CN107732186A - A kind of preparation method of positive composite material of lithium battery - Google Patents

A kind of preparation method of positive composite material of lithium battery Download PDF

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Publication number
CN107732186A
CN107732186A CN201710913962.XA CN201710913962A CN107732186A CN 107732186 A CN107732186 A CN 107732186A CN 201710913962 A CN201710913962 A CN 201710913962A CN 107732186 A CN107732186 A CN 107732186A
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China
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preparation
lifepo
lithium battery
composite material
tio
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CN201710913962.XA
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Chinese (zh)
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向勇
史家远
张晓晴
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University of Electronic Science and Technology of China
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University of Electronic Science and Technology of China
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Priority to CN201710913962.XA priority Critical patent/CN107732186A/en
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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
    • 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
    • H01M4/36—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
    • 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
    • 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

Abstract

Invention is related to the preparing technical field of lithium ion battery electrode material, and in particular to a kind of preparation method of positive composite material of lithium battery.The present invention adds nitrogenous carbon source by original position, makes LiFePO4Material adds the carbon source containing nonmetalloid in the preparation, after heat treatment, forms the LiFePO of nonmetal doping carbon coating4Composite.Hydrolysis and precipitation by titanium source, alkaline environment is provided for the polymerization of dopamine, avoid the use of Tris buffer solutions and eliminate the loss of product of trouble and product in centrifugal process caused by centrifugation after reaction.While the polymerization of the dopamine without Tris is realized, by TiO2Nano particle is incorporated into LiFePO4On surface, TiO in system2Introducing be also beneficial to lifted material stability.For the present invention while excellent material performance for ensureing to prepare, preparation technology is simple, cost is cheap, and does not lose product.

Description

A kind of preparation method of positive composite material of lithium battery
Technical field
The present invention relates to the preparing technical field of lithium ion battery electrode material, and in particular to a kind of lithium battery anode is compound The preparation method of material.
Background technology
Since the work of Goodenough in 1997 and its colleague, olivine-type LiFePO4 (LiFePO4, LFP) Received as the positive electrode of lithium battery extensively and in-depth study.In addition, LiFePO4Due to its parent material into Suitable (the 3.4V vs.Li of this low, theoretical capacity high (170mAh/g), operating voltage+/ Li), long circulating stability and nontoxicity etc. Numerous attracting advantages, and achieve huge business success.In spite of these advantages, pure LiFePO4Electrical conductivity it is low (~ 10-9) and Li S/cm+Slow etc. inherent shortcoming is spread, limits its further application and development.
, can be by LiFePO in order to overcome these defects4Combined with high conductivity carbonaceous material, to improve LiFePO4Appearance Amount and performance.Used carbon surface cladding can improve LiFePO4Electric conductivity, and prevent LiFePO4Directly contact electrolysis Matter, this will improve the rate capability and chemical property of material.Two-dimentional carbon material, as with flexible structure and bigger serface Graphene, can be LiFePO4Nano particle provides fixed substrate, prevents LiFePO4Reunite, effectively improve electrode material Lithium ion diffusion rate.Porous carbon structure can serve as electrolyte container, increase the contact between electrode and electrolyte.With 3D The porous carbon structure of network is alternatively Li+Transport and electronics transfer provide facility.Compared with carbon coating, the carbon material of N doping can To provide more electronic carriers, the electronic conductivity and lithium ion diffusion of effective reinforcing material in conduction band.It is nitrogenous The introducing of functional group is by increasing carbon and LiFePO4Between interaction, to strengthen carbon to the wetability of electrolyte and affine Power, this is beneficial to LiFePO4It is scattered.At the same time, Li can also be increased by adulterating the carbon coating of nitrogen+Storage site.
Research shows, dopamine polymerization and the carbonization of particle surface be electrode material carry out nitrogen carbon dope cladding have efficacious prescriptions Method.Dopamine can auto polymerization into poly-dopamine, because poly-dopamine has powerful cladding ability, it can be in nano particle Continuous and uniform film is formed on surface.Electrode material surface poly-dopamine coating, the calcining in its inert atmosphere can be passed through Handle and be carbonized, form the carbon coating layer of N doping.However, the polymerization process of dopamine needs weakly alkaline environment, therefore generally Carried out in Tris- cushioning liquid, products therefrom needs to separate and wash repeatedly, which increase the complexity of preparation process and leads Products therefrom is caused inevitably to lose.
TiO2It is widely used in due to its structural stability and chemical inertness in lithium ion battery.Because its cost is low Honest and clean, it is convenient to prepare, environment-friendly and high stability, TiO2It is the effective ways for improving lithium cell cathode chemical property.TiO2Bag The stabilization covered is TiO2Nano-particle can prevent cathode material from dissolving, and the pair suppressed between negative electrode and electrolyte is anti- Should.In addition, TiO2Li absorbabilities can be improved with the synergy of carbon and strengthen electronic conductivity.
The content of the invention
For problem or deficiency in the prior art be present, to overcome the complicated preparation of existing LFP anode material of lithium battery Journey and its problem of cause products therefrom unavoidably to lose, the invention provides a kind of preparation of positive composite material of lithium battery Method, the composite are TiO2The LiFePO coated altogether with nitrogen-doped carbon4。
Concrete technical scheme is as follows：
Step 1, by LiFePO4, titanium compound and nitrogenous carbon source ultrasonic dissolution it is scattered in organic solvent, then by it Stirring reaction 4~24 hours.
Step 2, step 1 resulting solution is evaporated, then grinds 5~30 minutes, finally in 500~700 DEG C of inert atmosphere Under the conditions of calcine 3~6h, naturally cool to room temperature and can obtain final product；Wherein TiO2Total content with nitrogen-doped carbon is 0.5wt%~20wt%, LiFePO4Content is 80wt%~99.5wt%, TiO2Mass ratio between nitrogen-doped carbon is 1/9 ~9/1.
Preferably, the compound of titanium is butyl titanate, titanyl sulfate, titanium tetrachloride and/or sulfuric acid in the step 1 Titanium.
Preferably, in the step 1 nitrogenous carbon source be dopamine, 1- ethyl-3-methylimidazoles cdicynanmide (EMI-DCA), Melamine, acetonitrile, aniline and/or pyrroles.
Preferably, inert atmosphere conditions are nitrogen or argon gas atmosphere in the step 2.
The present invention is first by LiFePO4, titanium source, nitrogenous carbon source dissolving in organic solvent, be evaporated, grind after in inert atmosphere Under the conditions of calcine, after furnace cooling i.e. obtain anode material for compound lithium ion battery.Raw material sources of the present invention enrich, preparation technology Simply, the positive electrode excellent conductivity prepared, cycle performance are excellent.
Compared with prior art, the present invention adds nitrogenous carbon source by original position, makes LiFePO4Material adds in the preparation Carbon source containing nonmetalloid, after heat treatment, form the LiFePO of nonmetal doping carbon coating4Composite.Nitrogen is former Son is in the ortho position of carbon atom in the periodic table of elements, and radius approaches, but its electronegativity is higher than carbon, therefore non-metallic atom adulterates Lattice structure and the duct of carbon can be kept, the extra lone pair electrons of non-metallic atom or hole can give carbon skeleton extended system Electric charge carrier, so as to effectively improve the surface polarity of carbon, strengthen the transmission performance and chemical reactivity of electronics.Effectively Enhance the electric conductivity and electrochemical reaction performance of LiFePO 4 material.At the same time, this method passes through the hydrolysis of titanium source and heavy Form sediment, alkaline environment is provided for the polymerization of dopamine, avoid the use of Tris buffer solutions and centrifuge institute after eliminating reaction Loss of product of the trouble and product brought in centrifugal process.While the polymerization of the dopamine without Tris is realized, by TiO2 Nano particle is incorporated into LiFePO4On surface, TiO in system2Introducing be also beneficial to lifted material stability.
In summary, for the present invention while excellent material performance for ensureing to prepare, preparation technology is simple, cost is cheap, And do not lose product.
Brief description of the drawings
The cycle charge-discharge test chart of Fig. 1 embodiments.
Embodiment
The present invention is described in further detail with reference to the accompanying drawings and examples.
A kind of TiO2The LiFePO coated altogether with nitrogen-doped carbon4The preparation method of anode material for compound lithium ion battery, step It is as follows：
Step 1, by LiFePO4, butyl titanate, dopamine according to mass ratio be 9:0.5:0.5 ultrasonic disperse is in isopropyl In alcohol, the reaction solution is stirred at room temperature 6 hours.
Step 2, by step 1 products therefrom dry overnight at room temperature, grinding 20 minutes, forge under the conditions of 600 DEG C of argon gas atmospheres After burning 6 hours, room temperature is naturally cooled to, you can final product is made.
As shown in figure 1, at 0.1C (17mA/g), LFP and LFP-TiO2- C-N specific discharge capacity is respectively 127.4mAh·g-1And 165.3mAhg-1, correspond respectively to LiFePO4The 75% of theoretical specific capacity and 97%.This result table Bright TiO2It is coated with the lifting beneficial to electrode material specific discharge capacity altogether with nitrogen-doped carbon.Abscissa in figure is the circulation number of turns (cycle number), ordinate are the specific discharge capacity (discharge capacity) of resulting materials.

Claims (4)

1. a kind of preparation method of positive composite material of lithium battery, is comprised the following steps that：
Step 1, by LiFePO4, titanium compound and nitrogenous carbon source ultrasonic dissolution it is scattered in organic solvent, be then stirred for Reaction 4~24 hours；
Step 2, step 1 resulting solution is evaporated, then grinds 5~30 minutes, finally in 500~700 DEG C of inert atmosphere conditions 3~6h of lower calcining, naturally cools to room temperature and can obtain final product；Wherein TiO2Total content with nitrogen-doped carbon is 0.5wt%~20wt%, LiFePO4Content is 80wt%~99.5wt%, TiO2Mass ratio between nitrogen-doped carbon is 1/9 ~9/1.
2. the preparation method of positive composite material of lithium battery as claimed in claim 1, it is characterised in that：Contain in the step 1 Nitrogen carbon source is dopamine, 1- ethyl-3-methylimidazole cdicynanmides EMI-DCA, melamine, acetonitrile, aniline and/or pyrroles.
3. the preparation method of positive composite material of lithium battery as claimed in claim 1, it is characterised in that：Inertia in the step 2 Atmospheric condition is nitrogen or argon gas atmosphere.
4. the preparation method of positive composite material of lithium battery as claimed in claim 1, it is characterised in that：Titanium in the step 1 Compound is butyl titanate, titanyl sulfate, titanium tetrachloride and/or titanium sulfate.
CN201710913962.XA 2017-09-30 2017-09-30 A kind of preparation method of positive composite material of lithium battery Pending CN107732186A (en)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2723638C1 (en) * 2019-02-05 2020-06-17 Автономная некоммерческая образовательная организация высшего образования "Сколковский институт науки и технологий" Method for creation of homogeneous carbon coating with controlled thickness on surface of cathode material for metal-ion accumulators and cathode material produced by said method
CN111613786A (en) * 2020-05-29 2020-09-01 东莞东阳光科研发有限公司 Composite material and preparation method thereof
CN111689527A (en) * 2020-06-22 2020-09-22 湖南金富力新能源股份有限公司 Preparation method of one-pot double-coated lithium ion battery NCM ternary cathode material
CN111900401A (en) * 2020-07-24 2020-11-06 贵州梅岭电源有限公司 Method for coating positive electrode material of lithium battery by using tungsten oxide and nitrogen-doped carbon composite
CN112151781A (en) * 2020-09-24 2020-12-29 贵州梅岭电源有限公司 Rapid composite coating modification method for lithium battery positive electrode material
CN112864368A (en) * 2021-03-18 2021-05-28 贵州梅岭电源有限公司 Preparation method of composite coated modified lithium manganese iron phosphate cathode material

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CN103618061A (en) * 2013-11-04 2014-03-05 中国科学院化学研究所 Method for carbon layer controllable coating to polyanion-type lithium ion batteries cathode materials
CN106129337A (en) * 2016-06-27 2016-11-16 华中农业大学 A kind of preparation method of cathode of lithium iron phosphate lithium ion battery electrode

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2723638C1 (en) * 2019-02-05 2020-06-17 Автономная некоммерческая образовательная организация высшего образования "Сколковский институт науки и технологий" Method for creation of homogeneous carbon coating with controlled thickness on surface of cathode material for metal-ion accumulators and cathode material produced by said method
CN111613786A (en) * 2020-05-29 2020-09-01 东莞东阳光科研发有限公司 Composite material and preparation method thereof
CN111689527A (en) * 2020-06-22 2020-09-22 湖南金富力新能源股份有限公司 Preparation method of one-pot double-coated lithium ion battery NCM ternary cathode material
CN111900401A (en) * 2020-07-24 2020-11-06 贵州梅岭电源有限公司 Method for coating positive electrode material of lithium battery by using tungsten oxide and nitrogen-doped carbon composite
CN111900401B (en) * 2020-07-24 2022-02-22 贵州梅岭电源有限公司 Method for coating positive electrode material of lithium battery by using tungsten oxide and nitrogen-doped carbon composite
CN112151781A (en) * 2020-09-24 2020-12-29 贵州梅岭电源有限公司 Rapid composite coating modification method for lithium battery positive electrode material
CN112864368A (en) * 2021-03-18 2021-05-28 贵州梅岭电源有限公司 Preparation method of composite coated modified lithium manganese iron phosphate cathode material

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