CN113471401A - High-safety high-load lithium ion electrode piece and manufacturing method thereof - Google Patents

High-safety high-load lithium ion electrode piece and manufacturing method thereof Download PDF

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CN113471401A
CN113471401A CN202110592327.2A CN202110592327A CN113471401A CN 113471401 A CN113471401 A CN 113471401A CN 202110592327 A CN202110592327 A CN 202110592327A CN 113471401 A CN113471401 A CN 113471401A
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electrolyte
conductive agent
lithium ion
lithium
electrode plate
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CN113471401B (en
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罗英
丁赵波
晏莉琴
闵凡奇
解晶莹
刘雯
吕桃林
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Shanghai Aerospace Power Technology Co Ltd
Shanghai Institute of Space Power Sources
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Shanghai Power Energy Storage Battery System Engineering Technology Co ltd
Shanghai Institute of Space Power Sources
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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    • 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
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    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract

The invention provides a high-safety high-load lithium ion electrode plate and a manufacturing method thereof, wherein the electrode plate comprises an electroactive material, a conductive agent, an electrolyte I, an electrolyte II and a porous current collector; the electrolyte I comprises an organic solvent, a polymer monomer and a lithium salt; the electrolyte II comprises an organic solvent and a polymerization initiator. In addition, the invention also provides a preparation method of the electrode plate and the lithium ion battery, and the weight proportion of the auxiliary material is favorably reduced by the electrode plate and the battery preparation method, so that the energy density of the battery is improved; the production efficiency is improved, the production energy consumption is reduced, and the pollution to the environment in the production process of the battery is reduced; meanwhile, the safety and the stability of the traditional organic electrolyte lithium ion battery are improved by utilizing the characteristics of safety and reliability of the polymer electrolyte.

Description

High-safety high-load lithium ion electrode piece and manufacturing method thereof
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a high-safety high-loading lithium ion electrode piece and a manufacturing method thereof.
Background
With the development of electric vehicle technology and electric energy storage technology, lithium ion batteries are required to have higher energy density and higher safety and stability. One of the means for increasing the energy density of lithium ion batteries is to reduce the quality of the auxiliary material and increase the loading of the electrodes in the pole pieces. The lithium ion battery generally comprises four parts, namely a positive electrode, a negative electrode, a diaphragm and electrolyte, wherein auxiliary materials comprise a binder, a conductive agent, a current collector and the like. The traditional manufacturing process of the lithium ion battery electrode comprises the steps of uniformly mixing an active material, a conductive agent and a binder according to a certain proportion to form slurry, then uniformly coating the slurry on a current collector, and finally drying, wherein the process is long in time consumption and involves the evaporation of an organic solvent. When a high-capacity electrode is manufactured, the solvent volatilization amount of a thick electrode is increased, so that a slurry coating is easy to crack in the drying process, the electric conductivity of an electrode plate is reduced, and the performance of a battery is influenced.
At the same time, the binder in the electrode is insulating and electrochemically inert, which can lead to uneven distribution of the active material. During use, the binder may also degrade, reducing its adhesion, causing the electrode material to peel off from the current collector. Once these materials make poor contact with the current collector, the performance of the battery is reduced. The patent CN201810752227.X discloses a method for preparing a tin dioxide/graphene composite anode without an adhesive by a dip coating method, and the thickness of the electrode is controlled by adjusting the dip coating times for many times. Although the method realizes the design of the binderless electrode and increases the contact area of the active material and the electrolyte, the method cannot realize the manufacture of a thick electrode, and the overlarge load can increase the unstable structure factor, thereby reducing the cycling stability and the rate capability. Cn202010995749.x discloses a lithium ion battery negative electrode with high rate capability without binder and carbon additives. The high-rate characteristic of the battery is realized by directly coating the PEDOT, which is a chlorine-doped high-molecular conductive polymer, on a current collector to form a PEDOT film electrode with a porous nano structure. In the method, the carbonate organic electrolyte is adopted, so that the dangers of liquid leakage, combustion, explosion and the like can occur in the production and use processes, and the safety problem of the battery is caused. With the continuous improvement of energy density, the problem of effectively improving the safety of the lithium ion battery is also a difficult problem to be overcome.
CN 202010801285.4 discloses a high-safety polymer battery positive plate protected by solid electrolyte coating. The composite solid electrolyte coating and the active substance coating are coated on the aluminum foil current collector, so that the contact between the positive active substance material and the aluminum foil is effectively prevented, and the safety of the battery is improved. In the method, the composite solid electrolyte coating and the active substance coating both adopt N-methyl pyrrolidone (NMP) organic solvent, and the pole piece can be obtained only by drying treatment, so that the loading capacity of the electrode is not improved, and the energy density of the battery is improved.
Therefore, it is a technical problem to be solved to provide a method for preparing a battery with high energy density, no drying, low production energy consumption and high safety and stability.
Disclosure of Invention
Aiming at the technical defects in the prior art, the invention discloses a high-safety high-load lithium ion electrode piece and a manufacturing method thereof.
The high-safety high-load lithium ion electrode plate comprises an electroactive substance, a conductive agent, a polymer electrolyte and a porous current collector. The fluidity of polymer electrolyte at normal temperature, the high viscosity and the high ionic conductivity of the polymer after high-temperature polymerization reaction are utilized to form an electrode plate without an adhesive with a high conductive network, and the assembled battery forms a polymer lithium ion battery through in-situ high-temperature polymerization reaction.
The technical scheme provided by the invention is as follows:
in a first aspect, the invention relates to a high-safety high-load lithium ion electrode plate, which comprises an electroactive material, a conductive agent, an electrolyte I, an electrolyte II and a porous current collector; the electrolyte I comprises an organic solvent, a polymer monomer and a lithium salt; the electrolyte II comprises an organic solvent and a polymerization initiator.
As an embodiment of the present invention, the electroactive material comprises a positively or negatively electroactive material; the positive electricity active material is selected from one or more of olivine-type materials, spinel-type materials or layered materials; the olivine material comprises lithium iron phosphate, lithium manganese phosphate and modified materials thereof; the spinel type material comprises lithium manganate, lithium nickel manganese and modified materials thereof; the layered material comprises lithium cobaltate, lithium nickel cobalt manganese oxide, lithium nickel cobalt aluminate and modified materials thereof; the average particle size of the particles of the positive electricity active material is 0.05-500 mu m; the negative electricity active material is selected from one or more of lithium-embeddable aluminum-based alloy, silicon-based alloy, tin-based alloy, lithium titanium oxide, lithium silicon oxide, metallic lithium powder, silicon-carbon composite and graphite; the average particle diameter of the particles of the negative electricity active material is 0.05-500 mu m.
As an embodiment of the present invention, the conductive agent is a combination of a particulate conductive agent and a fibrous conductive agent, wherein the mass percentage of the particulate conductive agent is 20% to 60%, and the mass percentage of the fibrous conductive agent is 40% to 80%; the granular conductive agent is selected from one or more of conductive carbon black, super carbon black and conductive graphite; the fibrous conductive agent is selected from one or more of single-walled carbon nanotubes, multi-walled carbon nanotubes and vapor-grown carbon fibers.
The mass percentage of the particle conductive agent in the conductive agent is 20-60%, and the mass of the fibrous conductive agent accounts for 40-80% of the mass of all conductive agents; if the content of the particulate conductive agent is too high, the particulate conductive agent is liable to agglomerate to cause a decrease in dispersibility, and if the content of the particulate conductive agent is too low, the point contact capability between the active material and the conductive agent is reduced, thereby affecting the battery performance.
In one embodiment of the present invention, in the electrolyte I, the mass percentage of the organic solvent is 30% to 70%, the mass percentage of the polymer monomer is 10% to 65%, and the mass percentage of the lithium salt is 5% to 30%.
The mass percent of the organic solvent is limited to 30-70%, the polymerization reaction is incomplete due to excessive content of the organic solvent, and a large amount of organic solution is dissociated in a battery system, so that the improvement of the safety of the battery is not facilitated; too little results in excessive polymerization, resulting in a decrease in the mechanical strength and adhesion of the polymer electrolyte, thereby reducing the close contact between the electrolyte and the active material; the mass percent of the lithium salt is 5-30%, if the content of the lithium salt is too much, the lithium salt can not be completely dissolved in the organic solvent to form an ionic state, so that the ionic conductivity of the electrolyte is reduced; too little results in a decrease in the ability of the electrolyte to conduct lithium, which is detrimental to the improvement of battery performance.
In one embodiment of the present invention, in the electrolyte II, the mass percentage of the organic solvent is 80 to 99%, and the mass percentage of the polymerization initiator is 1 to 20%.
As an embodiment of the present invention, the organic solvent is selected from one or more of EMC, EC, DMC, DEC, FEC; the polymer monomer is selected from one or more of ECA, PEG, PC, VC and PMMA; the lithium salt is selected from one or more of LiFSI, LiTFSI, LiClO4 and LiPF 6; the polymerization initiator is one or more of azodiisobutyronitrile, dibenzoyl peroxide and dilauroyl peroxide.
In a second aspect, the invention relates to a preparation method of a high-safety high-load lithium ion electrode plate, which comprises the following steps:
s1: preparing positive electrode slurry: respectively weighing a certain mass of electrolyte I, electrolyte II, a conductive agent and a positive electricity active material according to a certain proportion at the ambient dew point temperature of minus 55 ℃ and normal temperature; adding a conductive agent into the electrolyte I while stirring, and continuously stirring at a high speed for 3-5 h until the conductive agent is uniformly dispersed in the electrolyte; adding a positive electricity active material, and continuously stirring at a high speed for 10-20 h until the active material is uniformly dispersed; finally, adding the electrolyte II, and stirring at a low speed for 2-5 h;
s2: preparing a negative electrode slurry: respectively weighing a certain mass of electrolyte I, electrolyte II, a conductive agent and a negative electricity active material at the ambient dew point temperature of minus 55 ℃ and normal temperature; adding a conductive agent into the electrolyte I while stirring, and continuously stirring at a high speed for 3-5 h until the conductive agent is uniformly dispersed in the electrolyte; adding a negative electricity active material, and continuously stirring at a high speed for 10-20 h until the active material is uniformly dispersed; finally, adding the electrolyte II, and stirring at a low speed for 2-5 h;
s3: electrode manufacturing: coating the two sides of the positive electrode slurry on a positive porous current collector to form a positive electrode plate at the ambient dew point temperature of minus 55 ℃ and normal temperature; coating the negative electrode slurry on the surface of a negative porous current collector to form a negative electrode plate; wherein the coating thickness of the positive electrode slurry is 50 mu m-5 mm, and the coating thickness of the negative electrode slurry is 20 mu m-1 mm.
In one embodiment of the present invention, in step S1, the high-speed stirring speed is a revolution speed of 35 to 50r/min and a rotation speed of 2500r/min to 5000 r/min; the low-speed stirring speed is 15-30 r/min of revolution speed and 500-2000 r/min of rotation speed.
The high-speed stirring speed is selected to be 35-50 r/min of revolution speed and 2500 r/min-5000 r/min of rotation speed, wherein the energy consumption of equipment is increased when the revolution speed is too high, the dispersion between powder materials and electrolyte is not uniform when the revolution speed is too low, the stability of slurry is reduced, the energy consumption of the equipment is increased when the rotation speed is too high, and the coating quality is affected because the active substances cannot be uniformly dispersed due to insufficient shearing force when the rotation speed is too low; the low-speed stirring speed is limited to 15-30 r/min of revolution speed and 500-2000 r/min of rotation speed, wherein too high revolution speed can increase energy consumption of equipment, polymer monomers and polymer initiators can generate slow polymer reaction at the high-speed stirring speed and is not beneficial to improvement of battery performance, too low revolution speed can cause that electrolyte II can not be fully dispersed with active slurry, too high rotation speed can increase energy consumption of the equipment, polymer monomers and polymer initiators can generate slow polymer reaction at the high-speed stirring speed and is not beneficial to improvement of battery performance, and too low self-transmission speed can cause that electrolyte II can not be fully dispersed with the active slurry.
In one embodiment of the present invention, in step S2, the high-speed stirring speed is a revolution speed of 35 to 50r/min and a rotation speed of 2500r/min to 5000 r/min; the low-speed stirring speed is 15-30 r/min of revolution speed and 500-2000 r/min of rotation speed.
In step S1, the electrolyte i, the conductive agent, the positive electrode active material, and the electrolyte ii are added in a mass ratio of 5% to 20%: 1% -10%: 60% -90%: 1% -10%; in step S2, the electrolyte i, the conductive agent, the negative electroactive material, and the electrolyte ii are added in a mass ratio of 5% to 20%: 1% -10%: 50% -85%: 1 to 20 percent. In step S1, if the mass ratio of the electrolyte i, the conductive agent, the positive electrode active material, and the electrolyte ii is not within this range, the dispersion of the electrode active material may be uneven, which may affect the performance of the battery; in step S2, if the mass ratio of the electrolyte i, the conductive agent, the positive electrode active material, and the electrolyte ii is not within this range, the dispersion of the positive electrode active material may be uneven, which may affect the battery performance.
As an embodiment of the present invention, in step S3, the porous current collector is a porous conductive metal layer; the conductive metal layer is a metal net or a metal wire woven net; the mesh shape of the woven net is selected from square, diamond, rectangle or polygon.
As an embodiment of the present invention, in step S3, the positive porous current collector is aluminum metal; the negative porous current collector is copper metal.
In a third aspect, the invention also relates to an application of the electrode plate in a polymer lithium ion battery, and the preparation method of the lithium ion battery comprises the following steps:
s1: assembling the positive electrode plate, the negative electrode plate and the isolating film in a laminated manner, and packaging the positive electrode plate, the negative electrode plate and the isolating film by using an aluminum plastic film to form a lithium ion battery;
s2: standing, vacuumizing and hot pressing.
As one embodiment of the present invention, in step S1, the separator is one selected from a cellulose film, a polyolefin separator, a polyimide-based separator, and a Polyester (PET) -based separator.
As an embodiment of the present invention, the thickness of the separation membrane in S1 is 1 μm to 1000 μm, the porosity of the through hole of the separation membrane is 40% to 99%, and the pore diameter of the through hole of the separation membrane is in the range of 0.01 μm to 1 mm.
In one embodiment of the present invention, the temperature of the standing step in step S2 is 45 to 85 ℃ and the standing time is 1 to 24 hours.
The invention is selected to be kept for 1 h-24 h at the temperature of 45-85 ℃, because the electrolyte I and the electrolyte II can be polymerized to form the polymer electrolyte by the overheat excited polymerization reaction at the temperature, if the temperature is too high, the polymer reaction is excessive, so that the ion conductivity and the mechanical property of the polymer electrolyte are reduced; if the temperature is too low, incomplete polymerization reaction can be caused, and the chemical stability of the polymer electrolyte is reduced; if the standing time is less than 1h, the polymer reaction is incomplete, and the chemical stability of the polymer electrolyte is reduced; if the shelf life is too long, the polymer is excessively reacted, so that the ion conductivity and mechanical properties of the polymer electrolyte are reduced.
As an embodiment of the invention, the temperature of the rest is 60 ℃ and the time of the rest is 10 h.
Compared with the prior art, the invention has the following beneficial effects:
(1) the electrolyte I and the electrolyte II are used for fluidity at normal temperature and form a polymer with high viscosity and high ionic conductivity after high-temperature polymerization reaction, and finally the binderless electrode plate with a high-conductivity network is formed, so that the weight proportion of auxiliary materials is favorably reduced, and the energy density of the battery is improved.
(2) The electrode manufacturing process has no drying process, so that the long-time baking and organic solvent volatilization in the traditional electrode manufacturing process are avoided, the production efficiency is improved, the production energy consumption is reduced, and the pollution to the environment in the battery production process is reduced.
(3) The method can realize the manufacture of the thick electrode and is beneficial to improving the energy density of the battery. Meanwhile, the safety and the stability of the traditional organic electrolyte lithium ion battery are improved by utilizing the characteristics of safety and reliability of the polymer electrolyte.
Drawings
Other features, objects and advantages of the invention will become more apparent upon reading of the detailed description of non-limiting embodiments with reference to the following drawings:
fig. 1 is a flowchart of a method for manufacturing a high-safety high-capacity lithium ion electrode and a polymer battery provided in embodiments 1 to 3 of the present invention.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the spirit of the invention. All falling within the scope of the present invention.
Example 1
The preparation method of the polymer lithium ion battery related to the embodiment is as follows:
(1) preparing positive electrode slurry: under the conditions that the environmental dew point temperature is-60 ℃ and the normal temperature, the temperature is controlled according to the following formula (9): 1: 5: electrolyte I, electrolyte II, conductive agent and positive electricity active material are weighed according to a certain mass ratio of 85. The mass of the organic solvent, the polymeric monomer and the lithium salt in the electrolyte I are respectively as follows: 50% of organic solvent (EC, EMC), 40% of polymerized monomer (ECA) and 10% of lithium salt (LiTFSI). The mass of the organic solvent and the mass of the polymerization initiator in the electrolyte II are respectively as follows: 95% of organic solvent (EC, EMC) and 5% of polymerization initiator (azobisisobutyronitrile). The mass of the super carbon black and the multi-wall carbon nano tube in the conductive agent is respectively as follows: 30% of super carbon black and 70% of multi-wall carbon nano-tubes. The positive electricity active material is a nickel cobalt lithium aluminate ternary material, and the average particle size of the material particles is 1 mu m. And adding a mixture of super-grade carbon black and multi-wall carbon nano tubes into the electrolyte I at a high stirring speed of revolution of 35r/min and rotation speed of 3500r/min, and continuously stirring at a high speed for 5 hours until the conductive agent is uniformly dispersed in the electrolyte. And adding the nickel-cobalt-aluminum ternary material, and continuously stirring at a high speed for 20 hours until the active substances are uniformly dispersed. And adding the electrolyte II, and stirring at a low speed for 3 hours under the conditions of revolution of 15r/min and rotation speed of 800r/min to form high-viscosity positive electrode slurry.
(2) Preparing a negative electrode slurry: under the conditions that the environmental dew point temperature is-60 ℃ and the normal temperature is carried out, the temperature is controlled according to the following formula that 13: 2: 5: and respectively weighing certain mass of electrolyte I, electrolyte II, conductive agent and negative electricity active material according to a proportion of 80. The mass of the organic solvent, the polymeric monomer and the lithium salt in the electrolyte I are respectively as follows: 50% of organic solvent (EC, EMC), 40% of polymerized monomer (ECA) and 10% of lithium salt (LiTFSI). The mass of the organic solvent and the mass of the polymerization initiator in the electrolyte II are respectively as follows: 95% of organic solvent (EC, EMC) and 5% of polymerization initiator (azobisisobutyronitrile). The mass of the super carbon black and the multi-wall carbon nano tube in the conductive agent is respectively as follows: 30% of super carbon black and 70% of multi-wall carbon nano-tubes. The negative electroactive material is a graphite material, and the average particle size of the material particles is 5 μm. And adding a mixture of super-grade carbon black and multi-wall carbon nano tubes into the electrolyte I at a high stirring speed of revolution of 30r/min and rotation speed of 3500r/min, and continuously stirring at a high speed for 4 hours until the conductive agent is uniformly dispersed in the electrolyte. And adding the graphite material, and continuously stirring at high speed for 15h until the active substances are uniformly dispersed. And adding the electrolyte II, and stirring at a low speed for 2 hours under the conditions of revolution of 10r/min and rotation speed of 1000r/min to form high-viscosity negative electrode slurry.
(3) Electrode manufacturing: and coating the two sides of the formed positive electrode slurry on a porous aluminum net under the conditions that the ambient dew point temperature is-60 ℃ and the normal temperature, wherein the meshes are square. The thickness of the two sides of the positive plate is 400 μm. And coating the formed negative electrode slurry on a porous copper mesh with two sides, wherein the meshes are rhombic. The thickness of the two sides of the negative plate is 320 mu m.
(4) Manufacturing an electric core: and forming the formed positive electrode plate, negative electrode plate and cellulose diaphragm into the lithium ion battery in a laminated manner. The thickness of the cellulose diaphragm is 30 μm, the porosity of the through hole is 60%, and the aperture range is 1 μm-600 μm. And standing the prepared lithium ion battery for 10 hours at the temperature of 60 ℃, polymerizing the electrolyte to form polymer electrolyte through thermal excitation polymerization reaction, vacuumizing, and performing hot pressing to finally form the polymer lithium ion battery.
Example 2
In this example, a polymer lithium ion battery was prepared according to substantially the same method and conditions as in example 1. The difference is that in this embodiment: (1) the positive electricity active material is a nickel cobalt lithium manganate ternary material. The mass ratio of the electrolyte I to the electrolyte II to the conductive agent to the positive electricity active material is 10: 2: 6: 82. the conductive agent in the anode slurry is the combination of super carbon black and gas phase growing carbon fiber, and the mass is respectively as follows: 30% of super carbon black and 70% of vapor grown carbon fiber. (2) The negative electricity active substance is a silicon-carbon compound, the conductive agent in the negative electrode slurry is the combination of super carbon black and gas-phase grown carbon fiber, and the mass is respectively as follows: 30% of super carbon black and 70% of vapor grown carbon fiber. (3) The thickness of the positive electrode is 200 μm, and the thickness of the two sides of the negative plate is 150 μm.
Example 3
In this example, a polymer lithium ion battery was prepared according to substantially the same method and conditions as in example 1. The difference is that in this embodiment: (1) the positive electricity active material is a lithium iron phosphate material. The mass of the organic solvent, the polymeric monomer and the lithium salt in the electrolyte I are respectively as follows: 60% of organic solvent (EC, DMC), 30% of polymerized monomer (PC) and 10% of lithium salt (LiTFSI). The mass of the organic solvent and the mass of the polymerization initiator in the electrolyte II are respectively as follows: 97% of organic solvent (EC, DMC) and 3% of polymerization initiator (azobisisobutyronitrile). (2) The mass of the organic solvent, the polymeric monomer and the lithium salt in the electrolyte I in the cathode slurry are respectively as follows: 60% of organic solvent (EC, DMC), 30% of polymerized monomer (PC) and 10% of lithium salt (LiTFSI). The mass of the organic solvent and the mass of the polymerization initiator in the electrolyte II are respectively as follows: 97% of organic solvent (EC, DMC) and 3% of polymerization initiator (azobisisobutyronitrile). (3) The battery is kept at 50 ℃ for 20 h.
Fig. 1 is a flowchart of a method for manufacturing a high-safety high-capacity lithium ion electrode and a polymer battery provided in embodiments 1 to 3 of the present invention.
Comparative example 1
The process and conditions of this comparative example are essentially the same as example 1, except that: the composition of electrolyte II is identical to that of electrolyte I: the electrolyte solution I consists of an organic solvent, a polymerization monomer and a lithium salt, wherein the organic solvent (EC and EMC) is 50 percent, the polymerization monomer (ECA) is 40 percent, and the lithium salt (LiTFSI) is 10 percent; the electrolyte solution II is also composed of an organic solvent, a polymerized monomer and a lithium salt, and the organic solvent (EC, EMC) is 50%, the polymerized monomer (ECA) is 40%, and the lithium salt (LiTFSI) is 10%.
Comparative example 2
The process and conditions of this comparative example are essentially the same as example 1, except that: the composition of electrolyte I was different: the electrolyte solution I consists of an organic solvent and lithium salt. And 90% of organic solvent (EC, EMC) and 10% of lithium salt (LiTFSI).
Comparative example 3
The process and conditions of this comparative example are essentially the same as example 1, except that: the electrolyte solution I has different component contents: 15% of organic solvent (EC, EMC), 75% of polymerized monomer (ECA) and 10% of lithium salt (LiTFSI).
Comparative example 4
The process and conditions of this comparative example are essentially the same as example 1, except that: the electrolyte solution I has different component contents: 85% of organic solvent (EC, EMC), 5% of polymerized monomer (ECA) and 10% of lithium salt (LiTFSI).
Comparative example 5
The process and conditions of this comparative example are essentially the same as example 1, except that: the electrolyte solution II has different component contents: 60% of organic solvent (EC, EMC) and 40% of polymerization initiator (ECA).
Comparative example 6
The method and conditions of this comparative example are essentially the same as in example 1, except that in the cell fabrication: and standing the prepared lithium ion battery for 10 hours at the temperature of 30 ℃.
Performance testing
Positive electrode loading (mg/cm2) test: and dividing the total mass of the active substance and the conductive agent in the positive electrode by the area of the positive electrode sheet to obtain the positive electrode loading capacity.
And (3) energy density testing: the energy discharged by the polymer lithium ion battery at 0.1C was divided by the weight of the battery to obtain the energy density of the battery.
Testing the internal resistance of the battery: the polymer lithium ion battery is charged to a full state at 0.1C, and the internal resistance value of the battery is tested by using an internal resistance meter.
And (3) needle punching test: the test method refers to the GJB 2374A-2013 standard.
And (3) weight extrusion test: the test method refers to the GJB 2374A-2013 standard.
And (3) mechanical impact testing: the test method refers to the GJB 2374A-2013 standard.
The polymer lithium ion batteries prepared in examples 1 to 3 and comparative examples 1 to 5 were subjected to energy density, internal resistance of the battery, needle punching test, weight pressing test, and mechanical impact test, respectively, in accordance with the above test standards. The results of the above tests are shown in Table 1.
TABLE 1 physical Properties of Polymer lithium ion Battery electrodes and various test results
Figure BDA0003089701120000091
Figure BDA0003089701120000101
The foregoing description of specific embodiments of the present invention has been presented. It is to be understood that the present invention is not limited to the specific embodiments described above, and that various changes and modifications may be made by one skilled in the art within the scope of the appended claims without departing from the spirit of the invention.
Those skilled in the art will appreciate that those matters not described in detail in the present specification are well known in the art.

Claims (10)

1. The high-safety high-load lithium ion electrode plate is characterized in that the electrode plate comprises an electroactive material, a conductive agent, an electrolyte I, an electrolyte II and a porous current collector; the electrolyte I comprises an organic solvent, a polymer monomer and a lithium salt; the electrolyte II comprises an organic solvent and a polymerization initiator.
2. The high-safety high-load lithium ion electrode sheet according to claim 1, wherein the electroactive material comprises a positive electroactive material or a negative electroactive material; the positive electricity active material is selected from one or more of olivine-type materials, spinel-type materials or layered materials; the olivine material comprises lithium iron phosphate, lithium manganese phosphate and modified materials thereof; the spinel type material comprises lithium manganate, lithium nickel manganese and modified materials thereof; the layered material comprises lithium cobaltate, lithium nickel cobalt manganese oxide, lithium nickel cobalt aluminate and modified materials thereof; the average particle size of the particles of the positive electricity active material is 0.05-500 mu m; the negative electricity active material is selected from one or more of lithium-embeddable aluminum-based alloy, silicon-based alloy, tin-based alloy, lithium titanium oxide, lithium silicon oxide, metallic lithium powder, silicon-carbon composite and graphite; the average particle diameter of the particles of the negative electricity active material is 0.05-500 mu m.
3. The pole piece of the high-safety high-load lithium ion electrode according to claim 1, wherein the conductive agent is a combination of a granular conductive agent and a fibrous conductive agent, wherein the mass percent of the granular conductive agent is 20-60%, and the mass percent of the fibrous conductive agent is 40-80%; the granular conductive agent is selected from one or more of conductive carbon black, super carbon black and conductive graphite; the fibrous conductive agent is selected from one or more of single-walled carbon nanotubes, multi-walled carbon nanotubes and vapor-grown carbon fibers.
4. The pole piece of the high-safety high-load lithium ion electrode of claim 1, wherein in the electrolyte I, the mass percent of the organic solvent is 30-70%, the mass percent of the polymer monomer is 10-65%, and the mass percent of the lithium salt is 5-30%.
5. The high-safety high-load lithium ion electrode plate of claim 1, wherein in the electrolyte II, the mass percent of the organic solvent is 80-99%, and the mass percent of the polymerization initiator is 1-20%.
6. The high-safety high-load lithium ion electrode sheet according to claim 4 or 5, wherein the organic solvent is selected from one or more of EMC, EC, DMC, DEC and FEC; the polymer monomer is selected from one or more of ECA, PEG, PC, VC and PMMA; the lithium salt is selected from one or more of LiFSI, LiTFSI, LiClO4 and LiPF 6; the polymerization initiator is one or more of azodiisobutyronitrile, dibenzoyl peroxide and dilauroyl peroxide.
7. The preparation method of the high-safety high-load lithium ion electrode plate according to any one of claims 1 to 6, characterized by comprising the following steps:
s1: preparing positive electrode slurry: respectively weighing a certain mass of electrolyte I, electrolyte II, a conductive agent and a positive electricity active material according to a certain proportion at the ambient dew point temperature of minus 55 ℃ and normal temperature; adding a conductive agent into the electrolyte I while stirring, and continuously stirring at a high speed for 3-5 h until the conductive agent is uniformly dispersed in the electrolyte; adding a positive electricity active material, and continuously stirring at a high speed for 10-20 h until the active material is uniformly dispersed; finally, adding the electrolyte II, and stirring at a low speed for 2-5 h;
s2: preparing a negative electrode slurry: respectively weighing a certain mass of electrolyte I, electrolyte II, a conductive agent and a negative electricity active material at the ambient dew point temperature of minus 55 ℃ and normal temperature; adding a conductive agent into the electrolyte I while stirring, and continuously stirring at a high speed for 3-5 h until the conductive agent is uniformly dispersed in the electrolyte; adding a negative electricity active material, and continuously stirring at a high speed for 10-20 h until the active material is uniformly dispersed; finally, adding the electrolyte II, and stirring at a low speed for 2-5 h;
s3: electrode manufacturing: coating the two sides of the positive electrode slurry on a positive porous current collector to form a positive electrode plate at the ambient dew point temperature of minus 55 ℃ and normal temperature; coating the negative electrode slurry on the surface of a negative porous current collector to form a negative electrode plate; wherein the coating thickness of the positive electrode slurry is 50 mu m-5 mm, and the coating thickness of the negative electrode slurry is 20 mu m-1 mm.
8. The method for preparing the high-safety high-load lithium ion electrode plate according to claim 7, wherein in the step S1, the mass ratio of the electrolyte I, the conductive agent, the positive electricity active material and the electrolyte II is 5-20%: 1% -10%: 60% -90%: 1% -10%; in step S2, the electrolyte i, the conductive agent, the negative electroactive material, and the electrolyte ii are added in a mass ratio of 5% to 20%: 1% -10%: 50% -85%: 1 to 20 percent.
9. The application of the electrode plate prepared by the method according to claim 7 or 8 in a polymer lithium ion battery, wherein the preparation method of the lithium ion battery comprises the following steps:
s1: assembling the positive electrode plate, the negative electrode plate and the isolating film in a laminated manner, and packaging the positive electrode plate, the negative electrode plate and the isolating film by using an aluminum plastic film to form a lithium ion battery;
s2: standing, vacuumizing and hot pressing.
10. The use according to claim 9, wherein the temperature of the rest in S2 is 45 ℃ to 85 ℃; the standing time is 1-24 h.
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Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1315061A (en) * 1998-09-10 2001-09-26 韩国科学技术研究院 Solid polymer alloy electrolyte in homogeneous state and manufacturing method therefor, and composite electrode, lithium polymer battery and lithium ion polymer battery
CN1652376A (en) * 2005-01-28 2005-08-10 中国科学院成都有机化学有限公司 Positive electrode material for lithium ion cell, its preparing method and lithium ion cell
CN1684298A (en) * 2004-04-12 2005-10-19 黄穗阳 Design and production of colloidal polymer lithium ion cell
CN101278423A (en) * 2005-09-29 2008-10-01 株式会社Lg化学 Electrode with enhanced performance and electrochemical device comprising the same
CN101685878A (en) * 2008-09-27 2010-03-31 深圳市比克电池有限公司 Preparation method of polymer lithium ion battery
CN103311539A (en) * 2013-05-17 2013-09-18 深圳市慧通天下科技股份有限公司 High-voltage high-energy-density lithium ion battery
CN108232318A (en) * 2018-01-30 2018-06-29 陕西煤业化工技术研究院有限责任公司 A kind of production method of all solid state power lithium-ion battery
CN108281704A (en) * 2018-01-22 2018-07-13 厦门大学 A kind of solid electrolyte composite material and preparation method and application
CN111201639A (en) * 2017-10-10 2020-05-26 日产自动车株式会社 Method for manufacturing battery electrode
CN112103471A (en) * 2020-09-08 2020-12-18 东莞维科电池有限公司 Pole piece and lithium ion battery

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1315061A (en) * 1998-09-10 2001-09-26 韩国科学技术研究院 Solid polymer alloy electrolyte in homogeneous state and manufacturing method therefor, and composite electrode, lithium polymer battery and lithium ion polymer battery
CN1684298A (en) * 2004-04-12 2005-10-19 黄穗阳 Design and production of colloidal polymer lithium ion cell
CN1652376A (en) * 2005-01-28 2005-08-10 中国科学院成都有机化学有限公司 Positive electrode material for lithium ion cell, its preparing method and lithium ion cell
CN101278423A (en) * 2005-09-29 2008-10-01 株式会社Lg化学 Electrode with enhanced performance and electrochemical device comprising the same
CN101685878A (en) * 2008-09-27 2010-03-31 深圳市比克电池有限公司 Preparation method of polymer lithium ion battery
CN103311539A (en) * 2013-05-17 2013-09-18 深圳市慧通天下科技股份有限公司 High-voltage high-energy-density lithium ion battery
CN111201639A (en) * 2017-10-10 2020-05-26 日产自动车株式会社 Method for manufacturing battery electrode
CN108281704A (en) * 2018-01-22 2018-07-13 厦门大学 A kind of solid electrolyte composite material and preparation method and application
CN108232318A (en) * 2018-01-30 2018-06-29 陕西煤业化工技术研究院有限责任公司 A kind of production method of all solid state power lithium-ion battery
CN112103471A (en) * 2020-09-08 2020-12-18 东莞维科电池有限公司 Pole piece and lithium ion battery

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