CN104058449A - Preparation method of sodium titanate negative electrode material in hollow structure - Google Patents

Preparation method of sodium titanate negative electrode material in hollow structure Download PDF

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CN104058449A
CN104058449A CN201410242403.7A CN201410242403A CN104058449A CN 104058449 A CN104058449 A CN 104058449A CN 201410242403 A CN201410242403 A CN 201410242403A CN 104058449 A CN104058449 A CN 104058449A
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sodium
sodium titanate
preparation
source
hollow structure
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CN104058449B (en
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陈人杰
谢嫚
王康康
吴锋
陈实
李丽
管沛林
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Beijing Institute of Technology BIT
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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 preparation method of a sodium titanate negative electrode material in a hollow structure and belongs to the field of sodium-ion batteries. The preparation method comprises the following steps: first, dissolving a sodium source in a mixed solution of distilled water, acetic acid and anhydrous ethanol, and adding a titanium source to obtain a sol; second, dispersing carbon balls in anhydrous ethanol to obtain a turbid liquid; and finally, fully dropwise adding the turbid liquid into the sol, and after reaction at a constant temperature, standing, drying and roasting to obtain the hollow sodium titanate negative electrode material. The hollow sodium titanate negative electrode material is great in specific surface. Compared with sodium titanate structures in bulky structures, the contact area of the material and the electrolyte is effectively increased and the migration distance of electrons and sodium ions in the material is shortened, so that the problem of poor rate capability and cycle performance of the material can be effectively solved.

Description

A kind of preparation method of hollow structure sodium titanate negative material
Technical field
The preparation method who the present invention relates to a kind of hollow structure sodium titanate negative material, belongs to sodium-ion battery field.
Background technology
Mobile electronic product battery, electric automobile power battery, the great demand of the industrial batteries such as intelligent grid energy-accumulating power station makes finished product battery have potential great market, but the finiteness of lithium resource, makes development environment close friend, height ratio capacity, low price, safe and reliable sodium-ion battery of new generation become the emphasis of chemical power source research field.Sodium-ion battery has that cyclicity is good, energy density is large, safety performance good, self-discharge rate is low, can use the advantage such as aqueous electrolyte, low price, is considered to be the new generation of green battery of alternative lithium ion battery.Negative material is one of key factor affecting sodium-ion battery.Current commercial anode material of lithium-ion battery is mainly hard carbon, but hard carbon storage sodium current potential is low, approaches 0V, and reversibility is poor, easily forms dendrite at carbon surface, has potential safety hazard.Therefore, high, the good reversibility of exploitation specific storage, negative material cheap, that security is good are the keys of further widening the Application Areas of sodium-ion battery and realizing large-scale application development.
As the negative material of laminate structure, sodium titanate (Na 2ti 3o 7) can reversiblely embed/deviate from 2 Na +, on average store up sodium current potential 0.3V, there is higher theoretical capacity, simultaneously Na 2ti 3o 7have that raw material is easy to get, cost is low, the advantage such as safe and environment friendly, be extremely potential novel anode material of lithium-ion battery.2011, Premkumar Senguttuvan and research group thereof proved Na first 2ti 3o 7material can obtain comparatively desirable chemical property as anode material of lithium-ion battery.
Na 2ti 3o 7belong to oblique system, spacer P21/m, lattice parameter at Na 2ti 3o 7in crystal, O atom all forms octahedral structure centered by Ti atom the skeleton as stratiform framework with Ti atom, and Na atom is present in laminate structure.Due to Na atom indentation/deviate from process, follow Ti 4+/ Ti 3+variation, plateau potential is low.But electronic conduction and ionic conduction ability cause high rate during charging-discharging poor, and it follows the transformation to noncrystalline state by crystal form in storage sodium process, structure in its working cycle is easily distorted, cycle performance variation.In order to improve Na 2ti 3o 7chemical property, generally adopt the particle of refinement material, optimize the methods such as electrolytic solution.
At present, the typical preparation method of sodium titanate negative material have high temperature solid phase synthesis, sol-gel method, etc., and the sodium titanate material of preparation is bulk material.In above-mentioned preparation method, traditional high temperature solid-state method preparation temperature is high and preparation time is long, and the material granule obtaining is large; The material of preparation of sol-gel is easily reunited, and density is low, and the contact area of bulk material and electrolytic solution is little, the low amount of sodium ion transmission that makes of electronic conductivity is less, makes the high rate performance of sodium titanate negative material and cycle performance poor.The sodium titanate negative material that adopts template to utilize the agent of hydro-thermal carbon ball template to prepare hollow structure there is not yet report.
Summary of the invention
For sodium titanate negative material high rate performance and the poor problem of cycle performance, the object of the present invention is to provide a kind of preparation method of hollow structure sodium titanate negative material, be specially and adopt hydro-thermal carbon ball as template, prepare a kind of sodium titanate negative material that has chemical property and high specific surface area concurrently.
The object of the invention is to be achieved through the following technical solutions.
A preparation method for hollow structure sodium titanate negative material, described method concrete steps are as follows:
(1) under agitation, sodium source is dissolved in the mixing solutions of distilled water, acetic acid and dehydrated alcohol, obtaining concentration is the sodium source solution of 0.12～0.24mol/L, then titanium source is added drop-wise in the solution of described sodium source, obtains colloidal sol a;
(2) template is evenly spread in dehydrated alcohol, obtain turbid solution;
(3) under agitation, described turbid solution is all added drop-wise in colloidal sol a, at 40 DEG C～60 DEG C isothermal reaction 1～2h, obtains colloidal sol b;
(4) described colloidal sol b is at room temperature left standstill after 12～20h, dry, obtain sodium titanate presoma;
(5) sodium titanate presoma step (4) Suo Shu is carried out to roasting, remove template, obtain hollow sodium titanate negative material of the present invention;
Wherein, the described template of step (2) is hydro-thermal carbon ball, its surperficial hydroxyl and carboxyl, and diameter is 0.5～5 μ m, raw materials is carbohydrate;
Preferred 1:0.2～1:10～20 of volume ratio of the described distilled water of step (1), acetic acid and dehydrated alcohol; The preferred 2:3 of ratio of Yu Tai source, sodium source amount of substance, wherein, the one in the preferred sodium-acetate in sodium source, SODIUMNITRATE, sodium carbonate, sodium hydroxide and sodium oxalate, the one in the preferred tetrabutyl titanate in titanium source, titanium isopropylate, titanium sulfate and titanyl sulfate;
Step (1) and the preferred magnetic agitation of the described stirring of step (3);
Step (2) described hydro-thermal carbon ball and the described sodium source quality of step (1) are than preferred 1:5.298～11.26;
Preferred 1:80～150 of mass ratio of step (2) described hydro-thermal carbon ball and dehydrated alcohol; One in the preferred glucose of raw materials, fructose and the sucrose of hydro-thermal carbon ball;
60～80 DEG C of the preferred drying temperatures of the described drying parameter of step (4), time of drying 12h～24h;
500 DEG C～1000 DEG C of the preferred maturing temperatures of roasting parameter described in step (5), 5 DEG C/min of temperature rise rate, roasting time 6～12h;
Beneficial effect
(1) to have adopted the hydro-thermal carbon ball of surperficial hydroxyl and carboxyl be template to preparation method of the present invention, and He Tai source, sodium source is attached to the surface of template by the keying action of key and key, forms sodium titanate presoma coating layer.In roasting process, the crystallization of sodium titanate presoma, forms one time crystal grain, and intergranule interconnects, and due to the existence of template, has suppressed the hypertrophy of a crystal grain, after template is removed, forms the sodium titanate negative material of hollow structure;
(2) the hollow sodium titanate negative material specific surface area that prepared by preparation method of the present invention is large, compared with the sodium titanate material of lumphy structure, effectively increase the contact area of material and electrolytic solution, shorten electronics and the sodium ion migration distance in material, therefore, can effectively solve high rate performance and the poor problem of cycle performance of material.
Brief description of the drawings
Fig. 1 is the scanning electron microscope (SEM) photograph of the hydro-thermal carbon ball in embodiment 1 step (1);
Fig. 2 is the X-ray diffractogram of the hollow structure sodium titanate negative material of embodiment 1 step (6), and in figure, A is angle, unit degree of being (°), a certain crystal face of the corresponding crystal of specific angle, B represents the relative content of this crystal face;
Fig. 3 is the scanning electron microscope (SEM) photograph of the hollow structure sodium titanate negative material of embodiment 1 step (6).
Embodiment
Below in conjunction with the drawings and specific embodiments in detail the present invention is described in detail, but is not limited to this.
The key instrument information of mentioning in following examples is in table 1, and main medicine information is in table 2.
Table 1
Table 2
Embodiment 1
(1) vinylformic acid (4mL) is added drop-wise in the glucose solution (65mL) of 0.4mol/L, obtain mixing solutions a, described mixing solutions a is added in 90mL inner liner polytetrafluoroethylene autoclave, at 180 DEG C of reaction 20h, centrifugal, respectively product is carried out to 3 times with distilled water and dehydrated alcohol and wash, dry, obtain hydro-thermal carbon ball, as shown in Figure 1, the diameter of described hydro-thermal carbon ball is 0.5-5 μ m; Wherein, drying temperature is 80 DEG C, and be 4h time of drying;
(2) under magnetic agitation, by 1.086g CH 3cOONa is dissolved in the mixing solutions of distilled water (5mL), acetic acid (3mL) and dehydrated alcohol (70mL), obtains the CH that concentration is 0.17mol/L 3cOONa solution; Pipette 7mL C with transfer pipet 16h 36o 4ti dropwise joins CH 3in COONa solution, obtain faint yellow colloidal sol;
(3) 0.1g hydro-thermal carbon ball is added to ultrasonic dispersion 30min in 10mL dehydrated alcohol, obtains turbid solution;
(4) under magnetic agitation, described turbid solution is all added drop-wise in the described faint yellow colloidal sol of step (1), at 60 DEG C, react 1h, obtain brown wet gel;
(5) brown wet gel is at room temperature left standstill after 12h, dry, obtain sodium titanate presoma; Wherein, drying temperature is 80 DEG C, and be 12h time of drying;
(6) after sodium titanate presoma is ground, be placed in retort furnace roasting 10h, obtain hollow sodium titanate negative material, wherein, maturing temperature is 800 DEG C, and temperature rise rate is 5 DEG C/min; As shown in Figure 2, products therefrom is pure phase oblique system Na 2ti 3o 7; As shown in Figure 3, product is hollow structure.
Embodiment 2
(1) vinylformic acid (4mL) is added drop-wise in 0.4mol/L sucrose solution (65mL), obtain mixing solutions a, described mixing solutions a is added in 90mL inner liner polytetrafluoroethylene autoclave, at 180 DEG C, react 20h, centrifugal, respectively product is carried out to 3 times with distilled water and dehydrated alcohol and wash, dry, obtain hydro-thermal carbon ball; Wherein, drying temperature is 80 DEG C, and be 4h time of drying;
(2) under magnetic agitation, 0.5298g NaOH is dissolved in the mixing solutions of distilled water (5mL), acetic acid (1mL) and dehydrated alcohol (50mL), obtain the CH that concentration is 0.24mol/L 3cOONa solution; Pipette 7mL Ti{OCH (CH with transfer pipet 3) 2} 4dropwise join CH 3in COONa solution, obtain faint yellow colloidal sol;
(3) 0.1g hydro-thermal carbon ball is added to ultrasonic dispersion 30min in 8mL dehydrated alcohol, obtains turbid solution;
(4) under magnetic agitation, described turbid solution is all added drop-wise in the described faint yellow colloidal sol of step (1), at 40 DEG C, react 2h, obtain brown wet gel;
(5) brown wet gel is at room temperature left standstill after 20h, dry, obtain sodium titanate presoma; Wherein, drying temperature is 70 DEG C, and be 15h time of drying;
(6) after sodium titanate presoma is ground, be placed in retort furnace roasting 6h, obtain hollow sodium titanate negative material; Wherein, maturing temperature is 1000 DEG C, and temperature rise rate is 5 DEG C/min.
Embodiment 3
(1) vinylformic acid (4mL) is added drop-wise in the fructose soln (65mL) of 0.4mol/L, obtain mixing solutions a, described mixing solutions a is added in 90mL inner liner polytetrafluoroethylene autoclave, at 180 DEG C of reaction 20h, centrifugal, respectively product is carried out to 3 times with distilled water and dehydrated alcohol and wash, dry, obtain hydro-thermal carbon ball; Wherein, drying temperature is 80 DEG C, and be 4h time of drying;
(2) under magnetic agitation, by 1.126g NaNO 3be dissolved in the mixing solutions of distilled water (5mL), acetic acid (5mL) and dehydrated alcohol (100mL), obtain the CH that concentration is 0.12mol/L 3cOONa solution; Take 7.99g Ti (SO 4) 29H 2o dropwise joins CH 3in COONa solution, obtain faint yellow colloidal sol;
(3) 0.1g hydro-thermal carbon ball is added to ultrasonic dispersion 30min in 15mL dehydrated alcohol, obtains turbid solution;
(4) under magnetic agitation, described turbid solution is all added drop-wise in the described faint yellow colloidal sol of step (1), at 50 DEG C, react 1.5h, obtain brown wet gel;
(5) brown wet gel is at room temperature left standstill after 16h, dry, obtain sodium titanate presoma; Wherein, drying temperature is 60 DEG C, and be 24h time of drying;
(6) after sodium titanate presoma is ground, be placed in retort furnace roasting 12h, obtain hollow sodium titanate negative material; Wherein, maturing temperature is 500 DEG C, and temperature rise rate is 5 DEG C/min.
The present invention includes but be not limited to above embodiment, every any being equal to of carrying out under the principle of spirit of the present invention, replaces or local improvement, all will be considered as within protection scope of the present invention.

Claims (7)

1. a preparation method for hollow structure sodium titanate negative material, is characterized in that: described method concrete steps are as follows:
(1) under agitation, sodium source is dissolved in the mixing solutions of distilled water, acetic acid and dehydrated alcohol, obtaining concentration is the sodium source solution of 0.12～0.24mol/L, then titanium source is added drop-wise in the solution of described sodium source, obtains colloidal sol a;
(2) template is evenly spread in dehydrated alcohol, obtain turbid solution;
(3) under agitation, described turbid solution is added drop-wise in colloidal sol a, at 40 DEG C～60 DEG C isothermal reaction 1～2h, obtains colloidal sol b;
(4) described colloidal sol b is at room temperature left standstill after 12～20h, dry, obtain sodium titanate presoma;
(5) sodium titanate presoma step (4) Suo Shu is carried out to roasting, remove template, obtain described hollow sodium titanate negative material.
2. the preparation method of a kind of hollow structure sodium titanate negative material according to claim 1, it is characterized in that: the described sodium of step (1) source is the one in sodium-acetate, SODIUMNITRATE, sodium carbonate, sodium hydroxide and sodium oxalate, and titanium source is the one in tetrabutyl titanate, titanium isopropylate, titanium sulfate and titanyl sulfate; The described template of step (2) is hydro-thermal carbon ball, its surperficial hydroxyl and carboxyl, and diameter is 0.5～5 μ m, raw materials is carbohydrate.
3. the preparation method of a kind of hollow structure sodium titanate negative material according to claim 1, it is characterized in that: the ratio of Yu Tai source, the described sodium of step (1) source amount of substance is 2:3, and the volume ratio of distilled water, acetic acid and dehydrated alcohol is 1:0.2～1:10～20; Step (1) described sodium source and the described template mass ratio of step (2) are 5.298～11.26:1; The mass ratio of the described template of step (2) and dehydrated alcohol is 1:80～150.
4. the preparation method of a kind of hollow structure sodium titanate negative material according to claim 1, is characterized in that: the described drying parameter of step (4) is 60～80 DEG C of drying temperatures, time of drying 12h～24h.
5. the preparation method of a kind of hollow structure sodium titanate negative material according to claim 1, is characterized in that: the described roasting parameter of step (5) is 500 DEG C～1000 DEG C of maturing temperatures, 5 DEG C/min of temperature rise rate, roasting time 6～12h.
6. the preparation method of a kind of hollow structure sodium titanate negative material according to claim 1, is characterized in that: step (1) and the described stirring of step (3) are magnetic agitation.
7. the preparation method of a kind of hollow structure sodium titanate negative material according to claim 2, is characterized in that: described carbohydrate is the one in glucose, fructose and sucrose.
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Cited By (6)

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WO2016137401A1 (en) * 2015-02-25 2016-09-01 National University Of Singapore Sodium-ion battery anode
CN108511727A (en) * 2018-04-20 2018-09-07 南京林业大学 A kind of sodium titanate negative material and preparation method thereof of high-valence cationic doping
CN109148876A (en) * 2018-08-14 2019-01-04 厦门大学 Anode material of lithium-ion battery sodium titanate hierarchical structure and preparation method thereof
CN111613788A (en) * 2020-06-05 2020-09-01 哈尔滨工业大学（威海） Hollow spherical lithium nickel manganese oxide positive electrode material and preparation method thereof
CN113692668A (en) * 2018-12-17 2021-11-23 株式会社Lg新能源 Electrolyte solution for lithium secondary battery and lithium secondary battery comprising the same
WO2023241299A1 (en) * 2022-06-17 2023-12-21 深圳新宙邦科技股份有限公司 Sodium ion battery

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016137401A1 (en) * 2015-02-25 2016-09-01 National University Of Singapore Sodium-ion battery anode
CN107431200A (en) * 2015-02-25 2017-12-01 新加坡国立大学 Sodium-ion battery anode
CN108511727A (en) * 2018-04-20 2018-09-07 南京林业大学 A kind of sodium titanate negative material and preparation method thereof of high-valence cationic doping
CN109148876A (en) * 2018-08-14 2019-01-04 厦门大学 Anode material of lithium-ion battery sodium titanate hierarchical structure and preparation method thereof
CN113692668A (en) * 2018-12-17 2021-11-23 株式会社Lg新能源 Electrolyte solution for lithium secondary battery and lithium secondary battery comprising the same
CN111613788A (en) * 2020-06-05 2020-09-01 哈尔滨工业大学（威海） Hollow spherical lithium nickel manganese oxide positive electrode material and preparation method thereof
CN111613788B (en) * 2020-06-05 2022-10-14 哈尔滨工业大学（威海） Hollow spherical lithium nickel manganese oxide positive electrode material and preparation method thereof
WO2023241299A1 (en) * 2022-06-17 2023-12-21 深圳新宙邦科技股份有限公司 Sodium ion battery

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