CN111864262A - Lithium ion battery non-aqueous electrolyte and lithium ion battery - Google Patents
Lithium ion battery non-aqueous electrolyte and lithium ion battery Download PDFInfo
- Publication number
- CN111864262A CN111864262A CN201910352101.8A CN201910352101A CN111864262A CN 111864262 A CN111864262 A CN 111864262A CN 201910352101 A CN201910352101 A CN 201910352101A CN 111864262 A CN111864262 A CN 111864262A
- Authority
- CN
- China
- Prior art keywords
- lithium ion
- carbonate
- ion battery
- structural formula
- electrolyte solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
- H01M10/42—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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Secondary Cells (AREA)
Abstract
In order to overcome the problem that the cycle performance and the high-temperature storage performance of the lithium ion battery in the prior art are not ideal under the high-pressure state, the invention provides a lithium ion battery non-aqueous electrolyte, which comprises a compound shown in a structural formula 1,
wherein, X1、X2、X3Independently selected from a sulfur-containing group, a silicon-containing group, a nitrogen-containing group, a group containing 1-4 carbon atoms or a structure shown in a structural formula 2, and at least one of the groups has a structure shown in the structural formula 2. Meanwhile, the invention also discloses a lithium ion battery adopting the lithium ion battery non-aqueous electrolyte. Lithium ion adopting non-aqueous electrolyte provided by the inventionThe pool has excellent cycle performance and high-temperature storage performance under a high-pressure state, and simultaneously, the low-temperature performance of the pool is also very excellent.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a lithium ion battery non-aqueous electrolyte and a lithium ion battery using the same.
Background
Lithium ion batteries have been developed in the field of portable electronic products due to their high operating voltage, high safety, long life, no memory effect, and the like. With the development of new energy automobiles, the lithium ion battery has a huge application prospect in a power supply system for the new energy automobiles.
In a nonaqueous electrolyte lithium ion battery, a nonaqueous electrolyte is a key factor affecting high and low temperature performance of the battery, and particularly, an additive in the nonaqueous electrolyte is particularly important for exerting the high and low temperature performance of the battery. During the initial charging process of the lithium ion battery, lithium ions in the battery anode material are extracted and are inserted into the carbon cathode through electrolyte. Due to its high reactivity, the electrolyte reacts on the carbon negative electrode surface to produce Li2CO3、Li2O, LiOH, thereby forming a passivation film on the surface of the negative electrode, the passivation film being referred to as a solid electrolyte interface film (SEI). The SEI film formed during the initial charging process not only prevents the electrolyte from further decomposing on the surface of the carbon negative electrode, but also acts as a lithium ion tunnel, allowing only lithium ions to pass through. Therefore, the SEI film determines the performance of the lithium ion battery.
In order to improve the stability of the SEI film of a lithium ion battery, many researchers select different film-forming additives (such as vinylene carbonate, fluoroethylene carbonate, and ethylene carbonate) to improve various performances of the battery. Compared with organic solvents and lithium salts, the additive has the advantages of small requirement amount, remarkable effect and low cost, so the development of the additive becomes a core technology of electrolyte development. And D, researching Vinylene Carbonate (VC) serving as an additive by using an electrochemical method and a spectral method, wherein the VC is found to improve the cycle performance of the battery, particularly the cycle performance of the battery at high temperature and reduce irreversible capacity. The main reason is that VC can be polymerized on the surface of graphite to generate a polyalkyl lithium carbonate film, thereby inhibiting the reduction of solvent and salt anions. G.H.Wrodnigg, etc. adds 5% (volume fraction) of Ethylene Sulfite (ES) or Propylene Sulfite (PS) to 1mol/L LiClO4/PC, which can effectively prevent PC molecules from embedding into graphite electrodes and improve the low-temperature performance of the electrolyte. This is probably because the reduction potential of ES is about 2V (vs. Li/Li +), and an SEI film is formed on the surface of the graphite negative electrode in preference to the reduction by the solvent. Although it is important to study the functional additives to improve the performance of the battery. The addition of the additive makes up for some defects of the electrolyte. However, the research work in this area has not been done yet, and for example, there are few reports of additives for increasing the operating temperature range of lithium ion batteries, and the types of additives particularly used in high temperature applications are limited.
Disclosure of Invention
The invention aims to solve the technical problem that the cycle performance and the high-temperature storage performance of a lithium ion battery in a high-pressure state are not ideal in the prior art, and provides a lithium ion battery non-aqueous electrolyte.
The technical scheme adopted by the invention for solving the technical problems is as follows:
provides a lithium ion battery non-aqueous electrolyte, which comprises a compound shown in a structural formula 1,
wherein, X1、X2、X3Independently selected from a sulfur-containing group, a silicon-containing group, a nitrogen-containing group, a group containing 1-4 carbon atoms or a structure shown in a structural formula 2, and at least one of the groups has a structure shown in the structural formula 2.
The action mechanism of the compound shown in the structural formula 1 is not quite clear, but the inventor speculates that the action mechanism is that in the first charging process, the compound shown in the structural formula 1 can generate ring-opening reaction on the surface of an electrode, and further polymerize to form a firm passivation film, so that further decomposition of solvent molecules is inhibited. In addition, the structural formula 1 can possibly react with LiF, so that the content of high-impedance component LiF in the passivation film on the surface of the electrode is reduced, lithium ions can pass through the passivation film, and the high-temperature storage and cycle performance of the battery can be obviously improved.
Preferably, X 1、X2、X3Independently selected from sulfonate, sulfate, carbonyl, alkyl, alkenyl, alkynyl, siloxane group, cyano or the structure shown in the structural formula 2, and at least one of the structures contains the structure shown in the structural formula 2.
Preferably, X1、X2、X3Is selected from sulfonate, sulfate, carbonyl, methyl, ethyl, ethenyl, ethynyl, propenyl, propynyl, trimethoxy silane, triethoxy silane or a structure shown in a structural formula 2, and at least one of the structures contains the structure shown in the structural formula 2.
Preferably, the content of the compound represented by the structural formula 1 is 0.01 to 5% with respect to the total mass of the lithium ion battery nonaqueous electrolyte.
Preferably, the compound represented by the structural formula 1 includes one or more of the following compounds 1 to 12:
preferably, the lithium ion battery non-aqueous electrolyte further comprises one or more of vinylene carbonate, ethylene carbonate and fluoroethylene carbonate; the content of the vinylene carbonate, the ethylene carbonate and the fluoroethylene carbonate is respectively and independently 0.01-5% relative to the total mass of the electrolyte.
The lithium ion battery non-aqueous electrolyte also comprises one or more than two of 1, 3-propane sultone, 1, 4-butane sultone and 1, 3-propylene sultone;
Relative to the total mass of the electrolyte, the content of the 1, 3-propane sultone, the content of the 1, 4-butane sultone and the content of the 1, 3-propylene sultone are respectively and independently 0.01-5%.
Preferably, the lithium ion battery non-aqueous electrolyte further comprises a lithium salt and a non-aqueous organic solvent;
the lithium salt is selected from LiPF6、LiBF4、LiBOB、LiF2PO2、LiDFOB、LiSbF6、LiAsF6、LiN(SO2CF3)2、LiN(SO2C2F5)2、LiC(SO2CF3)3Or LiN (SO)2F)2One or more than two of the above;
the non-aqueous organic solvent is a mixture of cyclic carbonate and chain carbonate, the cyclic carbonate is selected from one or more of ethylene carbonate, propylene carbonate or butylene carbonate, and the chain carbonate is selected from one or more of dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate or propyl methyl carbonate.
Meanwhile, the invention also provides a lithium ion battery which comprises a positive electrode, a negative electrode, a diaphragm arranged between the positive electrode and the negative electrode, and the lithium ion battery non-aqueous electrolyte.
Preferably, the active material of the positive electrode is selected from LiCoO2、LiNiO2、LiMn2O4、LiCo1-yMyO2、LiNi1- yMyO2、LiMn2-yMyO4And LiNixCoyMnzM1-x-y-zO2Wherein M is selected from one or more of Fe, Co, Ni, Mn, Mg, Cu, Zn, Al, Sn, B, Ga, Cr, Sr, V and Ti, y is more than or equal to 0 and less than or equal to 1, x is more than or equal to 0 and less than or equal to 1, z is more than or equal to 0 and less than or equal to 1, and x + y + z is less than or equal to 1.
As another aspect of the present invention, the active material of the positive electrode is selected from LiFe1-xMxPO4, wherein M is selected from one or more of Mn, Mg, Co, Ni, Cu, Zn, Al, Sn, B, Ga, Cr, Sr, V or Ti, and x is more than or equal to 0 and less than 1.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects solved by the present invention more apparent, the present invention is further described in detail below with reference to the following 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 lithium ion battery non-aqueous electrolyte provided by the invention comprises a compound shown in a structural formula 1,
wherein, X1、X2、X3Independently selected from a sulfur-containing group, a silicon-containing group, a nitrogen-containing group, a group containing 1-4 carbon atoms or a structure shown in a structural formula 2, and at least one of the groups has a structure shown in the structural formula 2.
The lithium ion battery non-aqueous electrolyte contains the compound shown in the structural formula 1, and the compound 1 has an obvious positive electrode protection effect, can effectively inhibit the positive electrode material from being damaged, and also can inhibit the catalytic decomposition reaction of metal ions on the electrolyte and the damage effect on a negative electrode passivation film. In the full-electricity storage process, the side reaction between the anode material and the electrolyte under high voltage can be effectively reduced, so that the storage performance of the lithium ion battery under high voltage is improved. Meanwhile, the negative electrode has a good film forming effect and has little influence on film impedance, so that the stability of the negative electrode in the recycling process is improved, and the cycle performance is improved.
The compounds of formula 1 can be prepared in a manner that would be apparent to one skilled in the art of organic synthesis based on the structure of the compounds of formula 1, for example,
triethylamine is used as an acid-binding agent, Chlorinated Ethylene Carbonate (CEC) reacts with phosphate or phosphoric acid to generate phosphotriester, and the phosphotriester is prepared by recrystallization or column chromatography purification. The synthetic route is exemplified as follows:
preferably, X1、X2、X3Independently selected from sulfonate, sulfate, carbonyl, alkyl, alkenyl, alkynyl, siloxane group, cyano or the structure shown in the structural formula 2, and at least one of the structures contains the structure shown in the structural formula 2.
Preferably, X1、X2、X3Is selected from sulfonate, sulfate, carbonyl, methyl, ethyl, ethenyl, ethynyl, propenyl, propynyl, trimethoxy silane, triethoxy silane or a structure shown in a structural formula 2, and at least one of the structures contains the structure shown in the structural formula 2.
Preferably, the content of the compound represented by the structural formula 1 is 0.01 to 5% with respect to the total mass of the lithium ion battery nonaqueous electrolyte.
Controlling the content of the compound represented by the structural formula 1 in the nonaqueous electrolytic solution has a favorable influence on further optimization of high-pressure performance, high-temperature performance and low-temperature performance. In a preferred embodiment of the present invention, the content of the compound represented by structural formula 1 is 0.01% to 5% with respect to the total mass of the nonaqueous electrolytic solution for lithium ion batteries. When the content is less than 0.01%, it is not favorable to sufficiently form a passivation film on the surface of the negative electrode, thereby being unfavorable to sufficiently improve the high-temperature and low-temperature performance of the nonaqueous electrolyte battery, and when the content exceeds 5.0%, a thicker passivation film is formed on the surface of the negative electrode, but the internal resistance of the battery is increased, thereby reducing the performance of the battery. Research shows that the content of the compound shown in the structural formula 1 is less than 0.01% or more than 5% of the total mass of the non-aqueous electrolyte of the lithium ion battery, and compared with the content of the compound in the range of 0.01-5%, the high-temperature performance and the low-temperature performance of the lithium ion battery are reduced to different degrees, which indicates that the content of the compound shown in the structural formula 1 in the non-aqueous electrolyte is positively controlled.
Preferably, the compound represented by the structural formula 1 includes one or more of the following compounds 1 to 12:
preferably, the lithium ion battery non-aqueous electrolyte further comprises one or more of vinylene carbonate, ethylene carbonate and fluoroethylene carbonate;
the content of the vinylene carbonate, the ethylene carbonate and the fluoroethylene carbonate is 0.01 to 5 percent, preferably 0.1 to 3 percent and more preferably 0.5 to 2 percent respectively and independently relative to the total mass of the electrolyte.
Preferably, the lithium ion battery non-aqueous electrolyte further comprises one or more than two of 1, 3-propane sultone, 1, 4-butane sultone and 1, 3-propene sultone;
the content of the 1, 3-propane sultone, the 1, 4-butane sultone and the 1, 3-propene sultone is 0.01-5%, preferably 0.1-3%, more preferably 0.5-2% of the total mass of the electrolyte.
The additives can form a more stable SEI film on the surface of the graphite negative electrode, so that the cycle performance of the lithium ion battery is remarkably improved.
It has been found that the compound represented by formula 1 of the present invention, used in combination with the above-mentioned additive, can achieve superior effects to those achieved when they are used alone, and it is presumed that there is a synergistic effect between them, i.e., the compound represented by formula 1 and the above-mentioned additive cooperate to improve the cycle performance, high-temperature storage and/or low-temperature performance of the battery in a high-pressure state.
Preferably, the lithium ion battery nonaqueous electrolyte further comprises a lithium salt and a nonaqueous organic solvent.
The lithium salt is selected from LiPF6、LiBF4、LiBOB、LiDFOB、LiF2PO2、LiSbF6、LiAsF6、LiN(SO2CF3)2、LiN(SO2C2F5)2、LiC(SO2CF3)3Or LiN (SO)2F)2One or more ofMore than two kinds. The lithium salt is preferably LiPF6Or LiPF6And other lithium salts.
The non-aqueous organic solvent is a mixture of cyclic carbonate and chain carbonate, the cyclic carbonate is selected from one or more of ethylene carbonate, propylene carbonate or butylene carbonate, and the chain carbonate is selected from one or more of dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate or propyl methyl carbonate. The mixed solution of the cyclic carbonate organic solvent with high dielectric constant and the chain carbonate organic solvent with low viscosity is used as the solvent of the lithium ion battery electrolyte, so that the mixed solution of the organic solvent has high ionic conductivity, high dielectric constant and low viscosity.
Meanwhile, the invention also provides a lithium ion battery which comprises a positive electrode, a negative electrode, a diaphragm arranged between the positive electrode and the negative electrode, and the lithium ion battery non-aqueous electrolyte.
Preferably, the active material of the positive electrode is selected from LiCoO2、LiNiO2、LiMn2O4、LiCo1-yMyO2、LiNi1- yMyO2、LiMn2-yMyO4And LiNixCoyMnzM1-x-y-zO2Wherein M is selected from one or more of Fe, Co, Ni, Mn, Mg, Cu, Zn, Al, Sn, B, Ga, Cr, Sr, V and Ti, y is more than or equal to 0 and less than or equal to 1, x is more than or equal to 0 and less than or equal to 1, z is more than or equal to 0 and less than or equal to 1, and x + y + z is less than or equal to 1.
As another aspect of the present invention, the active material of the positive electrode is selected from LiFe1-xMxPO4, wherein M is selected from one or more of Mn, Mg, Co, Ni, Cu, Zn, Al, Sn, B, Ga, Cr, Sr, V or Ti, and x is more than or equal to 0 and less than 1.
The present invention will be further illustrated by the following examples.
Example 1
This example is for explaining a lithium ion battery nonaqueous electrolytic solution and a lithium ion battery disclosed in the present invention.
1) Preparation of the electrolyte
Ethylene Carbonate (EC), diethyl carbonate (DEC) and Ethyl Methyl Carbonate (EMC) were mixed in a mass ratio of EC: DEC: EMC ═ 1:1:1, and then lithium hexafluorophosphate (LiPF) was added6) To a molar concentration of 1mol/L, 1% by mass of compound 1 based on the total mass of the electrolyte was added (note: here compound 1 is compound 1 in table 1, the same as in the examples below).
2) Preparation of Positive plate
A positive electrode active material lithium nickel cobalt manganese oxide LiNi was mixed in a mass ratio of 93:4:30.5Co0.2Mn0.3O2Conductive carbon black Super-P and a binder polyvinylidene fluoride (PVDF), and then dispersed in N-methyl-2-pyrrolidone (NMP) to obtain a positive electrode slurry. And uniformly coating the slurry on two sides of the aluminum foil, drying, rolling and vacuum drying, and welding an aluminum outgoing line by using an ultrasonic welding machine to obtain the positive plate, wherein the thickness of the positive plate is 120-.
3) Preparation of negative plate
Mixing artificial graphite serving as a negative electrode active material, conductive carbon black Super-P, Styrene Butadiene Rubber (SBR) serving as a binder and carboxymethyl cellulose (CMC) according to a mass ratio of 94:1:2.5:2.5, and dispersing the materials in deionized water to obtain negative electrode slurry. Coating the slurry on two sides of the copper foil, drying, rolling and vacuum drying, and welding a nickel outgoing line by using an ultrasonic welding machine to obtain a negative plate, wherein the thickness of the negative plate is 120-150 mu m.
4) Preparation of cell
And placing three layers of isolating films with the thickness of 20 mu m between the positive plate and the negative plate, then winding the sandwich structure consisting of the positive plate, the negative plate and the diaphragm, flattening the wound body, then placing the wound body into an aluminum foil packaging bag, and baking for 48h at 75 ℃ in vacuum to obtain the battery cell to be injected with liquid.
5) Liquid injection and formation of battery core
And (3) in a glove box with the dew point controlled below-40 ℃, injecting the prepared electrolyte into the battery cell, carrying out vacuum packaging, and standing for 24 hours.
Then the first charge is normalized according to the following steps: charging at 0.05C for 180min, charging at 0.2C to 3.95V, vacuum sealing for the second time, further charging at 0.2C to 4.2V, standing at room temperature for 24hr, and discharging at 0.2C to 3.0V.
6) High temperature cycle performance test
Placing the battery in a constant-temperature oven at 45 ℃, charging to 4.5V by a current of 1C at a constant current, then charging at a constant voltage until the current is reduced to 0.02C, then discharging to 3.0V by the current of 1C at a constant current, so cycling, recording the discharge capacity of the 1 st circle and the discharge capacity of the last circle, and calculating the capacity retention rate of high-temperature cycling according to the following formula:
capacity retention rate ═ last round of discharge capacity/1 st round of discharge capacity × (100)%
7) High temperature storage Performance test
And (3) charging the formed battery to 4.2V at constant current and constant voltage of 1C at normal temperature, measuring the initial discharge capacity and the initial battery thickness of the battery, then storing the battery for 30 days at 60 ℃, discharging the battery to 3V at 1C, and measuring the retention capacity and recovery capacity of the battery and the thickness of the battery after storage. The calculation formula is as follows:
battery capacity retention (%) — retention capacity/initial capacity × 100%;
battery capacity recovery (%) — recovery capacity/initial capacity × 100%;
thickness expansion (%) (battery thickness after storage-initial battery thickness)/initial battery thickness × 100%.
8) Low temperature Performance test
At 25 ℃, the formed battery is charged to 4.2V by using a 1C constant current and constant voltage, then discharged to 3.0V by using a 1C constant current, and the discharge capacity is recorded. And then charging to 4.2V at constant current and constant voltage of 1C, standing for 12h in an environment at the temperature of minus 20 ℃, discharging to 3.0V at constant current of 0.2C, and recording the discharge capacity.
A low-temperature discharge efficiency value of-20 ℃ was 0.2C discharge capacity (-20 ℃) per 1C discharge capacity (25 ℃) x 100%.
Example 2
As shown in Table 1, the data of the high temperature performance and the low temperature performance obtained by the test are shown in Table 2, except that 1% of the compound 1 is replaced with 1% of the compound 2 in the preparation of the electrolyte, which is the same as that of example 1.
Example 3
As shown in Table 1, the data of the high temperature performance and the low temperature performance obtained by the test are shown in Table 2, except that 1% of the compound 1 is replaced with 1% of the compound 5 in the preparation of the electrolyte, which is the same as that of example 1.
Example 4
As shown in Table 1, the data of the high temperature performance and the low temperature performance obtained by the test are shown in Table 2, except that 1% of the compound 1 is replaced with 1% of the compound 6 in the preparation of the electrolyte, which is the same as that of example 1.
Example 5
As shown in Table 1, the data of the high temperature performance and the low temperature performance obtained by the test are shown in Table 2, except that 1% of the compound 1 is replaced with 1% of the compound 11 in the preparation of the electrolyte, which is the same as that of example 1.
Comparative example 1
As shown in Table 1, the data of the high temperature performance and the low temperature performance obtained by the test are shown in Table 2, which is the same as example 1 except that 1% of the compound 1 is not added in the preparation of the electrolyte.
Comparative example 2
As shown in Table 2, the data of the high temperature properties and the low temperature properties obtained by the test are shown in Table 3, except that 1% of Compound 1 was replaced with 1% of VC in the preparation of the electrolyte, which is the same as in example 1.
Comparative example 3
As shown in Table 2, the data of the high temperature performance and the low temperature performance obtained by the test are shown in Table 3, except that 1% of the compound 1 is replaced with 1% of PS in the preparation of the electrolyte, which is the same as that of example 1.
Comparative example 4
As shown in Table 2, the data of the high temperature performance and the low temperature performance obtained by the test are shown in Table 3, except that 1% of the compound 1 is replaced with 1% of DTD in the preparation of the electrolyte, which is the same as that of example 1.
TABLE 1
| Examples/comparative examples | Compound shown in structural formula 1 and content thereof | Additive and content |
| Example 1 | 1: 1% of compound | |
| Example 2 | 2: 1% of compound | |
| Example 3 | Compound 5: 1% | |
| Example 4 | The compound is 6: 1% | |
| Example 5 | The compound is 11: 1% | |
| Comparative example 1 | - | - |
| Comparative example 2 | - | VC:1％ |
| Comparative example 3 | - | PS:1％ |
| Comparative example 4 | - | DTD:1％ |
TABLE 2
The results in table 2 show that adding 1% of compound 1, compound 2, compound 5, compound 6, or compound 11 to the nonaqueous electrolytic solution can significantly improve the high-temperature performance and the low-temperature performance of the lithium ion battery, compared to adding no additive or adding a conventional additive. The lithium ion battery containing the electrolyte for the lithium ion battery has the excellent low-temperature discharge efficiency of more than 78 percent and the cycle and high-temperature storage efficiency of more than 83 percent in an excellent high-pressure state; furthermore, it was confirmed that the increase rate of the thickness of the battery was significantly low (3 to 7%) when the battery was maintained at a high temperature for a long time.
Example 6
As shown in Table 3, the data of the high temperature performance and the low temperature performance obtained by the test are shown in Table 4, except that 1% of the compound 1 is changed to 0.1% of the compound 1 in the preparation of the electrolyte, which is the same as that of example 3.
Example 7
As shown in Table 3, the data of the high temperature performance and the low temperature performance obtained by the test are shown in Table 4, except that 1% of the compound 1 was changed to 2% of the compound 1 in the preparation of the electrolyte, which is the same as that of example 3.
Example 8
As shown in Table 3, the data of the high temperature performance and the low temperature performance obtained by the test are shown in Table 4, except that 1% of the compound 1 was changed to 3% of the compound 1 in the preparation of the electrolyte, which is the same as that of example 3.
Example 9
As shown in Table 3, the data of the high temperature performance and the low temperature performance obtained by the test are shown in Table 4, except that 1% of the compound 1 was changed to 5% of the compound 1 in the preparation of the electrolyte, which is the same as that of example 3.
TABLE 3
| Examples/comparative examples | Compound shown in structural formula 1 and content thereof |
| Example 6 | Compound 1: 0.1 percent of |
| Example 7 | Compound 1: 2 percent of |
| Example 8 | Compound 1: 3 percent of |
| Example 9 | Compound 1: 5 percent of |
TABLE 4
Example 10
As shown in Table 5, the data of the high temperature performance and the low temperature performance obtained by the test are shown in Table 6, except that 1% of VC is additionally added in the preparation of the electrolyte, which is the same as that of example 3.
Example 11
As shown in Table 5, the data of the high temperature performance and the low temperature performance obtained by the test are shown in Table 6, except that 1% of PS is additionally added in the preparation of the electrolyte solution, which is the same as that of example 3.
Example 12
As shown in Table 5, the data of the high temperature performance and the low temperature performance obtained by the test are shown in Table 6, except that 1% of DTD was additionally added in the preparation of the electrolyte, which is the same as that of example 3.
TABLE 5
TABLE 6
The results show that the high-temperature performance and the low-temperature performance can be further improved by adding additives (VC, PS or DTD) on the basis of the compound shown in the structural formula 1. Or, the compound shown in the structural formula 1 of the invention is further added on the basis of the existing additive (VC, PS or DTD), so that the high-temperature performance and the low-temperature performance can be further improved.
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. A lithium ion battery non-aqueous electrolyte is characterized by comprising a compound shown as a structural formula 1,
wherein, X1、X2、X3Independently selected from a sulfur-containing group, a silicon-containing group, a nitrogen-containing group, a group containing 1-4 carbon atoms or a structure shown in a structural formula 2, and at least one of the groups has a structure shown in the structural formula 2.
2. The nonaqueous electrolyte solution for lithium ion batteries according to claim 1, wherein X is1、X2、X3Independently selected from sulfonate, sulfate, carbonyl, alkyl, alkenyl, alkynyl, siloxane group, cyano or the structure shown in the structural formula 2, and at least one of the structures contains the structure shown in the structural formula 2.
3. The nonaqueous electrolyte solution for lithium ion batteries according to claim 1, wherein X is1、X2、X3Is selected from sulfonate, sulfate, carbonyl, methyl, ethyl, ethenyl, ethynyl, propenyl, propynyl, trimethoxy silane, triethoxy silane or a structure shown in a structural formula 2, and at least one of the structures contains the structure shown in the structural formula 2.
4. The nonaqueous electrolyte solution for lithium ion batteries according to claim 1, wherein the content of the compound represented by the formula 1 is 0.01 to 5% based on the total mass of the nonaqueous electrolyte solution for lithium ion batteries.
5. The nonaqueous electrolyte solution for a lithium ion battery according to any one of claims 1 to 4, wherein the compound represented by the structural formula 1 comprises one or more of the following compounds 1 to 12:
6. the nonaqueous electrolyte solution for lithium ion batteries according to any one of claims 1 to 4, wherein the nonaqueous electrolyte solution for lithium ion batteries further comprises one or more of vinylene carbonate, ethylene carbonate, and fluoroethylene carbonate;
The content of the vinylene carbonate, the ethylene carbonate and the fluoroethylene carbonate is respectively and independently 0.01-5% relative to the total mass of the electrolyte.
7. The nonaqueous electrolyte solution for lithium-ion batteries according to claims 1 to 4, wherein the nonaqueous electrolyte solution for lithium-ion batteries further comprises one or more of 1, 3-propane sultone, 1, 4-butane sultone, and 1, 3-propene sultone;
relative to the total mass of the electrolyte, the content of the 1, 3-propane sultone, the content of the 1, 4-butane sultone and the content of the 1, 3-propylene sultone are respectively and independently 0.01-5%.
8. The nonaqueous electrolyte solution for lithium ion batteries according to claim 1, wherein the nonaqueous electrolyte solution for lithium ion batteries further comprises a lithium salt and a nonaqueous organic solvent;
the lithium salt is selected from LiPF6、LiBF4、LiBOB、LiDFOB、LiF2PO2、LiSbF6、LiAsF6、LiN(SO2CF3)2、LiN(SO2C2F5)2、LiC(SO2CF3)3Or LiN (SO)2F)2One or more than two of the above;
the non-aqueous organic solvent is a mixture of cyclic carbonate and chain carbonate, the cyclic carbonate is selected from one or more of ethylene carbonate, propylene carbonate or butylene carbonate, and the chain carbonate is selected from one or more of dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate or propyl methyl carbonate.
9. A lithium ion battery comprising a positive electrode, a negative electrode, and a separator interposed between the positive electrode and the negative electrode, characterized by further comprising the lithium ion battery nonaqueous electrolytic solution according to any one of claims 1 to 8.
10. The li-ion battery of claim 9, wherein the active material of the positive electrode is selected from LiCoO2、LiNiO2、LiMn2O4、LiCo1-yMyO2、LiNi1-yMyO2、LiMn2-yMyO4And LiNixCoyMnzM1-x-y-zO2Wherein M is selected from one or more of Fe, Co, Ni, Mn, Mg, Cu, Zn, Al, Sn, B, Ga, Cr, Sr, V and Ti, y is more than or equal to 0 and less than or equal to 1, x is more than or equal to 0 and less than or equal to 1, z is more than or equal to 0 and less than or equal to 1, and x + y + z is less than or equal to 1;
alternatively, the active material of the positive electrode is selected from LiFe1-xMxPO4, wherein M is selected from one or more of Mn, Mg, Co, Ni, Cu, Zn, Al, Sn, B, Ga, Cr, Sr, V or Ti, and x is more than or equal to 0 and less than 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910352101.8A CN111864262A (en) | 2019-04-29 | 2019-04-29 | Lithium ion battery non-aqueous electrolyte and lithium ion battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910352101.8A CN111864262A (en) | 2019-04-29 | 2019-04-29 | Lithium ion battery non-aqueous electrolyte and lithium ion battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111864262A true CN111864262A (en) | 2020-10-30 |
Family
ID=72965295
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910352101.8A Pending CN111864262A (en) | 2019-04-29 | 2019-04-29 | Lithium ion battery non-aqueous electrolyte and lithium ion battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111864262A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115485903A (en) * | 2021-03-31 | 2022-12-16 | 株式会社Lg新能源 | Electrolyte solution additive for secondary battery, non-aqueous electrolyte solution for secondary battery containing said additive, and secondary battery |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1358337A (en) * | 2000-01-10 | 2002-07-10 | Lg化学株式会社 | New electrolytes and lithium ion battery using the same |
| CN102394314A (en) * | 2011-11-30 | 2012-03-28 | 天津力神电池股份有限公司 | Lithium ion battery electrolyte and lithium ion secondary battery |
| JP2012084384A (en) * | 2010-10-12 | 2012-04-26 | Mitsubishi Chemicals Corp | Nonaqueous electrolyte and nonaqueous electrolyte secondary battery using the same |
| CN103081208A (en) * | 2010-09-02 | 2013-05-01 | 日本电气株式会社 | Secondary battery and secondary battery electrolyte used therein |
| CN103875117A (en) * | 2011-10-21 | 2014-06-18 | 三井化学株式会社 | Nonaqueous electrolyte solution containing phosphonosulfonic acid compound, and lithium secondary battery |
| CN105161763A (en) * | 2015-08-03 | 2015-12-16 | 深圳新宙邦科技股份有限公司 | Non-aqueous electrolyte of lithium ion battery and lithium ion battery |
| US20160056505A1 (en) * | 2014-08-22 | 2016-02-25 | Samsung Sdi Co., Ltd. | Electrolyte and rechargeable lithium battery including the same |
| CN106450438A (en) * | 2016-10-17 | 2017-02-22 | 广州天赐高新材料股份有限公司 | Lithium-ion battery electrolyte and lithium ion battery with the same |
| JP2017147130A (en) * | 2016-02-17 | 2017-08-24 | 宇部興産株式会社 | Non-aqueous electrolyte and power storage device using the same |
| CN108110318A (en) * | 2016-11-25 | 2018-06-01 | 深圳新宙邦科技股份有限公司 | A kind of nonaqueous electrolytic solution and lithium ion battery for lithium ion battery |
| CN109659617A (en) * | 2018-12-28 | 2019-04-19 | 蜂巢能源科技有限公司 | Lithium ion secondary battery and its electrolyte |
-
2019
- 2019-04-29 CN CN201910352101.8A patent/CN111864262A/en active Pending
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1358337A (en) * | 2000-01-10 | 2002-07-10 | Lg化学株式会社 | New electrolytes and lithium ion battery using the same |
| CN103081208A (en) * | 2010-09-02 | 2013-05-01 | 日本电气株式会社 | Secondary battery and secondary battery electrolyte used therein |
| JP2012084384A (en) * | 2010-10-12 | 2012-04-26 | Mitsubishi Chemicals Corp | Nonaqueous electrolyte and nonaqueous electrolyte secondary battery using the same |
| CN103875117A (en) * | 2011-10-21 | 2014-06-18 | 三井化学株式会社 | Nonaqueous electrolyte solution containing phosphonosulfonic acid compound, and lithium secondary battery |
| CN102394314A (en) * | 2011-11-30 | 2012-03-28 | 天津力神电池股份有限公司 | Lithium ion battery electrolyte and lithium ion secondary battery |
| US20160056505A1 (en) * | 2014-08-22 | 2016-02-25 | Samsung Sdi Co., Ltd. | Electrolyte and rechargeable lithium battery including the same |
| CN105161763A (en) * | 2015-08-03 | 2015-12-16 | 深圳新宙邦科技股份有限公司 | Non-aqueous electrolyte of lithium ion battery and lithium ion battery |
| JP2017147130A (en) * | 2016-02-17 | 2017-08-24 | 宇部興産株式会社 | Non-aqueous electrolyte and power storage device using the same |
| CN106450438A (en) * | 2016-10-17 | 2017-02-22 | 广州天赐高新材料股份有限公司 | Lithium-ion battery electrolyte and lithium ion battery with the same |
| CN108110318A (en) * | 2016-11-25 | 2018-06-01 | 深圳新宙邦科技股份有限公司 | A kind of nonaqueous electrolytic solution and lithium ion battery for lithium ion battery |
| CN109659617A (en) * | 2018-12-28 | 2019-04-19 | 蜂巢能源科技有限公司 | Lithium ion secondary battery and its electrolyte |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115485903A (en) * | 2021-03-31 | 2022-12-16 | 株式会社Lg新能源 | Electrolyte solution additive for secondary battery, non-aqueous electrolyte solution for secondary battery containing said additive, and secondary battery |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109950620B (en) | Non-aqueous electrolyte for lithium ion battery and lithium ion battery | |
| CN102119463B (en) | Nonaqueous electrolyte and lithium cell using the same | |
| KR102154803B1 (en) | Lithium ion battery non-aqueous electrolyte and lithium ion battery using the same | |
| CN105336987A (en) | Non-aqueous electrolyte of lithium ion battery and lithium ion battery | |
| CN108110318B (en) | Non-aqueous electrolyte for lithium ion battery and lithium ion battery | |
| CN105789698B (en) | A lithium ion battery non-aqueous electrolyte and lithium ion battery | |
| CN109768327B (en) | Non-aqueous electrolyte of lithium ion battery and lithium ion battery using same | |
| CN113130992B (en) | Non-aqueous electrolyte and lithium ion battery | |
| CN113130995A (en) | Lithium ion battery | |
| CN109390630B9 (en) | Non-aqueous electrolyte of lithium ion battery and lithium ion battery using same | |
| CN112310467A (en) | Lithium ion battery | |
| CN110911748B (en) | Lithium secondary battery electrolyte and lithium secondary battery | |
| CN111224159A (en) | Non-aqueous electrolyte and lithium ion battery | |
| EP4376150A1 (en) | Non-aqueous electrolyte and lithium-ion battery | |
| CN110911744B (en) | Lithium ion battery non-aqueous electrolyte and lithium ion battery | |
| CN112310466B (en) | Lithium-ion battery non-aqueous electrolyte and lithium-ion battery containing the same | |
| CN114122493A (en) | Lithium-ion battery non-aqueous electrolyte and lithium-ion battery | |
| CN110661028B (en) | Lithium ion battery non-aqueous electrolyte and lithium ion battery | |
| CN111370764A (en) | Non-aqueous electrolyte and lithium ion battery containing same | |
| CN112310474A (en) | Non-aqueous electrolyte for lithium ion battery and lithium ion battery containing the same | |
| EP4243146B1 (en) | Lithium ion battery non-aqueous electrolyte and lithium ion battery | |
| CN111864262A (en) | Lithium ion battery non-aqueous electrolyte and lithium ion battery | |
| CN114583271A (en) | An electrolyte additive, electrolyte and lithium secondary battery | |
| CN115995606B (en) | Non-aqueous electrolyte of lithium ion battery and lithium ion battery | |
| CN111725563B (en) | Non-aqueous electrolyte of lithium ion battery and lithium ion battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20201030 |