CN108899517A - One kind having lithium niobate/niobium base oxide/silicon composite cathode material and its preparation and application - Google Patents
One kind having lithium niobate/niobium base oxide/silicon composite cathode material and its preparation and application Download PDFInfo
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- CN108899517A CN108899517A CN201810721769.0A CN201810721769A CN108899517A CN 108899517 A CN108899517 A CN 108899517A CN 201810721769 A CN201810721769 A CN 201810721769A CN 108899517 A CN108899517 A CN 108899517A
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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
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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
- 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
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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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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Abstract
There is lithium niobate/niobium base oxide/silicon composite cathode material and its preparation and application the invention discloses one kind, described to have lithium niobate/niobium base oxide/silicon composite cathode material include silicon activated centre and the lithium niobate/niobium base oxide mixing shell for being evenly coated at silicon activated centre surface.It is provided by the invention that there is lithium niobate/niobium base oxide/silicon composite cathode material, lithium niobate is as fast-ionic conductor, not only it is effectively guaranteed the quick transmission of lithium ion under the room temperature even condition of high temperature, and it cooperates with blending to act on niobium base oxide, be conducive to structure of the silicon in electrochemical reaction process, surface stability, therefore, lithium niobate/niobium base oxide mixing shell can be used as stress-buffer layer, ion conductive layer and surface-stable layer, make that there is lithium niobate/niobium base oxide/silicon composite cathode material not only to have high coulombic efficiency for the first time, but also there is good electrochemical cycle stability performance.
Description
Technical field
The present invention relates to one kind to have lithium niobate/niobium base oxide/silicon composite cathode material and its preparation and application, specifically
It is related to lithium niobate/niobium base oxide/silicon that a kind of coulombic efficiency that can be used as lithium ion battery negative material is high, has extended cycle life
Composite negative pole system and its preparation method and application, belongs to field of lithium ion battery.
Background technique
Since the 21th century, energy and environmental problem is increasingly serious, and science and technology strength and fund are one after another thrown in countries in the world
Enter into the exploitation of green energy resource.Lithium ion battery has high-energy density, long-life and right as emerging energy and material
The characteristics such as environmental nonpollution are widely used in mobile terminal and transport the energy supplyystem of tool.Negative electrode material is to determine lithium
One of the key of ion battery comprehensive performance superiority and inferiority.However negative electrode material type in commercialized production is very little, just to high energy
Take baby battery, the demand of big power capacity battery increases requirement to negative electrode material.Current lithium ion battery is adopted extensively
For carbon negative pole material, due to the high speed development of processing technology and mounting technology, by the promotion of battery assemble ability into
The method that one step improves its reversible electrochemical energy storage efficiency has had reached bottleneck.Current lithium ion battery needs to develop newly
Electrode material system, so that its performance obtains substantive breakthrough.
From the point of view of alloy type and semiconductor type negative electrode material as far as is known, silicon substrate composite negative pole material is hybrid power vapour
One of the candidate of the energy resource supply of vehicle and pure power vehicle most advantage.Its specific advantage is：A. the theoretical capacity of superelevation：
4200mAh/g is 10 times of business Carbon anode；B. low economic cost：Abundance, technology of preparing are mature；C. security performance
It is high：Low operating voltage (0.37V vs.Li/Li+) however, the theoretical capacity of superelevation certainly will cause cubical expansivity larger, from
Son/electron conduction is poor, and formation of SEI film etc. all limits Si electrode capacity and maximumlly plays.Traditional method of modifying
More or less there is certain complexity and uncontrollability during the preparation process.It therefore, is exactly at present to adopt to the research emphasis of silicon
With various modified methods, the cycle performance of silicon is improved.
In numerous modified methods, relatively conventional solution：Silicon materials nanosizing and Composite.The nanometer of silicon
Change, including nano silicon particles, silicon thin film, porous silicon, silicon nanowires, the preparation of nano-tube etc..By improving silicon materials itself
Mechanical property to reach the problem of alleviating volume expansion, the structural stability of reinforcing material, while providing more active sites
Point, effectively shortens Li+Diffusion admittance, improve electronics and the diffusion rate of ion etc..These method for making Nano, not only effectively
The mechanical property of silicon active material itself is improved, the specific surface area of silicon is also substantially increased, reduces the relative volume of silicon
Expansion rate.Therefore, the nanosizing of silicon has become the universal method that silicon active material improves its electrochemistry cycle performance now；Silicon
Composite, by compound mode, by silicon mosaic in the basis material with relatively low volume expansion, with alleviate
Lithium ion during deintercalation caused by volume expansion, improve the structural stability of material.Relatively conventional basis material is carbon
Material, including Polymer-pyrolysis carbon, graphene, carbon nanotube etc..But for silicon, although graphite negative electrodes material has
There is better mechanical property, but absolute volume expansion still remains.In subsequent circular response, in basis material and silicon activity
The heart is caused silicon activated centre to fall off from substrate material surface and is caused declining for electrochemistry cycle performance due to the mismatch of volume expansion
Subtract.Therefore, the long-term electrochemical cycle stability of silicon class material is not significantly improved.In addition, silicon is during removal lithium embedded
Generating serious volume expansion causes its surface unstable, directly results in the side reaction aggravation on exposed surface and electrolyte, and
Generate very thick and heavy solid electrolyte film (SEI).And the electrolyte that this layer of unstable SEI film is lost is also that cause can not
One of inverse higher reason of capacity.Therefore, it is also one of common modification mode of silicon materials that surface is modified.It is more general at present
Method is silicon materials coated with carbon thin layer or other compound layers, guarantees can also have while the surface-stable of silicon activated centre
Effect alleviates bulk effect bring destructiveness consequence.
Up to the present, still rare research is related to lithium niobate and its mixed phase as clad raising silica-base material lithium ion
The problem of conductivity.Lithium niobate is not only effectively guaranteed under the condition of high temperature lithium ion in lithium niobate/niobium as fast-ionic conductor
The quick transmission of base oxide mixing shell, has more expanded the scope of application of silicium cathode material.It would therefore be highly desirable to construct a kind of uniqueness
With lithium niobate/niobium base oxide mixing shell silicon substrate composite negative pole material with improve silicon class negative electrode material electrochemistry take off
Embedding lithium performance.
Summary of the invention
To effectively improve the silicon based anode material stability of coulombic efficiency and the long-term electrochemistry circulation of improvement for the first time, this hair
The bright one kind that provides has lithium niobate/niobium base oxide/silicon composite cathode material and its preparation and application.
The purpose of the present invention and task are, overcome oxide cladding layers ionic conductivity difference and high temperature in the prior art
The problems such as ion transmission is unstable under state, provide a kind of lithium niobate with good lithium ion conductive/niobium base oxide/
Silicon composite cathode material and its preparation and application make lithium nitride and niobium base oxide using high temperature solid state reaction or high speed ball milling
Between fabricated in situ lithium niobate, prepare with lithium niobate/niobium base oxide mixing shell silicon substrate composite negative pole system.
The technological means that the present invention uses is as follows：
One kind having lithium niobate/niobium base oxide/silicon composite cathode material, including silicon activated centre and is evenly coated at silicon
The lithium niobate on activated centre surface/niobium base oxide mixing shell.
The silicon activated centre is silicon powder of the particle size at 20-100 nanometers, and main electricity is undertaken in charge and discharge process
Chemistry storage lithium effect；
The lithium niobate/niobium base oxide mixing shell is that niobium oxide and lithium nitride pass through high temperature solid state reaction or high speed
The lithium niobate and the mixed uniformly shell of niobium base oxide of ball milling fabricated in situ, play rock-steady structure, improve ionic conductivity
Function.
The lithium niobate/niobium base oxide mixing shell is with a thickness of 5-50 nanometers, and further preferably 5~25 nanometers.
It is i.e. described that there is lithium niobate/niobium base oxide/silicon composite cathode material to have following structure：
1, silicon activated centre is electrochemical reaction activated centre, and lithium niobate/niobium base oxide mixed phase is matrix；
2, silicon activated centre surface uniformly coats one layer of lithium niobate/niobium base oxide mixing shell；
3, the particle size in silicon activated centre is 20-100 nanometers；
4, lithium niobate/niobium base oxide mixing shell is with a thickness of 5-50 nanometers.
It is described that there is lithium niobate/niobium base oxide/silicon composite cathode material, the compound system of core-shell structure is presented, wherein
Nanoscale silicon activated centre uniformly coats one layer of lithium niobate/niobium base oxide mixing shell, lithium niobate/niobium base oxidation
Object mixing shell is effectively guaranteed the quick transmission of lithium ion under the condition of high temperature using the synergistic effect between material, improves
It is described that there is lithium niobate/niobium base oxide/silicon composite cathode material structural stability and high-temperature behavior, and then improve material
Electro-chemical activity.
The silicon activated centre is 1 with the lithium niobate/niobium base oxide mixing shell mass ratio:0.1~1:2, into
One step is preferably 1:0.15~1:1.
It is 0.5 that the lithium niobate/niobium base oxide mixing shell, which is molar ratio,:1~5:1 lithium nitride and niobium oxide is logical
Cross the lithium niobate and the mixed uniformly shell of niobium base oxide of high temperature solid state reaction or high speed ball milling fabricated in situ.
The invention also discloses a kind of with lithium niobate/niobium base oxide/silicon composite cathode material preparation method, has
Following steps：
S1, ultrasonic vibration in silicon powder addition alcoholic solution is more than or equal to 30 minutes, makes the silicon powder reunited due to skin effect
It obtains fully dispersed, obtains uniformly mixed silicon powder/alcoholic solution；
S2, niobium chloride or niobium oxalate are dissolved in alcoholic solution or by niobium chloride or the mixture of niobium oxalate and butyl titanate
It is dissolved in alcoholic solution, obtains uniform oxide precursor object/alcoholic solution；
S3, silicon powder/alcoholic solution obtained in step S1 is added to the object of oxide precursor obtained in step S2/alcoholic solution
Middle strong stirring is more than or equal to 30 minutes, obtains uniformly mixed silicon powder-oxide precursor object/alcoholic solution；
S4, silicon powder-oxide precursor object/alcoholic solution that step S3 is obtained is moved in sealing reaction kettle and is reacted 20 hours,
Nb in solution5+Or Ti4+With Nb5+Using core-shell structure is self-assembled under subcritical state, cooling later, precipitating filtering is washed
It washs, and vacuum drying, obtains silicon/niobium base oxide；
Silicon obtained in step S4/niobium base oxide and lithium nitride mixed grinding under protection of argon gas are moved into tubular type by S5
High temperature solid state reaction is carried out in furnace or is encapsulated into stainless steel jar mill carrying out high speed ball milling, the product reacted is to have niobium
Sour lithium/niobium base oxide/silicon composite cathode material.
It is described to have lithium niobate/niobium base oxide/silicon composite cathode material preparation method for subcritical solvent heat and height
Warm solid phase reaction or high speed ball milling.The mixture of niobium chloride or niobium oxalate or niobium chloride or niobium oxalate and butyl titanate is as system
The pre-reaction material of standby oxide matrix.Niobium base oxide is generated in silicon face first using the self assembly behavior of subcritical state
Shell, recycle high temperature solid state reaction or high speed ball milling to react with lithium nitride, make in-situ preparation lithium niobate in niobium base oxide,
Lithium niobate/niobium base oxide mixing shell is obtained, the quick transmission of lithium ion under the condition of high temperature is effectively guaranteed, ultimately forms
With lithium niobate/niobium base oxide/silicon composite cathode material.
The alcoholic solution in the step S1 and step S2 is methanol solution, ethanol solution or ethylene glycol solution；
Niobium chloride, niobium oxalate, butyl titanate are that analysis is pure in the step S2；
It is when using niobium chloride or niobium oxalate as solute, then described that there is lithium niobate/niobium base oxide/silicon composite cathode material
Niobium base oxide is niobium oxide in material；When using the mixture of niobium chloride or niobium oxalate and butyl titanate as solute, then institute
Stating with niobium base oxide in lithium niobate/niobium base oxide/silicon composite cathode material is then niobium oxide/titania mixture.
Nb in the oxide precursor object/alcoholic solution5+Molar concentration range be 0.01-0.1mol/L, further preferably
For 0.025-0.035mol/L；
In the step S5, lithium nitride and Li in silicon/niobium base oxide obtained in step S4+With Nb5+Molar ratio be
1:1~5:1.
Temperature in reaction kettle described in the step S4 is 150~210 DEG C, further preferably 170~190 DEG C；
The step S5 high temperature solid phase reaction process is：Muffle furnace first rises to reaction temperature and is preheated, in step S4
After obtained silicon/niobium base oxide and lithium nitride directly keep the temperature 0.5~3 hour at a temperature of 500~700 DEG C, it is furnace-cooled to room temperature,
Reacting obtained product is to have lithium niobate/niobium base oxide/silicon composite cathode material, and whole process carries out under argon gas.
High speed mechanical milling process described in the step S5 is：Silicon/niobium base oxide encapsulates under protection of argon gas with lithium nitride
High speed ball milling is carried out into stainless steel jar mill, the high speed rotational speed of ball-mill is 400~500r/min, the ball of the high speed ball milling
Time consuming is 8~12 hours.
Lithium niobate/niobium base oxide/silicon composite cathode material is had according to described above the invention also discloses a kind of
The cathode of preparation.
In traditional silicon/oxide composite negative pole material system, oxide is poor etc. due to the ionic conductivity of itself
Problem keeps the cycle performance of this kind of material unsatisfactory.It is provided by the invention that there is lithium niobate/niobium base oxide/silicon Compound Negative
Pole material, lithium niobate are not only effectively guaranteed the quick biography of lithium ion under the room temperature even condition of high temperature as fast-ionic conductor
It is defeated, and it cooperates with blending to act on niobium base oxide, be conducive to structure of the silicon in electrochemical reaction process, surface-stable
Property, therefore, lithium niobate/niobium base oxide mixing shell can be used as stress-buffer layer, ion conductive layer and surface-stable layer, make to have
There is lithium niobate/niobium base oxide/silicon composite cathode material that not only there is high coulombic efficiency for the first time, but also there is good electricity
Chemical cycle stability.It is of the present invention to have lithium niobate/niobium base oxide/silicon composite cathode material preparation method non-
It is often simple, using the method be prepared have lithium niobate/niobium base oxide/silicon composite cathode material with excellent lithium from
Subconductivity has high lot stability, it is easy to realize large-scale production, can be widely popularized in fields such as lithium ion batteries.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to do simply to introduce, it should be apparent that, the accompanying drawings in the following description is this hair
Bright some embodiments for those of ordinary skill in the art without any creative labor, can be with
It obtains other drawings based on these drawings.
Fig. 1 is prepared in the embodiment of the present invention 1 with lithium niobate/niobium base oxide/silicon composite cathode material (high temperature
Solid phase reaction) XRD diagram.
Fig. 2 is prepared in the embodiment of the present invention 1 with lithium niobate/niobium base oxide/silicon composite cathode material (high temperature
Solid phase reaction) the AC impedance figure of cathode pole piece that is assembled.
Fig. 3 is prepared in the embodiment of the present invention 7 with lithium niobate/niobium base oxide/silicon composite cathode material (high temperature
Solid phase reaction) charging and discharging curve figure of cathode pole piece assembled, in figure abscissa correspond to material electrochemical specific capacity it is (single
Position is mAh/g), ordinate corresponds to voltage (unit V), 1,2,5,10 respectively the 1st circulation shown on curve in figure, the
2 circulations, the 5th recycle and recycle corresponding charging and discharging curve the 10th time.
Fig. 4 is prepared in the embodiment of the present invention 7 with lithium niobate/niobium base oxide/silicon composite cathode material (high temperature
Solid phase reaction) the cycle life test chart of cathode pole piece assembled.
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, have lithium niobate/niobium base oxide/silicon composite cathode material preparation negative using of the present invention
The method of pole pole piece is as follows：
Carboxymethyl cellulose (binder) is dissolved in deionized water, is configured to 0.02g L-1Carboxymethyl cellulose go from
Sub- aqueous solution；To have lithium niobate/niobium base oxide/silicon composite cathode material (active material), acetylene black (conductive agent), carboxylic first
Base cellulose solution, by active material：Conductive agent：The mass ratio of binder is 60：25：After 15 mix, it is applied to 25 microns thick
On copper foil, which is moved into vacuum drying oven after being dried 8 hours under 120 DEG C of vacuum and taken out；The copper foil of drying is cut into diameter
For 16 millimeters of disk, that is, it is used with lithium niobate/niobium base oxide/silicon composite cathode material cathode that electro-chemical test is made
Cathode pole piece is directly done being assembled into button cell to electrode and test its chemical property by pole piece with metal Li, and electrolyte is
LiPF6/EC：DEC(1:1, volume ratio).Test charging and discharging currents density is 200mAg-1, cut-off charging/discharging voltage 0.02V~
1.5V。
Embodiment 1
It is a kind of with lithium niobate/niobium base oxide/silicon composite cathode material preparation method, there are following steps：
S1,0.538g silicon powder (average particle size 50nm) is added to ultrasonic vibration in the ethanol solution (analysis is pure) of 40mL
30min obtains uniformly mixed silicon powder/alcoholic solution：Silicon powder/ethanol solution；
S2,0.538g niobium chloride is dissolved in strong stirring 30min in the ethanol solution of 40ml, obtains uniform oxide
Predecessor/alcoholic solution：Clear niobium chloride ethanol solution；
S3, silicon powder/alcoholic solution obtained in step S1 is added in niobium chloride ethanol solution obtained in step S2 by force
Power stirs 30min, obtains 80mL silicon powder-niobium chloride alcohol mixed solution, Nb in solution5+Molar concentration is 0.0250mol L-1；
S4,80mL silicon powder-niobium chloride alcohol mixed solution that step S3 is obtained is moved to volume be 100mL sealing it is anti-
170 DEG C of reaction 20h in kettle are answered, after being cooled to room temperature later, precipitating filtering, and be washed with deionized 3 times, ethanol washing 1 time,
It is dried in vacuo 8 hours at 70 DEG C, obtains silicon-niobium oxide compound.
S5,0.2g silicon-niobium oxide and 0.0105g lithium nitride are ground under protection of argon gas, is sufficiently mixed, sealing is protected
It deposits；
S6, silicon-niobium oxide of encapsulation and nitridation lithium mixture are directly moved into the tube furnace of 600 DEG C of preheatings in advance, into
The high temperature solid state reaction of row 2h, whole process carry out under protection of argon gas.The product obtained after heat treatment is to have niobic acid
Lithium/niobium base oxide/silicon composite cathode material.
It is manufactured in the present embodiment have lithium niobate/niobium base oxide/silicon composite cathode material, including silicon activated centre and
The even lithium niobate for being coated on silicon activated centre surface/niobium base oxide mixing shell.Fig. 1 Fig. 2 confirms lithium niobate/niobium base oxidation
Object mixing shell significantly enhances lithium ion diffusion rate.
The process that obtained by the present embodiment will there is lithium niobate/niobium base oxide/silicon composite cathode material to be assembled into electrode slice
It is as follows：Carboxymethyl cellulose (binder) is dissolved in deionized water, is configured to 0.02g L-1Carboxymethyl cellulose deionization
Aqueous solution；To have lithium niobate/niobium base oxide/silicon composite cathode material (active material), acetylene black (conductive agent), carboxymethyl
Cellulose solution, by active material：Conductive agent：The mass ratio of binder is 60：25：After 15 mix, it is applied to 25 microns of thick copper
On foil, which is moved into vacuum drying oven after being dried 8 hours under 120 DEG C of vacuum and taken out；The copper foil of drying, which is cut into diameter, is
It is used with lithium niobate/niobium base oxide/silicon composite cathode material cathode pole that electro-chemical test is made in 16 millimeters of disk
Cathode pole piece is directly done being assembled into button cell to electrode and test its chemical property by piece with metal Li, and electrolyte is
LiPF6/EC：DEC(1:1, volume ratio).Test charging and discharging currents density is 200mAg-1, cut-off charging/discharging voltage 0.02V~
1.5V.Reversible capacity reaches 2654mAh/g to the electrode of preparation for the first time.
Embodiment 2
It is a kind of with lithium niobate/niobium base oxide/silicon composite cathode material preparation method, there are following steps：
S1,0.863g silicon powder (average particle size 50nm) is added to ultrasound shake in the ethylene glycol solution (analysis is pure) of 30mL
40min is swung, evenly dispersed silicon powder/ethylene glycol solution is obtained；
S2,0.807g niobium oxalate is dissolved in strong stirring 40min in the ethylene glycol solution of 30ml, obtains clear oxalic acid
Niobium ethylene glycol solution is spare；
S3, silicon powder/ethylene glycol solution obtained in step S1 is added to the niobium oxalate ethylene glycol solution that step S2 is obtained
Middle strong stirring 40min obtains 60mL silicon-niobium oxalate ethylene glycol mixed solution, Nb in solution5+Molar concentration is
0.0250mol L-1；
S4, silicon-niobium oxalate ethylene glycol mixed solution that step S3 is prepared is moved to the sealing reaction kettle that volume is 70mL
In 190 DEG C of reaction 20h, after being cooled to room temperature later, precipitating filtering and is washed with deionized 3 times, ethanol washing 1 time, 70
It is dried in vacuo 8 hours at DEG C, obtains silicon-niobium oxide of core-shell structure；
S5,0.2g silicon-niobium oxide and 0.035g lithium nitride are ground under protection of argon gas, is sufficiently mixed, sealing is protected
It deposits；
S6, silicon-niobium oxide of encapsulation and nitridation lithium mixture are directly moved into the tube furnace of 650 DEG C of preheatings in advance, into
The high temperature solid state reaction of row 1.5h, whole process carry out under protection of argon gas.The product obtained after heat treatment is to have niobium
Sour lithium/niobium base oxide/silicon composite cathode material.
The process and electrochemistry survey that there is gained lithium niobate/niobium base oxide/silicon composite cathode material to be assembled into electrode slice
Examination process is with embodiment 1, and reversible capacity reaches 3109mAh/g to the electrode of preparation for the first time.
Embodiment 3
It is a kind of with lithium niobate/niobium base oxide/silicon composite cathode material preparation method, there are following steps：
S1,0.538g silicon powder (average particle size 50nm) is added to ultrasonic vibration in the methanol solution (analysis is pure) of 40mL
30min obtains evenly dispersed silicon powder/methanol solution；
S2, the niobium chloride of 0.538g and 0.340g butyl titanate are successively dissolved in the methanol solution of 40ml and strongly stirred
1h is mixed, clear niobium chloride/butyl titanate methanol mixed solution is obtained；
S3, silicon powder/methanol solution obtained in step S1 is added to strong stirring in the mixed solution of step S2 preparation
40min obtains 80mL silicon-niobium chloride/butyl titanate methanol mixed solution, Nb in solution5+Molar concentration is 0.0250mol
L-1, Ti3+Molar concentration is 0.0125mol L-1；
S4, silicon-niobium chloride/butyl titanate methanol mixed solution that step S3 is obtained is moved to volume for 100mL's
180 DEG C of reaction 20h in reaction kettle are sealed, are cooled to room temperature, precipitating filtering later, and be washed with deionized 3 times, ethanol washing
It 1 time, is dried in vacuo 8 hours at 70 DEG C, obtains silicon-niobium oxide/titanium oxide of core-shell structure；
S5,0.2g silicon-niobium oxide/titanium oxide and 0.016g lithium nitride are ground under protection of argon gas, are sufficiently mixed,
It is sealed；
S6, the tube furnace that the mixture of silicon-niobium oxide/titanium oxide of encapsulation and lithium nitride is directly moved into 550 DEG C of preheatings
In, the high temperature solid state reaction of 3h is carried out, whole process carries out under protection of argon gas, and the product obtained after heat treatment is to have
Lithium niobate/niobium base oxide/silicon composite cathode material.
The process and electrochemistry survey that there is gained lithium niobate/niobium base oxide/silicon composite cathode material to be assembled into electrode slice
Examination process is with embodiment 1, and reversible capacity reaches 2501mAh/g to the electrode of preparation for the first time.
Embodiment 4
It is a kind of with lithium niobate/niobium base oxide/silicon composite cathode material preparation method, there are following steps：
S1,0.863g silicon powder (average particle size 50nm) is added to ultrasonic vibration in the ethanol solution (analysis is pure) of 30mL
40min obtains evenly dispersed silicon powder/ethanol solution；
S2,0.403g niobium chloride is dissolved in strong stirring 30min in the ethanol solution of 30ml, obtains clear niobium chloride
Ethanol solution is spare；
S3, silicon powder/ethanol solution obtained in step S1 is added in the niobium chloride ethanol solution prepared in step S2
Strong stirring 35min obtains 60mL silicon-niobium chloride alcohol mixed solution, Nb in solution5+Molar concentration is 0.025mol L-1；
S4, silicon-niobium chloride alcohol mixed solution that step S3 is obtained is moved in the sealing reaction kettle that volume is 70mL
185 DEG C of reaction 20h are cooled to room temperature, precipitating filtering later, and are washed with deionized 3 times, ethanol washing 1 time, at 70 DEG C
Vacuum drying 8 hours, obtains silicon-niobium oxide of core-shell structure；
S5,0.2g silicon-niobium oxide and 0.0035g lithium nitride are ground under protection of argon gas, is sufficiently mixed, sealing is protected
It deposits；
S6, silicon-niobium oxide of encapsulation and nitridation lithium mixture are directly moved into the tube furnace of 600 DEG C of preheatings, carries out 3h
High temperature solid state reaction, whole process carries out under protection of argon gas, and the product obtained after heat treatment is to have lithium niobate/niobium
Base oxide/silicon composite cathode material.
The process and electrochemistry survey that there is gained lithium niobate/niobium base oxide/silicon composite cathode material to be assembled into electrode slice
Examination process is with embodiment 1, and reversible capacity reaches 2987mAh/g to the electrode of preparation for the first time.
Embodiment 5
It is a kind of with lithium niobate/niobium base oxide/silicon composite cathode material preparation method, there are following steps：
S1,0.23g silicon powder (average particle size 50nm) is added to ultrasonic vibration in the methanol solution (analysis is pure) of 40mL
30min obtains evenly dispersed silicon powder/methanol solution；
S2, the niobium oxalate of 1.076g is dissolved in strong stirring 1h in the methanol solution of 40ml, obtains clear niobium oxalate
Methanol solution；
S3, silicon powder/methanol obtained in step S1 is added to strong stirring in mixed solution obtained in step S2
40min obtains 80mL silicon-niobium oxalate methanol mixed solution, Nb in solution5+Molar concentration is 0.025mol L-1；
S4, silicon-niobium oxalate methanol mixed solution that step S3 is obtained is moved in the sealing reaction kettle that volume is 100mL
170 DEG C of reaction 20h are cooled to room temperature, precipitating filtering later, and are washed with deionized 3 times, ethanol washing 1 time, at 70 DEG C
Vacuum drying 8 hours, obtains silicon-niobium oxide of core-shell structure；
S5,0.2g silicon-niobium oxide and 0.0263g lithium nitride are ground under protection of argon gas, is sufficiently mixed, sealing is protected
It deposits；
S6, silicon-niobium oxide/titanium oxide of encapsulation and nitridation lithium mixture are directly moved into the tube furnace of 700 DEG C of preheatings,
The high temperature solid state reaction of 1h is carried out, whole process carries out under protection of argon gas, and the product obtained after heat treatment is to have niobium
Sour lithium/niobium base oxide/silicon composite cathode material.
The process and electrochemistry survey that there is gained lithium niobate/niobium base oxide/silicon composite cathode material to be assembled into electrode slice
Examination process is with embodiment 1, and reversible capacity reaches 2108mAh/g to the electrode of preparation for the first time.
Embodiment 6
It is a kind of with lithium niobate/niobium base oxide/silicon composite cathode material preparation method, there are following steps：
S1,0.863g silicon powder (average particle size 50nm) is added to ultrasound shake in the ethylene glycol solution (analysis is pure) of 25mL
40min is swung, evenly dispersed silicon powder/ethylene glycol solution is obtained；
S2, the niobium oxalate of 0.74g and 0.109g butyl titanate are successively dissolved in the methanol solution of 30ml and strongly stirred
1h is mixed, clear niobium oxalate/butyl titanate ethylene glycol mixed solution is obtained；
S3, silicon powder/ethylene glycol solution obtained in step S1 is added to strength in mixed solution obtained in step S2
40min is stirred, 55mL silicon-niobium oxalate/butyl titanate ethylene glycol mixed solution, Nb in solution are obtained5+Molar concentration is
0.0250mol L-1, Ti3+Molar concentration is 0.0125mol L-1；
S4, silicon-niobium oxalate/butyl titanate ethylene glycol mixed solution that step S3 is prepared is moved to volume for 70mL's
190 DEG C of reaction 20h in reaction kettle are sealed, are cooled to room temperature, precipitating filtering later, and be washed with deionized 3 times, ethanol washing
It 1 time, is dried in vacuo 8 hours at 70 DEG C, obtains silicon-niobium oxide/titanium oxide of core-shell structure；
S5,0.2g silicon-niobium oxide/titanium oxide and 0.033g lithium nitride are ground under protection of argon gas, are sufficiently mixed,
It is sealed in stainless steel jar mill；
S6, by silicon-niobium oxide/titanium oxide of encapsulation and lithium nitride under protection of argon gas with the revolving speed high energy ball of 450r/min
10h is ground, washing is filtered, is dried in vacuo 8 hours at 70 DEG C, and products therefrom is to have lithium niobate/niobium base oxide/silicon compound
Negative electrode material.
The process and electrochemistry survey that there is gained lithium niobate/niobium base oxide/silicon composite cathode material to be assembled into electrode slice
Examination process is with embodiment 1, and reversible capacity reaches 3048mAh/g to the electrode of preparation for the first time.
Embodiment 7
It is a kind of with lithium niobate/niobium base oxide/silicon composite cathode material preparation method, there are following steps：
S1,0.23g silicon powder (average particle size 50nm) is added to ultrasonic vibration in the ethanol solution (analysis is pure) of 40mL
30min obtains evenly dispersed silicon powder/ethanol solution；
S2, the niobium chloride of 0.538g is dissolved in strong stirring 30min in the ethanol solution of 40ml, obtains clear chlorination
Niobium ethanol solution is spare；
S3, silicon powder/ethanol solution obtained in step S1 is added in niobium chloride ethanol solution obtained in step S2
Strong stirring 40min obtains 80mL silicon-niobium chloride alcohol mixed solution, Nb in solution5+Molar concentration is 0.0250mol L-1；
S4, the silicon for preparing step S3-niobium chloride alcohol mixed solution move into the sealing reaction kettle that volume is 100mL
180 DEG C of reaction 20h are cooled to room temperature, precipitating filtering later, and are washed with deionized 3 times, ethanol washing 1 time, at 70 DEG C
Vacuum drying 8 hours, obtains silicon-niobium oxide of core-shell structure；
S5,0.2g silicon-niobium oxide and 0.009g lithium nitride are ground under protection of argon gas, is sufficiently mixed, sealing is protected
It is stored in stainless steel jar mill.
S6, by silicon-niobium oxide of encapsulation and lithium nitride under protection of argon gas with the revolving speed high-energy ball milling 12h of 400r/min,
Washing filters, and is dried in vacuo 8 hours at 70 DEG C, and products therefrom is to have lithium niobate/niobium base oxide/silicon composite cathode material
Material.
The process and electrochemistry survey that there is gained lithium niobate/niobium base oxide/silicon composite cathode material to be assembled into electrode slice
Examination process is with embodiment 1, and the material of preparation embedding lithium activity with higher, reversible capacity reaches 2312mAh/g for the first time.It fills for the first time
To in 150 circulations after electric discharge, the range of coulombic efficiency has good electrochemical reversibility up to 98%~99.9%.
Charge and discharge of the Fig. 3 by the cathode pole piece manufactured in the present embodiment assembled with lithium niobate/niobium base oxide/silicon composite cathode material
Electric curve graph.Fig. 4 is by the cathode manufactured in the present embodiment assembled with lithium niobate/niobium base oxide/silicon composite cathode material
The cycle life test chart of pole piece.
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 (10)
1. one kind has lithium niobate/niobium base oxide/silicon composite cathode material, it is characterised in that：Including silicon activated centre and
The even lithium niobate for being coated on silicon activated centre surface/niobium base oxide mixing shell.
2. according to claim 1 have lithium niobate/niobium base oxide/silicon composite cathode material, it is characterised in that：It is described
Silicon activated centre is silicon powder of the particle size at 20-100 nanometers；
The lithium niobate/niobium base oxide mixing shell is that niobium oxide and lithium nitride pass through high temperature solid state reaction or high speed ball milling
The lithium niobate and the mixed uniformly shell of niobium base oxide of fabricated in situ；
The lithium niobate/niobium base oxide mixing shell is with a thickness of 5-50 nanometers.
3. according to claim 1 have lithium niobate/niobium base oxide/silicon composite cathode material, it is characterised in that：It is described
Silicon activated centre is 1 with the lithium niobate/niobium base oxide mixing shell mass ratio:0.1~1:2.
4. according to right want 2 described in have lithium niobate/niobium base oxide/silicon composite cathode material, it is characterised in that：The niobium
It is 0.5 that sour lithium/niobium base oxide mixing shell, which is molar ratio,:1~5:1 lithium nitride and niobium oxide passes through high temperature solid state reaction
Or the lithium niobate of high speed ball milling fabricated in situ and the mixed uniformly shell of niobium base oxide.
5. a kind of with lithium niobate/niobium base oxide/silicon composite cathode material preparation method, it is characterised in that have following step
Suddenly：
S1, ultrasonic vibration in silicon powder addition alcoholic solution is more than or equal to 30 minutes, obtains uniformly mixed silicon powder/alcoholic solution；
S2, niobium chloride or niobium oxalate are dissolved in alcoholic solution or dissolve the mixture of niobium chloride or niobium oxalate and butyl titanate
In alcoholic solution, uniform oxide precursor object/alcoholic solution is obtained；
S3, silicon powder/alcoholic solution obtained in step S1 is added in the object of oxide precursor obtained in step S2/alcoholic solution by force
Power stirring is more than or equal to 30 minutes, obtains uniformly mixed silicon powder-oxide precursor object/alcoholic solution；
S4, silicon powder-oxide precursor object/alcoholic solution that step S3 is obtained is moved in sealing reaction kettle and reacts 20 hours, later
Cooling, precipitating filtering, washing, and vacuum drying, obtain silicon/niobium base oxide；
S5 moves into silicon obtained in step S4/niobium base oxide and lithium nitride mixed grinding under protection of argon gas in tube furnace
Carry out high temperature solid state reaction or be encapsulated into stainless steel jar mill to carry out high speed ball milling, the product reacted is to have niobic acid
Lithium/niobium base oxide/silicon composite cathode material.
6. according to claim 5 have lithium niobate/niobium base oxide/silicon composite cathode material preparation method, spy
Sign is that the alcoholic solution in the step S1 and step S2 is methanol solution, ethanol solution or ethylene glycol solution；
Niobium chloride, niobium oxalate, butyl titanate are that analysis is pure in the step S2；
Nb in the oxide precursor object/alcoholic solution5+Molar concentration range be 0.01-0.1mol/L；
In the step S5, lithium nitride and Li in silicon/niobium base oxide obtained in step S4+With Nb5+Molar ratio be 1:1~
5:1。
7. according to claim 5 have lithium niobate/niobium base oxide/silicon composite cathode material preparation method, spy
Sign is that the temperature in reaction kettle described in the step S4 is 150~210 DEG C.
8. according to claim 5 have lithium niobate/niobium base oxide/silicon composite cathode material preparation method, spy
Sign is that the step S5 high temperature solid phase reaction process is：Muffle furnace first rises to reaction temperature and is preheated, in step S4
After the silicon arrived/niobium base oxide and lithium nitride directly keep the temperature 0.5~3 hour at a temperature of 500~700 DEG C, it is furnace-cooled to room temperature, instead
The product that should be obtained is to have lithium niobate/niobium base oxide/silicon composite cathode material, and whole process carries out under argon gas.
9. according to claim 5 have lithium niobate/niobium base oxide/silicon composite cathode material preparation method, spy
Sign is that high speed mechanical milling process described in the step S5 is：Silicon/niobium base oxide is encapsulated under protection of argon gas with lithium nitride
High speed ball milling is carried out in stainless steel jar mill, the high speed rotational speed of ball-mill is 400~500r/min, the ball milling of the high speed ball milling
Time is 8~12 hours.
10. there is lithium niobate/niobium base oxide/silicon composite cathode described in a kind of -4 any claims according to claim 1
The cathode of material preparation.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109755509A (en) * | 2018-12-21 | 2019-05-14 | 江苏大学 | A kind of lithium ion battery Si@Nb2O5The preparation method of composite negative pole material |
| CN110380048A (en) * | 2019-07-05 | 2019-10-25 | 南京理工大学 | Nanostructure LiNbO3/ Graphene electrodes material and preparation method thereof |
| CN111463419A (en) * | 2020-04-28 | 2020-07-28 | 苏州宇豪纳米材料有限公司 | Silicon-based @ titanium niobium oxide core-shell structure anode material and preparation method thereof |
| CN111463419B (en) * | 2020-04-28 | 2022-04-01 | 苏州宇豪纳米材料有限公司 | Silicon-based @ titanium niobium oxide core-shell structure anode material and preparation method thereof |
| CN112467097A (en) * | 2020-10-30 | 2021-03-09 | 安普瑞斯（南京）有限公司 | Negative electrode material, preparation method thereof, electrode and secondary battery |
| CN114142011A (en) * | 2021-11-29 | 2022-03-04 | 蜂巢能源科技有限公司 | Hard carbon composite material and preparation method and application thereof |
| CN114142011B (en) * | 2021-11-29 | 2023-06-16 | 蜂巢能源科技有限公司 | Hard carbon composite material and preparation method and application thereof |
| CN117438587A (en) * | 2023-12-19 | 2024-01-23 | 深圳市本征方程石墨烯技术股份有限公司 | Silicon-based anode material, preparation method and application thereof, and lithium ion battery |
| CN117438587B (en) * | 2023-12-19 | 2024-04-16 | 深圳市本征方程石墨烯技术股份有限公司 | Silicon-based anode material, preparation method and application thereof, and lithium ion battery |
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