CN117410485A - Method for improving fluidity of lithium titanate slurry, lithium titanate slurry and application - Google Patents

Method for improving fluidity of lithium titanate slurry, lithium titanate slurry and application Download PDF

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Publication number
CN117410485A
CN117410485A CN202311373984.3A CN202311373984A CN117410485A CN 117410485 A CN117410485 A CN 117410485A CN 202311373984 A CN202311373984 A CN 202311373984A CN 117410485 A CN117410485 A CN 117410485A
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China
Prior art keywords
lithium titanate
slurry
mixture
stirring
titanate slurry
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CN202311373984.3A
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Chinese (zh)
Inventor
徐能强
高峰
张要枫
赵冬梅
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Hubei Titanium Era New Energy Co Ltd
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Hubei Titanium Era New Energy Co Ltd
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Priority to CN202311373984.3A priority Critical patent/CN117410485A/en
Publication of CN117410485A publication Critical patent/CN117410485A/en
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/48Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485Selection 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
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • H01M10/0525Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/13Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139Processes of manufacture
    • H01M4/1391Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)

Abstract

The invention discloses a method for improving fluidity of lithium titanate slurry, the lithium titanate slurry and application thereof, and belongs to the technical field of manufacturing methods of electrodes. The method comprises the following steps: mixing lithium titanate, a binder and a conductive agent until all components are uniformly dispersed to obtain a mixture; and controlling the feeding speed of the mixture, performing ball milling treatment on the mixture, adding a solvent in the process for dilution, stirring the ball-milled mixture and a dispersing agent, and controlling the viscosity of the slurry to obtain the lithium titanate slurry. Simple process, convenient implementation and high production efficiency. The prepared lithium titanate slurry has more stable slurry adhesiveness, better leveling effect in the coating process, less defects of the battery in the preparation of the lithium battery, and good electrical property.

Description

Method for improving fluidity of lithium titanate slurry, lithium titanate slurry and application
Technical Field
The invention relates to the technical field of manufacturing methods of electrodes, in particular to a method for improving fluidity of lithium titanate slurry, the lithium titanate slurry and application.
Background
With the rapid development of the lithium battery industry, the energy is currently availableThe density lifting mode is mainly realized by increasing the monomer energy density lifting and reducing the weight of the module, and the main core technology for lifting the monomer cell energy density is the lifting of the performance of a material chemical system in terms of material system selection, cell structure design and the like for ensuring certain mechanical and physical strength and for the selection of lighter materials with cautions. The material system mainly comprises four main materials of a positive electrode material, a negative electrode material, a diaphragm and electrolyte, the coating thickness of the high-capacity negative electrode is increased by doubling the lithium price in a short time, so that the cost is higher and higher, and lithium dendrite growth is caused by uneven deposition in the charge and discharge cyclic process of lithium, so that a certain potential safety hazard is caused to the safety problem. Lithium titanate (Li) 4 Ti 5 O 12 ) The method is applicable to the stirring process, has the effect of improving the leveling effect of the lithium titanate material in the coating process, ensures that the slurry cohesiveness is more stable and greatly improves the production efficiency, and has important significance.
Disclosure of Invention
In view of the above-mentioned drawbacks of the prior art, in a first aspect of the present invention, there is provided a method for improving fluidity of lithium titanate slurry, comprising the steps of:
mixing lithium titanate, a binder and a conductive agent until all components are uniformly dispersed to obtain a mixture; and controlling the feeding speed of the mixture, performing ball milling treatment on the mixture, adding a solvent in the process for dilution, stirring the ball-milled mixture and a dispersing agent, and controlling the viscosity of the slurry to obtain the lithium titanate slurry.
Preferably, the content of each component in mass percent is as follows: 91.64 to 94.14 percent of lithium titanate, 1.5 to 4 percent of binder, 2.0 to 4.0 percent of conductive agent and 0.2 to 0.36 percent of dispersing agent.
Preferably, the binder is polyvinylidene fluoride (PVDF), the solvent is N-methyl pyrrolidone, and the dispersing agent comprises at least one of oxalic acid, citric acid and folic acid; the conductive agent is conductive carbon black and carbon nano tubes, and the mass ratio of the conductive agent to the carbon nano tubes is 1-2: 2.5.
preferably, the lithium titanate, the binder and the conductive agent are mixed by stirring, the stirring speed is 350-500 rpm, and the stirring time is 3-5 h.
Preferably, the feeding speed of the mixture is 5-8 kg/min.
Preferably, the ball milling treatment speed is 450-700 rpm, and the treatment time is 1-2 h.
Preferably, the viscosity is in the range of 6000 to 14000 mpa.s.
Preferably, planetary stirring is adopted in the stirring treatment, the revolution speed is 10-20 rpm, the dispersion speed is 1200-2200 rpm, and the treatment time is 2-4 h.
Based on the technical scheme, the method can improve the structural spinel, and the slurry powder is combined to ensure that the contact and storage performance of the spinel are more uniform. The contact property between powder material particles is effectively improved in slurry circulation flow stirring, so that the capability of maintaining viscosity is improved under the condition that stirring shearing stress is not generated during storage, floating among particles is more stable, the composition of upper powder and lower powder of the slurry is hardly changed with time, and the storage performance is improved. The method can also improve current collector foil surface defects by reducing the effect of reagglomeration leveling between solids when the negative electrode slurry composition is coated on a current collector. The ion intercalation and deintercalation in the ion storage battery is facilitated, and the charge and discharge speed is improved. The fluidity of the slurry under the condition of long-time uncoated state is reduced, so that the composite lithium titanate battery has excellent charging performance.
In a second aspect of the invention, a lithium titanate slurry with good fluidity is provided, and the lithium titanate slurry is prepared by the method provided by the first aspect of the invention.
In a third aspect of the invention, there is provided the use of the lithium titanate slurry of the second aspect of the invention, in particular the use of the lithium titanate slurry as a negative electrode slurry in the preparation of a battery.
Preferably, the application comprises the steps of:
preparing positive electrode slurry:
mixing a positive electrode material, a binder, a conductive agent and a solvent to prepare positive electrode slurry;
preparing a pole piece:
respectively coating positive electrode slurry and lithium titanate slurry on the pole pieces, and preparing positive and negative pole pieces through slitting, rolling and baking;
and (3) battery assembly:
and assembling the positive plate, the negative plate and the diaphragm, injecting electrolyte, and then preparing the battery through pre-forming.
Compared with the prior art, the invention has the following advantages and beneficial effects:
the invention provides a method for improving the fluidity of lithium titanate slurry, which has simple process and convenient implementation and can improve the production efficiency.
The invention provides the lithium titanate slurry with good fluidity, which has more stable slurry cohesiveness and better leveling effect in the coating process.
The invention provides application of lithium titanate slurry with good fluidity, and the prepared lithium battery with good fluidity has fewer defects and good electrical property.
Detailed Description
The invention is further illustrated by means of the following examples, which are not intended to limit the scope of the invention. The experimental methods, in which specific conditions are not noted in the following examples, were selected according to conventional methods and conditions, or according to the commercial specifications.
In the following examples:
ternary material Li (NiCoMn) O 2 The specific surface area is less than or equal to 0.270m 2 Per gram, tap density is not less than 0.80g/cm 3 The moisture content is less than or equal to 800ppm;
polyvinylidene fluoride (PVDF) with a molecular weight of 90-110 ten thousand.
Example 1
A lithium ion battery adopts a method for improving the fluidity of lithium titanate slurry, and the preparation process is as follows:
proportioning parameters of the cathode raw materials: 92.45wt.% lithium titanate content, 3.5wt.% conductive agent (consisting of 2.5wt.% conductive carbon black and 1wt.% carbon nanotubes), 3.85wt.% polyvinylidene fluoride (PVDF), 0.2wt.% oxalic acid;
slowly stirring lithium titanate, a binder and dry conductive agent powder in a sealed tank body at a speed of 350rpm for 3-5 hours to uniformly disperse the materials, so as to obtain a mixture; then, the mixture is dropped into a lower stirring tank at a feeding speed of 5kg/min, ball milling treatment is carried out on the mixture by adopting a high-energy ball mill, ball milling is carried out for 2 hours at a speed of 450rpm in a circulating mode, N-methylpyrrolidone (NMP) with the mass of 25% of the mixture is added in the process for dilution, planetary stirring is carried out on the ball-milled mixture and oxalic acid, stirring is carried out for 4 hours at a revolution speed of 10rpm and a dispersion speed of 1200rpm, and the low-viscosity lithium titanate slurry with the viscosity of 6000-9000 mpa.s is obtained after stirring;
preparing positive electrode slurry:
proportioning parameters of the positive electrode raw materials: ternary material Li (NiCoMn) O 2 Content 94.49wt.%, conductive agent 2.5wt.% (consisting of conductive carbon black 1.5wt.% and carbon nanotubes 1 wt.%), polyvinylidene fluoride (PVDF) 3.01wt.%;
ternary material Li (NiCoMn) O 2 Uniformly mixing polyvinylidene fluoride (PVDF), a conductive agent and N-methyl pyrrolidone (NMP), regulating the solid content to 55wt.%, stirring for 4 hours at a revolution rate of 35rpm and a dispersion rate of 1800rpm, and then carrying out evacuation and degassing treatment for 0.5 hour under the conditions of slow stirring at the revolution rate of 10rpm and the dispersion rate of 500rpm to obtain positive electrode slurry;
preparing a pole piece:
coating positive electrode slurry and lithium titanate slurry on carbon-coated aluminum foil with the thickness of 12-15 mu m, setting parameter coating (the coating speed is 5-20 m/min, the oven temperature is 65-110 ℃, the environment temperature is 25+/-5 ℃, the environment relative humidity is less than 20% RH), the rolling coefficient (the positive electrode is 3.4/negative electrode is 2.0, the rolling speed is 10-20 m/min, the pressure is 6-20 MPa), and the baking parameter (the baking time is 28h, the temperature is 120+/-2 ℃), and obtaining a positive plate and a negative plate after coating, rolling, cutting and baking;
and (3) battery assembly:
after the positive plate, the diaphragm (20 mu m thick PP dry diaphragm) and the negative plate are assembled by a winding process, the positive plate, the diaphragm and the negative plate are put into a square cylindrical shell to be subjected to three-edge sealing welding and sealing, and lithium hexafluorophosphate (LiPF) is injected 6 ) The electrolyte is prepared into a battery through pre-formation, and the lithium ion battery is prepared.
Example 2
The preparation flow of the lithium ion battery in this embodiment is basically the same as that in embodiment 1, except that in the preparation process of the lithium titanate slurry in this embodiment, N-methylpyrrolidone with a mass of 20% of the mixture is added for dilution, and finally the lithium titanate slurry with a viscosity of 9000-11000 mpa.s is obtained.
Example 3
The preparation flow of the lithium ion battery in this embodiment is basically the same as that in embodiment 1, except that in the preparation process of the lithium titanate slurry in this embodiment, N-methylpyrrolidone with a mass of 15% of the mixture is added for dilution, and finally the lithium titanate slurry with a viscosity of 11000-14000 mpa.s is obtained.
Example 4
The preparation process of the control group lithium ion battery is basically the same as that of the embodiment 1, except that in the preparation process of the lithium titanate slurry of the control group, the lithium titanate is directly mixed with the conductive agent, the binder and the dispersing agent, and then N-methyl pyrrolidone with the mass of 10% of the mixture is added for dilution, so that the lithium titanate slurry with the viscosity of 14000-17000 mpa.s is finally obtained.
The lithium ion batteries of examples 1 to 3 were used as experimental groups, and battery performance tests were performed in combination with control groups. The first coulombic efficiency of each lithium ion battery was tested by the formula: (charge capacity/discharge capacity) ×100% statistics. And the cycle performance of the battery is tested (1C constant current and voltage, 1C constant current discharges to the set voltage value, the charge and discharge voltage is limited to 1.5V-2.85V, the constant voltage cut-off current is 0.01C, and C represents the rated capacity value of the battery). After testing the battery performance, the peel strength of the negative electrode sheet was measured by a general method in the art, and then the binding capacity of the lithium titanate slurry and the electrode sheet was measured. The test results are shown in Table 1.
Table 1:
the test results show that the lithium titanate slurry prepared by ball milling and other treatments has strong bonding capability with the pole piece and high peel strength, and even if the viscosity of the slurry is lower than that of a control group, the slurry can still keep the viscosity so that floating among particles is more stable, and better effects are achieved on bonding with the pole piece and electrical properties. The method can improve spinel with a material structure, and improve the surface defects of the current collector foil by reducing the reagglomeration leveling effect among solids when the negative electrode slurry composition is coated on the current collector. The ion intercalation and deintercalation in the ion storage battery is facilitated, and the charge and discharge speed is improved.
The foregoing describes in detail preferred embodiments of the present invention. It should be understood that numerous modifications and variations can be made in accordance with the concepts of the invention by one of ordinary skill in the art without undue burden. Therefore, all technical solutions which can be obtained by logic analysis, reasoning or limited experiments based on the prior art by the person skilled in the art according to the inventive concept shall be within the scope of protection defined by the claims.

Claims (10)

1. A method for improving the fluidity of lithium titanate slurry, comprising the steps of:
mixing lithium titanate, a binder and a conductive agent until all components are uniformly dispersed to obtain a mixture; and controlling the feeding speed of the mixture, performing ball milling treatment on the mixture, adding a solvent in the process for dilution, stirring the ball-milled mixture and a dispersing agent, and controlling the viscosity of the slurry to obtain the lithium titanate slurry.
2. The method according to claim 1, characterized in that: the content of each component in mass percent is as follows: 91.64 to 94.14 percent of lithium titanate, 1.5 to 4 percent of binder, 2.0 to 4.0 percent of conductive agent and 0.2 to 0.36 percent of dispersing agent.
3. The method according to claim 1, characterized in that: the adhesive is polyvinylidene fluoride, the solvent is N-methyl pyrrolidone, and the dispersing agent comprises at least one of oxalic acid, citric acid and folic acid; the conductive agent is conductive carbon black and carbon nano tubes, and the mass ratio of the conductive agent to the carbon nano tubes is 1-2: 2.5.
4. the method according to claim 1, characterized in that: the mixing of the lithium titanate, the binder and the conductive agent is realized by stirring, the stirring speed is 350-500 rpm, and the stirring time is 3-5 h.
5. The method according to claim 1, characterized in that: the feeding speed of the mixture is 5-8 kg/min.
6. The method according to claim 1, characterized in that: the ball milling treatment speed is 450-700 rpm, and the treatment time is 1-2 h.
7. The method according to claim 1, characterized in that: the viscosity is in the range of 6000 to 14000 mpa.s.
8. The method according to claim 1, characterized in that: the stirring treatment adopts planetary stirring, the revolution speed is 10-20 rpm, the dispersion speed is 1200-2200 rpm, and the treatment time is 2-4 h.
9. A lithium titanate slurry, characterized in that: the method according to any one of claims 1 to 8.
10. Use of the lithium titanate slurry of claim 9, wherein: the application of lithium titanate slurry as negative electrode slurry in the preparation of batteries.
CN202311373984.3A 2023-10-23 2023-10-23 Method for improving fluidity of lithium titanate slurry, lithium titanate slurry and application Pending CN117410485A (en)

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Application Number Priority Date Filing Date Title
CN202311373984.3A CN117410485A (en) 2023-10-23 2023-10-23 Method for improving fluidity of lithium titanate slurry, lithium titanate slurry and application

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202311373984.3A CN117410485A (en) 2023-10-23 2023-10-23 Method for improving fluidity of lithium titanate slurry, lithium titanate slurry and application

Publications (1)

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CN117410485A true CN117410485A (en) 2024-01-16

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