CN115249839A - Electrolyte and lithium ion battery thereof - Google Patents

Electrolyte and lithium ion battery thereof Download PDF

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Publication number
CN115249839A
CN115249839A CN202210847272.XA CN202210847272A CN115249839A CN 115249839 A CN115249839 A CN 115249839A CN 202210847272 A CN202210847272 A CN 202210847272A CN 115249839 A CN115249839 A CN 115249839A
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China
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electrolyte
heterocyclic compound
formula
compound
additive
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CN202210847272.XA
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Chinese (zh)
Inventor
肖资龙
史柯
彭昌志
蒋珊
张昌明
胡大林
廖兴群
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Huizhou Highpower Technology Co Ltd
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Huizhou Highpower Technology Co Ltd
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Priority to CN202210847272.XA priority Critical patent/CN115249839A/en
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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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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 an electrolyte and a lithium ion battery thereof, which comprise lithium salt, an organic solvent and an additive; the additive at least comprises a heterocyclic compound A, and the content of the heterocyclic compound A is 0.5-8% of the total weight of the electrolyte; the structural general formula of the heterocyclic compound A is shown as the following formula I:
Figure DDA0003753336390000011
in the formula I, R 1 、R 2 、R 3 、R 4 、R 5 Are respectively and independently selected from alkyl with 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 or hydrogen atom; r is one of N, O, S, C atoms. The heterocyclic compound A in the electrolyte of the present invention can preferentially bind to the electrolyte when added in a small amount (0.5% to 8%)Proton H generated by oxidative decomposition of the components of the electrolyte + Thereby avoiding H + The method has the advantages that the complexing ability of the polynitrile compound in the electrolyte is weakened, and the anode terminal electrode/electrolyte interface property can be better stabilized by the synergistic effect of the heterocyclic compound A and the nitrile compared with that of a single polynitrile compound.

Description

Electrolyte and lithium ion battery thereof
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 is widely applied to the fields of 3C digital products, electric tools, spaceflight, energy storage, power automobiles and the like, and has the advantages of high specific energy, no memory effect, long cycle life and the like. The rapid development of electronic information technology and consumer products has put higher demands on the high voltage and high energy density of lithium ion batteries.
With the continuous improvement of the limiting voltage of the anode material, the high-temperature performance of the battery is obviously deteriorated, and the long cycle life is difficult to guarantee, for example, in the long-term cyclic charge and discharge process under high voltage (more than 4.5V), the volume of the anode material expands to crack, and at the moment, the solvent in the electrolyte can enter the inside of the anode material to damage the structure of the anode material, so that the capacity is seriously attenuated. 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 and high-temperature storage performance.
The invention discloses an electrolyte, which comprises lithium salt, an organic solvent and an additive; the additive at least comprises a heterocyclic compound A, and the content of the heterocyclic compound A is 0.5-8% of the total weight of the electrolyte; the structural general formula of the heterocyclic compound A is shown as the following formula I:
Figure BDA0003753336380000021
in the formula I, R 1 、R 2 、R 3 、R 4 、R 5 Are respectively and independently selected from alkyl with 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 or hydrogen atom; r is one of N, O, S, C atoms.
Alternatively, in formula I, R 1 、R 2 、R 3 、R 4 、R 5 At least one of them is CN-.
Alternatively, heterocyclic compound a has the formula ii:
Figure BDA0003753336380000022
optionally, the additive further comprises sulfonate compounds, fluorocarbon esters, and nitrile compounds.
Alternatively, the nitrile compounds are succinonitrile, adiponitrile, and 1,3,6-hexanetrinitrile.
Alternatively, the content of the heterocyclic compound a is 1% of the total weight of the electrolyte.
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.
Optionally, the lithium salt concentration is 0.5M to 1.5M.
Optionally, the lithium salt concentration is 0.8M to 1.3M.
The invention also discloses a lithium ion battery which comprises the electrolyte as claimed in the claim.
The heterocyclic compound A in the electrolyte of the present invention can preferentially bind protons H generated by oxidative decomposition of the electrolyte components with a small addition amount (0.5% to 8%) + Thereby avoiding H + Weakening the complexing ability of polynitrile compounds in the electrolyte, and the synergistic effect of the heterocyclic compound A and the nitriles can better stabilize the anode terminal electrode/electrolyte interface compared with the single polynitrile compoundAnd (4) properties.
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 not intended to be limiting, since 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 invention is described in detail below with reference to alternative embodiments.
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 heterocyclic compound A, and the content of the heterocyclic compound A is 0.5-8% of the total weight of the electrolyte; the structural general formula of the heterocyclic compound A is shown as the following formula I:
Figure BDA0003753336380000031
in the formula I, R 1 、R 2 、R 3 、R 4 、R 5 Are respectively and independently selected from alkyl with 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 CN or hydrogen atom; r is one of N, O, S, C atoms.
The heterocyclic compound A in the electrolyte of the present invention can preferentially bind protons H generated by oxidative decomposition of the electrolyte components with a small addition amount (0.5% to 8%) + Thereby avoiding H + The method has the advantages that the complexing ability of the polynitrile compound in the electrolyte is weakened, and the anode terminal electrode/electrolyte interface property can be better stabilized by the synergistic effect of the heterocyclic compound A and the nitrile compared with that of a single polynitrile compound.
Specifically, in the above formula I, R 1 、R 2 、R 3 、R 4 、R 5 May be different from each other or may be the same as each other. When R is 1 、R 2 Each independently selected from the group consisting of 1 to 4 carbon atomsThe specific type of the alkyl group in (b) is not particularly limited, and may be selected according to actual needs, for example, the alkyl group may include a linear group and a branched group, and the cyclic group may have a substituent or may not have a substituent. Specifically, the alkanyl group may be 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, 1,1,2-trimethylpropyl, 3,3-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.
In the formula I, R 1 、R 2 、R 3 、R 4 、R 5 At least one of them is CN-. In the formula I, R 1 、R 2 、R 3 、R 4 、R 5 When at least one of the functional groups is CN-, a specific functional group CN in 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 heterocyclic compound A is shown as the following formula II:
Figure BDA0003753336380000051
specifically, the additive also includes sulfonate compounds, fluorocarbon esters, and nitrile compounds. Specifically, the nitrile compounds are succinonitrile, adiponitrile, and 1,3,6-hexanetrinitrile. The sulfonate compound is 1,3-Propane Sultone (PS), and the fluorocarbon ester is fluoroethylene carbonate (FEC).
Specifically, the content of the heterocyclic compound a is 1% by weight of the total weight of the electrolyte. When the amount of the heterocyclic compound a added is 1%, the high-temperature cycle and high-temperature storage effects are good.
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 lithium salt is at least one selected from organic lithium salt or inorganic lithium salt. Specifically, the lithium salt is at least one selected from compounds containing a fluorine element and a lithium element. Preferably, 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.
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 0.8M to 1.3M.
The invention also discloses a lithium ion battery which comprises the electrolyte. Specifically, the lithium ion battery further comprises a positive plate, a negative plate 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 positive electrode active material and the positive electrode binder of the positive electrode active slurry layer are not particularly limited and can be selected according to requirements; the specific kind of the negative electrode active material is not particularly limited and may be selected as desired.
Preferably, the positive active material is selected from lithium cobaltate (LiCoO) 2 ) Lithium nickel manganese cobalt ternary material, lithium iron phosphate (LiFePO) 4 ) Lithium manganate (LiMn) 2 O 4 ) One or more of (a).
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 active material of the negative electrode.
The technical scheme of the invention is explained by combining specific embodiments.
Preparation of the electrolyte
The preparation steps of the electrolyte are as follows: EC (ethylene carbonate)/PC (propylene carbonate)/DEC (diethyl carbonate)/PP (propyl propionate) =1/1/2/6 by mass ratio was mixed as the organic solvent. Adding additives PS, FEC and nitrile compounds SN, ADN and HTCN into an organic solvent, uniformly mixing, and adding LiPF 6 Obtaining LiPF 6 The electrolytes of examples 1 to 5 were prepared as shown in Table 1 by mixing the solutions at a concentration of 1.1mol/L and adding the heterocyclic compound A to the mixed solution. PS is 1,3-propanesultone, FEC is fluoroethylene carbonate, SN is succinonitrile, ADN is adiponitrile, and HTCN is 1,3,6-hexanetricarbonitrile. Specifically, the structural formula of the heterocyclic compound A is as follows:
Figure BDA0003753336380000071
the electrolytes of examples 1 to 5 and the electrolyte of comparative example 1 were prepared according to the above-mentioned preparation procedure of the electrolytes, wherein the comparative example 1 is different from each example in that the heterocyclic 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
Figure BDA0003753336380000072
Manufacture of batteries
Manufacturing a positive plate:
the positive electrode active material lithium cobaltate, the conductive agent CNT and the binder polyvinylidene fluoride are fully stirred and mixed in an N-methyl pyrrolidone solvent according to the weight ratio of 97 to 1.5, so that uniform positive electrode slurry is formed. And coating the slurry on an Al foil of the positive current collector, drying, and performing 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 rate (%) = (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
Figure BDA0003753336380000091
As can be seen from examples 1 to 5 and comparative example 1 in Table 2, the high temperature cycle and high temperature storage effects of example 3 are the best, i.e., the effect of adding 1% of the heterocyclic compound A is the best.
To further investigate the synergistic effect of heterocyclic compound a and nitriles, examples and comparative examples are designed as in table 3 below, wherein examples 1 to 5 and comparative example 1 of table 3 are examples 1 to 5 and comparative example 1 described above, and comparative example 2 and comparative example 3 are newly added comparative examples.
TABLE 3
Figure BDA0003753336380000092
Comparative examples 2/3 were conducted to compare with example 3 to verify the high temperature effect of heterocyclic compound A and HTCN. Each electrolyte of table 3 was tested according to the above protocol and the results are given in table 4 below:
TABLE 4
Figure BDA0003753336380000093
Figure BDA0003753336380000101
As shown in table 4, the high temperature performance of comparative example 2, which does not contain the heterocyclic compound a and is only slightly better than that of comparative example 1, is poor under the condition of combining HTCN with other nitriles. Comparative example 3 the high temperature effect of heterocyclic compound a is superior to HTCN with equal amount of nitrile additive.
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, several simple deductions or substitutions can be made without departing from the spirit of the invention, and all shall be considered as belonging to the protection 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 heterocyclic compound A, and the content of the heterocyclic compound A is 0.5-8% of the total weight of the electrolyte; the structural general formula of the heterocyclic compound A is shown as the following formula I:
Figure FDA0003753336370000011
in the formula I, R 1 、R 2 、R 3 、R 4 、R 5 Are respectively and independently selected from alkyl with 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 or hydrogen atom; r is one of N, O, S, C atoms.
2. The electrolyte of claim 1, wherein R in formula I 1 、R 2 、R 3 、R 4 、R 5 At least one of them is CN-.
3. The electrolyte of claim 2, wherein the heterocyclic compound a has the formula ii:
Figure FDA0003753336370000012
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 claim 4, wherein the nitrile compound is succinonitrile, adiponitrile, and 1,3,6-hexanetrinitrile.
6. The electrolyte according to any one of claims 1 to 4, wherein the heterocyclic compound A is present in an amount of 1% by weight based on the total weight of the electrolyte.
7. 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, and tetrahydrofuran.
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 claim 8, wherein the lithium salt concentration is 0.8M to 1.3M.
10. A lithium ion battery comprising the electrolyte of any one of claims 1 to 9.
CN202210847272.XA 2022-07-19 2022-07-19 Electrolyte and lithium ion battery thereof Pending CN115249839A (en)

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