CN113130991B - Electrolyte, battery and formation method - Google Patents
Electrolyte, battery and formation method Download PDFInfo
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- CN113130991B CN113130991B CN202110388647.6A CN202110388647A CN113130991B CN 113130991 B CN113130991 B CN 113130991B CN 202110388647 A CN202110388647 A CN 202110388647A CN 113130991 B CN113130991 B CN 113130991B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0567—Liquid materials characterised by the additives
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/44—Methods for charging or discharging
- H01M10/446—Initial charging measures
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses electrolyte, which comprises an additive, wherein the additive is one or more of a compound containing a sulfonic acid group, a compound containing a phosphoric acid group, a phenol derivative containing an electron-withdrawing group substitution, and a carboxylic acid compound containing an electron-withdrawing group on alpha-C, and the pKa value of the additive is 0 to 5; wherein the electron-withdrawing group is a tertiary amine positive ion group, -F, -Cl, -NO2、‑CF3、‑CCl3One or more of them. The electrolyte of the invention contains the additive which can not only react with the 'dead lithium' such as lithium carbonate and lithium hydroxide on the surface of the positive electrode material to form 'active lithium', but also fully react with the 'dead lithium' such as lithium carbonate and alkyl lithium carbonate generated in the SEI to form 'active lithium', thereby fully exerting the capacity of the battery.
Description
Technical Field
The invention belongs to the field of batteries, and particularly relates to an electrolyte, a battery containing the electrolyte and a battery formation method.
Background
With the demand of people for high energy density of batteries, the larger the capacity of the batteries is, the higher the proportion of active materials used in the batteries is, the relatively higher the content of inactive dead lithium such as lithium carbonate and lithium hydroxide on the surface of the positive active material is, and as the content of lithium in a battery system is continuously increased, more dead lithium such as lithium carbonate, alkyl lithium carbonate and lithium hydroxide are formed in the process of forming SEI by formation, which leads to the reduction of the capacity of the batteries.
Disclosure of Invention
In order to overcome the defects, the invention provides an electrolyte, a battery containing the electrolyte and a battery formation method.
The invention provides an electrolyte, which comprises an additive, wherein the additive is one or more of a compound containing a sulfonic acid group, a compound containing a phosphoric acid group, a phenol derivative containing an electron-withdrawing group substitution, and a carboxylic acid compound containing an electron-withdrawing group on alpha-C, and the pKa value of the additive is 0 to 5; wherein the electron-withdrawing group is a tertiary amine positive ion group, -F, -Cl, -NO2、-CF3、-CCl3One or more of them.
In another aspect, the present invention provides a battery comprising the electrolyte.
In another aspect, the present invention provides a method for forming a battery, including: injecting an electrolyte into a battery housing containing a battery cell, the electrolyte containing an additive; forming the battery cell injected with the electrolyte; and initiating a polymerization reaction; the additive is one or more of a compound containing a sulfonic acid group, a compound containing a phosphoric acid group, a phenol derivative containing an electron-withdrawing group substitution and a carboxylic acid compound containing an electron-withdrawing group on alpha-C, and the pKa value of the additive is 0 to 5; the electron-withdrawing group is a tertiary amine positive ion group, -F, -Cl, -NO2、-CF3、-CCl3One or more of the above; the additive comprises double and/or triple bonds.
The electrolyte of the invention contains the additive which can react with 'dead lithium' such as lithium carbonate, lithium hydroxide and the like on the surface of the positive electrode material to form 'active lithium', and can also fully react with 'dead lithium' such as lithium carbonate, lithium alkyl carbonate and the like in the SEI film to form 'active lithium', thereby fully exerting the capacity of the battery. Furthermore, the electrolyte can be polymerized in situ after formation, so that dead lithium generated in the SEI forming process is converted into a single-ion conductor, the lithium ion transmission rate of an SEI film can be improved, meanwhile, the polymer formed by in situ polymerization can coat active substance particles, an active particle protective layer is formed in situ, the generated polymer has higher ion transmission rate, the dynamic performance of the battery is improved, and the coating layer also inhibits the growth of lithium dendrite.
Detailed Description
The present invention will be described in detail with reference to the following embodiments.
The electrolyte comprises an additive, wherein the additive is one or more of a compound containing a sulfonic acid group, a compound containing a phosphoric acid group, a phenol derivative containing an electron-withdrawing group substitution, and a carboxylic acid compound containing an electron-withdrawing group on alpha-C, and the pKa value of the additive is 0 to 5; wherein the electron-withdrawing group is a tertiary amine positive ion group, -F, -Cl, -NO2、-CF3、-CCl3One or more of them. The phrase "phenol derivative substituted with an electron-withdrawing group" means that the phenol derivative may contain other substituent groups in addition to the electron-withdrawing group substituent group, and of course the phenol derivative also includes a phenol derivative substituted with only an electron-withdrawing group. In the electrolyte of the present invention, the additive having a specific structure and having a Pka of 0 to 5 is contained, and this additive can react with "dead lithium" such as lithium carbonate and lithium hydroxide on the surface of the positive electrode material to form "active lithium", and can sufficiently react with lithium carbonate and lithium alkylcarbonate in the SEI film formed on the surface of the negative electrode of the battery to form "active lithium" such as a compound having a lithium sulfonate group, a compound having a lithium carboxylate group, a compound having a lithium phenolate group, and a compound having a lithium phosphate group, and thus can participate in an electrochemical reaction, whereby the capacity of the battery can be sufficiently exhibited. This is because the Pka of the additive is less than 6 for carbonic acid with a Pka of 6, which reacts with lithium carbonate and the like, but too strong acidity corrodes the current collector when the Pka is too small, for example, less than 0. In order to satisfy the sufficient reaction of the additive with the carbonate in the SEI film, it is preferable that the pKa of the additive satisfies 0. ltoreq. pKa. ltoreq.5.
In alternative embodiments, the inclusion additive comprises double and/or triple bonds. The additive contains polymerizable functional groups with double bonds and/or triple bonds, so that the additive can be polymerized, namely the additive is polymerized after the additive reacts with 'dead lithium' in an SEI film, the 'dead lithium' is converted into available 'active lithium', the generated 'active lithium' can participate in electrode reaction, the coulombic efficiency of the battery is improved, meanwhile, in-situ polymerization forms an in-situ coating layer on active particles, the in-situ coating layer formed by polymerization can play a role in protecting active materials, and the formed polymer is a single-ion conductor polymer (such as PAMPSLi) and has higher ion transmission rate, the lithium ion transmission performance can be improved, the dynamic performance of the battery is improved, the growth of lithium dendrites is inhibited, and the cycle life and the coulombic efficiency of the battery can be improved.
In alternative embodiments, the additive may be one or more of 2-acrylamido-2-methylpropanesulfonic acid, p-styrenesulfonic acid, monochloroacetic acid, dichloropropionic acid, trifluoroacetic acid, monochloro-p-vinylphenol, monochloro-m-propenylphenol, 2-nitro-4-propenylphenol, 2-nitrophenol, 4-nitrophenol, 2, 6-dichlorophenol, 4-propenyl-2, 6-dichlorophenol, cis-propenylphosphoric acid, propadienephosphoric acid, 2, 3-epoxypropanesulfonic acid, and cyclopropanesulfonic acid.
In an optional embodiment, the mass percent of the additive is 3% -10% based on 100% of the total electrolyte mass. When the additive content is less than 3%, the reaction with lithium carbonate and the like in the SEI is insufficient, and thus the improvement of the battery capacity is not large. When the additive content is more than 10%, the ionic conductivity of the electrolyte system is affected to some extent by the formation of too much polymer. One skilled in the art can select an appropriate content within this range according to the kind of the selected additive, such as, but not limited to, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, etc. The battery improvement effect is best when the mass percent of the additive is 5-7%, because the additive in the range can fully react the lithium carbonate and the lithium alkyl carbonate in the SEI film, and the polymerized polymer has better conductivity. .
In an alternative embodiment, the electrolyte further comprises an initiator for initiating polymerization of the electrolyte additive with the reaction product of lithium carbonate and lithium alkylcarbonate. The skilled person can select an appropriate initiator according to the kind of the additive, and the initiator can be, but is not limited to, azo initiator and peroxide initiator. As the azo initiator, there may be, but not limited to, one or more of azobisisobutyronitrile and azobisisoheptonitrile. For peroxide initiators, there may be, but is not limited to, benzoyl peroxide and the like. The mass percent of the initiator is 0.15-1% based on the total mass of the electrolyte as 100%. The person skilled in the art can select an appropriate content within this range according to the kind of initiator selected, such as but not limited to 0.15%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0%, etc.
The invention also provides a battery containing the electrolyte.
The invention also provides a formation method of a battery containing the electrolyte, which comprises the following steps: injecting an electrolyte into a battery housing containing a battery cell, the electrolyte containing an additive; forming the battery cell injected with the electrolyte; and initiating a polymerization reaction; the additive is one or more of a compound containing a sulfonic acid group, a compound containing a phosphoric acid group, a phenol derivative containing an electron-withdrawing group substitution and a carboxylic acid compound containing an electron-withdrawing group on alpha-C, and the pKa value of the additive is 0 to 5; wherein the electron-withdrawing group is a tertiary amine positive ion group, -F, -Cl, -NO2、-CF3One or more of-CCl3(ii) a Wherein the additive comprises double and/or triple bonds. According to the formation method, in the process after formation, the additive (such as AMPS) reacts with 'dead lithium' such as lithium carbonate and lithium alkyl carbonate in an SEI film to generate 'active lithium' (namely AMPSLi), so that the capacity exertion of the battery is improved.
In an alternative embodiment, the electrolyte further comprises an initiator. After the initiator is formed into a battery, the initiator initiates the polymerization reaction of the additive and a 'dead lithium' reaction product (such as AMPSLi) to form a single ion conductor (PAMPSLi), so that the dynamic performance of the PAMPSLi is improved, and meanwhile, an in-situ coating layer formed on an active material protects the active material, avoids the side reaction with electrolyte and improves the circulation stability.
The present invention is further described below by way of specific examples. However, these examples are merely illustrative and do not limit the scope of the present invention in any way.
In the following examples and comparative examples, reagents, materials and instruments used therefor were commercially available unless otherwise specified.
Example 1
Dimethyl carbonate (DMC) and Ethylene Carbonate (EC) are mixed according to a mass ratio of 8: 2, preparing a multi-element blending solvent, and adding lithium salt (lithium hexafluorophosphate) and an additive 2-acrylamide-2-methylpropanesulfonic Acid (AMPS) into the multi-element blending solvent, and an electrolyte initiator Azobisisobutyronitrile (AIBN) to prepare the electrolyte. Wherein the content of lithium hexafluorophosphate in the electrolyte is 1.5 mol/L; based on the total mass of the electrolyte as 100%, the mass content of the additive is 5%, and the mass content of the initiator is 0.75%.
Mixing the negative electrode material graphite with a conductive agent SP, a thickening agent CMC and an adhesive SBR according to the proportion of 95 percent to 2 percent to 1.8 percent to 1.2 percent, uniformly coating the prepared slurry on a copper foil, drying, cutting into pieces, and drying in a vacuum drying oven to obtain the negative electrode piece for later use.
The ternary positive electrode material NCM811 (LiNi)0.8Co0.1Mn0.1O2) Mixing the prepared slurry with a conductive agent SP and an adhesive PVDF according to the proportion of 96 percent to 2 percent, uniformly coating the prepared slurry on an aluminum foil, drying, cutting into pieces, and drying in a vacuum drying oven to obtain the positive plate for later use.
And assembling the prepared positive and negative electrode sheets and a diaphragm (celgard2400 diaphragm) into a battery, injecting liquid and then packaging to obtain the assembled battery to be tested.
The battery with the electrolyte injected is clamped, formed and tested under room temperature. The formation steps are as follows: 1) standing for 1h to stabilize the temperature of the battery; 2) charging to 4.2V at 0.1C constant current; 3) charging to current less than 0.05C (SEI film formation) at constant voltage; 4) standing for 1h (so that AMPS reacts with 'dead lithium' such as lithium carbonate, lithium alkyl carbonate and the like in an SEI film to generate 'active lithium', namely AMPSLi); 5) discharging at constant current until the voltage is less than 2.5V; 6) after circulating for 3 circles and stabilizing, standing for 6 hours at 70 ℃ to ensure that the AMPSLi is polymerized into the PAMPSLi to improve an SEI film. And (3) carrying out cycle rate test on the prepared battery, and specifically comprising the following steps: the cell was taken out and cycled at room temperature for 50 cycles at 0.3C, 50 cycles at 0.5C, and 50 cycles at 1C.
Example 2
The additive was changed to trifluoroacetic acid, and the other components and contents were the same as in example 1, an electrolyte was prepared, and a battery was assembled, formed and tested in the same manner as in example 1.
Example 3
An additive was changed to p-styrenesulfonic acid, and the other components and contents were the same as in example 1, an electrolyte was prepared, and a battery was assembled, and the assembled battery was subjected to formation and testing in the same manner as in example 1.
Example 4
The additive was changed to p-vinylphenol monochloride, the other components and contents were the same as in example 1, an electrolyte was prepared, and a battery was assembled, formed and tested in the same manner as in example 1.
Example 5
The additive was changed to cis-propenoic acid, and the other components and contents were the same as in example 1, and an electrolyte was prepared and assembled into a battery, and the assembled battery was subjected to formation and testing in the same manner as in example 1.
Example 6
An electrolyte was prepared with the additive content of 3% and the other components and contents being the same as in example 1, based on 100% of the total electrolyte mass, and a battery was assembled, formed and tested in the same manner as in example 1.
Example 7
An electrolyte was prepared in the same manner as in example 1, except that the content of the additive was 7% and the other components and contents were the same as in example 1, based on 100% of the total mass of the electrolyte, and a battery was assembled, and the assembled battery was formed and tested in the same manner as in example 1.
Example 8
An electrolyte was prepared in the same manner as in example 1 with the additive content of 10% and the other components and contents being the same as in example 1, based on 100% of the total electrolyte mass, and a battery was assembled, and the assembled battery was formed and tested in the same manner as in example 1.
Example 9
An electrolyte was prepared with the initiator content of 0.05% and the other components and contents being the same as in example 1, based on 100% of the total electrolyte mass, and a battery was assembled, and the assembled battery was subjected to formation and testing in the same manner as in example 1.
Example 10
An electrolyte was prepared with the initiator content of 0.1% and the other components and contents being the same as in example 1, based on 100% of the total electrolyte mass, and a battery was assembled, and the assembled battery was subjected to formation and testing in the same manner as in example 1.
Example 11
An electrolyte was prepared in the same manner as in example 1 with the initiator content of 0.15% and the other components and contents being the same as in example 1, based on 100% of the total electrolyte mass, and a battery was assembled, and the assembled battery was subjected to formation and testing in the same manner as in example 1.
Example 12
An electrolyte was prepared by changing the initiator to benzoyl peroxide (BOP) and the other components and contents were the same as in example 1, and assembled into a battery, and the assembled battery was subjected to formation and testing in the same manner as in example 1.
Example 13
An initiator was changed to Azobisisoheptonitrile (AIVN), and other components and contents were the same as in example 1, an electrolyte was prepared, and a battery was assembled, and the assembled battery was subjected to formation and testing in the same manner as in example 1.
Comparative example 1
Compared to example 1, the electrolyte solution does not contain additives and initiators, and other components and contents are the same, the electrolyte solution is prepared, and the battery is assembled, and the assembled battery is subjected to formation and testing in the same manner as in example 1.
Comparative example 2
The additive was changed to nitric acid, and the other components and contents were the same as in example 1, an electrolyte was prepared, and a battery was assembled, formed and tested in the same manner as in example 1.
Comparative example 3
The additive was changed to carbonic acid, and the other components and contents were the same as in example 1, an electrolyte was prepared, and a battery was assembled, and the assembled battery was formed and tested in the same manner as in example 1.
Comparative example 4
An electrolyte was prepared with the content of additives being 1% and the other components and contents being the same as in example 1, based on 100% of the total mass of the electrolyte, and a battery was assembled, and the assembled battery was formed and tested in the same manner as in example 1.
Comparative example 5
An electrolyte was prepared in the same manner as in example 1, except that the content of the additive was 12% and the other components and contents were the same as in example 1, based on 100% of the total mass of the electrolyte, and a battery was assembled, and the assembled battery was formed and tested in the same manner as in example 1.
Comparative example 6
An electrolyte was prepared with the same composition and content as in example 1, and assembled into a battery.
The formation steps of the battery are as follows: standing at 70 ℃ for 6h to polymerize AMPSLi into PAMPSLi and improve SEI film, and performing formation and cycle rate test in the same manner as in example 1.
Comparative example 7
An electrolyte was prepared with the same composition and content as in example 1, and a battery was assembled.
And directly carrying out formation on the assembled battery, and directly carrying out cycle rate test on the formed battery without standing.
Comparative example 8
An electrolyte was prepared with the initiator content of 0.1% and the other components and contents being the same as in example 1, based on 100% of the total electrolyte mass, and a battery was assembled, and the assembled battery was subjected to formation and testing in the same manner as in example 1.
Comparative example 9
An electrolyte was prepared with the initiator content of 1.2% and the other components and contents being the same as in example 1, based on 100% of the total electrolyte mass, and a battery was assembled, formed and tested in the same manner as in example 1.
The compositions of the electrolytes of examples 1 to 13 and comparative examples 1 to 9 and the polymerization time in the electrolytes are shown in table 1.
TABLE 1
The cycle rate performance of the batteries prepared in examples 1 to 13 and comparative examples 1 to 9 is shown in table 2.
TABLE 2
Combining examples 1-13 and comparative examples 1-9 and the test results thereof, it can be seen that the cycle performance of the battery can be significantly improved using the electrolyte of the present invention.
Specifically, comparing example 1 with comparative example 1, it can be seen that the first-turn capacity and cycle life of the battery are significantly improved upon addition of the additive. The additive can react with 'dead lithium' such as lithium carbonate, lithium alkyl carbonate and the like in the SEI film to generate 'active lithium', so that the capacity exertion of the battery is improved; and subsequent polymerization provides a protective layer for the active material particles, thereby improving cycle life and coulombic efficiency.
Comparing the test results of examples 1-3 and comparative examples 2-3, it can be seen that the cycle rate performance of the comparative battery is best when the additive is added to the electrolyte and the pKa value of the additive is between 0 and 5. It can be seen from the test results of comparative examples 1 to 3 and comparative example 1 that the smaller the pKa (the more acidic) has a greater influence on the battery capacity. It is likely that the more acidic the additive, the more sufficient the reaction with lithium carbonate and lithium alkyl carbonate is, and therefore the more the capacity of the battery is affected. It can be seen from the comparison of the test results of comparative example 1 and comparative examples 2 to 3 that the pKa values of the additives in the electrolyte are less than 0 or greater than 6, which decreases the discharge capacity and coulombic efficiency of the battery, decreasing the cycle performance of the battery. This may be that the additive was not able to activate the "dead lithium" in the cell without acting as an additive (comparative example 3) and even further corroded the current collector (copper and aluminum foils) (comparative example 2).
For examples 1-5, it can be seen that the additives AMPS, trifluoro acrylic acid, p-styrenesulfonic acid, p-vinylphenol monochloride, and cis-propenylphosphoric acid, respectively, exhibited substantially the same effect in the cells. This shows that when the pKa value of the additive is 0 to 5, the acidic groups contained in the additive can completely react with lithium carbonate and lithium alkyl carbonate, and can react with "dead lithium" such as lithium carbonate and lithium alkyl carbonate in the SEI film to generate "active lithium", thereby improving the capacity exertion of the battery; subsequent polymerization provides a protective layer of active material, thereby increasing cycle life and coulombic efficiency.
Comparing the test results of examples 1,6-8 and comparative examples 4-5, it can be seen that the content of the additive in the electrolyte is between 3-10% to provide a certain improvement effect on the battery, wherein the content of the additive of 5-7% is the best effect. The additive with the content in the range can improve the SEI film to ensure that lithium carbonate and alkyl lithium carbonate in the SEI film are fully converted into AMPSLi, and the PAMPSLi after polymerization has little influence on the conductivity of an electrolyte system, so that the performance of the battery is improved. And if the additive is too little, lithium carbonate and alkyl lithium carbonate in the SEI film can not fully react, and if the additive is too much, the additive can fully react with lithium carbonate and alkyl lithium carbonate in the SEI film, but if the additive is too much, the additive can have a certain influence on the ionic conductivity of an electrolyte system, so that the influence on the performance improvement of the battery is not large, and even the performance of the battery is reduced.
Comparing the test results of example 1 and comparative examples 1 and 8, it can be seen that the polymerization before formation is identical to the test results of the cells without additive. This indicates that polymerization before formation reduces the acidity of PAMPS, which results in PAMPS not reacting with carbonate in the SEI film after formation, and thus not acting as an additive.
Comparing the test results of example 1 and comparative examples 1 and 9, it can be seen that the non-polymerization in the battery fluid has little influence on the capacity of the first cycle of the battery, but has a certain influence on the cycle performance. The additive can react with 'dead lithium' such as lithium carbonate, lithium alkyl carbonate and the like in the SEI film to generate 'active lithium' in the formation stage, so that the capacity exertion of the battery is improved; however, subsequent non-polymerization cannot form a protective layer for the active material particles, and cannot protect the side reaction of the active material particles and the electrolyte, thereby causing rapid decay of cycle life and coulombic efficiency.
Comparing the test results of examples 1 and 9 to 13 with those of comparative examples 8 and 9, it can be seen that if the amount of the initiator is too low, for example, 0.15%, the subsequent polymerization is affected, such that the AMPSLi cannot be completely polymerized and a continuous polymer cannot be formed, and if the AMPSLi cannot be completely polymerized, the active material particles cannot be well coated and the active material particles cannot be well protected, such that the damage of the reaction of the AMPS with lithium carbonate and lithium alkyl carbonate to the SEI film cannot be repaired, thereby affecting the stability of the SEI film, and further causing the rapid decay of the battery cycle life and the coulombic efficiency. If the content of the initiator is too high, for example, 1.2%, the additive is too fast to be polymerized and cannot fully react with carbonate in an SEI film, and the first-cycle capacity exertion is influenced.
In comparative example 13 and example 1, when the initiator content was reduced to 0.15%, there was no significant decrease in performance as compared to example 1, since 0.15% of the initiator polymerized the product after the reaction with lithium carbonate and lithium alkylcarbonate, and polymerization was achieved with only a prolonged polymerization time.
The preferred embodiments of the invention disclosed above are intended to be illustrative only. The preferred embodiments are not intended to be exhaustive or to limit the invention to the precise embodiments disclosed. Obviously, many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, to thereby enable others skilled in the art to best utilize the invention. The invention is limited only by the claims and their full scope and equivalents.
Claims (15)
1. The electrolyte is characterized by comprising an additive, wherein the additive is one or more of a compound containing a sulfonic acid group, a compound containing a phosphoric acid group and a carboxylic acid compound containing an electron withdrawing group on alpha-C, and the pKa value of the additive is 0 to 5; wherein the electron-withdrawing group is a tertiary amine positive ion group, -F, -Cl, -NO2、-CF3、-CCl3One or more of them.
2. The electrolyte of claim 1, wherein the additive comprises double and/or triple bonds.
3. The electrolyte is characterized by comprising an additive, wherein the additive is a phenol derivative substituted by an electron-withdrawing group, and the electron-withdrawing group is a tertiary amine positive ion group, -F, -Cl, -NO2、-CF3、-CCl3Wherein the additive comprises double and/or triple bonds.
4. The electrolyte according to claim 1 or 3, wherein the additive is one or more of 2-acrylamide-2-methylpropanesulfonic acid, p-styrenesulfonic acid, monochloroacetic acid, dichloropropionic acid, trifluoroacetic acid, monochloro-p-vinylphenol, monochloro-m-propenylphenol, 2-nitro-4-propenylphenol, 2-nitrophenol, 4-nitrophenol, 2, 6-dichlorophenol, 4-propenyl-2, 6-dichlorophenol, cis-propenylphosphoric acid, propadienephosphoric acid, 2, 3-epoxypropanesulfonic acid, and cyclopropanesulfonic acid.
5. The electrolyte according to claim 1 or 3, wherein the additive is present in an amount of 3 to 10% by mass, based on 100% by mass of the total electrolyte.
6. The electrolyte according to claim 1 or 3, wherein the additive is 5-7% by mass based on 100% by mass of the total electrolyte.
7. The electrolyte of claim 2 or 3, further comprising an initiator.
8. The electrolyte of claim 7, wherein the initiator is an azo initiator and/or a peroxide initiator.
9. The electrolyte of claim 8, wherein the initiator comprises one or more of azobisisobutyronitrile, benzoyl peroxide, and azobisisoheptonitrile.
10. The electrolyte of claim 7, wherein the mass percent of the initiator is 0.15% -1% of the total mass of the electrolyte being 100%.
11. A battery comprising the electrolyte of any one of claims 1 to 10.
12. A method of forming a battery, comprising:
injecting an electrolyte into a battery housing containing a battery cell, the electrolyte containing an additive;
forming the battery cell injected with the electrolyte; and
initiating a polymerization reaction;
the additive is one or more of a compound containing a sulfonic acid group, a compound containing a phosphoric acid group, a phenol derivative containing an electron-withdrawing group substitution and a carboxylic acid compound containing an electron-withdrawing group on alpha-C, and the pKa value of the additive is 0 to 5; the electron-withdrawing group is a tertiary amine positive ion group, -F, -Cl, -NO2、-CF3、-CCl3One or more of the above; the additive comprises double and/or triple bonds.
13. The chemical formation method of claim 12, wherein the electrolyte further comprises an initiator.
14. The chemical synthesis method according to claim 13, wherein the initiator is an azo initiator and/or a peroxide initiator.
15. The chemical synthesis method of claim 13, wherein the initiator comprises one or more of azobisisobutyronitrile, benzoyl peroxide and azobisisoheptonitrile.
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| JP2017111927A (en) * | 2015-12-15 | 2017-06-22 | 株式会社アルバック | Electrolyte for secondary battery and lithium-sulfur secondary battery |
| CN111313093A (en) * | 2019-12-24 | 2020-06-19 | 安徽圣格能源科技有限公司 | Electrolyte and lithium battery |
| CN112271338A (en) * | 2020-11-27 | 2021-01-26 | 凯博能源科技有限公司 | Electrolyte and lithium ion battery containing same |
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| WO2010058717A1 (en) * | 2008-11-21 | 2010-05-27 | 宇部興産株式会社 | Non-aqueous electrolytic solution, and lithium battery comprising same |
| WO2018123751A1 (en) * | 2016-12-28 | 2018-07-05 | パナソニックＩｐマネジメント株式会社 | Non-aqueous electrolyte secondary cell |
| CN111564665B (en) * | 2020-05-08 | 2021-05-11 | 广东金光高科股份有限公司 | Ultra-high temperature safety lithium ion battery electrolyte and lithium ion battery using same |
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| JP2938430B1 (en) * | 1998-03-17 | 1999-08-23 | 株式会社東芝 | Lithium secondary battery |
| JP2000156245A (en) * | 1998-11-19 | 2000-06-06 | Japan Storage Battery Co Ltd | Nonaqueous electrolyte battery |
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| CN102683746A (en) * | 2012-05-04 | 2012-09-19 | 百顺松涛（天津）动力电池科技发展有限公司 | Lithium battery electrolyte additive and electrolyte using same as well as battery |
| JP2017111927A (en) * | 2015-12-15 | 2017-06-22 | 株式会社アルバック | Electrolyte for secondary battery and lithium-sulfur secondary battery |
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