CN107565155B - Lithium ion battery - Google Patents

Lithium ion battery Download PDF

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CN107565155B
CN107565155B CN201710728385.7A CN201710728385A CN107565155B CN 107565155 B CN107565155 B CN 107565155B CN 201710728385 A CN201710728385 A CN 201710728385A CN 107565155 B CN107565155 B CN 107565155B
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lithium ion
ion battery
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渠立刚
吴子文
颜雪冬
周侣佳
姜影影
胡丽娜
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Ningbo Vico Amperex Technology Ltd
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    • 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
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

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Abstract

The invention relates to a lithium ion battery, in particular to a lithium ion battery and a preparation method thereof, belonging to the technical field of energy materials. The lithium ion battery comprises a positive electrode, a negative electrode, a diaphragm, organic electrolyte and a battery shell, wherein the positive electrode comprises the following components in parts by weight: positive electrode active material: 85-95 parts of a conductive agent: 2-5 parts of PVDF binder: 5-10 parts, PVP reagent: 5-10 parts, PEG: 110-130 parts of titanium difluorooxide: 5-10 parts. The invention adds the PVP reagent into the anode of the lithium ion battery, and simultaneously adjusts the content of other components, so that the anode slurry has proper viscosity, good fluidity and dispersibility, reduces the use amount of PEG and the homogenate time, greatly reduces the cost of the lithium ion battery and improves the process efficiency.

Description

Lithium ion battery
Technical Field
The invention relates to a lithium ion battery, in particular to a lithium ion battery and a preparation method thereof, belonging to the technical field of energy materials.
Background
The lithium ion secondary battery is used as a novel recyclable green energy source, has the advantages of high working voltage, high specific energy, long cycle life, wide working range, good safety performance, no memory effect and the like, and has wide application prospect in the fields of portable electronic products, electric vehicles, power supply systems of national defense and military equipment, photovoltaic energy storage, energy storage peak shaving power stations, uninterruptible power supplies and the like which are rapidly developed in recent years.
At present, the anode of a commercial lithium battery is mainly lithium cobaltate, but the large-scale application of the material is greatly limited by expensive synthesis method, environmental pollution, poor high-temperature thermal stability, easy generation of side reaction and the like, and the lithium cobaltate is one of key technologies for limiting the development of the lithium battery. Among the numerous lithium battery cathode materials which appear in succession, the olivine lithium iron phosphate has relatively high specific capacity (170mAh/g), stable working voltage (3.5V) and good cycle life, is rich in raw materials, low in price, good in thermal stability and chemical stability, environment-friendly and is one of green cathode materials with great development prospects at home and abroad at present. However, the lithium iron phosphate material also has the disadvantages of low conductivity, small lithium ion diffusion coefficient and the like, which affects the utilization rate of the material and hinders the practical application thereof.
Disclosure of Invention
The invention provides a lithium ion battery with proper viscosity and excellent electrochemical performance aiming at the problems.
The purpose of the invention is realized by the following technical scheme: a lithium ion battery comprises a positive electrode, a negative electrode, a diaphragm, an organic electrolyte and a battery shell, wherein the positive electrode comprises the following components in parts by weight: positive electrode active material: 85-95 parts of a conductive agent: 2-5 parts of PVDF binder: 5-10 parts, PVP reagent: 5-10 parts, PEG: 110-130 parts of titanium difluorooxide: 5-10 parts.
The invention can greatly improve the solid content of the slurry by adding the PVP reagent into the lithium ion battery anode, simultaneously enables the anode slurry to have proper viscosity, good fluidity and dispersibility by adjusting the content of other components, reduces the use amount of PEG and the homogenate time, greatly reduces the cost of the lithium ion battery and improves the process efficiency.
The PVP is chemically named polyvinylpyrrolidone, the molecule of the PVP is of a butyrolactam structure, the PVP contains a lactam group with a dipole moment of 40 and large polarity, and the PVP has the capability of hydrophilic and polar groups. At the same time, PVP has nonpolar methylene (-CH2-) and hypomethylene (-CH) groups on the molecular ring and in the long chain, so that it has lipophilicity. The molecular structure of PVP ensures that PVP has good solubility, solution characteristics and surface activity, and can be used as a solubilizer, an emulsifier, a lubricant, a dispersion stabilizer, a bonding regulator and the like. The PVP is added into the positive electrode material of the lithium ion battery, so that the surface appearance of the positive electrode plate is a layer of porous, and the penetration of the electrolyte is facilitated, so that the lithium ions are favorably transmitted to the surface layer. Lithium ions are easily transported, polarization during discharge is reduced, and discharge temperature is also lowered. Meanwhile, the slurry can realize high solid content, so that the raw material cost is reduced, the drying temperature is also reduced, and the energy is saved.
Preferably, the PVP reagent is one of PVPK15, PVPK17, PVPK25 and PVPK 30.
Preferably, the molecular weight of the PVP agent is between 3500 and 37900.
In the lithium ion battery, titanium difluorooxide with a hexagonal nano structure is also added. The titanium difluoride has good thermal stability, and can enable a lithium ion battery to keep the electrochemical property at high temperature. Meanwhile, the titanium dioxide difluoride with a special hexagonal nano structure can ensure the stability of a main body structure of the material in the insertion and extraction type reaction of lithium ions, and the material is very important for the anode material of a lithium ion battery. In addition, the nanometer-sized hexagonal titanium dioxide difluoride material enhances the reaction rate of lithium ion insertion and extraction, the electron transport performance, and relieves the reaction tension in particles, and the like, and is also greatly helpful for enhancing the electrochemical performance.
In the above lithium ion battery, the positive electrode active material is one or two of nano lithium iron phosphate and nano lithium manganese iron phosphate. The nano-scale positive active substance has superplasticity and creep property, so that the nano-scale positive active substance has stronger bearing capacity on volume change and reduces the glass transition temperature of the polymer electrolyte; meanwhile, the nano-scale substance has small size, can better release the stress of lithium intercalation and deintercalation and accelerate Li+Thereby improving the charge and discharge capacity.
Preferably, the positive electrode active material has a particle diameter of 0.5 to 3.0 μm and a specific surface area of 15 to 20m2.g-1The tap density is 1.0-1.2g/cm3The carbon content is 1.5-2.0%. The particle diameter, specific surface area, and uniformity of particles of the positive active material have a great influence on the preparation of the slurry and the capacity, cycle stability, and safety of the battery. The smaller the particle size, the larger the specific surface, the stronger the liquid absorption, and the more solvents are needed under the same viscosity condition; and the particles with large specific surface area are easy to agglomerate, so the slurry uniformity is worse when the particle size of the positive electrode active material is smaller under the same batching process condition. The positive electrode active material of the present invention using the above conditionsAnd the obtained battery positive electrode has excellent electrochemical performance.
In the above lithium ion battery, the conductive agent is a binary or ternary composite conductive agent, and the binary or ternary composite conductive agent comprises a fixed component and an additive component, and the weight parts are as follows: 0.5-2:1. Wherein the fixed component is carbon nano tube, and the additive component is one or two of vapor-grown carbon fiber, graphene, superconducting carbon black and conductive graphite. By utilizing the synergistic effect among different carbon conductive agents, the conductivity of the pole piece can be improved, the internal resistance of the battery is reduced, and the electrochemical performance of the battery is improved.
In the lithium ion battery, the binder is PVDF. PVDF is a nonpolar chain substance, has stable chemical properties, good bonding effect and dispersion effect, moderate and balanced solvent resistance, good forming processing agent, good toughness and high mechanical strength. In addition, PVDF can form an elastic network structure in the electrode substrate, in which the positive electrode active materials are not only in good contact with each other, facilitating electron conduction, but also against expansion and contraction due to charging and discharging of the electrode.
In addition, the invention adopts PEG as a dispersing agent, has good dispersing effect, can ensure that the positive active substance is uniformly distributed on the surface of the electrode, thereby improving the electronic conductivity and the electrochemical performance, and simultaneously, the addition of PEG can improve Li+The insertion and extraction activity ensures that the cycling stability and the large current performance of the battery are good.
A preparation method of a lithium ion battery comprises the following steps:
preparing a positive plate: dissolving a PVDF binder into PEG, adding raw materials for preparing the lithium ion battery, stirring to form anode slurry, coating the obtained anode slurry on an aluminum foil current collector, heating, drying and volatilizing the PEG, rolling and slitting the coated electrode, and drying in vacuum to obtain a lithium ion battery anode sheet;
preparing a negative plate: mixing and stirring the negative active substance, the negative conductive agent, the negative adhesive and the negative solvent uniformly to prepare negative slurry, and coating the negative slurry on a negative current collector to prepare a negative plate;
assembling: and (4) placing the positive plate, the diaphragm and the negative plate into a battery shell, and sealing the battery core after injecting the electrolyte to obtain the lithium ion battery.
In the preparation method of the lithium ion battery, the electrolyte comprises the following components in parts by weight: solutes, solvents and additives. The solute is lithium salt, and can be halide, sulfate, nitrate or oxalate of lithium; the solvent is one or more of water, N-methylpyrrolidone, N-methylformamide, alcohol, methanol, dimethyl sulfoxide, diethyl ether, ethyl acetate and tetrahydrofuran; the additive is one or two of thiophene, diphenyl ether and sodium difluoro oxalate borate.
In the above preparation method of the lithium ion battery, the diaphragm is one or more of an inorganic lithium ion conductive membrane, a neutral ion membrane, a cation exchange membrane or an anion exchange membrane.
In the preparation method of the lithium ion battery, the lithium ion battery raw material is subjected to vacuum baking treatment, the baking temperature is 100-120 ℃, and the baking time is 2-3 h. After vacuum drying, the viscosity and the fluidity of the obtained slurry are obviously improved, and in the slurry drawing process, the pole piece is uniformly coated by illumination inspection, which shows that the slurry is uniformly dispersed.
In the above method for manufacturing a lithium ion battery, the thickness of the aluminum foil current collector is 12 to 16 μm. The aluminum foil current collector has good conductivity and soft texture, a layer of oxide film can be formed on the surface, and the aluminum foil oxide layer is very compact due to high anode potential, so that the current collector can be prevented from being oxidized.
In the above preparation method of the lithium ion battery, the temperature for heating and drying is 120-130 ℃.
In the above method for manufacturing a lithium ion battery, the stirring step includes a slow stirring step and a high stirring step, and specifically includes: stirring at 500r/min for 1-1.5h at 35-40 deg.C, and stirring at 3000r/min for 4-5 h. The early-stage stirring is slow stirring, which is used for breaking the agglomerated anode material, ensuring the concentration of the slurry and simultaneously controlling the temperature within the range to ensure the full dissolution of PVDF; high-speed stirring is adopted in the later stage, so that the dispersibility of the slurry can be ensured, the obtained slurry is uniformly dispersed, and the subsequent rolling process is promoted.
Compared with the prior art, the invention has the following advantages:
1. the PVP reagent is added into the positive electrode of the lithium ion battery, and the content of other components is adjusted, so that the positive electrode slurry has proper viscosity and good fluidity and dispersibility, the use amount of PEG and the homogenate time are reduced, the cost of the lithium ion battery is greatly reduced, and the process efficiency is improved;
2. according to the invention, the difluorotitanium oxide is added into the battery anode material, so that the reaction rate and the electron transmission performance of lithium ion insertion and extraction can be enhanced, the reaction tension in particles can be alleviated, and the electrochemical performance of the battery can be greatly improved;
3. according to the invention, through a specific preparation method and limitation of a stirring mode, the concentration of the slurry can be ensured, the obtained slurry is uniformly dispersed, and the subsequent rolling process is promoted.
Detailed Description
The following are specific examples of the present invention and further describe the technical solutions of the present invention, but the present invention is not limited to these examples.
Table 1: components and parts by weight of lithium ion batteries of examples 1 to 5
Figure BDA0001386515180000071
Example 1
Preparing a positive plate: dissolving a PVDF binder into PEG, adding a raw material for preparing a lithium ion battery, stirring to form a positive slurry, coating the obtained positive slurry on an aluminum foil current collector, heating, drying and volatilizing the PEG, rolling and slitting the coated electrode, and then drying in vacuum to obtain a lithium ion battery positive plate, wherein the weight parts of the positive material are shown in Table 1, example 1, the lithium ion battery raw material is subjected to vacuum drying intervention treatment, the baking temperature is 100 ℃, the baking time is 2 hours, the thickness of the aluminum foil current collector is 12 microns, the heating and drying temperature is 120 ℃, and the stirring step comprises a slow stirring process and a high stirring process, and specifically comprises the following steps: stirring at 300r/min for 1h, keeping the temperature at 35 ℃, and then stirring at a high speed of 3000r/min for 4 h;
preparing a negative plate: mixing and stirring the negative active substance, the negative conductive agent, the negative adhesive and the negative solvent uniformly to prepare negative slurry, and coating the negative slurry on a negative current collector to prepare a negative plate;
assembling: and (4) placing the positive plate, the diaphragm and the negative plate into a battery shell, and sealing the battery core after injecting the electrolyte to obtain the lithium ion battery.
Example 2
Preparing a positive plate: dissolving a PVDF binder into PEG, adding a raw material for preparing a lithium ion battery, stirring to form a positive slurry, coating the obtained positive slurry on an aluminum foil current collector, heating, drying and volatilizing the PEG, rolling and slitting the coated electrode, and then drying in vacuum to obtain a lithium ion battery positive plate, wherein the weight parts of the positive material are shown in table 1, example 2, the lithium ion battery raw material is subjected to vacuum drying intervention treatment, the baking temperature is 104 ℃, the baking time is 2.2 hours, the thickness of the aluminum foil current collector is 14 micrometers, the heating and drying temperature is 122 ℃, and the stirring step comprises a slow stirring process and a high stirring process, and specifically comprises the following steps: stirring at 350r/min for 1.1h, maintaining the temperature at 36 deg.C, and stirring at high speed of 3100r/min for 4.2 h;
preparing a negative plate: mixing and stirring the negative active substance, the negative conductive agent, the negative adhesive and the negative solvent uniformly to prepare negative slurry, and coating the negative slurry on a negative current collector to prepare a negative plate;
assembling: and (4) placing the positive plate, the diaphragm and the negative plate into a battery shell, and sealing the battery core after injecting the electrolyte to obtain the lithium ion battery.
Example 3
Preparing a positive plate: dissolving a PVDF binder into PEG, adding a raw material for preparing a lithium ion battery, stirring to form a positive slurry, coating the obtained positive slurry on an aluminum foil current collector, heating, drying and volatilizing the PEG, rolling and slitting the coated electrode, and then drying in vacuum to obtain a lithium ion battery positive plate, wherein the weight parts of the positive material are shown in Table 1, example 3, the lithium ion battery raw material is subjected to vacuum drying intervention treatment, the baking temperature is 110 ℃, the baking time is 2.5 hours, the thickness of the aluminum foil current collector is 15 micrometers, the heating and drying temperature is 125 ℃, and the stirring step comprises a slow stirring process and a high stirring process, and specifically comprises the following steps: stirring at 400r/min for 1.2h, maintaining the temperature at 37 ℃, and then stirring at a high speed of 3200r/min for 4.5 h;
preparing a negative plate: mixing and stirring the negative active substance, the negative conductive agent, the negative adhesive and the negative solvent uniformly to prepare negative slurry, and coating the negative slurry on a negative current collector to prepare a negative plate;
assembling: and (4) placing the positive plate, the diaphragm and the negative plate into a battery shell, and sealing the battery core after injecting the electrolyte to obtain the lithium ion battery.
Example 4
Preparing a positive plate: dissolving a PVDF binder into PEG, adding a raw material for preparing a lithium ion battery, stirring to form anode slurry, coating the obtained anode slurry on an aluminum foil current collector, heating, drying and volatilizing the PEG, rolling and slitting the coated electrode, and then drying in vacuum to obtain a lithium ion battery anode plate, wherein the weight parts of the anode material are shown in table 1, example 4, the lithium ion battery raw material is subjected to vacuum drying intervention treatment, the baking temperature is 115 ℃, the baking time is 2.7 hours, the thickness of the aluminum foil current collector is 16 micrometers, the heating and drying temperature is 128 ℃, and the stirring step comprises a slow stirring process and a high stirring process, and specifically comprises the following steps: stirring at 450r/min for 1.4h, keeping the temperature at 38 ℃, and then stirring at a high speed of 330r/min for 4.8 h;
preparing a negative plate: mixing and stirring the negative active substance, the negative conductive agent, the negative adhesive and the negative solvent uniformly to prepare negative slurry, and coating the negative slurry on a negative current collector to prepare a negative plate;
assembling: and (4) placing the positive plate, the diaphragm and the negative plate into a battery shell, and sealing the battery core after injecting the electrolyte to obtain the lithium ion battery.
Example 5
Preparing a positive plate: dissolving a PVDF binder into PEG, adding a raw material for preparing a lithium ion battery, stirring to form a positive slurry, coating the obtained positive slurry on an aluminum foil current collector, heating, drying and volatilizing the PEG, rolling and slitting the coated electrode, and then drying in vacuum to obtain a lithium ion battery positive plate, wherein the weight parts of the positive material are shown in the example 5 in the table 1, the lithium ion battery raw material is subjected to vacuum drying intervention treatment, the baking temperature is 120 ℃, the baking time is 3 hours, the thickness of the aluminum foil current collector is 16 micrometers, the heating and drying temperature is 130 ℃, and the stirring step comprises a slow stirring process and a high stirring process, and specifically comprises the following steps: stirring at 500r/min for 1.5h, maintaining the temperature at 40 deg.C, and stirring at 3500r/min for 5 h;
preparing a negative plate: mixing and stirring the negative active substance, the negative conductive agent, the negative adhesive and the negative solvent uniformly to prepare negative slurry, and coating the negative slurry on a negative current collector to prepare a negative plate;
assembling: and (4) placing the positive plate, the diaphragm and the negative plate into a battery shell, and sealing the battery core after injecting the electrolyte to obtain the lithium ion battery.
Comparative example 1
The difference from example 1 is that the positive electrode material of the lithium ion battery of the comparative example does not contain PVP reagent, and the rest is the same as example 1, and the description is omitted here.
Comparative example 2
The difference from the example 1 is that the positive electrode material of the lithium ion battery of the comparative example does not contain titanium dioxide difluoride, and the rest is the same as the example 1, and the description is omitted.
Comparative example 3
The only difference from example 1 is that the comparative lithium ion battery was not expected to be pretreated, and the rest is the same as example 1, and thus the description thereof is omitted.
Comparative example 4
The difference from example 1 is that only high-speed stirring is used in the preparation process of the lithium ion battery of the comparative example, and the rest is the same as example 1, and is not described again here.
The lithium ion batteries obtained in examples 1 to 5 and comparative examples 1 to 4 were subjected to performance tests, and the results are shown in tables 2 and 3:
table 2: performance test results of lithium ion batteries of examples 1 to 5 and comparative examples 1 to 4
Figure BDA0001386515180000121
Table 3: performance test results of lithium ion batteries of examples 1 to 5 and comparative examples 1 to 4
Figure BDA0001386515180000122
Figure BDA0001386515180000131
Therefore, the PVP reagent is added into the lithium ion battery anode, and the content of other components is adjusted, so that the viscosity of the anode slurry is proper, the fluidity and the dispersibility are good, the use amount of PEG is reduced, the homogenization time is shortened, the cost of the lithium ion battery is greatly reduced, and the process efficiency is improved.
The specific embodiments described herein are merely illustrative of the spirit of the invention. Various modifications or additions may be made to the described embodiments or alternatives may be employed by those skilled in the art without departing from the spirit or ambit of the invention as defined in the appended claims.
While the invention has been described in detail and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope thereof.

Claims (8)

1. The lithium ion battery is characterized by comprising a positive electrode, a negative electrode, a diaphragm, an organic electrolyte and a battery shell, wherein the positive electrode comprises the following components in parts by weight: positive electrode active material: 85-95 parts of a conductive agent: 2-5 parts of PVDF binder: 5-10 parts, PVP reagent: 5-10 parts, PEG: 110-130 parts of titanium dioxide fluoride: 5-10 parts;
the PVP reagent is one of PVPK15, PVPK17, PVPK25 and PVPK 30.
2. The lithium ion battery according to claim 1, wherein the positive electrode active material is one or both of nano lithium iron phosphate and nano lithium manganese iron phosphate.
3. The lithium ion battery according to claim 1 or 2, wherein the particle size of the positive electrode active material is 0.5 ~ 3.0.0 μm, and the specific surface area is 15-20m2.g-1The tap density is 1.0-1.2g/cm3The carbon content is 1.5-2.0%.
4. The lithium ion battery of claim 1, wherein the molecular weight of the PVP agent is between 3500 and 37900.
5. A method of making the lithium ion battery of claim 1, comprising the steps of:
preparing a positive plate: dissolving a PVDF binder into PEG, adding raw materials for preparing the lithium ion battery, stirring to form anode slurry, coating the obtained anode slurry on an aluminum foil current collector, heating, drying and volatilizing the PEG, rolling and slitting the coated electrode, and drying in vacuum to obtain a lithium ion battery anode sheet;
preparing a negative plate: mixing and stirring the negative active substance, the negative conductive agent, the negative adhesive and the negative solvent uniformly to prepare negative slurry, and coating the negative slurry on a negative current collector to prepare a negative plate;
assembling: and (4) placing the positive plate, the diaphragm and the negative plate into a battery shell, and sealing the battery core after injecting the electrolyte to obtain the lithium ion battery.
6. The method according to claim 5, wherein the electrolyte comprises a solute, a solvent and an additive; the solute is one or more of halide, sulfate, nitrate and oxalate of lithium; the solvent is one or more of water, N-methylpyrrolidone, N-methylformamide, alcohol, methanol, dimethyl sulfoxide, diethyl ether, ethyl acetate and tetrahydrofuran; the additive is one or two of thiophene, diphenyl ether and sodium difluoro oxalate borate.
7. The method for preparing the lithium ion battery anode according to claim 5, wherein the lithium ion battery raw material is subjected to vacuum baking treatment, the baking temperature is 100-120 ℃, and the baking time is 2-3 h.
8. The method for preparing the positive electrode of the lithium ion battery according to claim 5, wherein the stirring step comprises a slow stirring process and a high stirring process, and specifically comprises the following steps: stirring at 500r/min for 1-1.5h at 35-40 deg.C, and stirring at 3000r/min for 4-5 h.
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