CN113991176A - Nonaqueous electrolyte and lithium battery using same - Google Patents
Nonaqueous electrolyte and lithium battery using same Download PDFInfo
- Publication number
- CN113991176A CN113991176A CN202111209469.2A CN202111209469A CN113991176A CN 113991176 A CN113991176 A CN 113991176A CN 202111209469 A CN202111209469 A CN 202111209469A CN 113991176 A CN113991176 A CN 113991176A
- Authority
- CN
- China
- Prior art keywords
- lithium
- complex
- equal
- nonaqueous electrolyte
- carbonate
- 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.)
- Granted
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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic 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
Abstract
The invention discloses a nonaqueous electrolyte and a lithium battery using the same, belonging to the technical field of batteries; the nonaqueous electrolyte includes: a non-aqueous solvent; 5-20% of lithium salt by mass; the complex consists of organic matters of sulfonate and nitrogen and oxide of sulfur, and the mass percent of the complex is 0.1-5%. The complex contains sulfonic group and sulfur-containing compound, is an important organic film forming additive, can form a solid electrolyte liquid phase interfacial film on the surface of a battery electrode after being added into an electrolyte, inhibits the co-intercalation and reductive decomposition of solvent molecules at a negative electrode, and improves the cycle performance and the high-temperature performance of a lithium ion battery.
Description
Technical Field
The invention relates to the technical field of batteries, in particular to a nonaqueous electrolyte and a lithium battery using the same.
Background
The operating temperature range is one of the important performance indicators of the power supply system. The power system carried by the energy system and military equipment has a wide working temperature range which is not narrower than minus 40-55 ℃, however, the lithium ion battery is difficult to work in such a wide temperature range with high performance at present.
The wide temperature performance of the lithium ion battery has an obvious relationship with the anode, the electrolyte solution and the cathode. The positive electrode material is generally a determining factor for determining the working voltage and specific capacity of the lithium ion battery; the cathode material cooperates with the anode material to determine the capacity and voltage of the battery. The electrolyte acts to transfer Li+And the important role of communicating the internal circuitry,the requirements of higher boiling point, lower freezing point, higher ionic conductivity and the satisfaction of the charge-discharge chemical and electrochemical stability of the anode and the cathode are necessary conditions for the continuous and reversible work of the lithium ion battery. The wide temperature modification of the electrolyte is the most feasible and economic way for widening the working temperature range of the lithium ion battery at the present stage.
The main problems at high temperature of the electrolyte are the chemical decomposition of the electrolyte itself and the loss of the chemical passivation mechanism of the surface between the electrolyte and the positive and negative electrodes. Lithium salt in the electrolyte and a solvent may be subjected to chemical reaction at high temperature, and the surface chemical reaction rate of the positive and negative electrode materials and the electrolyte is increased, so that the dynamic stability is deteriorated, and the cyclic charge-discharge capacity of the battery is rapidly reduced at high temperature.
The lithium ion battery mainly has the diffusion problem at low temperature, and is a reversible process, and the diffusion does not cause obvious damage to the original battery composition and structure. Li+Diffusion rate in electrolyte and in electrode surface film, and Li+And electrons (e) are significantly reduced in charge transfer rate at the electrode electrolyte interface with decreasing temperature. Thus the resistance (R) of the electrolyte on the low temperature electrochemical impedance spectroscopy of the lithium ion battery0) Surface film resistance (R) of positive and negative electrodesi) And a charge transfer resistance (R)ct) Are significantly increased. Therefore, the problems of large resistance and poor wide-temperature performance of the conventional lithium ion battery need to be solved.
Disclosure of Invention
The present invention has been made to solve the above-mentioned problems occurring in the prior art, and an object of the present invention is to provide a nonaqueous electrolyte solution and a lithium battery using the same.
In order to achieve the purpose, the invention provides the following technical scheme:
a non-aqueous electrolyte comprising:
a non-aqueous solvent;
5-20% of lithium salt by mass;
the complex consists of organic matters of sulfonate and nitrogen and oxides of sulfur, and the mass percent of the complex is 0.1-5%; the complex has a structural formula as shown in formula 1:
in formula 1: r1 and R2 are alkyl or oxygen-containing alkyl with 1-6 carbon atoms, and x is 2 or 3.
As a further scheme of the invention: the complex is prepared by the following steps:
fully mixing fluorosulfonic acid and organic amine to obtain an intermediate product;
and (3) introducing sulfur oxide gas into the intermediate product, and completely reacting to obtain a complex.
As a further embodiment of the present invention, the lithium salt is LiPF6。
As a further aspect of the present invention, the nonaqueous electrolytic solution further includes:
the lithium salt additive accounts for 0.1 to 5 percent by mass.
As a further aspect of the invention, the lithium salt additive includes lithium difluorophosphate.
As a further aspect of the present invention, the lithium salt additive further includes at least one of a bis-oxalato borate salt, a lithium difluoro-oxalato borate salt, a lithium tetrafluorooxalato phosphate salt, and a lithium tetrafluoroborate salt.
In a further embodiment of the present invention, the nonaqueous solvent is at least one of ethylene carbonate, propylene carbonate and butylene carbonate, and at least one of dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate and propyl methyl carbonate.
As a further aspect of the present invention, the complex is one of formulae 2 to 9:
a lithium battery, comprising:
a positive electrode;
a negative electrode;
a separator disposed between the positive electrode and the negative electrode;
the nonaqueous electrolytic solution described above.
As a further scheme of the invention: the positive electrode comprises an active material, and the active material is LiNixCoyMnzL(1-x-y-z)O2、 Lix1MPO4、LiCox2L(1-x2)O2One of (1); wherein, L is one of Co, Al, Sr, Mg, Ti, Ca, Zr, Zn, Si and Fe; x is more than or equal to 0 and less than or equal to 1, y 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, x + y + z is more than 0 and less than or equal to 1, x1 is more than 0 and less than or equal to 1, x2 is more than 0 and less than or equal to 1, and M is one of Fe, Mn and Co.
Compared with the prior art, the invention has the beneficial effects that:
1. the complex contains sulfonic group and sulfur-containing compound, is an important organic film forming additive, and can form a solid electrolyte liquid phase interfacial film on the surface of a battery electrode after being added into an electrolyte, inhibit the co-intercalation and reductive decomposition of solvent molecules at a negative electrode, and improve the cycle performance and high-temperature performance of a lithium ion battery;
2. in the process of charging and discharging the lithium ion battery, LiPO2F2The film forming potential of the negative electrode is higher than that of a carbonate organic solvent, and the film forming potential of the negative electrode can effectively participate in the construction of a positive and negative electrode interface film, so that the positive and negative electrode interface film contains more inorganic compounds (phosphate and LiF) and promotes Li+The transfer and the stability of the SEI film act simultaneously, the stability of film formation of the battery cathode is ensured, the impedance is effectively reduced, and Li is promoted+The transfer of (2) improves the high-temperature and low-temperature performance of the battery;
3. one or more of lithium salt additives of bisoxalato borate (LiBOB), lithium difluorooxalato borate (LiODFB), lithium tetrafluorooxalato phosphate (LiTFOP) and lithium tetrafluoroborate (LiBF4) are added, a more stable anode passivation film can be formed in the battery cycle process, Fe ions of LiFePO4 can be effectively inhibited from being separated out under the high-temperature condition, the stability of the anode material under the high-temperature condition is ensured, meanwhile, the low charge transfer impedance is also realized, and the low-temperature storage discharge performance of the battery is effectively improved.
Detailed Description
The technical solution of the present patent will be described in further detail with reference to the following embodiments.
Examples 1 to 16
A lithium battery with positive electrode of LiFePO4The negative electrode is artificial graphite, the diaphragm is a microporous polyethylene film, and the used electrolyte is prepared from Ethylene Carbonate (EC): ethyl Methyl Carbonate (EMC): dimethyl carbonate (DMC) ═ 1: 1:1 (volume ratio) of mixed solvent in which LiPF is dissolved6Preparing 1mol/L solution, adding complex with corresponding mass concentration and LiPO with corresponding mass concentration2F2The complex has the following structural formula:
the electrolyte solution, the corresponding positive and negative electrodes, separator, and the like were fabricated into the nonaqueous cylindrical 18650 battery of the examples in tables 1 and 2 below, in the above manner.
TABLE 1
| Complex compounds | LiPO2F2 | LiODFB | |
| Example 1 | 0.5 | 0.25 | 1 |
| Example 2 | 0.5 | 0.5 | 1 |
| Example 3 | 0.5 | 1 | 1 |
| Example 4 | 0.5 | 2 | 1 |
| Example 5 | 1.0 | 0.25 | 1 |
| Example 6 | 1.0 | 0.5 | 1 |
| Example 7 | 1.0 | 1 | 1 |
| Example 8 | 1.0 | 2 | 1 |
| Example 9 | 1.5 | 0.25 | 1 |
| Example 10 | 1.5 | 0.5 | 1 |
| Example 11 | 1.5 | 1 | 1 |
| Example 12 | 1.5 | 2 | 1 |
| Example 13 | 2 | 0.25 | 1 |
| Example 14 | 2 | 0.5 | 1 |
| Example 15 | 2 | 1 | 1 |
| Example 16 | 2 | 2 | 1 |
| Comparative example 1 | Is free of | Is free of | 1 |
| Comparative example 2 | Is free of | 0.25 | 1 |
| Comparative example 3 | Is free of | 0.5 | 1 |
| Comparative example 4 | Is free of | 1 | 1 |
| Comparative example 5 | Is free of | 2 | 1 |
| Comparative example 6 | 0.25 | Is free of | 1 |
| Comparative example 7 | 0.5 | Is free of | 1 |
| Comparative example 8 | 1 | Is free of | 1 |
| Comparative example 9 | 2 | Is free of | 1 |
The batteries manufactured by the embodiment and the comparative example are subjected to performance test, and the test indexes and the test method are as follows:
(1) the normal-temperature cycle performance is embodied by testing the capacity retention rate of 1C cycle N times at room temperature, and the specific method comprises the following steps: charging the formed battery to 3.65V (LiFePO) at 25 ℃ by using a 1C constant current and constant voltage4Artificial graphite), the off current was 0.02C, and then the discharge was made to 2.0V with a constant current of 1C. After such charge/discharge cycles, the capacity retention rate after 500 weeks of cycles was calculated to evaluate the room temperature cycle performance.
The calculation formula of the capacity retention rate after 500 cycles at room temperature is as follows:
the 500 th cycle capacity retention (%) (500 th cycle discharge capacity/1 st cycle discharge capacity) × 100%.
(2) Testing battery impedance, namely charging the formed battery to 3.65V (LiFePO) by using 1C constant current and constant voltage4Artificial graphite), the cutoff current was 0.02C, and then constant current discharge was performed to 2.0V with 1C, and the initial discharge capacity of the battery was measured. The discharge was then carried out at 1C to 50% capacity, and after leaving for 1 hour, the discharge was carried out for 10S at 3C to calculate the value of the DC resistance DCIR.
(3) Low temperature discharge rate, charging the battery to 3.65V (LiFePO) with 1C constant current and constant voltage4Artificial graphite) and cutoff current of 0.02C, then discharging to 2.0V at constant current of 0.2C, and measuring the normal-temperature discharge capacity of the battery. The cell was charged to 3.65V at room temperature with a constant current and voltage of 1C and a cutoff current of 0.02C. The battery is cooled to-20 ℃, and after being placed for 20 hours, the battery is discharged to 2.0V by using 0.2C current, so that the discharge capacity at low temperature is obtained.
The calculation formula of the discharge capacity retention rate at-20 ℃ is as follows:
-20 ℃ discharge capacity retention (%) — (20 ℃ discharge capacity/room temperature discharge capacity) × 100%.
(4) High-temperature discharge rate, and charging the formed battery to 3.65V (LiFePO) by using 1C constant current and constant voltage4Artificial graphite) and cutoff current of 0.02C, then discharging to 2.0V at constant current of 0.2C, and measuring the normal-temperature discharge capacity of the battery. The cell was charged to 3.65V at room temperature with a constant current and voltage of 1C and a cutoff current of 0.02C. The battery was heated to 45 ℃ and left to stand for 4 hours, and then discharged to 2.0V with a current of 0.2C, to obtain the discharge capacity at high temperature.
The calculation formula of the discharge capacity retention rate at 45 ℃ is as follows:
discharge capacity retention (%) at 45 ℃ ═ 100% (discharge capacity at 45 ℃ per discharge capacity at room temperature).
TABLE 2
As is clear from tables 1 and 2, the cycle retention at room temperature of the battery containing the complex and lithium difluorophosphate in the nonaqueous electrolytic solution was improved, the impedance of the battery was reduced, and the high-temperature and low-temperature discharge capacity was also improved, as compared with comparative examples 1 to 5 which did not contain the complex. Further, the nonaqueous electrolytic solution containing both the complex and lithium difluorophosphate reduced the resistance of the battery and improved the high and low temperature discharge capacity of the battery, as compared with comparative examples 6 to 9 in which the complex was added alone.
Example 17
A lithium battery with positive electrode of LiNixCoyMnzL(1-x-y-z)O2Wherein L is one of Co, Al, Sr, Mg, Ti, Ca, Zr, Zn, Si and Fe, and can be specifically as follows: LiNi0.33Co0.33Mn0.3302，LiNi0.4Co0.2Mn0.402，LiNi0.4Co0.3Mn0.302， LiNi0.5Co0.2Mn0.302，LiNi0.6Co0.2Mn0.202，LiNi0.8Co0.1Mn0.102，LiNi0.9Co0.05Mn0.0502， LiNi0.33Co0.33Mn0.27Al0.0602，LiNi0.6Co0.17Mn0.2Mg0.0302，LiNi0.305Co0.33Mn0.33Ti0.02502， LiNi0.33Co0.305Mn0.33Ti0.02502，LiNi0.33Co0.33Mn0.305Ti0.02502，LiNi0.784Co0.1Mn0.1Ca0.01602， LiNi0.768Co0.1Mn0.1Ca0.03202，LiNi0.736Co0.1Mn0.1Ca0.06402，LiNi0.5Co0.2Mn0.29Zr0.0102， LiNi0.33 3Co0.292Mn0.333Zn0.04102，LiNi0.333Co0.25Mn0.333Zn0.08302，LiNi0.333Co0.166Mn0.333Zn0.16702， LiNi0.333Co0.3Mn0.333Fe0.03302，LiNi0.333Co0.233Mn0.333Fe0.102，LiNi0.333Co0.166Mn0.333Fe0.16602， LiNi0.333Co0.1Mn0.333Fe0.23302，LiNi0.333Co0.033Mn0.333Fe0.302(ii) a The negative electrode is artificial graphite, the diaphragm is a microporous polyethylene film, and the used electrolyte is prepared from Ethylene Carbonate (EC): dimethyl carbonate (DMC) ═ 1:1 (volume ratio) of mixed solvent in which LiPF is dissolved6Preparing 1mol/L solution, adding complex and phase with corresponding mass concentrationLiPO in accordance with mass concentration2F2The complex has the following structural formula:
the complex is prepared by the following method:
respectively weighing fluorosulfonic acid and organic amine with target mass in a closed glove box (water and oxygen content is less than or equal to 0.5PPM), adding fluorosulfonic acid into a clean beaker, slowly pouring an organic amine solvent into the beaker while stirring, and fully reacting to obtain organic matters; and (3) introducing sulfur oxide gas into the beaker by using a tetrafluoride pipe until complete reaction, wherein the reaction formula is as follows:
example 18
A lithium battery has LiCo as positive electrodex2L(1-x2)O2Wherein L is one of Co, Al, Sr, Mg, Ti, Ca, Zr, Zn, Si and Fe, and x2 is more than 0 and less than or equal to 1; the negative electrode is artificial graphite, the diaphragm is a microporous polyethylene film, and the used electrolyte is prepared from Ethylene Carbonate (EC): dimethyl carbonate (DMC) ═ 1:1 (volume ratio) of mixed solvent in which LiPF is dissolved6Preparing 1mol/L solution, adding complex with corresponding mass concentration and LiPO with corresponding mass concentration2F2With bis (oxalato) borate (LiBOB), the complex formula is as follows:
example 19
A lithium battery has a positive electrode of LiCoPO4The negative electrode is artificial graphite, the diaphragm is a microporous polyethylene film, and the electrolyte used is prepared from Propylene Carbonate (PC): diethyl carbonate (DEC) ═ 1:1 (volume ratio) of mixed solvent in which LiPF is dissolved6To prepare a 1mol/L solutionIn addition, a corresponding mass concentration of a complex is added, and a corresponding mass concentration of LiPO is added2F2With lithium difluorooxalato borate (LiODFB), the complex formula is as follows:
example 20
A lithium battery with anode of LiMnPO4The negative electrode is artificial graphite, the diaphragm is a microporous polyethylene film, and the used electrolyte is prepared from Ethylene Carbonate (EC): butylene Carbonate (BC): dimethyl carbonate (DMC): methyl Propyl Carbonate (MPC) ═ 1: 1: 1:1 (volume ratio) of mixed solvent in which LiPF is dissolved6Preparing 1mol/L solution, adding complex with corresponding mass concentration and LiPO with corresponding mass concentration2F2With lithium tetrafluoro oxalate phosphate (LiTFOP), the complex formula is as follows:
example 21
A lithium battery with anode of LiMnPO4The negative electrode is artificial graphite, the diaphragm is a microporous polyethylene film, and the electrolyte used is prepared from Propylene Carbonate (PC): butylene Carbonate (BC): diethyl carbonate (DEC): methyl Propyl Carbonate (MPC) ═ 1: 1: 1:1 (volume ratio) of mixed solvent in which LiPF is dissolved6Preparing 1mol/L solution, adding complex with corresponding mass concentration and LiPO with corresponding mass concentration2F2With lithium tetrafluoroborate (LiBF4), the complex formula is as follows:
example 22
A lithium battery has a positive electrode of LiCoPO4The negative pole is artificial graphite, the diaphragm is microporous polyethylene film, and the electrolyte is ethylene carbonateAlkenyl Ester (EC): propylene Carbonate (PC): butylene Carbonate (BC): dimethyl carbonate (DMC): diethyl carbonate (DEC): ethyl Methyl Carbonate (EMC) ═ 1: 1: 1: 1: 1:1 (volume ratio) of mixed solvent in which LiPF is dissolved6Preparing 1mol/L solution, adding complex with corresponding mass concentration and LiPO with corresponding mass concentration2F2Bisoxalato borate (LiBOB) and lithium tetrafluorooxalato phosphate (litfo), the complex formula is as follows:
example 23
A lithium battery has a positive electrode of LiCoPO4The negative electrode is artificial graphite, the diaphragm is a microporous polyethylene film, and the used electrolyte is prepared from Ethylene Carbonate (EC): propylene Carbonate (PC): butylene Carbonate (BC): dimethyl carbonate (DMC): diethyl carbonate (DEC): ethyl Methyl Carbonate (EMC): methyl Propyl Carbonate (MPC) ═ 1: 1: 1: 1: 1: 1:1 (volume ratio) of mixed solvent in which LiPF is dissolved6Preparing 1mol/L solution, adding complex with corresponding mass concentration and LiPO with corresponding mass concentration2F2Bisoxalato borate (LiBOB), lithium difluorooxalato borate (LiODFB), and lithium tetrafluorooxalato phosphate (LiTFOP), the complex structural formula being as follows:
example 24
A lithium battery has a positive electrode of LiCoPO4The negative electrode is artificial graphite, the diaphragm is a microporous polyethylene film, and the used electrolyte is prepared from Ethylene Carbonate (EC): propylene Carbonate (PC): butylene Carbonate (BC): dimethyl carbonate (DMC): diethyl carbonate (DEC): ethyl Methyl Carbonate (EMC): methyl Propyl Carbonate (MPC) ═ 1: 1: 1: 1: 1: 1:1 (volume ratio) of mixed solvent in which LiPF is dissolved6Preparing 1mol/L solution, adding complex with corresponding mass concentration and LiPO with corresponding mass concentration2F2Bisoxalato borate (LiBOB), lithium difluorooxalato borate (LiODFB), lithium tetrafluorooxalato phosphate (LiTFOP) and lithium tetrafluoroborate (LiBF4), the complex structural formula is as follows:
LiPO2F2is a commonly used lithium ion battery non-aqueous electrolyte additive at present. In the process of charging and discharging the lithium ion battery, LiPO2F2The film forming potential of the negative electrode is higher than that of a carbonate organic solvent, and the film forming potential of the negative electrode can effectively participate in the construction of a positive and negative electrode interface film, so that the positive and negative electrode interface film contains more inorganic compounds (phosphate and LiF) and promotes Li+The structural formula of (a) and the stability of the SEI film are as follows:
the two act simultaneously, ensure the stability of film formation of the battery cathode, effectively reduce the impedance and promote Li+The high and low temperature performance of the battery is improved.
One or more of lithium salt additives of bisoxalato borate (LiBOB), lithium difluorooxalato borate (LiODFB), lithium tetrafluorooxalato phosphate (LiTFOP) and lithium tetrafluoroborate (LiBF4) are added, so that a more stable anode passivation film can be formed in the battery cycle process, and LiFePO is effectively inhibited4The Fe ions are separated out under the high-temperature condition, so that the stability of the positive electrode material under the high-temperature condition is ensured, the low charge transfer impedance is realized, and the low-temperature storage discharge performance of the battery is effectively improved. Furthermore, it should be understood that although the description is provided in terms of embodiments, not every embodiment may include only a single embodiment, and such descriptions are provided for clarity only, and those skilled in the art will recognize that the embodiments described herein may be combined as a whole, and the embodiments described herein may be combined as appropriate to form a single embodiment, or that the embodiments described herein may be combined as a whole, or that the embodiments described herein may be combined as a part of a single embodiment, or that the embodiments described herein may be combined as appropriate to form a single embodiment, or that may be combined as a single embodiment, or that may be combined in any combination of embodiments described hereinOther embodiments are understood.
Claims (10)
1. A nonaqueous electrolyte solution characterized by comprising:
a non-aqueous solvent;
5-20% of lithium salt by mass;
the complex consists of organic matters of sulfonate and nitrogen and oxides of sulfur, and the mass percent of the complex is 0.1-5%; the complex has a structural formula as shown in formula 1:
in formula 1: r1、R2Is a hydrocarbon group or oxygen-containing hydrocarbon group having 1 to 6 carbon atoms, and x is 2 or 3.
2. The nonaqueous electrolyte solution according to claim 1, wherein the complex is prepared by:
fully mixing fluorosulfonic acid and organic amine to obtain an intermediate product;
and (3) introducing sulfur oxide gas into the intermediate product, and completely reacting to obtain a complex.
3. The nonaqueous electrolyte solution according to claim 1, wherein the lithium salt is LiPF6。
4. The nonaqueous electrolyte solution according to claim 1, further comprising:
the lithium salt additive accounts for 0.1 to 5 percent by mass.
5. The nonaqueous electrolyte of claim 4, wherein the lithium salt additive includes lithium difluorophosphate.
6. The nonaqueous electrolyte of claim 5, wherein the lithium salt additive further comprises at least one of a bisoxalato borate salt, a lithium difluorooxalato borate salt, a lithium tetrafluorooxalato phosphate salt, and a lithium tetrafluoroborate salt.
7. The nonaqueous electrolyte solution of claim 1, wherein the nonaqueous solvent is obtained by mixing at least one of ethylene carbonate, propylene carbonate, and butylene carbonate with at least one of dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, and propyl methyl carbonate.
8. The nonaqueous electrolyte solution according to claim 1, wherein the complex is one of formulae 2 to 9:
9. a lithium battery, comprising:
a positive electrode;
a negative electrode;
a separator disposed between the positive electrode and the negative electrode;
the non-aqueous electrolyte according to any one of claims 1 to 8.
10. The lithium battery of claim 9, wherein the positive electrode comprises an active material that is LiNixCoyMnzL(1-x-y-z)O2、Lix1MPO4、LiCox2L(1-x2)O2One of (1); wherein, L is one of Co, Al, Sr, Mg, Ti, Ca, Zr, Zn, Si and Fe; x is more than or equal to 0 and less than or equal to 1, y 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, x + y + z is more than 0 and less than or equal to 1, x1 is more than 0 and less than or equal to 1, x2 is more than 0 and less than or equal to 1, and M is one of Fe, Mn and Co.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111209469.2A CN113991176B (en) | 2021-10-18 | 2021-10-18 | Nonaqueous electrolyte and lithium battery using same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111209469.2A CN113991176B (en) | 2021-10-18 | 2021-10-18 | Nonaqueous electrolyte and lithium battery using same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113991176A true CN113991176A (en) | 2022-01-28 |
| CN113991176B CN113991176B (en) | 2022-08-19 |
Family
ID=79739069
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111209469.2A Active CN113991176B (en) | 2021-10-18 | 2021-10-18 | Nonaqueous electrolyte and lithium battery using same |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113991176B (en) |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005251523A (en) * | 2004-03-03 | 2005-09-15 | Samsung Sdi Co Ltd | Proton conductive electrolyte and fuel cell |
| CN104907088A (en) * | 2015-04-30 | 2015-09-16 | 北京化工大学 | Method for preparing transition metal sulfide/sulfur-nitrogen co-doped carbon composite material |
| US20170200974A1 (en) * | 2014-07-16 | 2017-07-13 | Daikin Industries, Ltd. | Electrolyte solution and method for producing sulfate salt |
| CN107074543A (en) * | 2014-04-18 | 2017-08-18 | 阿肯马法国公司 | Prepare the acid imide containing fluorosulfonyl group |
| WO2020109720A1 (en) * | 2018-11-28 | 2020-06-04 | Arkema France | Process for producing lithium bis(fluorosulfonyl)imide salt |
| CN111883834A (en) * | 2020-07-24 | 2020-11-03 | 香河昆仑化学制品有限公司 | Non-aqueous lithium ion battery electrolyte additive, electrolyte containing non-aqueous lithium ion battery electrolyte additive and lithium ion battery |
| CN111883841A (en) * | 2020-08-05 | 2020-11-03 | 香河昆仑化学制品有限公司 | Lithium ion battery non-aqueous electrolyte and lithium ion battery |
| CN113508485A (en) * | 2019-02-27 | 2021-10-15 | 大金工业株式会社 | Electrolyte solution, electrochemical device, lithium ion secondary battery, and module |
-
2021
- 2021-10-18 CN CN202111209469.2A patent/CN113991176B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005251523A (en) * | 2004-03-03 | 2005-09-15 | Samsung Sdi Co Ltd | Proton conductive electrolyte and fuel cell |
| CN107074543A (en) * | 2014-04-18 | 2017-08-18 | 阿肯马法国公司 | Prepare the acid imide containing fluorosulfonyl group |
| US20170200974A1 (en) * | 2014-07-16 | 2017-07-13 | Daikin Industries, Ltd. | Electrolyte solution and method for producing sulfate salt |
| CN104907088A (en) * | 2015-04-30 | 2015-09-16 | 北京化工大学 | Method for preparing transition metal sulfide/sulfur-nitrogen co-doped carbon composite material |
| WO2020109720A1 (en) * | 2018-11-28 | 2020-06-04 | Arkema France | Process for producing lithium bis(fluorosulfonyl)imide salt |
| CN113508485A (en) * | 2019-02-27 | 2021-10-15 | 大金工业株式会社 | Electrolyte solution, electrochemical device, lithium ion secondary battery, and module |
| CN111883834A (en) * | 2020-07-24 | 2020-11-03 | 香河昆仑化学制品有限公司 | Non-aqueous lithium ion battery electrolyte additive, electrolyte containing non-aqueous lithium ion battery electrolyte additive and lithium ion battery |
| CN111883841A (en) * | 2020-08-05 | 2020-11-03 | 香河昆仑化学制品有限公司 | Lithium ion battery non-aqueous electrolyte and lithium ion battery |
Non-Patent Citations (1)
| Title |
|---|
| DARJA RUDAN-TASIC等: "A conductometric study of aqueous solutions of some cyclohexylsulfamates", 《JOURNAL OF SOLUTION CHEMISTRY》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113991176B (en) | 2022-08-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104505535B (en) | A kind of nonaqueous electrolytic solution of high-voltage lithium ion batteries | |
| CN110911752A (en) | Low-internal-resistance lithium secondary battery electrolyte and lithium secondary battery | |
| CN108808071B (en) | Electrolyte for high-nickel ternary positive electrode material system battery and lithium ion battery | |
| CN107293781B (en) | Electrolyte and lithium ion battery | |
| CN109390628B (en) | Non-aqueous electrolyte and lithium ion battery | |
| CN109687026B (en) | High-voltage ternary lithium ion battery electrolyte and lithium ion battery containing same | |
| CN113517470A (en) | High-nickel high-voltage ternary lithium ion battery non-aqueous electrolyte and lithium ion battery | |
| CN112331914A (en) | Non-aqueous electrolyte of lithium ion battery without ethylene carbonate solvent and battery | |
| CN113381072A (en) | Electrolyte and battery containing the same | |
| CN110783628A (en) | Non-aqueous electrolyte of lithium ion battery and lithium ion battery using same | |
| CN112786964A (en) | High-voltage high-energy-density electrolyte and lithium battery thereof | |
| CN112531211A (en) | Electrolyte, preparation method thereof and lithium ion battery | |
| CN114024030B (en) | Non-aqueous electrolyte and battery containing same | |
| CN114725392A (en) | Lithium ion battery | |
| CN113972398B (en) | Nonaqueous electrolyte and nonaqueous electrolyte battery using same | |
| CN112490505A (en) | Electrolyte additive, non-aqueous electrolyte and lithium ion battery thereof | |
| CN114520371B (en) | Nonaqueous electrolyte and lithium ion battery comprising same | |
| CN110808413A (en) | Non-aqueous electrolyte of lithium ion battery and lithium ion battery using same | |
| CN111952667B (en) | Electrolyte additive, electrolyte containing additive and lithium ion battery | |
| CN113991176B (en) | Nonaqueous electrolyte and lithium battery using same | |
| CN114583281A (en) | High-voltage-resistant ether-based electrolyte for low-temperature lithium metal battery | |
| CN111342133B (en) | Novel non-aqueous electrolyte for lithium ion battery and lithium ion battery | |
| CN110556579B (en) | Electrolyte and lithium ion battery containing same | |
| CN114566711A (en) | Electrolyte, preparation method thereof and high-nickel lithium ion battery containing electrolyte | |
| CN113764731A (en) | Application of dioxazalone compound in battery electrolyte |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |