CN117080552A - Non-aqueous electrolyte of lithium ion battery and battery comprising same - Google Patents
Non-aqueous electrolyte of lithium ion battery and battery comprising same Download PDFInfo
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- CN117080552A CN117080552A CN202310911068.4A CN202310911068A CN117080552A CN 117080552 A CN117080552 A CN 117080552A CN 202310911068 A CN202310911068 A CN 202310911068A CN 117080552 A CN117080552 A CN 117080552A
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- lithium ion
- additive
- ion battery
- nonaqueous electrolyte
- lithium
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- 239000011255 nonaqueous electrolyte Substances 0.000 title claims abstract description 99
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 81
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 81
- 239000000654 additive Substances 0.000 claims abstract description 64
- -1 1, 3-propylene sultone Chemical class 0.000 claims abstract description 60
- 230000000996 additive effect Effects 0.000 claims abstract description 60
- 239000003792 electrolyte Substances 0.000 claims abstract description 28
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 22
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 22
- YMXAUZKYBMKSPP-UHFFFAOYSA-N C(CC)S(=O)(=O)O.C(C)N(CC)CC#C Chemical group C(CC)S(=O)(=O)O.C(C)N(CC)CC#C YMXAUZKYBMKSPP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000003960 organic solvent Substances 0.000 claims abstract description 21
- VEWLDLAARDMXSB-UHFFFAOYSA-N ethenyl sulfate;hydron Chemical group OS(=O)(=O)OC=C VEWLDLAARDMXSB-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000013538 functional additive Substances 0.000 claims abstract description 18
- 150000003839 salts Chemical class 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 10
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 8
- 229910052744 lithium Inorganic materials 0.000 claims description 8
- 229910002804 graphite Inorganic materials 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 4
- 150000007942 carboxylates Chemical class 0.000 claims description 4
- 150000005676 cyclic carbonates Chemical class 0.000 claims description 4
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000007773 negative electrode material Substances 0.000 claims description 2
- 239000007774 positive electrode material Substances 0.000 claims description 2
- 239000002210 silicon-based material Substances 0.000 claims description 2
- 239000007770 graphite material Substances 0.000 claims 1
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N dimethylmethane Natural products CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 abstract description 8
- 239000001294 propane Substances 0.000 abstract description 8
- 230000002195 synergetic effect Effects 0.000 abstract description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 18
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 17
- 229940021013 electrolyte solution Drugs 0.000 description 17
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 17
- 238000002156 mixing Methods 0.000 description 11
- 229910052786 argon Inorganic materials 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 8
- 239000001301 oxygen Substances 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 8
- 239000008151 electrolyte solution Substances 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 239000004743 Polypropylene Substances 0.000 description 6
- 229920001155 polypropylene Polymers 0.000 description 6
- ZPFAVCIQZKRBGF-UHFFFAOYSA-N 1,3,2-dioxathiolane 2,2-dioxide Chemical compound O=S1(=O)OCCO1 ZPFAVCIQZKRBGF-UHFFFAOYSA-N 0.000 description 5
- 239000010439 graphite Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 2
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 2
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 2
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 description 2
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 2
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- PFYQFCKUASLJLL-UHFFFAOYSA-N [Co].[Ni].[Li] Chemical compound [Co].[Ni].[Li] PFYQFCKUASLJLL-UHFFFAOYSA-N 0.000 description 1
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 229940090181 propyl acetate Drugs 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- 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
- H01M2300/0088—Composites
- H01M2300/0091—Composites in the form of mixtures
Abstract
The application discloses a non-aqueous electrolyte of a lithium ion battery and the lithium ion battery containing the same, and belongs to the technical field of lithium ion batteries. The non-aqueous electrolyte of the lithium ion battery comprises an organic solvent, electrolyte lithium salt and a functional additive; wherein: the functional additive comprises a first additive, a second additive and a third additive, wherein the first additive is 1, 3-propylene sultone, the second additive is N, N-diethyl propargylamine propane sulfonate, and the third additive is vinyl sulfate. According to the application, 1, 3-propylene sultone, N-diethyl propargylamine propane sulfonate and vinyl sulfate are used as functional additives, and the three additives have synergistic effect to form a stable and low-impedance interface film, so that the high-voltage charge-discharge cycle of the battery is more stable, and the low-temperature performance is more excellent.
Description
Technical Field
The application belongs to the technical field of lithium ion batteries, and particularly relates to a non-aqueous electrolyte of a lithium ion battery and a lithium ion battery containing the same.
Background
The lithium ion battery has the advantages of high specific energy, low cost, high stability, long service life and the like. Has wide application in the fields of electric automobiles, 3C numbers and the like. The rapid development of new energy industry has higher and higher performance requirements for lithium ion batteries.
The battery is taken as a complex whole, and each internal part component plays an important role on the performance of the battery; the electrode/electrolyte interface is used as a place where the electrode reaction occurs, plays a decisive role in the performance of the battery, and can keep a stable state in the battery during long-term charge and discharge cycles or in extreme environments. The property of the SEI film at the interface of the electrode and the electrolyte greatly affects the performance of the battery, and the unstable SEI film can lead to continuous decomposition of the electrolyte, thereby affecting the safety and the cycle performance of the battery; however, too thick SEI film can cause excessively high battery impedance, affect the rate performance and low temperature performance of the battery, and even cause lithium precipitation, and affect the safety performance and the service life of the battery. Therefore, a stable, low-resistance, dense SEI film is critical to the performance of a battery.
The present application has been made for the above reasons.
Disclosure of Invention
For the above reasons, in view of the problems or drawbacks of the prior art, an object of the present application is to provide a nonaqueous electrolyte for a lithium ion battery and a battery including the same, which solve or at least partially solve the above technical drawbacks of the prior art: the non-aqueous electrolyte is favorable for forming a stable interface film at the interface of the anode and the cathode of the battery, so that the battery can realize stable long cycle life, and can remarkably improve the low-temperature performance of the battery and the high-voltage performance of the battery.
In order to achieve the first object of the present application, the present application adopts the following technical scheme:
a non-aqueous electrolyte of lithium ion battery comprises an organic solvent, electrolyte lithium salt and a functional additive; wherein: the functional additive comprises a first additive, a second additive and a third additive, wherein the first additive is 1, 3-propylene sultone, the second additive is N, N-diethyl propargylamine propane sulfonate, and the third additive is vinyl sulfate; the structural formula of the 1, 3-propylene sultone is shown as a first formula, the structural formula of the N, N-diethyl propargylamine propane sulfonic acid inner salt is shown as a second formula, and the structural formula of the vinyl sulfate is shown as a third formula:
further, according to the above-mentioned nonaqueous electrolyte for lithium ion batteries of the present application, the content of the 1, 3-propenylsultone is 0.1 to 3wt%, for example, 0.1wt%, 0.2wt%, 0.3wt%, 0.4wt%, 0.5wt%, 0.6wt%, 0.7wt%, 1wt%, 2wt% or 3wt% of the nonaqueous electrolyte. But are not limited to, the recited values, and other non-recited values within the range of values are equally applicable.
Further, according to the nonaqueous electrolyte for lithium ion batteries of the present application, the content of the N, N-diethyl propargylamine propane sulfonic acid inner salt is 0.1 to 2wt%, for example, 0.1wt%, 0.2wt%, 0.3wt%, 0.4wt%, 0.5wt%, 0.6wt%, 0.7wt%, 0.8wt%, 1wt% or 2wt% of the nonaqueous electrolyte. But are not limited to, the recited values, and other non-recited values within the range of values are equally applicable.
Further, according to the above-described lithium ion battery nonaqueous electrolytic solution of the present application, the content of the vinyl sulfate is 0.1 to 2wt% of the nonaqueous electrolytic solution, for example, 0.1wt%, 0.2wt%, 0.3wt%, 0.4wt%, 0.5wt%, 0.6wt%, 0.7wt%, 0.8wt%, 1wt% or 2wt%. But are not limited to, the recited values, and other non-recited values within the range of values are equally applicable.
Further, according to the lithium ion battery nonaqueous electrolyte, the organic solvent comprises one or more of cyclic carbonate and linear carbonate or carboxylate.
Preferably, the cyclic carbonate comprises one or more of ethylene carbonate, propylene carbonate and fluoroethylene carbonate.
Preferably, the linear carbonate or carboxylate comprises one or more of dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, ethyl propionate, propyl acetate and ethyl acetate.
Further, according to the above-described lithium ion battery nonaqueous electrolytic solution of the present application, the electrolyte lithium salt includes lithium hexafluorophosphate (LiPF 6 ) Lithium perchlorate (LiClO) 4 ) Lithium bisoxalato borate (LiBOB), lithium difluorooxalato borate (LiDFOB), lithium tetrafluoroborate (LiBF) 4 ) One or more of lithium bis (trifluoromethylsulfonyl) imide (LiTFSI) and lithium bis (fluorosulfonyl) imide (LiFSI).
Further, according to the non-aqueous electrolyte for a lithium ion battery of the present application, the content of the electrolyte lithium salt is 10.0-20wt%, for example, 10wt%, 12wt%, 15wt%, 18wt%, 20wt% of the total mass of the non-aqueous electrolyte. But are not limited to, the recited values, and other non-recited values within the range of values are equally applicable.
The second purpose of the application is to provide the preparation method of the lithium ion battery nonaqueous electrolyte, which comprises the following specific steps:
in a glove box filled with argon, uniformly mixing cyclic carbonate and linear carbonate or carboxylate according to a proportion, then sequentially adding lithium hexafluorophosphate, 1, 3-propylene sultone, N-diethyl propargylamine propane sulfonate inner salt and vinyl sulfate according to a proportion, and dissolving to obtain the non-aqueous electrolyte of the lithium ion battery.
A third object of the present application is to provide an application of the above-mentioned nonaqueous electrolyte for lithium ion batteries in lithium ion batteries.
The lithium ion battery comprises a positive electrode, a negative electrode, a diaphragm arranged between the positive electrode and the negative electrode and a non-aqueous electrolyte, wherein the non-aqueous electrolyte is the non-aqueous electrolyte of the lithium battery.
Further, the positive electrode contains a positive electrode active material, which is preferably one or more of ternary material, lithium cobaltate, lithium manganate material. Wherein, the ternary material can be nickel cobalt lithium manganate or nickel cobalt lithium aluminate.
Further, the negative electrode contains a negative electrode active material including one or both of graphite and a silicon-based material.
Further, the separator is one of a polypropylene (PP) separator, a ceramic separator, or a polypropylene/polyethylene/polypropylene (PP/PE/PP) three-layer separator.
Further, the working voltage range of the lithium ion battery is 3-4.5V.
The application has the beneficial effects that:
the application provides a non-aqueous electrolyte and a battery comprising the same, wherein 1, 3-propylene sultone, N-diethyl propargylamine propane sulfonate and vinyl sulfate are used as functional additives, and the three additives have synergistic effect to form a stable and low-impedance interfacial film, so that the high-voltage charge-discharge cycle of the battery is more stable, and the low-temperature performance is more excellent. The specific functions are as follows: the 1, 3-propylene sultone (1, 3-propylene sultone) and the N, N-diethyl propargylamine propane sulfonate are used as excellent film forming additives, and the film forming resistance is high, but the high-voltage performance of the battery can be effectively improved, the low-temperature performance of the battery is deteriorated, and the internal resistance of the battery can be effectively reduced due to the synergistic effect of the vinyl sulfate and the N, N-diethyl propargylamine propane sulfonate, so that the low-temperature performance of the battery is improved.
Detailed Description
The application is described in further detail below by way of examples. The present embodiment is implemented on the premise of the present technology, and a detailed embodiment and a specific operation procedure are now given to illustrate the inventive aspects of the present application, but the scope of protection of the present application is not limited to the following embodiments.
Various modifications to the precise description of the application will be readily apparent to those skilled in the art from the information contained herein. It is to be understood that the scope of the application is not limited to the defined processes, properties or components, as these embodiments, as well as other descriptions, are merely illustrative of specific aspects of the application.
For a better understanding of the present application, and not to limit its scope, all numbers expressing quantities, percentages, and other values used in the present application are to be understood as being modified in all instances by the term "about". Accordingly, unless specifically indicated otherwise, the numerical parameters set forth in the specification are approximations that may vary depending upon the desired properties sought to be obtained. Each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.
The equipment and materials used in the present application are commercially available or are commonly used in the art. The methods in the following examples are conventional in the art unless otherwise specified.
The battery performance test method assembled in each of the following examples is specifically as follows:
(1) High pressure cycle life test at 25 ℃):
and (3) placing the corresponding battery in a constant temperature environment at 25 ℃ to perform charge and discharge test at a 1C/1C multiplying power, wherein the cut-off voltage range is 3.0V-4.45V, and the battery is subjected to charge and discharge circulation 500 times, and the circulation discharge capacity is recorded and divided by the discharge capacity of the first circulation to obtain the circulation capacity retention rate. The test results are shown in Table 2.
(2) Internal resistance test
And charging the battery to be tested to 4.45V at the current of 0.2C, applying alternating voltage to the battery, measuring the impedance of the battery, and calculating the internal resistance of the battery according to the impedance and the phase difference of the battery.
-20 ℃ low temperature performance test method: (1) after the battery to be tested is stood for 8 hours at 25 ℃, the battery to be tested is charged to 4.5V at a current of 0.2C, and then the battery to be tested is discharged to 3.0V at a current of 0.2C. (2) The above procedure was repeated twice and charged to 4.5V. (3) Then, the mixture was allowed to stand at-20℃for 8 hours, and discharged to 2V at a current of 0.1 ℃. The discharge capacities at 25℃and-20℃were recorded, and the low-temperature discharge capacity/25℃discharge capacity ratio (discharge capacity retention rate) was calculated.
Example 1
The non-aqueous electrolyte of the lithium ion battery consists of an organic solvent, electrolyte lithium salt and a functional additive; the functional additive consists of a first additive, a second additive and a third additive, wherein the first additive is 1, 3-propylene sultone, the second additive is N, N-diethyl propargylamine propane sulfonate, and the third additive is vinyl sulfate; wherein:
the organic solvent comprises the following components in percentage by mass: 7 ethylene carbonate and ethylmethyl carbonate;
the electrolyte lithium salt is lithium hexafluorophosphate, and the content of the lithium hexafluorophosphate in the nonaqueous electrolyte is 15wt%;
the content of the 1, 3-propylene sultone in the nonaqueous electrolyte is 0.5wt%;
the content of the N, N-diethyl propargylamine propane sulfonic acid inner salt in the nonaqueous electrolyte is 0.5wt%;
the content of the vinyl sulfate in the nonaqueous electrolyte is 0.5wt%;
the preparation method of the lithium ion battery nonaqueous electrolyte solution in the embodiment specifically comprises the following steps: in a glove box filled with argon (water is less than 0.1ppm, oxygen is less than 0.1 ppm), uniformly mixing ethylene carbonate and methyl ethyl carbonate according to a proportion, then sequentially adding lithium hexafluorophosphate, 1, 3-propylene sultone, N-diethyl propargylamine propane sulfonate and ethylene sulfate according to a proportion, and dissolving to obtain the non-aqueous electrolyte of the lithium ion battery.
The embodiment also provides a lithium ion battery, which comprises a lithium cobalt oxide positive electrode, a graphite negative electrode, a diaphragm arranged between the positive electrode and the negative electrode and a non-aqueous electrolyte, wherein the non-aqueous electrolyte is the non-aqueous electrolyte of the lithium ion battery; the diaphragm is a ceramic film; the lithium ion battery is prepared by the following steps:
1) Manufacturing a lithium cobalt oxide positive electrode: and (3) fully stirring and uniformly mixing a lithium cobaltate material, conductive Super P and a binder polyvinylidene fluoride (PVDF) in an N-methylpyrrolidone (NMP) solvent according to a mass ratio of 90:5:5, coating the mixture on an aluminum foil, and drying and cutting the aluminum foil to obtain the positive electrode plate.
2) Manufacturing a graphite negative electrode: graphite anode material (Gr), conductive Super P, styrene-butadiene rubber emulsion (SBR) and adhesive sodium carboxymethyl cellulose (CMC) are mixed according to the mass ratio of 92.5:2.5:3.5:1.5, fully stirring and uniformly mixing the materials in deionized water solvent, coating the materials on a copper foil, and drying and cutting the materials to obtain the negative electrode plate.
3) Lithium cobaltate// graphite cells were assembled in a glove box.
Example 2
The non-aqueous electrolyte of the lithium ion battery consists of an organic solvent, electrolyte lithium salt and a functional additive; the functional additive consists of a first additive, a second additive and a third additive, wherein the first additive is 1, 3-propylene sultone, the second additive is N, N-diethyl propargylamine propane sulfonate, and the third additive is vinyl sulfate; wherein:
the organic solvent comprises the following components in percentage by mass: 7 ethylene carbonate and ethylmethyl carbonate;
the electrolyte lithium salt is lithium hexafluorophosphate, and the content of the lithium hexafluorophosphate in the nonaqueous electrolyte is 15wt%;
the content of the 1, 3-propylene sultone in the nonaqueous electrolyte is 1wt%;
the content of the N, N-diethyl propargylamine propane sulfonic acid inner salt in the nonaqueous electrolyte is 1wt%;
the content of the vinyl sulfate in the nonaqueous electrolyte is 1wt%;
the preparation method of the lithium ion battery nonaqueous electrolyte solution in the embodiment specifically comprises the following steps: in a glove box filled with argon (water is less than 0.1ppm, oxygen is less than 0.1 ppm), uniformly mixing ethylene carbonate and methyl ethyl carbonate according to a proportion, then sequentially adding lithium hexafluorophosphate, 1, 3-propylene sultone, N-diethyl propargylamine propane sulfonate and ethylene sulfate according to a proportion, and dissolving to obtain the non-aqueous electrolyte of the lithium ion battery.
The lithium ion battery of this example was assembled by using the nonaqueous electrolyte solution of the lithium ion battery of this example as an electrolyte solution in the same manner as in example 1.
Example 3
The non-aqueous electrolyte of the lithium ion battery consists of an organic solvent, electrolyte lithium salt and a functional additive; the functional additive consists of a first additive, a second additive and a third additive, wherein the first additive is 1, 3-propylene sultone, the second additive is N, N-diethyl propargylamine propane sulfonate, and the third additive is vinyl sulfate; wherein:
the organic solvent comprises the following components in percentage by mass: 7 ethylene carbonate and ethylmethyl carbonate;
the electrolyte lithium salt is lithium hexafluorophosphate, and the content of the lithium hexafluorophosphate in the nonaqueous electrolyte is 15wt%;
the content of the 1, 3-propylene sultone in the nonaqueous electrolyte is 3wt%;
the content of the N, N-diethyl propargylamine propane sulfonic acid inner salt in the nonaqueous electrolyte is 3wt%;
the content of the vinyl sulfate in the nonaqueous electrolyte is 3wt%;
the preparation method of the lithium ion battery nonaqueous electrolyte solution in the embodiment specifically comprises the following steps: in a glove box filled with argon (water is less than 0.1ppm, oxygen is less than 0.1 ppm), uniformly mixing ethylene carbonate and methyl ethyl carbonate according to a proportion, then sequentially adding lithium hexafluorophosphate, 1, 3-propylene sultone, N-diethyl propargylamine propane sulfonate and ethylene sulfate according to a proportion, and dissolving to obtain the non-aqueous electrolyte of the lithium ion battery.
The lithium ion battery of this example was assembled by using the nonaqueous electrolyte solution of the lithium ion battery of this example as an electrolyte solution in the same manner as in example 1.
Example 4
The non-aqueous electrolyte of the lithium ion battery consists of an organic solvent, electrolyte lithium salt and a functional additive; the functional additive consists of a first additive, a second additive and a third additive, wherein the first additive is 1, 3-propylene sultone, the second additive is N, N-diethyl propargylamine propane sulfonate, and the third additive is vinyl sulfate; wherein:
the organic solvent comprises the following components in percentage by mass: 7 ethylene carbonate and ethylmethyl carbonate;
the electrolyte lithium salt is lithium hexafluorophosphate, and the content of the lithium hexafluorophosphate in the nonaqueous electrolyte is 15wt%;
the content of the 1, 3-propylene sultone in the nonaqueous electrolyte is 1wt%;
the content of the N, N-diethyl propargylamine propane sulfonic acid inner salt in the nonaqueous electrolyte is 1wt%;
the content of the vinyl sulfate in the nonaqueous electrolyte is 0.5wt%;
the preparation method of the lithium ion battery nonaqueous electrolyte solution in the embodiment specifically comprises the following steps: in a glove box filled with argon (water is less than 0.1ppm, oxygen is less than 0.1 ppm), uniformly mixing ethylene carbonate and methyl ethyl carbonate according to a proportion, then sequentially adding lithium hexafluorophosphate, 1, 3-propylene sultone, N-diethyl propargylamine propane sulfonate and ethylene sulfate according to a proportion, and dissolving to obtain the non-aqueous electrolyte of the lithium ion battery.
The lithium ion battery of this example was assembled by using the nonaqueous electrolyte solution of the lithium ion battery of this example as an electrolyte solution in the same manner as in example 1.
Example 5
The non-aqueous electrolyte of the lithium ion battery consists of an organic solvent, electrolyte lithium salt and a functional additive; the functional additive consists of a first additive, a second additive and a third additive, wherein the first additive is 1, 3-propylene sultone, the second additive is N, N-diethyl propargylamine propane sulfonate, and the third additive is vinyl sulfate; wherein:
the organic solvent comprises the following components in percentage by mass: 7 ethylene carbonate and ethylmethyl carbonate;
the electrolyte lithium salt is lithium hexafluorophosphate, and the content of the lithium hexafluorophosphate in the nonaqueous electrolyte is 15wt%;
the content of the 1, 3-propylene sultone in the nonaqueous electrolyte is 1wt%;
the content of the N, N-diethyl propargylamine propane sulfonic acid inner salt in the nonaqueous electrolyte is 1wt%;
the content of the vinyl sulfate in the nonaqueous electrolyte is 2wt%;
the preparation method of the lithium ion battery nonaqueous electrolyte solution in the embodiment specifically comprises the following steps: in a glove box filled with argon (water is less than 0.1ppm, oxygen is less than 0.1 ppm), uniformly mixing ethylene carbonate and methyl ethyl carbonate according to a proportion, then sequentially adding lithium hexafluorophosphate, 1, 3-propylene sultone, N-diethyl propargylamine propane sulfonate and ethylene sulfate according to a proportion, and dissolving to obtain the non-aqueous electrolyte of the lithium ion battery.
The lithium ion battery of this example was assembled by using the nonaqueous electrolyte solution of the lithium ion battery of this example as an electrolyte solution in the same manner as in example 1.
Comparative example 1
The non-aqueous electrolyte of the lithium ion battery of the comparative example consists of an organic solvent and electrolyte lithium salt, wherein:
the organic solvent comprises the following components in percentage by mass: 7 ethylene carbonate and ethylmethyl carbonate;
the electrolyte lithium salt is lithium hexafluorophosphate, and the content of the lithium hexafluorophosphate in the nonaqueous electrolyte is 15wt%.
The preparation method of the lithium ion battery nonaqueous electrolyte solution of the comparative example specifically comprises the following steps: in a glove box filled with argon (water is less than 0.1ppm, oxygen is less than 0.1 ppm), uniformly mixing ethylene carbonate and methyl ethyl carbonate according to a proportion, adding lithium hexafluorophosphate according to a proportion, and dissolving to obtain the non-aqueous electrolyte of the lithium ion battery.
The lithium ion battery of this comparative example was assembled in the same manner as in example 1 using the nonaqueous electrolyte of the lithium ion battery of this comparative example as the electrolyte.
Comparative example 2
The non-aqueous electrolyte of the lithium ion battery of the comparative example consists of an organic solvent, electrolyte lithium salt and 1, 3-propylene sultone; wherein:
the organic solvent comprises the following components in percentage by mass: 7 ethylene carbonate and ethylmethyl carbonate;
the electrolyte lithium salt is lithium hexafluorophosphate, and the content of the lithium hexafluorophosphate in the nonaqueous electrolyte is 15wt%;
the content of the 1, 3-propylene sultone in the nonaqueous electrolyte is 1wt%.
The preparation method of the lithium ion battery nonaqueous electrolyte solution in the embodiment specifically comprises the following steps: in a glove box filled with argon (water is less than 0.1ppm, oxygen is less than 0.1 ppm), uniformly mixing ethylene carbonate and methyl ethyl carbonate according to a proportion, then sequentially adding lithium hexafluorophosphate and 1, 3-propylene sultone according to the proportion, and dissolving to obtain the non-aqueous electrolyte of the lithium ion battery.
The lithium ion battery of this comparative example was assembled in the same manner as in example 1 using the nonaqueous electrolyte of the lithium ion battery of this comparative example as the electrolyte.
Comparative example 3
The non-aqueous electrolyte of the lithium ion battery of the comparative example consists of an organic solvent, an electrolyte lithium salt, 1, 3-propylene sultone and N, N-diethyl propargylamine propane sulfonic acid inner salt; wherein:
the organic solvent comprises the following components in percentage by mass: 7 ethylene carbonate and ethylmethyl carbonate;
the electrolyte lithium salt is lithium hexafluorophosphate, and the content of the lithium hexafluorophosphate in the nonaqueous electrolyte is 15wt%;
the content of the 1, 3-propylene sultone in the nonaqueous electrolyte is 1wt%;
the content of the N, N-diethyl propargylamine propane sulfonic acid inner salt in the nonaqueous electrolyte is 1wt%.
The preparation method of the lithium ion battery nonaqueous electrolyte solution in the embodiment specifically comprises the following steps: in a glove box filled with argon (water is less than 0.1ppm, oxygen is less than 0.1 ppm), uniformly mixing ethylene carbonate and methyl ethyl carbonate according to a proportion, then sequentially adding lithium hexafluorophosphate, 1, 3-propylene sultone and N, N-diethyl propargylamine propane sulfonate according to a proportion, and obtaining the nonaqueous electrolyte of the lithium ion battery after dissolution.
The lithium ion battery of this comparative example was assembled in the same manner as in example 1 using the nonaqueous electrolyte of the lithium ion battery of this comparative example as the electrolyte.
TABLE 1 additive formulations in lithium ion battery nonaqueous electrolyte solutions of examples 1-5 and comparative examples 1-2
Table 2 comparative table of the results of the performance tests of the lithium ion batteries assembled in examples 1 to 5 and comparative examples 1 to 3
As shown in the results of table 2, the electrolyte without the additive in comparative example 1 exhibited a poor cycle life, and the ohmic internal resistance was high and the low temperature performance was poor. When the second additive, the third additive and the third additive are not added at the same time in comparative examples 2 and 3, the cycle life of the battery is improved, but the ohmic internal resistance of the battery is higher, the low-temperature performance is poorer, and the cycle performance and the low-temperature performance cannot be effectively considered. When the three additives are used simultaneously, the ohmic internal resistance of the battery is reduced, the low-temperature performance is excellent, and the excellent cycle life can be realized.
In summary, the first additive, the second additive and the third additive are used as the electrode interface film forming additive at the same time, and the composition and structure of the formed interface film can be optimized by using the first additive, the second additive and the third additive at the same time, so that the battery performance can be obviously improved, and the low impedance, the long cycle life and the excellent low-temperature performance can be simultaneously considered.
It can be seen that the nonaqueous electrolyte technical scheme and the battery applying the nonaqueous electrolyte technical scheme provided by the application have excellent low-temperature performance and realize improved cycle life, and show extremely high application value. The foregoing is a specific description of a possible embodiment of the application, but is not intended to limit the scope of the application.
Claims (10)
1. A lithium ion battery nonaqueous electrolyte, characterized in that: comprises an organic solvent, electrolyte lithium salt and a functional additive; wherein: the functional additive comprises a first additive, a second additive and a third additive, wherein the first additive is 1, 3-propylene sultone, the second additive is N, N-diethyl propargylamine propane sulfonate, and the third additive is vinyl sulfate.
2. The lithium ion battery nonaqueous electrolyte according to claim 1, wherein: the content of the 1, 3-propylene sultone accounts for 0.1-3 wt% of the nonaqueous electrolyte.
3. The lithium ion battery nonaqueous electrolyte according to claim 1, wherein: the content of the N, N-diethyl propargylamine propane sulfonic acid inner salt accounts for 0.1-2 wt% of the nonaqueous electrolyte.
4. The lithium ion battery nonaqueous electrolyte according to claim 1, wherein: the content of the vinyl sulfate accounts for 0.1-2 wt% of the nonaqueous electrolyte.
5. The lithium ion battery nonaqueous electrolyte according to claim 1, wherein: the organic solvent comprises one or more of cyclic carbonate and linear carbonate or carboxylate.
6. The lithium ion battery nonaqueous electrolyte according to claim 1, wherein: the content of the electrolyte lithium salt accounts for 10.0-20wt% of the total mass of the nonaqueous electrolyte.
7. Use of the non-aqueous electrolyte for lithium ion batteries according to any one of claims 1 to 6 in lithium ion batteries.
8. A lithium ion battery, characterized in that: comprising a positive electrode, a negative electrode, a separator interposed between the positive electrode and the negative electrode, and a nonaqueous electrolyte, the nonaqueous electrolyte being the lithium ion battery nonaqueous electrolyte according to any one of claims 1 to 6.
9. The lithium ion battery of claim 8, wherein: the positive electrode active material is one or more than two of ternary materials, lithium cobaltate and lithium manganate materials; the negative electrode active material comprises one or two of graphite and silicon-based materials.
10. The lithium ion battery of claim 8, wherein: the working voltage range of the lithium ion battery is 3-4.5V.
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