CN112300117A - Novel additive and application thereof in lithium ion battery electrolyte - Google Patents

Novel additive and application thereof in lithium ion battery electrolyte Download PDF

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CN112300117A
CN112300117A CN202011194925.6A CN202011194925A CN112300117A CN 112300117 A CN112300117 A CN 112300117A CN 202011194925 A CN202011194925 A CN 202011194925A CN 112300117 A CN112300117 A CN 112300117A
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additive
lithium ion
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carbonate
novel additive
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刘磊
魏志凯
苗力孝
贾国文
张生安
杨献峰
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Shandong Haike Xinyuan Material Technology Co Ltd
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    • C07D327/00—Heterocyclic compounds containing rings having oxygen and sulfur atoms as the only ring hetero atoms
    • C07D327/02—Heterocyclic compounds containing rings having oxygen and sulfur atoms as the only ring hetero atoms one oxygen atom and one sulfur atom
    • C07D327/04—Five-membered rings
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    • 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
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    • H01M10/0567—Liquid materials characterised by the additives
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Abstract

The invention provides a novel additive and application thereof in lithium ion battery electrolyte, belonging to the field of lithium ion batteries. The novel additive is a compound which is composed of benzene rings and contains a multi-ring structure of sulfonic acid groups and nitrile groups. The nitrile functional group participates in film formation while the cyclic sulfonate structure in the novel additive can form a film on the surface of the anode, so that the high voltage stability of the formed anode CEI film is further improved, and the formed anode CEI film has good performance under the condition of the voltage of more than 4.2V. In addition, such novel additives also exhibit good high and low temperature stability and cycling stability. Therefore, the novel additive provided by the invention truly realizes that one additive has multiple functions, and has very wide application prospect in the field of lithium ion batteries.

Description

Novel additive and application thereof in lithium ion battery electrolyte
Technical Field
The invention belongs to the field of lithium ion batteries, and particularly relates to a novel additive and application thereof in lithium ion battery electrolyte.
Background
The lithium ion battery, as a new generation of green high-energy battery, has the remarkable advantages of large capacity, high working voltage, light weight, no memory effect and the like, and is widely applied to various portable electronic devices at present. The existing lithium ion battery consists of a positive electrode material, a negative electrode material, an electrolyte and a diaphragm, wherein the electrolyte consists of a solvent, lithium salt, an additive and the like. With the progress of the times, people have higher and higher performance requirements on lithium ion batteries, the traditional lithium ion batteries cannot meet the actual requirements due to the limitations of self stability and voltage, and the introduction of high-performance additives into the lithium ion batteries is one of effective means for improving the battery performance.
At present, the conventional additives have the defects of single film forming function, poor stability under high voltage, incapability of meeting the requirements of the battery on high and low temperature performance due to a large working temperature range of the battery in actual life, and the like, so how to develop a multifunctional additive with high cycle stability and high voltage stability is a very important research topic for technicians in the field.
Disclosure of Invention
Aiming at the problems of single film forming function, poor high-voltage stability, poor cycling stability and the like of the traditional additive in the prior art, the invention provides a novel additive with high cycling stability and strong high-voltage stability and application thereof in lithium ion battery electrolyte.
In order to achieve the purpose, the invention adopts the technical scheme that:
the novel additive is a compound which is composed of benzene rings and contains a multi-ring structure of sulfonic acid groups and nitrile groups, and the structural formula of the compound is shown as the formula 1:
Figure BDA0002753751910000021
wherein, R in the formula 1 is selected from nitrile group or nitrile group containing 2, 3 or 4 carbon atoms.
Preferably, when R is a nitrile group, the structural formula is shown as formula 2:
Figure BDA0002753751910000022
preferably, when R is a nitrile group having 2, 3 or 4 carbon atoms, the structural formula is shown in formula 3-formula 5:
Figure BDA0002753751910000023
the novel additive is applied to the electrolyte of the lithium ion battery.
Preferably, the lithium ion battery electrolyte comprises a nonaqueous organic solvent, a lithium salt and the novel sulfur-containing additive described in any one of the above technical schemes.
Preferably, the novel sulfur-containing additive is 0.01-5% of the total mass of the lithium ion battery electrolyte, and the concentration of the lithium salt is 0.15-1.5 mol/L.
Preferably, the non-aqueous organic solvent is selected from one or more of ethylene carbonate, propylene carbonate, vinylene carbonate, ethyl methyl carbonate, methyl propyl carbonate, dipropyl carbonate, ethylene carbonate, diethyl carbonate, dimethyl carbonate, propylene carbonate, methyl formate, methyl acrylate, methyl butyrate, ethyl acetate, acid anhydride, N-methyl pyrrolidone, N-methyl formamide, N-methyl acetamide, acetonitrile, N-dimethyl formamide, sulfolane, dimethyl sulfoxide, ethylene sulfite, propylene sulfite, methyl sulfide, diethyl sulfite, dimethyl sulfite, tetrahydrofuran, fluorine-containing cyclic organic esters, sulfur-containing cyclic organic esters, and unsaturated bond-containing cyclic organic esters.
Preferably, the lithium salt is selected from LiPF6、LiClO4、LiBF4、LiAsF6One or more of LiFSI and LiTFSI.
Compared with the prior art, the invention has the advantages and positive effects that:
1. the invention provides a novel additive and application thereof in lithium ion battery electrolyte, wherein the additive is a compound which is composed of benzene rings and contains a multi-ring structure of sulfonic acid groups and nitrile groups. The nitrile functional group participates in film formation while the cyclic sulfonate structure forms a film on the surface of the anode, so that the high voltage stability of the formed anode CEI film is further improved, and the formed anode CEI film can show good performance under the condition of voltage of more than 4.2V; in addition, such novel additives also exhibit good high and low temperature stability and cycling stability. Therefore, the novel additive provided by the invention truly realizes that one additive has multiple functions, and has very wide application prospect in the field of lithium ion batteries;
2. the invention provides a novel additive and application thereof in lithium ion battery electrolyte, wherein the effects of high cycle stability and high voltage stability can be achieved by only adding one additive, and the addition amount is only 0.01-5%. It can be seen that the additive has the advantages that: the multifunctional effect can be realized while the cost is saved and the use types and the use amount of the additive are reduced.
Drawings
FIG. 1 is a graph showing 300-week cycle performance tests of examples and comparative examples at room temperature (25 ℃ C.) as provided by examples of the present invention;
FIG. 2 is an infrared spectrum of the novel additive provided by the example of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The embodiment of the invention provides a novel additive, which is a compound which is composed of benzene rings and contains a multi-ring structure of sulfonic acid groups and nitrile groups, and the structural formula of the compound is shown as the formula 1:
Figure BDA0002753751910000041
wherein, R in the formula 1 is selected from nitrile group or nitrile group containing 2, 3 or 4 carbon atoms.
The above-mentioned novel additive is a compound having a polycyclic structure consisting of a benzene ring and containing both a sulfonic acid group and a nitrile group. The nitrile functional group participates in film formation while the cyclic sulfonate structure forms a film on the surface of the anode, so that the high voltage stability of the formed anode CEI film is further improved, and the formed anode CEI film can show good performance under the condition of voltage of more than 4.2V. In addition, such novel additives also exhibit good high and low temperature stability and cycling stability. Therefore, the novel additive provided by the invention truly realizes that one additive has multiple functions, and has very wide application prospect in the field of lithium ion batteries.
In addition, the technical effects of high cycle stability and strong high voltage stability can be achieved only by adding one additive, and the addition amount is only 0.01-5%. It can be seen that the additive has the advantages that: the multifunctional effect can be realized while the cost is saved and the use types and the use amount of the additive are reduced.
It needs to be further explained that, in order to improve the energy density of the battery, it is one of the important ways to improve the working voltage, the working voltage of the ordinary lithium ion battery is below 4.2V, and the novel additive provided by the invention still shows good cycling stability under the condition of above 4.4V.
In a preferred embodiment, when R is a nitrile group, it has a structural formula shown in formula 2:
Figure BDA0002753751910000051
in a preferred embodiment, when R is a nitrile group containing 2, 3 or 4 carbon atoms, the structural formula is shown in formula 3-formula 5:
Figure BDA0002753751910000052
the invention also provides application of the novel additive in lithium ion battery electrolyte.
In a preferred embodiment, the lithium ion battery electrolyte comprises a non-aqueous organic solvent, a lithium salt, and the novel sulfur-containing additive of any of the above preferred embodiments.
In a preferred embodiment, the novel sulfur-containing additive is 0.01-5% of the total mass of the lithium ion battery electrolyte, and the concentration of the lithium salt is 0.15-1.5 mol/L.
In the preferred embodiment, the reason why the addition amount of the novel sulfur-containing additive is limited to 0.01 to 5% is that: in the lithium battery industry, the actual addition amount of the additive is influenced by factors such as the solubility of the additive (part of the additive is low in solubility), the production cost and the stability of an electrolyte system, for example, lithium salt precipitation and solution discoloration can be caused by excessive addition amount; if the addition amount is too low, the desired effect cannot be achieved, and therefore, it is necessary to select an appropriate addition amount of the additive. Wherein, the addition amount of the novel sulfur-containing additive can be selected from 0.01, 0.1, 0.2, 0.3, 0.4, 0.5, 1.0, 1.5, 2.0, 2.5, 3.0, 3.5, 4.0, 4.5, 5.0% or any value within the above-defined range, and the addition amount falls within the protection range of the invention. In addition, the concentration of the lithium salt may be selected from 0.15, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5mol/L or any value within the above-defined range, which falls within the scope of the present invention.
In a preferred embodiment, the non-aqueous organic solvent is selected from one or more of ethylene carbonate, propylene carbonate, vinylene carbonate, ethyl methyl carbonate, propyl methyl carbonate, dipropyl carbonate, ethylene carbonate, diethyl carbonate, dimethyl carbonate, propylene carbonate, methyl formate, methyl acrylate, methyl butyrate, ethyl acetate, acid anhydride, N-methylpyrrolidone, N-methylformamide, N-methylacetamide, acetonitrile, N-dimethylformamide, sulfolane, dimethyl sulfoxide, ethylene sulfite, propylene sulfite, methyl sulfide, diethyl sulfite, dimethyl sulfite, tetrahydrofuran, fluorine-containing cyclic organic esters, sulfur-containing cyclic organic esters, and cyclic organic esters containing unsaturated bonds.
In a preferred embodiment, the lithium salt is selected from LiPF6、LiClO4、LiBF4、LiAsF6One or more of LiFSI and LiTFSI.
In the preferred embodiment, the lithium salt type of the electrolyte of the lithium ion battery is LiPF6Or LiPF6In admixture with other lithium salts, in which LiPF6Is mainly due to the following reasons: LiPF compared to other lithium salts6The cost is low; LiPF6Has good solubility, and the LiPF has good balance between cost and lithium salt performance6The proportion of the electrolyte in the lithium ion battery is superior.
In order to more clearly and specifically describe the novel additive provided by the embodiment of the present invention and the application thereof in the electrolyte of a lithium ion battery, the following description will be given with reference to specific embodiments.
Comparative example 1
The comparative example provides a lithium ion battery electrolyte added with vinylene carbonate, and the preparation method comprises the following steps:
(1) selecting an additive: vinylene Carbonate (VC);
(2) preparing lithium ion battery electrolyte: preparing a solution from vinyl carbonate, dimethyl carbonate and methyl ethyl carbonate according to the mass ratio of 1:1:1, uniformly mixing, adding lithium hexafluorophosphate to the final concentration of 1-1.2mol/L, adding the electrolyte additive VC with the addition of 1%, and uniformly stirring to obtain an electrolyte solution.
Comparative example 2
The comparative example provides a lithium ion battery electrolyte added with carboadiponitrile, and the preparation method comprises the following steps:
(1) selecting an additive: adiponitrile (ADN);
(2) the preparation method of the lithium ion battery electrolyte specifically comprises the following steps: preparing a solution from ethylene carbonate, dimethyl carbonate and methyl ethyl carbonate according to the mass ratio of 1:1:1, uniformly mixing, adding lithium hexafluorophosphate to the final concentration of 1-1.2mol/L, adding the electrolyte additive ADN with the addition of 1-2%, and uniformly stirring to obtain the electrolyte solution.
Comparative example 3
The comparative example provides a lithium ion battery electrolyte added with 1, 3-propane sultone, and the preparation method comprises the following steps:
(1) selecting an additive: 1, 3-propanesulfonic acid lactone (1, 3-PS);
(2) the preparation method of the lithium ion battery electrolyte specifically comprises the following steps: preparing a solution from ethylene carbonate, dimethyl carbonate and methyl ethyl carbonate according to the mass ratio of 1:1:1, uniformly mixing, adding lithium hexafluorophosphate to the final concentration of 1-1.2mol/L, adding the electrolyte additive 1,3-PS with the addition of 1%, and uniformly stirring to obtain the electrolyte solution.
Comparative example 4
The comparative example provides a lithium ion battery electrolyte added with adiponitrile and 1, 3-propane sultone, and the preparation method comprises the following steps:
(1) selecting an additive: adiponitrile (ADN) with 1, 3-propanesultone (1, 3-PS);
(2) the preparation method of the lithium ion battery electrolyte specifically comprises the following steps: preparing a solution from ethylene carbonate, dimethyl carbonate and methyl ethyl carbonate according to the mass ratio of 1:1:1, uniformly mixing, adding lithium hexafluorophosphate to enable the final concentration to be 1-1.2mol/L, then adding Adiponitrile (ADN) with the content of 1-2% and 1,3-PS with the content of 1% of the electrolyte additive, and uniformly stirring to obtain the electrolyte solution.
Example 1
The embodiment provides a novel additive and a lithium ion battery electrolyte prepared by using the same, wherein the novel additive has a material structure of a five-membered ring structure which is composed of benzene rings and contains a sulfonic group and a nitrile group structure, and the structural formula of the novel additive is shown as P1 and specifically comprises the following components:
Figure BDA0002753751910000081
(1) the raw materials of the novel additive and the preparation method thereof provided by the embodiment specifically comprise:
raw material:
Figure BDA0002753751910000082
(CAS number: 10284-44-3; raw material I for short), liquid bromine, NaCN and the like;
the preparation method specifically comprises the following steps: firstly, 5g of raw material I is weighed and mixed with 2ml of liquid bromine, and then 0.5g of scrap iron is added, and a hydrogen atom is replaced by a bromine atom to form an intermediate product I (CAS number: 27238-10-4), wherein the structural formula of the intermediate product I is as follows:
Figure BDA0002753751910000083
secondly, 5g of the intermediate product I is weighed and dissolved in ethanol, 5g of NaCN is added, the novel additive shown as P1 is prepared by reaction under the conditions of 90 ℃ and 0.3MPa, and the infrared spectrogram of the structural formula is shown as figure 1.
(2) The method for preparing the lithium ion battery electrolyte by using the novel additive prepared by the embodiment comprises the following steps:
preparing a solution from ethylene carbonate, dimethyl carbonate and ethyl methyl carbonate according to the mass ratio of 1:1:1, uniformly mixing, adding lithium hexafluorophosphate to the final concentration of 1mol/L, adding the electrolyte additive with the addition of 1%, and uniformly stirring to obtain the lithium ion battery electrolyte solution.
Example 2
The embodiment provides a novel additive and a lithium ion battery electrolyte prepared by using the same, wherein the novel additive has a material structure of a five-membered ring structure which is composed of benzene rings and contains a sulfonic group and a nitrile group structure, and the structural formula of the novel additive is shown as P2 and specifically comprises the following components:
Figure BDA0002753751910000091
(1) the raw materials of the novel additive and the preparation method thereof provided by the embodiment specifically comprise:
raw material:
Figure BDA0002753751910000092
(CAS number: 10284-44-3; raw material I for short), carbon tetrachloride, chlorine, NaCN and the like;
the preparation method specifically comprises the following steps: firstly, weighing 15g of raw material I, dissolving the raw material I in 200ml of carbon tetrachloride, and introducing chlorine gas into the solution to form an intermediate product, wherein the structural formula of the intermediate product is as follows:
Figure BDA0002753751910000093
and after the reaction is finished, distilling the solution under reduced pressure to obtain a target product.
Secondly, weighing 15g of the intermediate product I, dissolving the intermediate product I in ethanol, adding 20g of NaCN, and reacting at 90 ℃ and 0.3MPa to prepare the novel additive shown as P2.
(2) The method for preparing the lithium ion battery electrolyte by using the novel additive prepared by the embodiment comprises the following steps:
preparing a solution from propylene carbonate and diethyl carbonate according to the mass ratio of 1:1, uniformly mixing, adding 0.6mol of lithium hexafluorophosphate and 0.4mol of LiFSI to enable the final concentration to be 1mol/L, then adding the electrolyte additive with the addition of 1.5%, and uniformly stirring to obtain the lithium ion battery electrolyte solution.
Example 3
The embodiment provides a novel additive and a lithium ion battery electrolyte prepared by using the same, wherein the novel additive has a material structure of a five-membered ring structure which is composed of benzene rings and contains a sulfonic group and a nitrile group structure, and the structural formula of the novel additive is shown as P3 and specifically comprises the following components:
Figure BDA0002753751910000094
(1) the raw materials of the novel additive and the preparation method thereof provided by the embodiment specifically comprise:
raw material:
Figure BDA0002753751910000101
(raw material 2 for short), carbon tetrachloride, chlorine, NaCN and the like;
the preparation method specifically comprises the following steps: firstly, weighing 10g of raw material 2, dissolving the raw material 2 in 200ml of carbon tetrachloride, and introducing chlorine gas into the solution to form an intermediate product, wherein the structural formula of the intermediate product is as follows:
Figure BDA0002753751910000102
and after the reaction is finished, distilling the solution under reduced pressure to obtain a target product.
Secondly, 10g of the intermediate product I is weighed and dissolved in ethanol, 15g of NaCN is added, and the reaction is carried out at 100 ℃ and 0.2MPa to prepare the novel additive shown as P3.
(2) The method for preparing the lithium ion battery electrolyte by using the novel additive prepared by the embodiment comprises the following steps:
preparing a solution from ethylene carbonate and dipropyl carbonate according to the mass ratio of 1:1, uniformly mixing, adding lithium hexafluorophosphate to enable the final concentration to be 1mol/L, then adding the electrolyte additive with the addition amount of 2.0%, and uniformly stirring to obtain an electrolyte solution.
Example 4
The embodiment provides a novel additive and a lithium ion battery electrolyte prepared by using the same, wherein the novel additive has a material structure of a five-membered ring structure which is composed of benzene rings and contains a sulfonic group and a nitrile group structure, and the structural formula of the novel additive is shown as P4 and specifically comprises the following components:
Figure BDA0002753751910000103
(1) the raw materials of the novel additive and the preparation method thereof provided by the embodiment specifically comprise:
raw material: :
Figure BDA0002753751910000104
(raw material 3 for short), liquid bromine, NaCN and the like;
the preparation method specifically comprises the following steps: firstly, weighing 15g of raw material 3 and 5ml of liquid bromine, mixing, then adding 0.5g of scrap iron, and substituting hydrogen atoms by bromine atoms to form an intermediate product, wherein the structural formula is as follows:
Figure BDA0002753751910000111
secondly, weighing 15g of the intermediate product, dissolving the intermediate product in ethanol, adding 20g of NaCN, and reacting at 95 ℃ and 0.4MPa to prepare the novel additive shown as P4
(2) The method for preparing the lithium ion battery electrolyte by using the novel additive prepared by the embodiment comprises the following steps:
preparing a solution from ethylene carbonate, dimethyl carbonate and ethyl methyl carbonate according to the mass ratio of 1:1:1, uniformly mixing, adding lithium hexafluorophosphate to the final concentration of 1mol/L, adding the electrolyte additive with the addition of 1%, and uniformly stirring to obtain the lithium ion battery electrolyte solution.
Example 5
The embodiment provides a novel additive and a lithium ion battery electrolyte prepared by using the same, wherein the novel additive has a material structure of a five-membered ring structure which is composed of benzene rings and contains a sulfonic group and a nitrile group structure, and the structural formula of the novel additive is shown as P5 and specifically comprises the following components:
Figure BDA0002753751910000112
(1) the raw materials of the novel additive and the preparation method thereof provided by the embodiment specifically comprise:
raw material:
Figure BDA0002753751910000113
(raw material 4 for short), carbon tetrachloride, chlorine, NaCN and the like;
the preparation method specifically comprises the following steps: firstly, weighing 10g of raw material 4, dissolving the raw material 4 in 200ml of carbon tetrachloride, and introducing chlorine gas into the solution to form an intermediate product, wherein the structural formula of the intermediate product is as follows:
Figure BDA0002753751910000114
and after the reaction is finished, distilling the solution under reduced pressure to obtain a target product.
Secondly, 10g of the intermediate product I is weighed and dissolved in ethanol, 15g of NaCN is added, and the reaction is carried out at 100 ℃ and 0.2MPa to prepare the novel additive shown as P5.
(2) The method for preparing the lithium ion battery electrolyte by using the novel additive prepared by the embodiment comprises the following steps:
preparing a solution from ethylene carbonate, dimethyl carbonate and ethyl methyl carbonate according to the mass ratio of 1:1:1, uniformly mixing, adding lithium hexafluorophosphate to the final concentration of 1mol/L, adding the electrolyte additive with the addition of 1%, and uniformly stirring to obtain the lithium ion battery electrolyte solution.
Example 6
The embodiment provides a novel additive and a lithium ion battery electrolyte prepared by using the same, wherein the novel additive has a material structure of a five-membered ring structure which is composed of benzene rings and contains a sulfonic group and a nitrile group structure, and the structural formula of the novel additive is shown as P6 and specifically comprises the following components:
Figure BDA0002753751910000121
(1) the raw materials of the novel additive and the preparation method thereof provided by the embodiment specifically comprise:
raw material:
Figure BDA0002753751910000122
(raw material 5 for short), liquid bromine, NaCN and the like;
the preparation method specifically comprises the following steps: firstly, weighing 15g of raw material 5 and 5ml of liquid bromine, mixing, then adding 0.5g of scrap iron, and substituting hydrogen atoms with bromine atoms to form an intermediate product, wherein the structural formula is as follows:
Figure BDA0002753751910000123
secondly, weighing 15g of the intermediate product, dissolving the intermediate product in ethanol, adding 20g of NaCN, and reacting at 95 ℃ and 0.4MPa to prepare the novel additive shown as P6.
(2) The method for preparing the lithium ion battery electrolyte by using the novel additive prepared by the embodiment comprises the following steps:
preparing a solution from ethylene carbonate, dimethyl carbonate and ethyl methyl carbonate according to the mass ratio of 1:1:1, uniformly mixing, adding lithium hexafluorophosphate to the final concentration of 1mol/L, adding the electrolyte additive with the addition of 1%, and uniformly stirring to obtain the lithium ion battery electrolyte solution.
Example 7
The embodiment provides a novel additive and a lithium ion battery electrolyte prepared by using the same, wherein the novel additive has a material structure of a five-membered ring structure which is composed of benzene rings and contains a sulfonic group and a nitrile group structure, and the structural formula of the novel additive is shown as P7 and specifically comprises the following components:
Figure BDA0002753751910000131
(1) the raw materials of the novel additive and the preparation method thereof provided by the embodiment specifically comprise:
raw material:
Figure BDA0002753751910000132
(raw material 6 for short), carbon tetrachloride, chlorine, NaCN and the like;
the preparation method specifically comprises the following steps: firstly, weighing 10g of raw material 6, dissolving the raw material 6 in 200ml of carbon tetrachloride, and introducing chlorine gas into the solution to form an intermediate product, wherein the structural formula of the intermediate product is as follows:
Figure BDA0002753751910000133
and after the reaction is finished, distilling the solution under reduced pressure to obtain a target product.
Secondly, weighing 10g of the intermediate product, dissolving the intermediate product in ethanol, adding 15g of NaCN, and reacting at 100 ℃ and 0.2MPa to prepare the novel additive shown as P7.
(2) The method for preparing the lithium ion battery electrolyte by using the novel additive prepared by the embodiment comprises the following steps:
preparing a solution from ethylene carbonate, dimethyl carbonate and ethyl methyl carbonate according to the mass ratio of 1:1:1, uniformly mixing, adding lithium hexafluorophosphate to the final concentration of 1mol/L, adding the electrolyte additive with the addition of 1%, and uniformly stirring to obtain the lithium ion battery electrolyte solution.
Example 8
The embodiment provides a novel additive and a lithium ion battery electrolyte prepared by using the same, wherein the novel additive has a material structure of a five-membered ring structure which is composed of benzene rings and contains a sulfonic group and a nitrile group structure, and the structural formula of the novel additive is shown as P8 and specifically comprises the following components:
Figure BDA0002753751910000141
(1) the raw materials of the novel additive and the preparation method thereof provided by the embodiment specifically comprise:
raw material:
Figure BDA0002753751910000142
(raw material 7 for short), liquid bromine, NaCN and the like;
the preparation method specifically comprises the following steps: firstly, weighing 15g of raw material 7 and 5ml of liquid bromine, mixing, then adding 0.5g of scrap iron, and substituting hydrogen atoms with bromine atoms to form an intermediate product, wherein the structural formula is as follows:
Figure BDA0002753751910000143
secondly, weighing 15g of the intermediate product, dissolving the intermediate product in ethanol, adding 20g of NaCN, and reacting at 95 ℃ and 0.4MPa to prepare the novel additive shown as P8.
(2) The method for preparing the lithium ion battery electrolyte by using the novel additive prepared by the embodiment comprises the following steps:
preparing a solution from ethylene carbonate, dimethyl carbonate and ethyl methyl carbonate according to the mass ratio of 1:1:1, uniformly mixing, adding lithium hexafluorophosphate to the final concentration of 1mol/L, adding the electrolyte additive with the addition of 1%, and uniformly stirring to obtain the lithium ion battery electrolyte solution.
Infrared spectrum analysis:
FIG. 2 is an infrared spectrum of the structural formula shown in example 1 of the present invention, wherein 1000cm-1Corresponding to the characteristic peak of the sulfonic acid group in the novel additive described in example 1 of the invention, 1600cm-1The characteristic peak of the benzene ring in the novel additive of example 1 of the invention is 2200cm-1Corresponding to the characteristic peaks of the nitrile groups in the novel additive according to the invention described in example 1. In addition, as the sulfonic acid group, the benzene ring and the nitrile group are core functional groups in the structural formula of the novel additive according to each embodiment of the invention, the infrared spectrogram result of one embodiment is selected as an example for detailed analysis.
Performance test experiments:
the lithium ion battery electrolytes prepared by the comparative examples 1 to 4 and the novel additives prepared by the examples 1 to 8 are subjected to a plurality of performance tests, and the test contents mainly comprise: the first efficiency, rate capability, room temperature (25 ℃) cycle performance, 60 ℃ cycle performance, -20 ℃ discharge capacity, 4.5V voltage cycle performance and the like, and the test data are detailed in the following table (table 1):
TABLE 1 statistics of Performance test results for comparative examples 1-4 and examples 1-8
Figure BDA0002753751910000151
The performance test data of each comparative example and the example are shown in the table, and it can be seen from the data:
firstly, from the aspect of first efficiency, the first efficiency of selecting an additive containing a nitrile group to prepare an electrolyte, selecting an additive containing a sulfonic acid group to prepare an electrolyte, and selecting an additive containing a nitrile group and an additive containing a sulfonic acid group to prepare an electrolyte is about 87.5-89.6%, while the first efficiency of an electrolyte prepared by using the novel additive provided by the embodiment of the invention is 89.6-90.9%, so that the first efficiency of a battery electrolyte can be improved by using the novel additive provided by the embodiment of the invention;
secondly, analysis on the aspects of rate capability, room temperature 25 ℃ cycling performance, 60 ℃ cycling performance and the like shows that the rate capability of the comparative example, the cycling performance at room temperature 25 ℃ and high temperature 60 ℃ are respectively 58.9-65.0%, 78.6-84.1% and 70.2-76.1%, while the rate capability of the embodiment of the invention, the cycling performance at room temperature 25 ℃ and high temperature 60 ℃ are respectively 68.5-71.7%, 85.2-87.6% and 90.3-93.1%. Therefore, the rate performance and the cycle performance at room temperature of 25 ℃ of the embodiment of the invention are both improved by about 10 percent, and the cycle performance at high temperature of 60 ℃ is improved by about 20 percent;
thirdly, according to the analysis of the conservation rate of the discharge capacity at the temperature of-20 ℃ and the conservation rate of the circulation capacity at the period of 4.5V and 100 weeks, the conservation rate of the discharge capacity at the temperature of-20 ℃ and the conservation rate of the circulation capacity at the period of 4.5V and 100 weeks of the comparative example and the embodiment are 35.1-42.3 percent and 60.9-75.0 percent respectively; 45.3-49.2% and 84.1-87.2%. Therefore, the discharge capacity retention rate at-20 ℃ and the cycle capacity retention rate at 4.5V for 100 weeks are both improved by about 14% in the embodiment of the invention;
finally, the analysis proves that the novel additive and the electrolyte prepared by the novel additive provided by the embodiment of the invention show good high-temperature and low-temperature stability and cycle stability, so that the novel additive provided by the invention really realizes that one additive has multiple functions and has very wide application prospect in the field of lithium ion batteries.

Claims (8)

1. The novel additive is characterized in that the novel additive is a compound which is composed of benzene rings and contains a multi-ring structure of sulfonic acid groups and nitrile groups, and the structural formula of the compound is shown as formula 1:
Figure FDA0002753751900000011
wherein, R in the formula 1 is selected from nitrile group or nitrile group containing 2, 3 or 4 carbon atoms.
2. The novel additive according to claim 1, wherein when R is a nitrile group, it has a formula represented by formula 2:
Figure FDA0002753751900000012
3. the novel additive according to claim 2, wherein when R is a nitrile group having 2, 3 or 4 carbon atoms, the structural formula thereof is represented by formula 3 to formula 5:
Figure FDA0002753751900000013
4. use of the novel additive according to any one of claims 1 to 3 in electrolytes for lithium ion batteries.
5. The use according to claim 4, wherein the lithium ion battery electrolyte comprises a non-aqueous organic solvent, a lithium salt and the novel sulfur-containing additive according to any one of claims 1 to 3.
6. The use of claim 5, wherein the novel sulfur-containing additive is 0.01-5% of the total mass of the lithium ion battery electrolyte, and the concentration of the lithium salt is 0.15-1.5 mol/L.
7. The use according to claim 5, wherein the non-aqueous organic solvent is selected from one or more of ethylene carbonate, propylene carbonate, vinylene carbonate, ethyl methyl carbonate, propyl methyl carbonate, dipropyl carbonate, ethylene carbonate, diethyl carbonate, dimethyl carbonate, propylene carbonate, methyl formate, methyl acrylate, methyl butyrate, ethyl acetate, acid anhydride, N-methylpyrrolidone, N-methylformamide, N-methylacetamide, acetonitrile, N-dimethylformamide, sulfolane, dimethyl sulfoxide, ethylene sulfite, propylene sulfite, methyl sulfide, diethyl sulfite, dimethyl sulfite, tetrahydrofuran, fluorine-containing cyclic organic esters, sulfur-containing cyclic organic esters, and unsaturated bond-containing cyclic organic esters.
8. Use according to claim 5, wherein the lithium salt is selected from LiPF6、LiClO4、LiBF4、LiAsF6One or more of LiFSI and LiTFSI.
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