CN118693226A - Positive electrode plate, battery, electric device and preparation method of positive electrode plate - Google Patents
Positive electrode plate, battery, electric device and preparation method of positive electrode plate Download PDFInfo
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Abstract
The invention discloses a positive electrode plate, a battery, an electric device and a preparation method of the positive electrode plate, and relates to the technical field of lithium ion batteries, wherein the positive electrode plate comprises a current collector, a lignin layer, an active layer and a functional layer which are sequentially arranged; the lignin layer is arranged on the surface of the current collector and comprises lignin, and Li 2 S particles are distributed on the lignin layer; the active layer includes a positive electrode active material and a polar organic polymer; the functional layer comprises carbon nanotubes; the Li 2 S particles are connected with the polar organic polymer and the fluorinated chain-shaped hydrophobic particles through chemical bonds. The lignin layer provides excellent conductivity and structural stability; the Li 2 S particles enhance the internal resistance and electrochemical capacity of the battery through hydrogen bonding with the polar organic polymer while reducing self-discharge; the three-dimensional conductive network formed by the fluorinated chain-shaped hydrophobic particles and the carbon nano tubes optimizes the conductivity and the cycle efficiency of the battery; these characteristics together improve the overall performance and economy of the battery.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a positive electrode plate, a battery, an electric device and a preparation method of the positive electrode plate.
Background
Lithium ion batteries have been widely used in various commercial and industrial fields as a core energy technology in modern portable electronic devices, electric vehicles, and large-scale energy storage systems. This type of battery is favored for its higher energy density, long cycle life, and lower memory effect. Despite significant advances in lithium ion battery technology over the past decades, many challenges remain in material selection, battery design, and manufacturing processes.
In the existing lithium ion battery technology, the design and manufacture of the battery is focused on optimizing the energy output and charge-discharge efficiency of the battery. The main technologies include the use of a variety of active materials to increase energy storage capacity, and the development of sophisticated battery management systems to monitor and regulate the operating state of the battery. In addition, material processing and assembly techniques in the battery manufacturing process are continuously advanced to improve the integration degree and the operation efficiency of the battery assembly.
However, the prior art still has a number of problems that limit further improvement in the performance of lithium ion batteries. First, the internal resistance of the battery is high, which not only limits the charge-discharge rate of the battery, but also reduces energy efficiency. In addition, the volume expansion of the active material during charge and discharge of the battery may cause structural rupture of the battery, affecting the cycle life and overall stability of the battery. In addition, transition metal ions in the electrolyte may migrate to the anode, causing a self-discharge phenomenon, which further reduces the cycle stability of the battery. The ionic conductivity and structural integrity of the battery are also common problems in the art that affect the long-term performance and durability of the battery. Finally, the high cost of materials and manufacturing processes limits the market competitiveness of lithium ion batteries, especially in cost sensitive applications.
In summary, although the existing lithium ion battery technology has been significantly developed, there are significant limitations in terms of internal resistance, volume expansion management, self-discharge control, conductivity, and cost effectiveness. These technical obstacles prevent further optimization of the performance of lithium ion batteries and expansion of the application field, and therefore solving these problems is essential for future development of battery technology.
Disclosure of Invention
The invention aims to provide a positive electrode plate, a battery, an electric device and a preparation method of the positive electrode plate.
The invention is realized in the following way:
in a first aspect, the invention provides a positive electrode plate, which comprises a current collector, a lignin layer, an active layer and a functional layer which are sequentially arranged;
The lignin layer is arranged on the surface of the current collector, and the lignin layer comprises lignin with a three-dimensional network structure; li 2 S particles are distributed in the lignin layer;
the active layer includes a positive electrode active material and a polar organic polymer;
The functional layer comprises carbon nanotubes with fluorinated chain-shaped hydrophobic particles distributed on the surface;
Wherein the Li 2 S particles are connected with the polar organic polymer and the fluorinated chain-shaped hydrophobic particles through chemical bonds.
In an alternative embodiment, the carbon nanotubes are carbon nanotubes having a three-dimensional network structure.
In an alternative embodiment, the polar organic polymer includes at least one of poly (t-butyl acrylate), polyacrylamide, polyvinylidene fluoride, polytetrafluoroethylene, and polyimide.
In an alternative embodiment, the fluorinated chain hydrophobic particles include at least one of fluorinated chain titanium dioxide, fluorinated chain silica, fluorinated chain zinc dioxide, and fluorinated chain aluminum oxide.
In an alternative embodiment, the polar organic polymer is in the shape of microspheres with a particle size of 400 nm-800 nm;
the particle size of the fluorinated chain-shaped hydrophobic particles is 100 nm-380 nm;
The particle size of the Li 2 S particles is 100 nm-4 μm.
In an alternative embodiment, the mass ratio of the lignin, the Li 2 S particles, the polar organic polymer, the fluorinated chain-like hydrophobic particles and the carbon nanotubes is (10-30)/(5-10)/(20-70)/(5-10)/(10-30).
In an alternative embodiment, the lignin layer has a thickness of 1 μm to 5 μm;
The thickness of the functional layer is 1-5 mu m.
In a second aspect, the present invention provides a battery comprising a positive electrode sheet according to any one of the preceding embodiments.
In a third aspect, the invention provides an electrical device comprising a battery as described in the previous embodiments.
In a fourth aspect, the present invention provides a method for preparing a positive electrode sheet, including:
mixing Li 2 S particles and lignin in a first organic solvent to prepare a first slurry; coating the first slurry on the surface of a current collector to form a lignin layer on the surface of the current collector;
Mixing an anode active material, a polar organic polymer, a conductive agent and a binder in a second organic solvent to prepare a second slurry; coating the second slurry on the surface of the lignin layer to form an active layer on the lignin surface;
mixing the fluorinated chain-like hydrophobic particles and the carbon nanotubes in a third organic solvent to obtain a third slurry; coating the third slurry on the surface of the active layer to form a functional layer on the surface of the active layer;
and carrying out hot-pressing drying treatment to form the positive electrode plate.
The invention provides a positive pole piece, which comprises a current collector, a lignin layer, an active layer and a functional layer which are sequentially arranged; the lignin layer is arranged on the surface of the current collector, and the lignin layer comprises lignin with a three-dimensional network structure; li 2 S particles are distributed on the surface of the lignin layer; the active layer includes a positive electrode active material and a polar organic polymer; the functional layer comprises carbon nanotubes with fluorinated chain-shaped hydrophobic particles distributed on the surface; wherein the Li 2 S particles are connected with the polar organic polymer and the fluorinated chain-shaped hydrophobic particles through chemical bonds. The invention has the following beneficial effects:
(1) The lignin layer on the surface of the current collector has good conductivity and a three-dimensional network structure, so that the internal resistance of the battery can be reduced, and the volume expansion can be buffered in the charge and discharge processes. In addition, the cost of lignin is low, which is helpful for reducing the whole manufacturing cost.
(2) Li 2 S particles distributed on the surface of the lignin layer are connected with the polar organic polymer through strong hydrogen bonds, so that the compactness of the structure and the internal resistance of the battery are enhanced. In addition, the Li 2 S particles can react with transition metal ions in the electrolyte at a high potential to effectively adsorb the ions, thereby reducing the self-discharge problem of the cathode and improving the cycle stability of the battery. Li 2 S can also provide extra electrochemical capacity for the battery, and form a lithium-rich layer at the interface of the coating and the electrolyte, so that the rapid migration of lithium ions is promoted, and the ion conductivity of the battery is improved.
(3) The polar organic polymer is used as an intermediate layer, so that the binding force between the polar organic polymer and the current collector is improved, and the polar organic polymer is combined with the fluorinated chain-shaped hydrophobic particles to form an interpenetrating structure, so that the connection force between the polar organic polymer and Li 2 S particles and the hydrophobic nano particles is enhanced.
(4) The fluorinated chain-shaped hydrophobic particles are distributed on the surface of the carbon nano tube, so that the agglomeration phenomenon is reduced, and strong interaction is formed between the fluorinated chain-shaped hydrophobic particles and hydrogen in the polar organic polymer. The three-dimensional conductive network has good conductivity and pressure buffering property, is favorable for combining various layers of materials through a hot pressing process, and further forms a three-dimensional conductive network with a space structure, so that the overall conductivity and the cycle efficiency of the battery are improved.
In conclusion, the cathode plate of the invention obviously improves the internal structural stability, electrochemical performance and economic benefit of the lithium ion battery through the synergistic effect of the layers.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed in the embodiments will be briefly described below, it being understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and other related drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a schematic cross-sectional view of a positive electrode sheet according to an embodiment of the present application;
FIG. 2 is a schematic diagram of the connection relationship among a lignin layer, an active layer and a functional layer in a positive electrode sheet according to an embodiment of the present application;
Fig. 3 is a schematic flow chart of a method for preparing a positive electrode sheet according to an embodiment of the present application.
Reference numerals: 100-positive pole piece; 1-a current collector; a 2-lignin layer; 3-an active layer; 4-a functional layer; 21-Li 2 S particles; 31-a polar organic polymer; 41-fluorinated chain-like hydrophobic particles.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more clear, the technical solutions of the embodiments of the present invention will be clearly and completely described below. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
The features and capabilities of the present invention are described in further detail below in connection with the examples.
Referring to fig. 1, in an embodiment of the present application, there is provided a positive electrode sheet including a current collector, a lignin layer, an active layer, and a functional layer sequentially disposed;
The lignin layer is arranged on the surface of the current collector, and the lignin layer comprises lignin with a three-dimensional network structure; li 2 S particles are distributed in the lignin layer;
the active layer includes a positive electrode active material and a polar organic polymer;
The functional layer comprises carbon nanotubes with fluorinated chain-shaped hydrophobic particles distributed on the surface;
Wherein the Li 2 S particles are connected with the polar organic polymer and the fluorinated chain-shaped hydrophobic particles through chemical bonds.
In the positive electrode sheet in the embodiment of the application, the structure is composed of the following parts in sequence:
(1) Current collector: as a conductive path for electrons, a highly conductive material is generally used.
(2) Lignin layer: the three-dimensional network structure is positioned on the surface of the current collector, provides physical stability and participates in electrochemical reaction; in the preparation process, li 2 S particles and lignin are mixed in a solvent to prepare the composite material, so that Li 2 S particles are distributed in the lignin layer and on the surface of the lignin layer.
(3) Active layer: comprising a positive electrode active material and a polar organic polymer is the primary site for energy storage and release from a battery.
(4) Functional layer: comprises carbon nanotubes and fluorinated chain-like hydrophobic particles attached to the surface for improving the structural stability and electrochemical performance of the battery.
The lignin layer is arranged on the surface of the current collector, wherein lignin is a compound with good conductivity, so that the internal resistance of the battery can be obviously reduced, and the lignin layer has a three-dimensional net structure and can buffer the volume expansion in the charge and discharge processes of the battery; and the cost of lignin is low, so that the cost can be further reduced on the basis of maintaining and improving the electrochemical performance.
The Li 2 S particles are distributed in the lignin layer and on the surface of the lignin layer.
On the one hand, S in the Li 2 S particles can form strong interaction (such as hydrogen bond) with hydrogen in the polar organic polymer, so that the two are connected more tightly, and the internal resistance is reduced; on the other hand, li 2 S particles in the coating can react with free transition metal ions in the electrolyte at high potential (more than 2.5V) to generate polysulfide to deposit on the positive plate, so that the free transition metal ions in the electrolyte are effectively adsorbed, the problem of self-discharge of the transition metal ions at the negative electrode is solved, and the cycle stability of the battery is improved.
In addition, the Li 2 S particles can provide additional capacity as a positive electrode active material, so that the specific capacity of the battery is improved; meanwhile, li 2 S particles enrich lithium at the interface of the coating and the electrolyte to form a lithium-rich layer, and the lithium-rich layer is favorable for rapid migration of lithium ions, so that the ion conductivity of the battery can be effectively improved.
In a preferred embodiment, the Li 2 S particles are micro-nano structured.
Micro-nano scale Li 2 S particles have a larger surface area to volume ratio, which means that these particles can provide more reaction surface with the same mass. This increased active area may improve the interfacial contact between the electrode and the electrolyte, thereby increasing the rate and efficiency of the electrochemical reaction.
Since the Li 2 S particles are uniformly distributed on the surface of the lignin layer, the micro-nano structure can help to achieve more uniform ion distribution and faster ion transport. This helps to reduce localized overheating problems during battery operation, improving overall battery performance and life.
The micro-nano structured Li 2 S particles can provide additional electrochemically active sites in the active layer, helping to increase the total energy storage capacity of the cell. At the same time, the power output of the battery will be enhanced due to the increase in the electrochemical reaction rate.
Micro-nano Li 2 S particles can provide a more stable chemical structure, and reduce performance attenuation caused by material decomposition or structural collapse in charge-discharge cycles. This stability is mainly due to the micro-nano particles being more structurally resistant to stress and volume changes.
Due to their stable chemical nature, li 2 S micro-nano particles can reduce deleterious chemical reactions, such as dissolution and migration of transition metal ions, that may occur during battery operation. In addition, better structural stability also means that the battery is less prone to thermal runaway under extreme conditions.
In this design, li 2 S particles are hydrogen bonded to the polar organic polymer, and micro-nano scale particles can provide more binding sites, enhancing the strength of such bonding. This enhanced microscopic level of attachment helps to improve the mechanical strength and electrochemical integration of the overall electrode structure.
In summary, the Li 2 S particles are set to have a micro-nano structure, which is not only helpful to improve the basic performance index, such as energy density, power output and cycle stability, of the lithium ion battery, but also can improve the overall performance and safety of the battery by optimizing the fine parts of the battery structure. This design concept is of great importance for the development of next generation high performance battery technology.
The polar organic polymer has good binding force with Li 2 S particles due to the polar relationship, and is used as an 'intermediate layer', downward, so that the binding force with a current collector can be improved, and the internal resistance can be reduced; upward, can combine with fluorinated chain hydrophobic particles to construct a polar organic polymer big sphere and hydrophobic nanoparticle small sphere interpenetrating structure, and the polar organic polymer is used as a bridge to strengthen the connection force with Li 2 S and the hydrophobic nanoparticles. The polar organic polymer can be combined with Li 2 S particles to form a connection relationship, and can also form a connection relationship with fluorinated chain-shaped hydrophobic particles through chemical bonds, a specific connection manner is shown in fig. 2, namely, li 2 S particles, polar organic polymer and fluorinated chain-shaped hydrophobic particles are sequentially connected, and in addition, the substances can form a tight connection relationship with each other.
The fluorinated chain-shaped hydrophobic particles are distributed on the surface of the carbon nano tube, so that aggregation of the particles can be reduced, the fluorinated chain-shaped hydrophobic particles and hydrogen in the polar organic polymer form strong interaction (such as hydrogen bond), the binding force is strong, the fluorinated chain-shaped hydrophobic particles also have good conductivity and pressure buffering property, the positive electrode plate combines all layers through hot pressing, the carbon nano tube and lignin are partially contacted, the positive electrode plate integrally forms a three-dimensional conductive network in space, the conductivity of the battery is improved, and the circulation is improved.
Further, the Carbon Nanotubes (CNTs) are carbon nanotubes having a three-dimensional network structure.
The three-dimensional network structure of carbon nanotubes provides more electron conduction paths, and compared with the traditional linear or random distribution of carbon nanotubes, the structure promotes electrons to flow more efficiently, reduces resistance and improves electron transmission efficiency. Due to the unique geometric configuration, the three-dimensional netlike CNTs can bear higher mechanical stress and resist volume expansion and shrinkage in the charge and discharge processes of the battery, so that the structural stability of the battery is enhanced. The three-dimensional structure increases the porosity of the material, which is beneficial to the transmission of lithium ions in the electrode material, thereby improving the diffusion rate of the ions and accelerating the progress of electrochemical reaction.
In electrochemical aspect, as the three-dimensional network carbon nanotubes optimize the transmission of electrons and ions, the charge and discharge efficiency of the battery can be significantly improved, thereby being capable of realizing higher battery capacity and energy density. The three-dimensional netlike carbon nanotubes are beneficial to reducing the performance attenuation of the battery in the circulation process and prolonging the service life of the battery due to the excellent structural stability and electronic conductivity of the three-dimensional netlike carbon nanotubes. The better electron and ion transport characteristics mean that the battery can support faster charge and discharge rates, which is particularly important for applications requiring fast response (e.g., electric vehicles and large-scale energy storage systems).
The three-dimensional network helps to reduce the risk of local overheating by providing a more uniform heat distribution, thereby improving the overall safety of the battery. The three-dimensional structure increases the porosity of the material, which is beneficial to the transmission of lithium ions in the electrode material, thereby improving the diffusion rate of the ions and accelerating the progress of electrochemical reaction.
In a word, the electrochemical performance and the structural stability of the lithium ion battery can be obviously improved in the positive electrode plate by adopting the carbon nano tube with the three-dimensional reticular structure, so that the overall performance of the battery is optimized, and the application scene of higher performance requirements is met. This design also helps to promote innovations and developments in battery technology.
Further, the polar organic polymer includes at least one of poly (t-butyl acrylate), polyacrylamide, polyvinylidene fluoride, polytetrafluoroethylene, and polyimide.
Further, the fluorinated chain-like hydrophobic particles include at least one of fluorinated chain-like titanium dioxide, fluorinated chain-like silicon dioxide, fluorinated chain-like zinc dioxide, and fluorinated chain-like aluminum oxide.
Further, the polar organic polymer is in a microsphere shape, and the particle size is 400-800 nm; for example, it may be 400 nm, 500 nm, 600 nm, 700 nm, 800nm, etc.
The particle size of the fluorinated chain-shaped hydrophobic particles is 100 nm-380 nm; for example, it may be 100nm, 200 nm, 300 nm, 350 nm, 380nm, etc.
The particle size of the Li 2 S particles is 100 nm-4 μm. For example, 100nm, 200 nm, 400nm, 600 nm, 800 nm, 1 nm, 2 μm, 3 μm, 4 μm, etc.
Further, the mass ratio of the lignin to the Li 2 S particles to the polar organic polymer to the fluorinated chain-like hydrophobic particles to the carbon nanotubes is (10-30)/(5-10)/(20-70)/(5-10)/(10-30). In the mass ratio, lignin may be 10, 20, 30, etc., li 2 S particles may be 5, 6, 7, 8, 9, 10, etc., polar organic polymers may be 20, 30, 50, 60, 70, etc., fluorinated chain-like hydrophobic particles may be 5, 6, 7, 8, 9, 10, etc., and carbon nanotubes may be 10, 20, 30, etc.
Further, the thickness of the lignin layer is 1-5 mu m; for example, lignin thickness may be 1 μm, 2 μm, 3 μm, 4 μm, 5 μm, etc.
The thickness of the functional layer is 1-5 mu m. For example, the thickness of the functional layer may be 1 μm, 2 μm, 3 μm, 4 μm, 5 μm, or the like.
In addition, in the embodiment of the application, a battery is also provided, which comprises the positive electrode plate.
The above battery may include, but is not limited to, in addition to the positive electrode sheet: the negative electrode plate, the diaphragm and the electrolyte can further comprise a shell, packaging materials and a protection circuit, and can further comprise a Battery management system (Battery MANAGEMENT SYSTEM, BMS).
In addition, in the embodiment of the application, an electric device is also provided, which comprises the battery.
The power-related devices employing the above batteries can be widely distributed in various fields, and these devices generally require a power source with high efficiency, high energy density, and long life. For example, may include, but is not limited to: portable electronic devices (e.g., smartphones, tablet computers, notebook computers, digital cameras, etc.), electric vehicles (e.g., electric automobiles, electric bicycles, electric scooters, electric motorcycles, etc.), wearable devices (smart watches, health monitoring devices, VR/AR devices, etc.), medical devices (pacemakers, wheelchairs, monitoring devices), and aerospace devices (satellites, drones, communication devices, etc.), and the like.
In the electrical device, in addition to the battery, a controller, a power management system, a sensor, a display component, an input device, a communication interface, a protection circuit, a thermal management system, and the like may be included, but are not limited to.
In addition, referring to fig. 3, in an embodiment of the present application, a method for preparing a positive electrode sheet is further provided, including:
Step S1, mixing Li 2 S particles and lignin in a first organic solvent to prepare a first slurry; coating the first slurry on the surface of a current collector to form a lignin layer on the surface of the current collector;
In this step, li 2 S particles and lignin are mixed in a first organic solvent to form a first slurry. This slurry is then coated on the surface of the current collector. The mixing of lignin and Li 2 S particles in an organic solvent ensures a uniform distribution of both at the microscopic level, and the coating process ensures that the mixture covers the surface of the current collector uniformly.
The formation of the lignin layer not only increases the mechanical strength of the electrode, but also enhances the electrochemical activity of the electrode due to the intercalation of Li 2 S particles. This step improves the conductivity and structural stability of the electrode.
Step S2, mixing the positive electrode active material, the polar organic polymer, the conductive agent and the binder in a second organic solvent to prepare second slurry; coating the second slurry on the surface of the lignin layer to form an active layer on the lignin surface;
In the above steps, the positive electrode active material, the polar organic polymer, the conductive agent and the binder are mixed in a second organic solvent to prepare a second slurry, and then coated on the lignin layer.
The mixture in this step forms a uniform slurry by physical mixing, and the coating process ensures uniform distribution of the active material and good interfacial contact.
The formation of the active layer improves the electrochemical performance of the electrode, for example, the capacity and charge-discharge efficiency of the battery. The use of polar organic polymers improves adhesion and flexibility of the electrode.
Step S3, mixing the fluorinated chain-shaped hydrophobic particles and the carbon nano tubes in a third organic solvent to obtain third slurry; coating the third slurry on the surface of the active layer to form a functional layer on the surface of the active layer;
the fluorinated chain-like hydrophobic particles and the carbon nanotubes are mixed in a third organic solvent to form a third slurry, which is coated on the active layer. The mixing of the carbon nanotubes and fluorinated particles provides additional conductive pathways and enhanced chemical stability. Coating ensures that these materials are uniformly distributed on the active layer surface.
The addition of the functional layer enhances the hydrophobicity of the electrode, reduces the absorption of moisture and improves the cycle stability and safety of the battery. Meanwhile, the addition of the carbon nano tube improves the overall conductivity.
And S4, carrying out hot-pressing drying treatment to form the positive electrode plate.
After all the layers are prepared as described above, the entire electrode is cured by hot pressing and baking treatment. The hot pressing aids in sealing and bonding between the materials and the drying removes excess solvent and moisture.
This step improves the structural stability of the electrode and the uniformity of electrochemical properties, ensuring long-term performance maintenance.
In the preparation of the lithium battery pole piece, the first organic solvent, the second organic solvent and the third organic solvent may be the same or different. The choice of whether to use the same solvent depends mainly on the solubility of the material and the process requirements in the individual steps.
The solvent chosen must be able to effectively solubilize the various components of the step (e.g., lignin, li 2 S particles, active materials, polar organic polymers, conductive agents, etc.).
The solvent should be chemically compatible with other materials and should not cause chemical reactions or affect battery performance.
The rate of volatilization of the solvent affects the coating process and drying step, and higher volatility solvents can increase the drying rate, but may require tighter process control.
The safety (e.g., flammability, toxicity) of the solvent and the environmental impact are considered.
The first organic solvent, the second organic solvent and the third organic solvent can be any one or more of the following organic solvents respectively or simultaneously:
n-methylpyrrolidone (NMP): slurry preparation for battery electrode materials is due to its good solubility and relatively slow volatilization rate.
Ethyl Acetate (EA): is a relatively volatile solvent and is commonly used in applications requiring rapid drying.
Dimethylformamide (DMF): similar to NMP, has good solubility, and is used for various high molecules and small molecules.
Water: for certain water-soluble or partially water-soluble polymers, water may be selected as an environmentally friendly solvent.
Cyclohexanone: suitable for applications requiring specific dissolution properties.
If different solvents are used, it is advantageous that the optimal solvent can be selected for the specific needs of each step. For example, if a slower drying is required in the first step to ensure even distribution of lignin and Li 2 S particles, NMP might be selected; in the subsequent step, a more volatile solvent such as cyclohexanone or ethyl acetate may be selected in order to increase the drying rate.
The challenge with using different solvents is to ensure that the remaining previous step solvents do not adversely affect the materials or process of the subsequent steps in the transition from one step to another. Each solvent change requires a rigorous drying and cleaning process to avoid cross-contamination.
The invention is further illustrated by the following specific examples, but it should be understood that these examples are for the purpose of illustration only and are not to be construed as limiting the invention in any way.
Example 1:
in this example, a pole piece was prepared using the following method.
The preparation method comprises the following steps:
(1) Mixing Li 2 S particles with the particle size of 150nm and lignin in NMP (N-methyl pyrrolidone), and coating the mixture on a current collector aluminum foil to form a lignin layer, wherein the thickness of the lignin layer is 1 mu m;
(2) Ternary battery material (NCM 811, 96% by mass), polar organic polymer (polyacrylamide, particle size 400 nm), conductive carbon black (1.5%) and PVDF (2.5%) are mixed in NMP and coated on the surface of lignin to form an active layer, wherein the thickness of the active layer is 25 μm;
(3) Mixing fluorinated chain-shaped hydrophobic particles (fluorinated chain-shaped titanium dioxide) with the particle size of 150nm and carbon nano tubes in NMP, and coating the mixture on the surface of the active layer to form a functional layer, wherein the thickness of the functional layer is 2 mu m;
(4) And then carrying out hot-pressing and drying treatment to form the positive plate.
Wherein the mass ratio of lignin, li 2 S particles, polar organic polymer, fluorinated chain-like hydrophobic particles and carbon nanotubes is 20:5:40:10:25.
Example 2:
In this example, a positive electrode sheet was prepared by the method of example 1, which was substantially the same as example 1, except that: the particle size of the Li 2 S particles was 1. Mu.m.
Example 3:
in this example, a positive electrode sheet was prepared by the method of example 1, which was substantially the same as example 1, except that: the polar organic polymer is polyvinylidene fluoride.
Example 4:
in this example, a positive electrode sheet was prepared by the method of example 1, which was substantially the same as example 1, except that: the polar organic polymer is polyimide.
Example 5:
In this example, a positive electrode sheet was prepared by the method of example 1, which was substantially the same as example 1, except that: the particle size of the polyacrylamide was 800nm.
Example 6:
in this example, a positive electrode sheet was prepared by the method of example 1, which was substantially the same as example 1, except that: the fluorinated chain-like hydrophobic particles are fluorinated chain-like silica.
Example 7:
in this example, a positive electrode sheet was prepared by the method of example 1, which was substantially the same as example 1, except that: the fluorinated chain-like hydrophobic particles are fluorinated chain-like alumina.
Example 8:
In this example, a positive electrode sheet was prepared by the method of example 1, which was substantially the same as example 1, except that: the fluorinated chain-shaped hydrophobic particles are fluorinated chain-shaped titanium dioxide, and the particle size is 380nm.
Example 9:
In this example, a positive electrode sheet was prepared by the method of example 1, which was substantially the same as example 1, except that: the lignin layer had a thickness of 5 μm.
Example 10:
In this example, a positive electrode sheet was prepared by the method of example 1, which was substantially the same as example 1, except that: the thickness of the functional layer was 5. Mu.m.
Example 11:
in this example, a positive electrode sheet was prepared by the method of example 1, which was substantially the same as example 1, except that: lignin, li 2 S particles, polyacrylamide, fluorinated chain titanium dioxide, and carbon nanotubes in a mass ratio of 25:10:30:5:30.
Comparative example 1:
In this comparative example, compared with example 1, the difference is that: no Li 2 S particles were contained.
Comparative example 2:
in this comparative example, compared with example 1, the difference is that: does not contain lignin.
Comparative example 3:
In this comparative example, compared with example 1, the difference is that: does not contain polyacrylamide.
Comparative example 4:
in this comparative example, compared with example 1, the difference is that: does not contain fluorinated chain titanium dioxide.
Comparative example 5:
in this comparative example, compared with example 1, the difference is that: does not contain carbon nanotubes.
Comparative example 6:
in this comparative example, compared with example 1, the difference is that: the Li 2 S particles are disposed in the active layer.
Comparative example 7:
in this comparative example, compared with example 1, the difference is that: the Li 2 S particles are disposed in the functional layer.
Comparative example 8:
In this comparative example, compared with example 1, the difference is that: the fluorinated chain titanium dioxide is disposed in the active layer.
Comparative example 9:
in this comparative example, compared with example 1, the difference is that: the fluorinated chain titanium dioxide is disposed in lignin.
Comparative example 10:
In this comparative example, compared with example 1, the difference is that: the polyacrylamide is replaced with polypropylene.
Transverse comparison test:
the positive electrode sheets prepared in the above examples and comparative examples were fabricated into batteries, and the electrochemical properties of the batteries were tested, and specific test results are shown in table 1.
The specific test method comprises the following steps:
And (3) battery assembly: winding the positive pole piece, the diaphragm and the negative pole piece to obtain a pole core, loading the pole core into a shell, injecting electrolyte, assembling into a battery, and testing on a blue-electricity battery testing system; wherein, the negative pole piece is polished metal lithium, the diaphragm is Celgard 3000, and the electrolyte is 0.25M LiPF 6.
The positive electrode conductivity of the positive electrode plate is tested, and the test conditions are as follows: and (3) conducting conductivity test on the surface of the positive electrode material of the positive electrode plate by using a high-temperature four-probe tester HEST800 instrument.
The batteries prepared in examples 1 to 11 and comparative examples 1 to 10 were charged at a constant current of 1C at a normal temperature of 25 ℃, were subjected to a stop current of 0.05C, were left to stand for 10 minutes, were subjected to a discharge of 0.7C, were sequentially circulated 800 times, and were calculated for a capacity retention (%), a cyclic expansion (%), a first effect (%) of 800 times, a charging upper limit voltage of 4.0V, and were subjected to a cyclic performance test as follows: the capacity retention rate is more than or equal to 80 percent for 800 times, and the cyclic expansion thickness is less than or equal to 10 percent.
The needling test is that after a single battery is prepared according to a specified rule, a high temperature resistant steel needle (the circular cone angle of the needle point is 45-60 degrees, the surface of the needle is smooth and clean and has no rust, oxide layer and greasy dirt) with the speed of (25+/-5) mm/s penetrates from the direction vertical to a polar plate of the storage battery, the penetrating position is preferably close to the geometric center of a needling surface, and the steel needle stays in the storage battery; the results of observation for 1 hour are shown in Table 1.
Table 1, battery performance test results prepared in examples and comparative examples:
In the above table, "real" represents an embodiment, for example, "real 1" represents embodiment 1; "pair" represents a comparative example, e.g., "pair 1" represents comparative example 1.
Experimental results and analysis:
Compared with examples 1-11, the comparative example 1 does not contain Li 2 S particles, the Li 2 S particles cannot form hydrogen bonds inside the pole piece, the bonding force between the layers is weakened, the internal resistance is increased, the capacity retention rate is reduced, and the Li 2 S particles cannot provide additional capacity, so that the initial efficiency of the battery is low.
Compared with the embodiment 1-11, the three-dimensional structure of the lithium ion battery does not contain lignin, the lignin is a good conductive agent, has a certain promotion effect on the conductivity of the positive electrode of the electrode plate, and can buffer the volume expansion of the battery in the charge and discharge process, and the lack of lignin can influence the conductivity of the positive electrode plate and the cycle expansion rate of the battery to a certain extent.
Compared with the examples 1-11, the comparative example 3 does not contain polyacrylamide, the polyacrylamide can play a certain role in bonding, the polyacrylamide is not contained, the connection degree of two inorganic matters can be reduced, the internal resistance of the battery can be further increased, and finally the electrical performance of the battery can be influenced.
Compared with the comparative examples 1-11, the battery of comparative example 4 does not contain fluorinated chain-shaped titanium dioxide, has excellent mechanical properties, is connected with Li 2 S particles and polyacrylamide through hydrogen bonds, enhances the connection tightness between three layers, and cannot be subjected to needling 100% because the lack of fluorinated chain-shaped titanium dioxide can affect the safety performance of the battery.
Compared with the embodiment examples 1-11, the three-dimensional network structure of the carbon nano tube does not contain carbon nano tubes, on one hand, the carbon nano tubes provide more electron conduction paths, compared with the traditional carbon nano tubes which are linearly or randomly distributed, the structure promotes electrons to flow more efficiently, reduces resistance and improves the electron transmission efficiency, and on the other hand, the three-dimensional network structure can buffer the volume expansion and contraction in the charge and discharge process of the battery, and finally, the electrical performance of the battery can be influenced.
In comparative examples 6 and 7, if the Li 2 S particles were not disposed on the surface of lignin, li 2 S, polyacrylamide and fluorinated chain titanium dioxide were connected by hydrogen bonds, but the connection tightness between the three layers was not enhanced, and the electrical property data was lowered.
In comparative examples 8 and 9, the fluorinated chain-like titanium oxide was not provided on the surface of the functional layer, and similarly, li 2 S, polyacrylamide and fluorinated chain-like titanium oxide were connected by hydrogen bonds, but the tightness of connection between the three layers was not enhanced, and the electrical property data was lowered.
In comparative example 10, the polyacrylamide is replaced with polypropylene, and the non-polarity of the polypropylene causes Li 2 S, the polyacrylamide and the fluorinated chain-like titanium dioxide to be not connected through hydrogen bonds, so that the compactness of the three-layer connection is reduced, and the electrical performance of the battery is remarkably reduced.
In a word, the positive electrode plate provided by the invention obviously improves the internal structural stability, electrochemical performance and economic benefit of the lithium ion battery through the synergistic effect of the layers.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The positive electrode plate is characterized by comprising a current collector, a lignin layer, an active layer and a functional layer which are sequentially arranged;
The lignin layer is arranged on the surface of the current collector, and the lignin layer comprises lignin with a three-dimensional network structure; li 2 S particles are distributed in the lignin layer;
the active layer includes a positive electrode active material and a polar organic polymer;
The functional layer comprises carbon nanotubes with fluorinated chain-shaped hydrophobic particles distributed on the surface;
Wherein the Li 2 S particles are connected with the polar organic polymer and the fluorinated chain-shaped hydrophobic particles through chemical bonds.
2. The positive electrode sheet of claim 1, wherein the carbon nanotubes are carbon nanotubes having a three-dimensional network structure.
3. The positive electrode sheet of claim 1, wherein the polar organic polymer comprises at least one of poly-t-butyl acrylate, polyacrylamide, polyvinylidene fluoride, polytetrafluoroethylene, and polyimide.
4. The positive electrode sheet of claim 1, wherein the fluorinated chain-like hydrophobic particles comprise at least one of fluorinated chain-like titanium dioxide, fluorinated chain-like silicon dioxide, fluorinated chain-like zinc dioxide, and fluorinated chain-like aluminum oxide.
5. The positive electrode sheet according to claim 1, wherein the polar organic polymer is in the form of microspheres with a particle size of 400 nm to 800nm;
The particle size of the fluorinated chain-shaped hydrophobic particles is 100 nm-380 nm;
The particle size of the Li 2 S particles is 100 nm-4 μm.
6. The positive electrode sheet according to claim 1, wherein the mass ratio of the lignin, the Li 2 S particles, the polar organic polymer, the fluorinated chain-like hydrophobic particles, and the carbon nanotubes is (10-30): (5-10): (20-70): (5-10): (10-30).
7. The positive electrode sheet according to claim 1, wherein the lignin layer has a thickness of 1 μm to 5 μm;
The thickness of the functional layer is 1-5 mu m.
8. A battery comprising the positive electrode sheet according to any one of claims 1 to 7.
9. An electrical device comprising the battery of claim 8.
10. The preparation method of the positive electrode plate is characterized by comprising the following steps:
mixing Li 2 S particles and lignin in a first organic solvent to prepare a first slurry; coating the first slurry on the surface of a current collector to form a lignin layer on the surface of the current collector;
Mixing an anode active material, a polar organic polymer, a conductive agent and a binder in a second organic solvent to prepare a second slurry; coating the second slurry on the surface of the lignin layer to form an active layer on the lignin surface;
mixing the fluorinated chain-like hydrophobic particles and the carbon nanotubes in a third organic solvent to obtain a third slurry; coating the third slurry on the surface of the active layer to form a functional layer on the surface of the active layer;
and carrying out hot-pressing drying treatment to form the positive electrode plate.
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| CN113451541A (en) * | 2021-05-28 | 2021-09-28 | 上海空间电源研究所 | High-voltage lithium ion positive electrode piece, battery and manufacturing method thereof |
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| CN117476872A (en) * | 2023-10-23 | 2024-01-30 | 广东马车动力科技有限公司 | Lithium battery positive plate, preparation method thereof and lithium ion battery |
| CN117613239A (en) * | 2023-12-05 | 2024-02-27 | 惠州亿纬锂能股份有限公司 | Positive electrode plate, preparation method thereof and lithium ion battery |
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| CN116982173A (en) * | 2021-03-15 | 2023-10-31 | 韩国飞世龙电池有限公司 | Electrode for lithium secondary battery having active material encapsulated therein and method for manufacturing the same |
| CN113451541A (en) * | 2021-05-28 | 2021-09-28 | 上海空间电源研究所 | High-voltage lithium ion positive electrode piece, battery and manufacturing method thereof |
| CN117476872A (en) * | 2023-10-23 | 2024-01-30 | 广东马车动力科技有限公司 | Lithium battery positive plate, preparation method thereof and lithium ion battery |
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