CN115207466A - Electrolyte and lithium ion battery thereof - Google Patents
Electrolyte and lithium ion battery thereof Download PDFInfo
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- CN115207466A CN115207466A CN202210821349.6A CN202210821349A CN115207466A CN 115207466 A CN115207466 A CN 115207466A CN 202210821349 A CN202210821349 A CN 202210821349A CN 115207466 A CN115207466 A CN 115207466A
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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
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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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
- H01M10/058—Construction or manufacture
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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
- H01M2300/0028—Organic electrolyte characterised by the solvent
- H01M2300/0037—Mixture of solvents
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- 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
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- Condensed Matter Physics & Semiconductors (AREA)
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Abstract
The invention discloses an electrolyte and a lithium ion battery thereof, which comprise lithium salt, an organic solvent and an additive; the additive at least comprises a compound A, and the content of the compound A is 0.5-8% of the total weight of the electrolyte; the structural general formula of the compound A is shown as the following formula I:
in the formula I, at least one of R1, R2 and R3 is an alkoxyalkyl group having 1 to 20 carbon atoms, at least one is O-TMS, and the rest is selected from the group consisting of an alkoxyalkyl group having 1 to 20 carbon atoms, CN-, -CH 2 C、‑CH 2 CH 2 CN、‑CH 2 CH 2 CH 2 CN、‑CH 2 CH 2 CH 2 CH 2 One of CN and O-TMS, TMS is Si- (CH) 3 ) 3 . The compound A is added into the electrolyte of the invention, and LiPF is contained in the electrolyte 6 Generated PF 5 Will react with trace amounts of water to form HF which is scavenged by the siloxane functionality in compound A, wherein fluoride (F) ‑ ) Trapped by silicon (Si) to form TMSF, H + And also is captured by oxygen (O) to form HPO, thereby improving high-temperature cycle performance and high-temperature storage performance at high voltage.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to an electrolyte and a lithium ion battery thereof.
Background
The lithium ion battery has the advantages of high specific energy, no memory effect, long cycle life and the like, and is widely applied to the fields of 3C digital, electric tools, aerospace, energy storage, power automobiles and the like, and the rapid development of electronic information technology and consumer products puts higher requirements on the high voltage and high energy density of the lithium ion battery. In lithium ion batteries, high-voltage positive electrode materials are widely applied to portable electronic devices such as mobile phones and notebook computers, electric vehicles and large energy storage devices due to the advantages of high energy density, environmental friendliness, long cycle life and the like.
However, as the limiting voltage of the anode material is continuously increased, the gram capacity of the battery material is gradually increased, the high-temperature performance of the battery is seriously deteriorated, the long cycle life cannot be ensured, and particularly, in the process of long-term cyclic charge and discharge under high voltage (more than 4.5V), the volume of the material can expand and cause serious cracks, and a solvent in the electrolyte enters the inside of the anode material to damage the structure, so that the serious capacity attenuation is finally caused. Therefore, it is desirable to provide a lithium ion battery having good high-temperature cycle performance and high-temperature storage performance at high voltage.
Disclosure of Invention
The invention aims to provide an electrolyte and a lithium ion battery thereof, which have good high-temperature cycle performance and high-temperature storage performance under high voltage.
The invention discloses an electrolyte, which comprises lithium salt, an organic solvent and an additive; the additive at least comprises a compound A, and the content of the compound A is 0.5-8% of the total weight of the electrolyte; the structural general formula of the compound A is shown as the following formula I:
in the formula IWherein at least one of R1, R2 and R3 is an alkoxyalkyl group having 1 to 20 carbon atoms, at least one is O-TMS, and the remaining one is selected from an alkoxyalkyl group having 1 to 20 carbon atoms, CN-, -CH 2 C、-CH 2 CH 2 CN、-CH 2 CH 2 CH 2 CN、-CH 2 CH 2 CH 2 CH 2 One of CN and O-TMS, TMS is Si- (CH) 3 ) 3 。
Alternatively, in formula I, the remaining one of R1, R2, R3 is CN-.
Alternatively, the structural formula of the aromatic compound A is shown as the following formula II:
optionally, the additive further comprises sulfonate compounds, fluorocarbon esters, and nitrile compounds.
Optionally, the content of the compound a is 1% of the total weight of the electrolyte.
Optionally, the lithium salt is at least one selected from a compound containing fluorine and lithium.
Optionally, the lithium salt is selected from at least one of hexafluorophosphate, hexafluoroarsenate, perchlorate, lithium trifluorosulfonyl, lithium difluoro (trifluoromethylsulfonyl) imide, lithium tris (trifluoromethylsulfonyl) methide, lithium bis (fluorosulfonyl) imide sulfonate.
Optionally, the lithium salt concentration is 0.5M to 1.5M.
Optionally, the organic solvent is selected from at least two of ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, methyl formate, ethyl propionate, propyl propionate, methyl butyrate, tetrahydrofuran.
The invention also discloses a lithium ion battery which comprises the electrolyte.
The compound A is added into the electrolyte of the invention, and LiPF is contained in the electrolyte 6 Generated PF 5 Will react with trace amounts of water to form HF which is scavenged by the siloxane functionality in compound AWherein fluoride (F) - ) Trapped by silicon (Si) to form TMSF, H + And also is captured by oxygen (O) to form HPO, thereby improving high-temperature cycle performance and high-temperature storage performance at high voltage.
Detailed Description
It is to be understood that the terminology, the specific structural and functional details disclosed herein are for the purpose of describing particular embodiments only, and are representative, but that the present invention may be embodied in many alternate forms and should not be construed as limited to only the embodiments set forth herein.
The following alternative examples illustrate the invention in detail.
As an embodiment of the present invention, disclosed is an electrolyte including a lithium salt, an organic solvent, and an additive; the additive at least comprises a compound A, and the content of the compound A is 0.5-8% of the total weight of the electrolyte; the structural general formula of the compound A is shown as the following formula I:
in the formula I, at least one of R1, R2 and R3 is an alkoxyalkyl group having 1 to 20 carbon atoms, at least one is O-TMS, and the rest is selected from the group consisting of an alkoxyalkyl group having 1 to 20 carbon atoms, CN-, -CH 2 C、-CH 2 CH 2 CN、-CH 2 CH 2 CH 2 CN、-CH 2 CH 2 CH 2 CH 2 One of CN and O-TMS, TMS is Si- (CH) 3 ) 3 。
The compound A is added into the electrolyte of the invention, and LiPF is contained in the electrolyte 6 Generated PF 5 Will react with traces of water to form HF which is scavenged by the siloxane functionality in compound A, where fluoride (F) - ) Trapped by silicon (Si) to form TMSF, H + And also is captured by oxygen (O) to form HPO, thereby improving high-temperature cycle performance and high-temperature storage performance at high voltage.
Specifically, among the three R1, R2 and R3, two of them are an alkoxyalkyl group and O-TMS, and the remaining one may beSelected from the group consisting of 1-20 alkoxyalkyl, CN-, -CH 2 C、-CH 2 CH 2 CN、-CH 2 CH 2 CH 2 CN、-CH 2 CH 2 CH 2 CH 2 One of CN and O-TMS, TMS is Si- (CH) 3 ) 3 . The specific type of the C1-20 alkoxyalkyl group is not particularly limited, and may be selected according to the actual need, and examples thereof include a chain group and a cyclic group, wherein the chain alkyl group may further include a linear group and a branched group, and the cyclic group may or may not include a substituent. As examples of the hydrocarbon group, there may be mentioned ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclobutyl, n-pentyl, isopentyl, tert-pentyl, neopentyl, cyclopentyl, dimethylbutyl, 1-ethylpropyl, 1-methylbutyl, 2-methylbutyl, n-hexyl, isohexyl, 2-hexyl, 3-hexyl, cyclohexyl, 2-methylpentyl, 3-methylpentyl, 1, 2-trimethylpropyl, 3-dimethylbutyl, n-heptyl, 2-heptyl, 3-heptyl, 2-methylhexyl, 3-methylhexyl, 4-methylhexyl, isoheptyl, cycloheptyl, n-octyl, cyclooctyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl.
Specifically, in the formula I, the rest one of R1, R2 and R3 is CN-. The specific functional group CN of the electrolyte can be complexed with Co ions in the anode material to form coordination, so that the electrode has a good CEI/SEI film, the interface property of the anode end electrode/electrolyte is stabilized, and the cycle performance of the battery is further improved. Specifically, the structural formula of the aromatic compound A is shown as the following formula II:
specifically, the additive also comprises sulfonate compounds, fluorocarbon esters and nitrile compounds.
Specifically, the content of the compound a is 1% of the total weight of the electrolyte. When the amount of compound A added is 1%, the high-temperature cycle and high-temperature storage effects are best.
Specifically, the lithium salt is selected from at least one of an organic lithium salt or an inorganic lithium salt.
Specifically, the lithium salt is at least one selected from compounds containing a fluorine element and a lithium element. Specifically, the lithium salt is selected from at least one of hexafluorophosphate, hexafluoroarsenate, perchlorate, lithium trifluorosulfonyl, lithium difluoro (trifluoromethylsulfonyl) imide, lithium tris (trifluoromethylsulfonyl) methide and lithium bis (fluorosulfonyl) imide.
Specifically, the concentration of the lithium salt is 0.5M to 1.5M. The concentration of the lithium salt is too low, the conductivity of the electrolyte is low, and the multiplying power and the cycle performance of the whole battery system can be influenced; the lithium salt concentration is too high, the viscosity of the electrolyte is too high, and the multiplying power of the whole battery system is also influenced. Preferably, the lithium salt concentration is 0.8 to 1.3M.
Specifically, the organic solvent is selected from at least two of ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, methyl formate, ethyl propionate, propyl propionate, methyl butyrate and tetrahydrofuran.
The invention also discloses a lithium ion battery which comprises the electrolyte.
Specifically, the lithium ion battery further comprises a pole piece, a negative pole piece and a lithium battery diaphragm. The positive plate comprises a positive current collector and a positive active slurry layer positioned on the positive current collector, wherein the positive active slurry layer comprises a positive active material; the negative plate comprises a negative current collector and a negative active slurry layer positioned on the negative current collector, wherein the negative active slurry layer comprises a negative active material. The specific types of the positive electrode active material, the positive electrode binder and the negative electrode active material are not particularly limited and can be selected according to requirements.
Preferably, the positive active material is selected from lithium cobaltate (LiCoO) 2 ) Lithium nickel manganese cobalt ternary material and lithium iron phosphate (LiFePO) 4 ) Lithium manganate (LiMn) 2 O 4 ) One or more ofAnd (4) seed preparation.
Preferably, the negative active material is graphite and/or silicon, such as natural graphite, artificial graphite, mesophase micro carbon spheres (abbreviated as MCMB), hard carbon, soft carbon, silicon-carbon composite, li-Sn alloy, li-Sn-O alloy, sn, snO 2 Spinel-structured lithiated TiO 2 -Li 4 Ti 5 O 12 And Li-Al alloy can be used as the negative active material.
The technical scheme of the invention is illustrated by combining specific embodiments.
Preparing an electrolyte: as the organic solvent, EC (ethylene carbonate)/PC (propylene carbonate)/DEC (diethyl carbonate)/PP (propyl propionate) =1/1/2/6 by mass ratio was mixed. Adding additives PS, FEC and nitrile compounds SN, ADN and HTCN into an organic solvent, mixing uniformly, and adding LiPF 6 Obtaining LiPF 6 The electrolyte solutions of examples 1 to 5 were prepared by mixing a mixed solution having a concentration of 1.1mol/L and adding Compound A to the mixed solution. PS is 1, 3-propanesultone, FEC is fluoroethylene carbonate, SN is succinonitrile, ADN is adiponitrile, HTCN is 1,3, 6-hexanetrinitrile, and concretely, the additive is a compound A, and the structural formula is as follows:
the electrolytes of examples 1 to 5 and the electrolyte of comparative example 1 were prepared according to the above-described preparation procedure of the electrolytes, wherein the comparative example 1 is different from each example in that the compound a was not added.
The specific formulations of the electrolytes of examples 1 to 5 and comparative example 1 are as follows:
TABLE 1
Manufacture of batteries
Manufacturing a positive plate:
the positive electrode active material LCO, the conductive agent CNT, and the binder polyvinylidene fluoride were sufficiently stirred and mixed in an N-methylpyrrolidone solvent in a weight ratio of 97. And coating the slurry on an Al foil of a positive current collector, drying and cold pressing to obtain the positive plate.
And (3) manufacturing a negative plate:
fully stirring and mixing a negative electrode active material graphite, a conductive agent acetylene black, a binder styrene butadiene rubber and a thickener carboxymethylcellulose sodium in a proper amount of deionized water solvent according to a mass ratio of 95. Coating the slurry on a Cu foil of a negative current collector, drying and cold pressing to obtain a negative pole piece
Manufacturing the lithium ion battery:
the positive pole piece, the isolating membrane and the negative pole piece are sequentially stacked, so that the isolating membrane is positioned between the positive pole and the negative pole, the isolating effect is achieved, and then the bare cell can be wound. And (3) placing the bare cell into an outer packaging bag, respectively injecting the electrolyte in the table 1 into the dried battery, and performing vacuum packaging, standing, formation, shaping and other processes to complete the preparation of the lithium ion battery. Sequentially obtain the battery
High temperature cycling test of batteries
The test method comprises the following steps: and (3) placing the battery in an environment of 45 +/-2 ℃, and calculating the capacity retention rate of the battery after circulation according to the standard charge-discharge circulation, the circulation multiplying power of 1C and the charging voltage of 3.0-4.5V.
The calculation formula is as follows:
the nth cycle capacity retention (%) = (nth cycle discharge capacity)/(first cycle discharge capacity) · 100%
High temperature storage test of the battery:
the test method comprises the following steps: and (3) charging the partial-volume battery cell to 4.5V at the normal temperature by 0.5C, placing the fully-charged battery in an environment of 85 ℃ for 6 hours, measuring the thickness expansion rate by heat, discharging to 3.0V by 0.5C after the room temperature is recovered, and recording the discharge capacity.
The cell test conditions are shown in table 2:
TABLE 2
As can be seen from examples 1 to 5 and comparative example 1 in Table 2, in examples 2 to 5, the high temperature cycle and high temperature storage performance were superior to those of examples 1 and comparative example in the case of adding Compound A, wherein the high temperature cycle and high temperature storage effect of example 3 was the best, that is, the effect of adding 1% of Compound A was the best.
It should be noted that, the limitations of the steps involved in the present disclosure are not considered to limit the order of the steps without affecting the implementation of the specific embodiments, and the steps written in the foregoing may be executed first, or executed later, or even executed simultaneously, and as long as the present disclosure can be implemented, all should be considered to belong to the protection scope of the present disclosure.
The foregoing is a more detailed description of the invention in connection with specific alternative embodiments, and the practice of the invention should not be construed as limited to those descriptions. For those skilled in the art to which the invention pertains, numerous simple deductions or substitutions may be made without departing from the spirit of the invention, which shall be deemed to belong to the scope of the invention.
Claims (10)
1. An electrolyte comprising a lithium salt, an organic solvent and an additive; the additive at least comprises a compound A, and the content of the compound A is 0.5-8% of the total weight of the electrolyte; the structural general formula of the compound A is shown as the following formula I:
in the formula I, at least one of R1, R2 and R3 is an alkoxyalkyl group having 1 to 20 carbon atoms, at least one is O-TMS, and the rest is selected from the group consisting of an alkoxyalkyl group having 1 to 20 carbon atoms, CN-, -CH 2 C、-CH 2 CH 2 CN、-CH 2 CH 2 CH 2 CN、-CH 2 CH 2 CH 2 CH 2 One of CN and O-TMS, TMS is Si- (CH) 3 ) 3 。
2. The electrolyte of claim 1, wherein in formula I, the remaining one of R1, R2, R3 is CN-.
3. The electrolyte of claim 2, wherein the aromatic compound a has the formula ii:
4. the electrolyte of claim 1, wherein the additive further comprises a sulfonate compound, a fluorocarbon ester, and a nitrile compound.
5. The electrolyte of any one of claims 1 to 4, wherein the compound A is present in an amount of 1% by weight based on the total weight of the electrolyte.
6. The electrolyte of any one of claims 1 to 4, wherein the lithium salt is at least one selected from compounds containing elemental fluorine and elemental lithium.
7. The electrolyte of claim 6, wherein the lithium salt is selected from at least one of hexafluorophosphate, hexafluoroarsenate, perchlorate, trifluorosulfonyllithium, difluoro (trifluoromethylsulfonyl) imide lithium, tris (trifluoromethylsulfonyl) methide lithium, lithium bis (fluorosulfonyl) imide sulfonate.
8. The electrolyte of any one of claims 1 to 4, wherein the lithium salt concentration is 0.5M to 1.5M.
9. The electrolyte of any one of claims 1 to 4, wherein the organic solvent is selected from at least two of ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, methyl formate, ethyl propionate, propyl propionate, methyl butyrate, tetrahydrofuran.
10. A lithium ion battery comprising the electrolyte of any one of claims 1 to 9.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202210821349.6A CN115207466A (en) | 2022-07-13 | 2022-07-13 | Electrolyte and lithium ion battery thereof |
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| CN202210821349.6A CN115207466A (en) | 2022-07-13 | 2022-07-13 | Electrolyte and lithium ion battery thereof |
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