CN109192932A - A kind of preparation method of carbon titanium composite lithium ion battery negative electrode material - Google Patents

A kind of preparation method of carbon titanium composite lithium ion battery negative electrode material Download PDF

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Publication number
CN109192932A
CN109192932A CN201810760271.5A CN201810760271A CN109192932A CN 109192932 A CN109192932 A CN 109192932A CN 201810760271 A CN201810760271 A CN 201810760271A CN 109192932 A CN109192932 A CN 109192932A
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weight
solution
parts
titanium oxide
washing
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不公告发明人
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Suzhou Sichuang Yuanbo Electronic Technology Co Ltd
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Suzhou Sichuang Yuanbo Electronic Technology Co Ltd
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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
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • 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
    • 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
    • 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
    • H01M4/625—Carbon or graphite
    • 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)
  • Composite Materials (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention discloses a kind of preparation method of carbon titanium composite lithium ion battery negative electrode material, the method uses the high-performance titanium oxide with special micro-nano structure, can obtain the higher titanium oxide of crystallinity, is conducive to that storage lithium reaction occurs；The present invention is compound by carbon nitrogen, improves the electric conductivity of active material, in addition, the expansion of volume provides the useful space when cavity between the carbon-coating and titanium oxide of N doping is active material Li insertion extraction, it is therefore prevented that the dusting reunion of titanium oxide.

Description

A kind of preparation method of carbon titanium composite lithium ion battery negative electrode material
Technical field
The present invention relates to battery material fields, and in particular to a kind of preparation method of carbon titanium composite lithium ion battery negative electrode material.
Background technique
In recent years, domestic new-energy automobile industry development is rapid, and battery variety is rich and varied, demand of the market to battery and It is required that gradually increasing.Its most concerned key index is concentrated mainly on five broad aspects: safety and stability performance, cycle life, resistance to width Warm nature, charging rate and energy density.
Now, effect of the lithium ion battery in social development is higher and higher.Therefore, high-performance, environmentally protective is developed Electrode material becomes the research hotspot of lithium ion battery.Lithium ion battery negative material is based on graphitized carbon material at present, but Carbon material has the disadvantage that (1) generates SEI film in discharge process for the first time, causes irreversible capacity loss, or even causes carbon electric Pole internal structure change and poor contact；(2) because the decomposition of protective layer, leads to battery failure or cause safe sexual behavior when high temperature Therefore；(3) unit volume capacity is relatively low.Since metal, metal oxide and its composite material have high specific capacity, They become the substitute of lithium ion battery negative material, have biggish development potentiality.
Titanium oxide has the advantages such as theoretical specific capacity height, rich content, pollution-free, can be used as the cathode material of lithium secondary battery Material.However, there is also some disadvantages while titanium oxide highlights advantage as lithium cell negative pole material: first is that body phase oxidation titanium is led It is electrically poor, it is unfavorable for the transmission of electronics；Second is that the easy dusting of body phase oxidation titanium is reunited in charge and discharge process, lead to circulating battery Can sharply it decline.
Summary of the invention
The present invention provides a kind of preparation method of carbon titanium composite lithium ion battery negative electrode material, and the method is used with special micro- The high-performance titanium oxide of micro-nano structure can obtain the higher titanium oxide of crystallinity, be conducive to that storage lithium reaction occurs；The present invention passes through Carbon nitrogen it is compound, improve the electric conductivity of active material, in addition, the cavity between the carbon-coating and titanium oxide of N doping be active matter The expansion of volume provides the useful space when matter Li insertion extraction, it is therefore prevented that the dusting of titanium oxide is reunited.
To achieve the goals above, the present invention provides a kind of preparation method of carbon titanium composite lithium ion battery negative electrode material, the party Method includes the following steps:
(1) titania meterial is prepared
Solution one is prepared with butyl titanate, dehydrated alcohol, glacial acetic acid, PVP raw material, using dehydrated alcohol, deionized water as raw material Solution two is prepared, then solution two is slowly dropped in solution one, obtains TiO2Sol gel solution；
1-2h is stirred at room temperature, then under 40 DEG C of -60 DEG C of drying, argon atmospher, would be heated to 700 DEG C, and keep the temperature 2-3h, it is cooling Nano-titanium oxide is obtained to taking-up after room temperature；
(2) silica cladding titania precursor body is prepared
By the titanium oxide of 60 parts by weight be dispersed in 150-180 parts by weight by ethylene glycol and the water mixing that 3:1 is constituted by volume In liquid, 10-60min is stirred by ultrasonic, 2-4 parts by weight ammonium hydroxide and the positive silicic acid of 0.2-0.3 parts by weight are then added under agitation Tetra-ethyl ester continues to stir 8-14h, centrifugation, washing, i.e. acquisition silica coats titania precursor body；
(3) the silica cladding titania precursor body of acquisition is dispersed in 100 parts by weight of ethanol, 1-2 parts by weight is then added High molecular surfactant, stir 20-30h, centrifugation, washing；
It disperses silica cladding titania precursor body after washing in 80 parts by weight of deionized water, 0.3-0.35 weight is then added Part pyrrole monomer, ultrasonic 45-50min are measured, then it is drawing for 20-25mmol/L that 50 parts by weight concentration are added dropwise under agitation Send out agent solution, last polymerization reaction 4-12h, centrifugation, washing, drying；
(4) product after the drying is placed in atmosphere of inert gases, is warming up to 570 with the heating rate of 5 DEG C -8 DEG C/min DEG C -630 DEG C, anneal 1-3h, and polypyrrole is made to be carbonized；
Product after the carbonization is put into alkaline solution and is performed etching, to remove SiO2To get arrive carbon titanium composite negative pole material Material.
Preferably, butyl titanate in the solution one, dehydrated alcohol, glacial acetic acid volume ratio be 1:8:1, in solution two Dehydrated alcohol, deionized water volume ratio 7:1, the PVP and be added butyl titanate mass ratio be 1:5.
Preferably, the high molecular surfactant is poly amic acid, hydroxyethyl cellulose and polyoxyethylene copolymerization At least one of object；The initiator is at least one of ammonium persulfate, potassium bichromate and Potassiumiodate.
The invention has the advantages that and remarkable result:
(1) the method uses the high-performance titanium oxide with special micro-nano structure, can obtain the higher titanium oxide of crystallinity, Be conducive to that storage lithium reaction occurs；
(2) present invention improves the electric conductivity of active material, in addition, the carbon-coating and titanium oxide of N doping by the compound of carbon nitrogen Between cavity for active material Li insertion extraction when volume expansion provide the useful space, it is therefore prevented that the dusting of titanium oxide is reunited.
Specific embodiment
Embodiment one
Solution one is prepared with butyl titanate, dehydrated alcohol, glacial acetic acid, PVP raw material, using dehydrated alcohol, deionized water as raw material Solution two is prepared, then solution two is slowly dropped in solution one, obtains TiO2Sol gel solution；Titanium in the solution one Sour four butyl esters, dehydrated alcohol, glacial acetic acid volume ratio be 1:8:1, the volume ratio 7 of dehydrated alcohol, deionized water in solution two: 1, the PVP and the mass ratio that butyl titanate is added are 1:5.
1h is stirred at room temperature, is then dried at 40 DEG C DEG C, under argon atmospher, be would be heated to 700 DEG C, and keep the temperature 2h, is cooled to It is taken out after to room temperature and obtains nano-titanium oxide.
By the titanium oxide of 60 parts by weight be dispersed in 150 parts by weight by ethylene glycol and the water mixing that 3:1 is constituted by volume In liquid, 10min is stirred by ultrasonic, 2-4 parts by weight ammonium hydroxide and 0.2 parts by weight tetraethyl orthosilicate are then added under agitation, Continue to stir 8h, centrifugation, washing, i.e. acquisition silica coats titania precursor body.
The silica cladding titania precursor body of acquisition is dispersed in 100 parts by weight of ethanol, 1 parts by weight are then added High molecular surfactant stirs 20h, centrifugation, washing；80 weight are dispersed by silica cladding titania precursor body after washing In part deionized water, 0.3 parts by weight pyrrole monomer, ultrasonic 45min is then added, then 50 weight are added dropwise under agitation The initiator solution that part concentration is 20mmol/L, last polymerization reaction 4h, centrifugation, washing, drying；By the product after the drying It is placed in atmosphere of inert gases, is warming up to 570 DEG C with the heating rate of 5 DEG C/min, anneal 1h, and polypyrrole is made to be carbonized；It will be described Product after carbonization, which is put into alkaline solution, to be performed etching, to remove SiO2To get arrive carbon titanium composite negative pole material.
Wherein, the high molecular surfactant is poly amic acid, hydroxyethyl cellulose and polyoxyethylene analog copolymer At least one of；The initiator is at least one of ammonium persulfate, potassium bichromate and Potassiumiodate.
Embodiment two
Solution one is prepared with butyl titanate, dehydrated alcohol, glacial acetic acid, PVP raw material, using dehydrated alcohol, deionized water as raw material Solution two is prepared, then solution two is slowly dropped in solution one, obtains TiO2Sol gel solution；Titanium in the solution one Sour four butyl esters, dehydrated alcohol, glacial acetic acid volume ratio be 1:8:1, the volume ratio 7 of dehydrated alcohol, deionized water in solution two: 1, the PVP and the mass ratio that butyl titanate is added are 1:5.
Stir 2h at room temperature, then dried at 60 DEG C, under argon atmospher, would be heated to 700 DEG C, and keep the temperature 3h, be cooled to It is taken out after room temperature and obtains nano-titanium oxide.
By the titanium oxide of 60 parts by weight be dispersed in 180 parts by weight by ethylene glycol and the water mixing that 3:1 is constituted by volume In liquid, 60min is stirred by ultrasonic, 4 parts by weight ammonium hydroxide and 0.3 parts by weight tetraethyl orthosilicate are then added under agitation, after Continuous stirring 14h, centrifugation, washing, i.e. acquisition silica coat titania precursor body.
The silica cladding titania precursor body of acquisition is dispersed in 100 parts by weight of ethanol, 2 parts by weight are then added High molecular surfactant stirs 30h, centrifugation, washing；80 weight are dispersed by silica cladding titania precursor body after washing In part deionized water, 0.35 parts by weight pyrrole monomer, ultrasonic 50min is then added, then 50 weights are added dropwise under agitation Measure the initiator solution that part concentration is 25mmol/L, last polymerization reaction 12h, centrifugation, washing, drying；After the drying Product is placed in atmosphere of inert gases, is warming up to 630 DEG C with the heating rate of 8 DEG C/min, and anneal 3h, and polypyrrole is made to be carbonized；It will Product after the carbonization, which is put into alkaline solution, to be performed etching, to remove SiO2To get arrive carbon titanium composite negative pole material.
Wherein, the high molecular surfactant is polyoxyethylene analog copolymer；The initiator is Potassiumiodate.
Using above-described embodiment one, two products therefrom materials as being used for cathode of lithium battery, with just extremely LiFePO 4 material The test battery pack of composition carries out cyclical stability test, and discharge capacity is respectively 1144mAh/g and 1107mAh/g for the first time, is followed Capacity is 1035mAh/g and 974mAh/g after ring 200 times, has good cyclical stability.

Claims (3)

1. a kind of preparation method of carbon titanium composite lithium ion battery negative electrode material, this method comprises the following steps:
(1) titania meterial is prepared
Solution one is prepared with butyl titanate, dehydrated alcohol, glacial acetic acid, PVP raw material, using dehydrated alcohol, deionized water as raw material Solution two is prepared, then solution two is slowly dropped in solution one, obtains TiO2Sol gel solution；
1-2h is stirred at room temperature, then under 40 DEG C of -60 DEG C of drying, argon atmospher, would be heated to 700 DEG C, and keep the temperature 2-3h, it is cooling Nano-titanium oxide is obtained to taking-up after room temperature；
(2) silica cladding titania precursor body is prepared
By the titanium oxide of 60 parts by weight be dispersed in 150-180 parts by weight by ethylene glycol and the water mixing that 3:1 is constituted by volume In liquid, 10-60min is stirred by ultrasonic, 2-4 parts by weight ammonium hydroxide and the positive silicic acid of 0.2-0.3 parts by weight are then added under agitation Tetra-ethyl ester continues to stir 8-14h, centrifugation, washing, i.e. acquisition silica coats titania precursor body；
(3) the silica cladding titania precursor body of acquisition is dispersed in 100 parts by weight of ethanol, 1-2 parts by weight is then added High molecular surfactant, stir 20-30h, centrifugation, washing；
It disperses silica cladding titania precursor body after washing in 80 parts by weight of deionized water, 0.3-0.35 weight is then added Part pyrrole monomer, ultrasonic 45-50min are measured, then it is drawing for 20-25mmol/L that 50 parts by weight concentration are added dropwise under agitation Send out agent solution, last polymerization reaction 4-12h, centrifugation, washing, drying；
(4) product after the drying is placed in atmosphere of inert gases, is warming up to 570 with the heating rate of 5 DEG C -8 DEG C/min DEG C -630 DEG C, anneal 1-3h, and polypyrrole is made to be carbonized；
Product after the carbonization is put into alkaline solution and is performed etching, to remove SiO2To get arrive carbon titanium composite negative pole material Material.
2. the method as described in claim 1, which is characterized in that butyl titanate, dehydrated alcohol, glacial acetic acid in the solution one Volume ratio be 1:8:1, the volume ratio 7:1, the PVP of dehydrated alcohol, deionized water in solution two and four fourth of metatitanic acid is added The mass ratio of ester is 1:5.
3. method according to claim 1 or 2, which is characterized in that the high molecular surfactant is poly amic acid, hydroxyl At least one of ethyl cellulose and polyoxyethylene analog copolymer；The initiator is ammonium persulfate, potassium bichromate and acid iodide At least one of potassium.
CN201810760271.5A 2018-07-12 2018-07-12 A kind of preparation method of carbon titanium composite lithium ion battery negative electrode material Pending CN109192932A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110429256A (en) * 2019-08-02 2019-11-08 辽宁星空钠电电池有限公司 Titanium oxide-carbon superlattice structure anode material of lithium-ion battery and preparation method
CN114456872A (en) * 2022-02-18 2022-05-10 上海聚治新材料科技有限公司 Preparation method of high-temperature-resistant graphene composite heat-dissipation lubricating fluid

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106784711A (en) * 2016-12-28 2017-05-31 中天储能科技有限公司 A kind of lithium ion battery negative material Si/TiO2The preparation method of composite
CN106816595A (en) * 2017-03-09 2017-06-09 合肥工业大学 A kind of lithium ion battery coats di-iron trioxide negative material and preparation method thereof with nitrogen-doped carbon

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106784711A (en) * 2016-12-28 2017-05-31 中天储能科技有限公司 A kind of lithium ion battery negative material Si/TiO2The preparation method of composite
CN106816595A (en) * 2017-03-09 2017-06-09 合肥工业大学 A kind of lithium ion battery coats di-iron trioxide negative material and preparation method thereof with nitrogen-doped carbon

Non-Patent Citations (1)

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Title
SANG-JUN PARK等: ""Synthesis of carbon-coated TiO2 nanotubes for high-power lithium-ion batteries"", 《JOURNAL OF POWER SOURCES》 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110429256A (en) * 2019-08-02 2019-11-08 辽宁星空钠电电池有限公司 Titanium oxide-carbon superlattice structure anode material of lithium-ion battery and preparation method
CN114456872A (en) * 2022-02-18 2022-05-10 上海聚治新材料科技有限公司 Preparation method of high-temperature-resistant graphene composite heat-dissipation lubricating fluid
CN114456872B (en) * 2022-02-18 2022-10-11 上海聚治新材料科技有限公司 Preparation method of high-temperature-resistant graphene composite heat-dissipation lubricating fluid

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