CN105489889A - Preparation method for high-performance niobic acid titanium-silver composite material - Google Patents

Preparation method for high-performance niobic acid titanium-silver composite material Download PDF

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Publication number
CN105489889A
CN105489889A CN201510810988.2A CN201510810988A CN105489889A CN 105489889 A CN105489889 A CN 105489889A CN 201510810988 A CN201510810988 A CN 201510810988A CN 105489889 A CN105489889 A CN 105489889A
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composite material
preparation
hour
performance
silver composite
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Inventor
刘光印
郭佳莉
鲍克燕
冯玉全
孙瑞雪
张瑞雪
季晓广
柳文敏
刘炳佳
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Nanyang Normal University
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Nanyang Normal University
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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
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/626—Metals
    • 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

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)

Abstract

The invention provides a preparation method for a high-performance niobic acid titanium-silver composite material. The preparation method comprises the following steps of (a) weighing and adding TiO2 and Nb2O5 into a ball milling tank according to stoichiometric ratios, drying the mixture after carrying out ball milling with an absolute ethyl alcohol medium for 1 to 24 hours, calcining the mixture for 2 to 60 hours at 720-1,300 DEG C, and cooling the mixture to obtain Ti2Nb10O29; (b) dissolving polyvinylpyrrolidone in a reductive organic solvent, adding the Ti2Nb10O29 prepared in the step (a), carrying out ultrasound for 0.1 to 6 hours, adding silver nitrate, and continuously carrying out ultrasound for 0.1 to 15 hours; and (c) transferring a suspension liquid obtained in the step (b) after ultrasound treatment into a reaction kettle, carrying out reaction for 0.1 to 48 hours, and carrying out centrifugal separation and vacuum drying to obtain a Ti2Nb10O29/Ag composite material. The preparation method has the advantages that the electrochemical performance of the Ti2Nb10O29 is substantially improved without affecting the structural stability of the Ti2Nb10O29.

Description

A kind of preparation method of high-performance titanium niobate-silver composite material
Technical field
The invention belongs to technical field of lithium ion battery negative, especially relate to the preparation method of a kind of high-performance titanium niobate-silver composite material.
Background technology
Lithium ion battery has high energy density, environmental friendliness, the advantage such as without memory because of it, is widely used in small-sized electronic product.In recent years along with the enhancing of energy crisis and people's environmental consciousness, electric automobile is more and more subject to favor and the attention of people, and a kind of important content of ev industry development is the high performance electrokinetic cell of exploitation.Current business-like carbon negative pole material, due to its low intercalation potential, easily causes the formation of Li dendrite, there is potential safety hazard.In addition, the diffusion velocity of lithium ion in material with carbon element is lower.Therefore, the Novel anode material of exploitation high-performance and high security is badly in need of.
Ti 2nb 10o 29there is high charging/discharging voltage platform (1.65V), the decomposition of organic electrolyte can be suppressed, not easily form solid electrolyte oxidation film (SEI) and Li dendrite, there is high fail safe.The theoretical specific capacity of this material is 396mAh/g, is greater than business-like carbon negative pole material.Therefore, Ti 2nb 10o 29be considered to a kind of desirable high-performance power battery negative material, receive the concern of researcher.
Current Ti 2nb 10o 29synthetic method be high temperature solid-state method, be generally with titanium dioxide and niobium oxide for raw material, high-temperature calcination after ball milling.Due to its synthesis temperature higher (>=1000 DEG C), the particle size of synthetic sample is general comparatively large, and Ti 2nb 10o 29the conductivity of material self is lower, and these two aspects factor makes its chemical property not rationality, still can not meet people to the high performance demand of this material.Therefore, be necessary that exploitation one has high performance Ti 2nb 10o 29the preparation method of material.
Summary of the invention
The object of this invention is to provide the preparation method of a kind of high-performance titanium niobate-silver composite material, be intended to the conductivity improving material, and then improve the chemical property of material.
Technical scheme of the present invention is: a kind of preparation method of high-performance titanium niobate-silver composite material, comprises the following steps:
A () stoichiometrically takes titanium dioxide and niobium pentaoxide joins in agate jar, with anhydrous ethanol medium ball milling 1-24 hour post-drying, calcines 2-60 hour, namely obtain Ti after cooling at 720-1300 DEG C 2nb 10o 29;
B polyvinylpyrrolidone is dissolved in reproducibility organic solvent by (), add the Ti that step (a) is obtained 2nb 10o 29, ultrasonic 0.1-6 hour, then adds silver nitrate, continues ultrasonic 0.1-15 hour;
C ultrasonic for step (b) rear gained suspension-turbid liquid is transferred in the reactor of inner liner polytetrafluoroethylene by (), reaction 0.1-48 hour, centrifugation, namely vacuumize obtain Ti 2nb 10o 29/ Ag composite material.
Preferably, the reproducibility organic solvent described in step (b) is one or more in DMF, ethylene glycol.
Preferably, the concentration of the polyvinylpyrrolidone described in step (b) is 0.3-27mol/L, described Ti 2nb 10o 29concentration be 0.15-75mol/L.
Preferably, the TiNb described in step (b) 2o 7be 100: 0.01-100: 60 with the mass ratio of silver nitrate.
Preferably, the reaction kettle for reaction temperature described in step (c) is 70-260 DEG C.
Preferably, the vacuumize temperature described in step (c) is 60-110 DEG C.
The advantage that the present invention has and good effect are:
1) Ag does not enter Ti 2nb 10o 29the lattice of material, does not affect Ti 2nb 10o 29the stability of self.
2) Ag simple substance is dispersed in Ti 2nb 10o 29material surface, improves its conductivity, significantly improves Ti 2nb 10o 29chemical property, particularly high rate performance, under 5C multiplying power through 200 times circulation after specific capacity remain on 230mAh/g.
3) preparation condition of the present invention is gentle, technique is simple, is easy to suitability for industrialized production.
Accompanying drawing explanation
Fig. 1 is Ti prepared by the embodiment of the present invention 1 2nb 10o 29the XRD figure of/Ag composite material.
Fig. 2 is Ti prepared by the embodiment of the present invention 1 2nb 10o 29the stereoscan photograph of/Ag composite material.
Fig. 3 is Ti prepared by the embodiment of the present invention 1 2nb 10o 29/ Ag composite material thoroughly retouch electromicroscopic photograph.
Fig. 4 is Ti prepared by the embodiment of the present invention 1 2nb 10o 29the chemical property curve chart of/Ag composite material under 5C multiplying power.
Embodiment
Below in conjunction with accompanying drawing, the present invention is elaborated.
Embodiment one
A () stoichiometrically takes titanium dioxide and niobium pentaoxide joins in agate jar, with anhydrous ethanol medium ball milling 2-21 hour post-drying, calcines 3-56 hour, namely obtain Ti after cooling at 750-1310 DEG C 2nb 10o 29;
B 0.4g polyvinylpyrrolidone is dissolved in DMF by (), add the Ti that step (a) is obtained 2nb 10o 29, ultrasonic 0.1-5 hour, then adds silver nitrate by a certain percentage, continues ultrasonic 0.15-13 hour, and wherein the concentration of polyvinylpyrrolidone is 0.3-21mol/L, Ti 2nb 10o 29concentration be 0.17-57mol/L, TiNb 2o 7be 100: 0.023-100: 46 with the mass ratio of silver nitrate;
C above-mentioned ultrasonic rear gained suspension-turbid liquid is transferred in the reactor of inner liner polytetrafluoroethylene by (), at 75-240 DEG C, react 0.2-36 hour, centrifugation, namely 72-110 DEG C of vacuumize obtain Ti 2nb 10o 29/ Ag composite material.
As Figure 1-3, the Ti that the present embodiment is obtained is respectively 2nb 10o 29the XRD figure of/Ag composite material, stereoscan photograph and thoroughly retouch electromicroscopic photograph.
As shown in Figure 4, the Ti that the present embodiment is obtained is shown 2nb 10o 29/ Ag composite material has good chemical property, especially high rate performance.
Embodiment two
A () stoichiometrically takes titanium dioxide and niobium pentaoxide joins in agate jar, with anhydrous ethanol medium ball milling 5-26 hour post-drying, calcines 4-51 hour, namely obtain Ti after cooling at 780-1350 DEG C 2nb 10o 29;
B 8g polyvinylpyrrolidone is dissolved in ethylene glycol by (), add the Ti that step (a) is obtained 2nb 10o 29, ultrasonic 0.15-4 hour, then adds silver nitrate by a certain percentage, continues ultrasonic 0.32-10 hour, and wherein the concentration of polyvinylpyrrolidone is 0.9-24mol/L, Ti 2nb 10o 29concentration be 0.46-49mol/L, TiNb 2o 7be 100: 0.059-100: 42 with the mass ratio of silver nitrate;
C above-mentioned ultrasonic rear gained suspension-turbid liquid is transferred in the reactor of inner liner polytetrafluoroethylene by (), at 82-230 DEG C, react 0.4-30 hour, centrifugation, namely 78-115 DEG C of vacuumize obtain Ti 2nb 10o 29/ Ag composite material.
Embodiment three
A () stoichiometrically takes titanium dioxide and niobium pentaoxide joins in agate jar, with anhydrous ethanol medium ball milling 5-26 hour post-drying, calcines 6-46 hour, namely obtain Ti after cooling at 810-1290 DEG C 2nb 10o 29;
B 18g polyvinylpyrrolidone is dissolved in DMF by (), add the Ti that step (a) is obtained 2nb 10o 29, ultrasonic 0.31-4 hour, then adds silver nitrate by a certain percentage, continues ultrasonic 0.41-12 hour, and wherein the concentration of polyvinylpyrrolidone is 0.6-19mol/L, Ti 2nb 10o 29concentration be 0.36-50mol/L, TiNb 2o 7be 100: 0.79-100: 52 with the mass ratio of silver nitrate;
C above-mentioned ultrasonic rear gained suspension-turbid liquid is transferred in the reactor of inner liner polytetrafluoroethylene by (), at 87-225 DEG C, react 2-28 hour, centrifugation, namely 80-108 DEG C of vacuumize obtain Ti 2nb 10o 29/ Ag composite material.
Above one embodiment of the present of invention have been described in detail, but described content being only preferred embodiment of the present invention, can not being considered to for limiting practical range of the present invention.All equalizations done according to the present patent application scope change and improve, and all should still belong within patent covering scope of the present invention.

Claims (6)

1. a preparation method for high-performance titanium niobate-silver composite material, is characterized in that: comprise the following steps:
A () stoichiometrically takes titanium dioxide and niobium pentaoxide joins in ball grinder, with anhydrous ethanol medium ball milling 1-24 hour post-drying, calcines 2-60 hour, namely obtain Ti after cooling at 720-1300 DEG C 2nb 10o 29;
B polyvinylpyrrolidone is dissolved in reproducibility organic solvent by (), add the Ti that step (a) is obtained 2nb 10o 29, ultrasonic 0.1-6 hour, then adds silver nitrate, continues ultrasonic 0.1-15 hour;
C ultrasonic for step (b) rear gained suspension-turbid liquid is transferred in reactor by (), reaction 0.1-48 hour, centrifugation, namely vacuumize obtain Ti 2nb 10o 29/ Ag composite material.
2. the preparation method of a kind of high-performance titanium niobate-silver composite material according to claim 1, is characterized in that: the reproducibility organic solvent described in step (b) is one or more in DMF, ethylene glycol.
3. the preparation method of a kind of high-performance titanium niobate-silver composite material according to claim 1, is characterized in that: the concentration of the polyvinylpyrrolidone described in step (b) is 0.3-27mol/L, described Ti 2nb 10o 29concentration be 0.15-75mol/L.
4. the preparation method of a kind of high-performance titanium niobate-silver composite material according to claim 1, is characterized in that: the TiNb described in step (b) 2o 7be 100: 0.01-100: 60 with the mass ratio of silver nitrate.
5. the preparation method of a kind of high-performance titanium niobate-silver composite material according to claim 1, is characterized in that: the reaction kettle for reaction temperature described in step (c) is 70-260 DEG C.
6. the preparation method of a kind of high-performance titanium niobate-silver composite material according to claim 1, is characterized in that: the vacuumize temperature described in step (c) is 60-110 DEG C.
CN201510810988.2A 2015-11-12 2015-11-12 Preparation method for high-performance niobic acid titanium-silver composite material Pending CN105489889A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106082338A (en) * 2016-06-13 2016-11-09 东北大学 A kind of nano-oxide Ti2nb10o29preparation method
CN110571423A (en) * 2019-09-17 2019-12-13 上海理工大学 Preparation method of nitrogen-carbon-coated nano titanium niobate electrode material
CN111653764A (en) * 2020-05-27 2020-09-11 武汉工程大学 Nano-silver composite niobium titanium oxide electrode material and preparation method and application thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102479950A (en) * 2010-11-23 2012-05-30 中国科学院物理研究所 Titanium niobate composite material, preparation method thereof, and cathode and battery containing the same
CN102983316A (en) * 2012-11-05 2013-03-20 华中科技大学 Electrode material of secondary lithium ion battery, and its preparation method

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102479950A (en) * 2010-11-23 2012-05-30 中国科学院物理研究所 Titanium niobate composite material, preparation method thereof, and cathode and battery containing the same
CN102983316A (en) * 2012-11-05 2013-03-20 华中科技大学 Electrode material of secondary lithium ion battery, and its preparation method

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
CHENGYAN LIU等: ""Bottom-up assembly to Ag nanoparticles embedded Nb-doped TiO2 nanobulks with improved n-type thermoelectric properties"", 《JOURNAL OF MATERIALS CHEMISTRY》 *
TOSHIKI TAKASHIMA等: ""Characterization of mixed titanium-niobium oxide Ti2Nb10O29 annealed in vacuum as anode material for lithium-ion battery"", 《JOURNAL OF POWER SOURCES》 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106082338A (en) * 2016-06-13 2016-11-09 东北大学 A kind of nano-oxide Ti2nb10o29preparation method
CN110571423A (en) * 2019-09-17 2019-12-13 上海理工大学 Preparation method of nitrogen-carbon-coated nano titanium niobate electrode material
CN111653764A (en) * 2020-05-27 2020-09-11 武汉工程大学 Nano-silver composite niobium titanium oxide electrode material and preparation method and application thereof

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