CN112701290A - Lithium ion battery anode with titanium suboxide as additive, battery and preparation method - Google Patents

Lithium ion battery anode with titanium suboxide as additive, battery and preparation method Download PDF

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Publication number
CN112701290A
CN112701290A CN202011607556.9A CN202011607556A CN112701290A CN 112701290 A CN112701290 A CN 112701290A CN 202011607556 A CN202011607556 A CN 202011607556A CN 112701290 A CN112701290 A CN 112701290A
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lithium ion
ion battery
titanium
additive
positive electrode
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李明涛
龙志
易义坤
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Henan Longxing Titanium Industry Technology Co ltd
Xian Jiaotong University
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Henan Longxing Titanium Industry Technology Co ltd
Xian Jiaotong 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
    • H01M4/62—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
    • 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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • 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
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0404—Methods of deposition of the material by coating on electrode collectors
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • 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
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract

A lithium ion battery anode taking titanium suboxide as an additive, a battery and a preparation method thereof comprise an anode plate, wherein the anode plate is prepared by the following processes: mixing a compound of an active substance and titanium suboxide, a conductive agent and a binder according to a mass ratio of (16-18) to (1-2), then adding an organic solvent and uniformly mixing to obtain a slurry, coating the slurry on an aluminum current collector, and drying to obtain the lithium ion battery anode taking titanium suboxide as an additive. The invention provides a lithium ion battery anode, a lithium ion battery and a preparation method thereof, wherein the lithium ion battery anode and the lithium ion battery are prepared by adding a titanium suboxide additive to improve the conductivity of an electrode, the titanium suboxide has compatibility with an electrode active material oxide, and the coulombic efficiency of the battery is improved through a synergistic effect.

Description

Lithium ion battery anode with titanium suboxide as additive, battery and preparation method
Technical Field
The invention belongs to the technical field of electrochemistry, and particularly relates to a lithium ion battery anode with titanium suboxide as an additive, a lithium ion battery and a preparation method of the lithium ion battery anode.
Background
Due to the increasing global energy shortage problem, the development and utilization of new energy technology is imminent, thereby promoting the rapid development of the electrochemical energy storage industry. Since the introduction of lithium ion batteries by Sony corporation in the 90's last century, lithium ion batteries have gained wide acceptance immediately with the advantages of high voltage and high energy density, and with the annual increase in market share, they have gradually established a leading position in consumer electronics, and have now fully occupied the entire consumer electronics market.
The positive electrode is the most important component of the lithium ion battery and mainly comprises an active material, a conductive agent and a binder, and the lithium ion battery positive electrode active material which is mainly used in the current commercialization has a layered structure of lithium cobaltate (LiCoO)2) And ternary lithium nickel cobalt manganese oxide (LiNi)0.5Co0.2Mn0.3O2) Lithium manganate (LiMn) having spinel structure2O4) And olivine-structured lithium iron phosphate (LiFePO)4). The materials have the advantages and disadvantages in the aspects of cost, structural stability, specific capacity, energy density and the like, wherein the comprehensive performance of the ternary nickel-cobalt-manganese material is better than that of other materials, but the high rate performance and the cycle stability of the ternary nickel-cobalt-manganese material are still poorer. Therefore, modification of the positive electrode material or introduction of a dopant stabilizer into the positive electrode component is an effective way to improve the electrochemical performance and safety of the electrode.
Chinese patent CN110061226B discloses a titanium suboxide coated positive electrode material, a preparation method of the positive electrode material, and a lithium ion battery. Mixing TiCl4Dissolving in water, introducing ammonia gas to obtainTitanium oxide sol; adding LiNi0.5Co0.2Mn0.3O2 into the titanium oxide sol, and then carrying out hydrolysis precipitation, filtration, drying, sintering and cooling to obtain the titanium suboxide coated modified cathode material. The rate capability and the cycle stability of the lithium ion battery are improved by utilizing the properties of high conductivity, corrosion resistance and the like of the titanium suboxide, but the preparation process is more complicated and the process conditions are more dangerous.
Disclosure of Invention
The invention aims to provide a lithium ion battery anode taking titanium monoxide as an additive, a battery and a preparation method, which aim to solve the problems in the prior art; the invention has simple process and obvious effect of the prepared lithium ion battery, can effectively improve the conductivity and stability of the electrode, and obviously improves the coulombic efficiency, the multiplying power and the cycle performance of the battery.
In order to achieve the purpose, the invention adopts the following technical scheme:
the lithium ion battery positive electrode with titanium suboxide as an additive comprises a positive plate, and the positive plate is prepared by the following processes: mixing a compound of an active substance and titanium suboxide, a conductive agent and a binder according to a mass ratio of (16-18) to (1-2), then adding an organic solvent and uniformly mixing to obtain a slurry, coating the slurry on an aluminum current collector, and drying to obtain the lithium ion battery anode taking titanium suboxide as an additive.
In a further development of the invention, the complex of active substance and titanium suboxide is produced by the following process: ultrasonically dispersing titanium oxide and an active substance in ethanol, centrifuging, and drying to obtain a compound of the active substance and the titanium oxide; or mixing titanium oxide with the active substance, and uniformly grinding by hand to obtain a compound of the active substance and the titanium oxide; wherein, the titanium oxide is 5 to 20 percent of the total mass of the compound of the active substance and the titanium oxide.
The invention has the further improvement that the conductive agent is one or more of conductive carbon black, Ketjen black, Super P, Super C65, acetylene black, graphite, hollow carbon spheres, carbon nanotubes and biomass carbon, and the adhesive is polyvinylidene fluoride; the active material is LiCoO2、LiFePO4Or LiNi0.5Co0.2Mn0.3O2。
In a further development of the invention, the organic solvent is N-methylpyrrolidone.
The invention is further improved in that the adding amount of the organic solvent is 10-30 times of the amount of the composite of the active substance and the titanium suboxide.
The further improvement of the invention is that the thickness of the slurry coated on the aluminum current collector is 100-400 μm.
The lithium ion battery based on the lithium ion battery anode taking the titanium monoxide as the additive comprises an anode shell, the lithium ion battery anode taking the titanium monoxide as the additive, a diaphragm, electrolyte, a metal lithium negative piece and a cathode shell from bottom to top.
A preparation method of the lithium ion battery with the titanium suboxide as the additive for the lithium ion battery anode comprises the following steps:
1) preparing a complex of an active material and titanium suboxide;
2) mixing a compound of an active substance and titanium suboxide, a conductive agent and a binder according to a mass ratio of (16-18) to (1-2), then adding an organic solvent and uniformly mixing to obtain slurry, coating the slurry on an aluminum current collector, and drying to obtain a lithium ion battery anode taking titanium suboxide as an additive;
3) assembling the battery: assembling the positive electrode shell, the lithium ion battery positive electrode taking titanium suboxide as an additive, the diaphragm, the electrolyte, the metal lithium negative electrode and the negative electrode shell from bottom to top in an inert atmosphere to obtain the lithium ion battery taking titanium suboxide as the lithium ion battery positive electrode of the additive.
Compared with the prior art, the invention has the following beneficial effects:
the invention introduces the titanium suboxide dopant with high conductivity and high corrosion resistance into the ternary positive electrodes of lithium iron phosphate, lithium cobaltate, nickel cobalt manganese and the like through a simple process means, improves the conductivity of the electrode, improves the capacity, the coulombic efficiency, the multiplying power, the circulation and other performances of the battery by depending on the compatibility between the titanium suboxide and the active substance oxide of the electrode, and can influence the improvement degree of the performance of the battery by directly adjusting the addition proportion of the titanium suboxide. The method has the advantages of low cost, safety, reliability, suitability for industrial large-scale production and wide application prospect.
The invention provides a lithium ion battery anode, a lithium ion battery and a preparation method thereof, wherein the lithium ion battery anode and the lithium ion battery are prepared by adding a titanium suboxide additive to improve the conductivity of an electrode, the titanium suboxide has compatibility with an electrode active material oxide, and the coulombic efficiency of the battery is improved through a synergistic effect.
Detailed Description
The present invention is described in detail below.
The lithium ion battery anode taking the titanium suboxide as the additive comprises an anode plate and the titanium suboxide additive positioned on the anode plate; the positive plate is a ternary positive electrode of lithium iron phosphate, lithium cobaltate and nickel cobalt manganese;
the preparation method of the anode comprises the following steps: mixing an active substance, a titanium suboxide additive compound, a conductive agent and a binder according to a mass ratio of (16-18): 1-2, adding an organic solvent in the mixing process, uniformly stirring to obtain a slurry, uniformly coating the slurry on an aluminum current collector, wherein the thickness of the slurry coated on the positive plate is 100-400 microns, and drying in vacuum at 110 ℃ for 12 hours to obtain the positive plate; wherein the adding amount of the added organic solvent is 10-30 times of the mass of the added active substances.
The titanium suboxide compound is prepared by the following process: ultrasonically dispersing an active substance and titanium monoxide in ethanol, and centrifugally separating out a titanium monoxide compound; or directly mixing titanium suboxide and active substances according to a certain proportion, and uniformly grinding by hand to obtain the titanium suboxide compound. Wherein the mass fraction of the titanium suboxide is 5 to 20 percent of the total mass of the compound.
The conductive agent is one or more of conductive carbon black, Ketjen black, Super P, Super C65, acetylene black, graphite, hollow carbon spheres, carbon nanotubes and biomass carbon.
The binder is PVDF (polyvinylidene fluoride).
The organic solvent is NMP (N-methylpyrrolidone).
The invention provides a lithium ion battery taking titanium monoxide as an additive, which comprises the lithium ion battery anode taking titanium monoxide as the additive.
The lithium ion battery taking titanium monoxide as the additive comprises a positive electrode shell 5, a positive electrode plate 4 containing the titanium monoxide additive, a diaphragm 3, electrolyte, a lithium plate 2 and a negative electrode shell 1 from bottom to top.
The preparation method of the lithium ion battery with the titanium monoxide as the additive comprises the following steps:
1) preparing a titanium suboxide compound;
2) preparing a lithium ion battery anode taking titanium monoxide as an additive;
3) assembling the battery: assembling in inert atmosphere to obtain the lithium ion battery taking titanium suboxide as an additive.
Example 1
The lithium ion battery with titanium suboxide as the positive electrode additive includes positive electrode containing titanium suboxide additive, diaphragm, electrolyte and metal lithium negative electrode.
Preparation of a composite containing a titanium suboxide additive: titanium sub-oxide and positive electrode active material LiCoO2According to the following steps of 16: 1, ultrasonically dispersing in ethanol for 2 hours, and centrifugally separating out compound precipitate; vacuum drying the titanium suboxide compound at 110 deg.C for 12h to obtain titanium suboxide and LiCoO2The complex of (1).
Preparation of the positive electrode containing the titanium suboxide additive: titanium suboxide and LiCoO2The acetylene black conductive agent and the binder (PVDF) are mixed in a mass ratio of 17:1:2, mixing the materials, adding an organic solvent N-methyl pyrrolidone in the mixing process, and stirring for 1h to obtain slurry; then evenly coating the slurry on an aluminum foil current collector by using an adjustable scraper; and (3) placing the current collector in a vacuum drying oven at 60 ℃ for drying for 24h, and cutting the current collector into small wafers with the diameter of 1.2cm by using a tablet machine, namely the positive electrode wafers containing the titanium suboxide additive.
Assembling the battery: and in the glove box filled with argon, sequentially assembling an anode shell, an anode sheet containing a titanium suboxide additive, a diaphragm, electrolyte, a metal lithium cathode and a cathode shell from bottom to top to form the button cell.
And (3) testing the electrochemical performance of the battery: at room temperature, the battery was subjected to a charge and discharge test using a blue LAND CT2001A charge and discharge instrument manufactured by Wuhan blue electricity Co. The first discharge specific capacity of the battery at 0.2C is 153mAh g-1And the specific capacity after 100 cycles is 145mAh g-1The average coulombic efficiency is higher than 97%; the first discharge specific capacity of the battery at 1C is 132 mAh.g-1The specific capacity after 200 cycles is 120mAh g-1The average coulombic efficiency was higher than 99%.
Example 2
The lithium ion battery with titanium suboxide as the positive electrode additive includes positive electrode containing titanium suboxide additive, diaphragm, electrolyte and metal lithium negative electrode.
Preparation of the positive electrode containing the titanium suboxide additive: the anode active material LiFePO4Titanium oxide, an acetylene black conductive agent, and a binder (PVDF) in a mass ratio of 16: 1: 1:2, mixing the materials, adding an organic solvent N-methyl pyrrolidone in the mixing process, and stirring for 1h to obtain slurry; then evenly coating the slurry on an aluminum foil current collector by using an adjustable scraper; and (3) placing the current collector in a vacuum drying oven at 60 ℃ for drying for 24h, and cutting the current collector into small wafers with the diameter of 1.2cm by using a tablet machine, namely the positive electrode wafers containing the titanium suboxide additive.
Assembling the battery: and in the glove box filled with argon, sequentially assembling an anode shell, an anode sheet containing a titanium suboxide additive, a diaphragm, electrolyte, a metal lithium cathode and a cathode shell from bottom to top to form the button cell.
The electrochemical performance of the cell was tested as in example 1. The first discharge specific capacity of the battery at 0.2C is 157mAh g-1The specific capacity after 100 cycles is 134mAh g-1The average coulombic efficiency was higher than 99%.
Example 3
The lithium ion battery with titanium suboxide as the positive electrode additive includes positive electrode containing titanium suboxide additive, diaphragm, electrolyte and metal lithium negative electrode.
Preparation of the positive electrode containing the titanium suboxide additive: the anode active material LiFePO4Titanium oxide, an acetylene black conductive agent, and a binder (PVDF) in a mass ratio of 16: 1.5: 1: 1.5, mixing the materials, adding an organic solvent N-methyl pyrrolidone in the mixing process, and stirring for 1 hour to obtain slurry; then evenly coating the slurry on an aluminum foil current collector by using an adjustable scraper; and (3) placing the current collector in a vacuum drying oven at 60 ℃ for drying for 24h, and cutting the current collector into small wafers with the diameter of 1.2cm by using a tablet machine, namely the positive electrode wafers containing the titanium suboxide additive.
Assembling the battery: and in the glove box filled with argon, sequentially assembling an anode shell, an anode sheet containing a titanium suboxide additive, a diaphragm, electrolyte, a metal lithium cathode and a cathode shell from bottom to top to form the button cell.
The electrochemical performance of the cell was tested as in example 1. The first discharge specific capacity of the battery at 0.2C is 156mAh g-1And the specific capacity after 100 cycles is 153mAh g-1The average coulombic efficiency was higher than 99%.
Example 4
The lithium ion battery with titanium suboxide as the positive electrode additive includes positive electrode containing titanium suboxide additive, diaphragm, electrolyte and metal lithium negative electrode.
Preparation of the positive electrode containing the titanium suboxide additive: the anode active material LiFePO4Titanium oxide, an acetylene black conductive agent, and a binder (PVDF) in a mass ratio of 16:2: 1:1, mixing materials, adding an organic solvent N-methyl pyrrolidone in the mixing process, and stirring for 1h to obtain slurry; then evenly coating the slurry on an aluminum foil current collector by using an adjustable scraper; and (3) placing the current collector in a vacuum drying oven at 60 ℃ for drying for 24h, and cutting the current collector into small wafers with the diameter of 1.2cm by using a tablet machine, namely the positive electrode wafers containing the titanium suboxide additive.
Assembling the battery: and in the glove box filled with argon, sequentially assembling an anode shell, an anode sheet containing a titanium suboxide additive, a diaphragm, electrolyte, a metal lithium cathode and a cathode shell from bottom to top to form the button cell.
The electrochemical performance of the cell was tested as in example 1. 0.2C time batteryThe first discharge specific capacity is 141mAh g-1The specific capacity after 100 cycles is 137mAh g-1The average coulombic efficiency was higher than 99%.
Example 5
The lithium ion battery with titanium suboxide as the positive electrode additive includes positive electrode containing titanium suboxide additive, diaphragm, electrolyte and metal lithium negative electrode.
Preparation of the positive electrode containing the titanium suboxide additive: LiNi as positive electrode active material0.5Co0.2Mn0.3O2Titanium oxide, an acetylene black conductive agent, and a binder (PVDF) in a mass ratio of 16: 1: 1:2, mixing the materials, adding an organic solvent N-methyl pyrrolidone in the mixing process, and stirring for 1h to obtain slurry; then evenly coating the slurry on an aluminum foil current collector by using an adjustable scraper; and (3) placing the current collector in a vacuum drying oven at 60 ℃ for drying for 24h, and cutting the current collector into small wafers with the diameter of 1.2cm by using a tablet machine, namely the positive electrode wafers containing the titanium suboxide additive.
Assembling the battery: and in the glove box filled with argon, sequentially assembling an anode shell, an anode sheet containing a titanium suboxide additive, a diaphragm, electrolyte, a metal lithium cathode and a cathode shell from bottom to top to form the button cell.
The electrochemical performance of the cell was tested as in example 1. The first discharge specific capacity of the battery at 0.2C is 132mAh g-1After 20 times of circulation, the specific capacity is unchanged, and the average coulombic efficiency is higher than 99%.
Comparative example 1
The lithium ion battery without additive includes positive pole, diaphragm, electrolyte and metal lithium negative pole.
Preparation of the positive electrode: LiCoO as positive electrode active material2Mixing materials, an acetylene black conductive agent and a binder (PVDF) according to a mass ratio of 8:1:1, adding an organic solvent N-methyl pyrrolidone in the mixing process, and stirring for 1h to obtain slurry; then evenly coating the slurry on an aluminum foil current collector by using an adjustable scraper; and (3) placing the current collector in a vacuum drying oven at 60 ℃ for drying for 24h, and cutting the current collector into positive plates with the diameter of 1.2cm by using a tablet machine.
Assembling the battery: and in the glove box filled with argon, sequentially assembling an anode shell, an anode sheet containing a titanium suboxide additive, a diaphragm, electrolyte, a metal lithium cathode and a cathode shell from bottom to top to form the button cell.
The electrochemical performance of the cell was tested as in example 1. The first discharge specific capacity of the battery at 0.2C is 137 mAh.g-1The specific capacity after 100 cycles is 112mAh g-1The average coulombic efficiency is higher than 97%; the first discharge specific capacity of the battery at 1C is 121 mAh.g-1The specific capacity after 200 cycles is 111mAh g-1The average coulombic efficiency was higher than 98%.
Comparative example 2
The lithium ion battery without additive includes positive pole, diaphragm, electrolyte and metal lithium negative pole.
Preparation of the positive electrode: the anode active material LiFePO4Mixing materials, an acetylene black conductive agent and a binder (PVDF) according to a mass ratio of 8:1:1, adding an organic solvent N-methyl pyrrolidone in the mixing process, and stirring for 1h to obtain slurry; then evenly coating the slurry on an aluminum foil current collector by using an adjustable scraper; and (3) placing the current collector in a vacuum drying oven at 60 ℃ for drying for 24h, and cutting the current collector into positive plates with the diameter of 1.2cm by using a tablet machine.
Assembling the battery: and in the glove box filled with argon, sequentially assembling an anode shell, an anode sheet containing a titanium suboxide additive, a diaphragm, electrolyte, a metal lithium cathode and a cathode shell from bottom to top to form the button cell.
The electrochemical performance of the cell was tested as in example 1. The first discharge specific capacity of the battery at 0.2C is 138 mAh.g-1And the specific capacity after 100 cycles is 122mAh g-1The average coulombic efficiency was higher than 99%.
Comparative example 3
The lithium ion battery without additive includes positive pole, diaphragm, electrolyte and metal lithium negative pole.
Preparation of the positive electrode: LiNi as positive electrode active material0.5Co0.2Mn0.3O2Mixing materials, an acetylene black conductive agent and a binder (PVDF) according to a mass ratio of 8:1:1, adding an organic solvent N-methyl pyrrolidone in the mixing process, and stirring for 1h to obtain slurry; then useThe adjustable scraper uniformly coats the slurry on the aluminum foil current collector; and (3) placing the current collector in a vacuum drying oven at 60 ℃ for drying for 24h, and cutting the current collector into positive plates with the diameter of 1.2cm by using a tablet machine.
Assembling the battery: and in the glove box filled with argon, sequentially assembling an anode shell, an anode sheet containing a titanium suboxide additive, a diaphragm, electrolyte, a metal lithium cathode and a cathode shell from bottom to top to form the button cell.
The electrochemical performance of the cell was tested as in example 1. The first discharge specific capacity of the battery at 0.2C is 117 mAh.g-1After 20 cycles, the specific capacity is unchanged, and the average coulombic efficiency is higher than 98%.
Example 6
1) Preparation of a complex of active substance and titanium suboxide: titanium sub-oxide and positive electrode active material LiCoO2Mixing, ultrasonically dispersing in ethanol for 2h, and centrifuging to separate out compound precipitate; and (3) drying the titanium suboxide compound at 110 ℃ for 12h in vacuum to obtain the compound of the titanium suboxide and the positive active material. Wherein, the titanium oxide accounts for 5 percent of the total mass of the compound of the active material and the titanium oxide.
2) Mixing a composite of an active substance and titanium protoxide, a conductive agent (a mixture of Ketjen black, Super P, Super C65 and acetylene black) and polyvinylidene fluoride in a mass ratio of 16:2:2, adding N-methyl pyrrolidone, stirring for 1h to obtain slurry, uniformly coating the slurry on an aluminum foil current collector by using an adjustable scraper, drying for 24h in a vacuum drying box at 60 ℃, and cutting into small round pieces with the diameter of 1.2cm by using a tablet press to obtain the lithium ion battery anode with the titanium protoxide as an additive. The amount of N-methylpyrrolidone added is 30 times of the amount of the composite of the active substance and the titanium oxide.
3) Assembling the battery: assembling the positive electrode shell, the lithium ion battery positive electrode taking titanium suboxide as an additive, the diaphragm, the electrolyte, the metal lithium negative electrode and the negative electrode shell from bottom to top in an inert atmosphere to obtain the lithium ion battery taking titanium suboxide as the lithium ion battery positive electrode of the additive.
Example 7
1) Preparation of a complex of active substance and titanium suboxide: titanium oxide and a positive electrode active material LiNi0.5Co0.2Mn0.3O2Mixing, ultrasonically dispersing in ethanol for 2h, and centrifuging to separate out compound precipitate; and (3) drying the titanium suboxide compound at 110 ℃ for 12h in vacuum to obtain the compound of the titanium suboxide and the positive active material. Wherein, the titanium oxide accounts for 20 percent of the total mass of the compound of the active material and the titanium oxide.
2) Mixing a composite of an active substance and titanium suboxide, a conductive agent (a mixture of graphite, hollow carbon spheres, carbon nano tubes and biomass carbon) and polyvinylidene fluoride in a mass ratio of 18:1:1, adding N-methyl pyrrolidone, stirring for 1h to obtain slurry, uniformly coating the slurry on an aluminum foil current collector by using an adjustable scraper, drying the slurry in a vacuum drying box at 60 ℃ for 24h, and cutting the slurry into small round pieces with the diameter of 1.2cm by using a tablet press to obtain the lithium ion battery anode taking the titanium suboxide as an additive. The amount of N-methylpyrrolidone added is 10 times of the amount of the composite of the active substance and the titanium oxide.
3) Assembling the battery: assembling the positive electrode shell, the lithium ion battery positive electrode taking titanium suboxide as an additive, the diaphragm, the electrolyte, the metal lithium negative electrode and the negative electrode shell from bottom to top in an inert atmosphere to obtain the lithium ion battery taking titanium suboxide as the lithium ion battery positive electrode of the additive.
Example 8
1) Preparation of a complex of active substance and titanium suboxide: titanium sub-oxide and a positive electrode active material LiFePO4Mixing, ultrasonically dispersing in ethanol for 2h, and centrifuging to separate out compound precipitate; and (3) drying the titanium suboxide compound at 110 ℃ for 12h in vacuum to obtain the compound of the titanium suboxide and the positive active material. Wherein, the titanium oxide accounts for 10 percent of the total mass of the compound of the active material and the titanium oxide.
2) Mixing a compound of an active substance and titanium monoxide, acetylene black and polyvinylidene fluoride according to a mass ratio of 17:1:2, adding N-methyl pyrrolidone, stirring for 1h to obtain slurry, uniformly coating the slurry on an aluminum foil current collector by using an adjustable scraper, drying the slurry in a vacuum drying oven at 60 ℃ for 24h, and cutting the slurry into small round pieces with the diameter of 1.2cm by using a tablet press to obtain the lithium ion battery anode with the titanium monoxide as an additive. The addition amount of the N-methylpyrrolidone is 20 times of the amount of the composite of the active substance and the titanium oxide.
3) Assembling the battery: assembling the positive electrode shell, the lithium ion battery positive electrode taking titanium suboxide as an additive, the diaphragm, the electrolyte, the metal lithium negative electrode and the negative electrode shell from bottom to top in an inert atmosphere to obtain the lithium ion battery taking titanium suboxide as the lithium ion battery positive electrode of the additive.

Claims (9)

1. The lithium ion battery positive electrode taking titanium suboxide as an additive is characterized by comprising a positive plate, wherein the positive plate is prepared by the following processes: mixing a compound of an active substance and titanium suboxide, a conductive agent and a binder according to a mass ratio of (16-18) to (1-2), then adding an organic solvent and uniformly mixing to obtain a slurry, coating the slurry on an aluminum current collector, and drying to obtain the lithium ion battery anode taking titanium suboxide as an additive.
2. The positive electrode of the lithium ion battery taking titanium monoxide as the additive according to claim 1, wherein the compound of the active material and the titanium monoxide is prepared by the following steps: ultrasonically dispersing titanium oxide and an active substance in ethanol, centrifuging, and drying to obtain a compound of the active substance and the titanium oxide; or mixing titanium oxide with the active substance, and uniformly grinding by hand to obtain a compound of the active substance and the titanium oxide; wherein, the titanium oxide is 5 to 20 percent of the total mass of the compound of the active substance and the titanium oxide.
3. The lithium ion battery positive electrode using titanium sub-oxide as the additive according to claim 1, wherein the conductive agent is one or more of conductive carbon black, ketjen black, Super P, Super C65, acetylene black, graphite, hollow carbon spheres, carbon nanotubes, and biomass carbon.
4. The positive electrode of the lithium ion battery using titanium suboxide as the additive according to claim 1, wherein the binder is polyvinylidene fluoride; the active material is LiCoO2、LiFePO4Or LiNi0.5Co0.2Mn0.3O2。
5. The positive electrode for a lithium ion battery using titanium monoxide as an additive according to claim 1, wherein the organic solvent is N-methylpyrrolidone.
6. The positive electrode for a lithium ion battery using titanium monoxide as an additive according to claim 1, wherein the amount of the organic solvent added is 10 to 30 times the amount of the composite material of the active material and titanium monoxide.
7. The positive electrode for a lithium ion battery using titanium monoxide as an additive according to claim 1, wherein the thickness of the slurry applied on the aluminum current collector is 100 to 400 μm.
8. A lithium ion battery based on the lithium ion battery anode taking titanium monoxide as an additive in any one of claims 1 to 7 is characterized by comprising an anode shell, the lithium ion battery anode taking titanium monoxide as an additive, a diaphragm, an electrolyte, a metallic lithium negative piece and a cathode shell from bottom to top.
9. A method for preparing a lithium ion battery having a positive electrode of a lithium ion battery containing titanium monoxide as an additive according to claim 8, comprising the steps of:
1) preparing a complex of an active material and titanium suboxide;
2) mixing a compound of an active substance and titanium suboxide, a conductive agent and a binder according to a mass ratio of (16-18) to (1-2), then adding an organic solvent and uniformly mixing to obtain slurry, coating the slurry on an aluminum current collector, and drying to obtain a lithium ion battery anode taking titanium suboxide as an additive;
3) assembling the battery: assembling the positive electrode shell, the lithium ion battery positive electrode taking titanium suboxide as an additive, the diaphragm, the electrolyte, the metal lithium negative electrode and the negative electrode shell from bottom to top in an inert atmosphere to obtain the lithium ion battery taking titanium suboxide as the lithium ion battery positive electrode of the additive.
CN202011607556.9A 2020-12-29 2020-12-29 Lithium ion battery anode with titanium suboxide as additive, battery and preparation method Pending CN112701290A (en)

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105489863A (en) * 2015-12-31 2016-04-13 长沙矿冶研究院有限责任公司 C/Ti4O7 composite nanofiber based lithium-sulfur battery positive electrode material and preparation method therefor
CN105932261A (en) * 2016-06-30 2016-09-07 湖南桑顿新能源有限公司 Lithium manganate cathode material and preparation method thereof
CN105977466A (en) * 2016-06-30 2016-09-28 湖南桑顿新能源有限公司 Conductive oxide coated lithium ion battery tri-element anode material and preparation method thereof
JP2017152294A (en) * 2016-02-26 2017-08-31 Tdk株式会社 Positive electrode active material and lithium ion secondary battery
CN109713313A (en) * 2018-12-29 2019-05-03 珠海光宇电池有限公司 A kind of lithium-sulphur cell positive electrode piece and preparation method thereof and lithium-sulfur cell
CN110061226A (en) * 2019-05-07 2019-07-26 湖南金富力新能源股份有限公司 The positive electrode of sub- titanium-oxide-coated, the preparation method of positive electrode and lithium ion battery
JP2020202023A (en) * 2019-06-06 2020-12-17 トヨタ自動車株式会社 Positive electrode of secondary battery, and secondary battery using the same

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105489863A (en) * 2015-12-31 2016-04-13 长沙矿冶研究院有限责任公司 C/Ti4O7 composite nanofiber based lithium-sulfur battery positive electrode material and preparation method therefor
JP2017152294A (en) * 2016-02-26 2017-08-31 Tdk株式会社 Positive electrode active material and lithium ion secondary battery
CN105932261A (en) * 2016-06-30 2016-09-07 湖南桑顿新能源有限公司 Lithium manganate cathode material and preparation method thereof
CN105977466A (en) * 2016-06-30 2016-09-28 湖南桑顿新能源有限公司 Conductive oxide coated lithium ion battery tri-element anode material and preparation method thereof
CN109713313A (en) * 2018-12-29 2019-05-03 珠海光宇电池有限公司 A kind of lithium-sulphur cell positive electrode piece and preparation method thereof and lithium-sulfur cell
CN110061226A (en) * 2019-05-07 2019-07-26 湖南金富力新能源股份有限公司 The positive electrode of sub- titanium-oxide-coated, the preparation method of positive electrode and lithium ion battery
JP2020202023A (en) * 2019-06-06 2020-12-17 トヨタ自動車株式会社 Positive electrode of secondary battery, and secondary battery using the same

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
YUNKE WANG等: "Enhancing the rate performance of high-capacity LiNi0.8Co0.15Al0.15O2 cathode materials by using Ti4O7 as a conductive additive", 《JOURNAL OF ENERGY STORAGE》 *

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