CN106356523A - Preparation method of titanium dioxide sodium-ion battery cathode material and product thereof - Google Patents

Preparation method of titanium dioxide sodium-ion battery cathode material and product thereof Download PDF

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Publication number
CN106356523A
CN106356523A CN201610895448.3A CN201610895448A CN106356523A CN 106356523 A CN106356523 A CN 106356523A CN 201610895448 A CN201610895448 A CN 201610895448A CN 106356523 A CN106356523 A CN 106356523A
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preparation
titanium dioxide
preferably employs
ion battery
present
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CN106356523B (en
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蒋凯
陶宏伟
王康丽
周敏
程时杰
余丽红
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Huazhong University of Science and Technology
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Huazhong University of Science and Technology
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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
    • H01M4/485—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
    • 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
    • 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 belongs to the field of preparation method of an energy storage material and discloses a preparation method of a titanium dioxide sodium-ion battery cathode material and a product thereof. The method comprises the following steps: adding a titanium source compound into a solvent, and stirring to obtain a clear solution; adding certain amount of ammonia water for a solvothermal reaction to obtain a slurry; washing and drying the slurry to obtain a precursor material; and finally, performing high-temperature heat treatment on the precursor material in an inert gas to obtain the required carbon-coated titanium dioxide. Through the invention, the titanium dioxide sodium-ion battery cathode material can be quickly prepared at low cost; and the prepared cathode material has the characteristics of high first-week coulomb efficiency, large specific capacity, long service life and the like and is suitable for large-batch industrial production.

Description

A kind of preparation method of titanium dioxide anode material of lithium-ion battery and products thereof
Technical field
The invention belongs to the preparation method field of energy storage material, more particularly, to a kind of titanium dioxide sodium-ion battery Preparation method of negative material and products thereof.
Background technology
With China's rapid development of economy, energy problem is increasingly becoming the sustainable development of socio-economy of restriction China Bottleneck.Compared with rechargeable battery with other, lithium ion battery shows fabulous energy-storage property.In the many decades in past, Lithium ion battery is widely used on global portable electric appts.In recent years, its application is also expanded simultaneously Open up in extensive energy storage, especially on electric automobile.But on the earth elemental lithium resource reserve limited it is impossible to meet to lithium ion The continuous rapid growth of battery requirements.In period of element the exterior and the interior, sodium and lithium are located at same main group and in a lot of aspect chemical property Similar, on this basis it has been proposed that a kind of sodium-ion battery, it is approximate with the operation principle of lithium ion battery, furthermore sodium element Rich reserves on earth, and with low cost, therefore sodium-ion battery receives much attention.
But sodium ion radius is more than lithium ion, make people in terms of research height ratio capacity, long circulating sodium ion electrode material Run into extreme difficulties.In terms of sodium-ion battery negative pole, various hard carbon materials are developed, and have big specific volume Measure the cyclical stability become reconciled.However, current potential low and polarize big the shortcomings of significantly limit battery practical application.Titanium dioxide (tio2) there is cheap, Stability Analysis of Structures, in its various crystal formation, anatase tio2Due to its unique crystal structure exhibition Reveal extraordinary storage sodium performance.But tio2Its storage sodium capacity of electric conductivity official post itself is all undesirable with high rate performance.Lead at present Three kinds are had to put forward high performance approach.One of which approach is to be improved by changing material morphology and particle size space tio2Chemical property, people develop various tio in succession2Nano material, such as: nano-particle, nanotube, nanometer rods, Nanosphere and nano flower etc., improve specific capacity to a certain extent, but nanostructured is unstable, be also easy to produce side reaction so as to first All coulombic efficiency are relatively low, and cycle performance is poor.Another approach is dopant impurity atoms, adulterates other in relatively low charged state Element is to increase block tio2Fault of construction, effectively improves material electronicses and ionic conductivity, but its head of currently acquired material All coulombic efficiency remain a need for improving.The third approach is the method covered using charcoal bag, provides three-dimensional conductive network structure and formation Stable solid electrolyte interface film (sei film), improves its first all coulombic efficiency and high rate performance.But its circulation of the material obtaining Performance still needs to improve further, and synthesizes high cost, greatly hinders the application of its heavy industrialization.
Content of the invention
Disadvantages described above for prior art or Improvement requirement, the invention provides a kind of titanium dioxide sodium-ion battery is born Preparation method of pole material and products thereof, the method covered by charcoal bag is improved to titanium dioxide chemical property, thus solves The technical problem that certainly the anode material of lithium-ion battery first week coulombic efficiency of titanium dioxide is low, specific capacity is low and cycle life is short.
For achieving the above object, according to one aspect of the present invention, there is provided a kind of titanium dioxide sodium-ion battery negative pole The preparation method of material is it is characterised in that the method is as follows:
Titanium source compound is added to the solution that stirring solvent obtains clarifying, adds a certain amount of ammonia to enter in this solution Row solvent thermal reaction obtains slurry；This slurry washing obtains persursor material after being dried；By this persursor material in noble gases In carry out high-temperature heat treatment, required charcoal cladding titanium dioxide is thus obtained.
Preferably, described titanium source compound preferably employs titanium tetrachloride (ticl4), its addition preferably employ 1ml～ 6ml.
Preferably it is characterised in that described solvent preferably employs ethylene glycol, its addition preferably employs 70ml～90ml.
Preferably it is characterised in that described mixing time preferably employs 0.5h～2h.
Preferably it is characterised in that described ammonia addition preferably employs 2ml～5ml.
Preferably, the programming rate of described solvent thermal reaction preferably employs 1 DEG C/min～2 DEG C/min, and holding temperature is preferred Using 160 DEG C～200 DEG C, temperature retention time preferably employs 24h～48h.
Preferably, the programming rate of described high-temperature heat treatment preferably employs 2 DEG C/min～5 DEG C/min, holding temperature scope Preferably employ 500 DEG C～700 DEG C, temperature retention time preferably employs 2～6h.
Preferably, described noble gases preferably employ one of argon or nitrogen or two kinds.
According to another aspect of the present invention, additionally provide and a kind of cover two according to the charcoal bag obtained by described preparation method Titanium oxide product.
In general, by the contemplated above technical scheme of the present invention compared with prior art, can obtain down and show Beneficial effect:
1st, the present invention carries out solvent thermal reaction at a temperature of 160 DEG C～200 DEG C, makes reactor in the reaction that can bear At a temperature of guarantee that ethylene glycol can occur polyreaction；At a temperature of 500 DEG C～700 DEG C, high-temperature heat treatment reacts 2～6h, makes Ethylene glycol is guaranteeing that carbonization completely becomes unbodied charcoal in the case that titanium dioxide will not occur the transformation of crystal formation；
2nd, the present invention pass through using can dissolve well dispersion ticl4Ethylene glycol as solvent, simultaneously in solvent thermal mistake In journey, ethylene glycol occurs polymerization to be uniformly coated on ticl4Surface, thus serve as charcoal source it is not necessary to add other Organic substances make For charcoal source；
3rd, the preparation method step that the present invention provides and integrated artistic are simple, with low cost, and course of reaction is easy to quality control System, the step solvent thermal reaction using environmental protection has prepared the titanium dioxide (tio that charcoal bag is covered2) nano-particle；Obtained charcoal The features such as cladding titanium dioxide product possesses high first week coulombic efficiency, height ratio capacity and has extended cycle life is it is adaptable to large batch of Industrialized production.
Brief description
Fig. 1 is the flow chart according to the preparation method constructed by the preferred embodiments of the present invention；
Fig. 2 be according to the preferred embodiments of the present invention 1 obtained by charcoal bag cover tio2The X-ray diffraction pattern (xrd) of material；
Fig. 3 covers tio according to the charcoal bag obtained by the preferred embodiments of the present invention 12The thermogravimetric curve figure (tg) of material；
Fig. 4 covers tio according to the charcoal bag obtained by the preferred embodiments of the present invention 12The scanning electron microscope (SEM) photograph (sem) of material；
Fig. 5 covers tio according to the charcoal bag obtained by the preferred embodiments of the present invention 12The transmission electron microscope picture (tem) of material；
Fig. 6 covers tio according to the charcoal bag obtained by the preferred embodiments of the present invention 12Material is in 50ma g-1Under electric current density Cyclical stability schematic diagram；
Fig. 7 covers tio according to the charcoal bag obtained by the preferred embodiments of the present invention 12The high rate performance schematic diagram of material；
Fig. 8 covers tio according to the charcoal bag obtained by the preferred embodiments of the present invention 12Material is in 400ma g-1Under electric current density Cyclical stability schematic diagram；
Fig. 9 covers tio according to the charcoal bag obtained by the preferred embodiments of the present invention 22Material is in 50ma g-1Under electric current density Cyclical stability schematic diagram；
Figure 10 covers tio according to the charcoal bag obtained by the preferred embodiments of the present invention 32Material is in 50ma g-1Under electric current density Cyclical stability schematic diagram；
Figure 11 be according to the preferred embodiments of the present invention 4 obtained by charcoal bag cover tio2 material in 50ma g-1Electric current density Under cyclical stability schematic diagram.
Specific embodiment
In order that the objects, technical solutions and advantages of the present invention become more apparent, below in conjunction with drawings and Examples, right The present invention is further elaborated.It should be appreciated that specific embodiment described herein is only in order to explain the present invention, and It is not used in the restriction present invention.As long as additionally, involved technical characteristic in each embodiment of invention described below The conflict of not constituting each other just can be mutually combined.
Fig. 1 is the flow chart according to the preparation method constructed by the preferred embodiments of the present invention.As shown in figure 1, the method It is that titanium source compound is added to the solution that stirring solvent obtains clarifying, be subsequently adding a certain amount of ammonia and carry out solvent thermal reaction Obtain slurry；Persursor material is obtained after slurry washing is dried；Finally this persursor material is carried out in noble gases height Warm is processed, thus required charcoal cladding titanium dioxide is obtained.
Below with reference to the technological process of Fig. 1, and to be further elaborated with the present invention with reference to following multiple embodiments.
Embodiment 1
The present embodiment comprises the following steps:
(1) by the ticl of 1ml4It is added in 80ml ethylene glycol solvent, after stirring 1h, obtain uniform yellow clarification molten Liquid, is subsequently adding the ammonia of 2ml, is stirred vigorously 1h, the solution obtaining is poured in 100ml reactor, carries out molten in baking oven Agent thermal response.Heating schedule is: heated up with the speed of 1 DEG C/min, 180 DEG C be incubated 24h, by the slurry obtaining carry out from After heart washing, it is vacuum dried 12h at 80 DEG C, obtains persursor material.
(2) persursor material obtaining is carried out high-temperature heat treatment, concrete heating schedule is: enter with the speed of 3 DEG C/min Row heats up, and is incubated 2h at 700 DEG C, the process of whole high-temperature heat treatment is carried out all in the atmosphere of argon, obtains target product.
Fig. 2 be according to the preferred embodiments of the present invention 1 obtained by charcoal bag cover tio2The X-ray diffraction pattern (xrd) of material. As shown in Fig. 2 charcoal bag is obtained cover tio2The intensity at x-ray diffraction peak of material and peak value and anatase tio2Jcpds (powder Diffraction standard joint committee) card (21-1272) matches, and display has synthesized the anatase tio of single-phase2.
Fig. 3 covers tio according to the charcoal bag obtained by the preferred embodiments of the present invention 12The thermogravimetric curve figure (tg) of material, such as schemes Shown in 3, the charcoal bag synthesizing covers tio2Carbon content in material is 7.3%.
Fig. 4 covers tio according to the charcoal bag obtained by the preferred embodiments of the present invention 12The scanning electron microscope (SEM) photograph (sem) of material.As Shown in Fig. 4, the charcoal bag synthesizing covers tio2Material is the nano-particle that particle diameter is about 50nm.
Fig. 5 covers tio according to the charcoal bag obtained by the preferred embodiments of the present invention 12The transmission electron microscope picture (tem) of material.As Shown in Fig. 5, the charcoal bag synthesizing covers tio2Material is that particle diameter is about the nano-particle of 50nm and is uniformly coated with one layer greatly It is about the layer of charcoal of 1nm.
Fig. 6 covers tio according to the charcoal bag obtained by the preferred embodiments of the present invention 12Material is in 50ma g-1Under electric current density Cyclical stability schematic diagram.As shown in fig. 6, charcoal bag covers tio2Material is in 50ma g-1Electric current density under, first week reversible specific capacity Up to 317ma h g-1, after circulating 100 weeks, still there is 298ma h g-1Specific discharge capacity, capability retention reaches 94% And the coulombic efficiency in head week is up to 48.9%.
Fig. 7 covers tio according to the charcoal bag obtained by the preferred embodiments of the present invention 12The high rate performance schematic diagram of material.As figure Shown in 7, charcoal bag covers tio2Material is in 50,100,200,400,800,1600,3200 and 6400ma g-1Electric current density under, can Inverse specific capacity is respectively 311.5,277.8,257,235,214.6,181.8,125.5,91.3ma h g-1, when electric current density weight Newly return to 50ma g-1When, reversible specific capacity still has 289ma h g-1, show excellent high rate performance.
Fig. 8 covers tio according to the charcoal bag obtained by the preferred embodiments of the present invention 12Material is in 400ma g-1Under electric current density Cyclical stability schematic diagram.As shown in figure 8, charcoal bag covers tio2Material is in 400ma g-1Electric current density under, circulation 500 circle Afterwards, there is 241ma h g-1Reversible specific capacity, capability retention is up to 85%, shows excellent cycle performance.
Embodiment 2
The present embodiment comprises the following steps:
(1) by the ticl of 3ml4It is added in 80ml ethylene glycol solvent, after stirring 1.5h, obtain uniform yellow clarification molten Liquid, is subsequently adding the ammonia of 3ml, is stirred vigorously 1h, the solution obtaining is poured in 100ml reactor, carries out molten in baking oven Agent thermal response.Heating schedule is: is heated up with the speed of 1.5 DEG C/min, is incubated 48h at 180 DEG C, the slurry obtaining is carried out After centrifuge washing, it is vacuum dried 12h at 80 DEG C, obtains persursor material.
(2) persursor material obtaining is carried out high-temperature heat treatment, concrete heating schedule is: enter with the speed of 3 DEG C/min Row heats up, and is incubated 2h at 500 DEG C, the process of whole high-temperature heat treatment is carried out all in the atmosphere of argon, obtains target product.
Fig. 9 covers tio according to the charcoal bag obtained by the preferred embodiments of the present invention 22Material is in 50ma g-1Under electric current density Cyclical stability schematic diagram.As shown in Figure 9 it can be seen that embodiment 2 charcoal bag covers tio2Material is in 50ma g-1Electric current density Under, reversible specific capacity is up to 319mah g-1, after circulating 100 weeks, there is 258ma h g-1Reversible specific capacity, capability retention Reach 44.9% for 81%, head week coulombic efficiency.
Embodiment 3
The present embodiment comprises the following steps:
(1) by the ticl of 4ml4It is added in 80ml ethylene glycol solvent, after stirring 1.5h, obtain uniform yellow clarification molten Liquid, is subsequently adding the ammonia of 4ml, is stirred vigorously 1h, the solution obtaining is poured in 100ml reactor, carries out molten in baking oven Agent thermal response.Heating schedule is: heated up with the speed of 2 DEG C/min, 180 DEG C be incubated 24h, by the slurry obtaining carry out from After heart washing, it is vacuum dried 12h at 80 DEG C, obtains persursor material.
(2) persursor material obtaining is carried out high-temperature heat treatment, concrete heating schedule is: enter with the speed of 3 DEG C/min Row heats up, and is incubated 3h at 600 DEG C, the process of whole high-temperature heat treatment is carried out all in the atmosphere of argon, obtains target product.
Figure 10 covers tio according to the charcoal bag obtained by the preferred embodiments of the present invention 32Material is in 50ma g-1Under electric current density Cyclical stability schematic diagram.As shown in Figure 10 it can be seen that embodiment 3 charcoal bag covers tio2Material is in 50ma g-1Electric current close Under degree, reversible specific capacity is up to 322mah g-1, after circulating 100 weeks, there is 177mah g-1Reversible specific capacity, capability retention It is 40.6% for 55%, head week coulombic efficiency.
Embodiment 4
The present embodiment comprises the following steps:
(1) by the ticl of 6ml4It is added in 90ml ethylene glycol solvent, after stirring 2h, obtain uniform yellow clarification molten Liquid, is subsequently adding the ammonia of 5ml, is stirred vigorously 1h, the solution obtaining is poured in 100ml reactor, carries out molten in baking oven Agent thermal response.Heating schedule is: heated up with the speed of 1 DEG C/min, 200 DEG C be incubated 48h, by the slurry obtaining carry out from After heart washing, it is vacuum dried 12h at 80 DEG C, obtains persursor material.
(2) persursor material obtaining is carried out high-temperature heat treatment, concrete heating schedule is: enter with the speed of 2 DEG C/min Row heats up, and is incubated 2h at 700 DEG C, the process of whole high-temperature heat treatment is carried out all in the atmosphere of argon, obtains target product.
Figure 11 be according to the preferred embodiments of the present invention 4 obtained by charcoal bag cover tio2Material is in 50ma g-1Electric current density Under cyclical stability schematic diagram.As shown in figure 11 it can be seen that embodiment 4 charcoal bag covers tio2Material is in 50ma g-1Electric current Under density, reversible specific capacity is up to 310ma h g-1, after circulating 100 weeks, there is 274ma h g-1Reversible specific capacity, capacity protect Holdup is 88%, and first all coulombic efficiency reach 42.7%.
Embodiment 5
The present embodiment comprises the following steps:
(1) by the ticl of 1ml4It is added in 80ml ethylene glycol solvent, after stirring 1h, obtain uniform yellow clarification molten Liquid, is subsequently adding the ammonia of 2ml, is stirred vigorously 1h, the solution obtaining is poured in 100ml reactor, carries out molten in baking oven Agent thermal response.Heating schedule is: heated up with the speed of 2 DEG C/min, 200 DEG C be incubated 36h, by the slurry obtaining carry out from After heart washing, it is vacuum dried 12h at 80 DEG C, obtains persursor material.
(2) persursor material obtaining is carried out high-temperature heat treatment, concrete heating schedule is: enter with the speed of 3 DEG C/min Row heats up, and is incubated 4h at 700 DEG C, the process of whole high-temperature heat treatment is carried out all in the atmosphere of argon, obtains target product.
Cover tio according to the charcoal bag obtained by the preferred embodiments of the present invention 52Material is in 50ma g-1Electric current density under, can Inverse specific capacity is up to 300mah g-1, after circulating 100 weeks, there is 288ma h g-1Reversible specific capacity, capability retention is 96%, first all coulombic efficiency reach 39%.
Embodiment 6
The present embodiment comprises the following steps:
(1) by the ticl of 1ml4It is added in 80ml ethylene glycol solvent, after stirring 0.5h, obtain uniform yellow clarification molten Liquid, is subsequently adding the ammonia of 2ml, is stirred vigorously 1h, the solution obtaining is poured in 100ml reactor, carries out molten in baking oven Agent thermal response.Heating schedule is: is heated up with the speed of 1.5 DEG C/min, is incubated 36h at 160 DEG C, the slurry obtaining is carried out After centrifuge washing, it is vacuum dried 12h at 80 DEG C, obtains persursor material.
(2) persursor material obtaining is carried out high-temperature heat treatment, concrete heating schedule is: enter with the speed of 5 DEG C/min Row heats up, and is incubated 2h at 700 DEG C, the process of whole high-temperature heat treatment is carried out all in the atmosphere of argon, obtains target product.
Cover tio according to the charcoal bag obtained by the preferred embodiments of the present invention 62Material is in 50ma g-1Electric current density under, can Inverse specific capacity is up to 305mah g-1, after circulating 100 weeks, there is 288.8ma h g-1Reversible specific capacity, capability retention is 94.7%, first all coulombic efficiency reach 46%.
Embodiment 7
The present embodiment comprises the following steps:
(1) by the ticl of 1ml4It is added in 70ml ethylene glycol solvent, after stirring 1h, obtain uniform yellow clarification molten Liquid, is subsequently adding the ammonia of 2ml, is stirred vigorously 1h, the solution obtaining is poured in 100ml reactor, carries out molten in baking oven Agent thermal response.Heating schedule is: heated up with the speed of 1 DEG C/min, 180 DEG C be incubated 24h, by the slurry obtaining carry out from After heart washing, it is vacuum dried 12h at 80 DEG C, obtains persursor material.
(2) persursor material obtaining is carried out high-temperature heat treatment, concrete heating schedule is: enter with the speed of 5 DEG C/min Row heats up, and is incubated 6h at 500 DEG C, the process of whole high-temperature heat treatment is carried out all in the atmosphere of argon, obtains target product.
Cover tio according to the charcoal bag obtained by the preferred embodiments of the present invention 72Material is in 50ma g-1Electric current density under, can Inverse specific capacity is up to 320mah g-1, after circulating 100 weeks, there is 224ma h g-1Reversible specific capacity, capability retention is 70%, first all coulombic efficiency reach 41%.
As it will be easily appreciated by one skilled in the art that the foregoing is only presently preferred embodiments of the present invention, not in order to Limit the present invention, all any modification, equivalent and improvement made within the spirit and principles in the present invention etc., all should comprise Within protection scope of the present invention.

Claims (9)

1. a kind of preparation method of titanium dioxide anode material of lithium-ion battery is it is characterised in that the method is as follows:
Titanium source compound is added to the solution that stirring solvent obtains clarifying, adds a certain amount of ammonia to carry out in this solution molten Agent thermal response obtains slurry；This slurry washing obtains persursor material after being dried；This persursor material is entered in noble gases Row high-temperature heat treatment, is thus obtained required charcoal cladding titanium dioxide.
2. preparation method according to claim 1 is it is characterised in that described titanium source compound preferably employs titanium tetrachloride (ticl4), its addition preferably employs 1ml～6ml.
3. it is characterised in that described solvent preferably employs ethylene glycol, it adds preparation method according to claim 1 and 2 Enter amount and preferably employ 70ml～90ml.
4. the preparation method according to any one of claim 1-3 is it is characterised in that described mixing time preferably employs 0.5h ～2h.
5. the preparation method according to any one of claim 1-4 is it is characterised in that described ammonia addition preferably employs 2ml～5ml.
6. the preparation method according to any one of claim 1 is it is characterised in that the programming rate of described solvent thermal reaction is excellent Choosing adopts 1 DEG C/min～2 DEG C/min, and holding temperature preferably employs 160 DEG C～200 DEG C, and temperature retention time preferably employs 24h～48h.
7. the preparation method according to any one of claim 1-6 is it is characterised in that the programming rate of described high-temperature heat treatment Preferably employing 2 DEG C/min～5 DEG C/min, holding temperature scope preferably employs 500 DEG C～700 DEG C, temperature retention time preferably employs 2～ 6h.
8. the preparation method according to any one of claim 1-7 is it is characterised in that described noble gases preferably employ argon Or one of nitrogen or two kinds.
9. the titanium dioxide sodium-ion battery negative pole material obtained by preparation method described in a kind of utilization any one of claim 1-8 Material.
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CN110534709A (en) * 2018-05-25 2019-12-03 深圳格林德能源有限公司 A kind of sodium-ion battery carbon coating titanium oxide nanotube cathode material preparation method
CN111600008A (en) * 2020-04-23 2020-08-28 江苏师范大学 Preparation method of titanium dioxide sodium-ion battery negative electrode material

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