CN108493408A - A kind of compound porous titanium niobate lithium cell cathode material of modified clay and preparation method - Google Patents
A kind of compound porous titanium niobate lithium cell cathode material of modified clay and preparation method Download PDFInfo
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- CN108493408A CN108493408A CN201810192881.XA CN201810192881A CN108493408A CN 108493408 A CN108493408 A CN 108493408A CN 201810192881 A CN201810192881 A CN 201810192881A CN 108493408 A CN108493408 A CN 108493408A
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- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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Abstract
The present invention relates to a kind of compound porous titanium niobate lithium cell cathode material of modified clay and preparation methods, belong to electrode material preparation field.A kind of compound porous titanium niobate lithium cell cathode material of modified clay of the present invention and preparation method, include the following steps：A, niobium source, titanium source and organic solvent are prepared into porous niobic acid titanium precursors gel by sol-gal process, porous titanium niobate negative material is obtained by high temperature sintering；B, the negative material is compound by modes such as compacting, ball millings under anaerobic with the paste clay that is adsorbed with ionic liquid, make clay uniformly fill in negative material hole；C, surface is coated after removing the paste clay of surface residual, obtains the compound titanium niobate negative material of modified clay.The present invention reduces negative material internal driving, improves the ionic conduction efficiency of electrode interior, solves the problems, such as that the ionic conductivity of traditional titanium niobate material is low.
Description
Technical field
The present invention relates to a kind of compound porous titanium niobate lithium cell cathode material of modified clay and preparation methods, belong to electrode
Field of material preparation.
Background technology
Lithium ion battery is a kind of secondary cell（Rechargeable battery）, it relies primarily on lithium ion and moves between a positive electrode and a negative electrode
It moves and carrys out work.Due to lithium ion battery have voltage it is high, it is bigger than energy, have extended cycle life, have a safety feature, self discharge is small,
The advantages that quick charge, makes it be obtained in various electronic products and is widely applied.Current commercialized lithium ion battery
Negative material be mainly graphite.Conventional graphite cathode is easy to form lithium in surface lithium deposition since the insertion ability of lithium is poor
Dendrite causes large effect to the cycle performance and security performance of battery.The cathode of titanium-based structure due to its stable structure,
Deformation is small during lithium ion deintercalation, is not easy during surface formation lithium deposition, battery first charge-discharge, formation is covered in
The solid electrolyte interface film of electrode material surface（SEI films）Influence to reaction is smaller, has numerous studies personnel by mixing
The modes such as miscellaneous, modified have carried out a large amount of research.Niobic acid Ti electrode is due to multiple redox couples, each titanium niobate lattice
Five lithium ions can be embedded in, embeddable lithium ion capacity higher is caused, there is higher theoretical capacity.But titanium niobate material is deposited
In some disadvantages, such as low ion and electronic conductivity, its chemical property is limited, therefore have for the modification of its conductivity
Highly important practical significance.
Application No. is a kind of preparation sides of porous titanium niobate/carbon complex microsphere of 201610706550 Introduction To Cn Patent
Method.The present invention selects titanium dioxide as titanium source, and niobium pentaoxide is as niobium source, and sucrose is as carbon source, and deionized water is as molten
Porous titanium niobate/carbon with multilevel hierarchy is successfully prepared successively by techniques such as ball milling, spray drying, heat treatments in agent
Complex microsphere.The material is due to higher theoretical specific capacity（388 mAh/g）, larger specific surface area, therefore it is expected to
Lithium titanate is substituted as lithium ion battery negative material.In addition to this, the present invention has preparation process simple, and manufacturing cycle is shorter
The advantages that, it is very suitable for industrialized production, has broad application prospects.
It discloses application No. is 201511011431 Chinese patent and a kind of preparing three-dimensional porous titanium niobate using template
The method of oxide and its application in lithium ion battery, the method are：One, by equimolar than titanium source compound and niobium
Source compound is dispersed and dissolved in organic solvent, and being sufficiently stirred makes it be uniformly dispersed；Two, a certain amount of mould material is added
In above-mentioned solution, then it is filtered under vacuum filtration or baking oven in dry, obtain presoma；Three, by presoma in height
It is calcined in air atmosphere at 800 ~ 1400 DEG C in warm stove, removes mould material, you can obtain porous TiNb2O7Negative material.
Titanium niobium composite oxides TiNb prepared by the present invention2O7Have compared with high reversible capacity and head when being used as lithium ion battery negative material
Secondary efficiency, excellent high rate charge-discharge performance and security performance, and raw material cost is low, it is nontoxic, have extremely wide
General application prospect.
Application No. is 201610107404 Chinese patents to disclose a kind of preparation side of titanium niobate/carbon composite electrode material
Method belongs to lithium ion battery material technical field.By titanium dioxide, niobium oxide and carbon source, ball milling mixes this method by a certain percentage
It closes, then calcines the mixture after drying up to titanium niobate/carbon composite electrode material under inert gas protection.The application is also
Disclose a kind of titanium niobate/carbon composite electrode material being prepared by above-mentioned preparation method.The present invention is improved using carbon coating
The conductivity of material, while the cladding of carbon-coating increases phenomenon to the particle of titanium niobate has certain inhibiting effect, is used as lithium
Ion battery cathode material shows excellent high rate performance and cycle performance.In addition, preparation process of the present invention is simple, operation side
Just, production cost is low, is easy to scale industrial production.
The prior art is directed to the shortcomings that low ion of titanium niobate material and electronic conductivity, is mainly prepared by solid reaction process
Titanium niobate composite material, template prepare the methods of titanium niobate porous material to improve the conductivity of material.But the degree that promoted has
Limit, fails fundamentally to solve the problems, such as that titanium niobate negative material conductivity is low.
Invention content
For the low defect of ion existing for existing titanium niobate negative material and electronic conductivity, the present invention is to its conductivity
It is modified, a kind of preparation method of the compound porous titanium niobate lithium cell cathode material of modified clay is provided.
A kind of preparation method of the compound porous titanium niobate lithium cell cathode material of modified clay, includes the following steps：
A, titanium source and niobium source are added separately in organic solvent, are stirred to clarify, wherein a concentration of 0.001-32 of titanium ion
mol/L；Gained mixed liquor is fitted into the stainless steel cauldron of inner liner polytetrafluoroethylene, is placed in thermostatic drying chamber, in 100-260
It is heated 2-72 hours at DEG C, reaction postcooling obtains white powder to room temperature；Gained white powder is placed in tube furnace, lazy
Under property gas shield, 2-48 hours are roasted at 600-1200 DEG C to get porous titanium niobate negative material.
B, by porous titanium niobate negative material obtained by step a and the paste clay for being adsorbed with lithium ion liquid, in indifferent gas
Compound under body protection, the mass ratio of titanium niobate negative material and paste clay is 1:10-10:1, obtain composite material.
C, the paste clay that removing composite material surface remnants are cleaned with ethyl alcohol is placed in thermostatic drying chamber, in 80-150
It is heated 1-24 hours at DEG C, the composite material after drying is finally subjected to surface cladding with acetylene cracking process, obtains modified clay
Compound titanium niobate negative material.
The technology of the present invention point is：The spongy niobic acid with good porous structure is prepared by sol-gal process
Titanium material reuses and adsorbs clay absorption ionic liquid by force, in embedded spongy titanium niobate hole, forms lithium ion transport and leads to
Road forms while having the filler of heat resistant solid performance and the ionic conduction performance of liquid, to reduce in negative material
Portion's impedance improves the ionic conduction efficiency of electrode interior.
Titanium niobate (TiNb2O7) as a kind of novel negative material, there is the charging/discharging voltage similar with lithium titanate material
Platform (1.65Vvs.Li+/Li) can effectively avoid solid electrolyte from aoxidizing film (SEI films) compared to graphite-like carbon material
It is formed, there is higher volume and capacity ratio and better safety；In addition, material volume change in charge and discharge process is small,
With excellent cyclical stability；The theoretical specific capacity of the material is 388 mAh/g, is twice of lithium titanate material.Therefore, exist
There is vast potential for future development in terms of lithium ion battery especially power-type lithium ion battery, it is considered to be very excellent high-performance
Cell negative electrode material, by the extensive concern of researcher.However, due to TiNb2O7 materials native electronic and ion conductivity
Relatively low, so that it is polarized when charge and discharge under high current density, big, capacity attenuation is very fast, high rate performance is poor, constrains its big rule
Mould commercial applications.
Have lot of documents report and points out that the appearance structure and size of electrode material have larger shadow to its chemical property
It rings.Electrode material with special appearance structure can increase the contact area with electrolyte, and small particle size can shorten
The diffusion length of lithium ion, is all conducive to the diffusion of lithium ion, and then helps to improve the chemical property of material.
Sol-gel method is exactly to make presoma with the compound containing high chemical active ingredient, by these raw materials under liquid phase
Uniformly mixing, and be hydrolyzed, be condensed chemical reaction, stable vitreosol system, the aged glue of colloidal sol are formed in the solution
Intergranular slowly polymerize, and forms the gel of three-dimensional net structure, and the solvent to lose flowability is filled between gel network, is formed solidifying
Glue.Gel can prepare molecule or even the material of nanometer substructure by dry, sintering curing.Sol-gel method and its
Its method is many unique compared to having the advantages that：（1）Since raw material used in sol-gel method is dispersed to solvent first
In and form the solution of low viscosity, accordingly, it is possible to obtain the uniformity of molecular level in a short period of time, forming gel
When, it is likely to be uniformly mixed on a molecular scale between reactant.（2）Due to passing through solution reaction step, then just
It mixes some trace elements with being easy to equal and quantitative, realizes the Uniform Doped on molecular level.（3）Compared with solid phase reaction,
Easy progress is only needed lower synthesis temperature by chemical reaction, it is considered that the expansion of component in so-gel system
It is dispersed in nanometer range, and diffusion of components is therefore to react in micron range and be easy to carry out when solid phase reaction, temperature is relatively low.
The present invention uses sol-gal process, and it is logical that the spongiform titanium niobate material being prepared can form lithium ion transport well
Road, and then promote the conductivity of material.
Ionic liquid（Or ionic liquid）Refer to the liquid being composed entirely of ions, in room temperature or close to being at room temperature
Salt showing liquid, being made of completely zwitterion, also referred to as low temperature molten salt.Ionic liquid as ionic compound,
Lower melting-point main cause is because the asymmetry of certain substituent groups in its structure prevents ion from being regularly piled into crystal
It is caused.It is generally made of organic cation and inorganic or organic anion, and common cation has quaternary ammonium salt ion, quaternary alkylphosphonium salt
Ion, imidazolium ion and pyrroles's salt ion etc., anion has halide ion, tetrafluoroborate ion, hexafluorophosphoricacid acid ions
Deng.When with conventional organic solvents and electrolyte phase ratio, ionic liquid has the advantages that a series of protrusions：（1）Liquid state range is wide,
, to 300 DEG C or more, there are high thermal stability and chemical stability from below or near to room temperature；（2）Vapour pressure is very small, does not wave
Hair, it is lost using, will not be evaporated in storage, it can recycle, eliminate volatile organic compounds（VOCs, i.e.,
volatile organic compounds）Problem of environmental pollution,（3）Conductivity is high, and electrochemical window is big, can be used as many objects
The electrolyte of matter electrochemical research；（4）It is adjusted to inorganic matter, water, organic matter and polymer by the design of zwitterion
Dissolubility, and its acidity is adjustable to super acid.（5）With larger polarity Modulatory character, viscosity is low, and density is big, can be with shape
At two-phase or heterogeneous system, it is suitable as separation solvent or constitutes reaction-separation coupling new system；（6）To a large amount of inorganic and organic
Good solvability at substance all performances, and the dual function with solvent and catalyst, can be used as many chemical reactions
Solvent or catalytic activity carrier.Due to these special natures of ionic liquid and performance, it is considered and supercritical CO 2 and double
Water phase constitutes three big green solvents together, has broad application prospects.The present invention uses the ionic liquid containing lithium ion, with
After clay mixing, it is mixed into porous niobic acid titanium electrode material, forms good lithium ion tunnel in the material, improve material
The lithium ion conduction performance of material.
Preferably：In step a, the middle titanium source is titanyl sulfate, titanium tetrafluoride, titanium tetraisopropylate, titanium sulfate, titanium oxalate
One or more of potassium, titanium tetrachloride, titanium trichloride, butyl titanate.In order to form the excellent gel of structure faster, preferably
The titanium dioxide that relative density is smaller, surface area is larger.
Preferably：In step a, the middle niobium source is one or more of niobium oxalate, ethyl alcohol niobium, columbium pentachloride.In order to
The excellent gel of structure is faster formed, preferred alcohol niobium is as niobium source.
Preferably：In step a, the titanium niobium molar ratio in the titanium source and niobium source is titanium/niobium=0.4-0.9.For bigger journey
The conversion ratio of the promotion raw material of degree, preferably titanium niobium molar ratio are titanium/niobium=0.5.
Preferably：In step a, the organic solvent is the one or more of ethyl alcohol, isopropanol, glycerine.It is furthermore preferred that
The organic solvent is ethyl alcohol.
Preferably：In step a or step b, the inert gas is the one or two of argon gas, nitrogen.
Preferably：In step b, the clay is strong adsorptivity clay.
Preferably：In step b, the mass ratio of the titanium niobate negative material and paste clay is 1: 2-2:1.More preferably
, the mass ratio of the titanium niobate negative material and paste clay is 1:1.
Preferably：In step b, the complex method is ball-milling, and drum's speed of rotation is 100-500 r/min, ball milling
Time is 10-60 minutes.It is furthermore preferred that drum's speed of rotation is 200 r/min, Ball-milling Time is 30 minutes.
The invention solves second technical problem to be to provide a kind of compound porous titanium niobate lithium battery of modified clay negative
Pole material.
A kind of compound porous titanium niobate lithium cell cathode material of modified clay is prepared by above-mentioned preparation method.
Compared with prior art, the present invention has advantageous effect below：
1, the compound porous titanium niobate lithium cell cathode material of a kind of modified clay prepared by the present invention：Composite material has porous
Spongelike structure can increase the contact area with electrolyte, and small particle size can shorten the diffusion length of lithium ion, all
Be conducive to the diffusion of lithium ion, and then help to improve the chemical property of material, while the clay for being adsorbed with lithium ion is answered
It closes, lithium ion transport channel can be formed in electrode material, form while having the ion of heat resistant solid performance and liquid
The filler of conductive performance improves the ionic conduction efficiency of electrode interior to reduce negative material internal driving.
2, a kind of preparation method of the compound porous titanium niobate lithium cell cathode material of modified clay of the present invention, realizes material
Special construction, while technical maturity is easily operated.
Specific implementation mode
In the following, the present invention will be further described in detail by way of specific embodiments, but this should not be interpreted as to the present invention
Range be only limitted to example below.Without departing from the idea of the above method of the present invention, according to ordinary skill
The various replacements or change that knowledge and customary means are made, should be included in the scope of the present invention.
A kind of preparation method of the compound porous titanium niobate lithium cell cathode material of 1 modified clay of embodiment
It prepares according to the following steps：
A, titanium source and niobium source are added separately in ethyl alcohol, are stirred to clarify, wherein a concentration of 0.001 mol/L of titanium ion,
Titanium niobium molar ratio is titanium/niobium=0.4；Gained mixed liquor is fitted into the stainless steel cauldron of inner liner polytetrafluoroethylene, is placed in constant temperature
It in drying box, is heated 48 hours at 100 DEG C, reaction postcooling obtains white powder to room temperature；Gained white powder is placed in
In tube furnace, 12 hours are roasted under inert gas protection, at 800 DEG C to get porous titanium niobate negative material.
B, by porous titanium niobate negative material obtained by step a and the paste clay for being adsorbed with lithium ion liquid, in indifferent gas
Compound under body protection, the mass ratio of titanium niobate negative material and paste clay is 1:10, obtain composite material.
C, the paste clay that removing composite material surface remnants are cleaned with ethyl alcohol is placed in thermostatic drying chamber, at 150 DEG C
Lower heating 15 hours, finally carries out surface cladding with acetylene cracking process by the composite material after drying, it is compound to obtain modified clay
Titanium niobate negative material.
Wherein, the titanium source used in above-mentioned preparation process is titanium tetrachloride, and niobium source is ethyl alcohol niobium, two step of described a, b
Inert gas be argon gas, the complex method be ball-milling, drum's speed of rotation be 200 r/min, Ball-milling Time be 20 points
Clock.
A kind of preparation method of the compound porous titanium niobate lithium cell cathode material of 2 modified clay of embodiment
It prepares according to the following steps：
A, titanium source and niobium source are added separately in ethyl alcohol, are stirred to clarify, wherein a concentration of 4 mol/L of titanium ion, titanium niobium
Molar ratio is titanium/niobium=0.5；Gained mixed liquor is fitted into the stainless steel cauldron of inner liner polytetrafluoroethylene, is placed in freeze-day with constant temperature
It in case, is heated 32 hours at 150 DEG C, reaction postcooling obtains white powder to room temperature；Gained white powder is placed in tubular type
In stove, 14 hours are roasted under inert gas protection, at 1000 DEG C to get porous titanium niobate negative material.
B, by porous titanium niobate negative material obtained by step a and the paste clay for being adsorbed with lithium ion liquid, in indifferent gas
Compound under body protection, the mass ratio of titanium niobate negative material and paste clay is 1:8, obtain composite material.
C, the paste clay that removing composite material surface remnants are cleaned with ethyl alcohol is placed in thermostatic drying chamber, at 110 DEG C
Lower heating 14 hours, finally carries out surface cladding with acetylene cracking process by the composite material after drying, it is compound to obtain modified clay
Titanium niobate negative material.
Wherein, the titanium source used in above-mentioned preparation process is titanium tetrachloride and titanyl sulfate molar ratio 1:1 aggregate sample
Product, niobium source are columbium pentachloride, and the inert gas of two step of described a, b is nitrogen, and the complex method is that compacting is compound.
A kind of preparation method of the compound porous titanium niobate lithium cell cathode material of 3 modified clay of embodiment
It prepares according to the following steps：
A, titanium source and niobium source are added separately in ethyl alcohol, are stirred to clarify, wherein a concentration of 8 mol/L of titanium ion, titanium niobium
Molar ratio is titanium/niobium=0.9；Gained mixed liquor is fitted into the stainless steel cauldron of inner liner polytetrafluoroethylene, is placed in freeze-day with constant temperature
It in case, is heated 32 hours at 180 DEG C, reaction postcooling obtains white powder to room temperature；Gained white powder is placed in tubular type
In stove, 36 hours are roasted under inert gas protection, at 700 DEG C to get porous titanium niobate negative material.
B, by porous titanium niobate negative material obtained by step a and the paste clay for being adsorbed with lithium ion liquid, in indifferent gas
Compound under body protection, the mass ratio of titanium niobate negative material and paste clay is 1:3, obtain composite material.
C, the paste clay that removing composite material surface remnants are cleaned with ethyl alcohol is placed in thermostatic drying chamber, at 140 DEG C
Lower heating 16 hours, finally carries out surface cladding with acetylene cracking process by the composite material after drying, it is compound to obtain modified clay
Titanium niobate negative material.
Wherein, the titanium source used in above-mentioned preparation process is titanium tetraisopropylate, and niobium source is that ethyl alcohol niobium and columbium pentachloride rub
You are than being 2:The inert gas of 1 sample, two step of described a, b is nitrogen, and the complex method is ball-milling, and ball mill turns
Speed is 100 r/min, and Ball-milling Time is 40 minutes.
A kind of preparation method of the compound porous titanium niobate lithium cell cathode material of 4 modified clay of embodiment
It prepares according to the following steps：
A, titanium source and niobium source are added separately in ethyl alcohol, are stirred to clarify, wherein a concentration of 18 mol/L of titanium ion, titanium niobium
Molar ratio is titanium/niobium=0.7；Gained mixed liquor is fitted into the stainless steel cauldron of inner liner polytetrafluoroethylene, is placed in freeze-day with constant temperature
It in case, is heated 56 hours at 200 DEG C, reaction postcooling obtains white powder to room temperature；Gained white powder is placed in tubular type
In stove, 40 hours are roasted under inert gas protection, at 1100 DEG C to get porous titanium niobate negative material.
B, by porous titanium niobate negative material obtained by step a and the paste clay for being adsorbed with lithium ion liquid, in indifferent gas
Compound under body protection, the mass ratio of titanium niobate negative material and paste clay is 1:1, obtain composite material.
C, the paste clay that removing composite material surface remnants are cleaned with ethyl alcohol is placed in thermostatic drying chamber, at 110 DEG C
Lower heating 20 hours, finally carries out surface cladding with acetylene cracking process by the composite material after drying, it is compound to obtain modified clay
Titanium niobate negative material.
Wherein, the titanium source used in above-mentioned preparation process is the molar ratio of titanyl sulfate, titanium tetrafluoride, titanium tetraisopropylate
It is 3:2:1 sample, niobium source is ethyl alcohol niobium and columbium pentachloride molar ratio is 3:1 sample, the inert gas of two step of described a, b
For argon gas, the complex method is that compacting is compound.
A kind of preparation method of the compound porous titanium niobate lithium cell cathode material of 5 modified clay of embodiment
It prepares according to the following steps：
A, titanium source and niobium source are added separately in ethyl alcohol, are stirred to clarify, wherein a concentration of 20 mol/L of titanium ion, titanium niobium
Molar ratio is titanium/niobium=0.8；Gained mixed liquor is fitted into the stainless steel cauldron of inner liner polytetrafluoroethylene, is placed in freeze-day with constant temperature
It in case, is heated 60 hours at 220 DEG C, reaction postcooling obtains white powder to room temperature；Gained white powder is placed in tube furnace
In, 24 hours are roasted under inert gas protection, at 800 DEG C to get porous titanium niobate negative material.
B, by porous titanium niobate negative material obtained by step a and the paste clay for being adsorbed with lithium ion liquid, in indifferent gas
Compound under body protection, the mass ratio of titanium niobate negative material and paste clay is 2:1, obtain composite material.
C, the paste clay that removing composite material surface remnants are cleaned with ethyl alcohol is placed in thermostatic drying chamber, at 90 DEG C
Lower heating 15 hours, finally carries out surface cladding with acetylene cracking process by the composite material after drying, it is compound to obtain modified clay
Titanium niobate negative material.
Wherein, the titanium source used in above-mentioned preparation process is titanium tetraisopropylate, titanium sulfate, titanium potassium oxalate, titanium tetrachloride
Molar ratio is 1:2:6:1 mixing sample, niobium source are ethyl alcohol niobium, and the inert gas of two step of described a, b is nitrogen and argon gas
Product ratio 1:1, the complex method is that compacting is compound.
A kind of preparation method of the compound porous titanium niobate lithium cell cathode material of 6 modified clay of embodiment
It prepares according to the following steps：
A, titanium source and niobium source are added separately in ethyl alcohol, are stirred to clarify, wherein a concentration of 32 mol/L of titanium ion, titanium niobium
Molar ratio is titanium/niobium=0.9；Gained mixed liquor is fitted into the stainless steel cauldron of inner liner polytetrafluoroethylene, is placed in freeze-day with constant temperature
It in case, is heated 70 hours at 260 DEG C, reaction postcooling obtains white powder to room temperature；Gained white powder is placed in tubular type
In stove, 36 hours are roasted under inert gas protection, at 1200 DEG C to get porous titanium niobate negative material.
B, by porous titanium niobate negative material obtained by step a and the paste clay for being adsorbed with lithium ion liquid, in indifferent gas
Compound under body protection, the mass ratio of titanium niobate negative material and paste clay is 5:1, obtain composite material.
C, the paste clay that removing composite material surface remnants are cleaned with ethyl alcohol is placed in thermostatic drying chamber, at 100 DEG C
Lower heating 10 hours, finally carries out surface cladding with acetylene cracking process by the composite material after drying, it is compound to obtain modified clay
Titanium niobate negative material.
Wherein, the titanium source used in above-mentioned preparation process is titanium tetrachloride, titanium trichloride, butyl titanate molar ratio are 5:
2:7 sample, niobium source are columbium pentachloride, and the inert gas of two step of described a, b is nitrogen, and the complex method is multiple for ball milling
It closes, drum's speed of rotation is 300 r/min, and Ball-milling Time is 60 minutes.
A kind of preparation method of the compound porous titanium niobate lithium cell cathode material of 7 modified clay of embodiment
It prepares according to the following steps：
A, titanium source and niobium source are added separately in ethyl alcohol, are stirred to clarify, wherein a concentration of 25 mol/L of titanium ion, titanium niobium
Molar ratio is titanium/niobium=0.5；Gained mixed liquor is fitted into the stainless steel cauldron of inner liner polytetrafluoroethylene, is placed in freeze-day with constant temperature
It in case, is heated 65 hours at 230 DEG C, reaction postcooling obtains white powder to room temperature；Gained white powder is placed in tubular type
In stove, 24 hours are roasted under inert gas protection, at 900 DEG C to get porous titanium niobate negative material.
B, by porous titanium niobate negative material obtained by step a and the paste clay for being adsorbed with lithium ion liquid, in indifferent gas
Compound under body protection, the mass ratio of titanium niobate negative material and paste clay is 8:1, obtain composite material.
C, the paste clay that removing composite material surface remnants are cleaned with ethyl alcohol is placed in thermostatic drying chamber, at 150 DEG C
Lower heating 1 hour, finally carries out surface cladding with acetylene cracking process by the composite material after drying, it is compound to obtain modified clay
Titanium niobate negative material.
Wherein, the titanium source used in above-mentioned preparation process is titanium tetrachloride, butyl titanate molar ratio is 1:2 sample,
Niobium source is ethyl alcohol niobium, and the inert gas of two step of described a, b is argon gas, and the complex method is ball-milling, drum's speed of rotation
For 250 r/min, Ball-milling Time is 20 minutes.
A kind of preparation method of the compound porous titanium niobate lithium cell cathode material of 8 modified clay of embodiment
It prepares according to the following steps：
A, titanium source and niobium source are added separately in ethyl alcohol, are stirred to clarify, wherein a concentration of 20 mol/L of titanium ion, titanium niobium
Molar ratio is titanium/niobium=0.9；Gained mixed liquor is fitted into the stainless steel cauldron of inner liner polytetrafluoroethylene, is placed in freeze-day with constant temperature
It in case, is heated 48 hours at 200 DEG C, reaction postcooling obtains white powder to room temperature；Gained white powder is placed in tubular type
In stove, 36 hours are roasted under inert gas protection, at 1200 DEG C to get porous titanium niobate negative material.
B, by porous titanium niobate negative material obtained by step a and the paste clay for being adsorbed with lithium ion liquid, in indifferent gas
Compound under body protection, the mass ratio of titanium niobate negative material and paste clay is 10:1, obtain composite material.
C, the paste clay that removing composite material surface remnants are cleaned with ethyl alcohol is placed in thermostatic drying chamber, at 80 DEG C
Lower heating 5 hours, finally carries out surface cladding with acetylene cracking process by the composite material after drying, it is compound to obtain modified clay
Titanium niobate negative material.
Wherein, the titanium source used in above-mentioned preparation process is titanium sulfate, titanium potassium oxalate, titanium tetrachloride molar ratio are 3:2:
4 sample, niobium source are columbium pentachloride, and the inert gas of two step of described a, b is nitrogen, and the complex method is ball-milling,
Drum's speed of rotation is 350 r/min, and Ball-milling Time is 60 minutes.
Comparative example 1
A, titanium source and niobium source are added separately in ethyl alcohol, are stirred to clarify, wherein a concentration of 20 mol/L of titanium ion, titanium
Niobium molar ratio is titanium/niobium=0.9；Gained mixed liquor is fitted into the stainless steel cauldron of inner liner polytetrafluoroethylene, and it is dry to be placed in constant temperature
It in dry case, is heated 48 hours at 200 DEG C, reaction postcooling obtains white powder to room temperature；Gained white powder is placed in pipe
In formula stove, 36 hours are roasted under inert gas protection, at 1200 DEG C to get porous titanium niobate negative material.
B, porous titanium niobate negative material obtained by step a is subjected to surface cladding with acetylene cracking process, obtains compound niobium
Sour titanium negative material.
Wherein, the titanium source used in above-mentioned preparation process is titanium sulfate, titanium potassium oxalate, titanium tetrachloride molar ratio are 3:2:
4 sample, niobium source are columbium pentachloride.
Test example
By Examples 1 to 8, comparative example 1 is prepared as electrode material, is used for lithium electricity ternary lithium battery, under same use condition,
25 DEG C carry out constant current charge-discharge test with 5C, and the results are shown in Table 1.
Table 1
| First discharge specific capacity/mAh.g-1 | Specific capacity/mAh.g after 100 cycles-1 | |
| Embodiment 1 | 296 | 280 |
| Embodiment 2 | 346 | 327 |
| Embodiment 3 | 351 | 334 |
| Embodiment 4 | 334 | 313 |
| Embodiment 5 | 319 | 301 |
| Embodiment 6 | 329 | 315 |
| Embodiment 7 | 317 | 302 |
| Embodiment 8 | 293 | 279 |
| Comparative example 1 | 167 | 142 |
Claims (10)
1. a kind of preparation method of the compound porous titanium niobate lithium cell cathode material of modified clay, which is characterized in that including following
Step：
A, titanium source and niobium source are added in organic solvent, stir to clarify to obtain mixed liquor, the concentration of titanium ion in mixed liquor
For 0.001-32 mol/L；Gained mixed liquor is fitted into the stainless steel cauldron of inner liner polytetrafluoroethylene, freeze-day with constant temperature is placed in
It in case, is heated 2-72 hours at 100-260 DEG C, reaction postcooling obtains white powder to room temperature；Gained white powder is placed in
In tube furnace, 2-48 hours are roasted under inert gas protection, at 600-1200 DEG C to get porous titanium niobate negative material；
B, it by porous titanium niobate negative material obtained by step a and the paste clay for being adsorbed with lithium ion liquid, is protected in inert gas
Compound under shield, the mass ratio of titanium niobate negative material and paste clay is 1:10-10:1, obtain composite material；
C, the paste clay that removing composite material surface remnants are cleaned with ethyl alcohol is placed in thermostatic drying chamber, at 80-150 DEG C
Composite material after drying is finally carried out surface cladding by lower heating 1-24 hours with acetylene cracking process, and it is multiple to obtain modified clay
The titanium niobate negative material of conjunction.
2. a kind of preparation method of the compound porous titanium niobate lithium cell cathode material of modified clay according to claim 1,
It is characterized in that：In step a, the titanium source is titanyl sulfate, titanium tetrafluoride, titanium tetraisopropylate, titanium sulfate, titanium potassium oxalate, four
One or more of titanium chloride, titanium trichloride, butyl titanate.
3. a kind of preparation method of the compound porous titanium niobate lithium cell cathode material of modified clay according to claim 1,
It is characterized in that：In step a, the niobium source is one or more of niobium oxalate, ethyl alcohol niobium, columbium pentachloride.
4. a kind of preparation method of the compound porous titanium niobate lithium cell cathode material of modified clay according to claim 1,
It is characterized in that：In step a, the titanium niobium molar ratio in the titanium source and niobium source is titanium/niobium=0.4-0.9.
5. a kind of preparation method of the compound porous titanium niobate lithium cell cathode material of modified clay according to claim 1,
It is characterized in that：In step a, the organic solvent is the one or more of ethyl alcohol, isopropanol, glycerine.
6. a kind of preparation method of the compound porous titanium niobate lithium cell cathode material of modified clay according to claim 1,
It is characterized in that：In step a or step b, the inert gas is the one or two of argon gas, nitrogen.
7. a kind of preparation method of the compound porous titanium niobate lithium cell cathode material of modified clay according to claim 1,
It is characterized in that：In step b, the clay is strong adsorptivity clay.
8. a kind of preparation method of the compound porous titanium niobate lithium cell cathode material of modified clay according to claim 1,
It is characterized in that：In step b, the mass ratio of the titanium niobate negative material and paste clay is 1: 2-2:1.
9. a kind of preparation method of the compound porous titanium niobate lithium cell cathode material of modified clay according to claim 1,
It is characterized in that：In step b, the complex method is ball-milling, and drum's speed of rotation is 100-500 r/min, Ball-milling Time
It is 10-60 minutes.
10. the compound porous titanium niobate of a kind of modified clay being prepared by claim 1-9 any one of them preparation methods
Lithium cell cathode material.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110970665A (en) * | 2018-09-29 | 2020-04-07 | 江苏师范大学 | SnS2Preparation method of/HNTs composite lithium ion battery |
| CN112701260A (en) * | 2020-12-25 | 2021-04-23 | 华中科技大学 | In-situ carbon-coated titanium niobate composite material and preparation method and application thereof |
| CN114477284A (en) * | 2022-03-16 | 2022-05-13 | 中物院成都科学技术发展中心 | Method for preparing titanium niobium oxide |
| CN118516684A (en) * | 2024-05-22 | 2024-08-20 | 哈尔滨工业大学 | Electrocrystallization preparation method and application of titanium niobate material with entropy reduction characteristic |
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2018
- 2018-03-09 CN CN201810192881.XA patent/CN108493408A/en not_active Withdrawn
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110970665A (en) * | 2018-09-29 | 2020-04-07 | 江苏师范大学 | SnS2Preparation method of/HNTs composite lithium ion battery |
| CN112701260A (en) * | 2020-12-25 | 2021-04-23 | 华中科技大学 | In-situ carbon-coated titanium niobate composite material and preparation method and application thereof |
| CN112701260B (en) * | 2020-12-25 | 2022-05-20 | 华中科技大学 | In-situ carbon-coated titanium niobate composite material and preparation method and application thereof |
| CN114477284A (en) * | 2022-03-16 | 2022-05-13 | 中物院成都科学技术发展中心 | Method for preparing titanium niobium oxide |
| CN114477284B (en) * | 2022-03-16 | 2023-12-05 | 中物院成都科学技术发展中心 | Method for preparing titanium niobium oxide |
| CN118516684A (en) * | 2024-05-22 | 2024-08-20 | 哈尔滨工业大学 | Electrocrystallization preparation method and application of titanium niobate material with entropy reduction characteristic |
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