CN109309208B - Positive electrode slurry, positive plate and electrochemical energy storage device - Google Patents
Positive electrode slurry, positive plate and electrochemical energy storage device Download PDFInfo
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Abstract
The application provides a positive electrode slurry, a positive electrode plate and an electrochemical energy storage device. The positive electrode slurry includes a solid component and a solvent. The solid component includes a positive electrode active material. The solid component also comprises an additive which is an organic compound containing a thienyl group. The organic compound containing the thienyl group can play a role in passivating the anode active material, and can effectively inhibit continuous electrochemical oxidation reaction between the electrolyte and the anode active material, so that the oxidation resistance of the anode plate can be improved, the cycle performance, the high-temperature storage performance and the overcharge safety performance of the electrochemical energy storage device can be improved, and the gas production rate of the electrochemical energy storage device can be reduced. In addition, the preparation process of the positive plate is simple, easy to operate and suitable for large-scale production.
Description
Technical Field
The application relates to the field of energy storage devices, in particular to anode slurry, an anode plate and an electrochemical energy storage device.
Background
Lithium ion batteries have rapidly captured the consumer electronics market and have expanded their applications in the field of power storage rapidly due to their advantages of high operating voltage, large specific capacity, small self-discharge, long cycle life, no memory effect, environmental friendliness, and good safety. With the application of lithium ion batteries in new fields such as electric vehicles, hybrid electric vehicles, large-scale energy storage power stations, mobile energy storage devices and the like, further improvement of energy density and safety performance of lithium ion batteries is urgent.
The high nickel anode material becomes a research hotspot due to the characteristic that the theoretical specific capacity of the high nickel anode material is higher than that of other anode active materials. However, during the use process, the high voltage of the interface of the high-nickel anode material and the catalytic and surface effects of transition metal atoms in the high-nickel anode material cause the conventional electrolyte to generate a significant oxidative decomposition reaction, thereby causing the electrochemical performance of the lithium ion battery to be deteriorated; in addition, the high-nickel cathode material has larger amount of lithium-released under the same voltage, so that the structure stability is poor, the transition metal is dissolved out through a reduction reaction, and an interface side reaction is easily caused, so that the safety risk of the lithium ion battery is increased.
In the lithium ion battery, for the problems, a method of introducing a film forming additive into an electrolyte is commonly adopted at present to passivate the interface of a high-nickel anode material, so that the dynamic performance of the high-nickel anode material can be improved while side reactions are reduced; functional additives such as overcharge prevention, flame retardance and the like are introduced to improve the safety performance of the flame-retardant coating. But the simultaneous introduction of a plurality of additives can not lead the lithium ion battery to effectively take both the dynamic performance and the safety performance into consideration.
Disclosure of Invention
In view of the problems in the background art, an object of the present application is to provide a positive electrode slurry, a positive electrode sheet, and an electrochemical energy storage device, wherein the positive electrode slurry includes an organic compound containing a thiophene group, which can passivate a positive electrode active material, thereby improving oxidation resistance of the positive electrode sheet, improving cycle performance, high-temperature storage performance, and overcharge safety performance of the electrochemical energy storage device, and reducing gas production of the electrochemical energy storage device.
In order to achieve the above objects, in one aspect of the present application, there is provided a positive electrode slurry including a solid component and a solvent. The solid component includes a positive electrode active material. The solid component also comprises an additive which is an organic compound containing a thienyl group.
In another aspect of the present application, the present application provides a positive electrode sheet including a positive electrode current collector and a positive electrode slurry layer. The positive slurry layer is arranged on the positive current collector. The positive electrode slurry layer is formed by drying the positive electrode slurry according to an aspect of the present application.
In yet another aspect of the present application, an electrochemical energy storage device is provided that includes a positive electrode sheet of another aspect of the present application.
Compared with the prior art, the beneficial effects of this application do:
the positive electrode slurry comprises the organic compound containing the thienyl, can play a role in passivating the positive electrode active material, and can effectively inhibit continuous electrochemical oxidation reaction between electrolyte and the positive electrode active material, so that the oxidation resistance of a positive electrode plate can be improved, the cycle performance, the high-temperature storage performance and the overcharge safety performance of an electrochemical energy storage device are improved, and the gas production rate of the electrochemical energy storage device is reduced.
The preparation process of the positive plate is simple, easy to operate and suitable for large-scale production.
Detailed Description
The positive electrode slurry, the positive electrode sheet, and the electrochemical energy storage device according to the present application are described in detail below.
First, the positive electrode slurry according to the first aspect of the present application is explained.
The positive electrode slurry according to the first aspect of the present application includes a solid component and a solvent. The solid component includes a positive electrode active material. The solid component further comprises an additive. The additive is an organic compound containing a thienyl group.
In the cathode slurry according to the first aspect of the present application, the organic compound containing a thienyl group is prone to an electrochemical polymerization reaction, and the generated conductive polymer can be stably coated on the surface of the cathode active material to passivate the cathode active material, so that an electrochemical oxidation reaction between the electrolyte and the cathode active material can be effectively inhibited, oxygen release of the cathode active material can be reduced to a certain extent, oxidation resistance of the cathode sheet is improved, the gas production of the electrochemical energy storage device can be reduced, the cathode interface impedance of the electrochemical energy storage device during a circulation process can be reduced, the circulation performance and high-temperature storage performance of the electrochemical energy storage device can be improved, and in addition, the conductive polymer generated after the organic compound containing a thienyl group is electrochemically polymerized can also be effectively reduced to generate heat by a side reaction at a high pressure on the cathode interface, meanwhile, due to the characteristic that the self high-temperature electronic impedance of the conductive polymer is increased rapidly, the overcharge safety performance of the electrochemical energy storage device can be greatly improved. According to the electrochemical energy storage device and the preparation method thereof, the organic compound containing the thienyl group is used as the anode slurry additive, on one hand, the passivation effect of the organic compound on the anode active material can be kept, the oxidation resistance of the anode plate is improved, and further, the electrochemical performance of the electrochemical energy storage device is improved, and on the other hand, the phenomenon that when the organic compound is used as the electrolyte additive in the prior art, electrochemical polymerization reaction occurs at the anode and the cathode at high temperature, and the generated conductive polymer penetrates through the isolating membrane to possibly cause serious self-discharge and even short circuit of the electrochemical energy storage device can be overcome.
In the positive electrode slurry according to the first aspect of the present application, the organic compound containing a thienyl group is selected from one or more compounds represented by formula 1 and formula 2; in formula 1, R1、R2Each independently selected from one of H, F, Cl, Br, I, nitro, cyano, carboxyl, sulfonic group, substituted or unsubstituted alkyl with 1-10 carbon atoms, substituted or unsubstituted alkenyl with 2-10 carbon atoms, substituted or unsubstituted alkynyl with 2-10 carbon atoms, substituted or unsubstituted aryl with 6-10 carbon atoms, substituted or unsubstituted alkoxy with 1-10 carbon atoms, substituted or unsubstituted alkenyloxy with 2-10 carbon atoms, substituted or unsubstituted alkynyloxy with 2-10 carbon atoms and substituted or unsubstituted aryl alkoxy with 6-10 carbon atoms, wherein the substituent is selected from one or more of halogen, nitro, cyano, carboxyl and sulfonic group, R is selected from one or more of hydroxyl, carboxyl, aryl, heteroaryl1And R2Can also be connected with each other to form a ring; in formula 2, n is an integer of 0 to 4, R3、R4、R5、R6、R7、R8Each independently selected from H, F, Cl, Br, I, nitro, cyano, carboxyl, sulfonic group, substituted or unsubstituted alkyl group with 1-10 carbon atoms, substituted or unsubstituted alkenyl group with 2-10 carbon atoms, substituted or unsubstituted alkynyl group with 2-10 carbon atoms, substituted or unsubstituted aromatic alkyl group with 6-10 carbon atoms, substituted or unsubstituted alkoxy group with 1-10 carbon atoms, and substituted or unsubstituted COne of an alkene oxyl with the atomic number of 2-10, a substituted or unsubstituted alkyne oxyl with the carbon number of 2-10 and a substituted or unsubstituted aromatic hydrocarbyloxy with the carbon number of 6-10, wherein the substituent is selected from one or more of halogen, nitryl, cyano, carboxyl and sulfonic group, R is3And R4、R5And R6、R7And R8It is also possible to interconnect the rings independently of one another.
In the positive electrode slurry according to the first aspect of the present application, in formula 2, n is an integer of 0 to 4, and if the value of n is too large, it is difficult for the organic compound containing a thienyl group to be uniformly distributed in the positive electrode slurry, which may seriously affect the appearance of the positive electrode sheet, and preferably, n is 0, 1 or 2.
In the positive electrode slurry according to the first aspect of the present application, the organic compound containing a thienyl group is selected from one or more of the following compounds;
in the positive electrode slurry according to the first aspect of the present application, the mass of the organic compound containing a thienyl group is 0.1% to 2% of the total mass of the solid components. Within the mass range, on one hand, the oxidation resistance of the positive plate can be effectively improved; on the other hand, the organic compound containing the thienyl, which is solidified in the positive slurry layer after drying, cannot be obviously dissolved into the electrolyte, so that the electrochemical polymerization reaction cannot occur at the positive and negative interfaces at the same time at high temperature in the electrochemical energy storage device, and the generated conductive polymer penetrates through the isolating membrane to cause the self-discharge of the electrochemical energy storage device, thereby ensuring the high-temperature storage performance of the electrochemical energy storage device. If the dosage is too small, the passivation effect on the anode active material is limited, so that the electrochemical performance improvement effect on the electrochemical energy storage device is not obvious; conversely, excessive use of the positive electrode plate may affect the transfer of ions in the positive electrode plate, thereby deteriorating the performance of the electrochemical energy storage device.
In the positive electrode slurry according to the first aspect of the present application, the kind of the positive electrode active material is not particularly limited and may be selected according to actual needs, and specifically, the positive electrode active material may be selected from a lithium-containing transition metal oxide or a sodium-containing transition metal oxide.
In the cathode slurry according to the first aspect of the present application, the kind of the lithium-containing transition metal oxide is not particularly limited and may be selected according to actual needs, and specifically, the lithium-containing transition metal oxide may be selected from LiCoO2、LiNixCoyMn(1-x-y)O2、LiNixCoyAl(1-x-y)O2、LiNixMn1-xO2、LiNiO2、LiMnO2、Li2MnO4Wherein x, y, and x + y are less than 1, preferably, the transition metal oxide of lithium can be selected from LiCoO2、LiNi1/ 3Co1/3Mn1/3O2、LiNi0.5Co0.2Mn0.3O2、LiNi0.6Co0.2Mn0.2O2、LiNi0.8Co0.1Mn0.1O2、LiNi0.8Co0.15Mn0.05O2、LiNi1.5Mn0.5O2、LiNiO2、LiMnO2、Li2MnO4Further preferably, the lithium-containing transition metal oxide may be selected from LiNi0.6Co0.2Mn0.2O2。
In the positive electrode slurry according to the first aspect of the present application, the kind of the transition metal oxide containing sodium is not particularly limited, and may be selected according to actual needs.
In the positive electrode slurry according to the first aspect of the present application, the solid component further includes a conductive agent and a binder.
In the positive electrode slurry according to the first aspect of the present application, the kind of the conductive agent is not particularly limited, and may be selected according to actual needs, specifically, the conductive agent may be selected from one or more of conductive carbon black, acetylene black, superconducting carbon black, graphene, conductive graphite, carbon fiber, and carbon nanotube, preferably, the conductive agent is selected from one or more of conductive graphite, acetylene black, superconducting carbon black, and carbon nanotube, and further preferably, the conductive agent is selected from superconducting carbon black.
In the positive electrode slurry according to the first aspect of the present application, the mass of the conductive agent is 0.5% to 3% of the total mass of the solid components, when the content of the conductive agent is too small, a good conductive effect cannot be achieved, and when the content of the conductive agent is too large, the mass of the positive electrode active material in the electrochemical energy storage device is reduced, which is disadvantageous for increasing the energy density of the electrochemical energy storage device, and preferably, the mass of the conductive agent is 0.8% to 2% of the total mass of the solid components.
In the positive electrode slurry according to the first aspect of the present application, the type of the binder is not particularly limited, and may be selected according to actual needs, and specifically, the binder may be selected from one or more of a polyvinyl alcohol binder, a polyurethane binder, a polyacrylate binder, a polyvinylidene fluoride binder, a styrene butadiene rubber binder, an epoxy resin binder, a vinyl acetate resin binder, and a chlorinated rubber binder, and preferably, the binder is selected from a polyvinylidene fluoride binder.
In the positive electrode slurry according to the first aspect of the present application, the mass of the binder is not greater than 5% of the total mass of the solid components, when the content of the binder is too small, a good binding effect cannot be achieved, and when the content of the binder is too large, on the one hand, the mass of the positive electrode active material in the electrochemical energy storage device is reduced, which is not favorable for increasing the energy density of the electrochemical energy storage device, and on the other hand, the ionic conductivity of the positive electrode sheet is reduced, which increases the polarization during the charge and discharge of the electrochemical energy storage device, which deteriorates the electrochemical performance, and preferably, the mass of the conductive agent is 0.8% to 2% of the total mass of the solid components.
In the positive electrode slurry according to the first aspect of the present application, the solid component may further include other additives, and specific kinds and contents of the other additives may be selected according to actual needs.
Next, a positive electrode sheet according to the second aspect of the present application will be described.
The positive plate according to the second aspect of the present application includes a positive current collector and a positive slurry layer. The positive slurry layer is arranged on the positive current collector. The positive electrode slurry layer is formed by drying the positive electrode slurry according to the first aspect of the present application.
In the positive electrode sheet according to the second aspect of the present application, the kind of the positive electrode current collector is not particularly limited, and may be selected according to actual needs, specifically, the current collector may be selected from metal foils, preferably, the positive electrode current collector may be selected from one of aluminum foils, silver foils, copper foils, and stainless steel foils, and further preferably, the positive electrode current collector is selected from aluminum foils.
In the positive electrode sheet according to the second aspect of the present invention, the thickness of the positive electrode current collector is 5mm to 30mm, preferably 8mm to 25mm, more preferably 12mm to 20mm, and still more preferably 14 mm.
In the positive electrode sheet according to the second aspect of the present invention, the thickness of the positive electrode slurry layer is 10mm to 70mm, preferably, the thickness of the positive electrode slurry layer is 30mm to 60mm, and more preferably, the thickness of the positive electrode slurry layer is 40mm to 50 mm.
In the positive electrode sheet according to the second aspect of the present application, the method for preparing the positive electrode sheet is not particularly limited, and the positive electrode sheet can be prepared by a conventional method, and specifically may include the steps of: uniformly mixing a positive electrode active material, a conductive agent and a binder, then adding a solvent for dispersion, and then adding an additive containing an organic compound containing thienyl for further mixing and dispersion to obtain positive electrode slurry; coating the obtained positive slurry on the surface of a positive current collector, and then drying to form a positive slurry layer on the positive current collector; and then sequentially rolling, slitting and slicing to obtain the positive plate.
In the positive electrode sheet according to the second aspect of the present application, in the above step, the temperature at which the positive electrode active material, the conductive agent, the binder, and the additive are mixed and dispersed is not particularly limited, and may be room temperature or heating, and may be selected according to actual needs.
In the positive electrode sheet according to the second aspect of the present application, in the above-described step, a specific kind of the solvent is not particularly limited as long as it can dissolve the organic compound containing a thienyl group, and specifically, the solvent may be an organic solvent, preferably, the solvent may be selected from one or more heterocyclic organic solvents, further preferably, the solvent may be selected from one or more of tetrahydrofuran, pyridine, N-methylpyrrolidone, and pyrrole, and more preferably, the solvent may be selected from N-methylpyrrolidone. The amount of the solvent to be added is not particularly limited, and may be selected according to actual requirements.
In the positive electrode sheet according to the second aspect of the present application, in the above step, the positive electrode slurry is coated on both surfaces of the positive electrode current collector.
In the positive plate according to the second aspect of the present application, in the above steps, the positive slurry coated on the surface of the positive current collector may be dried by heating, blowing and drying, the drying temperature of the positive slurry is 80 ℃ to 120 ℃, the drying temperature is too low, the curing of the positive slurry is insufficient, and part of the additive may be dissolved in the electrolyte, so as to deteriorate the performance of the electrochemical energy storage device to a certain extent, the drying temperature is too high, the additive may volatilize, thereby causing the loss of the additive, and preferably, the drying temperature of the positive slurry is 90 ℃.
In the positive electrode sheet according to the second aspect of the present application, the amount of the positive electrode slurry applied to the surface of the positive electrode current collector in the above step is not particularly limited as long as the positive electrode slurry layer formed of the positive electrode slurry covers the surface of the positive electrode current collector and satisfies a certain thickness.
In the positive electrode sheet according to the second aspect of the present application, in the above step, the manner of coating is not particularly limited and may be selected according to actual requirements.
An electrochemical energy storage device according to the third aspect of the present application is explained again.
An electrochemical energy storage device according to a third aspect of the invention comprises a positive electrode sheet according to the second aspect of the invention.
In the electrochemical energy storage device according to the third aspect of the present invention, it should be noted that the electrochemical energy storage device may be a super capacitor, a lithium ion battery or a sodium ion battery. In the embodiments of the present invention, only the embodiment in which the electrochemical energy storage device is a lithium ion battery is shown, but the present invention is not limited thereto.
In the lithium ion battery, the positive plate comprises a positive current collector and a positive slurry layer positioned on the positive current collector. The positive electrode slurry layer is obtained by drying the positive electrode slurry according to the first aspect of the present invention. The positive current collector is aluminum foil.
In the lithium ion battery, the negative plate comprises a negative current collector and a negative membrane positioned on the negative current collector. The negative current collector is a copper foil.
In the lithium ion battery, the negative active material is selected from artificial graphite or natural graphite. The negative electrode conductive agent is selected from one or more of acetylene black, conductive carbon black (Super P, Super S, 350G), carbon fiber (VGCF), Carbon Nanotube (CNT) and Ketjen black.
In a lithium ion battery, the electrolyte may be a liquid electrolyte, which may include a lithium salt and an organic solvent.
In the lithium ion battery, the specific kind of the lithium salt is not limited. Specifically, the lithium salt may be selected from LiPF6、LiBF4、LiN(SO2F)2(abbreviated LiFSI), LiN (CF)3SO2)2(abbreviated as LiTFSI) and LiClO4、LiAsF6、LiB(C2O4)2(abbreviated as LiB)OB)、LiBF2C2O4(abbreviated as LiDFOB).
In the lithium ion battery, the specific type of the organic solvent is not particularly limited, and may be selected according to actual needs. Preferably, a non-aqueous organic solvent is used. The non-aqueous organic solvent may include any kind of carbonate, carboxylate. The carbonate may include a cyclic carbonate or a chain carbonate. The non-aqueous organic solvent may further include a halogenated compound of a carbonate. Specifically, the organic solvent is selected from one or more of ethylene carbonate, propylene carbonate, butylene carbonate, pentylene carbonate, fluoroethylene carbonate, dimethyl carbonate, diethyl carbonate, dipropyl carbonate, methylethyl carbonate, gamma-butyrolactone, methyl formate, ethyl propionate, propyl propionate and tetrahydrofuran.
In the lithium ion battery, the type of the isolation film is not particularly limited, and may be selected according to actual requirements.
The present application is further illustrated below with reference to examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present application. In the embodiment, only the case where the electrochemical energy storage device is a lithium ion battery is shown, but the present invention is not limited thereto.
In the following examples, reagents, materials and instruments used are commercially available unless otherwise specified.
Example 1
(1) Preparation of positive plate
Calculating the positive electrode slurry layer according to the mass fraction of 100 percent, and adding LiNi which is a positive electrode active material0.6Co0.2Mn0.2O2The positive electrode conductive agent Super P and the binder PVDF are uniformly mixed, then a solvent NMP is added for dispersion, and then a compound 4 serving as an organic compound containing thienyl is added into a dispersion liquid for further mixing and dispersion to obtain positive electrode slurry, wherein the solid content of the positive electrode slurry is 77 wt%, and LiNi is0.6Co0.2Mn0.2O2The mass ratio of Super P to PVDF to compound 4 is 96:2:1:1, and then the positive electrode slurry is uniformly coated on the positive electrode slurryAnd (3) blowing and drying the surface of the positive current collector aluminum foil with the thickness of 12 mu m at 80 ℃ to obtain a positive slurry layer, and then sequentially rolling, slitting and slicing to obtain the positive plate.
(2) Preparation of negative plate
Mixing a negative electrode active material graphite, a conductive agent Super P, a thickening agent sodium carboxymethyl cellulose (CMC) and a binder styrene butadiene rubber emulsion (SBR) according to a mass ratio of 96:1.5:0.5:2, adding the mixture into solvent deionized water, and obtaining negative electrode slurry under the action of a vacuum stirrer, wherein the solid content in the negative electrode slurry is 60 wt%; and uniformly coating the negative electrode slurry on a negative electrode current collector copper foil with the thickness of 8 mu m, drying at 85 ℃, then carrying out cold pressing, edge cutting, sheet cutting and strip dividing, and finally drying for 12h at 120 ℃ under a vacuum condition to obtain the negative electrode sheet.
(3) Preparation of the electrolyte
At water content<In a 10ppm argon atmosphere glove box, EC and EMC were mixed at a mass ratio of EC to EMC of 30:70 to prepare an organic solvent, and then a sufficiently dried lithium salt LiPF was added6Dissolving in mixed organic solvent, and mixing uniformly to obtain the electrolyte. Wherein, LiPF6The concentration of (2) is 1 mol/L. In addition, in order to better illustrate the technical effect of the invention, different contents of thiophene compounds are adopted as electrolyte additives in the comparative examples.
(4) Preparation of the separator
A polyethylene film (PE) having a thickness of 14 μm was used as a separator.
(5) Preparation of lithium ion battery
The positive plate, the isolation film and the negative plate are stacked in sequence, the isolation film is positioned between the positive plate and the negative plate to play the isolation role, then the positive plate and the negative plate are wound into a square naked battery cell, a tab is welded, the naked battery cell is arranged in a packaging foil aluminum plastic film, then the naked battery cell is baked at 80 ℃ to remove water, corresponding electrolyte is injected and sealed, and then the finished product of the soft package lithium ion battery is obtained through the processes of standing, hot cold pressing, formation (0.02C constant current charging to 3.3V, 0.1C constant current charging to 3.6V), shaping, capacity testing and the like, wherein the thickness of the finished product of the soft package lithium ion battery is 4.0mm, the width of the finished product of the soft package lithium ion battery.
Example 2
The lithium ion battery was prepared in the same manner as in example 1, except that,
(1) preparation of positive plate
And drying the positive slurry at 90 ℃ to obtain a positive slurry layer.
Example 3
The lithium ion battery was prepared in the same manner as in example 1, except that,
(1) preparation of positive plate
And drying the positive electrode slurry at 100 ℃ to obtain a positive electrode slurry layer.
Example 4
The lithium ion battery was prepared in the same manner as in example 1, except that,
(1) preparation of positive plate
And drying the positive electrode slurry at 120 ℃ to obtain a positive electrode slurry layer.
Example 5
The lithium ion battery was prepared in the same manner as in example 2, except that,
(1) preparation of positive plate
LiNi in positive electrode slurry0.6Co0.2Mn0.2O2The mass ratio of Super P, PVDF and compound 4 is 96.8:2:1: 0.2.
Example 6
The lithium ion battery was prepared in the same manner as in example 2, except that,
(1) preparation of positive plate
LiNi in positive electrode slurry0.6Co0.2Mn0.2O2The mass ratio of Super P, PVDF and compound 4 is 96.5:2:1: 0.5.
Example 7
The lithium ion battery was prepared in the same manner as in example 2, except that,
(1) preparation of positive plate
LiNi in positive electrode slurry0.6Co0.2Mn0.2O2The mass ratio of Super P, PVDF and compound 4 is 95.5:2:1: 1.5.
Example 8
The lithium ion battery was prepared in the same manner as in example 2, except that,
(1) preparation of positive plate
LiNi in positive electrode slurry0.6Co0.2Mn0.2O2The mass ratio of Super P, PVDF and compound 4 is 95:2:1: 2.
Example 9
The lithium ion battery was prepared in the same manner as in example 2, except that,
(1) preparation of positive plate
The compound 2 is an organic compound containing a thienyl group.
Example 10
The lithium ion battery was prepared in the same manner as in example 2, except that,
(1) preparation of positive plate
The compound 3 is an organic compound containing a thienyl group.
Example 11
The lithium ion battery was prepared in the same manner as in example 2, except that,
(1) preparation of positive plate
Compound 6 is an organic compound containing a thienyl group.
Example 12
The lithium ion battery was prepared in the same manner as in example 2, except that,
(1) preparation of positive plate
The compound 7 was used as an organic compound containing a thienyl group.
Example 13
The lithium ion battery was prepared in the same manner as in example 2, except that,
(1) preparation of positive plate
The compound 8 was used as an organic compound containing a thienyl group.
Example 14
The lithium ion battery was prepared in the same manner as in example 2, except that,
(1) preparation of positive plate
Compound 9 is an organic compound containing a thienyl group.
Example 15
The lithium ion battery was prepared in the same manner as in example 2, except that,
(1) preparation of positive plate
The compound 11 was used as an organic compound containing a thienyl group.
Example 16
The lithium ion battery was prepared in the same manner as in example 2, except that,
(1) preparation of positive plate
The compound 12 is an organic compound having a thienyl group.
Comparative example 1
The lithium ion battery was prepared in the same manner as in example 2, except that,
(1) preparation of positive plate
The positive electrode slurry does not contain an organic compound containing a thienyl group.
LiNi in positive electrode slurry0.6Co0.2Mn0.2O2The mass ratio of Super P to PVDF is 97:2: 1.
Comparative example 2
The lithium ion battery was prepared in the same manner as in example 2, except that,
(1) preparation of positive plate
The positive electrode slurry does not contain an organic compound containing a thienyl group.
LiNi in positive electrode slurry0.6Co0.2Mn0.2O2The mass of Super P and PVDF is 97:2: 1.
(3) Preparation of the electrolyte
The compound 4 was added to the electrolyte as an organic compound containing a thienyl group, and the mass percentage content thereof in the electrolyte was 0.5%.
Comparative example 3
The lithium ion battery was prepared in the same manner as in example 2, except that,
(1) preparation of positive plate
The positive electrode slurry does not contain an organic compound containing a thienyl group.
LiNi in positive electrode slurry0.6Co0.2Mn0.2O2The mass of Super P and PVDF is 97:2: 1.
(3) Preparation of the electrolyte
The compound 4 is added to the electrolyte as an organic compound containing a thienyl group, and the mass percentage of the compound in the electrolyte is 1%.
Comparative example 4
The lithium ion battery was prepared in the same manner as in example 2, except that,
(1) preparation of positive plate
The positive electrode slurry does not contain an organic compound containing a thienyl group.
LiNi in positive electrode slurry0.6Co0.2Mn0.2O2The mass of Super P and PVDF is 97:2: 1.
(3) Preparation of the electrolyte
The compound 4 is added to the electrolyte as an organic compound containing a thienyl group, and the mass percentage of the compound in the electrolyte is 5%.
Comparative example 5
The lithium ion battery was prepared in the same manner as in example 2, except that,
(1) preparation of positive plate
LiNi in positive electrode slurry0.6Co0.2Mn0.2O2The mass ratio of Super P, PVDF and compound 4 is 92:2:1: 5.
TABLE 1 parameter settings for examples 1-16 and comparative examples 1-5
Next, a test procedure of the lithium ion battery is explained.
(1) High-temperature storage gas production test of lithium ion battery
The initial volume of the lithium ion battery is tested by adopting a drainage method and is marked as V0, the lithium ion battery is placed into a thermostat at 85 ℃ for storage after being fully charged (the lithium ion battery is charged to 4.2V by a constant current of 1C and then is charged to 0.05C by a constant voltage of 4.2V) at 25 ℃, the lithium ion battery is taken out on the 10 th day, and the volume of the lithium ion battery is tested and is marked as V10.
The lithium ion battery has a volume expansion ratio (%) of (V10-V0)/V0 × 100% after being stored at 85 ℃ for 10 days.
(2) Cycle performance testing of lithium ion batteries
At 25 ℃, the lithium ion battery is charged to a voltage of 4.2V at a constant current of 1C, then charged to a current of 0.05C at a constant voltage of 4.2V, and then discharged to a voltage of 2.8V at a constant current of 1C, wherein the charge-discharge cycle is the first discharge capacity of the lithium ion battery. And (3) carrying out 100 charge-discharge cycles on the lithium ion battery according to the conditions, and recording the discharge capacity of the lithium ion battery after the 100 th cycle. .
Capacity retention (%) after the lithium ion battery was cycled 100 times ═ 100% of (discharge capacity at 100 th cycle/discharge capacity at first cycle).
(3) High temperature storage capacity retention test for lithium ion batteries
At 25 ℃, recording the initial discharge capacity of the lithium ion battery as C0, then storing the fully charged lithium ion battery (namely, charging the battery to 4.2V at a constant current of 1C and then charging the battery to 0.05C at a constant voltage of 4.2V) in an environment at 60 ℃, taking out the battery after storing for 30 days, and testing the discharge capacity and recording as C30.
The capacity retention (%) of the lithium ion battery after 30 days of storage at 60 ℃ was (C30/C0) × 100%.
(4) Overcharge safety performance test of lithium ion battery
At 25 ℃, charging a lithium ion battery to a voltage of 4.2V at a constant current of 1C, then charging to a current of 0.05C at a constant voltage of 4.2V, wherein the lithium ion battery is 100% SOC, then charging the lithium ion battery to 1.5U at a constant current of 1C, and recording the required time as t(s), wherein the SOC state at the time can represent the overcharge safety performance of the lithium ion battery: the SOC (%) of the lithium ion battery reaching 1.5U is t/3600 × 100%.
TABLE 2 results of the Performance test of examples 1 to 16 and comparative examples 1 to 5
As can be seen from the data analysis in tables 1 and 2, in examples 1 to 16 and comparative example 1, when the organic compound containing a thienyl group of the present application is added as an additive to the positive electrode slurry (examples 1 to 16), the lithium ion battery has good cycle performance, high-temperature storage performance, and overcharge safety performance, and also has a low volume expansion rate. The reason is that the organic compound containing thienyl group is easy to generate electrochemical polymerization reaction, and the generated conductive polymer can effectively coat the positive active material, play a role in passivating the positive active material, improve the oxidation resistance of the positive plate, reduce the positive interface impedance of the electrochemical energy storage device in the circulating process and improve the circulating performance and the high-temperature storage performance of the lithium ion battery. In addition, the conductive polymer coated on the positive active material can effectively reduce the heat generated by the side reaction of the positive interface under high temperature and high pressure, and can greatly improve the overcharge safety performance of the lithium ion battery by combining the characteristic of the sharp increase of the self high-temperature electronic impedance. In addition, when the organic compound containing the thienyl group is added into the positive electrode slurry as the additive, the situation that the organic compound containing the thienyl group is used as the electrolyte additive (comparative examples 2-4) and electrochemical polymerization reaction is simultaneously carried out on the positive electrode and the negative electrode under a high-temperature condition, the formed conductive polymer spreads from the positive electrode and the negative electrode to the isolating membrane, finally adheres to the isolating membrane and even pierces the isolating membrane, and the risk that the lithium ion battery has internal self-discharge and even short circuit is caused is avoided, so that the overcharge safety performance of the lithium ion battery can be further improved by adding the organic compound containing the thienyl group into the positive electrode slurry as the additive.
As is apparent from the analysis of examples 2, 6, and 5, the positive electrode slurry has different additive contents and different effects of improving the electrochemical performance of the lithium ion battery, and when the additive content is too large, the volume expansion of the lithium ion battery can be effectively suppressed, but when the additive content is too large, the excessive additive forms a film on the positive electrode to block the migration of lithium ions to some extent, and therefore, the cycle capacity retention rate of the lithium ion battery is deteriorated conversely.
From the analysis in examples 7-14, it can be seen that different kinds of additives all have similar effects on improving the electrochemical performance of lithium ion batteries. However, due to different molecules of the additive, the size of the substituent group and the length of the molecule can influence the residual quantity of the additive in the positive plate and influence the conductivity of the conductive polymer formed in the positive plate, so that the improvement effect of the lithium ion battery is slightly different. The volatility of the additive and the difficulty of diffusion of the additive in the electrolyte can influence the improvement effect of the additive on the electrochemical performance of the lithium ion battery, but the additive can improve the cycle performance, the high-temperature storage performance and the overcharge safety performance of the lithium ion battery on the whole.
The content of sulfur in the positive plate was measured by using inductively coupled atomic emission spectroscopy (ICP-OES), and the residual content of the additive in the positive plate was calculated, with the results shown in table 3.
Table 3 additive content test results for examples 1-4
With reference to table 3, as can be seen from the analysis in examples 1 to 4, the drying temperature of the positive electrode slurry is different from the improvement of the electrochemical performance of the lithium ion battery, the drying temperature is low, the curing of the positive electrode slurry is not sufficient, a part of the additives are dissolved in the electrolyte to deteriorate the performance of the lithium ion battery to a certain extent, as the drying temperature increases, the additives volatilize to cause additive loss, and the improvement effect on the dynamic performance and safety performance of the lithium ion battery decreases, and in comprehensive comparison, the drying temperature of the positive electrode slurry is preferably 90 ℃.
Those skilled in the art to which the present application pertains can also make appropriate changes and modifications to the above-described embodiments, based on the disclosure of the above description. Therefore, the present application is not limited to the specific embodiments disclosed and described above, and some modifications and variations of the present application should fall within the scope of the claims of the present application.
Claims (8)
1. The positive electrode slurry comprises a solid component and a solvent, wherein the solid component comprises a positive electrode active material, and is characterized by further comprising an additive A, wherein the additive A is an organic compound containing a thienyl group;
the organic compound containing thienyl is selected from one or more compounds shown in a formula 2;
in formula 2, n is 0, 1 or 2, R3、R4、R5、R6、R7、R8Each independently selected from one or more of H, F, Cl, Br, I, nitro, cyano, carboxyl, sulfonic group, substituted or unsubstituted alkyl with 1-10 carbon atoms, substituted or unsubstituted alkenyl with 2-10 carbon atoms, substituted or unsubstituted alkynyl with 2-10 carbon atoms, substituted or unsubstituted aryl with 6-10 carbon atoms, substituted or unsubstituted alkoxy with 1-10 carbon atoms, substituted or unsubstituted alkenyloxy with 2-10 carbon atoms, substituted or unsubstituted alkynyloxy with 2-10 carbon atoms and substituted or unsubstituted aryl alkoxy with 6-10 carbon atoms, wherein the substituent is selected from one or more of halogen atom, nitro, cyano, carboxyl and sulfonic group, R is selected from the group consisting of alkyl, alkenyl, alkynyl, aryl, heteroaryl, and the like3And R4、R5And R6、R7And R8Are respectively and independently connected with each other to form a ring;
the positive electrode active material is a high-nickel positive electrode material;
the weight of the organic compound containing the thienyl group accounts for 0.1 to 2 percent of the total weight of the solid component.
2. The positive electrode slurry according to claim 1, wherein the solid component further comprises an additive B, and the additive B is one or more selected from compounds represented by formula 1;
in formula 1, R1、R2Each independently selected from one or more of H, F, Cl, Br, I, nitro, cyano, carboxyl, sulfonic group, substituted or unsubstituted alkyl with 1-10 carbon atoms, substituted or unsubstituted alkenyl with 2-10 carbon atoms, substituted or unsubstituted alkynyl with 2-10 carbon atoms, substituted or unsubstituted aryl with 6-10 carbon atoms, substituted or unsubstituted alkoxy with 1-10 carbon atoms, substituted or unsubstituted alkenyloxy with 2-10 carbon atoms, substituted or unsubstituted alkynyloxy with 2-10 carbon atoms and substituted or unsubstituted aryl alkoxy with 6-10 carbon atoms, wherein the substituent is selected from one or more of halogen atom, nitro, cyano, carboxyl and sulfonic group, R is selected from the group consisting of alkyl, alkenyl, alkynyl, aryl, heteroaryl, and the like1And R2And may also be interconnected to form a ring.
3. The positive electrode slurry according to claim 1, wherein the additive A is one or more selected from the following compounds;
4. the positive electrode slurry according to claim 2, wherein the additive B is one or more selected from the following compounds;
5. the positive electrode slurry according to claim 1, wherein the solid component further comprises a conductive agent and a binder.
6. A positive electrode sheet, comprising:
a positive current collector; and
the positive slurry layer is arranged on the positive current collector;
it is characterized in that the preparation method is characterized in that,
the positive electrode slurry layer is formed by drying the positive electrode slurry according to any one of claims 1 to 5.
7. The positive electrode sheet according to claim 6, wherein the drying temperature of the positive electrode slurry is 80 to 120 ℃.
8. An electrochemical energy storage device, comprising the positive electrode sheet according to any one of claims 6 to 7.
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