CN116082548A - Normal-temperature molten salt polymeric material and application thereof in ion conducting material - Google Patents

Normal-temperature molten salt polymeric material and application thereof in ion conducting material Download PDF

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CN116082548A
CN116082548A CN202310364082.7A CN202310364082A CN116082548A CN 116082548 A CN116082548 A CN 116082548A CN 202310364082 A CN202310364082 A CN 202310364082A CN 116082548 A CN116082548 A CN 116082548A
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付道松
朱利敏
张帆
龚元兵
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Tianmu Lake Institute of Advanced Energy Storage Technologies Co Ltd
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Abstract

The invention discloses a normal-temperature molten salt polymeric material, which has a structure shown in a formula I:
Figure ZY_1
wherein X is selected from imidazolyl or pyridyl; y is Y — One of charged groups selected from carboxylate, sulfonate, silicate, phosphate and borate; n is an integer greater than 1; n' is an integer from 0 to 10; y is Y — To the N atom on the imidazole or pyridine ring of X. The ion conduction material with the normal-temperature molten salt polymeric material has the advantages of high ion conductivity, easy preparation and low cost, and has the following characteristics in actual useObvious advantages. The normal-temperature molten salt polymeric material designed by the invention can solve the technical problem of the reduction of the battery electrical performance caused by concentration polarization due to high-concentration negatively charged groups in the traditional normal-temperature molten salt.

Description

Normal-temperature molten salt polymeric material and application thereof in ion conducting material
Technical Field
The invention relates to the technical field of materials, in particular to a normal-temperature molten salt polymeric material and application thereof in ion conducting materials.
Background
At present, the world energy failure, the battery is used as renewable energy, and the problem of energy failure can be relieved to a certain extent. In a battery, ion migration is a guarantee that the battery will function properly. The electrolyte is taken as an important component of the lithium battery, has very important influence on the performance of the lithium battery, but has certain potential safety hazard due to the adoption of an organic solvent with a lower flash point. Therefore, batteries prepared by using solid electrolytes instead of organic solvents have higher safety performance. Among them, polymer solid electrolytes have received much attention for their excellent mechanical properties, safety and processability. On one hand, the battery diaphragm needs to isolate the electronic conduction between the positive electrode and the negative electrode of the battery, so that the phenomenon of short circuit of the battery during operation is avoided; on the other hand, the ion transmission between the anode and the cathode needs to be ensured, and the normal operation of the battery is ensured.
In the prior art, the normal-temperature molten salt has the advantages of low volatility, incombustibility, high heat and chemical stability, wide electrochemical window, high ionic conductivity, designable structure and the like, and is widely researched and applied. In addition, the normal-temperature molten salt polymerization generates a normal-temperature molten salt polymerization material, has excellent performances of normal-temperature molten salt and polymer, and is often used as a raw material for preparing ion conduction materials. However, the common normal-temperature molten salt polymeric material has the problems of low capacity and poor cycle performance due to low ionic conductivity; in addition, the normal temperature molten salt polymeric material in the prior art may also cause degradation of battery performance due to concentration polarization generated by the material.
Disclosure of Invention
The normal temperature molten salt is a room temperature organic molten salt composed of organic positively charged groups and organic or inorganic negatively charged groupsThe fused salt has the advantages of low volatility, incombustibility, high heat and chemical stability, wide electrochemical window, high ionic conductivity, tunable structure and the like, and is widely researched and applied. The normal-temperature molten salt polymerization material is formed by polymerizing normal-temperature molten salt monomers, has a group with negative electricity and a group with positive electricity on a repeating unit, has excellent performances of normal-temperature molten salt and a polymer, and is commonly used for preparing one of raw materials of ion conduction materials. Ion conducting materials in batteries include electrolytes and separator materials, where the use of normal temperature molten salt polymers for electrolytes is exemplified by the high viscosity of normal temperature molten salt polymeric materials and the resulting moderate ion conducting capacity hamper their battery cycling performance at room temperature. In order to promote better coordination between the normal-temperature molten salt polymeric material and salt to generate electrolyte, the conventional normal-temperature molten salt polymeric material can generate negatively charged groups and/or positively charged groups in the preparation process, and the type of anionic groups which are the same as those generated by the salt in the preparation process of the normal-temperature molten salt polymeric material can be selected, so that the negatively charged groups of the normal-temperature molten salt polymeric material can be charged in the preparation process of the electrolyte by the conventional normal-temperature molten salt polymeric material and the salt, and the internal resistance of the battery is further increased. Therefore, the normal-temperature molten salt polymeric material can increase the concentration of anionic groups in the electrolyte, reduce the migration number of lithium ions/sodium ions/potassium ions of the electrolyte and finally influence the performance of the battery. The research shows that the negatively charged groups in the normal temperature molten salt polymeric material have the most obvious influence on the electric performance of the battery, firstly, when the battery is in an equilibrium state under the condition of no working voltage, concentration polarization can be generated along with the directional movement of anions in the electrolyte in the charging and discharging process of the battery, and potential difference can be formed in the electrolyte, so that the internal resistance of the battery is increased, and the negatively charged groups in the normal temperature molten salt polymeric material can promote the increase of the resistance in the battery; second, when the battery is charged and discharged, the internal anions and cations of the electrolyte are directionally migrated, the addition of negatively charged groups in the normal temperature molten salt polymeric material reduces the proportion of ions, and then the migration number of ions in the electrolyte is reduced, thereby reducing the circulation of the battery Performance. In order to reduce the overpotential caused by concentration polarization, one popular strategy is to attach negatively charged groups to the polymer matrix to immobilize the negatively charged groups. However, the reduction in the number of mobile ions and their transport in the polymer matrix can severely affect the overall ionic conductivity of the single lithium ion polymer electrolyte (slimpe). Another common approach is to reduce or eliminate solvent usage in the liquid electrolyte by preparing a highly concentrated electrolyte or preparing a room temperature molten salt electrolyte. However, both of these methods still suffer from salt concentration gradient polarization problems, because preventing such polarization requires stringent solvent removal and ensures Li + /Na + /K + Plasma is the only potentially mobile cation in the system. In addition, concentration polarization can occur when the normal-temperature molten salt polymeric material is used in a battery diaphragm material, and the electrical performance of a battery is affected.
The invention aims at the problems in the prior art and discloses a normal-temperature molten salt polymerization material and application thereof in ion conduction materials. The normal-temperature molten salt polymeric material obtained by the invention is used in battery ion conducting materials, and the battery can not increase the internal resistance of the battery and reduce the migration number of lithium ions/sodium ions/potassium ions due to concentration polarization generated by the movement of negatively charged groups in the traditional normal-temperature molten salt polymeric material.
The invention is realized by the following technical scheme:
the invention provides a normal-temperature molten salt polymeric material, which has a structure shown in a formula I:
Figure SMS_1
；
wherein X is selected from imidazolyl or pyridyl; y is Y — Selected from the group consisting of carboxylate, sulfonate, silicate, phosphate, and borateOne of the charged groups; n is an integer greater than 1; n' is an integer from 0 to 10; y is Y — To the N atom on the imidazole or pyridine ring of X.
The normal temperature molten salt polymerization material designed by the invention refers to the charge balance of the normal temperature molten salt polymerization material, and free positively charged groups and negatively charged groups are not generated in the solution with the normal temperature molten salt polymerization material. The normal-temperature molten salt polymeric material is used in ion conducting materials of batteries, and can solve the problems that the internal resistance of the batteries is increased and the migration number of lithium ions/sodium ions/potassium ions is limited due to concentration polarization generated by movement of negatively charged groups, thereby being beneficial to improving the electrochemical performance of the batteries.
As a further scheme, the Y — Has the structure of formula II:
Figure SMS_2
；
wherein M is M/2, M is a positive integer; and R is selected from one of carboxylate radical, sulfonate radical, silicon hydroxyl radical, phosphate hydroxyl radical and boron hydroxyl radical.
As a further scheme, M is a positive integer and M is 2-6.
As a further scheme, n' is an integer of 0-5. Is beneficial to obtaining normal-temperature molten salt polymeric materials with more proper chain length.
The invention also provides an ion conduction material with the normal-temperature molten salt polymerization material, wherein the ion conduction material comprises the normal-temperature molten salt polymerization material, salt and an initiator.
As a further option, the ion conducting material may be used as an electrolyte and separator material.
As a further scheme, the ion conducting material comprises monomer, salt and initiator of the normal-temperature molten salt polymerization material, wherein the adding amount of the salt is 5-50% of the monomer mass of the normal-temperature molten salt polymerization material, and the adding amount of the initiator is 0.1-5% of the monomer mass of the normal-temperature molten salt polymerization material. Under the action of an initiator, the monomer and the salt of the normal-temperature molten salt polymerization material are mutually matched, and then the ion conduction material with the ion channel with a stable structure is formed by polymerization. When the ion conducting material is electrolyte, the salt should be easy to dissociate from the anions and cations, and can conduct ions in the polymer. The ion conducting material is a diaphragm material, and can isolate electrons and conduct ions. The cations of the salts in the present invention are consistent with the cations absorbed and released by the battery electrode material. The monomer of the normal-temperature molten salt polymerization material can be combined with the positive electrode active material and the negative electrode active material to prepare slurry, and the slurry is polymerized in situ to prepare the pole piece.
As a further scheme, the addition mass of the salt is 25-35% of the monomer mass of the normal-temperature molten salt polymerization material. The salt in the range has higher ionic conductivity on the basis of proper viscosity, and is beneficial to improving the electrical property of the battery.
As a further scheme, the addition mass of the initiator is 0.5% -1.5% of the monomer mass of the normal-temperature molten salt polymerization material. In this range, it is advantageous to obtain a polymer chain having a more appropriate polymerization degree of the monomer of the normal-temperature molten salt polymerization material and a molecular weight of the polymer in the finally obtained ion conduction material, thereby facilitating the transfer of ions in the ion conduction material.
As a further scheme, the salt comprises one or more of ABx, and when the ABx is used for an electrolyte, anions and cations can be dissociated, wherein a is selected from one of lithium ion, sodium ion, potassium ion, magnesium ion, aluminum ion and zinc ion, and B is selected from one of chloride-based salt, boron-based salt, arsenic-based salt, phosphorus-based salt, sulfonic acid-based salt, sulfonimide-based salt and aluminum-based salt, and the value of x is determined according to the charge balance of a and B in the salt. The chloride-based salt, the boron-based salt, the arsenic-based salt, the phosphorus-based salt, the sulfonic acid-based salt, the sulfimide-based salt and the aluminum-based salt are salts containing anions and cations, wherein anions in the salts contain corresponding elements or groups, for example, anions in the chloride-based salts contain Cl elements, for example, anions in the sulfonic acid-based salts contain sulfonic acid groups. The perchlorate is suitable for use in short-term cycling battery systems, has high solubility, high ionic conductivity, relatively good oxidation stability, and is suitable for use in high-voltage batteries. The borate salt has good thermal stability in the battery cycle process, is not easy to decompose at high temperature, and has a structure which leaves enough space for migration of ions; in addition, the borate salt and the monomer of the normal-temperature molten salt polymerization material are matched, so that the electrochemical stability of the monomer of the normal-temperature molten salt polymerization material is improved, and a stable ion migration channel is constructed with the normal-temperature molten salt polymerization material. Arsenate salts are suitable for use in cells of Al current collectors and have high electrochemical stability. The phosphate salt has relatively good ionic conductivity and chemical stability in aprotic organic solvents, and is suitable for battery systems for short-term circulation. The electrolyte has rich S-O bond sulfonate and maximum metal electron exchange affinity, and is favorable for the exertion of the electric performance of the battery. The negative ions in the sulfonimide salt are composed of nitrogen (N) atoms with strong electronegativity and sulfur (S) atoms connected with strong electron withdrawing groups, and the structure disperses negative charges, so that the positive ions and the negative ions are more easily dissociated, thereby obviously improving the ion conductivity of the sulfonimide salt and being beneficial to the improvement of the ion conductivity of a battery.
As a still further aspect, the anion of the chloride-based salt comprises ClO 4 - 。
As a still further aspect, the boron-based salt includes a borate, and the anion in the borate includes tetrafluoroborate (BF 4 - ) Difluoro oxalato borate ion (DFOB) - ) Bisoxalato borate ion (BOB) - ) One or more of the following.
As a still further aspect, the anion in the arsenical salt comprises hexafluoroarsenate ion (AsF) 6 - ）。
As a still further aspect, the anion in the phosphorus-based salt comprises hexafluorophosphate (PF 6 - ) Tris (pentafluoroethyl) trifluorophosphate ion [ (C) 2 F 5 ) 3 PF 3 - ]One or more of the following.
As a still further aspect, the anion in the sulfonate salt comprises a trifluoromethane sulfonate ion (CF 3 SO 3 - ）。
As a still further aspect, the anion in the sulfonimide salt comprises bis-fluorosulfonimide ion (FSI) - ) Bis (trifluoromethylsulfonyl) imide (TFSI) - ) Fluorosulfonyl- (trifluoromethylsulfonyl) imide ion (FTFSI) - ) Bis (perfluoro-ethylsulfonyl) imide (BETI) - ) One or more of them.
As a still further aspect, the anions in the aluminum-based salt comprise tetrachloroaluminate ions (AlCl) 4 - ) Tetrafluoroaluminate ion (AlF) 4 - ) One or more of the following.
As a further aspect, the initiator comprises a thermal initiator or a photoinitiator.
As a still further aspect, the thermal initiator comprises one or more of azobisisobutylamidine hydrochloride, azobisiso Ding Mi hydrochloride, azobiscyano valeric acid, azobisisopropylimidazoline.
As a still further aspect, the photoinitiator comprises one or more of 2-hydroxy-2, 2-dimethyl acetophenone, 2 '-azo-bis (2-amidinopropane), tris (2, 2' -bipyridine) ruthenium (ii).
As a further scheme, the raw materials of the ion conduction material comprise a monomer of a normal-temperature molten salt polymerization material with a structure of a formula III, a salt of an anion in a boron-based salt and a thermal initiator, wherein the addition amount of the salt of the anion in the boron-based salt is 25-35% of the monomer of the normal-temperature molten salt polymerization material, and the addition amount of the thermal initiator is 0.5-1.5% of the monomer of the normal-temperature molten salt polymerization material by mass;
Figure SMS_3
；
wherein n' is an integer of 0 to 10; x is selected from imidazolyl; y is Y — One selected from charged groups having a phosphorus hydroxyl group; y is Y — To the N atom of the imidazole ring of X. Five-membered heterocyclic compound in imidazole normal-temperature fused salt structure improves N absorption The oxygen in the phosphate hydroxyl has electron withdrawing capability and is better matched with the phosphorus element in the phosphate hydroxyl, so that the monomer structure of the normal-temperature molten salt polymeric material is more stable, and the phosphorus of the phosphate hydroxyl can endow the monomer surface of the normal-temperature molten salt polymeric material with abundant electrons and can be better matched with the salt with borate ions. The thermal initiator can promote the sufficient combination between the monomer and the salt of the normal temperature molten salt polymeric material, thereby being beneficial to forming the ion conducting material with stable structure.
The invention also provides a preparation method of the monomer of the normal-temperature molten salt polymerization material, which comprises the steps of carrying out quaternization reaction on vinyl imidazole or vinyl pyridine and alkane of a group Y, wherein a solvent of the quaternization reaction comprises alkyl sulfoxide, so that the monomer and halogen salt of the normal-temperature molten salt polymerization material with an imidazole ring or pyridine ring, wherein N atoms of the monomer are connected with a structure of a formula II; then the primary distillation and desalination reagent is monohydric alcohol, and the secondary distillation is carried out;
wherein the alkane of the group Y has a structure shown in the following formula IV, M is M/2, M is a positive integer, and preferably 2-6; r is selected from one of carboxylate radical, sulfonate radical, silicon hydroxyl radical, phosphate hydroxyl radical and boron hydroxyl radical; a comprises halogen, and specifically comprises Cl, br and I; d comprises metal ions, and specifically comprises one of sodium ions, lithium ions and potassium ions.
Figure SMS_4
；
The reaction route of the step is as follows:
Figure SMS_5
；
Figure SMS_6
；
wherein X is selected from imidazolyl or pyridyl; y is Y — One of charged groups selected from carboxylate, sulfonate, silicate, phosphate and borate; n' is an integer from 0 to 10; y is Y — To N atoms on imidazole or pyridine rings of X。
In the method, the monomer of the normal-temperature molten salt polymerization material with better purity is obtained through the mutual coordination of primary distillation, desalination and secondary distillation. If distillation and desalination are performed simultaneously, on the one hand, byproducts may occur in the solution, which is disadvantageous for the purity of the product, and on the other hand, crystals may be easily precipitated due to the polarity difference between the solvent for the quaternization reaction and the desalted reagent, which may directly affect the monomer product obtained from the normal temperature molten salt polymerization material of the present invention. In the invention, alkyl sulfoxide and monohydric alcohol are firstly adopted to ensure the polarity of the solvent, so that on one hand, the quaternization reaction can be promoted, and on the other hand, the desalting of the monomer of the normal-temperature molten salt polymerization material is facilitated. The primary distillation is used for removing the solvent of the quaternization reaction, is beneficial to reducing impurities in the solution, can reduce the generation of byproducts during desalination, and also reduces the consumption of other substances in the solution on the desalination reagent, thereby influencing the desalination effect. The secondary distillation is firstly to directly obtain the monomer of the normal-temperature molten salt polymerization material, and secondly to avoid the influence of the residue of the desalted reagent on the purity and performance of the product. It can be seen that the combination of the primary distillation, desalination and secondary distillation of the present invention facilitates the obtaining of excellent monomers for normal temperature molten salt polymeric materials.
As a further scheme, in the step, the solvent for the quaternization reaction comprises alkyl sulfoxide, wherein the number of carbon in the alkyl sulfoxide is preferably 6, 5, 4, 3 and 2 in sequence; the temperature of the primary distillation is not lower than 90 ℃; the desalting agent is selected from one of monohydric alcohols of C1-C6; the temperature of the secondary distillation is not lower than 60 ℃. The invention selects low molecular weight alkyl sulfoxide and monohydric alcohol, which have higher polarity.
As a further scheme, the quaternization reaction condition is that the quaternization reaction is carried out for 24 to 72 hours at a temperature of between 60 and 100 ℃, and the reaction solution comprises dimethyl sulfoxide; the condition of the primary distillation is that the primary distillation is carried out for 1.5 to 2.5 hours at the temperature of 90 to 110 ℃ and the pressure of 8 to 12 mbar; the desalting reagent comprises absolute ethyl alcohol, and the monomer of the normal-temperature molten salt polymerization material is obtained by reduced pressure distillation for 30-50 min at the temperature of 60-80 ℃ under the condition of secondary distillation.
As a best example of the invention, at least 6 washes with monohydric alcohol are used in desalting.
The invention also provides a preparation method of the ion conduction material with the normal-temperature molten salt polymerization material, which comprises the steps of dissolving monomers and salts of the normal-temperature molten salt polymerization material in an organic solvent under inert atmosphere, adding an initiator, stirring to obtain a uniform solution, heating for polymerization or illumination polymerization, and removing the organic solvent to obtain the ion conduction material film, namely the ion conduction material.
As a further aspect, the organic solvent includes an amide-based solvent; the stirring time is not less than 2 hours; the heating temperature is 40-90 ℃, and the heating time is 6-72 h; the illumination condition is 365nm ultraviolet light, and the time is 5s-1h; the method for removing the organic solvent comprises the steps of vacuumizing and removing at 75-85 ℃.
As a further scheme, the amide solvent comprises one or more of formamide, acetamide, N-dimethylformamide and N, N-dimethylacetamide.
As a further scheme, the heating polymerization is carried out at the temperature of 75-85 ℃ for 6-72 h. Firstly, the monomer polymerization of the normal-temperature molten salt polymerization material in the ion conduction material can be more sufficient by using heating polymerization; secondly, at the heating temperature, the polymerization degree of the monomer of the normal-temperature molten salt polymerization material and the polymer chain with more proper molecular weight of the polymer in the finally obtained ion conduction material are facilitated, so that the ion transmission in the ion conduction material is facilitated.
The invention also provides application of the ion conduction material with the normal-temperature molten salt polymeric material in a battery.
The invention has the characteristics and beneficial effects that:
(1) The ion conduction material with the normal-temperature molten salt polymeric material has the advantages of high ion conductivity, easiness in preparation and low cost, and has obvious advantages in actual use.
(2) The monomer of the normal-temperature molten salt polymerization material designed by the invention can solve the technical problem of the reduction of battery performance caused by concentration polarization due to negatively charged groups in the traditional normal-temperature molten salt polymerization.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed in the embodiments or the description of the prior art will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and other drawings can be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a nuclear magnetic resonance spectrum of a monomer of a normal temperature molten salt polymerization material provided in examples 1 to 8 of the present invention.
Fig. 2 is a graph showing specific discharge capacity and charge-discharge efficiency of a battery 200 turns according to example 4 of the present invention.
FIG. 3 is a reaction scheme of examples 1 to 8 of the present invention.
FIG. 4 is a reaction scheme of example 9 of the present invention.
FIG. 5 is a reaction scheme of example 10 of the present invention.
FIG. 6 is a reaction scheme of example 11 of the present invention.
FIG. 7 is a reaction scheme of example 12 of the present invention.
FIG. 8 is a reaction scheme of comparative example 1 of the present invention.
Detailed Description
In order to facilitate understanding of a room temperature molten salt polymeric material of the present invention and its use in ion conducting materials, a more complete description of a room temperature molten salt polymeric material of the present invention will now be given, without thereby limiting the scope of the invention. It should be understood that these examples are for the purpose of more detailed description only and should not be construed as limiting the invention in any way, i.e., not intended to limit the scope of the invention; relational terms such as "primary" and "secondary" and the like may be used solely to distinguish one element from another element having the same name, and do not necessarily require or imply any such actual relationship or order between the elements.
The ion conducting material obtained by the method is beneficial to improving the electrical property of the battery, the embodiment of the invention takes a lithium battery as an example, the obtained ion conducting material is taken as a battery electrolyte, the coordination between the monomer of the normal-temperature molten salt polymeric material and the salt and the initiator is further elaborated, and the optimization of the electrical property of the finally obtained ion conducting material is beneficial to improving the electrical property of the battery. The ion conductive material obtained by the invention is not limited to be used for lithium batteries, but can also be sodium batteries, potassium batteries and the like. The ion conducting material obtained by the invention can be battery electrolyte or battery separator material.
Example 1
(1) Preparation of monomer of normal temperature molten salt polymeric material
50g of sodium 2-bromoethane sulfonate and 30g of 1-vinylimidazole are dissolved in 50mL of dimethyl sulfoxide and reacted for 48 hours at 80 ℃. After the reaction, distillation was carried out at 80℃and 10mbar for 2h to give a pale yellow powder. Stirring the pale yellow powder with 50mL absolute ethanol, filtering, repeating for six times, and distilling at 80 ℃ and 10mbar for 40min to obtain monomer powder product of the pale yellow normal temperature molten salt polymeric material.
(2) Ion conductive material precursor solution composition: monomer of normal temperature molten salt polymerization material, salt: lithium bis (trifluoromethanesulfonyl imide): 30% of monomer mass of a normal-temperature molten salt polymerization material, and an initiator: azodicyanovaleric acid (0.1% of monomer mass of molten salt polymeric material at normal temperature).
(3) Preparation of ion-conducting materials
Under inert atmosphere, monomer and salt of the normal temperature molten salt polymerization material are dissolved in formamide, then initiator is added and stirred for 2 hours to obtain uniform solution, the solution is uniformly coated on a glass plate, the solution is heated at 80 ℃ for 24 hours, and then the formamide is removed by vacuumizing at 80 ℃ to obtain the ion conduction material with the normal temperature molten salt polymerization material.
(4) Battery assembly
Lithium cobalt oxide (LiCoO) 2 ) +carbon black (SP) +polyvinylidene fluoride (HSV 900) (mass ratio 8:1:1) is positive electrode The material, ion conductive material is used as electrolyte, lithium piece is negative pole, assemble button cell, test electrochemical impedance spectrum through electrochemical workstation, calculate ion conductivity, and charge and discharge test with 0.5C (first two circles) -1C multiplying power.
Example 2
(1) Preparation of monomer of normal temperature molten salt polymeric material
50g of sodium 2-bromoethane sulfonate and 30g of 1-vinylimidazole are dissolved in 50mL of dimethyl sulfoxide and reacted for 48 hours at 80 ℃. After the reaction, distillation was carried out at 80℃and 10mbar for 2h to give a pale yellow powder. Stirring the pale yellow powder with 50mL absolute ethanol, filtering, repeating for six times, and distilling at 80 ℃ and 10mbar for 40min to obtain monomer powder product of the pale yellow normal temperature molten salt polymeric material.
(2) Ion conductive material precursor solution composition: monomer of normal temperature molten salt polymerization material, salt: lithium bis (trifluoromethanesulfonyl imide): 5% of monomer mass of a normal-temperature molten salt polymerization material, and an initiator: azodicyanovaleric acid (0.1% of monomer mass of molten salt polymeric material at normal temperature).
(3) Preparation of ion-conducting materials
Under inert atmosphere, monomer and salt of the normal temperature molten salt polymerization material are dissolved in formamide, then initiator is added and stirred for 2 hours to obtain uniform solution, the solution is uniformly coated on a glass plate, the solution is heated at 80 ℃ for 24 hours, and then the formamide is removed by vacuumizing at 80 ℃ to obtain the ion conduction material of the normal temperature molten salt polymerization material.
(4) Battery assembly
Lithium cobalt oxide (LiCoO) 2 ) +carbon black (SP) +polyvinylidene fluoride (HSV 900) (mass ratio 8:1:1) is used as a positive electrode material, an ion conducting material is used as an electrolyte, a lithium sheet is used as a negative electrode, the button cell is assembled, electrochemical impedance spectroscopy is tested through an electrochemical workstation, ion conductivity is calculated, and charge and discharge tests are carried out with a 0.5C (first two circles) -1C multiplying power.
Example 3
(1) Preparation of monomer of normal temperature molten salt polymeric material
50g of sodium 2-bromoethane sulfonate and 30g of 1-vinylimidazole are dissolved in 50mL of dimethyl sulfoxide and reacted for 48 hours at 80 ℃. After the reaction, distillation was carried out at 80℃and 10mbar for 2h to give a pale yellow powder. Stirring the pale yellow powder with 50mL absolute ethanol, filtering, repeating for six times, and distilling at 80 ℃ and 10mbar for 40min to obtain monomer powder product of the pale yellow normal temperature molten salt polymeric material.
(2) Ion conductive material precursor solution composition: monomer of normal temperature molten salt polymerization material, salt: lithium bis (trifluoromethanesulfonyl imide): 50% of monomer mass of a normal-temperature molten salt polymerization material, and an initiator: azodicyanovaleric acid (0.1% of monomer mass of molten salt polymeric material at normal temperature).
(3) Preparation of ion-conducting materials
Under inert atmosphere, monomer and salt of the normal temperature molten salt polymerization material are dissolved in formamide, then initiator is added and stirred for 2 hours to obtain uniform solution, the solution is uniformly coated on a glass plate, the solution is heated at 80 ℃ for 24 hours, and then the formamide is removed by vacuumizing at 80 ℃ to obtain the ion conduction material with the normal temperature molten salt polymerization material.
(4) Battery assembly
Lithium cobalt oxide (LiCoO) 2 ) +carbon black (SP) +polyvinylidene fluoride (HSV 900) (mass ratio 8:1:1) is used as a positive electrode material, an ion conducting material is used as an electrolyte, a lithium sheet is used as a negative electrode, the button cell is assembled, electrochemical impedance spectroscopy is tested through an electrochemical workstation, ion conductivity is calculated, and charge and discharge tests are carried out with a 0.5C (first two circles) -1C multiplying power.
Example 4
(1) Preparation of monomer of normal temperature molten salt polymeric material
50g of sodium 2-bromoethane sulfonate and 30g of 1-vinylimidazole are dissolved in 50mL of dimethyl sulfoxide and reacted for 48 hours at 80 ℃. After the reaction, distillation was carried out at 80℃and 10mbar for 2h to give a pale yellow powder. Stirring the pale yellow powder with 50mL absolute ethanol, filtering, repeating for six times, and distilling at 80 ℃ and 10mbar for 40min to obtain monomer powder product of the pale yellow normal temperature molten salt polymeric material.
(2) Ion conductive material precursor solution composition: monomer of normal temperature molten salt polymerization material, salt: lithium bis (trifluoromethanesulfonyl imide): 30% of monomer mass of a normal-temperature molten salt polymerization material, and an initiator: azodicyanovaleric acid (1% of monomer mass of molten salt polymeric material at normal temperature).
(3) Preparation of ion-conducting materials
Under inert atmosphere, monomer and salt of the normal temperature molten salt polymerization material are dissolved in formamide, then initiator is added and stirred for 2 hours to obtain uniform solution, the solution is uniformly coated on a glass plate, the solution is heated at 80 ℃ for 24 hours, and then the formamide is removed by vacuumizing at 80 ℃ to obtain the ion conduction material with the normal temperature molten salt polymerization material.
(4) Battery assembly
Lithium cobalt oxide (LiCoO) 2 ) +carbon black (SP) +polyvinylidene fluoride (HSV 900) (mass ratio 8:1:1) is used as a positive electrode material, an ion conducting material is used as an electrolyte, a lithium sheet is used as a negative electrode, the button cell is assembled, electrochemical impedance spectroscopy is tested through an electrochemical workstation, ion conductivity is calculated, and charge and discharge tests are carried out with a 0.5C (first two circles) -1C multiplying power.
Example 5
(1) Preparation of monomer of normal temperature molten salt polymeric material
50g of sodium 2-bromoethane sulfonate and 30g of 1-vinylimidazole are dissolved in 50mL of dimethyl sulfoxide and reacted for 48 hours at 80 ℃. After the reaction, distillation was carried out at 80℃and 10mbar for 2h to give a pale yellow powder. Stirring the pale yellow powder with 50mL absolute ethanol, filtering, repeating for six times, and distilling at 80 ℃ and 10mbar for 40min to obtain monomer powder product of the pale yellow normal temperature molten salt polymeric material.
(2) Ion conductive material precursor solution composition: monomer of normal temperature molten salt polymerization material, salt: lithium bis (trifluoromethanesulfonyl imide): 30% of monomer mass of a normal-temperature molten salt polymerization material, and an initiator: azodicyanovaleric acid (5% of monomer mass of normal temperature molten salt polymeric material).
(3) Preparation of ion-conducting materials
Under inert atmosphere, monomer and salt of the normal temperature molten salt polymerization material are dissolved in formamide, then initiator is added and stirred for 2 hours to obtain uniform solution, the solution is uniformly coated on a glass plate, the solution is heated at 80 ℃ for 24 hours, and then the formamide is removed by vacuumizing at 80 ℃ to obtain the ion conduction material with the normal temperature molten salt polymerization material.
(4) Battery assembly
Lithium cobalt oxide (LiCoO) 2 ) +carbon black (SP) +polyvinylidene fluoride (HSV 900) (mass ratio 8:1:1) is used as a positive electrode material, an ion conducting material is used as an electrolyte, a lithium sheet is used as a negative electrode, the button cell is assembled, electrochemical impedance spectroscopy is tested through an electrochemical workstation, ion conductivity is calculated, and charge and discharge tests are carried out with a 0.5C (first two circles) -1C multiplying power.
Example 6
(1) Preparation of monomer of normal temperature molten salt polymeric material
50g of sodium 2-bromoethane sulfonate and 30g of 1-vinylimidazole are dissolved in 50mL of dimethyl sulfoxide and reacted for 48 hours at 80 ℃. After the reaction, distillation was carried out at 80℃and 10mbar for 2h to give a pale yellow powder. Stirring the pale yellow powder with 50mL absolute ethanol, filtering, repeating for six times, and distilling at 80 ℃ and 10mbar for 40min to obtain monomer powder product of the pale yellow normal temperature molten salt polymeric material.
(2) Ion conductive material precursor solution composition: monomer of normal temperature molten salt polymerization material, salt: lithium bis (trifluoromethanesulfonyl imide): 30% of monomer mass of a normal-temperature molten salt polymerization material, and an initiator: azodicyanovaleric acid (1% of monomer mass of molten salt polymeric material at normal temperature).
(3) Preparation of ion-conducting materials
Under inert atmosphere, monomer and salt of the normal temperature molten salt polymerization material are dissolved in formamide, then initiator is added and stirred for 2 hours to obtain uniform solution, the solution is uniformly coated on a glass plate, heating is carried out at 90 ℃ for 24 hours, and vacuum pumping is carried out at 80 ℃ to remove the formamide, so that the ion conduction material with the normal temperature molten salt polymerization material is obtained.
(4) Battery assembly
Lithium cobalt oxide (LiCoO) 2 ) +carbon black (SP) +polyvinylidene fluoride (HSV 900) (mass ratio 8:1:1) is used as a positive electrode material, an ion conducting material is used as an electrolyte, a lithium sheet is used as a negative electrode, the button cell is assembled, electrochemical impedance spectroscopy is tested through an electrochemical workstation, ion conductivity is calculated, and charge and discharge tests are carried out with a 0.5C (first two circles) -1C multiplying power.
Example 7
(1) Preparation of monomer of normal temperature molten salt polymeric material
50g of sodium 2-bromoethane sulfonate and 30g of 1-vinylimidazole are dissolved in 50mL of dimethyl sulfoxide and reacted for 48 hours at 80 ℃. After the reaction, distillation was carried out at 80℃and 10mbar for 2h to give a pale yellow powder. Stirring the pale yellow powder with 50mL absolute ethanol, filtering, repeating for six times, and distilling at 80 ℃ and 10mbar for 40min to obtain monomer powder product of the pale yellow normal temperature molten salt polymeric material.
(2) Ion conductive material precursor solution composition: monomer of normal temperature molten salt polymerization material, salt: lithium bis (trifluoromethanesulfonyl imide): 30% of monomer mass of a normal-temperature molten salt polymerization material, and an initiator: azodicyanovaleric acid (1% of monomer mass of molten salt polymeric material at normal temperature).
(3) Preparation of ion-conducting materials
Under inert atmosphere, monomer and salt of the normal temperature molten salt polymerization material are dissolved in formamide, then initiator is added and stirred for 2 hours to obtain uniform solution, the solution is uniformly coated on a glass plate, heating is carried out for 24 hours at 70 ℃, vacuum pumping is carried out at 80 ℃ to remove the formamide, and the ion conduction material with the normal temperature molten salt polymerization material is obtained.
(4) Battery assembly
Lithium cobalt oxide (LiCoO) 2 ) +carbon black (SP) +polyvinylidene fluoride (HSV 900) (mass ratio 8:1:1) is used as a positive electrode material, an ion conducting material is used as an electrolyte, a lithium sheet is used as a negative electrode, the button cell is assembled, electrochemical impedance spectroscopy is tested through an electrochemical workstation, ion conductivity is calculated, and charge and discharge tests are carried out with a 0.5C (first two circles) -1C multiplying power.
Example 8
(1) Preparation of monomer of normal temperature molten salt polymeric material
50g of sodium 2-bromoethane sulfonate and 30g of 1-vinylimidazole are dissolved in 50mL of dimethyl sulfoxide and reacted for 48 hours at 80 ℃. After the reaction, distillation was carried out at 80℃and 10mbar for 2h to give a pale yellow powder. Stirring the pale yellow powder with 50mL absolute ethanol, filtering, repeating for six times, and distilling at 80 ℃ and 10mbar for 40min to obtain monomer powder product of the pale yellow normal temperature molten salt polymeric material.
(2) Ion conductive material precursor solution composition: monomer of normal temperature molten salt polymerization material, salt: lithium bis (trifluoromethanesulfonyl imide): 30% of monomer mass of a normal-temperature molten salt polymerization material, and a water-soluble photoinitiator: 2-hydroxy-2, 2-dimethyl acetophenone (1% of monomer mass of normal temperature molten salt polymeric material).
(3) Preparation of ion-conducting materials
Under inert atmosphere, monomer and salt of the normal temperature molten salt polymerization material are dissolved in formamide, then initiator is added and stirred for 2 hours to obtain uniform solution, the solution is uniformly coated on a glass plate, and after irradiation for 1 hour by a 365nm ultraviolet lamp, the formamide is removed by vacuum pumping at 80 ℃, so that the ion conduction material with the normal temperature molten salt polymerization material is obtained.
(4) Battery assembly
Lithium cobalt oxide (LiCoO) 2 ) +carbon black (SP) +polyvinylidene fluoride (HSV 900) (mass ratio 8:1:1) is used as a positive electrode material, an ion conducting material is used as an electrolyte, a lithium sheet is used as a negative electrode, the button cell is assembled, electrochemical impedance spectroscopy is tested through an electrochemical workstation, ion conductivity is calculated, and charge and discharge tests are carried out with a 0.5C (first two circles) -1C multiplying power.
Example 9
(1) Preparation of monomer of normal temperature molten salt polymeric material
51g of sodium 3-bromopropanesulfonate and 32g of 4-vinylpyridine are dissolved in 50mL of dimethyl sulfoxide and reacted at 80℃for 48 hours. After the reaction, distillation was carried out at 80℃and 10mbar for 2h to give a pale yellow powder. Stirring the pale yellow powder with 50mL absolute ethanol, filtering, repeating for six times, and distilling at 80 ℃ and 10mbar for 40min to obtain monomer powder product of the pale yellow normal temperature molten salt polymeric material.
(2) Ion conductive material precursor solution composition: monomer of normal temperature molten salt polymerization material, salt: lithium bis (trifluoromethanesulfonyl imide): 30% of monomer mass of a normal-temperature molten salt polymerization material, and an initiator: azodicyanovaleric acid (1% of monomer mass of molten salt polymeric material at normal temperature).
(3) Preparation of ion-conducting materials
Under inert atmosphere, monomer and salt of the normal temperature molten salt polymerization material are dissolved in formamide, then initiator is added and stirred for 2 hours to obtain uniform solution, the solution is uniformly coated on a glass plate, the solution is heated at 80 ℃ for 24 hours, and then the formamide is removed by vacuumizing at 80 ℃ to obtain the ion conduction material with the normal temperature molten salt polymerization material.
(4) Battery assembly
Lithium cobalt oxide (LiCoO) 2 ) +carbon black (SP) +polyvinylidene fluoride (HSV 900) (mass ratio 8:1:1) is used as a positive electrode material, an ion conducting material is used as an electrolyte, a lithium sheet is used as a negative electrode, the button cell is assembled, electrochemical impedance spectroscopy is tested through an electrochemical workstation, ion conductivity is calculated, and charge and discharge tests are carried out with a 0.5C (first two circles) -1C multiplying power.
Example 10
(1) Preparation of monomer of normal temperature molten salt polymeric material
45g of sodium 2-bromomethyldimethoxysilanol and 40g of 4-vinylimidazole were dissolved in 50mL of dimethyl sulfoxide and reacted at 80℃for 48 hours. After the reaction, distillation was carried out at 80℃and 10mbar for 2h to give a pale yellow powder. Stirring the pale yellow powder with 50mL absolute ethanol, filtering, repeating for six times, and distilling at 80 ℃ and 10mbar for 40min to obtain monomer powder product of the pale yellow normal temperature molten salt polymeric material.
(2) Ion conductive material precursor solution composition: monomer of normal temperature molten salt polymerization material, salt: lithium hexafluorophosphate: 30% of monomer mass of a normal-temperature molten salt polymerization material, and an initiator: azodicyanovaleric acid (1% of monomer mass of molten salt polymeric material at normal temperature).
(3) Preparation of ion-conducting materials
Under inert atmosphere, monomer and salt of the normal temperature molten salt polymerization material are dissolved in formamide, then initiator is added and stirred for 2 hours to obtain uniform solution, the solution is uniformly coated on a glass plate, the solution is heated at 80 ℃ for 24 hours, and then the formamide is removed by vacuumizing at 80 ℃ to obtain the ion conduction material with the normal temperature molten salt polymerization material.
(4) Battery assembly
Lithium cobalt oxide (LiCoO) 2 ) +carbon black (SP) +polyvinylidene fluoride (HSV 900) (mass ratio 8:1:1) is used as a positive electrode materialThe ion conductive material is used as electrolyte, the lithium sheet is used as a negative electrode, the button cell is assembled, the electrochemical impedance spectrum is tested through an electrochemical workstation, the ion conductivity is calculated, and the charge and discharge test is carried out by using the multiplying power of 0.5C (first two circles) -1C.
Example 11
(1) Preparation of monomer of normal temperature molten salt polymeric material
45g of sodium hydrogen 2-bromoethylphosphonate and 40g of 4-vinylimidazole were dissolved in 50mL of dimethyl sulfoxide and reacted at 80℃for 48h. After the reaction, distillation was carried out at 80℃and 10mbar for 2h to give a pale yellow powder. Stirring the pale yellow powder with 50mL absolute ethanol, filtering, repeating for six times, and distilling at 80 ℃ and 10mbar for 40min to obtain monomer powder product of the pale yellow normal temperature molten salt polymeric material.
(2) Ion conductive material precursor solution composition: monomer of normal temperature molten salt polymerization material, salt: lithium difluorooxalato borate: 30% of monomer mass of a normal-temperature molten salt polymerization material, and an initiator: azodicyanovaleric acid (1% of monomer mass of molten salt polymeric material at normal temperature).
(3) Preparation of ion-conducting materials
Under inert atmosphere, monomer and salt of the normal temperature molten salt polymerization material are dissolved in formamide, then initiator is added and stirred for 2 hours to obtain uniform solution, the solution is uniformly coated on a glass plate, the solution is heated at 80 ℃ for 24 hours, and then the formamide is removed by vacuumizing at 80 ℃ to obtain the ion conduction material with the normal temperature molten salt polymerization material.
(4) Battery assembly
Lithium cobalt oxide (LiCoO) 2 ) +carbon black (SP) +polyvinylidene fluoride (HSV 900) (mass ratio 8:1:1) is used as a positive electrode material, an ion conducting material is used as an electrolyte, a lithium sheet is used as a negative electrode, the button cell is assembled, electrochemical impedance spectroscopy is tested through an electrochemical workstation, ion conductivity is calculated, and charge and discharge tests are carried out with a 0.5C (first two circles) -1C multiplying power.
Example 12
(1) Preparation of monomer of normal temperature molten salt polymeric material
45g of sodium 2-bromoethyl borate and 40g of 4-vinylimidazole were dissolved in 50mL of dimethyl sulfoxide and reacted at 80℃for 48 hours. After the reaction, distillation was carried out at 80℃and 10mbar for 2h to give a pale yellow powder. Stirring the pale yellow powder with 50mL absolute ethanol, filtering, repeating for six times, and distilling at 80 ℃ and 10mbar for 40min to obtain monomer powder product of the pale yellow normal temperature molten salt polymeric material.
(2) Ion conductive material precursor solution composition: monomer of normal temperature molten salt polymerization material, salt: lithium bis-fluorosulfonyl imide: 30% of monomer mass of a normal-temperature molten salt polymerization material, and an initiator: azodicyanovaleric acid (1% of monomer mass of molten salt polymeric material at normal temperature).
(3) Preparation of ion-conducting materials
Under inert atmosphere, monomer and salt of the normal temperature molten salt polymerization material are dissolved in formamide, then initiator is added and stirred for 2 hours to obtain uniform solution, the solution is uniformly coated on a glass plate, the solution is heated at 80 ℃ for 24 hours, and then the formamide is removed by vacuumizing at 80 ℃ to obtain the ion conduction material with the normal temperature molten salt polymerization material.
(4) Battery assembly
Lithium cobalt oxide (LiCoO) 2 ) +carbon black (SP) +polyvinylidene fluoride (HSV 900) (mass ratio 8:1:1) is used as a positive electrode material, an ion conducting material is used as an electrolyte, a lithium sheet is used as a negative electrode, the button cell is assembled, electrochemical impedance spectroscopy is tested through an electrochemical workstation, ion conductivity is calculated, and charge and discharge tests are carried out with a 0.5C (first two circles) -1C multiplying power.
Comparative example 1
(1) Preparation of monomer of conventional normal-temperature molten salt
25g of 1-bromobutane was taken and dissolved with 25g of 1-vinylimidazole in 50mL of ethyl acetate and reacted at 80℃for 48 hours. After the reaction has ended, distillation is carried out at 80℃and 10mbar for 40min. After the distillation was completed, the mixture was washed three times with 20mL of ethyl acetate (liquid separation), and distilled at 80℃and 10mbar for 40 minutes to obtain a product.
Dissolving 10g of the product obtained in the previous step in 10mL of chloroform; 10g of lithium bistrifluoromethane sulphonimide (LiTFSI) was dissolved in 10mL of deionized water and slowly added dropwise at 40℃and stirring was continued for 24h at 40 ℃. After the reaction was completed, the reaction mixture was washed three times with deionized water. And (3) distilling at 70 ℃ under reduced pressure for 40 min, and freeze-drying after the distillation is finished to obtain the conventional normal-temperature molten salt monomer.
(2) Polymer ion conducting material precursor solution composition: conventional normal temperature molten salt monomer, salt: 30% of monomer mass of normal temperature molten salt polymerization material, and an oil-soluble initiator: azobisisobutyronitrile (1% of the monomer mass of the normal temperature molten salt polymeric material).
(3) Preparation of conventional normal-temperature-polymerization fused salt ion conducting material
Under inert atmosphere, the monomer and salt of the normal temperature molten salt polymerization material are dissolved in NMP, then an initiator is added and stirred for 2 hours to obtain a uniform solution, the solution is uniformly coated on a glass plate, the solution is heated at 80 ℃ for 24 hours, and then the NMP is removed by vacuumizing at 80 ℃ to obtain the ion conduction material with the conventional normal temperature molten salt polymerization.
(4) Battery assembly
Lithium cobalt oxide (LiCoO) 2 ) +carbon black (SP) +polyvinylidene fluoride (HSV 900) (mass ratio 8:1:1) is used as a positive electrode material, an ion conducting material is used as an electrolyte, a lithium sheet is used as a negative electrode, the button cell is assembled, electrochemical impedance spectroscopy is tested through an electrochemical workstation, ion conductivity is calculated, and charge and discharge tests are carried out with a 0.5C (first two circles) -1C multiplying power.
Table 1 test results of examples and comparative examples
Figure SMS_7
The monomer of the normal-temperature molten salt polymerization material is successfully obtained by the method, the monomer of the normal-temperature molten salt polymerization material obtained in the examples 1-8 is characterized by taking the example 1 as an example, the result is shown in the figure 1, and the method can be verified from the figure 1. The ion conductive material having the room temperature molten salt polymerization material was formed by compounding the monomer of the room temperature molten salt polymerization material with a salt and an initiator, and the obtained ion conductive material was used in a battery as shown in examples 1 to 12. As a result of comparison between example 1-example 12 and comparative example 1, it was found that the electrical properties of the cells of the examples of the present invention were significantly superior to those of the comparative examples, as shown in table 1. Therefore, the ion conducting material with the normal-temperature molten salt polymeric material can reduce the resistance of the battery, thereby being beneficial to the exertion of the electric performance of the battery. It is considered that it is possible that firstly, by designing the normal-temperature molten salt, negatively charged groups and positively charged groups in the normal-temperature molten salt are removed by a desalting mode, so that the normal-temperature molten salt without negatively charged groups and positively charged groups (namely, the monomer of the normal-temperature molten salt polymeric material) is obtained. In the battery circulation process, the electric performance reduction of the battery caused by the directional migration of negatively charged groups in the traditional normal-temperature molten salt polymeric material is reduced. On the basis, the structure of the monomer of the normal-temperature molten salt polymerization material is further designed, and under the action of an initiator, the monomer of the normal-temperature molten salt polymerization material and salt are combined with each other, so that the monomer of the normal-temperature molten salt polymerization material and the salt form an ion conduction material which is stable and has an ion migration channel and is provided with the normal-temperature molten salt polymerization material, and the electric performance of the battery is further improved.
Based on the above, we further research that when the types and the addition amounts of monomers, salts and initiators of the normal-temperature molten salt polymeric material and the conditions for forming the ion conductive material are different, the application results of the generated ion conductive material in the battery are different.
We first studied the optimization of the addition amount of salt on the electrical properties of the produced room temperature molten salt polymeric material, as shown in examples 1-3. It was found that the battery of example 1 had the best electrical performance, and it was thought that the ionic conductivity of the ion conducting material tended to increase and then decrease with increasing salt addition. When the addition amount of the salt is increased, the salt in the ion conducting material can be promoted to dissociate more lithium ions, so that the transmission amount of the ions in the ion conducting material is promoted, and the electric performance of the battery is promoted; when the addition amount of the salt is too large, the viscosity in the slurry is increased, so that the dispersion is not facilitated, a uniformly dispersed lithium ion migration channel cannot be formed by matching the salt with the normal-temperature molten salt polymerization material, the migration of ions in the ion conduction material is not facilitated, and the electrical performance of the battery is reduced. We further prefer that the salt is added in an amount of 25% -35% of the monomer mass of the normal temperature molten salt polymeric material.
We have also studied the optimization of the amount of initiator added to the electrical properties of the resulting ion-conducting material, as shown in example 1, examples 4-5. We can find that the electrical performance of the battery of example 4 is optimal and we can also verify by sample injection from fig. 2 that the battery of example 4 maintains a high capacity retention after 200 cycles. It is believed that it is possible that as the amount of initiator added increases, the ionic conductivity of the ion conducting material will also tend to decrease as it increases. It is considered that when the addition amount of the initiator is small, the polymerization degree of the monomer of the normal-temperature molten salt polymerization material is small during polymerization, so that the molecular weight of the polymer in the finally obtained ion conduction material is large, the peristaltic movement of the polymer chain is difficult, and the lithium ion transmission is not facilitated; when the additive amount of the initiator is larger, the polymerization degree of the monomer of the normal-temperature molten salt polymerization material is larger, so that the molecular weight of the polymer in the finally obtained ion conduction material is smaller, the long-chain polymer cannot be effectively plasticized, the polymer chain peristalsis is difficult, and the lithium ion transmission is also difficult. It is further preferable that the addition amount of the initiator is 0.5% -1.5% of the monomer mass of the normal temperature molten salt polymerization material.
We have further studied the optimisation of the formation of ion-conducting materials without the use of a type of initiator and compared example 4 with example 8, example 4 is found to be superior to example 8. The photoinitiator and the thermal initiator are used in the invention, so that the ionic conduction material with a lithium ion migration channel can be formed under the mutual coordination of the monomer and the salt of the normal-temperature molten salt polymerization material, and compared with the photoinitiator, the thermal initiator can promote the coordination between the monomer and the salt of the normal-temperature molten salt polymerization material to be more sufficient, so that the ionic conduction material with a more stable structure can be formed. We further prefer thermal initiators.
On this basis, we have also studied the optimization of the polymerization conditions for the formation of the ion-conducting material with respect to the electrical properties of the ion-conducting material produced, as compared with examples 1, 6-7. We found that example 7 has the best electrical performance. We have found that as the polymerization temperature increases, the ionic conductivity of the ion conducting material also tends to decrease as it increases. It is considered that when the polymerization temperature is low, the molecular weight of the polymer of the finally obtained ion conducting material is large, the peristaltic movement of the polymer chain is difficult, and the lithium ion transmission is difficult; when the polymerization temperature is high, the polymerization degree of the monomer of the normal-temperature molten salt polymerization material is high, the content of small molecular polymer in the polymer is low, long-chain polymer cannot be effectively plasticized, the peristaltic movement of polymer chains is difficult, and lithium ion transmission is also difficult. We further prefer the heating temperature for the polymerization to be 75℃to 85 ℃.
The coordination between different systems of the ion conduction material is also studied, and five-membered heterocycle in the monomer structure of the imidazole-based normal-temperature molten salt polymerization material is considered to be a conjugated system with closed large pi bond, so that the electron withdrawing capability of N is improved, oxygen in hydroxyl in phosphorus hydroxyl also has an electron withdrawing effect, phosphorus element in phosphorus hydroxyl can provide rich electrons, and the crystal structure of the monomer forming the stable normal-temperature molten salt polymerization material is promoted, so that the lithium ion transmission channel is constructed in the ion conduction material, the stability of the normal-temperature molten salt polymerization material in the ion conduction material is facilitated, and the electrochemical performance of the battery is improved in the circulation process of the battery; the salt with anions in the boron-based salt has better thermal stability, the salt with anions in the boron-based salt is characterized by electron deficiency, the phosphorus element with phosphorus hydroxyl promotes the surface of the normal-temperature molten salt polymerization material to have rich electrons, and the monomer of the imidazole type normal-temperature molten salt polymerization material with phosphorus hydroxyl can better combine with the salt with anions in the boron-based salt, thereby being beneficial to laying the foundation of forming the ion conduction material with a stable structure. The thermal initiator can promote the sufficient combination between the monomer and the salt of the normal temperature molten salt polymeric material, thereby being beneficial to forming the ion conducting material with stable structure. Comparison of examples 4, 9 and 12 shows that the battery of example 11 has optimal electrical performance, and the resistance of the battery of example 11 is reduced by more than 51 times compared with that of comparative example 1, the ionic conductivity is improved by more than 51 times, and the capacity retention rate is improved by about 2 times. Therefore, the invention can obviously improve the electrochemical performance of the battery. We further prefer that the monomer of the normal temperature molten salt polymeric material having an imidazole group and a phosphorus hydroxyl group, the salt having an anion in a boron-based salt, and the ion conductive material of a thermal initiator are added in an amount of 25 to 35% by mass of the monomer of the normal temperature molten salt polymeric material, and the thermal initiator is added in an amount of 0.5 to 1.5% by mass of the monomer of the normal temperature molten salt polymeric material.
In conclusion, the monomer of the normal-temperature molten salt polymerization material designed by the invention not only can solve the problem of the reduction of the electric performance of the battery caused by negatively charged groups in the traditional normal-temperature molten salt, but also can form an ion conduction material under the mutual coordination of salt and an initiator, thereby being beneficial to improving the electrochemical performance of the battery.
It should be noted that the above-mentioned embodiments are only preferred embodiments of the present invention, and are not intended to limit the present invention, and any modifications, equivalent substitutions, improvements, etc. within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. The normal-temperature molten salt polymeric material is characterized by having a structure of formula I:
Figure QLYQS_1
；
wherein X is selected from imidazolyl or pyridyl; y is Y — One of charged groups selected from carboxylate, sulfonate, silicate, phosphate and borate; n is an integer greater than 1; n' is an integer from 0 to 10; y is Y — To the N atom on the imidazole or pyridine ring of X.
2. The molten salt polymeric material of claim 1 wherein Y is — Has the structure of formula II:
Figure QLYQS_2
；
wherein M is M/2, M is a positive integer; r is selected from one of carboxylate radical, sulfonate radical, silicon hydroxyl radical, phosphate hydroxyl radical and boron hydroxyl radical; the n' is preferably an integer from 0 to 5;
Further preferably, M is a positive integer and M is 2-6.
3. An ion conducting material having the ambient temperature molten salt polymeric material of any one of claims 1 to 2.
4. The ion conducting material according to claim 3, wherein the ion conducting material comprises a normal temperature molten salt polymeric material, salt;
further preferably, the raw materials of the ion conduction material comprise monomer, salt and initiator of the normal-temperature molten salt polymerization material, wherein the adding amount of the salt is 5-50% of the monomer mass of the normal-temperature molten salt polymerization material, and the adding amount of the initiator is 0.1-5% of the monomer mass of the normal-temperature molten salt polymerization material;
further preferably, the addition mass of the salt is 25% -35% of the monomer mass of the normal-temperature molten salt polymerization material;
further preferably, the addition mass of the initiator is 0.5% -1.5% of the monomer mass of the normal-temperature molten salt polymerization material.
5. The ion conducting material of claim 4, wherein the salt comprises one or more of ABx, wherein a is selected from one of lithium ion, sodium ion, potassium ion, magnesium ion, aluminum ion, zinc ion, and B is selected from one of chloride-based salt, boron-based salt, arsenic-based salt, phosphorus-based salt, sulfonic acid-based salt, sulfonimide-based salt, aluminum-based salt;
Further preferably, the anion of the chloride-based salt comprises ClO 4 - ；
Further preferably, the boron-based salt comprises a borate, wherein the anions in the borate comprise one or more of tetrafluoroborate ion, difluoro oxalato borate ion and bis oxalato borate ion;
further preferably, the anions in the arsenical salt comprise hexafluoroarsenate ions;
further preferably, the anions in the phosphorus-based salt include one or more of hexafluorophosphate ions, tris (pentafluoroethyl) trifluorophosphate ions;
further preferably, the anions in the sulfonate comprise trifluoromethane sulfonate ions;
further preferably, the anion in the sulfonimide salt comprises one or more of bis (fluorosulfonyl) imide ion, bis (trifluoromethylsulfonyl) imide ion, fluorosulfonyl- (trifluoromethylsulfonyl) imide ion, and bis (perfluoro-ethylsulfonyl) imide ion;
further preferably, the anions in the aluminum-based salt comprise one or more of tetrachloroaluminate ions and tetrafluoroaluminate ions.
6. The ion conducting material of claim 4, wherein the initiator comprises a thermal initiator, a photoinitiator;
Further preferably, the thermal initiator comprises one or more of azobisisobutylamidine hydrochloride, azobisiso Ding Mi hydrochloride, azobiscyano valeric acid, azobisiso propyl imidazoline;
further preferably, the photoinitiator comprises one or more of 2-hydroxy-2, 2-dimethyl acetophenone, 2 '-azo-bis (2-amidinopropane), tris (2, 2' -bipyridine) ruthenium (ii).
7. The ion conductive material according to claim 4, wherein the raw materials of the ion conductive material comprise a monomer of a normal temperature molten salt polymeric material having a structure of formula III, a salt having an anion in a boron-based salt, and a thermal initiator, wherein the addition amount of the salt having the anion in the boron-based salt is 25 to 35% of the monomer mass of the normal temperature molten salt polymeric material, and the addition amount of the thermal initiator is 0.5 to 1.5% of the monomer mass of the normal temperature molten salt polymeric material, in mass;
Figure QLYQS_3
；
wherein n' is an integer of 0 to 10; x is selected from imidazolyl; y is Y — Selected from the group consisting of having a phosphorus hydroxyl radical; y is Y — To the N atom of the imidazole ring of X.
8. The method for preparing the monomer of the normal-temperature molten salt polymerization material according to any one of claims 1 to 2, wherein the preparation method comprises the steps of carrying out quaternization reaction on vinyl imidazole or vinyl pyridine and alkane of a group Y, wherein a solvent for the quaternization reaction comprises alkyl sulfoxide, so that the monomer of the normal-temperature molten salt polymerization material with the structure of a formula II connected with N atoms on imidazole rings or pyridine rings and halogen salts are obtained; then, carrying out primary distillation; desalting, wherein the desalted reagent is monohydric alcohol; secondary distillation;
Wherein the alkane of the group Y has a structure shown in the following formula IV, M is M/2, M is a positive integer, and preferably 2-6; r is selected from one of carboxylate radical, sulfonate radical, silicon hydroxyl radical, phosphate hydroxyl radical and boron hydroxyl radical; a comprises halogen, and specifically comprises Cl, br and I; d comprises metal ions, and specifically comprises one of sodium ions, lithium ions and potassium ions;
Figure QLYQS_4
；
the reaction route of the step is as follows:
Figure QLYQS_5
；/>
Figure QLYQS_6
；
wherein X is selected from imidazolyl or pyridyl; y is Y — One of charged groups selected from carboxylate, sulfonate, silicate, phosphate and borate; n's'An integer of 0 to 10;
Y — to the N atom on the imidazole or pyridine ring of X.
9. The preparation method according to claim 8, wherein the solvent for the quaternization reaction comprises alkyl sulfoxide, wherein the number of carbons in the alkyl sulfoxide is preferably 6, 5, 4, 3, 2 in sequence; the temperature of the primary distillation is not lower than 90 ℃; the desalting agent is selected from one of monohydric alcohols of C1-C6; the temperature of the secondary distillation is not lower than 60 ℃;
further preferably, the quaternization reaction is carried out at 60-100 ℃ for 24-72 hours, and the reaction solution comprises dimethyl sulfoxide; the conditions of the distillation are that the distillation is carried out at 90-110 ℃ and 8-12 mbar for 1.5-2.5 h; the desalted reagent comprises absolute ethanol; and distilling under reduced pressure at 60-80 ℃ for 30-50 min under the condition of secondary distillation to obtain the monomer of the normal-temperature molten salt polymerization material.
10. The method for producing an ion conductive material according to any one of claims 3 to 7, wherein the method comprises dissolving monomers and salts of a normal temperature molten salt polymerization material in an organic solvent under an inert atmosphere, then adding an initiator, stirring to obtain a uniform solution, heating for polymerization or light polymerization, and then removing the organic solvent to obtain an ion conductive material;
further preferably, the organic solvent includes an amide-based solvent; the stirring time is not less than 2 hours; the heating temperature is 40-90 ℃, and the heating time is 6-72 h; the illumination condition is 365nm ultraviolet light, and the time is 5s-1h; the method for removing the organic solvent comprises the steps of vacuumizing and removing at 75-85 ℃;
further preferably, the amide solvent comprises one or more of formamide, acetamide, N-dimethylformamide and N, N-dimethylacetamide;
further preferably, the heating polymerization is carried out at a temperature of 75-85 ℃ for a time of 6-72 h.
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