CN112886054A - Lithium-rich manganese-based lithium ion battery - Google Patents

Lithium-rich manganese-based lithium ion battery Download PDF

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CN112886054A
CN112886054A CN201911201284.XA CN201911201284A CN112886054A CN 112886054 A CN112886054 A CN 112886054A CN 201911201284 A CN201911201284 A CN 201911201284A CN 112886054 A CN112886054 A CN 112886054A
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lithium
ion battery
rich manganese
lithium ion
electrolyte
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邓永红
马鑫
钱韫娴
王军
肖映林
康媛媛
胡时光
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Shenzhen Capchem Technology Co Ltd
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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
    • 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
    • H01M10/0567—Liquid materials characterised by the additives
    • 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
    • H01M10/058—Construction or manufacture
    • 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
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • 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
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • 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
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Abstract

The invention provides a lithium-rich manganese-based lithium ion battery which comprises a positive electrode material, a negative electrode material and electrolyte, wherein the positive electrode material comprises a lithium-rich manganese-based oxide, the electrolyte comprises a solvent and an additive, and the additive comprises a compound shown in the following structural formula:
Figure DDA0002295929610000011
wherein R is1And R3Each independently selected from
Figure DDA0002295929610000012
Or
Figure DDA0002295929610000013
R4Selected from S or Se; r5Selected from C, Si, Ge, Sn, S or Se; and R is4And R5At least one of them is selected from S, R2Selected from carbon chains having some or all of the hydrogens replaced with other elements or groups; m1Selected from N, B, P, As, Sb or Bi; m2Selected from Li, Na, K, Ru, Cs, Fr, Al, Mg, Zn, Be, Ca, Sr, Ba or Ra, and n is selected from 1,2 or 3. The lithium-rich manganese-based lithium ion battery provided by the invention can effectively inhibit the irreversible dissolution of oxygen in the charging activation process of the lithium-rich manganese-based oxide, and the problems of voltage drop and capacity attenuation of the lithium ion battery are greatly improved.

Description

Lithium-rich manganese-based lithium ion battery
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a lithium-rich manganese-based lithium ion battery.
Background
In recent years, along with the popularization of electronic equipment and the popularization of electric vehicles, lithium ion batteries gain favor of people due to the characteristics of high capacity, high voltage, environmental friendliness and the like. With the increasing demand of society, the energy density of lithium ion batteries needs to be further improved. One key to the increase in energy density is the use of positive electrode materials. The energy density can be effectively improved by using the anode material with high specific capacity. Lithium-rich manganese-based oxide xLi2MnO3-(1-x)LiMO2(M＝Co、Ni、Mn，0<x<1) The specific capacity is up to 300mAh g-1And because the lithium ion battery anode material contains more manganese elements, compared with a ternary material, the lithium ion battery anode material has lower cost, so the lithium ion battery anode material becomes a hot point of the current research on the lithium ion battery anode material. However, the lithium-rich manganese-based oxide has a major problem in that, during the first charge, since the upper cut-off voltage of charge is as high as 4.6V or more, the dissolution of lattice oxygen occurs, and a large irreversible capacity (low first coulombic efficiency) is exhibited, and further, the capacity of the material rapidly decreases during the cycle, and the output voltage plateau decreases. Specifically, the method comprises the following steps: in one aspect, a lithium-rich manganese-based oxygenO generated by the material during the first charge activation process2Readily available electrons at high potential to generate free radical ion O2-。O2-The free radical ions and the carbonate solvent can rapidly generate nucleophilic reaction, and reaction products of the reaction include organic lithium carboxylate and lithium carbonate which can be deposited on the surface of the positive electrode, so that the interface impedance of the battery is increased, and the capacity loss is brought; on the other hand, due to the dissolution of oxygen, the structure of the material of the lithium-rich manganese-based oxide is gradually changed from a layered structure to a spinel structure on the surface in the circulation process, so that the voltage platform is reduced, and the corresponding energy density is reduced. Therefore, how to inhibit the irreversible elution of oxygen is a key to solve the above-mentioned problems. One of the effective methods for irreversible elution of oxygen is to develop an electrolyte solution compatible with a lithium-rich manganese-based oxide.
Patent CN105720304A discloses a non-aqueous electrolyte having good resistance to nucleophilic attack and high activity of radical ion O2-The lithium-rich material is difficult to perform nucleophilic reaction with the solvents, so that the structure of the lithium-rich material is stabilized, and the voltage hysteresis of the material is effectively relieved.
Patent CN110112465A discloses an electrolyte system containing thiophene-2-methoxy boronic acid pinacol ester (TMBP) suitable for lithium-rich manganese-based oxide materials. Because TMBP has higher HOMO energy level, the TMBP can be oxidized in preference to a solvent, and can be polymerized on the surface of a positive electrode to form a stable CEI film, thereby improving the performance of the battery.
In patent CN107331892A, phenyl boronic acid pinacol esters, pyridine boronic acid pinacol esters, alkyl boronic acid pinacol esters, and alkylene boronic acid pinacol ester compounds are added to the electrolyte, and polymerized to form a film on the surface of the positive electrode material, so as to prevent the electrolyte from side reaction on the surface of the positive electrode, protect the solvent from oxidative decomposition at high potential, and prolong the service life of the battery.
Through the existing research, a CEI film can be formed on the surface of the lithium-rich manganese-based positive electrode material by introducing an additive, and the electrochemical performance of the battery is favorably improved. However, only forming the CEI film on the lithium-rich manganese-based positive electrode material has a limited improvement in the electrochemical performance of the lithium-rich manganese-based oxide. The problem of low coulombic efficiency of the first circle of the lithium-rich manganese-based lithium ion battery is still not effectively solved.
Disclosure of Invention
The invention provides a lithium-rich manganese-based lithium ion battery, aiming at the problem that the first coulomb efficiency is low due to irreversible dissolution of oxygen during the first charging and activation of the existing lithium-rich manganese-based lithium ion battery.
The technical scheme adopted by the invention for solving the technical problems is as follows:
the invention provides a lithium-rich manganese-based lithium ion battery which comprises a positive electrode material, a negative electrode material and electrolyte, wherein the positive electrode material comprises a lithium-rich manganese-based oxide, the electrolyte comprises a solvent and an additive, and the additive comprises a compound shown in the following structural formula:
Figure BDA0002295929590000021
wherein R is1And R3Each independently selected from
Figure BDA0002295929590000022
R4Selected from S or Se; r5Selected from C, Si, Ge, Sn, S or Se; and R is4And R5At least one of them is selected from S, R2Selected from carbon chains having some or all of the hydrogens replaced with other elements or groups; m1Selected from N, B, P, As, Sb or Bi; m2Selected from Li, Na, K, Ru, Cs, Fr, Al, Mg, Zn, Be, Ca, Sr, Ba or Ra, and n is selected from 1,2 or 3.
Optionally, R2Selected from carbon chains in which some or all of the hydrogens are replaced with halogen elements or halogenated hydrocarbon groups.
Optionally, the carbon chain is selected from saturated or unsaturated carbon chains having a length of 1-4 carbons.
Optionally, the halogenated hydrocarbon group is an alkyl group having 1 to 3 carbons in which part or all of the hydrogens are replaced with a halogen element.
Optionally, the additive comprises one or more of the following compounds:
Figure BDA0002295929590000031
Figure BDA0002295929590000041
optionally, in the electrolyte, the content of the additive is 0.01% -5%.
Optionally, the cathode material comprises xLi2MnO3﹒(1-x)LiMO2Wherein M is selected from one or more of Ni, Co and Mn, 0<x<1。
Optionally, xLi2MnO3﹒(1-x)LiMO2In the formula, x is more than or equal to 0.1 and less than or equal to 0.9.
Optionally, the electrolyte further comprises one or more of unsaturated cyclic carbonate, fluorinated cyclic carbonate, 1, 3-propane sultone and dinitrile compounds.
Optionally, the electrolyte further includes a lithium salt, the concentration of the lithium salt is 0.5M to 3M, and the lithium salt includes LiPF6、LiBF4、LiBOB、LiClO4、LiCF3SO3、LiDFOB、LiN(SO2CF3)2And LiN (SO)2F)2One or more of (a).
According to the lithium-rich manganese-based lithium ion battery provided by the invention, the inventor discovers through a large number of experiments that how to inhibit the dissolution of oxygen in the lithium-rich manganese-based oxide is the key for further improving the electrochemical performance of the lithium-rich manganese-based oxide, and the compound shown in the structural formula 1 is added into the electrolyte of the lithium-rich manganese-based lithium ion battery, so that the irreversible dissolution of oxygen in the first charging and activating process of the lithium-rich manganese-based oxide can be effectively inhibited, and the problems of voltage drop and capacity fading of the obtained lithium ion battery are greatly improved.
Drawings
FIG. 1 is a graph showing the relationship between the first charge and discharge voltage and the first charge and discharge capacity of the lithium-rich manganese-based lithium ion battery obtained in example 1 and comparative example 1 of the present invention;
FIG. 2 is a graph showing the relationship between the number of cycles and the specific discharge capacity of the lithium-rich manganese-based lithium ion battery obtained in example 1 and comparative example 1;
fig. 3 is a relationship curve of specific capacity and voltage in the cycling process of the lithium-rich manganese-based lithium ion battery obtained in example 1 of the present invention;
FIG. 4 is a graph showing the relationship between specific capacity and voltage in the cycling process of the lithium-rich manganese-based lithium ion battery obtained in comparative example 1;
FIG. 5 is a graph showing the relationship between the number of cycles and the specific discharge capacity of the high nickel ternary positive ion battery obtained in comparative example 2 and comparative example 3;
FIG. 6 is a graph showing the relationship between the cycle number and specific discharge capacity of spinel lithium nickel manganese oxide lithium ion batteries obtained in comparative examples 4 and 5 according to the present invention;
FIG. 7 is a dQ/dV relationship curve for lithium-rich manganese-based lithium ion batteries obtained in example 1 of the present invention and comparative example 1;
FIG. 8 is a LC-MS test chart of the electrolytes of example 1 and comparative example 1 of the present invention.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects solved by the present invention more clearly apparent, the present invention is further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The embodiment of the invention provides a lithium-rich manganese-based lithium ion battery which comprises a positive electrode material, a negative electrode material and electrolyte, wherein the positive electrode material comprises a lithium-rich manganese-based oxide, the electrolyte comprises a solvent and an additive, and the additive comprises a compound shown in the following structural formula:
Figure BDA0002295929590000051
wherein R is1And R3Each independently selected from
Figure BDA0002295929590000052
R4Selected from S or Se; r5Selected from C, Si, Ge, Sn, S or Se; and R is4And R5At least one of them is selected from S, R2Selected from carbon chains having some or all of the hydrogens replaced with other elements or groups; m1Selected from N, B, P, As, Sb or Bi; m2Selected from Li, Na, K, Ru, Cs, Fr, Al, Mg, Zn, Be, Ca, Sr, Ba or Ra, and n is selected from 1,2 or 3.
The compound shown in the structural formula 1 is added into the electrolyte of the lithium-rich manganese-based lithium ion battery, so that the irreversible dissolution of oxygen in the first charge activation process of the lithium-rich manganese-based oxide can be effectively inhibited, and the problems of voltage drop and capacity attenuation of the obtained lithium ion battery are greatly improved.
In some embodiments, R2Selected from carbon-containing chains in which part or all of the hydrogens are replaced with halogen elements or halogenated hydrocarbon groups.
In a more preferred embodiment, the carbon chain is selected from saturated or unsaturated carbon chains having a length of 1-4 carbons.
If the carbon chain is too long, the stability of the compound shown in the structural formula 1 is easily reduced, so that the effect of the compound in the electrolyte is influenced.
In a more preferred embodiment, the halogenated hydrocarbon group is an alkyl group having 1 to 3 carbons in which part or all of the hydrogens are replaced with a halogen element.
The halogen element and the halogen element in the halogenated hydrocarbon group are selected from fluorine, chlorine, bromine and iodine.
In some embodiments, the additive comprises one or more of the following compounds:
Figure BDA0002295929590000061
Figure BDA0002295929590000071
the above is a part of the claimed compounds, but the invention is not limited thereto, and should not be construed as being limited thereto.
In some embodiments, the additive is present in the electrolyte in an amount of 0.01% to 5%.
In a more preferred embodiment, the additive is present in the electrolyte in an amount of 0.5% to 5%.
In some embodiments, the positive electrode material comprises xLi2MnO3﹒(1-x)LiMO2Wherein M is selected from one or more of Ni, Co and Mn, 0<x<1。
More preferably, xLi2MnO3﹒(1-x)LiMO2In the formula, x is more than or equal to 0.1 and less than or equal to 0.9.
In some embodiments, the electrolyte further comprises a lithium salt, and the concentration of the lithium salt is 0.5M to 3M. Specifically, the concentration of the lithium salt may be 0.5M, 0.7M, 0.9M, 1M, 1.2M, 1.4M, 1.7M, 2.2M, 2.5M, 2.8M, or 3M.
In some embodiments, the lithium salt comprises LiPF6、LiBF4、LiBOB、LiClO4、LiCF3SO3、LiDFOB、LiN(SO2CF3)2And LiN (SO)2F)2One or more of (a).
In a more preferred embodiment, the lithium salt is selected from LiPF at a concentration of 1M6。
In some embodiments, the solvent comprises one or more of ethylene glycol dimethyl ether, dimethyl carbonate, 1, 3-dioxolane, vinylene carbonate, propylene carbonate, ethylene carbonate, diethyl carbonate, ethyl methyl carbonate, propylene sulfite, and methyl acetate, ethyl acetate, methyl propionate, ethyl propionate, methyl butyrate, methyl isobutyrate, methyl pivalate, and ethyl pivalate.
In a preferred embodiment, the solvent is a mixture of dimethyl carbonate and ethylene carbonate, and more preferably, the mass ratio of the dimethyl carbonate to the ethylene carbonate is 1: 1.
In some embodiments, the electrolyte further includes one or more of an unsaturated cyclic carbonate, a fluorinated cyclic carbonate, 1, 3-propane sultone, and a dinitrile compound.
In a more preferred embodiment, the unsaturated cyclic carbonate includes one or more of vinylene carbonate (VC, CAS: 872-36-6), ethylene carbonate (CAS: 4427-96-7), methylene ethylene carbonate (CAS: 124222-05-5). Preferably, the content of the unsaturated cyclic carbonate in the nonaqueous electrolytic solution is 0.01% to 10%, more preferably 0.1% to 5%.
The fluorinated cyclic carbonate includes one or more of fluoroethylene carbonate (FEC, CAS: 114435-02-8), trifluoromethyl ethylene carbonate (CAS: 167951-80-6) and difluoroethylene carbonate (CAS: 311810-76-1). Preferably, the content of the fluorinated cyclic carbonate in the nonaqueous electrolytic solution is 0.01% to 30%, more preferably 0.1% to 3%.
In some embodiments, the lithium-rich manganese-based lithium ion further includes a positive electrode current collector and a negative electrode current collector, the positive electrode material is mixed with a positive electrode binder and a positive electrode conductive agent and then covers the positive electrode current collector, and the negative electrode material is mixed with a negative electrode binder and a negative electrode conductive agent and then covers the negative electrode current collector.
In some embodiments, the negative electrode material includes one or more of metallic lithium, a carbon-based negative electrode material, a silicon-based compound, a tin-based compound, an antimony-based compound, an aluminum-based compound, and a transition metal compound.
The carbon-based negative electrode material includes one or more of a graphite-based carbon material, hard carbon, and soft carbon.
In some embodiments, the lithium-rich manganese-based lithium ion battery further includes a separator, and the separator includes one or more of a polyolefin separator, a polyamide separator, a polysulfone separator, a polyphosphazene separator, a polyethersulfone separator, a polyetherketoneketone separator, a polyetheramide separator, and a polyacrylonitrile separator.
The present invention will be further illustrated by the following examples.
TABLE 1
Figure BDA0002295929590000091
Figure BDA0002295929590000101
Figure BDA0002295929590000111
Example 1
The embodiment is used for explaining the lithium-rich manganese-based lithium ion battery and the preparation method thereof, and the preparation method comprises the following operation steps:
1) preparation of nonaqueous electrolyte:
mixing Ethylene Carbonate (EC) and dimethyl carbonate (DMC) according to the mass ratio of EC to DMC of 1:1, and then adding lithium hexafluorophosphate (LiPF)6) To a molar concentration of 1mol/L, 2 wt% of an additive 1,1,2,2,3, 3-hexafluoro-1, 3-disulfonylimide lithium as shown in example 1 in Table 1 was added based on the total weight of the nonaqueous electrolytic solution as 100%.
2) Preparing a positive plate:
according to the following steps of 8: 1:1 mass ratio of the mixed positive electrode active material Li1.14Ni0.14Co0.14Mn0.56O2The positive electrode paste is evenly coated on two sides of an aluminum foil, and the positive electrode plate is obtained after drying, rolling and vacuum drying.
3) Preparing a battery:
and assembling the button half-cell by using a lithium sheet as a negative electrode, the positive electrode plate as a positive electrode and the nonaqueous electrolyte.
Then the conventional formation is carried out according to the following steps:
the first three circles of the assembled button half-cell are formed at a current density of 0.1C within a voltage range of 2-4.8V and then cycled at a current density of 1C within a voltage range of 2-4.6V.
Examples 2 to 19
This example is used to illustrate a lithium-rich manganese-based lithium ion battery and a method for manufacturing the same disclosed in the present invention, and includes most of the operation steps in example 1, except that:
the preparation step of the nonaqueous electrolyte comprises the following steps:
the nonaqueous electrolytic solution was added with the components in the amounts shown in examples 2 to 19 in Table 1.
The preparation steps of the positive plate are as follows:
the positive electrode materials shown in example 2 to example 19 in table 1 were used.
The preparation steps of the battery are as follows:
the formation and cycling test parameters shown in example 2 to example 19 in table 1 were used.
Comparative examples 1 to 5
Comparative examples 1 to 5 are provided for comparative purposes to illustrate the lithium ion battery and the preparation method thereof disclosed in the present invention, and include most of the operation steps in example 1, except that:
the preparation step of the nonaqueous electrolyte comprises the following steps:
the nonaqueous electrolytic solution was added with the components in the amounts shown in comparative examples 1 to 5 in table 1.
The preparation steps of the positive plate are as follows:
the positive electrode materials shown in comparative examples 1 to 5 in table 1 were used.
The preparation steps of the battery are as follows:
the formation and cycle test parameters shown in comparative examples 1 to 5 in table 1 were used.
Performance testing
The above prepared and the following performance tests were performed:
the first-turn charge-discharge voltage and capacity relationship curves of the lithium-rich manganese-based lithium ion batteries obtained in example 1 and comparative example 1 were recorded, and the records are shown in fig. 1.
As can be seen from the test results shown in FIG. 1, the compound shown in the structural formula 1 is used as an additive of the electrolyte, so that the first-turn coulomb efficiency of the lithium-rich manganese-based lithium ion battery can be effectively improved.
The relationship curve between the number of cycles and the specific discharge capacity of the lithium-rich manganese-based lithium ion batteries obtained in example 1 and comparative example 1 was recorded and recorded as shown in fig. 2.
As can be seen from the test results of FIG. 2, the compound shown in the structural formula 1 is used as the additive of the electrolyte, so that the capacity retention rate of the lithium-rich manganese-based lithium ion battery can be effectively improved.
The relation curve of the specific capacity and the voltage in the cycle process of the lithium-rich manganese-based lithium ion battery obtained in example 1 is recorded, and the record is shown in fig. 3.
The relation curve of the specific capacity and the voltage in the cycle process of the lithium-rich manganese-based lithium ion battery obtained in the comparative example 1 is recorded, and the record is shown in figure 4.
As can be seen from the test results of fig. 3 and 4, the use of the compound represented by formula 1 as an additive to the electrolyte can effectively suppress the decrease in the voltage plateau of the battery during the cycling process.
The number of cycles of the high nickel ternary positive ion battery obtained in comparative example 2 and comparative example 3 was recorded as a function of specific discharge capacity, and the record is shown in fig. 5.
The cycle number versus specific discharge capacity curves of the spinel lithium nickel manganese oxide lithium ion batteries obtained in comparative examples 4 and 5 were recorded as shown in fig. 6.
As can be seen from the test results of fig. 5 and fig. 6, in other types of lithium ion batteries (such as a high-nickel ternary positive ion battery and a spinel lithium nickel manganese oxide lithium ion battery), the cycle performance of the battery is not effectively improved by using the compound shown in the structural formula 1 as an additive of the electrolyte, and therefore, the protection effect of the compound shown in the structural formula 1 as an additive to form a CEI film is limited, which explains from the side that the improvement of the electrochemical performance of the lithium-rich manganese-based lithium ion battery by adding the electrolyte containing the compound shown in the structural formula 1 provided by the present invention is not from the common film formation protection, but exists an interaction with the lithium-rich manganese-based oxide, so that the oxygen precipitation of the lithium-rich manganese-based oxide is effectively reduced, and the stability of the lithium-rich manganese.
The dQ/dV relationship curves for the lithium-rich manganese-based lithium ion batteries obtained in example 1 and comparative example 1 were recorded and are shown in FIG. 7.
As can be seen from the test results of fig. 7, the peak value of example 1 containing the compound additive of formula 1 was smaller after 4.5V, indicating that the material was less oxygen evolved.
The electrolytes of example 1 and comparative example 1 were subjected to LC-MS testing after cycling and recorded as shown in fig. 8.
As can be seen from the test results of fig. 8, the compound shown in the structural formula 1 is used as an additive, so that the decomposition of the electrolyte cannot be avoided, and it can be known that the improvement of the electrochemical performance of the lithium-rich manganese-based lithium ion battery by adding the electrolyte containing the compound shown in the structural formula 1 provided by the invention is not the improvement of the stability of the electrolyte.
Electrochemical data of the lithium ion batteries obtained in examples 1 to 19 and comparative examples 1 to 5 are filled in table 2.
TABLE 2
Figure BDA0002295929590000131
Figure BDA0002295929590000141
Comparing the results of example 1 and comparative examples 1-5 in table 2, it can be seen that the compound shown in formula 1 as an additive does not effectively improve the cycle performance of the high-nickel ternary cathode material and the spinel lithium nickel manganese oxide cathode material in consideration of the film forming effect of the common CEI. The improvement of the electrochemical performance of the lithium-rich manganese-based oxide anode material is mainly not from the common film-forming protection effect. As shown in fig. 8, the use of the compound represented by formula 1 does not prevent the decomposition of the electrolyte. As shown in fig. 7, it can be seen that the set of peaks containing the compound represented by formula 1 is smaller after 4.5V, indicating that the lithium-rich manganese-based oxide precipitates less oxygen at this time. Therefore, the compound shown in the structural formula 1 interacts with the lithium-rich manganese-based oxide cathode material, so that irreversible precipitation of oxygen of the lithium-rich manganese-based oxide cathode material at a voltage of more than 4.5V can be effectively inhibited, reduction of a voltage platform in a circulation process is inhibited, and the capacity retention rate is effectively improved.
As can be seen from the results of comparing example 1 and examples 2 to 4 in table 2, the compound represented by formula 1 exhibited a better effect when an electrolyte solution in which EC: DMC ═ 1:1 was used as a solvent was used.
As can be seen from the comparison of the test results of example 1 and examples 5 to 7 in table 2, the compound represented by the structural formula 1 has the best effect of avoiding the voltage drop and improving the first coulomb efficiency when the mass concentration of the compound in the electrolyte is 2%.
As can be seen from the results of comparing example 1 with examples 13 to 17 in Table 2, the compound represented by the formula 1 and lithium hexafluorophosphate had a good complexing effect.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.

Claims (10)

1. The lithium-rich manganese-based lithium ion battery is characterized by comprising a positive electrode material, a negative electrode material and electrolyte, wherein the positive electrode material comprises a lithium-rich manganese-based oxide, the electrolyte comprises a solvent and an additive, and the additive comprises a compound shown in the following structural formula:
Figure FDA0002295929580000011
wherein R is1And R3Each independently selected from
Figure FDA0002295929580000012
R4Selected from S or Se; r5Selected from C, Si, Ge, Sn, S or Se; and R is4And R5At least one of them is selected from S, R2Selected from carbon chains having some or all of the hydrogens replaced with other elements or groups; m1Selected from N, B, P, As, Sb or Bi; m2Selected from Li, Na, K, Ru, Cs, Fr, Al, Mg,Zn, Be, Ca, Sr, Ba or Ra, and n is selected from 1,2 or 3.
2. The lithium-rich manganese-based lithium ion battery of claim 1, wherein R is2Selected from carbon chains in which some or all of the hydrogens are replaced with halogen elements or halogenated hydrocarbon groups.
3. The lithium manganese-rich lithium ion battery of claim 2, wherein the carbon chain is selected from saturated or unsaturated carbon chains having a length of 1-4 carbons.
4. The lithium-rich manganese-based lithium ion battery according to claim 2, wherein the halogenated hydrocarbon group is an alkyl group having 1 to 3 carbons in which part or all of hydrogen is substituted by a halogen element.
5. The lithium-rich manganese-based lithium ion battery of claim 1, wherein the additive comprises one or more of the following compounds:
Figure FDA0002295929580000021
Figure FDA0002295929580000031
6. the lithium-rich manganese-based lithium ion battery according to claim 1, wherein the additive is present in the electrolyte in an amount of 0.01% to 5%.
7. The lithium-rich manganese-based lithium ion battery of claim 1, wherein the positive electrode material comprises xLi2MnO3﹒(1-x)LiMO2Wherein M is selected from one or more of Ni, Co and Mn, 0<x<1。
8. Root of herbaceous plantThe lithium-rich manganese-based lithium ion battery of claim 7, wherein xLi2MnO3﹒(1-x)LiMO2In the formula, x is more than or equal to 0.1 and less than or equal to 0.9.
9. The lithium-rich manganese-based lithium ion battery of claim 1, wherein the electrolyte further comprises one or more of an unsaturated cyclic carbonate, a fluorinated cyclic carbonate, 1, 3-propane sultone, and a dinitrile compound.
10. The lithium-rich manganese-based lithium ion battery of claim 1, wherein the electrolyte further comprises a lithium salt, the concentration of the lithium salt is 0.5M to 3M, and the lithium salt comprises LiPF6、LiBF4、LiBOB、LiClO4、LiCF3SO3、LiDFOB、LiN(SO2CF3)2And LiN (SO)2F)2One or more of (a).
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