CN116960319A - Lithium ion battery and electricity utilization device - Google Patents
Lithium ion battery and electricity utilization device Download PDFInfo
- Publication number
- CN116960319A CN116960319A CN202311184123.0A CN202311184123A CN116960319A CN 116960319 A CN116960319 A CN 116960319A CN 202311184123 A CN202311184123 A CN 202311184123A CN 116960319 A CN116960319 A CN 116960319A
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- China
- Prior art keywords
- positive electrode
- active material
- lithium ion
- equal
- electrode active
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 70
- 230000005611 electricity Effects 0.000 title abstract description 4
- 239000007774 positive electrode material Substances 0.000 claims abstract description 111
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims abstract description 47
- -1 C 1 ‐C 6 Alkyl Chemical group 0.000 claims abstract description 46
- 239000003792 electrolyte Substances 0.000 claims abstract description 38
- 125000004122 cyclic group Chemical group 0.000 claims abstract description 33
- 125000005843 halogen group Chemical group 0.000 claims abstract description 28
- 125000004093 cyano group Chemical group *C#N 0.000 claims abstract description 21
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 19
- 150000002148 esters Chemical class 0.000 claims abstract description 18
- 125000004438 haloalkoxy group Chemical group 0.000 claims abstract description 15
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 claims abstract description 14
- 125000004429 atom Chemical group 0.000 claims abstract description 6
- 239000001257 hydrogen Substances 0.000 claims abstract description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 6
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 6
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 5
- 125000006677 (C1-C3) haloalkoxy group Chemical group 0.000 claims abstract description 4
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 44
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- 229910021384 soft carbon Inorganic materials 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
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Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0569—Liquid materials characterised by the solvents
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2220/00—Batteries for particular applications
- H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The application discloses a lithium ion battery and an electricity utilization device, wherein the lithium ion battery comprises a positive electrode plate and electrolyte, the positive electrode plate comprises a positive electrode active material, and the positive electrode active material comprises Li [ Li ] x Ni a Co b Mn c M d ]O 2‑e X+a+b+c+d=1, x is 0 < 1, a is 0 < 1, b is 0 < 1, c is 0 < 1, d is 0 < 1, e is 0 < 2, M comprises at least one of Mg, nb, cr, ce, fe, ta, B, al, V, ti, zr, sn or Mo, the electrolyte comprises a cyclic sulfate, the cyclic sulfate comprises，R 1 、R 2 、R 3 、R 4 Each independently includeHydrogen atom, C 1 ‑C 6 Alkyl, halogen atom, C 1 ‑C 3 Haloalkyl, C 1 ‑C 3 Alkoxy, C 1 ‑C 3 Haloalkoxy, alkenyl, ester, cyano or sulfonate, R 5 And R is 6 Each independently includeHydrogen atom, C 1 ‑C 6 Alkyl, halogen atom, C 1 ‑C 3 Haloalkyl, C 1 ‑C 3 Alkoxy, C 1 ‑C 3 A haloalkoxy, alkenyl, ester, cyano or sulfonate group.
Description
Technical Field
The application belongs to the field of batteries, and particularly relates to a lithium ion battery and an electric device.
Background
Lithium ion batteries are not only applied to energy storage power supply systems such as hydraulic power, firepower, wind power and solar power stations, but also widely applied to electric vehicles such as electric bicycles, electric motorcycles, electric automobiles, and the like, as well as a plurality of fields such as military equipment, aerospace, and the like. Along with the increasing requirements of people on the energy density of lithium ion batteries, the development of lithium-rich manganese-based anode materials is an effective method. However, the first-ring coulombic efficiency and cycle performance of the existing lithium ion battery containing the lithium-rich manganese-based cathode material are poor.
Disclosure of Invention
In view of the technical problems in the background art, the application provides a battery, and aims to solve the problems of poor initial coulombic efficiency and poor cycle performance of the existing lithium ion battery containing a lithium-rich manganese-based positive electrode material.
In order to achieve the above object, a first aspect of the present application provides a lithium ion battery comprising a positive electrode sheet including a positive electrode active material including Li [ Li x Ni a Co b Mn c M d ]O 2-e Wherein x+a+b+c+d=1, 0 < x < 1, 0.ltoreq.a < 1, 0.ltoreq.b < 1,0 < c < 1, 0.ltoreq.d < 1, 0.ltoreq.e < 2, M comprises at least one of Mg, nb, cr, ce, fe, ta, B, al, V, ti, zr, sn or Mo,
the electrolyte includes a cyclic sulfate, the cyclic sulfate includingWherein R is 1 、R 2 、R 3 、R 4 Each independently include->Hydrogen atom, C 1 -C 6 Alkyl, halogen atom, C 1 -C 3 Haloalkyl, C 1 -C 3 Alkoxy, C 1 -C 3 Haloalkoxy, alkenyl, ester, cyano or sulfonate, R 5 And R is 6 Each independently include->Hydrogen atom, C 1 -C 6 Alkyl, halogen atom, C 1 -C 3 Haloalkyl, C 1 -C 3 Alkoxy, C 1 -C 3 A haloalkoxy, alkenyl, ester, cyano or sulfonate group.
The application at least comprises the following beneficial effects: in the lithium ion battery, the CEI film (positive electrode electrolyte interface) containing the S-O bond is formed on the surface of the positive electrode active material, and the SEI film (solid electrolyte interface) with higher strength is formed on the surface of the negative electrode active material, so that the first-circle coulomb efficiency and the cycle performance of the lithium ion battery can be improved.
In some embodiments of the application, the R 1 、R 2 、R 3 、R 4 Each independently includeHydrogen atom, C 1 -C 6 Alkyl, halogen atom, C 1 -C 3 Haloalkyl of (2)、C 1 -C 3 Alkoxy or cyano, R 5 And R is 6 Each independently includeHydrogen atom, C 1 -C 6 Alkyl or halogen atoms of (a). Thus, the first-ring coulomb efficiency and the cycle performance of the lithium ion battery can be improved.
In some embodiments of the application, theThe number of sulfate groups in the structure is less than or equal to 7. Thus, the first-ring coulomb efficiency and the cycle performance of the lithium ion battery can be improved.
In some embodiments of the application, the cyclic sulfate comprises at least one of formulas 1-16:
、/>、/>、/>、、/>、/>、/>、、/>、/>、/>、/>、/>、、/>. Thus, the first-ring coulomb efficiency and the cycle performance of the lithium ion battery can be improved.
In some embodiments of the application, the cyclic sulfate content W is based on the total mass of the electrolyte 1 The method meets the following conditions: w is more than or equal to 0.005 percent 1 Less than or equal to 10 percent, and can be selected as 0.05 percent or less than or equal to W 1 Less than or equal to 5 percent, more preferably less than or equal to 0.1 percent of W 1 Less than or equal to 3 percent. Thus, the first-ring coulomb efficiency and the cycle performance of the lithium ion battery can be improved.
In some embodiments of the present application, the positive electrode sheet includes a positive electrode current collector and a positive electrode active material layer formed on at least one side of the positive electrode current collector, the positive electrode active material layer including the positive electrode active material, the content W of the positive electrode active material based on the total mass of the positive electrode active material layer 2 And W is equal to 1 The method meets the following conditions: w is more than or equal to 0.003 percent 1 /W 2 Less than or equal to 12 percent, and can be selected as 0.04 percent or less than or equal to W 1 /W 2 Less than or equal to 6 percent. Thus, the first-ring coulomb efficiency and the cycle performance of the lithium ion battery can be improved.
In some embodiments of the application, 90% or less of W 2 Less than or equal to 98 percent, and can be selected as 93 percent or less than or equal to W 2 Less than or equal to 97 percent. Thus, the first-ring coulomb efficiency and the cycle performance of the lithium ion battery can be improved.
In some embodiments of the application, M comprises at least one of Cr, fe, or Al.
In some embodiments of the application, li [ Li ] x Ni a Co b Mn c M d ]O 2-e At least one of the following conditions is satisfied:
0.1≤x≤0.6；
0≤a≤0.5；
0≤b≤0.1；
0.5≤c＜1；
0≤d≤0.1；
0.001≤e≤0.05。
in some embodiments of the application, the positive electrode active material has a BET specific surface area of 0.4m 2 /g-1.5m 2 /g, optionally 0.4m 2 /g-1.0m 2 And/g. Thus, the first-ring coulomb efficiency and the cycle performance of the lithium ion battery can be improved.
In some embodiments of the present application, the particle size distribution span= (Dv 90-Dv 10)/Dv 50 of the positive electrode active material satisfies: SPAN is more than or equal to 0.7 and less than or equal to 1.8, and optionally more than or equal to 0.8 and less than or equal to 1.4. This facilitates the capacity of the positive electrode active material.
In some embodiments of the application, at least one of the following conditions is met:
the Dv90 of the positive electrode active material is 8-16 μm; optionally 8 μm to 9 μm;
the Dv50 of the positive electrode active material is 6-10 μm; optionally 6 μm to 7 μm;
The Dv10 of the positive electrode active material is 2 μm to 5 μm; optionally 2 μm to 3 μm.
In some embodiments of the application, the residual alkali amount of the positive electrode active material is less than or equal to 1000ppm based on the total weight of the positive electrode active material. Thus, the first-ring coulomb efficiency and the cycle performance of the lithium ion battery can be improved.
In some embodiments of the application, the residual alkali amount of the positive electrode active material is less than or equal to 500ppm based on the total weight of the positive electrode active material. Thus, the first-ring coulomb efficiency and the cycle performance of the lithium ion battery can be improved.
According to a second aspect of the application, there is provided an electrical device comprising a lithium ion battery according to the first aspect of the application. Thus, the electric device has excellent cycle performance.
Additional aspects and advantages of the application will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of the application.
Drawings
Various other advantages and benefits will become apparent to those of ordinary skill in the art upon reading the following detailed description of the preferred embodiments. The drawings are only for purposes of illustrating the preferred embodiments and are not to be construed as limiting the application. Also, like reference numerals are used to designate like parts throughout the accompanying drawings. In the drawings:
Fig. 1 is a schematic view of a battery according to an embodiment of the present application.
Fig. 2 is an exploded view of the battery of the embodiment of the present application shown in fig. 1.
Fig. 3 is a schematic view of a battery module according to an embodiment of the present application.
Fig. 4 is a schematic view of a battery pack according to an embodiment of the present application.
Fig. 5 is an exploded view of the battery pack of the embodiment of the present application shown in fig. 4.
Fig. 6 is a schematic view of an electric device using a battery as a power source according to an embodiment of the present application.
Reference numerals illustrate:
1, a battery cell; 11 a housing; 12 electrode assembly; 13 cover plate; 2 a battery module; 3, a battery pack; 31 upper case; 32 lower box.
Detailed Description
Embodiments of the technical scheme of the present application are described in detail below. The following examples are only for more clearly illustrating the technical aspects of the present application, and thus are merely examples, and are not intended to limit the scope of the present application.
Reference herein to "an embodiment" means that a particular feature, structure, or characteristic described in connection with the embodiment may be included in at least one embodiment of the application. The appearances of such phrases in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments. Those of skill in the art will explicitly and implicitly appreciate that the embodiments described herein may be combined with other embodiments.
The "range" disclosed herein is defined in terms of lower and upper limits, with the given range being defined by the selection of a lower and an upper limit, the selected lower and upper limits defining the boundaries of the particular range. Ranges that are defined in this way can be inclusive or exclusive of the endpoints, and any combination can be made, i.e., any lower limit can be combined with any upper limit to form a range. For example, if ranges of 60-120 and 80-110 are listed for a particular parameter, it is understood that ranges of 60-110 and 80-120 are also contemplated. Furthermore, if the minimum range values 1 and 2 are listed, and if the maximum range values 3,4 and 5 are listed, the following ranges are all contemplated: 1-3, 1-4, 1-5, 2-3, 2-4 and 2-5. In the present application, unless otherwise indicated, the numerical range "a-b" represents a shorthand representation of any combination of real numbers between a and b, where a and b are both real numbers. For example, the numerical range "0-5" means that all real numbers between "0-5" have been listed throughout, and "0-5" is simply a shorthand representation of a combination of these values. When a certain parameter is expressed as an integer of 2 or more, it is disclosed that the parameter is, for example, an integer of 2, 3,4, 5, 6, 7, 8, 9, 10, 11, 12 or the like.
All embodiments of the application and alternative embodiments may be combined with each other to form new solutions, unless otherwise specified.
All technical features and optional technical features of the application may be combined with each other to form new technical solutions, unless specified otherwise.
All the steps of the present application may be performed sequentially or randomly, preferably sequentially, unless otherwise specified. For example, the method comprises steps (a) and (b), meaning that the method may comprise steps (a) and (b) performed sequentially, or may comprise steps (b) and (a) performed sequentially. For example, the method may further include step (c), which means that step (c) may be added to the method in any order, for example, the method may include steps (a), (b) and (c), may include steps (a), (c) and (b), may include steps (c), (a) and (b), and the like.
The lithium ion battery becomes the most popular energy storage system due to the characteristics of high working potential, long service life, environmental friendliness and the like, and is widely applied to the fields of pure electric vehicles, hybrid electric vehicles, smart grids and the like. However, the current lithium ion battery is difficult to meet the high demand of people on endurance, and to solve the problem of 'mileage anxiety' of people on electric automobiles, the development of lithium ion batteries with higher energy density is urgently needed.
To further increase the energy density of lithium ion batteries, it is desirable to develop high energy density positive electrode materials. In the existing positive electrode material, the discharge specific capacity of the lithium-rich manganese-based positive electrode material is up to 300mAh/g, which is about twice of the discharge specific capacity of the current commercial positive electrode materials such as lithium iron phosphate, ternary materials and the like, and the lithium-rich manganese-based positive electrode material contains more manganese elements, has lower cost compared with the ternary materials, and is considered as the positive electrode material of the lithium ion battery with the most development potential.
However, in the charging process, with activation of the lithium-rich oxide in the lithium-rich manganese-based positive electrode material, the oxyanion is activated to participate in the reaction in the delithiation process (O 2- /O - ) Oxygen on the surface of the lithium-rich manganese-based positive electrode material is released from lattice positions, and part of the oxygen is oxidized into O 2 2- And O 2 - ，O 2 2- And O 2 - Can accelerate the oxidative decomposition of the organic solvent in the electrolyte to generate RH ＋ (R represents an organic solvent), RH ＋ The SEI film can be destroyed, active lithium can be consumed along with recombination of the SEI film, so that the initial cycle coulomb efficiency of the battery is reduced, and on the other hand, the electrolyte and the negative electrode are in vigorous contact reaction due to the destruction of the SEI film, so that the problems of interface black spots, local lithium precipitation and the like of the negative electrode plate are caused, and the initial cycle coulomb efficiency and the cycle performance of the battery core are further deteriorated.
In the present application, the "black spot" formation mechanism includes: the gas generated during the battery cycle or storage process prevents lithium ions from being intercalated into the negative graphite, resulting in the occurrence of black spots on the surface of the negative electrode tab.
The electrolyte of the lithium ion battery comprisesThe cyclic sulfate with the structure, in the process of battery circulation, sulfate groups in the cyclic sulfate can form a flexible CEI film with S-O bond on the surface of the positive electrode plate, and the CEI film reduces the contact between the lithium-rich manganese-based positive electrode material and electrolyte, thereby reducing RH ＋ On the other hand, the sulfuric acid ester group in the structure has high reduction potential, can receive electrons from the surface of the anode during the charging of the battery to generate self reduction, and the generated reduction products, namely lithium sulfite and the like are deposited on the surface of the anode to participate in the formation of an SEI film, so that the SEI film has higher strength and can effectively inhibit RH + Damage to SEI film, thus reducing consumption of active lithium and improving initial coulombic efficiency and cycle performance of battery.
The lithium ion battery disclosed by the embodiment of the application can be used for electric equipment using the battery as a power supply or various energy storage systems using the battery as an energy storage element. The powered device may include, but is not limited to, a cell phone, tablet, notebook computer, electric toy, electric tool, battery car, electric car, ship, spacecraft, and the like. Among them, the electric toy may include fixed or mobile electric toys, such as game machines, electric car toys, electric ship toys, electric plane toys, and the like, and the spacecraft may include planes, rockets, space planes, and spacecraft, and the like.
The first aspect of the application provides a lithium ion battery, which comprises a positive electrode plate and electrolyte, wherein the positive electrode plate comprises a positive electrode active material, and the positive electrode active material comprises Li [ Li ] x Ni a Co b Mn c M d ]O 2-e Wherein x+a+b+c+d=1, 0 < x < 1, 0.ltoreq.a < 1, 0.ltoreq.b < 1, 0.ltoreq.c < 1, 0.ltoreq.d < 1, 0.ltoreq.e < 2, M comprising at least one of Mg, nb, cr, ce, fe, ta, B, al, V, ti, zr, sn or MoThe seed is used for the seed,
the electrolyte includes a cyclic sulfate, the cyclic sulfate includingWherein R is 1 、R 2 、R 3 、R 4 Each independently include->Hydrogen atom, C 1 -C 6 Alkyl, halogen atom, C 1 -C 3 Haloalkyl, C 1 -C 3 Alkoxy, C 1 -C 3 Haloalkoxy, alkenyl, ester, cyano or sulfonate, R 5 And R is 6 Each independently include->Hydrogen atom, C 1 -C 6 Alkyl, halogen atom, C 1 -C 3 Haloalkyl, C 1 -C 3 Alkoxy, C 1 -C 3 A haloalkoxy, alkenyl, ester, cyano or sulfonate group.
In the present application, it will be appreciated that whenR in (B) 1 、R 2 、R 3 、R 4 Comprises->，R 5 And R is 6 Comprises->When (I)>The structure of (2) is not endless, i.e. the last substitution +.>R on 5 And R is 6 Each independently includes a hydrogen atom, C 1 -C 6 Alkyl of (2)Halogen atom, C 1 -C 3 Haloalkyl, C 1 -C 3 Alkoxy, C 1 -C 3 A haloalkoxy, alkenyl, ester, cyano or sulfonate group.
The application at least comprises the following beneficial effects: the positive electrode active material in the positive electrode plate of the lithium ion battery comprises Li x Ni a Co b Mn c M d ]O 2-e Wherein x+a+b+c+d=1, x is more than 0 and less than 1, a is more than or equal to 0 and less than or equal to 1, b is more than or equal to 0 and less than 1, c is more than or equal to 0 and less than or equal to 1, d is more than or equal to 0 and less than or equal to 2, M comprises at least one of Mg, nb, cr, ce, fe, ta, B, al, V, ti, zr, sn or Mo, namely the positive electrode active material is a lithium-rich manganese-based positive electrode material, and the electrolyte comprisesThe cyclic sulfate with the structure, in the process of battery circulation, sulfate groups in the cyclic sulfate can form a flexible CEI film with S-O bond on the surface of the positive electrode plate, and the CEI film reduces the contact between the lithium-rich manganese-based positive electrode material and electrolyte, thereby reducing RH ＋ On the other hand, the sulfuric acid ester group in the structure has high reduction potential, can receive electrons from the surface of the anode during the charging of the battery to generate self reduction, and the generated reduction products, namely lithium sulfite and the like are deposited on the surface of the anode to participate in the formation of an SEI film, so that the SEI film has higher strength and can effectively inhibit RH + Damage to SEI film, thus reducing consumption of active lithium and improving initial coulombic efficiency and cycle performance of battery. In addition, the cyclic sulfate has at least two sulfate groups, and by introducing substituent groups such as alkyl and the like, an elastic SEI film with longer organic chain can be generated on the surface of the negative electrode, the damage of the SEI film can be avoided by coping with the volume change generated by the negative electrode in the circulating process, and meanwhile, halogen atoms and/or N-containing substituent groups are introduced into the cyclic sulfate structure, so that the SEI film rich in more inorganic components such as lithium halide, lithium nitride and the like can be formed on the surface of the negative electrode, and the mechanical strength of the SEI film is further improved.
In some embodiments of the application, the above Li [ Li ] x Ni a Co b Mn c M d ]O 2-e Wherein x is more than 0 and less than 1, for example, x is more than 0.001 and less than or equal to 0.99,0.005 and less than or equal to 0.99,0.01 and less than or equal to 0.99,0.05 and less than or equal to 0.99,0.1 and less than or equal to x and less than or equal to 0.99,0.2 and less than or equal to 0.9,0.3 and less than or equal to 0.8, x is more than or equal to 0.4 and less than or equal to 0.7,0.5 and less than or equal to 0.6,0.55 and less than or equal to 0.6, etc. Thus, the positive electrode active material contains the lithium ions in the content, so that the battery has higher capacity. In other embodiments of the application, li [ Li ] x Ni a Co b Mn c M d ]O 2-e X in the formula is as follows: x is more than or equal to 0.1 and less than or equal to 0.6.
The battery is charged and discharged with the release and consumption of Li, and the molar contents of Li are different when the battery is discharged to different states. In the application, the molar content of Li is the initial state of the material, namely the state before charging, and the molar content of Li can be changed after charge and discharge cycles when the positive electrode material is applied to a battery system.
In some embodiments of the application, the above Li [ Li ] x Ni a Co b Mn c M d ]O 2-e Wherein a is more than or equal to 0 and less than or equal to 1, for example, a is more than or equal to 0 and less than or equal to 0.99,0.001, a is more than or equal to 0 and less than or equal to 0.99,0.005, a is more than or equal to 0.99,0.01, a is more than or equal to 0.99,0.05, a is more than or equal to 0.99,0.1, a is more than or equal to 0.99,0.2, a is more than or equal to 0.9,0.3, a is more than or equal to 0.8, a is more than or equal to 0.4, 0.7,0.5, a is more than or equal to 0.6,0.55, a is more than or equal to 0.6, and the like. Thus, the nickel ions are contained in the positive electrode active material in such a content that the specific capacity of the positive electrode active material can be increased. In other embodiments of the present application, the above Li [ Li ] x Ni a Co b Mn c M d ]O 2-e The following formula a: a is more than or equal to 0 and less than or equal to 0.5.
In some embodiments of the application, the above Li [ Li ] x Ni a Co b Mn c M d ]O 2-e Wherein b is more than or equal to 0 and less than or equal to 1, for example, b is more than or equal to 0 and less than or equal to 0.99,0.001, b is more than or equal to 0 and less than or equal to 0.99,0.005, b is more than or equal to 0.99,0.01, b is more than or equal to 0.99,0.05, b is more than or equal to 0.99,0.1, b is more than or equal to 0.99,0.2, b is more than or equal to 0.9,0.3, b is more than or equal to 0.8, b is more than or equal to 0.4, b is more than or equal to 0.7,0.5, b is more than or equal to 0.6,0.55, b is more than or equal to 0.6, and the like. Therefore, the cobalt element with the content is included in the positive electrode active material, so that the electronic impedance and the ion impedance of the positive electrode active material can be obviously improved, and DCR (direct current) in the battery cycle process can be inhibitedResistance) increase rate. In other embodiments of the present application, the above Li [ Li ] x Ni a Co b Mn c M d ]O 2-e B of (b) satisfies the following: b is more than or equal to 0 and less than or equal to 0.1.
In some embodiments of the application, the above Li [ Li ] x Ni a Co b Mn c M d ]O 2-e Wherein, c is more than 0 and less than 1, for example, c is more than 0.001 and less than or equal to 0.99,0.005 and less than or equal to c is more than or equal to 0.99,0.01 and less than or equal to 0.99,0.05 and less than or equal to 0.99,0.1 and less than or equal to c is more than or equal to 0.99,0.2 and less than or equal to 0.9,0.3 and less than or equal to 0.8, c is more than or equal to 0.4 and less than or equal to 0.7,0.5 and less than or equal to c is more than or equal to 0.6,0.55 and less than or equal to 0.6, etc. Therefore, the positive electrode active material contains the manganese with the content, so that the structural stability of the positive electrode active material can be effectively improved, and the cycle stability of a battery containing the positive electrode active material can be improved. In other embodiments of the present application, the above Li [ Li ] x Ni a Co b Mn c M d ]O 2-e The following is satisfied: c is more than or equal to 0.5 and less than 1.
In some embodiments of the application, the above Li [ Li ] x Ni a Co b Mn c M d ]O 2-e Wherein M comprises at least one of Mg, nb, cr, ce, fe, ta, B, al, V, ti, zr, sn or Mo. In other embodiments of the present application, the above Li [ Li ] x Ni a Co b Mn c M d ]O 2-e Wherein M comprises at least one of Cr, fe or Al.
In some embodiments of the application, the above Li [ Li ] x Ni a Co b Mn c M d ]O 2-e Wherein d is more than or equal to 0 and less than 1, for example, d is more than or equal to 0.001 and less than or equal to 0.99,0.005 and less than or equal to 0.99,0.01 and less than or equal to 0.99,0.05 and less than or equal to 0.99,0.1 and less than or equal to 0.99,0.2 and less than or equal to 0.9,0.3 and less than or equal to 0.8, d is more than or equal to 0.4 and less than or equal to 0.7,0.5 and less than or equal to 0.6,0.55 and less than or equal to 0.6, etc. In other embodiments of the present application, the above Li [ Li ] x Ni a Co b Mn c M d ]O 2-e D satisfies the following: d is more than or equal to 0 and less than or equal to 0.1.
In some embodiments of the application, the above Li [ Li ] x Ni a Co b Mn c M d ]O 2-e Wherein e is more than or equal to 0 and less than 2, for example 0.ltoreq.e.ltoreq. 1.99,0.001.ltoreq.e E is more than or equal to 1.99,0.005 and less than or equal to 1.99,0.01e is not less than 1.99,0.05, e is not less than 1.99,0.1, e is not less than 1.99,0.2, e is not less than 1.99,0.5, e is not less than 1.9,0.8, e is not less than 1.7,1, e is not less than 1.5,1.2, e is not less than 1.4, etc. In other embodiments of the present application, the above Li [ Li ] x Ni a Co b Mn c M d ]O 2-e The e of (b) satisfies the following conditions: e is more than or equal to 0.001 and less than or equal to 0.05.
In the application, the molar content of O in the positive electrode active material is only a theoretical state value, the molar content of oxygen can be changed due to lattice oxygen release, and the actual molar content of O can float.
In some embodiments of the application, theR in (B) 1 、R 2 、R 3 、R 4 Each independently includeHydrogen atom, C 1 -C 6 Alkyl, halogen atom, C 1 -C 3 Haloalkyl, C 1 -C 3 Alkoxy or cyano, R 5 And R is 6 Each independently include->Hydrogen atom, C 1 -C 6 Alkyl or halogen atoms of (a).
The above-mentionedBending key in structure->"means the site of attachment on the molecular structure, i.e. the substitution +.>R in the structure 1 、R 2、 R 3 Or R is 4 Is a ligation site of (2).
As an example, C 1 -C 6 Alkyl radicals of (C1-6) are understood as meaning alkyl radicals, such as the methyl radical (-CH) 3 ) Ethyl (-CH) 2 CH 3 ) N-propyl (-CH) 2 CH 2 CH 3 ) Isopropyl (-CH (CH) 3 ) 2 ) N-butyl (-CH) 2 CH 2 CH 2 CH 3 ) Tert-butyl (-C (CH) 3 ) 3 ) N-pentyl (-CH) 2 CH 2 CH 2 CH 2 CH 3 ) N-hexyl (-CH) 2 CH 2 CH 2 CH 2 CH 2 CH 3 ) Etc.; the halogen atom may include F, cl, br or I.
As an example, C 1 -C 3 By haloalkyl of (C1-3) is understood a radical in which at least one hydrogen atom of an alkyl radical is replaced by a halogen atom, for example-CH 2 Cl、-CH 2 CH 2 Cl、-CH 2 CH 2 CH 2 Cl, and the like.
As an example, C 1 -C 3 Alkoxy of (C) is understood to mean an alkoxy radical having 1 to 3 carbon atoms, for example methoxy (CH) 3 O-), ethoxy (CH) 3 CH 2 O-), propoxy (CH) 3 CH 2 CH 2 O-) and the like.
As an example, C 1 -C 3 By haloalkoxy is understood a group of an alkoxy group having 1 to 3 carbon atoms, at least one hydrogen atom of which is replaced by a halogen atom, e.g. ClCH 2 O-、ClCH 2 CH 2 O-、ClCH 2 CH 2 CH 2 O-, and the like.
By way of example, alkenyl is understood to mean a radical of the molecular structure of an olefin from which one or more hydrogen atoms have been omitted, for example vinyl CH 2 =ch-, propenyl-ch=ch-CH 3 Etc.
In some embodiments of the application, theThe number of sulfate groups in the structure is less than or equal to 7, for example 2-7,3-6, 4-5. Thus, the present application employs the cyclic sulfate groups of the above-mentioned several sulfate groups, so that the cyclic sulfateHas excellent stability, reduces side reaction of electrolyte and improves cycle performance of the battery.
By way of example, the followingWhen the number of sulfate groups in the structure is 2, R 1 、R 2 、R 3 、R 4 Each independently includes a hydrogen atom, C 1 -C 6 Alkyl, halogen atom, C 1 -C 3 Haloalkyl, C 1 -C 3 Alkoxy, C 1 -C 3 A haloalkoxy, alkenyl, ester, cyano or sulfonate group.
By way of example, the followingWhen the number of sulfate groups in the structure is 3, R 1 、R 2 、R 3 、R 4 One of them isFor example +.>Wherein R is 1 、R 2 、R 3 、R 5 And R is 6 Each independently includes a hydrogen atom, C 1 -C 6 Alkyl, halogen atom, C 1 -C 3 Haloalkyl, C 1 -C 3 Alkoxy, C 1 -C 3 A haloalkoxy, alkenyl, ester, cyano or sulfonate group.
By way of example, the followingWhere there are 4 sulfate groups in the structure, e.g. Wherein R is 1 、R 3 、R 5 And R is 6 Each independently includes a hydrogen atom, C 1 -C 6 Alkyl, halogen atom, C 1 -C 3 Haloalkyl, C 1 -C 3 Alkoxy, C 1 -C 3 A haloalkoxy, alkenyl, ester, cyano or sulfonate group. Or (I)>Wherein R is 1 、R 2 、R 3 、R 5 And R is 6 Each independently includes a hydrogen atom, C 1 -C 6 Alkyl, halogen atom, C 1 -C 3 Haloalkyl, C 1 -C 3 Alkoxy, C 1 -C 3 A haloalkoxy, alkenyl, ester, cyano or sulfonate group.
By way of example, the followingWhere there are 5 sulfate groups in the structure, e.g.Wherein R is 1 、R 2 、R 3 、R 5 And R is 6 Each independently includes a hydrogen atom, C 1 -C 6 Alkyl, halogen atom, C 1 -C 3 Haloalkyl, C 1 -C 3 Alkoxy, C 1 -C 3 A haloalkoxy, alkenyl, ester, cyano or sulfonate group.
By way of example, the followingIn the structure where the number of sulfate groups is 6, e.g. +.>Wherein R is 1 、R 2 、R 3 、R 5 And R is 6 Each independently includes a hydrogen atom, C 1 -C 6 Alkyl, halogen atom, C 1 -C 3 Haloalkyl, C 1 -C 3 Alkoxy, C 1 -C 3 A haloalkoxy, alkenyl, ester, cyano or sulfonate group; or->Wherein R is 1 、R 3 、R 5 And R is 6 Each independently includes a hydrogen atom, C 1 -C 6 Alkyl, halogen atom, C 1 -C 3 Haloalkyl, C 1 -C 3 Alkoxy, C 1 -C 3 A haloalkoxy, alkenyl, ester, cyano or sulfonate group.
By way of example, the followingIn the case of 7 sulfate groups in the structure, for example +.>Wherein R is 1 、R 2 、R 3 、R 5 And R is 6 Each independently includes a hydrogen atom, C 1 -C 6 Alkyl, halogen atom, C 1 -C 3 Haloalkyl, C 1 -C 3 Alkoxy, C 1 -C 3 A haloalkoxy, alkenyl, ester, cyano or sulfonate group; or->Wherein R is 1 、R 3 、R 5 And R is 6 Each independently includes a hydrogen atom, C 1 -C 6 Alkyl, halogen atom, C 1 -C 3 Haloalkyl, C 1 -C 3 Alkoxy, C 1 -C 3 A haloalkoxy, alkenyl, ester, cyano or sulfonate group.
As an example, the cyclic sulfate includes at least one of formulas 1-16:
、/>、/>、/>、/>、/>、/>、/>、、/>、/>、/>、/>、/>、、/>。
synthesis example 1:the synthesis method of (2) comprises the following steps:
step 1: 300g (2 mol) of solid 1,6 dideoxy galactitol (CAS number: 25289-20-7) is added into a 5L three-mouth bottle, stirring is started, 523g (4.4 mol) of thionyl chloride is dripped into the three-mouth bottle, the temperature is controlled to be about 15 ℃ in the dripping process, the reaction is carried out for 4 hours at 45 ℃ after the dripping is finished, a large amount of pasty solid is separated out from the reaction liquid, 1L of deionized water is slowly dripped after cooling, the reaction system is rapidly stirred and scattered, the solid obtained by filtering is pulped and washed to be neutral in pH value for many times by using deionized water, and a filter cake is dried at 60 ℃ under reduced pressure, thus obtaining an intermediate product 1.
Step 2: 184.2g (0.8 mol) of intermediate 1 is added into a 3L three-port bottle, 1000mL of acetonitrile is added, 80mg of ruthenium trichloride trihydrate catalyst is added, after nitrogen is used for replacing the system, the system is cooled to 20 ℃, stirring is started, 2000g of sodium hypochlorite aqueous solution with the mass concentration of 20% is dripped into the system within 1h, and the reaction temperature is controlled to be 10-20 ℃; after the dripping is finished, stirring for 10min at the temperature of 10-20 ℃, separating liquid, and quenching an organic phase by using sodium sulfite aqueous solution until the starch potassium iodide test paper does not change blue; separating again, concentrating the organic layer, crystallizing with acetonitrile to obtain white powder solid as the above formula 1 (1H-NMR, CD) 3 CN, δ ppm 5.42-5.39 (m, 2H), 5.36-5.34 (m, 2H), 1.67-1.65 (d, 6H)）。
Synthesis example 2:the synthesis method of (2) comprises the following steps:
step 1: 356.5g (2 mol) of solid 3,4,5, 6-octanetetraol (CAS number: 2165939-88-6) is added into a 5L three-mouth bottle, stirring is started, 523g (4.4 mol) of thionyl chloride is dropwise added into the three-mouth bottle, the temperature is controlled to be about 15 ℃ in the dropwise adding process, the reaction is carried out for 4 hours at 45 ℃ after the dropwise adding is finished, a large amount of pasty solid is separated out from the reaction liquid, deionized water 1L is slowly dropwise added after cooling, the reaction system is rapidly stirred and scattered, the solid obtained through filtering is pulped and washed to be neutral in pH value by deionized water for multiple times, and a filter cake is dried at 60 ℃ under reduced pressure, so that an intermediate product 2 is obtained.
Step 2: 216.2g (0.8 mol) of intermediate 2 is added into a 3L three-mouth bottle, 1000mL of acetonitrile is added, 80mg of ruthenium trichloride trihydrate catalyst is added, after nitrogen is used for replacing the system, the system is cooled to 20 ℃, stirring is started, 2000g of sodium hypochlorite aqueous solution with the mass concentration of 20% is dripped in 1h, and the reaction temperature is controlled to be 10-20 ℃; after the dripping is finished, stirring for 10min at the temperature of 10-20 ℃, separating liquid, and quenching an organic phase by using sodium sulfite aqueous solution until the starch potassium iodide test paper does not change blue; separating again, concentrating the organic layer, and crystallizing with acetonitrile to obtain the compound of formula 2.
Synthesis example 3:the synthesis method of (2) comprises the following steps:
step 1: 328.4g (2 mol) of solid 2,3,4, 5-heptanyl tetrol (CAS number: 2629309-49-3) is added into a 5L three-mouth bottle, stirring is started, 523g (4.4 mol) of thionyl chloride is dropwise added into the three-mouth bottle, the temperature is controlled to be about 15 ℃ in the dropwise adding process, the reaction is carried out for 4 hours at 45 ℃ after the dropwise adding is finished, a large amount of pasty solid is separated out from the reaction liquid, deionized water 1L is slowly dropwise added after cooling, the reaction system is rapidly stirred and broken up, the solid obtained by filtering is pulped and washed to be neutral in pH value by deionized water for multiple times, and a filter cake is dried at 60 ℃ under reduced pressure, so that an intermediate product 3 is obtained.
Step 2: 205g (0.8 mol) of intermediate 3 is added into a 3L three-mouth bottle, 1000mL of acetonitrile is added, stirring is carried out until the solid is fully dissolved, 80mg of ruthenium trichloride trihydrate catalyst is added, after nitrogen is replaced by a system, the system is cooled to 20 ℃, stirring is started, 2000g of sodium hypochlorite aqueous solution with the mass concentration of 20% is dripped into the system within 1h, and the reaction temperature is controlled to be 10-20 ℃; after the dripping is finished, stirring for 10min at the temperature of 10-20 ℃, separating liquid, and quenching an organic phase by using sodium sulfite aqueous solution until the starch potassium iodide test paper does not change blue; separating again, concentrating the organic layer, and crystallizing with acetonitrile to obtain the compound of formula 3.
Synthesis example 4:the synthesis method of (2) comprises the following steps:
step 1: 300g (2 mol) of solid(CAS number: 7460-93-7) into a 5L three-necked flask, stirring, dropwise adding 523g (4.4 mol) of thionyl chloride into the three-necked flask, controlling the temperature at about 15deg.C in the dropwise adding process, keeping the temperature at 45deg.C for reaction for 4h after the dropwise adding is finished, precipitating a large amount of pasty solid from the reaction solution, cooling, slowly dropwise adding deionized water 1L, stirring and scattering the reaction system rapidly, and filtering to obtain solid by deionized waterPulping and washing with water for many times until the pH is neutral, and drying the filter cake at 60 ℃ under reduced pressure to obtain an intermediate product 9.
Step 2: 184.2g (0.8 mol) of intermediate 1 is added into a 3L three-port bottle, 1000mL of acetonitrile is added, 80mg of ruthenium trichloride trihydrate catalyst is added, after nitrogen is used for replacing the system, the system is cooled to 20 ℃, stirring is started, 2000g of sodium hypochlorite aqueous solution with the mass concentration of 20% is dripped into the system within 1h, and the reaction temperature is controlled to be 10-20 ℃; after the dripping is finished, stirring for 10min at the temperature of 10-20 ℃, separating liquid, and quenching an organic phase by using sodium sulfite aqueous solution until the starch potassium iodide test paper does not change blue; separating again, concentrating the organic layer, and crystallizing with acetonitrile to obtain the compound of formula 4.
Synthesis example 5:the synthesis method of (2) comprises the following steps:
step 1: adding 392.4g (2 mol) of solid 1,2,3,4,5.6-heptanes hexaol into a 5L three-mouth bottle, starting stirring, dropwise adding 784.5g (6.6 mol) of thionyl chloride into the three-mouth bottle, controlling the temperature at about 15 ℃ in the dropwise adding process, carrying out heat preservation reaction for 4 hours at 45 ℃ after the dropwise adding is finished, precipitating a large amount of pasty solid from the reaction solution, slowly dropwise adding deionized water 1L after cooling, rapidly stirring and scattering the reaction system, pulping and washing the solid obtained by filtering with deionized water for many times until the pH is neutral, and drying a filter cake at 60 ℃ under reduced pressure to obtain an intermediate product.
Step 2: 140g (0.4 mol) of intermediate 4 is added into a 4L three-mouth bottle, 1000mL of acetonitrile is added, 110mg of ruthenium trichloride trihydrate catalyst is added, after nitrogen is used for replacing the system, the system is cooled to 20 ℃, stirring is started, 1500g of sodium hypochlorite aqueous solution with the mass concentration of 20% is dripped in 1h, and the reaction temperature is controlled to be 10-20 ℃; after the dripping is finished, stirring for 10min at the temperature of 10-20 ℃, separating liquid, and quenching an organic phase by using sodium sulfite aqueous solution until the starch potassium iodide test paper does not change blue; separating again, concentrating the organic layer, and crystallizing with acetonitrile to obtain the compound of formula 5.
Synthesis example 6:the synthesis method of (2) comprises
Step 1: 392.4g (2 m)ol)(CAS number: 2236586-56-2) into a 5L three-mouth bottle, stirring, dropwise adding 784.5g (6.6 mol) of thionyl chloride into the three-mouth bottle, controlling the temperature at about 15 ℃ in the dropwise adding process, carrying out heat preservation reaction for 4 hours at 45 ℃ after the dropwise adding is finished, precipitating a large amount of pasty solid from the reaction liquid, cooling, slowly dropwise adding deionized water 1L, stirring and scattering the reaction system rapidly, pulping and washing the solid obtained by filtering with deionized water for multiple times until the pH is neutral, and drying a filter cake at 60 ℃ under reduced pressure to obtain an intermediate product.
Step 2: 140g (0.4 mol) of intermediate 4 is added into a 4L three-mouth bottle, 1000mL of acetonitrile is added, 110mg of ruthenium trichloride trihydrate catalyst is added, after nitrogen is used for replacing the system, the system is cooled to 20 ℃, stirring is started, 1500g of sodium hypochlorite aqueous solution with the mass concentration of 20% is dripped in 1h, and the reaction temperature is controlled to be 10-20 ℃; after the dripping is finished, stirring for 10min at the temperature of 10-20 ℃, separating liquid, and quenching an organic phase by using sodium sulfite aqueous solution until the starch potassium iodide test paper does not change blue; separating again, concentrating the organic layer, and crystallizing with acetonitrile to obtain the compound of formula 6.
Synthesis example 7:the synthesis method of (2) comprises the following steps:
step 1: adding 484g (2 mol) of solid octyl sugar alcohol into a 5L three-mouth bottle, starting stirring, dropwise adding 1046g (8.8 mol) of thionyl chloride into the three-mouth bottle, controlling the temperature at about 15 ℃ in the dropwise adding process, carrying out heat preservation reaction for 4 hours at 45 ℃ after the dropwise adding is finished, separating out a large amount of pasty solid from reaction liquid, slowly dropwise adding deionized water 1L after cooling, rapidly stirring and scattering a reaction system, pulping and washing the solid obtained by filtering with deionized water for multiple times until the pH value is neutral, and drying a filter cake at 60 ℃ under reduced pressure to obtain an intermediate product.
Step 2: 183.2g (0.4 mol) of intermediate 5 is added into a 4L three-port bottle, 1000mL of acetonitrile is added, 150mg of ruthenium trichloride trihydrate catalyst is added, after nitrogen is used for replacing the system, the system is cooled to 20 ℃, stirring is started, 2000g of sodium hypochlorite aqueous solution with the mass concentration of 20% is dripped in within 1h, and the reaction temperature is controlled to be 10-20 ℃; after the dripping is finished, stirring for 10min at the temperature of 10-20 ℃, separating liquid, and quenching an organic phase by using sodium sulfite aqueous solution until the starch potassium iodide test paper does not change blue; separating again, concentrating the organic layer, and crystallizing with acetonitrile to obtain the compound of formula 7.
CAS number: 2793408-99-6.
CAS number: 1431298-10-0.
In some embodiments of the application, the cyclic sulfate content W is based on the total mass of the electrolyte 1 The method meets the following conditions: w is more than or equal to 0.005 percent 1 10% or less, for example 0.008% or less of W 1 ≤10%，0.01%≤W 1 ≤10%，0.05%≤W 1 ≤10%，0.08%≤W 1 ≤10%，0.1%≤W 1 ≤10%，0.5%≤W 1 ≤10%，0.8%≤W 1 ≤10%，1%≤W 1 ≤10%，2%≤W 1 ≤9%，3%≤W 1 ≤8%，4%≤W 1 ≤7%，5%≤W 1 Less than or equal to 6 percent, etc. Thus, the content of the cyclic sulfate in the electrolyte is controlled within the above range, and on one hand, the sulfate group provided by the cyclic sulfate with the content can form a flexible CEI film with S-O bond on the surface of the positive electrode plate, and the CEI film reduces the contact between the lithium-rich manganese-based positive electrode material and the electrolyte, thereby reducing RH ＋ On the other hand, the sulfate group provided by the cyclic sulfate with the content can receive electrons from the surface of the anode during the charging of the battery to generate self-reduction, and the generated reduction products, namely lithium sulfite and the like are deposited on the surface of the anode to participate in the formation of an SEI film, and the SEI film has higher strength and can effectively inhibit RH + Damage to SEI film, thus reducing consumption of active lithium and improving initial coulombic efficiency and cycle performance of battery. In other embodiments of the present application, the cyclic sulfate content W is based on the total mass of the electrolyte 1 The method meets the following conditions: w is more than or equal to 0.05 percent 1 Less than or equal to 5 percent, further 0.1 percent or less than or equal to W 1 ≤3%。
In some embodiments of the application, the electrolyte further comprises an electrolyte salt and other solvents.
In some embodiments of the application, the electrolyte salt may include at least one of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium perchlorate, lithium hexafluoroarsenate, lithium bis-fluorosulfonyl imide, lithium bis-trifluoromethanesulfonyl imide, lithium trifluoromethanesulfonate, lithium difluorophosphate, lithium difluorooxalato borate, lithium difluorodioxaato phosphate, or lithium tetrafluorooxalato phosphate.
In some embodiments of the present application, the other solvent may include a solvent that may include at least one of ethylene carbonate, propylene carbonate, methylethyl carbonate, diethyl carbonate, dimethyl carbonate, dipropyl carbonate, methylpropyl carbonate, ethylene carbonate, butylene carbonate, fluoroethylene carbonate, methyl formate, methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, propyl propionate, methyl butyrate, ethyl butyrate, 1, 4-butyrolactone, sulfolane, dimethyl sulfone, methyl sulfone, or diethyl sulfone.
In some embodiments of the application, the electrolyte further optionally includes an additive. For example, the additives may include negative electrode film-forming additives, positive electrode film-forming additives, and may also include additives capable of improving certain properties of the battery, such as additives that improve the overcharge performance of the battery, additives that improve the high or low temperature performance of the battery, and the like.
In some embodiments of the present application, the positive electrode sheet includes a positive electrode current collector and a positive electrode active material layer formed on at least one side of the positive electrode current collector, the positive electrode active material layer including the positive electrode active material, the content W of the positive electrode active material based on the total mass of the positive electrode active material layer 2 And W is equal to 1 The method meets the following conditions: w is more than or equal to 0.003 percent 1 /W 2 Less than or equal to 12%, for example, 0.005% less than or equal to W 1 /W 2 ≤12%，0.008%≤W 1 /W 2 ≤12%，0.01%≤W 1 /W 2 ≤12%，0.03%≤W 1 /W 2 ≤12%，0.05%≤W 1 /W 2 ≤12%，0.08%≤W 1 /W 2 ≤12%，0.1%≤W 1 /W 2 ≤12%，0.3%≤W 1 /W 2 ≤12%，0.5%≤W 1 /W 2 ≤12%，0.7%≤W 1 /W 2 ≤12%，1%≤W 1 /W 2 ≤12%，2%≤W 1 /W 2 ≤11%，3%≤W 1 /W 2 ≤10%，4%≤W 1 /W 2 ≤9%，5%≤W 1 /W 2 ≤8%，6%≤W 1 /W 2 Less than or equal to 7 percent, etc. Thus, the application controls the content W of cyclic sulfate in the electrolyte 1 And the content W of the positive electrode active material in the positive electrode active material layer 2 On the one hand, the sulfate group provided by the cyclic sulfate can form a flexible CEI film with S-O bond on the surface of the positive electrode plate, and the CEI film reduces the contact between the lithium-rich manganese-based positive electrode material and the electrolyte, thereby reducing RH ＋ On the other hand, the sulfate group provided by the cyclic sulfate can receive electrons from the surface of the negative electrode during the charging of the battery to generate self-reduction, and the generated reduction products, namely lithium sulfite and the like are deposited on the surface of the negative electrode to participate in the formation of an SEI film, and the SEI film has higher strength and can effectively inhibit RH + Damage to SEI film, thus reducing consumption of active lithium and improving initial coulombic efficiency and cycle performance of battery. In other embodiments of the present application, the content W of the positive electrode active material is based on the total mass of the positive electrode active material layer 2 And W is equal to 1 The method meets the following conditions: w is more than or equal to 0.04 percent 1 /W 2 ≤6%。
In some embodiments of the present application, the content W of the positive electrode active material is based on the total mass of the positive electrode active material layer 2 The method meets the following conditions: w is more than or equal to 90 percent 2 98% or less, for example 91% or less of W 2 ≤98%，92%≤W 2 ≤97%，93%≤W 2 ≤96%，94%≤W 2 Less than or equal to 95 percent, etc. In other embodiments of the present application, the content W of the positive electrode active material is based on the total mass of the positive electrode active material layer 2 The method meets the following conditions: w is 93 percent or less 2 Less than or equal to 97 percent. Thus, the present application controls the content W of the positive electrode active material in the positive electrode active material layer 2 The energy density of the lithium ion battery can be improved by meeting the conditions.
In some embodiments of the application, the positive electrode active material has a BET specific surface area of 0.4m 2 /g-1.5m 2 /g, e.g. 0.5m 2 /g-1.4m 2 /g，0.6m 2 /g-1.3m 2 /g，0.7m 2 /g-1.2m 2 /g，0.8m 2 /g-1.1m 2 /g，0.9m 2 /g-1m 2 /g, etc. Thus, the present application controls the BET specific surface area of the positive electrode active material in the above range, which is advantageous in improving the first coulombic efficiency and gram capacity of the positive electrode active material and improving the storage performance and gassing problems of the battery. In other embodiments of the present application, the positive electrode active material has a BET specific surface area of 0.4m 2 /g-1.0m 2 /g。
In the present application, the BET specific surface area of the positive electrode active material is in the meaning known in the art, and can be measured by an instrument and a method known in the art, and can be measured, for example, by referring to the following method: about 7g of the sample was put into a 9cc bulb-equipped long tube using a American microphone multi-station type full-automatic specific surface area and pore analyzer GeminiVII2390, deaerated at 200 ℃ for 2 hours, and then put into a host machine for testing to obtain BET specific surface area data of the positive electrode active material.
In some embodiments of the present application, the particle size distribution span= (Dv 90-Dv 10)/Dv 50 of the positive electrode active material satisfies: SPAN is more than or equal to 0.7 and less than or equal to 1.8, for example, SPAN is more than or equal to 0.8 and less than or equal to 1.7,0.9 and less than or equal to 1.6, SPAN is more than or equal to 1 and less than or equal to 1.5,1.1 and SPAN is more than or equal to 1.4,1.2 and SPAN is more than or equal to 1.3, etc. Therefore, when the particle size distribution of the positive electrode active material is controlled within the range, the space utilization rate can be improved, and the capacity of the material can be exerted. In other embodiments of the present application, the particle size distribution span= (Dv 90-Dv 10)/Dv 50 of the positive electrode active material satisfies: SPAN is more than or equal to 0.8 and less than or equal to 1.4.
In some embodiments of the application, the Dv90 of the positive electrode active material may be 8 μm to 16 μm, for example, 9 μm to 15 μm,10 μm to 14 μm,11 μm to 13 μm,12 μm to 13 μm, etc. In other embodiments of the present application, the Dv90 of the positive electrode active material may be 8 μm to 9 μm.
In some embodiments of the application, the Dv50 of the positive electrode active material may be 6 μm to 10 μm, for example 7 μm to 9 μm,7 μm to 8 μm, etc. In other embodiments of the present application, the Dv50 of the positive electrode active material may be 6 μm to 7 μm.
In some embodiments of the application, the Dv10 of the positive electrode active material may be 2 μm to 5 μm, for example, 2 μm to 4 μm,2.5 μm to 3 μm, and the like. In some embodiments of the application, the Dv10 of the positive electrode active material may be 2 μm to 3 μm.
In the present application, dv90 means a particle size corresponding to a cumulative volume distribution percentage of 90%, dv50 means a particle size corresponding to a cumulative volume distribution percentage of 50%, dv10 means a particle size corresponding to a cumulative volume distribution percentage of 10%, and Dv90, dv50 and Dv10 can be measured by a laser particle size analyzer (for example Malvern Master Size 3000) with reference to standard GB/T19077-2016.
In some embodiments of the application, the residual alkali amount of the positive electrode active material is less than or equal to 1000ppm based on the total weight of the positive electrode active material.
In some embodiments of the application, the residual lithium amount of the positive electrode active material is less than or equal to 500ppm based on the total weight of the positive electrode active material.
Residual alkali remaining during the preparation of the positive electrode active material reduces the electron conductivity and ion diffusion rate of the material, thereby causing an increase in polarization and deterioration in gram-volume of the positive electrode active material, and in addition, li 2 CO 3 Is easily decomposed to generate gas, resulting in swelling of the battery. Thus, the present application is advantageous in improving the gram capacity and the first coulombic efficiency of the positive electrode active material by limiting the residual alkali amount and the residual lithium amount of the positive electrode active material to the above-described ranges.
In the application, the residual alkali and the residual lithium amount of the positive electrode active material can be tested by referring to GB/T9736-2008 free lithium potentiometric titration, the contents of lithium carbonate and lithium hydroxide can be obtained respectively according to the test, the total amount of the lithium carbonate and the lithium hydroxide is the residual alkali amount when the total amount is converted into the content of the lithium carbonate, and then the concentration of the total amount of lithium ions in the lithium hydroxide and the lithium carbonate accounting for the total amount of the lithium carbonate and the lithium hydroxide is the residual lithium amount according to the content of the lithium hydroxide and the lithium carbonate.
As an example, the positive electrode current collector has two surfaces opposing in its own thickness direction, and the positive electrode active material layer is provided on either one or both of the two surfaces opposing the positive electrode current collector.
In some embodiments of the application, the positive current collector may be a metal foil or a composite negative current collector. For example, as the metal foil, aluminum foil may be used. The composite anode current collector may include a polymer material base layer and a metal layer formed on at least one surface of the polymer material base layer. The composite negative electrode current collector may be formed by forming a metal material (aluminum, aluminum alloy, nickel alloy, titanium alloy, silver alloy, etc.) on a polymer material substrate (e.g., a substrate of polypropylene (PP), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polystyrene (PS), polyethylene (PE), etc.).
In some embodiments of the present application, the positive electrode active material layer may further optionally include a conductive agent. As an example, the conductive agent may include at least one of superconducting carbon, acetylene black, carbon black, ketjen black, carbon dots, carbon nanotubes, graphene, or carbon nanofibers.
In some embodiments of the present application, the positive electrode active material layer may further optionally include a binder. As an example, the binder may include at least one of polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), a vinylidene fluoride-tetrafluoroethylene-propylene terpolymer, a vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene terpolymer, a tetrafluoroethylene-hexafluoropropylene copolymer, or a fluoroacrylate resin.
In some embodiments of the present application, the positive electrode sheet may be prepared by: dispersing the above components for preparing the positive electrode sheet, such as the positive electrode active material, the conductive agent, the binder and any other components, in a solvent (such as N-methylpyrrolidone) to form a positive electrode slurry; and (3) coating the positive electrode slurry on a positive electrode current collector, and obtaining a positive electrode plate after the procedures of drying, cold pressing and the like.
Typically, a battery includes a positive electrode tab, a negative electrode tab, an electrolyte, and a separator. During the charge and discharge of the battery, active ions are inserted and extracted back and forth between the positive electrode plate and the negative electrode plate. The electrolyte plays a role in ion conduction between the positive electrode plate and the negative electrode plate. The isolating film is arranged between the positive pole piece and the negative pole piece, and mainly plays a role in preventing the positive pole piece and the negative pole piece from being short-circuited, and meanwhile ions can pass through the isolating film.
The negative electrode tab includes a negative electrode current collector and a negative electrode active material layer disposed on at least one surface of the negative electrode current collector, the negative electrode active material layer including a negative electrode active material.
As an example, the anode current collector has two surfaces opposing in its own thickness direction, and the anode active material layer is provided on either one or both of the two surfaces opposing the anode current collector.
In some embodiments of the application, the negative electrode current collector may employ a metal foil or a composite current collector. For example, as the metal foil, copper foil may be used. The composite current collector may include a polymeric material base layer and a metal layer formed on at least one surface of the polymeric material base material. The composite current collector may be formed by forming a metal material (copper, copper alloy, nickel alloy, titanium alloy, silver alloy, etc.) on a polymer material substrate (such as a substrate of polypropylene (PP), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polystyrene (PS), polyethylene (PE), etc.).
In some embodiments of the present application, the anode active material may employ an anode active material for a battery, which is well known in the art. As an example, the anode active material may include at least one of the following materials: artificial graphite, natural graphite, soft carbon, hard carbon, silicon-based materials, tin-based materials, lithium titanate, and the like. The silicon-based material may include at least one of elemental silicon, a silicon oxygen compound, a silicon carbon compound, a silicon nitrogen compound, or a silicon alloy. The tin-based material may include at least one of elemental tin, a tin oxide, or a tin alloy. However, the present application is not limited to these materials, and other conventional materials that can be used as a battery anode active material may be used. These negative electrode active materials may be used alone or in combination of two or more.
In some embodiments of the application, the anode active material layer further optionally includes a binder. The binder may include at least one of Styrene Butadiene Rubber (SBR), polyacrylic acid (PAA), sodium Polyacrylate (PAAs), polyacrylamide (PAM), polyvinyl alcohol (PVA), sodium Alginate (SA), polymethacrylic acid (PMAA), or carboxymethyl chitosan (CMCS).
In some embodiments of the present application, the anode active material layer may further optionally include a conductive agent. The conductive agent may include at least one of superconducting carbon, acetylene black, carbon black, ketjen black, carbon dots, carbon nanotubes, graphene, or carbon nanofibers.
In some embodiments of the present application, the anode active material layer may optionally further include other auxiliary agents, such as a thickener (e.g., sodium carboxymethyl cellulose (CMC-Na)), and the like.
In some embodiments of the application, the negative electrode sheet may be prepared by: dispersing the above components for preparing the negative electrode sheet, such as a negative electrode active material, a conductive agent, a binder and any other components, in a solvent (e.g., deionized water) to form a negative electrode slurry; and coating the negative electrode slurry on a negative electrode current collector, and obtaining a negative electrode plate after the procedures of drying, cold pressing and the like.
The type of the separator is not particularly limited, and any known porous separator having good chemical stability and mechanical stability can be used.
In some embodiments of the present application, the material of the isolation film may include at least one of glass fiber, non-woven fabric, polyethylene, polypropylene, or polyvinylidene fluoride. The separator may be a single-layer film or a multilayer composite film, and is not particularly limited. When the separator is a multilayer composite film, the materials of the respective layers may be the same or different, and are not particularly limited.
In some embodiments of the present application, the positive electrode tab, the negative electrode tab, and the separator may be manufactured into an electrode assembly through a winding process or a lamination process.
In some embodiments of the application, the secondary battery may include an outer package. The outer package may be used to encapsulate the electrode assembly and electrolyte described above.
In some embodiments of the present application, the exterior package of the secondary battery may be a hard case, such as a hard plastic case, an aluminum case, a steel case, or the like. The exterior package of the secondary battery may also be a pouch type pouch, for example. The material of the flexible bag may be plastic, and examples of the plastic include polypropylene, polybutylene terephthalate, and polybutylene succinate.
The shape of the battery is not particularly limited in the present application, and may be cylindrical, square, or any other shape. For example, fig. 1 is a battery cell 1 of a square structure as one example.
In some embodiments of the application, referring to fig. 2, the outer package may include a housing 11 and a cover 13. The housing 11 may include a bottom plate and a side plate connected to the bottom plate, where the bottom plate and the side plate enclose a receiving chamber. The housing 11 has an opening communicating with the accommodation chamber, and the cover plate 13 can be provided to cover the opening to close the accommodation chamber. The positive electrode sheet, the negative electrode sheet, and the separator may be formed into the electrode assembly 12 through a winding process or a lamination process. The electrode assembly 12 is enclosed in the accommodating chamber. The electrolyte is impregnated in the electrode assembly 12. The number of the electrode assemblies 12 included in the battery cell 1 may be one or more, and one skilled in the art may select according to specific practical requirements.
In some embodiments of the present application, the cells may be assembled into a battery module, and the number of cells included in the battery module may be one or more, and the specific number may be selected by one skilled in the art according to the application and capacity of the battery module.
Fig. 3 is a battery module 2 as an example. Referring to fig. 3, in the battery module 2, a plurality of battery cells 1 may be sequentially arranged in the longitudinal direction of the battery module 2. Of course, the arrangement may be performed in any other way. The plurality of battery cells 1 may be further fixed by fasteners.
Alternatively, the battery module 2 may further include a housing having an accommodating space in which the plurality of battery cells 1 are accommodated.
In some embodiments, the battery modules 2 may be further assembled into a battery pack, and the number of battery modules 2 included in the battery pack may be one or more, and a specific number may be selected by those skilled in the art according to the application and capacity of the battery pack.
Fig. 4 and 5 are battery packs 3 as an example. Referring to fig. 4 and 5, a battery case and a plurality of battery modules 2 disposed in the battery case may be included in the battery pack 3. The battery case includes an upper case 31 and a lower case 32, and the upper case 31 can be covered on the lower case 32 and forms a closed space for accommodating the battery module 2. The plurality of battery modules 2 may be arranged in the battery case in any manner.
In addition, the application also provides an electric device which comprises at least one of the secondary battery, the battery module or the battery pack. The secondary battery, the battery module, or the battery pack may be used as a power source of the power consumption device, and may also be used as an energy storage unit of the power consumption device. The power utilization device may include mobile devices (e.g., cell phones, notebook computers, etc.), electric vehicles (e.g., electric-only vehicles, hybrid electric vehicles, plug-in hybrid electric vehicles, electric bicycles, electric scooters, electric golf carts, electric trucks, etc.), electric trains, ships and satellites, energy storage systems, etc., but is not limited thereto.
As the electricity consumption device, a secondary battery, a battery module, or a battery pack may be selected according to the use requirements thereof.
Fig. 6 is an electrical device as an example. The electric device is a pure electric vehicle, a hybrid electric vehicle, a plug-in hybrid electric vehicle or the like. In order to meet the high power and high energy density requirements of the secondary battery by the power consumption device, a battery pack or a battery module may be employed.
As another example, the power consumption device may be a mobile phone, a tablet computer, a notebook computer, or the like. The device is generally required to be light and thin, and a battery can be used as a power source.
Hereinafter, embodiments of the present application are described. The following examples are illustrative only and are not to be construed as limiting the application. The examples are not to be construed as limiting the specific techniques or conditions described in the literature in this field or as per the specifications of the product. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
Example 1
1. Preparation of positive electrode plate
Positive electrode active material Li [ Li ] 0.2 Ni 0.2 Co 0.05 Mn 0.5 Al 0.05 ]O 2 The positive electrode slurry is prepared from Super P as a conductive agent, polyvinylidene fluoride (PVDF) as a binder and N-methyl pyrrolidone (NMP), wherein the solid content of the positive electrode slurry is 50wt%, and Li [ Li ] is the solid content 0.2 Ni 0.2 Co 0.05 Mn 0.5 Al 0.05 ]O 2 The mass ratio of Super P to PVDF is 95:2.5:2.5, positive electrode slurry is coated on the upper and lower surfaces of a current collector aluminum foil, and is dried at 100 ℃ for 30min, then cold-pressed, and then subjected to trimming, cutting and slitting to prepare the positive electrode plate.
2. Preparation of negative electrode plate
Uniformly mixing graphite, hard carbon, a conductive agent Super P, a thickener carboxymethyl cellulose (CMC) and an adhesive styrene-butadiene rubber (SBR) in deionized water to prepare negative electrode slurry, wherein the solid content of the negative electrode slurry is 50wt%, the mass ratio of the graphite, the hard carbon, the conductive agent Super P, the CMC and the adhesive styrene-butadiene rubber (SBR) in the solid components is 90:5:2:1:2, coating the negative electrode slurry on the upper surface and the lower surface of a current collector copper foil, drying at 120 ℃, and then carrying out cold pressing, trimming, cutting and slitting to prepare the negative electrode plate.
3. Preparation of electrolyte
In a glove box filled with argon (water content < 10ppm, oxygen content < 1 ppm), a compound represented by formula 1 was preparedAdded to an organic solvent (the organic solvent comprises ethylene carbonate)(EC) and Ethyl Methyl Carbonate (EMC), EC to EMC mass ratio of 3: 7) After being evenly mixed, the LiPF is slowly added 6 After the lithium salt is completely dissolved, the electrolyte with the lithium salt concentration of 1mol/L is obtained.
4. Isolation film
A16 μm polyethylene film was used as a separator.
5. Lithium ion battery preparation
And stacking the positive electrode plate, the isolating film and the negative electrode plate in sequence, enabling the isolating film to be positioned between the positive electrode plate and the negative electrode plate to play a role in isolating the positive electrode from the negative electrode plate, winding to obtain a bare cell, welding the electrode lug, placing the bare cell in an outer package, injecting the prepared electrolyte into the dried cell, packaging, standing, forming, shaping, testing the capacity and the like, and thus completing the preparation of the lithium ion battery.
The lithium ion batteries of examples 2 to 45 and comparative examples 1 to 3 were prepared in the same manner as in example 1, except that the composition of the positive electrode active material and the composition of the additive in the electrolyte were different, and the cyclic sulfate in comparative example 3 was represented by formula 17As shown in table 1.
TABLE 1
The lithium ion batteries obtained in examples 1 to 45 and comparative examples 1 to 3 were characterized for initial cycle coulombic efficiency and cycle performance, and the characterization results are shown in table 2.
(1) First circle coulombic efficiency of lithium ion battery:
the lithium ion battery was charged to 4.5V at 25 ℃ with a constant current of 0.1C, and then charged to 0.05C with a constant voltage of 4.5V, to obtain a first charge capacity (C c1 ) The method comprises the steps of carrying out a first treatment on the surface of the Then discharging to 2.0V with 0.1C constant current to obtain the first discharge capacity (C d1 ) And the lithium ion battery first-cycle coulombic efficiency=first discharge capacity (Cd 1)/first charge capacity (Cc 1) ×100% was calculated.
(2) And (3) testing the cycle performance:
the lithium ion battery was tested after full discharge at 0.1C at 25 ℃. The test flow is as follows: the battery was charged to 4.5V at 0.5C, then charged to 0.05C at constant voltage, left for 10min, and then discharged to 2.0V at 0.2C, which is a cyclic process. And carrying out repeated cyclic charge and discharge tests on the lithium ion battery according to the method until the discharge capacity of the lithium ion secondary battery is reduced to 80%, and recording the cycle times of the lithium ion battery.
TABLE 2
As can be seen from Table 2, the lithium ion batteries of examples 1 to 45 have higher initial cycle coulombic efficiency and cycle performance than those of the lithium ion batteries of comparative examples 1 to 3, and thus, it is shown that the problem of poor initial cycle coulombic efficiency and cycle performance of the conventional lithium ion battery containing a lithium-rich manganese-based positive electrode material can be solved by adding the cyclic sulfate of the present application to the electrolyte.
The present application is not limited to the above embodiment. The above embodiments are merely examples, and embodiments having substantially the same configuration and the same effects as those of the technical idea within the scope of the present application are included in the technical scope of the present application. Further, various modifications that can be made to the embodiments and other modes of combining some of the constituent elements in the embodiments, which are conceivable to those skilled in the art, are also included in the scope of the present application within the scope not departing from the gist of the present application.
Claims (21)
1. A lithium ion battery is characterized by comprising a positive electrode plate and electrolyte, wherein the positive electrode plate comprises a positive electrode active material, and the positive electrode active material comprises Li [ Li ] x Ni a Co b Mn c M d ]O 2-e Wherein x+a+b+c+d=1, 0 < x < 1, 0.ltoreq.a < 1, 0.ltoreq.b < 1,0 < c < 1, 0.ltoreq.d < 1, 0.ltoreq.e < 2, M comprises at least one of Mg, nb, cr, ce, fe, ta, B, al, V, ti, zr, sn or Mo,
the electrolyte comprises a cyclic sulfate ester,the cyclic sulfate comprisesWherein R is 1 、R 2 、R 3 、R 4 Each independently include->Hydrogen atom, C 1 -C 6 Alkyl, halogen atom, C 1 -C 3 Haloalkyl, C 1 -C 3 Alkoxy, C 1 -C 3 Haloalkoxy, alkenyl, ester, cyano or sulfonate, R 5 And R is 6 Each independently include->Hydrogen atom, C 1 -C 6 Alkyl, halogen atom, C 1 -C 3 Haloalkyl, C 1 -C 3 Alkoxy, C 1 -C 3 A haloalkoxy, alkenyl, ester, cyano or sulfonate group.
2. The lithium ion battery of claim 1, wherein R 1 、R 2 、R 3 、R 4 Each independently includeHydrogen atom, C 1 -C 6 Alkyl, halogen atom, C 1 -C 3 Haloalkyl, C 1 -C 3 Alkoxy or cyano, R 5 And R is 6 Each independently include->Hydrogen atom, C 1 -C 6 Alkyl or halogen atoms of (a).
3. The lithium ion battery of claim 1 or 2, wherein the The number of sulfate groups in the structure is less than or equal to 7.
4. The lithium ion battery of claim 1, wherein the cyclic sulfate comprises at least one of formulas 1-16:
、/>、/>、/>、/>、、/>、/>、/>、、/>、 />、/>、/>、、/>。
5. the lithium ion battery of claim 1, wherein the content W of the cyclic sulfate is based on the total mass of the electrolyte 1 The method meets the following conditions: w is more than or equal to 0.005 percent 1 ≤10%。
6. The lithium ion battery of claim 5, wherein the content W of cyclic sulfate is based on the total mass of the electrolyte 1 The method meets the following conditions: w is more than or equal to 0.05 percent 1 ≤5%。
7. The lithium ion battery of claim 6, wherein the content W of cyclic sulfate is based on the total mass of the electrolyte 1 The method meets the following conditions: w is more than or equal to 0.1 percent 1 ≤3%。
8. The lithium ion battery according to any one of claims 5 to 7, wherein the positive electrode sheet includes a positive electrode current collector and a positive electrode active material layer formed on at least one side of the positive electrode current collector, the positive electrode active material layer including the positive electrode active material, the content W of the positive electrode active material based on the total mass of the positive electrode active material layer 2 And W is equal to 1 The method meets the following conditions: w is more than or equal to 0.003 percent 1 /W 2 ≤12%。
9. The lithium ion battery of claim 8, characterized in thatCharacterized in that W is more than or equal to 0.04 percent 1 /W 2 ≤6%。
10. The lithium ion battery of claim 8, wherein 90% W 2 ≤98%。
11. The lithium ion battery of claim 10, wherein 93% W 2 ≤97%。
12. The lithium ion battery of claim 1, wherein M comprises at least one of Cr, fe, or Al.
13. The lithium ion battery of claim 1 wherein Li [ Li x Ni a Co b Mn c M d ]O 2-e At least one of the following conditions is satisfied:
0.1≤x≤0.6；
0≤a≤0.5；
0≤b≤0.1；
0.5≤c＜1；
0≤d≤0.1；
0.001≤e≤0.05。
14. the lithium ion battery according to claim 1, wherein the BET specific surface area of the positive electrode active material is 0.4m 2 /g-1.5m 2 /g。
15. The lithium ion battery according to claim 1 or 14, wherein the BET specific surface area of the positive electrode active material is 0.4m 2 /g-1.0m 2 /g。
16. The lithium ion battery according to claim 1, wherein the particle size distribution span= (Dv 90-Dv 10)/Dv 50 of the positive electrode active material satisfies: SPAN is more than or equal to 0.7 and less than or equal to 1.8.
17. The lithium ion battery of claim 1 or 16, wherein 0.8 +.span +.1.4.
18. The lithium ion battery of claim 11, wherein the positive electrode active material satisfies at least one of the following conditions:
The Dv90 of the positive electrode active material is 8-16 μm;
the Dv50 of the positive electrode active material is 6-10 μm;
the Dv10 of the positive electrode active material is 2 μm to 5 μm.
19. The lithium ion battery of claim 1, wherein the residual alkali content of the positive electrode active material is less than or equal to 1000ppm based on the total weight of the positive electrode active material.
20. The lithium ion battery of claim 1, wherein the amount of residual lithium of the positive electrode active material is less than or equal to 500ppm based on the total weight of the positive electrode active material.
21. An electrical device comprising the lithium ion battery of any one of claims 1-20.
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Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101453036A (en) * | 2007-12-04 | 2009-06-10 | 中信国安盟固利新能源科技有限公司 | Non-aqueous electrolytic solution for lithium ion secondary battery and manufacturing method thereof |
| CN103441238A (en) * | 2013-08-27 | 2013-12-11 | 上海电力学院 | Mg-doped Li-rich anode material and preparation method for same |
| CN104718658A (en) * | 2012-10-29 | 2015-06-17 | 株式会社杰士汤浅国际 | Nonaqueous electrolyte secondary battery and method for manufacturing nonaqueous electrolyte secondary battery |
| JP2015176760A (en) * | 2014-03-14 | 2015-10-05 | 三井化学株式会社 | lithium secondary battery |
| CN109904521A (en) * | 2017-12-08 | 2019-06-18 | 宁德时代新能源科技股份有限公司 | Electrolyte and battery comprising same |
| CN110504415A (en) * | 2018-05-17 | 2019-11-26 | 宁德时代新能源科技股份有限公司 | Lithium ion battery |
| CN113661589A (en) * | 2019-04-10 | 2021-11-16 | 株式会社村田制作所 | Lithium ion secondary battery |
| WO2023134334A1 (en) * | 2022-01-14 | 2023-07-20 | 深圳新宙邦科技股份有限公司 | Lithium ion battery |
| WO2023142693A1 (en) * | 2022-01-25 | 2023-08-03 | 深圳新宙邦科技股份有限公司 | Lithium-ion battery |
-
2023
- 2023-09-14 CN CN202311184123.0A patent/CN116960319A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101453036A (en) * | 2007-12-04 | 2009-06-10 | 中信国安盟固利新能源科技有限公司 | Non-aqueous electrolytic solution for lithium ion secondary battery and manufacturing method thereof |
| CN104718658A (en) * | 2012-10-29 | 2015-06-17 | 株式会社杰士汤浅国际 | Nonaqueous electrolyte secondary battery and method for manufacturing nonaqueous electrolyte secondary battery |
| CN103441238A (en) * | 2013-08-27 | 2013-12-11 | 上海电力学院 | Mg-doped Li-rich anode material and preparation method for same |
| JP2015176760A (en) * | 2014-03-14 | 2015-10-05 | 三井化学株式会社 | lithium secondary battery |
| CN109904521A (en) * | 2017-12-08 | 2019-06-18 | 宁德时代新能源科技股份有限公司 | Electrolyte and battery comprising same |
| CN110504415A (en) * | 2018-05-17 | 2019-11-26 | 宁德时代新能源科技股份有限公司 | Lithium ion battery |
| CN113661589A (en) * | 2019-04-10 | 2021-11-16 | 株式会社村田制作所 | Lithium ion secondary battery |
| WO2023134334A1 (en) * | 2022-01-14 | 2023-07-20 | 深圳新宙邦科技股份有限公司 | Lithium ion battery |
| WO2023142693A1 (en) * | 2022-01-25 | 2023-08-03 | 深圳新宙邦科技股份有限公司 | Lithium-ion battery |
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