CN114156533B - Lithium ion battery gel electrolyte and preparation method of lithium ion battery - Google Patents
Lithium ion battery gel electrolyte and preparation method of lithium ion battery Download PDFInfo
- Publication number
- CN114156533B CN114156533B CN202210123894.8A CN202210123894A CN114156533B CN 114156533 B CN114156533 B CN 114156533B CN 202210123894 A CN202210123894 A CN 202210123894A CN 114156533 B CN114156533 B CN 114156533B
- Authority
- CN
- China
- Prior art keywords
- lithium ion
- gel
- ion battery
- gel electrolyte
- electrolyte
- 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.)
- Active
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
- H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2220/00—Batteries for particular applications
- H01M2220/10—Batteries in stationary systems, e.g. emergency power source in plant
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2220/00—Batteries for particular applications
- H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2220/00—Batteries for particular applications
- H01M2220/30—Batteries in portable systems, e.g. mobile phone, laptop
-
- 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
- H01M2300/0085—Immobilising or gelification of electrolyte
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention discloses a lithium ion battery gel electrolyte, wherein raw materials for preparing the gel electrolyte comprise a gel factor and a non-aqueous electrolyte; the gel factor comprises a gel monomer, a cross-linking agent and an initiator; the gel monomer is methoxy vinyl pyridine compound, R on pyridine ring thereof1Is a hydrogen atom or an alkyl group; r2‑R5Independently selected from one of a hydrogen atom, a methoxyvinyl group and an alkoxy group, and R2‑R5At least one of which is a methoxyvinyl group. The pyridine in the lithium ion battery gel electrolyte improves the thermal stability of lithium hexafluorophosphate and inhibits the dissolution of transition metal ions of the anode; and nitrogen atoms and methoxyl groups in the monomers construct a short-range transmission continuous channel for repeated lithium ion deintercalation, so that the resistance of lithium ion transmission between adjacent structural units is reduced, a long-chain reticular channel which is continuous in the repeated lithium ion deintercalation and short-range lithium ion transmission and can be conducted remotely is formed, and the cycle performance, the high-temperature performance and the low-temperature performance of the battery are improved.
Description
Technical Field
The invention belongs to the technical field of gel lithium ion batteries, and particularly relates to a lithium ion battery gel electrolyte and a preparation method of a lithium ion battery.
Background
With excellent application of lithium ion batteries in aspects such as storage systems of renewable energy power plants, electric vehicles, unmanned aerial vehicles and portable electronic devices, people have higher and higher requirements on lithium ion batteries. Although the lithium ion battery with the liquid electrolyte has higher conductivity, the battery has serious potential safety hazard due to the defects of flammability, volatility and easy leakage of the electrolyte. The lithium ion battery with the all-solid electrolyte improves the safety of the battery because the non-combustible electrolyte replaces the flammable liquid electrolyte, but the practical application of the all-solid electrolyte is still limited by the defects of low room-temperature ionic conductivity of the all-solid electrolyte, slow electrode/electrolyte interface transmission dynamics and the like.
The gel lithium ion battery has the advantages of higher safety of a solid battery and good ionic conductivity of a liquid battery due to the gel electrolyte formed by in-situ polymerization of the liquid electrolyte, and becomes a hot point of research. Research on gel lithium ion batteries has focused on extending cycle life, broadening operating temperature range, and improving battery safety. However, in the prior art, the problem that the electrolyte cannot be compatible with high and low temperatures generally exists in the in-situ polymerization gel electrolyte battery, which greatly limits the working temperature range of the gel lithium ion battery.
Disclosure of Invention
The purpose of the invention is as follows: the gel electrolyte of the lithium ion battery is provided, and the prepared gel lithium ion battery has good cycle performance, and excellent high-temperature performance and low-temperature performance.
The technical scheme of the invention is as follows:
a lithium ion battery gel electrolyte is prepared by the steps that raw materials for preparing the gel electrolyte comprise a gel factor and a non-aqueous electrolyte; the gel factor comprises a gel monomer, a cross-linking agent and an initiator; the gel monomer is a methoxy vinyl pyridine compound, and the chemical structural formula of the gel monomer is as follows:
wherein: r1Is a hydrogen atom or an alkyl group; r2- R5Independently selected from one of a hydrogen atom, a methoxyvinyl group and an alkoxy group, and R2- R5At least one of which is a methoxyvinyl group.
The raw materials of the lithium ion battery gel electrolyte comprise a methoxy vinyl pyridine compound serving as a gel monomer, when the gel monomer is subjected to in-situ polymerization in a lithium ion battery to form the gel electrolyte, the gel monomer is polymerized in the presence of a cross-linking agent to generate a long-chain mesh polymer gel containing a plurality of pyridines and methoxyl groups, a long-chain mesh structure containing a plurality of pyridines and methoxyl groups serves as a skeleton in the gel, and lithium ions in a nonaqueous electrolyte are filled in the mesh skeleton; because the nitrogen atom and the methoxyl group in the pyridine structure can perform repeated deintercalation on lithium ions in the charging and discharging processes of the battery, the methoxyl group and the nitrogen atom in the same structural unit interact with each other in the charging and discharging processes of the battery, a phase continuous channel for short-range transmission of the repeated deintercalation of the lithium ions is constructed, and the resistance of the transmission of the lithium ions between two adjacent structural units is reduced; the interaction of a plurality of nitrogen atoms and a plurality of methoxyl groups in a plurality of pyridines in the plurality of reticular polymer gels with long chains forms a reticular channel with long chains, wherein the reticular channel is used for repeatedly deintercalating lithium ions, and the transmission of short-range lithium ions is continuous and can be conducted remotely, so that the transmission channel of the lithium ions is longer and continuous, the conduction rate and efficiency of the lithium ions are improved, and the battery is favorable for maintaining good electrical property after multiple cycles, thereby improving the cycle performance of the battery; the capacity of the battery in a low-temperature environment can be exerted, and the low-temperature performance of the battery is improved. The network polymer gel structure having a long chain contributes to improvement of mechanical strength of the electrolyte gel. The pyridine in the network polymer gel with long chains can also form a stable complex with transition metal ions dissolved out of the positive active material, so that the transition metal ions are prevented from migrating to the surface of the negative electrode in the electrolyte, the transition metal is prevented from depositing on the surface of the negative electrode to influence the behavior of the battery for releasing and inserting lithium ions, and the interface stability of the electrode and the high-temperature performance of the battery are improved. In addition, nitrogen atoms in pyridine rings in the long-chain reticular polymer gel have Lewis basicity, so that phosphorus pentafluoride generated by decomposition of lithium hexafluorophosphate under a high-temperature condition can be effectively compounded, ring-opening decomposition of a cyclic carbonate solvent in the non-aqueous electrolyte caused by the phosphorus pentafluoride is avoided, the stability of the non-aqueous electrolyte under the high-temperature condition is improved, generation of hydrofluoric acid caused by decomposition of lithium hexafluorophosphate is inhibited, side reactions on an electrolyte and electrode interface are reduced, and the high-temperature performance of the battery is improved.
The lithium ion battery gel electrolyte has a long-chain net structure, has good mechanical strength, can be always in good contact with the surface of a negative electrode, and has small contact resistance, good conductivity and good cycle performance. In addition, the compact structure of the gel electrolyte promotes the surface of the negative electrode to form a uniform and stable solid electrolyte intermediate phase layer, so that the interface impedance can be reduced, the reaction of an organic solvent and a negative electrode active material is reduced, the growth of lithium dendrites is inhibited, and the low-temperature performance and the cycling stability of the battery are improved.
Preferably, the gel monomer is at least one of 2-methoxy-5- [ (E) -2-methoxyvinyl ] pyridine, 2- [ (Z) -2-methoxyvinyl ] pyridine, 3- [ (E) -2-methoxyvinyl ] pyridine, 4- [ (E) -2-methoxyvinyl ] pyridine and 5- [ (E) -2-methoxyvinyl ] -2-methylpyridine.
Preferably, the mass of the gel monomer is 1-5% of the total mass of the raw materials.
Preferably, the cross-linking agent is a chain acrylate compound, and the cross-linking agent at least contains two carbon-carbon double bonds. In the gel monomer formed by the chain acrylic ester crosslinking agent with two carbon-carbon double bonds, the filling and the detaching of lithium ions are high in efficiency, and the prepared battery has good cycle performance.
Preferably, the crosslinking agent contains at least two acrylate groups.
Preferably, the crosslinking agent is at least one of tetraethylene glycol diacrylate, diethylene glycol diacrylate, 1, 9-nonanediol diacrylate, triethylene glycol diacrylate, 1, 3-propane diol diacrylate, 1, 4-butanediol diacrylate, 1, 6-hexanediol diacrylate, 1, 10-decanediol diacrylate, 1, 5-pentanediol diacrylate, and but-2-enylene diacrylate.
Preferably, the mass of the cross-linking agent is 1-5% of the total mass of the raw materials.
Preferably, the initiator is dibenzoyl peroxide, acetyl peroxide, di-tert-butyl peroxide, azobisisobutyronitrile or azobisisoheptonitrile, and the mass of the initiator is 0.1-0.5% of the total mass of the raw materials.
Preferably, the nonaqueous electrolytic solution is a solution in which lithium hexafluorophosphate is dissolved in at least one of ethylene carbonate, diethyl carbonate, dimethyl carbonate, and ethyl methyl carbonate.
The invention also provides a preparation method of the lithium ion battery containing the lithium ion battery gel electrolyte, which comprises the following steps:
step one, preparing gel electrolyte:
uniformly mixing the methoxy vinyl pyridine compound monomer and the cross-linking agent, then adding the obtained mixture into the non-aqueous electrolyte, uniformly mixing, adding the initiator, and uniformly mixing to obtain a gel electrolyte;
step two, preparing the lithium ion battery:
and (3) adding the gel electrolyte prepared in the step one into a soft package lithium ion battery cell, sealing, standing, forming, heating to 65-85 ℃ for polymerization for 5-9 hours, exhausting air, and sealing.
In the method, after the methoxy vinyl pyridine compound monomer, the cross-linking agent and the non-aqueous electrolyte are mixed in the first step, the initiator is added, and in-situ polymerization is carried out at the temperature of 65-85 ℃ in the second step to generate the electrolyte of the network polymer gel with long chains, and the electrolyte is attached to the positive electrode and the negative electrode, sealed and formed to prepare the gel lithium ion battery.
The invention has the beneficial effects that:
the lithium ion battery gel electrolyte is prepared from methoxy vinyl pyridine compounds, is a long-chain reticular polymer gel containing a plurality of pyridines and methoxy groups, is filled with a non-aqueous electrolyte in a long-chain reticular structure skeleton, and the interaction between nitrogen atoms and the methoxy groups in the pyridine structure constructs a continuous channel for short-range transmission for repeated deintercalation of lithium ions, reduces the resistance for lithium ion transmission between two adjacent structural units, forms a long-chain reticular channel for continuous transmission and long-range conduction of the repeated deintercalation and short-range lithium ions of the lithium ions, improves the speed and efficiency of lithium ion conduction, and improves the cycle performance and the low-temperature performance of the battery; the nitrogen atoms in the pyridine rings in the long-chain mesh polymer gel are also compounded with phosphorus pentafluoride generated by the decomposition of lithium hexafluorophosphate at high temperature, so that the high-temperature performance of the battery is improved; the battery prepared by the lithium ion gel electrolyte can be used in a wider temperature range.
Detailed Description
The present invention will be described in detail with reference to examples.
Example 1
Step one, preparing gel electrolyte:
in an argon-filled glove box (moisture < 0.1ppm, oxygen < 0.1ppm), ethylene carbonate, diethyl carbonate, dimethyl carbonate and ethyl methyl carbonate were mixed in a ratio of 1: 1: 1: 3, then slowly adding lithium hexafluorophosphate into the mixed solution to enable the concentration of the lithium hexafluorophosphate to be 1.1mol/L, and stirring until the lithium hexafluorophosphate is completely dissolved to obtain the nonaqueous electrolytic solution.
Firstly, uniformly mixing gel monomer 2-methoxy-5- [ (E) -2-methoxyvinyl ] pyridine and cross-linking agent tetraethyleneglycol diacrylate, then adding the obtained mixture into the prepared non-aqueous electrolyte for fully stirring, adding initiator azobisisobutyronitrile into the non-aqueous electrolyte, and completely dissolving and uniformly stirring to obtain the gel electrolyte. Wherein the mass ratio of each substance is as follows: 2-methoxy-5- [ (E) -2-methoxyvinyl ] pyridine 1%, tetraethyleneglycol diacrylate 1%, nonaqueous electrolyte 97.8%, azobisisobutyronitrile 0.2%.
Step two, preparing the lithium ion battery
And (3) adding 9g of the gel electrolyte prepared in the step one into a 1.8Ah soft package lithium ion battery cell with lithium cobaltate as a positive electrode and composite graphite as a negative electrode, sealing, standing at 40 ℃ for 24 hours, fully infiltrating, forming, heating the battery to 65 ℃, polymerizing for 5 hours, exhausting, and sealing to obtain the gel electrolyte lithium ion battery.
Examples 2 to 12
A gel electrolyte was prepared in the same manner as in example 1, and then a lithium ion battery was prepared. The mass percentages of the substances in the gel electrolyte are shown in table 1, and the polymerization temperature and the polymerization time when the lithium ion battery is prepared are shown in table 1.
Comparative example 1
The comparative example is different from example 2 only in that a gel monomer used in preparing a gel electrolyte is different, the gel monomer used in the comparative example is [ (vinyloxy) methoxy ] ethylene without a pyridine ring, and the preparation methods of the rest of the gel electrolyte and the preparation method and model of the lithium ion battery are completely the same.
And (3) testing the battery performance:
the lithium ion gel batteries prepared in the above examples and comparative examples were subjected to the following battery performance tests, respectively:
1. normal temperature cycle performance: charging the lithium ion gel battery to 4.35V at a constant current of 0.5C at 25 ℃, and then charging to a cut-off current of 0.01C at a constant voltage; then discharged to 3.0V at a constant current of 0.5C. The capacity retention rate at the 300 th cycle was calculated after 300 cycles according to the above charge-discharge system, and the results are shown in table 2.
Capacity retention ratio (%) at 300 th cycle = (300 th cycle discharge capacity/1 st cycle discharge capacity) × 100%.
2. High temperature storage performance: charging the lithium ion gel battery to 4.35V at a constant current of 0.5C at 25 ℃, then charging to a cut-off current of 0.01C at a constant voltage, then discharging to 3.0V at a constant current of 0.5C, and recording the discharge capacity which is taken as the initial capacity of the battery before storage; then the battery is charged to 4.35V by a constant current of 0.5C, and then is charged to a cut-off current of 0.01C by a constant voltage, namely, a full state; then the battery is placed in a 60 ℃ oven for storage for 14 days, after the storage is finished, the battery is taken out and cooled to 25 ℃, and then the battery is discharged to 3.0V at 0.5C, and the discharge capacity of the battery is the holding capacity of the battery; and continuously charging to 4.35V at a constant current of 0.5C at 25 ℃, then charging to a cut-off current of 0.01C at a constant voltage, then discharging to 3.0V at a constant current of 0.5C, recording the discharge capacity as the recovery capacity, and calculating the capacity retention rate and the capacity recovery rate of the battery, wherein the results are shown in a table 2.
Battery capacity retention (%) = retention capacity/initial capacity × 100%;
battery capacity recovery (%) = recovered capacity/initial capacity × 100%.
3. Low temperature cycle performance: the lithium ion gel battery is charged to 4.35V at a constant current of 0.5C, then charged to a cutoff current of 0.01C at a constant voltage, and then discharged to 3.0V at a constant current of 0.5C at 0 ℃. The capacity retention rate at the 100 th cycle was calculated after 100 cycles of charge and discharge according to the above charge and discharge system, and the results are shown in Table 2.
Capacity retention ratio (%) at 100 th cycle = (100 th cycle discharge capacity/1 st cycle discharge capacity) × 100%.
4. Low-temperature discharge performance: at 25 ℃, charging the lithium ion gel battery to 4.35V at a constant current of 0.5C, then charging to a cut-off current of 0.01C at a constant voltage, discharging to 2.5V at 0.2C, recording the initial discharge capacity of the battery, continuing to charge to 4.35V at the constant current and the constant voltage of 0.5C, and then charging to the cut-off current of 0.01C at the constant voltage. The battery was left to stand in a-40 ℃ cold box for 4 hours, and discharged to 2.5V at 0.2C under this temperature condition, the low-temperature discharge capacity of the battery was recorded, and the low-temperature discharge retention rate of the battery was calculated, and the results are shown in Table 2.
Low-temperature discharge capacity retention (%) — low-temperature discharge capacity/initial discharge capacity × 100%.
TABLE 1
| Examples of the invention | Gel monomer | Crosslinking agent | Initiator | Electrolyte solution | Polymerization temperatureDegree of rotation | Time of polymerization |
| Example 1 | 1% of 2-methoxy-5- [ (E) -2-methoxyvinyl]Pyridine compound | 1% tetraethyleneglycol diacrylate | 0.2% azobisisobutyronitrile | 97.8% | 65℃ | 5h |
| Example 2 | 5% of 2-methoxy-5- [ (E) -2-methoxyvinyl]Pyridine compound | 5% of diethylene glycol diacrylate | 0.2% azobisisoheptonitrile | 89.8% | 85℃ | 9h |
| Example 3 | 1% of 2- [ (Z) -2-methoxyvinyl]Pyridine compound | 2% of 1, 9-nonanediol diacrylate | 0.2% of di-tert-butyl peroxide | 96.8% | 80℃ | 8h |
| Example 4 | 5% of 2- [ (Z) -2-methoxyvinyl]Pyridine compound | 1% of 1, 9-nonanediol diacrylate | 0.2% of acetyl peroxide | 93.8% | 70℃ | 5h |
| Example 5 | 1% of 3- [ (Z) -2-methoxyvinyl]Pyridine compound | 5% triethylene glycol diacrylate | 0.2% of dibenzoyl peroxide | 93.8% | 80℃ | 8h |
| Example 6 | 5% of 3- [ (Z) -2-methoxyvinyl]Pyridine compound | 2% of 1, 3-propane diol diacrylate | 0.1% of dibenzoyl peroxide | 92.9% | 70℃ | 6h |
| Example 7 | 1% of 3- [ (E) -2-methoxyvinyl]Pyridine compound | 2% of 1, 3-propane diol diacrylate | 0.5% of acetyl peroxide | 96.5% | 75℃ | 7h |
| Example 8 | 5% of 3- [ (E) -2-methoxyvinyl]Pyridine compound | 1% of 1, 4-butanediol diacrylate | 0.2% azobisisoheptonitrile | 93.8% | 65℃ | 9h |
| Example 9 | 1% of 4- [ (E) -2-methoxyvinyl]Pyridine compound | 3% of 1, 6-hexanediol diacrylate | 0.3% of dibenzoyl peroxide | 95.7% | 80℃ | 6h |
| Example 10 | 5% of 4- [ (E) -2-methoxyvinyl]Pyridine compound | 5% of 1, 10-decanediol diacrylate | 0.5% of acetyl peroxide | 89.5% | 85℃ | 5h |
| Example 11 | 1% of 5- [ (E) -2-methoxyvinyl]-2-methylpyridine | 3% of 1, 5-pentanediol diacrylate | 0.3% of dibenzoyl peroxide | 95.7% | 80℃ | 6h |
| Example 12 | 5% of 5- [ (E) -2-methoxyvinyl]-2-methylpyridine | 4% of but-2-enylene diacrylate | 0.2% azobisisoheptonitrile | 90.8% | 65℃ | 9h |
| Comparative example 1 | 5% of [ (vinyloxy) methoxy group]Ethylene | 5% of diethylene glycol diacrylate | 0.2% azobisisoheptonitrile | 89.8% | 85℃ | 9h |
TABLE 2
As can be seen from the results of the battery performance tests of each example and comparative example 1 in table 2: the lithium ion battery prepared by the embodiments of the invention has good normal temperature cycle performance, high temperature performance and low temperature performance. For example, the batteries prepared in example 2 and comparative example 1 are different from those prepared in example 2 in that comparative example 1 uses a gel monomer different from that of example 2, the gel monomer used in comparative example 1 is [ (vinyloxy) methoxy ] ethylene containing no pyridine ring, and the gel monomer used in example 2 is 2-methoxy-5- [ (E) -2-methoxyvinyl ] pyridine containing both a pyridine ring and a methoxy group. Because the gel monomer in example 2 contains pyridine ring and methoxy group at the same time, in the polymerization reaction during the preparation of the lithium ion battery, 2-methoxy-5- [ (E) -2-methoxyvinyl ] pyridine containing a plurality of pyridine and methoxy group and the cross-linking agent diethylene glycol diacrylate are polymerized into the gel electrolyte with long-chain network structure under the action of the initiator azobisisoheptonitrile, lithium ions are filled in the skeleton of the network polymer with long chain, because the nitrogen atom and methoxy group in the pyridine structure can both de-intercalate lithium ions, two groups for de-intercalation of lithium ions exist in the same structural unit, the steric hindrance of lithium ions in the transmission process is accelerated, the channel for continuous migration of lithium ions between different structural units is built, and the migration rate of lithium ions is improved, the low-temperature performance of the battery is improved; and the migration channel formed by the same structural unit is not easily influenced by the external environment, so that the good migration speed can be kept after the battery is cycled for many times, and the normal-temperature cycle performance and the high-temperature storage performance of the battery are improved. And due to complexation of nitrogen atoms in the pyridine ring with transition metal elements dissociated from the anode, the influence of deposition of the transition metal on the surface of the cathode on the deintercalation of lithium ions is prevented, and the interface stability of the electrode and the high-temperature performance of the battery are improved.
It should be noted that the description of the embodiments is provided to help understanding of the present invention, but the present invention is not limited thereto. For example, for the nonaqueous electrolytic solution used in the preparation of the gel electrolyte, although only ethylene carbonate, diethyl carbonate, dimethyl carbonate and ethyl methyl carbonate were used in the above examples in a ratio of 1: 1: 1: 3, but as can be inferred by those skilled in the art, as the non-aqueous electrolyte, ethylene carbonate, diethyl carbonate, dimethyl carbonate and ethyl methyl carbonate are similar in properties, and the effects on the performances thereof are not large when they are used in various proportions or separately. In addition, the technical features related to the embodiments of the present invention described above may be combined with each other as long as they do not conflict with each other. In addition, the above embodiments are only some embodiments of the present invention, not all embodiments, and all other embodiments obtained by those skilled in the art without any inventive work based on the embodiments of the present invention belong to the protection scope of the present invention.
Claims (10)
1. The lithium ion battery gel electrolyte is characterized in that raw materials for preparing the gel electrolyte comprise a gel factor and a non-aqueous electrolyte; the gel factor comprises a gel monomer, a cross-linking agent and an initiator; the gel monomer is a methoxy vinyl pyridine compound, and the chemical structural formula of the gel monomer is as follows:
wherein: r1Is a hydrogen atom or an alkyl group; r2- R5Independently selected from one of a hydrogen atom, a methoxyvinyl group and an alkoxy group, and R2- R5At least one of which is a methoxyvinyl group.
2. The lithium ion battery gel electrolyte of claim 1, wherein the gel monomer is at least one of 2-methoxy-5- [ (E) -2-methoxyvinyl ] pyridine, 2- [ (Z) -2-methoxyvinyl ] pyridine, 3- [ (E) -2-methoxyvinyl ] pyridine, 4- [ (E) -2-methoxyvinyl ] pyridine, and 5- [ (E) -2-methoxyvinyl ] -2-methylpyridine.
3. The lithium ion battery gel electrolyte of claim 2, wherein the mass of the gel monomer is 1-5% of the total mass of the raw materials.
4. The lithium ion battery gel electrolyte of claim 2, wherein the cross-linking agent is a chain acrylate compound, and the cross-linking agent contains at least two carbon-carbon double bonds.
5. The lithium ion battery gel electrolyte of claim 4, wherein the cross-linking agent comprises at least two acrylate groups.
6. The lithium ion battery gel electrolyte of claim 5, wherein the cross-linking agent is at least one of tetraethyleneglycol diacrylate, diethylene glycol diacrylate, 1, 9-nonanediol diacrylate, triethylene glycol diacrylate, 1, 3-propane diol diacrylate, 1, 4-butanediol diacrylate, 1, 6-hexanediol diacrylate, 1, 10-decanediol diacrylate, 1, 5-pentanediol diacrylate, and but-2-enylene diacrylate.
7. The lithium ion battery gel electrolyte of claim 5, wherein the mass of the cross-linking agent is 1-5% of the total mass of the raw materials.
8. The lithium ion battery gel electrolyte of claim 5, wherein the initiator is dibenzoyl peroxide, acetyl peroxide, di-tert-butyl peroxide, azobisisobutyronitrile or azobisisoheptonitrile, and the mass of the initiator is 0.1-0.5% of the total mass of the raw materials.
9. The lithium ion battery gel electrolyte of any of claims 1 to 8, wherein the nonaqueous electrolyte is a solution of lithium hexafluorophosphate dissolved in at least one of ethylene carbonate, diethyl carbonate, dimethyl carbonate and ethyl methyl carbonate.
10. A method of making a lithium ion battery comprising the lithium ion battery gel electrolyte of any of claims 1-9, comprising the steps of:
step one, preparing gel electrolyte:
uniformly mixing the methoxy vinyl pyridine compound monomer and the cross-linking agent, then adding the obtained mixture into the non-aqueous electrolyte, uniformly mixing, adding the initiator, and uniformly mixing to obtain a gel electrolyte;
step two, preparing the lithium ion battery:
and (3) adding the gel electrolyte prepared in the step one into a soft package lithium ion battery cell, sealing, standing, forming, heating to 65-85 ℃ for polymerization for 5-9 hours, exhausting air, and sealing.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210123894.8A CN114156533B (en) | 2022-02-10 | 2022-02-10 | Lithium ion battery gel electrolyte and preparation method of lithium ion battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210123894.8A CN114156533B (en) | 2022-02-10 | 2022-02-10 | Lithium ion battery gel electrolyte and preparation method of lithium ion battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114156533A CN114156533A (en) | 2022-03-08 |
| CN114156533B true CN114156533B (en) | 2022-04-22 |
Family
ID=80450315
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210123894.8A Active CN114156533B (en) | 2022-02-10 | 2022-02-10 | Lithium ion battery gel electrolyte and preparation method of lithium ion battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114156533B (en) |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1161691A (en) * | 1994-10-22 | 1997-10-08 | 大金工业株式会社 | Conjugated N-fluoropyridinium salt polymer and use thereof |
| US5783331A (en) * | 1995-08-01 | 1998-07-21 | Ricoh Company, Ltd. | Second battery comprising a gel polymer solid electrolyte and a copolymer of vinyl pyridine with a hydroxyl-group-containing (meth) acrylate as binder for the negative electrode |
| CN104380516A (en) * | 2013-01-28 | 2015-02-25 | 株式会社Lg化学 | Composition for gel polymer electrolyte and lithium secondary battery comprising the same |
| CN106450453A (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 containing same |
| CN108808078A (en) * | 2018-07-25 | 2018-11-13 | 北京大学 | Safety-type gel electrolyte materials of polyimide nonwoven fabric base and preparation method thereof |
| CN109994779A (en) * | 2017-12-29 | 2019-07-09 | 深圳新宙邦科技股份有限公司 | A kind of non-aqueous electrolyte for lithium ion cell and lithium ion battery |
| WO2019221267A1 (en) * | 2018-05-18 | 2019-11-21 | Ｊｘｔｇエネルギー株式会社 | Liquid crystalline compound, ionic conductor, electrolytic film, and secondary battery |
| CN113555603A (en) * | 2021-07-19 | 2021-10-26 | 远景动力技术(江苏)有限公司 | Composite electrolyte layer, preparation method thereof and lithium ion battery |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI449236B (en) * | 2009-11-13 | 2014-08-11 | Ind Tech Res Inst | Gel type electrolyte, method of fabrication thereof and dye-sensitized solar cell using the same |
| EP2790260B1 (en) * | 2013-01-28 | 2016-03-23 | LG Chem, Ltd. | Composition for gel polymer electrolyte and lithium secondary battery comprising same |
-
2022
- 2022-02-10 CN CN202210123894.8A patent/CN114156533B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1161691A (en) * | 1994-10-22 | 1997-10-08 | 大金工业株式会社 | Conjugated N-fluoropyridinium salt polymer and use thereof |
| US5783331A (en) * | 1995-08-01 | 1998-07-21 | Ricoh Company, Ltd. | Second battery comprising a gel polymer solid electrolyte and a copolymer of vinyl pyridine with a hydroxyl-group-containing (meth) acrylate as binder for the negative electrode |
| CN104380516A (en) * | 2013-01-28 | 2015-02-25 | 株式会社Lg化学 | Composition for gel polymer electrolyte and lithium secondary battery comprising the same |
| CN106450453A (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 containing same |
| CN109994779A (en) * | 2017-12-29 | 2019-07-09 | 深圳新宙邦科技股份有限公司 | A kind of non-aqueous electrolyte for lithium ion cell and lithium ion battery |
| WO2019221267A1 (en) * | 2018-05-18 | 2019-11-21 | Ｊｘｔｇエネルギー株式会社 | Liquid crystalline compound, ionic conductor, electrolytic film, and secondary battery |
| CN108808078A (en) * | 2018-07-25 | 2018-11-13 | 北京大学 | Safety-type gel electrolyte materials of polyimide nonwoven fabric base and preparation method thereof |
| CN113555603A (en) * | 2021-07-19 | 2021-10-26 | 远景动力技术(江苏)有限公司 | Composite electrolyte layer, preparation method thereof and lithium ion battery |
Non-Patent Citations (2)
| Title |
|---|
| A comparative study of gel polymer electrolytes based on PVDF-HFP and liquid electrolytes,containing imidazolinium ionic liquids of different carbon chain lengths in DSSCs;Vembu suryanarayanan etal;《solar energy materials and solar cells》;20070509;第1467-1471页 * |
| 聚合物锂离子二次电池;赵培正;《河南师范大学学报（自然科学版）》;20020831;第54-57页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114156533A (en) | 2022-03-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109888380B (en) | Solid polymer electrolyte and application thereof in lithium metal battery | |
| CN106374139B (en) | A kind of gel electrolyte materials monomer, polymer, preparation method and applications | |
| CN108493486B (en) | Preparation method of in-situ polymerization solid-state battery | |
| CN113270586B (en) | Preparation and application of in-situ polymerization coated modified silicon-based negative electrode material | |
| CN111533851A (en) | Preparation method of polymer electrolyte and application of polymer electrolyte in all-solid-state battery | |
| CN102117932B (en) | Polymer electrolyte membrane and preparation method thereof, and polymer cell | |
| CN102610817B (en) | Lithium iron phosphate material wrapped by fluorine-doped tin oxide and preparation method of lithium iron phosphate material | |
| CN111653825B (en) | Preparation method of gel polymer electrolyte | |
| CN113429504B (en) | Preparation method of semi-solid polyion liquid electrolyte for lithium battery | |
| CN110911739A (en) | Solid polymer electrolyte, preparation method thereof and lithium battery | |
| CN111934020B (en) | High-pressure-resistant all-solid-state lithium battery interface layer and in-situ preparation method and application thereof | |
| CN109301178A (en) | A kind of sodium Dual-ion cell of the novel carbon negative pole material preparation of doping phosphorus | |
| CN114039097A (en) | Lithium ion battery | |
| CN114156533B (en) | Lithium ion battery gel electrolyte and preparation method of lithium ion battery | |
| CN114725313B (en) | Silicon-based negative plate and preparation method and application thereof | |
| CN104752760B (en) | A kind of porous self-cross linking type gel polymer electrolyte, the electrolyte preparation method and its application in lithium ion battery | |
| CN114221029A (en) | UV (ultraviolet) photocuring PEO (polyethylene oxide) chain segment-containing solid lithium battery polymer electrolyte and preparation method thereof | |
| CN104744722A (en) | Porous self-crosslinking polymer film and preparation method, electrolyte prepared from the film and application of electrolyte in lithium ion battery | |
| CN109671978B (en) | High-voltage-resistant solid polymer electrolyte, preparation method and application thereof | |
| CN113964380A (en) | Self-repairing polymer electrolyte capable of being thermally polymerized in situ and preparation method thereof | |
| CN115677931A (en) | Polymer material, electrolyte and battery | |
| CN116779969B (en) | Sodium ion battery electrolyte, sodium ion battery and method for improving performance of sodium ion battery | |
| CN115632161B (en) | Polydioxolane copolymerization type all-solid-state polymer electrolyte, preparation method and application | |
| CN116259831A (en) | Liquid crystal/in-situ ring-opening polymer electrolyte, lithium ion battery and preparation method of lithium ion battery | |
| CN117577932A (en) | Gel polymer electrolyte composition, gel polymer electrolyte and sodium ion battery thereof |
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 |