CN115810729A - High-voltage quick-charging lithium ion battery and manufacturing method thereof - Google Patents
High-voltage quick-charging lithium ion battery and manufacturing method thereof Download PDFInfo
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Abstract
The invention relates to the technical field of battery materials, and discloses a high-voltage quick-charging type lithium ion battery and a manufacturing method thereof, wherein the high-voltage quick-charging type lithium ion battery comprises the steps of preparing conductive glue solution by using a dispersing agent, water and conductive slurry, stirring and mixing anode active substances, metal oxides, an anode conductive agent and anode binder powder, adding part of the conductive glue solution, kneading, adding the rest conductive glue solution, uniformly mixing and coating to obtain an anode; uniformly mixing and coating the nickel cobalt lithium manganate single crystal particles, the cathode binder and the cathode conductive agent to obtain a cathode; and assembling the anode, the diaphragm and the cathode, and injecting electrolyte to prepare the high-voltage quick-charging lithium ion battery. The invention has the beneficial effects that: the metal oxide is mixed in the anode to be used as an active substance supplement, the nickel cobalt lithium manganate single crystal particles are adopted as the anode, and meanwhile, the conductive composition is optimized, so that the anode can be rapidly embedded with lithium and the cathode can be rapidly removed with lithium, the fast charging performance and higher energy density of the battery are effectively improved, and the battery still has excellent cycle life and stability when working under high voltage.
Description
Technical Field
The invention relates to the technical field of battery materials, in particular to a high-voltage quick-charging type lithium ion battery and a manufacturing method thereof.
Background
The lithium ion battery has the characteristics of high specific capacity, small self-discharge, wide working temperature range, high voltage platform, long cycle life, no memory effect, environmental friendliness and the like, is widely applied to the fields of mobile phones, notebook computers, electric tools and the like, and is gradually popularized in the field of electric automobiles.
At present, important cities such as Beijing, tianjin, shenzhen, shanghai and the like in China are built into charging stations for charging hybrid electric vehicles and pure electric vehicles. However, according to the current charging mode of lithium batteries, the electric vehicle often needs 7 to 8 hours for one-time charging, and people hope that the lithium ion batteries have good quick charging capability to shorten the charging time of the batteries along with the acceleration of life pace. Meanwhile, higher and higher requirements are also put forward on the cycle life and the stability of the quick charge of the battery.
Researchers are gradually increasing the investment in lithium ion battery research, and in order to achieve higher energy density of lithium ion batteries, the voltage system research of lithium ion batteries is gradually transiting from a low voltage system to a high voltage system. However, compared with the low voltage, the fast charge cycle performance of the lithium ion battery under the high voltage system is greatly influenced, the cycle performance is extremely unstable, and the cycle life is difficult to be ensured, so that the application of the high voltage fast charge lithium ion battery is severely limited. Therefore, a lithium ion battery having high energy density, good cycle performance, and rapid charge and discharge is urgently needed.
Disclosure of Invention
The invention aims to provide a high-voltage quick-charging lithium ion battery which has high energy density and good cycle performance and can be quickly charged and discharged and a manufacturing method thereof.
The invention solves the technical problems through the following technical means:
the invention provides a manufacturing method of a high-voltage quick-charging type lithium ion battery on the one hand, which comprises the following steps:
(1) Preparing a conductive glue solution by using a dispersing agent, water and a conductive slurry, stirring and mixing an anode active material, an active material replenisher, an anode conductive agent and anode binder powder, adding part of the conductive glue solution into the mixed powder, kneading, adding the rest conductive glue solution, uniformly mixing to obtain a negative paste, and coating the negative paste on a negative current collector to obtain an anode; the active agent supplement is a metal oxide;
(2) Uniformly mixing the nickel cobalt lithium manganate single crystal particles, a cathode binder and a cathode conductive agent to obtain a cathode slurry, and coating the cathode slurry on a cathode current collector to obtain a cathode;
(3) And assembling the anode, the diaphragm and the cathode, and injecting electrolyte to prepare the high-voltage quick-charging lithium ion battery.
Has the advantages that: according to the method, metal oxide is mixed into negative electrode slurry to serve as an active substance supplement, nickel cobalt lithium manganate single crystal particles are adopted as positive electrode active substances, and meanwhile, the conductive composition is optimized; on one hand, the metal oxide increases the graphite interlayer spacing, so that the anode has the rapid lithium insertion capacity, and meanwhile, the combined action of the nickel cobalt lithium manganate single crystal particles and the optimized conductive composition optimizes the cathode conductive network, so that the electron transmission rate is improved, the cathode has the rapid lithium removal capacity, and the rapid charging performance of the battery is effectively improved; on the other hand, the mixed metal oxide also improves the negative electrode potential in the charging process of the battery, the lithium precipitation risk is greatly reduced, the lithium storage capacity of the negative electrode material is effectively improved, the battery has high safety performance and energy density, and the structural stability of the single crystal material is combined.
Preferably, the active substance supplement package in the step (1)MnO included 2 、Fe 3 O 4 、Co 3 O 4 At least one of CuO and NiO.
Preferably, the anode active material in the step (1) is petroleum coke as a raw material, the petroleum coke is graphitized, 1-15% of soft carbon is coated on the surface of the petroleum coke according to the mass ratio, and then granulation is performed to obtain the artificial graphite secondary particles.
Has the advantages that: the application discloses anode active material is with petroleum coke as the raw materials, through graphitization, soft carbon coating after, carries out the granulation again to this forms even soft carbon coating on graphitized petroleum coke surface, and the artificial graphite secondary particle who obtains with this has better electric conductivity, more is favorable to improving the fast performance of filling of battery.
Preferably, in the step (1), the dispersing agent is prepared into a glue solution with the concentration of 1.3-2.0% by using water, then the conductive slurry is added, the mixture is stirred and dispersed until the mixture is uniformly mixed, and then the mixture is kept stand for defoaming to prepare a conductive glue solution; the quantity of the conductive glue solution added into the mixed powder is 30-70% of the total quantity of the conductive glue solution, and the residual conductive glue solution is added after kneading.
Preferably, sodium carboxymethylcellulose is further added into the conductive glue solution in the step (1) as a thickening agent, and the solid content of the conductive glue solution prepared by the method is 1.5-2.0%.
Preferably, the molecular formula of the lithium nickel cobalt manganese oxide in the step (2) is Li (Ni) (1-x-y) Co y Mn x )O 2 Wherein x is more than or equal to 0 and less than or equal to 0.4, y is more than or equal to 0 and less than or equal to 0.3, and D of the nickel cobalt lithium manganate single crystal particles 50 Is 4-7 μm.
Preferably, the mass ratio of the anode active material, the active material supplement, the anode conductive agent, the anode binder and the dispersing agent in the step (1) is 80-97: 1 to 10:0.1 to 3:0.5 to 5:0.5 to 3; the mass ratio of the nickel cobalt lithium manganate single crystal particles, the cathode binder and the cathode conductive agent in the step (2) is 93-99: 0.2 to 5:0.5 to 3.
Preferably, the anode conductive agent in the step (1) is at least one of conductive carbon black, carbon nanotubes, graphene, ketjen black and nanofibers; the anode binder is at least one of acrylate and modified styrene butadiene rubber; in the step (2), the cathode conductive agent is at least one of conductive carbon black, carbon nano tubes, graphene, ketjen black and nano fibers, the cathode binder is modified polyvinylidene fluoride, and the solvent is N-methylpyrrolidone.
Preferably, the coating density of the negative electrode slurry on the negative electrode current collector in the step (1) is 40 to 100g/m 2 。
Preferably, the diaphragm in the step (3) adopts a polyethylene-based film double-sided coating ceramic layer and an adhesive layer, and the porosity of the polyethylene-based film is 42-55%; the ceramic layer is Al 2 O 3 Or AlOOH; the glue layer is at least one of spray polyvinylidene fluoride and polymethyl methacrylate, the spray area is 10-60%, and the density of the glue layer is 0.3-1.0 g/m 2 。
Preferably, the electrolyte in step (3) comprises a lithium salt, a solvent and an additive; the lithium salt comprises at least one of ferric hexafluorophosphate, lithium difluorosulfonimide, lithium difluorooxalato borate, lithium tetrafluoroborate, lithium dioxaoxalato borate and lithium bistrifluoromethanesulfonimide; the solvent comprises at least two of ethylene carbonate, methyl ethyl carbonate, dimethyl carbonate, ethyl acetate and ethyl propionate; the additive comprises at least three of vinylene carbonate, vinyl sulfate, lithium difluorophosphate, fluoroethylene carbonate, 1, 3-propane sultone, lithium difluorooxalato borate, methylene methanedisulfonate, tris (trimethylsilyl) phosphonium and tris (trimethylsilyl) borate; and the mass ratio of the lithium salt to the additive is 12-18: 2 to 10.
The invention also provides a high-voltage quick-charging lithium ion battery prepared by the preparation method.
The invention has the advantages that:
1. according to the method, metal oxide is mixed into negative electrode slurry to serve as an active substance supplement, nickel cobalt lithium manganate single crystal particles are adopted as positive electrode active substances, and meanwhile, the conductive composition is optimized; on one hand, the metal oxide increases the graphite interlayer spacing, so that the anode has the rapid lithium insertion capacity, and meanwhile, the combined action of the nickel cobalt lithium manganate single crystal particles and the optimized conductive composition optimizes the cathode conductive network, so that the electron transmission rate is improved, the cathode has the rapid lithium removal capacity, and the rapid charging performance of the battery is effectively improved; on the other hand, the mixed metal oxide also improves the negative electrode potential in the charging process of the battery, the risk of lithium precipitation is greatly reduced, the lithium storage capacity of the negative electrode material is effectively improved, the battery has higher safety performance and energy density, and the battery is difficult to precipitate lithium in the large-current charging process by combining the structural stability of the single crystal material, so that the battery still has excellent cycle life and stability when working at high voltage of 4.35V or above.
2. The application discloses an anode active material uses petroleum coke as a raw material, and forms an even coating layer through graphitization granulation treatment and soft carbon coating, so that the obtained artificial graphite secondary particles have better conductivity, and the quick charging performance of the battery is better facilitated to be improved.
Drawings
Fig. 1 is a comparative graph of the rapid charge cycle of each battery in test example 1 of the present application.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The test materials and reagents used in the following examples, etc., are commercially available unless otherwise specified.
The specific techniques or conditions not specified in the examples can be performed according to the techniques or conditions described in the literature in the field or according to the product specification.
Example 1
The embodiment provides a manufacturing method of a high-voltage quick-charging lithium ion battery, which comprises the following steps:
(1) Dissolving cellulose dispersant with water to prepare glue solution with the concentration of 1.6 percent; and adding conductive slurry graphene and thickener sodium carboxymethyl cellulose into the glue solution, dispersing at the rotating speed of 30r/min until the mixture is uniformly mixed, standing for defoaming, and obtaining the conductive glue solution with the solid content of 1.5%.
Anode active material, active material replenisher, anode conductive agent, anode binder and dispersant are mixed according to the weight ratio of 93:3:0.8:2:1.2, anode active material graphite powder and active material supplement MnO 2 Uniformly stirring and mixing the powder, the conductive agent, the conductive carbon black powder and the anode binder modified styrene butadiene rubber powder at the rotating speed of 5r/min to obtain mixed powder; dissolving the mixed powder with water, adding 50% of the conductive glue solution, kneading, stirring, kneading into a sphere, adding the rest conductive glue solution, mixing uniformly to obtain cathode slurry, and mixing the cathode slurry according to the proportion of 65g/m 2 The coating density is coated on the copper foil of the negative current collector to obtain the anode.
The anode active material is prepared by taking petroleum coke as a raw material, coating 1% of soft carbon on the surface of the petroleum coke according to the mass ratio after the graphitization treatment of the petroleum coke, and then performing granulation processing treatment to obtain the artificial graphite secondary particles.
(2) With the molecular formula Li (Ni) 0.6 Co 0.1 Mn 0.3 )O 2 ，D 50 Taking nickel cobalt lithium manganate single crystal particles with the particle size of 4-7 mu m as a cathode active substance, and mixing the nickel cobalt lithium manganate single crystal particles, cathode binder modified polyvinylidene fluoride (PVDF) and cathode conductive agent Carbon Nanotubes (CNTs) according to the weight ratio of 97.3:1.5:1.2, dissolving in N-methyl pyrrolidone, mixing uniformly to obtain positive electrode slurry, and mixing the positive electrode slurry according to the mass ratio of 140g/m 2 The surface density of the anode is coated on a positive current collector to prepare a cathode.
(3) The polyethylene base film with ceramic layer and adhesive layer coated on both sides is used as a diaphragm, wherein the porosity of the polyethylene base film is 45%, and the ceramic layer is Al 2 O 3 The glue layer is formed by spraying polyvinylidene fluoride, the spraying area is 10-60%, and the density of the glue layer surface is 0.6g/m 2 。
The method comprises the following steps of (1) taking a mixed solution containing lithium salt, a solvent and an additive as an electrolyte, wherein the lithium salt consists of ferric hexafluorophosphate and lithium difluorosulfonimide; the solvent comprises ethylene carbonate and methyl ethyl carbonate; the additives include vinylene carbonate, vinyl sulfate, lithium difluorophosphate, lithium difluorooxalato borate, methylene methanedisulfonate, tris (trimethylsilyl) phosphonium. The electrolyte comprises the following components in percentage by weight: 24.3% of ethylene carbonate, 56.6% of ethyl methyl carbonate, 0.5% of vinylene carbonate, 1% of vinyl sulfate, 0.8% of lithium difluorophosphate, 0.5% of lithium difluorooxalato borate, 0.5% of methylene methanedisulfonate and 0.3% of tris (trimethylsilyl) phosphorus.
And assembling the anode, the diaphragm and the cathode, and injecting electrolyte to prepare the high-voltage quick-charging lithium ion battery.
Example 2
The embodiment provides a manufacturing method of a high-voltage quick-charging lithium ion battery, which comprises the following steps:
(1) Dissolving cellulose dispersant with water to prepare glue solution with the concentration of 1.3 percent; and adding the conductive slurry carbon nano tube and the thickener sodium carboxymethyl cellulose into the glue solution, dispersing at the rotating speed of 40r/min until the mixture is uniformly mixed, standing for defoaming, and obtaining the conductive glue solution with the solid content of 1.6 percent.
Anode active material, active material replenisher, anode conductive agent, anode binder and dispersant are mixed according to a ratio of 90:5:1.2:2.5:1.3, graphite powder as anode active material and Co as active material replenisher 3 O 4 Uniformly stirring and mixing the powder, the conductive agent, the conductive carbon black powder and the anode binder modified styrene butadiene rubber powder at the rotating speed of 8r/min to obtain mixed powder; dissolving the mixed powder with water, adding 60% of the conductive glue solution, kneading, stirring, kneading into a sphere, adding the rest conductive glue solution, mixing uniformly to obtain cathode slurry, and mixing the cathode slurry according to the ratio of 75g/m 2 The coating density is coated on the copper foil of the negative current collector to prepare the anode.
The anode active material is prepared by taking petroleum coke as a raw material, coating 3% of soft carbon on the surface of the petroleum coke according to the mass ratio after the graphitization treatment of the petroleum coke, and then performing granulation processing treatment to obtain the artificial graphite secondary particles.
(2) With the molecular formula Li (Ni) 0.65 Co 0.07 Mn 0.28 )O 2 ，D 50 Taking nickel cobalt lithium manganate single crystal particles with the diameter of 5 mu m as a cathode active substance, and mixing the nickel cobalt lithium manganate single crystal particles, cathode binder modified polyvinylidene fluoride (PVDF) and cathode conductive agent Carbon Nanotubes (CNTs) according to the weight ratio of 96.7:1.8:1.3, dissolving in N-methyl pyrrolidone, mixing uniformly to obtain positive electrode slurry, and mixing the positive electrode slurry according to the mass ratio of 140g/m 2 The surface density of the anode is coated on a positive current collector to prepare a cathode.
(3) The polyethylene base film with ceramic layer and adhesive layer coated on both sides is used as a diaphragm, wherein the porosity of the polyethylene base film is 48%, and the ceramic layer is Al 2 O 3 The glue layer is formed by spraying polyvinylidene fluoride, the spraying area is 30 percent, and the density of the glue layer surface is 0.7g/m 2 。
The method comprises the following steps of (1) taking a mixed solution containing lithium salt, a solvent and an additive as an electrolyte, wherein the lithium salt consists of ferric hexafluorophosphate and lithium bis (fluorosulfonyl) imide; the solvent comprises ethylene carbonate, methyl ethyl carbonate and dimethyl carbonate; the additives comprise fluoroethylene carbonate, vinylene carbonate, vinyl sulfate, lithium difluoro oxalate borate and 1, 3-propane sultone. The electrolyte comprises the following components in percentage by weight: 12.5 percent of ferric hexafluorophosphate, 1.5 percent of lithium difluorosulfonimide, 24.4 percent of ethylene carbonate, 48.7 percent of methyl ethyl carbonate, 8.1 percent of dimethyl carbonate, 2 percent of fluoroethylene carbonate, 0.5 percent of vinylene carbonate, 1 percent of vinyl sulfate, 0.5 percent of lithium difluorooxalato borate and 0.8 percent of 1, 3-propane sultone.
And assembling the anode, the diaphragm and the cathode, and injecting electrolyte to prepare the high-voltage quick-charging lithium ion battery.
Example 3
The embodiment provides a manufacturing method of a high-voltage quick-charging lithium ion battery, which comprises the following steps:
(1) Dissolving cellulose dispersant with water to prepare glue solution with the concentration of 1.3 percent; and adding the conductive slurry carbon nano tube and the thickener sodium carboxymethyl cellulose into the glue solution, dispersing at the rotating speed of 50r/min until the mixture is uniformly mixed, standing for defoaming, and obtaining the conductive glue solution with the solid content of 2.0 percent.
Anode active material, active material replenisher, anode conductive agent, anode binder and dispersing agent are mixed according to the weight ratio of 85:10:1.2:2.5:1.3, graphite powder as anode active substance and Fe as active substance supplement 3 O 4 Uniformly stirring and mixing the powder, the conductive agent conductive carbon black powder and the anode binder modified styrene butadiene rubber powder at the rotating speed of 10r/min to obtain mixed powder; dissolving the mixed powder with water, adding 70% of the conductive glue solution, kneading, stirring, kneading into a sphere, adding the rest conductive glue solution, mixing uniformly to obtain cathode slurry, and mixing the cathode slurry according to the ratio of 75g/m 2 The coating density is coated on the copper foil of the negative current collector to obtain the anode.
The anode active material is prepared by taking petroleum coke as a raw material, coating 15% of soft carbon on the surface of the petroleum coke according to the mass ratio after the graphitization treatment of the petroleum coke, and then performing granulation processing treatment to obtain the artificial graphite secondary particles.
(2) With the molecular formula Li (Ni) 0.63 Co 0.08 Mn 0.29 )O 2 ，D 50 Taking nickel cobalt lithium manganate single crystal particles with the particle size of 7 mu m as a cathode active substance, and mixing the nickel cobalt lithium manganate single crystal particles, cathode binder modified polyvinylidene fluoride (PVDF) and cathode conductive agent Carbon Nanotubes (CNTs) according to the weight ratio of 96.7:1.8:1.3, dissolving in N-methyl pyrrolidone, mixing uniformly to obtain positive electrode slurry, and mixing the positive electrode slurry according to the mass ratio of 140g/m 2 The surface density of the anode is coated on a positive current collector to prepare a cathode.
(3) The polyethylene base film with ceramic layer and adhesive layer coated on both sides is used as a diaphragm, wherein the porosity of the polyethylene base film is 48%, and the ceramic layer is Al 2 O 3 The glue layer is formed by spraying polyvinylidene fluoride, the spraying area is 60 percent, and the density of the glue layer surface is 0.7g/m 2 。
The method comprises the following steps of (1) taking a mixed solution containing lithium salt, a solvent and an additive as an electrolyte, wherein the lithium salt consists of ferric hexafluorophosphate and lithium bis (fluorosulfonyl) imide; the solvent comprises ethylene carbonate, methyl ethyl carbonate and dimethyl carbonate; the additives comprise fluoroethylene carbonate, vinylene carbonate, vinyl sulfate, lithium difluoro oxalate borate and 1, 3-propane sultone. The electrolyte comprises the following components in percentage by weight: 12.5 percent of ferric hexafluorophosphate, 1.5 percent of lithium difluorosulfonimide, 24.4 percent of ethylene carbonate, 40.6 percent of methyl ethyl carbonate, 16.2 percent of dimethyl carbonate, 1.5 percent of fluoroethylene carbonate, 0.5 percent of vinylene carbonate, 1.5 percent of vinyl sulfate, 0.5 percent of lithium difluorooxalatoborate and 0.8 percent of 1, 3-propane sultone.
And assembling the anode, the diaphragm and the cathode, and injecting electrolyte to prepare the high-voltage quick-charging lithium ion battery.
Example 4
The embodiment provides a manufacturing method of a high-voltage quick-charging lithium ion battery, which comprises the following steps:
(1) Dissolving cellulose dispersant with water to prepare glue solution with the concentration of 2.0 percent; and adding the conductive slurry carbon nano tube and the thickener sodium carboxymethyl cellulose into the glue solution, dispersing at the rotating speed of 50r/min until the mixture is uniformly mixed, standing for defoaming, and obtaining the conductive glue solution with the solid content of 1.8%.
Anode active material, active material replenisher, anode conductive agent, anode binder and dispersing agent are mixed according to the weight ratio of 84:5:3:5:3, stirring and uniformly mixing anode active substance graphite powder, active substance supplement CuO powder, conductive agent conductive carbon black powder and anode binder modified styrene butadiene rubber powder at the rotating speed of 10r/min to obtain mixed powder; dissolving the mixed powder with water, adding 30% of the conductive glue solution, kneading, stirring, kneading into a sphere, adding the rest conductive glue solution, mixing uniformly to obtain cathode slurry, and mixing the cathode slurry according to the ratio of 100g/m 2 The coating density is coated on the copper foil of the negative current collector to obtain the anode.
The anode active material is prepared by taking petroleum coke as a raw material, coating 1% of soft carbon on the surface of the petroleum coke according to the mass ratio after the graphitization treatment of the petroleum coke, and then performing granulation processing treatment to obtain the artificial graphite secondary particles.
(2) With the molecular formula Li (Ni) 0.63 Co 0.08 Mn 0.29 )O 2 ，D 50 Taking nickel cobalt lithium manganate single crystal particles with the diameter of 4 mu m as cathode active substances, and mixing the nickel cobalt lithium manganate single crystal particles and cathodePolar binder modified polyvinylidene fluoride (PVDF), cathode conductive agent Carbon Nanotubes (CNTs) were mixed in a ratio of 93.5:4.8:1.7, dissolving in N-methyl pyrrolidone, uniformly mixing to obtain positive electrode slurry, and mixing the positive electrode slurry according to the mass ratio of 140g/m 2 The surface density of the anode is coated on a positive current collector to prepare a cathode.
(3) The polyethylene base film with ceramic layer and adhesive layer coated on both sides is used as a diaphragm, wherein the porosity of the polyethylene base film is 50%, and the ceramic layer is Al 2 O 3 The adhesive layer is formed by spraying polyvinylidene fluoride, the spraying area is 10 percent, and the density of the adhesive layer surface is 0.7g/m 2 。
The method comprises the following steps of (1) taking a mixed solution containing lithium salt, a solvent and an additive as an electrolyte, wherein the lithium salt consists of ferric hexafluorophosphate and lithium bis (fluorosulfonyl) imide; the solvent comprises ethylene carbonate, methyl ethyl carbonate and dimethyl carbonate; the additives comprise fluoroethylene carbonate, vinylene carbonate, vinyl sulfate, lithium difluoro oxalate borate and 1, 3-propane sultone. The electrolyte comprises the following components in percentage by weight: 12.5% of ferric hexafluorophosphate, 1.5% of lithium difluorosulfonimide, 24.4% of ethylene carbonate, 40.6% of methyl ethyl carbonate, 16.2% of dimethyl carbonate, 1.5% of fluoroethylene carbonate, 0.5% of vinylene carbonate, 1.5% of ethylene sulfate, 0.5% of lithium difluorooxalato borate and 0.8% of 1, 3-propane sultone.
And assembling the anode, the diaphragm and the cathode, and injecting electrolyte to prepare the high-voltage quick-charging lithium ion battery.
Example 5
The embodiment provides a manufacturing method of a high-voltage quick-charging lithium ion battery, which comprises the following steps:
(1) Dissolving cellulose dispersant with water to prepare glue solution with the concentration of 1.3 percent; and then adding the conductive slurry carbon nano tube and the thickening agent sodium carboxymethyl cellulose into the glue solution, dispersing at the rotating speed of 40r/min until the materials are uniformly mixed, standing for defoaming, and preparing the conductive glue solution with the solid content of 1.8%.
Anode active material, active material replenisher, anode conductive agent, anode binder and dispersant are mixed according to a ratio of 90:5:1.2:2.5:1.3, the anode active material graphite powder and the activityUniformly stirring NiO powder serving as a substance replenisher, conductive carbon black powder serving as a conductive agent and styrene butadiene rubber powder modified by an anode binder at the rotating speed of 8r/min to obtain mixed powder; dissolving the mixed powder with water, adding 60% of the conductive glue solution, kneading, stirring, kneading into a sphere, adding the rest conductive glue solution, mixing uniformly to obtain cathode slurry, and mixing the cathode slurry according to the proportion of 40g/m 2 The coating density is coated on the copper foil of the negative current collector to prepare the anode.
The anode active material is prepared by taking petroleum coke as a raw material, coating 6% of soft carbon on the surface of the petroleum coke according to the mass ratio after the graphitization treatment of the petroleum coke, and then performing granulation processing treatment to obtain the artificial graphite secondary particles.
(2) With the molecular formula Li (Ni) 0.65 Co 0.07 Mn 0.28 )O 2 ，D 50 Taking nickel cobalt lithium manganate single-crystal particles with the particle size of 6 microns as a cathode active substance, and mixing the nickel cobalt lithium manganate single-crystal particles, cathode binder modified polyvinylidene fluoride (PVDF) and cathode conductive agent Carbon Nanotubes (CNTs) according to the weight ratio of 98.7:0.5:0.8 in the mass ratio, is dissolved in N-methyl pyrrolidone and is uniformly mixed to obtain anode slurry, and the anode slurry is mixed according to the proportion of 140g/m 2 The surface density of the anode is coated on a positive current collector to prepare a cathode.
(3) The polyethylene base film with a ceramic layer and a glue layer coated on both sides is used as a diaphragm, wherein the porosity of the polyethylene base film is 42%, the ceramic layer is AlOOH, the glue layer is formed by spraying polymethyl methacrylate, the spraying area is 20%, and the density of the glue layer surface is 0.3g/m 2 。
The method comprises the following steps of (1) taking a mixed solution containing lithium salt, a solvent and an additive as an electrolyte, wherein the lithium salt consists of ferric hexafluorophosphate and lithium bis (fluorosulfonyl) imide; the solvent comprises ethylene carbonate, methyl ethyl carbonate and dimethyl carbonate; the additives comprise fluoroethylene carbonate, vinylene carbonate, vinyl sulfate, lithium difluoro oxalate borate and 1, 3-propane sultone. The electrolyte comprises the following components in percentage by weight: 12.5% of ferric hexafluorophosphate, 1.5% of lithium difluorosulfonimide, 24.4% of ethylene carbonate, 48.7% of methyl ethyl carbonate, 8.1% of dimethyl carbonate, 2% of fluoroethylene carbonate, 0.5% of vinylene carbonate, 1% of ethylene sulfate, 0.5% of lithium difluorooxalato borate and 0.8% of 1, 3-propane sultone.
And assembling the anode, the diaphragm and the cathode, and injecting electrolyte to prepare the high-voltage quick-charging lithium ion battery.
Comparative example 1
The comparative example provides a manufacturing method of a high-voltage quick-charging type lithium ion battery, which comprises the following steps:
(1) Dissolving cellulose dispersant with water to prepare glue solution with the concentration of 1.3 percent; and adding the conductive slurry carbon nano tube and the thickener sodium carboxymethyl cellulose into the glue solution, dispersing at the rotating speed of 40r/min until the mixture is uniformly mixed, standing for defoaming, and obtaining the conductive glue solution with the solid content of 1.6 percent.
The anode active material, the anode conductive agent, the anode binder and the dispersing agent are mixed according to the following ratio of 95:1.2:2.5:1.3, stirring and uniformly mixing anode active substance graphite powder, conductive agent conductive carbon black powder and anode binder modified styrene butadiene rubber powder to obtain mixed powder; dissolving the mixed powder with water at the rotating speed of 8r/min, adding 50% of the conductive glue solution, kneading, adding the rest conductive glue solution after stirring and kneading into a sphere, mixing uniformly to obtain negative electrode slurry, and mixing the negative electrode slurry according to the proportion of 90g/m 2 The coating density is coated on the copper foil of the negative current collector to prepare the anode.
The anode active material is prepared by taking petroleum coke as a raw material, coating 4% of soft carbon on the surface of the petroleum coke according to the mass ratio after the graphitization treatment of the petroleum coke, and then performing granulation processing treatment to obtain the artificial graphite secondary particles.
(2) With the molecular formula Li (Ni) 0.63 Co 0.08 Mn 0.29 )O 2 ，D 50 Taking nickel cobalt lithium manganate single crystal particles with the diameter of 5 mu m as a cathode active substance, and mixing the nickel cobalt lithium manganate single crystal particles, cathode binder modified polyvinylidene fluoride (PVDF) and cathode conductive agent Carbon Nanotubes (CNTs) according to the weight ratio of 96.7:1.8:1.3, dissolving in N-methyl pyrrolidone, mixing uniformly to obtain positive electrode slurry, and mixing the positive electrode slurry according to the mass ratio of 140g/m 2 The surface density of the anode is coated on a positive current collector to prepare a cathode.
(3) In pairThe polyethylene base film of the top coating ceramic layer and the glue layer is a diaphragm, wherein the porosity of the polyethylene base film is 50%, and the ceramic layer is Al 2 O 3 The glue layer is formed by spraying polyvinylidene fluoride, the spraying area is 20 percent, and the density of the glue layer surface is 0.7g/m 2 。
Taking a mixed solution containing lithium salt, a solvent and an additive as an electrolyte, wherein the lithium salt is ferric hexafluorophosphate; the solvent comprises ethylene carbonate, methyl ethyl carbonate and dimethyl carbonate; the additive comprises fluoroethylene carbonate, vinylene carbonate, ethylene sulfate and 1, 3-propane sultone. The electrolyte comprises the following components in percentage by weight: iron hexafluorophosphate 14%, ethylene carbonate 24.4%, ethyl methyl carbonate 40.6%, dimethyl carbonate 16.2%, fluoroethylene carbonate 1.5%, vinylene carbonate 0.5%, ethylene sulfate 2%, 1, 3-propane sultone 0.8%.
And (3) assembling the anode, the diaphragm and the cathode, and injecting electrolyte to prepare an aluminum shell 27148101A58Ah cell so as to prepare the high-voltage quick-charging lithium ion battery.
Comparative example 2
The comparative example provides a manufacturing method of a high-voltage quick-charging type lithium ion battery, which is different from the embodiment 2 in that: in the step (2), the nickel cobalt lithium manganate adopts D 50 10 μm non-monocrystalline particles, the other operating and process parameters were the same as in example 2.
Comparative example 3
The comparative example provides a manufacturing method of a high-voltage quick-charging type lithium ion battery, which is different from the embodiment 2 in that: in the step (3), the electrolyte takes ferric hexafluorophosphate as a lithium salt; ethylene carbonate, methyl ethyl carbonate and dimethyl carbonate are used as solvents; fluoroethylene carbonate, vinylene carbonate, ethylene sulfate and 1, 3-propane sultone are used as additives. The electrolyte comprises the following components in percentage by weight: iron hexafluorophosphate 14%, ethylene carbonate 24.4%, ethyl methyl carbonate 40.6%, dimethyl carbonate 16.2%, fluoroethylene carbonate 1.5%, vinylene carbonate 0.5%, vinyl sulfate 2%, 1, 3-propane sultone 0.8%, and other operating and process parameters are the same as in example 2.
Test example 1
The average charging capacity of each cell was determined by examining the lithium analysis windows of the lithium ion cells prepared in examples 1-5 and comparative examples 1-3. The specific method of the lithium separation window comprises the following steps: the method comprises the following steps of adopting a three-electrode battery, wherein the three-electrode battery comprises a negative electrode and a reference electrode, plating lithium on the surface of the reference electrode, charging the battery at a set temperature and a set charging current, continuously reducing the potential of the negative electrode in the charging process, and testing the overpotential value: and after the over-potential of the battery is determined, judging that the lithium analysis occurs in the battery when the potential difference between the charged negative electrode and the reference electrode is lower than the over-potential, and determining a lithium analysis window of the battery by combining actual interface disassembly as a final judgment standard.
In this test example, the batteries were charged at a temperature of 25 ℃ at charging rates of 2C, 3C, 4C and 5C, respectively, and the charging windows of the batteries of the respective groups under these conditions are shown in table 1.
TABLE 1 lithium ion Battery charging Window
As can be seen from table 1, the lithium ion battery prepared in the embodiment of the present application has a fast charging capability of 4C to 5C, and the charging capability of the charging window is above 3.8C at a large current, which is significantly better than the average charging capability of about 3.5C in the comparative example, and the average charging capability of the embodiment 2 of the present application is the largest, which is followed by the embodiment 1.
Test example 2
The lithium ion batteries prepared in examples 1 to 5 and comparative examples 1 to 3 were charged at 25 ℃ at an average charge rate of 3.5C to 80% SOC, and then charged at 0.5C to 100% SOC (upper charge limit voltage of 4.4V), 1C constant current discharged. The rapid charge cycle comparison curve for each cell is shown in fig. 1. In the figure, examples 1 to 5 correspond to curves (1) to (1), and comparative examples 1 to 3 correspond to curves (6) to (6).
As can be seen from fig. 1, compared with the comparative example, the high-voltage quick-charge lithium ion batteries prepared in examples 1 to 5 all have excellent normal-temperature quick-charge performance, and the quick-charge life is over 2000 weeks, which is significantly improved compared with 720 weeks of the comparative example. Example 3 deterioration occurred in the late cycle because the addition of a large amount of the active material supplement affected the cycle stability of the battery, indicating that the incorporation of a small amount of the active material supplement did not significantly affect the cycle stability of the battery, and thus, the amount of the active material supplement was strictly controlled in the production.
The application has the implementation principle that: according to the method, metal oxide is mixed into negative electrode slurry to serve as an active substance supplement, nickel cobalt lithium manganate single crystal particles are adopted as positive electrode active substances, and meanwhile, the conductive composition is optimized; on one hand, the metal oxide increases the graphite interlayer spacing, so that the anode has the capability of quickly inserting lithium, and meanwhile, the combined action of the nickel-cobalt lithium manganate single crystal particles and the optimized conductive composition optimizes the cathode conductive network, improves the electron transmission rate, so that the cathode has the capability of quickly removing lithium, and effectively improves the quick charging performance of the battery; on the other hand, the mixed metal oxide also improves the negative electrode potential in the charging process of the battery, the risk of lithium precipitation is greatly reduced, the lithium storage capacity of the negative electrode material is effectively improved, the battery has higher safety performance and energy density, and the battery is difficult to precipitate lithium in the large-current charging process by combining the structural stability of the single crystal material, so that the battery still has excellent cycle life and stability when working at high voltage of 4.35V or above.
The application discloses an anode active material uses petroleum coke as a raw material, and forms an even coating layer through graphitization granulation treatment and soft carbon coating, so that the obtained artificial graphite secondary particles have better conductivity, and the quick charging performance of the battery is better facilitated to be improved.
The above examples are only intended to illustrate the technical solution of the present invention, and not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (10)
1. A manufacturing method of a high-voltage quick-charging type lithium ion battery is characterized by comprising the following steps: the method comprises the following steps:
(1) Preparing a conductive glue solution by using a dispersing agent, water and a conductive slurry, stirring and mixing an anode active substance, an active substance replenisher, an anode conductive agent and anode binder powder, adding part of the conductive glue solution into the mixed powder, kneading, adding the rest conductive glue solution, uniformly mixing to obtain a negative electrode slurry, and coating the negative electrode slurry on a negative electrode current collector to obtain an anode; the active agent supplement is a metal oxide;
(2) Uniformly mixing the nickel cobalt lithium manganate single crystal particles, a cathode binder and a cathode conductive agent to obtain a cathode slurry, and coating the cathode slurry on a cathode current collector to obtain a cathode;
(3) And assembling the anode, the diaphragm and the cathode, and injecting electrolyte to prepare the high-voltage quick-charging lithium ion battery.
2. The method for manufacturing the high-voltage fast-charging lithium ion battery according to claim 1, wherein the method comprises the following steps: the active agent supplement in step (1) comprises MnO 2 、Fe 3 O 4 、Co 3 O 4 At least one of CuO and NiO.
3. The method for manufacturing the high-voltage fast-charging lithium ion battery according to claim 1, wherein the method comprises the following steps: in the step (1), the anode active material is prepared by using petroleum coke as a raw material, graphitizing the petroleum coke, coating 1-15% of soft carbon on the surface of the petroleum coke according to the mass ratio, and granulating to obtain artificial graphite secondary particles.
4. The method for manufacturing the high-voltage fast-charging lithium ion battery according to claim 1, wherein the method comprises the following steps: in the step (1), firstly, a dispersing agent is prepared into a glue solution with the concentration of 1.3-2.0% by using water, then, a conductive slurry is added, and after the uniform mixing, standing and defoaming are carried out to prepare a conductive glue solution; the amount of the conductive glue solution added into the mixed powder is 30-70% of the total amount of the conductive glue solution, and the residual conductive glue solution is added after kneading.
5. The method for manufacturing the high-voltage fast-charging lithium ion battery according to claim 1, wherein the method comprises the following steps: the molecular formula of the lithium nickel cobalt manganese oxide in the step (2) is Li (Ni) (1-x-y) Co y Mn x )O 2 Wherein x is more than or equal to 0 and less than or equal to 0.4, y is more than or equal to 0 and less than or equal to 0.3, and D of the nickel cobalt lithium manganate single crystal particles 50 Is 4-7 μm.
6. The method for manufacturing a high-voltage fast-charging lithium ion battery according to claim 1, characterized in that: in the step (1), the mass ratio of the anode active substance, the active substance replenisher, the anode conductive agent, the anode binder and the dispersing agent is 80-97: 1 to 10:0.1 to 3:0.5 to 5:0.5 to 3; the mass ratio of the nickel cobalt lithium manganate single crystal particles, the cathode binder and the cathode conductive agent in the step (2) is 93-99: 0.2 to 5:0.5 to 3.
7. The method for manufacturing a high-voltage fast-charging lithium ion battery according to claim 1, characterized in that: the anode conductive agent in the step (1) is at least one of conductive carbon black, carbon nano tubes, graphene, ketjen black and nano fibers; the anode binder is at least one of acrylate and modified styrene butadiene rubber; in the step (2), the cathode conductive agent is at least one of conductive carbon black, carbon nano tubes, graphene, ketjen black and nano fibers, the cathode binder is modified polyvinylidene fluoride, and the solvent is N-methylpyrrolidone; the coating density of the negative electrode slurry on the negative electrode current collector in the step (1) is 40-100 g/m 2 。
8. The method for manufacturing a high-voltage fast-charging lithium ion battery according to claim 1, characterized in that: the diaphragm in the step (3) adopts a polyethylene base film with a ceramic layer and an adhesive layer coated on both sides, and holes of the polyethylene base filmThe porosity is 42-55%; the ceramic layer is Al 2 O 3 Or AlOOH; the glue layer is at least one of spray-coating polyvinylidene fluoride and polymethyl methacrylate, the spray-coating area is 10-60%, and the glue layer surface density is 0.3-1.0 g/m 2 。
9. The method for manufacturing the high-voltage fast-charging lithium ion battery according to claim 1, wherein the method comprises the following steps: the electrolyte in the step (3) comprises lithium salt, a solvent and an additive; wherein the lithium salt comprises at least one of ferric hexafluorophosphate, lithium bis (fluorosulfonyl) imide, lithium difluoro (oxalato) borate, lithium tetrafluoroborate, lithium bis (oxalato) borate and lithium bis (trifluoromethanesulfonyl) imide; the solvent comprises at least two of ethylene carbonate, methyl ethyl carbonate, dimethyl carbonate, ethyl acetate and ethyl propionate; the additive comprises at least three of vinylene carbonate, vinyl sulfate, lithium difluorophosphate, fluoroethylene carbonate, 1, 3-propane sultone, lithium difluorooxalato borate, methylene methanedisulfonate, tris (trimethylsilyl) phosphorus and tris (trimethylsilyl) borate; and the mass ratio of the lithium salt to the additive is 12-18: 2 to 10.
10. The high-voltage fast-charging lithium ion battery prepared by the preparation method according to any one of claims 1 to 9.
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