CN106252638B - A kind of silicon/oxide composite negative pole material and preparation method with lithium metasilicate boundary layer - Google Patents

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

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CN106252638B
CN106252638B CN201610887984.9A CN201610887984A CN106252638B CN 106252638 B CN106252638 B CN 106252638B CN 201610887984 A CN201610887984 A CN 201610887984A CN 106252638 B CN106252638 B CN 106252638B
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silicon
alcohol
lithium
oxide
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CN106252638A (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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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H—ELECTRICITY
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Abstract

The present invention provides a kind of with silicon/oxide composite negative pole material of lithium metasilicate boundary layer and preparation, belongs to field of lithium ion battery.Silicon/the oxide composite negative pole material with lithium metasilicate boundary layer, including silicon activated centre, oxide matrix and the lithium metasilicate boundary layer between silicon activated centre and oxide matrix.The method that the present invention uses chemical precipitation to combine with high temperature solid state reaction; excessive lithium ion is adsorbed using the high absorption property of precipitation reaction product; make its silica with silicon face trace in high temperature solid state reaction; one layer of lithium metasilicate boundary layer is formed in situ between silicon activated centre and oxide matrix; provide not only the continuous passage of lithium ion transport; and it can be used as the reactivity being effectively protected between interface reduction activated centre and oxide matrix; therefore, there is good electrochemistry cycle performance.It is very simple to invent the technical process being related to, the composite material being prepared in this way has excellent interface compatibility.

Description

It is a kind of with silicon/oxide composite negative pole material of lithium metasilicate boundary layer and preparation Method
Technical field
The present invention relates to a kind of lithium ion battery negative materials, preparation method and application, belong to field of lithium ion battery.Tool Say to body, be related to it is a kind of can be used as negative electrode of lithium ion battery have height ratio capacity, the silicon/oxide in high circulation service life compound Material and its preparation method and application.
Background technique
Relative to other secondary chemical sources of electric energy systems, lithium ion battery has high-energy density, long-life and to environment The characteristics such as pollution-free, and be widely used in mobile terminal and transport the energy supplyystem of tool.For current lithium-ion electric For the carbon negative pole material that pond is widely used, due to the high speed development of processing technology and mounting technology, pass through battery assemble ability The promotion method that further increases its reversible electrochemical energy storage efficiency had reached bottleneck.Current lithium ion battery needs New electrode material system is developed, so that its performance obtains substantive breakthrough.
In alloy type and semiconductor type negative electrode material known today, silicon is due to having the theoretical of up to 4200mAh/g to hold Measure and become the research hotspot of high-capacity cathode material.But since silicon will appear serious volume during electrochemistry removal lithium embedded Expansion deteriorates its electrochemistry cycle performance sharply.Therefore, various modified methods are used to the research emphasis of silicon at present, improves silicon Cycle performance.
In numerous modified methods, relatively conventional is using the material conduct with relatively low volume expansion Basis material, by compound method, by silicon mosaic in these basis materials, to alleviate insertion and abjection due to lithium ion Caused by volume change.Basis material plays a part of buffer mechanism stress.Relatively conventional basis material is Carbon materials, packet Include graphite, Polymer-pyrolysis carbon, carbon nanotube, carbon nano-fiber etc..But for silicon, although graphite negative electrodes material With better mechanical property, lower cubical expansivity (only 9%, far below the 400% of silicon), but since absolute volume is swollen Swollen to still remain, therefore, the building method of this kind of composite material can alleviate the bulk effect of silicon, but silicon to a certain extent The long-term electrochemical cycle stability of class material is not significantly improved.Moreover, in following cycle, with circular response Continue, due to the mismatch of volume expansion, interface cohesion between the two also will be by for basis material and silicon activated centre It is serious to destroy, cause the decaying of electrochemistry cycle performance.
Another effective ways of silicium cathode material modification are the nanosizing of silicon.The nanosizing of silicon, including nano silicon particles, It is swollen to reach alleviation volume by improving the mechanical property of silicon materials itself for silicon nanowires, nano-tube, the preparation of silicon wafer palpus etc. Swollen problem.Preparing silicon nanowires is to overcome its volume 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 not only effectively increase the mechanical property of silicon active material itself Can, the specific surface area of silicon is also substantially increased, the relative volume expansion rate of silicon is reduced.Therefore, the nanosizing of silicon has been now Through the universal method for becoming silicon active material.
Surface is modified and one of the method for modifying of silicon materials.Silicon will cause its table during serious volume expansion Face it is unstable, fresh active surface is constantly exposed in electrolyte, is aggravated side reaction between the two, is thus generated Very thick and heavy solid electrolyte film (SEI film), and the electrolyte that this layer of SEI film is lost is also to cause in all previous cyclic process One of the reason of low coulombic efficiency.At present more general method be silicon materials surface deposit or wrap up one layer of carbon thin layer or other Compound layer, to stablize the interface of electrolyte and electrode, to improve the electrochemistry cycle performance of material.In addition, passing through bonding Bulk effect bring destructiveness consequence can be also effectively relieved in the change of agent.
Up to the present, still rare research is related to the method connected by interface, constructs the unique silicon with transition zone Base negative electrode material is to improve the Electrochemical Lithiation/Delithiation of silicon class negative electrode material.
Summary of the invention
For the volume expansion mismatch for solving silicon and basis material in the prior art, the influence factors such as surface instability of silicon The problem of separation of silicon activated centre and basis material is easily caused in subsequent cyclic process, the present invention provides a kind of with silicon Silicon/the oxide composite negative pole material and preparation method of sour lithium boundary layer.
The present invention uses following technological means:
A kind of silicon/oxide composite negative pole material with lithium metasilicate boundary layer, including silicon activated centre and oxide-base Body, and the lithium metasilicate boundary layer between silicon activated centre and oxide matrix.It is of the present invention that there is lithium metasilicate circle Silicon/oxide composite negative pole material of surface layer, the lithium metasilicate boundary layer refers to be formed in situ in composite material preparation Lithium silicate, change between silicon activated centre and oxide matrix and chromatograph out.
Silicon/oxide composite negative pole material provided by the invention with lithium metasilicate boundary layer, the silicon activated centre are Refer to silicon powder of the particle size at 20-100 nanometers, main electrochemical lithium storage effect is undertaken in charge and discharge process；The oxidation Object matrix refers to niobium pentaoxide or niobium pentaoxide and titania composite oxide；The lithium metasilicate boundary layer, refers to The lithium silicate being formed in situ in composite material preparation plays biography between silicon activated centre and oxide matrix Pass the function of lithium ion.Silicon/oxide composite negative pole material i.e. provided by the invention with lithium metasilicate boundary layer has following Structure:
(1) silicon activated centre is electrochemical reaction activated centre, and oxide is matrix, is located at silicon activated centre and oxide There is one layer of nanoscale lithium metasilicate boundary layer between matrix；
(2) particle size in silicon activated centre is 20-100 nanometers；
(3) oxide-base bulk layer thickness is at 10-50 nanometers；
(4) lithium metasilicate interfacial layer thickness is 1-20 nanometers.
Silicon/oxide composite negative pole material preparation method with lithium metasilicate boundary layer that the present invention also provides a kind of, packet Include following steps:
(1) alcohol-water mixed solution is prepared；
(2) mixture of niobium chloride or niobium chloride and tetrabutyl titanate ester is dissolved in the mixed solution of step (1) preparation In, obtain uniform oxide precursor object/alcoholic solution；
(3) silicon powder is added at least 30 points of ultrasonic vibration in oxide precursor object/alcoholic solution obtained in step (2) Clock is obtained the silicon powder reunited due to skin effect fully dispersed, obtains uniform silicon powder-oxide precursor object/alcoholic solution；
(4) lithium hydroxide is dissolved in alcohol-water mixed solution of step (1) preparation, obtains lithium hydroxide/alcohol-water mixing Liquid；
(5) by lithium hydroxide/alcohol-water mixtures obtained in step (4), silicon powder-oxygen that step (3) obtains is added dropwise In compound predecessor/alcoholic solution, make the Nb in solution5+Or Ti4+With Nb5+It is sufficiently precipitated under the action of lithium hydroxide.It will be abundant Solution filtering after reaction precipitating is to collect solid reaction products, and by obtained solid product alcohol-obtained in step (1) Water mixed solution is washed to filtrate neutrality, and vacuum drying.
(6) solid product obtained in step (5) is moved into the tube furnace protected with argon gas, is heat-treated, entirely Heat treatment process carries out under protection of argon gas.The product obtained after heat treatment is the silicon/oxidation with lithium metasilicate boundary layer Object composite negative pole material.
Step (1) alcohol-water mixed solution of the present invention, alcohol can be methanol, ethyl alcohol, ethylene glycol, and water is deionized water. The two mixes by volume, alcohol: in the range of the volume ratio of water is preferably 2:1-2:10.In the same preparation process, made Alcohol-water mixed solution is all made of same alcohol: water volume ratio.
Step (2) the of the present invention niobium chloride or tetrabutyl titanate ester niobium chloride are that analysis is pure.Using niobium chloride conduct When solute, then the oxide precursor object/alcoholic solution being configured to is preferably niobium chloride/ethanol solution, obtains final product with silicon In silicon/oxide composite negative pole material of sour lithium boundary layer, oxide is then niobium pentaoxide；Using niobium chloride and tetrabutyl titanium When acid ester mixtures are as solute, then in the silicon/oxide composite negative pole material for the lithium metasilicate boundary layer being finally prepared, oxygen Compound is then niobium pentaoxide/titanium dioxide mixture.Preferably, in oxide precursor object/alcoholic solution, Nb5+Or Nb5 +With Ti4+The molar concentration range of total cation is 0.01-0.1mol/L, further preferred Nb5+Or Nb5+With Ti4+Total cation Molar concentration range be 0.025-0.05mol/L.
Further, step (2) using niobium chloride and tetrabutyl titanate ester admixture as solute when, preferred tetrabutyl titanium Acid esters: the molar ratio of niobium chloride is 1:1-1:4, titanium in the two molar ratio and the silicon/oxide composite negative pole material finally prepared/ Niobium atom is than suitable.
The additional amount of step (3) the of the present invention silicon powder is by Nb in oxide precursor object/alcoholic solution5+Or Nb5+With Ti4+'s Moles total number determines.The calculation of silicon powder additional amount is as follows: pressing metal ion in solution Nb5+Mole or Nb5+With Ti4+ Moles total number be converted into the quality of corresponding metal oxide, then the additional amount control of silicon powder is in corresponding metal oxide quality 40-100% within the scope of, preferably 60-100%.Finally obtained product has silicon/oxide of lithium metasilicate boundary layer compound The specific discharge capacity of negative electrode material and the additional amount of silicon are related, and the additional amount of silicon is higher, then the specific discharge capacity for corresponding to product is got over It is high.
The concentration of lithium ion is 0.01-0.5mol/L in step (4) lithium hydroxide/alcohol-water mixtures of the present invention, excellent Selecting lithium concentration is 0.02-0.4mol/L.
The dropwise addition total amount of step (5) lithium hydroxide/alcohol-water mixtures of the present invention, the silicon powder-obtained by step (3) Nb in oxide precursor object/alcoholic solution5+Or Nb5+With Ti4+Moles total number determine.Generally, lithium hydroxide/alcohol-of addition In water mixed liquid, Li+Moles total number control in silicon powder-oxide precursor object/alcoholic solution Nb5+Mole or Nb5+With Ti4+ Moles total number 500-650%.Vacuum drying described in step (5), refers in vacuum drying oven, and 60 DEG C of -80 DEG C of vacuum are dry It is 6-10 hours dry.
Step (6) the of the present invention heat treatment process are as follows: since room temperature, be warming up to according to the heating rate of 10 DEG C/min Heat treatment temperature is set, after keeping the temperature 8-18 hours at this temperature, is furnace-cooled to room temperature.Obtained sample is to have lithium metasilicate circle Silicon/oxide composite negative pole material of surface layer.The heat-treatment temperature range that sets is 580-800 DEG C.
The method that the present invention uses chemical precipitation to combine with high temperature solid state reaction is adsorbed using the height of precipitation reaction product Performance adsorption excess lithium ion makes its silica with silicon face trace in high temperature solid state reaction, in silicon activated centre and oxygen One layer of lithium metasilicate boundary layer is formed in situ between compound matrix, provides not only the continuous passage of lithium ion transport, Er Qieke As the reactivity being effectively protected between interface reduction activated centre and oxide matrix.
Method provided by the invention, when that silicon powder-oxide precursor object/alcohol is added dropwise is molten for lithium hydroxide/alcohol-water mixtures Nb after in liquid, in solution5+Or Ti4+/Nb5+It is sufficiently precipitated under the action of lithium hydroxide, forms corresponding metal hydroxides Precipitating, the precipitating are coated on the silicon powder surface being dispersed in oxide precursor object/alcoholic solution, and it is multiple to form core-shell structure copolymer with silicon powder Close structure.In precipitation process, due to the suction-operated of precipitating, while excessive lithium ion can be adsorbed.The lithium ion is subsequent Heat treatment process in, at a suitable temperature, the micro silicon dioxde reaction with silicon powder surface, in-situ preparation lithium metasilicate chemical combination Object forms lithium metasilicate boundary layer between silicon powder surface and oxide matrix.There is the silicic acid lithium compound good ion to lead Electrically, therefore, the lithium ion diffusion admittance of silicon activated centre and oxide skin(coating) is constituted, lithium in this kind of material is greatly promoted The high efficiency of transmission of ion.Furthermore due to the presence of lithium metasilicate, so that the surface in silicon activated centre forms more complete protection Layer, can effectively prevent the oxygen atom of oxide skin(coating) in heat treatment process to the diffusion in silicon activated centre, to reduce into one Step generates a possibility that inertia silica, has ensured the electro-chemical activity in silicon activated centre.
Traditional silicon/oxide composite negative pole material needs precision due to the direct contact of silicon/oxide, heat treatment process Control is to prevent silicon from reacting with the excessive chemical of oxide.It is shown further, since the removal lithium embedded voltage of oxide and silicon itself has Difference is write, therefore, oxide is only used as stress-buffer layer to exist, but the low ion-electron conductivity problems of itself, makes this kind of The cycle performance of material is unsatisfactory.Silicon/oxide composite negative pole material provided by the invention with lithium metasilicate boundary layer, by In constructing one layer of lithium metasilicate interface between silicon activated centre and oxide matrix, the continuous of lithium ion transport is provided not only Channel, and can be used as the reactivity for interface is effectively protected reducing between activated centre and oxide matrix and therefore have Good electrochemistry cycle performance.Technical process of the present invention is very simple, and what is be prepared in this way is compound Material has excellent interface compatibility, has high lot stability, it is easy to realize large-scale production, it can be in lithium ion battery Equal fields are widely popularized.
Detailed description of the invention
The present invention will be further described in detail below with reference to the accompanying drawings and specific embodiments.
Fig. 1 is the electron microscope picture of target product prepared by the embodiment of the present invention 1.Scale is 100 nanometers.
Fig. 2 is the transmission electron microscope constituency analysis photo of target product prepared by the embodiment of the present invention 1, and scale is 10 nanometers, The interior illustration of Fig. 2 is corresponding structural schematic diagram.
The charging and discharging curve figure for the negative electrode tab that the target product that Fig. 3 is prepared by the embodiment of the present invention 1 assembles, it is corresponding in figure Arabic numerals represent corresponding circulating cycle number.
Fig. 4 is the X-ray photoelectron spectroscopic analysis figure of target product prepared by the embodiment of the present invention 1.
Fig. 5 is the cycle life test chart of target product prepared by the embodiment of the present invention 1.
Specific embodiment
Following non-limiting embodiments can with a person of ordinary skill in the art will more fully understand the present invention, but not with Any mode limits the present invention.
Test method described in following embodiments is unless otherwise specified conventional method；The reagent and material, such as Without specified otherwise, commercially obtain.
In following embodiments, silicon/oxide composite negative pole material system of the present invention with lithium metasilicate boundary layer is used The method of standby negative electrode tab is as follows:
Kynoar (binder) is dissolved in N-Methyl pyrrolidone, is configured to the Kynoar of 0.02 grams per liter N-Methyl pyrrolidone solution；By silicon/oxide composite negative pole material (active material) with lithium metasilicate boundary layer, acetylene black (conductive agent), Kynoar solution, by active material: conductive agent: the mass ratio of binder is after 7:2:1 is mixed, to be applied to 25 On the thick copper foil of micron, which is moved into vacuum drying oven after being dried 8 hours under 110 DEG C of vacuum and taken out；By the copper foil of drying It is cut into the disk that diameter is 16mm, that is, electro-chemical test silicon/oxide composite negative pole used with lithium metasilicate boundary layer is made Material negative electrode tab.Negative electrode tab is directly done with metal Li and button cell is assembled into electrode 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 corresponds to the process of lithium ion insertion silicon nanowires combination electrode, and charging process corresponds to the abjection of lithium ion Journey.
Embodiment 1
(1) dehydrated alcohol (analysis is pure) is uniformly mixed with deionized water with the volume ratio of 1:1, it is molten to obtain alcohol-water mixing Liquid, it is spare；
(2) 0.27g niobium chloride is dissolved in spare in 40ml ethanol solution；
(3) 0.11g nano silica fume (average particle size 40nm) is put into niobium chloride/ethanol solution, ultrasonic vibration Silicon powder-niobium chloride/ethanol solution is made in 30min；
(4) lithium hydroxide is configured to lithium hydroxide/alcohol-water mixed solution (ethyl alcohol: the volume ratio of water of 0.02mol/L For 1:1)；
(5) 250ml lithium hydroxide/alcohol-water mixed solution (20mmol/L) is taken, silicon powder-niobium chloride/second is added dropwise to In alcoholic solution, after the reaction was completed, precipitating filtering, and washed with alcohol-water mixed solution (volume ratio 1:1) and to filtrate to be in for 3 times Property, it is dried in vacuo 8 hours at 70 DEG C；
(6) dried sample is placed in tube furnace, with the heating rate of 10 DEG C/min from room temperature to 600 DEG C, heat Processing 8 hours, then be cooled to room temperature with furnace body, entire heat treatment process carries out under protection of argon gas.Product after heat treatment As silicon/oxide composite negative pole material of the target product with lithium metasilicate boundary layer.
Silicon/oxide composite negative pole material (as shown in Figure 1) manufactured in the present embodiment with lithium metasilicate boundary layer, including Silicon activated centre and oxide matrix also have lithium metasilicate boundary layer, such as Fig. 2 institute between silicon activated centre and oxide matrix Show.
It is process that target product obtained by the present embodiment is assembled into electrode slice is as follows: Kynoar (binder) is dissolved in N-Methyl pyrrolidone is configured to the N-Methyl pyrrolidone solution of the Kynoar of 0.02 grams per liter；There to be lithium metasilicate circle Silicon/oxide composite negative pole material (active material) of surface layer, acetylene black (conductive agent), Kynoar solution, by active matter Matter: conductive agent: the mass ratio of binder is after 7:2:1 is mixed, to be applied on 25 microns of thick copper foils, which is moved into vacuum and is dried It is taken out after being dried 8 hours under 110 DEG C of vacuum in case；The copper foil of drying is cut into the disk that diameter is 16mm, that is, electrochemistry is made Test silicon/oxide composite negative pole material negative electrode tab used with lithium metasilicate boundary layer.Negative electrode tab is directly done with metal Li Button cell is assembled into electrode and tests its chemical property, electrolyte 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 and is embedded in silicon nanowires The process of combination electrode, charging process correspond to the abjection process of lithium ion.
Reversible capacity reaches 2754mAh/g to the electrode of preparation for the first time.Fig. 3 is assembled by target product manufactured in the present embodiment Negative electrode tab charging and discharging curve figure.
Embodiment 2
(1) ethylene glycol (analysis is pure) is uniformly mixed with deionized water with the volume ratio of 2:1, it is molten to obtain ethylene glycol-water mixing Liquid, it is spare；
(2) 0.27g niobium chloride is dissolved in spare in 40ml ethylene glycol solution；
(3) 0.13g nano silica fume (40nm) is put into niobium chloride/ethylene glycol solution, silicon is made in ultrasonic vibration 30min Powder-niobium chloride/ethylene glycol solution；
(4) by the lithium hydroxide lithium hydroxide/ethylene glycol-mixed solution (ethyl alcohol: the volume of water for preparing title 20mmol/L Than for 2:1)；
(5) 250ml lithium hydroxide/ethylene glycol-mixed solution (20mmol/L) is taken, silicon powder-niobium chloride/second two is added dropwise In alcoholic solution, after the reaction was completed, precipitating filtering, and wash 2 times with alcohol-water mixed solution (2:1) and be in neutrality to filtrate, 60 It is dried in vacuo 10 hours at DEG C；
(6) dried sample is placed in tube furnace, with the heating rate of 10 DEG C/min from room temperature to 650 DEG C, heat Processing 8 hours, then be cooled to room temperature with furnace body, entire heat treatment process carries out under protection of argon gas.Product after heat treatment As target product.
The process and Electrochemical Test Procedure that products therefrom is assembled into electrode slice with embodiment 1, for the first time may be used by the electrode of preparation Inverse capacity reaches 2815mAh/g.
Embodiment 3
(1) ethyl alcohol (analysis is pure) is uniformly mixed with deionized water with the volume ratio of 1:1, obtains alcohol-water mixed solution, It is spare；
(2), by 0.27g niobium chloride, 0.34g butyl titanate is dissolved in spare in 40ml ethanol solution；
(3) 0.15g nano silica fume (40nm) is put into niobium chloride-tetrabutyl titanate ester/ethanol solution, ultrasonic vibration Silicon powder-niobium chloride-tetrabutyl titanate ester/ethanol solution is made in 30min；
(4) by the lithium hydroxide lithium hydroxide/ethyl alcohol-mixed solution (ethyl alcohol: the volume ratio of water for being configured to 20mmol/L For 1:1)；
(5) 500ml lithium hydroxide/ethyl alcohol-mixed solution (20mmol/L) is taken, it is molten that silicon powder-niobium chloride/ethyl alcohol is added dropwise In liquid, after the reaction was completed, precipitating filtering, and wash 3 times with alcohol-water mixed solution (1:1) and be in neutrality to filtrate, at 70 DEG C Vacuum drying 8 hours；
(6) dried sample is placed in tube furnace, with the heating rate of 10 DEG C/min from room temperature to 580 DEG C, heat Processing 14 hours, then be cooled to room temperature with furnace body, entire heat treatment process carries out under protection of argon gas.Product after heat treatment As target product.
The process and Electrochemical Test Procedure that products therefrom is assembled into electrode slice with embodiment 1, for the first time may be used by the electrode of preparation Inverse capacity reaches 2108mAh/g.
Embodiment 4
(1) methanol (analysis is pure) is uniformly mixed with deionized water with the volume ratio of 1:1, obtains methanol-water mixed solution, It is spare；
(2), by 0.27g niobium chloride, 0.34g butyl titanate is dissolved in spare in 40ml methanol solution；
(3) 0.15g nano silica fume (40nm) is put into niobium chloride-tetrabutyl titanate ester/methanol solution, ultrasonic vibration Silicon powder-niobium chloride-tetrabutyl titanate ester/methanol solution is made in 30min；
(4) by the lithium hydroxide lithium hydroxide/methanol-mixed solution (methanol: the volume ratio of water for preparing title 40mmol/L For 1:1)；
(5) 250ml lithium hydroxide/methanol-mixed solution (40mmol/L) is taken, it is molten that silicon powder-niobium chloride/methanol is added dropwise In liquid, after the reaction was completed, precipitating filtering, and wash 4 times with methanol-water mixed solution (1:1) and be in neutrality to filtrate, at 70 DEG C Vacuum drying 10 hours；
(6) dried sample is placed in tube furnace, with the heating rate of 10 DEG C/min from room temperature to 600 DEG C, heat Processing 12 hours, then be cooled to room temperature with furnace body, entire heat treatment process carries out under protection of argon gas.Product after heat treatment As target product.
The process and Electrochemical Test Procedure that products therefrom is assembled into electrode slice with embodiment 1, for the first time may be used by the electrode of preparation Inverse capacity reaches 1885mAh/g.
Embodiment 5
(1) dehydrated alcohol (analysis is pure) is uniformly mixed with deionized water with the volume ratio of 1:5, obtains alcohol-water mixing Solution, it is spare；
(2) 0.27g niobium chloride is dissolved in spare in 10ml ethanol solution；
(3) 0.08g nano silica fume (average particle size 40nm) is put into niobium chloride/ethanol solution, ultrasonic vibration Silicon powder-niobium chloride/ethanol solution is made in 30min；
(4) lithium hydroxide is configured to lithium hydroxide/alcohol-water mixed solution (ethyl alcohol: the volume of water of 0.02mol/L Than for 1:5)；
(5) take 250ml lithium hydroxide/alcohol-water mixed solution (0.02mmol/L), be added dropwise to silicon powder-niobium chloride/ In ethanol solution, after the reaction was completed, precipitating filtering, and wash 3 times to filtrate with alcohol-water mixed solution (volume ratio 1:5) and be in Neutrality is dried in vacuo 8 hours at 70 DEG C；
(6) dried sample is placed in tube furnace, with the heating rate of 10 DEG C/min from room temperature to 600 DEG C, Heat treatment 8 hours, then be cooled to room temperature with furnace body, entire heat treatment process carries out under protection of argon gas.Production after heat treatment Object is silicon/oxide composite negative pole material that target product has lithium metasilicate boundary layer.
The process and Electrochemical Test Procedure that products therefrom is assembled into electrode slice with embodiment 1, for the first time may be used by the electrode of preparation Inverse capacity reaches 1123mAh/g.
Embodiment 6
(1) dehydrated alcohol (analysis is pure) is uniformly mixed with deionized water with the volume ratio of 1:2, obtains alcohol-water mixing Solution, it is spare；
(2) 0.27g niobium chloride is dissolved in spare in 100ml ethanol solution；
(3) 0.10g nano silica fume (average particle size 40nm) is put into niobium chloride/ethanol solution, ultrasonic vibration Silicon powder-niobium chloride/ethanol solution is made in 30min；
(4) lithium hydroxide is configured to lithium hydroxide/alcohol-water mixed solution (ethyl alcohol: the volume of water of 0.01mol/L Than for 1:2)；
(5) take 500ml lithium hydroxide/alcohol-water mixed solution (0.01mmol/L), be added dropwise to silicon powder-niobium chloride/ In ethanol solution, after the reaction was completed, precipitating filtering, and wash 4 times to filtrate with alcohol-water mixed solution (volume ratio 1:2) and be in Neutrality is dried in vacuo 8 hours at 70 DEG C；
(6) dried sample is placed in tube furnace, with the heating rate of 10 DEG C/min from room temperature to 600 DEG C, Heat treatment 8 hours, then be cooled to room temperature with furnace body, entire heat treatment process carries out under protection of argon gas.Production after heat treatment Object is silicon/oxide composite negative pole material that target product has lithium metasilicate boundary layer.
The process and Electrochemical Test Procedure that products therefrom is assembled into electrode slice with embodiment 1, for the first time may be used by the electrode of preparation Inverse capacity reaches 1323mAh/g.
Embodiment 7
(1) ethyl alcohol (analysis is pure) is uniformly mixed with deionized water with the volume ratio of 1:1, obtains alcohol-water mixed solution, It is spare；
(2) by 0.27g niobium chloride, 0.085g butyl titanate is dissolved in spare in 40ml ethanol solution；
(3) 0.11g nano silica fume (40nm) is put into niobium chloride-tetrabutyl titanate ester/ethanol solution, ultrasonic vibration Silicon powder-niobium chloride-tetrabutyl titanate ester/ethanol solution is made in 30min；
(4) by the lithium hydroxide lithium hydroxide/ethyl alcohol-mixed solution (ethyl alcohol: the volume ratio of water for being configured to 0.5mol/L For 1:1)；
(5) 16.25ml lithium hydroxide/ethyl alcohol-mixed solution (0.5mol/L) is taken, silicon powder-niobium chloride/ethyl alcohol is added dropwise In solution, after the reaction was completed, precipitating filtering, and wash 3 times with alcohol-water mixed solution (1:1) and be in neutrality to filtrate, at 70 DEG C Lower vacuum drying 8 hours；
(6) dried sample is placed in tube furnace, with the heating rate of 10 DEG C/min from room temperature to 580 DEG C, Heat treatment 14 hours, then be cooled to room temperature with furnace body, entire heat treatment process carries out under protection of argon gas.Production after heat treatment Object is target product.
The process and Electrochemical Test Procedure that products therefrom is assembled into electrode slice with embodiment 1, for the first time may be used by the electrode of preparation Inverse capacity reaches 1120mAh/g.
The foregoing is only a preferred embodiment of the present invention, but scope of protection of the present invention is not limited thereto, Anyone skilled in the art in the technical scope disclosed by the present invention, according to the technique and scheme of the present invention and its Inventive concept is subject to equivalent substitution or change, should be covered by the protection scope of the present invention.

Claims (6)

1. a kind of silicon/oxide composite negative pole material method prepared with lithium metasilicate boundary layer, it is characterised in that have such as Lower step:
(1) alcohol-water mixed solution is prepared；
(2) niobium chloride or niobium chloride/tetrabutyl titanate ester mixture are dissolved in step (1) to obtain in solution, are obtained uniformly Oxide precursor object/alcoholic solution；
(3) silicon powder is added in oxide precursor object/alcoholic solution that step (2) obtains ultrasonic vibration at least 30 minutes, makes silicon Powder is fully dispersed, obtains uniform silicon powder-oxide precursor object/alcoholic solution；
(4) lithium hydroxide is dissolved in alcohol-water mixed solution that step (1) obtains, obtains lithium hydroxide/alcohol-water mixtures；
(5) lithium hydroxide/alcohol-water mixtures that step (4) obtains are added dropwise to silicon powder-oxide that step (3) obtains In predecessor/alcoholic solution, make the Nb in solution5+Or Nb5+/Ti4+It is sufficiently precipitated under the action of lithium hydroxide；It will sufficiently react Solution afterwards is filtered to collect solid reaction products, and alcohol-water mixed solution that obtained solid product is prepared with step (1) Washing to filtrate at neutrality, and vacuum drying；
(6) solid product after step (5) drying is moved into the tube furnace protected with argon gas and is heat-treated, after heat treatment To product be that there is silicon/oxide composite negative pole material of lithium metasilicate boundary layer.
2. according to the method described in claim 1, it is characterized by: step (1) alcohol-water mixed solution alcohol by volume: Water is 2:1-2:10 mixing.
3. according to the method described in claim 1, it is characterized by: in step (2) oxide precursor object/alcoholic solution, Nb5+ Or Nb5+/Ti4+Concentration be 0.01-0.1mol/L.
4. according to the method described in claim 1, it is characterized by: pressing Nb5+Or Nb5+/Ti4+Corresponding metal oxide meter, step Suddenly the additional amount of (3) described silicon powder is the 40-100% of metal oxide quality.
5. according to the method described in claim 1, it is characterized by: lithium in step (4) lithium hydroxide/alcohol-water mixtures Ion concentration is 0.01-0.5mol/L.
6. according to the method described in claim 1, it is characterized by: the lithium hydroxide/alcohol-water being added in step (5) is mixed The mole for closing lithium ion in liquid is Nb in solution5+Or Nb5+/Ti4+The 500-650% of mole.
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