composite negative pole material of surface layer, described Lithium metasilicate boundary layer refers to that preparing situ at described composite is formed Lithium silicate, change between silicon active center and oxide matrix and chromatograph out.
Silicon/the oxide composite negative pole material with Lithium metasilicate boundary layer that the present invention provides, described silicon active center is Refer to that particle size, at the silica flour of 20-100 nanometer, undertakes main electrochemical lithium storage effect in charge and discharge process；Described oxidation Thing matrix, refers to niobium pentaoxide, or niobium pentaoxide and titania composite oxide；Described Lithium metasilicate boundary layer, refers to Prepare, at described composite, the lithium silicate that situ is formed, between silicon active center and oxide matrix, play biography Pass the function of lithium ion.Silicon/the oxide composite negative pole material with Lithium metasilicate boundary layer that i.e. present invention provides has following Structure:
(1) silicon active center is electrochemical reaction active center, and oxide is matrix, is positioned at silicon active center and oxide One layer of nano level Lithium metasilicate boundary layer is had between matrix；
(2) particle size in silicon active center is 20-100 nanometer；
(3) oxide-base bulk layer thickness is in 10-50 nanometer；
(4) Lithium metasilicate interfacial layer thickness is 1-20 nanometer.
The present invention also provides for the preparation method of a kind of silicon/oxide composite negative pole material with Lithium metasilicate boundary layer, bag Include following steps:
(1) preparation alcohol-water mixed solution；
(2) mixture of niobium chloride or niobium chloride and tetrabutyl titanate ester is dissolved in the mixed solution that step (1) is prepared In, obtain uniform oxide precursor thing/alcoholic solution；
(3) silica flour is joined ultrasonic vibration at least 30 points in the oxide precursor thing/alcoholic solution obtained in step (2) Clock, makes the silica flour reunited due to skin effect obtain fully dispersed, obtains uniform silica flour-oxide precursor thing/alcoholic solution；
(4) Lithium hydrate is dissolved in alcohol-water mixed solution that step (1) is prepared, obtains Lithium hydrate/alcohol-water mixing Liquid；
(5) Lithium hydrate/alcohol-water mixtures that will obtain in step (4), is added dropwise over silica flour-oxygen that step (3) obtains In compound predecessor/alcoholic solution, make the Nb in solution5+Or Ti4+With Nb5+Fully precipitate under the effect of Lithium hydrate.Will be fully Solution after reaction precipitation filters to collect solid reaction products, and the alcohol obtained in the solid product step (1) that will obtain- Water mixed solution washing is neutral to filtrate, and vacuum drying.
(6) solid product obtained in step (5) is moved in the tube furnace of band argon shield, carry out heat treatment, whole Heat treatment process is all carried out under argon shield.The product obtained after heat treatment is the silicon/oxidation with Lithium metasilicate boundary layer Thing composite negative pole material.
Described alcohol-the water mixed solution of step of the present invention (1), alcohol can be methanol, ethanol, ethylene glycol, and water is deionized water. The two mixes by volume, alcohol: the volume ratio of water is preferably in the range of 2:1-2:10.In same preparation process, made Alcohol-water mixed solution all use same alcohol: water volume ratio.
Step of the present invention (2) described niobium chloride or tetrabutyl titanate ester niobium chloride are analytical pure.Use niobium chloride conduct During solute, then the oxide precursor thing/alcoholic solution being configured to is preferably niobium chloride/ethanol solution, obtains end product and has silicon In the silicon/oxide composite negative pole material of acid lithium boundary layer, oxide is then niobium pentaoxide；Use niobium chloride and tetrabutyl titanium When acid ester mixtures is as solute, in the silicon/oxide composite negative pole material of the Lithium metasilicate boundary layer the most finally prepared, oxygen Compound is then niobium pentaoxide/titanium dioxide mixture.Preferably, in described oxide precursor thing/alcoholic solution, Nb5+Or Nb5 +With Ti4+The molar concentration scope of total cation is 0.01-0.1mol/L, further preferred Nb5+Or Nb5+With Ti4+Total cation Molar concentration scope be 0.025-0.05mol/L.
Further, when step (2) uses niobium chloride and tetrabutyl titanate ester admixture as solute, preferably tetrabutyl titanium Acid esters: the mol ratio of niobium chloride is 1:1-1:4, the two mol ratio and titanium in the silicon/oxide composite negative pole material of final preparation/ Niobium atom is than quite.
The addition of step of the present invention (3) described silica flour is by Nb in oxide precursor thing/alcoholic solution5+Or Nb5+With Ti4+'s Mole total amount determines.The calculation of silica flour addition is as follows: by metal ion in solution Nb5+Mole or Nb5+With Ti4+ Mole total amount be converted into the quality of metal-oxide of correspondence, then the addition of silica flour controls in corresponding metal-oxide quality 40-100% in the range of, preferably 60-100%.The product finally given has the silicon/oxide of Lithium metasilicate boundary layer and is combined The specific discharge capacity of negative material is relevant to the addition of silicon, and the addition of silicon is the highest, then the specific discharge capacity of corresponding product is more High.
In the described Lithium hydrate/alcohol-water mixtures of step of the present invention (4), the concentration of lithium ion is 0.01-0.5mol/L, excellent Selecting lithium concentration is 0.02-0.4mol/L.
The dropping total amount of the described Lithium hydrate/alcohol-water mixtures of step of the present invention (5), step (3) silica flour obtained- Nb in oxide precursor thing/alcoholic solution5+Or Nb5+With Ti4+Mole total amount determine.Usually, the Lithium hydrate/alcohol of addition- In water mixed liquid, Li+Mole overall control Nb in silica flour-oxide precursor thing/alcoholic solution5+Mole or Nb5+With Ti4+ The 500-650% of mole total amount.Vacuum drying described in step (5), refers in vacuum drying oven, and 60 DEG C of-80 DEG C of vacuum are done Dry 6-10 hour.
Step of the present invention (6) described heat treatment process is: from the beginning of room temperature, be warming up to according to the heating rate of 10 DEG C/min Setting heat treatment temperature, after being incubated 8-18 hour at this temperature, stove is cooled to room temperature.The sample obtained is has Lithium metasilicate circle Silicon/the oxide composite negative pole material of surface layer.The described heat-treatment temperature range that sets is as 580-800 DEG C.
The present invention uses the method that chemical precipitation combines with high temperature solid state reaction, utilizes the high absorption of precipitation product Performance adsorption excess lithium ion so that it is with the silicon oxide of silicon face trace in high temperature solid state reaction, in silicon active center and oxygen It is formed in situ one layer of Lithium metasilicate boundary layer between compound matrix, provide not only the continuous passage of lithium ion transport, Er Qieke As the reactivity being effectively protected between reduction active center, interface and oxide matrix.
The method that the present invention provides, when Lithium hydrate/alcohol-water mixtures, to be added dropwise over silica flour-oxide precursor thing/alcohol molten Nb after in liquid, in solution5+Or Ti4+/Nb5+Fully precipitate under the effect of Lithium hydrate, form corresponding metal hydroxides Precipitation, this precipitation is coated on the silicon powder surface being dispersed in oxide precursor thing/alcoholic solution, forms core-shell structure copolymer again with silica flour Close structure.In precipitation process, due to the adsorption of precipitation, the lithium ion of excess can be adsorbed simultaneously.This lithium ion is follow-up Heat treatment process in, at a suitable temperature, with the trace silicon dioxde reaction of silicon powder surface, in-situ preparation Lithium metasilicate chemical combination Thing, forms Lithium metasilicate boundary layer between silicon powder surface and oxide matrix.This Lithium metasilicate compound has good ion guide Electrically, therefore, constitute the lithium ion diffusion admittance of silicon active center and oxide skin(coating), be greatly promoted lithium in this kind of material The high efficiency of transmission of ion.Furthermore, due to the existence of Lithium metasilicate so that the surface in silicon active center defines the most complete protection Layer, can effectively stop in heat treatment process the oxygen atom of oxide skin(coating) to the diffusion in silicon active center, thus reduce into one Step generates the probability of inertia silicon dioxide, has ensured the electro-chemical activity in silicon active center.
Traditional silicon/oxide composite negative pole material is due to the directly contact of silicon/oxide, and heat treatment process needs precision Control to prevent silicon from reacting with the excessive chemical of oxide.Additionally, due to the removal lithium embedded voltage of oxide and silicon itself has aobvious Writing difference, therefore, oxide is only used as stress-buffer layer and exists, but the low ion-electron conductivity problems of itself, make this kind of The cycle performance of material is unsatisfactory.Silicon/the oxide composite negative pole material with Lithium metasilicate boundary layer that the present invention provides, by In constructing one layer of Lithium metasilicate interface between silicon active center and oxide matrix, provide not only the continuous of lithium ion transport Passage, and therefore, can have as the reactivity being effectively protected between reduction active center, interface and oxide matrix Good electrochemistry cycle performance.The technical process that the present invention relates to is very simple, adopts be prepared from this way compound Material has the interface compatibility of excellence, has high lot stability, it is easy to realize large-scale production, can be at lithium ion battery It is widely popularized in field.
Accompanying drawing explanation
The present invention is further detailed explanation with detailed description of the invention below in conjunction with the accompanying drawings.
Fig. 1 is the electron microscope picture of the target product of the embodiment of the present invention 1 preparation.Scale is 100 nanometers.
Fig. 2 is that photo is analyzed in the transmission electron microscope constituency of the target product of the embodiment of the present invention 1 preparation, and scale is 10 nanometers, The interior illustration of Fig. 2 is corresponding structural representation.
The charging and discharging curve figure of the negative plate that the target product that Fig. 3 is prepared by the embodiment of the present invention 1 is assembled is corresponding in figure Arabic numerals represent corresponding circulating cycle number of times.
Fig. 4 is the X-ray photoelectron spectroscopic analysis figure of the target product of the embodiment of the present invention 1 preparation.
Fig. 5 is the cycle life test figure of the target product of the embodiment of the present invention 1 preparation.
Detailed description of the invention
Following non-limiting example can make those of ordinary skill in the art that the present invention be more fully understood, but not with Any mode limits the present invention.
Test method described in following embodiment, if no special instructions, is conventional method；Described reagent and material, as Without specified otherwise, the most commercially obtain.
In following embodiment, use the silicon/oxide composite negative pole material system with Lithium metasilicate boundary layer of the present invention The method of standby negative plate is as follows:
Kynoar (binding agent) is dissolved in N-Methyl pyrrolidone, is configured to the Kynoar of 0.02 grams per liter N-Methyl pyrrolidone solution；To there is the silicon/oxide composite negative pole material (active substance) of Lithium metasilicate boundary layer, acetylene black (conductive agent), Kynoar solution, by active substance: conductive agent: after the mass ratio of binding agent is 7:2:1 mixing, be applied to 25 On the Copper Foil that micron is thick, this Copper Foil is moved into and takes out after vacuum drying oven dries 8 hours under 110 DEG C of vacuum；The Copper Foil that will dry It is cut into the disk of a diameter of 16mm, i.e. makes the silicon/oxide composite negative pole used by electro-chemical test with Lithium metasilicate boundary layer Material negative plate.Negative plate is directly done with metal Li electrode is assembled into button cell tests its chemical property, electrolyte For LiPF6/EC:DEC (1:1, volume ratio).Test charging and discharging currents density is 0.05mA, ends charging/discharging voltage 0V～1.5V. Discharge process is corresponding to the process of Lithium-ion embeding silicon nanowires combination electrode, and charging process is corresponding to the abjection of lithium ion Journey.
Embodiment 1
(1) dehydrated alcohol (analytical pure) is mixed homogeneously with the volume ratio of 1:1 with deionized water, obtain alcohol-water mixing molten Liquid, standby；
(2) 0.27g niobium chloride is dissolved in 40ml ethanol solution standby；
(3) 0.11g nano silica fume (average particle size is 40nm) is put in niobium chloride/ethanol solution, ultrasonic vibration 30min, makes silica flour-niobium chloride/ethanol solution；
(4) Lithium hydrate is configured to Lithium hydrate/alcohol-water mixed solution (ethanol: the volume ratio of water of 0.02mol/L For 1:1)；
(5) take 250ml Lithium hydrate/alcohol-water mixed solution (20mmol/L), be added dropwise to silica flour-niobium chloride/second In alcoholic solution, after having reacted, precipitation filter, and with alcohol-water mixed solution (volume ratio 1:1) wash 3 times to filtrate in Property, it is vacuum dried 8 hours at 70 DEG C；
(6) dried sample is placed in tube furnace, with the programming rate of 10 DEG C/min from room temperature to 600 DEG C, heat Processing 8 hours, then be cooled to room temperature with body of heater, whole heat treatment process is all carried out under argon shield.Product after heat treatment It is target product and there is the silicon/oxide composite negative pole material of Lithium metasilicate boundary layer.
Prepared by the present embodiment has the silicon/oxide composite negative pole material (as shown in Figure 1) of Lithium metasilicate boundary layer, including Silicon active center and oxide matrix, also have Lithium metasilicate boundary layer between silicon active center and oxide matrix, such as Fig. 2 institute Show.
By as follows for process that the present embodiment gained target product is assembled into electrode slice: Kynoar (binding agent) is dissolved in N-Methyl pyrrolidone, is configured to the N-Methyl pyrrolidone solution of the Kynoar of 0.02 grams per liter；To have Lithium metasilicate circle Silicon/the oxide composite negative pole material (active substance) of surface layer, acetylene black (conductive agent), Kynoar solution, by active matter Matter: conductive agent: after the mass ratio of binding agent is 7:2:1 mixing, be applied on 25 microns of thick Copper Foils, moves into vacuum by this Copper Foil and dries Take out after case dries 8 hours under 110 DEG C of vacuum；The Copper Foil of drying is cut into the disk of a diameter of 16mm, i.e. makes electrochemistry There is used by test the silicon/oxide composite negative pole material negative plate of Lithium metasilicate boundary layer.Negative plate is directly done with metal Li Electrode being assembled into button cell and tests its chemical property, electrolyte is LiPF6/ EC:DEC (1:1, volume ratio).Test is filled Discharge current density is 0.05mA, ends charging/discharging voltage 0V～1.5V.Discharge process corresponds to Lithium-ion embeding silicon nanowires The process of combination electrode, charging process is corresponding to the abjection process of lithium ion.
The electrode reversible capacity first of preparation reaches 2754mAh/g.The target product that Fig. 3 is prepared by the present embodiment is assembled The charging and discharging curve figure of negative plate.
Embodiment 2
(1) ethylene glycol (analytical pure) is mixed homogeneously with the volume ratio of 2:1 with deionized water, obtain ethylene glycol-water mixing molten Liquid, standby；
(2) 0.27g niobium chloride is dissolved in 40ml ethylene glycol solution standby；
(3) 0.13g nano silica fume (40nm) is put in niobium chloride/ethylene glycol solution, ultrasonic vibration 30min, makes silicon Powder-niobium chloride/ethylene glycol solution；
(4) Lithium hydrate is claimed with preparation Lithium hydrate/ethylene glycol-mixed solution (ethanol: the volume of water of 20mmol/L Ratio is 2:1)；
(5) take 250ml Lithium hydrate/ethylene glycol-mixed solution (20mmol/L), be added dropwise over silica flour-niobium chloride/second two In alcoholic solution, after having reacted, precipitation filters, and to wash 2 times to filtrate with alcohol-water mixed solution (2:1) be neutrality, 60 It is vacuum dried 10 hours at DEG C；
(6) dried sample is placed in tube furnace, with the programming rate of 10 DEG C/min from room temperature to 650 DEG C, heat Processing 8 hours, then be cooled to room temperature with body of heater, whole heat treatment process is all carried out under argon shield.Product after heat treatment It is target product.
Products therefrom is assembled into the process of electrode slice and Electrochemical Test Procedure first may be used with embodiment 1, the electrode of preparation Inverse capacity reaches 2815mAh/g.
Embodiment 3
(1) ethanol (analytical pure) is mixed homogeneously with the volume ratio of 1:1 with deionized water, obtains alcohol-water mixed solution, Standby；
(2), by 0.27g niobium chloride, 0.34g butyl titanate is dissolved in 40ml ethanol solution standby；
(3) 0.15g nano silica fume (40nm) is put in niobium chloride-tetrabutyl titanate ester/ethanol solution, ultrasonic vibration 30min, makes silica flour-niobium chloride-tetrabutyl titanate ester/ethanol solution；
(4) by the Lithium hydrate Lithium hydrate/ethanol-mixed solution (ethanol: the volume ratio of water being configured to 20mmol/L For 1:1)；
(5) take 500ml Lithium hydrate/ethanol-mixed solution (20mmol/L), be added dropwise over silica flour-niobium chloride/ethanol molten In liquid, after having reacted, precipitation filters, and to wash 3 times to filtrate with alcohol-water mixed solution (1:1) be neutrality, at 70 DEG C It is vacuum dried 8 hours；
(6) dried sample is placed in tube furnace, with the programming rate of 10 DEG C/min from room temperature to 580 DEG C, heat Processing 14 hours, then be cooled to room temperature with body of heater, whole heat treatment process is all carried out under argon shield.Product after heat treatment It is target product.
Products therefrom is assembled into the process of electrode slice and Electrochemical Test Procedure first may be used with embodiment 1, the electrode of preparation Inverse capacity reaches 2108mAh/g.
Embodiment 4
(1) methanol (analytical pure) is mixed homogeneously with the volume ratio of 1:1 with deionized water, obtains methanol-water mixed solution, Standby；
(2), by 0.27g niobium chloride, 0.34g butyl titanate is dissolved in 40ml methanol solution standby；
(3) 0.15g nano silica fume (40nm) is put in niobium chloride-tetrabutyl titanate ester/methanol solution, ultrasonic vibration 30min, makes silica flour-niobium chloride-tetrabutyl titanate ester/methanol solution；
(4) Lithium hydrate is claimed with preparation Lithium hydrate/methanol-mixed solution (methanol: the volume ratio of water of 40mmol/L For 1:1)；
(5) take 250ml Lithium hydrate/methanol-mixed solution (40mmol/L), be added dropwise over silica flour-niobium chloride/methanol molten In liquid, after having reacted, precipitation filters, and to wash 4 times to filtrate with methanol-water mixed solution (1:1) be neutrality, at 70 DEG C It is vacuum dried 10 hours；
(6) dried sample is placed in tube furnace, with the programming rate of 10 DEG C/min from room temperature to 600 DEG C, heat Processing 12 hours, then be cooled to room temperature with body of heater, whole heat treatment process is all carried out under argon shield.Product after heat treatment It is target product.
Products therefrom is assembled into the process of electrode slice and Electrochemical Test Procedure first may be used with embodiment 1, the electrode of preparation Inverse capacity reaches 1885mAh/g.
Embodiment 5
(1) dehydrated alcohol (analytical pure) is mixed homogeneously with the volume ratio of 1:5 with deionized water, obtain alcohol-water mixing Solution, standby；
(2) 0.27g niobium chloride is dissolved in 10ml ethanol solution standby；
(3) 0.08g nano silica fume (average particle size is 40nm) is put in niobium chloride/ethanol solution, ultrasonic vibration 30min, makes silica flour-niobium chloride/ethanol solution；
(4) Lithium hydrate is configured to Lithium hydrate/alcohol-water mixed solution (ethanol: the volume of water of 0.02mol/L Ratio is 1:5)；
(5) take 250ml Lithium hydrate/alcohol-water mixed solution (0.02mmol/L), be added dropwise to silica flour-niobium chloride/ In ethanol solution, after having reacted, precipitation filter, and with alcohol-water mixed solution (volume ratio 1:5) wash 3 times to filtrate in Neutrality, is vacuum dried 8 hours at 70 DEG C；
(6) dried sample is placed in tube furnace, with the programming rate of 10 DEG C/min from room temperature to 600 DEG C, Heat treatment 8 hours, then it is cooled to room temperature with body of heater, whole heat treatment process is all carried out under argon shield.Product after heat treatment Thing is target product and has the silicon/oxide composite negative pole material of Lithium metasilicate boundary layer.
Products therefrom is assembled into the process of electrode slice and Electrochemical Test Procedure first may be used with embodiment 1, the electrode of preparation Inverse capacity reaches 1123mAh/g.
Embodiment 6
(1) dehydrated alcohol (analytical pure) is mixed homogeneously with the volume ratio of 1:2 with deionized water, obtain alcohol-water mixing Solution, standby；
(2) 0.27g niobium chloride is dissolved in 100ml ethanol solution standby；
(3) 0.10g nano silica fume (average particle size is 40nm) is put in niobium chloride/ethanol solution, ultrasonic vibration 30min, makes silica flour-niobium chloride/ethanol solution；
(4) Lithium hydrate is configured to Lithium hydrate/alcohol-water mixed solution (ethanol: the volume of water of 0.01mol/L Ratio is 1:2)；
(5) take 500ml Lithium hydrate/alcohol-water mixed solution (0.01mmol/L), be added dropwise to silica flour-niobium chloride/ In ethanol solution, after having reacted, precipitation filter, and with alcohol-water mixed solution (volume ratio 1:2) wash 4 times to filtrate in Neutrality, is vacuum dried 8 hours at 70 DEG C；
(6) dried sample is placed in tube furnace, with the programming rate of 10 DEG C/min from room temperature to 600 DEG C, Heat treatment 8 hours, then it is cooled to room temperature with body of heater, whole heat treatment process is all carried out under argon shield.Product after heat treatment Thing is target product and has the silicon/oxide composite negative pole material of Lithium metasilicate boundary layer.
Products therefrom is assembled into the process of electrode slice and Electrochemical Test Procedure first may be used with embodiment 1, the electrode of preparation Inverse capacity reaches 1323mAh/g.
Embodiment 7
(1) ethanol (analytical pure) is mixed homogeneously with the volume ratio of 1:1 with deionized water, obtains alcohol-water mixed solution, Standby；
(2) by 0.27g niobium chloride, 0.085g butyl titanate is dissolved in 40ml ethanol solution standby；
(3) 0.11g nano silica fume (40nm) is put in niobium chloride-tetrabutyl titanate ester/ethanol solution, ultrasonic vibration 30min, makes silica flour-niobium chloride-tetrabutyl titanate ester/ethanol solution；
(4) by the Lithium hydrate Lithium hydrate/ethanol-mixed solution (ethanol: the volume ratio of water being configured to 0.5mol/L For 1:1)；
(5) take 16.25ml Lithium hydrate/ethanol-mixed solution (0.5mol/L), be added dropwise over silica flour-niobium chloride/ethanol In solution, after having reacted, precipitation filters, and to wash 3 times to filtrate with alcohol-water mixed solution (1:1) be neutrality, at 70 DEG C Lower vacuum drying 8 hours；
(6) dried sample is placed in tube furnace, with the programming rate of 10 DEG C/min from room temperature to 580 DEG C, Heat treatment 14 hours, then it is cooled to room temperature with body of heater, whole heat treatment process is all carried out under argon shield.Product after heat treatment Thing is target product.
Products therefrom is assembled into the process of electrode slice and Electrochemical Test Procedure first may be used with embodiment 1, the electrode of preparation Inverse capacity reaches 1120mAh/g.
The above, the only present invention preferably detailed description of the invention, but protection scope of the present invention is not limited thereto, Any those familiar with the art in the technical scope that the invention discloses, according to technical scheme and Inventive concept equivalent or change in addition, all should contain within protection scope of the present invention.

Claims (7)

1. silicon/oxide composite negative pole material with Lithium metasilicate boundary layer, it is characterised in that: include silicon active center and Oxide matrix, also has Lithium metasilicate boundary layer between described silicon active center and oxide matrix.
2. the method preparing the silicon/oxide composite negative pole material with Lithium metasilicate boundary layer, it is characterised in that have as Lower step:
(1) preparation alcohol-water mixed solution；
(2) mixture of niobium chloride or niobium chloride/tetrabutyl titanate ester is dissolved in step (1) and obtains in solution, obtain uniformly Oxide precursor thing/alcoholic solution；
(3) silica flour is joined ultrasonic vibration at least 30 minutes in oxide precursor thing/alcoholic solution that step (2) obtains, makes silicon Powder is fully dispersed, obtains uniform silica flour-oxide precursor thing/alcoholic solution；
(4) Lithium hydrate is dissolved in alcohol-water mixed solution that step (1) obtains, obtains Lithium hydrate/alcohol-water mixtures；
(5) Lithium hydrate/alcohol-water mixtures that step (4) obtains is added dropwise to silica flour-oxide that step (3) obtains In predecessor/alcoholic solution, make the Nb in solution5+Or Nb5+/Ti4+Fully precipitate under the effect of Lithium hydrate；To fully react After solution filter to collect solid reaction products, and alcohol-water mixed solution that the solid product step (1) obtained is prepared Wash and become neutral to filtrate, and vacuum drying；
(6) tube furnace of the solid product immigration band argon shield after step (5) being dried carries out heat treatment, after heat treatment To product be there is the silicon/oxide composite negative pole material of Lithium metasilicate boundary layer.
Method the most according to claim 2, it is characterised in that: step (1) described alcohol-water mixed solution alcohol by volume: Water is 2:1-2:10 mixing.
Method the most according to claim 2, it is characterised in that: in step (2) described oxide precursor thing/alcoholic solution, Nb5+ Or Nb5+/Ti4+Concentration be 0.01-0.1mol/L.
Method the most according to claim 2, it is characterised in that: by Nb5+Or Nb5+/Ti4+Corresponding metal-oxide meter, step Suddenly the 40-100% that addition is metal-oxide quality of (3) described silica flour.
Method the most according to claim 2, it is characterised in that: lithium in the described Lithium hydrate/alcohol-water mixtures of step (4) Ion concentration is 0.01-0.5mol/L.
Method the most according to claim 2, it is characterised in that: the described Lithium hydrate/alcohol-water added in step (5) mixes Closing the mole of lithium ion in liquid is Nb in solution5+Or Nb5+/Ti4+The 500-650% of mole.
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