CN111116659A - Compound, electrolyte and lithium ion battery - Google Patents

Compound, electrolyte and lithium ion battery Download PDF

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CN111116659A
CN111116659A CN201811284512.XA CN201811284512A CN111116659A CN 111116659 A CN111116659 A CN 111116659A CN 201811284512 A CN201811284512 A CN 201811284512A CN 111116659 A CN111116659 A CN 111116659A
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electrolyte
compound
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lithium
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秦虎
陈黎
袁杰
王峰
陈晓琴
甘朝伦
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Zhangjiagang Guotai Huarong New Chemical Materials Co Ltd
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    • C07F9/02—Phosphorus compounds
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    • C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
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Abstract

The invention relates to a compound, an electrolyte and a lithium ion battery, wherein the structural general formula of the compound is shown as a formula (1) or a formula (2),
Figure DDA0001848741290000011
wherein R is1、R2Independently H, halogen, CN, NO2Alkyl, haloalkyl, phosphate or polyether groups; or, R1And R2Combined together to form a ring shape; r3、R4Independently H, halogen, CN, NO2Alkyl, haloalkyl, phosphate or polyether groups; or, R3And R4Joined together to form a ring. Hair brushIt is clear that by adding the compound represented by formula (1) or formula (2) to an electrolyte, the compound can effectively suppress the occurrence of side reactions in the electrolyte, maintain the stability of the electrode, and improve the charge-discharge cycle performance and high-temperature performance of the full cell.

Description

Compound, electrolyte and lithium ion battery
Technical Field
The invention belongs to the technical field of materials, and particularly relates to a compound, an electrolyte and a lithium ion battery.
Background
The lithium ion battery has the characteristics of high energy density, high power density, good cycle performance, no memory effect, environmental protection and the like, is widely applied to various electronic products such as mobile phones, mobile cameras, notebook computers, mobile phones and the like, and is also a strong candidate in energy supply systems of future electric automobiles. Chain organic solvents used in lithium battery electrolytes often include: dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, propyl methyl carbonate and the like and mixtures of two or more thereof, and the lithium salt used is usually: lithium hexafluorophosphate, lithium perchlorate, lithium tetrafluoroborate, lithium dioxalate borate, lithium trifluoromethanesulfonate, lithium bis fluorosulfonylimide and the like and mixtures of two or more thereof. Since lithium hexafluorophosphate is easily decomposed, the decomposition rate of the lithium salt is further increased particularly in the presence of a small amount of moisture in the nonaqueous electrolytic solution. The high-temperature use environment of the lithium battery can promote the HF content of the electrolyte to be remarkably increased, and the HF can damage SEI films on the surfaces of the anode and the cathode of the lithium battery, so that the electrochemical performance of the lithium battery is seriously influenced. In 1999, the patent (application No. 97198512.8) disclosed a lithium fluorophosphate and its use as a conductive salt, providing a preparation method and its conductive salt applied to an electrolyte in a lithium battery, such as: lithium heptafluoroisopropyl pentafluorophosphate, Li [ (C3F7)2PF4, and the like, which have an electrochemical window greater than 5.0V when dissolved in DME.
Another type of derivative which is widely used is lithium difluorophosphate, and patent application No. 200780031231.7 discloses a method for producing lithium difluorophosphate, a method for producing a nonaqueous electrolytic solution, and a secondary battery using a nonaqueous electrolytic solution electrolyte of the nonaqueous electrolytic solution, which can obtain a battery having excellent low-temperature discharge characteristics and large-current discharge characteristics, as well as excellent high-temperature storage characteristics and cycle characteristics.
By subjecting the lithium ion battery to LiPF6The modification is carried out to obtain a new compound, and the electrochemical performance of the corresponding electrolyte adopted by the battery can be obviously improved. The invention obtains a new compound by a chemical method, and can further improve the electrochemical performance of the battery.
Disclosure of Invention
The invention aims to provide a novel compound, and an electrolyte and a lithium ion battery using the compound.
In order to achieve the purpose, the invention adopts the technical scheme that:
the invention aims to provide a compound, the structural general formula of the compound is shown as formula (1) or formula (2),
Figure BDA0001848741270000021
wherein R is1、R2Independently H, halogen, CN, NO2Alkyl, haloalkyl, phosphate or polyether groups; or, R1And R2Combined together to form a ring shape;
R3、R4independently H, halogen, CN, NO2Alkyl, haloalkyl, phosphate or polyether groups; or, R3And R4Joined together to form a ring.
Preferably, R1、R2、R3、R4Independently H, halogen, C1-C4 alkyl, C1-C4 haloalkyl, or polyether group having 2 to 20 carbon atoms.
Further preferably, R1、R2、R3、R4Independently H, methyl, ethyl, n-propyl, n-butyl, isobutyl, tert-butyl, F, Cl or Br.
More preferably, R1、R3Independently H, methyl, ethyl, n-propyl, n-butyl, isobutyl, or tert-butyl; r2、R4Independently H, F, Cl or Br.
According to a particular and preferred embodiment, the compound has the specific formula:
Figure BDA0001848741270000031
the invention also aims to provide a preparation method of the compound, which comprises the step of reacting lithium hexafluorophosphate with a compound shown as a formula (3) in the presence of a non-aqueous solvent and silicon tetrafluoride or silicon tetrachloride at 30-50 ℃ to obtain the compound shown as the formula (1) or the formula (2), wherein the compound shown as the formula (3) is a compound shown as the formula (3)
Figure BDA0001848741270000032
R5、R6Independently H, halogen, CN, NO2Alkyl, haloalkyl, phosphate or polyether groups; or, R5And R6Combined together to form a ring shape; r7, R8 are independently H or alkyl.
Preferably, the non-aqueous solvent is one or more of absolute ethyl alcohol, carbonate, carboxylic ester and halogenated ester thereof.
Preferably, the feeding molar ratio of the lithium hexafluorophosphate to the compound shown in the formula (3) is 1: 1-2.5.
Preferably, the feeding molar ratio of the silicon tetrafluoride or the silicon tetrachloride to the lithium hexafluorophosphate is 1: 1-1.2.
The third purpose of the invention is to provide an electrolyte, which comprises an organic solvent and an alkali metal salt, and the electrolyte further comprises one or more of the compounds.
Preferably, the electrolyte has a moisture content of <150PPM and an HF content of <150 PPM.
Preferably, the electrolyte has a color<50PHAT, conductivity>0.1ms/cm2。
Preferably, the mass fraction of the compound shown as the formula (1) or the formula (2) in the electrolyte is 0.1-5%, and more preferably 0.5-1%.
Preferably, the organic solvent is one or more of esters, ethers, sulfones, nitriles, aromatic compounds, acid anhydride compounds and fluoro compounds.
In the present invention, esters include carbonates, carboxylates, sulfates, sulfites, sultones, phosphates, phosphites, lactones.
The carbonate includes ethylene carbonate, vinylene carbonate, propylene carbonate, butylene carbonate, vinyl ethylene carbonate, methylene ethylene carbonate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, dipropyl carbonate, dibutyl carbonate, methyl propyl carbonate and ethyl propyl carbonate.
The carboxylic acid ester includes methyl formate, ethyl formate, propyl formate, butyl formate, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl propionate, ethyl propionate, propyl propionate, butyl propionate, methyl butyrate, ethyl butyrate, propyl butyrate, butyl butyrate.
The sulfate includes dimethyl sulfate, diethyl sulfate, ethyl methyl sulfate, vinyl sulfate, and allyl sulfate.
The sulfite includes dimethyl sulfite, diethyl sulfite, ethyl methyl sulfite, ethylene sulfite and propylene sulfite.
The sultone includes 1, 3-propane sultone and 1, 4-butane sultone.
The phosphate ester includes trimethyl phosphate, triethyl phosphate, tripropyl phosphate, triphenyl phosphate, tris (trifluoromethyl) phosphate, tris (trifluoroethyl) phosphate, tris (trifluoropropyl) phosphate, tris (fluorophenyl) phosphate.
Phosphites include trimethyl phosphite, triethyl phosphite, tripropyl phosphite, triphenyl phosphite, tris (trifluoromethyl) phosphite, tris (trifluoroethyl) phosphite, tris (trifluoropropyl) phosphite, tris (fluorophenyl) phosphite.
The lactones include butyrolactone, 2-methyl-butyrolactone, 3-methyl-butyrolactone, 4-methyl-butyrolactone, propiolactone and valerolactone.
Ethers include tetrahydrofuran, 2-methyltetrahydrofuran, 1, 3-dioxolane, 1, 4-dioxane, 1, 2-dimethoxyethane, 1, 2-diethoxyethane, 1, 2-dibutoxyethane, methyl nonafluorobutyl ether and ethyl nonafluorobutyl ether.
Sulfones include dimethyl sulfone, ethyl methyl sulfone, methyl trifluoromethyl sulfone, ethyl trifluoromethyl sulfone, methyl pentafluoromethyl pentafluoroethyl sulfone, ethyl pentafluoroethyl sulfone, bis (trifluoromethyl) sulfone, bis (pentafluoroethyl) sulfone, trifluoromethyl pentafluoroethyl sulfone, trifluoromethyl nonafluorobutyl sulfone, and pentafluoroethyl butyl sulfone.
Nitriles include acetonitrile, propionitrile, butyronitrile and dinitriles CN (CH) having various alkane chain lengths (n ═ 1 to 8)2)nCN, trinitrile CN (CH)2)nCHCN(CH2)nCN and polynitrile.
The aromatic compound includes toluene, ethylbenzene, propylbenzene, butylbenzene, tert-butyl, tert-pentylbenzene, o-xylene, m-xylene, p-xylene, biphenyl, terphenyl, o-fluoromethyl, m-fluorotoluene, p-fluorotoluene, cyclohexyl ester, o-fluorocyclohexyl, m-fluorocyclohexyl benzene, p-fluorocyclohexyl benzene.
The acid anhydride compound comprises succinic anhydride and phthalic anhydride.
Fluoro compounds include organic and inorganic fluoro compounds.
Organofluoro compounds include fluorinated carbonates, fluorinated ethers, fluorinated esters, fluorinated alkanes, fluorinated alkyl phosphates, fluorinated aromatic phosphates, fluorinated alkyl phosphonates, and fluorinated aromatic phosphonates. For example, fluorinated ethylene carbonate, fluoroethyl fluoromethyl carbonate, methyl trifluoroacetate, ethyl trifluoroacetate, fluoromethylethyl ether, perfluoromethylethyl ether, fluorobenzene and the like.
According to a specific and preferred embodiment, the organic solvent is a mixed solvent of ethylene carbonate, diethyl carbonate and ethyl methyl carbonate in a mass ratio of 1-2: 1: 2-3.
Preferably, the alkali metal salt is LiPF6、LiBF4、LiAsF6、LiClO4、LiBOB、LiDFOB、LiCF3SO3、LiC4F9SO3、Li(CF3SO2)2N and Li (C)2F5SO2)2N，LiCO3、LiNO3、Li2SO4、Li3PO4、LiOH、Al2O3、SiO2、SnO2And SnO.
Preferably, the concentration of the alkali metal salt is 0.5-1.5 mol/L.
Preferably, the electrolyte solution further includes an initiator and a polymerization monomer, so that a gel electrolyte may be formed.
Preferably, the electrolyte further comprises an additive accounting for 0.01-20% of the total mass of the electrolyte, and the additive is one or more of lithium difluoro oxalato borate, 1, 3-propane sultone, biphenyl, succinonitrile, vinylene carbonate, ethylene carbonate, cyclohexylbenzene, propylene sulfate, trioctyl phosphate, vinyl sulfate, 4-methyl vinyl sulfate, vinyl sulfite and lithium difluorophosphate.
The fourth purpose of the invention is to provide a lithium ion battery, which comprises a positive electrode, a negative electrode and an electrolyte, wherein the electrolyte is the electrolyte.
Preferably, the positive electrode is an inorganic compound with a layered structure; the negative electrode is carbon, silicon, carbon-silicon composite, graphite, tin alloy, silicon alloy, intermetallic compound or lithium metal.
For example, the positive electrode is spinel, olivine, a layered material, LiFePO4、LiCoO2、LiNiO2、LiNixCoyMn1-x-yO2、LiMn0.5Ni1.5O2、LiMn2O4、LiFeO2、ZrO2、TiO2、ZnO2、Al2O3、WO3、MgO2、SiO2WhereinX is a number between 0 and 1, and y is a number between 0 and 1.
Preferably, the lithium ion battery further comprises a porous separator, and the positive electrode and the negative electrode are separated by the porous separator.
Due to the application of the technical scheme, compared with the prior art, the invention has the following advantages:
according to the invention, the compound shown in the formula (1) or the formula (2) is added into the electrolyte, so that the compound can effectively inhibit the occurrence of side reactions in the electrolyte, the stability of an electrode is maintained, and the charge-discharge cycle performance and the high-temperature performance of the full battery are improved.
Drawings
Fig. 1 is a nuclear magnetic H spectrum of compound (a), and 3.17 represents the chemical shift of the H atom in the compound.
FIG. 2 is the application of the electrolyte of example 7 to Li/LiNi1/3Co1/3Mn1/3O2In the battery, a charge-discharge curve at a current density of 0.1C.
FIG. 3 the electrolyte of example 7 was used for Li/LiNi1/3Co1/3Mn1/3O2Cycling profile at 0.1C current density in the cell.
FIG. 4 is the use of the electrolyte of example 7 for carbon/LiNi1/3Co1/3Mn1/3O2In the cell, a formation efficiency map at a current density of 0.1C was recorded.
Detailed Description
The present application will be described in detail with reference to examples, but the present application is not limited to these examples. In this specification, "%" represents mass% unless otherwise specified.
In the present invention, the synthetic route of compound (a) and compound (D) is:
Figure BDA0001848741270000071
example 1 Synthesis method of Compound (A)
In a non-aqueous solvent diethyl carbonate, lithium hexafluorophosphate (CAS:21324-40-3) and malonic acid (CAS: 141-82-2) are reacted according to a molar ratio of 1:2.1, then silicon tetrachloride (the molar ratio of the silicon tetrachloride to the lithium hexafluorophosphate is 1:1.05) is added, the reaction is carried out for 6 hours at 40 ℃, after the reaction is finished, the compound (A) is obtained by purification, drying and recrystallization in an organic solvent, and the magnetic nuclear magnetic spectrum of the compound (A) is shown in figure 1.
The detection data of the compound (A) are as follows: c13The nuclear magnetic data are as follows: 38.1PPM and 174.2 PPM; h1The nuclear magnetic data are as follows: 3.17 PPM.
Example 2 Synthesis method of Compound (D)
In a non-aqueous solvent diethyl carbonate, lithium hexafluorophosphate (CAS:21324-40-3) and malonic acid (CAS: 141-82-2) are reacted according to a molar ratio of 1:1.2, then silicon tetrachloride (the molar ratio of the silicon tetrachloride to the lithium hexafluorophosphate is 1:1.05) is added, the reaction is carried out for 6 hours at 40 ℃, and after the reaction is finished, the compound (D) is obtained by purification, drying and recrystallization in an organic solvent.
Compound D assay data are as follows: c13The nuclear magnetic data are as follows: 37.8PPM and 174.1 PPM; h1The nuclear magnetic data are as follows: 3.07 PPM.
Example 3 Synthesis method of Compound (B)
In a non-aqueous solvent diethyl carbonate, lithium hexafluorophosphate (CAS:21324-40-3) and 2-fluoro diethyl malonate (CAS:685-88-1) are reacted according to a molar ratio of 1:2.1, then silicon tetrachloride (the molar ratio of silicon tetrachloride to lithium hexafluorophosphate is 1:1.05) is added, the reaction is carried out for 6 hours at 40 ℃, and after the reaction is finished, the compound (B) is obtained by purification, drying and recrystallization in an organic solvent.
The detection data of the compound (B) are as follows: c13The nuclear magnetic data are as follows: 111PPM and 174.2 PPM; h1The nuclear magnetic data are as follows: 4.99 PPM.
Example 4 Synthesis method of Compound (E)
Lithium hexafluorophosphate (CAS:21324-40-3) and diethyl 2-fluoro malonate (CAS:685-88-1) are reacted in a non-aqueous solvent of diethyl carbonate in a molar ratio of 1:1.2, then silicon tetrachloride (the molar ratio of silicon tetrachloride to lithium hexafluorophosphate is 1:1.05) is added, the reaction is carried out for 6 hours at 40 ℃, and after the reaction is finished, the compound (E) is obtained by purification, drying and recrystallization in an organic solvent.
The detection data of compound (E) are as follows: c13 nuclear magnetic data are as follows: 109PPM and 173.9 PPM; h1 nuclear magnetic data are as follows: 4.95 PPM.
Example 5 Synthesis method of Compound (C)
In a non-aqueous solvent diethyl carbonate, lithium hexafluorophosphate (CAS:21324-40-3) and 2-methyl-2-fluoro malonic acid (CAS:94721-44-5) are reacted according to a molar ratio of 1:2.1, then silicon tetrachloride (the molar ratio of silicon tetrachloride to lithium hexafluorophosphate is 1:1.05) is added, the reaction is carried out for 6 hours at 40 ℃, and after the reaction is finished, the compound (C) is obtained by purification, drying and recrystallization in an organic solvent.
The detection data of compound (C) are as follows: c13 nuclear magnetic data are as follows: 23.2, 119PPM and 175.2 PPM; h1 nuclear magnetic data are as follows: 1.73 PPM.
Example 6 Synthesis method of Compound (F)
In a non-aqueous solvent diethyl carbonate, lithium hexafluorophosphate (CAS:21324-40-3) and 2-methyl-2-fluoro malonic acid (CAS:94721-44-5) are reacted according to a molar ratio of 1:1.2, then silicon tetrachloride (the molar ratio of silicon tetrachloride to lithium hexafluorophosphate is 1:1.05) is added, the reaction is carried out for 6 hours at 40 ℃, and after the reaction is finished, the compound (F) is obtained through purification, drying and recrystallization in an organic solvent.
The detection data of compound (F) are as follows: c13 nuclear magnetic data are as follows: 21.8PPM and 175.5 PPM; h1 nuclear magnetic data are as follows: 1.75 PPM.
Examples 7 to 18
Preparing electrolyte: preparing a conventional electrolyte: 30% Ethylene Carbonate (EC), 20% diethyl carbonate (DEC) and 50% Ethyl Methyl Carbonate (EMC) are taken according to the weight ratio, and are fully and uniformly mixed in a glove box with the humidity less than 1% to prepare the electrolyte solvent. Then, an electrolyte salt LiPF was added in portions in a total amount of 1mol/L6After the electrolyte salt was sufficiently dissolved, 0.5% or 1% of the compounds (a), (B), (C), (D), (E) and (F) obtained in examples 1 to 6 were added, respectively; respectively adding 0.3% lithium difluoro (oxalato) borate (LiBOB), 1% 1, 3-Propane Sultone (PS), 0.2% Biphenyl (BP) AND 1% succinonitrile (AND), stirring for 2 hours, AND standingStanding for 24 hours; thus, the electrolytes used in examples 7 to 18 were obtained.
The kinds and amounts of the compounds (A), (B), (C), (D), (E) and (F) added in examples 7 to 18 are shown in Table 1. The electrolyte of each example was tested for HF value by acid-base assay, and the electrolyte was tested for moisture by the card reagent, the results of which are shown in table 1. The electrolytes of examples 7 to 18 were used for silicon carbon/LiNi1/3Co1/3Mn1/3O2The cells were tested for their normal temperature 300 cycle and high temperature shelf performance and the results are shown in table 1.
TABLE 1
Figure BDA0001848741270000091
The electrolyte of example 7 was used for Li/LiNi1/3Co1/3Mn1/3O2In the battery, a charge-discharge curve at a current density of 0.1C was recorded, as shown in fig. 2. The charge-discharge efficiency of the battery is observed to be kept about 90%, and the compound (A) can effectively inhibit the side reaction of the electrolyte.
The electrolyte of example 7 was used for Li/LiNi1/3Co1/3Mn1/3O2In the cell, the cycling profile at a current density of 0.1C is recorded, see fig. 3. It was observed that the discharge capacity of the battery was maintained at about 136mAh/g during 10-week cycling, and the compound (A) was effective in maintaining the stability of the cathode.
The electrolyte of example 7 was used for carbon/LiNi1/3Co1/3Mn1/3O2In the cell, a graph of formation efficiency at 0.1C current density is recorded, see fig. 4. The compound (a) can effectively improve the charge-discharge cycle performance of the full cell.
The above embodiments are merely illustrative of the technical concept and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the content of the present invention and implement the invention, and not to limit the scope of the invention, and all equivalent changes or modifications made according to the spirit of the present invention should be covered by the scope of the present invention.

Claims (12)

1. A compound characterized by: the structural general formula of the compound is shown as a formula (1) or a formula (2),
Figure FDA0001848741260000011
wherein R is1、R2Independently H, halogen, CN, NO2Alkyl, haloalkyl, phosphate or polyether groups; or, R1And R2Combined together to form a ring shape;
R3、R4independently H, halogen, CN, NO2Alkyl, haloalkyl, phosphate or polyether groups; or, R3And R4Joined together to form a ring.
2. The compound of claim 1, wherein: r1、R2、R3、R4Independently H, halogen, C1-C4 alkyl, C1-C4 haloalkyl, or polyether group having 2 to 20 carbon atoms.
3. The compound of claim 2, wherein: the specific structural formula of the compound is as follows:
Figure FDA0001848741260000012
4. a process for the preparation of a compound according to any one of claims 1 to 3, characterized in that: reacting lithium hexafluorophosphate with a compound shown as a formula (3) at 30-50 ℃ in the presence of a non-aqueous solvent and silicon tetrafluoride or silicon tetrachloride to obtain the compound shown as the formula (1) or the formula (2), wherein the compound shown as the formula (3) is
Figure FDA0001848741260000021
R5、R6Independently H, halogen, CN, NO2Alkyl, haloalkyl, phosphate or polyether groups; or, R5And R6Combined together to form a ring shape; r7, R8 are independently H or alkyl.
5. An electrolyte comprising an organic solvent and an alkali metal salt, wherein: the electrolyte further comprising one or more of the compounds of any one of claims 1 to 3.
6. The electrolyte of claim 5, wherein: the moisture content of the electrolyte<150PPM, HF content<150PPM, chroma<50PHAT, conductivity>0.1ms/cm2。
7. The electrolyte of claim 5, wherein: the mass fraction of the compound shown as the formula (1) or the formula (2) in the electrolyte is 0.1-5%.
8. The electrolyte of claim 5, wherein: the organic solvent is one or more of esters, ethers, sulfones, nitriles, aromatic compounds, acid anhydride compounds and fluoro compounds; the alkali metal salt is LiPF6、LiBF4、LiAsF6、LiClO4、LiBOB、LiDFOB、LiCF3SO3、LiC4F9SO3、Li(CF3SO2)2N and Li (C)2F5SO2)2N，LiCO3、LiNO3、Li2SO4、Li3PO4、LiOH、Al2O3、SiO2、SnO2And SnO.
9. The electrolyte of claim 5, wherein: the electrolyte also comprises an initiator and a polymerization monomer.
10. The electrolyte of claim 5, wherein: the electrolyte also comprises an additive accounting for 0.01-20% of the total mass of the electrolyte, and the additive is one or more of lithium difluoro oxalato borate, 1, 3-propane sultone, biphenyl, succinonitrile, vinylene carbonate, ethylene carbonate, cyclohexylbenzene, propylene sulfate, trioctyl phosphate, vinyl sulfate, 4-methyl vinyl sulfate, vinyl sulfite and lithium difluorophosphate.
11. A lithium ion battery comprises a positive electrode, a negative electrode and electrolyte, and is characterized in that: the electrolyte solution according to any one of claims 5 to 10.
12. The lithium ion battery of claim 11, wherein: the positive electrode is an inorganic compound with a layered structure; the negative electrode is carbon, silicon, carbon-silicon composite, graphite, tin alloy, silicon alloy, intermetallic compound or lithium metal.
CN201811284512.XA 2018-10-31 2018-10-31 Compound, electrolyte and lithium ion battery Pending CN111116659A (en)

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