CN107134575A - A kind of preparation method of anode material of lithium-ion battery - Google Patents
A kind of preparation method of anode material of lithium-ion battery Download PDFInfo
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- CN107134575A CN107134575A CN201710202293.5A CN201710202293A CN107134575A CN 107134575 A CN107134575 A CN 107134575A CN 201710202293 A CN201710202293 A CN 201710202293A CN 107134575 A CN107134575 A CN 107134575A
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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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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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
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a kind of preparation method of anode material of lithium-ion battery.Titanium source and other two kinds of exotic atom compounds are produced through steps such as collosol and gel, heat treatment, concentrated base immersion and high-temperature calcinations successively and obtain exotic atom codope titanium dioxide nanotube anode material of lithium-ion battery.The exotic atom codope titanium dioxide nanotube pattern that this method is prepared by simple common equipment is homogeneous, and electric conductivity is excellent, and ion diffusion rates are improved, therefore it has storage sodium capacity greatly, and cycle performance is good, the excellent chemical property such as coulombic efficiency height.Preparation technology of the present invention is simple, and raw material is easy to get, with low cost, environment-friendly, and repeatability is high, and yield is big, beneficial to industrialized production, with extensive commercial applications prospect.
Description
Technical field
The present invention relates to a kind of sodium-ion battery, more particularly to a kind of preparation method of anode material of lithium-ion battery.
Background technology
The energy is the material base that the mankind depend on for existence with development.With population and economic growth, human society is to energy
The demand in source is also growing.Lithium ion battery has energy density high due to it, has extended cycle life, memory-less effect etc. is excellent
Point, in the extensive use of energy storage field.However, it is contemplated that the cost of lithium ion battery, security performance, lithium resource is rare etc. to ask
Topic, in the urgent need to finding a kind of more rich more cheap safer alternative energy storage system of resource.
Sodium-ion battery is similar battery system with lithium ion battery.On the one hand, sodium element and elemental lithium are same masters
The metal of race, performance comparision is approached, and sodium resource is more more rich than lithium resource on the earth.On the other hand, the electricity of sodium ion half-cell
Position about 0.3V higher than lithium ion half-cell, the adaptation liquid electrolyte systems that chemical property is excellent but decomposition voltage is low, with more
High security.Therefore, more and more is studied to sodium-ion battery in worldwide in recent years.However, due to sodium ion
Radius ratio lithium ion it is big, and its kinetics is slower, and then causes that the cycle performance of battery is poor, and reversible specific capacity is low.For
Problem above is solved, suitable sodium ion battery electrode material is found and seems most important.At present, the positive pole material of sodium-ion battery
Material has obtained extensive research, and has made some progress, but with the good negative material of high rate performance that has extended cycle life
Still suffer from bottleneck.The carbon material that commercial Li-ion battery is used can not be avoided because voltage platform is too low（<0.1V）Cause sodium branch
The potential safety hazard that crystals growth is brought；It is due to that huge volumetric expansion is led though alloy material is with higher theoretical specific capacity
The structural instability of battery material is caused, cycle life is short.Therefore, developing new cheap has height ratio capacity, cyclical stability
Good negative material is the key for lifting sodium-ion battery performance.
Titanium dioxide, because its storage sodium current potential is low（≈0.7V）, theoretical specific capacity height (335mAhg -1), it is cheap and easy to get, peace
The advantages of performance is good entirely, is a kind of very promising sodium ion negative material.However, being limited to titanium dioxide electrical conductivity itself
The shortcoming of low and ionic mobility slowly etc., its high rate during charging-discharging is poor.It is different to improve the chemical property of titanium dioxide
Atom doped is a kind of common and fruitful method.Jiangfeng Ni（Adv. Mater. 2016, DOI:
10.1002/adma.201504412）Et al. synthesized a kind of sulfur doping titanium dioxide nano-tube array first, be used as negative pole
Materials application achieves excellent chemical property in sodium-ion battery system.But due to being needed in preparation process in high temperature
It is lower to use sulphur simple substance as sulphur source progress titania additive, easily cause huge potential safety hazard.On the other hand, the experimentation
Complexity, and material homogeneity prepared by the electrochemical deposition method used is poor.In addition, in Application No. 201410328415.1
State's patent discloses " a kind of to can be used as titanium oxygen compound negative material of sodium-ion battery and preparation method thereof ", and the patent system is standby
A kind of negative material of titanium oxide of single mass element doping as sodium-ion battery.Due to the limit of macroscopic property
System, part doped chemical may adulterate into the bad gap of lattice, so that causing the electrical conductivity of titanium oxide can not improve very
To being deteriorated, its thermodynamic stability be able to may also be deteriorated in addition.On the other hand, the standby titanium oxide of the patent system is deposited on pattern
In deficiency, and then influence the chemical property of sodium-ion battery.
The content of the invention
The technical problem to be solved in the present invention be overcome the deficiencies in the prior art there is provided a kind of energy consumption it is low, pollution-free be easy to
The preparation method of the anode material of lithium-ion battery of industrialized production.
In order to solve the above technical problems, technical scheme proposed by the present invention is：A kind of system of anode material of lithium-ion battery
Preparation Method, comprises the following steps：1）The preparation of exotic atom codope titanium dioxide presoma,Titanium source compound is scattered in short
In chain element alcohol, mixed proportion is 1:2-1:8, magnetic agitation 10-30 minutes obtains clarifying homogeneous mixed solution；The titanium
Source compound is butyl titanate, tetraethyl titanate, titanium tetrachloride, tetraisopropyl titanate, the one or more in titanium propanolate；
The short chain units alcohol is methanol, ethanol, propyl alcohol, n-butanol, the one or more in isobutanol；Titanium source used in the present invention
Compound all has following characteristics：Easily hydrolysis, it is easy to control its dissolution velocity, can reach after short chain units alcohol is added and be adapted to this
The granular size and pattern of invention.
Soluble metallic compound and nonmetallic compound are completely dissolved in short chain units alcohol, magnetic agitation 20-
60 minutes, obtain well mixed settled solution；
By solutionSolution is added slowly to dropwiseIn, magnetic agitation is carried out successively 2-4 hours, still aging 10-24 is small
Preserved at Shi Hou, 60-100 DEG C until supernatant liquor evaporating completely obtains spawn；
It is fully ground, is calcined 1-5 hours at 300-800 DEG C, natural cooling obtains exotic atom codope titanium dioxide forerunner
Body；
The exotic atom codope titanium dioxide is nano tubular structure, and external diameter is 4-15 nm, and internal diameter is the nm of 2- 8, and length is
20-100 nm。
2）The preparation of exotic atom codope titanium dioxide nanotube,By step 1）Obtained exotic atom codope titanium dioxide
Titanium precursors are dispersed in concentrated alkali solution according to 5 ~ 20g/L solid-to-liquid ratio, it is therefore an objective to will be doped to the ion of TiO 2 precursor
In being dispersed in lattice, stirring is transferred in sealing autoclave for 1-4 hours, is preserved 10-24 hours at 120-180 DEG C, from
So cooling；
By step 2 the step ofIn solution after obtained natural cooling filtered, the solid diluted acid obtained after filtering
Solution and deionized water are washed to neutrality, the then drying process under the conditions of 50-100 DEG C, by 400-800 DEG C of high-temperature calcination 2-
8 hours, room temperature is cooled to, exotic atom codope titanium dioxide nanotube is obtained；
3）The exotic atom codope titanium dioxide nanotube that step 2 is obtained is prepared into the negative pole or electricity of secondary sodium-ion battery
The negative pole of container.
The preparation method of above-mentioned anode material of lithium-ion battery, it is preferred that the metallic compound be iron, copper, nickel,
One or more in cobalt, tin, chromium, lead, zinc or rare earth compound；The nonmetallic compound be sulphur, boron, nitrogen, carbon or
The one or more of halogen compound.
The preparation method of above-mentioned anode material of lithium-ion battery, it is preferred that the concentrated base is sodium hydroxide and hydroxide
One or two kinds of in potassium.
The preparation method of above-mentioned anode material of lithium-ion battery, it is preferred that the dilute acid soln is watery hydrochloric acid, dilute sulfuric acid
Or the one or more in dust technology；The concentration of the dilute acid soln is the mol/L of 0. .1 ~ 0.5.
The preparation method of above-mentioned anode material of lithium-ion battery, it is preferred that the exotic atom codope titanium dioxide is received
The atomicity percentage composition ratio of metallic element is 0.01 ~ 5% in mitron, and doping can promote the transformation between crystalline phase, influences crystal
Pattern, but when doping is too high, lattice Severe distortion can be caused, and part is managed easy embrittlement, therefore obtained nanotube chi
It is very little to diminish relatively；In the exotic atom codope titanium dioxide nanotube atomicity percentage composition of nonmetalloid than 0.1 ~
5%.Same metallic element, doping can improve the structure and electrical conductivity of titanium dioxide.
The preparation method of above-mentioned anode material of lithium-ion battery, it is preferred that the exotic atom codope titanium dioxide is received
Mitron is one or both of Anatase, Rutile Type.
Compared with prior art, the advantage of the invention is that：（1）The present invention causes two by the effect of exotic atom codope
The band gap of titanium oxide reduces, so as to improve titanium dioxide electronic conductance inherently and ionic conductance.In addition, being co-doped with
Miscellaneous system can preferably provide acceptor or donor, and electronics is provided respectively or electronics is combined, thus material thermodynamics more
It is stable.（2）Exotic atom codope titanium dioxide prepared by the present invention is the big nano tubular structure of mechanical strength.The physical dimension
Homogeneous, specific surface area is big, is substantially shorter the migration distance of ion and electronics, contributes to fully connecing for electrode material and electrolyte
Touch, and then lift the chemical property of sodium-ion battery.（3）The present invention is easy to operate, and energy consumption is low, pollution-free, repeatability it is strong and
Without expensive equipment, it is adapted to industrial mass production.The exotic atom codope titanium dioxide nanotube of preparation is a kind of
Preferable sodium-ion battery negative material.（4）The required raw material of the present invention are cheap and easy to get, it is easy to mass produce.
In summary, the present invention is low, pollution-free and be easy to the method that is combined to of industry by designing energy consumption, and preparing has height
The titanium dioxide sodium ion negative material of electric conductivity, nano tubular structure exotic atom codope, realizes storage sodium capacity height,
Have extended cycle life, the excellent chemical property such as good rate capability.
Brief description of the drawings
Fig. 1 is the preparation flow figure of exotic atom codope titanium dioxide nanotube in the present invention.
Fig. 2 is obtained XRD analysis figure in the embodiment of the present invention 1.
Fig. 3 schemes for the TEM obtained in the embodiment of the present invention 1.
Fig. 4 is the cycle performance curve map of the embodiment of the present invention 2 and comparative example.
Fig. 5 is the curve of double curvature figure that embodiment 2 is obtained.
Embodiment
For the ease of understanding the present invention, present invention work more comprehensively, is meticulously described below in conjunction with preferred embodiment,
But protection scope of the present invention is not limited to embodiment in detail below.
It should be strongly noted that when a certain element, to be described as " be fixed on, be fixed in, be connected to or be communicated in " another
When on element, it can be directly fixed, affixed, connection or connect on another element or by connecting in the middle of other
Fitting is indirectly fixed, affixed, connection or connection are on another element.
Unless otherwise defined, the implication that all technical terms used hereinafter are generally understood that with those skilled in the art
It is identical.Technical term used herein is intended merely to describe the purpose of specific embodiment, is not intended to the limitation present invention
Protection domain.
Embodiment 1
10mL tetraisopropyl titanates are pressed in 20mL propyl alcohol, magnetic agitation 30 minutes, obtain clarifying homogeneous mixed solution 1.Separately
By 0.6g urea and 0.25g Cu (NO3)2·3H2O is substantially soluble in 50mL propyl alcohol, is stirred 60 minutes, obtains well mixed clear
Clear solution 2.Then by solution 1 dropwise slow addition solution 2, magnetic agitation is carried out successively 3 hours, still aging 10 is small
When, 100 DEG C preserve lower up to supernatant liquor evaporating completely obtains spawn, and after being fully ground, 2 are calcined at 600 DEG C
Hour, natural cooling is to obtain copper, nitrogen co-doped titanium dioxide presoma.
The above-mentioned presomas of 2g are scattered in 8mol/L KOH solution, stirring is transferred in autoclave after 4 hours, 180 DEG C
It is lower to preserve 10 hours, natural cooling.Then 0.2mol/L HNO is used respectively3Solution, it is neutrality that deionized water, which is washed to pH,.So
Afterwards by above-mentioned material via drying process at 50 DEG C, it is put into Muffle furnace after 600 DEG C of high-temperature calcinations handle 4 hours, is cooled to room
Temperature obtains high performance copper nitrogen co-doped titanium dioxide nanotube.
The electrode of copper nitrogen co-doped titanium dioxide nanotube negative material is prepared and electrochemical property test：
By copper nitrogen co-doped titanium dioxide nanotube negative material, conductive carbon, binding agent made from example 1（PVDF）In mass ratio
For 7:2:1 is sufficiently mixed, with METHYLPYRROLIDONE (NMP) as dispersant, and hand lapping is to obtaining homogeneous slurry.
Obtained slurry is coated on copper foil, 60 DEG C of the h of vacuum oven 12 is put into, then breaks into a diameter of 10 mm
Collar plate shape pole piece.Then using the pole piece as working electrode, metallic sodium piece be reference electrode, whatman glass fibres as every
Film, 1mol/L NaClO4/ EC+DEC/5% FEC are assembled into CR2032 buttons as electrolyte in the glove box full of argon gas
Formula battery.In room temperature（25 ℃）Under, limitation voltage is that 0.1 ~ 2.5 V carries out constant current charge-discharge test.The institute of the embodiment of the present invention 1
Copper nitrogen co-doped titanium dioxide negative material XRD and TEM the figure difference of preparation are as shown in Figures 2 and 3.
Test result shows that the structure of the copper nitrogen co-doped titanium dioxide prepared by the above method is nanotube-shaped knot
Structure, wherein copper content are 0.2 at%, and nitrogen content is 0.3 at%.XRD shows that the crystal formation of the material is Anatase titanium dioxide
Titanium.It is 0.1 A g in size of current-1, battery first discharge specific capacity is 579.4 mA h g-1, specific capacity after 120 circulations
For 155.8 mA h g-1。
Embodiment 2
5mL butyl titanates are dissolved in 20mL absolute ethyl alcohols, magnetic agitation 20 minutes obtains well mixed settled solution 1.Separately
0.274g thiocarbamides are added in 20mL absolute ethyl alcohols, fully 0.48g FeCl are added after dissolving3·6H2O, is persistently stirred 30 minutes
Obtain mixed solution 2.Then solution 1 is slowly added dropwise in solution 2, magnetic agitation 2 hours, still aging is carried out successively
Preserved at 12 hours, 80 DEG C, treat solvent evaporating completely, ground to be transferred in Muffle furnace at 500 DEG C and calcine 3 hours, cooling is produced
To the presoma of iron sulphur codope titanium dioxide.
The above-mentioned presomas of 1.2g are scattered in 100mL 10mol/L NaOH solution, stirs 2 hours, is transferred to high pressure
150 DEG C of reactor is preserved 12 hours.After room temperature cooling, cleaned respectively with 0.1mol/L HCl solution, deionized water, until molten
Liquid pH is neutrality.It is transferred in Muffle furnace 500 degrees Celsius after drying to calcine 2 hours, natural cooling is to obtain iron sulphur codope two
Titanium oxide nanotubes.
Electrochemical property test and example 1 are identical.Iron sulphur codope titanium dioxide nanotube prepared by the embodiment of the present invention 2 is followed
Ring performance curve and curve of double curvature difference are as shown in Figures 4 and 5.
Test result shows that iron content is 2 at%, sulphur in the iron sulphur codope titanium dioxide prepared by the above method
Content is 0.25 at%.XRD shows that the crystal formation of the material is anatase phase titanium dioxide.It is 0.1 A g in size of current-1, electricity
Pond first discharge specific capacity is 531.1 mA h g-1, specific capacity is 177.1 mA h g after 100 circulations-1.In addition, working as electric current
Size is respectively 0.05,0.1,0.2,0.5,1,2 A g-1When, its specific discharge capacity is respectively 238,192,156,
110, 82, 59 mA h g-1, after 60 circle circulations, the near 0.1 A g of electric current-1, its specific discharge capacity is returned to 190 mA h
g-1。
Embodiment 3
10mL tetraethyl titanate is scattered in 30mL butanol, magnetic agitation 10 minutes, the mixed solution 1 clarified.Separately
By 0.6g boric acid and 4g Cr (SO4)3It is substantially soluble in butanol, 20 ~ minute of magnetic agitation, obtains well mixed settled solution 2.
Then by solution 1 dropwise slow addition solution 2, magnetic agitation is carried out successively after 4 hours, still aging 24 hours, 60 protect
Deposit 15 hours, until supernatant liquor evaporating completely obtains spawn, after being fully ground, calcined 5 hours at 300 times, from
So cooling, that is, obtain chromium boron codope titanium dioxide presoma.
The above-mentioned presomas of 1g are scattered in 50mL 15mol/L KOH solution, stirring is transferred to autoclave after 4 hours
It is interior, preserved 24 hours at 120 DEG C, natural cooling.Then 0.5mol/L H is used respectively2SO4Solution, deionized water, which is washed to pH, is
It is neutral.Then by above-mentioned material via drying process at 100 DEG C, it is put into Muffle furnace after 400 DEG C of high-temperature calcinations handle 5 hours,
It is cooled to room temperature and obtains high performance chromium boron codope titanium dioxide nanotube.
The electrode of chromium boron codope titanium dioxide nanotube negative material is prepared and electrochemical property test：
By chromium boron codope titanium dioxide nanotube negative material, conductive carbon, binding agent made from example 3（CMC）In mass ratio
For 8:1:1 is sufficiently mixed, with deionization as dispersant, and hand lapping is to obtaining homogeneous slurry.By the coating of obtained slurry
On copper foil, 60 DEG C of the h of vacuum oven 12 is put into, a diameter of 10 mm collar plate shape pole piece is then broken into.Then
Using the pole piece as working electrode, metallic sodium piece is reference electrode, and Cegard 2300 is barrier film, 1mol/L NaClO4/EC+
DMC/5% FEC are assembled into CR2025 button cells as electrolyte in the glove box full of argon gas.In room temperature（25 ℃）
Under, limitation voltage is 0.1 ~ 2.5 V, and constant current charge-discharge test is carried out with 1A/g.The XRD of the embodiment of the present invention 3 such as Fig. 2 institutes
Show.
Test result shows that the chromium codope boron titania nanotube prepared by the above method is Anatase dioxy
Change titanium.It is 1 A g in size of current-1, battery first discharge specific capacity is 373.1 mA h g-1, specific capacity after 1000 circulations
For 73.2 mA h g-1。
Comparative example：
5mL butyl titanates are dissolved in 20mL absolute ethyl alcohols, magnetic agitation 20 minutes obtains well mixed settled solution, according to
Secondary progress magnetic agitation 2 hours, still aging 12 hours, preserve 12 hours at 80 DEG C, treat solvent evaporating completely, grind and be transferred to
Calcined 3 hours at 500 DEG C in Muffle furnace, cooling obtains the crude product of titanium dioxide.
The above-mentioned crude products of 1.2g are scattered in 100mL 10mol/L NaOH solution, stirs 2 hours, is transferred to high pressure
150 DEG C of reactor is preserved 12 hours.After room temperature cooling, cleaned respectively with 0.1mol/L HCl solution, deionized water, until molten
Liquid pH is neutrality.It is transferred in Muffle furnace 500 degrees Celsius after drying to calcine 2 hours, natural cooling is to obtain nano titania
Pipe.
Electrochemical property test and example 1 are identical.The XRD and cycle performance of titania nanotube prepared by comparative example of the present invention
Curve difference is as shown in Figures 2 and 4.
Test result shows that the titania nanotube prepared by comparative example is Anatase and Rutile Type titanium dioxide
The mixture of titanium.It is 0.1 A g in size of current-1, battery first discharge specific capacity is 219.6 mA h g-1, 100 circulations
Specific capacity is 41.5 mA h g afterwards-1.It can be seen that the unit for electrical property parameters of titania nanotube prepared by comparative example is significantly lower than
Embodiment 1, embodiment 2 and embodiment 3.
Claims (6)
1. a kind of preparation method of anode material of lithium-ion battery, it is characterised in that：Comprise the following steps：1）Exotic atom codope
The preparation of TiO 2 precursor,Titanium source compound is scattered in short chain units alcohol, mixed proportion is 1:2-1:8, magnetic force
Stirring 10-30 minutes, obtains clarifying homogeneous mixed solution；The titanium source compound be butyl titanate, tetraethyl titanate,
One or more in titanium tetrachloride, tetraisopropyl titanate, titanium propanolate；The short chain units alcohol be methanol, ethanol, propyl alcohol,
One or more in n-butanol, isobutanol；
Soluble metallic compound and nonmetallic compound are completely dissolved in short chain units alcohol, 20-60 points of magnetic agitation
Clock, obtains well mixed settled solution；
By solutionSolution is added slowly to dropwiseIn, while carry out magnetic agitation 2-4 hours, it is still aging 10-24 hours
Afterwards, preserve at 60-100 DEG C until supernatant liquor evaporating completely obtains spawn；
It is fully ground, is calcined 1-5 hours at 300-800 DEG C, natural cooling obtains exotic atom codope titanium dioxide forerunner
Body；
2）The preparation of exotic atom codope titanium dioxide nanotube,By step 1）Before obtained exotic atom codope titanium dioxide
Drive body to be dispersed in concentrated alkali solution according to 5 ~ 20g/L solid-to-liquid ratio, stirring is transferred in sealing autoclave for 1-4 hours, in 120-
180 DEG C preserve 10-24 hours, natural cooling；
In stepIn obtained solution filtered, obtained solid is washed to neutrality with dilute acid soln and deionized water,
Then the drying process under the conditions of 50-100 DEG C, by 400-800 DEG C of high-temperature calcination 2-8 hours, is cooled to room temperature, obtains different original
Sub- codope titanium dioxide nanotube；
3）The exotic atom codope titanium dioxide nanotube that step 2 is obtained is prepared into the negative pole or electricity of secondary sodium-ion battery
The negative pole of container.
2. the preparation method of anode material of lithium-ion battery according to claim 1, it is characterised in that：The metal compound
Thing is the one or more in iron, copper, nickel, cobalt, tin, chromium, lead, zinc or rare earth compound；The nonmetallic compound is
Sulphur, boron, nitrogen, the one or more of carbon or halogen compound.
3. the preparation method of anode material of lithium-ion battery according to claim 1, it is characterised in that：The concentrated base is hydrogen
One or two kinds of in sodium oxide molybdena and potassium hydroxide.
4. the preparation method of anode material of lithium-ion battery according to claim 1, it is characterised in that：The dilute acid soln
For the one or more in watery hydrochloric acid, dilute sulfuric acid or dust technology；The concentration of the dilute acid soln is the mol/L of 0. .1 ~ 0.5.
5. the preparation method of anode material of lithium-ion battery according to claim 1, it is characterised in that：The exotic atom is total to
The atomicity percentage composition ratio of metallic element is 0.01 ~ 5% in doped titanic oxide nano tube；The exotic atom codope dioxy
Change the atomicity percentage composition of nonmetalloid in titanium nanotube than 0.1 ~ 5%.
6. the preparation method of anode material of lithium-ion battery according to claim 1, it is characterised in that：The exotic atom is total to
Doped titanic oxide nano tube is one or both of Anatase, Rutile Type.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108807921A (en) * | 2018-06-20 | 2018-11-13 | 湖南辰砾新材料有限公司 | A kind of lithium cell cathode material and preparation method thereof |
| CN109926907A (en) * | 2017-12-19 | 2019-06-25 | 上海瑞钼特金属新材料有限公司 | The polishing method of tungsten-molybdenum alloy foil and the product of acquisition |
| CN112886013A (en) * | 2021-01-28 | 2021-06-01 | 陕西科技大学 | Preparation method of titanium dioxide/carbon nanofiber anode material with multilevel structure |
| CN113184901A (en) * | 2021-04-22 | 2021-07-30 | 西安交通大学 | Chlorine-doped titanium dioxide/carbon porous structure and preparation method thereof |
| CN117756195A (en) * | 2024-02-22 | 2024-03-26 | 贵州振华新材料股份有限公司 | pre-sodium treated copper-zinc-based sodium ion battery positive electrode material and preparation method thereof |
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| CN101478035A (en) * | 2009-01-09 | 2009-07-08 | 中国科学院上海硅酸盐研究所 | Electrode material used for organic inorganic composite cell and manufacturing process |
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