CN109818062B - Ternary lithium ion battery and electrolyte thereof - Google Patents
Ternary lithium ion battery and electrolyte thereof Download PDFInfo
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- CN109818062B CN109818062B CN201910175991.XA CN201910175991A CN109818062B CN 109818062 B CN109818062 B CN 109818062B CN 201910175991 A CN201910175991 A CN 201910175991A CN 109818062 B CN109818062 B CN 109818062B
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 81
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 40
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 59
- 239000000654 additive Substances 0.000 claims abstract description 52
- 230000000996 additive effect Effects 0.000 claims abstract description 48
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 40
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 22
- 239000000203 mixture Substances 0.000 claims abstract description 12
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 claims description 52
- -1 tris (2, 4, 6-trifluoromethylphenyl) phosphite Chemical compound 0.000 claims description 35
- ZRZFJYHYRSRUQV-UHFFFAOYSA-N phosphoric acid trimethylsilane Chemical compound C[SiH](C)C.C[SiH](C)C.C[SiH](C)C.OP(O)(O)=O ZRZFJYHYRSRUQV-UHFFFAOYSA-N 0.000 claims description 26
- 229910003002 lithium salt Inorganic materials 0.000 claims description 16
- 159000000002 lithium salts Chemical class 0.000 claims description 16
- 239000003960 organic solvent Substances 0.000 claims description 16
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 13
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 9
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 8
- 239000002131 composite material Substances 0.000 claims description 7
- 229910021450 lithium metal oxide Inorganic materials 0.000 claims description 7
- 229910017052 cobalt Inorganic materials 0.000 claims description 6
- 239000010941 cobalt Substances 0.000 claims description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 6
- 239000011149 active material Substances 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 239000010405 anode material Substances 0.000 claims description 3
- 239000000919 ceramic Substances 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 3
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 3
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 3
- 239000011572 manganese Substances 0.000 claims description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 239000007773 negative electrode material Substances 0.000 claims description 2
- 239000013543 active substance Substances 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 17
- 125000000217 alkyl group Chemical group 0.000 abstract description 13
- 125000003545 alkoxy group Chemical group 0.000 abstract description 9
- 125000005843 halogen group Chemical group 0.000 abstract description 8
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 239000002000 Electrolyte additive Substances 0.000 description 38
- 230000014759 maintenance of location Effects 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- 238000000034 method Methods 0.000 description 13
- 125000004432 carbon atom Chemical group C* 0.000 description 8
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 238000006864 oxidative decomposition reaction Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 229910013872 LiPF Inorganic materials 0.000 description 3
- 101150058243 Lipf gene Proteins 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000003247 decreasing effect Effects 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 238000006056 electrooxidation reaction Methods 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 2
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 2
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 2
- 239000002775 capsule Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000011162 core material Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 150000007517 lewis acids Chemical class 0.000 description 2
- RSNHXDVSISOZOB-UHFFFAOYSA-N lithium nickel Chemical compound [Li].[Ni] RSNHXDVSISOZOB-UHFFFAOYSA-N 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 description 1
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910013075 LiBF Inorganic materials 0.000 description 1
- 229910013716 LiNi Inorganic materials 0.000 description 1
- 229910003005 LiNiO2 Inorganic materials 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 229920002472 Starch Polymers 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
- LHIJANUOQQMGNT-UHFFFAOYSA-N aminoethylethanolamine Chemical compound NCCNCCO LHIJANUOQQMGNT-UHFFFAOYSA-N 0.000 description 1
- 239000006183 anode active material Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000006182 cathode active material Substances 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 238000005524 ceramic coating Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000005002 finish coating Substances 0.000 description 1
- 206010016766 flatulence Diseases 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 101150091094 lipA gene Proteins 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 229910000032 lithium hydrogen carbonate Inorganic materials 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000011356 non-aqueous organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
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- 238000003756 stirring Methods 0.000 description 1
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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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Abstract
The invention relates to the field of lithium ion batteries, and discloses a ternary lithium ion battery and electrolyte thereof. The electrolyte includes: the electrolyte comprises a base electrolyte and an additive, wherein the additive comprises one or a mixture of a first additive and a second additive, and the molecular structural formula of the first additive is shown in the specification
R1 is any one of halogen group, alkoxy and alkyl, R2 is any one of halogen group, alkoxy and alkyl, and R3 is any one of halogen group, alkoxy and alkyl; the molecular structural formula of the second additive is
Description
Technical Field
The invention relates to the field of lithium ion batteries, and discloses a ternary lithium ion battery and electrolyte thereof.
Background
In recent 20 years, with the gradual exhaustion of petrochemical energy and the increasing severity of greenhouse effect, people are continuously prompted to explore sustainable and clean energy. The lithium ion battery as a novel green high-energy battery attracts attention of many scientific research technicians because of the advantages of high working voltage, large specific capacity, long cycle life, low self-discharge rate, no memory effect, environmental friendliness and the like.
With the continuous increase of energy density, the commercialized ternary material has been updated from NCM333 to NCM523, and even NCM622 and NCM811 have been produced on a large scale by a plurality of manufacturers. Increasing the Ni content without changing the charge cut-off voltage is one of the methods for increasing the gram capacity of a layered lithium-nickel composite oxide (so-called ternary material) because Ni2+/Ni3+Oxidation to Ni3+/Ni4+Desired potential ratio Co3+Conversion to Co4+And lower. The ternary material (nickel cobalt lithium manganate) can greatly improve the specific capacity of the material by improving the content of nickel, so that the high-nickel ternary material is inevitably an ideal material for large-scale batteries in the future.
However, as the content of nickel is increased, the chemical formula of nickel is already similar to that of LiNiO2Almost, the carbonate electrolyte of the conventional lithium ion battery is easily decomposed under high voltage, so that the charging and discharging efficiency of the lithium ion battery is obviously reduced, the cycle performance is deteriorated, and the commercial application of the high voltage lithium ion battery is not facilitated. Meanwhile, active oxygen and high-valent nickel in the lithium-nickel composite oxide oxidize the carbonate electrolyte, and LiPF is contained in the electrolyte6Will be decomposed and will further react with trace moisture in the solvent to form HF, which will further react with Li2CO3、LiHCO3Reaction with LiOH impurities to produce CO2Gas and H2And O. Hydrofluoric acid destroys SEI film, causing secondary film formation, and at the same time, flatulence may bulge and break, H2O as an initiator to further catalyze LiPF6And produce a large amount of CO2Affecting the electrochemical performance of the cell.
The patent CN 201810227145.3 invention discloses a safety additive for high-nickel ternary lithium battery electrolyte. The preparation method comprises the following steps: mixing monoethanolamine and hydroxyethyl ethylenediamine to obtain a core material mixture; mixing polyurethane glue and porous starch to obtain a capsule wall material; and allowing the obtained capsule material fluid to flow down from a high position to form a waterfall-shaped fluid, simultaneously atomizing the core material mixture to spray out at a high speed, and quickly condensing the sprayed mixture after the sprayed mixture passes through the waterfall-shaped fluid to finish coating, thereby obtaining the safety additive for the high-nickel ternary lithium battery electrolyte.
The invention discloses an electrolyte with high safety for a high-nickel high-voltage lithium battery in the patent CN 201611064569.X, wherein the electrolyte mainly comprises a non-aqueous organic solvent, a lithium salt, an additive and a negative film-forming agent; the negative electrode film-forming agent is any one or a mixture of several of vinylene carbonate, ethylene carbonate, 1, 3-propane sultone or fluoroethylene carbonate. The electrolyte can play a role in protecting the electrode, improve the compatibility of the electrolyte and high-voltage battery materials, and improve the cycle performance of the battery
Disclosure of Invention
One of the purposes of the embodiments of the present invention is to provide a ternary lithium ion battery and an electrolyte thereof, and the technical solution of the embodiments of the present invention is applied to a high-capacity high-nickel ternary lithium battery, which is beneficial to improving the compatibility of the electrolyte and a high-voltage battery material. The cycle performance of the battery is improved.
In a first aspect, an electrolyte suitable for a ternary lithium ion battery provided in an embodiment of the present invention includes:
a base electrolyte comprising: lithium salts, and organic solvents;
the additive comprises one of the first additive and the second additive or is mixed,
the molecular structural formula of the first additive is as follows:
the molecular structural formula of the second additive is as follows:
Optionally, the additive comprises, in parts by mass: 0.3 to 10 percent.
Optionally, the first additive is: tris (2, 4, 6-trifluoromethylphenyl) phosphite, triphenyl phosphite, either alone or in combination.
Optionally, the tris (2, 4, 6-trifluoromethylphenyl) phosphite accounts for 10% of the electrolyte by mass.
Optionally, the triphenyl phosphite accounts for 10% of the electrolyte by mass.
Optionally, the second additive is: tris (trimethylsilane) phosphate.
Optionally, the tris (trimethylsilane) phosphate accounts for 10% by mass of the electrolyte.
Optionally, the additive is formed by mixing tris (2, 4, 6-trifluoromethylphenyl) phosphite, triphenyl phosphite and tris (trimethylsilane) phosphate.
Optionally, the additive is formed by mixing a first additive and a second additive,
the first additive is formed by mixing tris (2, 4, 6-trifluoromethylphenyl) phosphite and triphenyl phosphite, and the second additive is tris (trimethylsilane) phosphate.
Optionally, the molar mass ratio of the tris (2, 4, 6-trifluoromethylphenyl) phosphite to the triphenyl phosphite to the tris (trimethylsilane) phosphate is (1-2) to (1-2).
Alternatively, the number of carbon atoms of the alkoxy group is any one of 1 to 5.
Optionally, the number of carbon atoms of the alkyl group in the first additive is any one of 1 to 13.
Optionally, the number of carbon atoms of the alkyl group in the first additive is any one of 1 to 10.
Alternatively, the lithium salt is: one or a mixture of two or more of lithium hexafluorophosphate, lithium hexaarsenophosphate, lithium tetrafluoroborate and lithium perchlorate.
Optionally, the concentration of lithium ions in the base electrolyte is 0.8mol/L to 1.5 mol/L.
Optionally, the concentration of lithium ions in the base electrolyte is 1 mol/L.
Optionally, the organic solvent consists of: ethylene carbonate, diethyl carbonate, and dimethyl carbonate.
Optionally, the ethylene carbonate, the diethyl carbonate, and the dimethyl carbonate are in a molar mass ratio of: (2-3): (1-3): (4-7).
Optionally, the ethylene carbonate, the diethyl carbonate, and the dimethyl carbonate are in a molar mass ratio of: 3: 2: 5.
In a second aspect, an embodiment of the present invention provides a ternary lithium ion battery including any one of the above-mentioned electrolytes.
Optionally, the active material in the cathode material is a composite lithium metal oxide containing three elements of nickel, cobalt and manganese, or three elements of nickel, cobalt and aluminum.
Optionally, the complex lithium metal oxide has a molecular formula of Li (Ni)xCoyMnz)O2，
0.6＜x≤0.8，y＞0，z＞0，x+y+z＝1。
Optionally, the complex lithium metal oxide has a molecular formula of Li (Ni)xCoyAlz)O2，
0.7＜x≤0.8，y＞0，z＞0，x+y+z＝1。
Optionally, the active material in the negative electrode material is metallic lithium or graphite.
Optionally, wherein at least one surface of the membrane is coated with a ceramic layer.
Therefore, by adopting the technical scheme of the embodiment, the additive in the electrolyte has higher oxidability relative to organic solvent molecules in the basic electrolyte, the additive preferentially generates electrochemical oxidation on the surface of the anode of the lithium battery, and an SEI film is formed on the surface of the anode, so that the oxidative decomposition of the organic solvent in the electrolyte in the high-voltage charge-discharge cycle process can be effectively inhibited, the oxidative decomposition of the electrolyte and the damage of the hydrolysis and pyrolysis reactions of lithium salts in the electrolyte to the structure of the anode material can be effectively inhibited, the electrochemical window of the electrolyte is widened, and the cycle multiplying power performance of the battery is improved.
Experiments prove that the additive of the electrolyte has a wider electrochemical window, is suitable for a charging voltage of 2.8-5.0V, is not easy to oxidize and decompose in a high-nickel ternary lithium ion battery, has good cycle and safety performance under a high voltage (4.5-5V), and improves the cycle capacity retention rate by more than 10% after the electrolyte is adopted in the high-nickel ternary material lithium ion battery and subjected to charge and discharge cycles for 200 times under the charge and discharge multiplying power of 0.5C.
In addition, under higher voltage (4.5-5V), the electrolyte containing the electrolyte additive can inhibit the organic solvent from undergoing oxidative decomposition and lithium salt hydrolysis reaction, and reduce CO2And hydrofluoric acid and various Lewis acids are generated, so that the gas generation problems of secondary film formation, bulge rupture and the like caused by gas expansion and the like caused by the damage of an SEI film are prevented.
Drawings
Fig. 1 is a comparative schematic diagram of capacity retention ratios of some examples and comparative examples provided in the examples of the present invention.
Detailed Description
The invention will be described in detail with reference to the specific drawings and examples, which are illustrative of the invention and are not to be construed as limiting the invention.
This example provides an electrolyte suitable for a high-capacity high-nickel ternary lithium ion battery, which includes a conventional basic electrolyte composed of a mixture of lithium salt and an organic solvent, and further mixed with the additive of this example.
As an illustration of the present embodiment, the additive is added in a range of 0.3 to 10 mass% of the electrolyte.
According to the preparation method of the lithium battery electrolyte, provided by the embodiment of the invention, only the additive of the lithium battery electrolyte is mixed with the basic electrolyte. The usual preparation method is as follows: the organic solvent can be stirred and mixed uniformly at normal temperature according to the proportion, then the lithium salt is added and mixed uniformly while stirring, and finally the prepared additive of the lithium battery electrolyte is added and mixed uniformly to obtain the electrolyte of the embodiment of the invention.
As an illustration of the present embodiment, the lithium salt in the basic electrolyte of the present embodiment is selected from lithium hexafluorophosphate (chemical formula LiPF)6) Lithium hexa-arsenate phosphate (chemical formula LiPAs)6) Lithium tetrafluoroborate (chemical formula is LiBF)4) Lithium perchlorate (chemical formula LiClO)4) At least one of (1). Wherein the concentration of lithium ions in the selected lithium salt in the basic electrolyte is 0.8-1.5 mol/L, for exampleFor example, the concentration of the lithium salt is any one of 1.0mol/L, 1.20mol/L, and 1.30 mol/L. Preferably, the lithium salt concentration is 1.0 mol/L.
As an illustration of this example, the organic solvent of this example includes ethylene carbonate (commonly known as EC), diethyl carbonate (commonly known as DEC), and dimethyl carbonate (commonly known as DMC) mixed with each other.
Wherein the molar mass ratio of EC, DEC and DMC is EC, DEC and DMC: (1-2): (1-2). The preferred scheme is as follows: EC, DEC and DMC were 3: 2: 5.
The additive of the embodiment comprises one of the first additive and the second additive or a mixture of the first additive and the second additive.
Wherein the molecular structural formula of the first additive is as follows:
r2 may be selected from any of a halogen group, an alkoxy group (having 1 to 5 carbon atoms) and an alkyl group (having 1 to 13 carbon atoms).
As an illustration of this embodiment, any one of tris (2, 4, 6-trifluoromethylphenyl) phosphite, triphenyl phosphite, or a mixture thereof may be used as the first additive.
The molecular structure of the second additive is as follows:
As an illustration of this embodiment, tris (trimethylsilane) phosphate, for example, can be used as the second additive.
Wherein the molecular structural formulas of the tris (2, 4, 6-trifluoromethylphenyl) phosphite, the triphenyl phosphite and the tris (trimethylsilane) phosphate are respectively as follows:
the additive of this example is prepared by mixing tris (2, 4, 6-trifluoromethylphenyl) phosphite, triphenyl phosphite, and tris (trimethylsilane) phosphate.
In this example, tris (2, 4, 6-trifluoromethylphenyl) phosphite, triphenyl phosphite, and tris (trimethylsilane) phosphate were mixed in the following molar mass ratios: (1-2): (1-2).
The electrolyte of the embodiment can be suitable for a ternary lithium ion battery, and is particularly suitable for a high-capacity high-nickel ternary lithium battery. For example, a lithium ion battery includes a positive electrode, a negative electrode, a separator, and the electrolyte of this embodiment. Wherein the preparation processes of the positive electrode, the negative electrode, the separator and the battery can be, but are not limited to, see the prior art. The battery can be various types of batteries in the prior art, and is preferably, but not limited to, a button type lithium ion battery.
As an illustration of the present embodiment, the active material in the positive electrode may be selected from a composite lithium metal oxide of nickel, cobalt and manganese or three elements of nickel, cobalt and aluminum.
Such as but not limited to, the following formula: li (Ni)xCoyMnz)O2The high nickel-cobalt-manganese ternary material is characterized in that x is more than 0.6 and less than or equal to 0.8, y is more than 0, z is more than 0, and x + y + z is 1;
also for example, but not limited to, the formula: li (Ni)xCoyAlz)O2The high nickel-cobalt-aluminum ternary material is characterized in that x is more than 0.7 and less than or equal to 0.8, y is more than 0, z is more than 0, and x + y + z is 1.
As an illustration of this embodiment, the active material of the negative electrode may be metallic lithium or graphite.
As an illustration of the present embodiment, the separator of the present embodiment may be a separator coated with a ceramic coating on one side or both sides.
The additive in the electrolyte has higher oxidability relative to organic solvent molecules in the basic electrolyte, the additive is preferentially subjected to electrochemical oxidation on the surface of the anode of the lithium battery, and an SEI film is formed on the surface of the anode, so that the oxidative decomposition of the organic solvent in the electrolyte in the high-voltage charge-discharge cycle process can be effectively inhibited, the oxidative decomposition of the electrolyte and the damage of hydrolysis and pyrolysis reactions of lithium salts in the electrolyte to the structure of an anode material can be effectively inhibited, the electrochemical window of the electrolyte is widened, and the cycle rate performance of the battery is improved.
Experiments prove that the additive of the electrolyte has a wider electrochemical window, is suitable for a charging voltage of 2.8-5.0V, is not easy to oxidize and decompose in a high-nickel ternary lithium ion battery, has good cycle and safety performance under a high voltage (4.5-5V), and improves the cycle capacity retention rate by more than 10% after the electrolyte is adopted in the high-nickel ternary material lithium ion battery and subjected to charge and discharge cycles for 200 times under the charge and discharge multiplying power of 0.5C.
In addition, under higher voltage (4.5-5V), the electrolyte containing the electrolyte additive can inhibit the organic solvent from undergoing oxidative decomposition and lithium salt hydrolysis reaction, and reduce CO2And hydrofluoric acid and various Lewis acids are generated, so that the gas generation problems of secondary film formation, bulge rupture and the like caused by gas expansion and the like caused by the damage of an SEI film are prevented.
The present application is further illustrated below with reference to examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present application. In the following examples, the materials and reagents used were commercially available without specific reference.
Example 1:
0.3 wt% of tris (2, 4, 6-trifluoromethylphenyl) phosphite is dissolved as an electrolyte additive in a basic electrolyte, wherein the molar mass ratio EC: DEC: DMC of the organic solvents ethylene carbonate, diethyl carbonate and dimethyl carbonate in the basic electrolyte is 3: 2: 5, and the lithium salt LiPF is6The molar concentration of the nickel-cobalt-manganese ternary material LiNi is 1.0mol/L0.8Co0.1Mn0.1O2As the anode active material, the metal lithium is used as the cathode active material, the anode current collector and the cathode current collector respectively adopt aluminum foil and copper foil,the diaphragm adopts a ceramic diaphragm and is assembled into a 2032 type button cell of ternary 811/metallic lithium.
Example 2:
a ternary 811/lithium metal button cell was prepared according to the method of example 1 except that the electrolyte additive was 0.5 weight percent tris (2, 4, 6-trifluoromethylphenyl) phosphite.
The remaining conditions were the same as in example 1.
Example 3:
a ternary 811/lithium metal button cell was prepared according to the method of example 1 except that the electrolyte additive was 2 wt% tris (2, 4, 6-trifluoromethylphenyl) phosphite.
The remaining conditions were the same as in example 1.
Example 4:
a ternary 811/lithium metal button cell was prepared according to the method of example 1 except that the electrolyte additive was 6 wt% tris (2, 4, 6-trifluoromethylphenyl) phosphite.
The remaining conditions were the same as in example 1.
Example 5:
a ternary 811/lithium metal button cell was prepared according to the method of example 1 except that the electrolyte additive was 8 wt% tris (2, 4, 6-trifluoromethylphenyl) phosphite.
The remaining conditions were the same as in example 1.
Example 6:
a ternary 811/lithium metal button cell was prepared according to the method of example 1 except that the electrolyte additive was 10 weight percent tris (2, 4, 6-trifluoromethylphenyl) phosphite.
The remaining conditions were the same as in example 1.
Example 7:
a ternary 811/lithium metal button cell was prepared according to the method of example 1 except that the electrolyte additive was 11 weight percent tris (2, 4, 6-trifluoromethylphenyl) phosphite.
The remaining conditions were the same as in example 1.
Example 8:
a ternary 811/lithium metal button cell was prepared according to the method of example 1 except that the electrolyte additive was 15 wt% tris (2, 4, 6-trifluoromethylphenyl) phosphite.
The remaining conditions were the same as in example 1.
Example 9:
a ternary 811/lithium metal button cell was prepared as in example 1 except that the electrolyte additive was 0.3 wt% triphenyl phosphite.
The remaining conditions were the same as in example 1.
Example 10:
a ternary 811/lithium metal button cell was prepared as in example 1 except that the electrolyte additive was 0.5 wt% triphenyl phosphite.
The remaining conditions were the same as in example 1.
Example 11:
a ternary 811/lithium metal button cell was prepared as in example 1 except that the electrolyte additive was 2 wt% triphenyl phosphite.
The remaining conditions were the same as in example 1.
Example 12:
a ternary 811/lithium metal button cell was prepared as in example 1 except that the electrolyte additive was 6 wt% triphenyl phosphite.
The remaining conditions were the same as in example 1.
Example 13:
a ternary 811/lithium metal button cell was prepared as in example 1 except that the electrolyte additive was 8 wt% triphenyl phosphite.
The remaining conditions were the same as in example 1.
Example 14:
a ternary 811/lithium metal button cell was prepared as in example 1 except that the electrolyte additive was 10 wt% triphenyl phosphite.
The remaining conditions were the same as in example 1.
Example 15:
a ternary 811/lithium metal button cell was prepared as in example 1 except that the electrolyte additive was 11 wt% triphenyl phosphite.
The remaining conditions were the same as in example 1.
Example 16:
a ternary 811/lithium metal button cell was prepared as in example 1 except that the electrolyte additive was 15 wt% triphenyl phosphite.
The remaining conditions were the same as in example 1.
Example 17:
a ternary 811/lithium metal button cell was prepared as in example 1 except that the electrolyte additive was 0.3 wt% tris (trimethylsilane) phosphate.
The remaining conditions were the same as in example 1.
Example 18:
a ternary 811/lithium metal button cell was prepared as in example 1 except that the electrolyte additive was 0.5 wt% tris (trimethylsilane) phosphate.
The remaining conditions were the same as in example 1.
Example 19:
a ternary 811/lithium metal button cell was prepared as in example 1 except that the electrolyte additive was 2 wt% tris (trimethylsilane) phosphate.
The remaining conditions were the same as in example 1.
Example 20:
a ternary 811/lithium metal button cell was prepared as in example 1 except that the electrolyte additive was 6 wt% tris (trimethylsilane) phosphate.
The remaining conditions were the same as in example 1.
Example 21:
a ternary 811/lithium metal button cell was prepared as in example 1 except that the electrolyte additive was 8 wt% tris (trimethylsilane) phosphate.
The remaining conditions were the same as in example 1.
Example 22:
a ternary 811/lithium metal button cell was prepared as in example 1 except that the electrolyte additive was 10 wt% tris (trimethylsilane) phosphate.
The remaining conditions were the same as in example 1.
Example 23:
a ternary 811/lithium metal button cell was prepared as in example 1 except that the electrolyte additive was 11 wt% tris (trimethylsilane) phosphate.
The remaining conditions were the same as in example 1.
Example 24:
a ternary 811/lithium metal button cell was prepared as in example 1 except that the electrolyte additive was 15 wt% tris (trimethylsilane) phosphate.
The remaining conditions were the same as in example 1.
Example 25:
a ternary 811/lithium metal button cell was prepared as in example 1 except that the electrolyte additive was 3 wt% tris (2, 4, 6-trifluoromethylphenyl) phosphite and 6 wt% triphenyl phosphite.
The remaining conditions were the same as in example 1.
Example 26:
a ternary 811/lithium metal button cell was prepared according to the method of example 1 except that the electrolyte additive was 3 wt% tris (2, 4, 6-trifluoromethylphenyl) phosphite and 3 wt% tris (trimethylsilane) phosphate.
The remaining conditions were the same as in example 1.
Example 27:
a ternary 811/lithium metal button cell was prepared as in example 1 except that the electrolyte additive was 3 wt% triphenyl phosphite and 3 wt% tris (trimethylsilane) phosphate.
The remaining conditions were the same as in example 1.
Example 28:
a ternary 811/lithium metal button cell was prepared as in example 1 except that the electrolyte additive was 2 wt% tris (2, 4, 6-trifluoromethylphenyl) phosphite, 2 wt% triphenyl phosphite and 2 wt% tris (trimethylsilane) phosphate.
The remaining conditions were the same as in example 1.
Example 29:
a ternary 811/lithium metal button cell was prepared as in example 1 except that the electrolyte additive was 3 wt% tris (2, 4, 6-trifluoromethylphenyl) phosphite, 2 wt% triphenyl phosphite and 2 wt% tris (trimethylsilane) phosphate.
The remaining conditions were the same as in example 1.
Example 30:
a ternary 811/lithium metal button cell was prepared as in example 1 except that the electrolyte additive was 2 wt% tris (2, 4, 6-trifluoromethylphenyl) phosphite, 3 wt% triphenyl phosphite and 2 wt% tris (trimethylsilane) phosphate.
The remaining conditions were the same as in example 1.
Example 31:
a ternary 811/lithium metal button cell was prepared as in example 1 except that the electrolyte additive was 2 wt% tris (2, 4, 6-trifluoromethylphenyl) phosphite, 2 wt% triphenyl phosphite and 3 wt% tris (trimethylsilane) phosphate.
The remaining conditions were the same as in example 1.
Comparative example 1
A base electrolyte and a lithium battery were prepared according to the method of example 1, except that no electrolyte additive was added.
The remaining conditions were the same as in example 1.
Comparative example 2
A base electrolyte and a lithium cell were prepared according to the method of example 1, except that the electrolyte additive of patent CN 201810227145.3 was used, and the other conditions were the same as in example 1.
The remaining conditions were the same as in example 1.
Comparative example 3
A base electrolyte and a lithium cell were prepared as in example 1, except that the electrolyte additive of patent CN 201611064569.X was used, and the other conditions were the same as in example 1.
The remaining conditions were the same as in example 1.
After the button lithium battery prepared in examples 1-31 and comparative examples 1-3 were left to stand for 24 hours, the capacity retention of the lithium battery was measured according to the conventional method for measuring the capacity retention of the battery after 200 cycles of charging and discharging at room temperature with a potential range of 2.8-5V and a charging and discharging rate of 0.5C, and the results are shown in Table I. FIG. 1 is a comparative graph of capacity retention in some examples and comparative examples.
Table one:
as is apparent from the table I, the lithium batteries prepared by adding different types or different mass fractions of electrolyte additives in the lithium batteries prepared in the examples 1 to 31 are respectively compared with the lithium battery prepared in the comparative example 1 without adding the electrolyte additive, and the room temperature and high temperature cycle performance of the lithium battery prepared by the electrolyte in each example is obviously better than that of the lithium batteries prepared in the comparative examples 1 to 3. The inventor of the invention finds that the phosphite ester compound additive has higher oxidizability than organic solvent molecules, electrochemical oxidation can be preferentially carried out on the surface of the positive electrode, a stable and uniform interface film can be formed, decomposition of an organic solvent in the electrolyte is inhibited, side reaction between the electrolyte and a positive electrode material is avoided as far as possible, and meanwhile, the problem of gas generation of a high-voltage ternary lithium battery is solved.
From the test results in table one, it can be seen that in comparative examples 1 to 8, when the addition amount of tris (2, 4, 6-trifluoromethylphenyl) phosphite is 0.3 wt% to 10 wt% after the charge and discharge cycle is performed 200 times at the charge and discharge rate of 0.5C, the capacity retention rate is increased with the increase of the addition amount, when the addition amount exceeds 10 wt%, the capacity retention rate is decreased with the increase of the addition amount, and the optimum addition amount is between 6% and 10%.
In comparative examples 9 to 16, after the charge and discharge cycle was performed 200 times at a charge and discharge rate of 0.5C, when the amount of triphenyl phosphite added was 0.3 wt% to 10 wt%, the capacity retention rate increased with the increase of the amount of addition, and when it exceeded 10 wt%, the capacity retention rate decreased with the increase of the amount of addition, and the optimum amount of addition was 6% to 10%.
In comparative examples 17 to 24, after the charge and discharge cycles were performed 200 times at a charge and discharge rate of 0.5C, when the amount of tris (trimethylsilane) phosphate added was 0.3 wt% to 10 wt%, the capacity retention rate increased with the increase in the amount of addition, and when it exceeded 10 wt%, the capacity retention rate decreased with the increase in the amount of addition, and the optimum amount of addition was 6% to 10%.
Comparing examples 1-24 with examples 25-27, the capacity retention of the battery is higher when the electrolyte is mixed by two additives compared with the electrolyte with a single additive component; comparing examples 25 to 27 with examples 28 to 31, the capacity retention rate of the battery was higher with the electrolyte in which three additives were mixed, compared with the electrolyte in which two additives were mixed.
The above-described embodiments do not limit the scope of the present invention. Any modification, equivalent replacement, and improvement made within the spirit and principle of the above-described embodiments should be included in the protection scope of the technical solution.
Claims (14)
1. An electrolyte suitable for a ternary lithium ion battery is characterized by comprising:
a base electrolyte comprising: lithium salts, and organic solvents;
additives including a mixture of tris (2, 4, 6-trifluoromethylphenyl) phosphite, triphenyl phosphite, tris (trimethylsilane) phosphate;
the additive comprises the following components in parts by weight: 6 to 10 percent.
2. The electrolyte for a ternary lithium ion battery according to claim 1,
the molar mass ratio of the tris (2, 4, 6-trifluoromethylphenyl) phosphite to the triphenyl phosphite to the tris (trimethylsilane) phosphate is (1-2) to (1-2).
3. The electrolyte for a ternary lithium ion battery according to claim 1,
the lithium salt is: one or a mixture of two or more of lithium hexafluorophosphate, lithium hexaarsenophosphate, lithium tetrafluoroborate and lithium perchlorate.
4. The electrolyte for a ternary lithium ion battery according to claim 1,
the concentration of lithium ions in the basic electrolyte is 0.8 mol/L-1.5 mol/L.
5. The electrolyte for a ternary lithium ion battery according to claim 4,
the concentration of lithium ions in the base electrolyte was 1 mol/L.
6. The electrolyte for a ternary lithium ion battery according to claim 1,
the organic solvent consists of: ethylene carbonate, diethyl carbonate, and dimethyl carbonate.
7. The electrolyte for a ternary lithium ion battery according to claim 6,
the ethylene carbonate, the diethyl carbonate and the dimethyl carbonate have the following molar mass ratios: (2-3): (1-3): (4-7).
8. The electrolyte for a ternary lithium ion battery according to claim 7,
the ethylene carbonate, the diethyl carbonate and the dimethyl carbonate have the following molar mass ratios: 3: 2: 5.
9. A ternary lithium ion battery comprising the electrolyte of any of claims 1 to 8.
10. The ternary lithium ion battery according to claim 9,
the active substance in the anode material is a composite lithium metal oxide containing three elements of nickel, cobalt and manganese or nickel, cobalt and aluminum.
11. The ternary lithium ion battery according to claim 10,
the molecular formula of the composite lithium metal oxide is Li (Ni)xCoyMnz)O2，
0.6＜x≤0.8，y＞0，z＞0，x+y+z＝1。
12. The ternary lithium ion battery according to claim 11,
the molecular formula of the composite lithium metal oxide is Li (Ni)xCoyAlz)O2，
0.7＜x≤0.8，y＞0，z＞0，x+y+z＝1。
13. The ternary lithium ion battery according to claim 10,
the active material in the negative electrode material is metallic lithium or graphite.
14. The ternary lithium ion battery according to claim 10,
wherein at least one surface of the separator is coated with a ceramic layer.
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| CN108539267A (en) * | 2018-03-14 | 2018-09-14 | 中航锂电（洛阳）有限公司 | A kind of lithium-ion battery electrolytes functional additive, electrolyte and lithium ion battery |
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